Technology of cellulose esters; a theoretical and practical treatise on the origin, history, chemistry, manufacture, technical application and analysis of the products of acylation and alkylation of normal and modified cellulose ..

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Library

: TECHNOLOGY OF
CELLULOSE ESTERS

A THEORETICAL AND PRACTICAL TRKA TISK ON THE ORIGIN,
HISTORY, CHEMISTRY. MANUFACTURE. TECHNICAL APPLICA-
TION AND ANALYSIS OF THE PRODUCTS OF ACYLATION AND
ALKYLATIOxN OF NORMAL AND MODIFIED CELLULOSE. INCLUD-
ING NITROCELLULOSE, CELLULOID, PYROXYLIN. COLLODION,
CELLOIDIN. GUNCOTTON. ACETYLCELLULOSE AND VISCOSE,
AS APPLIED TO TECHNOLOGY, PHARMACY. MICROSCOPY,
MEDICINE, PHOTOGRAPHY, AND THE WARLIKE
AND PEACEFUL ARTS

IN TEN VOLUMES

BY

EDWARD CHAUNCEY ^VORDEiN, Ph.C, B.S., M.A., F.C.S.

AUTHOR ** NITROCKLLULOSE INDUSTRY"

VOLUME ONE — FART ONE

Cellulose Starch Cotton

Xondon

E. & F. xN. SPON, Ltd., 57 HAYMARKET, S.W. i

1921

To

Wf^oBt tn-mtitkttB

Who by Thbir Inspiration, Counsbi* and Matbrzai*

Assistance Have Madb its Preparation Possiblb

ThisjWork» in Gratbpul Appreciation

is

Af&cti0itatelg BriiUateii

381863

Work for the night
is coming, when
Man*s work is done.

ANNOUNCEMENT

AHD

PREFACE TO VOLUME ONE

The projected ten volumes constituting this series on the Technology
of Cellulose Esters — of which Volume VIII on the Carbohydrate Carboxyl-
ates (Cellulose Acetate) issued in 1916 — is the outgrowth and amplification
of the author's 1239-page, 2-volume work on Nitrocellulose Industry pub-
lished in 1911 which contained selections from the nitrocellulose art in gen-
eral, and, so far as the author is aware, was the first and only attempt to
correlate and publish a survey of the entire subject of the commercial util-
ization of the cellulose nitrates, both in the peaceful arts and the warlike fields.
It was not free from defects due to a first edition, and otherwise. In the
Preface to that work, the author invited criticisms and suggestions from
his readers along lines of improving a possible future edition, but the re-
sponse was so widespread and specific (communications from over 300 sep-
arate sources being received), as to justify the hope that an entirely new
work along broad lines might be accepted appreciatively.

Be it monumental or otherwise — every effort of attempted merit has
a definite aim. The aim of this work is to present the entire subject of the
combinations of normal and modified cellulo^ with acidyl and alkyl rad-
icals in such completeness, clarity, accuracy and detail, that inability to
locate the information desired in the Collective Indices, will be trustworthy
evidence that the matter sought was either ephemeral, irrelevant, inac-
curate, non-existent or valueless.

The success, utility and perpetuity of any undertaking, be it literary
or otherwise, primarily rests Upon the solidity and breadtl\ of the founda-
tion upon which the superstructure is proposed to be erected. This Volume
I is to be regarded as the foundation upon which the succeeding volumes are
to be built and expanded, while Chapter XII herein may not inaptly be
likened to the framework of the superstructure which it is hoped will follow.

Furthermore, every proposition of maximum utility must be self-
contained. This is the reason and the explanation for the insertion herein
in detail and extent — perhaps greater than has heretofore been published
in any language — ^the subject matter of the basic materials entering into these
topics, and represented by Cellulose, Starch, Cotton, Nitric and Sulfuric
Acids, forming the subject matter of Parts One and Two of this volume.
The value of so doing will be more obvious when judged in the perspective
of the succeeding volumes. Some may say that this first volume in the ser-
ies is so broad as to include much that is irrelevant, but this point has been
very carefully considered, and bearing in mind the exceeding complexity
and almost limitless possilsilities of the entire art sought to be encompassed
within these volumes, it is felt that such criticisms should perhaps be withheld
until the work has been completed. On this point, the author is undoubt-
edly better informed than the reader, being conversant with the entire ma-
terial to be incorporated in the succeeding volumes, and the sequence of
presentation.

It is, of course, beyond human mentality to hope to completely encom-
pass a given technical subject and register the multitudinous ramifications
which have been recorded. To closely approach such an ideal also requires
extensive finance for organization, library facilities, and long sustained mental

VI ANNOUNCEMKNT AND PREFACE

perseverance. In the first of these requisites we are lacking; in the second^
amply equipped by a private library containing full sets of the usual reposi-
tories of the science; and in the third, we hope, not strikingly deficient.
This projected ten volume work, therefore, represents rather an attempt
to circumscribe the subject with a completeness limited by the finances at
oiu* disposal, but with an earnest endeavor to record the subject in com-
pleteness, logical sequence and accuracy commensurate with the importance
of the matter involved and its present activity and transitional state of
development. Although realizing that conciseness is the essence of clarity,
yet some ideas cannot be properly conveyed without a somewhat involved
technique of utterance. Above all, it has continually been borne in mind
that the statements are aimed at the intelligence of a sympathetic human
being.

Unhasting and imresting, for nearly twenty-five years we have been
accumulating significant material from every available source, and focussing
our activities toward this one purpose — of recording in a permanent and
readily available form, the rise, development and potentialities of this ftm-
damental division of human progress. The data comprehending the entire
series has now been arranged on some 365,000 cards.

While in no way attempting to perpetuate on paper every brain-wave
which has afilicted the would-be inventor and literary aspirant, yet a work
which aims at approaching completeness must not be bounded by the intel-
lectual horizon alone of the author as including only those ideas, processes
and products in which he may be able to perceive merit, for many a hazy
idea and nebulous thought which has failed in the hands of one inventor,
has been taken up in after years by those of clearer perception or more subtle
intuition, and been made successfid by the addition or omission of some
seemingly unimportant detail. Therein lies the possible value and justifica-
tion for the enumeration of those processes which appear to be capable of
developing merit. The improvements in the entire cellulose ester art is an
exemplification of the successes of one having been built upon the failures
of another, for a knowledge of their failm^s is often of more importance than
an acquaintance with their successes.

No attempt has been made to produce a work radically new, novel,
different or revolutionary, but rather to approach the subject from the point
of concrete analysis, logical deduction and historical continuity in develop-
ment. In endeavoring to encompass such a broad subject with maximum
clarity, all matter considered not strictly relevant has been relegated to the
note (fine print) portion, as well as the more or less abstruse data for ad-
vanced thinkers.

An author can do little more than select that which the art has dis-
closed to him as being trustworthy, indicating the salient points, editing
both sides of controversial questions, and interpreting them in the light of
his personal knowledge. However, wherever his inferences are fallacious,
his reasoning illogical, or his interpretation faulty, then his deductions
may be distinctly harmful. But where the author has backed up his
statements by references to the original literature, it then becomes possible
for the student to refer to these repositories and draw an independent con-
clusion, and therein lies the value of original citations. In the amplification
of these subjects, it seems as if the above idea had been carried out to a
painstaking degree as incUcated by the 80,504 references contained in this
volume, and the more than 335,000 references in the woik as a whole.

Erroneous deductions are often made of methods, ideas and processes
which have not had the opportunity to mature under the mellowing per-
spective of elapsed time and therefore may be faulty, for it is true that until
an art has had some years of commercial application, it is well nigh impos-
sible to analyze and draw sotmd conclusions from the economics of the situa-
tion— the final arbiter in determining the social value of any process.

ANNOUNCEMENT AND PREFACE Vll

The attempt has been made to present the matter in as simple, terse,
and lucid a manner as consistent with the intricacy of the subject involved,
relying upon the references in the footnotes to furnish additional informa-
tion to those particularly interested in a special topic.

Considerable thought and much attention has been given to the questi6n of
understandingly compressing the maximum of information into the minimum of
space and bulk. Over 65 % of this volume consists of fine print (notes) , one page
of which is equivalent (in ems) to 2.66 pages of text portion. The indices and
prefatory portion are entirely in fine print. In this manner it has been
possible to encompass the equivalent of 8700 pages of text into 3709 pages.
Paper has been selected of thinnest super-stock compatible with proper wear-
ing qualities, and in this manner the bulk (thickness and weight) have been
reduced nearly a half over the usual.

The belief formerly held by us that the index was the most important
part of a technical work has long since become a conviction, many an other-
wise valtiable book having been materially impaired by the omission, incom-
pleteness, brevity or faulty construction of the index — in our judgment
without question, the most important and painstaking portion of a work of
this character. Recorded information remains practically valueless when
rendered unavailable and inaccessible by omission in the index. In the
39,468 citations of 27,372 patents, 33,740 references to 23,642 separate names,
and 20,370 entries under 20,601 subject headings, an earnest effort has been
made to adequately cover the information recorded herein. However, it is
obviously impossble without unwarranted expansion and useless repetition
to correlate all the facts of one subject tmder a distinct heading, and there-
fore the indices should always be consulted in endeavoring to obtain the
maximtun of information upon a specified topic. The stupendous drudgery
entailed in the indices preparation has been undertaken and superintended
by Leo Rutstein, who also prepared the indices for Volume VIII of this
series. Many dozens of temporary indices have we prepared of sections of
this work during its progress, only to be discarded upon the completion of the
section or chapter.

For convenience of handling and reference, it is proposed to divide the
entire work into ten volumes paged separately, averaging about 1,000 pages
per volume, with 108 chapters detailing the information imder 3,340 topical
headings and 6,775 sub-headings, and including 450 tables and 1,150 illustra-
tions. The topics record the work of some 55,000 separate investigators,
and include 58,000 patents. Each volume will close with patent, name and
subject indices. Volume X being a collective index of the preceding volumes
and including a formula index.

The plan of this voliune is indicated on pages 1933, 2273, and 2377,
comprehending 12 chapters, 637 topics, 3087 pages, 296 illustrations, 151
tables, and 19,611 notes in the text, and is divided as follows: Part One.
The raw materials cellulose and its modifications (Chapter I), starch and
similar carbohydrates (II), cotton as being the cellulose more often esterified
(III), and the preparation of cotton for the esterifying process (IV). Part
Two. Nitric acid is naturally divided into the five sections, (a) nitrogen and
the five nitrogen oxides; (b) manufactiue of nitric acid from niter and vitriol;
(c) fixation of atmospheric nitrogen and the electrolytic manufactiu-e of
nitrogen oxides; (d) the catalytic manufactiu-e of anunonia and its oxi-
dation to nitric acid; (e) concentration, storage and analysis of nitric acid,
all being Chapter V. Sulfur, sulfiu- dioxide and trioxide, and the mechanics
and chemistry of the chamber, contact and other processes of sulfuric acid
manufacture (VI). The physics, chemistry and analysis, rejuvenation,
preparation and application of mixed and waste acids (VII). Physical
constants, tables, and conversion factors involved in the preceding topics
(VIII). Part Three. History and theory of the cellulose nitrates and ni-
trated carbohydrates, phsrsical and chemical properties and ballistics (IX);
manufacture of cellulose esters (X); analytical examination of nitrated

VIU ANNOUNCKMENT AND PREFACE

carbohydrates (XI). Part Four. Synoptical development of the cellulose
ester industry (XII). Part Five. Patent, Name and Subject Indices
for the entire volume.

The general scope of the succeeding volumes is as follows: Volume Two.
Vol. I closed with cellulose nitrate in the dry state and without commercial
application, but inasmuch as the cellulose esters have comparatively few
uses when dry, exhibitiiig their usefulness more forcibly when in solution
either in the fluid or plastic state. Vol. II enumerates the cellulose ester Sol-
vents, non-solvents, ancillary bodies, activators, plasticizers, gelatinants
and high-boilers, including fusel oil, alkyl and aryl esters, amyl alcohol and
acetate, natural, artificial and synthetic camphor and the large number of
bodies which have been proposed as adjuncts, accelerators, or substitutes for
camphor in the cellulose ester thermoplastic arts. These solvents are largely
used in the formation of paint and vaniish removers, and in the preparation
of substitutes for spirits of turpentine. The volume closes with the various
processes for solvent recovery which have been proposed.

In respect to the data of which this Vol. II forms the subject matter,
our progress has naturally been slow and laborious due to the immense amount
of conflicting and contradictory information contained in the technical and
patent literatiu-e, and to the time involved in endeavoring to check up this
work ourselves in the laboratory, in order to be in a position to state authori-
tatively as to the real facts involved in the points at issue.

Volume Three. Having nitrocellulose (Vol. I) and the solvents (Vol.
II), next comprizes an enumeration of the various 'appliances for bringing the
two together for specific purposes — the transformation of the raw cellulose
esters into finished products for employment in the arts. The manufactiu-e
and uses of the fluid pyroxylin preparations, lacquers, bronzing liquids, water-
proofing solutions, enamels, impregnating media, the formation of artificial
and imitation leather, coating of skins and hides with cellulose ester solutions
are described and illustrated.

Volume four. Those solutions which, when projected through capillary
orifices into coagulating or hardening media result in the formation of fila-
ments of artificial silk, broadly comprise the subject matter of this volume,
and include the cuprammonium cellulose preparations, nitrocellulose silks,
animal silks, and the entire subject of the commercial application of viscose,
viscoid and the cellulose sulfocarbonates.

Volume five. The entire subject of the history, chemistry, development,
and ramification of the pyroxylin plastic industries typified by celluloid,
xylonite and the various analogous products and substitutes, constitutes this
volume, which probably will be issued in parts.

Volume Six. The multiplicity of uses to which collodion and other
nitrated celluloses have been applied in pharmacy, botany, histology, pathol-
ogy and especially photography, and including the industry of moving
picture technique and continuous film formation, are involved in the volume.

Volume Seven. The higher cellulose nitrates, guncotton, the history,
development, manufacture, application and composition of the various
smokeless powders, gelatins, dynamites and all nitrocellulose-containing
explosive preparations and guncotton combinations are embraced in this
volume.

Volume Eight. The carbohydrate carboxylates (cellulose acetate),
including the cellulose acetates, formates and other cellulose esters, the
alkylated celluloses and acidylized derivatives, was published in 1916 as
a 578-page volume, containing the citation of 3,272 patents, and 6,334 refer-
ences in topical headings to the work of 1,292 investigators. This volume is
under revision and considerable expansion.

Volume Nine, constitutes a Bibliography of Explosives, issued in parts,
now in the press, exceeding 1,000 pages, and is being prepared under the
able supervision of Dr. Carl Marx. This volume aims to separate the entire

ANNOUNCEMENT AND PREFACE ix

field of explosives into sectional topics, chronologically and alphabetically
arranged, thus constituting a series of bibliographic monographs with abstract
references, and copious indices.

Volume Ten. Patent, Name, Subject and Formulae Indices of the
preceding nine volumes. The Collective Index.

It may be of interest to mention the existence of a series of collective
indices of chemical patents of various countries which we have prepared as
an aid to our. work in the location, checking up and verification of patented
processes, and which has been found exceedingly useful. We have examined
page by page and have written on slips of paper all the patents where patent
indices have not been published, or have photostatted them where printed,
of all the patents mentioned in complete sets of the following journals for the
periods indicated. Chem. Abst. 1907-1920; Jour. Amer. Chem. Soc. 1878-
1920; Jour. Soc. Chem. Ind. 1882-1920; Jour. Chem. Soc. 1873-1920; Jour.
Soc. Dyers & Col. 1881-1919; Arms & Expl. 1892-1920; Mon. Sci. 1857-
1919; Bull. Soc. Chim. 1860-1919; Chem. et Ind. Jul. 1918-1920; Chem.
Tech. Jahrb. 1881-1901; Wagner's Jahr. Chem. 1855-1918; Zts. ang. Chem.
1887-1920; Chemische Ind. 1878-1919; Ber. deut. Chem. Ges. 1874r-1919;
Chem. Ztg. 1879-1920; Chem. Tech, Repert. 1862-1900; Chem. Zentr. 1870-
1920; Meyer Jahr. Chem. 1891-1918; Zt3. Schiess. Sprengs. 1906-1920;
Kunstoffe 19U-1920; Liebig-Kopp. Jahr. Chem. 1848-1910; Winther
Organische Patent, 1877-1905; Friedlander, Teer Farbenfabriken, vols.
I-XII.

The references thus obtained have been thrown in numerical order as
to the patent numbers, typed, classified and the sheets thus obtained pasted
in a series of large loose-leaf ledgers. In this manner we have available
in a readily accessible form (all the U. S. patents, for instance, appearing in
any of the above mentioned periodicals from 1,000 000-1,001,000, being
located on the same page) over three million citations and abstracts of chemical
patents. The labor involved in the preparation of this series of collective
patent indices has been enormous, requiring the uninterrupted labor of four
people for the past four and a half years. It is admitted that had we an
adequate conception of the labor and cost involved before the work was com-
menced, it woidd not have been undertaken by us.

Those conversant with chemical literature research will recall that so
often where the earlier encyclopedias and year books have happened to make
an error in citation authors and bibliographers in succeeding years have
copied the error without apparently taking the trouble to verify the accuracy
of the reference or information by taking the time and trouble of consultation
of the original repository. In this manner, inacctu'acies appearing in such
sets as Liebig-Kopp's Jahr. Chem. and Chem. Centr. have been accepted and
transmitted verbatim through the works of succeeding years down to the
present day, being copied from one work to another without verification.
In contradistinction to the above, the author in at least 90% of the references
contained herein, has verified the information from consultation of the
original sources. It is imfortunate that the French in many instances content
themselves with the prefix M. instead of the authors surname or initial, and
that the English patent office practice puts forward the patent attorneys
name in preference to that of the patentee, thus increasing the difficulty in
according credit. It is but necessary to glance at the Index of Names in this
volume to realize how essential it is that at least the initials of writers should
always be given.

Many have been the gentlemen who have so willingly given of their
time and mentality in contributing special topics to this volume, and if merit
there be herein, to them in a large measure belongs the credit. Mr. Leo
Rutstein, Dr. Carl Marx, and Messrs. DeWitt Bell, Clarence E. Lehmann,
P. H. Bodenstein and John W. Bruce have constituted the staff responsible
for the issuance of this volume.

Dr. Joseph Reilly has allowed us to draw upon his time and experience

X ANNOUNCEMENT AND PREFACE

in elucidating abstruse points, and has contributed several of the topics.
J. F. Briggs prepared the entire topic upon the analysis of cellulose (pp.
348-388), and is contributing to several of the more important portions of
succeeding volumes. Professor J. R. Partington, M.B.E., D.Sc., of London
University contributed the entire text portion of the Sulfuric Acid chapter
with unimportant exceptions, from data supplied by the author. The com-
pleteness with which this subject has been handled by Professor Partington
is indicated from the 6560 references in the several indices to this chapter.
Professor E. J. Wall, F.R.P.S., has allowed us to draw from his life of ex-
perience in the broad subject of collodion as applied to photography, and has
undertaken the preparation of substantially the entire text of one of the
succeeding voltunes. Dr. J. N. Goldsmith is engaged in arranging, writing,
and editing the author's data upon the general subject of pyroxylin plastics.

It is a pleasure to acknowledge the unfailing courtesy of such firms
as E. I. du Pont de Nemours & Co., New Explosives Co., and Nobel's Ex-
plosives Co., Ltd., and their technical staffs, for illustrations, manufacturing
details and historical information. Especially have Messrs. Nobel's Explo-
sives Co., and William Rintoul, O.B.E., P.I.C., prolifically contributed inac-
cessible data on the general subject of smokeless powder and nitrocellulose
development and practice in Great Britain, much of the data being reserved
for incorporation in Volume VII upon which we are actively engaged. Mr.
F. W. Jones has also supplemented and amplified much of the above infor-
mation from his expert knowledge and private archives of information. The
Government of Great Britain through its several departments, with com-
mendable broad-mindedness, has allowed the author to use information of
great value. The English Patent Office Library — so far as the author's
experience goes the most complete and readily accessible technical library in
the world — has placed its facilities at our disposal, and Miss Nina Fovargue
has been uninterruptedly engaged therein for the past two years in collating, .
collecting, amplifying and checking data for this work, and who is also
responsible for the compilation of the entire Name Index.

Grateful appreciation is acknowledged to the Eschenbach Printing Co.
and to Harvey F. Mack, the President, for the presswork of this volume,
which must be conceded — ^with its 19,611 individual notes — as a diffictdt and
intricate piece of typography, and especially to Miss Helen W. Smith, who
furnished the nervous energy and administrative ability involved in the
planning and execution of the printing. Mrs. E. S. Ketchledge did the
proofreading.

The text is 10-point Ronaldson, and the notes 8-point Roman printed
on 25' X 38', 70 lb. "olde Style" paper from monotype which was dismantled
after the printing of each folio. The entire cost of the preparation, printing
and publishing of this work has been met by the author personally, from his
private funds.

Great care has been taken to record the various sources from which
information has been drawn, and it is sincerely hoped that such sources have
been duly acknowledged. 'The author would greatly appreciate suggestions
and criticisms from readers of this work, with a view to extending its useful-
ness and increasing its accuracy in a possible future edition.

Edward Chauncby Worden, First.

MiLBURN, NBW JeRSBY,

October 15, 1920.

TABLE OF CONTENTS

This Table of Contents contains an enumeration of the 637 main topics
only, the five hundred forty sub- topics not being indicated herein.

CHAPTER I.

CELLULOSE.

Carbohydrates 4

Classification of Celluloses .... 8

Constitution of Cellulose 14

Preparation of Pure Cellulose . . 26

Cellulose as a Colloid 30

Reactivity of Cellulose 36

Properties of the Celluloses .... 38

Viscosity of Cellulose Solutions 46

Optical Properties of Cellulose , 47

Cellulose and Heat 52

Action of Light and Air upon

Cellulose 59

Absorption of Tannins by Cel-
lulose 61

Cellulose and Dyestuff s 63

Cellulose Solvents 66

Action of Cuprammonium Solu-
tions on Cellulose 68

Physical Constants of Cupram-
monium Solutions 79

Application of the Cuprammon-
ium Celluloses 85

Cellulose and Hydrcichloric

Acid 92

Cellulose and Sulfuric Acid 95

Action of Ziifc Chloride on Cel-
lulose 101

Vulcanized Fiber 104

Other Cellulose Solvents 106

Action of Salts on Cellulose .... Ill

Acid Celluloses 122

Amyloid 125

Hydrocellulose 127

Action of Ozone on Cellulose ... 151

Cellulose Peroxide 154

Cellulose and Oxidizing Agents . 1 58

Oxycellulose 164

Acetolysis and Octa-Acetylcel-

lobiose 181

Hydrolysis and Saccharification 194
Cellulose Hydrates. Alkali Cel-
lulose 213

Mercerization 224

Cellulose Condensations 234

Cellulose and Benzene 235

Cellulose and Phenol 236

Hemi-Celluloses 237

Ash 239

Producing Amorphous Cellulose

for Subsequent Nitration 240

Lignocelluloses — Qute and

Wood) 241

Wood Pulp 266

Wood Pulp for Esterification . . . 293

Cellulose Carbamates 324

Animal Celluloses 325

Esparto.. 327

Cellulose Filters 334

Cellulose Plastics and Aggre-
gates 335

Pergamyn 337

Cellulith 338

Bacterial Action on Cellulose

Materials 338

Analytical Examination of Cel-
lulose Raw Materials 348

The CeUulose Complex 350

The Lignin Complex 353

The Cutin Complex 354

Alkaline Hydrolysis 356

Chlorination and Isolation of

Ultimate Fibers 357

Examination of Celltilose Fibers 357

Moisture 358

Oil, Fat, Wax and Resin 359

Aqueous Extract 360

Alkaline Hydrolysis 361

Cellulose 362

Furfural Value or Pentosans. . 365

Methylpentosan 367

Acetic Acid Group 368

Methoxyl Group 368

Lignin 370

Chlorine Absorption 371

Phloroglucinol Absorption 371

Examination of Isolated Cellu-
lose 372

Xll

TABLE OF CONTENTS

Modified Cellulose 377

Hydrated Cellulose 377

Oxycellulose and Hydrocellulose 381

Viscosity 385

CHAPTER II.

STARCH.

Origin and Transformation of

Starch 389

Occurrence of Starch 405

Molecular Weight of Starch 406

Starch Iodide 408

Starch Ester^ 413

Action of Enzymes on Starch . . . 416

Formaldehyde and Starch 420

Starch and Heat 422

Soluble and Modified Starch ... 424
Microscopic Appearance of

Starch 433

Chemical Properties of Starch . . 433

Starch Paste 441

Manufacture of Starch 445

Manufacture of Statch from

Potatoes 457

Rice Starch 462

Com Starch 465

Action of Diastatic Ferments

on Starch 467

Action of Acids on Starch 475

Amylose 481

CHAPTER III.

COTTON.

History of Cotton 485

Botany of Cotton 487

Microscopy of Cotton 497

Anatomical Structure of tht

Cotton Fiber 501

Dimensions of Individual Cot-
ton Fibers 503

Moisture in Cotton 508

Nitrogen in Cotton 520

Mineral Constituents of Cotton 524

Tensile Strength of Cotton 527

Absorption of Gases by Cotton 529
Effect of Reagents on Cotton

Fiber 529

Composition of Cotton 530

Tissue Paper 532

Cotton Wax 534

Absorbent Cotton 537

Methods of Cotton Analysis. . . 541
Tests of Cotton for Nitration

Purposes 552

Inspection of Cotton for Nitra-
tion Purposes 552

U. S. Ordnance Requirements

for Cotton 554

English Requirements for Ni-
trating Cotton 554

Specifications of Cotton for Ni-
tration in Germany 555

Cellulose Used for Nitration . . . 555
Preparation of Cotton for Ni-
tration 560

The Utilization of Short Fibers 568

Cotton Hull Fibers 579

Impurities in Cotton 580

Cop Bottoms 582

CHAPTER IV.

PREPARATION OF COTTON

FOR ESTERIFICATION

Weight of Cotton Bales 583

Opening the Bale 586

BoU-off 588

Bleaching the Cotton 604

Preliminary Drying 619

Teasing 620

WUlowing 627

Conveying 632

Final Drying 634

Saco-Lowell Method of Cotton

Preparation 642

Treatment of Cotton for Esteri-

fication in Great Britain 644

CHAPTER V.

NITRIC ACID.

Historical 665

Nitrogen 679

Separation of Nitrogen from

the Air 684

Preparation of Pure Nitrogen. . 691

Properties of Nitrogen 691

Nitrogen Oxides 693

Nitrogen Monoxide 709

Nitrogen Dioxide 712

Nitrogen Trioxide 716

Nitrogen Tetroxide 717

Nitrogen Pentoxide 721

Manufacture of Nitric Acid with

Chili Saltpeter 722

Origin and Occurrence of So-
dium Nitrate 725

Formation and Composition of

Chili Saltpeter 728

Extraction and Purification of

Chili Saltpeter 728

Chili Saltpeter Statistics 731

Potassium Perchlorate 732

Analysis of Sodium Nitrate. . . . 732

TABLE OF CONTENTS

XUl

Estimation of Nitrate in Chili
Saltpeter 735

Recovery of Niter from Chili
Saltpeter Bags 739

Manufacture of Nitric Acid
from Sodium Nitrate 741

Manufacture of Nitric Acid
from Chili Saltpeter in Great
Britain 754

Nitric Acid Manufacture at
Queen's Ferry Plant 773

The Commercial Utilization of
Niter Cake 786

Hough Niter Cake Flaking Ma-
chine 808

Analysis of Niter Cake 810

The Manufacture of Nitric
Acid and Caustic Soda Si-
multaneously 81 1

Other Nitric Acid Processes
Using Metallic Nitrates 812

Uebel Nitric Acid Process 815

The Valentiner Vacuum Proc-
ess for Making Nitric Add ... 818

Hough Nitric Acid System 829

The Griesheim Nitric Acid
Plant 834

Condensation of Nitric Acid . . . 836

Condensing Nitric Acid by
Means of Plate Towers 845

Continuous Nitric Acid Manu-
facture with Chili Salt-
peter 845

Fixation of Atmospheric Nitro-
gen 847

Schonherr Process for Manu-
facturing Nitric Acid 853

K. Birkeland and S. Eyde
Nitric Acid Process 869

Pauling Process of Nitric Acid
Manufacture 881

Other Nitrogen Fixation Pro-
cesses 892

Oxidation of Ammonia to
Nitric Acid 894

Haber Method for the Synthetic
Production of Ammonia -900

Badische Process for Synthetic
Ammonia Formation 904

The Ostwald Process 911

Catalysts 915

Nitrides, Cyanides and Cyan-
amides as Sources of Nitric
Acid 918

Nitric Acid from Nitrides 919

Cyanides and Cyanamides as
Sources of Nitric Acid 925

Technical Production of Cyan-
amides 927

Other Processes for the Cata-
lytic Production of Ammonia 934

Recovery of Nitric Acid from
Various Sources 946

Recovery of Nitric Acid from
Absorbents 948

Action of Nitric Acid on Alu-
minium . . T 950

Properties of Nitric Acid 951

Storage and Transportation of
Nitric Acid 955

Fuming Nitric Acid 960

Detection of Nitrous Acid 962

Detection of Nitric Acid 962

Determination of Nitrogen by
Nitrometer 964

Determinations of Nitrogen by
Lunge Two-Bulb Nitrometer 966

Determination of Nitrogen with
the Gas- Volumeter 968

Determination of Nitrogen by
du Pont Nitrometer 972

Estimation of Nitrogen by Fer-
rous Ammonium Sulfate. . . . 976

Determination of Nitric Acid
in Niter Cake by Ferrous
Ammonium Sulfate 978

Estimation of Nitrogen in
Nitrocellulose by Ferrous
Ammonium Sulfate 978

Determination of Nitric Acid
by Nitron 979

Determination of Nitric Acid by •
Titration 981

Determination of Nitrous Acid
by Permanganate 981

Manufacture of Absolute Nitric
Add 982

Refinement and Bleaching of
Nitric Acid 984

Concentration of Nitric Acid. . . 985

CHAPTER VI.

SULFURIC ACID.

History of Sulfuric Add 1007

Sulfur 1011

Occurrence of Sulfur 1020

Sulfur in Sidly 1020

Sulfur in Louisiana and Texas . . 1023
Production of Sulfur from Sul-
fides 1024

Sulfur from Sulfates 1027

Sulfur from Sulfur Dioxide 1027

Sulfur from Alkali Waste 1028

Other Sources of Sulfur 1030

Sublimed Sulfur 1032

Properties of Sulfur 1034

Determination of Sulfur 1037

XIV

TABLE OF CONTENTS

Pyrites 1043

Analysis of Pyrites 1046

Volumetric Analysis of Pyrites . 1050
Gravimetric Analysis of Pyrites 1051

Sulfur Dioxide 1057

Sulfur Burners 1062

Sulfur Dioxide 1069

Pyrites Burners 1070

Sulfiu: Dioxide from Copper

Pyrites 1076

Sulfur Dioxide from Blende 1076

Sulfur Dioxide from Galena 1081

The Composition of Biuner

Gases 1082

Stdftu: Dioxide from Sulfates . . . 1084
Other Sources of Sulfur Di-
oxide 1084

Absorption of Sulfur Dioxide . . 1087
Purification of Sulfur Dioxide . . 1089

Liquid Sulfur Dioxide 1092

Propel ties of Sulfur Dioxide. . . 1094

Analysis of Sulftu: Dioxide 1096

Uses of Sulfur Dioxide 1099

Stdfur Trioxide and Contact

Sulfuric Acid 1100

Apparatus Used in the Contact

Process 1106

Processes in the Contact Meth-
ods 1108

Platinum Catalysts 1113

Oxide of Iron Catalysts 1116

Chromium Catalysts 1119

Titanium Catalysts 1120

Vanadium Compounds 1120

Radioactive Catalysts 1121

Other Catalysts 1121

Electrical Processes 1122

Absorption of Sulfur Trioxide . . 1 123
Properties of Sulfur Trioxide. . 1124

Analysis of Oleum 1 126

Plant Tests 1127

Manufacture of Oleum from

Sulfates 1128

Production of Oleum Other than

by the Contact Process 1131

Theory of the Contact Process . 1 133

The Badische Process 1137

The Tentelew Process 1151

The Meister, Lucius and Briin-

ing Process 1 157

The Schroeder-Grillo Process. . 1161
Grillo Process at Queen's Ferry 1174
Preparation of Contact Mass

for Grillo Plant. .) 1183

The Freiburg Process 1189

The Rabe Process 1190

The Properties of Oleum 1191

Contact Processes in the United
States 1191

Miscellaneous Contact Proc-
esses 1192

Lead Chamber Process of Sul-
furic Acid Manufacture 1203

General Construction of the

Lead Chamber 1205

The Erection of Lead Chamber 1207
Intensive Working of Cham-
bers 1211

The Moritz Chambers 1212

The Niedenfiihr Chamber 1213

Falding's Chamber 1213

The Mills-Packard Chamber . . 1214

Tangential Chambers 1215

Intermediate Reaction Towers . 1217
Replacement of the Lead Cham-
ber by Other Apparatus 1222

The Opl System 1225

Chamber Fittings 1226

The Supply of Niter to the

Chambers 1227

Water Supply of Chambers 1232

The Supply of Air to the Vitriol

Chambers 1237

Anemometers 1240

Intensive Working and Reduc-
tion of Chamber Space 1242

Starting the Chamber Process. . 1244

Vitriol Chamber Temperatures . 1245

Irreguliarities in Chamber Work 1246
Gas Distribution and Speed of

Acid Formation 1247

Analysis of the Chamber Exit

Gases 1252

Theory of the Lead Chamber

Process 1254

Recovery of Nitrogen Com-
pounds 1261

The Gay-Lussac Tower 1262

Tower Packing 1267

Distributing the Feed Acid 1272

Pumping the Acid 1274 .

The Glover Tower 1276

Recovery of Nitrogen Com-
pounds 1284

Combined Chamber and Con-
tact Process 128^

Various Processes for the

Manufacture of Sulfuric Acid 1289

Pyrosulfuric Acid 1292^

Persulfuric Acid and Persul-

fates 1293i

Miscellaneous Methods for Sul-
furic Acid M^inufacture 1294

Sulfuric Acid from Sulfates 1299-

Sulfuric Acid and Nitrogen

Oxides 1304

Recovery of Waste Sulfuric

Acid 1306.

TABLE OF CONTENTS

XV

Preparing Mixtures of Oleum

and Sulfuric Acid 1310

The properties of Pure Sul-
furic Acid (Monohydrate) . . 1311
Transportfition of Sulfuric Acid 1312
Properties of Sulfuric Acid; ... 1313
Action of Sulfuric Acid on

Metals. > 1319

Action of Stdfuric Acid on Iron

and Steel 1319

Action of Sulfuric Acid on Lead 1322
Action of Sulfuric Acid on

Platinum 1324

The Analysis of Sulfuric Acid. . 1325
Gravimetric Estimation of Sul-
furic Add 1325

The Volumetric Estimation of

Sulfuric Acid 1327

The Analysis of Oleum 1329

Detection and Estimation of

Stdfur Dioxide and Sulfites. . 1332
Detection of Impurities in Sul-
furic Acid 1334

Impurities in Commercial Sul-
furic Acid 1336

Estimation of Acidity in Flue

and Exit Gases 1337

De-arsenication of Sulftuic Acid 1338
Separation of Arsenic as Tri-
chloride 1340

Removal of Arsenic as Sulfide . . 1342
Chemically Pure Sulfuric Acid . 1345
Pur^cation from Nitrogen

Oxides 1347

Decolorizing Sulfuric Acid 1348

Special Methods of Purification 1348
Geneml Methods of Concen-
tration 1350

Theory of the Concentration of

Sulfuric Acid 1352

Concentration in Iron Vessels . . 1353
Concentration in Lead Pans. . . 1358
Concentration in Glass Vessels 1360

Concentration in Silica 1361

Porcelain or Enamel Apparatus 1363
Concentration in Platinum

Apparatus 1364

Concentration in Cascades 1367

The Gaillard Tower 1372

Gaillard Towers at Gretna

Plant 1376

Concentration by Electricity . . . 1380
Concentration in Vacuum Pans 1380
The Manufacture of Monohy-
drate 1382

Concentration in a Curreht of

Gas 1382

Other Methods of Concentra-
tion 1390

Electrostatic Precipitation 1392

The Gilchrist Concentrator 1396

Recent Advancement 1399

CHAPTER VII.
MIXED ACIDS.

Properties of Mixtures of Nitric
and Sulfuric Acids 1403

Fortification and Acid Recov-
ery 1412

Clarifying Spent Acid 1412

Recovery and Fortification of
Spent Acid 1414

Nitrocotton Spent Acid Recov-
ery. Gretna Practice 143Q

Denitration of Waste Acids .... 1440

Evers Denitration Process 1447

The V. Vender Denitration
System 1460

Guttmann Nitric Acid Deni-
trating System 1462

Recovery of Nitrous Fumes as
Nitric Acid 146^

Nitric Acid Recovery by Sol-
vents 1467

Acid Valves 1468-

Manufacture of Nitrocotton
Mixed Acid, English Practice 1474

Nitration and Nitrous Fume
Poisoning 1485

Calculation of Acid Baths 1485

Acid Calculation by Method of
Clement and Riviere 1489

The Redpath Method of Acid
Calculation 1490

The R. Fowler Method of Spent
Acid Graph Construction. . . 1499

The Craven Method of Acid
Calculation 1504

Analysis of Mixed and Spent
Acids 1504

Analysis of Mixed Nitrating
Acids (English Practice) 1511

CHAPTER VIII.
ACID TABLES.

Acid Tables 1519 to 1565

CHAPTER IX.
NITROCELLULOSE THEORY.

Historical 1567

The Xyloidine of Braconnot. . . 1567

Nitramidine of Dumas 1571

Schonbein and Guncotton 1574

Guncotton Investigations 1848-

1850 1586

Guncotton Development 1851-

1860 1588

XVI

TABLE OF CONTENTS

Stability of Guncotton, and
Baron von Lenk 1593

F. Abel and the Pulping of Gun-
cotton 1599

Nitrocellulose Development,
Period 1865-1870 1616

Celltilose Nitrate Advancement,
Period 1871-1880 1620

Fluxation of the Art, Period

lool~~lcftK/ •• • lOoU

Cellulose Nitrate Research,

Period 1891-1900 1638

Chemistry of the Cellulose Ni-
trates 1640

The Cellulose Nitrates of Eder. 1646

Researches of Vieille 1650

Investigations of Lunge 1656

Chemistry of the Cellulose Ni-
trates. Investigations 1901-

1910 1667

Developments in Chemistry of
Cellulose Nitrates, 1911-

1920 1677

Theory of Nitration 1682

Nomenclature of the Cellulose

Nitrates 1690

Pharmacopeial Nitrocelluloses. 1694
Properties of the Cellulose Ni-
trates 1697

Stability of the Cellulose Ni-
trates 1700

NitroceUulose Solubility 1720

Viscosity of Nitrocellulose 1729

Hygroscopicity of Cellulose Ni-
trates 1750

Density of Nitrocellulose 1755

Optical Properties 1757

Electrical Properties 1766

Physical Properties of Collodion

Membranes 1768

Reduction of Inflammability. . . 1776

Ballistics of Nitrocellulose 1793

The Action of Fungi on Nitro-
cellulose 1802

Straw Nitrocellulose 1803

Nitrated Com Pith 1805

Nitrojute 1807

Nitrolignin 1808

Nitrated Paper 1815

Nitrated Starch 1816

Nitrates of the Carbohydrates. 1843

Nitrosaccharose 1849

Nitrodextrin (Nitrodextrose) . . 1853

Nitroglucose 1854

Nitrated Molasses 1855

Nitrolactose 1856

Nitroerythrite 1857

Nitromannite 1862

Nitrated Resins 1869

Other Nitrated Celluloses 1871

Pyroxylins of Low Nitrogen

Content 1882

Recovery of Nitrocellulose 1884

Uses of Nitrocellulose in the Dry

State.; 1886

Preparations of Acid-Proof Ni-
trated Filterdoth 1890

Dyeing Nitrocellulose 1893

Amorphous Nitrocellulose 1895

Indurating Nitrocellulose 1897

Denitration of Nitrocellulose. . 1898
Nitrates of Hydrocellulose and

Oxycellulose 1900

Xyloidins 1903

Cellulose Nitrites 1905

Cellulose Sulfuric Esters 1907

Nitrated and Chlorated Gun-
cotton 1911

Layout and Construction of

Modem Guncotton Plant. . . . 1912
Dangers in Connection with the

Nitration of Cellulose 1925

Transportation of Nitrocellulose 1927

CHAPTER X.

NITRATION OF CELLULOSE.

Synopsis of This Chapter 1933

Nitration of Cellulose by Hand 1934

Abel Method of Nitration 1940

Direct Dipping Method of Cel-
lulose Nitration 1943

The Centrifuge in Cellulose

Nitration 1952

Centrifugal Nitration of Cellu-
lose 1955

Selwig & Lange Nitrating Cen-
trifugals 1956

Wolfshohl Automatic Cotton

Steeper 1964

Tolhurst Nitrating Centrifugal 1968
Vacuum Cellulose Nitration .. . 1970
Other Centrifugal Nitration

Processes 1973

The Thomson Displacement

Process 1978

The Dupont Mechanical System

of Cotton Nitration 1994

Other Nitration Methods 2003

Nitration of Cotton for Cheaper

Grades of Pyroxylin 2032

Nitration of Paper 2033

V. Tribouillet and L. de Be-
sauncele Process for Paper

Nitration 2037

Hyatt's Paper Nitration Process 2038
The Swan Apparatus for Paper
Nitration 2046

TABLE OF CONTENTS

XVll

Other Methods of Paper Nitra-
tion 2047

Manufacture of Nitrolignin. . . . 2050
Efficiency of Various Nitration

Metho<Js 2054

Preliminary Washing of Ni-
trated Cellulose 2059

Utilization of Wash Water 2067

Bleaclung Nitrocellulose 2069

Preliminary Boiling of the

Nitrocellulose 2071

Pulpmg the Nitrocellulose 2083

Settling the Pulped Nitrocellu-
lose 2095

Poaching the Nitrocellulose 2098

Removal of Foreign Matter 2102

Blending 2107

Screening the Pulped Nitrocel-
lulose 2112

Dehydration of the Nitrocellu-
lose • 2114

Centrifugal Dehydration 2117

Centrifugal Solvent Dehydra-
tion 2124

Hydraulic Dehydration 2127

Solvent Hydraulic Dehydration 2139
Solvent Displacement without

Pressure 2140

Drying Nitrocelltdose 2145

Determining the Yield 2159

Compressed Guncotton 2160

Nitration of Cellulose in Great

Britain 2188

Nitration of Cellulose at Gretna 2188
Wet Nitrocellulose Magazines. 2229
Granulation of NitroceUulose . . 2246

CoUoidmg Nitrocellulose 2249

Co-nitration 2254

Classes of Cellulose Nitrates

Produced in the United States 2256
Specifications for Guncotton

for the United States Navy. . 2258
United States Specifications for

Nitrocelltdose or Pyroxylin. . 2264
British Specifications for Gun-
cotton 2265

French Guncotton and Smoke-
less Powder Requirements . . . 2267
British Admiralty Specifications
A-121 for Guncotton Slabs for

Mines 2268

Prussian Regulations Regard-
ing Moist Nitrocellulose 2271

- CHAPTER XI.

ANALYTICAL DBTERMINATIONS

OF THE CELLULOSE NITRATES.

Detection of the Cellulose Ni-
trates 2273

Determination of Moisture .... 2274
Determination of Viscosity .... 2275
Viscosity by Ostwald Viscosim-

eter 2282

Viscosity ' by ' the' "Ball' Fall"

Method 2285

Determination of Solubility 2287

Determination of Insoluble

Nitrocellulose 2294

Unaltered Cellulose 2295

Mineral Constituents 2296

Acidity 2298

Alkalinity 2299

Sulfate (SOi) in Nitrocotton . . . 2300
Mercuric Chloride in Nitrocel-
lulose 2302

Determination of Fineness 2305

Determination of Density 2306

The Determination of Nitrogen 2308

Stability Tests 2321

Heat Tests 2324

The Guttmann Stability Test. . 2335

Fume Tests (Stability) 2343

WiU's Stability Test 2350

The Bergmann and Jtmk Test.. 2354

The Obermuller Test 2362

Other Stability (Heat) Tests... 2365

Other Stability Tests 2367

United States Ordnance Meth-
ods for Testing Nitrocellulose 2370
Guncotton Specifications in
Great Britain 2373

CHAPTER XII.

HTSTORICAL DEVELOPMENT OF
THE CELLULOSE ESTERS.

Cellulose Ester Solvents 2382

Acetone and the Ketones 2395

Diacetone Alcohol 2401

Methyl Alcohol 2402

Ethyl Alcohol 2412

Propyl Alcohol 2428

Butyl Alcohol 2437

Amyl Alcohol 2446

Fusel Oil 2469

Amyl Acetate 2486

Other Alkyl Esters 2496

Camphor 2510

Natural Camphor 2510

Artificial Camphor 2517

Synthetic Camphor 2520

Camphor Substitutes 2535

Proteid Substitutes 2550

Ureas 2551

Solvent Recovery 2553

Handling of Solvents 2558

Paint and Varnish Removers. . 2562

Turpentine Substitutes 2568

XVlll

TABLE Ol? CONTENTS

Cellulose Nitrate Lacquers,
Varnishes and Bronzing

Liquids 2572

Collodion Lacquers 2573

Celluloid Lacquers 2577

Amyl Acetate Pyroxylin Lac-
quers 2580

Bronzing Liquids 2585

Imitation Gold Leaf 2586

Mother of Pearl 2588

Pyroxylin-Resin Lacquers 2590

Nitrocotton Electric Light Fila-
ments 2594

Nitrocotton Incandescent Gas

Mantles 2595

Nitrocellulose in the Electrical

Industries 2597

Solid Alcohol 2598

Other Applications of the Nitro-
cotton Lacquers 2599

Artificial Leather 2599

Pyroxylin Imitation Leathers . . 2604
Nitrocellulose Waterproofing

Compositions 2610

Enameled Paper 2615

Printing on Fabrics with Nitro-
cellulose 2616

Pyroxylin Leather, Textile and

Paper Cements 2617

Coating of Leather with Cellu-
lose Esters 2618

Artificial Filaments 2621

Nitrocellulose Silks 2621

Artificial Filament Formation.. 2626
Cuprammonium Artificial Fila-
ments 2652

Pyroxylin Plastics, Cellidoid

Substitutes 2655

Development of P)rroxylin

Plastic Industry 2657

Pyroxylin Plastic Manufacture . 2669

Re-working Celluloid 2676

Cutting of Celluloid 2679

Inlaying Metal Goods with

Celluloid 2680

Dyeing of Pyroxylin Plastics. . 2681
Forming Pyroxylin Plastic

Sheets 2682

Veneering Celluloid 2684

Embossing of Celluloid 2685

Extrusion of Plastic Rods and

Tubes 2688

Inlaying Celluloid with Pigment

Colors 2690

Celluloid in Electrical Industries 2699

Celluloid Studs 2703

Celluloid Eyelets 2704

Celluloid Collars, CuflFs and
Shirt Bosom Fronts 2706

Celluloid Balls 2722

Celluloid in Phonography 2731

Celltdoid in Photography 274^

CeUuloid Substitutes 2759

Phenol-Aldehyde Substitutes... 2767
Celloidin and Development of
Cellulose Nitrates in Micro-
scopy 2779^

Celloidin or Collodion Sacs 2784

Pharmaceutical Collodions 2786

Collodion in the Photographic

Art 2795

Photographic Collodions 2800

Precipitated Pyroxylin 2803

Dry Plates 2825

Collodion Emulsions 2836

Pyroxylin 2839

Process of Emulsification 2840

Ripening the Emulsion 2842

Methods of Manufacture 2843

Collodion Emulsion Manipula-
tion 2845

Actions of Acids on Collodion

Emulsions 2845

Keeping Properties of Col-
lodion Emtilsions 2846

Preservatives, Organifiers,

Densitizers 2846

Sensitizing Leather and

Fabrics 2847

Collodion Positives 2848

Collodio-chloride Paper 2851

Collodio-chloride Bromide

Print Outs 2856

Collodio-chloride Gold Toning. 2856
Collodio-chloride Developing. . 2858

Collodion Carbon Prints 2863

Collodion Transparencies.

Lantern Slides 2865

Enlarging Positives on Paper

and Glass 2867

Collodion Positives and Trans-
fers 2868

Orthochromatic Emulsion 2869

Light Filters. Color Screens. . 2874

Color Photography 2875

Screen Plates 2876

Color Cinematography 2880

Subtractive Fihns 2881

Cinematography 2884

Stripping Films 2900

Halation and Solarization 2902

Celluloid Film Varnishes 2903

Pyroxylin Flash Light Powder. 2904

Collodion in Ceramics 2905

Photomechanical Processes. . . . 2907

X-Ray Screens 2912

Collodion for Solar and Astro-
nomical Work 2912

TABLE OF CONTENTS

XIX

Collodion in Spectroscopy 2912

Photoxylography 2915

Celluloid Cements 2916

Celltiloid Dishes and Measures . 29 16

CeUuloid ReUefs 2917

Celluloid Focussing Screens 2917

Celltdose Nitrate Smokeless

Powders 2921

Development of Cellulose Ni-
trates in War-like Arts . . . 2922
Classification of Nitrocellulose-
containing Powders 2942

I^itrocellulose-nitro glycerol

Powders 2948

Nitrocellulose in Cartridge
Manufacture 2980

Carbohydrate Carboxylates
(Cellulose Acetate) 2987

Manufacture of Acetated Cellu-
lose 3005

Cellulose Formate 3015

Cellulose Acetate Solvents and
Plastifiers 3022

Commercial Applications of
Cellulose Acetates 3041

Cellulose Xanthates 3062

Viscose 3062

Errata 3085

Index of Patents 3087

Index of Names 3253

Index of Subjects 3489-3709

LIST OF ILLUSTRATIONS.

1. Sphere Viscosimeter for Celltdose Solutions (Woolwich Method) . 551

2. Cotton Purification (U. S. Scheme) 584

3. Cotton Purification (English Scheme) 585

4. Cummins Hydraulic Cotton Baling Press 587

5. Mechanical Handling of Cotton Bales (Gretna, Scotland) 589

6. Cotton Dry House 591

7. Sectional View of Cotton Picking Machine 593

8. Cotton Picker Room (H. M. Explosives Factory, Gretna, Scot-

land 595

9. The E. Lehmann Hard Waste Opener for Cotton and all Vege-

table Fibers 596

10. Tipping Pressure Kier with Entire Top to Open 597

11. Cotton Purification Building, Ground Floor (E. I. du Pont de

Nemours Co.) 599

12. Cotton Purification Building, Top Floor (E. I. du Pont de Ne-

mours Co.) 601

13. Cotton Purification Building (E. I. du Pont de Nemours Co.) . . . 603

14. Cotton Purification Building, Top Floor (E. I. du Pont de Ne-

mours Co.) 605

15. Interior Filtration Plant Showing Tubes and Valve Control (E. I.

du Pont de Nemours Co.) 607

16. Cotton Dry House (E. I. du Pont de Nemours Co.) 609

17. Sargent Drying Cotton Rinser 620

18. The Davis & Furber Mixing Picker for Cotton 621

19. Coggswell Mill 622

20. Scotch Picker with Condenser Roll and Apron Screens Drawn

Out from Under Cylinder for Cleaning 623

21. Scotch Picker Arranged with Condenser Roll and Apron 625

22. The W. Tatham Thread Extractor for Printing Purposes 626

23. The Gamett Preparer or Knot Breaker 628

24. Hetherington Improved Willowing Machine 629

25. Cdtton Dry House, Showing Delivery Aprons at End of Dryers

(E. I. du Pont de Nemours Co.) 631

26. The "Proctor" Dryer for Cotton— Single Conveyor Type 633

27. "Proctor" Single Conveyor Dryer Showing Feed 635

28. Single Conveyor Dryer Viewed from Delivery End 637

29. Looking at the Feed End of "Proctor" Three Conveyor Type ... 639

30. Drying Cotton on "Proctor" Three Conveyor Dryer (Delivery

End) 641

31. Side View of Chain Conveyor with Two Wire Screen Sections At-

tached 643

32. Cotton Bale Breaker Attached to Vertical Opener 645

33. Feeder Attached to Vertical Cotton Opener 647

34. Saco-Lowell Condenser 648

35. One-Beater Cotton Breaker with Feeder 649

36. Intermediate or Finisher Lapper for Cotton 651

37. Cotton Teasing (Nobel's Explosives Co.) 653

38. Hand Picking of Cotton for Nitration (Nobel's E.xplosives Co.). . 654

39. Cotton Drying Machine (Nobel's Explosives Co.) 656

40. Cyclone Dust Collector (Nobel's Explosives Co.) 657

41. Cotton Disintegrator 659

42. Nitric Acid Still (Buffalo Foundry & Machine Co.) 744

LIST OF ILLUSTRATIONS xxi

43. Nitric Acid Still (Buffalo Foundry & Machine Co.) 745

44. Hart Nitric Acid Condensing Manifold 748

46. Hart Nitric Acid Condenser 749

46. Niter Storage House (H. M. Explosives Factory, Gretna) 774

47. Loading Niter into Nitric Retort (H. M. Explosives Factory,

Gretna) 775

48. Nitric Acid Manufacture (H. M. Explosives Plant, Gretna) 777

49. Nitric Acid Manufacture (H. M. Explosives Plant, Gretna) 778

60. HNOi Manufacture (H. M. Explosives Factory, Gretna) 780

61. HNOi Manufacture (H. M. Explosives Factory, Gretna) 781

52. Hough Niter Cake Flaker 809

63. Uebel Process for Nitric Acid Manufacture 816

64. The Valentiner Vacuum Process for Nitric Acid Manufacture 819

55, 56. The Valentiner Nitric Acid Process 820

57, 58. The Valentiner Nitric Acid Process 821

59. The Valentiner Vacuum Process for Nitric Acid Manufacture 822

60. The Valentiner Vacuum Process for Nitric Acid Manufacture 823

61. The Hough Nitric Acid Plant, as Constructed by the Buffalo

Foundry & Machine Co 827

62. The Hough Nitric Acid Condenser 830

63. The Nash Vacuum Pump 831

64. The Greisheim Plant for Nitric Acid Manufacture 835

65. The Niedenfuhr Nitric Acid Plant 839

66. The Skoglund Nitric Acid Condenser 840

67. The Guttmann Nitric Acid Condensing System 842

68. Schonherr Furnaces, Badische System 859

69. SchSnherr Furnace 860

70. 71. Synthetic Nitric Acids (Poudrerie Nationale D'Angouleme) . . 865

72. Transportation of Cyanamide 866

73. Autoclaves 866

74. 75. S3rnthesis of Ammonia from the Air 867

76. Catalyzers for Synthetic Nitric Acid Manufacture 868

77. The Birkeland-Eyde Nitrogen Fixation Furnace 871

78. Birkeland-Eyde Nitrogen Fixation Furnace 872

79. Birkeland-Eyde Furnace 878

80. Birkeland-Eyde Electric Furnace (Diagrammatic) 879

81. Birkeland-Eyde Furnaces (Bjukan Saltpeter Factory) 880

82. The Badische Synthetic Ammonia Apparatus 905

83. Lunge Two-Bulb Nitrometer 965

84. Lunge Gas- Volumeter 969

85. du Pont Nitrometer 973

86. Jensen Nitric Acid Concentration Plant 988

87. Sulfur Storage (H. M. Factory, Gretna) 1065

88. Weighed Sulfur Charges to be Burned 1066

89. Sulfur Burners in Operation (H. M. Factory, Gretna) 1067

90. The Sachsenburgher SO2 Burner 1069

91. The Clemm and Hasenbach Process of Sulfuric Anhydride Manu-

facture 1118

92. The Badische Process of HtS04 Manufacture 1139

93. The Badische Contact Process for H1SO4 Manufacture 1140

94. The Badische Contact Furnace 1143

95. The Badische Contact Furnace! 1144

96. The Badische Process of SO. Manufacture 1148

97. Badische Process for Producing Sulfur Trioxide 1 149

98. The Tentelew Sulfuric Acid Contact Method 1153

99. The Tentelew Process for Sulfuric Acid Manufacture 1156

100. The Meister, Lucius & Briining Process of Contact H2SO4 Manu-
facture ^ 1159

XXll LIST OF ILLUSTRATIONS

101. The Schroeder-Grillo Process of SO3 Manufacture 1165

102. The Schroeder-Grillo Process of SO3 Manufacture 1166

103. The Schroeder-Grillo Process of Sulfiu-ic Anhydride Manufacture. 1168

104. The Schroeder-Grillo Sulfuric Anhydride Process 1169

105. The Lihme Process of Sulfuric Acid Manufacture 1193

106. Raynaud and Pierron Process of Making Sulfuric Anhydride 1194

107. Raynaud and Pierron Sulfuric Anhydride Process 1196

108. The Stone Apparatus for H2SO4 Manufacture \ 1 197

109. The Herreshoff Apparatus for SOs Manufacture 1199

110. Ferguson Process of Making Sulfuric Anhydride 1201

111. Herreshoff Process for Making Sulfuric Acid 1202

112. Molecular Composition of Mixed Acid 1407

113. Cellulose Nitrate Solubility as a Function of the Acid Compo-

sition 1408

114. The Brockbank Apparatus for Filtering Corrosive Liquids 1414

115. Mowbray Apparatus for Restoring Nitrating Baths 1416

116. du Pont System for Removal of Acids from Nitrocellulose 1418

117. du Pont System for Removal of Acids from Nitrocellulose 1419

118. du Pont Apparatus for Condensing and Mixing Acids 1428

119. Fairbanks Scale 1429

120. Fairbanks Scale 1429

121. The Evers Denitrating Plant 1449

122. The Evers Denitration System 1450

123. The Evers Denitrating System 1451

124. The Evers Denitrating System 1452

125. The Evers Denitrating System 1453

126. The Evers Denitration System 1454

127. Guttmann Denitrating Stones 1463

128. Guttmann System 1464

129. The Jahn Nitration Process 1465

130. Everlasting Valve, Acid Type 1469

131. Everlasting Valve, Acid Type, Screwed 1470

132. Everlasting Valve, Acid Type, Flanged 1471

133. Everlasting Valve, Acid Type, Double Disc 1472

134. Everlasting Valve, Acid Type, with Shield 1472

135. Mixed Nitrating Acid Tanks, Showing Installation of Acid Valves 1473

136. Everlasting Valve, Acid Form, with Extension Handle 1474

137. Redpath Graphic Method of Nitrating Acid Calculation 1492

138. Redpath Graphic Method of Nitrating Acid Calculation 1493

139. Fowler Method of Spent Acid Calculation 1500

140. Fowler Method of Spent Acid Calculation 1501

141. Fowler Method of Spent Acid Calculation 1504

142. Hygroscopicity of Cellulose Nitrates 1752

143. The Miihlhauser Nitrostarch Manufacturing Method 1821

144. The Miihlhauser Process of Nitrostarch Manufacture 1822

145. Pot Nitration of Cellulose in France 1943

146. Dippmg Cotton 1944

147. Steeping the Cotton After Dipping 1945

148. The Direct Dipping of Cellulose 1947

149. Nobel's Explosives Co.'s Tank Method of Nitration 1949

150. The Assadas Method of Cellulose Nitration 1951

151. Selwig & Lange Nitrating Centrifugal 1957

152. Selwig & Lange Nitrating Centrifugal 1958

153. Selwig & Lange Centrifugal with Acid Circulation 1959

154. Selwig & Lange Nitrating Centrifugal (Top View) 1960

155. Selwig & Lange Centrifugal with Fume Conveyor. . ." 1964

156. Selwig & Lange Nitrating Equipment in France 1965

157. Selwig & Lange Nitrating Installation in France 1965

LIST OF ILLUSTRATIONS xxiu

158. Wolfshohl Automatic Cotton Steeper'. . : 1966

159. Wolfshohl Automatic Cotton Steeping Appliance 1987

160. Tolhurst Nitrating Centrifugal '. 1969

161. Tolhurst Acid Wringer 1970

162. Tolhurst Finishing Centrifugal 1971

163. Dumons Vacuum Nitrating Apparatus .- 1972

164. Kron Nitrating Centrifugal 1975

165. Thomson Displacement Cotton Nitrating Apparatus 1981

166. Thomson Displacement Apparatus (Sectional Elevation). 1981

167. Thomson Displacement Nitration 1982

168. Thomson Displacement Nitrating Pan 1982

169. Unit of Four Thomson Displacement Pans 1983

170. Thomson Displacement Process at Picatinny 1985

171. Thomson Displacement Nitration in France 1986

172. Plumbing Installation for Displacement Plant 1986

173. View Showing Arrangement of Units in Rows 1987

174. Thomson Displacememt Nitration Pans 1989

175. Cocking Method of Cotton Nitration 1992

176. Amqtt Acid Distributing System 1993

177. Add Mixing and Weighing Tanks 1996

178. Top Floor. Nitrating House 1997

179. du Pont Mechanical Cotton Nitration 1998

180. Nitrating House, Dipper Floor 1999

181. du Pont Mechanical Cotton Nitration 2000

182. Matousek Nitrating Centrifugal 2003

183. Diamanti Method of Cotton Nitration 2005

184. Briailles Electrolytic Nitration Method 2006

185. Schniter Cotton Nitration Process 2007

186. France Method of Cotton Comminution. . . : 2009

187. Mackie's Process for Cotton Nitration 2010

188. Maxim Process for Cotton Nitration 2013

189. Maxim Cotton Nitration Process 2014

190. Beck and Nenninger Guncotton Apparatus 2016

191. Henchman's Nitration Process 2019

192. Cotton Nitration Process, Zellstoffabrik 2020

193. Chardonnet Nitrating Apparatus 2023

194. Kaltenbach Nitration Process 2027

195. Muller Process for Cotton Nitration 2028

196. Morane Nitrating Apparatus 2029

197. Schupphaus & White Paper Nitration Process 2035

198. Schupphaus & White Paper Nitration Process 2035

199. Mowbray's Paper Nitrating Apparatus 2036

200. Mowbray's Paper Nitrating Apparatus 2037

201. Tribouillet & Besaucele Nitrating Apparatus 2038

202. Hyatt Tissue Paper Nitrator •. 2041

203. Hyatt Tissue Paper Nitrator 2041

204. Hyatt Tissue Paper Nitrator (Plan View) 2042

205. Hyatt Tissue Paper Nitratoi (Side View) 2043

206. Swan Apparattis for Paper Nitration 2046

207. Swan Apparatus for Paper Nitration 2047

208. Delpy Paper Nitration Apparatus 2049

209. Selwig & Lange Automatic Guncotton Conveyor 2061

210. Flack Gimcotton Washer 2064

211. Flack Guncotton Washer 2065

212. Percolator Boiling Tub House 2073

213. Guncotton Boiling House 2075

214. Selwig & Lange Guncotton Steam Centrifugal 2080

215. Installation of Hollander Pulpers 2085

XXiV LIST OF ILLUSTRATIONS

216. Miller Patent Duplex Beating Engine 2086

217. Miller Duplex Beater 2086

218. Pulping House Showing Corliss Engines 2091

219. Stabilization of Nitrocellulose in France 2096

220. Centrifugal Pump Poachers 2097

221. Poachers as Installed at Stowmarket 2099

222. Centrifugal Pump Poachers and Blending Tuns 2101

223. Poacher House 2103

224. Chutes for Removing Foreign Matter 2105

225. Installation of Electro-Magnets 2106

226 Nitrocellulose Blenders 2109

227. Nitrocellulose Blenders Showing Stirring Arrangement 2110

228. Miller Open Screen 2113

229. Packer Open Diaphragm Screen 2115

230. Union- Witham Screen Plate Vat and Fasteners 2116

231. Witham Screen Plates 2117

232. Sectional View of Tolhurst Bottom Discharge Extractor 21 19

233. Tolhurst Self-balancing Dehydrating Centrifugal 2120

234. Installation of Centrifugals (Bottom Discharge) 2121

235. Leflaive Centrifugal Wringer 2123

236. Muller Centrifugal Extractor 2124

237. Selwig & Lange Centrifugal Pyroxylin Dehydrator 2126

238. Running Pulped Nitrocellulose Through the Wet Machine 2129

239. Dehydrating House Showing Presses 2131

240. Block or Cheese of Nitrocotton 2132

241. Breaker fw Disintegrating Nitrocotton Blocks 2133

242. du Pont Pressure Dehydrator 2134

243. Alcohol Displacement Nitrocotton Dehydration 2142

244. Alcohol Dehydration — Underside of Pot 2143

245. Gentieu Guncotton Dehydrator 2144

246. Edson Process for Drying Nitrocellulose 2149

247. Stove for Drying Nitrocotton in Loose Form 2152

248. Passbiu-g Patent Drying Chamber 2154

249. Passburg Safety Vacuum Drying Apparatus 2155

250. du Pont Method of Nitrxxellulose Drying 2157

251. Hydraulic Press for Alcohol Dehydration 2161

252. Hydraulic Guncotton Press (From Below) 2163

253. Compression of Guncotton 2165

254. Guncotton Sectional Charges 2167

255. Machine for Breaking or Sieving Nitrocotton. 2169

256. Block Breaker House Discharge 2170

257. Guncotton Block Breaker 2171

258. Stove for Drying Nitrocotton in Primer Form 2177

259. Installation of Moulding Presses 2178

260. Hydraulic Nitrocotton Press. 2179

261. Press for Moulding Nitrocotton into Primer Forms 2180

262. Cotton and Guncotton at Different Stages of Manufacture 2181

263. Block of Guncotton and Press 2183

264. Compression of Guncotton into Blocks 2185

265. Guncotton Block 2187

266: Solid Block of Compressed Guncotton 2189

267. Unpulped Nitrocellulose 2191

268. Nitration of Cellulose 2192

269. Thomson Method of Cotton Nitration 2193

270. Boiling the Nitrated Cellulose 2196

271. Nitrocellulose Beaters or Pulpers 2198

272. Introducing Nitrocotton into the Beater 2199

273. Bagging the Nitrocotton 2204

LIST OF ILLUSTRATIONS XXV

274. Centrifugalizing the Nitrocotton 2205

275. Picking over the Nitrocellulose '. 2206

276. Loading the Nitrocotton into the Preliminary Boiling Tubs 2213

277. Quinan Nitrocotton Dryer 2221

278. Quinan Nitrocellulose Dryer 2222

279. Individual Quinan Nitrocotton Dryer 2223

280. Nitration of Cotton at Gretna 2231

281. Du Pont Process for Granulating Nitrocellulose 2248

282. Du Pont Process for Granulating Nitrocellulose 2248

283. Cochins Viscosimeter 2277

284. Speedy Viscosimeter 2279

285. Ostwald Viscosimeter 2283

286. Viscosity Determination by Ball Fall Method 2286

287. Oddo Nitrogravimeter 2312

288. Abel Heat Test Apparatus 2342

289. Brame Constant Temperature Heating Apparatus 2350

290. Will's Apparatus for Testing Nitrocellulose 2351

291. Nitrocellulose Powders— Eight Hour Test 2354

292. Bergmann & Junk Stability Test Apparatus 2356

293. Bergmann and Junk Tubes 2357

294. Housing for Bergmann & Jimk Stability Apparatus 2358

295. Dr. Camille Dreyfus 2989

296. Dr. Henry Dreyfus 2990

297. Leo Rutstein 3487

I.

II.

III.

IV.

V.

VI.

VII.

VIII.

IX.

X.

XI.

XII.

XIII.

XIV.

XV.

XVI.

XVII.

XVIII.

XIX.

XX.

XXI.

XXII.

XXIII.

XXIV.

XXV.

XXVI.

XXVII.

XXVIII.

XXIX.

XXX.

XXXI.

XXXII.

XXXIII.

XXXIV.

XXXV.

XXXVI.

XXXVII.

XXXVIII.

XXXIX.

XL.

XLI.

XLII.

XLIII.

xuv.

XLV.

XLVI.

XLVII.

XLVIII.

XLIX.

L.

LI.

LIST OF TABLES.

PAGE.

Composition of the Celluloses 10

Distillation of Carbohydrates 41

Specific Rotatory Power of Different Types of Cellulose . 50

Distillation of Cellulose and Wood 58

Absorption of Tannin by Celltdose 62

Absorption of Tannin by Cellulose in Acid Solution. . ... 62

Action of Sulfuric Acid on Cotton 118

Cotton 119

Acid Decomposition of Cellulose 122

Reducing Properties of Hydrocellulose 138

Action Sodium Hydroxide on Hydrocellulose 144

Copper Number of Hydrolyzed Cellulose 145

Action of Ozone on Cotton and Viscose 153

Action of Ozone on Mercerized Cotton 154

Products from Oxidation of Cellulose 166

Cellulose to Glucose 199

Cellulose to Glucose (2.7 Atms. Pressure) 199

Hydrolysis of Pine Wood 212

Action of Caustic Soda on Cellulose 218

Action of Alkali on Cellulose 221

Benzoylation of Cellulose 222

Mercerization of Cotton 229

Vegetable Fibrous Materials 244

Carbon and hydrogen in Jute and Cotton 247

Composition of Flax, Hemp and Spruce Wood 250

Composition of Wood 254

Destructive Distillation of Lignin 256

Wood, Analyses of 258

Color Reactions of Lignocellulose 262

Analysis of Waste Sulfite Liquor 280

Resins in Wood Pulp 288

Products of Fermentation of Cellulose 341

Temperature Increases of Starch and Water 434

Lengths and Diameters of Cotton Fibers 480

Length of Cotton Fibers 504

Variation in Length and Diameter of Cotton Fibers 507

Length of Staple of Cotton 507

Diameter of Fibers 508

Length of Cotton Staples 509

Regain for Cotton at Various Temperatures and Per-
centages of Humidity 510

Hygroscopicity of Cottons 513

Hygroscopicity of Purified Cottons 514

Percentage Moisture Absorption in Cotton 517

Mineral Constituents of Cotton 525

Ash in Different Varieties of Cotton 525

Mineral Constituents of Cotton Fiber 526

Analyses of Cotton Fiber 527

Tensile Strength of Cotton 572

Strength of Single Cotton Yarns 528

Composition of Cotton Fiber 531

Analyses of Mercerized Egyptian Cotton 532

LIST O^ TABLES XXVJl

LII. Copper Absorption of Cotton 647

LIII. Analyses of Nitrated Cotton -?.... 558

LIV. Solubility of Aluminium in Nitric Acid 951

LV. Production of Sulftu* in Various Countries, 1906-1914 In-
clusive 1021

LVI. Analyses of Pyrites 1047

LVII. Analyses of Pyrites 104a

LVIII. Dimensions of Mechanical Pyrites Burners 1064

LIX. Sulfur Trioxide Content of Oleum 1126

LX. Sulfur Trioxide Content of Feed Acid, 96%-100% 1126

LXI. Sulfur Trioxide Content of Oleum, 88%-96% 1126

LXII. Conversion of SOi and Og at Various Temperatures 1135

IJCIII. Sulfur Dioxide and Oxygen without Nitrogen 1135

LXrV. Burner-Gas Diluted with Air 1135

LXV. Specific Heat of Sulfuric Acid 1318

LXVI. Percentage of Arsenic Compoimds in Sulfuric Acid 1338-

LXVII. Cascade Plant and Condensers 1371

LXVIII. Electric Conductivity of Sulfuric Acid 1405

LXIX. Vapor pressure of Mixed Sulf uric-nitric Acid 1405

LXX. Approximate Weights of Mixed Acid 1513

LXXI. Reduction of Gas. Volumes 0° and 760 mm 152a

LXXII. Corrections of Barometer Readings for Temperature. .. . 1521

LXXIII. Density of Water at 0** to 36** 1521

LXXIV. Density of Water at 30'' to 102° 1522

LXXV. Density of Water at 100° to 320° 1522

LXXVI. Volume in Cubic Centimeters of One Gram of Water at

0° to 36° C 1522

LXXVII. Volume in Cubic Centimeters of One Gram of Water at

30° to 102° C 1523

LXXVIII. Volume in Cubic Centimeters of One Gram of Water at

100° to 320° C 1523

LXXIX. Specific Gravity of Sodium Nitrate Solutions at 20.2° C. 1523

LXXX. Solubility of Sodium Nitrate in 100 Parts Water at t° C. 1524

LXXXI. Solubility of Sulfur Dioxide in Water 1524

LXXXII. SolubiUty of Sulfur Dioxide in Water 1524

LXXXIII. Equivalent of Degrees Baum^ and Specific Gravity at

gQop 1*625

LXXXIV. Specific Gravity of Fuming Sulfuric acid at 35° C .... . . 1527

LXXXV. Fuming Sulfuric Acid 1528-

LXXXVI. Fuming Sulfuric Acid 1529

LXXXVII. Sulfuric Acid 1530

i;XXXVIII. Sulfuric Acid 1532

LXXXIX. Sulfuric Acid 1535

XC. Temperature Corrections in Sidfuric Acid Gravities 1536

XCI. Influence of Temperature on the Sp. gr. of Sulfuric Acid 1537

XCII. Temperature Correction Table for Sulfuric Acid 1538

XCIII. The Thermal Properties of Sulfuric Acid and Water Mix-
tures 1539

XCrV. Sulfimc Acid and Water Mixtures 1540

XCV. Corrections for Hydrometer Readings 1541

XCVI. Centigrade Fahrenheit Conversion Tables. . . , 1542

XCVII. Specific Gravity Tables for Nitric Acid 1544

XCVIII. Correction of Specific Gravity of Nitric Acid Containing

Nitrous Fumes 1545

XCIX. Densities of Concentrated Nitric Acid at Different Tem-

peratiu-es 1546

C. Nitric Acid 154^

CI. Weight of 1 cc. of Moist Nitrogen in Milligrams 1549

XXVIU

LIST OI^ TABLES

CII.

cm.

CIV.
. CV.

CVI.

CVII.

CVIII.

CIX.

ex.

CXI.

CXII.

CXIII.

CXIV.

cxv.

CXVI.

CXVII.

CXVIII.

CXIX.

CXX.

CXXI..

CXXIII.

CXXIV.

cxxv.

CXXVI.

CXXVII.

CXXVIII.

CXXIX.

cxxx.

CXXXI.

CXXXII.

CXXXIII.

CXXXIV.

cxxxv.

CXXXVI.

CXXXVII.

CXXXVIII.

CXXXIX.

CXL.

CXLI.

CXLII.

CXLIII.

CXLIV.

CXLV.

CXLVI.

CXLVII.

CXLVIII.

CXLIX.

CL.

CLI.

Reducing Nitric Acid to Standard Temperattire and

Pressure 1550

Percentages of Nitrogen in Substances Taken 1557

Composition of Gas from Combustion of Gtmcotton 1627

Cellulose Nitrates of Vieiile 1652

Nitration Experiments of Vieiile 1654

Nitration Experiments of Vieiile 1655

Effect of Washing on Guncotton 1657

Effect of Ptdping on Guncotton 1657

Effect of Washing on Viscosity of Guncotton 1657

Influence of Water on Nitration of Cotton 1659

Nitration of Cellulose Derivatives 1663

Nitration Experiments of Bonge 1667

Action Concentrated Nitric and StUfuric Acids on Cotton 1672

Saponification of Nitrocellulose by Caustic Soda 1676

Saponification of Nitrocellulose by Ammonium Sulfide. . . 1676

Heat Test of Nitrocellulose Combinations 1704

Loss of Nitrogen in Heating Nitrocellulose 1707

Solubility of Nitrocellulose 1725

Solubility of Nitrocellulose 1726

Viscosity of Nitrocellulose Solutions 1737

Viscosity of Nitrocellulose in Ether- Alcohol 1744

Alteration of Viscosity with Time 1745

Nitrocellulose Viscosity in Ether- Alcohol 1745

Viscosity /Concentration of Nitrocellulose 1746

Viscosity of Ether-Alcohol Nitrocellulose Solutions 1746

Effect of Water on Nitrocellulose Viscosity 1748

Viscosity Nitrocellulose in Anhydrous Acetone 1749

Density of Nitrocellulose 1756

Action Ultraviolet Rays on Smokeless Powders 1764

Ultraviolet Ray Decomposition of Nitrocellulose 1764

Permanent Gases in Explosion of Strand Guncotton 1799

Permanent Gases in Explosion of Pellet Guncotton 1799

Gases in Detonating Gtmcotton 1800

Gases Evolved in Firing Cordite Powder 1800

' Pressures in Firing Cordite Powder 1801

SolubiHty of Nitrated vStarch 1833

Viscosity of Nitrated Starch 1833

Composition of Trojan Explosive and Grenite 1841

Colors Produced in Dyeing Nitrocellulose 1896

Nitrates of Oxycellulose and Hydrocellulose 1902

Spent Acid from Thomson Nitration Process 1989

Temperature Rise of Spent Acid, Thomson Process 1989

Comparison of Nitrated Processes 2059

Materials Required for One Ton Nitrocellulose 2059

Boiling Periods for Nitrocellulose 2077

Boiling Periods for Nitrocelltilose 2078

Determination of Nitrogen in Gimcotton 2320

Analysis of Nitrocellulose Compounds by Nitrometer . . . 2322

Stability Nitrocellulose for Military Powder 2348

ABBREVIATIONS.

A. At At !d.

Anon,

A. O. A. C.

abs.

A. C.

Act.

Add.

ale.

alk.

amp.

ami.

approx.

at.

atm.

atm. pr.

as-

av.

b.

b. pt.
c.

cal.

cc.

chem.

C. I.

com.

comp.

compd.

cone.

cor.

C. O. V.

c. p.
crys.
cu.

cu. ft.
cu. m.
cwt.

D. C.
d-

d.

diam.

dcm.

dil.

dr. •

fl.

Farb.

f. pt.

gal.

Ges.

gm.

American Association
for the Advancement
of Science

Anonyme (Anonymotis)

Association of Official
Agricultural Chem-
ists

absolute

Alternating current

Actien

Addition Patent

alcohol ethyl

alkaline

ampere

amount

approximate

atom, atomic

atmosphere (s)

atmospheric pressure

assymmetric

average

boil(s), boiling

boiling point

asymmetric carbon
atom

calorie

cubic centimeter (s)

chemitol

cast iron

commercial

composition

compound

conicentrat-ed, ion

corrected

Concentrated oil of vit-
riol

candle power

crystals, crystallized

cubic

cubic foot (feet)

cubic meter (s)

hundredweight

Direct current

dextro

density

diameter

decimeter

dilute

dram

fluid

Parbenfabriken

freezing point

U. S. gallon, 3785 cc.

Gesellschaft

gram(s)

grain(s)

h. p. horse power

hr. hour(s)

insol. insoluble

in. inch

k. kilogram

kw. kilowatt

1. liter(s)

i. laevo

lab. laboratory

lb. Avoirdupois pound(s)

Ltd. Limited

m. meter

m. meta

mfr. manufacturer

mfg. manufacturing

mgm. milligram

min. minute (s)

mm. millimeter

mol. molecule (s)

mol. wt. molecular weight

m. pt. melting point

M. S. Mild steel

nor. normal

n. t. p. normal temperature

and pressure (0° C,
760 mm.)

0- ortho

ord. ordinary

oz. Avoirdupois ounce

p- para

pp. precipitate

p. pint

qt. quart

quant. quantitative •

recryst. recrystallized

r. p. m. revolution per minute

sat. saturate (d)

sc. scruple

sec. second (s)

soln. solution

Soc. Societe

sp. gr. specific gravity

sq. square

S. T. P. Standard temperature

(15.56° C.) and pres-
sure (760 mm.)

sym. symmetrical

temp. temperature (s)

V' vicinal

vac. vacuum

vol. volume (s)

wt. weight

" degrees Centigrade (al-
ways)

% per cent, by weight

TABLE OF SUMMARIES TO VOLUME ONE

Foot
Notes

Literature

Chapt.

Pages

Topics

Tables

Cuts

Patents

Refer-
ences

Names

I

388

75

32

0

1124

3624

13665

5042

II

96

' 19

2

0

798

896

6583

1839

III

98

27

19

1

174

143

565

211

IV

82

11

0

40

111

238

508

466

V

344

71

1

41

1199

5116

10386

4994

VI

396

141

13

25

1676

4609

9376

5911

VII

116

21

2

30

100

111

509

155

VIII

48

0

34

0

12

—

7

20

IX

366

65

33

3

1420

1175

8359

1988

X

340

54

11

138

320

577

1014

351

XI

104

27

3

14

204

6

1216

302

XII

707

88

0

2

12473

22963

28316

12461

Total

3085

599

150

294

19611

39458

80504

33740

LIST OP ABBREVIATIONS TO LITERATURE

A. and N. J.

Aarau, Archiv der Med.

Aarau, Mitth.

Abbeville, Bull. Soc. Linn.

Abbeville, Mem. Soc. Emul.
Abeille, J.
Abeille mem.
Abeille Soc.

Acad.

Acad. Caes. Leop. Nova

Acta
Acad. Natur. Curios. Nova

Acta
Acireale Accad. Atti

Adreale, Soc. Ital. Micro.

Boll.
Acquoy, Tijdschrift
Acta Math.
Actes Soc. Helvetique
Adansonia
Adelaide Phil. Soc. Trans.

Aeronaut. J.
Aeronaut. Soc. Reports

Aeronaute

Afhandl. Fysik.
African Assoc. Proc.

Agen, Soc. Agric. Recueil.

Agram., Program Gynmas.

Agric. Gaz.

Agric. Gaz. N. S. Wales

Agric. J. India

Agrk. Ledg.

Agric. Soc. J.

Agric. Stud. Gaz.

Agron. Ztg.
Aix, Acad. Mem.

Prepared by Ds. Cakl Marx

Army and Naval Journal

Archiv. der Medizin, Chirurgie, und Pharmazie

Mittheilungen des Aargauischen Naturforschenden

Gesellschaft
Compte Rendu et Bulletin de la Soci6t^ Linneenne du

Nord de la Prance
Memoires de la Soci^t6 d'Emulation d'Abbeville
L'Abeille, Journal d'Entomologie
L' Abeille: memoires d'Entomologie
(Publications de la Soc. Entomologiede France.)

LaAbeille. Journal de Entomologie
Memoires de I'Academie des Sciences
Nova Acta physico-medica Academiae Caes. Leopol-

dino-Carolinae Naturae Curiosorum
Nova Acta Academiae Caesareae Leopoldino-Carolinae

Germanicae Naturae Curiosorum
Atti e Rendiconti dell' Accademia di Scienze, Lettere

e Arti dei Zelanti e PP. dello Studio di Acireale
Bollettino della Societa Italiana dei Microscopisti

Tijdschrift voor Wis-, Natuur-, en Wertuiglnmde

Acta Mathematica

Actes de la Soci^t^ Helvetique des Sciences Naturelles

Adansonis: Recueil d'observations botaniques

Transactions and Proceedings and Report of the Philo-
sophical Society of Adeliade, South Australia

The Aeronautical Journal

Annual Reports of the Aeronautical Society of Great
Britain

L' Aeronaute: bulletin mensuel international de la
Navigation Aerienne

Afhandlingar i Fysik, Kemi, och Mineralogi

Proceedings of the. African Association for promoting
the Discovery of the Interior Parts of Africa

Recueil des Travaux de la Soci^t^ d'Agiiculture,
Sciences, et Arts d'Agen

Program des k. k. Akademischen Gymnasiums zu
Agram

The Agriculttu^ Gazette

Agricultural Gazette of New South Wales, The

Agricultural Journal of India

Agricultural Ledger

The Journal of the Royal Agricultural Society of
England

Agricultural Students' Gazette. A Quarterly Jour-
nal edited by Students at the College, Cirencester

Agronomische Zeitung

Recueil de Memoires de la Soci^t^ des Amis des
Sciences, des Lettres, de I'Agricultur, et des Arts
a Aix

XXXIV

LIST O^ ABBREVIATIONS TO LITERATURE

Albany Inst. Proc.

Albany Inst. Trans.

Alger. Bull. Soc. Climat.

Alk.

AUelod. Soc. Trans.

Allg. Berg. Ztg.

Allg. Bot. Zts.

Allg. Deut. Naturhist. Ztg.
Allg. Deut. Omith. Ges.
Allg. Fischerei Ztg.
Allg. Forst-Jagd-Zts.
Allg. Gerber-Ztg.
Allg. Schweiz. Ges. Gesam.

Naturwiss.
Allg, Syn. Suikerfab.

Allg. Zts. Bierbr. Malz-

fabr.
Allier, Bull. Soc. Emul.

Alpina

Altenburg Mitth.

Amat. Mechan. Soc. J.

Amer. Acad. Mem.

Amer. Acad. Proc.

Amer. Agric.
Amer. Ann. Phot.
Amer. Apoth. Ztg.
Amer. Artisan
Amer. Assoc. Proc.

Amer. Brewers Rev.

Amer. Btiilder

Amer. Chem. J.

Amer. Chemist

Amer. Drug.

Amer. Electrochem. Soc.

Amer. Engin. & Railroad J.

Amer. Ethnol. Soc. Trans.
Amer. Entom. Soc. Trans.

Amer. Fertilizer
Amer. Food J.
Amer. Gas Light J.
Amer. Geogr. Soc. Bull.

Amer. Geogr. Soc. J.
Amer. Geogr. Soc. Proc.

Proceedings of the Albany Institute

Transactions of the Albany Institute

Bulletin de la Societe de Climatologie Algerienne

Alkohol

The transaction of the AUelodidactic Society

Allgemeine berg- und hiittenmannische Zeitung

AUgemeine Botanische Zeitscrift fur Systematik,

Floristik, Pflanzengeographie, etc.
Allgemeine Deutsche naturhistorische Zeitung
See J. Omith

Allgemeine Fischerei Zeitung
Allgemeine Forst- und Jagd-Zeitimg
Allgemeine Gerber-Zeitung
See Zurich, Schweiz. Ges. N. Denkschr.

Algemeen Syndicat van Suikerfabrikanten in Nederl.-

Indie. With Arch-Suikerind, etc.
Allgemeine Zeitschrift fiir Bierbrauerei und Maz.l

fabrikation
Bulletin de las Soci^t6 d' Emulation du d^partement de

r Allier: Sciences, Arts, et Belles-Lettres
Alpina, eine Schrift der genauen Kenntniss der Alpen

gewidmet; von Carl Ulisses von Salis und J. R.

Steinmueller
Mittleilungen aus dem Osterlande ; herausgegeben von

der Naturforschenden Gesellschaft zu Altenburg
The (Quarterly) Journal of the Amateur Mechanical

Society
Memoirs of the American Academy of Arts and

Sciences
Proceedings of the American Academy of Arts and

Sciencess
American Agricultiu-ist
American Annual of Photography
Deutsch-Amerikanische Apotheker Zeitung
American Artisan

Proceedings of the American Association for the Ad-
vancement of Science
American Brewers Review
The American Builder
American Chemical Journal
American Chemist

American Druggist and Pharmaceutical Record
American Electrochemical Society
American Engineer (Car Builder), and Railroad

Journal
Transactions of the American Ethnological Society
Transactions of the American Entomological Society

and Proceedings of the Entomological Section of the

Academy of Natural Sciences
American Fertilizer, The
American Food Journal
American Gas Light Journal, The
Bulletin of the American Geographical and Statistical

Society
Journal American Geographical Society, New York
Proceedings of the American Geographical and Sta-
tistical Society of New York

LIST OF ABBREVIATIONS TO LITERATURE

XXXV

Amer. Geol. and Nat. As-
soc. Reports
Amer. J. Conchol.
Amer. J. Dent. Sci.
Am. J. Math.
Amer. J. Med. Sci.
Amer. J. Otol.
Amer. J. Pharm.
Amer. J. Physiol.
Amer. J. Physiol., Boston
Amer. J. Psychol.
Amer. J^Pub. Health
Amer. J. Sci.
Amer. Mach.
Amer. Math. Soc.
Amer. Med.

Amer. Med. Assoc. Trans.
Amer. Med. Phil. Reg.

Amer. Med. Recorder
Amer. Meteorol. J.
Amer. Micro. J.

Amer. Micro. Soc. Proc.
Amer. Micro. Soc. Trans.
Amer. Mineral. J.
Amer. Min. Gaz.

Amer. Monthly Micro. J.
Amer. Mus. Bull.
Amer. Mus. Mem.
Amer. Natur.
Amer. Ophthalm. Soc.

Trans.
American Perfumer
Amer. Phil. Soc. Proc.

Amer. Phil. Soc. Trans.

Amer. Phot.
Amer. Poly. J.
Amer. Quart. J. Agric.
Amer. Reports State

Entom.
Amer. Soc. Agr. Sci. Proc.

Amer. Soc. Civ. Engin.
Trans.

Amer. Soc. Micro. Proc.

Amer. Sugar. Ind.

Amer. Vet. Rev.. N. Y.

Amherst. Agric. Sta. Re-
port

Amid, Giom. Loscano

Amiens Acad. Sci. Mem.

Reports of the Meetings of the Association of Ameri-
can Geologists and Naturalists at Philadelphia

American Journal of Conchology

American Joiunal of Dental Science

American Journal of Mathematics

American Journal of the Medical Sciences.

The American Joiunal of Otology

American Joiunal of Pharmacy

The American Journal of Physiology

American Journal of Physiology, Boston

The American Journal of Psychology

American Journal of Public Health

The American Journal of Science

American Machinst

See N. Y. Amer. Math. Soc,

American Medicine

Transactions of the American Medical Association

The American Medical and Philosophical Register;
or Annals of Medicine, Natural History, Agricidture,
and the Arts

American Medical Recorder

American Meteorological Journal

The American Quarterly Microscopical Journal. With
which is also published the Transaction of the
New York Microscopical Society

Proceedings of the American Microscopical Society

Transactions of the American Microscopical Society

The American Mineralogical Journal

The American Mining Gazette and Geological Maga-
zine

American Monthly Microscopical Journal

Bulletin of the American Museum of Natural History

Memoirs of the American Museum of Natural History

American Naturalist

Transactions of the American Ophthalmological So-
ciety

American Perfiuner and Essential Oil Review, The

Proceedings of the American Philosophical Society
held at Philadelphia

Transactions of the American Philosophical Society,
held at Philadelphia, for promoting useful knowledge

American Photography

The American Polytechnic Journal

American Quarterly Journal of Agriculture and Science

See III., Mass., Mo., N. Y.

Proceedings of the Society for the Promotion of Agri-
cultural Science
Transactions of the American Society of Civil Engineers

Proceedings of the American Society of Microscopists
American Sugar Industry and Beet Sugar Gazette, The
American Veterinary Review, N. Y.
Annual Report of the State Agricultural Experiment

Stations, at Amherst, Mass.
Giomale Loscano di Scienze medichi, fisiche e naturali
Memoirs de I'Academie des Sciences, des Lettres et

des Arts d'Amiens

USX OP ABBREVIATIONS TO LITERATURE

Ammon, Monatschr. Med.

Ammon, Zts. Opthalm.
Amsterdam

Amsterdam, Akad. Jaarb.

Amsterdam, Akad. Proc.

Amsterdam, Akad. Verh.

Amsterdam, Akad. Versl.

Mededeel.
Amsterdam, Akad. Wet.

Proc.

Amsterdam, Archief Wisk.

Genoots.
Amsterdam Bijdr. Dierk.

Amsterdam, Bull. Congr.

Bot.
Amsterdam Congr. Bot.

Actes
Amsterdam Genootsch.

"Natm^ Artis Magistra"
Amsterdam Genootsch.

Nat.-, Genees- en Heel-

kmide
Amsterdam, Het Inst.
Amsterdam, Mengelwerk

Amsterdam, Nieuw. Verh.

Amsterdam, Nieuw. Wis.
Voorstel.

Amsterdam Nederl. Aardr.

Genootsch. Tijdschr.
Amsterdam, Onderz. Phys.

Lab.

Amsterdam, Tijdschr.

Natuurk. Wetens.
Amsterdam, Tijdsthr. Wis.

Natuurk. Wetens.

Amsterdam, Verh.

Amsterdam, Verh. Ge-
noots. Geneesk.

Amsterdam, Verzam. Ber.
Navig.

Monatschrift fiir Medecin, Augenheilkunde, und
Chirurgie

Zeitschrift fur die Ophthahnologie

Werken van het Genootschap ter Bevordering der
Natuur-, Geneesen Heelkimde. See MaandbL Nat.

Jaarboek van de koningklijke Akademie van Weten-
schappen gevestigd te Amsterdam

Koninklijke Akademie van Wetenschappen te Amster-
dam. Proceedings of the Section of Sciences

Verhandelingen der koninklijke Akademie van Weten-
schapp.

Verslagen en Mededeelingen der Koninklijke Akademie
van Wetenschappen. Afdeeling Naturkuiibe

Processen-Verbaal van de gewone Vergaderingen der
Koninklijke Akademie van Wetenschappen. Af-
deeling Natuiu-kunde.

Archief uitgegeven door het Wiskundig Genootschap

Bijdragen tot de Dierkunde uitgegeven door the

(Konincklijk Zoologisch) Genootschap Natura Artis

Magistra, te Amsterdam
Bulletin du Congres International de Botanique et

d'Horticulture reuni a Amsterdam
Actes du Congres International de Botanistes, d'Horti-

culteurs tenu a Amsterdam, en 1877

See Amsterdam Bijdr. Dierk

See Maandbl. Nat.

Het Instituut

Mengelwerk von uitgeleezene en andere Wisen Natuur-
kundige Verhandelingen

Nieuwe Verhandelingen der eerste Klasse van het
Koninklijk Nederlandsche Instituut van Weten-
schapen, en Schoone Ktmsten te Amsterdam

Verzameling van nieuwe wiskundige Voorstellen door
de Leden van het Wisktmdig Genootschap, onder de
zinspreuk: Een onvennoeide arheid komt alles te
boven, elkander tot onderlinge oefening opgegeven

Tijdschrift van het (Kon.) Nederlandsch. Aardrijks-
kundig Genootschap, gevestigd te Amsterdam

Onderzoekingen gedaan in het Physiologisch Labora-
toriiun van de Doorluchtige en Klinische Scholen te
Amsterdam
Tijdschrift voor Natuurkundige Wetenschappen en
Kimsten

Tijdschrift voor de Wis- en Natuurkimdige Weten-
schappen, Letterkunde, en Schoone Kunsten te
Amsterdam

Verhandelingen der Eerste Klasse van het Koninklijk
Nederlandsche Instituut van Wetenschappen, Let-
terkunde, en Schoone Ktmsten te Amsterdam

Verhandelingen van het Genootschap ter Bevordering
der Geneesen Heilkunde, en Schoone Kimsten te
Amsterdam

Verzameling van Berichten over eenige onderwcrpen
des Navigatie

LIST OF ABBREVIATIONS TO LITERATURE

XXXVU

Amsterdam Zool. Genoot-
sch. "Natura Artis Mag-
istra"

Anales agron.

Anales fis. quim.

Anales inst. med. nadonal

Anales Mineria Mex.

Analyst

Anat.
Anat. Anz.

Anat. Ges.
Anat. Hefte

Anat. Soc Proc.

Anat. Studien

Angers Acad. Sci. Mem.

Angers, Ann. Soc. Linn.

Angers, Mem. Soc. Agric.

Angers, Soc. Sci. Bull.

Ann.

Ann. Bot.

Ann. Chim.

Ann. Chim. anal.

Ann. chim. farm.
Ann. Chim. Phys.
Ann. Chimica

Ann. Conduct. Fonts et

Chauss.
Ann. Conserv. Arts Met.
Ann. Dermatol.
Ann. Ecole norm.

Ann. Palsif.

Ann. Farm. Chim.

Ann. Pis. Chim.

Ann. G^e Civil

Ann. G^. Set. Phys.

Ann. Geogr.

Ann. Hydrogr.

Ann. Hydrogr. Mar. Met.

Ann. hyg. pub.

Ann. Ind.

Ann. Inst. Pastuer

Ann. Landw.

Ann. Landw. Wochenbl.

Ann. Mag. Natur. Hist.

See Nederl. Tijdschr. Dierk. •

Anales Agronomicos

Anales de la«ociedad espanola de fisica y quimica

Anales del instituto medico nacional

Anales de la Mineria Mexicana, Revista de
Minas

The Analyst, including the Proceedings of the Society
of Public Analysts

Anatomic

Anatomischer Anzeiger. Centralblatt fur die Gesamte
Wissenschaftliche Anatomic. (Amtliches Organ der
Anatomischen Gesellschaft)

See Anat. Anz.

Anatomische Hefte. Referate tmd Beitrage (Beitrage
und Referate) zur Anatomic und Entwickelungs-
geschichte.

See J. Anat. Physiol.

Anatomische Studien

Memoires de TAcademie des Sciences et Belles-Lettres
d'Angers

Annales de la Soci^t^ Linneenne du departement de
Maine et Loire

Memoires de la Soci^t^ d'Agriculture, Sciences, et
Arts

Bulletin de la Soci^t^ d'Etudes Scientifiques d' Angers

Liebig's Annalen der Chemie

Annals of Botany

Annales de Chimie

Annales de Chimie analytique applique & Tlndustrie,
a TAgriculture, 4 la Pharmacie et 4 la Biologic

Annali di Chimica e de farmacologia

Annales de Chimie et de Physique

Annali di Chimica (Medico-Parmaceutica e di Farma-
cologia)

Annales des Conducteurs des Ponts et Chaussees et
des Gardes-Mines

Annales du Conservatoire des Arts et Metiers

Annales de Dermatologie et de Syphiligraphie

Annales scientifiques de T Ecole Normale superieure

(L. Pasteur)

Annales des Falsifications

Annali di Parmacoterapia e Chimica (Biologica)

Annali di Fisica, Chimica, etc.

Annales du G6nie Civil

Annales g6n6rales des Sciences Physiques

Annales de Geographic

Annales Hydrographiques

Annalen der Hydrographie und Maritimen Meteoro-
logie. Organ des Hydrographischen Bureaus
(Amtes) und der Deutschen Seewarte

Annales d'hygiene publique

Annales industrielles, par Fredureau, etc.

Annales de I'lnstitut Pasteur

Annalen der Landwirthschaft in den K. Staaten

Annalen der Landwirtschaft, Wochenblatt

The Annals and Magazine of Natural History, in-
cluding Zoology, Botany and Geology

xxxvm

LIST O^ ABBREVIATIONS TO LITERATURE

Ann. Matemat.
Ann. Math.
Ann. Med.
Ann. Med. PsychoL

Ann. Med. Surg.

Ann. Microgr.

Ann. Mines

Ann. Museo Ind. Ital.

Ann. Natur. Hist.

Ann. Oculist

Ann. Pharm.

Ann. Pharm. Louvain

Ann. Phil.

Ann. Phys.

Ann. Phys. Chem.

Ann. Ponts et Chauss.

Ann. R. Staz. Chira.

Ann. Rep., U. S. Dept.

Agric.
Ann. sci. agron.

Ann. Sci. Bot. Nat.
Ann. Sci. Lomb. Veneto
Ann. Sci. Nat.

Ann. Sci. Univ. Jassy
Ann. Scott. Natur. Hist.
Ann. Surg.
Ann. Storia Natur.
Ann. Telegr.
Annab.-Buchh. Ver. Na-

turk. Ber.
Annab.-Buclih. Ver. Na-

turk. Jahr.
Annaes Sci. Natur.
Anne^ Biol.

Annot. Zool. Jap.

Annuaire Ancienne Nor-

mandie
Annuaire Inst. Provinces

Annuaire met. France
Annuaire Mines Russie
Anthropol. (Paris)

Anthropol. Congr.
Anthropol. Inst. J.

Annali di Matematica pura ed applicata

Annals of Mathematics

Annali di Medicina

Annales medico-psychologiques;' Journal de V ana-

tomie. Physiologic, etc., du systeme nerveux
Annals of Medicine and Surgery, or Records of the

occurring Improvements and Discoveries in Medi-
cine, Surgery, and their immediately connected Arts

and Sciences
Annales de Micrographie specialement consacrees a la

Bacteriologie, aux Protophytes et aux Protozoaires
Annales des Mines. . .redigees et publiees sous TAutori*

sation du Ministre des Travaux Publics
Annali del R. Museo Industriale Italiano
Annals of Natm-al History
Annales d'Oculistique et de Gynecologic
Annals of Pharmacy
Annales de Pharmacie, Louvain
Annals of Philosophy
Annalen der Physik
Annalen der Physik und Chemie
Annales des Ponts et Chaussees
Annali della R. Stazione Chimico Agraria Sperimentale

di Roma
Annual Report of the United States Department of

Agriculture
Annales de la science agronomique francaise et 4tran-

g^re
Annales des Sciences Naturelles, Botanique
Annali delle Sdenze del Regno Lombardo-Veneto
Annales des Sciences Naturelles. Botanique. Zo-

ologie et Paleontologie, comprenant I'Anatomie, la

Physiologic, la Classification et THistoirie Naturelle

des Animaux
Annales scientifiques de I'Universit^ de Jassy
The Annals of Scottish Hatural History
Annals of Surgery
Annali di Storia Naturale*
Annales Telegraphiques
Bericht iiber den Annaberg-Buchholzer Verein fur

Naturkunde
Jahresbericht des Annaberg-Buchholzer Vereins fiir

Naturkunde
Annaes de Sciencias Naturaes
L'Anne^ Biologique. Comptes Rendus annuers des

Travuax de Biologic Generale
Annotationes Zoologicae Japonenses, Auspiciis So-

cietatis Zoologicae Tokyonensis seriatim editae
Annuaire des cinq. Departements de TAncienne

Normandie, par I'Association Normandie
Annuaire de I'lnstitut des Provinces, des Societes

Savantes, et des Congres Scientifiques
Annuaire Meteorologique de la France
Annuaire du Journal des Mines de Russie
Materiaux pour I'Histoire de I'Homme. Revue

d'Anthropologie. Revue d'Ethnographie reonis.
See Congr. Int. Anthrop. C. R.
The Journal of the Anthropological Institute of Great

Britain and Ireland

UST O^ ABBREVIATIONS TO I^ITERATURE

XXXIX

Anthropol. Rev.
Anthropol. Soc. Mem.

Antwerpen, Verb. Genoots.

Occ. qui non.
Anvers, Ann. Soc. Med.
Anvers, Congr. Sci. Geogr.

Anvers, J. Pharm.

Apoth. Ztg.
Apothecary
Appreturzeitung
Apt, Ann. Soc. Sci.

Aquila

Arb. Kais. Gesundhts.

Arb. pharm. Inst., D. Univ.

Berlm
Arcachon Soc. Sq. Stat.

Zool. Trav.
Arcetri Oss. PubbL
Archief Suikerind.
Archief Wisk. Genoots.
Archit. and Kng.
Archiv. Agriculturchem.
Archiv. Anat. Micro.
Archiv. Anat. Physiol.

Archiv. Anthropol.

Archiv. Anthropol. Etnol.
Archiv. Augenheilk.
Archiv. Augen-. Ohren-

heilk.
Archiv. beiges m^d. mil.
Archiv. Biol.

Archiv. Bot. Nord. France
Archiv. Chem. Mikros.
Archiv. Cosmol.

Archiv. Dent.

Archiv. Elect.

Archiv. Entwickl. Organ.

Archiv. exper. Path.

Pharm.
Archiv. Farmacol. sper.

Roma
Archiv. fisiol.
Archiv. gen. Med.
Archiv. ges. Physiol.

Archiv. Heilk.

The Anthropological Review

Memoirs read before the Anthropological Society of

London
Verhandelingen van het Genootschap: "Occidit qui

non servat"
Annales de la Societe de Medecine d'Anvers
Compte-Rendu du Congres des Sciences Geographi-

ques, Cosmographiques et Commerciales
Journal de Pharmacie, publ. par la Soc. de Pharmacie

d'Anvers
Apotheker Zeittmg, Berlin
Apothecary, Boston
Appreturzeitung
Annales de la Societe litteraire, scientifique et artistique

d'Art (Vaucluse)
Aquila. A Magyar Omithologiai Kdzpont Folyoirata.

Periodical of Ornithology
Arbeiten aus dem kaiserlichen Gesundheitsamte,

Berlin
Arbeiten aus dem pharmazeutischen Institut der Uni-

versitat Berlin
Soci^t6 Scientiiique et Station Zoologique d' Arcachon

See Firenze R. 1st. Pubbl. (Arcetri Oss)

Archief Suikerindustrie in Nederlandsch-Indie

Archief uitgegeven door het Wisktmdig Genootschap

Architect and Engineer

See Hermbstadt

Archives d' Anatomic Microscopique

Archiv. fiir Anatomic, Physiologic imd wissenschaft-

liche Medicin
Archiv. fiir Anthropologic . . . Organ der deutschen

Gesellschaft fiir Anthropologic, Ethnologic und

Urgeschichte ^

Archivio per I'Anthropologia e la Etnologia
Archiv. fiir Augenheilkunde
Archiv. fiir Augen- und Ohrenheilkimde

Archives beiges de medicine militaire

Archives de Biologic

Archives Botaniques du Nord de la France

Archiv. Chemie und Mikroskopie

Archives cosmologiques. Revue des Sciences Natur-

elles, avec leurs applications a la Medecine, a I'Agri-

culture, aux Arts, et a 1' Industrie
Archives of Dentistry: A record of Dental knowledge;

medical, surgical, microscopical, chemical, and

mechanical
Archives de TElectricite

Archiv. fiir Entwicklungsmechanik der Organismen
Archiv. fiir experimentdle Pathologie imd Pharmako-

logie
Archivio di Farmacolagia speriraentale e Scienze

affini, Roma
Archivio di fisiologia
Archives generates de Medecine
Archiv. fiir die gesammte Physiologic des Menschen

und der Thiere (Pfliiger)
Archiv der Heilkunde

xl

LIST OF ABBREVIATIONS TO UTERATURE

Archiv. Hyg.
Archiv. Internal Med.
Archiv. intl. pharmacodyn.

Archiv. Ital. Biol.

Archiv. Kinderheilk.
Archiv. Math. Naturvid.
Archiv. Math. Phys.
Archiv. Med.
Archiv. Med. comparee.
Archiv. med. eicp.

Archiv. Med. Navale
Archiv. M\ed. Phann.

MiUtair.
Archiv. Mikro. Anat.

Archiv. Miss. Sci.
Archiv. Naturgesch.
Archiv. Naturk. (Dorpat)

Archiv. Neerland.

Archiv. Ohrenheilk.
Archiv. Ophthalm.
Archiv. Ophthalm. Otol.
Archiv. Otol.
Archiv. Parasit.
Archiv. path. Anat.

Archiv. Pharm.

Archiv. Pharm. og Chemi
Archiv. Physiol.
Archiv. Psychiatr.
Archiv. Sci.

Archiv. sci. med.
Archiv. Sci. Phys. Nat.

Archiv. Sci. Pract. Med.
Archiv. Slaves Biol.
Archiv. Verdauungs-

krankh.
Archiv. Wiss. Heilk.

Archiv. Wiss. Prakt. Thier-

heilk.
Archiv. Zool. Anat. Fis.
Archiv. 2kx>l. Exper.
Arcueil, Mem. Phys.

Argent. Inst. Geogr. Bol.

Argent. P.

Axsent. Soc. Ci. An.

Archiv. fiir Hygiene

Archives of Internal Medicine

Archives intemationales de pharmacodynamic et de

thereapie
Archives Italiennes de Biologic. Revues, R6sum^s

Reproductions des Travaux Scientifiques Italiens
Archiv. fur Kinderheilkunde
Archiv. for Mathematik og Naturvidenskab
Archiv. der Mathematik und Physik
Archives of Medicine
See Rayer
Archives de medicine experimentale et d'anatomie

pathologique
Archives de Medecine Navale (et Coloniale)
Archives de Medecine et de Pharmacie Militaires

Archiv. fiir Mikroskopische Anatomic (und Ent-

wickelungsgeschichte)
Archives des Missions Sdentifiques et Litteraires
Archiv. fur Naturgeschichte
Archiv. fiir die Naturkunde Liv-, Ehst- und Kur-

lands. Herausgegeben von der Dorpater Natur-

forscher-Gesellschaft
Archives Neerlandaises des Sciences Exactes et

Naturelles publiees par la Societe Hollandaise des

Sciences a Harlem
Archiv. fiir Ohrenheilkunde

Albrecht von Graefe's Archiv fiir Ophthalmologic
Archives of Opthalmology and Otology
Archives of Otology
Archives de Parasitologic
Archiv fiir pathologische Anatomic und Physiologic

und fur klinische Medizin (Virchow's)
Archiv. der Pharmacie; Archiv des Apothekervereins

im nordlichen Deutschland.
Archiv. de Pharmaci og Chemi, Copenhagen
Archives de Physiologic Normale et Pathologique
Archiv. fiir Psychiatric und Nervenkrankheiten
Archives of Science and Transactions of the Orleans

County Society of Natural Sciences
Archivio per les scienze mediche
Bibliotheque Universelle. Archives des Sciences

Physiques et Naturelles
Archives of Scientific and Practical Medicine
Archives Slaves de Biologic
Archiv. fiir Verdauungs-krankheiten

Archiv. des Vcreins fur gemeinschaftliche Arbeiten
zur Forderung der wissenschaftlichen Heilkunde

Archiv. fiir wissenschaftliche und *praktische Thier-
heilkunde

Archivio per la Zoologia, TAnatomia, e la Eisiologia

Archives de Zoologie Experimentale et Generale

Memoires de Physique et de Chimie de la Societe
d'Arcueil

Boletin del Instituto Geografico Argentino

Argentine Patent

Anales de la Sociedad Cientifica Argentina

UST OF ABBREVIATIONS TO LITERATURE

xli

Arkiv. Kemi, Minerol.

Geol.
Arkiv. Math. Astron.

Fysik
Armagh Nat. Hist. & Phil.

Soc.
Arms and Expl.
Amhem, Natuurk.

Arras, Mem. Acad.

Arras, Mem. Soc. Roy.

Art. J.

Artiz.

Artus, Jahr. okon. Chemie

Artus, Vierteljahresschrift

Ashmol. Soc. Proc.

Asiat. Researches

Asiot. Soc. J.

Assoc. Franc. Compt. rend.

Assoc. Med. J.
Assur. Mag.

Astron. Nachr.
Astron. Soc. Mem.
Astron. Soc. Month. Not.

Astrophys. J.

Atelier Phot.

Ateneo Ital.

Athenes Obs. Nat. Ann.

Atlantis

Atti. Accad. Ital.

Atti. accad. Lincei

Atti. CoU. Ing. Archit
Atti. inst. incoragg.

Atti. R. Accad. Sci. Torino

Atti Sci. Ital.

Atti Soc. Elvet.

Aube, Mem. Soc. Agric.

Augsb. Naturhist. Ver.

Ber.
Auk
Ausland
Aust. P.
Au8t.-Hung. P.
Australasian Assoc. Rep.

Australasian J. Pharm.
Australian Med. J.

Arkiv for Kemi, Mineralogi och Geologi

Arkiv for Mathematik Astronomi och Fysik

See Irish Natlist.

Arms and Explosives

Natuurkunde. Tijdschrift, inhoudende Phijsica,

Chemie, Pharmacie, Natuurlijke Historie en Littera-

tuur, uitgegeven van wege het Genootschap: Tol nut

en vergenoegen, te Amhem
Memoires de I'Academie d' Arras
Memoires de la Societe Royale d'Arras
The Art Journal
The Artizan (London)
Jahrbuch fiir dkonomische Chemie, etc.
Vierteljahresschrift fiir technische Chemie, Land-

wirthschaftliche Gewerbe, Fabrickwesen und Gc-

werbetreibende uberhaupt.
Abstracts of the Proceedings of the Ashmolean So-
ciety
Asiatic Researches; or Transactions of the (Bengal)

Society
Journal of the Royal Asiatic Society
Association Francaise pour I'avancement des Sciences.

Comptes Rendus
See Med. Assoc. Joum.
The Assurance Magazine (and Journal of the Institute

of Actuaries)
Astronomische Nachrichten
Memoirs of the Astronomical Society of London
Monthly Notices of the Astronomical Society of

London
Astrophysical Journal
Atelier des Photographen
L'Ateneo Italiano

Annales de I'Observatoire National d' Athenes
The Atlantis, or Register of Literature and Science
Atti dell'Accademia Italiana di Scienze
Atti della reale accademia dei Lined, rendiconti,

dasse di scienze fisiche, mathematiche e naturali
Atti de CoUe^io degli Ingegneri ed Architetti in Milano
Atti del R. mstituto d'incoraggiamento di Napoli,

Naples, Italy
Atti della Reale Accademia della Scienze di Torino
Riunione degli Scienziati Italiani
Atti della Societa Elvetica delle Scienze Naturali
Memoires de la Societe d'Agriculture, des Sdences, et

des Lettres du department de I'Aube
Berichte des Naturhistorischen Vereins in Augsburg

The Auk. A Quarterly Journal of Ornithology

Das Ausland

Austrian Patent

Austro-Hungarian Patent

Report of the. . . Meeting of the Australasian Assoda-

tion for the Advancement of Sdence
Australasian Journal of Pharmacy, Mdt>oume
Australian Medical Journal

xlii

LIST OP ABBREVIATIONS TO LITERATURE

Australia Med. Rec.
Australian P.
Australian Sugar J.
Autun, Mem. Soc. Eduenne
Auvergne, Ann. Sci.

Auxerre, Bull. Soc. Sci.

Badischeu Aerzt. Verein.
Mitth.

Bah. P.

Ballenstedt, Archiv.

Ballot, Mag. Landbouw.

Baltimore Med. Phys. Re-
corder

Bamb. Natiuf . Ges. Ber.

Barb. P.

Barcelona Acad. Bol.

Barcelona Acad. Mem.
Barrow Field Club Report

Basel, Ber.

Batavia Genootsch. Verb.
Batavia, Natuur. Archief.
Batavia, Natuiu-k. Tijdschr.

Batavia, Notulen

Batavia Obs. Obsns.

Batavia, Tijdschr.

Batavia, Verh. Natuurk.

Vereen.
Bath Micro. Soc. Minutes

Bath Natur. Hist. Club.

Proc.
Bath Soc. Agric. Letters

Baugew. Ztg.
Baumgartner Zts.

Bayer. Gewerbeztg.
Bayer. Kunst. Gewerbebl.

Bayer, Landw. Ver. Erg.

Medical Records of Australia

Australian P.

Australian Sugar Journal

Memoires de la Societe Eduenne

Annales Scientifiques, Litteraires, et Industrielles de

I'Auvergne
Bulletin de la Societe des Sciences Historiques et

Naturelles de I'Yonne
Mittheilungen des Badischen arztlichen Vereins

Bahamas Patent

Archiv fiir die neuesten Entdeckungen aus der Urwelt
Magazin voor Landbouw en Kruidkunde
Baltimore Medical and Physical Recorder

Bericht der naturforschenden Gesellschaft zu Bamberg

Barbados Patent

Boletin de la Real Academia de Ciencias y Artes de

Barcelona
Memorias de la Real Academia de Ciencias Naturales

y Artes de Barcelona
Barrow Natiu-alists' Field Club and Literary and

Scientific Association. Annual Report and Pro-
ceedings
Bericht iiber die Verhandlungen der Naturforschenden

Gesellschaft in Basel
Verhandlingen van het Bataviaasch Genootschap der

Kunsten en Wetenschappen
Natuur- en Geneeskundig Archief voor Nederlandsch-

Indifi
Natuurkundig Tijdschrift voor Nederlandsch-Indifi,

uitgegeven door de Koninklijke Natuiu-kundige

Vereeniging in Nederlandsch-Indi^
Notulen van de Allgemeene en. Bestuurs-Vergader-

ingen van het Bataviaasch Genootschap van Kun-
sten en Wetenschappen
Observations made at the (Royal) Magnetical and

Meteorological Observatory at Batavia
Tijdschrift voor Indische Taal-, Land-, en Volken-

kunde
Verhandlingen der Natuurkundige Vereeniging in

Nederlandsch-IndiC
Extracts from the Minutes of the Bath Microscopical

Society
Proceedings of the Bath Natural History and Anti-
quarian Field Club
Letters and Papers of the Bath and West of England

Society for the Encouragement of Agriculture,

Arts, Manufactures, and Commerce
Baugewerks-Zeitung
Zeitschrift fur Physik, Mathematik, und verwandte

Wissenschaften
Bayerische Gewerbezeitung
Kunst und Gewerbeblatt (Poletechn. Verein Konigreich

Bayem)
Ergebnisse landwirthschaftlicher und agrikultiu*chemis-

cher Versuche an der Station des General-Comite

des Bayerischen Landwirthschaftlichen Vereines in

Mtinchen

LIST OP ABBREVIATIONS TO UTERATURlS

xliii

Bayeux, Mem. Soc. Agric.

Bd. Trade J.

Beauvais, Soc. Acad. Mem.

Beitr. Anat. Physiol
Beitr. Anthropol. Bay ems

Beitr. Biol. Pflanz.
Beitr. Geophys.

Beitr. Kryptog. Schweiz
Beitr. Mecklenb. Aerzte

Beitr. Morphol.

Beitr. Nattirk. Preussens

Beitr. Palaont. Oesterr.*

Ung.
Beitr. Path. Anat.

Beitr. Physiol. Morphol.

Beitr. Russ Reich.

Belfast, Clin. Soc. Trans.

Belfast Field Club Rep.

Belfast Natur. Hist. Soc.

Proc.
Belg. Horticole

Belg. P.

Bengal Asiat. Soc. J.
Bengal Asiat. Soc. Proc.
Bengal Govt. Records

Bengal, Phot. Soc. J.
Ber.

Ber. deut. bot. Ges.
Ber. pharm. Ges.

Ber. phys. Ges.

Ber. Sachs. Ges. Wiss.

Ber. Veter. K6nig. Sach.

Berg. Huttenm. Jahr.
Berg. Huttenm. Ztg.

Memoires de la Societe d'Agriculture, Sciences, Arts,
et Belles-Lettres de Bayeux

Board of Trade Journal

Memoires de la Societe Academique d'Archeologie,
Sciences et Arts du Department de I'Oise

See Eckhard

Beitrage zur Anthropologic und Urgeschichte Bayerns.
Organ der Miinchener Gesellschaft fiir Anthro-
pologic, Ethnologic und Urgeschichte

Beitrage zur Biologic der Pflanzen

Beitrage zur Geophysik. Abhandlungen aus dem
Geographischen Seminar der Universitat Strass-
burg. Beitrage zur Geophysik. Zeitschrift fiir
Physikalische Erdkunde

Beitrage zur Kryptogamenflora der Schweiz

Beitrage Mecklenburgischer Aerzte zur Medicin und
Chirurgie

Beitrage zur Morphologie und Morphogenie. Unter-
suchungen aus dem Anatomischen Institut su
Erlangen

Beitrage zur Naturkunde Preussens. Herausgegeben
von der Koniglichen Physikalisch-Oekonomischen
Gesellschaft zu Konigsberg

Beitrage zur Palaontoiogie Oesterreich-Ungams und
des Orients

Beitrage zur Pathologischen Anatomic und Physio-
logic. Beirtage zur Pathologischen Anatomie und
zur AUgemeinen Pathologic

Beitrage zur Physiologic und Morphologie Niederer
Organismen.

Beitrage zur Kenntniss des Russischen Reiches und
der angrenzenden Lander Asiens

Transactions of the Clinical and Pathological Society
of Belfast

Annual Reports and Proceedings of the Belfast
Naturalists' Field Club

Proceedings of the Belfast Natural History and
Philosophical Society

La Belgique Horticole. Annales de Botanique et
d'Horticulture

Belgian Patent

Journal of the Asiatic Society of Bengal

Proceedings of the Asiatic Society of Bengal

Selections from the Records of the Bengal Govern-
ment

Journal of the Photographic Society of Bengal

Berichte der Deutschen Chemischen Gesellschaft,
Berlin

Berichte der deutschen botanischen Gesellschaft

Berichte der deutschen pharmazeutischen Gesell-
schaft

Berichte der deutschen physikalischen Gesellschaft

Berichte uber die Verhandlungen der Konigl. Sachs.
Gesellschaft der Wissenschaften zu Leipzig

Berichte iiber das Veterinarwesen im Konigreich
Sachsen

Berg- und hiittenmannisches Jahrbuch

Berg- und hiittenmannische Zeitung

xUv

LIST OF ABBREVIATIONS TO UTERATURS

Bergens Mtis. Aarb.

Berggeist
Berghaus, Ann.
Berghaus, Zts. Erdk.
Berlin Afrik. Ges. Mitth.

Berlin Akad. Abh.

Berlin Akad. Monatsber.

.Berlin Akad. Sitzber.

Berlin Ann. Telegr.
Berlin Astron. Jahr.
Berlin Bot. Gartens Jahr.

Berlin Bot. Gartens Notizbl.

Berlin Ent. Ges.
Berlin Entom. Zts.

Berlin Ges. Anthrop. Verb.
Berlin Ges. Erdk. Verb.

Berlin Ges. Erdk. Zts.
Berlin Ges. Geburtsblf.

Gynok.
Berlin Ges. Naturf . Preunde

Mag.

Berlin Ges. Naturf. Freunde

N. Schr.
Berlin Ges. Naturf. Preunde

Verb.
Berlin Ges. Psycbiatr.
Berlin Gesundheitsamt Biol.

Abth. Arb.

Berlin Ind. Ztg.
Berlin Jahr. Pharm.

Berlin Klin. Wocbenschr.
Berlin Mem. Acad.

Berlin Mitth. Ges. Naturf.

Berlin Monatsber.

Berlin Monatsber. Ges.

Erdk.
Berlin Naturf. Preunde

Sitzber.
Berlin Neue Zts. Geburtsk.
Berlin Physiol. Ges. Verb.
Berlin Physik. Reichsanst.

Abh.
Berlin Verb. Med. Ges.

Bergens Museums Aarbog for. . .Afhandlinger og

Aarsberetning udgivne af Bergens Museum
Der Berggeist

Annalen der Erd-, V6lker- und Staatenktmde
Zeitschrift fur vergleichende Erdkunde
Mittheilungen der Afrikanischen Gesellschaft in

Deutscb^nd
Abhandlungen der k. Akademie der Wissenschaften

zu Berlin
Monatsberichte der k. Preussischen Akademie der

Wissenschaften zu Berlin
Sitzungsberichte der Koniglich Preussischen Akademie

der Wissenschaften zu Berlin
Annalen der Telegraphic
Berliner Astronomisches Jahrbuch
Jahrbuch des Kdniglichen Botanischen Gartens und

des Botanischen Museums zu Berlin
Notizblatt des Kdnigl. Botanischen Gartens imd

Museums zu Berlin
See 111. Wschr. Ent.
Berliner Entomologische Zeitschrift; herausg. von

dem Entomologischen Verein in Berlin
See Ztschr. Ethnol.
Verhandlungen der Gesellschaft fur Erdkunde zu

Berlin
See Berlin Zts. Erdk.
See Zts. Gebtulshlf. Gynak.

Magazin der Gesellschaft Naturf orschender Freunde
zu Berlin, fur die neuesten Entdeckungen in der
gesammten Nattu'kunde

Neue Schriften derGesellschaft Naturforschender
Preunde in Berlin

Verhandlungen der Gesellschaft Naturforschender
Freunde zu Berlin

See Arch. Psycbiatr.

Arbeiten aus der Biologischen Abtheilung fur Land-
und Forstwirthschaft am Kaiserlichen Gesund-
heitsamte

Industrie Zeitung, Berlin

Berlinisches Jahrbuch fur die Pharmacie imd fur die
damit verbimdenen Wissenschaften

Berliner klinische Wochenschrift

Memoires de I'Academie Royale des Sciences de
Berlin

Mittheilungen aus den Verhandlungen der Gesell-
schaft Naturforschender Freunde zu Berlin

Monatsberichte der K. Preuss. Akademie der Wissen-
schaften zu Berlin

Monatsberichte uber die Verhandlungen der Gesell-
schaft fur Erdkunde zu Berlin

Sitzungs-Berichte der Gesellschaft Naturforschender
Freunde zu Berlin

Neue Zeitschrift fiir Geburtskunde

See Arch. Anat. Physiol

Wissenschaftliche Abhandltmgen der Physikalisch
Technischen Reichsanstalt

Verhandlungen der Berliner medidnischen Gesell-
schaft

LIST OF ABBREVIATIONS TO LlTieRATURB

xlv

Berlin Zool. Mus. Mitth.

Berlin Zts. Erdk.
Berlin Mitth.

Berwick, Natur. Club Hist.
Berz. Jahr. Chem.
Besancon, Mem. Soc. Emul.

Besancon, Seances Publ.

Beton Bisen

Betterave

Beziers Soc. Sci. Bull.

Bianconi, Rep. Ital.
Bibl. Anat.

Bibl. Bot.
Bibl. Brit.

Bibl. Ital.
Bibl. Math.

Bibl. Univ.

Bibl. ZooIT
Bied. 2^tr.

Bierbrauer

Bijdr. tot de Dierkunde

Biochem. Bull.

Biochem. J.

Biochem. Zentr.

Biochem. Zts.

Biol. Bull.

Biol. 2^tr.

Biopfays. Zentr.

Birmingham Natur. Hist. &

Micro. Soc. Trans.
Birmingham Phil. Soc. Proc.
Blankenburg, Ber.

Blatter Blech-Arb.
Blatter Kunstgew.
Blatter Zuckerrub.
Bleekrode, Nieuw Tijd-
schrift

Blots, Mem. Soc. Sci.

Blois, Soc. Loir et Cher
Mem.

Mittheilungen aus der Zoologischen Sammlung dea

Museums fur Naturkunde in Berlin
Zeitschrift der Gesellschaft ffir Erdkunde zu Berlin
Mittheilungen der Nattuforschenden Gesellschaft in

Bern
History of the Berwickshire Naturalists' Club
Berzelius Jahresberichte der Chemie
Meim>ires et Comptes Rendus de la Sodete (Libre)

d'Emulation du Doubs
Seances publiques de I'Academie des Sciences, Arts,

et Belles-Lettres de Besancon
Beton und Eisen
Betterave
Bulletin de la Soci^t^ d'Etude des Sciences Naturelles

de Beziers
Repertorio Italiano Per la Storia Naturale
Bibliographic Anatomique. Revue des Travauz en

langue francaise. Anatomie. Histologic. Embryo-

ologie. Anthropologic
Bibliotheca Botanica. Abhandlungen aus dem

Gesammtgebiete der Botanik
Bibliotheque Britannique, ou Recueil extrait des

Ouvrages Anglais periodiques et autres; partie des

Sciences et Arts
Giomale dell' I. R. Istituto Lomgardo di Scienze,

Lettere ed Arti, e Biblioteca ItaUana
Bibliotheca Mathematica. Zeitschrift ftir Geschichte

der Mathematik. Journal d'Histoire des Mathe-

matiques. Bibliotheca Mathematica. Zeitschrift

fur Geschichte der mathematischen Wissenschaften
Bibliotheque Universelle des Sciences, Archives des

Sciences Physiques et Naturelles
Bibliotheca Zoologica
Biedermann's 2^tralblatt ftIr Agrikulturchemie und

rationellen Landwirtschafts-Betrieb
Der Bierbrauer
Bijdragen tot de Dierkunde
Biochemical Bulletin
The Bio-Chemical Journal
Biochemisches Zentralblatt, Leipzig
Biochemische Zeitschrift
Biological Bulletin
Biologisches Zentralblatt
Biophysikalisches Zentralblatt, Leipzig
See Midland Natlist Trans.

Proceedings of the Birmingham Philosophical Society
Berichte des Naturwissenschaftlichen Vereins des

Harzes zu Blankenbtu'g
Deutsche Blatter fur Blecharbeiter
Blatter ftir Kunstgewerbe
Blatter f iir Zuckerriibenbau
Nieuw Tijdschrift gewijd aan alle takken van Volk-

svlijt, Nijverheid, Landbouw, Mijnwezen, Handel,

Spoorwegen, Telegraphic en Scheepvaart
Memoires de la Soci6t6 des Sciences et des Lettres

de Blois
Memoires de la Soci^t6 des Sciences et Lettres de

Loir et Cher

xlvi

LIST OP ABBREVIATIONS TO LITERATURE

Boerhaave
Bobm. G€S. Abh.

B6bm. Gfes. Wiss. Jahr.

Bobm. Monatschr. Ges.

Mus.
Bol. P.

Boll. chim. farm.
Boll, estac. agr. Ciudad

Juarez
Boll, ingen.
Boll. Natur. Siena

Bologna Accad. Sci. Mem.

Bologna, Mem. Inst. Naz.

Ital.
Bologna, Mem. Soc. Med.
Bologna, Mem. Soc. Med.

Cbir.
Bologna, Nov. Comment.

Bologna, Opusc.
Bologna, Opusc. Sci.
Bologna, Opusc. Sci. N. Coll.
Bologna Rend.

Bombay, Agric. Hort. Soc.

Proc.
Bombay Govt. Records

Bombay, Med. Phys. Soc.

Trans.
Bombay Natur. Hist. Soc.

J.
Bombay, Roy. Asiat. Soc.

J.
Bone, Acad. Hippone Bull.
Bonn, Corresp. Blatt Nat.

Hist. Vei.
Bonn, Niederrhein. Ges.

Sitzber.
Bonn, Untersuch. Physiol.

Lab.
Bonn, Verb. Naturhist.

Ver.
Bonplandia
Bordeaux, Acad. Sci.

Seances Publ.
Bordeaux, Actes Acad. Sci.

Bordeaux, J. Med.
Bordeaux, J. Med. Prat.

Bordeaux, Mem. Soc. Med.

Chir.
Bordeaux, Mem. Soc. Sci.

Phys.

Boerhaave

Abhandlungen der Koniglich Bdhmischen Gesell-

schaft der Wissenschaften
Jahresbericht der kdnigl. bohm. Gesellschaft der

Wissenschaften
Monatschrift des Gesellschaft des Vaterlandischen

Museums in Bohmen
Bolivia Patent

Bolletino chimico farmaceutico, Milan
Boletin de la estacion agricola experimental de Ciudad

Juarez
Boletin de ingenieros
BoUettino del Naturalista Collettore, AUevatore,

Coltivatore
Memorie della (R.) Accademi delle Scienze dell'

Istituto di Bologna
Memorie dell 'Istituto Nazionale Italiano

Memorie della Societa Medica di Bologna

Memorie della Societa Medico-chinu-gica di Bologna

Novi Commentarii Academiae Scientiarum Instituti
Bononiensis

Opuscoli della Societa Medico-chirurgica di Bologna

Opuscoli Scientifici

Nuova collezione d 'Opuscoli Scientifici

Rendiconto delle Sessioni dell' Accademia Reale delle
Scienze dell' Istituto di Bologna

Proceedings of the Agricultiu-al and Horticultural
Society of Western India

Selections from the Records of the Bombay Govern-
ment

Transactions of the Medical and Physicai*Society of
Bombay

The Journal of the Bombay Natural History Society

The Jotunal of the Bombay Branch of the Royal

Asiatic Society
Bulletin de 1 'Academic d'Hippone
Correspondenzblatt des Naturhistorischen Vereins fur

Rheinland und Westphalen
Sitzungsberichte der Niederrheinischen Gesellschaft

fiir Natur- und Heilkunde zu Bonn
Untersuchungen aus dem physiologischen Labora-

torium zu Bonn
Verhandlimgen des Natiu-historischen Vereins der

Preussischen Rheinlande imd Westphalens
Bonplandia
Seances publiques de I'Academie Royale des Sciences,

Belles- Lett res, et Arts de Bordeaux
Recueil des Actes de I'Academie des Sciences, Belles-

Lettres, et Arts de Bordeaux
Journal de Medecine de Bordeaux
Journal de Medecine pratique, ou Recueil des Travaux

de la Societe de Medecine de Bordeaux
Memoires et Bulletins de la Soci^t^ Medico- ~

Chirurgicale des Hopitaux et Hospices de Bordeaux
Memoires de la Soci6t6 des Sciences Physiques et

Naturellcs de Bordeaux

LIST OF ABBRKVIATIONS TO LITERATURE

xlvii

Bordeaux, Soc. Lmn. Actes
Bordeaux, Soc. Linn. Bull.

Bordeaux, Soc. Med. Mem.

Bordeaux, Soc. Sci. P.-V.

Bomemann, Der Ingenieur
Boston J. Phil.
Boston J. Natur. Hist.
Boston Med. Siu-g. J.
Boston, Mem. Amer. Acad.

Boston, Mem. Natiu*.

Hist. Soc.
Boston Pap. Soc. Natur.

Hist.
Boston, Proc. Natiu-. Hist.

ooc.
Boston Soc. Med. Sci. J.
Bot. Centr.

Bot. Centr. Beihefte
Bot. Cong. Proc.

Bot. Gaz.

Bot. Jahr. (Engler)
Bot. Mag., Tokyo
Bot. Notiser
Bot. Tidsskr.

Bot. Untersuch.

Bot. Untersuch. (Brefeld's)

Bot. Ver. Gesamtthuringen

Botan. Ztg.

Bot. Zentr.

Botaniste

Bouchardat, Archiv.

Boue, J. Geol.

Boulogne, Mem. Soc. Agric.

«
Bourse cuirs Liege
Brandenb. Bot. Ver. Verh.

Brass World

Braunk.

Braunschw. Ver. Natiuiviss.

Jahr.
Braz. P.
Bremen Abh.

Brenn. Ztg.

Brera, Giom. Med. Prat.

Brera, Nuovi Comment.

Actes de la Soci^t^ Linneeime de Bordeaux

Bulletin d'Histoire Naturelle de la Soci^t6 Linneenne

Bordeaux
Memoires et Bulletins de la Soci6t4 de Medecine et

de Chirurgie de Bordeaux
Proces-Verbaux des Seances de la Soci6t6 des Sciences

Physiques et Naturelles de Bordeaux
Der Ingenieur

The Boston Journal of Philosophy and the Arts
Boston Journal of Natural History
Boston Medical and Stu'gical Jotunal
Memoirs of the American Academy of Arts and

Sciences
Memoirs read before the Boston Society of Natural

History
Occasional papers of the Boston Society of Natural

History
Proceedings of the Boston Society of Natiu-al History

Journal of the Boston Society of Medical Sciences
Botanisches Centxalblatt. Referirendes Organ fiir das

Gesammtgebiet der Botanik des In- und Auslandes
Beihefte zum Botanischen Centralblatt
The International Horticultural Exhibition and

Botanical Congress: Report of Proceedings
The Botanical Gazette
Botanische Jahrbucher, Engler, Leipzig
The Botanical Magazine, Tokyo
Botaniska Notiser
Botanisk Tidsskrift udgivet af den Botaniske Forening

i Kjobenhavn
Botanische Untersuchungen aus dem Physiologischen

Laboratorium -der landwirthschaf tlichen Lehranstalt

in Berlin
Untersuchungen aus dem Gesammtgebiete der

Mykologie
See Jena Geogr. Ges. Mitth.
Botanische 2^itung
Botanisches Zentralblatt
Le Botaniste
Archives de Physiologic, de Therapeutique, et

d 'Hygiene
Journal de Geologic
Memoires de la Soci6t6 d'Agriculture, etc., de

Boulogne-sur-Mer
Bourse aux cuirs de Liege, bulletin hebdomadaire
Verhandlungen des botanischen Vereins fiir die

Provinz Brandenburg
Brass World and Platers Guide, The
Braunkohle
Jahresbericht des Vereins fur Nattuiyissenschaft zu

Braunschweig
Brazilian Patent
Abhandlungen herausgegeben vom Naturwissenschaft-

lichen Verein zu Bremen
Brennerei 2^itimg
Giomale di Medicina Pratica
Nuovi Commentari di Medicina

xlviii

LIST OF ABBRISVIATIONS TO LITERATURE

Brescia, Comment. Ateneo

Breslau, Ann. Klin. Inst.

Breslau, Bot. Garten Arb.

Breslau, Gewerbebl.
Breslau, Jahr. Schles. Ver.

Berg.
Breslau, Schles. Ges.

Jahr.
Breslau, Studien Physiol.

Inst.
Breslau, Zts. Klin. Med.
Brest Soc. Acad. Bull.
Brewers J. (Lon.)

Brewers J., N. Y.

Brick

Brick J.

Brick and Clay Record

Brighton, Proc. Natur.

Hist. Soc.
Bristol Proc. Nat. Soc.
Brit. Assoc. Rep.

Brit. Clay Worker

Brit. Food J.

Brit. For. Med. Chir. Rev.

Brit. Inst. Publ. Health

Brit. J. Almanac

British J. Dent. Sci.

Brit. J. Phot.

Brit. Med. J.

Brit. Mycol. Soc. Trans.

Brit. Pharm. Confer. Proc.

Brit. Pharm. Confer. Trans.

Brit. Colon. Drug.
Brit. Guiana Agr. Soc.
Brit. Guiana P.
Brit. Hond. P.
Brooklyn Entom. Soc.

Bull.
Brosche, Zts.
Broussais, Ann.
Brown-Sequard, J. Physiol.
Brugnatelli, Giom.
Brunn Verh.

Brux. Acad. Bull.

Brux. Acad. Cent. Anniv.

Brux. Acad. Med. Belg.

Bull.
Brux. Acad. Sci. Mem.

Commentarj della Accademia di Scienze, Lettre, ed

dell' Ateneo di Brescia
Annalen des Klinisch-chinirgischen Instituts auf der

Universitat zu Breslau
Arbeiten aus dem Konigl. Botanischen Garten zu

Breslau
Breslauer Gewerbeblatt
Jahrbuch des Schlesischen Vereins fur Berg- und

Huttenwesen
Jahresbericht des Akademischen Naturwissenschaft-

lichen Vereins zu Breslau
Studien des Physiologischen Instituts zu Breslau

Zeitschrift fur Klinische Medicin

Bulletin de la Soci^t^ Academique de Brest

Brewers Journal and Hop and Malt Trades Review,

The (London)
Brewers Journal, New York
Brick

Brick, Pottery and Glass Journal
Brick and Clay Record
Reports and Abstracts of the Proceedings of the

Brighton and Sussex Natiu'al History Society
Proceedings of the Bristol Natturalists' Society
Report of the Meetings of the British Association for

the Advancement of Science
British Clay Worker, The
British Food Jotunal

British and foreign Medico-Chirurgical Review
See J. State Med.

British Journal of Photography Almanac
The British Journal of Dental Science
British Journal of Photography
British Medical Journal

The British Mycological Society. Transactions
Proceedings of the British Pharmaceutical Conference
Year Book of Pharmacy, comprizing Abstracts of

Papers. With the Transactions of the British

Pharmaceutical Conference
British and Colonial Druggist, London
See Timehri
British Guiana Patent
British Hondiu^s Patent
Bulletin of the Brooklyn Entomological Society

Zeitschrift ftir Natur- und Heilkunde

Annales des la Medicine Physiologique

Journal de la Physiologie de THomme et des Animaux

Giomale di Fisica, Chimica, e Storia Naturale

Verhandlungen des Naturforschenden Vereines in

Brunn
Bulletins de FAcademie Royale des Sciences, etc., de

Belgique
Centieme Anniversaire de Foundation de I'Academie

Royale de Belgique
Bulletin de I'Academie Royale de Mededne Belgique

Nouveaux memoires de TAcademie Royale, des
Sciences et Belles-lettres de BruxeUes

UST OP ABBREVIATIONS TO UTBRATURB

xlix

Bnix. Actes Soc. Med.
Bniz. Ann. Soc. Kntom.

Beige
iBrux. Ann. Soc. Malacol.
Brux. Ann. Trav. Pub.
Bnix. Ann. Univ. Belg.
Brux. Bull. Beige Phot.
Brux. Bull. Soc. Bot.

Brux. Congr. Bot. Act.

Brux. Congr. Bot. (C. R.)

Brux. J. Med.

Brux. J. Soc. Centr. Agric.

Brux. Mem. Couronn.

Brux. Mus. Congo Aim.

Brux. Mus. Hist. Natur.

Ann.
Brux. Mus. Hist. Natur.

Bull.
Brux. Mus. Hist. Natiu*.

Mem.
Brux. Soc. Agric. Joum.

Brux. Soc. Beige Micro.

Ann.
Brux. Soc. Beige Micro.

Bull.
Brux. Soc. Entom. Ann.
Brux. Soc. Entom. Mem.
Brux. Soc. Linn. Bull.
Brux. Soc. Sd.
Brux. Soc. Sci. Ann.
Bucarest. Acad. Rom. Anal.
Bucarest Soc. Sd. Bui.

Buchholz

Buda, Evkonyvei

Buda, Palyamtmkak.
Buda, Tudomanytar.

Buffalo Bull.

Builder

Buitenzorg Inst. Bot. Bull.

Buitenzorg Jard. Bot. Ann.
Bull. Acad. Med.
Bull. Acad. roy. Belg.

Bull. Acad. Sd., Cracow.

Actes de la Society Medicale de Bruxelles
Annales de la Sod^t6 Entomologique Bdge

Annales de la Sod6t6 Malacologique de Belgique

Annales des Travaux Publics de Belgique

Annales des Universites de Bdgique

Bulletin Bdge de la Photographic

Bulletins de la Sod6t6 Royale de Botanique de

Bdgique
Actes du Congres de Botanique horticole retmi a

Bruxdles
Congres de Botanique et d'Horticulture de 1880 tenu a

Bruxelles
Journal de Mededne, de Chirurgie, et de Pharma-

cologie
Jotunal de la Sod^t^ Centrale d'Agriculture de

Bdgique
Memoires Couronnes et Memoires des Savants

Entrangers
Etat Independant du Congo. Annales du Musee du

Congo, publiees par ordre du Secretaire d'Etat
Annales du Musee Royal d'Historie Naturdle de

Belgique
Bulletin du Musee Royal d'Histoire Naturdle de

Belgique
Memoires du Musee Royal d'Histoire Naturdle de

Bdgique
Journal de la Soci6t^ Centrale d'Agriculture de

Belgique
Annales de la Sod^t6 Bdge de Microscopic

Bulletin (des Seances) de la Soci^t6 Beige de

Microscopic
Aimales de la Sod4t6 Entomologique de Bdgique
Memoires de la Sod^t6 Entomologique de Bdgique
Bulletin de la Sod^t^ Linneenne de Bruxdles
See Rev. Quest. Sd.

Aimales de la Sod6t6 Sdentifique de Bruxelles
Analde Academiei Romane
Bulettnul Sodetatii de Sciinte (Pizice, Pixica, Chimia si

Mineralogia) din Bucuresd-Romania. Bulletin de

la Sod^t^ des Sdences, Bucarest-Roumanie
See Annab.-Buchh. Ver. Nat. Jber.
A' Magyar Tudos Tarsasag' EvkOnyvei (Year Books

of the Hungarian Scientific Association)
Termeszettudomanyi Palyamunkak
Tudomanytar Kdzre. bocsatja a' Magyar Tudos

Tarsasag
Bulletin of the Buffalo Society of Natural Sciences

The Builder
's Lands Plantentuin. Bulletin de I'lnstitut Botanique

de Buitenzorg
Annales du Jardin Botanique de Buitenzorg
Bulletin of the Academy of Medicine
Academic royale de Belgique; Bulletin de la Classes

des Sciences
Bulletin international de I'Academie des Sciences de

Cracovie

LIST OF ABBREVIATIONS TO LITERATURE

BuU. Acad. Sci., Petrograd

BiUL Amer. Inst. Min.

Eng.
Bull. Amer. Pharm. Assoc.
Bull, assoc. chim. sucr.

dist.
Bull. Bur. Agric.

Bull. Bur. Chem. U. S.

Dept. Agric.
Bull. Bur. Mines
Bull. Bur. Standards
Bull. Col. School Mines
Bull. Dept. Agric. Jamaica
Bull. Dept. Agric. Trinidad

Bull. Geol. Inst. Univ.

Upsala
Bull. Geol. Soc. Amer.
Bull. Hyg. Lab.

Bull. Imp. Inst.

Bull. Iron Assoc.

Bull. Johns Hopkins Hosp.

Bull. Mass. Inst. Tech.

Bull. Med. Beige.

Bull. Musee

Bull. Pharmacie

Bull. Pharmacy

Bull. Pharm. Sud-est

Bull. Sci. France Belg.

Bull. Sd. Nord

Bull. Sci. pharmacolog.
Bull. Soc. Bot. France
Bull. Soc. Bot. Belg.
Bull. Soc. Chim.
Bull. Soc. Chim. Belg.
Bull. Soc. Encourag.
Bull. Soc. franc. Mineral.
Bull. Soc. franc. Phot.
Bull. Soc. geol. France
Bidl. Soc. Ind. Amiens
Bull. Soc. Ind. Marseille
Bull. Soc. Ind. Minerale
Bull. Soc. Ind. Mulh.
Bull. Soc. Ind. Nord
Bull. Soc. Ind. Rouen
Bull. Soc. intematl. elect.
Bull. Soc. Med. Amiens
Bull. Soc. med. Gand
Bull. Soc. Mycol.
Bull. Soc. pharm. Bord.
Bull. Soc. phot. Belg.
Bull. Soc. Romane Stiin.
Bull. Soc. roy. pharm.
Bull. Soc. sci. med. Rennes

Bulletin de I'Academie Imperiale des Sciences de

Petrograd a

Bulletin American Institute of Mining Engineers

Bulletin of the American Pharmaceutical Association
Bulletin de I'association des chemists de sucrerie

distillerie de France
Bulletin of the Bureau of Agricultural Intelligence and

of Plant Diseases
Bulletins, Bureau of Chemistry, U. S. Department of

Agricultiu-e
Bureau of Mines Bulletin, Department of the Interior
Bulletin of the Bureau of Standards
Bulletin of the Colorado School of Mines
Bulletin of the Department of Agriculture, Jamaica
Bulletin of Agricultural Information, Department of

Agriculture, Trinidad
Bulletin of the Geological Institute of the University

of Upsala
Bulletin of the Geological Society of America
Bulletins of the Hygienic Laboratory, United States

Public Health and Marine Hospital Service
Bulletin of the Imperial Institute, London
Bulletin of the American Iron and Steel Association
Bulletin of Johns Hopkins Hospital
Bulletin of the Massachusetts Institute of Technology
Bulletin Medical Beige.

Bulletin du Musee de I'industrielle de Belgique
Bulletin de Pharmacie
Bulletin of Pharmacy

Bulletin de Pharmacie du Sud-est, Montpellier
Bulletin Scientifique de la France et de la Belgique
Bulletin Scientifique, Hlstorique et Litteraire du

Department du Nord et'des pays voisins
Bulletin des Sciences pharmacologiques
Bulletin de la Soci^t6 Botanique de France
Bulletin de la Soci6t6 Royale de Botanique de Belgique
Bulletin de la Soci^t^ Chimique de France
Bulletin de la Soci^t^ Chimique de Belgique
Bulletin de la Soci^t^ d'Encoiu^gement
Bulletin de la Soci6t6 Francaise de Mineralogie
Bulletin de la Soci6t^ Francaise de Photographic
Bulletin de la Soci6t6 geologique de France
Bulletin de la soci6t6 industrieile d 'Amiens 1
Bulletin de la Soci6t£ industrieile de Marsei le
Bidletin de la soci6t6 de Tindustrie minerale
Bulletin de la soci^t6 industrieile de Mulhouse
Bulletin mensuel de la soci6t6 industrieile du Nord
Bulletin de la soci6t6 industrieile de Rouen
Bulletin de la Society intemationale des electridens
Bulletin des Travaux de la Soci6t6 Medicale d' Amiens
Bulletin de la Soci6t6 de Medecine de Gand
Bulletin de la Soci6t6 Mycologique de France
Bulletin de la soci6t6 pharmacie de Bordeaux
Bulletin de la Soci6t6 photographique de Belgique
Buletintil societatii Romane de Stiinte
Bulletin de la soci^t6 de pharmacie de Bruxelles royale
Bulletin de la soci6t6 scientifique et medicale de

I'ouest, Rennes

UST OF ABBREVIATIONS TO UTBRATURB

U

Bull. Soc. vaudoise

BulL Torrey Bot. Club
BuU. Vulc. Ital.

C.A.

Cabanis, J. Omithol.
Cadiz, Period. Mens. Cien.
Caen, Acad. Mem.

Caen, Bull. Soc. Linn.

Normandie
Caen, Mem. Soc. Linn.

Normandie
Caen, Travaux

Calcutta, J. Natur. Hist.
Calcutta, Quart. J.
Calcutta Roy. Bot. Card.

Ann.
Calcutta, Trans. Med.

Phys. Soc.
Cal. Acad. Bull.
Cal. Acad. Mem.
Cal. Acad. Natur. Sci.

Proc.
Cal. Acad. Pap.

Cal. Min. Bur. Bull.
Cal. Min. Bur. Rep.

Calvados, Mem. Soc. Linn.
Cambrai, Mem. Soc. Emul.
Cambridge Mem. Analyt.

Soc.
Cambridge Mus. Comp.

Zool. Bull.
Cambr. Omith. Club Bull.

Cambridge Phil. Soc. Proc.
Cambridge Phil. Soc.

Trans.
Cambridge, Studies Phjrsiol.

Labor
Camera Oscura

Can.

Can., Bot. Soc. Ann.

Can. Chem. J.

Can. Drug.

Can. Eng.

Can. Entom.

Can. Entom. Soc. Rep.

Can. Inst. Proc.

Can. Inst. Trans.
Can. J.

Bulletin de la Soci^t^ vaudoise des Ingenieurs et des

Architects
Bulletin of the Torrey Botanical Club, New York
Bullettino del Vulcanismo Italiano (e di Geodinamica

generale)
Chemi<^ Abstracts
Journal fur Omithologie

Periodico mensual de Ciencias matematicas y fisicas
Memoires de I'Academie des Sciences, Belles Lettres,

et Arts de Caen
Bulletin de la Soci6t6 Linneene de Normandie

Memoires de la Soci6t6 Linneenne de Normandie

Precis des Travaux de la Soci6t6 d'Agriculture, &c. de

Caen
The Calcutta Journal of Natural History
Quarterly Journal of the Medico-Physical Society
Annals of the Royal Botanic Garden, Calcutta

■

Transactions of the Medical and Physical Society of

Calcutta
Bulletin of the California Academy of Sciences
Memoirs of the California Academy of Sciences
Proceedings of the Califomian Academy of Natural

Sciences
Occasional Papers of the California Academy of

Sciences
California State Mining Bureau. Bulletin
(California State Mining Bureau). Report of the

State Mineralogist
Memoires de la Soci^t6 Linneenne du Calvados
Memoires de la Soci6t6 d'Emulation de Cambrai
Memoirs of the Cambridge Analytical Society

Proceedings of the Museum of Comparative Zoology
at Harvard College, Cambridge, Mass.

Bulletin of the Nuttall Ornithological Club. A
Quarterly Journal of Ornithology

Proceedings of the Cambridge Philosophical Society

Transactions of the Cambridge Philosophical Society

Studies from the Physiological Laboratory in the

University of Cambridge
La Camera Oscura; rivista periodica universale del

progressi della Fotografia
Canadian — Canada

Annals of the Botanical Society of Canada
The Canadian Chemical Journal
Canadian Druggist
Canadian Engineer, The
The Canadian Entomologist
First Annual Report on the Noxious Insects of the

Province of Ontario
Proceedings of the Canadian Institute (Toronto,

being a continuation of "The Canadian Journal

of Science, Literature and History")
Transactions of the Canadian Institute
The Canadian Journal of Industry, Science, and Art

m

LIST OF ABBREVIATIONS TO LITQRATURB

Can. Naturalist

Can. P.

Can. Pat. Off. Rec.

Can. Pharm. J.

Can. Rec. Sci.

Soc. Proc.

Can. Roy.

Trans.
Canestrini
Canestrini, Archiv.
Cannes Soc. Mem.

Cantu, Crooaca
Caout. Gutta-p.
Caradoc Field Club Trans.

Cardiff Natur. Soc. Trans.

Carinthia

Carl, Rep. Physik.

Carlsberg Lab.

Carlsrube

Carlsrube, Verb. Nattu^ss.

Ver.
Carloinisches Medico-Cbir-

urgiscbes Institut.
Cams, 2kx>l. Anzeiger
Casopis

Casopis Cesketbo Lekam.
Casper Vierteljabrsscb.

Casper Wocbenscb.
Cassel Jabr.

Cassier's Mag.

Castings

Catania Atti Accad. Gioen.

Catania Boll. Accad. Gioen.

Cattaneo Bibl. di Farm.

Cattaneo Giom. Farm.

Cell. Ind.

CeUule

Cement

Cement Age

Cement Eng. News

Cement Record

Centr. Agrik. Cbem.

Centr. Allg. Path.

Tbe Canadian Naturalist and Geologist, and Por-
ceedings of tbe Natural History Society of Montreal

Canadian Patent

Canadian Patent Office Record

C>anadian Pbarmaceutical Journal and Pharmacal
Gazette

Tbe Canadian Record of Science, including tbe. Pro-
ceedings of tbe Natural History Society of Mont-
real, and replacing tbe Canadian Naturalist

Proceedings and Transactions of tbe Rojral Society
of Canada

See Arcbivio Zool.

Arcbivio per la Zoologia, I'Anatomia, e la Pisiologia

Memoires de la Soci6t6 des Sciences Naturelles (et
Historiques), des Lettres et des Beaux-Arts de
Cannes, et de Tarrondissement de Grasse

Cronaca

Caoutcbouc et la Gutta-percba

Transactions of tbe Caradoc and Severn Valley
Field aub

Cardiff Naturalists' Society. Report and Transac-
tions

See Kamten

Repertorium fiir Experimental-Pbirsik., etc. (Rep.
der Physik)

See under Kiobenb.

See Karlsruhe

Verbandlungen des Naturwissenscbaftlicben Vereins

See under Stockb. Physiol. Lab. Mittb.

Zoologischer Anzieger

Casopis pro Pestovani Mathematiky a Fysiky.

(Journal for the Advancement of Mathematics and

Physica)
Casopis Cesketbo Lekamitura
Vierteljabrsscbrift fur gerichtliche und dffentlicbe

Medidn
Wochenschrift ftir die gesammte Heilkunde
Jahresbericht, dann Bericht, uber die Thatigkeit det

Vereins fiir Nattu-kunde in Cassel
Cassiers's Magazine
Castings
Atti deU'Accademia Gioenia di Scienze Naturali di

Catania '
Boliettino delle Sedute della Accademia Gioenia
Biblioteca di Farmacia, Chimica, etc.
Giomaie di Farmacia
Die Celluloid Industrie
La cellule
Cement
Cement Age

Cement and Engineering News
Cement Record
Central-Blatt fiir Agrikulturchemie und rationellen

Wirthschafts-Betrieb. Referirendes Organ fiir

naturwissenschaftliche Forschungen in ibrer

Anwendimg auf die Landwirthscbaft
Centralblatt ftir allgemeine Pathologic

LIST OF ABBREVIATIONS TO LITERATURE

liii

Centr. Bakt.
Centr. Med. Wiss.
Centr. Mineral.

Centr. Papierfabr.
Centr. Path.

Centr. Physiol.
Centr. Text. Ind.
Centr. Zuckerind.
Centrztg. Optik.

Ceramique

Cette Stat. Maritime

Ccy. P.

Chamb. Conun. J.

Chambery Mem. Acad.

Savoie.
Charente-Inf. Soc. Sd.

Aim.
Charkofif.

Charleston Med. Joum.
Charleston South J. Med.
Chem. Age
Chem. Centr.
Chem. Coll. Reports

Chem. Drug.

Chem. Drug. Australasia

Chem. Eng.

Chem. Gaz.

Chem. Ind.

Chem. Listy

Chem. News

Chem. Pharm. Centr.

Blatt.
Chem. Rev.

Chem. Rev. Pett-Harz-Ind.
Chem. Tech. Mitth.
Chem. Tech. Rep.

Chem. Tech. Neuzeit
Chem. Tech. Ubers.

Chem. Tech. Ztg.
Chem. Trade J.
Chem. Weekbl.
Chem. World
Chem. Zentr.
Chem. Ztg.
Chem. Ztg. Rep.
Chem. Zts.
Chemist
Chemnitz Ber.

Cherbourg, Mem. Soc.

Acad.
Cherbourg, Mem. Soc.

Sd.

Centralblatt fur Bacteriologie und Parasitenkunde
Centralblatt fur die medidnischen Wissenschaften
Centralblatt fur Mineralogie, Geologic und Palaeon-

tologie
Centralblatt fur Papierfabrikation
Centralblatt fur Allgemeine Pathologic und Patholo-

gische Anatomic
Centralblatt fur Physiologic
Centralblatt fur die Textil-Industrie
Centralblatt fur die Zuckerindustrie
Central-Zeitung fOr Optik imd Mechanik (Elektro-

technik tmd verwandte Berufszweige)
Ceramique, La

See MontpelUer Inst. Zool. Trav.
Ceylon Patent

Chamber of Commerce Journal
Memoires de la Sodete Academique de Savoie.

Academic de la Rochelle. Sodete des Sdences
Nattu-elles de la Charente-Inferieure. Annales

See Kharkov.

Charleston Medical Journal and Review

The Southern Journal of Medicine

Chemical Age

Chemisches Centralblatt (1830-1906).

Reports of the Royal College of Chemistry, and Re-
searches conducted in the Laboratories

Chemist and Druggist, London

Chemist and Druggist of Australasia

Chemical Engineer

Chemical Gazette, The

Chemische Industrie

Chemicke Listy

Chemical News

Chemisch-pharmaceutisches Central-Blatt

The Chemical Review

Chemische Revue fiber die Fett-und Harz-Industrie
Eisner's Chemisch-Technische Mittheilungen
Chemisch-Technisches Repertorium Qacobsen 1862-

1901)
Chemische Technologie der Neuzeit
Chemisch-Technische tJbersicht (supplement to Chem.

Ztg.)
Chemiker-und Techniker-Zdtung
Chemical Trade Journal and Chemical Engineer
Chemisch Weekblad
Chemical World, The
Chemisches Zentralblatt (1907-)
Chemiker-Zdtimg
Repertorium der Chemiker Zeitung
Chemische Zeitschrift
The Chemist
Bericht der Naturwissenschaftlichen Gesellschaft zu

Chemnitz
Memoires de la Sod^t4 Academique de Cherbourg

Memoires de la Soci6t6 Imperiale des Sdences
Naturelles de Cherbourg

liv

LIST OF ABBREVIATIONS TO LITERATURE

Cherbourg Soc. Sci. Natl.

Mem.
Chester Soc. Sci. Proc.

Chicago Acad. Sci. Bull.
Chicago Acad. Sci. Bull.

Nat. Hist. Surv.
Chicago Acad. Sci. Trans.
Chicago Entom. Soc. Mem.

Chicago Field Columb.

Mus. Publ.
Chile, Anales Univ.
ChUe P.
Chili Soc. Sci. Act.

Chim. et Ind.
Chimiste

Christiania, Forh.
Christiania, Norsk Mag.
Christiania Skr. (Math.-

Nat. Kl.)
Christiania, Univers. Lab.

Chron. ind.

Chur, Jahresber. Naturf.

Gesell.
Ciment
Cincin. Soc. Natur. Hist.

Jl.
Cistula Entom.

Civil Eng. Inst. Trans.

Civil Eng. J.

Civilingenieiu-

Clay Worker

Clermont, Mem. Acad.

Sci.

Cleveland Med. J.

Clin. Soc. Trans.

Coblentz, Jahr. bot. Ver.

Cohn, Beitr. Biol. Pflanz.

Coimbra, Inst.

Coimbra, Soc. Broter. Bol.

Col. P.

Collegium

Colliery Guardian

Colmar Soc. Hist. Natiu".

Bull.
Colombia, Contrib.

Colombo

Colorado Sci. Soc. Proc.

Comment. Fauna &c. Ven.

Trent.
Compt. rend.

Memoires de la Soci4t6 Nationale des Sciences

Natiu-elles et Mathematiques de Cherbourg
Proceedings of the Chester Society of Natural Science

(and Literatiu-e)
Bulletin of the Chicago Academy of Sciences
The Chicago Academy of Sciences. Bulletin. . .of the

Natural History Survey
Transactions of the Chicago Academy of Sciences
Occasional Memoirs of the Chicago Entomological

Society
Publications of the Field Columbian Museum

Anales de la Universidad de Chile

Chilean Patent

Actes de la Soci6t4 Scientiiique du Chili (Actas de la

Sociedad Cientifica de Chile)
Chimie et Industrie
Chimiste, Le

Forhandlinger i Videnskabs-Selskabet i Christiania
Norsk Magazin for Laegevidenskaben
Skrifter udgivne af Videnskabsselskabet i Christiania.

Mathematisk-naturvidenskabelig Klasse
Das chemische Laboratorium der Universitat Chris-
tiania
Chronique de I'industrie
Jahresbericht der Naturforschenden Gesellschaft von

Graubiindten in Chur
Ciment, Le
The Journal of the Cincinnati Society of Natural

History
Cistula Entomologica

Transactions of the Institution of Civil Engineers
The Civil Engineer and Architect's Journal, etc.
Der Civilingenietu*
Clay Worker, The
Memoires de I'Academie des Sciences, Belles Lettres,

Arts de Clermont-Ferrand
Cleveland Medical Journal
Transactions of the Clinical Society of London
Jahresbericht des botanischen Vereines am Mitten

und Niederrheine, mit botanis6hen Abhandlungen
Beitrage zur Biologic der Pflanzen
O Instituto, journal scientifico et letterario
Sociedade Broteriana. Boletim Anual
Colombian Patent
Collegium (Scientific technical supplement to Leder-

markt)
Colliery Guardian and Journal of the Iron and Coal

Trades
Bulletin de la Soci6t6 d'Histoire Naturelle de Colmar

Contribucione^ de Colombia a las Ciencias i a las

Artes
See Ceylon

Proceedings of the Colorado Scientific Society
Commentario della Fauna, Flora e Gea del Veneto e

Trentino
Comptes rendus hebdomadaires des Seances de

I'Academie des Sciences

I,IST OI^ ABBREVIATIONS TO LITERATURB

Iv

Compt. rend. Assoc. Franc.

Compt. rend, minerale
Compt. rend. Soc. biol.

Compt. rend. trav. lab.

Carlsberg
Concrete
Concrete Age
Concrete Constr. Eng.
Concrete Eng.

Conegliano Scuola Vit. Enol.

Ann.
Conegliano Scuola Vit.

Enol. N. Rassegna
Conegliano Scuola Vit.

Enol. Riv.

Cong. P.

Congr. Anthropol. Compt.

Rend.
Congr. Hot. Crittog. Atti

Congr. Hot. Int. Atti
Congr. Int. Hot. Bull.

Congr. Intematl. Hortic.

Bull.
Congr. Intematl. Med.

Atti
Congr. Intematl. Med. C. R

Congr. Intematl. Sci. Med.

C. R.
Congr. Intematl. Zool.

(C. R.)
Connecticut, Acad. Mem.

Connecticut Acad. Trans.

Contrib. Biol. Veg.
Copenhagen
Copenhagen
Copenhague, R6sum^

Cordoba, Acad. Bol.

Cordoba Acad. Ci. Act.
Com Trade J.
Cornwall, J. Roy. Inst.
Cornwall Poly. Soc. Rep.
Cornwall, Poly. Soc.

Trans.
Corresp. Blatt. Schweiz.

Aerzte
Conesp. Blatt Zahn.
Cosmos

Association Francaise pour I'Avancement des Sciences.

Compte Rendu de la 1« (-12*) Session; 1872-83
Comptes rendus de la Soci^t^ de I'industrie minerale
Comptes rendus des seances et memoires de la Soci^t^

de biologic, Paris
Comptes rendus du travaux du laboratoire de Carls-
berg
Concrete
Concrete Age

Concrete and Constructional Engineering
Concrete Engineering (no longer published separately.

Combined with Cement Age)
Annali della R. Scuola di Viticoltura e di Enologia

in Conegliano
Nuova Rassegna di Viticoltura de Enologia della R.

Scuola di Conegliano
La Rivista. Periodico (quindicinale, Organo) della

R. Scuola di Viticoltura e di Enologia (e del Comizio

Agrario) di Conegliano
Congo Free State Patent
Congres international d' Anthropologic et d'Archeologie

prehistoriques. Comptes Rendus
Societa Crittogamologica Italiana. Atti del Congresso

Nazion^e di Botanica Crittogamica in Parma
Atti del Congresso Intemazionale di Genova
Bulletin du Congres International de Botanique et

d'Horticulture reuni a St. Petersbourg . . .
Bulletin du Congres International d'Horticulture a

Bruxelles
Atti deir XI. Congresso Medico Intemazionale

Comptes-Rendus du XII Congres International de
Medecine
Congres Periodique International des Sciences Medi-

cales. Compte-Rendu
Congres International de Zoologie

Memoirs of the Connecticut Academy of Arts and

Sciences .
Transactions of the Connecticut Academy of Arts and

Sciences
Contribuzioni alia Biologia Vegetale
See Kjobenhavn.

See Congr. Int. Sci. Med. C. R., 1884
R6sum6 du Bulletin de la Soci^t6 Royale Danoise des

Sciences
Boletin de la Academia Nacional de Ciencias Exactas

existente en la Universidad de Cordoba
Actas de la Academia Nacional de Ciencias en Cordoba
Com Trade Journal

Journal of the Royal Institution of Cornwall
Royal Cornwall Polytechnic Society, Annual Report
Reports and Transactions of the Royal Geological

Society of Cornwall
Correspondenz-Blatt fur Schweizer Aerzte

Correspondenzblatt ftir Zahnarzte

Cosmos: Revue Encyclopedique hebdomadaire

Ivi

UST OF ABBREVIATIONS TO UTERATUR^

Costa, Corrisp. Zool.

Cotteswold Club Proc.

Cracovie Acad. Sd. Bull

Cracow
Crell. Ann.

Crichton, Russ. Sammlung.

Cron. med. mex.
Croydon Micro. Club Proc.

Croydon Micro. Club Rep.

Cuba P.

Cuba, Rep. Fis. Nat.

Cuir

Cumberland Assoc. Trans.

Cuyper, Rev. Univ.
D'Alton u. Burm. Ztg.

Zool.
Dan. Biol. Stat. Rep.

Dan. P.

Danzig, Neu. Schrift.

Danzig, Schrift.
Darmst. Beitr. Geol.

Darmst. Ver. Erdk. Notiz.

Davenport Acad. Proc.

Dax Soc. Borda Bull.
Delft Ecole Poly. Ann.
Delhi, Med. J.

Denison Univ. Set. Lab.

BuU.
Dent. Cosmos
Dent. Digest
Dent. Rev.

Deut. Amer. Apoth. Ztg.
Deut. Amer. Gewerbeztg.

Deut. Arch. Klin. Med.
Deut. Bot. Ges. Ber.
Deut Bot. Monats.
Deut. Buchdr. Ztg.
Deut. Eisenbahn Ztg.

Deut. Elektro. Ges.

Corrispondenza Zoologica, destinata a diffondere nel
regno delle Due Sicilie tutto cio che si va discuop-
lendo entro e fuori Europa (e vice-versa), ris
guardante la Zoologia in generate

Proceedings of the Cotteswold Naturalists' Field
Club

Bulletin International de I'Academie des Sciences de
Cracovie

See Krakow

Chemische Annalen fur die Preunde der Naturlehre,
etc.

Russische Sammlimg fur Nattuwissenschaft und
Heilkunst

Cronica medica mexicana, Mexico

Proceedings and Transactions of the Croydon Micro-
scopical and Natural History Club

. . . Report and Abstract of Proceedings of the Croydon
Microscopical (and Natural History) Club

Cuban Patent

Repertorio fisico-naturale de la isla de Cuba

Cuir, Le

Transactions of the Cumberland and Westmorland
Association for the Advancement of Literature and
Science

Revue Universelle des Mines, de la Metallurgie, &c.

Zeitung ftir Zoologie, Zootomie, und Palaeozoologie

Report of the Danish Biological Station to the Home

Department (Board of Agriculture)
Danish Patent
Neueste Schriften der Naturforschenden Gesellschaft

in Danzig
Schriften der Nattu^orschenden Gesellschaft in Danzig
Beitrage zur Geologic des Grossherzogthums Hessen

und der angrenzenden Gegenden
Notizblatt des Vereins fur Erdkunde zu Darmstadt

und des Mittelrheinischen Geologischen Vereins
Proceedings of the Davenport Academy of Natural

Sciences •
(Bulletin de la) Soci6t6 de Borda, Dax (Landes)
Annales de TEcole Polytechnique de Delft
Quarterly Medical and Surgical Journal for the North-
west Provinces
Bulletin of (the Scientific Laboratories of) Denison

University
Dental Cosmos, Philadelphia
The Dental Digest, Chicago
The Dental Review

Deutsch-Amerikanische Apotheker Zeitung, New York
lUustrierte Deutsch-Amerikanische Gewerbe imd In-

dustrie-Zeitung (Newark, N. J.)
Deutsches Archiv. fiir Klinische Medizin
Berichte der Deutschen Botanischen Gesellschaft
Deutsche Botanische Monatsschrift
Deutsche Buchdruker-Zeitung
Zeitimg des Vereins Deutscher Eisenbahn-Verwalt-

ungen
See Zts. ElekUoch.

LIST OF ABBREVIATIONS TO LITERATURE

Ivii

Deut. Entom. Zts.

Deut. Geol. Ges. Zts.
Deut. Gerber Ztg.
Deut. Ind. Ztg.
Deut. Klinik
Deut. Mechan. Ztg.
Deut. med. Wochenschr.
Deut. Monats.
Deut. Naturf . Ber.

Deut. Naturf. Pestschr.

Deut. Naturf. Tagebl.

Deut. Naturf. Versamml.

Ber.
Deut. Poly. Ztg.

Deut. Phys. Ges. Verb.

Deut. Tech. Ztg.
Deut. T6pfer Ziegl. Ztg.
Deut. Vierteljalirschr. Oeff.

Gesundh.
Deut Zool. Ges.
Deut. ZooL Ges. Verh.

Deut. Zts. Chirurg.
Deut. Zts. Thiermed.

Deut. Zuckeriud. .
Devon. Assoc. Trans.

Devon & Cornwall Hatur.

Hist. Soc.
Diamant Ztg.
Dietet. Hyg. Gaz.
Dijon, Acad. Sci. Mem.

Dijon, J. Agric.
Dijon, Seances Acad.

Dinant, Soc. Natur. Bull.
Dingl. Poly.
Donders, Archiv

Dorpat, Archiv
Dorpat, Biol. Naturk.
Dori>at, Naturf. Ges.
Doipat, Naturwiss. Abh.
Dorpat Pharm. Inst. Arb.
Dorimt Sitzber.

Dorpat Schr.

Dorset Field Club Proc.

Deutsche Entomologische Zeitschrift (formerly Ber-
liner EfUomohgische Zeitschrift)

Zeitschrift der Deutschen Geologischen Gesellschaft

Deutsche Gerber Zeitung

Deutsche Industrie Zeitung

Deutsche Klinik

Deutsche Mechaniker-Zeitung

Deutsche medizinische Wochenschrift

Deutsche Monatshefte

Amtlicher Bericht der. ! .Versammlung Deutscher
Naturforscher und Aerzte

Festschrift fur die 59. Versammlung Deutscher
Naturforscher und Aerzte

Tageblatt der. Versammlung Deutscher Naturfor-
scher und Aerzte

Bericht uber die Versammlung der Deutschen Natur-
forscher und Aerzte

Allgemeine Deutsche Polytechnische Zeitung (H.
Grothe)

Verhandlimgen der Deutschen Physikalischen Gesell-
schaft. . .

Deutsche Techniker Zeitung

Deutsche Tdpfer tmd Ziegler Zeitung

Deutsche Vierteljahrsschrift ftir Gesundheitspflege

See Zool. Anz.

Verhandlungen der Deutschen Zoologischen Gesell-
schaft

Deutsche Zeitschrift fur Chirurgie

Deutsche Zeitschrift fur Thiermedidn und vergleich-
ende Pathologie

Deutsche Zuckerindustrie

Transactions of the Devonshire Association for the
Advancement of Science, Literature and Art

See Plymouth Inst. Trans.

Diamant, Glas-Industrie Zeitimg

Dietetic and Hygienic Gazette, The

Memoires de I'Academie des Sciences, Arts et Belles-
Lettres de Dijon

Journal d'Agriculture de la Cote d'Or.

Seances pubUques de I'Academie des Sciences, Arts,
et Belles-Lettres de Dijon

Bulletin de la Soci6t6 des Naturalistes Dinantais

Dinglers Polytechnisches Journal

Archiv fur die HoUandischen Beitrage zur Natur- und
Heilkunde

Archiv fur die Naturkunde Liv-, Ksth-, und Kurlands

Biologische Naturkind.

See Arch. Nat. (Dorpat)

Naturwissenschaftliche Abhandlungen aus Dorpat

Arbeiten des Pharmakologischen Institutes zu Dorpat

Sitzungsberichte der Naturforscher-Gesellschaft bei
der Universitat (Jurjew) Dorpat

Schriften herausgegeben von der Naturforscher
Gesellschaft bei der Universitat (Jurjew) Dorpat

Proceedings of the Dorset Natural History and Anti-
quarian Field Club

Iviii

UST Ol? ABBREVIATIONS TO LITERATURE

Douai Mem. Soc. Agric.
Doubs Soc. Emul. Mem.
Dove Rep. Physik.

Dresden Ausz. Protokol.

Dresden Denkschr. Natur-

wiss. Ges. Isis.
Dresden Bntom. Ver. "Iris"

Corresp.-Bl.
Dresden Isis Festschr.

Dresden Isis Sitzber.

Dresden, Jahr. Natur.

Heilk.
Dresden, Mitth. Poly.

Schule
Dresden, Schr. Ges.

Mineral.
Dresden, Sitzber. Natur.

Heilk.
D. R. P.
Drug. Circ.
Drug Topics
Dublin, Geol. Soc. J.
Dublin, Hosp. Gaz.
Dublin J. Med. Chem.

Sci.
Dublin J. Med. Sci.
Dublin Med. Trans.
Dublin Micro. Club
Dublin, Natur. Hist. Soc.

Proc.
Dublin Natur. Field Club
Dublin, Pathol. Soc. Proc.
Dublin Quart. J.
Dublin Quart. J. Med.
Dublin, Roy. Soc. J.
Dublin Soc. J., Dublin Soc.

Trans.
Dublin Soc. Sci. Proc.

Dublin Soc. Sci. Trans.

Dublin, Zool. Bot. Assoc.

Proc.
Dudley, Geol. Soc. Proc.

Dumfr. Gallow. Soc. Trans.

Dunkerque, Mem. Soc.

Encour.
Durham Univ. Phil. Soc.

Proc.

Memoires de la Soci6t6 d'AgricuIture, de Sciences, ct
d'Arts, scant a Douai

Memoires de la Soci6t6 d'Emulation du Departement
du Doubs

Repertorium der Physik. Enthaltend eine vollstandige
Zusammenstellung der neuem Fortschritte dieser
Wissenschaft

Auszuge aus den Protokollen der Gesellschaft fur
Natur- und Heilktmde in Dresden

Denkschriften der Naturwissenschaftlichen Gesell-
schaft Isis zu Dresden
See Iris

Festschrift der Naturwissenschaftlichen Gesellschaft

Isis in Dresden
Sitzungsberichte und Abhandlungen der Natuninssen-

schaftlichen Gesellschaft Isis in Dresden
Jahresberichte fiir 1868-60 v. d. Gesellschaft fiir

Natur- und Heilkunde in Dresden
Mittheiltmgen der K. Sachs. Polytechnischen Schule

Auswahl aus den Schriften der unter Werner's Mit-
wirkung gestifteten Gesellschaft fur Mineralogie

Sitztmgsberichte der Gesellschaft fiir Natur- und
Heilktmde

German Patent (Deutsches Reichs-Patent)

Druggist's Circular

Drug Topics, New York

Journal of the Geological Society of Dublin

Dublin Hospital Gazette

Dublin Journal of Medical an^ Chemical Science

The Dublin Journal of Medical Science

Dublin Medical Transactions

See Irish Natur.

Proceedings of the Natural History Society of Dublin

See Irish Natur.

Proceedings of the Pathological Society of Dublin
The Dublin Quarterly Joiunal of Science
Dublin Quarterly Journal of Medical Science
Journal of the Royal Dublin Society
Transactions and Journal of the Dublin Society

The Scientific Proceedings of the Royal Dublin

Society
The Scientific Transactions of the Royal Dublin

Society
Proceedmgs of the Dublin University Zoological and

Botanical Association
Transactions of the Dudley and Midland Geological

and Scientific Society
The Transactions and Journal of Proceedings of the

Dumfriesshire and Galloway Natural History and

Antiquarian Society
Memoires de la So€i6t6 Dunkerquoise pour TEn-

couragement des Sciences, des Lettres, et des Arts
Proceedings of the University of Durham Philosophical

Society

LIST OF ABBREVIATIONS TO LITERATURE

lix

Dyer, Calico Ptr.

Dzondi, Aeskulap
Eastbourne Natur. Hist.

Soc. Papers (& Trans.)
Eastbourne Natur. Hist.

Soc. Proc.
Eastbourne Natur. Hist.

Soc. Trans.
Echange

Eckhard, Beitr.
Eclairage Elect.

Eclect. Med. J., Cincin.

Econ. Geol.

Ecu. P.

Edinb. Bot. Soc. Proc.

Edinb. Bot. Soc. Trans.
Edinb. Field Club Trans.

Edinb., Fish. Bd. Rep.
Edinb. J. Med. Sci.
Edinb. J. Natur. Geogr.

Sci.
Edinb. J. Sci.
Edinb. Med. Chir. Soc.

Trans.
Edin. Med. J.
Edinb. Mem. Wem. Soc.
Edinb. Monthly J. Med.

Sci.
Edinb. Natur. Soc. Trans.

Edinb. N. Phil. J.
Edinb. Phil. J.
Edinb. Plin. Soc. Trans.
Edinb. Proc. Phys. Soc.

Edinb. Roy. Coll. Physns.

Lab. Rep.
Edinb. Roy. Soc. Proc.
Edinb. Roy. Soc. Trans.
Edinb. Trans. Scot. Soc.

Arts
Eisen Ztg.
Ekaterinburg
Elberfeld Naturwiss, Ver.

Jahr.
Elec. Rev.
Elec. Soc. Trans.

Elec. Telegr. Rev.
Elec. World
Electrician
Electricite
Electrochem. Met. Ind.

Dyer, Calico Printer, Bleacher, Finisher, and Textile

Review
Aeskulap
Papers (Transactions) of the Eastbourne Natural

History Society
The Sixth Annual Report of the Eastbourne Natural

History Society
Transactions of the Eastbourne Natural History

Society
I'Echange. .Organe (Mensuel) des Naturalistes de la

Region Lyonnaise . . .
Beitrage zur Anatomic und Physiologic
I'Eclairage Electrique. Revue (hebdomadaire)

d(el) 'Electricite
Eclectic Medical Journal, Cincinnati
Economic Geology
Ecuador Patent
Proceedings of the Botanical Society of Edinburgh

for the years 1855-56
Transactions of the Botanical Society of Edinburgh
Transactions of the Edinburgh Naturalists' Field

Club
Annual Report of the Fishery Board for Scotland .
Edinburgh Jotunal of Medical Science
The Edinburgh Journal of Natural and Geographical

Science
The Edinburgh Journal of Science
Transactions of the Medico-Chirurgical Society of

Edinburgh
Edinburgh Medical Journal

Memoirs of the Wemerian Natural History Society
Edinburgh Monthly Jotunal of Medical Science

Transactions of the Edinburgh Field Naturalists' and
Microscopical Society, instituted as the Edinburgh
Naturalists' Field CluB

The Edinburgh New Philosophical Journal

The Edinburgh Philosophical Journal

Transactions of the Plinian Society

Proceedings of the Royal Physical Society of Edin-
burgh

Reports from the Laboratory of the Royal College of
Physicians, Edinburgh

Proceedings of the Royal Society of Edinburgh

Transactions of the Royal Society of Edinburgh

Transactions of the Royal Scottish Society of Arts

Eisen Zeitung

See lekaterinenb.

Jahres-Bericht des Naturwissenschaftlichen Vereins in

Elberfeld
The Electrical Review
The Transactions and Proceedings of the London

Electrical Society
The Electric Telegraph Review
Electrical World
The Electrician
I'Electricite
Electrochemical and Metallurgical Industry

Ix

LIST OF ABBREVIATIONS TO UTBRATURB

Elektrochem. Zts.
Elektrotech. Zts.
EUiott Soc. J.
Elliott Soc. Proc.
Eisner, Mitth.
Emden Naturf. Ges. Jahr.

Emden Naturf. Ges. Schr.

Eng.

Eng. Contr.

Eng. Digest

Eng. Mag.

Eng. Mining J. (Eng. Min.

J.)
Eng. News

Eng. Record

Engineer
Engineers' J.

Engineers Soc. Trans.
Engl. Mech.
Engler, Hot. Jahr.

Engrais, V

Entom. Annual

Entom. Mag.

Entom. Medd. (Kjobenh.)

Entom. Month. Mag.
Entom. Nachr.
Entom. Record
Entom. Soc. Trans.

Entom. Tidskr.

Entomologica Amer.

Entomologist

E. P.

Epicure

Epidem. Soc. Trans.

Epinal (Vosges) Ann.

Erdel. Muz.-Egyl. Ertek.

Erdmann, Sveriges Geol.

Undersdk.
Erfurt, Abh. Akad. Wiss.

Erfurt, Akad. Jahr.

Erfurt, Denkschr.

Erfurt, Nova Acta

Elektrochemische Zeitschrift

Electrotechnische Zeitschrift

Jotunal of the Elliott Society of Natural History

Proceedings of the Elliott Society of Natural History

See Chem. Tech. Mitth.

. . . Jahresbericht der NatUrforschenden Gesellschaft

in Emden
Kleine Schriften der Naturforschenden Gesellschaft in

Emden
Engineering

Engineering and Contracting
Engineering Digest
Engineering Magazine, The
Engineering and Mining Journal, The

Engineering News

Enginering Record, Building Record and Sanitary
Engineer

Engineer, The

The Engineers' Journal and Railway Gazette of India
and the Colonies

Society of Engineers. Transactions

English Mechanic

Botanische Jahrbucher ftir Systematik, Pflanzenge-
schichte imd Pflanzengeographie

Engrals, V

The Entomologist's Annual

The Entomological Magazine

Entomologi^e Meddeldser udgivne af Entomologisk
Porening

The Entomologist's Monthly Magazine

Entomologische Nachrichten

The Entomologist's Record and Journal of Variation

The Transactions of the Entomological Society td
London

Entomologisk Tidskrift pa Pdranstaltande af Entomo-
logiska Foreningen i Stockholm

Entomologica Americana

The Entomologist

English ^ritish) Patent

Epicure, The

Transactions of the Epidemiological Society of Lon-
don

Annales de la Soci6t6 d'Emulation du departement des
Vosges

Az Erdelyi Muzeum-Egylet Kiadvanyai Ertekezesek.
(Publications of the 'Transylvanian Museum Asso-
ciation. Memoirs)

Sveriges geologiska Undersdkning, pa offentlig
bekostnad, utfdrd under Ledning af A. Erdmann

Abhandlungen der Kurfurstlich Mainzer Akademie
nutzhcher Wissenschaften zu Erfurt

Jahrbucher der koniglichen Akademie gemeinnutziger
Wissenschaften zu Erfurt

Denkschrift der Akademie gemeinnutziger Wissen-
schaften in Erfurt

Nova Acta Academiae Electoralis Moguntinae
Scientiarum utilium quae Erftirti est.

UST Ol? ABBREVIATIONS TO UTERATURE

ixi

Ergeb. Physiol.
Eriangen, Abh.

Erlangen Anat. Inst.
Eriangen, Mitth. Phys.

Med. Soc.
Erlangen Phys. Med. Soc.

Sitzber.
Erythea

Essex Field Club Proc.
Essex Field Club Spec.

Mem.
Essex Field Club Trans.
Essex Inst. Bull.
Essex Inst. Conunun.
Essex Inst. Proc.
Essex Natur. Hist. Soc. J.
Essex Natlist.
Essig. Ind.

Etudes Gites Mineraux
Eure, Bull. Acad. Ebroic.
Eure, J. Agric.

Eure, Recueil Trav.

Eure, Soc. Agric. Bull.

Eure, Soc. Agric. Recueil

Evkonjrv

Exner. Rep.

Exper. Sta. Rec.

Eyr

Fachgenosse

Falaise, Mem. Soc. Acad.

Farben Ztg.
Farb. Ztg.
Fechner Centr.

Fechner, Rep.

Fed. Inst. Min. Engin.

Trans.
Fer.
Ferussac, Bull. Sci. Math.

Ferussac, Bull. Sd. Natur.
Feuille Jeunes Natur.
Field Mus. Natur. Hist.

Fij. P.
Fin. P.
Finistere Soc. Sci. Bull.

Finlande Soc. Geogr.
Pinska Lak. SaUsk. Handl.
Finska Vet.-Soc.

Ergebnisse der Physiologic, Wiesbaden

Abhandlimgen der Physikalisch-medicinischen
Societat in Erlangen

See Bietr. Morphol.

Wissenschaftliche Mittheilungen der Physikalisch-
medicinischen Societat zu Erlangen

Sitzungsberichte der Physiksdisch-Medizinischen
Societat zu (in) Erlangen

Ersrthea. A Jotunal of Botany, West American and
General

Journal of Proceedings of the Essex Field Club

Essex Field Club Special Memoirs

Transactions of the Essex Field Club

Bulletin of the Essex Institute

Communications read before the Essex Institute

Proceedings of the Essex Institute

Journal of the Essex County Natural History Society

The Essex Naturalist

Deutsche Essigindustrie

See France Gites Min. Etudes

Bulletin de TAcademie Ebroicienne

Journal d'Agriculture, de Medicine et des Sciences
acceissoires

Recueil des Travaux de la Soci^t6 Libre d' Agriculture,
des Sciences, des Arts et des Belles-Lettres du
departmente de I'Eure

Bulletin de la Soci6t6 d'Agriculture, des Sciences, et
des Arts du departement de TEure

Recueil de la Sod^t^ d'Agriculture, Sciences, Arts, et
Belles-Lettres du departement de I'Eurs

A' Magyar Tudos Tarsasag' Evkdnyvei

Repertorium der Physik.

Experiment Station Record

Eyr, et Medicinisk Tidsskrift

Fachgenosse, Der

Memoires de la Soci^t6 Academique des Sciences,
&c., de Falaise

Farb^ Zeitung

Farber Zeitung (Lehne's)

Centralblatt fiir Naturwissenschaften und Anthro-
pologic

Repertorium der Experimental-Physik.

Transactions of the Federated Institution of Mining
Engineers

Ferrum, Halle

Bulletin des Sciences Mathematiques, Astronomiques,
Physiques, et Chimiques par le Baron de Ferussac

Bulletin des Science Naturelles et de Geologic

Feuille des Jeunes Naturalistes

Field Museum of Natural History, Chicago, Publica-
tion

Fiji Islands Patent

Finland Patent

Bulletin de la Soci6t£ d'Etudes Scientifiques du
Finistere

See Fennia

Finska Lakare Sallskapets Handlingar ,

See Helsingfors, Bidrag. Helsingfors, &fvers

Ixii

LIST OP ABBREVIATIONS TO LITERATURB

Firenze Accad. Georgofili

Atti
Firenze, Ann. Mus. Fis.
Firenze, Ann. Mus. Imp.

Firenze Congr. Bot. Atti

Firenze, Mem. Soc. Ital.
Firenze, Opusc. Sci.
Firenze R. Inst. Pubbl.

Firenze Soc. Georgofili Atti

Firenze Soc. Studi Geogr.

Boll.
Flora
Flore Jardins

Flore Serres
Florence
Florke, Repert.

Foldt. Kozlon

Folia Clin.
Folia haematol.
Folia Therap. Lond.
Forbes, Med. Rev.

Forsch. Agr.-Phys.
Forster, AUg. Bauztg.
Fortschr. Chem.

Fortschr. Med.
Fortschr. Phys.
Fortschr. Rontgenstr.
Fortschr. Theerfarben-

Fabrikation
Foundry
F. P.

France, Congr. Med. Chir.
France, Congr. Sci.
France Gites Miner. Etudes
France, Inst. Provinces

Annuaire
France, Inst. Provinces

Mem.
France Soc. Agric. Bull.

France Soc. Agric. Mem.

France Soc. Bot. Bull.
France Soc. Entom.

Franc Soc. Miner. Bull.

France Soc. Zool.
France Soc. Zool. Bull.

Atti della Reale Accademia Economico-Agraria dei

Georgofili di Firenze
Annali del R. Museo di Fisica e Storia Naturale
Annali del Museo Imperiale di Fisica e Storia Naturale

di Firenze
Atti del Congresso Intemazionale Botanico tenuto in

Firenze nel mese di Maggio 1874
See Modena

Collezione d'Opuscoli scientifici.
Pubblicazioni del R. Istituto di Studi Superior i Pratici

e di Perfezionamento in Firenze
Atti della (Real) Societa Economica di Firenze ossia

de* Georgofili
See Riv. Geogr. Ital.

Flora Oder Allgemeine Botanische Zeittmg

Annales d' Horticulture et de Botanique, ou Flore des

Jardins du Royaume des Pays-Bas
Flore des Serres et des Jardins de I'Europe
See Firenze
Repertorium des neuesten und wissenwtirdigsten aus

der gesammten Naturkunde
Foldtani Kozlony, Havi folyoirat kiadja a Magyarhoni

Foldtani Tarsulat
Folia clinica chimico et miscroscopica
Folia haematplogica
Folia Therapeutica, London
The British and Foreign Medical Review, or Quarterly

Jotunal of Practical Medicine and Surgery
Forschungen auf dem Gebiete der Agrikultur-Physik.
Allgemeine Bauzeitung
Fortschritte der Chemie, Physik und Physikalischen

chemie
Fortschritte der Medicin.
Die Fortschritte der Physik.

Fortschritte auf dem Gebiete der Rontgenstrahlen
Fortschritte der Theerfarbenfabrikation und ver-

wendter Industriezweige
Foundry, The
French Patent

Congres Medico-Chirurgicale de France
Sessions des Congres Scientifiques de France
Etudes des Gites Mineraux de la France
Annuaire de I'lnstitut des Provinces et des Congres

Scientifiques de France
Memoires de I'lnstitut des Provinces de France:

Sciences physiques et naturelles
Bulletin des Seances de la Soci^t^ Nationale d'Agri-

culture de France
Memoires publics par la Soci6t6 Nationale d' Agri-
culture de France
Bulletin de la Soci6t6 Botanique de France
See Abeille., Paris, Soc. Ent. Ann., Paris, Soc. Ent.

Bull., Rev. Ent.
Bulletin de la Soci^t^ Mineralogique de France.

Bulletin de la Soci^t6 Francaise de' Mineralogie.

(Ancienne Soci6t6 Mineralogique de France)
See Paris, Caus. Sci.
Bulletin de la Soci^t^ Zoologique de France

UST Ol? ABBREVIATIONS TO I^ITERATURB

Ixiii

France Soc. Zool. Mem.

Frankfurt

Frankfurt, Jahr. Phys. Ver.

Frankf. Ver. Pflege Phot.
Frankfurt, Zool. Garten
Frankfurter Zts. Pathol.
Franzos. Ann.

Freiberg, Jahr. Berg. Hiitt.

Freiburg, Beitr.
Freiburg, Ber.

Freie K.

Freloo

Fries, Bot. Notiser

Froricp, Notizen

Ftibling's Ztg.

Gac. ind.

Gand, Ann. Soc. Agric.

Gand, Ann. Soc. Med.
Gand, Bull. Soc. Med.
Gard, Apercu Trav.

Gard, Mem. Acad.
Gard, Notice Trav. Acad.
Garden & Forest

Gardeners Chron.
Gamett, Ann. Phil.

Garten-Flora
Garten-Ztg.

Gartenwdt

Gas World

Gaz

Gazz. del. Clin.

Gazz. med. ital lomb.

Gazz. Chim. Ital.

Geelong Field Natur. Club

Gehlen J.

Gendrin, Trans. Med.

Geneeskundig Mag.

Geneve, Archiv.

Geneve, Bull. Soc. Omith

Suisse.
Geneve Conserv. Bot. An-

nuaire
Geneve, Inst. Natl. Bull.
Geneve, Inst. Natl. Mem.
Geneve, Mus. Hist. Natur.

Ann.
Geneve, Recueil Trav. Soc.

Med.
Qeneve, Soc. Geogr. Mem.

Memoires de la Soci^t^ Zoologique de France

See Senckenberg

Jahrbuch zur Verbreitung naturwissensdiaftlicher

Kenntnisse, veranstaltet vom Physikalischen

Verein zu Frankfurt a/Main
See Wien, Photogr. Correspond.
Der Zoologische Garten Frankfurt a/M,
Frankfurter Zeitschrift ftir Pathologic
Franzosische Annalen fiir die allgemeine Natiu'ges-

chichte, Physik, &c.
Jahrbuch 'fiir den Berg- und Huttenmann. Herausg.

von der Konigl. Berg-Akademie zu Freiberg
Beitrage zur Rheinischen Naturgeschichte
Berichte iiber die Verhandlungen der Naturfor-

schenden Gesellschaft zu Freiburg i. B.
Freie Kunste

Le Frelon. Journal d'Entomologie descriptive
Botaniska Notiser

Notizen aus dem Gebiete der Natur- und HeiUnmde
Fuhlings landwirtschaftliche Zeitung
La Gaceta industrial
Annales de la Soci^td Royale d' Agriculture et de

Botanique
Annales de la Soci6t6 de Medecine de Gand
Bulletin de la Soci6t6 de Medecine de Gand
Notice ou Apercu analytique des Travaux de

TAcademie Royale du Gard
Memoires de TAcademie du Gard
Notice des Travaus del'Academie du Gard
Garden and Forest. A Journal of Horticulture,

Landscape Art and Forestry
The Gardeners Chronicle
Annals of Philosophy, Natural History, Chemistry

&c.
Garten-Flora
Neue allgemeine Deutsche Garten- imd Bltunen-

zeitung
Gartenwelt, The
Gas World, The
Le Gaz

Gazzetta della Cliniche
Gazzetta medica italiana lombardia, Milano
Gazzetta Chimica Italiana
See Wombat

Journal ftir dei Chemie und Physik
Transactions Medicales
Geneeskimdig Magazijn
See Archives Sci. Phys. Nat.
Bulletin de la Societe Omithologique Suisse

Annuaire du Conservatoire du Jardin Botanique de

Geneve
Bulletin de I'lnstitut National Genevois
Memoires de I'lnstitut National Genevois
See Rev. Suisse Zool. •

Recueil des Travaux de la Soci^t6 Medicale de Geneve

Memoires de la Society de Geographic de Geneve

Ixiv

LIST O^ ABBREVIATIONS TO LITERATURB

Geneve, Soc. Phys. Mem.

Genie civ.

Geneva

Geneva, Ann. Mus. Phys.

Geneva, Giom.

Geneva, Mem. Accad.

Geneva, Mem. 1st. Ligure.
Geneva, Mem. Soc. Med.

Emul.
Geneva Mus. Civ. Ann.
Geneva Mus. Zeel. Anat.

Cemp. Bell.
Geneva, Sec. Ligust. Atti

Geneva Univ. Atti
Geegr. Soc. J.
Geegr. Soc. Proc.

Geegr. Soc. Suppl. Pap.
Geel. Mag.
Geel. Survey, Can.
Gera, Naturwiss. Jahr.

Gerber

Germar, Mag. Entom.

Germar, Zts. Entom.

Gergonne, Ann. Math.

Gesundh. Ing.

Gew. Ztg.

Gewerbebl. Schw.

Gewerbebl. Wurt

Gewerbeh.

Gewerks Ztg.

Giessen, Oberhess. Ges.

Ber.
Gievel, Zts.
Gilbert, Ann. Phys.
Gill. Tech. Micro. Repos.
Giom. Arcad.
Giom. farm. chim.
Giom. Gen. civ.
Giron. 1st. Lomb.
Giom. Mineral. Crist. Petr.
Gironde Comm. Meteorel.
Gironde, J. Med.
Gistl, Faunus
Glasgow. Inst. Engin.

Trans.
Glasgow Med. Chir. Sec.

Trans.
Glasgow Med. J.
Glasgow Natur. Hist. Soc.

Proc. & Trans.
Glasgow Path. Clin. Soc.

Trans.

Memeires de la Soci^t^ de Physique et d'Histeire

Naturelle de Geneve
Genie Civil

See Congr. Bet. Int. Atti. 1892
Annali del Musee Civice di Steria Naturale
Giemale degli Studies! di Lettere, Science, arti e

Mestieri
Memeire dell'Accademia Imperiale delle Scienze di

Geneva
Memorie deir Istituto Ligure
Memorie della Societa Medica di Emulaziene di

Geneva
Annali del Musee Civico di Stepa Naturale di Geneva
BoUettino dei Musei di Zoologia e Anatomia Cem-

parata della R. Universita di Geneva
Atti della Societa Ligustica di Scienze Naturali e

Geografiche
Atti della R. Universita di Geneva
Journal of the Royal Geographical Society of London
Proceedings of the Royal Geographical Society and

Monthly Record of Geography
Royal Geograhical Society. Supplementary Papers
Geological Magazine
Geological Survey, Canada
Jahresbericht der Gesellschaft von Freunden der

Naturwissenschaften in Gera, nebst Nachrichten

uber den Naturwissenschaftlichen Verein in Schleiz
Der Gerber

Magazin der Entemologie
Zeitschrift fur die Entemologie
Annales de Mathematique
Gesundheits-Ingenieur
Wieck's Gewerbezeitung
Schweizerisches Gewerbeblatt
Gewerbeblatt aus Wurttemberg
Gewerbehalle

Oesterreichische Gewerkszeitimg
Berichte der Oberhessischen Gesellchaft fiir Natur-

imd Heillamde
See Zts. Gesammt. Naturwiss.
See Ann. Phys.

Technical and Microscopical Repository
Giemale Arcadico di Scienze
Giemale de farmada, di chimica
Giemale del Genie civile
See Bibl. Ital.

Giemale di Mineralogia, Cristallegrafia e Petrografia
See Bordeaux Soc. Sci. Mem.
Journal Medical de la Gironde
Faunus

Transactions of the Institution of Engineers and Ship-
builders in Scotland
Transactions of the Medico-Chimrgical Society of

Glasgow
Glasgow Medical Jotimal
Proceedings and Transactions of the Natural History

Society of Glasgow
Transactions of the Glasgow Pathological and Clinical

Society

LIST O^ ABBREVIATIONS TO LITERATURE

Ixv

Glasgow Phil. Soc. Proc.

Glashatte

Glas-Ind.

Gleanings Sci.

Globe

Gluckauf

Good Roads

Goodsir, Ann. Anat.

Physiol.
Gordon Coll. Phot. Assoc.
Gdrlitz, Abh.

Gotheborg, Handl.

Gatheborg, Nya Handl.

Gdttingen, Abh.

Gdttingen, Comment.
Gdttingen, Nachr.

Gdttinger Studien
Gdttingen, Studien Ver.

Grafe, J. Chir. Augen-

heilk.
Graph. Mitth.
GraubQnden Naturf. Ges.

Jahr.
Gravenhage, Athenaeum
Gravenhage, Inst. Ingen.

Tijdschr.
Gravenhage, Inst. Ingen.

Uittrek.
Gravenhage, Inst. Ingen.

Verb.
Gravenhage, Inst. Ingen.

Verslag.
Gravenhage, Tijdschr.

Graves, Natur. J.
Graz Bot. Inst. Mitth.
Graz, Unters. Physiol.

Histol.
Great. Brit. Phil. Soc.
Greifswald Nattu^ss. Ver.

Mitth.
Grenoble, Acad. Delph.

Bull.
GreviUea

Groningen, Ann. Acad.
Gruithuisen, Neue Ana-

lekt.
Grunert Archiv.
Gnmert, Meteor. Optik
Guat. P.

Proceedings of the Philosophical Society of Glasgow

Glashutte, Die

Glas-Industrie, Die

Gleanings in Science

See Geneve Soc. Geogr. Mem.

Gliickauf ; Berg- und Hfittenmannische-Zeitschrift

Good Roads

Annals of Anatomy and Physiology

See Wombat.

Abhandltmgen der Naturforschenden Gesellschaft zu

Gorlitz
Gdtheborgs Kongl. Vetenskaps och Vitterhets Sam-

halles Handlingar
Nya Handlingar af Kongl. Vettenskaps och Vitterhets

Samhallet i Gdtheborg
Abhandlungen der Kdniglichen Gesellschaft der Wis-

senschaften zu Gdttingen
Commentationes recentiores Sodetatis, etc.
Nachrichten von der Georg- Augusts Universitat imd
der Kdnigl. Gesellschaft der Wissenchaften zu Gdt-

tingen
Gdttinger Studien
Studien des Gdttingischen Vereins Bergmannischer

Freimde
Journal der Chirurgie und Augen-Heilkimde

Schweizer graphische Mitteilungen

Jahresberi(£t der Nattirforschenden Gesellschaft

Graubtindens
Athenaetun
Tijdschrift van het Koninklijk Instituut van Ingen-

ieurs
Uittreksels uit Vreemde Tijdschriften voor de Leden

van het Koninklijk Instituut van Ingenieurs
Verhandelingen van het Koninklijk Instituut van

Ingenieurs
K. Instituut van Ingenieurs. Algemeen Verslag van

de Werkzaamheden en Notulen der Vergaderingen
Tijdschrift voor Entomologie, door de Nederlandsche

Entomologische Vereeniging
The Naturalists' Journal and Miscellany
Mittheilungen aus dem Botanischen Institute zu Graz
Untersuchungenaus dem Institute fur Physiologic und

Histologic
See Victoria Inst. J.
See Neu-Vorpommem Mitth.

Bulletin de I'Academie Delphinale, ou Soci£t6 des

Sciences et Arts de Grenoble
Grevillea, a Quarterly Record of Cryptogamic Botany

and its Literature
Annales Academiae Groninganae
Neue Analekten fur Erd- und Himmels-kunde

Archiv fur Mathematik und Physik
Beitrage zur meteorologischen Optik, etc.
Guatemala Patent

Ixvi

LIST OP ABBREVIATIONS TO LITERATURE

Guia Minero

Guillemin, Archiv. Hot.

Gummi-Ztg.

Gtmsbtirg, Zts. Klin. Med.

Gurlt, Mag. Ges. Thier-

heilk.
Guy's Hosp. Rep.
Haarlem Kolon. Mus.

BuU.
Haarlem, Mus. Teyler

Archiv.
Haarlem, Natuurk. Verh.

Maatsch. Wet.

Haaxman, Tijdschr.
Habana Acad. Anales.

Haeser, Archiv. Med.
Hage

Hahnemann. Month.
Haidinger, Abh.
Haidinger, Ber.

Hainaut Soc. Mem.

Hall, Bijdragen
Halle, Abr. Naturwiss.

Ver.
Halle aux cuirs. La
Halle, Jahr. Naturwiss.

Ver.
Halle Kryptog. Lab.
Halle, Naturf. Ges. Abh.

Halle, Naturf. Ges. Ber.
Halle, Nattui. Ges. Neu.

Schr.
Halle, Zts. Ges. Naturwiss.
Hamburg, Abh. Geb.

Naturwiss.
Hamburg Bot. Ges.
Hamburg, Mitth.

Hamb. Mus. Ber.
Hamb. Mus. Jahr.

Hamb. Mus. Mitth.

Hamb. Nattuiviss^ Ver.
Abh.

Hamb. Ver. Naturwiss.

Unterh. Verh.
Hamb. Wiss. Anst. Jahr.

Guia del Minero: Periodico cientifico, industrial y

inercantil
Archives de Botanique, ou Recueil Mensuel de Me-

moires originaux, etc.
Gummi-Zeitung
Zeitschrift fur klinische Medizin, mit dem Verein fur

physiologische Heilkunde in Breslau
Magazin fiir die gesammte Thier-Heilkunde

Guy's Hospital Reports

Bulletin van het Koloniaal Museum te Haarlem

Archives du Musee Teyler

Natutu'kundige Verhandelingen van de (Bataafsch)

HoUandsche Maatschappij der Wetenschappente

Haarlem
Tijdschrift voor Wettenschappelijke Pharmacie, etc.
Anales de la (Real) Academic de Ciencias Medicaes

Fisicas y Naturales de la Habana
Archiv ftir die gesammte Medicin
See Gravenhage

Hahnemannian Monthly, Philadelphia
Nattuwissenschaftliche Abhandltmgen
Berichte tlber die Mittheilungen von Freimden der

Nattuwissenschaften in Wien
Memoires et Publications de la Soci6t^ des Sciences,

des Arts et des Lettres du Hainaut
Bijdragen tot de Natuurkundige Wetenschappen
Abhandlungen des Naturwissenschaftlichen Vereins

fiir Sachsen und Thtiringen in Halle
Halle aux cuirs, La
Jahresbericht des Naturwissenshaftlichen Vereins in

Halle
See Beitr. Physiol. Morphol.
Abhandlungen der Nattuforschenden Gesellschaft zu

HaUe
Bericht der Nattu'forschenden Gesellschaft zu Halle
Neue Schriften der Natiurforschenden Gesellschaft zu

Halle
Zeitschrift ftir die gesammten Nattu-wissenschaften
Abhandlungen aus dem Gebiete der Naturwissen-

schaften
See Bot. Centrbl.

Mittheiltmgen aus den Verhandlungen der Natur-
wissenschaftlichen Gesellschaft in Hamburg
Naturhistorisches Museum zu Hamburg. Berichte
Jahresbericht uber das Naturhistorische Museum zu

Hamburg
Mittheilung aus dem Naturhistorischen Museum in

Hamburg
Abhandlungen aus dem Gebiete der Naturwissen-

schaf ten herausgegeben vom Naturwissenschaftlichen

Verein in Hamburg
Verhandltmgen des Vereins fur Naturwissenschaft-

liche Unterhaltung zu Hamburg
Jahrbuch der Hamburgischen Wissenschaftlichen An-

stalten

LIST OB ABBREVIATIONS TO UTKRATURE

Ixvii

Hampshire Field Club Pap.

&Proc.
Hannover Architekt.-Ver.

Zts.

Hannover Jahr.

Hanndverische Ann.
Harlem Soc. Holland. Sd.
Hartford, Trans.

Harvard Mus. Zool. Mem.

Harvard Mus. Zool. Bull.

Harz, Naturwiss.

Ber.
Havre, Cercle Bot.

Haw. P.
Haye
Heart
Hedwigia

Ver.

Heidelb. Jahr. Lit.

Hddelb. Naturhist. Med.
Festschr.

Heidelb. Naturhist. Med.

Verb.
Heidelb., Verb.

Heis, Wochenschr.

Heller, Archiv.

Helsingfors, Acta Soc.

Sci. Fenn.
Helsingfors, Bidrag Fin«

lands Natur o. Fd[k.
Helsingfors, Bidrag Fin-
lands Naturkann.
Helsingfors, Faun. Flor.

Fenn. Acta.
Helsingfors, Fauna Flora

Fenn. Medd.
Helsingfors, Faun. Flor.

Fenn. Notiser
Helsingfors, Ofvers, Finaka

Vet. Soc.
Helv. Chim. Acta
Henle und Pfeufer, Zts.
Hermannstader Verb.

Papers and Proceedings of the Hampshire Field Club

Zeitschrift des Architekten- und Ingenieur-Vereins zu
Hannover. Zeitschrift fur Architektur und In-
genieurwesen

. . . Jahresbericht der Naturhistorischen Gesellschaft
zu Hannover

Hanndverische Annalen fur die gesammte Heilkunde

See Arch. Neerland

Transactions of the Natural History Society of Hart-
ford

Memoirs of the Museum of Comparative Zoology at
Harvard College

Btdletin of the Museum of Comparative Zoology at
Harvard College, in Cambridge

Berichte des Naturwissenschaftlichen Vereins des
Harzes zu Blankenburg

Cercle pratique d'Horticulture et de Botanique de
I'arrondissement du Havre: Bulletins

Hawaiian Patent

See Congr. Int. Hyg. C. R., 1884

Heart

Hedwigia. Bin Notizblatt fur Kryptogamische Stu-
dien nebst Repertorium ftir Kryptogamische Litera-
tur. Hedwigia. Organ fur (spedeUe) Krypto-
gamenkunde (und Phytopathologie) nebst Reper-
toritim fur (Kryptogamische) Literatur.

Jahrbucher der Literatur. Verhandltmgen des Natur-
historisch-Medicinischen Vereins zu Hddelberg

Festchrift zur Feier des funfhundertjahrigen Bestehens
der Ruperto-Carola dargebracht von dem Natur-
historisch-Medicinischen Verdn zu Heiddberg

Verhandlungen des Naturhistorisch-Medicinischen
Vereins au Heiddberg

Verhandltmgen der in Hddelberg versammdten
Augenarzte

Wochenschrift fur Astronomic, Meteorologie, imd
Geographic

Archiv fur physiologische und pathologische Chemie
und Mikroskopie

Acta Sodetatis Scientiarum Fennicae

Bidrag till kannedom om Finlands Natur och Folk,
utgifna af Finska Vetenskaps-Societeten

Bidrag till Finlands Naturkannedom, Etnografi och
Statistik, utgifna af Finska Vetenskaps-Sodeteten

Acta Sodetatis pro Fauna et Flora Fennica

Meddelanden af Societas pro Fauna et Flora Fennica

Notiser ur Sallskapets pro Fauna et Flora Feennica

,. F5rhandlmgar

Ofversigt af Finska Vetenskaps-Sodetatens F6r-

handlingar **

Hdvetica Chimica Acta
See Zeitschrift fur rationelle Medicin
Verhandlungen tmd Mittheilungen des Siebenburg-

ischen Vereins ftir Naturwissenschaften in Hermann-

stadt

Ixviii

UST OF ABBREVIATIONS TO LITERATURE

HermbstStt, Archiv.
Hermstadt, Bull.
HermbstAdt, Museum

Hertha

Herts. Natur. Hist. Soc.

Trans.
Hessen, Naturhist. Verg.

Heusinger, Zts.
Hide and Leather
High Wycombe Natur.

Hist. Mag.
Highland Soc. Trans.

Hildesheim Roemer-Mus.

Mitth.
Himly, Bibl. Ophthahn.
Hippone
Hisinger, Afh.
Hobart Town
Hoeven en Vriese, Tijd-

schr.
Hofif, Mag.

HoflFman, Phjrtogr. Blatt.
HoU. P.
Holland, Beitr.

Holland, Mag.
Holmesdale Natur. Hist.

Club Proc.
Homme

Hooker, Bot. Miscell.
Hooker, Comp. Bot. Mag.
Hooker, Ixmd. J. Bot.
Hoppe, Bot. Taschenb.

Horae Soc. Kntom. Rossi-

cae
Horkel, Archiv.
Horn, Archiv. Med.
Horn's Phot. J.
Homschuch, Archiv.
Horolog. J.
Hortic. Soc. J.
Hortic. Soc. Trans.
Hufeland, J. Arzn.
Humboldt.

Humming Bird

Archiv der Agriculturchemie ftir denkende Land-

wirthe
Btdletin des Neuesten und Wissenwurdigsten aus der

Naturwissenschaft, etc.
Museum des Neuesten imd Wissenwurdigsten aus

dem Gebiete der Naturwissenschaft, der Kunste,

der Fabriken, der Manufakturen, der technischen

Gewerbe, der Landwirthschaft, der Produkten-

waaren und Handelskunde, tmd der burgerlichen

Haushaltung, &c.

Hertha
Transactions of the Hertfordshire Natural History

Society and Field Club
Verhandlungen des Naturhistorischen Vereins fur das

Gross herzogthum Hessen imd Umgebung
Zeitschrift fur die organische Physik
Hide and Leather
The Quarterly Magazine of the High Wycombe Nattu^l

History Society
Transactions of the Highland and Agricultural Society

of Scotland with an abstract of the Proceedings
Mittheilungen aus dem Roemer-Museum Hildesheim

Bibliothek fur Ophthalmologic

See Bone

Afhandlingar i Fysik, Kemi, och Mineralogie

See Tasmania

Tijdschrift voor Natutu'lijke Geschiedenis en Physio-
logic

Magazin fur die gesammte Mineralogie, Geognosie,
etc.

Phytographische Blatter

Holland Patent

Hollandsiche Beitrage zu den anatomischen und
physiologischen Wissenscaften

Hollandisches Magazin der Naturkunde

Proceedings and Annual Reports of the Holmesdale
Natural History Club, Reigate, for the 3rears 1865-67

L'Homme: Journal illustre des Sciences Anthro-
pologiques

The Botanical Miscellany

Companion to the Botanical Magazine

London Journal of Botany

Neues Botanisches Taschenbuch fur die Anfanger
dieser Wissenschaft und der Apothekerktmst

Horae Societatis Kntomologicae Rossicae variis ser-
monibus Rossicae usitatis

Archiv. fiir die thierische Chemie

Archiv. ftir praktische Medizin und Klinik

Horn's photographisches Journal

Archiv Skandinavischer Beitrage zur Naturgeschichte

The Horological Journal

Journal of the Royal Horticultural Society of London

Transactions of the Horticultiu^ Society of London

Journal der practischen Arzneiktmde

Humboldt. Monatsschrift fiir die Gesamten Natur-
wissenschaften

The Humming Bird scientific, artistic and in-
dustrial Review

UST Ol? ABBRBVIATIONS TO UTERATURE

Ixix

Hongkong P.
Hung. P.
Hutm. Ztg.
Hyg. Congr.

Hyg. Rundschau.
Hyg. viande
Idcaterinenb., Soc. Oural.

BuU.
II Berico
n Cimento

II. Giamb-Vico
n Progresso

II Subalpino
II Tempo

III. Insects Rep.

HL Lab. Natur. Hist. Bull.

HI. Mus. Natur. Hist. Bull.

niiger, Magazin
Illumin. Bngin. (London)
lUust. Hortic.

niust. landw. Ztg.
Illust. OfiF. J.

Illust. Wochenschr. Kn-
tom.

Impr.
Ind. Chim.
Ind. lait. >
Ind. Text.
Ind. Ztg.
Index Med.
India Agric. Soc. J.

India, Agric. Soc. Proc.

India Agric. Soc. Trans.

India Bot. Surv. Records

India Dept. Agric.

India, Govt. Records (For,

Dept,)
India, Govt. Records

(Home Dept.)
India P.
India Rev.

India Rub. J.

India Rub. World

Indian Ann.

Indian J. Med. Phys. Sci.

Indian Med. Gaz.

Hongkong Patent

Hungarian Patent

Deutsche Hutmacher-Zeitung

See Congr. Int. Hig. Act.; Congr. Int. Hyg. C. R.;

Int. Congr. Hyg. Arb.; Int. Congr. Hyg. Trans.
Hygienische Rtmdschau. Berlin
Hygiene de la viande et du lait, L*
Bulletin de la Soci6t6 Ouralienne d'Amateurs des

Sciences Naturelles
II Berico
II Cimento
II Giambattista-Vico
II Progresso delle Scienze, Lettere, ed Arti.
II Subalpino, Giomale di Scienze
II Tempo, Giomale Italiano di Medidna
. . .Report of the State Entomologist. . .on the Noxious

and Beneficial Insects of the State of Illinois
Bulletin of the Illmois SUte Laboratory of Natural

History
Bulletin. . .of the Illinois State Museum of Natural

History
Magazin fur Insektenkunde
Illuminating Engineer (London), The
Illustration hcoticole; journal special des Serres et des

Jardins
Illtistrierte landwirtschaftliche Zeitung
Illustrated Official Journal, The (Patents)
Illustrierte Wochenschrift fur Entomologie. Inter-
nationales Organ ftir alle Interessen der Insekten-

kimde. Offizielles Organ der Berliner Entomolo-

gischen Gesellschaf t
L*imprimerie
Industria chimica
L'Industrie laitiere
L'industrie textile
Deutsche Industrie Zeitung
Index Medicus, Washington
Journal of the Agricultural and Horticultttral Society

of India
Proceedings of the Agricultural and Horticultural

Society of India
Transactions of the Agricultttral and Horticultural

Society of India
Records of the Botanical Survey of India
India Department of Agriculture, Publications
Selections from the Records of the Government of

India. (Foreign Department)
Selections from the Records of the Government of

India
Indian Patent
India Review and Journal of Foreign Science and

the Arts
India Rubber Journal
India Rubber World
Indian Annals of Medical Science
Indian Journal of Medical Science
The Indian Medical Gazette, a monthly record of

Medicine, &c.

Ixx

UST OP ABBREVIATIONS TO tITERATURE

Indian Meteorol. Mem.

Indian Mus. Notes
Industrieztg. Ungam
Ingenieur

Inghirami, Opuscoli
Innsbruck, Jahr.
Innsbruck Naturwiss.

Med. Ber.
Innsbruck, Neue Zts.
Innsbruck, Zts. Ferdinan-

deums
Inst.
Inst. Act. J.

Inst. Brewing Trans.
Inst. Civ. Eng. Proc.

Inst. Egypt. Bull.
Inst. Egypt. Mem.

Inst. Elect. Engin. J.
Inst. Mechan. Engin.

Proc.
Inst. Min. Eng. Ttsjis.
Inst. Min. Met. Trans.

Inst. Solvay Trav.

Intell. Observer

Intl. Beitr. Path. Therap.

Intl. Congr. Appl. Chem.
Intl. Congr. Hyg. Trans.

Intl. Congr. 2^1. Proc.
Intl. Entom.-Ver.
Intl. Med. Congr. Trans.
Intl. Med. Congr. Verb.

Intl. J. Anat.

Intl. Mschr. Anat.

Intl. Sugar J.

Intl. Zentr. Baukeram.

Glasind.
Intl. Zts. Metallog.
Invent. Rec.
Iowa Acad. Sd. Proc.
Iowa Univ. Lab. Natur.

Hist. Bull.
Ireland, Coll. Physicians

Trans.

Ireland, Inst. Civ. Eng.
Trans.

Indian Meteorological Memoirs: being occasional
Discussions and Compilations of meteorological
data relating to India and the neighboring coun-
tries
Indian Museum Notes
Industriezeitung fiir Ungam
Der Ingenieur

Nuova CoUezione di Opuscoli e Notizie di Scienze
Jahresbericht der k. k. Ober-Realschule zu Innsbruck
Berichte des Naturwissenschaftlich-medizinischen

Vereines in Innsbruck
Neue 2yeitschrift des Perdinandeums fiir Tirol
Zeitschrift des Perdinandeums fiir Tirol und Voralberg

L'Institut

Journal of the Institute of Actuaries (and Assurance

Magazine)
Transactions of the Institute of Brewing
Minutes of the Proceedings of the Institution of Civil

Engineers
Bulletin de I'lnstitut Egyptien
Memoires (ou Travaux priginaux) presentes (et lus)

a rinstitut Egyptien
Journal of the Institution of Electrical Engineers
Institution of Mechaniod Engineers. Proceedings

Transactions of the Institution of Mining Engineers

Transactions of the Institution of Mining and Metal-
lurgy

Institut Solvay. Travaux de Laboratoire

The Intellecttial Observer

Internationale Beitrage zur Pathologic imd Therapie,
die Emahrungsstorungen, Stoffwechsel und Ver-
dauungkrankheiten

International Congress of Applied Chemistry

Transactions of the International Congress of Hygiene
and Demography

Proceedings International Congress of Zoology

See Zurich, Soc. Ent.

Transactions of the International Medical Cougress

Verhandltmgen des Intemationalen Medicinischcn
Congresses

Monthly International Joiunal of Anatomy and His-
tology (Physiology)

See Intl. J. Anat.

International Sugar Journal, The

Internationales Zentralblatt ftir Baukeramik und
Glasindustrie

Internationale Zeitschrift fur Metallographie

Inventor's Record, The

Proceedings of the Iowa Academy of Sciences

Bulletin from the Laboratories of Natural History of
the State University of Iowa

Transactions of the Association of Fellows and Licen-
tiates of the King's and Queen's College of Physi-
cians in Ireland

The Transactions of the Institute of Civil Engineers of
Ireland

LIST OP ABBREVIATIONS TO LITBRATURB

Ixxi

Ireknd Roy. Soc. Ant.

Proc. & Pap.
Ireland ZooL Soc.
Iris

Irish Acad. Cunningham

Mem.
Irish Acad. Proc.
Irish Acad. Trans.
Irish Natur.

Iron

Iron Age

Iron Coal Trades Rev.

Iron Steel Inst. J.

Iron Steel Inst. Trans.

Isenflamm, Beitr. Zerg-

lied.
Isere Soc. Bull.

Isle of Man Natur. Hist. &
Antiq. Soc.

tal. P.

talia, Soc. Bot. Bull.

talia Soc. Crittog. Atti

talia Soc. Crittog. Com-
ment.

talia Soc. Crittog. Mem.

talia» Soc. Entom. Bull.

talia, Soc. Zool. Boll.

thaca, Cornell Univ. Bull.
Amer. Paleont.

. A, w. o.

. Adv. Therap.
Agric.

. agric. Hort.

. Agric. Prat.

. Agric. Sci.

. agric. Soc.

. Agric. Tropicale

. allied Soc.

. Amer. Lea. Chem. As-
soc.

. Amer. Med. Assoc.

. Amer. Pharm. Assoc.

. Amer. Soc. Mechan.
Bng.

. AnaL Chem.

. Anat.

. Anat. Physiol.
. Appl. Chem.

See Dublin, Roy. Soc. Ant. Ir. Jl.

See Irish Natlist

Correspondenz-Blatt des Entomologischen Vereins
Iris zu Dresden. Iris, Dresden. Deutsche Entomo-
logische 2^tschrift herausgegeben von der Gesell-
schaft Iris zu Dresden in Verbindung mit der
Deutschen Entomologischen Gesellschaft zu Berlin. .
Fortsetztmg des "Correspondenz-Blattes des Ento-
mologischen Vereins Iris."

Royal Irish Academy. Cunningham Memoirs

Proceedings of the Royal Irish Academy

The Transactions of the Royal Irish Academy

The Irish NaturaMst: a monthly Journal of general

Irish Natural History
Iron

Iron Age

Iron Coal Trades Review
The Journal of the Iron & Steel Institute
Transactions of the Iron and Steel Institute
Bdtrage ftir die Zergliederungskunst

Bulletin de la Sod^t^ de Statistique, des Sciences
naturelles et des Arts industriels du Departement de
risere

See Yn Lioar Manninagh

Italian Patent

Bullettino della Societa Botanica Italiana

Atti della Societa Crittogamologica Italiana

Commentario della Societa Crittogamologica Italiana

Memorie della Societa Crittogamologica Italiana
Bullettino della Societa Entomologica Italiana
BoUettino della Societa Zoologica Italiana
Bulletins of American Paleontology

Journal

Journal of the American Chemical Society
Journal of Advanced Therapeutics, New Yozk
The (Quarterly) Journal of Agriculture
Journal de I'Agriculture, le Horticulttu^, etc.
Journal d'Agriculture pratique, etc.
Journal of Agricultural Science
Journal of the Agricultural Society
Journal d'Agriculture tropicale
Journal of the Allied Societies (Dental)
Journal of the American Leather Chemists' Associa-
tion
Journal of the American Medical Association
Journal of the American Pharmaceutical Association
Journal of the American Society of Mechanical Engi-
neers
The Journal of Analytical (and Applied) Chemistry
Journal de Tanatomie de la Physiologic normales et

pathologiques de Thomme et des animaux
The Journal of Anatomy and Physiology
Journal of Applied Chemistry

Ixxii

UST O? ABBREVIATIONS TO LITERATURE

J. Appl. Micr.

J. Assoc. Eng. Soc.

J. Biol. Chem.

J. Bot.

J. Buchdr.

J. C. S.

J. Camera Club

J. Can. Min. Inst.

J. Chem. Met. Soc. South

Af.
J. chim. med.

-J. chim. phys.

J. Chir.

J. Chir. Augenheilk.

J. Coll. Agric. Imp. Univ.

Tokyo
J. Comp. Path. Therap.

J. Conch.
J. ecole poly.
J. Kntom.
J. Exp. Med.
J. Exp. Zool.
J. fabr. Sucre
J. Prank. Inst.
J. Gasbeleucht
J. Gaslighting
J. Gen. Physiol.
J. Genie Civ.
J. Geol.
J. Goldschm.

t Heb. Med.
J. Heb. Sci. Med.

J. Home Econ.

J. Hygiene

J. Ind. Eng. Chem.

J. Indian Archipel.

J. Infect. Dis.

J. Inst. Brewing

J. Inst. Metals

J. Intl. Anat.

J. Invent.

J. Landw.

J. Med. Chir. Pharm.

J. Med. Paris

J. Med. Research

J. Microgr.

J. Micro. Sci.

J. Mines

J. mines met.
J. Morphol.

Journal of Applied Microscopy

Journal of the Association of Engineering Societies

Journal of Biological Chemistry

Journal de Botanique

Journal ffir Buchdruckerktmst

Journal of the Chemical Society, London

Journal of the Camera Club

Journal of the Canadian Mining Institutes

Journal of the Chemical, Metalliu-gical and Mining
Society of South Africa

Journal de chimie medicale, de pharmacie et de toxi-
cologic

Journal de chimie, physique, electrochemie, thermo-
chimie, radiochimie, mechanique, chimie, stoichio-
metric

Journal de Chirurgie

Journal der Chirurgie und Augenheilkunde

Journal of the College of Agriculture, Imperial Uni-
versity of Tokyo

The Journal of Comparative Pathology and Thera-
peutics

The Journal of Conchology

Journal de TEcole polytechnique

Journal of Entomology, descriptive and geographical

Journal of Experimental Medicine

Journal of Experimental 2^1ogy, The

Journal des fabricants de sucre

Journal of the Franklin Institute

Journal fur Gasbeleuchtung

Journal of Gas Lighting

Jotunal of General Physiology

Journal du Genie Civil des Sciences et des Arts

Journal of Geology

Journal der Gc^c^chmiedektmst imd verwandter Ge-
werbe

Journal Hebdomadaire de Medecine

Journal Hebdomadaire des Progres des Sciences et
Institutions Medicales

Journal of Home Economics, The

Journal of Hygiene

Journal of Industrial and Engineering Chemistry

Journal of the Indian Archipelago and Eastern Asia

Journal of Infectious Diseases

Journal of the Institute of Brewing

Journal of the Institute of Metals

See Int. J. Anat.

Journal des Inventeurs

Journal ftir Landwirtschaft

Journal de Medecine, Chirurgie, Pharmacie

Journal de medicine de Paris

Journal of Medical Research

Journal de micrographie

Quarterly Journal of Microscopical Science

Journal des Mines, ou Recueil de Memoires sur Tex-
ploitation des Mines, et sur les Sciences et les Arts
qui s*y rapportent

Journal des mines et de metallurgie

Joiunal of Morphology

UST OF ABBREVIATIONS TO UTERATURB

Ixxiii

J. Mus. Godeffroy

. Mycol.

. N. Engl. Water Works
Assoc.

. Opthalmol.
. Omith.
. Papier

Path. Bact.

Petrole

Pharm.

Phartn. Anvers

Pharm. Chim.

Pharm. Elsass*Loth-

ringen

Pharm. Soc. Japan

Pharmacol.

. Phot. Suppl.

. Phot. Soc.

.Phys.

. Phys. Chem.

. Phys. Chim.

. Physiol.

. phjrsiol. path. gen.
. prakt. Chem.
. Psychol. Med.

. Roy. Agric. Soc.

Roy. Astron. Soc.
Canada

. Roy. Inst. Pub. Health
. Roy. San. Inst.
. Roy. Soc. N. S. Wales
. Roy. U. S. Inst
. Russ. Phys. Chem. Soc.

. Savants

.Sd.

. sd. math, physi. nat.

. Soc. Arts

. Soc. Dyers Col.

. soc. pharm. Anvers

. Soc. Telegr. Eng.

. State Med.

. Suisse chim. pharm.

. Travd

. Trop. Med.

U. S. ArtiU.

Univ. Med.

Univ. Sd. Med.
Wash. Acad. Sd.
Western Soc. Eng.

X*

Journal des Museum Godeffroy. Geogpraphische,
Sthnographische und Natiu^issenschaftHche Mitt-
heilungen

The Journal of Mycology

Journal New England Water Works Association

Journal d'Ophthalmologie

Journal ftir Omithologie

Journal de Pabricants de Papier, fonde et pubiie par

L. Piette
The Journal of Pathology and Bacteriology
Journal du petrole
Journal de Pharmade
Journal de Pharmade d' Anvers
Journal de Pharmade et de Chimie
Journal de pharmade von Elsass-Lothringen

Yakagakuzasshi (Journal of the pharmaceutical
sodety of Japan)

Journal of Pharmcology and Experimental Thera-
peutics

Journal of Photographic Supplies

Journal of the Photographic Sodety

Journal de Physique theorique et appliquee

The Joiunal of Physical Chemistry

Journal de Physique, de Chimie, et de THistoire
Naturelle

The Journal of Physiology

Journal de physiologic et de pathologic general, Paris

Erdmann's Joiunal fur praktische Chemie

Journal of Psychological Medicine and Mental Path-
ology

Journal of the Royal Agricultural Sodety

Journal of the Royal Astronomical Sodety of Canada

Journal of the Royal Institute of Public Health

Journal of the Royal Sanitary Institute

Joiunal of the Royal Sodety of New South Whales

Journal Royal United Service Institution

Journal of the Russian Physical Chemical Society

Journal of the Society of Chemical Industry

Journal des Savants

The Joiunal of Sdence

Journal de sciencias mathematicas, physicas naturaes

Journal of the Royal Sodety of Arts

Journal of the Sodety of Dyers and Colorists

Journal de pharmade, organe de la sodet6 de pharmacie

d'Anvers
Journal of the Society of Telegraphic Engineers
The Journal of State Medicine
Journal Suisse de chimie et pharmacie
The Journal of Travd and Natural History
The Journal of Tropical Medicine
Journal of the United States Artillery
Journal universd et hebdomadaire de Medecine et de

Chirurgie pratiques et des Institutions medicates
Journal LFniversel des Sdences Medicales
Journal of the Washington Academy of Sdences
Journal of the Western Sodety of Engineers

body

LIST OF ABBREVIATIONS TO UTERATURB

Jaarb. Mijnw. Nederl.

Ind.
Jahr. = Jahresbericht
Jahr. Agrik.-Chem.

Jahr. Berg- u. Huttenw.

Jahr. KJnderheilk.

Jahr. Chem.
Jahr. Gahr. Organ.

Jahr. Mineral.

Jahr. Mineral Beil.-Bd.

Jahr. Pharm.

Jahr. Phot,

Jahr. Phot. Reprod.

Jahr. Phy. Ver. Frank-
furt

Jahr. Physiol.

Jahr. Radioactiv. Elec-
tronik.

Jahr. rein. Chem.

Jahr. Tier-Chem.

Jahr. wiss. Bot.

Jamaica Inst. J.

Jamaica P.

Jamaica Soc. Arts. Trans.

Jamain, Archives Oph-
thalm.

Jap. P.

Jardine, Mag. Zool. Bot.

Jena Ann. Acad.

Jena Ann. Phys. Med.

Jena Ann. Soc. Mineral

Jena Denkschr.
Jena Geogr. Ges. Mitth.
Jena Sitzber.
Jena Zts.

Jem-Kontoret's Ann.
Johns Hopkins Biol. Lab.

Mem.
Johns Hopkins Biol. Lab.

Stud.
Johns Hopkins Univ. Circ.
Jura, Trav. Soc. Emul.

Jurjew

Just's bot. Jahr.

KaH

Jaarboek van het Mijnwezen in Nerderlandsch Oost-

Indie ^

Jahrbuch
Jahresbericht iiber die Fortschritte der Agrikultur-

chemie mit besonderer Berucksichtigung der Pflanz-

enchemie tmd Pflanzenphysiologie
Jahrbuch fur das Berg- imd Huttenwesen im Kdnig-

reiche Sachsen
Jahrbuch fiir Elinderheilkunde tmd physische Erzieh-

ung
Jahresbericht der Chemie (Liebig-Kopp)
Jahresbericht iiber die Fortschritte in der Lehre von

den Gahrungs-Organismen (Koch)
Neues Jahrbuch fur Mineralogie, Geologic und Palaeon-

tologie
Neues Jahrbuch fur Mineralogie, Geologic, und

Palaeontologie, Beilage-Band
Jahresbericht der Pharmacie
Jahrbuch der Photographic (Eder)
Jahrbuch fur Photographic tmd Reproduktiontechnik
See Frankfurt, Jahr. Phys. Ver.

Jahresbericht uber die Fortschritte der Physiologic
Jahrbuch der Radioaktivitat tmd Electronik

Jahresbericht der reinen Chemie

Jahresbericht uber der Fortschritte der Tier-Chemic

Jahrbiicher fur wissenschaftliche Botanik

Journal of the Institute of Jamaica

Jamaica Patent

Transactions of the Jamaica Society of Arts

Archives d'Ophthalmolgie

Japanese Patent

The Magazine of Zoology and Botany

Annales Academiae Jenensis

Die Jenaischen Aimalen fur Physiologic und Medicin

Annalen der Societat ftir die gesammte Mineralogie zu

Jena
Denkschriften der Medicinisch-Natiuirissenschaft-

lichen Gesellschaft zu Jena
Mittheiltmgen der geographischen Gesellschaft (fur

Thtiringen) zu Jena
Sitzungsberichte der Jenaischen. Gesellschaft fur

Medicin und Naturwissenschaft
Jenaische Zeitschrift ftir Naturwissenschaft herausge-

geben von der Medicinisch-naturwissenschaft-

lichen Gesellschaft zu Jena
Jem-Kontoret's Annaler
Memoirs from the biological laboratory of the Johns

Hopkins University
Johns Hopkins University. Studies from the Bio-
logical Laboratory
The Johns Hopkins University Circulars
Travaux de la Socidt^ d'^mtikition du Department du

Jttfa
See Dorpat

Jtist's botanischer Jahresbericht, Leipzig and Berlin
Kali

LIST OF ABBREVIATIONS TO LITSRATUR«

Ixxv

Kampen, Mag.

Kan. Acad. Sci. Trans.

Elan. Univ. Quart.
Karlsmhfi-Bact. Inst. Arb.

Karlsruhe Naturwiss. Ver.

Verb.
Kamten, Berg-Verein, Zts.

Kamten Landesmus. Jahr.

Kamten, Zts.

Karsten
Karsten, Archiv.

Kassel Ver. Naturk. Ber.
Kassel Ver. Naturk. Fest-

schr.
Kastner, Archiv. Chem.
Kastner, Archiv. Natur-

lehre
Kazan Soc. Phys.-Math.

BuU.
Kazan Soc. Natur. Proc.

Kazan Soc. Natur. Trans.

Kazan Univ. Bull.
Kazan Univ. Mem.

Kekule, Krit. Zts. Chem.

KerauL Rundschau
KewBull.

Kharkov. Math. Soc. Com-

mun.
Kiel. Mitth. Ver. Elbe.

Kid, Physiol. Inst. Arb.

Kie],Schr.

Kid Univ. Mineral. Inst.

Mitth.
Kiev Soc Natur. Mem.
Kldbenh. Bot. For.
Kidbenh. Bot. For. Fest-

skr.

KiObenh. Bot. For. Medd.
Kidbenh. Carbb. Lab.

Medd.
KiObenh. Dansk. Vid.

Selsk. Afh.

Magazin voor Wetenschappen, Kunsten, &c.
Transactions of the annual meeting of the Kan?as

Academy of Science
The Kansas University Quarterly
Arbeiten aus dem bacteriologischen Institut der tech-

nischen Hochschtde zu Karlsruhe
Verhandlungen des Nattui¥issenschaftlischen Vereins

in Karlsruhe
Zdtschrift des Berg- u. Huttenmannischen Vereins

fur Kamten
Jahrbuch des natiu-historischen Landes-Museums von

Kamten
2^tschrift des berg- und huttenmannischen Vereines

fiir Kamten
See Botan. Untersuch.
Archiv fiir Mineralogie, Geognosie, Bergbau, und

Huttenkunde
Bericht des Vereins fur Naturktmde zu Cassd
Festschrift des Vereins fiir Naturkunde zu Cassel zur

Feier seines Ftinfzigjahrigen BestehenS'
Archiv. fiir Chemie und Meteorologie
Archiv. fiir die gesammte Naturlehre

Bulletin de la Soci6t6 Physico-Mathematique de
Kazan

Proceedings of the Physico-Mathematical Section of
the Society of Naturalists of the Imperial Univer-
sity of Kazan

Transactions of the Society of Naturalists of the Im-
perial University of Kazan

Bulletin of the Imperial University of ICazan

Scientific Memoirs of the Imperial University of
Kazan

Kritische Zeitschrift fiir Chemie, Physik, tmd Mathe-
matik; see also Zts. Chem.

Keramische Rundschau

Royal (Botanic) Gardens, Kew. Bulletin of Mis-
cdlaneous Information

Communications de la Soci6t6 Mathematique de
Kharkov

Mittheilungen des Vereins nordlich der Elbe zur
Verbreitung naturwissenschaftlicher Kenntnisse in
Kid

Arbeiten aus dem Kider physiologischen Institut

Schriften der Universitat zu Kid

Mittheiltmgen aus dem Mineralogischen Institut der
Universitat Kid

Memoires de la Soci^t^ des Naturalistes de Kiev

See Bot. Tidsskr.

Festskrift, udgivet af den Botaniske Forening i
Kidbenhavn i Anledning af dens Halvhundredaars
fest, den 12 April, 1890

Meddddser fra den Botaniske Forening i Kjobenhavn

Meddddser fra Carlsberg Laboratoriet

Det Kongelige Danske Videnskabemes Sdskabs
naturvidenskabdige og mathematiske Afhand-
linger

Ixxvi

LIST OP ABBREVIATIONS TO LITERATURie

Kiobenh., Dansk.
Selsk. Skrift.

Kidbenh. Ent. For.
Kidbenh.» Oversi^

Vid.

Kidbenh., Reg. Soc. Med.

Acta.
Kidbenh., Vidensk. Forh.

Kidbenh, Vidensk. Meddel.

K. K. Ges. Aerzte
Klausenburg
Kliniek

Klug, Jahr. Insect.
Koll. Chem. Beihefte
KoUoid-Zts.

Kolozsvar Orvos-Termesz.
Tars. Ertes.

K. Svenska Vet-Akad.
Kdnigsb. Archiv.

Kdnigsb. Med. Jahr.

Konigsb. Schr.
Kosmos (Lwow)

Krain Mus.-Ver. Mitth.
Krakow Akad. (Mat.-Przy-
rod) Pam.

Krakow Akad. (Mat.-Przy-
rod) Rozpr.

Krakow, Akad. (Mat.-
Pr^rod.) Rozpr. &
Spraw.

Krakow Kom. Fizyogr.
Spraw.

Krakow, Roczn. Tow.

Nauk.
Krakau, Untersuch. Path.

Anat.

Det Kongelige Danske Videnskabemes Selskabs
Skrifter. Nattuiddenskabelig og Mathematisk
Afdeling

See Ent. Medd. (Kiobenh.)

Oversigt over det Kongelige Danske Videnskabemes
Selskabs Forhandlinger og dets Medlemmers
Arbejder i Aaret 1874(-83) . . .samt. med en Rdsum^
du Bulletin de VAcademie Royale Danoise des Sciences
el des LeUres pout Tannee 1874(-83)

Acta Regiae Societatis Medicae Havniensis .

Videnskabelige Forhandlinger ved Sioelland Stifts
Landemde

Videnskabelige Meddelelser fra den Naturhistoriske
Forening i Kjdbenhavn

See Med. Jahr.

See Kolozsvar

Kliniek

Jahrbticher der Insectenkunde, etc.

Kolloidchemische Beihefte

KoUoid-Zeitschrift

Ertesitd a "Kolozsvari Orvos-Termeszettudomanyi
Tarsulat" >nak az . . . orvosi, termeszettudomanyi

szakiileseirdl Proceedings of the Medical and

natural history sections of the Klausenburg Medical
and Natural History Society

Kongl. Svenska Vetenskaps-Akademiens Handlingar

Kdnigsberger Archiv fur Naturwissenschafften und
Mathematik

Kdnigsberger medicinische Jahrbticher; herausgegeben
von dem Verein fur wissenschaftliche Heilkunde zu
Kdnigsberg

Schriften der physikalisch-dkonomischen Gesellschaft
zu Kdnigsberg in Preussen

Kosmos. Czasopismo polskiego Towarzystwa
przjrrodnikow imienia Kopemika. (Cosmos. The
Journal of the Polish Society Naturalists founded
in honor of Copernicus)

See Laibach, Mus.-Ver. Krain Mitth.

Pamietnik Akademii Umiejetnosci w Krakowie. Wyd-
zial Matematyczno-Przyrodniczy. (Memoires of
the Academy of Science in Cracow. Section of
Mathematics and Natural Science)

Rozprawy i Spawozdania z Posiedzen Wydzialu
Matematyczno-Przyrodniczego Akademii Umiejet-
nosci. (Proceedings of the Section of Mathematics
and Natural Science of the Academy of Science)

Rozprawy i Sprawozdania z Posiedzen Wydzialu
Matematyczno-Przyrodniczego Akademii Umiejet-
nosci. (Proceedings of the Section of Mathematics
and Natural Science of the Academy of Science)

Akademija Umiejetnosci w Krakowie. Sprawozdanie

Komisyi Fizyograficznej (Academy of Science

in Cracow. Report of the Physiographical Com-
mission)

Rocznik Towarzystwa Naukowego z Uniwersytetem
Jagiellonskim Zlaczonego

Untersuchungen aus dem Pathologisch-Anatomischen
Institute in Krakau

LIST OP ABBREVIATIONS TO LITERATURE

Ixxvii

Kreutzcr's Jahr. Phot.
KrJstiania, Geogr. Sdsk.

Arb.
Kristiania, Norw. Mar.

Investig. Rep.
Kroyer, Naturhist. Tidssk.
Kuhn-Archiv.

Kult. lug.

Ktmst

Lab. Club. Trans.

Laboratory

Laibach, Jahr. Gynmas.

Laibach, Jahr. Realschule

Laibach, Jahresh.

Laibach, Mus.-Ver. Kram

Mitth.
Lancet
Landb. Cour.
Landshut Bot. Ver. Ber.
Landw. Centr.
Landw. Jahr.

Landw. Jahr. Schweiz
Landw. Presse
Landw. Versuchs-Stat.
Landw. Ztg.
Laon, Soc. Acad. Bull.
Laurent Ann. Anat.

Laurent Gerhardt, Compt.

rend.
Lausanne, Bull. Soc. Med.
Lausanne, Bull. Soc. Vaud.

Lausitz. Monatschr.

Leather

Leather Mfr.

Leather Tr. Rev.

Leather World

Lederind.

Ledermarkt

Leeds, Trans. Phil. Soc.

Leicester, Lit. Phil Soc.

Selection
Leicester Soc. Rep.

Leicester Soc, Trans.

Kreutzer's Jahresbericht der Photographic
Det Norske Geografiske Selskabs Arbog

Report on Norwegian Fishery and Marine Investiga-
tions

Naturhi^orisk Tidsskrift

Kuhn-Archiv. (formerly Berichte aus dem physio-
logischen Laboratorium und der Versuchsanstalt des
Landwirtschaftlichen Instituts der Universitat Halle

Der Kultur-Ingenieur (F. Dunkelberg)

Kunstoffe

Transactions of the Laboratory Club

The Laboratory

Jahresbericht des k. k. Ober-Gynma^ums in Laibach

Jahresbericht der k. k. selbstandigen Unter-Realschule
zu Laibach

Jahresheft des Vereins des Krainischen Landes Mus-
eums in Laibach

Mittheilungen des Museal-Vereins fur Krain

The Lancet, London

Landbouw-Courant

Bericht des Botanischen Vereines in Landshut

Landwirthschaftliches Centralblatt fiflr Deutschland

Landwirthschaftliche Jahrbiicher. Ze tschrift f fir wis-

senschaftliche Landwirthschaft und Archiv. des

Kdniglich Preussischen Landes-Oekonomie-KoUeg-

iums
Landwirtschaftliches Jahrbuch der Schweiz
Landwirtschaftliche Presse
Die landwirthschaftlichen Versuchs-Stationen
Landwirtschaftliche Zeitung
Bulletin de la Sod^t^ Academique de Laon
Annales Prancaises et Etrangeres d* Anatomic et de

Physiologic, appHquees a la Medecine et a THistoire

Naturelle
Comptes rendus Mensuels des Travaux Chemiques

Bulletin de la Sod^t^ Medicale de la Suisse Romande

Bulletin des Seances de la Soci^t^ Vaudoise des Sciences
Naturelles

Lausitzische (und neue Lausitzische) Monatschrift
Organ der Oberlausitzischen Gesellschaft der Wissen.
schaften

Leather

Leather Manufacturer

Leather Trades Review

Leather World, The

Lederindustrie (Deutsche Gerber-Zeitung)

Ledermarkt, Der. (See also Collegium)

Transactions of the Philosophical and Literary So-
ciety of Leeds

Selection of Papers, of the Literary and Philo-
sophical Society of Leicester

Leicester Literary and Philosophical Society. . .Re-
port of the Council »*. p ► 'i

Transactions^oflthe Leicester Literary and Philo-
sophical Society

Ixxviii

UST OF ABBREVIATIONS TO LITERATURE

Leide

Leiiden, Ann. Acad.
Leiden, Tijdschr. Entom.
Leipzig, Abh. Jablon. Ges.

Leipzig, Abh. Math. Phys.

Leipzig, Arbeit. Physiol.

Anst.
Leipzig, Astron. Ges. Vier-

telj.
Leipzig, Ber. Math. Phys.

Leipz. Parb. Ztg.
Leipzig Jablon. Preisschr.

Leipzig, Monatschr. Text.

Ind.
Leipzig, Naturf. Ges. Sitz-

ber.
Leipzig, Physiol. Anst.

Arb.
Leipzig, Schr. Naturf. Ges.
Leipzig, Verh. Med. Ges.
Leyden Mus. Notes
Leo, Mag.

Leoben, Berg. u. Htitt.

Jahr.
Leonhard Bronn
Leonhard Bronn, Jahr.

Leonhard Bronn, Neu.

Jahr.
Leonhard, Taschenbuch
Leonhard, Zts.
Leopold.-Carol. Deutsch.

Alcad. Naturf.
Leopoldina

Letters on Brewing
Les Mondes
Licht.

Liege, Ann. Acad.
Liege Assoc. Ingen. Annu.
Liege, Mem. Soc. Emtd.
Liege, Mem. Soc. Sd.

Leige Lab. Fredericq Trav.

Lille Inst. Zool. Trav.

See Leyden

Annales Academiae Lugdtmo-Batavae

Tijdschrift voor Entomolc^e

Abhandlungen bei Begriindung der k. Sachsischen
Gesellschaft der Wissenschaften am Tage der
zweihundertjahrigen Geburtsfeier Leibnizens

Abhandlungen der Mathematisch-Physischen Classe
der Koniglich Sachsischen Gesellschaft der Wissen-
schaften

Arbeiten aus der physiologischen Anstalt zu Leipzig

Vierteljahrsschrift der Astronomischen Gesellschaft

Berichte uber die Verhandlungen (Math. Phys.

Classe) der K5niglich Sachsischen Gesellschaft der

Wissenschaften zu Leipzig
Leipziger Farber- und Zeugdrucker-Zeitung
Preisschriften gekr5nt und herausgegeben von der

furstlich Jablonowski' schen Gesellschaft zu Leipzig
Leipziger Monatsschrift fur Textil Industrie

Sitztmgsberichte der Naturforschenden Gesellschaft

zu Leipzig
Arbeiten aus der Physiologischen Anstalt zu Leipzig

Schriften der Naturforschenden Gesellschaft zu Leipzig
Verhandlungen der Medicinischen Gesellschaft
Notes from the Leyden Museum
Magazin ftir Heilkunde und Natiuivissenschaft in

Pohlen
Berg- tmd Huttenmannisches Jahrbuch der k. k.

Montan. Lehranstalten zu Leoben und Pribram
See Neues Jahr. Mineral
Jahrbuch fur Mineralogie, Geognosie, Geologic, und

Petrefaktenkimde
Neues Jahrbuch fur Mineralogie, Geognosie, Geologie

und Petrefaktenkunde
Taschenbuch fiir die gesammte Mineralogie
Zeitschrift fur Minendogie
See Ac. Nat. Curios. Nova Acta. Leopoldina

Leopoldina. Amtliches Organ der Kaiserlichen Leo-
poldino-Carolinischen Deutschen Akademie der
Naturf orscher

Letters on Brewing

Revue hebdomadaire des Sciences et de leurs application

Licht: Zeitschrift fur Photographic: herausgegeben
vom Photographischen Verein. ziu* Berlin

Annales Academiae Leodiensis

See Rev. Univ. Mines

Memoires de la Socidt^ Libre d' Emulation de Leiege

Memoires de la Soci^t^ (Royale) des Sciences de TAgri-
culture, et des Arts a Liege

Universite de Liege. Institut de Physiologic. Tra-
vaux du Laboratoire de Leon Fredericq

Travaux de 1' Institut Zoologique de Lille et du Labora-
toire de Zoologie Maritime de Wimereux (Pas-de-
Calais). Travaux de la Statign Zoolo^que de
Wimereux

LIST OF ABBREVIATIONS TO UTERATURB

Ixxix

Lille Mem. Soc.

Lille, Mem. Soc. Sci.

Lille, Seances Publ.
Lille, Trav.

Lille, Trav. Mem.
Lima, Mem. Cien. Nat.

Limbourg, Soc. Sci. Bull.

Limoges, Assises

Lindblom, Bot. Notiser

Limi

Linn Hntom.

Linn. Soc. J.

Linn. Soc. Trans.
Linn. Soc. Proc.
Linneska Samf. Handl.
Linz, Ber.

Lisboa, Acad. Sci. Mem.

Lisboa, Actas

Lisboa, Ann.
Lisboa, J. Math. Sci.

Litterar. Annal.
Liverpool Biol. Soc. Proc.

Liverpool, Lit. Phil. Soc.

Proc.
Liverpool Mar. Biol.

Comm.
Liverpool Med. Chir. J.
Liverpool School Trop.

Med. Mem.
Liverpool, Thompson

Yates Lab. Rep.
Loc. Gov. Bd. Rep. (Med.

Off.)

London

London, Ann. Med. Surg.

London, Cryst. Soc. Proc.
London Elec. Soc. Proc.
London, Fed. Inst. Brew-
ing J.
London J. Med.

London, Med. Phys. J.
Ixmdon, Med. Soc. Trans.

Memoires de la Soci4t6 (Imperiale) des Sciences, de

I'Agriculture et des Arts de Lille
Memoires de la Soci6t6 (Royale) des Sciences, etc., a

LiUe
Seances Publiques de la Soci6t6 des Amateurs
Recueil des Travaux de la Soci6t6 d' Amateurs des

Sciences, de I'Agriculture, et des Arts a Lille
Travaux et Memoires de I'Universite de Lille
Memorias de Ciencias Naturales y de Industrial

(Lima)
Bulletin de la Soci6t6 Scientifique et Litteraire du

Limbourg
Assises scientifiques de Limoges (Institut des Provices

de France) *

Botaniska Notiser

Linnaea: ein Journal fiir die Botanik
Linnaea Entomologica
The Jotunal of the Linnean Society. Botany and

Zoology
The Transactions of the Linnean Society of London
Proceedings of the Linnean Society of London
Linneska Samfundets Handlmgar for ar 1832
Bericht tiber das Museum Frandsco-Carolinum in

Linz
Historia e Memorias da Academia Real das Sciencias

de Lisboa
Actas das Sessoes da Academia Real das Sciencias de

Lisboa
Annaes das Sciencias e Lettras
Jomal de Sciencias Mathematicas, Physicas e Naturaes

publicado sob os Auspicios da Academia Real das

Sciencias de Lisboa
Litterarische Annalen der gesammten Heilkunde
Proceedings and Transactions of the Liverpool Bio*

logical Society
Proceedings of the Literary and Philosophical Society

of Liverpool
See Liverpool Biol. Soc. Proc.; Liverpool Biol. Soc.

Proc. & Trans.; Liverpool Lit. Phil. Soc. Proc.
Liverpool Medico-Chirurgical Journal
Liverpool School of Tropical Medicine. Memoirs

The Thompson Yates Laboratories Report

. . . Annual Report of the Local Government Board.
Supplement containing the Reports of the Medical
Officer

See Int. Congr. Hyg. Trans., 1891; Int. Congr. Zool.
Proc. 1898

Annals of Medicine and Surgery, Records of the oc-
curring Improvements, &c.

Proceedings of the Crystallological Society

Proceedings of the London Electrical Society

Journal of the Federated Institutes of Brewing con-
taining the Transactions of the various Institutes

London Journal of Medicine

The Medical and Physical Journal

Transactions of the Medical Society of London

Ixxx

LIST OF ABBREVIATIONS TO LITERATURB

London, Obstet. Soc.

Trans.
London, Odont. Soc. Trans.
London Path. Soc. Trans.
Lond. Phot. Soc.
London Phys. Soc. Proc.
London PhysioL J.
London Poly. Rev.
London, Poly. Mag.

London, Sci. Soc. Proc.
London, Soc. Imp. Med.

Trans.
Lotos

Lousiana Planter
Louvaine, Ann. Acad.
Lowell Obs. Ann.
Lucca, Atti Accad.

Lumi^e
Ltuni^re elec.
Lund, Acta Univ.

Lund Bot. F6r.

Lund, Phys. Sallsk. Tidskr.

Luneb., Denkschr.

Luneb., Jahr. Naturwiss.

Ver.
Luneb. Jheft. Naturwiss.

Ver.
Luxemb., Inst. Roy. Publ.

Luxemb. P.

Luxemb. Soc. Bot. Rec.

Mem. Trav.
Luxemb. Soc. Sci. Natur.

Lyon

Lyon, Acad. Sci. Mem.

Lyon Mus. Hist. Natiu*.

Archiv.
Lyon Soc. Agric. Ann.

Lyon Soc. Bot. Ann.
Lyon, Soc. Linn. Ann.
Lyon, Soc. Linn. Compt.

rend.
Lyon, Soc. Sci. Med. Mem.

Lyon Univ. Ann.
Maandbl. Natuurweten.

Transactions of the Obstetrical Society of London

Transactions of the Odontological Society of London

Transactions of the Pathological Society of London

London Photographic Society

Proceedings of the Physical Society of London

London Physiological Journal

The London Polytechnic Review and Magazine

Polytechnic Magazine and Journal of Science, Letters,

and Pine Arts
Proceedings of the Scientific Society of London
Transactions of the Society for the Improvement of

Medical and Chirugical Knowledge
Lotos, Jahrbuch ftir Naturwissen^rhaft im Auftrage

der Vereines "Lotos"
Louisiana Planter and Sugar Maufacttirer, The
Annales Academiae Lovaniensis
Annals of the Lowell Observatory
Atti della R. Accademia Lucchese di Scienze, Lettere,

et Arti
La Lumi^re; Revue de la Photographic
Lumidre electrique. La
Acta Universitatis Lundensis. Lunds Iniverdtets

Ars-skrift. Afdelningen for Mathematik och Natur-

vetenskap
See Bot. Centrbl.; Bot. Notiser
Physiografiska Sallskapets Tidskrift
Denkschriften des natiuivissenschaftlichen Vereins

fur das Fusrtenthum Liinebtu-g
Jahresbericht iiber die Thatigkeit des naturwissen-

schaf tUchen Vereins in Lunebiu'g
Jahresheite des Naturwissenschaftlichen Vereins fur

das Fiirstentum Ltineburg
Publications de Tlnstitut Royal Grand-Ducal de

Luxembourg: Section des Sciences Naturelles
Luxembourg Patent
Recueil des Memoires et des Travaux publics par la

Soci6t6 Botanique du Grant-Duche de Luxembourg
Soci6t6 des Sciences Naturelles du Grand-Duche de

Luxembourg
Lyon scientifique et industriel
Memoires de TAcademie des Sciences, Belles-Lettres,

et Arts de Lyon
Archives du Museum d'Histoire naturelle de Lyon

Annales de la Soci6t^ d' Agriculture, Histoire naturelle
et Arts utiles de Lyon. Annales de kt Soci^t6
d'Agricultiu^, Sciences et Industrie de Lyon

Annales de la Soci^t^ Botanique de Lyon

Annales de Soc^ti6 Linneenne de la Lyon

Comptes Rendus des Travaux de la Soci^t^ de Mededne

Memoires et Comptes-Rendus de la Soci^t^ des

Sciences Medicales de Lyon
Annales de TUniversite de Lyon
Maandblad voor Natuurwetenschappen, uitgegeven

door de Sectie voor Natuurwetenschappen van het

Gennotschap ter Bevordering van Natuur-, Geneea-

en Heelkunde te Amsterdam

UST OF ABBREVIATIONS TO UTKRATURE

Ixxxi

Madurian Lyceum, Con-

trib.
Macon Acad. Ann.

Macon, Soc. Agric. Compt.

rend.
Macon Soc. Compt. rend.

Madras J.

Madras Quart. J.

Madrid

Madrid Acad. Cien. Mem.

Madrid, Anales Hist.

Natur.
Madrid, Anales Minas
Madrid, Anuar.
Madrid, Bol.

Madrid, Ingen. Ind. Anales
Madrid, Mem.
Madrid, Revista

Madrid, Soc. Hist. Natur.

Anales
Mag. Gesammt. Thierheilk.
Mag. Natur. Hist.

Mag. Natur. Phil.

Mag. Naturvid.

.Mag. Zool.

Magdeb. V. Ver. Abh.

Naturwiss.
Magdeb. V. Ver. Pestschr.

Naturwiss.

Magdeb. V. Ver. Jahr. Abh.

Naturwiss.
Magendie, J. Physiol.
Magyar Akad. Ertes.

(Math. Termesz.)

Magyar Boripar
Magyar Nemzeti Muzeum^
Magirar Termt. Tars.
Magyar Tud. Akad. Ertes.

Magyar Tud. Akad. Ertek.

(Math.)

Contributions of the Maclurian Lyceum to the Arts

and Sciences
Annales de I'Academie de Macon. Soci^t^ des Arts,

Sciences, Belles-Lettres et (d*) Agriculture (de

Saone-et-Loire)
Comptes Rendus des Travaux de la Soci^t^ d' Agri-
culture, Sciences, et Belles-Lettres
Compte Rendu des Travaux de la Soci^t^ (d'Agri-

culture), des Sciences, Arts et Belles-lettres, de

Macon
The Madras Journal of Literatiu'e and Science
Madras Quarterly Journal of Medical Science
See Congr. Int. Hig. Act. 1898
Memoires de la Real Academia de Ciencias Exactas,

Fisicas y Naturales de Madrid
Anales de Historia Natural

Anales de Minas

Anuario del Real Observatorio de Madrid

Boletin Ofidal del Ministerio de Comercio

Anales de la Asociacion de Ingenieros Industriales

Memorias de la Real Academia de Ciencias

Revista de los Progresos de las Ciencias exactas,

fisicas, y naturales
Anales de la Sociedad Espanola de Historia Natural

Magazin ftir die gesammte Thierheilkimde

The Magazine of Natural History, and Journal of
2^1ogy, Botany, Mineralogy, Geology, and
Meteorology

The Magazine of Natural Philosophy

Magazin for Naturvidenskabeme

Magasin de Zoologie

Abhandlungen des Natiuivissenschaftlichen Verehis
zu Magdeburg

Festschrift zur Feier des 25 jahrigen Stiftungstages
des Naturwissenschaftlichen Vereins zu Magde-
burg

Jahresbericht und Abhandlungen des naturwissen-
shaftlichen Vereins in Magdeburg.

Journal de Physiologic, experimentale et pathologique

Maprar Akademiai Ertesitd. A mathematikal, es
Termeszettudomanyi osztalyok kdzldnye. (Re-
port of the Himgarian Academy. Communications
of the Mathematical and Natural Science
Sections)

Magyar Bdripar

See Termr. Fuz.

See Termt. Kozldn.

A Magyar Tudomanyos Akademia Ertesitoje. (Re-
port of the Hungarian Academy of Science)
Akademiai Ertesito a Maigyar Tud. Akademia
Megbizasabol. (Report by the Committee of the
Hungarian Academy of Science)

Ertekezesek a Mathematikal Tudomanyok kOrebol.
Kiadja a Magyar Tudomanyos Akademia.
(Memoirs in the Mathematical Sciences, Pub-
lished by the Himgarian Academy of Science)

Ixxxii

UST OF ABBREVIATIONS TO LITERATURE

Magyar Tud. Akad. Ertek.
(Termt.)

Magyar Tud. Akad. Evk.

Maine Loire Soc. Mem.

Acad.
Majocchi, Ann. Fis. Chim.
Malpighia
Malta P.

Malvern Field Club Trans.
Manufact. and Build.
Manchester, Engin. Proc.

Manchester, Lit. Phil. Soc.

Mem.
Manchester, Lit. Phil. Soc.

Proc.
Manchester Micro. Soc.

Trans.
Manchester, Owens Coll.

Biol. Lab. Stud.
Manchester, Owens Coll.

Stud. Biol.
Mannheim, Jahr.

Mans, Soc. Agric. Bull.
Mans, Soc. Bull.

Mans, Soc. Roy. Trav.

Marburg, Ges. Naturwiss.

Schr.
Marianini
Mame, Soc. Agric. Compte

Annuel
Mame, Soc. Agric. Seance

Marseille, Ann. Sci.

Marseille Fac. Sci. Ann.
Marseille Lab. Zool. Mar.

Trav.
Marseille, Mem. Acad.
Marseille, Mem. Soc. Emul.
Marseille Mus. Ann.
Maschin. -Constr .
Maschinenb.
Mass. Bd. Health Report

Mass. Insects Report

Mass. Med. Soc. Coraraun.
Mat. grasses

Maurice, Soc. Hist. Natur.
Rapp.

Ertekezesek a Termeszettudomanyok korebol.

Kiadja a Magyar Tudomanyos Akademia.

(Memoirs in the Natural Sciences. Published by

the Hungarian Academy of Science)
A Magyar Tudomanyos Akademia Evkonyvci.

(Annals of the Hungarian Academy of Science)
Memoires de la Societ6 Academique de Maine et

Loire
Annali di Fisica, Chimica, etc.
Malpighia. Rassegna mensuale di Botanica
Malta Patent

The Transactions of the Malvern Natiu'alists' Club
The Manufacturer and Builder
Proceedings of the Manchester Institution of Engi-
neers
Memoirs of the Literary and Philosophical Society of

Manchester
Proceedings of the Literary and Philosophical Society

of Manchester
Manchester Microscopical Society. Transactions and

Annual Report
Studies from the Biological Laboratories of the Owens

College
Studies in Biology from the Biological Department of

the Owens College
Jahresbericht des Mannheimer Vereins ftir Natur-

kunde
Bulletin de la Soci6t6 d' Agriculture, etc., de la Sarthe
Bulletin de la Soci6t6 (Royale) d*Agricultiu'e, Sciences

et Arts du Mans
Analyse des Travaux de la Soci6t6 (Royale) des Arts

du Mans
Schriften der Gesellschaft zur Beforderung der

gesammten Natiuwissenschaften zu Marburg
See Mem. Fis. Sperim.
Compte annuel et Sommaire des Travaux de la

Soci6te Agricole, etc., du departement de la Mame
Seance publique de la Soci^t^ d'Agrictdtiu-e, etc., du

departement de la Mame
Annales de Sciences et de 1' Industrie du midi de la

France
Annales de la Faculte des Sciences de Marseille
See Marseille Mus. Ann.

Memoires publics par I'Ac^demie de Marseille

Memoires de la Society d' Emulation de la Provence

Annales du Musee d'Histoire naturelle de Marseille

Der praktische Maschinen-Construkteur (W. Uhland)

Der Maschinenbauer

Annual Report of the State Board of Health, Lunacy
and Charity of Massachusetts. Annual Report of
the State Board of Health of Massachusetts

. . .Annual Report on the Injurious and Beneficial In-
sects of Massachusetts

Massachusetts Medical Society's Communications

Le Matieres grasses

Septieme Rapport Annuel sur les Travaux de la
Societe d'Histoire Naturelle de I'Lle Maiu'ice

LIST OF ABBREVIATIONS TO LITERATURE

Ixxxiii

Mauritius, Meteorol. Soc.

Proc.
Mauritius, Meteorol. Soc.

Trans.
Matuitius P.
Mauritius Roy. Soc. Trans.

Meaux, Bull. Soc. Archeol.

Mechan. Kngin. Inst. Proc.
Meckel, Archiv.
Meckel, Deut. Archiv.
Med. Assoc. J.

Med. Bot. Soc. Trans.

Med. Chem. Unters.

Med. Chir. Soc. Proc.

Med.-Chir. Trans.
Med. Chir. Ztg.
Med. Congr.

Med. Jahr.

Med. Klinik.

Med. nattuiinss. Archiv.

Med. Off. India Sci. Mem.

Med. Phys. J.

Med. Rec.

Med. Times

Med. Trans.

Med. Wochenschr.

Med. Ztg. Russ.

Medd. Gronland

Medd. K. Vetenskapsakad.

Nobel-inst.
Meisner, Ann.

Meisner, Anzeiger

Melbourne

Mem. accad. Lined

Mem. Accad. Sci. Torino

Mem. Chem. Soc.

Mem. Coll. Sci. Eng. Kyoto

Mem. Fis. Sperim.

Mem. Imp. Mineral. Soc.

Petrograd
Mem. Lepidopt., St.

Petersb.

Proceedings, &c., of the Meteorological Society of

Mauritius
Transactions of the Meteorological Society of Mau-
ritius
Mauritius Patent
Transactions de la Soci^t^ Royale des Arts et des

Sciences de Maurice
Bulletin de la Soci6t6 d'Archeologie, Sciences, Lettres

et Arts du dept. de Seine et Mame
Institution of Mechanical Engineers. Proceedings
Archiv. fur Anatomic und Physiologic «

Deutsches Archiv. fur die Physiologic
Jotunal edited for the Provincial Medical and Surgical

Association
Transactions of the Medico-Botanical Society of

London
Medidnish-chemische Untersuchungen; aus dem

Laboratorium fur angewandte Chemie zu Tubingen
Proceedings of the Royal Medical and Chirurgical

Sodety of London
Medico-Chirurgical Transactions
Medidnisch-chirurgische Zeitung
See Congr. Int. Med. C. R., Congr. Int. Sci. Med.

C. T., Congr. Med. Int. Atti., Int. Med. Congr.

Trans., Int. Med. Congr. Verb.
Medizinische Jahrbiicher, von der K. K. Gessellschaft

in Wien
Medizinische Klinik

Medizinisch-naturwissenschaftliches Archiv.
Scientific Memoirs by Medical Officers of the Army of

India
The Medical and Physical Jotunal
The Medical Record, N. Y.
The Medical Times, London
Medical Transactions
Medizinische Wochenschrift
Medidnische Zeitung Russlands
Meddddser om Gronland
Medddanden fran K. Vetenskapsakademiens Nobel-

institut
Annalen der allgemdnen Schweizerischen Gesdlschaft

ftir die gesammten Naturwissenschaften
NaturwissenschaftUcher Anzdger der Allgemdnen

Schweizerischen Gesdlschaft ftir die gesammten

Naturwissenschaften
See Victoria
Memorie della r. accademia dd Lined, Classe di

scienze fisiche> mathematiche e nattu^i
Memorie della Reale Accademia delle Scienze di

Torino
Memoirs and proceedings of the Chemical Sodety of

London prior to 1848
Memoirs of the College of Science and Engineering,

Kyoto Imperial University
Memorie di Fisica sperimental
Memoirs of the Imperial Mineralogical Sodety of

Petrograd
Memoires stu- les Lepidopteres

Ixxxiv

UST OF ABBREVIATIONS TO LITERATURE

Mem. Manch. Lit. Phil.

Soc.
Mem. Med. Milit.

Mem. poud. salp.
Mem. rev. soc. den.

"Antonio Alzate"
Mem. Soc. Ing. civ.

Mem. Soc. Nat. Kiev.
Mem. Vfildamesi
Mende, Soc. Agric. BulL

Mende, Soc. Agric. Mem.

Merck's Ann. Rep.

Merck's Archiv.

Messenger Math.

Met.

Met. Chem. Eng.

Met. ital.

Met. Rev.

Metal Ind.

Metal Tech.

MetaU. Ind. Ztg.

Metallarb.

Metallurgie

Metaxa, Ann. Med. Chir.

Metz Acad. Mem.

Metz, Assises

Metz, Seance Gen.

Metz Soc. Hist. Natur.

BuU.
Mex.
Mex. P.

Mex. Mus. Anales
Mex. Registro Trim.

Mex. Soc. "Alzate" Mem.
Mexique Archiv. Comm.
Sci.

Meyer Bros. Drug.
Meyer Jahr. Chem.
Michigan, Fish Comm. Re-
port

Micro. J.

Micro. Soc. J.

Micro. Soc. Trans.

Midi. Drug.

Midi. Med. Surg. Rep.

Midi. Quart. J. Med. Sci.

Milano, Ann. Sdenz.

Memoirs and Proceedings of the Manchester Literary

and Philosophical Society
Recueil de Memoires de Mededne, de Chirurgie et de

Pharmade Militaires
Memorial des poudres et salpetres
Memorias y revista de la sociedad cientifica "Antonio

Alzate"
Memoires et Compte-Rendu des travaux de la Sod^t6

des Ingenieurs Civils, etc.
Memoirs of the Sodety Nat. Kiev.
Memorie Valdamesi
Bulletin de la Sod^t^ d' Agriculture, Industrie,

Sdences, et Arts de departement de la Lozere
Memoires et Analyses des Travaux de la Sod^t6

d'Agriculture, Commerce, Sdences, et Arts de la

ville de Mende, departement de la Lozere
Merck's Annual Report
Merck's Archives, New York
The Messenger of Mathematics
Metallurgical-Metallurgia
Metalltu-gical and Chemical Engineering
Metallurgia italiana, La
The Metallurgical Review
The Metal Industry
Metal Technik

Deutsche Metall-Industrie-Zeittmg
Der Metallarbeiter
Metallurgie

Annali medico-chirurgici.
Memoires de I'Academie (Imperiale) de Metz
Assises sdentifiques de Metz (Institut des Provinces

de France)
Sod^t6 des Lettres, Sdences, Arts, et Agriculture de

Metz
Bulletin de la Soci6t^ d'Histoire natureUe de Metz

Mexican, Mexico, Mexicane
Mexican Patent

Anales dd Museo Nadonal de Mexico
Registro trimestre, o Colecdon de Memorias de
Historia, Literatura, Ciendas, etc., por una
Sodedad de Literatos
Memorias de la Sodedad Cientifica "Antonio Alzate"
Archives de la Commission Sdentifique du Mexique,
publiees sous les auspices du Ministere de I'ln-
struction Publique
Meyer Brothers Druggist, St. Louis
R. Meyer's Jahrbuch der Chemie
Biennial Report of the State Board of Fish Com-
missioners. (Contains the Michigan Fish Comm.
Bull.)
Quarterly Journal of Microscopical Sdence
Journal of the Royal Microscopical Society
Transactions of the Microscopical Society of London
Midland Druggist and Pharmaceutical Review
Midland Medical and Surgical Reporter
The Midland Quarterly Journal of Medical Sdences
Annali di Sdenze e Lettere

I.IST OF ABBREVIATIONS TO UTHRATURB

Ixxxv

MDano, Atti Ginnas.

Milano, Atti 1st. Lomb.

Milano, Atti Soc. Ital.
Milano, Cagnola Atti

Milano, Giom. Soc. Incor.

Milano, 1st. Lomb.

Adunanze
Milano, 1st. Lomb. Rap-

porti
Milano, 1st. Lomb. Rend.

Milano, Mem. 1st. Lomb.

Milano, Mem. 1st. Lomb.

Vcneto
Milch. Zentr.
MUch Ztg.
Min. Eng. World
Min. J.
Min. Rev.
Min. Sci.
Min. Sci. Press
Min. Smelt. Mag.

Min. Soc. J.
Mineral. Mag.

Mineral. Mitth.
Mineral. Petr. Mitth.

Mines and Minerals
Minn. Acad. Sci. Btdl.

Minn. Acad. Sci. Pap.

Minn. Bot. Stud.

Miquel, Btdl.

Misc. Ent.
Mitau, Quatember
Mitth. Artil. Geniew.

Mitth. Bdhmen. Archit.

Ing. Ver.
Mitth. Centralst. Wiss.-

tech. Unters.
Mitth. Gewerbever. Nassau
Mitth. Kais. Gesundhts.

Mitth. Kdnigl. Material-
pruhmgsamt

Mitth. Hannov. Gewer-
bever.

Atti dell' I. R. Ginnasio Liceale Convitto Longone in

Milano
Atti deir L R. Istituto Lombardo di Scienze, Lettere,

ed Arti
Atti della Societa Italiana di Scienze Natural!
Atti della Pondazione Scientifica Cagnola dalla sua

istituzione in poi.
Giomale della Societa d'Incorragiamento delle Scienze,

etc., stabilita in Milano
Solenni Admianze del R. Istituto Lombardo di Scienze

e Lettere
Rapporti sui Progress! delle Scienze del R. Istituto

Lombardo di Scienze
Rendiconti dell' Istituto Lombardo di Scienze e

Lettere : — Classe di Scienze matematiche e natural!
Memorie dell' I. R. Istituto Lombardo di Scienze,

etc.
Memorie dell' I. R. Istituto del regno Lombardo-

Veneto
Milchwirtschaftliches Zentralblatt
Milch Zeitung

Mining and Engineering World
The Mining Journal

Mining Review, a Monthly Record of Geology
Mining Science
Mining and Scientific Press
The Mining and Smelting Magazine: a monthly

review of Practical Mining, Quarrying, and Metal-
lurgy
See Min. Mag.
The Mineralogical Magazine and Journal of the

Mineralogical Society of Great Britain and Ireland
Mineralogische Mitthdlungen
(Tschermak's) Mineralogische und Petrographische

Mittheilungen
Mines and Minerals
Bulletins of the Minnesota Academy of Natural

Sciences
The Minnesota Academy of Natural Sciences at

Minneapolis, Minn. Occasional Papers
Geological and Natural History Survey of Minnesota.

Minnesota Botanical Studies
Bulletin des Sciences Physiques et Naturelles en

Neerlande
Miscellanea Entomologica
Die Quatember

Mittheilungen tiber Gegenstande des Artillerie- und
- Genie-wesens
Mittheilungen des Architekten und Ingenieur Vereins

im Kdnigrdche Bdhmen
Mittheilungen aus der Centralstelle fur wissen-

schaftlichtechnische Untersuchungen
Mittheilungen fur den Gewerbeverin ftir Nassau
Mittheilungen aus dem Kaiserlichen Gesundheitsamte,

Berlin
Mitteilungen aus dem Kdniglichen Material prufung-

samt zu Gross Lichterfelde West
Mittheilungen des Gewerbevereins ftir Hannover

Ixxxvi

LIST OF ABBREVIATIONS TO LITERATURE

Mitth. Lebensm. Hyg.

Mifth. Malerei
Mitth. konig. Prufungsans.
Wasser-versorgung

Mitth. Tech. Gew. Mus.
Mitth. Techn. Versuch-

samtes
Mitth. Zool. Sta. Neai)el

Mo. Insects Report

Mod. Sugar Planter
Modena, Accad. Sci. Mem.

Modena, Annu. Soc. Natur.
Modena Atti Soc. Natur.
Modena, Mem. Soc. Ital.

Modena, Relazione

Moigno, Annu. Cosmos
Mois chim. electrochim.
Mois min. met.
Mois sci. ind.
Moleschott, Unters.

Moll, Ann.
Moll, Efemeriden
Moll, Jahr. Berg.
Moll, Neue Jahr.
Mon. ceram. verr.

Mon. cord.
Mon. fils. tiss.
Mon. Ind.
Mon. Ind. Beige
Mon. Pap.
Mon. Sci.
Mon. teint.

Monats.

Monats. Dermatol.
Monatsbl. Hannover Gewer-

bever.
Monatschr^ Text.-Ind.
Monatschr. Zahn.
Montevideo Mus. Nac.

Anales
Monthly Amer. J. Geol.
Monthly Archiv. Med. Sci.

Mitteilungen aus dem Gebiete der Lebensmittelimter-

suchung und Hygiene veroffentlicht vom Schweizer

Gcsundheitsamt
Technische Mitteilungen fur Malerei
Mitteilungen aus der koniglichen Priifungsanstalt fflr

Wasser-versorgung und Abwasser beseitung zu

Berlin
Mitteilimgen aus dem Technischen Gewerbe Museum
Mittheilungen des k. k. Technischen Versuchsamtea

Mittheilungen aus der zoologischen Station zu Neapel.

etc.
Annual Report on the Noxious, Beneficial and other

Insects, of the State of Missouri, made to the State

Board of Agriculture
Model Sugar Planter, The
Memorie della Regia Accademia di Scienze, Lettere

ed Arti di Modena
Annuario della Societa dei Naturalisti in Modena
Atti della Societa dei Naturalisti di Modena
Memorie di Matematica e di Fisica della Societa

Italiana delle Scienze
Relazione delle Adunanze della R. Accademia di

Scienze, Lettere, ed Arti di Modena, nell' Anno

Academico 1842-43
Annuaire du Cosmos
Mois chimique et electrochimique, Le
Mois minier et metallurgique, Le
Mois scientifique et industriel, Le
Untersuchungen zur Naturlehre des Menschen und

der Thiere
Annalen der Berg- und Hiittenkimde
Efemeriden der Berg- und Hiittenkunde
Jahrbiicher der Berg- und Hiittenkunde
Neue Jahrbucher der Berg- und Hiittenkimde
Moniteur de la ceramique de la verrerie et jotunal du

ceramiste et du chaufoumier (renins)
Moniteur de la cordonnerie
Moniteur 'des fils et tissus
Moniteur Industriel
Moniteur Industriel Beige
Moniteur Papeterie
Moniteiu- Scientifique (Quesneville)
Moniteur de la teinture des apprets et de Timpression

des tissus
Monatshefte fiir Chemie und verwandte Theile

anderer Wissenschaften. Gesammelte Abbhand-

lungen aus den Sitzungsberichten der kaiserlichen

Akademie der Wissenschaften
Monatshefte fur praktische Dermatologie
MonatsbLatt des Gewerbevereins fiir Hanover

Leipziger Monatsschrift fiir Textil-Industrie

Monatschrift fiir Zahnarzte

Anales del Museo Nacional de Montevideo

The monthly Journal of Geology and Natural Science
Monthly Archives of the Medical Sciences

LIST OF ABBREVIATIONS TO LITERATURE

Ixxxvii

Monthly Cons. & Trade

Report
Montpellier, Acad. Proces-

Verb.
Montpellier, Acad. Sci.

Mem.
Montpellier Inst. Zool.

Trav.

Montpellier, Mem. Acad.

Sect. Med.
Montpellier, Recueil. Bull.

Montreal Natur. Hist. Soc.

Proc.
iMontreal Pharm. J.
Montsouris
Morphol. Arb.
Morphol. Jahr.
Moscou

M06COU, Comment. Soc.

Phys. Med.
Moscou, Soc. Natur. Bull.
Moscou, Soc. Natur. Mem.

Moscou, Soc. Natur. Nouv.

Mem.
Moscow Soc. Sd. Bull.

Moscow Univ. Mem.

(Natur. Hist.)
Moscow Univ. Mem. (Phys.

Math.)
Moselle, Bull. Soc. Hist.

Natur.
Moselle, Trav. Soc. Sci.

Med.
Mov. Pict. World
Mulder, Archief .
Mulder, Scheik. Verh.
MuUer, Archiv.

Munchen, Akad. Abh.

Mtinchen, Akad. Sitzber.

Munchen Bot. Ver.
Munchen, Bull. Akad.
Munchen, Denkschr.

Munchen, Kntom. Ver.

Mitth.
Mtinchen, Gelehrte Anz.

The monthly Consular and Trade Reports

Extraits des Proces-Verbaux des Seances de I'Academie

des Sciences et Lettres
Academic des Sciences et Lettres de Montpellier

Travaux originaux du Laboratoire Zoolique de la

Faculte des Sciences de Montpellier et de la Station

Maritime de Cette
Memoires de TAcademie des Sciences et Lettres:

Section de la Medecine
Recueil des Bulletins publics par la Soddt^ Libre des

Sciences, etc.
See Canad. Rec. Sci.

Montreal Pharmaceutical Journal

See under Paris

Morphologische Arbeiten

Morphologisches Jahrbuch

See Congr. Int. Anthrop. C. R. 1892, Congr. Int. Med.

C. R. 1897, Congr. Int. ZooL (C. R.) 1892
Commentationes Societatis Physico-Medicae apud

Universitatem Mosquensem institutae
Bulletin de la Soddtd Impeiiale des Nattu^istes
Memoires de la Socidtd Imperiale des Naturalistes de

Moscou
Nouveaux Memoires de la Soci^t^ Imperiale des

Naturalistes de Moscou
Bulletin of the Imperial Society of Lovers of Natural

Science, Anthropology and Ethnography, in connec-
tion with the Imperial University of Moscow
Scientific Memoirs of the Imperial University of

Moscow. . Natural History Section
Scientific Memoirs of the Imperial University of

Moscow. Physico-Mathematical Section
Bulletin de la Socidt^ d'Histoire Naturelle du departe-

ment de la Moselle
Expose des Travaux de la Socidtd des Sciences Medi-

cales de la Moselle
Moving Picture World
Natuur- en Scheikundig Archief.
Scheikundige Verhandelingen en Onderzoekingen
Archiv. fiir Anatomic, Physiologic, und wissenschaft-

liche Medicin.
Abhandlungen der Mathematisch-Physikalisch

Classe der kdniglich Bayerischen Akademie der

Wissenschaften
Sitztmgsberichte der Mathematisch-Physikalischen

Classe der k. B. Akademie der Wissenschaften

Munchen
See Bot. Centrbl.

Bulletin der k. Akademie der Wissenschaften
Denkschriften der Konigl. Baierischen Akademie der

Wissenschaften zu Munchen
Mittheilungen des Miinchener Entomologischen

Vereins
Gelehrte Anzeigen

Ixxxviii

UST OF ABBREVIATIONS TO I^ITERATURB

Munchen Ges. Morphol.

Physiol. Sitzber.
Mtinchen, Nattirwiss. Tech.

Comm. Abh.
Munchen Phot. Ges.
Munchen, Sitzber.

Munchen Thierarznei-

Schule Jahr.
Munchen Thierarztl. Hoch-

schule Jahr.
Munchen, Zts. Archit.

Munic. Engin.
Munic. J. Engin.
Miinster, Abh. Aerzt. Ges.

■

Museum Senckenb.

Must. Ztg.

N. Brunsw. Natur. |Iist.

Soc. Bull.
N. England Bot. Club
N. Engl. Eng.
N. England J. Med.
N. Erf. Erfahr.
N. Hampshire San. Bull.
N. Haven
N. Idea

N. Med. Phys. J.
N. Mex. Agric. Coll. Bull.

N. Orleans Med. Surg. J.

N. Orleans Proc.

N. Russ. Soc. Natur.

Mem.
N. S. Wales, Acdim. Soc.

Report
N. S. Wales Dept. Mines

Report
N. S. Wales, Entom. Soc.

Trans.
N. S. Wales Linn. Soc.

(Macleay Mem. Vol.)
N. S. Wales, Linn. Soc.

Proc.
N. S. Wales P.
N. S. Wales, Phil. Soc.

Trans.
N. S. Wales, Roy. Soc. J.

N. S. Wales, Roy. Soc.

Trans.
N. Y. Acad. Ann.

N. Y. Acad. Mem.
N. Y. Acad. Trans.

Sitzungsberichte der GeseUschaft fur Morphologie
und Physiologie in Mtinchen

Abhandlungen der naturwissenschaftlichtechnischen
Commission bei der Kdnigl. Baierischen Akademie

See Wien, Photogr. Correspond.

Sitzungsberichte der Kdmgl. Baierischen Akademie
der Wissenschaften zu Munchen

Jahresbericht der k. Central-Thierarznei-Schule in
Munchen

Jahresbericht der k. Thierarztlichen Hochschule in
Mtinchen

Zeitschrif t des Bayerischen Architekten- und Ingenieur-
Vereins

Municipal Engineer

Municipal Journal and Engineer

Abhandltmgen und Beobachtungen der arztlichen
GeseUschaft zu Munster

Museum Senckenbergianum

Leipziger Farber Zeitung (Parberes Musterzdttmg)

Bulletin of the Natural History Society of New Bruns-
wick

See Rhodora

New England Engineer, The

New England Journal of Medicine and Surgery.

Neuste Erfindungen und Erfahrungen

New Hampshire Sanitary Bulletin

See Connecticut

New Idea (The), Detroit

New Medical and Physical Journal

New Mexico Agricultural College. Experiment Sta-
tion. Las Crues, N. M. Bulletin. New Mexico
College of Agriculture and the Mechanic Arts.
Agricultural Experimental Station Bulletin

New Orleans Medical and Surgical Journal

Proceedings of the New Orleans Academy of Sciences

Memoirs of the New Russian Society of Naturalists

Annual Reports (3, 6, and 7) of the Acclimatisation

Society of N. S. W.
Annual Report of the Department of Mines (and

Agricultiue), New South Wales
The Transactions of the Entomological Society of

New South Wales
Linnean Society of New South Wales. The Macleay

Memorial Voltune
The Proceedings of the Linnean Society of New South

IVales
New South Wales Patent
Transactions of the Philosophical Society of New

South Wales
Journal and Proceedings of the Royal Society of

New South Wales
Transactions of the Royal Society of New South

Wales
Annals of the New York Academy of Sciences, late

Lyceum of Natural History
New York Academy of Sciences. Memoirs
Transactions of the New York Academy of

Late Lyceum of Natural History

LIST OF ABBREVIATIONS TO LITERATURE

Ixxxix

N. Y. Acad. Med. Bull.
N. Y. Acad. Med. Trans.
N. Y. Agric. Soc Trans.

N. Y. Bot. Club Bull.
N. Y. Entom. Soc. J.
N. Y. Insects Report

N. Y. J. Med.

N. Y. Linn. Soc. Trans.
N. Y. Lit. Phil. Soc. Trans.

N\ Y. hyceum Ann.

N. Y. Ijyoasm, Proc.

N. Y. Med. J.
N. Y. Med. Repo6.
N. Y. Med. Soc Trans.

N. Y. Mus. BulL

N. Y. Mus. Mem.
N. Zeal. Inst. Trans.

N. Zeal. Inst Min. Engin.

Trans.
N. Zeal. J. Set.
N. Zeal. P.
N. ZeaL Pap. & Rep.

Nachr. kdiiig. Ges.

Nancy, Acad. Stanislas.

Mem.
Nancy Soc. Set. Bull.
Nancy Soc. Sd. Mem.

Nancy Soc. Sd. Trav.

Nantes J. Med.

Nantes, Ann. Soc. Acad.

Nantes Soc. Sd. Natur. Bull.

Napcdi Accad. Aspir. Ann.
Napoli Accad. Atti

Napcdi Accad. Pontan. Atti
Napoli Accad. Sd. Atti

Napoli Accad. Sd. Mem.
Napoli Giom. Mat.
Napoli, Atti 1st. Incorr.

Bulletin of the New York Academy of Medicine
Transactions of the New York Academy of Medicine
Transactions of the New York State Agricultural

Sodety
Bulletin of the Torrey Botanical Club
Journal of the New York Entomological Society
Report on the Noxious, Beneficial and other Insects

of the State of New York
New York Journal of Medicine and the CoUateral

Sdences
Transactions of the Linnaean Society of New York
Transactions of the Literary and Philosophical Sodety

of New York
Annals of the Lyceum of Natural History of New

York
Proceedings of the Lycetun of Natural History in the

City of New York
New York Medical Journal
Medical Repository of New York
Transactions of the Medical Sodety of the State of

New York
University of the State of New York. Bulletin of the

New York State Museum
Memoirs of the New York State Museum
Transactions and Proceedings of the New Zealand

Institute
Transactions of the New Zealand Institute of Mining

Engineers
The New Zealand Journal of Sdence
New Zealand Patent
New Zealand. Papers and Reports relating to

Minerals and Mining
Nachrichten von der kOniglichen Gesellschaft der

Wissenschaften zu Gdttingen. (Mathematische-

ph3rsikalische Klasse)
Academic de Stanislas. Memoires de la Sod6t^

(Royak) des Sdences, etc., de Nancy
Bulletin de la Sod4t4 des Sdences de Nancy
Memoires de la Sod^t^ (Royale) des Sciences, Lettres,

et Arts de Nancy
Preds analytique des Travaux de la Sod4t6 (Royale)

des Sdences, Arts, et Agricultture de Nancy
Journal de la Section de Medecine de la Sod6t6

Academique du departement de la Loire Inferieure
Annales de la Sod^td Academique de Nantes et du

departement de la Loire Inferieure
Bulletin de la Soddt^ des Sdences naturelles de

rOuest de la France
Annali della Accademia degll aspiranti Naturalisti
Atti della Reale Accademia deUe Sdenze Fisiche e

Matematiche
Atti dell' Accademia Pontaniana
Atti della Reale Accademia della Sdenze e Belle

Lettere; Sezione della Sodeta R. Borbonica
Memorie della R. Accademia ddla Sdenze
See Giomale di Matemat.
Atti dd Real Istituto d'Incorraggiamento alle Sdenze

Naturali di Napoli

xc

I.IST OF ABBREVIATIONS TO LITERATURJS

Napoli Lucifero

Napoli Mus.

Napoli, Ann. Mus. Zool.

Napoli Rend.

Napoli Soc. Natur. Boll.
Natl. Assoc. Retail Drug,

Notes
Natl. Disp.
Natl. Drug.
Natl. Eclect. Med. Assoc.

Quart.
Natl. Glass Budget
Natl. Inst. Bull.

Natur. Can.

Natur. Sicil.
Natur. J.
Naturaleza

Naturalist (Yorks)

Naturaliste

Nature

Naturf.

Natur. Hist. Review

Naturhist. Notizen

Naturhist. Tidsskr.
Naturwiss. Umschau

Chem. Ztg.
Natuurk Tijdschr.

Nauche, J. Galvan.
Naval Archit. Trans.
Naval Sci.

Neapel Zool. Sta., Fauna &
Flora

Neapel Zool. Sta. Mitth.
Nebraska Univ. Stud.

Nederl. Archiv,

Nederl. Archief Natuurk.

Nederl. Bot. Ver. Versl. en
Meded.

Nederl. Dierk. Ver. Tijd-
schr.

Nederl. Entom. Ver.

II Lucifero

Museo di Letteratura e Filosofia

Annuario del Museo Zoologico della R. Universita di

Napoli
Rendiconto dell' Accademia delle Scienze Fisiche e

Matematiche. (Sezione della Societa Reale di

Napoli)
BoUettino della Societa di Naturalisti in Napoli
The Journal of the National Association of Retail

Druggists, Chicago
National Dispensatory
National Druggist
The National Eclectic Medical Association Quarterly,

Cincinnati
National Glass Budget

Bulletin of the Proceedings of the National Institu-
tion for the Promotion of Science
Le Naturaliste Canadien. Bulletin de Recherches,

Observations et Decouvertes se rapportant a

I'Histoire naturelle du Canada
II Naturalista Siciliano. Giomale di Scienze Natiirali
The Natiu-alists' Journal
La Naturaleza. Periodico cientifico de la Sociedad

Mexicana de Historia Natural
The Naturalist: Jotunal of the West Riding Con-
solidated Naturalists' Society
Le Naturaliste
Nature

Der Natiurforscher
The Natural History Review and Quarterly Journal of

Science
Nattu-historische und chemisch-technische Notizen

nach den neuesten Erfahrungen
Nattu'historisk Tidsskrift
Naturwissenschaftliche Umschau der Chemiker-

Zeittmg
Natuurkundige Tijdschrift, inhoudende Phijsica,

Chemie, Pharmacie, Nat. Hist., &c., uitg. van wcge

het Genootschap: "Tot nat en vergenoegen," te

Amhem.
Journal du Galvanisme, de Vaccine, etc.
Transactions of the Institution of Naval Architects
Naval Science: a Quarterly Magazine for promoting

the improvement of Naval Aichitecturc, Marine

Engineering, Steam Navigation, and Seamanship
Fauna und Flora des Golfes von Neapel und der

ang^enzenden Meeres-Abschnitte herausgegeben von

der Zoologischen Station zu Neapel
Mittheilungen aus der Zoologischen Station zu Neapel
University Studies. Published by the University of

Nebraska
See Selenka

Nederlandsch Archief voor Genees-en Natuurkunde
Sec Nederl. Kruidk. Arch.

Tijdschrift der Nederlandsche Dierkundige Vereenig-

ing
See Tijdschr. Ent.

LIST OP ABBREVIATIONS TO LITERATURE

xa

NederL Kruidk. Archief.
Nederl. Lancet

Nederl. Tijdschr. Dier-
kunde

Nederl. Tijdschr. Geneesk.

Neuchatel Soc. Sci. BulL

Neues Bergmann J.
Neues Jahr. Min.

Neues Lausitz. Mag.

Neue med.-chir. Ztg.
Neues Nord. Archiv.

Neue Preuss. Provinz.

Blatt.
Neu-Vorpommem Mitth.

Newbury Field Club Trans.
Newcastle Chem. Soc.

Trans.
Newf. P.

Newman. Entom.
Newport Natur. Hist. Soc.

Proc.
Nicholson J.

Nick.

Niederl. Archiv. Zool.

Niederdsterr. Gewerb-Ver.

Verh.
Niederrhein. Ges. Naturk.

Sitzber.
Niederrhein. Ges. Organ.

Nieuw Archief Wisk.
Nimes Soc. Sci. Bull.

Nor. Amer. Med. Chir.

Rev.
Nor. Eng. Inst. Min. Engin.

Trans.
Nor. Stafif. Field Club Rep.

Nord. Braband, Handel.

prov. Genoots.
Nord France Soc. Linn.

Bull.
Nord France Soc. Linn.

Mem.

Nederlandsch Kruidkundig Archief

Nederlandsch Lancet. Tijdschtift aan de praktische

Chirurgie, etc.
Nederlandsch Tijdschrift voor de Dierkunde, uitge-

geven door het koninklijk Zoologisch Genootschap

Natura Artis Magistra te Amsterdam
Nederlandsch Tijdschrift voor Geneeskunde, tevens

orgaan der Nederlandsche Maatschappij tot de

Bevordering der Geneeskunst
Bidletin de la Soci^t6 des Sciences Naturelles de

Neuchatel
Neues bergmannisches Journal
Neues Jahrbuch fiir Mineralogie, Geologie und

Palaeontologie
Neues Lausitizisches Magazin; unter Mitwirkung der

Oberlausitzischen Gesellschaft der Wissenschaften
Neue medicinisch-chirurgische Zeittmg
Neues nordisches Archif fiir Natur und Arzneikunde,

verfasst von einer Gesellschaft nordischer Gelehrten
Neue Preussische Privinzial-Blatter

Mittheilungen aus dem naturwissenschaftlichen
Vereins fiir Neu-Vorpommem und Rugen in Greifs-
wald

Transactions of the Newbury District Field Club

Newcastle-upon-Tyne Chemical Society. Transac-
tions

Newfoundland Patent

The Entomologist

Proceedings of the Newport Natural History Society

Journal of Natural Philosophy, Chemistry, and the

Arts
The Nickelodeon

Niederlandisches Archiv. fiir Zoologie
Verhandlungen des Niederdsterreichischen Gewerbe-

Vereins
Sitzungsberichte der Niederrheinischen Gesellschaft

fiir Natur- und Heilkunde zu Bonn
Organ fiir die gesammte Heilkunde; herausgegeben

von der Niederrheinischen Gesellschaft ffir Natur-

tmd Heilkunde zu Bonn
Nieuw Archief voor Wiskimde
Bulletin de la Soci6t6 d'Etude des Sciences Naturelles

de Nimes
The North-American Medico-Chirurgical Review

North of England Institute of Mining and Mechanical

Engineers. Transactions
(The) North Staffordshire (Naturalists') Field Club

(and Archaeological Society). Annual Report (and

Transactions)
Handelingen van het provinciaal Genootschap van

Kunsten en Wetenschappen in Nord Braband
Bulletin de la Soci6t6 Linneenne du Nord de la France

Memoires de la Soci^t6 Linneenne du Nord de la
France

xcu

UST OP ABBRJSVIATIONS TO UTRRATURB

/

Nord, Mem. Soc. Agric.
Nord, Soc. Agric. Seance

Publ.
Nordamerik. Monatsber.

Norddeut. Landwirth
Nordisches Archiv.

Norf. Norw. Nattir. Soc.

Trans.
Normandie

Normandie Soc. Linn. Btdl.
Normandie Soc. Linn. Mem.
Normandie Soc. Linn.

Seance Publ.
Norsk Tidsk. Vid. Litt.
Norske Videnskab. Skrift.

Nortliampton Natur. Hist.

Soc. J.
Northern J. Med.
Northumb. Nattir. Hist.

Soc. Trans.
Ncttthwestem Drug.
Norw. P.
Notarisia

Notices of Judgment, U. S.

Dept. Agric.
Notiz. Archit. Ver. Nieder-

rhein
Notiz. Riga
Nouv. Aim. Math.
Nouv. Archiv. Miss. Sci.

Nouv. remedes

Nova Acta Acad. Nat.

Curios.
Nova Scotia Inst. Sci. Proc.

& Trans.
Nova Scotia, Trans. Lit.

Sci. Soc.
Novitates Zool.

Nuov. Ann. Sci. Natur.
Nuov. Antol. Sci.

Nuov. Cimento

Nuov. Giom. Bot. Ital.

Nuov. Notarisia

Niimb. Natur. Ges. Abh.
Nye Hygaea

See Douai

Seance Publique de la Soci^t^ d'Agriculture. Sciences,

et Arts, etc, du departement du Nord
Nordamerikanischer Monatsbericht fur Natur- und

Heilkunde
Der norddeutsche Landwirth
Nordisches (u. Neues Nordisches) Archiv. fQr Natur-

kunde und Arzneiwissenschaft
Transactions of the Norfolk and Norwich Naturalists'

Society
See Caen

Bulletin de la Sod^t^ Linneenne de Normandie
Memoires de la Soci6t6 Linneenne de Normandie
Seance Publiques de la Soci^t^ Linneenne de Nor-
mandie
Norsk Tidskrift for Videnskab og Litteratur.
Det Kongelige Norske Videnskaber^elskabs Skrifter i

det 19 de Aarhundrede
Journal of the Northampton(shire) Natural History

Society and Field Club
Northern Journal of Medicine

Transactions of the Natural History Society of North-
umberland, Durham, and Newoistle-upon-Tyne
Northwestern Druggist (The), Minneapolis
Norwegian Patent
Notarisia. Commentarium Phyoologicum. La

Notarisia. Commentario Picologico Generale.

Parte spedale della Rivista Neptunia
Notices of Judgment, U. S. Department of Agri-
culture
Notizblatt des Architekten und Ingenieur Vereins

ftir Niederrhein und Westfalen
Notizblatt des technischen Vereins zu Riga
Nouvelles Annales de Mathematiques
Nouvelles Archives des Missions Sdentifiques et

Litteraires
Nouveaux remedes, Paris
Novorum Actorum Academiae Caesareae Leopoldino-

Carolinae Germanicae Naturae Curiosorum
(The) Proceedings and Transactions of the Nova

Scotian Institute of (Natural) Science
Transactions of the Literary and Scientific Society of

Nova Scotia
Novitates Zoologicae. A Journal of Zoology in

connection with the Tring Museum
Nuovi Annali delle Sdenze natural!
Nuova Antologia di Scienze, Lettere (Lettere, Sdenze)

ed Arti
II Nuovo Cimento, Giomale di Fisica, di Chimica, e

di Storia Naturale
Nuovo Giomale Botanico Italiano (e BuUettino della

Sodeta Botanica Italiana)
La Nuova Notarisia. Rassegna (trimestrale) con-

sacrata alio Studio delle Alghe (e CoroUario aUa

"Sylloge Algarum Qmnium")
Abhandlungen der Naturbistorischen Gesdlachaft zu

Niimberg
Nye Hygaea

LIST OF ABBREVIATIONS TO LITERATURE

XCUl

l>iyt Mag. Nattirvid.
:N3rt Tidsskr. Pys. Kem.
Oberhess. Ges. Ber.

'Odontol. Soc. Trans.

OesteiT. Bot. Zts.
Oesterr. Chem. Ztg.
Oesterr. landw. Wochenbl.
Oesterr. Med. Jahr.

Oesterr. Med. Wochenschr.

Oesterr. Wochenschr.

Oesterr. Zts. Berg. Hut-

tenw.
Oesterr.-ung. Zts. Zucker-

ind.
Off. Gaz.
Offenbach. Ver. Naturk.

Ber.
Oil Colour J.
Oil, Pamt Drug. Rep.
Oise
Oise Mem. Soc. Acad.

Oken Isis

Omaha Drug.

Omodei Ann. Univ.

Ontario Entom. Soc. Rep.

Oporto

Ophthahn. Bibliothek

Qphthalm. Hosp. Reports

Ophthalmic Rev.

Organ Rubenzuckerind.

Oigelb.

Orleans Ann.

Orleans, Bull.

Omis

Omith. Jahr.
Omith. Monatsber.
Omith<4.
Omithd. Ool.
5rsted Tidsskrif t
Orvos-Termesz. Ertes.

Nyt Magazin for Naturvidenskaberne

Nyt Tidsskrift for Fysik og Kemi.

Berichte der Oberhesstschen Gesellschaft fdr Natur-
kunde und Heilkunde in Giessen

Transactions of the Odontological Society of Great
Britain

Oesterreichische Botanische Zeitschrift

Oesterreichische Chemiker Zeitung

Oesterreichisches landwirtschaftliches Wochenblatt

Medidnisches Jahrbuch des k. k. Oesterreichischen
Staates

Oesterreichische Medidnische Wochenschrift, als
Erganzungsblatt der medicinischen Jahrbfkcher

Oesterreichische Wochenschrift fur Wissenschaft,
Kunst, und dffentliches Leboi

Oesterreichsche Zeitschrift tiir Berg- und Hutten-
wesen

Oesterreichisch-ungarische Zeitschrift ftir Zucker-
industrie imd Landwirtschaft

Official Gazette, United States Patent Office

Bericht des Offenbacher Vereins fur Naturkunde uber
seine Thatigkeit

Oil and Colourman's Trade Journal

Oil, Paint and Drug Reporter

See Beauvais

Memoires de la Soci6t^ Academique d'Archeologie,
Sciences, et Arts du departement de TOise

Isis, Oder Encydopadische Zdtung

Omaha Druggist (The), Omaha

Annali Universali di Medidna

Report of the Entomological Sodety of Ontario

See Porto

Ophthalmologische Bibliothek

Ophthalmic Hospital Reports and Journal of the
Royal London Ophthalmic Hospital

The Ophthalmic Review: a Quarterly Journal of
Ophthalmic Surgery and Sdence

Organ des Centralvereins fur Rtibenzuckerindustrie

Die Orgdbauzdtung

Aimales de la Sod6t6 Royale des Sdences, Bdles-
Lettres, et Arts d'Orleans

Bulletin des Sciences Physiques, Medicales, et
d' Agriculture d'Orleans

Omis, Oder das Neuste und Wichtigste der Vogel-
kunde, etc.

Omithologisches Jahrbuch

Omithologische Monatsberichte

The Omithok)gist

The Ornithologist and Oologist

Tidsskrift for Nattu^denskabeme

Orvos-Termeszettudomanyi Ertesit6 a Kolozsvari
Orvos-Termeszettudomanyi Tarsulat es az Erddyi
Museum-Egylet Termeszettudomanyi Szakosz-
talyanak az. .szaktileseirol. .(Medical and Natural
History Proceedings of the sections of the Klausen-
burg Medical and Natural History Society and of
the Natural History section of the Museum Associa-
tion of Transylvania

XCIV

LIST O^ ABBREVIATIONS TO LITERATURE

Osnabrilck, Jahr.

Ottawa Field-Natur. Club

Trans.
Ottawa Natur.
Ouest Prance Soc. Sci. Nat.

Bull.
Oversigt K. D a n s k e

Vidensk. Selsk. Forh.
Pacific Drug. Rev.
Pacific Pharm.
Padova, Mem. Acad.

Padova, Nuovi Saggi

Padova, Rivista Period.

Padova, Soc. Sci. Atti
Padova Soc. Sci. Bull.

Palermo Accad. Atti

Palermo Circ. Mat. Rend.
Palermo, Effemeridi

Palermo, Giom. Sci. Natur.

Palermo, Mem. Spettrosc.

Ital.
Palermo Oss. Bull. Meteorol

Palermo Oss. Ossvz. Me-
teorol.
Palomba, Raccolta

Palyamimkak

Pander, Beitr. Naturk.

Paper

Paper-Maker Brit. Trade J.

Paper Makers' Monthly J.

Paper Making

Paper Mill

Papers Naval Archit.

Paper Trade J.

Papier-Fabr.

Papier Ztg.

Papierhandel

Papilio

Papir J.

Par. P.

Para, Mus. Hist. Natur.

Bol.
Paris, Acad. Med. Bull.

Jahresbericht des Naturwissenschaftlichen Vereins zu

Osnabruck
Ottawa Field-Naturalists' Club Transactions

The Ottawa Naturalist
See Nantes . . .

Oversigt over det Kongelige Danske Videnskabemes

Selskabs Forhandlinger
Pacific Drug Review, Portland
Pacific Pharmacist
Memorie dell' Accademia di Scienze, Lettere, ed Arti

di Padova
Nuovi Saggi dell' Accademia di Scienze, Lettere, ed

Arti di Padova
Rivista Periodica dei Lavori della I. R. Accademia di

Scienze, Lettere, ed Arti di Padova
Atti della Societa Veneto-Trentina di Scienze naturali
Bullettino della Societa Veneto-Trentina di Scienze

Naturali residente in Padova
Atti della Reale Accademia di Scienze, Lettere e

Belle Arti di Palermo
Rendiconti del Circolo Matematico di Palermo
Effermeridi scientifiche e letterarie per la Sicilia;

coi Lavori del R. Instituto d'Incorraggiamento per

la Sicilia
Giomale di Scienze naturali ed economiche, pubblicato

per Cura della Societa di Scienze naturali ed eco-
nomiche di Palermo
Memorie della Societa degli Spettroscopisti Italiani

. Bullettino Meteorologico del Reale Osservatorio di

Palermo
R. Osservatorio di Palermo. Stazioni di Valverde

Osservazioni meteorologiche
Raccolta di Lettere, etc., intonno alia Fisica ed alle

Mathematiche
Palyamunkak. Termerzetlud (Prize Essays of the

Hungarian Academy)
Beitrage zur Naturlainde aus den Ostseeprovinzen

Russlands
Paper

Paper Maker and British Trade Journal
Paper Makers' Monthly Journal
Paper Making

Paper Mill and Woodpulp News
Papers on Naval Architecture and other subjects

connected with naval science
Paper Trade Journal
Papier-Fabrikant, Der
Papier Zeitung
Der Papierhandel
Papilio

Papir Joumalen
Paraguay Patent
Boletim do Museu Paraense de Historia Natural e

Ethnographia
Bulletin de T Academic de Medecine

I^IST OF ABBREVIATIONS TO LITERATURB

XCV

Paris, Acad. Med. Mem.
Paris, Acad. Sci. Compt.

rend.
Paris, Acad. Sci. Mem.

Paris, Ami. Cere. Med.
Paris, Ami. Conserv.
Paris, Ami. Ecole Norm.
Paris, Ami. Ponts Chauss.

Paris, Ami. Soc. Entom.
Paris, Amiaes Sci..

Paris, Amiu. Med. Chir.

Hosp.
Paris, Amiu. Soc. Met.
Paris, Anthropol. Soc. Btill.
Paris, Antliropol; Soc. Mem.
Paris, Bull. Fac. Med.

Paris, Bull. Soc. Aerost!

Parist Bull. Soc. Sci. Natur.
Paris, Bur. Long. Annu.

Paris, Caus. Sci.

Paris, Club Alpin Franc.

Annu.
Paris, Com. Intl. Carte Ciel

Bull.

Paris Congr. Bot. Act.

Paris Congr. Bot. Compt.

rend.
Paris, Congr. Med. Intl.
Paris, Ecole Norm. Ann.

Paris, Ecole Poly. Corresp.

Paris, Ecole Poly. J.

Paris, EtHnog. Soc. Compt.

rend.
Paris, Hautes Etudes Bibl.

Paris, Ingen. Civ. Mem.

Paris, J. Bot.

Paris, J. Chir.

Paris, Lab. Histol. Trav.

Paris, Mem. Acad. Med.
Paris, Mem. Acad. Sci.
Paris, Mem. Inst.

Memoires de I'Academie de Medecine

Comptes Rendus bebdomadaires des Seances de^

I'Academie des Sciences " '

Memoires de I'Academie des Sciences de, I'lnstitut de

France
Annales du Cercle Medicale
Annales du Conservatoire des Arts et Metiers
Annales scientifiques de I'Ecole Normale Superieure
Annales des Ponts et Chaussees. Memoires et docu-
ments relatifs a I'Art des Constructions et au

Service de I'lngenieur
Annales dt la Soci6t^ Entomologique de Fiance
Annaes das Sciencias, etc., vor huma S<xnedade de

Portuguezes residentes em Paris
Annuaire medico chirurgical des Hopitaux, etc., de

Paris
Aimuaire de la Soci6t6 Meteorologique de France
Bulletin de la Soci6t^ d' Anthropologic de Paris
Memoires de la Soci^t6 d'Anthropologie de Paris
Bulletins de la Faculte de Medecine de Paris et de la

Society etablie dans ^n sein
Bulletin de la Soci6t6 Aerostatique et Meteorologique

de France
Bulletin de la Soci^t^ des Sciences Naturelles de France
Annuaire pour I'An . . . public par le Bureau des

Longitudes
Causeries Scientifiques de la Soci^te Zoologique de

France
Annuaire du Club Alpin Francais

Institut de France. Academic des Sciences. Bulletin

du Comite International Permanent pour 1' Execution

Photographique de la Carte du Ciel
Actes du Congres International de Botanique tenu a

Paris in aout 1867
. . . Comptes Rendus . . . Congres International de

Botanique et d'Horticulture
Congres Medical International de Paris, 1867
Annales Scientifiques de I'Ecole Normale Superieure,

publics sous les auspices du Ministre de I'lnstruc-

tion Publique
Correspondance sur I'Ecole Polytechnique, a I'usage

des Eleves de cette Ecole
Journal de I'Ecole Polytechnique public par le Conseil

d' Instruction de cet Etablissement
Comptes Rendus des Seances de la Soci6t6 d' Ethno-
graphic Americaine et Orientale
Bibliotheque de I'Ecole des Hautes Etudes. . .Section

des Sciences Naturelles
Memoires et Compte Rendu des Travaux de la Soc6it6

des Ingenieurs Civils (de France)
Journal de Botanique, par une Soci^t^ de Botanistes
Journal de Chinu-gie
Ecole Pratique des Hautes Etudes. Laboratoire

d'Histologie du College de France. Travaux
Memoires de I'Academie (Royale) de Medecine
Memoires de I'Academie des Sciences
Memoires de la Classe des Sciences mathematiques

et physiques de I'lnstitut

XCVl

I^IST OF ABBREVIATIONS TO LITERATURE

Paris, Mem. Soc. Savants Memoires des Sod4t6s Savants et Litteraires de la

Republique Prancaise
Paris, Mem. Savants Etrang. Memoires presentes par divers Savants a 1' Academic

des Sciences de Tlnstitut de France
Paris, Mem. Soc. Ethnol. Memoires de la Soci6t6 Ethnologique
Paris, Mem. Soc. Pac. Med. Memoires de la Soci^td de la Faculte de Medecine
Paris, Mem. Soc. Linn. Memoires de la Soci6t6 Linneenne de Pails

Paris, Mem. Soc. Med. Memoires de la Soci6t6 de Medecine

Paris, Mem. Soc. Med. Memoires de la Soci^td Medicale d'Observation

Observ.
Paris, Mus. Hist. Natur. Annales du Museum d'Histoire Naturelltt

Ann.
Paris, Mus. Hist. Natur. Archives du Museum d'Histoire Nattuelle

Archiv.
Paris, Mus. Hist. Natur.

Bull.
Paris, Mus. Hist. Natur.

Cent.
Paris, Mus. Hist. Natur.

Mem.
Paris, Mus. Hist. Natur.

Nouv. Ann.
Paris, Mus. Hist. Nattur.

Nouv. Archiv.
Paris Obs. Ann. Annales de TObservatoire de Paris

Paris, Obs. Montsouris Annu. (Ville de Paris.) Annuaire de TObservatoire (mtmici-

pal de Paris, dit Observatoire) de Montsouris. . .
Paris, Poids Mes. Proc.- Comite International des Poids et Mesures. Proces-

Verb. Verbaux des Seances

Paris, Poids Mes. Trav. Mem. Travaux et Memoires du Bureau International des

Bulletin du Museum d'Histoire Naturelle

Centenaire de la Fondation du Museum d'Histoire

Naturelle
Memoires du Museum d'Histoire Naturelle

NoUvelles Annales du Musetun d'Histoire Naturelle

Nouvelles Archives du Museum d'Histoire Naturelle

Paris, Recueil Soc. Med.

Observ.
Paris, Recueil. Trav. Soc.

Med. AUemande
Paris, Soc. Acdim. Bull.
Paris, Soc. Anat. Bull.
Paris, Soc. Anthrop. Bull.
Paris, Soc. Anthrop. Mem.
Paris, Soc. Biol. Mem.

Paris, Soc. Chir. Bull.
Paris, Soc. Chir. Mem.
Paris, Soc. Entom. Ann.
Paris, Soc. Entom. Bull.
Palis, Soc. Geogr. Bull.
Paris, Soc. Geogr. Compt.

rend.
Paris, Soc. Hist. Natur.

Mem.
Paris, Soc. Ing. Civ. Mem.

Poids et Mesures
Recueil des travaux de la Socidt^ Medicale d'Observa-

tion de Paris
Recueil des Travaux lus a la Soci6t6 Medicale Alle-

mande de Paris
Bulletin de la Soci6t6 Zoologique d'Acdimatation
Bulletin de la Soci4t6 Anatomique de Paris
Bulletins de la Soci6t^ d' Anthropologic de Paris
Memoires de la Soci6t6 d'Anthrbpologie de Paris
Comptes Rendus des Seances et Memoires de la

Soci6t4 de Biologic
Bulletin de la Socilt6 de Chirurgie de Paris
Memoires de la Socidt^ de Chirurgie de Faris
Annales de la Soci^t^ Entomologique de France
Bulletin de la Soci^t^ Entomologique de France
Bulletin de la Soci6t6 de Geographic
Compte Rendu des Seances de la Soci6t6 de Geographic

et de la Commission Centrale
Memoires de la Soci6t6 d'Histoire Naturelle de Paris

Paris Soc. Linn. Bull.
Paris, Soc. Math. Bull.

Memoires et Comptes Rendus des Travaux de la

Soci6t6 des Ingenieurs Civils
Bulletin mensuel de la Soci6t4 Linneenne de Paris
Bulletin de la Soci6t6 Mathematique de France
Paris! Soc. Med. Emul. Bull. Bulletins de la Soci^t6 Medicale d'6raidation
Paris, Soc. Med. Emul. Memoires de la Soci^t6 Medicale d' Emulation

Mem.
Paris, Soc. Philom. Bull. Bulletin des Sciences de la Soci6t6 Philomathique de

Paris

UST OF ABBRJSVIATIONS TO LITERATURE XCvil

Paris, Soc. Philom. Mem. Memoires publics par la Soci6t^ Philomatliique a

Cent. I'occasion du Centenaire de sa Fondation, 178^1888-

Paris, Soc. Philom. Nouv. Nouveau BuUetin des Sciences de la Soci6t6 Philomat-

BulL ique de Paris

Paris, Soc. Philom. Proc. Extraits des Proces-Verbaux des Seances de la Soci£t6

Verb. Philomatique

Paris, Soc. Phys. Seances Seances de la Socidtd Francaise de Physique
Paris, Soc. Speleol. Mem. Memoires de la Soci^t^ de Speleologie
Paris Tow. Nauk Sdsl. Pam. Pamietnik Towarzystwa Nauk Scislych w Paryzu
Paris, Trav. Soc. Amat. Notice des Travaux de la Soci6t^ des Amatuers des

Sciences physiques et naturelles de Paris
Parlatore, Giom. Bot. Giomale Botanico Italiano

Parma, Giom. Soc. Med. Giomale della Societa Medico-Chirurgica di Parma

Chir.
Passau Ber. Nat. Ver. . . . Bericht des Naturhistoischen Vereins in Passau

fur.. .
Passau, Jahr. Naturhist. Jahresbericht des Naturhistorischen Vereins

Ver.
Pathol. Soc. Trans. Transactions of the Pathological Society of London

Pavia 1st. Bot. Atti Atti dell' Istituto Botanico dell' Universita di Pavia.

Seguito dell' Axchivio Triennale del Laboratorio di.

Botanica Crittogamica
Pavia Lab. Crittog. Archiv. Archivio del Laboratorio di Botanica Crittogamica

presso la R. Universita di Pavia
Peabody Acad. Mem. Memoirs of the Peabody Academy of Science

Peabody Acad. Report Sixth Annual Report of the Trustees of the Peabody

Academy of Science.
Penn. Univ. Publ. Publications of the University of Pennsylvania

Penzance Soc. Trans. Transactions of the Natural History and Antiquarian

Society of Penzance
Perf. Essent. Oil Rec. Perfumery and Essential Oil Record

Perthsh. Soc. Sd. Trans. & Transactions and Proceedihgs of the Perthshire

Proc. Society of Natural Science

Pern P. Pemvian Patent

Pet. Nouv. Entom. Petites Nouvelles Entomologiques

Petermann, Mitth. Dr. A. Petermann's Mittheiltmgen aus Justus Perthes'

Geographischer Anstalt
Peters, Zts. Zeitschrift fur populare Mittheilungen aus dem

Gebiete der Medicin, Chirurgie, und Pharmacie;

in Verbindtmg mit einem Vereine von Aerzten-

und Pharmaceuten der Herzogthiimer Schleswig

und Holstein
Petroletun Petroleum

Petroleum Gaz. Petroleum Gazette

Petroleum Rev. Petroletun Review

Pfluger, Archiv. Physiol. Archiv. fur die gesammte Physiologic des Menschen

und der Thiere
Pharm. Pharmakologie

Pharm.-Ber. Deut.-Arzbuch. Pharmakopoe-Bericht. Die vegetablischen Drogen

des Deutschen Arzneibuches, 5^<. Ausgabe, Caesar

& Loretz, Halle
Pharm. Centr. Pharmaceutisches Central-Blatt

Pharm. Centralh. Pharmaceutische Centralhalle fiir Deutschland

Pharm. Era Pharmaceutical Era

Pharm. J. The Pharmaceutical Journal (and Transactions)

Pharm. Post Pharmazeutische Post

Pharm. Weekblad Pharmazeutische Weekblad

Pharm. Ztg. Pharmazeutische Zeitung

XCVIU

LIST OF ABBREVIATIONS TO LITERATURE

Pharm. Zts.

Pharm. Zts. Russland

PhU. Mag.

Phih Stud.

PhiL Trans.

Phila. Acad. Natur. Sci. J.

Phila., Acad. Natur. Sci.

Proc.
Phila. Amer. Entom. Soc.
Phila. Coll. Pharm. Joum.
Phila. Eng. Club
Phila. Entom. News

Phila. Entom. Soc. Proc.

Phila. Med. Mus.
Phila. Med. Phys. J.
Phila. Phot.
Philippine J. Sci.
Phot. Archiv
Phot. Bull.
Phot. Chronik.

Phot. J.

Phot. Corr. (Korr.)
Phot. Mag.
Phot. Mitth.
Phot. Monats.
Phot. News
Phot. Rundsch.

Phot. Soc. J.

Phot. Soc. Trans.

Phot. Times

Phot. Wochenbl.

Phot. World

Phot. Centr.

Phot. Ztg.

Phys. Rev.

Physikal.-Chem. Zentr.

Physikal. Meddel.

Physikal. Zts.

Physiol. Russe

Physiol. Soc. Proc.

Phytologist

Pisa, Ann. Scuola Norm.

Pisa, Ann. Univ. Tosc. Sci.

Cosm.
Pisa, Miscell. Med. Chir.

Pisa, Nuov. Giom.
Pisa Soc. Sci. Proc.

Pharmazeutische Zeitschrift

Pharmaceutische Zeitschrift ffir Russland

Philosophical Magazine

Philosophische Studien

Philosophical Transactions of the Royal Society of
London

Journal of the Academy of Natural Sciences of Phila-
delphia

Proceedings of the Academy of Natural Sciences of
Philadelphia

See Amer. Entom. Soc.

Journal of the Philadelphia College of Pharmacy

Proceedings of the Engineers' Club of Philadelphia

Entomological News (and Proceedings of the Ento-
mological Section of the Academy of Natural
Sciences of Philadelphia)

Proceedings of the Entomological Society of Phila-
delphia

Philadelphia Medical Museum

The Philadelphia Medical and Physical Journal

The Philadelphia Photographer

Philippine Journal of Science

Photographisches Archiv

Anthony's Photographic Btdletin

Photographische Chronik und allgemeine Photo-
graphen-Zeitung

Wilhelm Horn's Photographische Journal

Photographische Korrespondenz

Photographisches Magazine

Photographische Mittheilungen

Photographische Monatshefte

Photographic News

Photographische Rundschau und Photographisches
Centralblatt

Journal of the Photographic Society of London

Trans, of the Photographic Society of London

The Photographic Times

Photographisches Wochenblatt

The Photographic World

Photographisches Centralblatt

Deutsche Photographen-Zeitung

Physical Review

Physikalisch-chemisches Zentralblatt

Physikalske Meddelelser

Physikalische Zeitschrift

Le Physiologiste Russe

See J. Physiol.

The Ph3rtologist: a popular Botanical Miscellany

Annali della R. Scuola Normale Superiore di Pisa.
Scienze Fisiche e Matematiche

Annali della Universita Toscana. Scienze Cos-
mologiche

Miscellanea medico-chirurgico-farmaceutiche raccolte
in Pisa

Nuovo Giomale de* Letterati

Atti della Soci^t6 Toscana di Scienze Naturali residente
in Pisa

LIST OF ABBREVIATIONS TO LlTERATtTRE

XCIX

Pisa Soc. Tosc. Atti (Mem.)

Pisa Soc. Tosc. Atti (Proc.

Verb.)
Pistoja, Atti Accad.

Plant World
Plata Mtis. Anales

Plata Mtis. Revista

Pldn Biol. Sta. Forschungs-

ber.
Plsrmouth Inst. Trans.

Pogg. Ann.
Pogg. Ann. Beibl.

Poligrafo
PoUt.
PoUichia, Jahr.

Polsk. Tow. Przyrod. Koper

nika
Poly. Centr.
Poly. Centralh.
Poly. Mitth.
Poly. Notiz.
Polygraph. Centr.
Pommer, Zts.
Pop. Mag. Anthropol.
Pop. Sci. Mon.
Popular Sci. Rev.

Pontif. Univ. Gregor.

Port. P.

Portland, Soc. Natur. Hist.

Proc.
Porto, Ann. Soc. Lit.
Porto Soc. Instruc. Rev.
Potsdam Astrophys. Obs.

Publ.
Pottery Gaz.
Pottery and Glass
Power
Prace Mat.-Fiz.

Pract. Drug.

Pract. Mag.
Pract. Mechan. J.
Practitioner
Prag, Abh.

Atti della Societa Toscana di Scienze Naturali resi-

dehte in Pisa. Memorie
Arti della Societa Toscana di Scienze Naturali residente

in Pisa. Processi Verbali
Atti della R. Accademia Pistojese di Scienze, Lettere,

ed Arti; Memorie di Matematica e Fisca
Plant World, The
Anales del Museo de La Plata. Materiales para la

Historia fisica y moral del Continente Sud-Americano
Revista del Museo de La Plata
Forschungsberichte aus der Biologischen Station zu

P16n
Annual Reports and Transactions of the Pljrmouth

Institution and Devon and Cornwall Natimd

History Society
PoggendorfT's Annalen der Physik und Chemie
Poggendorff's Annalen der Physik tmd Chemie Bei-

blatter
II Poligrafo: Giomale di Science, Lettere, ed Arti
II Politecnico
Jahresbericht der Pollichia, eines nattu-wissenschaft-

lichen Vereins der Baierischen Pfalz (der Rhein-

pfalz)

See Kosmos (Lwow)

Polytechnisches Centralblatt

Polytechnische Centralhalle

Polytechnische Mittheilungen

Polytechnisches Notizblatt

Polygraphisches Centralblatt

Schweizerische Zeitschrift fiir Natur- tmd Heilkunde

The Popular Magazine of Anthropology

Popular Science Monthly

The Popular Science Review: a Quarterly Miscellany

of entertaining and instructive articles on Scientific

subjects
Pontificia Universita Gregoriana. Continuazione del

Bullettino Meteorologico dell' Observatorio del

Cellegio Romano
Portuguese Patent
Proceedings of the Portland Society of Natural

History
Annaes da Sociedade Lit. Portuense
Revista da Sociedade de Instruccao do Porto
Publicationen des Astrophysikalischen Observa-

torituns zu Potsdam
Pottery Gazette
Pottery and Glass
Power
Prace Matematyczno-Fizyczne. (Mathematical and

Physical Papers)
Practical Druggist and Pharmaceutical Review of

Reviews, New York
The Practical Magazine (London)
The Practical Mechanics Journal
The Practitioner
Pojednani Krai. Ceske Spolecnosti Nauk. Abhandl-

ungen der Kdnigl. Bdhmischen Gesellschaft der

Wissenschaften

UST OF ABBREVIATIONS TO LITBRATURB

Prag, Ceske Ak. Fr. Jos.
Pam.

Prag, Ceske Akad. Fr. Jos.
Rozpr. (Trida 2)

Prag. Fr. Jos. Acad. Sci.

Bull.
Prag, Jahr. Bohm. Mus.

Prag, Jahr. Realschule

Prag, Lotos Abh.

Prag, Monatschr. Mus.

Prag, Sitzber.

Prag Sternw. Magn. Me-

reorol. Beob.
Prag, Verh.

Prag, Vierteljahrschr.
Pressburg, Ccftresp. Blatt.

Pressburg, Verh.

Presse Sci.

Preuss. Bot. Ver. Sitzber.
Preuss. Geod. Inst. Publ.
Preuss. Geod. Inst. Veroflf.

Preuss. Landes-Oekon.-Kol-

leg. Archiv.
Pribram Bergakad
Princeton Mus. Contr.

Pringsheim, Jahr. Wiss. Bot.
Print. Reg.
Prog, agric. viti.
Proc. Amer. Acad.

Proc. Amer. Inst. Elec.

Eng.
Proc. Amer. Micro. Soc.
Proc. Amer. Pharm. Assoc.

Proc. Amer. Phil. Soc.

Pomatnik na oslavu padesaitketeho panovnickeho
Jubilea jeho Velicenstva Cisare a iCrale Frantiska
Josef a I. Vydala Ceska Akademie Cisare Frantisks
Josefa pro Vedy, Slovesnost a Umeni. (Memoira
in celebration of the fifty years Jubilee of the reign
of H. I. & R. M. Francis Joseph I. Published by
the Bohemian Imperial Francis Joseph Academy of
Science, Literature and Art)

Rozpravy Ceske Akademie Cisare Frantiska Josefa
pro Vedy, Slovesnost a Umeni v Praze. (Trida II.)
(Transactions of the Bohemian Imperial Francis
Joseph Academy of Science, Literature and Art
in Prague. Class II)

Academie des Sciences de TEmpereur Francois Joseph
I. Bulletin International

Jahrbticher des Bohmischen Museums fur Natur- und
Landerkunde

Jahresbericht der k. k. Bdhmi^hen Ober-Realschule zu
Prag

Abhandlungen des Deutschen Naturwissenschaftlich-
Medicinischen Vereines fur Bohmen "Lotos"

Monatsschrift der Gessellschaft des vaterlandischen
Museums in Bdhmen

Zpravy o Zasedani (Vestnik) Kralovske Ceske Spolec-
nosti Nauk. Trida. Mathematicko-Prirodove-dec-
ka. Sitzungsberichte der Konigl. Bohmischen Gesell-
schaft der Wissenschaften. Mathematisch-Natur-
wissenschaftliche Classe

Magnetische und Meteorologische Beobachtungen an
der K. K. Stemwarte zu Prag

Verhandlungen der Gesellschaft des vaterlandisches
Museums in Bdhmen

Vierteljahrschrift fur die praktische Heilkunde

Correspondenzblatt des Vereins fiir Naturkunde zu
Pressburg

Verhandlungen des Vereins fiir Natiu-kundc zu Press-
biu-g

Presse Sctentifique des Deux Mondes

See Konigsberg Schriften '

Publication des Kdnigl. Preuss. Geodatischen Institute

Veroffentlichung des Kdnigl. Preussischen Geod-
atischen Instituts

See Landw. Jbiich.

See Wien, Berg- u. Hiittenm. Jbuch.

Contributions from the (E. M.) Museum of Geology

and Archaeology of Princeton College
, Jahrbiicher fiir Wissenschaftliche Botanik

Printers' Register

Progres agricole et viticole

Proceedings of the American Academy of Arts Sci-
ences

Proceedings of the American Institute of Electrical
Engineers

Proceedings of the American Microscopical Society

Proceedings of the American Pharmaceutical Associa-
tion

Proceedings of the American Philosophical Society

LIST OF ABBREVIATIONS TO LITKRATURS

a

Proc. Amer. Soc. Civil

Eng.
Proc. Amer. Soc. Micro.
Proc. Amer. Soc. Test. Mat.

Proc. Amer. Water Works

Assoc.
Proc. Assoc. Ofif. Agric.

Chem.
Proc. Austral. Inst. Min.

Eng.
Proc. Cambr. Phil. Soc.
Proc. Chem. Soc.
Proc. Eng. Soc. Western

Penn.
Proc. Inst. Civil Eng.
Proc. Inst. Mech. Eng.
Proc. Natl. Wholesale Drug.

Assoc.
Proc. Phjrsiol. Soc.
Proc. Roy. Soc. Edinb.
Proc. Roy. Soc. London
Proc. Roy. Soc. Med.
Proc. Soc. Exp. Biol. Med.

Proc. U. S. Naval Inst.
Progres Med.

Progressive Age
Propogation ind.

Prov. Med. Assoc. J.
Prov. Med. Surg. Assoc.

Trans.
Psyche

Psychol. Med. J.

Publ. Carnegie Inst.

Publ. ind.

Public Analysts Proc.

Public Health

Pulp Paper Mag. Can.

Pure Products

Puy, Soc. Agric. Ann.

Quart. J. Chem. Soc.
Quart. J. Dent. Sci.
-Quart. J. exp. Physiol.
Quart. J. Gcol. Soc.
-Quart. J. Math.

Quart. J. Micro. Sci.
Quart. J. Micro. Soc.
<Quart. J. Sci.

Proceedings
neers

of the American Society of Civil Engi-

of the American Society of Microscopists
of the American Society for Testing

Proceedings
Proceedings
Materials
Proceedings of American Water Works Association

Proceedings

Chemists,

Proceedings

of the Association of Official Agricultural

Washington

Australian Institute of Mining Engineers

Proceedings of the Cambridge Philosophical Society
Proceedings of the Chemical Society (London)
Proceedings of the Engineers' Society of Western

Pennsylvania
Proceedings of the Institution of Civil Engineers
Proceedings of the Institution of Mechani<^ Engineers
Proceedings of the National Wholesale Druggists'

Association
Proceedings of the Physiological Society
Proceedings of the Royal Society of Edinburgh
Proceedings of the Royal Society of London
Proceedings of the Royal Society of Medicine
Proceedings of the Society for Experimental Biology

and Medicine
Proceedings of U. S. Naval Institute
Le Pipgres Medical. Journal de Medecine, de

Chirurgie et de Pharmacie
Progressive Age
La Propogation industrielle. Revue mensuelle illustre

des inventions, machines, appareils et precedes de la

France, etc.
Journal of the Provincial Medical Association
Transactions of the Provincial Medical and Surgical

Association
Psyche. Organ of the Cambridge Entomological

Club
Journal of Psychological Medicine
Publications of the Carnegie Institution of Washington
Publication industrielle des machines par Armengaud
Proceedings of the Society of Public Analysts
Public Health

Pulp and Paper Magazine of Canada
Pure Products. Scientific Station for Piu^ Products,

New York
Annales de la Soci4t6 d 'Agriculture, Sciences, etc., du

Puy
Quarterly Journal of the Chemical Society
Quarterly Journal of Dental Science.
Quarterly Journal of experimental Physiology
Quarterly Journal of the Geological Society
The Quarterly Journal of Pure and Applied Mathe-
matics
Quarterly Jotunal of Microscopical Science
Quarterly Journal of the Microscopical Society
The Journal of Science and the Arts Continued as the

Quarterly Journal of Science, Literature, and Arts

Cll

LIST OF ABBREVIATIONS TO LITERATURE

Quebec, Lit. Hist. Soc.

Trans.
Queensl. P.
Queensl. Annu. Rep. Brit.

N. Guinea
Queensl. Natur. Hist. Soc.

Trans.
Queensl. Mus. Ann.
Queensl. Roy. Soc. Proc.
Quekett Micro. Club J.
Quetelet, Corresp. Math.
Radium
Railroad Eng. J.

Ranuzzi, Annuario Geogr.
Rass. minerar.
Ranch Staub
Rayer, Archiv.
Reclam, Kosmos

Records Min.

Recueil Math. (Moscou)

Rec. Trav. Chim. Pays-

Bas
Rec. Zool. Suisse

Regensburg Bot. Ges.
Regensburg Bot. Ges.

Denkschr.
Regensburg, Bot. Ztg.

Regensburg, Korresp. Blatt,

Reichert, Archiv.

Reil, Archiv.

Reimann's Ztg.

Reims, Seances Acad.

Rend. soc. chim. ital.

Rep.

Rep. Anal. Chem.

Rep. Anat. Physiol.

Rep. Chim.

Rep. Chim. pure (appl.)

Rep. Pat. Inv.
Rep. Math.

Transactions of the Literary and Historical Society of

Quebec
Queensland Patent
Annual Report on British New Guinea

Transactions of the Natural History Society of Queens-
land

Annals of the Queensland Musetmi

The Proceedings of the Royal Society of Queensland

Jotunal of the Quekett Microscopical Club

Correspondance Mathematique et Physique

Radium, Le

The Railroad and Engineering Journal. The Amer-
ican Railroad Journal and Van Nostrand's Engi-
neering Magazine have been consolidated in this-
publication

Annuario geographico Italiano

Rassegna mineraria metallurgica e chimica

Ranch und Staub

Archives de Medecine comparee

Kosmos: Zeitschrift fiir angewandte NattuiRrissen-
schaften

Records of Mining

Recueil Mathematique. Public par la Sod6t6 Mathe-
matique de Moscou

Recueil des Travaux Chimiques des Pays-Bas (et
de la Belgique) ,

Recueil Zoologique Suisse, comprenant I'Embryologie,
r Anatomic et 1' Histologic comparees, la Physiologic,
I'Ethologie, la Classification des Animaux vivants
et fossiles

See Flora

Denkschriften der Koniglich (Bayerischen) Botan-
ischen Gesellschaft zu Regensbiu-g

Botanische Zeitung; herausg. von der k. Baier. Botan-
ischen Gesellschaft zu Regensburg

Korrespondenz-Blatt des Zoologischmineralogischen
Vereins in Regensburg

Archiv fur Anatomic, Physiologic, und wissenschaft-
liche Medicin

Archiv. fur die Physiologic

Reimann's Farberzeitung

Seances et Travaux de I'Academie de Reims

Rendiconti della societa chimica italiana

Repertorium, Repertoire Repertory

Repertorium der analytischen Chemie ... Organ des
Vereins Analytischer Chemiker

Repertoire generate d'Anatomie et de Physiologic
pathologiques et de Clinique chirurgicale

Repertoire generale de Chimie (1901- ), G. Jaubert

Repertoire de Chimie pure (et appliqu6e) (Societe
Chimique de Paris, 1859-1864)

The Repertory of Patent Inventions and other dis-
coveries and improvements in arts, manufactures
and agriculture

Repertorium der literarischen Arbeiten aus dem.
Gebi^te der reinen und angewandten Mathematik

LIST OF ABBREVIATIONS TO LITERATURE

cm

Rep. Meteorol.

Rep. Pharm.

Rep. Phys.

Rep. Phys.-Tech.

Rep. Chem. Lab. Amer.

Med. Ass.
Rep. Council Pharm. Chem

Rep. H. M. Insp. Expl.

Rep. N. Y. Bd. Pharm.

Rev. Anthrop.

Rev. Artill.

Rev. Biol. Nord France

Rev. Bot.

Rev. Bryol.

Rev. chim. ind.

Rev. Cours. Sci.

Rev. deux Mondes
Rev. Entom.

Rev. gen. Bot.
Rev. gen. chim.
Rev. gen. lait
Rev. gen. mat. color.

Rev. gen. sci.

Rev. Hortic.

Rev. hyg. pol. sanitaire

Rev. Ind.

Rev. Ind. Chim.

Rev. Mag. Zool.

Rev. Maritime Colon.

Rev. Med. Chir.

Rev. Med. Franc. Etrang.

Rev. Met.

Rev. Mycol.

Rev. phot.
Rev. Quest. Sci.

Rev. Sci.

Rev. Sci. Natur.

Rev. Soc. Hyg. Aliment.

Rev. Suisse Zool.

Rev. Univ. Mines

Repertorium fur Meteorologie, herausgegeben von

der Kaiserlichen Akademie der Wissenschaften
Repertorium fiir die Pharmacie
Repertorium der Physik
See Carl
Reports of the Chemical Laboratory of the American

Medical Association, Chicago
Reports of the Council of Pharmacy and Chemistry,

American Medical Association, Chicago
Report of His Majesty's Inspectors of Explosives
Report of the New York State Board of Pharmacy
Revue d'Anthropologie
Revue d'Artillerie

Revue Biologique du Nord de la France
Rev. de Botanique. Bulletin mensuel dc la Soci6t6

Francaise de Botanique
Revue Bryologique. Bulletin bimestriel consacre

a I'Etude des Mousses et des Hepatiques
Revue de chimie industrielle et La revue de physique

et de chimie
Revue des Cours Scientifiques de la France et dc

I'Etranger
Revue des deux Mondes (Paris)
Revue d'Entomologie publiee par la Soci6t6 Francaise

d'Entomologie
Revue generale de Botanique

Revue generale de chimie pure et appliquee (G. Jaubert)
Revue generale du lait
Revue generale de matieres colorantes et de leurs

applications aux textiles
Revue generale des sciences pure et appliquee
Revue Horticole, Journal d' Horticulture pratique
Revue d'hygiene et de police sanitaire
Revue Industrielle

Revue des industries chimiques et agricoles
Revue et Magazin de Zoologie, pure et appliquee
Revue Maritime (et Coloniale)
Revue Medico-Chirurgicale de Paris
Revue Medicale Francaise et Etrangere
Revue de Metallurgie

Revue Mycologique. Recueil trimestriel illustre con-
sacre a I'Etude des Champignons
Revue de photographic
Revue des Questions scientifiques publiee par la

Soci6t^ Scientifique de Bruxelles
(la) Revue Scientifique (de la France et dc I'Etranger.

Revue des Cotu's Scientifiques)
Revue des Sciences Naturelles
Revue de la soci^t6 scientifique d'Hygiene alimentairc

et de I'alimentation rationelle de I'homme
Revue Suisse de Zoologie (et) Annales (de la Soci€t6

Zoologique Suisse et) du Musec d'Histoire Nattu^Ue

de Gcieve
Revue universelle des Mines, de la Metallurgie, des

Travaux Publics, des Sciences et des Arts Appliquee

a rindustrie. Annuaire de 1' Association des In-

genieurs sortis de I'Ecole de Liege

av

LIST OF ABBREVIATIONS TO LITERATURE

Rev. Vit.
Rev. ZooL
Revista Brazil.

Revista, Chim. pure app.
Revista ind. agric. Tucu-

maii
Revista Ligure
Revista Med. Chile
Revista Med. Cirug. Habana
Revista Minera
Revista real acad. cien.

Madrid
Revista Telegr.
Revista Trim. Microgr.

Rhea

Rheinische Monatsschr.
Rheinh Westphal.
Rheinl. Westphal. Corresp.

Rheinl. Westphal. Verh.

Rheinl. Westphal. Sitzber.

Rheinpfalz PolHchia Pest-
schr.

Rheinpfalz Pollichia Jahr.

Rheinpfalz Pollichia Mitth.

Rheinpfalz Pollichia Sep.-

Ausg.
Rhodora

Riga, Arb. Naturf. Vei.
Riga, Corresp. Blatt.

Naturf. Ver.
Rio de Janeiro Archiv.

Palestr.
Rio de Janeiro Mus. Nac.

Archiv.
Rio de Janeiro Mus. Nac.

Revista
Rio de Janeiro Obs. Annaes
Rio de Janeiro Obs. Bol.
Rio de Janeiro Obs. Revista

Rio, Revista

Rio, Soc. Veil. Trabal.

Riv.

Riv. Bolognese

Riv. Geogr. Ital.

Revue Viticulture

Revue Zoologique, par la Soci6t6 Cuvierienne

Revista Brazileira, Journal de Sciencias, Lettras, e

Artes
Revista de chimica pure applicada
Revista industrial y agrocoki de Tucuman

Revista Ligure, giomale di Lettere, Scienze, etc.
Revista medica de Chile
Revista de Medicina y Cirugia, Habana
Revista Minera, periodico cientifico e industrial
Revista de la real academia de ciencias de Madrid

Revista de Telegrafos

Revista Trimestral Micrografica. Organo del Lab-
oratorio Histologico de la Pacultad de Medicina de
Madrid

Rhea, Zeitschrift ftir die gesammte Omithologie

Rheinische Monatsschrift ftir praktische Aerzte

See Bonn.

Correspondenzblatt des Naturhistorischen Vereins
der Preussischen Rheinlande und Westphalens

Verhandltmgen des Naturhistorischen Vereins der
Preussischen Rheinlande tmd Westphalens

Sitzungsbericht des Naturhistorischen Vereins der
Preussischen Rheinlande und Westphalens

Festschrift zur Ptinfzigjahrigen Stiftungsfeier der
Pollichia, Naturwissenschaftlichen Vereines der
Rheinpfalz

Jahresbericht der Pollichia, eines Naturwissenschaft-
lichen Vereins der Rheinpfalz

Mittheilungen der Pollichia, eines Naturwissenschaft-
lichen Vereins der Rheinpfalz

. . . Separat-Ausgabe der Pollichia, des Naturwissen-
schaftlichen Vereines der Pfalz

Rhodora. Journal of the New England Botanical
Club

Arbeiten des Naturf orschenden Vereins in Riga

Correspondenz-Blatt des Naturforschenden Vereins
in Riga

Archivos da Palestra Scientifica do Rio de Janeiro

Archivos do Museu Nacional do Rio de Janeiro

Revista do Museu Nacional do Rio de Janeiro. . .

(Seguimento aos Archivos do Museu Nacional)
(Annaes do Imperial Observatorio do Rio de Janeiro^
Boletim mensal do Observatorio do Rio de Janeiro
Revista do Observatorio. Publicacao mensal do

Imperial Observatorio do Rio de Janeiro
Revista tri mensal de Historia e Geographis: Journal

do Institute Historico e Geographico Brasileiro
Trabalhos da Sociedade Vellosiana (Bibliotheca

Guanabarense)
Rivista

Rivista Bolognese di Scienze e Lcttere
Rivista Geografica Italiana (e BoUetino della Societa

di Studi Geografici e Coloniali in Pirenze)

LIST OF ABBREVIATIONS TO LITERATURE

CV

Riv. Ital. Sci. Natur. Napoli Rivista Italiana di Scienze Nattirali e loro Applicazioni

pubblicata per cura degli Aspirant! Naturalist!
Riv. Ital. Sci. Natur. Siena Rivista Italiana d! Scienze Natural! e Bollettino del

Riv. Mat.

Riv. Mineral. Crist.
Riv. Patol. Veg.
Riv. Sci.-Ind.

Riv. Sper. di Preniatria

Riv. Vit. Ital.
Robin, J. Anat.

Rochelle

Rochester Acad. Sci. Proc.

Rochester Trans. Elec.

Med. Assoc.
Rock Products
Rohr, Notizen
RoUett
Roma

Roma, Atti Nuovi Lincei
Roma, Atti Reale Accad.
Roma, Corrisp. Sci.

Roma 1st. Bot. Annuario
Roma Lab. Anat. Norm.

Ric.
Roma, Nuovi Lincei Mem.
Roma, Oss. Coll. Rom.

Mem.
Roma, R. Accad. Lincei
(Roma), Soc. Ital. Mem.

Naturalista CoUettore, Allevatore, Coltivatore
Rivista di Matematica

Rivista di Mineralogia e Cristallografia Italiana
Rivista di Patologia Vegetale
Rivista Scientiiico-Industriale delle principali Scoperte

ed Invenzion! fatte nelle Scienze e nelle Industrie
Rivista Sperimentale di Preniatria e di Medidna

legale. . .
Rivista di Viticoltura ed Enologia Italiana . . .
Journal de I'Anatomie et de la Physiologic normales

et pathologiques de I'homme et des animaux
See under Charente-Inf .
Proceedings of the Rochester New York Academy of

Science
Transactions of the National Electic Medical Associa-
tion at its Third Meeting, at Rochester, U. S.
Rock Products

Notizen aus dem Gebiete der practischen Pharmacie
See Graz.

See Congr. Med. Int. Atti, 1894
Atti deir Accademia Pontificia de' Nuovi Lincei
Atti della Reale Accademia de! Lincei
Corrispondenza Scientiiica in Roma per le avanza-

mento delle Scienze, etc.
Annuario del R. Istituto Botanico di Roma
Ricerche fatte nel Laboratorio di Anatomia Normale

della R. Universita di Roma
Memorie della Pontificia Accademia de! Nouvi Lincei
Memorie del R. Osservatorio'del CoUegio Romano

Atti della R. Accademia de! Lincei
Memorie di Mathematica e di Pisica della Societa
Italiana delle Scienze
Roma, Soc. Stud! Zool. Boll. Bolletino della Societa Romana per gU Stud! Zoologici
Roma, Specola Vaticana Pubblicazioni della Specola Vaticana

Pubbl.
Roma, Ufif. Centr. Meterol. Annali dell' Ufficio Centrale di Meterologia Italiana
Ann.

Rdmer, Archiv Bot.
Roser Wunderlich, Archiv

Rotterdam Nieuwe Verb.

Rouen, Bull. Soc. Emul.

Rouen, Soc. Sci. Bull.

Rouen, Trav. Acad.

Roumanie Inst. Meteorol.

Ann.
Roy. Engin. Papers

Roy. Inst. J.

Archiv fur die Botanik

Archi-v ftir physiologische Heilkunde. Continued as

the Archiv. d. Heilk.
Nieuwe Verhandelingen van het Bataafsch Genoot-

schap der Proefondervindelijke Wijsbegeerte

Rotterdam
Bulletins (des travaux) de la Soci^t^ Libre d']£mula-

tion de Rouen
Bulletin de la Soci6t^ des Amis des Sciences Naturelles

de Rouen
Precis analytique des Travaux de 1' Academic des

Sciences, Belles-Lettres, et Arts de Rouen
Annales de I'lnstitut Meteorologique de Roumanie

Annalele Institutului Meteorologio al Romaniei
Papers on subjects connected with the duties of the

Corps of Royal Engineers
Journal of the Royal Institution of Great Britain

CVl

LIST OF ABBREVIATIONS TO LITERATURE

Roy. Inst. Proc.

Roy. School Naval Archit.

Ann.
Roy. Soc. Proc.

Rugby, Natur. Hist. Soc.

Reports
Russ. Annu. Geol. Mineral.
Russ. Annuaire Mines
Russ. Chem. Soc: J.
Russ. Geogr. Ges.

Denksclu*.
Russ. J. exp. Landw.
Russ. Jahr. Pharm.
Russ. P.

Russ. Pharm. Zts.
Russ. Phys.-Chem. Soc. J.

Rust, Mag.

S. Africa Chem. Metall.

Soc.
S. Africa Chem. Metall.

Soc. Proc.
S. Africa. Mus. Ann.
S. Africa. Phil. Soc. Trans.

S. Austral. P.

S. Austral. Roy. Soc. Mem.

S. Austral. Roy. Soc.

Trans.
S. C. Med. Assoc. Trans.

S. London Entom. Natur.

Hist. Soc. Proc.
S. Wales Inst. Civ. Kngin.

Proc.
S. Wales Roy. Inst. Report

Sachs. Ingen. Ver. Mitth.
Sachs. Meteorol. Inst. Abh.

Sachs. Thiiring. Naturwiss.

Ver.
Salem
San Fernando Obs. Marina

An.
Sanitary Record

Santiago Chile, Univ.

Anales
Sao Paulo, Rev. Mus.

Paulista

Notices of the Proceedings at the Meetings of the
Members of the Royal Institution of Great Britain,
with Abstracts of the Discotu-ses delivered at the
Evening Meetings

The annual of the Royal School of Naval Architecture
and Marine Engineering

Abstracts of the Papers printed in the Philosophical
Transactions of the Royal Society of London, from
1800 to 1864 inclusive. Continued as the Proceed-
ings of the Royal Society of London

Reports of the Rugby School Natural History Society

Russian Annual of Geology and Mineralogy

Annuaire du Journal des Mines de Russie

Journal of the Russian Chemical Society

Denkschriften der Russischen Geographischen Gesell
schaft zu St. Petersburg

Russiches Journal fiir experimentelle Landwirtschaft

Russisches Jahrbuch der Pharmacie

Russian Patent

Pharmaceutische Zeitschrift fur Russland

Journal of the Russian Physico-Chemical Society of
the Imperial Univeisity of St. Petersburg

Magazin fur die gesammte Heilkunde, etc.

The Journal of the Chemical and Metallurgical Society
of South Africa

The Proceedings of the Chemical and Metallurgical
Society of South Africa

Annals of the South African Museum

The Transactions of the South African Philosophical
Society

South Australian Patent

Memoirs of the Royal Society of South Australia

Tran sactions and Proceedings and Report of the Royal
Society of South Australia

Transactions of the South Carolina Medical Asso-
ciation

(Abstract of) Proceedings of the South London Ento-
mological and Natural History Society

Proceedings of the South Wales Institute of Civil
Engineers

The annual report of the Council of the Royal Insti-
tution of South Wales, with Appendix of Original
Papers on Scientific Subjects

Mittheilungen des Sachsischen Ingenieur-Vereins;
herausg. v. d. Verwaltungsrathe des Vereins

Abhandlungen des Konigl. Sachs. Meteorologischen
Institutes

See Zts. Naturwiss.

See Essex Institute
Anales del Instituto y Observatorio de Marina de San

Fernando
Sanitary Record and Journal of Municipal Engineering,

The
(Republica de Chile.) Anales de la L^niversidad

Revista do Museu Paulista

LIST OF ABBREVIATIONS TO LITERATURE

evil

Saone-et-Loire Soc. Sci.

BuU.
Saone-et-Loire Soc. Sd.

Mem.
Sarthe, Bull. Soc. Agric.

Savoie Acad. Mem.

Savoie Soc. Hist. Natur.

BuU.
Savoie Soc. Hist. Natur.

(Compt. rend.)
Schaffhausen
Scheik. Onderz.
Schemnitz Bergakad.
Scherer, J. Chem.
Schlesw.-Holst. Naturwiss.

Ver. Schr.
Schldmilch, Zts.
Schneider, Ann. Staatsarz-

neik.
School Mines Quart.
School of Mines, Records
Schrader, J. Bot.
Schrdder, Berig. Zeevaart.

Schrdder, Verh. Zeevaart.

Schuh Ind.
Schtmiacher, Jahr.
Schwab. Ges. Denkschr.

Schwalbe

Schweigger, J. (Schw. J.)
Schweiz. Alpenclub Jahr.
Schweiz. Bot. Ges. Ber.
Schweiz. Entom. Ges.

Mitth.
Schweiz. Ges. Neue

Denkschr.
Schweiz. Ges. Verh.

Schweiz. Monatsschr.
Schweiz. Naturf. Ges.
Schweizer. Naturf. Ges.

Verh.
Schweiz. Phot.-Ver.
Schweiz. Poly. Zts-

Schweiz. Wochenschr.

Schweiz. Zts. Heilk.

Sd.

Sd. Abst.

Sd. Amer.

Bulletins de la Soci^t6 des Sdences Naturelles de

Saone-et-Loire
Memoires de la Sodet4 des Sdences Naturelle de

Saone-et-Loire
Bulletin de la Sod6t6 d' Agriculture, Sciences, etc., de

la Sarthe
Memoires de TAcademie dea Sdences, Belles-Lettres

et Arts de Savoie
Bulletins de la Sod6t6 d'Histoire Naturdle de Savoie

Sod6t6 d'Histoire Naturdle de Savoie a Chambcry

See Schweizer. Entom. Gesell.

See Utrecht. Scheik. Onderzoek

See Wien, Berg- u. Huttenm. Jahr.

Allgemeines Journal der Chemie

Schriften jdes Naturwissenschaftlichen Vereins fiir

Schleswig-Holstein
Zdtschrift fur Mathematik und Physik
Annalen der gessammten Staatsarzneikunde

School of Mines, Quarterly, The

Records of the School of Mines

Journal fur die ^otanik

Berigten en Verhanddingen over eenige onderwerpen

des Zeevaarts
Verhandelingen en Berigten over eenige onderwerpen

der Zeevaart-Kunde
Schuh Industrie

Jahrbuch, (H. C. Schumacher, (1836-38))
Denkschriften der Schwabischen Gesdlschaft der Aerzte

tmd Naturforscher
Omithologische Section der k. k. Zoologisch-Botan-

ischen Gesdlschaft in Wien. Die Schwalbe. Ber-

ichte des Comites fiir Omithologische Beobachtungs-

Stationen in Oesterreich
Journal fiir Chemie und Physik
Jahrbuch des Schweizer Alpenclub
Berichte der Schweizerischen Botanischen Gesdlschaft
Mittheilungen der Schweizerischen Entomologischen

Gesellschaft
Neue Denkschriften der allgemeinen Schweizerischen

Gesdlschaft fiir die gesammten Naturwissenschaften
Verhandltmgen der Schweizerischen Gesdlschaft fiir

die geasmmten Naturwissenschaften
Schweizerische Monatsschrift fiir praktische Medizin
See Beitr. Kryptog. Schweiz.
Verhandlungen der Schweizerischen Naturforschenden

Gesdlschaft
See Wien, Phot. Correspond.
Schweizerische pol3rtechnische 2^itschrift. Unter Mit-

wirktmg des Schweizerischen Polytechnikums, etc.
Schweizerisch Wochenschrift fur Chemie und Pharm-

acie
Schweizerische Zdtschrift fiir Heilkunde
Sdence

Sdence Abstracts. Physics and Electrical Engineering
Scientific American

CVIU

UST OF ABBREVIATIOl^S TO LITERATURE

Sci. Amer. Suppl.

Sci. Can.

Sci. Ind. Bull. Roure-

Bertrand Fils
Sci. Proc. Roy. Dublin

Soc.
Sci. Rev.

Sci. Trans. Roy. Dublin

Soc.
Sdenz. Ital. Congr.

Sclater, Ibis

Scott. Arbor. Soc. Trans.
Scott. Geogr. Mag.
Scott. Meteorol. Soc. J.
Scott. Micro. Soc. Proc. &

Trans.
Scott. Natur.

Scott. Soc. Arts Trans.
Seeman, J. Bot.
Seifenfabr.
Seifens. Ztg.

Seine (Dep. de la)
Seine, Mem. Soc. Agric.

Seine-et-Oise, Mem.

Seism. J. Japan
Selenka, Archiv Zool.
Semi-Ann. Rep. Schimmel

&Co.
Senckenberg. Naturf. Gcs.

Abh.
Senckenberg, Naturf. Ges.

Ber.
Shanghai, J.

Shanghai, J. Lit. Soc.

Shoe Lea. Reporter
Shropsh. Soc. Trans.

Sicilia, Atti Soc. Acclim.

Sidereal Messenger
Siebenb. Karpath. - Ver.

Jahr.
Siebold, J. Geburtshiilfe

Siebold Kolliker, Zts.
Siebold, Lucina

Siena, Atti Accad.

Silbermann, Rev. Entom.

Scientific American Supplement

Scientific Canadian

Scientific et Industrial Bulletin Roure-Bertrand Fils

Scientific Proceedings of the Royal Dublin Society

The Scientific Review and Journal of the Inventors

Institute
Scientific Transactions of the Royal Dublin Society

Nuovo Congresso degli Sdenziati Italiani in Venezia;
porzione geologica

The Ibis, a Magazine of General Ornithology

Transactions of the Scottish Arboricultural Society

The Scottish Geographical Magazine

Journal of the Scottish Meteorological Society

Proceedings and Transactions of the Scottish Micro-
scopical Society

A Magazine of Scottish Natural History (and Jour-
nal of the Perthshire Society of Natural Science)

Transactions of the Royal Scottish Society of Arts

The Journal of Botany, British and Foreign

Seifenfabrikant, Der

Seifensieder Zeittmg und Revue iiber die Harz, Fett
und Oelindustrie

See (France) Soc. Agr. Mem.

Memoires d'Agricultiu-e par la Soci6t6 Agricole de la
Seine

Memoires de la Soci6t6 des Sciences Naturelles de
Seine et Oise

Seismoiogical Journal of Japan

Nederlandisches Archiv fiir Zoologie

Semi-Annual Report, Schimmel & Co., Miltitz

Abhandltmgen herausg. von der Senckenbergischen

Naturforschenden Gesellschaft
Bericht fiber die Senckenbergische naturforschende

Gesellschaft in Frankfurt am Main
Journal of the North-fhina Branch of the Royal

Asiatic Society
Journal of the Literary and Scientific Society of

Shanghai
Shoe and Leather Reporter
Transactions of the Shropshire Archaeological and

Natural History Society
Atti della Societa di Acclimazione e di Agricoltura in

Sicilia
The Sidereal Messenger
Jahrbuch des Siebenbtirgischen Karpathen-Vereins

Journal fiir die Gebtutshiilfe, Frauenzimmer, etc., von

Elias von Siebold
Zeitschrift fur wissenschaftliche Zoologie
Lucina; eine Zeitschrift zur VervoUkommung der

Entbindungskunst
Atti deir Accademia delle Scienze di Siena detta de*

Fisio-critici
Revue Entomologique

LIST OF ABBRBVIATIONS TO UTERATURB

OX

Silliman, J.

Singapore Roy. Asiat. Soc.

J.
Sitzber. kais. Akad. Wiss.
Wicn.

Sitzb. k d n i g Akad.

Munchen
Sitzber. kdnig. Akad. Wiss.

Berlin
Sitzber. kdnig. preuss.

Akad.
Skand. Archiv Physiol.
Skand. Naturf. Fdrh.

Skand. Naturf. Mod.
Forh.

Skand.
Fdrh.

Skandia

Natur. Mot.

Skofitz

Skofitz, Bot. Wochenbl.
Skofits, Bot. Zts.
Smithsonian Contrib.
Smithsonian Inst. Astro-

phys. Obs. Ann.
Smithsonian Inst. Bur.

Ethnol. Repcnrt
Smithsonian Misc. Coll.
Smithsonian Report

Snelling's Phot. J.

Soc. Bot. Ital Bull.

Soc. Broteriana

Soc. Elvet. Sci., Naturf.

Atti
Soc. Entom. Ross. Horae

Soc. Franc. Bot.
Soc. Franc. Entom.
Soc. Freniatr. Ital.
Soc. Geogr. Finland
Soc. Helvet. Actes.
Soc. Helvet. Sci. Naturf.

Act.
Soc. Ital. Antrop.
Soc. Ital. Fis.
Soc. Ital. Micro. Boll.
Soc. Ital. Sci.
Soc. Ital. Sd. Nat.
Soc. Ligust. Sci. Natur.

Geogr.
Soc. Malacol. France

The American Journal of Science and Arts

Journal of the Straits Branch of the Royal Asiatic

Society. Singapore
Sitzungsberichte der kaiserlichen Akademie der Wis-

senschaften, Wien (Mathematisch-naturwissen-

schaftHche Klass) Abteiltmgen I, Ila, lib, III
Sitzungsberichte der kdniglich bayerischen Akademie

der Wissenschaften zu Munchen
Sitzungsber der kdniglich preussischen Akademie der

Wissenschaften zu Berlin
Sitzungsberichte der kdniglich preussischen Akademie

der Wissenschaften
Skandinavisches Archiv fur Physiologic
Forhandlingar vid det af Skandinaviska Naturforskare

och Lakare hallna Mote i Gdtheborg
Forhandlingeme ved de Skandinaviske Naturforskeres

lite Mode i Kjobenhavn fra den Sdie til den 9de

Juli, 1873
Fdrhandlingar vid de Skandinaviska Naturforskames

Tolfte Mote i Stockhohn frail den 7 till den 14 Juli,

1880
Skandia. Tidskrift f5r Vetenskap och Koiist; utgifven

af Svenska Litteratur-Fdreningen
See Oesterreich. Botan. Zeitschr.
Oesterreichisches Botanisches Wochenblatt
Oesterreichische Botanische Zeitschi'ift
Smithsonian Contributions to Knowledge
Annals of the Astrophysical Observatory of the

Smithsonian Institution
Annual Report of the Bureau of (American) Ethnology

to the Secretary of the Smithsonian Institution
Smithsonian Miscellaneous Collections
Annual Report of the Board of Regents of the Smith-
sonian Institution, showing the Operations, Expendi-
tures and Condition of the Institution
Snelling's Photographisches Journal
See Nuovo Giotn. Bot. Ital.
See Coimbra, Soc. Broter. Biol.
S6e Schweiz. Natiuf. Ges. Verb.

Horae Societatis Entomologicae Rossicae variis ser-

monibtts in Rossia usitatis editae
See Rev. Bot.
See Rev. Ent.
See Riv. Sper. di Freniatria
See Fennia

Actes de la Soci^td Helvetique des Sciences Naturelles
See Schweiz. Natf. Ges. Verb.

See Arch. Antropologia

See Nuovo Cimento

See Acireale, Soc. Ital. Micr. Boll.

See (Roma), Soc. Ital. Mem.

See Milano, Soc. Ital.

See Genova, Soc. Ligust. Atti

See Ann. Malacol.

ex

LIST OF ABBREVIATIONS TO LITHRATURB

Soc. Malacol. Ital. Bull.
Soc. Meteorol. Ital.
Soc. Mez. Hist. Natur.
Soc. Napoli

Soc. Nat. Sicil.
Soc. Pharm. Anvers
Soc. Public Analysts
Soc. Speleol.

Soc. Telegr.-Engin. Elect.
Soc. Tosc. Sci. Nat.
Soc. Ven.-Trent. Sci. Nat.
Soc. Zool. Suisse Ann.
Soc. Zool. Tokyo
Somerset. Archaeol. Soc.

Proc.
Somerset. Sov. Proc.

Somme (Dep. de la)

Southern Pharm. J.

Span. P.

Spatula

Speltmca. Paris

Sperimentale

Spettatore Vesuvio

Spettrosc. Ital. Mem.

Spongia, Comm. Med.

Sprechsaal

Spregnel, Jahr.

Six-engst. Wafifen Mun.

St. Andrew's Med. Grad.
Assoc. Trans.

St. Barthol. Hosp. Reports

St. Etienne, Bull. Soc. Ind.
Mineral

St. Gallen. Ber. Natur-
wiss. Ges.

St. Louis, Bot. Gard. Re-
port

St. Louis, Trans. Acad. Sci.

St. Petersb. Acad. Sci.

BuU.
St. Petersb. Acad. Sci.

Compt. rend.
St. Petersb. Acad. Sci.

Mem.
St. Petersb. Acad. Sci.

Nova Acta.
St. Petersb. Acad. Sci.

Recucil
St. Petersb. Ann. Mines

Russ.
St. Petersb. Archiv. Sci.

Biol.

St. Petersb., Congr. Bot.
Bull.

See Bull. Malacol. Ital.

See Moncalieri Oss. Boll.

See Naturaleza

Societa reale di Napoli. Rendiconto dell' Academia

delle Scienze fisiche e mathematiche
See Nat. Sicil.
See J. de Pharm.
See Analyst
See Spelunca, Paris
See Telegr. Eng. J.
See Pisa Soc. Tosc.
See Padova Soc. Sci.
See Rev. Suisse.: Zool.
See Annot. Zool. Jap.
Proceedings of the Somersetshire Archaeological and

Natural History Society
Somersetshire Archaeological and Natural History

Society's Proceedings
See imder Amiens
Southern Pharmaceutical Journal
Spanish Patent
Saptula (The), Boston

Spelunca. Bulletin de la Soci6t^ de Speleologie
Lo Sperimentale. Giomale Italiano di Scienze Meidche
Lo Spettatore del Vesuvio e de' Campi Flegrei
Memorie della Societa degli Spettroscopisti Italiani
Commentarii di Medidna
Sprechsaal

Jahrbucher der Gewachskunde
Sprengstoffe, Wafifen und Munition
Transactions of the St. Andrew's Medical Graduates

Association
St. Bartholomew's Hospital Reports
Bulletin de la Soci6t6 de 1' Industrie Minerale

Berichte uber die Thatigkeit der St. Gallischen Natur-

wissenschaftlichen Gesellschaft
Missouri Botanical Garden Report

The Transactions of the Academy of Science of St.

Louis
Bulletin scientifique public par I'Academie Imperiale

des Sciences de St. Petersbourg
Compte Rendu de I'Academie Imperiale des Sciences

de St. Petersbourg
Memoires de I'Academie Imperiale des Sciences de St.

Petersbourg
Nova Acta Academiae Scientiarum Imperialis Petro-

politanae
Recueil des Actes des Seances Publiques de I'Academie

Imperiale des Sciences de St. Petersbourg
Annuaire du Journal des Mines de Russie

Archives des Sciences Biologiques publiees par I'lnsti-

tut Imperial de Medecine Experimentale a St.

Petersbourg
Bulletin du Congres International de Botanique et

d'Horticulture de St. Petersbourg le 6/18, le 8/20

et le 10/22 Mai 1869

LIST OF ABBREVIATIONS TO LITERATURE

CXI

St. Petersb. Inst. Med.

Exper.
St. Petersb. Med. Zts.
St. Petersb. Med. Wochen-

schr.
St. Petersb. Mem. Savants

Etrang.
St. Petersb. Mineral. Gcs.

Verb.
St. Petersb., Russe Geogr.

Mem. (Geogr.)
St. Petersb., Russ. Geogr.

Soc. Bull.
St. Petersb. Schr. Mineral.

St. Petersb. Verb. Mineral.

Ges.
St. Petersb. Verm. Abh.

St. Quentin, Ann.

St. Quentin, Mem.

St. Quentin, Seances Publ.

St. Quentin, Travaux

St. Thomas's Hosp. Reports
Stahl Eisen (Zts.)

Stavanger Mus. Aarsber.
Staz. sper. agrar. ital.
Steiermark. C^eog. Mont.

Ver. Ber.
Steiermark Mitth.

Steiermark. Mont. Lehr-

anst. Jahr.
Stein, Ann.

Stettin, Entom. Ztg.

Steyermark. Zts.
Stirling Field Club Trans.
Stirling Soc. Trans.

Stockholm, Akad. Handl.

Stockholm, Bihang Akad.

Handl.
Stockhohn Bot. Sallsk.

See St. Petersb. Arch. Sci. Biol.

St. Petersburger Medicinische Zeitschrift
St. Petersburger Medicinische Wochenschrift

Memoires presentes a V Academic Imperiale des
Sciences de St. Petersbourg par divers Savants

Verhandltmgen der Russisch-Kaiserlichen Mineralog-
ischen Gesellschaft zu St. Petersbourg

Memoirs de la Soci6t6 Imperiale Russe de C^eographie
Section de Geographic generale

Btdletins of the Imperial Russian Geographical So-
ciety

Schriften der in St. Petersburg gestifteten Kaiserlich-
Russischen Gesellschaft fur die gesammte Minera-
logie

Verhandlungen der KaiserUch-Russischen Mineralog-
ischen Gesellschaft zu St. Petersburg

Vermischte Abhandlungen a'us dem Gebiete der
HeiUcunde von einer Gesellschaft pract. Aerzte zu
St. Petersburg. Additional title in 1835, Medizin-
isch-praktische Abhandlung von Deutschen in Russ-
land lebenden Aerzten. Continued as the Neue
Abhandlung St. Petersburg •

Annales Agricoles du department de TAisne, publiees
par la Soci4t6 des Sciences, Arts, Belles-Lettres,
et Agriculture de St. Quentin. Annales. Sdentiiiques,
Agricoles, et IndustrieUes du departement de I'Aisne
(Soci6t6 Academique de Saint Quentin)

Memoires de la Soci6t6 des Sciences, Arts, Belles-
Lettres, et Agriculture de la ville de St. Quentin

Soci6t6 des Sciences, Arts, Belles-Lettres, et Agricul-
ture de la ville de St. Quentin: Seances publiques.

Soci4t6 Academique des Sciences, Arts, Belles-Ivettres,
et Agriculture de St. Quentin (Aisne)

St. Thomas's Hospital Reports

Stahl und Eisen, Zeitschrift ftir das deutsche Eisen-
huttenwesen

Stavanger Museums Aarsberetning

Stazioni sperimentali agraria italiana, La

Bericht des Geognostisch-montanistischen Vereins ftir
Steiermark

Mittheilungen des Natiuivissenschaftlichen Vereines
fiir Steiermark

Die Steiermarkisch standische montanistische Lehran-
stalt zu Vordemberg

Annalen der Geburtshulfe utberhaupt und der Ent-
bindungsanstalt zu Marburg insbesondere

Entomologische Zeitung; herausg. v. d. Entomo-
logischen Vereine zu Stettin

Steyermarkische 2^itschrift

Stirling Field Club Transactions

Stirling Natural History and Archaeological Society.
Transactions

Kongliga Svenska Vetenskaps Akademiens Hand-
lixigar

Bihang till Kongl. Svenska Vetenskaps Akademiens
Handlingar

See Bot. Centrbl.

cxu

LIST OF ABBREVIATIONS TO LITERATURE

Stockholm Hntom. Fdr.
Stockholm, Hortt Bergiani
Acta

Stockholm, 5fversigt

Stockholm Physiol. Lab.
Mitth.

Stockholm, Svenska Lak.

Sallsk Handl.
Stockholm, Vet. Akad.

Lefnadsteckn.
Stockholm, Ymer

Strasbourg Soc. Hist.

Natur. Mem.
Strasbourg Soc. Sci. Bull.

Strasbourg Soc. Sci. J.

Strasbourg Soc. Sci. Mem.

Stray Feathers

Strieker
Sts. Settl. P.
Student

Sturgeon, Ann. Elect.

Sturgeon, Ann. Phil.

Sucr.

Sucr. Beige

Sucr. ind. colon.

Suddeut. Apoth. Ztg.

Suisse Soc. Zool. Ann.

Surveyor

Sussex Natur. Hist. Soc.

Proc.
Svea

Svensk farm. Tidskr.
Svensk Kem. Tidskr.
Svenska Lak. Sallsk.

Forh.
Svenska Mosskulturfdr.
Svenska Sallsk. Antrop. &

Geogr.
Swart, Verh.

Swed. P.

Swiss P.

Sydney

Sydney Aust. Mus. Mem.

Sydney, Austral. Mus

Records
Symons, Meteorol. Mag.
Tablettes Zool.

See Ent. Tidskr.

Acta Horti Bergiani. Meddelanden fran Kongl.

Svenska Vetenskaps-Akademiens Tradgard Bergie-

lund utgifna af Bergianska Stiftelser
5fversigt af Kongl. Vetenskaps Akademiens Forhand-

lingar
Mittheilungen vom Physiologischen Laboratorium des

Carolinischen Medico-Chirurgischen Instituts in

Stockholm
Handlingar ved Svenska Lakare-Sallskapet

Lefnadsteckningar dfver Kongl. Svenska Vetenskaps-
Akademiens efter ar 1854 aflidna Ledamoter
Ymer. Tidskrift utgifven af Svenska Sallskapet for

Antropologi och Geografi
Memoires de la Soci6t6 du Museum d'Histoire Natur-

elle de Strasbourg
Bulletin de la Soci^t6 des Sciences Naturelles de

Strasbourg
Joiunal de la Soci6t6 des Sciences, Agriculture, et

Arts, du departement du Bas-Rhin
Memoires de la Soci^t6 des Sciences, Agriculture, et

Arts, de Strasbourg
Stray feathers. . A journal of Ornithology for India

and its dependencies
See Medizin. Jahr.
Straits Settlement Patent
The Student and Intellectual Observer of Science,

Literature, and Art
Annals of Electricity, Magnetism, and Chemistry,

and Guardian of Experimental Science
Annals of Philosophical Discovery and Monthly

Reporter of the Progress of Practical Science
La sucrerie indigene
Sucrerie Beige, La
Sucrerie indigene et colonaile. La
Suddeutsche Apotheker 2^ittmg
See Rev. Suisse Zool.

Surveyor and Municipal and County -Engineer, The
See Brighton Nat. Hist. Soc. Proc.

Svea. Tijdskrift for Vetenskap och Konst

Svensk farmaceutisk Tidskrift, Stockholm

Svensk Kemisk Tidskrift

Forhandlingar ved Svenska Lakare-SalUkapets Sam-

mankomster
Svenska Mosskulturfdreningens .
See Stockh., Ymer

Verhandelingen en Berigten betrekkelijk het Zeewezcn

en de Zeewaartkunde
Swedish Patent
Swiss Patent
See New South Wales

The Australian Museum, Sydney. Memoirs
Records of the Australian Museum

Symon's monthly Meteorological Magazine
Tablettes Zoologiques

LIST OF ABBREVIATIONS TO LITERATURE

CXIU

Tagbl. Frankf. Naturf.
Taprobanian

Tasmania J. Natur. Sci.

Tasmania P.

Tasmania, Roy. Soc.
Monthly Not.

Tasmania, Roy. Soc. Re-
ports

Taylor, Sci. Mem.

Tech. Blatter

Tech. Chem. Jahr.
Tech. Gemeindebl.
Technikum
Technol.
Technol. Quart.
Teign Field Club Proc.

Tekn. Tidskr.
Telegr. Eng. J.

Telegr. J.
Telegr. Ver. Zts.

Temminck, Verh.

Termr. Fuz.

Termt. K6zl0n.

Terrestrial Magn.

Texas Acad. Sci. Trans.
Text. Amer.
Text. Col.
Text. Farb. Ztg.
Text. Mfr.
Text. Rec.
Text. World Rec.
Text. Ztg.
TextUfremid
Teyler's Verh.

Therap. Gaz.
Therap. Monats.
Therap. Neuheit
Therapist

Tageblatt Frankfurter Naturforscher

The Taprobanian, a Dravidian Journal of Oriental
Studies in and around Ceylon, in Natural History,
Archaeology, Philology, History

The Tasmanian Journal of Natural Science, Agricul-
ture, Statistics, etc.

Tasmanian Patent

Monthly Notices of Papers and Proceedings of the
Royal Society of Tasmania

Reports of the Royal Society of Tasmania

Scientific Memoirs, selected from the Transactions of

Foreign Academies and Learned Societies and from

Foreign Journals
Technische Blatter. Vierteljahrschrift des Deutschen

Polytechnischen Vereins m Bohmen
Technisch-Chemisches Jahrbuch (Biedermann)
Technisches Gemeindeblatt
Technikum des Ledermarkts
Le Technologiste (F. Malepeyre)
Technology Quarterly
Reports of the Proceedings of the Teign Naturalists'

Field Club
Teknisk Tidskrift
Journal of the Society of Telegraph-Engineers and

Electricians
The Telegraphic Jotunal and Electrical Review
Zeitschrift des Deutsch-dsterreichischen Telegraphen-

Vereins
Verhandelingen over de natuurlijke Geschiedenis der

Nederlandsche overzeesche bezittingen, door de

leden der Natuurktmdige Commissie in Oost-Indie

en andere schrijvers
Termeszetrajzi Fiizetek. . .Kiadja a Magyar Nemzeti

Muzeum. (Natural History Magazine ... published

by the Hungarian National Museum)
Termeszettudomanyi K5zldny . . . Kiadja a K. M.

Termeszettudomanyi Tarsulat. (Natural Science

Papers . .. . Published by the Royal Hungarian

Natural Science Society)
Terrestrial Magnetism (and Atmospheric Electricity).

An International Quarterly Journal
Transactions of the Texas Academy of Science
Textile American
The Textile Colorist
Textil und Farberei-Zeittmg
The Textile Manufacturer
The Textile Record
Textile World Record
Textil Zeitung
Der Textilfreund
Geologische Verhandel af Antwoord af de in 1828

uitgeschrevene en in 1830 herhaalde Prysvraag:

Wat men van Geologic, etc.
The Therapeutic Gazette
Therapeutische Monatshefte
Therapeutischen Neuheiten, Leipzig
Therapist (The) London

CXIV

UST OF ABBREVIATIONS TO LITERATURE

Thomson, Ann. Phil.

Thomson, Archiv. Entom.
Thomson, Rec.
Thonind. Ztg.
Throndhjem, Skrifter

Tidskr. Kemi. Farm.

Terapi
Tidskr. Mat.
Tidskr. Mat. Fys.

Tidskr. Phys. Chem.

Tiedemann, Zts.
Tijdschr. Entom.

Tijschr. Genootsch. Vis.
Unita

Tijdschr. Ing.
Tijdschr. nijv.
Tijdstroom.

Tilesius, Jahr.

Timehri

Tirol, Ber. Ver. Durchf.

Tischl. Ztg.
Tokio Univ. Mem.

Tokyo Bot. Soc.
Tokyo, Coll. Sci. J.

Tokyo Geogr. Soc. J.
Tonind. Ztg.
Topfer Ztg.

Torino, Accad. Sci. Atti
Torino, Accad. Sci. Mem.
Torino, Ann. Clin.
Torino, Lavori Sci. Fis.
Mat.

Torino Mus. Boll.

Torrey Bot. Club Bull.
Torrey Bot. Club Mem.
Tortolini, Ann.
Toulouse Acad. Sci. Bull.

Toulouse, Acad. Sci. Mem.

Toulouse Fac. Sci. Ann.

Toulouse Obs. Ann.

Annals of Philosophy, or Magazine of Chemistry,
Mineralogy, Mechanics, and the Arts

Archives Entomologiques

Records of General Science

Thonindustrie-Zeitung

Der Kongelige Norske Videnskabers-Selskabs Skrifter
i det 19 de Aarhundrede

Tidskrfit for Kemi Farmaci Terapi

Tidsskrift for Matematik

Tidskrift fdr Matematik och Fysik, tillegnad den

Svenska Elementar-Undervisningen
Tidskrift for Physik og Chemi samt disse Videnskabers

Anvendelse
Zeitschrift fiir Physiologic
Tijdschrift voor Entomologie; uitgegeven door de

Nederlandsche Entomologische Vereeniging
Tijdschrift voor Genees-, Heel-, Verlos-, en Schei-

kundige Wetenschappen, van Wege et Genootschap:

"Vis Unita Fortior," te Hoom.
Tijdschrift van het Koninklijk Instituut van Ingenieurs
Tijdschrift t.er befordering van nijverhed
De Tijdstroom; Maandschrift gewijd van Wetenschap,

etc.
Jahrbuch der Naturgeschichte zur Anzeige und

Priifung
Timehri being the Journal of the Royal Agricultural

and Commercial Society of British Guiana
Bericht iiber die General- Versammlung des Vereins

zur geogr. montan. Durchforschung des Landes

Tirol, etc.
Deutsche Tischlerzeitung
Memoirs of the Science Department, University of

Tokio, Japan
See Bot. Mag., Tokyo

The Jotunal of the College of Science, Imperial Uni-
versity, Japan
Journal of the Tokio Geographical Society
Tonindustrie Zeitung
Deutsche Topfer luid Ziegler Zeitung
Atti della R. Accademia delle Scienze di Torino
Memoire della R. Accademia delle Scienze di Torino
Annali Clinici
Notizia storica dei lavori fatti dalla Classe di Scienze

Fisiche e Mathematiche della R. Accademia delle

Scienze negli anni 1864-65
BoUettino dei Musei di Zoologia ed Anatomia com-

parata della R. Universita di Torino
Bulletin of the Torrey Botanical Club
Memoirs of the Torrey Botanical Club
Annali di Scienze, Matematiche, e Fisiche
Bulletin de I'Academie des Sciences, Inscriptions et

Belles-Lettres de Toulouse
Memoires de I'Academie des Sciences, Inscriptions et

Belles-Lettres de Toulouse
Annales de la Faculte des Sciences de Toulouse, pour

les Sciences Mathematiques et les Sciences Physiques
Annales de I'Observatoire Astronomique, Magnetique

et Meteorologique de Toulouse.

LIST OF ABBREVIATIONS TO LITERATURE

CXV

"Toulouse Soc. Hist. Natur.

Bull.
• Toulouse Soc. Sci. Bull.

Trans. Acad. Sci. St. Louis
Trans. Amer. Ceram. Soc.
Trans. Amer. Electrochem.

Soc.
Trans. Amer. Inst. Chem.

Eng.
Trans. Amer. Inst.

Homoeop.
Trans. Amer. Inst. Min.

Eng.
Trans. Amer. Med. Assoc.

Sec. Pharm. Therap.
Trans. Amer. Micro. Soc.
Trans. Amer. Soc. Civ.

Eng.
Trans. Cambr. Phil. Soc.
Trans. Can. Inst.
Trans. Engl. Ceram. Soc.
Trans. Faraday Soc.
Trans. Geol. Soc. S. Africa
Trans. Illimi. Eng. Soc.
Trans. Inst. Brew.
Trans. Jenner Inst. Prev.

Med.
Trans. Kansas Acad. Sci.
Trans. Med.
Trans. Min. Geol. Inst.

India
Trans." Natl. Eclec. Med.

Assoc.
Trans. Nova Scotia Inst.

Sci.
Trans V. P.
Trans. Path. Soc.
Trans. Roy. Irish Acad.
Trans. Roy. Soc. Can.
Trans. Roy. Soc. Edinb.
Trans. Roy. Soc. London
Trans. Soc. Engin.
Trav. Com. Hyg. Publ.

Trenton Natur. Hist. Soc.

J.
Treviso, Mem. Ateneo

Trier, Jahr.

Triest Zool. Sta. Arb.
Trieste, Boll.

Trieste Mus. Civ. Atti
Trieste, Program. Civ.
Scuola

Bulletin de la Soci6t6 d'Histoire Naturelle de Toulouse

Bulletin de la Soci6t£ des Sciences Physiques et

Naturelles de Toulouse
Transactions of the Academy of Sciences of St. Louis
Transactions of the American Ceramic Society
Transactions of the American Electrochemical Society

Transactions of the American Institute of Chemical
Engineers

Transactions of the American Institute of Homoe-
opathy, Philadelphia

Transactions of the American Institute of Mining
Engmeers

Transactions of the Section on Pharmacology and
Therapeutics of the American Medical Association

Tran^ctions of the American Microscopical Society

Transactions of the American Society of Civil Engi-
neers

Transactions of the ^Cambridge Philosophical Society

Transactions of the Canadian Institute

Transactions of the English Ceramic Society

Transactions of the Faraday Society

Transactions of the Geological Society of South Africa

Transactions of the Illuminating Engineering Society

Transactions of the Institute of Brewing

Transactions of the Jenner Institute of Preventive
Medicine

Transactions of the Kansas Academy of Science

Transactions Medicales; Journal de Medecine pratique

Transactions of the Mining and Geological Institute
of India

Transactions National Eclectic Medical Association
Indianapolis

Transactions of the Nova Scotia Institute of Science

Transvaal Patent

Transactions of the Pathological Society

Transactions of the Royal Irish Academy

Transactions of the Royal Society of Canada

Transactions of the Royal Society of Edinbtu-gh

Transactions of the Royal Society of Lcmdon

Society of Engineers, Transactions

Recueil des Travaux du Comite consultatif d'Hygiene

Publique de France et des Actes Officiels de I'Ad-

ministration Sanitaire
Journal of the Trenton, New Jersey, Natural History

Society
Memorie Scientifiche e Litterarie dell' Ateneo di

Treviso
Jahresbericht der Gesellschaft fiir niltzliche Forsch-

ungen zu Trier
See Wien. Zool. Inst. Arb.
Bollettino della Societa Adriatica di Scienze Naturali

in Trieste
Atti del Museo Civico di Storia Naturale di Trieste
Prog^amma della Civica Scuola Reale autonoma in

Trieste

CXvi LIST OF ABBREVIATIONS TO UTERATURE

Trinidad Field Natur. Journal of the Trinidad Field Nauralists' Club
Club J.

Trinidad P. Trinidad Patent

Trinidad, Proc. Sci. Assoc. Proceedings of the Scientific Association of Trinidad

Trinidad, Sci. Assoc. Proc. Proceedings of the Scientific Association of Trinidad

Trommsdorff, J. Pharm. Journal der Pharmacie fur Aerzte und Apotheker,.

und Chemiker

Tromso. Mus. Aarsh. Tromso Museums Aarshefter

Tropenpflanzer Tropenpfianzer (Der). Berlin

Tsch. Mineral. Mitth. Tschermak's Mineralogische Mitteilungen

Tuberculosis Tuberculosis. The Journal of the National Associa-

tion for the Prevention of Consiunption and other
forms of Tuberculosis

Tubinger Blatter Tubinger Blatter fur Naturwissenschaften imd Arznei-

ktmde

Tiibingen Bot. Inst. Un- Untersuchtmgen aus dem Botanischen Institut zu
ters. Tubingen •

Tunis P. Tunis Patent

Tiuin, Mem. Acad. Memoires de TAcademie Royale des Sciences de Turin

Tyneside Natur. Field Club Transactions of the Tyneside Naturalist's Field Club
Trans.

U. K. Mar. Biol. Assoc. J. Jotunal of the Marine Biological Association of the

United Kingdom

U. S. Bur. Anim. Ind. Bull. U. S. Department of Agriculture. Bureau of Animal

Industry

U. S. Bur. Anim. Ind. Re- Annual Report of the Bureau of Animal Industry
port

U. S. Chief Signal Off . Ann. Annual Report of the Chief Signal Officer (of the
Report Army) to the Secretary of War

U. S. Coasb Geod. Surv. United States Coast and Geodetic Survey. Bulletin
BuU.

U. S. Comm. Agric. Report Report of the Commissioner of Agriculture

U. S. Dept. Agric. Bull. Bulletins of the Department of Agriculture, U. 6.

U. S. Dept. Agric. Report Reports of the Department of Agriculture, U. S.

U. S. Dept. Agric. Yearb. Yearbook of the United States Department of Agri-

culture

U. S. Disp. United States Dispensatory

U. S. Div. Biol. Surv. Bull. U. S. Department of Agriculture. Division of Bio-
logical Survey. Bulletin

U. S. Div. Chem. Bull. U. S. Department of Agriculture. Division of Chemis--

try. Bulletin

U. S. Div. Entom. Bull. U. S. Department of Agriculture. Division of Ento-

mology

U. S. Div. Entom. Insect U. S. Department of Agriculture. Division of Ento-
Life mology. (Periodical Bulletin.) Insect Life

U. S. Div. Entom. Tech. U. S. Department of Agriculture. Division of Ento-
Ser. mology. Technical Series

U. S. Div. Omith. Mamm. U. S. Department of Agriculture. Division of Eco-
Bull. nomic Ornithology and Mammalogy. Bulletin

U. S. Div. Soils Bull. U. S. Department of Agriculture. Division of (Agri-

cultural) Soils. Bulletin

U. S. Entom. Comm. Bull. Department of the Interior. . .Bulletin of the United

States Entomological Commission

U. S. Entom. Comm. Re- (U. S.) Department of the Interior (Agriculture) . . .
port Report of the United States Entomological Com-

mission

U. S. Fish Comm. Bull. Bulletin of the United States Fish Commission

U. S. Fish Comm. Report United States Commission of Fish and Fisheries.

Report of the Commissioner

LIST OF ABBREVIATIONS TO LITERATURE

CXVll

V. S. GeoL Stirv.

V. S. Monthly Weath. Rev.

U. S. Mus. Bull.

U. S. Mus. Proc.

U. S. Mus. Report
U. S. Mus. Spec. Bull.

U. S. Naval Inst. Proc.
U. S. Naval Med. Bull.
U. S. Naval Obs. Publ.
U. S. N. Amer. Fauna

U. S. P.

U. S. Ph.

U. S. Secty. Agric. Report

U. S. Signal Sa^. Notes

U. S. Signal Serv. Pap.

U. S. Surv. Terr. Reports

U. S. Weath. Bur. Bull.

U. S. Weath. Bur. Report

U. Serv. Inst. J.

Udine, Relazioni

Uhland's Tech. Rund.

Umschau

Ung. Natiu^iss. Ver. Jahr.

Univ. lU. Bull.
Unters. Naturlehre

Upsala, Arsskrift

Upsala Bot. F6r.
Upsala, Diss. Acad.
Upsala, Frey Tidskr.
Upsala Lakarefor. Fdrh.
Upsala Naturvet. Student-

sallsk.
Upsala, Soc. Sd. Nova

Acta
Urug. P.
UtTttJit, Aanteek. Prov.

Genoots.

Utrecht, Ann. Acad.
Utrecht, Kliniek

Utrecht, Nieuwe Verh.
Prov. Genootsch.

United States Geological Survey

(United States) Monthly Weather Review

Department of the Interior. . .Bulletin of the United
States National Museum

Department of the Interior. . . Proceedings of the
United States National Museum

See Smithsonian Rep.

Smithsonian Institution. United States National
Museum. Sp>ecial Bulletin

United States Naval Institute Proceedings

United States Naval Medical Bulletin

Publications of the United States Naval Observatory

U. S. Department of Agriculture. Division of Orni-
thology and Mammalogy. North American Fatma

United States Patent

United States Pharmacopoeia

Report of the secretary of agriculture

United States of America: War Department. Signal
Service Notes

United States of America, War Department. Pro-
fessional Papers of the Signal Service

. . . Annual Report of the United States Geological
(and Geographical) Survey of the Territories

U. S. Department of Agriculture. Weather Bureau.
Bulletin

U. S. Department of Agriculture. Weather Bureau.
Report of the Chief of the Weather Btireau

Journal of the royal United Service Institution,
WhitehaU Yard

Relazioni intomo agli Atti dell' Accademia di Udine

Uhland's Technische Rtmdschau

Umschau, Die

Abhandlungen aus dem dritten Bande der Jahrbucher
des Ungarischen naturwissenschaftlichen Vereins
zu Pest, in Deutscher Uebersetzimg Red. von J.
Szabo

University of Illinois Bulletin

Untersuchungen zur Natnrlehre des Menschen imd
der Thiere

Universitets Arsskrift utgifven af Kongl. Vetenskaps-
Societeten i Upsala

See Bot. Notiser

Dissertationes Academicae Upsaliae habitae

Frey Tidskrift for Vetenskap och Konst

Upsala Lakaref6renings Fdrhandlingar

See Bot. Centrbl.

Nova Acta Regiae Societatis Scientiarum Upsaliensis

Uruguay Patent

Aanteekeningen van het Verhandelde in de Sectie-

Vergaderingen van het Provinciaal Utrechtsch

Genootschap van Kunsten en Wetenschappen
Annales Academiae Rheno-Trajectinae
Kliniek: Tijdschrift voor Wetenschappenlijke Genees-

kunde
Nieuwe Verhandelingen van het Provinciaal Utrechsch

Genootschap van Kunsten en Wetenschappen

CXVIU

LIST OF ABBREVIATIONS TO LITERATURB

Utrecht, Onderzoek.

Utrecht, Scheik. Onder-
zoek.

Utrecht, Verh. Prov.
Genootsch.

Valais Soc. Murith.

Valencia, Act. Med.

Valenciennes, Mem. Soc.
Agric.

Valentin, Rep.

Van Diemen's Land, Roy.
Soc. Papers

Van Diemen's Land, Roy.
Soc. Reports

Van Nostrand's Mag.
Vargasia

Varsovie Soc. Natur. Trav.

Varsovie Soc. Natur. Trav.

(Mem.)
Vaucluse Acad. Mem.
Venez. P.
Venezia, Ateneo

Venezia, Ateneo Esercit.

Venezia, Atti

Venezia, Atti Ateneo
Venezia, lat. Atti

Venezia, 1st Mem.

Venezia, Mem. 1st Beneto

Ver. Anal. Chem.

Verh. Genootsch. Dec. Qui

Non.
Verh. Ges. deut. Naturf.

Aerzte
Verh. poly. Ges.
Verh. Ver. Gewerbefleis.

Veroffent. kais. Gesundh.
Verona, Soc. Ital. Mem.

Vet. J. London

Vet. Med. Assoc. Trans.

Veterinarian

Victoria Dept. Mines Spec.

Reports
Victoria Field Natur. Club
Victoria Inst. J.

Victoria Natur.

Onderzoekingen gedaan in het Physiologisch Labora-

torium der Utrechtsche Hoogeschool
Scheikundige Onderzoekingen, gedaan in het Labora-

torium der Utrechtsche Hoogeschool
Verhandelingen van het Provinciaal Utregtsch Genoot-

schap van Kunsten en Wetenschappen
See Bull. Murith.

Actas del Instituto Medico Valenciano
Memoires de la Soddt^ d* Agriculture, des Sciences, ct

des Arts, de TArrondissement de Valenciennes
Repertorium ^r Anatomic und Physiologic
Papers and Proceedings of the Royal Society of Van

Diemen's Land
Reports of the Royal Society of Van Diemen's Land

(For Horticulture, Botany, and the Advance of

Science)
Van Nostrand's Engineering Magazine
Vargasia: Boletin de la Sodedad de Ciencias fisicas y

naturales de Caracas
Comptes Rendus et Memoires de la Soci^t^ des Natur-

listes (a I'Universite Imperiale) de Varsovie
Travaux de la Soci6t^ des Naturalistes de I'Univsite

Imperiale de Varsovie
Memoires de I'Academie de Vaucluse
Venezuela Patent
L' Ateneo Veneto: Rivista mensile di Science, Lettere

ed Arti
Esercitazioni Scientifiche e Letterarie dell' Ateneo >

di Venerzia
Atti delle Adunanze dell' I. R. Istituto Veneto di

Scienze, Lettere, ed Arti
Atti deir Ateneo Veneto
Atti del Reale Istituto Veneto di Scienze, Lettere ed

Arti
Memorie del Reale Istituto Veneto di Scienze, Lettere

ed Arti
Memorie dell' I. R. Istituto Veneto di Scienze, Lettere,

ed Arti
See Repert. Anal. Chem.
Verhandelingen van het Genootschap: "Occidir qui

qui non servat."
Verhandlung der Gesellschaft deutscher Nattuiorscher

und Aerzte
Verhandlimgen der poltechnischen Gesellschaft
Verhandlungen des Vereins zur Beforderung des

Gewerbefleisses in Preussen
Verdffentlichtmgen des kaiserlichen Gesundheitsamts
Memorie di Matematica e Fisica della Sodeta Italiana

della Scienze
Veterinary Journal, London

Transactions of the Veterinary Medical Association
The Veterinarian
Victoria. Department of Mines. Special Reports

See Victorian Natlist.

Journal of the Transactions of the Victoria Institute

or Philosophical Society of Great Britain
The Victorian Naturalist. The Journal and Magazine

of the Field Natiu-alists' Club of Victoria

LIST OF ABBREVIATIONS TO LITERATURE

CXIX

Victoria P.

Victoria Pharm. Soc. J.

«

Victoria Proc. Roy. Soc.
Victoria Trans. Phil. Inst.

Victoria Trans. Roy. Soc.
Victoria Zool. Soc. Proc.

Vierteljahrschr. arzt. poly.
Vierteljahrschr. gericht.

Med.
Vierteljahrschr. gesund-

heitspf.
Vierteljahrschr. Zahnheilk.
Virchow's Archiv path.

Viviani, Ann. Bot.
Voget, Notizen
Voigt, Mag.

Vosges Soc. Emul. Ann.

W. Austral. P.

Wag. Free Inst. Sci. Trans.

Wag. Jahr.
Walker, Elect. Mag.
Warwick. Field Club Proc.

Warwick. Natur. Hist. Soc.

Rep.
Washburn Obs. Publ.

Washington
Washington
Washington Biol. Soc.

Proc.
Washington, Mem. Natl.

Acad.
Washington, Natl. Inst.

Bull.
Washington Phil. Soc.

Bull.
Wasser Abwasser
Water Supply Papers
Watford Nat. Hist. Soc.

Trans.
Weale, Quart. Papers
Weber, Archiv
Weimer, Zts. Geburtsk.
Weinlaube
Wemigerode Naturwiss.

Vcr. Schr.
West. Brewer
West. Chem. Met.
West. Drug.

Victoria Patent

Quarterly Journal and Transactions of the Pharma-
ceutical Society of Victoria
Proceedings of the Royal Society of Victoria
Transactions of the Philosophical Institute (afterwards

Royal Society) of Victoria
Transactions of the Royal Society of Victoria
Proceedings of the Zoological and Acclimatisation

Society of Victoria
Vierteljahrschrift der arztlichen Poljrtechnik
Vierteljahrschrift fur gerichtliche Medizin und 6fTent-

Hches Sanitatwesen
Vierteljahrschrift fur Gestmdheitspflege

Vierteljahrschrift fiir Zahnheilkunde

Virchows Archiv fiir pathologic. Anatomic, und His-^

tologie
Annali di Botanica

Notizen aus dem Gebeite der practischen Pharmacie
Magazin fur den neuesten Zustand der Naturkimden,.

mit Rucksicht auf die dazu gehdrigen Htilfswissen-

schaften
Annales de la Soci6t6 d'Emulation du Department de&

Vosges
West Australian Patent
Transactions of the Wagner Free Institute of Science

of Philadelphia
(Wagner's) Jahresbericht fiber Chemische Technologie
The Electric^ Magazine
Proceedings of the Warwickshire Naturalists' and

Archaeologists' Field Club
Annual Reports of the Warwickshire Natural History

and Archaeological Society
Publications of the Washburn Observatory of the

University of Wisconsin
Int. Med. Congr. Trans., 1887
See also tmder U. S.
Proceedings of the Biological Society of Washington

Memoirs of the National Academy of Sciences

Bulletin of the Proceedings of the National Institu-
tion for the Promotion of Science
Bulletin of the Philosophical Society of Washington

Wasser und Abwasser

Water Supply Papers

Transactions of the Watford Natural History Society

and Hertfordshire Field Club
Quarterly Papers on Engineering
Archiv fur die systematische Naturgeschichte
Gemeinsame Deutsche Zeitschrift fiir Geburtskunde
Die Weinlaube
Schriften des Naturwissenschaftlichen Vereins des

Harzes in Wemigerode
Western Brewer, The
Western Chemist and Metallurgist
Western Druggist

cxx

LIST OF ABBREVIATIONS TO LITERATURE

Westphfil, Prov. Blatt.

Westphal, Ver. Jahr.

Wetter

Wetterau. Ges. Ann.

Wetterau. Ges. Festgabe.

Wetterau. Ges. Jahr.

Wetterau. Ges. Naturk.

Ber.
Wiad. Mat.
Wieck's Gewerbeztg.
Wied. Ann. Phys.
Wied. Archiv
Wied. ZooL Mag.
Wiegmann, Archiv
Wien Abh.
Wien Akad. Ber.

Wien Akad. Denkschr.

Wien Akad. Sitzber.

Wien Almanach

Wien Alpen-Verein, Jahr.
Wien Anthrop. Ges. Mitth.
Wien Anz.

Wien Denkschr.

Wien EmbryoL Inst.

Mitth.
Wien Geogr. Ges. Abh.

Wien Geogr. Ges. Fest-

schr.
Wien Geogr. Ges. Mitth.

Wien Med. Chir. Acad.

Abh.
Wien Med. Chir. Acad.

Beob.
Wien Naturhist. Hofmus.

Ann.
Wien Omith. Vrr. Mitth.
Wien Phot. Corresp.

Wien Schr.

Westphalische Provincial-Blatter. Verhandlungen der
Gesellschaft zvi Beforderung der vaterlandischen
Culttu' in Minden

Jahres-Bericht des Westfalichen Provinzial-Vereins
fiir Wissenschaft und Kunst

Das Wetter. Meteoroiogische Montasschrift fur Ge-
bildete aller Stande

Annalen der Wetterauischen Gesellschaft ftir die
gesammte Naturkunde

Naturhistorische Abhandlungen aus dem Gebiete der
Wetterau

Jahresbericht der Wetterauischen Gesellschaft fiir die
gesammte Naturkunde

Bericht der Wetterauischen Gesellschaft fiir die ge-
sammte Naturkunde zu Hanau

Wiadomosci Matematyczne

Deutsche Gewerbezeitimg (F. Wieck)

Annalen der Physik tmd Chemie (Wiedemann's)

Archiv fur Zoologie tmd Zootomie

Zoologisches Magazin

Archiv fiir Naturgeschichte

Naturwissenschaftliche Abhandlimgen

Sitztmgsberichte der kaiserlichen Akademie der Wis-
senschaf ten ; Mathematisch-Nattunvissenschaf tliche
Klasse, II Abthlg. Wien

Denkschriften der kaiserlichen Akademie der Wissen-
schaften. Mathematisch - Natiurwissenschaftliche
Classe

Sitzungsberichte der Mathematisch-Naturwissen-
schaftlichen Classe der kaiserlichen Akademie der
Wissenschaften

Almanach der kaiserlichen Akademie der Wissen-
schaften ,

Jahrbuch des Oesterreichishcen Alpen-Vereins

Mittheilimgen der Anthropologischen Gesellschaft

Anzieger der kaiserlichen Akademie ker Wissen-
schaften: Math.-Naturwissensch. Classe

Denkschriften der Kaiselichen Akademie der Wissen-
schaften: Mathematisch - natiu^issenschaftliche
Classe

Mittheilimgen aus dem Embryologischen Institute der
k. k. Universitat in Wien

Abhandlungen der k. k. Geographischen Gesellschaft
in Wien

Festschrift der k. k. Geographischen Gesellschaft 1884-
1898

Mittheilimgen der k. k. Geographischen Gesell-
schaft in Wien

Abhandlungen der k. k. medidnisch-Chirurgischen
Josephs-Academie zu Wien

Beobachtungen der k. k. medicinisch-chirurgischen
Josephs-Academie zu Wien

Annalen des k. k. Naturhistorischen Hofmuseums

Mittheilungen des Omithologischen Vereins in Wien
Photographische Correspondenz. Organ der Photo-
graph. Gesellsch. in Wien
Schriften des Vereines zur Verbreitung naturwissen-
schaftlicher Kenntnisse

UST OF ABBREVIATIONS TO LITERATURE

CXXl

Wien Sitzber.

Wien, Sonnblick-Ver. Jahr.
Wien. technol. Blatter
Wien Ver. Naturwiss.

Kennt. Schr.
Wien, Ver. Ges. Aerzte.

Wien Verb. Gewerb-

Vereins.
Wien Wochenbl. Aerzte
Wien Zts. Ges. Aerzte
Wien, Zool. Bot. Ges. Fest-

schr.

Wien, Zool. Bot. Verb.

Wien, Zool. Inst. Arb.

Wiener Entom. Monatscbr.
Wiener Entom. Ver. Jabr.
Wiener Entom. Ztg.
Wiener klin. Wocbenscbr.
Wiener landw. Ztg.
Wiener Med. Wocbenscbr.
Wiener Mittb. Pbot.
Wiener Mus. Ann.
Wiener Poly. J.
Wiener Ztg.
Wiener Zts. Pbysik.
Wild, Rep. Meteorol.

Wihia, Collect. Med. Cbir.

Wilts, Arcbaeol. Natur.

Hist. Mag.
Wimereux I^ab. (Stat.)

Zool.
Wincbester, J. Sci. Soc.

Wisconsin Acad. Trans.

Wisconsin Natur. Hist.

Soc Bull.
Wisconsin Natur. Hist.

Soc. Pap.
Wisconsin Natur. Hist.

Soc. Proc.
Wisconsin Univ. Bull. Sci.

Wiss. Abb. Pbys.-Tecb.

Reicbsanstalt
IViss. Meeresuntersucb.

Sitzungsbericbte der Matbematiscb-naturwissenscbaft-

li<:ben Classe der Kaiserlicben Akademie der Wissen-

scbaften
Jabres-Bericbt des Sotmblick-Vereines. Wien
Wiener tecbnologisbe Blatter
Scbriften des Vereins zur Verbreitung Naturwissen-

scbaftlicber Kexmtnisse in Wien
Verbandlungen der k. k. Gesellscbaft der Aerzte zu

Wien
Verbandlungen des Neiderosterreicbiscben Gewerb-

Vereins
Wocbenblatt der k. k. Gesellscbaft der Aerzte in Wien
Zeitscbrift der k. k. Gesellscbaft der Aerzte zu Wien
Pestscbrift zur Feier des funftmdzwanzigjabrigen

Bestebens der k. k. Zoologiscb-Botaniscben Gesell-
scbaft in Wien
Verbandltmgen der k. k. Zoologiscb-Botaniscben

Gesellscbaft in Wien
Arbeiten aus dem Zoologischen Institute der Uni-

versitat Wien ind der Zoologiscben Station in Triest
Wiener Entomologiscbe Monatscbrif t
Jabresbericbt des Wiener Entomologischen Vereins
Wiener Entomologiscbe Zeittmg
Wiener kliniscbe Wocbenscbrift
Wiener landwirtscbaftlicbe Zeitung
Wiener mediciniscbe Wocbenscbrift
Wiener Mitteilungen (Pbotograpbiscben Inbalts)
Annalen des Wiener Museums der Naturgescbicbte
Allgemeines Wiener polytecbniscbes Jotunal
Wiener Zeitung

Zeitscbrift fur Pbysik, Cbemie, tmd Mineralogie
RepcTtorium fur Meteorologie, berausg. von der

kaiserlicben Akad. der Wissenscbaften
Collectanea medico-cbirurgica Caesarea Academiae

Medico-Cbirurgicae cura edita
Magazine of tbe Arcbaeological and Natural History

Society of Wiltsbire
See Lille Inst. Zool. Trav.

Journal of Proceedings and Annual Reports of tbe
Wincbester and Hampsbire Scientific and Literary
Society

Transactions of tbe Wisconsin Academy of Sciences,
Arts, & Letters

Bulletin of tbe Wisconsin Natural History Society

Occasional Papers of tbe Natural History Society of
Wisconsin

Proceedings of tbe Natural History Society of Wis-
consin *

Bulletin of tbe University of Wisconsin. Science
Series

Wissenscbaftlicbe Abbandlungen der Pbysikalisb-
Tecbniscben Reicbsanstalt

Wissenscbaftlicbe Meeresuntesucbtmgen berausge-
geben von der Kommission zur wissenscbaftlicben
Untersucbung der deutscben Meere in Kiel tmd der
biologiscben Anstalt auf Helgoland

CXXll

LIST OF ABBREVIATIONS TO LITERATURE

Wochenbl. Archit. Ver.

Wochenbl. Papierfabr.
Wochensch. Brau.
Wochenschr. Centr.-Ver.

Rubezuker-ind.
Wochenschr. osterr. Ing.

Ver.
Wochenschr. Ver. deut.

Ing.
WoUen-Gewerbe
WoUen Ztg.
Wombat

Woods Holl Mar. Biol.
Lab. Btdl.

Woods Holl Mar. Biol.

Lab. Lect.
Woolhope Field Club

Trans.
Woolwich, Proc.

World's Paper Trade Rev.
Wimderlich, Archiv. Heilk.
Wiirttemberg. Aerzt. Ver.

Mitth.
Wiirttemberg, Jahresh.

Wiirzburg, Arb. Hot. Inst.
Wiirzburg, Arb. Phys. Lab.

Wurzburg. Med. Zts.
Wiirzburg. Naturwiss. Zts.

Wurzburg Phys. Med.
Festschr.

Wiirzburg, Phys. Med.

Sitzber.
Wiirzburg, Phys. Med.

Verb.
Wiirzburg, Zool Inst. Arb.

Year Book Pharm.
Year-book of Pharm.
Yn X'ioar Manninagh

Yokohama, Mitth. Deut.

Ges.
Yonne
Yonne,' Bull.

Yorksh. Natur. Union

Trans.
Yorksh. Phil. Soc. Report

Wochenblatt, herausgegeben von mitgliedem des

Architekten-Vereins zu Berlin
Wochenblatt der Papierfabriken
Wochenschrift fur Brauerei
Wochenschrift des Central- Vereins fiir Rubenzuker-

industrie in der Oe.sterr-Ung-Monarchie
Wochenschrift des osterreichischen Ingenieur und

Architekten Vereins
Wochenschrift des Vereins deutscher Ingenieure

Das Deutsche WoUen-Gewerbe

Wollen Zeitung

The Wombat. The Journal of the Geelong Field

Naturalists' Club, and the Gordon College Amateur

Photographic Association
Biological Bulletin. Edited by the Director and

Members of the Staff, of the Marine Biological

Laboratory, Woods Holl, Mass.
Biological Lextures delivered at (from) the Marine

Biological Laboratory (of) Woods Holl (Mass.)
Transactions of the Woolhope Naturalists' Field Club

Minutes of Proceedings of the Royal Artillery Insti-
tution
World's Paper Trade Review
See Roser imd Wunderlich
Mittheiltmgen des Wiirttembergischen Aerztlichen

Vereins
Jahreshef te des Vereins fiir vaterlandische Naturkunde

in Wiirttemberg
Arbeiten des Botanischen Instituts in Wiirzburg
Arbeiten aus dem Physiologischen Laboratorium der

Wiirzburger Hochschule
Wiirzburger medicinische Zeitschrift
Wiirzburger Naturwissenschaftliche Zeitschrift;

Herausgegeben von der Physikalisch-Medicinischen

Gesellschaft
Festschrift zur Feier ihres funfzigjahreign Bestehens

herausgegeben von der Physikalisch-Medizinischen

Gesellschaft zu Wiirzburg
Sitzimgsberichte der Physikalisch-Medicinischen

Gesellschaft zu Wiirzburg
Verhandlimgen der Physikalisch-Medicinischen Gesell-
schaft
Arbeiten aus dem Zoologisch-Zootomischen Institut

in Wiirzbiu"g
See Brit. Pharm. Confer. Proc.
Year-book of Pharmacy
Yn Lioar Manninagh. The Journal of the Isle of

Man Natural History and Antiquarian Society
Mittheilungen der Deutschen Gesellschaft fiir Natur

und Volkerkunde Ostasiens
See Auxere
Bulletin de la Soci^td des Sciences Historiques et

Naturelles de 1' Yonne
The Transactions of the Yorkshire Naturalists' Union

Annual Report of the Council of the Yorkshire Philo-
sophical Society

LIST OF ABBREVIATIONS TO LITERATURE

CXXIU

Yorksh. Proc. Phil. Soc.
Zach, Corresp.

Zach, Monat. Corresp.

Zahntech.

Zantcdeschi. Ann. Fis.
Zeeuwsch Genootsch.

Nieuwe Verh.
Zeeuwsch Genootsch. Wet.

Archief

Zentr. Biochem. Biophys.
Zentr. exp. Med.

2^entr. inn. Med.

Zentr. oesterr - ungar

Papierind.
Zentr. Physiol. •
Zentr. Physiol. Path. Stoff-

wech.
2^tmer, Civilingenietir
Ziva

Zool. Anz.
Zool. Beitr.
Zool. Bull.
Zool. Congr.
Zool. Jahr.

Zool. J.

Zool. Soc. Proc.

Zool. Soc. Trans.
Zool. Vortr.
Zoologica

Zoologist
Ztg. Blechind.
Zts. Akklimat.

Zts. allg. Erdkunde
Zts. allg. osterr. Apoth.

Ver.
Zts. allg. Physiol.
Zts. anal. Chem.
Zts. Anat.
Zts. ang. Chem.

Zts. ang. Mikr.

Zts. anorg. Chem.

Zts. Bauwesen

Zts. Berg-Hutten Salmenw.

Zts. Biol.

Proceedings of the Yorkshire Philosophical Society
Correspondence Astronomique, Geographique, Hydro-

graphique, et Statistique
Monatliche Correspondenz zur Befdrderung der Erd-

und Himmels-Kunde
Die Zahntechnische Reform
Annali di Fisica
Nieuwe Verhandelingen van het Zeeuwsch Genootschap

der Wetenschappen
Archief Vroegere en Latere Mededeelingen voor-

namelijk in Betrekking tot Zeeland, uitgegeven door

het Zeeuwsch Genootschap der Wetenschappen
Zentralblatt fur Biochemie tmd Biophysik
Zentralblatt der experimentellen Medizin (former

name Zentralblatt ftir die gesamte Physiologie und

Pathologie des Stoffwechsds)
Zentralblatt fur innere Medizin
Zentralblatt fiir die oesterr-ungar Papierindustrie

Zentralblatt fur Physiologie

Zentralblatt fiir die gesammte Physiologie und Patho-
logie des Stoffwechsels, Berlin und Wien
Der Civilingenieur, Zeitschrift fur das Ingenieurwesen

fiva: Casopis prirodnicky
oologischer Anzeiger

2^oologische Beitrage

2^oological Bulletin

See Congr. Int. Zool. C. R. Int. Congr. Zool. Proc.

Zoologische Jahrbiicher. Zeitscluift fiir Systematik,
Geographic und Biologic der Thiere

The Zoological Journal

Proceedings of the Scientific Meetings (General Meet-
ings for Scientific Business) of the Zoological Society
of London

Transactions of the Zoological Society of London

Zoologische Vortrage

Zoologica. Original- Abhandltmgen aus dem Ges-
ammtgebeite der Zoologie

The Zoologist; a monthly Journal o( Natural History

Illustrierte Zeitimg fiir Blechindustrie

Zeitschrift fiir Akklimatisation : Organ des Akklima-
tisations-Vereins in Berlin

Zeitschrift fiir allgemeine Erdkunde

Zeitschrift des allgemeinen dsterreichischen Apotheker-
Vereins

Zeitschrift fiir allgemeine Physiologie

Zeitschrift fiir analytische Chemie

Zeitschrift fiir Anatomic und Entwickelungsgeschichte

Zeitschrift fiir angewandte Chemie, imd Zentralblatt
fiir technische Chemie

Zeitschrift fur angewandte Mikroskopie mit besond-
erer Riicksicht auf die mikroskopischen Unter-
suchungen von Nahnmgs- tmd Genussmitteln,
technischen Produkten, Krankheitsstoflen, etc.

Zeitschrift fiir anorganische Chemie

Zeitschrift fiir Bauwesen

Zeitschrift ftir das Berg-Hiitten und Salinenwesen im
Preussichen Staate

Zeitschrift fiir Biologie

CXXIV

UST OF ABBREVIATIONS TO LITBRATURB

Zts. Hot.

Zts. Chem.

Zts. chem. Apparat.

Zts. Chem. Jnd.

Zts. chem. Ind. Kolloide
Zts. Chemotherap.

Zts. deut. geol. Ges. Abh.

Zts. deut. Landw.
Zts. Dreschler

Zts. Diingerw.
Zts. Hlectrochem.
Zts. Entom. (Breslau)

Zts. Ethnol.

Zts. exper. Path. Therap.

Zts. Farben-Ind.
Zts. Feuerwehr.
Zts. Fischerei
Zts. Fleisch. Milchhyg.
Zts. Geburtsh.
Zts. Geburtsh. Gynakol.
Zts. ges. Brauw.
Zts. ges. Getreidew.
Zts. ges. Naturwiss.
Zts. Ges. Omith.
Zts. ges. Textilind.
Zts. ges. Wasserwirts.
Zts. Heilk.

Zts. Hyg.

Zts. Immunit. Abt. I. 13.
Abt. Ref.

Zts. Induk. Abst. Vererb-

ungslehre
Zts. Instrumentenk.
Zts. Klin. Med.
Zts. Krebsforsch.
Zts. Kryst. Mineral.
Zts. landw. Versuchsw.

Zts. Malakozool.
Zts. Math. Phys.
Zts. math. Unterf.

Zts. Mikro. Tek.

Zts. Morphol. Anthrop.

Zts. Nahr. Genuss. (Z.

genuss)
Zts. Naturwiss.

Zeitschrift fiir Botanik
Zeitschrif t fiir Chemie

Zeitschrift fur chemische Apparatenkunde (Discon-
tinued)
Zeitschrift fiir die Chemische Industrie mit besonderer

Beriicksichtigung der chemisch-technischen Unter-

suchungsverfahren 1887; later Zts. ang. Chem.
Zeitschrift fiir Chemie und Industrie der Kolloide
Zeitschrift fiir Chemotherapie tmd verwandte Gebiete.

(formerly Folia Serologia)
Zeitschrift der deutschen geologischen Gesellschaft

Abhandltmgen
Zeitschrift fiir deutsche Landwirthe
Zeitschrift fiir Dreschsler, Elfenbdngraveure und

Holzbildhauer
Zeitschrift fiir Diingerwesen
Zeitschrift fiir Electrochemie
Zeitschrift fiir Entomologie im Auftrage des Vereins

fur schlesische Insektenkimde zu Breslau
Zeitschrift fflr Ethnologie
Zeitschrift fiir experimentelle Pathologic und Therapie,

Berlin
Zeitschrift fur Farben-Industrie
lUustrirte Zeitschrift fiir die deutsche Feuerwehr
Zeitschrift fur Fischerei
Zeitschrift fiir Fleisch- und Milchhygiene
Zeitschrift fiir Geburtshiilfe tmd Frauenkrankheiten
Zeitshrift fiir Gebtutshiilfe und Gynakologie
lUustrirte Zeitschrift das gesammte Branwesen
Zeitschrift fiir das gesamte Getreidewesen
Zeitshrift fiir die Gesammten Naturwissenschaften
Zeitschrift fur die gesammte Omithologie
Zeitschrift fdr die gesamte Textilindustrie
Zeitschrift fiir die gesamte Wasserwirtschaft
Zeitschrift fur Heilkimde, als Fortsetzung der Prager

Vierteljahrsschrift fur praktische Heilkunde
Zeitschrift fiir Hygiene und Infektionskrankheiten
Zeitschrift fiir Immunitatsforschtmjg und experimen-
telle. Therapie. Abteilung I. 13. Abteilung II. or

Ref. 1 vol.
Zeitschrift fiir Induktive Abstammungs- und Vererb-

ungslehre
Zeitschrift fiir Instrumentenkunde
Zeitschrift fiir Klinische Medizin
Zeitschrift fiir Krebsforschung
Zeitschrift fiir Krystallographie und Mineralogie
Zeitschrift fiir das landwirtschaftliche Versuchswesen

in Oesterreich
Zeitschrift fiir Malakozoologie
Zeitschrift fiir Mathematik und Physik
Zeitschrift fiir mathematischen und naturwissenschaft-

lichen Unterrricht
Zeitschrift fiir Mikroscopischen Teknik.
Zeitschrift fiir Morphologie und Anthropologie
Zeitschrift fiir Untersuchung der Nahrungs und

Genussmittel, sowie der Gebrauchsgegenstande
Zeitschrift fur Naturwissenshaften. . .im Auftrage

(Organ) des NaturwissenschafHichen Vereins fOr

Sachsen und Thiiringen

LIST OF ABBREVIATIONS TO LITERATURE

CXXV

Zts. offentl. Chem.
Zts. Ohrenheilk.

Zts. osterr. Ing. Ver.

Zts. paraf. Ind.

Zts. Parasit.

Zts. Pflanzenkrankheiten

Zts. physik. Chem.

Zts. Physik. Chem. Unterr.

Zts. Physiol. Chem.
Zts. prakt. Geol.
Zts. PsychoL

Zts. ration. Med.
Zts. Reprodiikt.
Zts. Rubenzuckeiind.
Zts. Schiess Spreng.

Zts. Spiritusind.
Zts. Telegr. Ver.

Zts. Thiermed.
Zts. Tuberkulose
Zts. Ver. deut. Ingen.
Zts. Ver. Rubenzuckerind.

Zts. Ver. Zuckeiind.
Zts. Wiss. Geogr.
Zts. wiss. Mikro.
Zts. wiss. Photochem.

Zts. wiss. Zool.

Zts. Zuckerind.

Zts. Zuckerind. Bdhm.

Zurich Denkschr. Med.

Chir. Ges.
Zurich Mitth.

Zurich, Monats.

Zurich natw^. Ges.

Zurich Physik. Ges. Jahr.

Zurich, Schweiz. Ges. Neue.
Denkschr.

Zurich, Sec. Hntom.

Zurich, Unters. Physiol.

Lab.
Zurich, Verh.

Zurich, Vierteljahrschr.

Zwickau Ver. Naturk. Jahr
ZwoUe. Vooruitgang.

Zeitschrift fur dffentliche Chemie

Zeitschrift fur Ohrenheilkimde in deutscher tmd

englischer Sprache
Zeitschrift des dsterreichischen Jngenieur und Archi-

tekten Vereins
Zeitschrift fur Parafin Industrie
Zeitschrift fur Parasitenkunde
Zeitschrift fur Pflanzenkrankheiten
Zeitschrift ftir physikalische Chemie, Stdchiometrie

und Verwandschaftslehre
Zeitschrift fur dem physikalischen imd chemischen

Unterricht
Zeitschrift fur physiologische Chemie (Hoppe-Seylers)
Zeitschrift ftir praktische Geologie
Zeitschrift fur Psychologic und Physiologic der Sinnes-

organe
Zeitschrift ftir rationelle Medidn
Zeitschrift fur Reproduktiontechnik
Neue Zeitschrift ftir Rtibenzuckerindtistrie ^

Zeitschrift ftir das gesammte Schiess- und Spreng-

stoffwesen
Zeitschrift ftir Spiritusindustrie
Zeitschrift des deutsch-osterreichischen Telegraphen-

Vereins
Zeitschrift fur Thiermedicin

Zeitschrift ftir Tuberktilose tmd Heilstattenwesen
Zeitschrift des Vereins deutscher Ingenieiu'e
Zeitschrift des Vereins ftir die Rtibenzucker-Industrie

des deutschen Reichs
Zeitschrift des Vereins der deutschen Zuckerindustrie
Zeitschrift ftir wissenschaftliche Geographic
Zeitschrift fiir wissenschaftliche Milo'oscopie
Zeitschirft fur wissenschaftliche Photographic, Photo-

physik, tmd Photochemie
Zeitschrift fur wissenschaftliche Zoologie
Zeitschrift fur Zuckerindustrie
Zeitschrift ftir Zuckerindtistrie in Bdhmen
Denkschrift der medizinisch-chirurgischen Gesell-

schaft des Kantons Zurich
Mittheilungen der Naturforschenden Gesellschaft in

Zurich
Monatsschrift des wissenschaftlichen Vereins in

Zurich
Viertdjahrschrift der nattu^orschenden Gesellschaft

in Zurich
. . . Jahresbericht der physikalischen Gesellschaft in

Zurich
Neue Denkschriften der allgmeinen Schweizerischen

Gesellschaft fiir die gesammten Natiuwissen-

schaften
Sodetas Entomologica. Organ fiir den intemationalen

Entomologenverein. Ziirich
Untersuchtmgen aus dem Physiologischen Labora-

torium der Ziiricher HochschtUe
Verhandltmgen der Medicinisch-chinirgischen Gesell-
schaft des Kanton Ziirich im Jahr 1826
Vierteljahrsschrift der Naturforschenden Gesell-
schaft in Ziirich
Jahresbericht des Vereins fiir Nattu-kunde zu Zwickau
De Vooruitgang; Tijdschrift voor Wetenschap

CHAPTER I.

CELLULOSE. »

Comprehensive knowledge of the nature, limitations and
inner mechanics of cellulose esterification and etherification
presupposes a thorough understanding of the substituent groups
or aggregates entering into and comprizmg those esters and ethers,
including an intimate fimdamental acquaintance with the various
normal and modified celluloses and cognate carbohydrates — ^the
predominating constituent of plant tissues, and the structural
basis of the vegetable world.

Comparatively speaking, there are few substances more
intricate in composition, complex in constitution, or ramified in

1. For general information upon the subject of cellulose development, see
T. Anderson, N. Ed. Phil. J. 1849, 47, 132; J. prakt. Chem. 1849, 47, 449;
Jahr. Chem. 1849, 2, 484. Barreswil and Rilliet, N. J. Pharm. 21, 205;
J. prakt. Chem. 1852, 56, 334; abst. Jahr. Chem. 1852, 5, 657. v. Baumhauer,
Scheik. Onderzoek, 2, 62, 194; abst. Ann. 1843, 48, 356; J. prakt. Chem.
l&H, 32, 204, 210; N. Br. Arch. 53, 68; Berz. Jahr. 1846, 25, 585. A.
Bechamp, Compt. rend. 1853, 37, 134; 1856, 42, 1210; Inst. 1853, 261; Ann.
Chim. Phys. 1856, (3). 48, 461; Ann." -4856, 100, 367; J. prakt. Chem. 1856,
OS, 449; Jahr. Chem. 1856, 9, 670, 674. Blondeau de Carolles, Rev. Sci.

1843, 14, 476; abst. J. prakt. Chem. 1844, 32, 427; Berz. Jahr. 1846, 25, 582.
Boettger, J. prakt. Chem. 1843, 30, 257; Ann. 1843, 47, 329; Berz. Jahr. 1845,
24, 464. Braconnot, Ann. Chim. Phys. 1819, (2), 12, 172; Schw. J. 1819, 27,
328; Gilb. Ann. 1847, 03, 347; abst. Berz. Jahr. 1822, 1, 107. Chodnew, Ann.

1844, 51, 393. C. Cramer, J. prakt. Chem. 1858, 73, 1; abst. Chem. Centr.

1858, 60. P. Damis, Dingl. Poly. 1855, 137, 376; Mon. Ind. 1855, No. 1986;
abst. Jahr. Chem. 1855, 8, 901. L. de Koninck, Dingl. Poly. 1857, 144, 359;
Rev. univ. 1857, 131; abst. Jahr. Chem. 1857, 10, 648. DuUo, Dinel. Poly.
1860, 158, 392; Chem. Centr. 1860, 25; abst. Jahr. Chem. 1860, 13, 715;
J. Emmet (SiU.), Am. Jour. Sci. 1837, 32, 140; J. prakt. Chem. 1837,
12, 120; abst. Berz. Jahr. 1839, 18, 275. O. Erdmann and M. Mittenzwey,
J. prakt. Chem. 1859, 70, 386; Chem. Centr. 1859, 642; abst. Jahr.
Chem. 1859, 12, 541. A. Franchimont, Compt. rend. 1879,89,711, 713,
755; Ber. 1879, 12, 1939; abst. Jahr. Chem. 1879, 832. E. Fremy,
Compt. rend. 1859, 48, 202; N. J. Pharm. 35, 81; abst. Rep. Chim.
Pure, 1859, 1, 269; Compt. rend. 1859, 48, 325, 360, 667, 862; J.
Pharm. 35, 321, 401; abst. Inst. 1859, 121. 151; Rep. Chim. Pure,

1859, 1, 357, 433; Pharm. Vierteljahr. 9, 221. N. J. Pharm. Inst.
1&59, 357; Rep. Chim. Pure, 1869, 1, 602; Chem. Centr. 1860, 4. Compt. rend.
1859, 49, 661; Jahr. Chem. 1859, 12, 529, 530, 532, 533, 534, 537, 540. E.
Fremy and Terrell, J. Pharm. Chim. 1868, 7, 241; Chem. Centr. 1868, 616;
abst. Jahr. Chem. 1868, 762. Fromberg, Scheik. Onderzoek, 2, 36; abst. Ann.
1843, 48, 353; J. prakt. Chem. 1844, 32, 198; Mulder, Physiol. Chem. 1844,

2 TECHNOLOGY OF CELLULOSE ESTERS

reactivity, or about which it is more difficult to arrive at tangible,
definite conclusions than with the celluloses. This is partially
accountable from the fact that what we call "cellulose" is not the
distinctive name of a definitely characterized chemical individual,
but rather the collective name of a closely interrelated series of
allied members, which often by imperceptible gradations merge
one into another.

Their ready susceptibility to oxidation and reduction;
hydrol3rsis and dehydration; condensation and depol3anerization;
either before, dtuing or after alkylation or acidylation, thus

198; Berz. Jahr. 1845, 24, 462. Fourcroy, Systeme des Connaissances chim-
iques, 8, 87. J. Gladstone, Mem. Chem. Soc. 1850, 3, 412. E. Gilson, La
Cellule, 1893, 9, 397; abst. J. C. S. 1894, 66, i, 107; Chem. Centr. 1893, II,
530; Jahr. organ. Chem. 1893, 1, 265; J. S. C. I. 1894, 13, 1106; Bull. Soc.
Chim. 1894, 11, 590; Jahr. Chem. 1893, 881. Gay-Lussac, Ann. Chim. Phys.
1829, (2), 41, 398; Pogg. Ann. 1829, 17, 171 ; Schw. J. 1830, 58, 87; abst. Berz.
JahA 1831, 10. 183. Gmelin, Schw. J. 1830, 58, 374, 377. W. Henneberg,
Ann. 1868, 146, 130; abst. BuU. Soc. Chim. 1868, (2), 10, 414; Jahr. Chem.
1868, 761. Compare Ritter, Jahr. Chem. 1868, 761. Harting, Scheik. Onder-
zoek. 3, 17; abst. Berz. Jahr. 1847, 26, 613; J. prakt. Chem. 1846, 37, 329;
Annuaire de Chim. 1847, 606. W. HofFmeister, Landw. Versuchstat. 1886,
33, 153; abst. Jahr. Chem. 1886, 2103; 1891, 39, 461; 1897, 48, 401; 1901,
55, 115; Undw. Jahr. 1888, 17, 239; 1889, 18, 767; J. C. S. 1886, 50, 954;
1890, 58, 581; 1892, 62, 129; 1898, 74, ii, 148, 544; 1901, 80, ii, 205; Ber. 1893,
26, R, 497; Jahr. Chem. 1898, 1368; 1901, 889; Chem. Centr. 1890, I. 112;
1897, 1, 1004; 1901, 1, 862; J. S. C. 1. 1897, IS, 940. Hermann, J. prakt. Chem.
1841, 23, 380; 1842, 27, 165; abst. Berz. Jahr. 1843, 22, 499; 1844, 23, 315.
Johnson, Bot. Gaz. 1895, 20, 16. John, Chem. Schriften, 4, 204. G. Kindt,
Dingl. Poly. 1846, Utt, 334; 1847, 105. 189; Chem. Centr. 1865, 320; Ann.
1847, 61, 253; Phil. Mag. 1847, (3), 31, 157; J. Pharm. (3), 11, 324; Jahr.
Chem. 1847-8, 1, 1122. F. Koch, Pharm. Zts. Russ. 25, 619, 635, 651, 667.
683, 699, 730, 747, 763; abst, Ber. 1887, 20, 145. W. Kirchner and B. ToUens,
Ann. 1875, 175, 221; abst. J. C. S. 1875, 28, 1179; Jahr. Chem. 1875, 799;
Jahr. rein Chem. 1875, 3, 381. H. Kopp, Ann. 1840, 35, 39. Mitscherlich,
Berl. Akad. Ber. 1850, 102; Ann. 1850, 75, 305; J. prakt. Chem. 1850, 50,
144; abst. Pharm. Centr. 1850, 385; Chem. Gaz. 1851, 61; Instit. 1850, 228;
Jahr. Chem. 1850, 3, 541. H. v. Mohl, Flora, 1840; Vermischte Schriften,
1845, 335; Bot. Ztg. 1847, 497. A. Morin, Ann. Chun. Phys. 1832, (2), 49,
311 ; Bull, univers. 50, 337; Schw. J. 66, 362; abst. Berz. Jahr. 1834, 13, 77. G.
Mulder, Scheik. Onderzoek. 2, 76; abst. J. prakt. Chem. 1844, 32,336; Ann.
1841, 39, 150. A. Miintz, Compt. rend. 1882, 94, 453; abst. Jahr. Chem.
1882, 1151; Bull. Soc. Chim. 1882, (2), 37, 409; Ber. 1882, 15, 937; J. C. S.
1882, 42, 707; Chem. News, 1882, 45, 99. Compt. rend. 1886, 102, 624, 681;
abst. J. C. S. 1886, 50, 575; BuU. Soc. Chim. 1886, (2), 46, 486; Ber. 1886, 19,
299; J. S. C. 1. 1886, 5, 386; Chem. News, 1886, 53. 167, 180; Jahr. Chem. 1886,
1809. A. Payen, N. Ann. Sc. Nat. Bot. 1839, 11, 21, 27;l4,37; Compt. rend.
1840, 10, 941 ; 1844, 18, 271 ; 1859, 48, 210, 275. 319, 326, 328, 358, 362, 772, 893 ;
abst. Rep. Chim. Pure, 1859, 1, 270, 359, 434; N. J. Pharm. 35, 88, 185. Jahr.
Chem. 1859, 12, 530, 531, 532, 533, 534, 536, 539; Ann. Sc. Nat. 1839, (2),
2, 21; 1840, (2), 3, 73. E. Peligot, Compt. rend. 1839, 9, 135; 1858, 47, 1037;
abst. Berz. Jahr. 1841, 20, 541; abst. Jahr. Chem. 1858,11,574. See also C.
Gerbardt, Ann. Chim. Phys. 1839, (2), 72, 208, (Cuprammonium). J. Pelouze,

CBW.UU>SE . 3

giving rise to an indeterminate number of products often similar
in appearance, analogous in properties yet differing from the
original cellulose, only complicates the subject. Especially is
this true, where the elementary composition remains the same
and the chemical changes are analytically indistinguishable.

All plant tissues — ^from the minute imicellular organism to
the giant conifers of California — are comprised of cells, and the
envelope or investing matrix of these cells is composed of cellulose.
In the higher plants the individual cells co-apt and coalesce in
such a manner that their walls are broken up with the formation of

Compt. rend. 1859, 48, {310, 327; N. J. Pharm. 35, 88; Rep. Chim. Pure, 1859'
1, 272; Dingl. Poly. 1859, lO, 394; Jahr. Chem. 1859, U, 532. A. Poggiale'
N. J. Pharm. 36, 121; Compt. rend. 1859, 49, 128; abst. Rep. Chim. Pure,
1859, 1, 521: Chem. Centr. 1859, 844; Jahr. Chem. 1859, 12, 733. J. Porter,
Ann. 1849, 71, 115; Am. J. Sci. (Sill.) 1850, (2), 9, 20; abst. Pharm. Centr
1849, 777; Chem. Gaz. 1849, 469; Jahr. Chem. 1849, 2, 474. L. Pozzoz, Compt.
rend. 1858, 47, 207; J. prakt. Chem. 1859, 7G, 314; abst. Jahr. Chem. 1858,
242. J. Poumarede and O. Piguter, Memoire sur le Ligneux, etc. Paris,
1847; N. J. Pharm. U, 458; 12, 81 ; J. prakt. Chem. 1847, 42, 25; Compt. rend.
1846, 23, 918; 1847, M, 17: Ann. 1847, 64, 387; Repert. Pharm. (2), 47,
344; Jahr. Chem. 1847-8, 1, 795, 797. J. Proust, J. Phys. 48, 469; Schw.
J. 7, 707. L. Radikofer, Ann. 1855, 94, 332; abst. J. prakt. Chem. 1855, 66,
127; Pharm, Centr. 1855, 26, 566; Dingl. Poly. 1855, 138, 152; Jahr. Chem.
1855, 8, 821. T. Ransome, Phil. Mag. 1887, 30, 4. J. Reade, Lon. Ed. Phil.
Mag. 1837, 11, 421. H. Reinsch, Jahr. Pr. Pharm. 14, 25; Dingl. Poly. 1860,
156, 156; Chem. Centr. 1860, 491; Bayer. Gewerbeztg. 1860, No. 8; Jahr.
Chem. 1859, 12, 746. R. Reiss, Ber. 1889; 22, 609; Jahr. Chem. 1889, 2086;
1890, 2183. Landw. Jahr. 1889, 18, 707; Chem. Centr. 1889, I, 541; 1890,
I, 165; Bot. 7, 322; J. S. C. I. 1889, 8, 406; J. C. S. 1889, 56, 687; 1891,
60, 366; BuU. Soc. Chim. 1890, (3), 3, 713; Rev. g€n. Sd. 1890, 1, 244. F.
Rochleder and W. Heidt, Ann. 1843, 48, 8; abst. Berz. Jahr. 1845, 24,
382; J. Pharm. 1844, 5, 89. P. Rochleder, Ann. 1844, 50, 225; abst. Berz.
Jahr. 1846, 25, 864; Ann. 1846, 59, 300; 1847, 63, 193; J. prakt. Chem. 1846,
39, 367; J. Pharm. 1844, 6, 161; 1848, 14, 445. J. Rossignon, Compt. rend.
1842, 14, 873; B. Rumford, Schw. J. 8, 160. F. Sacc, Ann. Chim. Phys. 1849,
(3), 25, 218; J. prakt. Chem. 1849, 46, 430; Pharm. Centr. 1849, 235; Chem.
Gaz. 1849, 274; Jahr. Chem. 1849, 2, 473. N. Saussure, N. AUg. J. Chem.
(Gehl.) 1804, 4, 681. Ann. Chim. Phys. 1804, 50, 225; Ann. Phys. (Gilb.) 1804,
is, 208; J. de Phys. 1804. 58, 393; PhU. Mag. 1805, 20, 307. Schaefer,
Ann. 1871, 160, 312; abst. Jahr. Chem. 1871, 789; Bull. Soc. Chim. 1872, 17,
371; J. C. S. 1872, 25, 309. J. Schlossberger, Ann. 1858, 107, 22; J. prakt.
Chem. 1868, 73, 370; N. Br. Arch. 95, 145; Ann. 1859, HO, 246; N. Jahr. Pharm.
12, 6; abst. J. prakt. Chem. 1859, 77, 508; Rep. Chim. Pure, 1859, 1, 432;
Chem. Centr. 1858, 474; Jahr. Chem. 1858, 11, 199; J. prakt. Chem. 1859,
78, 370; abst. Rep. Chim. Pure. 1860, 2, 142; Jahr. Chem. 1859, 12, 542; see
also J. prakt. Chem. 1859, 78, 372. J. Schrader. Schw. J. 33, 410. E. Schweizer,
Chem. Centr. 1858, 49; J. prakt. Chem. 1857, 72, 109; 1859, 78, 370; Rep.
Chim. Pure, 1860, 2. 142; Vierteljahrsch. Zurich, naturforsch. Gess., abst.
Dingl. Poly. 1857, 146, 361; Jahr. Chem. 1857, 10, 246. M. Schleiden,
Berz. Jahr. 1841, 20, 342; Wiegm. Arch. 1838, 59; Pogg. Ann. 1838, 43, 391;
Grundz. d. wissensch. Botanik, Leipzig. 1849, 1, 172; Ann. 1836, 17, 139;
1839, 30, 2660; 1842, 42, 306; Flora, 1^2, 237. J. Schlossberger and O. Doep-

4 TECHNOLOGY OF CELI^UI^OSE ESTERS

tubular structures, which often attain extraordinary lengths — i. e. ,
several hundred times their diameter.

Carbohydrates are a widely distributed and numerous
class of bodies, found in the vegetable kingdom primarily, although
carbohydrates of animal origin are not unknown. Strictly
speaking, they contain six or a multiple of six carbon atoms, and
from the fact that they always contain carbon,' and the ratio of
the hydrogen and oxygen atoms is the same as in water, accounts
for their name.

The carbohydrates form the basis of alcoholic drinks and

ping, Ann. 1844, S2, 113; abst. Berz. Jahr. 1846, 25, 588; Annuaire Chim.

1846, 636. E. Schmidt and Hecker, J. prakt. Chem. 1847, 40, 257; abst.
Jahr. Chem. 1847-8, 1, 1130; Poly. Centr. 1847, 36. F. Schulze, Beitrage
zur Kenntniss des Lignins, Rostock, 1856; abst. Chem. Centr. 1857, 321;
Jahr. Chem. 1855, 702, 1019. E. Schulze and E. Steiger, Ber. 1887, 20,
290; abst. Jahr. Chem. 1887, 2270; Bull. Soc. Chim. 1887, 48, 280. J. C. S.
1887, 52, 460; Chem. News, 1889, 59, 377; J. S. C. 1. 1887, 6, 446. C. Schmidt,
J. prakt. Chem. 1846, 38, 433. L. SchaflFner, Ann. 1^44, 50, 148; abst. Berz.
Jahr. 1846, 25, 586. P. Schuetzenberger, Zts. Chem. Pharm. 1861, 4, 65;
abst. Bull. Soc. Chim. 1861, (1), 3, 16. P. Thenard, Compt. rend.
1861, 52, 444; Rep. Chim. Pure, 1861, 3, 207; BuU. Soc. Chim. 1861, (1),
3, 33; Jahr. Chem. 1861, 14, 908; Chem. News, 1861, 4, 136. G. Staedeler,
Ann. 1859, 111, 27; J. prakt. Chem. 1859, 78, 169; Chem. Centr. 1859,705;
J. Pharm. (3), 36, 229; Rep. Chim. Pure, 1859, 1, 569; Tahr. Chem. 1859,12,
598. J. Stenhouse, Phil. Mag. 1841, 18, 122; Ann. 1840, 35, 301. J. Thomson,
Ann. 1849, 69, 128; J. prakt. Chem. 1840, 19, 146; Phil. Mag. 1834, 5, 365.
L. Vauquelin, Schw. J. 12, 2530. F. Versmann and A. Oppenheim, Pharm. J.
Trans. (2), 1, 385, 422; Chem. News, 1860, 1, 20; Jahr. Chem. 1860, 13, 715;
Br. Assoc. Rep. No. 29, 86; J. prakt. Chem. 1860, 80, 433; Dingl. Poly. 1860,
158, 66; Zts. Chem. Pharm. 1860, 240; see also Dingl. Poly. 1860, 156, 157;
abst. Chem. Centr. 1860, 352; Rep. Chim. Appl. 1860, 2, 59. M. Vincent,
Compt. rend. 1847, 24, 542; abst. Pharm. Centr. 1848, 500; Jahr. Chem.
1847-8, 1, 1122; see also Gaudichaud, Boussingault and Payen; Compt. rend.

1849, 29, 491; abst. Instit. 1849, 353; Mon. ind. 1849, No. 1397; Dingl. Poly.

1850, 115, 150; Pharm. Centr. 1849, 909; Jahr. Chem. 1849, 2, 711. Weiss,
Chem. Centr. 1871, 179; Mon. Sci. 1869, 11, 342; 1870, 12, 23; Bull. Soc.
Chim. 1870, 13, 93 ; Jahr. Chem. 1869, 1 ia3. H. Weber, Pharm. Viertelj, 7, 538 ;
Pharm. Centr. 1858, 864 ; Jahr. Chem. 1858, U, 577. E. Winterstein, Ber. 1893,
26, 362; abst. Chem. Centr. 1893, I, 602; Jahr. organ. Chem. 1893, 1, 266; Zts.
Physiol. Chem. 1893, 18, 43; Bull. Soc. Chim. 1893, 10, 699; J. C. S. 1893, 64, i,
380, 497 ; Meyer Jahr. Chem. 1893, 3, 236 ; J. S. C. I. 1893, 12, 702. F. Winkler,
J. prakt. Chem. 1839, 17, 65. Bachet, Jahr. Chem. 1866, 663. N. Basset,
Belg. P. 138952, 1898. J. Batka, Chem. Centr. 1859, 865; abst. Poly. Notiz.
1860, 15, 3; Dingl. Poly. 1859, 154, 395; Vierteljarhsch. Pharm. 9, 275; Rep.
Chim. Pure, 1860, 2, 142; Jahr. Chem. 1859, 12, 543. E. von Baumhauer and
P. Fromberg, Ann. 1^43, 48, 356; J. prakt. Chem. 1844, 32, 204. Chem. Gazz.

1847, 5, 413; J. prakt. Chem., 1844, 32, 210. A. Bacycr, Ber. 1869, 2, 54; abst.
Bull. Soc. Chim. 1869, 12, 292. F. Bayer & Co. Belg. P. 220582, 1910; F. Beltzer
Rev. gen. Chim. 1910, 13, 20; abst. Chem. Zentr. 1910, I, 1596; C. A. 1910, 4,
1369. C. Beadle, J. Frank. Inst. 1894, 138, 100; abst. Jahr. Chem. 1894, 1134;
Chem. Trade J. 1894, 128; J. S. C. I. 1894, 13, 900. J. Beggaard and B. Gott-
schalk, Norw. P. 20847, 1909. R. Boettgcr, Chem. Centr. 1874, 309; Dingl.

CELLULOSE 5

the majority of foodstuffs, starch being the chief ingredient of
flour, from which bread is made. Cellulose, related to it, is of
interest in this work from the fact that organic and inorganic
esters may be prepared therefrom, of increasing interest both m
the peaceful and warlike arts.

According to the older system of carbohydrate classifica-
tion three groups were recognized, one containing isomeric

Poly. 1874, 213, 362; Jahr. phys. Ver. Frankfurt, 1872-73, 70; Zts. anal. Chem.
1874, U, 246; Jahr. Chem. 1874, 1031. A^folassi. Caout. Guttap. 1918,
15, 9604; abst. J. S. C. 1. 1918, 37, 686- A. T. Chaudhuri, Modern Chemistry
and Chemical Industry of Starch and Cellulose, 156 pages. C. Cross and E.
Bevan, J. Soc. Arts, 1896-7, 45, 225, 684, 703.716 ; Proc. U. S. Nav. Inst. 1886, 12,
624; Chem. News, 1889, 60, 163, 254; abst. Chem. Centr. 1889, II, 790; 1890,
I, 21; Jahr. Chem. 1889, 2066; 1890, 2152. J. C. S. 1890, 57, 1. Compagnie
Industrielle des alcools de I'Ardeche, Swiss P. 53961, 1910; A. Deiss, Span.
P. 47327, 1910; Port. P. 7164, 1910. A. Deiss and C. Foumier, Aust. P.
Anm. 6861, 1909. K. Dimcan, Sci. Amer. Suppl. Apr. 28, 1900. E. Durin,
Ber. 1876, 9, 1430, 1446; Compt. rend. 1876, 83, 128; abst. Chem. News,
1876, 34, 63; J. C. S. 1877, M, 106; Jahr. Chem. 1876, 947. E. Jandrier,
Schw. Wochensch. f. Pharm. u. Chem. 1899, 489; abst. Amer. J. Pharm. 1900,
72, 497; Compt. rend. 1899, 128, 1407; Chem. Centr. 1899, II, 184; Bull. Soc.
Chim. 1899, (3), 21, 895; Jahr. Chem. 1899, 1295, 1297; J. A. C. S. 1899, 21,
1175; J. C. S. 1899, 76, i, 788; 1900, 78, ii, 177; Chem. News, 1899, 80, 11.
C. KeUner, U. S. P. 773941, 1904; abst. J. S. C. I. 1904, 23, 1159; F. P. 326313,
1902, abst. J. S. C, I. 1903, 22, 817, 1304; Mon. Sci. 1904, 81, 46. A. Klein,
Papier Ztg. 31, 4286; Chem. Ztg. 1906, 30, 1259; abst. C. A. 1907, 1, 485, 2492;
Wochenbl. Papierfabr. 38, 1813; Zts. ang. Chem. 1907, 20, 610; Bull. Soc.
Chim. 1907, (4), 2, 905; Chem. Centr. 1907, I, 381. W. Massot, Zts. ang.
Chem. 1909, 22, 241, 299; 1911, 24, 433; abst. Kunst. 1911, 1, 452; Chem.
Zentr. 1909, I, 801; 1911, I, 1259; C. A. 1910, 4, 1240; 1911, 5, 1995. P.
Marino, Ital. P. 302/5/101627, 1909. P. Michela, Ital. P. 30024, 1892. H.
Mork, J. Frank. Inst. 1917, 184, 353; abst. C. A. 1917, U, 3430. A. Sander,
Fortschritte Chem. 4, 293; abst. C. A. 1912, 6, 153. C. Schwalbe, Chem.
Zts. 1908, 32, 287; abst. J. C. S. 1908, 84, i, 260, 321; Mon. vSci. 1910, 72, 825;
J. Frank. Inst. 170, 371; Papier Ztg. 36, 2496, 2531, 2667. 2699, 2735, 2769;
abst. C. A. 1911, 5, 3908; Papier Ztg. 36, 2599, 2631; abst. C. A. 1911, 5,
3729; Papier Ztg. 39, 2486, 2543; abst. C. A. 1915, 9, 713. J. Schmitt, F. P.
377979, 1907; abst. J. S. C. I. 1907, 26, 1088; Mon. Sci. 1908, 69, 29; C. A.
1908, 2, 1368. F. Schulz, Zts. physiol. Chem. 1900, 29, 124; abst. J. C. S.
1900, 78, ii, 292; Chem. Centr. 1900, I, 729; Bull. Soc. Chim. 1901, 26, 32.
Societe Thirion et Bonnet, F. P. 308446, 1901. W. Walker, Mon. Sci. 1908,
69, 461; J. Frank. Inst. 1907, 164, 131; abst. C. A. 1908, 2, 318, 2619. W.
Whitney, U. S. P. 923745; abst. J. S. C. I. 1909, 28, 743; see also U. S. P.
923227; abst. J. S. C. I. 1909, 28, 743; C. A. 1909, 3, 2091. Wichelhaus,
Inter. Cong. London, abst. Zts. ang. Chem. 1909, 22, 1119. Ber. 1910, 43,
2922; abst. J. S. C. I. 1910, 29, 1369; Chem. Zentr. 1910, II, 1961; J. C. S.
1910, 98, i, 868; Meyer Jahr. Chem. 1910, 20, 317; Bull. Soc. Chim. 1911,
(4), 10, 1054; C. A. 1911, 5, 2953; Rep. Chim. Appl. 1911, 11, 138. W.
Viewer, Wochenblatt fiir Papier fabrikat ion, 1911, 3541, 3729; abst. Kunst.
1911, 1, 452; C. A. 1911, 5, 3907. Papier Ztg. 1907, 32, 309. 398; Chem. Ztg,
1907, 31, 85; Chem. Zentr. 1907, I, 677; C. A. 1907, 1, 1319. E. Vitrebert,
Papier, 1914, 17, 134; abst. C. A. 1915, 9, 148. Worlds Paper Tr. Rev. 67,
No. 8, p. 32; No. 12, p. 22. See Caout. et Guttap. 1919, 16, 9888; C. A. 1919,
13, 3314.

6 TECHNOUKJY OF CEl<I.ULOSE ESTERS

compounds of the type CeHuOa termed the glucose or grape
sugar group; a second containing compounds of the formula
CisHasOii and designated as the saccharose or cane-sugar group;
while a third division was made of the highly complex, crypto-
crystalline or amorphous compounds, to which starch and cellu-
lose are t3rpes. This classification, although inadequate is still
retained, the word "glucose" being now reserved for the dextro
and laevo enantiomorphs of grape sugar to take the place of the
older word **dextrose," wt4^ became unsuitable after the discovery
of the laevo enantiomorphic form. As a comprehensive class-
ification, the three older groups of carbohydrates may be distin-
guished by the names:

Monosaccharoses, Monosaccharides, Monoses (formerly

glucoses).
Disaccharoses, Disaccharides, Saccharobioses (formerly

saccharoses).
Polysaccharoses, Polysaccharides (formerly amyloses).

After E. Fischer had succeeded in synthesizing a number of
new sugars containing more or less than six carbon atoms, a
further subdivision of the monosaccharoses became necessary.
Many new compounds were synthesized, containing two to nine
carbon atoms and possessing the general characteristics of the
monosaccharoses, and being distinguished by the names biose,
triose, tetrose, etc. Inasmuch as some of the monosaccharoses
combine the properties of alcohol and aldehydes, while others
partake of the properties of alcohols and ketones, the fiuther
distinction of "aldose" and "ketose" has been necessary.

ToUens* has devised the following comprehensive scheme of
classification of the carbohydrates:

I. Monosaccharides (Glycoses).

(a) Monose, Formaldehyde.

(b) Diose, Glycolaldehyde, Glycolose.

(c) Triose, Aldotriose (Glycerose), Ketotriose (Dioxy-

acetone).

(d) Methyltriose, Methylglycerolaldehyde.

1. "Kurtz Lehrbuch der Kohlenhydrate," 1914. E. v. Lippmann,
"Die Chemie der Zuckerarten," 1904. L. Macquenne, "Les Sucres et leurs
principaux derives," 1900. E. Armstrong, "The Simple Carbohydrates,"
1910. E. Fischer, "Untersuchungen ueber Kohlenhydrate 1884r-1908/'
1909.

CELLULOSE 7

(e) Tetrose, Aldotetrose (Er3rthrose), Ketotetrose (Ery-

thrulose).

(f) Pentose, Arabinose, Xylose, Ribose.

(g) Methylpentose, Rhanmose, Rhodeose, Fucose.

(h) Hexose, Glucose, Mannose, Galactose, Fructose,

Sorbose,
(i) Glycose with 7 carbon atoms, Rhamnohexose.
(]) Glycose with 8 carbon atoms, Rhanmoheptose,

Mannooctose.
(k) Glycose with 9 carbon atoms, Rhamnooctose,

Mannononose.
(1) Glycose with 10 carbon atoms, Glucodecose.

II. Di- and Poly-saccharides.

(a) Disaccharide, Arabiose, Saccharose, Maltose, Cel-
lose, Lactose.

(b) Trisaccharide, Rhamnotriose, Raffinose, Melezitose,
Triamylose.

(c) Tetrasaccharide, Lupeose, Stachyose, Manneo-

tetrose.

III. Polysaccharide (Saccharo-coUoids).

(a) Pentosan-coUoids, Araban, Xylan.

(b) Arabin, Tragacanth, Bassorin, Pectins.

(c) Starch, Dextran, Glycogen, Hemicellulose, Amyl-

oid, Lichenin.

(d) Paramanan, Seminin.

(e) Gelactan, Gelose, Gelan.

(f) Levulosin, Fructosan, Inulin, Asparagose.

(g) Glucosamine.

(h) Cellulose, Hydrocellulose, Oxycellulose, Cellulose
Esters.

In general, the molecular magnitude is the basis of arrangement
of these polyhydroxy-aldehydes and ketones, and to the sub-
stances which give these when hydrolyzed by heating with mineral
acids.

Nearly all of the naturally occurring carbohydrates are
optically active, the specific rotatory power being influenced not
only by the temperature and concentration of their solutions,
but also not infrequently by the presence of optically inactive

8 TECHNOU)GY OF CELLULOSE ESTERS

bodies.^ Some representatives also exhibit the phenomena of
birotation and semirotation. By heating the solutions for a
brief period, constant rotation is usually obtained. The deter-
mination of the rotatory power of the carbohydrates by means of
the saccharometer, not only aseertains their purity, but may be
made quantitative.

As to their general characteristics. The members may be
either soluble or insoluble, in water, those soluble being usually
of a sweet taste, and the insoluble carbohydrates may be trans-
formed into soluble by hydrolytic treatment. The mono-
saccharoses are colorless crystalline compoimds, reducing alka-
line solutions of the heavy metals as copper. Characteristic
compoimds are formed with phenylhydrazine.

The di- and poly-saccharoses are converted into simple car-
bohydrates when hydrolyzed, either by mineral acids or by
enzymes.

The complicated carbohydrates of which cellulose is a type
are amorphous, tend to form colloidal solutions, and relatively
speaking, are chemically inert. By virtue of the hydroxyl groups
which they contain, they react with nitric acid, organic acids and
alkylating agents, forming esters, and ethers, the detailed descrip-
tion of which forms the subject matter of the volumes in this
series.

Classification of Celluloses. E. Premy,^ who has classified
the celluloses and allied bodies, has distinguished them according
to their chemical basis as follows:

(a) Celluloses proper, including normal cellulose, meta-
cellulose and para-cellulose.

(b) Vasculose, identical with lignocellulose and found
chiefly in woody fiber.

(c) Cutose, and

(d) Pectose, found in unripe, fleshy fruits and roots, and
transformed under the influence of acids into
pectins

1. R. Pribram, Ber. 1888, 21, 2599; Wien. Akad. Ber. II b, $7, 375;
Monatsh. $, 395; abst. J. C. S. 1888, 54, 1229; Bull. Soc. Chim. 1889, (3), 1,
782; Chem. Ind. 1888, 11, 554; Jahr. Chem. 1888, 2580; J. S. C. I. 1888, 7, 594.

2. Compt. rend. 1859, 48, 667; abst. J. Pharm. (3), 35, 321; Instit.
1859, 121; Rep. Chim. Pure, 1, 351; Jahr. Chem. 1859, 534. Compt. rend.
1876, 83, 1136; abst. Bull. Soc. Chim. 1877, 28, 174; Ber. 1877, 10, 90. His
classification has not found favor with some critical writers.

CELLULOSE 9

There are a large number of substances, more or less, intimately
related to cellulose, to which the term "compound-celluloses**
has been applied. These compoimd celluloses are usually sub-
divided into the three following groups:

I. Pectocelluloses, which include most of the vegetable
textile fibers with the exception of cotton, which forms a class
by itself, and jute, which is a lignocellulose. The non-cellulose
constituents are usually pectic substances, characterized as
vegetable extractive bodies of an acid nature which readily gelati-
nize.^ Unlike the adipocelluloses, they are said to be slightly
richer in oxygen than normal cellulose, an analysis of raw flax
(which is typical of this class) giving C. 43.7, H. 5.9, O. 50.4. On
boiling with dilute alkali the pectocelluloses are readily resolved
into cellulose, the pectic matters being transformed into soluble
derivatives, and this is what takes ^lace in tlie bleaching of linen.
Many other fibers contain or consist of pectocelluloses,^ these
derivatives having been identified by E- Schunk in the products
of the alkaline boiling of raw cotton.' The cellular portion of
certain fruits (apple, pear, plum), and roots (turnip, carrot, beet)
contain large amounts of pectocellulose.

Pectin, found in ripe fruit, is precipitable by alcohol and
gelatinizes in boiling water, whereas pectose, found in unripe
fruit, is substantially insoluble in water. Both are hydrolyzed
by the action of alkalis and acids to intermediate compounds and
finally to the hexoses and pentoses.

2. Lignocellulose comprises the main portion of all woody
tissues as well as one textile fiber, jute, which in its raw state is
richer in carbon than cellulose, and is readily attacked by acids,
alkalis and oxidizing agents. Freely soluble in cuproammonium
but incompletely precipitated upon acidifying, hence of but
little value for the formation of artificial filaments in imitation
of silk. Nitric and sulfuric acids, nitrate jute (see nitro-jute),
the gain in weight being approximately the same as that of cotton

1. A. Mullcr (Leipzig, 1904), abst. Zts. anorg. Chem. 3$, 121; Jahr.
Chem. 1904, 100; Zts. ang. Chem. 1904, 17, 970; has compiled a bibliography
of colloids with 350 original publications cited ; and Whitney and Ober (J. A.
C. S. 1901, 23, 856; abst. J. C. S. 1902, 82, 65; Jahr. Chem. 1901, 133) have
compiled an index to the literature of the same subject.

2. C. Webster, J. C. S. 1883, 43, 23; abst. Jahr. Chem. 1883, 1638;
Chem. News, 1882, 46, 240.

3. Proc. Manchester Lit. Phil. Soc. (3), 4, 95.

10

TECHNOLOGY OF CElrLULOSE ESTERS

cellulose, and like the cellulose nitrates, give no amido products
upon reduction, thus indicating true nitric esters. According to
Sachsse lignocellulose consists of about 75 per cent, cellulose and
the balance lignin, a body of an aldehydic character. Iodine
is absorbed- by jute, the resulting compound being about as un-
stable as starch iodide. This reaction has been taken advantage
of in the quantitative determination of lignocelluloses in combi-
nation with other forms of cellulose. Dilute nitric acid acts
upon jute at 80 degrees, forming oxycellulose, oxalic acid, carbon
dioxide and a peculiar derivative of imdetermined composition.
The lignocelluloses hydrolyze much more readily than the simple
celluloses, furftu'ol being obtained in considerable quantity when
the temperattu'e is raised to boiling. Glycolignose, the substance
of fir and other Abies woods, and glycodrupose, the substance in
the stony concretion of pears^ are other forms of lignocellulose.
*'Crude fiber," a name applied to the residue obtained by boiling
fodder plants with alkaline and acid solutions, has been found in
most cases to consist of lignocellulose.

C. Cross and E. Bevan^ have drawn attention to certain
diversities in the cellulose group as a whole, especially as to the
degree of resistance to hydroly tic and oxidizing agents ; the amount
of furfural yielded by decomposition with aqueous HCl; and the
ratio between carbon and oxygen. The following table has been
constructed by them as indicating these points of divergence:

Type

Cotton Group.

Bleached

Cotton

Wood Cellulose

Group.
Jute Cellulose

Cereal Cellulose

Group.
Straw Cellulose

Carbon content. .
Oxygen content. .

Furfural

Other character-
istics

44.0-44.4
0.50
0.1-0.4

No active CO
groups

43.0-43.5
0.51
30.-6

Some free CO
groups

41.5-52.5
53
12.0-16

CO groups very
reactive

The lignocelluloses are in general, therefore, compounds of
the formula ROCH3 in which "R" represents, probably, aromatic

1. Bcr. 1899, 32, 2493; abst. J. S. C. I. 1899, IS, 940; Chem. Centr.
1899, II, 752; Meyer Jahr. Chem. 1899, 9, 300; J. C. S. 1899, 76, i, 852; Jahr.
Chem. 1899, 1290; Bull. Poc. Chim. 1900, 24, 620.

2. J. C. vS. 1895, 67, 433; abst. Jahr. Chem. 1895, 1349; Rev. g^n.
sci. 1895, 6, 295; Ber. 1895, 28, R, 645; Wag. Jahr. 1895, 41, 1028.

CBLLUI.OSE 1 1

groups. These celluloses are characterized by formmg com-
pounds with the halogens and are resolved by chlorination into
cellulose and chlorinated derivatives of aromatic compounds
which are soluble in alkalis and in dilute sulfite solution, the
pure cellulose thus being liberated.

3. Adipocellulose forms the outer or epidermal layer of
leaves and fibers, readily transformed by oxidation with nitric
acid into products similar to those split off by the oxidation of
fats, together with cellulose. They are of a cellular rather than of
a fibrous character, richer in carbon and poorer in oxygen than
cotton cellulose and comprise the main constituents of the leaves,
fleshy fruits and stems of annuals. The chief adipocelluloses are
cork and bark, which, when the impurities are removed, leave a
neutral body called cutose. Such materials always contain also
a large proportion of oils. The chemistry of these bodies as yet
has been but imperfectly investigated.

The waxes contain lignocellulose and nitrogenous substances.
The adipocelluloses and cutocelluloses contain a larger percentage
of carbon than pure cellulose, whereas the pectocelluloses have a
higher proportion of oxygen.

B. Tollens* states that both hydrocellulose and all crude
oxycellulose preparations contain cellulose, and that from the
action of alkalis upon these bodies the conclusion is drawn that
the true products of reaction (e. g., celloxin) are combined with
these celluloses somewhat after the manner of esters. Tollens
divides the cellulose group into the following four classes:

(a) Celluloses.

(b) Hydrated celluloses, i. e., hydrocellulose and hemi-
celluloses, bodies which are non-reducing, but
readily hydrolyzed to reducing compounds.

(c) Cellulose with acid, i. e., carboxyl groups; this class

includes the pectins, etc.

(d) Celluloses with both acid (carboxyl) groups and
aldehydic or ketonic groups; this class includes
the oxycelluloses which are cupric reducing bodies.

The more highly oxidized classes (c) and (d) are distin-

1. Ber. 1901. 34, 1434; abst. J. S. C. I. 1901, 20, 740; Bull. Soc. Chim.
1902, (3). 28, 269; J. C. S. 1901, 80, i, 453; Jahr. Chem. 1901, 897; Chem.
Centr. 1901, II, 39.

12 TECHNOWXJY OF CEW.UU)S^ ESTERS

guished from (a) and (b) by elementary analysis, the ratio of
H : O being 1 : 8-9, instead of 1 : 8, as in the (a) and (b) classes.

G. Bumcke and R. Wolff enstein^ have described a product
of the action of hydrogen dioxide on cellulose which they termed
**hydralcellulose." They assign a H:0 ratio of 1:8 to this body,
but it has been pointed out that their analyses might be equally
within the limits of error for a body of the oxycellulose type with
a ratio of 1:8.3. Judging from the imdoubted oxycellulose
properties of "hydralcellulose/* Tollens regards it as belonging to
class (d) and sees no reason for modifying the view that oxycel-
luloses are true oxidation products of cellulose.

The acid cellulose derivatives and pectins are gelatinous
bodies containing an excess of oxygen corresponding to the
presence of carboxyl groups, aldehydic or cupric reducing groups
being absent. The natural members of this class often contain
besides the Ce cellulose aggregate, groups which yield pentoses
on hydrolysis. The author also includes gum tragacanth in class
(c). Although A. Hilger and W. Dreyfus^ came to the conclusion
that the acid properties of tragacanth and oxybassorin could not
be due to carboxyl groups, the author taking into account the
inconclusive natiu"e of the elementary analyses in this respect, pre-
fers to regard both bodies as containing excess of oxygen over the
normal carbohydrate 1 : 8 ratio, owing to the presence of carboxyl
groups.

R. Wolff enstein and G. Bumcke' have shown that in
ToUen's classification of the cellulose group of carbohydrates,
the hydrocelluloses are recorded as hydrated or hydrolyzed deriv-
atives, while the oxycelluloses are merely oxidized products.
They contend it is hardly probable that the natural hydrolyzing
tendencies of the acid reagents employed should be inhibited
by the presence of the oxidizing agents. Tollens suggests that
the cellulose in these products may be present combined with the

1. Ber. 1899, 32, 2493; abst. J. S. C. I. 1899, 18, 940; Chem. Centr.

1899, II, 752; Meyer Jahr. Chem. 1899, 9, 300; J. C. S. 1899, 76, i, 852; Jahr.
Chem. 1899, 1290; Bull. Soc. Chim. 1900, 24, 620.

2. Ber. 19(X), 33, 1178; abst. J. S. C. I. 1900, 19, 677; Chem. Centr.

1900, I, 1217; Jahr. Chem. 1900, 838; Chem. Ztg. Rep. 1900, 24, 159; Bull.
Soc. Chim. 1901, (3), 26, 269; J. C. S. 1900, 78, i, 379.

3. Ber. 1901, 34, 2415; abst. J. S. C. I. 1901, 20, 925; Chem. Centr.

1901, ir. 529; Jahr. Chem. 1901, 888; J. C. S. 1901, 80, i, 582; Bull. Soc.
Chim. 1902. (3), 28, 368.

CELI<UW)SS 13

oxidized portion in the form of an ester but as this view implies
condensation rather than hydrolysis, and the molecule of the
product must be at least twice as large as that of the original
cellulose, attention is drawn to the fact that if this were so the
oxycelluloses ought to be more resistant to hydrolyzing conditions
than the celluloses, whereas the reverse is invariably the case.
These authors would classify this group of carbohydrates as
follows:

A. Cellulose

B. Hydrated cellulose (hydrocelluloses)

(a) Reducing (**Hydralcellulose");

(b) Reducing and with carboxylic groups;

(c) With carboxylic groups but non-reducing (acid-
cellulose) ;

(d) Neither reducing nor with carboxylic groups
(lactone configuration).

"Hydrocellulose" being produced by so mild a reagent as a
3 per cent, solution of hydrogen peroxide, is regarded as a purely
hydrolytic product without the formation of any more highly oxi-
dized groupings. Cellulose may be isolated from vegetable raw
material by boiling the tissue in solutions of 1 to 5 per cent, sodium
hydroxide and after washing, exposure of the moist mass to the
vapors of chlorine or fluorine gas or to bromine water at the
ordinary temperature. Alkaline hydrolysis, i. e., boiling in alka-
line solutions as sodium sulfite, sodium carbonate or sodium
hydrate, dissolves away the products formed from the non-
cellulose constituents in the preceding treatment. In dealing
with unusually refractory materials such as the hard woods, it
may be necessary to repeat this cycle of processes several times.
The material is finally completely extracted with alcohol and
ether in a Soxhlet extractor to remove resinous and fatty prod-
ucts not completely saponified by the previous alkaline treatments.

From this it follows that the typical celluloses are not sepa-
rable from plant tissue in the pure state but in admixture or in
intimate chemical union with other compounds or groups of com-
pounds, which groups are distinguished by greater reactivity in
that they more readily yield to alkaline hydrolysis, such as the
pectic bodies; or to oxidation, as the coloring matters or to the
action of the halogens. In this latter classification is properly in-

14 TECHNOLOGY OF CELLUI<OSE ESTERS

duded the very iniportant group of lignone celluloses which are
distmguishedy according to Cross and Bevan, by the presence
of cutohexane groups in imion with the cellulose, and therefore
capable of directly combining with the halogens.

Constitution of Cellulose. The various modifications of
cellulose have been extensively investigated and many con-
stitutional formulas for the normal cellulose molecule have been
suggested. The percentage composition of the purest form of
cellulose obtainable is: Carbon 44.2-44.4 per cent., hydrogen
6.2-6.3 per cent., and oxygen 49.4r49.5 per cent. These figures
lead to the general formula (C6Hio06)„. It is difficult to deter-
mine the molecular weight of cellulose, owing both to its non-
crystalline nature, and to the fact that no cellulose derivative
is known which has been volatilized without imdergoing chemical
change. Although many formulas have been put forward no
particular one hitherto has received general acceptation.^

Being a colloid, cellulose — ^like starch — comprises an aggre-
gate of reactive constituent groups whose equilibria is continually
being modified by the reactive process. It has variously been
regarded as a polycydohexane or polyhexose derivative containing
CHjOH, CHCOH and CO in addition to OH groups. Their
number, as yet, has not been definitely ascertained.

The properties and reactions of normal and modified cellu-
lose have as yet thrown but little light on the inner mechanics
of cellulose orientation, but the following observatipns have been
recorded, from which certain generalizations with profit may be
drawn.*'***

1. Cross and Bevan, "Cellulose," 3, 10.

2. Cross and Bevan, "Cellulose." 75.

3. A. Green, J. Soc. Dyers Col. 1904, 20, 117; Zts. Farb. Text. Chem.
1904, 3, 97; abst. J. S. C. I. 1904, 23, 382; Zts. ang. Chem. 1904, 17, 1121;
Chem. Centr. 1904, I, 1069; II, 980; J, C. S. 1904, i6, i, 652; 1905, 88, i, 22;
Jahr. Chem. 1904, 1160, 1161; Chem. Ztg. Rep. 1904, 28, 115; Wag. Jahr.
1904, 50, II, 398.

4. E. Schulze, Ber. 1889. 22, 1192; 1890, 23. 2579; 1891, 24, 2277;
abst. J. C. S. 1889, 56, 916; 1890, 58, 1456; 1891, 60, 238, 1178; 1892, 62,
907; Bull. Soc. Chim. 1890. 4, 522; 1891, 5, 787; 1892, 8, 491; Jahr. Chem.
1891, 44, 2208; J. S. C. I. 1890, 9, 1051 ; 1892, U, 49. W. WiU, Ber. 1891. 24,
400; abst. J. C. S. 1891, 60, 542; Bull. Soc. Chim. 1891, 6, 668; J. S. C.
I. 1891, 10, 578; Jahr. Chem. 1891, 44, 1624. Chem. Centr. 1891, 62, 1, 630;
Meyer Jahr. Chem. 1891, 1, 333; Chem. Ztg. Rep. 1891, 15, 90. H. Penton
and M. Gostling, J. C. S. 1898, 73, 557; abst. Chem. Centr. 1898, 60, II,
181, 421 ; Jahr. Chem. 1898, 51, 1312; Meyer Jahr. Chem. 1898, 8, 202; Chem.
Ztg. 1898, 22, 493.

CBLtULOSE 15

(1) The action of hydrochloric acid releases carbonyl
groups.

(2) Resolution by inorganic acids and subsequent
hydrolysis into simple carbohydrate (dextrose)
molecules.

(3) Formation of the crystalline w-bromomethylfur-
f tiral by the action of hydrobromic acid :

H — C = C — CHO

>

H — C = C — CHjBr,

(4) Oxidation of cellulose to oxycellulose.

(5) Formation of furfural from oxycellulose by acid
hydrolysis.

(6) Formation of isosaccharic acid from oxycellulose.

H — C — OH — CH — COOH

>

H — C — OH — CH — COOH

in addition to dioxybutyric acid by the action of a
solution of calcium hydroxide.

(7) Resolution of cellulose by alkali fusion into oxalic
acetic and hydroxypyruvic acids, carbon dioxide
and hydrogen.

(8) Decomposition by bacterial action into methane,
hydrogen, carbon dioxide and fatty acids (mainly
acetic and butyric).

(9) Distillation in vacuo gives a good yield of /-gluco-
san.

(10) Stable nature of the cellulose molecule shown by its
partial resistance to alkali hydrolysis, oxidizing
agents and acetylation. When acted upon by con-
centrated alkaline solutions, such as caustic soda,
an tmstable sodium compound is formed. When
this solution is diluted with water a cellulose is
obtained which is more soluble in such solvents as

16 TBCHNOI.OGY OF CELLXJlyOSE J^ST^RS

concentrated acid zinc chloride than the untreated
cellulose.

(11) Synthetic reactions — ^formation of various nitrates,
acetates and benzoates, and ethers.

(12) Formation of a trimethylglucose from methylated
cellulose.

(13) Formation of oxypyruvic acid (CH2 OH.CO.-
COOH) by the action of dilute alkalis on nitro-
cellulose.

(14) The thiocarbonate reaction which gives indication
of the nature of the hydroxyl groups and the re-
sistance of the molecule to hydrolysis.

(15) Specific volume and solution volume determinations
indicate that the cellulose molecule is, compara-
tively speaking, probably small.

The activity of certain groups in the cellulose molecule is
suppressed. Thus, there are no free carbonyl groups present
capable of reaction with phenylhydrazine or hydroxylamine. A
study of the number of hydroxyl groups which react with acids
to yield esters shows that there are probabljr only three such
groups. (Ce). The highest nitrate of the unaltered cellulose
complex is probably the trinitrate and the highest acetate prob-
ably the triacetate (Ce). It is possible to obtain analytical
figures indicating a tetra-acetylcellulose, but this compound is
most likely derived from a condensation product or other cellulose
derivative. The three hydroxyl groups would require to be ar-
ranged in such a manner as to show their alcoholic function.

Again, any suggested formula for cellulose must show that
one carbon atom is capable, on hydrolysis, of reacting as part
of a carbonyl group. The results of the fusion with alkali indicate
that the linking CO.CH2 functions as an important unit in the
grouping.

From the above considerations the choice lies between a
cyclic and an open chain structure. As opinions differ in the
interpretation of the known reactions and since no chemical
synthesis of cellulose has been carried out, both types of formulas
have their adherents. The formulas in some cases are proposed
only tentatively. They are suggested in the main so as to offer

cEi.i.uu)SE 17

a stimulus to future investigators and to act as a guide. ^'^

L. Vignon,^ from a study of the nitration of cellulose, oxy-
cellulose and hydrocellulose, concludes that the cellulose mole-
cule is a simple one. By the action of alkali on the nitration
product of oxycellulose, W. Will obtained hydroxypyruvic acid.*

His proposed constitutional formula is as follows :

O CH^

O >(CHOH)3

CH2 — CH'

The oxycellulose is considered to have the grouping :

COH
(CH0H)3<^

^CH— CO

O

1. E. Grandinougin, Chem. Ztg. 1908, 32» 241; abst. J. C. S. 1908,
94, i, 250; Chem. Zentr. 1908, 79, I, 1617; Bull. Soc. Chim. 1909, 6, 231. C.
Schwalbe, Chem. Ztg. 1908, 32, 287; abst. J. C. S. 1908, 94, i, 321; C. A.
1908, 2, 3142; Chem. Zentr. 1908, 79, I, 1617. Compare A. Pictet, Arch. Sci.
phys. et. nat. Geneva, 1915, (4), 40, 181; abst. Chem. Zentr. 1916. 87, I, 68;
C A. 1916 10 1754.

2. f! Beltzer, Rev. g6n. chim. 1910, 13, 72; abst. C. A. 1910, 4, 1369;
Chem. Zentr. 1910, 81, I, 1596; Chem. Ztg. Rep. 1910, 34, 135.

3. Compt. rend. 1898, 126, 1355; abst. J. C. S. 1898, 74, i, 620; J. S. C. I.
1898, 17, 680; Chem. Centr. 1898, 69, II, 24, 792; tahr. Chem. 1898, 51, 2265;
Chem. Ztg. 1898, 22, 425; Bull. Soc. Chim. 1898, 19, 810; Mon. Sci. 1898, 51,
454; Rev. g^n. sci. 1898, 9, 918. He obtained furfuraldehyde from various
products as follows: hydrocellulose, 0.854%; oxycellulose, 2.113%; oxycel-
lulose from chromic acid, 3.5%; reduced cellulose, 0.86%; starch, 0.8%;
bleached cotton 1.8%. "R6sum6 of Investigations of Oxycellulose," Rey,
Lyon, 1900.

4. W. Will, Ber. 1891, 24, 400; abst. J. S. C. I. 1891, 10, 578; J. C. S.
1891, 60, 542; Chem. Centr. 1891, 62, I, 530; Jahr. Chem. 1891, 44, 1624;
Chem. Ztg. Rep. 1891, IS, 90; Bull. Soc. Chim. 1891, 6, 668; Meyer Jahr.
Chem. 1891, 1, 333. Compare in this connection, A. Bechamp, Compt. rend.
1853, 37, 134; abst. Jahr. Chem. 1853, 6, 550. A. Hofmann, Ann. 1860,
115, 283; abst. J. C. S. 1860, 13, 76; Chem. Centr. 1860, 31, 976; Rep.
Chim. Appl. 1861, 3, 119; Jahr. Chem. 1860, 13, 499. S. De Luca, Compt.
rend. 1861, 53, 298; 1864, 59, 487; abst. Jahr. Chem. 1861, 14, 713; 1864, 17,
570; Instit. 1861, 275; Dingl. Poly. 1861, 162, 135; J. prakt. Chem. 1862,
85, 378; J. Pharm. (3), 41, 483; Poly. Centr. 1862, 28, 221; Dingl. Poly. 1864,
174, 388; Wag. Jahr. 1864, 10, 243; Mon. Sci. 1864, 12, 951; Poly. Centr.
1865, 31, 197. Maurey, Compt. rend. 1849, 28, 343; abst. Jahr. Chem. 1849,
2, 471 ; Annuaire de Chim. 1850, 360. E. Divers, J. C. S. 1863, 16, 91 ; Chem.
News, 1863, 7, 154; Zts. Chem. Pharm. 1863, 237; J. prakt. Chem. 1864, 91,
58; Chem. Centr. 1863, 34, 690; Bull. Soc. Chim. 1864, 1, 46; abst. Jahr. Chem.
1863, 16, 569. F. Kuhlmann, Compt. rend. 1856, 42, 676; abst. Jahr. Chem.
1856. 9, 821; Dingl. Poly. 1856, 142, 221 ; Poly. Centr. 1856, 22, 870; J. prakt.
Chem. 1856, 69, 288; Chem. Gaz. 1856, 192; Wag. Jahr. 1856, 2, 327.

18 TECHNOLOGY OF CELI.UU)SE ESTERS

united with varying proportions of residual cellulose.

C. Cross and E. Bevan are of the opinion that a cyclic structure
for cellulose best represents its relative stability compared with
that of the hexoses. The formation of a cellulose tetra-acetate
of the composition CeHeO (Ac.)4 in which only 2 carbon valen-
cies are taken up in outside*' combination would point to a sym-
metrical formula. In the plant world the transition of cellulose
to R-keto-R-hexene, and benzene derivatives, also support the
formulation of cellulose as a cyclo-hexane derivative. The process
of lignification in the plant cells is characterized by the formation
of groups of the type of a cyclic tetra-hydroxyketohexene of the

general formula:

CH = CH

Co/ \CH2

c — c

(0H)2 (0H)2

This form of grouping behaves in a similar manner to cellu-
lose and it is considered probable that some such type of grouping
would represent the simple cellulose molecule.

C. Cross and E. Bevan put forward the suggestion that
cellulose may be a special form of a general carbohydrate of the
formula:

n.[(CHOH)3COC2H40]

leaving the position of the carbonyl group and its type, i. e.,
whether aldehydic, ketonic or cycloketonic an open question.
The special function of the oxygen atom is also not defined.
The Ce unit on the basis of 3 (OH) groups for the normal cellulose
has been represented by the formula :

r— O ,

— CH.CH.OH.CH.CH.OH.CH.OH.CH2 —

! O '

A. Green' regards celluloses as having the constitution of an
intermolecular anhydride of glucose, and to have the structural
formula

1. A. Green, Zts. Farb. Text. Chem. 1904, 3, 97; abst. J. S. C. I. 1904,
23, 382; Chem. Centr. 19()4, I, 10(59; II, 980; Jahr. Chem. 1904, 1160. 1161;
J. C. S. 1905, 88, i, 22; Chem. News, 1906, 93, 243; Soc. Dyers Col. 1904,
20, 117; Zts. ang. Chem. 1904, 17, 1121; abst. Wag. Jahr. 1904, II, 398; J. C.
S. 1904, 86, i, 052.

CBLI.UU)SE 19

graphically rq)resented by the following:

H — C(OH) — CH — CHOH

I \

O O

I /

H — C(OH) — CH — CH2

By such a formula most of the reactions of cellulose can be satis-
factorily explained. It lends a ready explantion of the formation
of dextrose by hydrolysis, and is also in agreement with the for-
mation of a trinitrate and triacetate as the highest esters, for
higher derivatives could only be obtained by the transformation
of the two central oxygen atoms into two hydrooxyl groups.^
The production of co-bromo- and co-chloromethylfurfuraldehyde
in the cold, in good yield from normal cellulose, by the action of
dry hydrogen bromide and chloride respectively, is explained on
Green's formula, as well as why cellulose does not react with either
phenylhydrazine or hydroxylamine, because it does not contain
either aldehydic or ketonic carbonyls (CO) groups.

This is shown by the initial dehydration (I) and addition
of the hydrogen halide (II), followed by further loss of the ele-
ments of water (III), thus:

CH = C — CH — OH CH = C — CH(0H)2 CH = C — CHO

»o .

- > -

- >

CH=C — CH2
I

CH = C — CHjBr
II

CH = C— CHjBr.
Ill

The dehydrated product (CeHeOa) has the empirical formula
of lignone and is probably related to this latter substance.

He claims that an acceptable formula for cellulose must
satisfactorily explain the following:

(1) A trinitrated derivative.

(2) A triacetated compound.

(3) Concentrated sodium hydroxide gives a compound,
decomposable by water to form cellulose hydrate,
and in this condition more soluble in zinc chloride and
cuprammonium solutions than untreated cellulose.

(4) Treated with alkali and carbon bisulfide, cellulose

1. C. Cross and E. Bevan, Zts. Farb. Text. Tnd. 1904, 3, 197, 441; abst.
Chem. Centr. 1904, 75, II, 197; 1905, 76,1, 225; J. C. vS. 1904, 86, 1161; 1905,
, i, 119; Chem. Zts. 19(M, 3, 807; Jahr. Chem. 1904, 86, 1161.

20 TECHNOWGY OP CELLULOSE ESTERS

thiocarbonate forms, easily soluble in water.

(5) With phenylhydrazine or hydroxylamine, no re-
action.

(6) When hydrolyzed with sulfuric acid, the ultimate
product is glucose.

(7) Must respond to the Fenton reaction for chlor-
methylfurfural.

(8) Formation of oxycellulose by oxidation, which
upon distillation with dilute sulfuric acid, gives
furfiu*al.

(9) The oxycellulose when boiled with milk of lime,

gives dioxybutyric and isoglucosic acids.
(10) When nitrated, and the nitrocellulose treated
with dilute NaOH, oxypyruvic acid is formed.
When normal cellulose is referred to, one generally associates
it with the purest form of Swedish filter paper. This class of
paper, however, receives very drastic treatment in purification
and the cellulose is slightly attacked. It is claimed that cotton
fiber, purified of its pectic bodies, fat and nitrogenous matter by
the mildest possible treatment, gives the purest cellulose. Cotton
as prepared in calico manufacture, is considered by C. Cross and
E. Bevan to represent normal cellulose.

The behavior of cellulose on mercerization may be explained
according to Green's formula by the * 'opening out" of the central

oxide group:

= Cv =C — ONa

>0 —^
= C^ =C — OH

— C— OH\

on washing with water a hydrated cellulose is formed — C — OH j '
In a similar manner the regeneration of cellulose from mono-
nitrocellulose^ may be explained.

In the viscose reaction a similar "opening out'* of the central
oxygen occurs and on the elimination of the thiocarbonate group
a hydrated cellulose again results.

The latent aldehydic character of cellulose is explained by

1. E. Knecht. Ber. 1904, 37, ^9; abst. J. Soc. Dyers Col. 1904, 20, 68;
Rev. g6n. chim, 1904, 4,413; J.S.C.1. 19()4,23,33r>;Cheni. Centr. 1904,75,1,
872; J. C. S. 1904, 86, i, 293; Bull. Soc. Chim. 1905, 34, 514; Jahr. Chem.
1904, 1165; Chem. Ztg. Rep. 1904, 28, 92.

CELLULOSE 21

assuming that the — CHa — O — CH — OH group is able to function

as an aldehyde by the simultaneous taking up and removal of

a molecule of water.

X)H
CHOH — CH<; — CHO .

>

OH

— CH2 — CH2 — OH — CH2OH

Against the formula of Green the objection has been raised
that it does not account for the stability of cellulose towards
alkali compared with the ease with which alkali attacks monoses.
In addition, when viscose and alkali cellulose are hydrolyzed
the reacting groups unite to form aggregates of higher molecular
weight, a fact not made clear by Green's formula.

The doubt expressed by Green on the existance of a tetra-
acetyl-cellulose obtained from a normal cellulose was finally
settled by A. Green and A. Perkin.^ They determined the
amount of acetic acid obtainable from so-called tetraacetyl-
cellulose by hydrolysis, both with sulfuric acid and with sodium
hydroxide. The result of three series of determinations carried
out under dififerent conditions agreed with the theoretically
possible values for a tri-acetylcellulose. This result is in conflict
with the yield of ester obtained by other workers. It is in agree-
ment, however, with the A. Green's formula and brings the highest
normal acetate into line with the cellulose nitrates and benzoates.
If "three" is regarded as the maximum number of reactive hydroxyl
groups in the cellulose molecule, any cellulose esters containing
more than three acid residues or their equivalent, should be con-
sidered as derived from hydrated celluloses. In this case the central
oxygen group is converted into 2 (OH). Into this category would
be placed the aceticsulfuric ester (C6H702)4S04(CH3COO)io
obtained by C. Cross and E. Bevan, as well as certain other
cellulose acetates.

Green's formula is intended to represent cellulose in its

1. J. C. S. 1906, W, 811; abst. J. Soc. Dyers Col. 1906, 22, 230; Rev.
g^n. mat. color, 11, 51; C. A, 1907, 1, 1062; Bull. Soc. Chim. 1910, (4) 2, 37;
Jahr. Chem. 1905-1908, II, 985; Zts. ang. Chem. 1907, 20, 459; J. S. C. I.
1906,25,652;Chem.Ztg. 1906, 30, 517; Rep. g^n. chim. 1906, 6, 331, 381;
Chem. Centr. 1906, II, 321.

22 TECHNOI/DGY OP CELLU1X>SE ESTERS

simplest or unpolymerized form. In such a form it may be sup-
posed to exist in an ammoniacal cupric solution. The cellulose
of fiber may be regarded either as a physical aggregate of these
simple molecules, or less hkley as a chemical polymer made up of
a number of Ce complexes united by their oxygen atoms.

H. Barthelemy^ gives to cellulose the following constitutional
formula:

O

/\
(OH)CH CHCH2(OH)

(OH)CH CR

I I >

.CH CW

<

CH CH(OH)

(0H)CH2CH CH(OH)

\/
O

The formation of oxycellulose of the general type n (CeHioOa)-
m (CeHioOe) is explained by assuming that one of the terminal
— CH2OH groups is oxidized to an aldehydic group. This view
explains (a) the strong reducing power of oxycellulose; (b) it
shows the hydrolyzing action of oxidizing reagents in the acety-
lation and formylation of cellulose, and (c) explains the formation
of furfural in the distillation of cellulose in the presence of hydro-
chloric and sulfuric acids.

The formation of hydrocelluloses of the type nCC^HioOs)-
H2O is explained by assuming that a molecule of water is attached
to the =HC — O — C = group in a manner similar to that postu-
lated by A. Green. This viscose may be regarded as a product of
the reaction

C,2H2iOioO Na -f CS2 = C12H21O10O

NaS^

and the "ripening" as a polymerization

1. Caout. & Guttap. 1917, 14, 9274, 9328; abst. C. A. 1917, 11, 3428;
1918, 12, 223.

CELI.UU)SE 23

O — CJ2H21O10 yO — C24H41O20 J^^

2CS<( = CS<( + CS<(

^Na ^SNa ^SNa

The general formula for cellulose xanthates being

<0 Ceni Hiom -h 1 Osm

SNa
and hydrocellulose

^601 HiOm + 1 Osm OH, i. e., m(C6Hio06)ni*H20.

The condensation of the cellulose molecule is considered to take
place laterally, an OH of the side chain splitting off with H from
one of the groups functioning as a primary alcohol. The con-
stitutional formula of the condensed product would be:

o 0 0 •

(OH)CHCH CH2 CH CHCHaCOH)

(OH)CHCH(OH) (OH)CH C)

<

\o.

CHCH(OH) (OH)CH CW

CHCH(OH) (OH)CH CH(OH)

(0H)CH2CHCa CH2 CH CH(OH)

00 O

H. Barthelemy considers that the highest normal ester con-
tains three acid residues (Ce). He was unable to obtain a formyl-
cellulose containing more than three formyl groups (Cg). Simi-
larly in trying to substitute other groups for NO2 he notes that
nitrocellulose dissolves in formic acid with denitrification.

From a study of the methylation of cellulose as undertaken
by W. Denham and H. Woodhouse^ further insight may be

1. J. C. S. 1913, 103, 1735; 1914, 105, 2357; abst. C. A. 1914, 8, 243;
1915,9,203;Chem.Zentr. 1913,84,11, 1857; 1915,88, 1,81; J. S. C. I. 1913,32,
974;J.Soc. Dyers Col. 1913, 29, 327; Bull. Soc. Chim. 1913, (4), 14, 1495;
see also L. Lilienfield, F. P. 447974, 1912; abst. J. S. C. I. 1913, 32, 420,
940; E. P. 12854, 1912; Belg. P. 254591, 1912; abst. J. C. S. 1913, 103, 1747;
C. A. 1&13, 7, 3839; Mon. Sci. 1914, 80, 3; Kunst. 1913, 3, 195. See also E. P.
6035, 1913; abst. J. S. C. I. 1914, 33, 417.

24 TECHNOI/DGY OP CELI.ULOSE BSTERS

obtained with respect to the constitution of cellulose. These
workers first allowed their fibrous material to be impregnated
with a 15% solution of caustic soda, the material after removal
from this solution being methylated by the direct action of methyl
sulfate. Various alkyl substituted sugars were obtained. From
the number and distribution of these alkyl groups it is suggested
that a clue may be obtained regarding the union of the mono-
saccharide residues in the original cellulose material. From the
methylated cellulose is obtained a crystalline trimethyl-glucose:

r-CH.OH

CH.OMe

O I

CH.OMe

•-CH
CH.OMe

CH2.OH

This result indicates the probable existence of at least three
hydroxyl groups in the original cellulose aggregate.

Although the dry distillation of an organic compound is
often so drastic a treatment as to fundamentally alter the con-
stitution, yet a reference may be made to an experiment by A.
Pictet and J. Sarasin.^ In the dry distillation of cellulose
they obtained /-glucosan in good yield (45%) and upon this the
claim has been made that cellulose may be considered as a poly-
mer ide of /-glucosan. A constitution similar to that suggested
by Green is proposed. The trimethylglucose obtained by W.
Denham and H. Woodhouse from methylated cellulose by hy-
drolysis is not readily explained on the assumption that cellulose
is a derivative of /-glucosan. Throughout the literature on
cellulose, some confusion exists whether cellulose should be
regarded as CeHioOs, or some multiple of this, due to the fact that

1. Compt. rend. 1918, 166, 38; abst. J. C. vS. 1918, 114, i, 59; C. A.
1918, 12, 804; Helvetica chim. acta. 1918, 1, 78; abst. C. A. 1918, 12, 2187;
Arch. sci. phys. nat. 1918, 46, 5; Chim. and Ind. 1918, 1, 279; J. S. C. I.
1918, 37, 49-A.

CELI.ULOSH 25

up to the present the molecular weight of cellulose is unknown.
Determinations of the molecular weight of cellulose esters such as
nitrates, acetates, and benzoates have given abnormal results,
and have usually varied sufficiently to prevent useful comparisons
being made. By determinations of the molecular weight of tri-
acetylcellulose by the boiling point method in a Beckmann
apparatus a value of approximately 40 for the molecular weight
of cellulose is indirectly obtained.^ This is approximately a
quarter of the molecular weight required for the simplest formula
QHioOb. Much of the difficulty in the way of determining the
molecular weight is due to the colloidal and amorphous nature of
both celulose and the majority of its derivatives.

W. Dreaper regards cellulose as an aggregate of ions which
take their origin in the plant cells in which the celluloses are
present as mass aggregates. From this standpoint cellulose is a
typical colloid with no fixed constitutional formula, and is to be
regarded rather as a unit in dynamic equilibrium, its reacting unit
at any moment being a function of the condition under which
it is placed.

A. Green advocates the use of the simple formula CeHioOs for
cellulose rather than a multiple of this. He argues that although
cellulose is a colloid, there is no reason why it should be regarded
as having a high molecular weight, as inorganic colloids are
known to which simple formulas are given. The formula
C12H20O10 for cellulose has also been advocated. The existance of
tri- and penta-cellulose nitrates of the type Ci2Hi70io(N02)3 and
Ci2HibOio(N02)5 would require a molecule containing twelve car-
bon atoms. Other reactions furnish evidence as to the com-

1. A. Nastjukow, J. Russ. Phys. Chem. Soc. 32, 543; Ber. 190(), 33,
2237; 1901, 34. 719; abst. Chem. Centr. 1901, 72, 1, 93, 932; J. C. S. 1900, 78,
i. 540; 1901, 80, i, 315; Bull. Soc. Chim. 1901, 28, 123, 557; Jahr. Chem. 1900,
53, 844; 1901,54, 897, 898; J. S. C. I. 1900, 19, 733; 1901, 20, 573; 1902; 21,
63. O. Faber and B. Tollens, Ber. 1899, 32, 2589; abst. Chem. Centr. 1899,
70, II, 901; J. S. C. I, 1899, 18, 1014; J. C. S. 1899, 76, i, 854; Jahr. Chem.
1899, 52, 1292; Chem. Ztg. Rep. 1899, 23, 321 ; Chem. Tech. Rep. 1899, 38, 550;
BuU. Soc. Chim. 1900, 24, 621 ; compare also V. Zanotti, Annaurio Soc. Chim.,
Milano, 1899, 27; abst. Jahr. Chem. 1899, 52, 1288; J. C. S. 1899, 76, i. 851 ;
Chem. Centr. 1899, 70, 1, 1209. G. Bumcke and R. Wolffenstein, Ber. 1899, 32,
2493; abst. Chem. Centr. 1899, 70, II, 752. Meyer Jahr. Chem. 1899,9,300;
J. C. S. 1899,76, i, 852; Jahr. Chem. 1899, 52, 1290; Bull. Soc. Chim. 1900,24,620;
J. S. C. I. 1899, 18, 940. A. Sabanejew, Jour, Russ. Phys. Chem. Soc. 1891,
23, I, 80; abst. Zts. Physik. Chem. 1892, 9, 89; Ber. 1891, 24, R, 606; Bull.
Soc. Chim. 1891, 6, 719; Jahr. Chem. 1891, 44, 122.

26 TECHNOI/XJY OF CEl^l^ULOSE ESTERS

plexity of the cellulose molecule, as an aggregate.

Thus the production of cellobiose by Z. Skraup,^ from
cellulose, involves the assumption that the substance Ci2H220ii is
either a degradation product of cellulose, or that it has been syn-
thesized during the reaction. However, it may be tmsafe to
attach too much reliance on the evidence of reactions and combi-
nations as the equilibrium of the molecule is prone to be modified
by the process of reaction, the cellulose complex being regarded as
a labile aggregate. Hydration or even condensation may also
occur coincidental with, or previous to, chemical combination.
As yet no accurate picture of the cellulose molecule can be presented,
and suggested equations of reactions involving the cellulose
complex can only be approximate representations of what takes
place.

Preparation of Pure Cellulose. In order to obtain pure
cellulose for industrial purposes or for scientific investigation,
it is necessary to remove the extraneous impurities, coloring
matter and incrusting materials.

This may be conveniently carried out according to the fol-
lowing suggested method of treatments. The cotton (or other
form of cellulose) is first mechanically treated for the removal
of foreign impurities, and then boiled preferably under 3 to 5
atmospheres pressure with a l%-2% solution of sodium hy-
droxide, either with or without the presence of saponified oils.
After thorough washing until the wash waters are colorless or
substantially so, the cellulose is exposed in the moist state to the
action to dilute chlorine, washed, treated with a dilute mineral
acid in the cold, washed again to neutrality, and once again
submitted to hot alkali trejitment with subsequent removal of
the alkali by washing. After drying, the cellulose may be ex-
tracted with hydrofluoric acid to remove fractions of a per cent,
of iron and silica, and the cellulose finally exhausted with ether
or petroleum benzine to remove the last trace of cholestrin and
fatty materials. If the above indicated processes of purifica-

1. Ber. 1899. 32, 2413; abst. J. C. S. 1899, 76, 852; Jahr. Chem. 1899,
52, 1288; J. S. C. I. 1899, 18, 941; Chem. Centr. 1899, 70, II, 752; Bull. Soc.
Chim. 1900, (3), 24, 619. Z. Skraup and J. Kocnig, Ber. 1901, 3*. 1115;
J. S. C. I. 1901, 20, 740; J. C. S. 1901, 80, i, 370; Jahr. Chem. 1901, 54, 878;
Chem. Centr. 1901, 72, 1, 1 197; Monatsh. 1901, 22, 1011 ; abst. Chem. Centr.
1902, 73, 1, 183; J. S. C. I. 1902, 21, 144.

CEI.LXJU)SB 27

tion have been carefully carried out, but little change in the
structure of the cellulose will result.

F. Beltzer has described the following process for the prepa-
ration of normal ptu-e cellulose from cotton: The cotton is first
carefully combed in order to remove all mechanical impimties,
than boiled for 6-8 hours in a solution of caustic soda of 1.013
sp. gr. The liquor is then squeezed out and the material
washed until the waters are colorless or nearly so. The cotton is
then treated with HCl of 1.01 sp. gr. at 45°-50'' for 3-4 hours,
and thoroughly washed. The fiber is next carefully bleached in a
solution of sodium hjrpochlorite of 1.01 sp. gr. at 30° for 6-8
hours and washed in warm water. A second treatment as above
is given the cotton. The cellulose is finally treated with a solu-
tion of sodium bisulfite of 1.01 sp. gr. at 55° for 5 hours, then well
washed. When dried at a moderately low temperature, the
cotton should give on ignition not over 0.05% ash. Cellulose
thus prepared should be substantially insoluble in weak caustic
soda or potash upon boiling, thus indicating the absence of hydro-
cellulose or oxycellulose. Should these impurities be present,
they may be removed by again boiling the cellulose with caustic
soda solution as before, followed by acidulation with hydrofluoric
acid, treated with bisulfite, and washing. Cellulose thus prepared
should give no furftu'al upon distillation with hydrochloric acid,
nor show a rose color with phloroglucinolhydrochloric acid. The
copper value with Fehling's solution should be nearly, if not
quite, zero.

B. Rinman^ ptuifies cellulose substances by boiling in a
solution of calcium hydroxide in the presence of substances which
increase the solubility of the calcium hydroxide. The method of
the Zellstoffabrik Waldhof * is similar. W. Whitney' has described

1. Can. P. 180925. 1917; abst. C. A. 1918. 12, 1125; U. S. P. 1202317.
1916; abst. Mon. Sci. 1917, 85, 50; J. S. C. I. 1916, 35, 1215; C. A. 1917.
11, 99. D. R. P. 285752, 1914; abst. J. S. C. I. 1915, 34, 1139. Norw. P. 20645,
1909; abst. Mon. Sci. 1915, S3, 56. C. Flodquist, U. S. P. 525540, 1894.

2. Swiss P. 3194. 1891. E. P. 336, 1891; abst. J. S. C. I. 1892, 11, 180.
D. R. P. 64878. 1890; abst. Ber. 1893. 26, R, 78; Wag. Jahr. 1892, 38, 371;
Ztg. ang. Chem. 1892. 5, 706.

3. U. S. P. 923227, 923745, 1909; abst. J. S. C. I. 1909, 28, 743; C. A.
1909, 3, 2091. C. Kellner (Belg. P. 166688, 1902; 170871, 171192. 1903)
bleaches the fiber by the electrolysis of soluble chlorides. E. Nemethy (Belg.
P. 196647, 1906) prefers magnesium mono- or bi-sulfite. See Elektro-Osmose
Akt.-Ges. (Graf Schwerin-Ges.) D. R. P. 296053, 1917; Chem. Zentr. 1917,

28 TECHNOLOGY OP CEI.I.UW)SE ESTERS

a process for the purification of porous cellulose materials, wherein
the porous material is washed with a solvent which is isotonic
with respect to the impurity it is desired to remove and only
contains a small quantity of it, while at the same time an electric
current may be passed through the solvent. The process is more
particularly applied to the removal of zinc chloride from cellulose,
by suspending the cellulose in a liquid which will dissolve the
impurity and passing an electric current through the solution.

P. Girard^ proposed to purify the cellulose by a final treat-
ment with methyl alcohol and formaldehyde. The I. Kitsee*
process for cellulose purification preliminary to the emplo)rment
of the cellulose for nitration purposes, and its utilization for
battery cell jars and insulation plates, embraces first treating the
cellulose with sodium carbonate solution as long as extractive
forms, when it is washed until neutral, carefully dried and is
then considered suitable for purposes of nitration.

In the purification of cellulose, especially for the manufac-
ture of spinning solutions, the Verein f. Chemische Industrie in
Mayence' have found that while readily soluble varieties of
cellulose yield compounds which spin easily, the artificial silk
threads thus produced are inferior in respect to tensile strength.
On the other hand the observation has been made, that the most .
difficultly soluble varieties of cellulose yield filaments of the
maximum tensile strength.

Their process has in view the treatment of the cellulose to
render it sufficiently soluble without impairing the strength of
the filaments therefrom, and this is accomplished by treating
the spinning solutions with such small amounts of acid or acid

, T, 354; Chem. Ztg. Repert. 1917, 41, 104; J. S. C. I. 1917, 36, 593; D. R. P.
249983; 265628, 1911; abst. C. A. 1914, 8, 303; D. R. P. 295043, 1915; Addn.
to D. R. P. 265628, 1911; abst. C. A. 1918, 12, 791; E. P. 2379, 27930, 1911.
F. P. 16642, Addn. to F. P. 448230.

1. Belg. P. 247992, 1912; abst. Kunst. 1913, 3, 178. F. P. 443897, 1912;
abst. J. S. C. I. 1912, 31, 1120; Kunst. 1913, 3, 15. See also D. R. P. 266140,
1912; abst. C. A. 1914, 8. 827; Chem. Ztg. Repcrt. 1913, 37, 684. See C.
Piest, Papicrfabr. 1914, 12, 860; abst. C. A. 1914, 8, 3362; J, S. C. I. 1914,
33, 8.56.

2. U. S. P. 900744, 1908; abst. J. S. C. I. 1908, 27, 1220; C. A. 1909,
3, 515.

3. D. R. P. 290131, 1913; abst. C. A. 1916, 10, 2803; Kunst. 1916, 6,
109; Chem. Ztg. Repert. 1916, 40, 96; Zts. ang. Chem. 1916, 29, 144; Chem.
Zentr., 1916, 87, 1, 352; J. S. C. I. 1916, 35, 533. The J. Daniel and F. Benoist
process for the manufacture of pure cellulose is described in Belg. P. 260276,
1913.

CElrLUIvOSE 29

salts that the formation of oxycellulose or hydrocellulose is pre-
vented. The cotton which is to be worked up into artificial
silk is carefully bleached for the prevention of the formation of
oxycellulose or hydrocellulose, then rinsed and acidified with
dilute sulfiu*ic acid. The mass is then rinsed with very soft water
(condensation or distilled water if possible) until the wash liquor
after the concentration of a large quantity no longer shows an
acid reaction.

The cotton fiber itself then shows a strongly acid reaction.
It need only be carefully treated to be ready for the preparation
of spinning solutions. The cotton is allowed to stand for several
days in a dry place before subjecting it to the solution process.
If sufiBciently soft water is not available the de-acidified cotton
must be rinsed with water at 10°-12° hardness, then immersed
in a final bath which contains 0.01-0.10% acid calculated on the
weight of the material.

E. BerP has called attention to the fact that in the treat-
ment of cellulose by technical processes, in order to dissolve or
esterify the cellulose, certain methods of treatment are customary
which, according to the opinion of this author, signify an increase
of reaction of the cellulose by the decrease of the molecular size.
According to Berl relative differences in the molecular size of
cotton can be established by meastuement of the internal friction
of solutions of the same percentage of esters prepared in an iden-
tical manner.

If for the manufacttu'e of cuproammonia silk, the cellulose
is subjected beforehand to mercerization the greater reactivity
is considered due to the size of the molecule. If mercerized or
unmercerized cottons are nitrated in an identical manner, the
acetone solution of the cellulose nitrates show entirely different
viscosities, so that the time of efflux of nitrate solution of the

1. Zts. Schiess. Sprengst. 1909, 4, 81; abst. J. S. C. I. 1909, 28, 380;
C. A. 1909, 3, 1926; Chem. Zentr. 1909, 80, 1, 1275; Jahr. Chem. 1909, fit, 384;
Chem. Tech. Rep. Qacob.) 1909, 33, 194; Wag. Jahr. 1909, 55, 1, 431; D. R. P.
199885, 1907; abst. Chem. Zentr. 1908, 79, II, 466; Chem. Ztg. Repert. 1908,
32, 382; Zts. ang. Chem. 1908, 21, 2233; Mon. Sci. 1911, 74, 93; Chem. Tech.
Rep. Qacob.) 1908, 32, 382; Chem. Ind. 1908; 31, 454; J. S. C. I. 1908, 27,
937; Wag. Jahr. 1908, 54, II, 355; C. A. 1908. 2, 3154; Meyer Jahr. Chem.
1908, 18, 309. Berl reduces the size of the cellulose molecule by heating to
100 degrees in the presence of an indifferent inert gas, as nitrogen, and claims
it as especially advantageous for the preliminary treatment of cellulose
intended for subsequent nitration.

30 THCHNOU)GY OP CBl.I*UI<OSK ESTERS

mercerized cotton is very much shorter than that of the cellulose
nitrate prepared from ordinary cotton. Similarly the bleaching
recommended in the preparation process, if oxycellulose is pro-
duced thereby, also shows a decrease in molecular size.

G. and A. Schaefer^ prepare cellulose for artificial silk and
esterification purposes by boiling the cellulose under pressure,
and at a correspondingly high temperattu-e, in a weak solution
of sodium carbonate, a caustic alkali, and **tar benzin." It is
then washed, treated with dilute sulfuric acid, the excess of water
is removed, and is finally bleached with hydrogen peroxide.

Cellulose as a Colloid. The Technology of the Cellulose
Esters is an enumeration of the commercial applications of typical
colloid bodies. Cellulose, as well as its nitrates, acetates, xan-
thates and ethers, in all their soluble and thermoplastic modifi-
cations, constitute a group of exceedingly important industries,
which may, in the true sense of the word be called colloid. Pure
cellulose is a typical gel possessed of a beautiful ultramicroscopic
structure, showing well-developed swelling phenomena and on
solution yielding the highly viscous solutions which are character-
istic of the hydrated emulsoids. From these solutions it may be
precipitated by means of neutral salts or in presence of dehy-
drating agents such as ethyl alcohol.

Cellulose resists dissolution in all neutral liquid solvents, and
those solutions, like zinc chloride, cuprammonium and the con-
centrated inorganic acids, are all of a colloidal nature. There is
no question but what the cellulose complex is altered in consti-
tution during the solution process, more or less hydrated cellulosic
bodies being regenerated. The method of dissolving cellulose in
various fluids and the characteristics of the solution thus formed,
constitute a separate topic in this chapter.

If hydration is a condition of intramolecular distension where-
by tlie surface reactions are largely increased and the absorption
phenomena correspondingly developed,^ the phenomena is rever-
sible. F. Clyster' expresses it as ''a progressive gelatinization of
fiber walls, or the formation of a coating of colloidal cellulose on
the surface of the fibers with a consequent loss of capillary power,"

1. U, S. P. 879416, 1908; abst. J. S. C. I. 1908, 27, 278.

2. Ann. Rep. Soc. Chem. Ind. 1917, 2, 128.

3. Paper, 1915, 16, 13; abst. C. A. 1915, 9, 3129.

CEI.I.ULOSC 31

but in general, the action instead of being superficial is usually
deep-seated.

The more general investigation of the preparation of colloidal
solutions from cellulose has been undertaken by P. v. Weimarn,^
who has studied in detail the conversion of cellulose into a gelati-
nous plastic material, and the physical characteristics of colloidal
cellulose solutions. He has found that treatment of various
forms of cellulose with aqueous salt solutions under definite con-
ditions of concentration, pressure, temperature and duration of
action, can bring about a multitude of changes in the physical
conditions of the cellulose, often anal)rtically indistinguishable,
but susceptible of differentiation on physical grounds. The
greater the solubility of the salt, the greater the ease with which
it forms hydrates, and the more readily soluble (peptisable) is the
cellulose in the solution. From these solutions various hydrated
modifications are recoverable by the use of selective coagulants
and predpitants, these cellulose gels being best known as consti-
tuting the artificial silk industries of the viscose, cuprammonium
and nitrocellulose processes. The final products all show the
characteristics of a hydrated emulsoid. The ageing of viscose
preliminary to yielding a solution optimal for spinning ; the ripening
of cuprammonium solutions; the clarification of nitrocellulose
lacquers and bronzing liquids, and the velocity of the internal
changes in state of combination of cellulose esters with solid and
semi-fluid plastifiers and high boilers, together with that scien-
tifically little studied solid solution of nitrocellulose and camphor
constituting celluloid, all represent industries comprising an
unbroken change of colloid-chemical processes. The formation
of vulcanissed fiber; the preparation of parchment from the action
of zinc chloride or sulfuric acid upon cellulose; the manufacture
of cellulose acetate gels in benzol-alcohol mixture are additional
examples of the intricate and almost complete permeation of col-
loidal phenomena constituting the industries of the technical
application of cellulose and its esters.

The colloidal structure of cellulose was conjectured in a
rather hazy and nebulous manner by Hellot^ away back in 1800,

1. Zts. Chem. Ind. KoU. 1912, U, 41; abst. J. S. C. I. 1912, 13, 768;
C, A. 1912, 6, 3516; J. C, S. 1912, 102, i, 679; Chem. Zentr. 1912, S3, II, 817.

2. Sec Schwalbc. "Neue Farbentheoren," Stuttgart, 1907.

32 TECHNOLOGY OF CELLULOSE ESTERS

in describing the spongy, net-like, honey-combed structure of
"the pores of the wool/* E. Mills and J. Takamine in 1883
speak of the absorption of acids and bases from solutions by means
of "organic fibrous colloids**.* A. MuUer- Jacobs^ two years later
looked to the colloidal contents of the cells and the dififusion or
osmosis through the membranes of the cell walls of plants as an
explanation of the plausibility of his theory of dyeing.

M. Dekhuyzen' dilates on the "spongy** structures of the
fibers in his researches published in 1886. In 1894, G. Schmidt*
accepting as a fact that the absorption of gases by porous substances
such as charcoal has been shown to obey Henry's law, made
experiments with dilute solutions including picric acid with
cellulose — the concentration being calculated for the undis-
sociated acid — but found that in no case was the law of Henry
obeyed.

0. Witt* regarded all fibers without exception to consist of
substances strictly to be classed as colloids, and hence all endowed
with osmotic properties, i. e., they permit, owing to their mole-
cular constitution, unobstructed passage for the dialysis and
osmosis^ of the class of crystalloids. This idea was corroborated

1. Jour. Chem. Soc. 1883, 43, 153; abst. Jahr. Chem. 1883, 36, 1784;
Ber. 1883, 16, R, 973; C. N. 1882, 46, 299.

2. J. Soc. Dyers Col. 1885, 2, 95.

3. Centr. Med. Wiss. 1886, 931, 945; abst. Ber. 1887, 20, 518. W.
Lewis, J. S. C. I. 1919, 38, 1-T. W. Bancroft, Jour. Frank. Inst. 1918, IBS,
29, 199, 373; abst. C. A. 1918, 12, 111, 552, 783; J. S. C. I. 1918, 37, 173-A;
J. C. S. 1918, 114, ii, 13; Chimie et Ind. 1918, 1, 278; J. Phys. Chem. 1918,
22 22.

4.- Zts. physikal. Chem. 1894, 15, 56; abst. J. Chem. Soc. 1895, 68,
ii, 39; Chem. Centr. 1894, 65, II, 830; Jahr. Chem. 1894, 47, 98; Meyer Jahr.
Chem. 1894', 4, 32, 576; Ber. 1894, 27, 845-R. See also Monatsh. Chem.
14, 8; abst. Zts. anorg. Chem. 1894, 5, 96. W. Harkins, E. Davies and G.
Clark, J. A. C. S. 1917, 39, 354, 541; abst. C. A. 1917, 11, 731, 1588; J. C. S.
1917, 112, ii, 238, 239. See also I. Langmuir, Phys. Rev. 1915, 6, 79; abst.
C. A. 1916, 10, 992. R. Tolman and A. Steam, J. A. C. S. 1918, 40, 264;
abst. C. A. 1918, 12, 589; J. S. C. I. 1918, 37, 131-A. See also R. Tolman,
J. A. C. S. 1913, 35, 307, 317; Science, 1916, 44, 565; C. A. 1917, U, 4. Patrick,
Science 1916 43 747.

5.' Faerb. Ztg. 1890-1891, Pt. 1; Zts. Phys. Chem. 1891, 7, 93; abst.
J. S. C. I. 1891, 10, 42; Zts. ang. Chem. 1891, 4, 62; Chem. Centr. 1890, 61, II,
1039; Jahr. Chem. 1892, 45, 2918; Meyer Jahr. Chem. 1891, 1, 20; Chem. Ztg.
1890, 14, 310; Wag. Jahr. 1890, 36, 1121; Bull. Soc. Chim. 1891, 6, 613; Mon.
Sci. 1891, 37. 694. H. Proctor and J. Wilson, J. C. S. 1916, 109, 307; abst.
C. A. 1916, 11, 1051; J. S. C. I. 1916, 35, 645; J. Amer. Leather Assoc. 1917,
12, 76. See also J. C. S. 1914, 105, 313, 326; J. S. C. I. 1916, 35, 156, 404,
675; J. Amer. Leather Assoc. 1916, U, 399; abst. C. A. 1915, 9, 875; 1916,
10, 1807, 2052.

CEI.I.UI.OSE 33

and carried a step further in 1900 by P. Zacharias^ who established
in considerable detail the colloidal nature of the textile fibers, and
especially that of cotton cellulose. He emphasized the fact that
will be repeatedly exemplified in the succeeding pages of this
series of volumes, that the high molecular weight and proneness
to reactivity of cellulose and the esters and ethers derived there-
from, and the fact that none of these compounds have been crys-
tallized, distilled unchanged, or otherwise lent themselves to the
usual methods of purification preparatory to analysis, have
materially deterred investigators from penetrating into the inner
histological anatomy of cellulose and its esters.

It is peculiar that in the various detailed bibliographies of
colloids which have been published from time to time, cellulose is
conspicuous by its absence among the materials investigated and
reported upon, and this shows how virgin is, the entire field even
at the present day. Colloid chemistry up to the present has
concerned itself principally with inorganic substances, gelatin
and agar-agar, and to a lesser degree with starch. The inter-
relations of nitrocellulose stability and colloid chemistry, and the
practically untouched field of uni- and poly-solvent cellulose ester
combinations offer an oasis for investigation of practically limit-
less potentialities.

C. Cross holds to the view that, regarding cellulose from the
viewpoint of the ionic theory, it must be considered as a mole-
cular aggregate consisting of a mixture of ions of heterogeneous
dimensions. Hence, as a typical colloid, cellulose has no definite
reactive imit as a body which takes the crystalline form, nor a
fixed molecular constitution which may be represented within the
limits of a constitutional formula; for the cellulose molecule
cannot be regarded as a static unit, but rather as a dynamic
equilibrium; its reacting unit at any one time being a function of

1. Faerb. Ztg. 1901, 12, 149, 158, 'l61, 167; abst. J. S. C. I. 1901, 20,
804; J. C. S. 1902, 82, i, 635, 725; Chem. Centr. 1901, 72, II, 379, 513; Jahr.
Chem. 1901. 54, 1408; Meyer Jahr. Chem. 1901, U, 450; Chem. Ztg. 1902,
28, 289, 680; Repert. Chimie, 1901, 1, 111; Meyer Jahr. Chem. 1901, 11,
450; Rev. Mat. Col. 1900, 4, 307; Rev. g6n. sci. 1902, 13, 166; Rev. Phys.
et Chimie, 1901, 41; Zts. Phys. Chem. 1902, 39,468; abst. Bull. Soc. Chim.
1902, 28, 678. See also C. Weber. J. S. C. 1. 1894, 13, 120. Krafft, Ber. 1899,
32, 1608; abst. J. S. C. I. 1899, 18, 757. A. Sunderland, Paper. 1917, 20, No.
4. p. 13; abst. C. A. 1917, 12, 1544; J. S. C. I, 1917, 36, 592. R. Hatch,
Paper, 1917, 21, No. 4, p. 41. C. Moe, Paper, 1911, 15, No. 26, p. 18.

34 TECHNOLOGY OI^ CELLULOSE ESTERS

the conditions surroimding it. This view has been disputed.

W. Bovard^ defines cellulose as a sponge-li^ce structure of
colloidal particles held together by capillary attraction. To this
aggregate he attributes the power of absorbing hydroxyl ions,
which would naturally be more abundant in an alkaline solution,
and thus explains the more rapid hydration of cellulose in the
presence of alkalis.

It should be remembered that the gel-forming properties of
cellulose are produced as the result of chemical treatment which
entirely destroys the morphological structure of the fiber, i. e., the
fibrous structure is obliterated in passing into the colloid phase.
This has recently been elaborated by J. de Cew,^ and W. Gesell
and J. Minor,' in investigating the conditions under which pulp
hydrates upon prolonged beating.

In Volume Eight of this series, published in 1915, are to be
found many examples in connection with the various normal
and partially hydrated cellulose acetates and formates of
gelatinization in alcohol or alcohol-benzol solutions, which are
soluble and fluid when^ warm, but gelatinize as the solution
cools, and finally solidify to a paste which may be again
liquified by the application of heat.

According to J. Minor,^ "cellulose may be considered as
a sponge-like structure of colloidal particles, held together by cer-
tain unused, residual affinities, and these particles are only brought
into solution by some salt like zinc chloride which, through the
formation of a double salt, is capable of breaking apart the sponge-
like structure. As a colloid with a very large amount of surface
exhibiting positive residual affinity, cellulose is capable of adsorbing
from the water solvent sufficient hydroxyl ions to give to the mole-
cule as a whole a very strong negative charge. These highly charged
particles are capable of swelling, or absorbing water, as dried

1. Paper, 1918, 22, 11; abst. C. A. 1918, 11, 1251. S. Webb, U.S. P.
1201402, 1916; abst. J. S. C. I. 1916, 35, 1215. V. Fishbum and O. Weber,
Paper, 1916, 19, No. 5, p. 13; abst. C. A. 1917, 11, 887.

2. Paper, 1916, 20, No. 11, p. 13; Paper Makers Monthly, 55, 175. See
also J. S. C. I. 1917, 36, 357; abst. C. A. 1917, 11, 1901. Paper Makers
Monthly, 1916, 54, 334; abst. C. A. 1917, 11, 209. O. Kress and G. Mc-
Naughton, Paper, 1917,20, No. 17, p. 13, 443, 527; abst. C. A. 1917, 11, 2542.

3. Paper, 1919. 24, 527; abst. C. A. 1919, 13, 1925. See W. Bovard,
Paper, 1918, 22, 43.

4. Private communication.

CEI.I.ULOSE 35

jelly does. The hydration of cellulose may be defined as the
absorption of hydroxyl ions by the surface of the colloid,
followed by the slower absorption of water."

**Also, the close proximity of- these adsorbed hydroxyl ions
on the surface of the colloid is quite sufficient to bring about
the formation of hydrocellulose by hydrolysis. This process is
apparently the one utilized by plant life for the conversion of the
cellulose of the cell wall into mucilage, as well as the explana-
tion of the formation of artificial parchment by the long beating
of wood pulp. This hydrolyzed cellulose is very much more
susceptible to oxidizing^gents than is cellulose and its formation
is probably an intermediate step in the formation of oxycellu-
lose."

The gelatinization of non-esterified cellulose has engaged
the attention of J. Briggs,^ who has investigated the pulp slime
produced in a paper makers hollander. He perceives it as a
hydrogel influenced by both chemical and mechanical means,
and in which the hydration which enters only with water — and
not with alcohol or benzene — is reversible in certain grades.
Mechanical attrition favors gel formation. Concomitant with
hydration goes increased absorptive powers and greater hygros-
copicity. Briggs Has conceived this as a special case of absorption
between the solid and gaseous phases. Coincidental with hydra-
tion appears a lessening of the internal friction by the formation
of viscous solutions of hydrated celluloses.

Cellulose fibers swelled with water, appear to again give up
this moisture in an atmosphere of steam, a property also noted
with gelatin. The removal of moisture from wood by superheated
steam, and the coagulation of artificial cellulosic filaments by
steam are corresponding illustrations.

The characteristic coagulation phenomena of colloids may
be observed in many cases in cellulose solutions. In the forma-
tion of the cellulose of Guignet the material is said to be separable
in flakes by precipitation with brine. Cuprammonium, zinc
chloride and viscose solutions of cellulose are obtained in the
solid form by precipitating or coagulating operations. Certain
celluloid substitutes, as the phenol-aldehyde condensations are
interesting from a colloid-chemical viewpoint in that they are

1. Papierfabr. 1910, 8, 46; abst. J. S. C. I. 1910, 29, 874.

36 TECHNOI.OGY OP CEI.I.UU)SE ESTERS

typical isocolloids, i. e., dispersoids in which the dispersed phase
and the dispersion medium are polymers of each other.

As to the question as to which class of colloids cellulose is
to be grouped, MuUer^ considers them to be a colloid gel,
capable of swelling and possessing cell-like structure as indicated
by the phenomena of swelling, gelatinization and absorption and
therefore most appropriately falling into the "emulsoids.** If
Cross and Bevan are correct in that cellulose does not act as a
polymer formation from degraded or depolymerized hexose
groups of known structure, but as labile complex of groups with
varying dimensions which are in a condition analogous to a salt
solution of an electrolyte, then it appears that the cellulose is
more reactive as a solvent aggregate than by succeeding mole-
cular combinations. In the succeeding topics of the properties of
the celluloses, are indicated some of the physical explanations of
the foregoing statements and conceptions.

Reactivity of Cellulose. The observation of A. MuUer^
that filter paper possesses the property of precipitating from
baryta water quite considerable quantities of baryta, finds corrob-
oration in the work of H. Weiske.' Cold, dilute acids,
either mineral or organic, have an almost inappreciable action
upon purified cellulose, at most but a slight adsorption of com-
pounds taking place. With acids of higher concentration (up
to 40%) hydrocellulose formation results,* whereas with acids
of 6%-8% strength, the tendency toward the formation of cel-
lulose hydrates is apparent.^

Concentrated mineral acids form esters or. cellulose acids
according to the general principles of esterification. With strong

1. Allgemeine Kolloidchemie. See also C. Schwalbe, Zts. Chem. Ind.
KoU. 1908, 2, 217, 229; Zts, ang. Chem. 1908, 21, 1377; J. S. C. I. 1908, 27,
278; Chem. Zentr. 1908, 79, I, 719, 1216; Jahr. Chem. 1905-1908, I, 337;
Chem. Ztg. 1908, 32, 126, 204. A. Klein, Paper, 1919, 24, 35.

2. J. prakt. Chem. 1861, 83, 384; Jahr. Chem. 1861, 14, 820.

3. Lands. Versuchs. Stat. IS, 155; abst. J. C. S. 1876, 30, 662.

4. A. Girard, Compt. rend. 1875, 81, 1105; 1879, 88, 1322; 89. 170;
Ann. Chim. Phys. 1881, (5), 24, 337-384; abst. J. C. S. 1879, 36, 911; 1882.
42, 378; Jahr. Chetn. 1875, 28, 786 ; 1879. 32. 835, 1116; 1881, 34, 985; Wag. Jahr.
1879, 25, 419; Ber. 1879, 12, 2158; 1881, 14, 2834; Bull. Soc. Chim. 1880, 34,
507; Mon. vSci. 1879, 21, 958; Chem. News, 1881, 44, 216; J. A. C. S. 1879, 1,
400; Proc. U. S. Nav. Inst. 1882, 8, 309; Jahr. rein Chem. 1875, 3, 142;
1881, 9, 460.

5. G. Witz, Bull. Rouen, 1881, 342; 1882, 438; Farb. u. Musterztg.
17, 129; abst. J. vS. C. I. 1883, 2, 378. C. Guignet, Compt. rend. 1889, 108,
1258; abst. J. S. C. I. 1889, 8, 1001; J. C. S. 1889, 56, 847; Chem. Centr.

c^i.i.ui.osE 37

vitriol, the cellulose-sulfuric acids fonned are very unstable, and
have, as yet, not been isolated in an undecomposed state. The
prolonged action of acids upon cellulose — more readily upon
starch — especially upon subsequent dilution with water, and
boiling, converts the cellulose quantitatively into glucoses,
and important manufacturing processes have been established
based upon the recognition of this fact.^

Concentrated nitric acid produces the corresponding cellu-
lose nitrates, of manifold importance alike in the peaceful and war-
like arts. The limit of acid radical substitution appears to be a tri-
nitro derivative, based upon the simple expression of cellulose as
a Ce formula. With organic acids, the esterification is compli-
cated by the phenomena of polymerization subsequent to, con-
comitant with, or following the normal acetylation process, and in
addition the phenomena of hydration occurs, wherein a variable
amount of acetic acid is withdrawn from the cellulose ester after
the esterification process has been concluded. This "ripen-
ing" of the acetated cellulose, whereby the product is rendered
soluble in acetone and other desirable ^Ivents, has, as yet, not
been satisfactorily explained, notwithstanding the immense
amount of painstaking investigation to which the cellulose acetates
have necessarily been subjected incident to their employment in
such vast quantities as airplane lacquers in the conflict just ended.

The recent researches of H. Dreyfus,^ L. Lilienfeld,' W.

1889, 60, II, 124; Jahr. Chem. 1889, 42, 2839; Chem. Ztg. Rep. 1889, 13, 194;
Chem. Tech. Rep. 1889,23, 1, 145; Wag. Jahr. 1889, 35, 1180; Ber. 1889, 22,
R, 574; Mon. Sci. 1889, 33, 986; Chem. News, 1889, 60, 24.

1. A. Scheurer, BuU. Soc. Mulhouse, 1888, 364, 399, 439; Mon. Sci.
1889, 33. 267; abst. J. S. C. I. 1888, 7,841, 843; Jahr. Chem. 1889,42,2841;
Chem. Tech. Rep. 1888, 27, II, 60, 105; Chem. Ind, 1889,12,40, 556; Wag.
Jahr. 1888, 34, 1099.

2. F. P. 462274, 1912; abst. J. S. C. I. 1914, 33, 248; C. A. 1914. 8, 3859.

3. U. S. P. 1188376, 1916; abst. C. A. 1916, ID, 2145; J. S. C. I. 1916,
35, 887; Mon. Sci. 1917, 84, 28; Kunst. 1916, 6, 282. U. S. P. 1217027, 1217028,
1917; abst. C. A. 1917, 11, 1545; J. S. C. I. 1917, 36, 3&3; Mon. Sci. 1918,
85,4. E. P. 12854, 1912; abst. C. A. 1913, 7, 3&39; J. S. C. I. 1913, 32, 940.
E. P. 6035, 1913; abst. G. A. 1914, 8, 2947; J. S. C. I. 1914, 33, 417. E. P.
6387, 1913; abst. C. A. 1914, 8, 2947; J. S. C. I. 1914, 33, 417; Kunst. 1914,
4, 236; see also R. Willstaetter, D. R. P. 273800; abst. Kunst. 1914, 4, 179.
E. P. 3370, 1914; abst. J. S. C. I. 1916, 35, 534. P.P. 447974, 1912; abst.
J. S. C. I. 1913, 32, 420; Mon. Sci. 1914, 80, 3. F. P. 459972, 1913; abst. J. S. C.
I. 1913, 32, 1153; F. P. 468162, 1914; abst. J. S. C. I. 1914, 33, 958; D. R. P.
133542, E. Merck; abst. Chem. Centr. 1901, 72, II, 314; Zts. ang. Chem.
1902, 15, 739; Jahr. Chem. 1902, 55, 807; Wag. Jahr. 1 902, 48, II, 5;
Mon. Sci. 1903, 59, 74. Belg. P. 2M591, 1912. Swiss P. 66512. Aust. P.
63526, 1914. Norw. P. 27507.

38 TECHNOI/>GY O^ CEI.I.UU)SE ASTERS

Suida^ and W. Denham and H. Woodhouse^ on the cellulose
ethers, have unfolded a hitherto unknown group of bodies,
comprising a large number of members which differ from one
another in properties according to the number and nature of
the alcohols which are linked ether fashion with the cellulose
molecule. They result from the replacement of hydroxyl hydro-
gens in cellulose or its conversion products by alcohol radicals
and only await less expensive methods of commercial manufacture
for extensive industrial recognition as uninflammable nitrocellulose
substitutes, and direct competitors of the more widely known
acetylated celluloses. They are white, amorphous powders
stable, neutral, soluble in general in the solvents of nitrocellulose
and cellulose acetate, the penta-ethylcellulose being most defi-
nitely characterized. The combination of esterfication and
alkylation in the same cellulose molecule — the acetylation of
methylcellulose, or the methylation of formylcellulose — whereby
etherfied cellulose esters and esterfied alkylcelluloses result, with
their possible industrial applications, apparently is a field, which
as yet, has not been approached.

When the celluloses are treated with the alkali hydroxides
and carbon bisulfide, solution takes place, the product of cellulose
xanthate or sulfocarbonate, under the name of viscose having
many industrial applications as in the formation of artificial
filaments (wood silk) and described in detail elsewhere in this
work.

Properties of the Celluloses. The so-called "true** or "nor-
mal" celluloses as obtained from different sources are not identical
in chemical and physical deportment, although anal)rtically
indistinguishable. Even the highest grade of cotton contains a
determinable proportion of material which can only be completely
removed by such energetic chemical treatment that the cellulosic

1. Monatsh. Chem. 1905, 28, 413; Wein. Akad. Ber. 1905, lli, II b;
Farberztg. 16, 105, 140; abst. J. S. C. I. 1905, 24, 543; J. C. S. 1905, 88, 457;
Zts. ang. Chem. 1905, 18, 1990; Chem. Centr. 1905, 76, I, 1348; Jahr. Chem.
1905-1908, II,3158;Chem.Ztg. 1905,29, 103; Bull. Soc. Chim. 1905, 34, 971;
Meyer Jahr. Chem. 1905, 15, 512; Rev. g6n. sci. 1905, 16, 239; Rep. de Chim.
1905, 5, 393; Tschermaks Mitth. 23, 534; Chem. Zts. 1905. 4, 444.

2. J. C. S. 1913, 103, 1735; 1914, 105, 2357; abst. C. A. 1914, 8, 243;
1915, 9, 203; Chem. Zentr. 1913, 84, II, 1857; 1915, 85, 1, 81; J. S. C. I. 1913,
32, 974; 1914, 33, 1084; Bull. Soc. Chim. 1913, 14, 1495; Rev. gen. sci. 1913,
24, 910. See P. vSeel. U. S. P. 1281080; abst. C. A. 1919, 13, 73, for plastic
cellulose ethers.

CEI.I.UW>SB 39

portion is modified, irrespective of how carefully conducted the
treatment has been carried on. In the esterification (nitration or
acetylation) or alkylation (methylation or ethylation) of cellu-
lose, no definite stages or well-characterized steps are possible, and
esters and alkyl derivatives are formed, which analytically imper-
ceptibly blend one into the other, so that, for instance, it is possible
to produce by what appears a continuous process, cellulose esters
from 6% to 13.5% nitrogen.

And the physical properties and chemical reactions are also
not always indicative of well-defined composition, for nitric and
acetic esters of cellulose are known, of the same percentage com-
position, which are or are not soluble in a given solvent or solvent
combination. Especially are these diffefences noticeable in en-
deavoring to obtain the solvent capacity for a given cellulose
ester or compound, where two apparently identical esters, in solu-
tion in a known solvent of pre-determined strength and purity
may be precipitated from such solutions by entirely different
amounts of cellulose ester non-solvents, as benzene or benzine.

The celluloses, when pure are white,' amorphous, firm, elastic
substances, burning quietly with a luminous, smoky flame. The
heat of combustion to CO2 and H2O has been given as 4208 calories.
G. Fleury* has determined the specific heat of some organic sub-
stances with the following results: cellulose, 0.366; wool, 0.393;
leather, 0.357. In the ordinary moist state, these substances
were found to contain 7%, 11%, and 16% of water respectively,
and the specific heats in this condition to be: cellulose 0.41;
wool, 0.459; leather, 0.45.

Under the term **cellulose," E. Gilson* includes the carbo-
hydrates of the membranes which are insoluble in dilute acids or

1. Compt. rend. 1900, 130, 437; abst. J. C. S. 1900, 78, ii, 188; Chem.
Centr. 1900, 71, I, 680; Jahr. Chem. 1900, 53, 840; Chem. Ztg. 1900,24, 175;
Bull. Soc. Chim. 1900, 23, 340; Rev. Phys. et Chim. 1900, 4, 117.

2. La Cellule, 9, No. 2; abst. Chem. Centr. 1893, 64, II, 530; J. C. S.
1894, €6, i, 107; J. S. C. I. 1894, 13, 1106; Jahr. Chem. 1893, 46, 881; BuU.
Soc. Chim. 1894, U, 590; Jahr. organ. Chem. 1893, 1, 265. S. Linder and H.
Picton (J. C. S. 1892, 61, 156; abst. J. S. C. I. 1892, 11, 64; Chem. Centr.
1892, 63, I, 367, 516; Ber. 1892, 25, R, 368; Bull. Soc. Chim. 1895, 14, 148;
Chem. News, 1892, 65, 47; Chem. Ztg. 1892, 16, 81, dissolved cellulose in
Schweizer's reagent and allowed the clear liquid to settle for several days.
The Schweizer's solution itself showed a very feeble luminous beam when a
ray of light was passed through it. When the experiment of Tyndal was
applied, the cellulose solution showed a well-marked glow when the ray of
light was passed through it, the light of the glow being polarized.

40 TECHNOUKJY O^ CKI.I.UI.OSH ESTERS

alkalis, but soluble in sulfuric acid, and which are colored blue by
iodine in the presence of concentrated sulfuric or phosphoric acids.
This author has found that if sections of cellular tissue are allowed
to remain for a time in contact with Schweizer's reagent, then
carefully washed, first with ammonia and then with water so
that the copper is dissolved gradually and the cellulose is precipi-
tated slowly, the latter is found in the interior of the cells in the
form of nodular or arborescent crystals. These are insoluble in
dilute acids and alkalis but soluble in concentrated sulfuric acid,
and show also other characteristics of cellulose. To obtain the
crystals certain precautions must be observed, one being the
complete removal of starch before treatment with Schweizer's
reagent. The reaction Jias been carried out with a large number
of phanerogams and cryptogams.

The action of light on cellulose has seldom been studied
critically, although the darkening effect which age bestows upon
cellulose such as a lace curtain, has been known for some time.
G. Witz^ has examined old curtains, which have been subjected
to the action of the sun for thirty years, and by the methylene
blue reaction, found the presence of oxycellulose therein. To
what extent (if any) this, oxidation was accelerated by atmospheric
oxygen and the presence of sulfur dioxide or other sulfur compounds
was impossible to determine. A. Girard,^ however, considers that
hydrocellulose is more probably produced and that the action of
ozone with methylene blue might give analogous color reactions.

In the study of the dry distillation of cellulose, starch and
sugar, G. Bantlin^ has made comparisons by heating them under
the same conditions in an iron retort electrically heated. The

1. Bull. Soc. Rouen, 1883, U, 169, 188; abst. Jahr. Chem. 1883, 36,
1782; Wag. Jahr. 1883, 29, 1068; Mon. Sci. 1884, 26, 1 161. See also H. Schmid,
Dingl. Poly. 1883, 250, 271; abst. J. C. S. 1884,46,528. For reactions of
cellulose with iodine, see F. Mylius, Ber. 1895, 28, 390; abst. J. C. S. 1895,
68, 313; Chem. Centr. 1895, 66, I, 792; Jahr. Chem. 1895, 48, 514; Bull. Soc.
Chim. 1895, 14, 901. For the effect of cellufose hydration on structure, see
Sindal and Bacon, Paper, 1919, 24, 1140.

2. Ann. Chim. Phys. 1881, (3), 24, 382; Compt. rend. 1875, 81, 1105;
1879, 88, 1322; 89, 170; abst. J. C. S. 1879, 36, 911 ; 1882, 42, 378; Jahr. Chem
1875, 28, 786; 1879, 32, &35, 1116; 1881, 34, 985; Wag. Jahr. 1879, 25, 419
Ber. 1879, 12, 2158; 1881, 14, 2834; Bull. Soc. Chim. 1880, 34, 507; Mon. Sci
1879, 21, 958; Chem. News, 1881, 44, 216; J. A. C. S. 1879, 1, 400; Proc
U. S. Nav. Inst. 1882, 8, 309; Jahr. rein Chem. 1875, 2, 142; 1881, 8, 460.

3. J. Gasbeleucht, 1914, 57, 32, 55; abst. J. S. C. I. 1914, 33, 129;
Chem. Zentr. 1914, 85, 1, 922; C. A. 1914, 8, 1344.

CBLI^ULOSE

41

temperature was raised gradually so as to reach 100° in 1.5 hours,
and 500*" in 7-8 hours.

The products of distillation in percentage by weight of the
dry substance, were as follows:

TABLE II.—DISTILLATION OF CARBOHYDRATES

Coke

Water %

Tar

Acetic acid

Aldehydes

Ketones

Total gases

Carbon dioxide

Ethylene

Hydrogen

Carbon monoxide. . . .

Ethane

Methane

Loss or not determined.
Composition of tar:

Carbon

Hydrogen

Oxygen

Cellulose

Starch

Sugar

32.9

28.6

12.2

31.7

29.7

6.29

3.25

2.69

55.04

3.28

5.29

8.78

5.82

6.66

6.15

0.11

1.11

0.34

17.33

22.70

5.96

11.26

13.08

4.37

0.24

0.39

0.05

0.02

0.03

0.01

4.78

7.64

1.29

0.35

0.74

0.11

0.68

0.82

0.13

6.23

4.20

5.38

52.20

45.02

38.91

6.86

6.31

6.19

40.94

48.67

54.90

The time-temperature curves showed that with cellulose
an exothermic decomposition takes place between 250° and 300°
and that this reaction is complete at 320°. This phenomenon
is not shown by starch and sugar. The stability towards heat
increases in the order cellulose, starch, sugar, but the first two are
more nearly alike in this respect than either is to sugar. Since
cellulose does not yield methyl alcohol on dry distillation, it has
been supposed that waste sulfite-cellulose lyes contain the con-
stituents of wood which yield valuable distillation products.
The lye was therefore partially separated from sulfur compounds by
passing through it a current of air and steam, evaporated to dry-
ness, and distilled. A very small yield of liquid products was
obtained, and no methyl alcohol, while large quantities of hydro-
gen sulfide and of mercaptan were evolved.

The sp. gr. of cotton cellulose according to L. Vignon^ and

1. Conapt. rend. 1892, 114, 424; abst. J. S. C. I. 1892, U, 1002; Chem.
Centr. 1892, G, I, 616; Jahr. Chem. 1892, 45, 2906; Chem. Tech. Rep. 1892,
n, I, 103; Ber. 1892, 2S, R, 268; Bull. Soc. Chim. 1892, 7, 247; Mon. Sci.
1894, 39, 309; Rev. g^n. sci. 1892, 3, 170; Deutsch. Chem. Ztg. 1892, 92.

42 TECHNOUXJY OP CHhhVUOSH ESTERS

others is 1.50, although considerable variation often occurs.

In vacuo distillation of cellulose and starch, A. Pictet and
J. Sarasin^ gradually heated pure cotton cellulose under a pres-
sure of 12-15 mm. After the aqueous fractions, there distilled
between 200° and 300°, a thick yellow oil which'on cooling solid-
ified to a semi-crystalline mass amounting to 45% of the original
cellulose, 10% of carbon remaining in the retort. Upon recrys-
tallization from hot water or alcohol, the pasty mass gave white,
tabular, anhydrous crystals, m. pt. 179.5°, formula CeHioOj.
The substance was strongly laevorotatory, and could not be dis-
tilled under atmospheric pressure without decomposition. From
the triacetate (m. pt. 110°) and tribenzoate (m. pt. 199.5°)
the material appeared to be identical with the laevoglucosan of
C. Tanret,* obtained from the glucosides of the Coniferae. This
behaves as a trihydric alcohol and yields ordinary dextrose when
boiled with dilute mineral acids. In a later paper' J. Sarasin
proposes for /-glucosan a structural formula identical with that
put forward by A. Green* for the unit complex of cellulose.
Sarasin maintains that in the polymerization of Z-glucosan the
middle ring opens, giving two free valencies for the polymerization,
because 2.5-dimethylfuran is found among the decomposition
products of starch and cellulose. This body does not yield bro-
momethyl-furfural when treated with Fenton*s reagent, and is
thus sharply differentiated from cellulose and starch. The
author therefore suggests that the middle ring is closed in the case
of the glucosan but opens in the polymerized form. There may

1. Compt. rend. 1918, 166, 38; abst. J. S. C. I. 1918, 37, 49-A; Chem.
Zentr. 1918, W, I, 1151 ; J. C. S. 1918, 114, i, 59; C. A. 1918, 12, 804. See also
J. Sarasin, Arch. Sci. Phys. Nat. 1918, 46, 5; abst. C. A. 1918, 12, 2187; J. C. S.
1918, 114, i, 375. See O. Rau and G. Lambris, J. Gasbeleucht, 1913. 56,
33; abst. Gas World, 1913, 59, 259; C. A. 1913, 7, 3655. H. HoUings and J.
Cobb, J. Gasbeleucht, 1914, 57, 126, 917; abst. Gas World, 1914, 60, 872;
C. A. 1914,8,3110

2. Compt. rend. 1894, US, 158; abst. J. C. S. 1894, 66, i, 564; Chem.
Centr. 1894, 65, II, 360; Jahr. Chem. 1894, 47, 1112; Chem. Ztg. Rep. 1894, IS,
194; Ber. 1894, 27, R, 665; Bull. Soc. Chem. 1894, (3), 11, 949; Mon. Sci.
1894, 43, 717; Rev. g^n. sci. 1894, 5, 552; Jahr. organ. Chem. 1894, 2, 219;
Chem. News 1894 70 72 282.

3. Helvetica chim. acta, 1918, 1, 78; abst. C. A. 1918, 12, 2187; Chem.
Zentr. 1918, 89, II, 711; J. C. S. 1918, 114, i. 59; Chim. et Ind. 1918, 1, 279.

4. Zts. Farb. Te.xt. Chem. 1904, 3, 97; abst. J. S. C. I. 1904, 23,
382; J. Soc. Dyers Col. 1904, 20, 117; Zts. ang, Chem. 1904, 17, 1121; Chem.
Centr. 1904, 75, 1, 1069; II, 980; J. C. S. 1904, 86, i, 652; 1905, 88, i, 22; Jahr.
Chem. 1904, 57, 1160, 1161; Chem. Ztg. Rep. 1904, 28, 115; Wag. Jahr. 1904,
50, II, 398.

CEi.i.uu)SE 43

or may not be any connection between this simple product of the
destructive distillation of cellulose and the observation of C.
Cross and E. Bevan^ that maltol is formed under analogous con-
ditions.*

E. Erdmann and C. Schaefer' have obtained the following
substances by subjecting cellulose to dry, destructive distillation :

(a) Gas containing carbon dioxide, 0.2%; heavy hydrocar-
bons, 0.5%; oxygen, 0.9%; CO, 65.5%; methane, 19%; H, 11.5%;
N, 2.4%.

(b) Aqueous liquid, about 40% of the original cellulose; this
forms a reddish brown, strongly ^cid liquid, of pungent odor,
with reducing properties, and gives a deep purple coloration with
ferric chloride.

(c) Brown, viscous tar, in amount about 5% of the cellu-
lose. After neutralization with sodium carbonate, and fractional
distillation, the aqueous distillate yielded the following products :
formaldehyde, furfuraldehyde, maltol,* hydroxymethylfurfur-

1. J. Soc.. Dyers Col. 1916, 32. 135; abst. J. S. C. I. 1916, 35, 628;
C. A. 1916. 10, 2303; J. C. S. 1916, UO, i, 467.

2. See E. Vongerichten and F. Miiller, Ber. 1906, 39, 241 ; abst. J. C. S.
1906, 90, i, 198; Chem. Centr. 1906, 77, I, 748; Jahr. Chem. 1905-1908, II,
1948; Bull. Soc. Chim. 1906. 36, 1145; Rep. de Chim. 1906, 6, 229.

3. Ber. 1910, 43. 2398; abst. J. C. S. 1910, 98, i, 718; C. A. 1910, 4,
3223; J. S. C. I. 1910, 29, 1198; Chem. Zentr. 1910, 81, II. 1304; Jahr. Chem.
1910, 83, II. 418; Bulk Soc. Chim. 1911, (4), 10,445; Meyer Jahr. Chem. 1910,
20, 317. It will be recalled that in 1891 (E. P. 19560, 1891; abst. J. S. C. I.
1892. 11, 939; D. R. P. 64031. 1891; abst. Zts. ane. Chem. 1892. 5, 499;
Chem. Centr. 1892, 83, II, 1088; Chem. Ztg. 1892, 18, 1432; 1893, 17, 1004;
Chem. Tech. Rep. 1892, 31, II, 164; Chem. Ind. 1892, 15, 485; Wag. Jahr.
1892; 38, 376; Ber. 1892. 25, 892; Mon. Sci. 1892. 40, 166; Indbl. 1892. 358;
Meyer Jahr. Chem. 1892, 2, 362; Tech. Chem. Jahr. 1892-1893, 15, 169) a
patent was issued to H. de Chardonnet for the methodical application of high
temperatures for modifying the composition of cellulose materials, in which
cotton, lignin or ramie was directed to be heated continuously during
4-8 hours at a constant temperature of 150 to 170 degrees. The cellulose
was placed in stoves having shelves composed to tubes through which steam
circulated at a pressure of 8-10 atmospheres, air circulation being maintained
to regulate the temperature to which the cellidose was exposed. At the
conclusion of this heating operation the cellulose is immersed still warm in a
nitrating mixture, whereby there is produced a cellulose nitrate of much
lower viscosity and greater solubility, so that for the formation of artificial
filaments, collodions of as high concentration as 20-25 per cent, of pyroxylin
could be produced and spun. See E. Berl, D. R. P. 199885, 1907; abst. C. A.
1908. 2, 3154; J. S. C. I. 1908, 27, 937; Zts. ang. Chem. 1908. 21, 2233; Chem.
Zentr. 1908. 79, II. 466; Meyer Jahr. Chem. 1908, 18, 309; Chem. Ztg. Rep.
1908, ^ 382; Wag. Jahr. 1908, 54, II, 355.

4. J. Brand, Ber. 1894, 27, 806; abst. J. C. S. 1894, 88, i. 270; J. S. C. I.
1894, 13, 1215; Chem. Centr. 1894, 85, I, 863; Jahr. Chem. 1894, 47, 1119;
Chem. Ztg. Rep. 1894. 18, 115; Wag. Jahr. 1894, 40, 804; Bull. Soc. Chim.

44 TECHNOU)GY Olf CEI^LULOSE ESTERS

aldehyde and valerolactone, as wel) as other bodies.

Although Pettenkofer failed to obtain pyrocatechol by the dry
distillation of straw and paper, F. Hoppe-Seyler^ upon heating
Swedish filter paper at 200° for 4 to 6 hoiu-s along with water in a
sealed tube, obtained formic acid and pyrocatechol. This body
was also yielded by starch, cane sugar and milk sugar by the same
treatment.

P. Klason, G. v. Heidenstam and E. Norlin^ have also
investigated the products obtained by the dry distillation of
cellulose obtained from various sources. They foimd that the
velocity of charring action begins to become considerable at

1894, 12, 1096; Mon. Sci. 1895, 4S, 63; Jahr. organ. Chem. 1894, 2, 671;
Meyer Jahr. Chem. 1894, 4, 261. H. Kiliani and M. Bazlen, Ber. 1894, 27,
3113; abst. J. C. S. 1895, 68, i, 80; J. S. C. I. 1895, 14, 378; Chem. Centr.

1895, W, I, 27; Chem. Ztg. Rep. 1894, IS, 306; Wag. Jahr. 1894, 40, 904; Jahr.
Chem. 1894. 47, 1120; Bull. Soc. Chim. 1896, 14, 600; Tech. Chem. Jahr. 1894-
1895, 17, 286; Meyer Jahr. Chem. 1894, 4, 261. A. Peratoner and A. Ihm-
burello, Giom. Sci. Nat. Econ. 2S, 272; Gaz. chim. ital. 1906, 36, I, 33;
abst. J. C. S. 1905, 88, i, 807; Chem. Centr. 1905, 76, II, 680; Jahr. Chem.
1905-1908, II, 3814; Meyer Jahr. Chem. 1905, 15, 213; Rep. de Chim. 1906,

6, 276. See also, Ber. 1903, 36, 3407; abst. J. C. S. 1904, 86, i, 61 ; J. S. C. I.
1903, 22, 1265; Chem. Centr. 1903, 74, II, 1020; Chem. Ztg. Rep. 1903, 27,
326; Bull. Soc. Chim. 1904, ^ 819. F. Bergius, J. S. C. I. 1913, 32, 462; abst.
C. A. 1914, 8, 1004; J. C. S. 1913, 104, ii, 679; Chem. Zentr. 1913, 84, II,
932; Mon. Sci. 1913, 78, 664; Rev. g^n. sci. 1913, 24, 452. H. Suringar and

B. ToUens, Zts. ang. Chem. 1896, 9, 749; abst. J. C. S. 1897, 72, ii, 235; Chem.
Centr. 1897, 68, I, 199; Jahr. Chem. 1896, 49, 2281; Chem. Ztg. Rep. 1897,
21, 27. Grosseteste and A. Scheurer, Bull. Soc. Ind. Mulhouse, 1883, 65, 68;
abst. Wag. Jahr. 1883, 29, 1052; Mon. Sci. 1883, 25, 40, 139. G. Buettner and
H. Wislicenus, J. prakt. Chem. 1909, (2). 79, W; abst. C. A. 1910, 4, 1235;
J. S. C. I. 1909, A, 417; J. C. S. 1909, 96, i, 290; Zts. ang. Chem. 1909, 22,
1514; Chem. Zentr. 1909, 80, I, 1518; Jahr. Chem. 1909, 62, II, 33; Meyer
Jahr. Chem. 1909, 19, 324; Bull. Soc. Chim. 1910, 8, 242.

1. Ber. 1871, 4, 15; abst. J. C. S. 1871, 24, 226; Chem. Centr. 1871, 42,
84; BuU. Soc, Chim. 1871, 16, 98; Chem. News, 1871, 23, 131; Jahr. Chem
1871, 24, 476. A. Scheurer, Bull. Soc. Mulhouse, 1888, 361, 399, 439; Mon
Sci. 1889, 33, 257; abst. J.S. C. I. 1888, 7, 841, 843; Jahr. Chem. 1889, 42
2841; Chem. Tech. Rep. 1888, 27, II, 60, 105; Chem. Ind. 1889, 12, 40. 556
Wag. Jahr. 1888, 34, 1099. H. Ost and F. Westhof, Chem. Ztg. 1909
33, 197; abst. C. A. 1909, 3, 1394; J. S. C. I. 1909, 28, 325; J. C. S. 1909
96, i, 210; Ztg. ang. Chem. 1909, 22, 1856; Chem. Zentr. 1909, 80, I, 1231
Jahr. Chem. 1909, 62, II, 385; Wag. Jahr. 1909, 55, II, 514; BuU. Soc. Chim
1909, (4), 6, 685; Rep. de Chim. 1909, 9, 321. P. Klason, Wochenbl. Papierfab
1898, 29, 2176; Pap. Ztg. 1898, 23, 528; Ber. 1900, 33, 2343; Pap. Fab. 1900

7, 26, 446, 627, 671, 701, 796; Pap. Ztg. 1909, 34, 996, 1315; 1910, 35, 2116
Zts. ang. Chem. 1909, 22, 1205, 1423; Wochenbl. Papierfab. 1909, 40, 2668
Chem. Ztg. 1906, 30, 770.

2. Arkiv. Kem. Min. Geol. 1908, 3, 1; abst. J. C. S. 1908; 94, i, 717

C. A. 1908, 2, 3280; J. S. C. I. 1909, 28, 132; Zts. ang. Chem. 1909, 22, 1205
Chem. Zentr. 1909, 80, I, 109; Jahr. Chem. 1905-1908, 11,4749; Meyer Jahr
Chem. 1909, 18, 302; Chem. Ztg. Rep. 1908. 32, 252, 602; Wag. Jahr. 1908
54, II, 20; Bull. Soc. Chim. 1909, (4), 6, 1152.

about 270°, at which temperature the dry distillation of cellulose
is an exothermic process, the heat of the reaction being about
6% of the heat of combustion of cellulose. The gases evolved
during the distillation were foimd to possess a heating value of
about 3.5% of the heat of combustion of the cellulose, and include
hydrogen and aromatic hydrocarbons. They found the lignocellu-
loses )rielded more acetic acid than cotton cellulose.

According to H. Hofmann^ sulfite cellulose and paper under-
go a chemical change upon being dried, which begins at about
90*^, increases considerably above 100°, and is dependent upon
the temperatiu-e and the time of heating. This change renders
the cellulose easily attacked by acid, but the sugar obtained from
it is the same as before, i. e., xylose.*

Upon boiling with water, pure cellulose )rields little or no
sugar, but under a pressure of 10 atmospheres, the amount of
sugar ro^y rise to as high as 13.5% of the cellulose boiled.' By
heating with water in a closed tube to 200°, the cellulose breaks
down and forms a dark brown solution with the production of
formic acid,* and by solution of alkali from the glass composing
the ' tube, small amounts of pyrocatechol and protocatechuic
acid are formed. When the glass is replaced by platinum^ these
products cannot be found.

When cellulose is heated with barium hydroxide to 150°-180°
fermentation lactic acid is formed together with small quantities
of formic, propionic, oxalic, oxybutyric and glycoUic acids.®
With ammonia and calcium chloride, heating for six hours at
100° transforms the cellulose into an amidized cellulose,' which

1. Papier Ztg. 1906, 31, 4331; abst. C. A. 1907, 1, 486; Wochenbl.
Papierfabr. 1907, 38, 1289.

2. H. Hofman, Papier Ztg. 1907, 32, 2558; abst. G. A. 1907, 1, 2634;
T. S. C. I. 1907 28 942.

3. H. Tauss, Dingl. Poly. 1889, 273, 276; abst. J. S. C. I. 1890, 9,
883; Chem. Centr. 1889, 60, II, 444; Jahr. Chem. 1889, 42, 2838; Chem. Ztg.
Rep. 1890, 14, 232; Chem. Tech. Rep. 1890, 29, II, 105; Chem. Ind. 1889,
12, 614; Wag. Jahr. 1889, 35, 1; Ber. 1889, 22, R, 769; Mon. Sci. 1890, 35,
164; Chem. News, 1890, 81, 169.

4. F. Hoppe-Seyler, Ber. 1871, 4, 15; abst. J. C. S. 1871, 24, 226;
Chem. Centr. 1871, 42, 84; Jahr. Chem. 1871, 24, 476; Bull. Soc. Chim.
1871, 15, 98; Chem. News, 1871, 23, 131.

5. F. Hoppe-Seyler, Zts. physiol. Chem. 1889, 13, 73.

6. P. Schuetzenberger, Jour. Pharm. Chim. 1877, 25, 141.

7. L. Vignon and L. Casella & Co., D. R. P. 57846, 1890; abst. Zts.
ang. Chem. 1891, 4, 560; Chem. Centr. 1892, 83, I, 80; Chem. Tech. Rep.
1891, 30, II, 119; Wag. Jahr. 1891, 37, 1121; Ber. 1892, 25, R, 139; Indbl.

46 TECHNOLOGY OP CELLULOSE ESTERS

enhances its affinity for dyestuffs. Patterns may thus be executed
for differential dyeing in calico printing.

Viscosity of Cellulose Solutions. H. Ost^ has made a number
of viscosity determinations of cuprammonium solutions of various
forms of cellulose such as cotton, wood pulp, filter paper, etc.,
which has led to the conclusion that viscosity determinations
supply useful information as to the nature and technical value of
cellulose.

The cuprammonium solution used was prepared by treating
a solution containing 59 gm. copper sulfate with ammonium
hydroxide, and dissolving the basic copper sulfate thus obtained
in ammonium hydroxide of sp. gr. 0.90 to form one liter of solution.
A quantity of cellulose was dissolved in this solution in each case
to correspond with one gram of the anhydrous cellulose in 50 cc.
The viscosity was determined in a special form of Ostwald*s
capillary viscometer. It has been established that previous
treatment of the cellulose with bleaching agents produces a marked
decrease in viscosity of the cuprammonium solution, the same
result also being brought about by heating cellulose for about 15
hours at 120°- 125°. On the other hand, treatment of the cellulose
with a cold 5% solution of sodium hydroxide for about 24 hours,
or with a cold 20% solution for one hour, does not affect the
viscosity of the solution.

From this observation the conclusion is drawn tliat cotton
does not undergo a chemical change during mercerization. NaOH
however, does exert a chemical action on cotton — although the
action is a very slow one — because cotton which has been soaked
in a 20% solution of sodium hydroxide, pressed, and kept in a
stoppered bottle for several months, dissolves very readily in a
cuprammonium solution, and the solution possesses a low viscosity.

Cuprammonium solutions of hydrocellulose obtained by the
action of dilute mineral acids on cellulose, are much less viscous
than equivalent weight solutions of cellulose which previously
have been acted upon by bleaching agents. The commercial

1891, 382; Tech. Chcm. Jahr. 1891-1892, 14, 485. See also Compt. rend.
1891, 112, 487; abst. Bull wSoc. Chini. 1891. (3), 5, 472; Jahr. Chem. 1891,
44, 2814; Chcm. Ztg. Rep. 1891, 15, 76.

1. Zts. ang. Chem. 1911, 24, 1892; abst. Kun.st. 1911, 1, 452; J. C. S.
1911, 100, i, 838; J. vS. C. I. 1911, 30, 1247; Chcm. Zcntr. 1911, 82, II,
1518; Meyer Jahr. Chem. 1911, 21, 220; C. A. 1912. 6, C84.

CELLUI.OSE 47

application of the viscosity test to cellulose is given at the close
of this chapter.

Optical Properties of Cellulose. In his polarimetric inves-
igations of various forms of cellulose, A. Levallois* prepared the
latter by the action of ferrous chloride solution on guncotton and
on pyroxylin, which were then dissolved in a cuprammonium
solution and the rotatory power of this solution compared with
that of a similar solution of pure cellulose from paper, with the
following results:

Deviation

Pure cellulose 9.5*^

Cellulose from trinitrocellulose 8.5°

Cellulose from pyroxylin 8.5°

The differences observed were attributed by Levallois to
hydration produced by prolonged washing of the reduced cellu-
lose with HCl. Similar determinations were made with a cup-
rammonium solution of cellulose which* had been immersed in
sulfmic acid of a predetermined strength for a definite period
of time. In the first series the acid was of 06° Be. strength diluted
with its own volume of water, whereas in the second series the
same acid was diluted with only half its volume of water.

First series Second series

Immersed 10 seconds. ... 8.8

Immersed 30 seconds 9.5

Immersed 1 minute 9.5 Immersed 1 minute 9.0

Immersed 5 minutes. . . 8.7 Immersed 5 minutes .... 9.0

Immersed 15 minutes. . 8.7 Immersed 15 minutes. . . 8.8

The above results are practically identical. As A. Bechamp
has shown, 2 the cellulose is converted into a pasty mass by the
acid, which is entirely dissolved in about 5 minutes. The solu-

1. Compt. rend. 1881, 98, 732; 99, 43, 1027; abst, J. C. S. 1884, 48,
577, 1288; Bull. Soc. Chim. 1885, 43, 83; Bcr. 1884, 17, R, 206, 427; 1885. 18,
64; Jahr. Chem. 1884, 302, 303; Mon. Sci. 1884, 26, 199; Chem. News, 1884,
49, 124, 190; 50, 79; 1885, 51, 147. H. Ambronii, Zts. Chem. Ind. Koll.
1913, 13, 200; abst. J. S. C. I. 1913. 32, 991 ; C. A. 1914, 8, 422; Chem. Zentr.
1913, II, 1275; J. C. vS. 1913, 104, ii, 897; Wag. Jahr. 1913, I, 457.

2. Compt. rend. 1884, 99, 1027, 1122; 1885, 100, 117, 279, 308, 4.-G;
abst. Ber. 1885, 18, 113; Chem. News, 1885. 51, 117; Jahr. Chem. 1881. 303;
Mon. Sci. 1885, 27, 88; Bull. Soc. Chim. 1885, 43, 611; J. C. S. 1885,48,237.
C. Naegeli, Ber. d. Bayer Akad. 1862, I, 307; abst. Instit. 1863, 263; Jahr.
Chem. 1863, 671.

48 TECHNOI.OGY OF CHI^LUI^OSE ESTERS

tion is at once precipitated if poured into alcohol, and when
dried forms a friable mass slightly soluble in water, and very
soluble in cuprammonium solution. The latter solution, how-
ever, has only about half the rotatory power of a cuprammo-
nium solution of pure cellulose.

According to W. Harrison^ double refraction in textile fibers
is due to the presence of internal stresses, and may be increased
by compressing the fibers, for instance, between a thick glass
plate and a grooved celluloid film placed on a second glass plate,
the whole being examined on the stage of a microscope in polar-
ized light between crossed nicols and the difference between the
compressed and uncompressed portions noted. Examined in
this way under a pressure of 5 tons per sq. in., wool fibers showed
interference figiu'es indicating spreading of the fiber substance
in all directions away from the center of pressure; cotton fibers
offer greater resistance to deformation than wool fibers and
shov no interference figures.

After removal of the pressure, in both cases, the fibers did
not return to their original shape; the increased double refraction
of the compressed portions remain until the stresses are relieved
by immersion in water. The return to the original shape in cold
water is much more rapid in the case of wool than in that of cotton.
Similar results were obtained when fibers which had been bent
or twisted were placed in cold water. Fibers subjected to a limited
amount of extension when dry do not returti to their original
length when kept loose in a dry atmosphere, but do so rapidly
when placed in the water; the effect of a humid atmosphere is
the same as that of cold water but much less rapid.

At high temperatures, water renders fibers truly plastic;
deformation is produced by compression, but this causes little
or no internal stresses. These experiments have a bearing on the
"feer* and finish of textile fabrics. The double refraction shown
by cotton fibers in the natural state is due to permanent strain
produced by internal stresses; it disappears when the fiber is

1. Proc. Roy. Soc. 1918. A-94, 460; abst. J. S. C. I. 1918, 37, 460-A;
C. A. 1918, 12, 1928; Ann. Rep. Soc. Chem. Ind. 1918, 3, 116. See also W.
Harrison, J. Text. Inst. 1916, 7, 233; abst. C. A. 1917, 11, 233. According to
J. Larguier des Bancels, Compt. rend. 1909, 149, 316; C. A. 1911, 5, 2333;
J. C. S. 1909, 96, ii, 720; Chem. Zentr. 1909, II, 1297; Jahr. Chem. 1909,
1055. See also J. Larguier des Bancels, Compt. rend. 1903, 136, 1388; abst.
Chem. Centr. 1903, II, 175. The electric charge of cotton fibers is negative.

CBI.I.ULOSB 49

swollen by cuprammonium solution, except in those bands where
swelling has not occurred. The direction of strain is parallel to
the axis of the fiber and the natural condition of cotton fibers
correspond with that produced by tension on an elastic body;
all the other natiural fibers appear to be subject to similar stresses.
The shrinkage in length which takes place on mercerization
appears to be due to the balancing of the internal stresses. The
condition of a highly nitrated cotton fiber containing more than
12.5% of nitrogen is just the reverse and corresponds to that
produced in an elastic body by compression in the direction of
the axis.

In both cotton and wool the distribution of the internal
stresses is irregular. The modification of the internal stress pro-
duced by boiUqg wool in water is similar to that produced by
treating cotton fibers with concentrated alkali. Cold water has no
influence in relieving the natural stresses, probably because these
are due to changes in voliune, whereas stresses caused by external
compression are only due to changes in shape. Artificial fibers
are generally produced with internal stresses which cause double
refraction, similar to those occurring in natural cotton, and the
physical forces which are operative in the formation of artificial
fibers from viscous fluids are analogous to those acting in the for-
mation of natural fibers from plastic cell materials.

J. Koenig and F. Huehn^ have determined the specific rotatory
power of different types of cellulose, 0.5 gm. of the previously
dried cellulose being dissolved in zinc chloride, the solution being
finally made up to 25°. The measurements were made at 18°,
but were rendered difficult by the opacity of the solutions. The
solutions presented the phenomena of multi-rotation, indicated in
the following table:

1. Zts. Farbenind. S, 80; 6, 102. The preparation and drying of the
various celluloses used are given in the original article. Behrens "Anleitung
zur Mikrochemischen Analyse," has studied dichroism on dyed fibers and has
noticed it much less with cotton fiber than with flax, hemp and ramie. C.
Schwalbe, abst. J. Soc. Dyers Col. 1920, 36, 26, in an investigation of hy-
dro- atad oxy-celluloses"from wood cellulose, has found that these products,
in common with naturally occurring degradation products of cellulose such as
cellulose, dextrin and the hemicelluloses, are converted into mucilage by
mechanical means, and particularly by pressure. This mucilage is converted
into an irreversible colloid on drying, which has lost the property of swell-
ing in an atmosgphere s^tursited with water vapor.

50

TECHNOLOGY OP CELLULOSE ESTERS

TABLE III.— SPECIFIC ROTATORY POWER OF DIFFERENT

TYPES OF CELLULOSE

Material

Raw cotton fiber

Cotton cellulose

Cotton cellulose

Cotton cellulose

Jute cellulose

Jute cellulose

Swedish filter paper. .

Dissolved cold

Same, dissolved hot. .

Absorbent cotton

(dissolved cold)

Same, dissolved hot. .
Cotton hydrocellulose

Oxy cellulose

I

Observer

Time in
Hours

' Specific
Rotation

r 1 '8

K6nig

h
0
72
112

m
15
15
15

0

80.03
80.03

Konig

72
92

15
30
30

0
82.55
80.40?

Tollens

1
78
94

30

2.92
72.02
69.15?

Cross

and Sevan

4
73
76

•»

13.17
53.57
53.42

Konig

1
56
71

30
30
30

4.28
71.50
66.92

Tollens

1
49
61

30

6.57
71.57
45.91?

Munktell

107
124

30

0.27
66.15
62.69?

5
71

,30

59.25
69.21
52.22?

6

78

99

30
30

18.21
71.45
58.84?^

47
75

30
30

41.59
71.65
60.59?

Girard

15
34
31

30

1.06
39.73
45.02?
37.08?

Vignon

30
45

30

3.98
62.29
40.00?

CELLUIvOSE

51

TABLE III (continued)

Material

Oxyccllulose,

Spruce cellulose.

Beech cellulose.

Glucose.

Xylose.

Observer

Vignon and
von Hauff

Konig.

Konig.

Schuchardt-
Gorlitz

Schuchardt-
Gorlitz

Time in
Hours

54
71

71
78

31

47

m
45

30

30
30

15

Specific
Rotation

r 1 *®

0.80
44.84
37.00?

10.35
60.51
57.02

0.27
60.33
59.24?

60.0

32.0

W. Hartley^ has recorded that cellulose in the form of white
blotting paper is fluorescent and capable of rendering visible
the whole of the ultra-violet spectrum as far as wave length 2000.
S. Lewis* has continued these studies and photographically recorded
the relative intensity of the degradation of ultra-violet light at
various wave lengths to visible rays capable of passing through
glass and affecting the photographic plate. His general results
show that the power and distribution of the fluorescent prop-
erties are definite functions of the chemical constitution, and their
variations conform to what is known of the influence of substit-
uent groups on the properties of the original substance.

Normal cellulose, from whatever source it is derived, gives a
fairly uniform spectrum, but the intensity varies with the speci-
men under obeservation. The cellulose from rhubarb stalk

1. J. C. S. 1893, S3, 245; Chem. News, 1892, €6| 298; abst. Chem.
Centr. 1893. 1, 76; Meyer Jahr. Chem. 1892, 2, 11.

2. J. Soc. Dyers Col. 1918, 34, 167; abst. J. S. C. I. 1918. 37, 642-A.
For the ultramicroscopic behavior of celliilose, consult N. Gaidukow, Parb.
Ztg. 1907, 18, 392; Zts. Farbenind. 7, 251, 267; Ber. Botan. Ges. 1907, 24,
581; Zts. ang. Chem. 1908, 21, 393; Chem. Zentr. 1907, I, 643; 1908, I. 1217;
Jahr. Chem. 1905-8, II, 3181; BuU. Soc. Chim. 1908, (4), 4, 637. Com-
pare G. Quincke, Pogg. Ann. 1861, 93, 513; Bibl. Univ. Archives, 1862, 13,
185; Nuovo Cimento, 1862, 15, 29.

52 TKCHNOU)GY OP CKLLUU)SE ESTKRS

and cuticle falls in the same group. Modified celluloses, such as
viscose fabric and parchmentized paper, show a considerable
divergence from the normal; well beaten "bank" paper falls in the
same class, which is characterized by a strong effect at a wave-
length of 2750. Ground wood paper (lignocellulose) is devoid of
fluorescent properties, and the cellulose nitrates are nearly, if
not quite, inactive.

On the other hand, the acetylcelluloses exhibit a fluorescence
which is generally much stronger than that of the normal cellulose,
and which is much stronger toward the visible region than toward
the extreme ultra-violet. For media of the same chemical con-
stitution the resulting degraded spectrum is much the same for
the transparent film through which the ultraviolet light is trans-
mitted as for the opaque network in which it is reflected at the
surface of the fibers.

Cellulose and Heat. At ordinary atmospheric tempera-
tures, the celluloses appeaf to be stable for\an indefinite period
if kept dry unless decomposition processes are started by the
presence of ferments, molds or bacteria. This has been proven
conclusively in the examination of paper of hundreds if not
thousands of years old. The resistance against the action of the
air is exceedingly great.

According to Bowman, cellulose, like animal charcoal, pos-
sesses the function of condensing upon its surface large quantities
of oxygen. The normal hygroscopic moistiu^e present in cellulose
gradually escapes upon heating, but if this heating is carried out
in a partial vacuum it is possible to dry it to constant weight —
cotton cellulose at 30-40 degrees — although temperatures of 70°-
90° are more effective. It would appear that the dehydration
of cellulose in a cathode ray vacuum has as yet not been attempted.
Prolonged drying, however, causes again an appreciable increase
in weight, either due to a gradual decomposition of the cellulose
itself or more rationally to a decomposition of the impiuities in
the cellulose fiber. It has been assumed that prolonged heating
leads to a gradual oxidation, but it appears more probable that
the oxycellulose formed during the bleaching process is the cause
of this increase in weight during this heating. It has long been
known that certain oxycelluloses undergo decomposition at 100°

CELI.UI.OSS 53

whereby they become yellow,^ and tend to eventually disintegrate.

The changes in cellulose observed by E. Wint«"stein* appar-
ently were made upon a material containing relatively large
amounts of oxycellulose. On heating cellulose (cotton) to 110®,
W. Schramm' and A. Schweizer* observed on the thermometer
stuTOunded by a mass of fibers, a rise in temperature of 9°. Such
a rise in temperature is not infrequent with cotton waste contain-
ing fat or other readily oxidizable impurities.

F. Cohn^ and Kraut* have been able to only partially cor-
roborate this.

Drying of cotton is stated to reduce the strength, this weak-
ening in the opinion of some^ being due to the presence of traces
of acid which forms hydrocellulose, whereby the strength is re-
duced. This assumption has been doubted by other investigators.
The affinity of dyes for cotton shows in a marked degree that
drjdng produces changes in the nature of the cellulose.

J. Hiibner® and E. Knecht* have pointed out that cotton
dried at 100° absorbs moisture from the air, wherefore it is diffi-
cult to obtain uniform absorption.- For instance, absorbent cot-
ton loses its principal property of absorption if over-dried.^® How-
ever, the property of absorbing acids also seems to be affected by
excessive drying. In general, therefore, it is always preferable
to dry at as low a temperature as is consistent, especially for
cotton intended for subsequent nitration. After cellulose has
been dried at lOO^'-llO® and is then further heated to ISO"*, it
loses more water, but on cooling to 110° this amount of water is

1. C. Schwalbe, Zts. ang. Chem. 1908, 2L 1322; abst. Chem. Zentr.

1908, II, 447; C. A. 1908, 2, 2448; J. C. S. 1908, 94, ii. 627; Bull. Soc. Chim.

1909, 6, 68; Jahr. Chem. 1906-8, II, 960; Meyer Jahr. Chem. 1908, 18, 504.

2. Zts. Physiol. Chem. 1892, 17, 391; abst. Jahr. Chem. 1892, 2476;
J. C. S. 1893, 64, i, 127; Chem. Centr. 1893, I, 22.

3. Zts. ang. Chem. 1908. 21, 254; abst. Chem. Zentr. 1908, I, 1217;
J. S. C. I. 1908, 27, 221; Bull. Soc. Chim. 1908, 4, 634; Chem. Ztg. Rep.
1908, 32, 137.

4. Leipziger Monatschrift. f. Text. Ind. 1908, 23, 139; abst. Chem.
Ztg. Rep. 1908, 32, 436.

6. Ber. botan. Ges. 1893, U, 66.

6. Chem. Ztg. 1893, 17, 1388.

7. Wochenblatt. 1905, 36, 3498, 3737; 1908. 37, 88.

8. J. S. C. I. 1909, 28, 644; abst. Chem. Zentr. 1909. II, 1284; C. A,

1910, 4, 1241; Bull. Soc. Chim. 1910. 8, 59; Zts. ang. Chem. 1909, 22, 1120.

9. J. Soc. Dyers Col. 1908, 24, 67. 68; abst. J. S. C. I. 1908, 27,
400; Chem. Ztg. Rep. 1908. 32, 272; Wag. Jahr. 1908, II, 467.

10. Zts. ges. Text. Ind. 1909, 12, 780.

54 TECHNOWXJY OP CKLLUW>SE ESTERS

again regained.^ The water given off at 100® has been desig-
nated as "water of constitution," but experiments made by C.
Schwalbe* to effect dehydration of the cellulose with toluol or
xylol gave at first an excessive water in the case of the hydrat-
celluloses and mercerized cellulose. Later experiments with
larger quantities showed no difference between mercerized cot-
ton and ordinary cotton, regarding the readiness of dehydration.
These results were confirmed by H. Ost and F. Westhoff,' the
latter investigators being of the opinion that complete expelling
of the hygroscopic moisture requires temperatures of 120° to
125**, they recommending that the heating be done in a current
of hydrogen or carbon dioxide.

According to the investigations of A. Scheurer,* decompo-
sition of cellulose" commences at 140® to 150°. The effects of the
heating of cotton fabrics to these temperatures has been further
studied by Grosseteste, who observed but a slight yellowing at
150® and a decrease in the tensile strength of the fabric, while
at 210® the cellulose became brown and very weak. The diura-
tion of the heating of the boiled raw cotton fabric to 180® reduces
the strength which originally was 16 to 17, while two hours
heating at the same temperature brought the value down to 15;
four hours to 13; 8 hoiurs to 8.75. The resistance, therefore, of
cotton towards heat depends primarily upon the duration of the
time to which it is exposed.

C. Koechlin* found that when cotton was exposed for several
months to the temperature of steam pipes, through which steam
of two to three atmospheres circulated and which therefore was
of the temperature of about 120® to 130®, the cotton was com-

1. Schweizer, Leipz. Mon. Text. Ind. 1908, 23, 139; abst. Chem.
Ztg. Rep. 1908, 32, 435.

2. Zts. ang. Chem. 1908, 21, 1321; abst. Chem. Zentr. 1908, II, 447;
C. A. 1908, 2, 2448; J. C. S. 1908, 94, ii, 627; Bull. Soc. Chim. 1909, 6, 58;
Jahr. Chem. 1905-8, II, 960; Meyer Jahr. Chem. 1908, 18, 504.

3. Chem. Ztg. 1908, 33, 197; abst. J. S. C. I. 1909, 28, 325; J. C. S.
1909, 96, i, 210; Chem. Zentr. 1909, I, 1231; C. A. 1909, 3, 1394; Zts. ang.
Chem. 1909, 22, 1856; Rep. de chim. 1909, 9, 321; Bull. Soc. Chim. 1909,
6, 685; Meyer Jahr. Chem. 1908, 18, 504.

4. A. Scheurer, Bull. Soc. Mulhouse, 1883, 53, 68; abst. Mon. Sci. 1883,
2S, 139. See also Dingl. Polv. 1885, 255, 349; abst. J. S. C. I. 1885, 4, 340.

5. Bull. Soc. Mulhouse, 1888, 55, 547; abst. Mon. Sci. 1888, 31,
509, 1385; J. S. C. I. 1888, 7, 841; Chem. Ind. 1888, 11, 400; 1889, 12, 15;
Chem. Tech. Rep. 1888, I, 37, 71; II, 60; Chem. Ztg. 1888, 12, 375; Jahr.
Chem. 1888, 2859.

cEi^i^uivOSB 55

pletely carbonized, and insoluble in all simple or mixed solvents.

The action of heat and dry and moist air, has also been
studied by A. Scheurer^ who found that at 140° the strength of
a piece of cotton fabric is but little aflfected in the presence of
water and pressure, while at 150° to 160° a material reduction
in the strength appears. Dry, hot air, if anything, is more dan-
gerous.

According to C. Bartsch* both dry and moist air readily
injures paper. The German patent of H. de Chardonnet' for
the preparation of cotton preliminary to nitration, advocates
among other things, heating cotton to 180°, upon the assumption
that this temperature leads to favorable changes in the molecule.
A refinement of this crude method has been recommended by
E. Berl* for the purpose of preparing material especially suitable
for the manufacture of guncotton. Berl considers the process to
be that of depolymerization.

The heating of cotton cellulose in indifferent gases has been
described by Cross and Bevan.

Bowman states that upon the heating of ceUulose, and es-
pecially cotton, to temperatures above 100°, as long as no car-
bonization of the fiber occurs, the temperature may with safety
reach 112° to 114°. J. Matthews,* however, considers that de-

1. BuU. Soc. Mulhouse, 1893, 62, 89; abst. J. S. C. I. 1893, 12, 1025;
Wag. Jahr. 1893, 39, 999; Farberztg. 1892, 4, 290; Meyer Jahr. Chem. 1893,
3, 519.

2. Mitt. Kgl. Materialprufungsamt, 1909, 27, 138; abst. Chem.
Zentr. 1909, II, 850; Papierfabr. 1909, 8, 774; Zts. ang. Chem. 1909, 22,
2205; Chem. Ztg. Rep. 1909, 33, 450; C. A. 1909, 3, 2871.

3. D. R. P. 64031, 1891; abst. Wag. Jahr. 1892, 38, 376; Ber. 1892,
2S, 699; Zts. ang. Chem. 1892, S, 499; Chem. Centr. 1892, II, 1088; Meyer
Jahr. Chem. 1892, 2, 362; Tech. Chem. Jahr. 1892, 15, 169; Chem. Ztg. 1892,

8, 1432; 1893, 17, 1004; Chem. Tech. Rep. 1892, II, 164; Chem. Ind. 1892,
, 485; Mon. Sci. 1892, 40, 166; Indbl. 1892, 358.

4. D. R. P. 199885, 1907; abst. Zts. Schiess. Sprengs. 1909, 4, 81;
Mon. Sci. 1911, 74, 93; Zts. ang. Chem. 1908, 21, 2233; Chem. Zentr. 1908,
II, 466; Cfiem. Ztg. Rep. 1908, 32, 382; Chem. Ind. 1908, 31, 454; J. S. C. I.
1908, 27, 937; Wag. Jahr. 1908, II, 355.

5. "Textile Fibres" page 147. H. Pringsheim and H. Magnus (Zts.
physiol. Chem. 1919, lOS, 179; abst. J. S. C. I. 1919, 38, 714-A; J. C. S.
1919, 116, i, 473) have determined the acetyl content of lignin, determining
that the acetic acid formed from wood products by treatment with caustic
alkalis. C. Scagliarini and T. Minganti (Annali Chim. Appl. 1919, 12, 52;
abst. J. S. C. I. 1919, 38, 810- A) have studied the products of distillation of
hemp waste. Samples distilled inan iron laboratory retort between 350° and
400° C. yielded gas containing COj, 26.3; CO, 25.5; CH4, 8.0, and Hi, 14.0%.
The liquid products consisted of 50.8% of pyroligneous acid, with traces of

56 TECHNOI.OGY OF CELLULOSE ESTERS

hydration occurs when cellulose is heated to 160° in either dry
or wet air and is accompanied by a destruction of the structiu-e.
Will was unable to find a difference as to the water absorption
of Texas cotton in samples dried at 170° and those dried at 40°.
Where cellulose is heated to temperatiu'es above 200° it is grad-
ually decomposed with the evolution of gases.

According to P. Klason, G. von Heidenstam and E. Norlin,^
who studied this process very minutely, no substantial amount of
gases are evolved on heating cellulose between 100° and 260°,
but that the gas evolution becomes a substantial one at the real
reaction temperature of 270°. Towards the end of the reaction,
carbon monoxide gas is generated and the carbon dioxide content
falls to 50%; finally only methane is evolved. The gas evolu-
tion is very sensitive against variation of temperature; accidental
rise in tlie temperature materially increases the gas evolution.
Expressed in volume per cents., the composition of the gases, if
they are formed from hydrogen and aromatic hydrocarbons, is

CO2 57.87%

CaH* 1.53%

CO 36.37%

CH4 4.23%

100.00%

According to a previous investigation of E. Chorley and W.
Ramsay,* the gases contain a small amount of free oxygen.
Liquid products are also liberated in addition to the gases as has
been determined by E. Chorley and W. Ramsey, who have found
the following:

ammonia, a small amount of methyl alcohol, and from 5% to 6% of tar. The
tar was composed of 57.55% of water, 2.35% of an oil distilling at 100°.
1.09% at 100 '^ to 170° C, 14.507o at 170° to 230° C, and 24.47% of residue.
The solid products consisted of 57.02% of charcoal containing 5.10% of ash.
The charcoal is porous, and has pronounced decolorizing properties. In the
phenomenon of wood drying, H. Tiemann (J. Frank. Inst. 1919, 188, 27;
abst. J. S. C. I. 1919, 38, 863-A) has given an account of the internal stresses
which occur in wood during the progress of drying from the green condition,
and the relationship between them is mathematically shown.

1. Zts. ang. Chera. 1909, 22, 1205; 1910, 23, 1252; Arkiv. for Kemi.
Min. Geol. 1908, 3, No. 10, 1; abst. Chem. Zentr. 1909, I, 110; J. S. C. I.
1909, 28, 132; see also abst. J. C. S. 1908, 84, i, 717, 955; C. A. 1908, 2, 3280;
1909, 3, 1810; 1910, 4, 1803, 3135; Chem. Ztg. Rep. 1909, 33, 435.

2. J. S. C. I. 1892. 11, 395, 872; abst. Jahr. Chem. 1892, 28-)7, 2898;
Chem. Centr. 1893, I, 189; Chem. Ztg. 1893, 17, 653, 1709. See also Cross
and Bevan, "Cellulose," page 69.

CELLUU>S^ 57

Cellulose carbon 34.33%

DistiUate 43.32%

CO, 6,22%

Other indifferent gases 17. 13%

They calculate the distillate in percentage from the cellulose
molecule as

Oxygen 8.60%

CO 54.14%

Readual gas 37.36%

Acetic acid 1 . 75%

Methyl alcohol 3.94%

Tar and other empyreumatic matters. . 9.70%

In contradistinction to the above results Klason was unable
to even detect the presence of methyl alcohol, his results being
confirmed by G. Biittner and H. Wislicenus.* Their figures cal-
culated on 100% dry substance are as follows:

1 2

Carbon 20.07% 30.66%

Tar 6.97% 7. 10%

Acetic acid 2.76% 2.60%

Reducing substances 7.66% .6.91%

Ketones 0.04% 0.24%

The dijfference in the results of Experiments 1 and 2 are explained
by the authors by the different manner of heating; in the first in-
stance a gas stove was used, while in the second series of experi-
ments an electric furnace was employed. Of the liquid products
formed in the dry distillation of cotton cellulose, according to
Cross and Bevan,^ water, fiu^fural, phenols, and liquid and solid
hydrocarbons are contained in the tar. B. ToUens' adds allyl
alcohol and creosote.

According to A. Scheurer* the exposure of cotton and dyes
to sunlight and under a mercury quartz lamp with an exposure
of 24 to 176 hours with cotton dyed a light shade with indigo,
showed a series of color degradations. Prolonged exposure
tinned the samples yellow and an odor of ozone was perceptible.

1. J. prakt. Chem. 1909, 79, 177; abst. J. S. C. I. 1909, 28, 417;
Chem. Zentr. 1909, I, 1518; J. C. S. 1909, 96, i, 290; Zts. ang. Chem. 1909,
22, 1614; Chem. Ztg. Rep. 1909, 33, 266; C. A. 1910, 4, 1236; Jahr. Chem.
1909, II, 33; Meyer Jahr. Chem. 1909, 19, 324.

2. "Cellulose," page 69.

3. "Cellulose" I 233

4! Bull. Soc. Mulhoiise, 1912, 80, 324; abst. C. A. 1911, 5, 1998;
J. S. C. I. 1911, 30, 279; Rev. g^n. mat. col. 1910, 14, 247; Rev. de Chim.
1911. 11, 38; Meyer Jahr. Chem. 1910, 20, 496.

58

TECHNOLOGY OI^ CELLULOSE ESTERS

Samples protected from the Ozone by quartz plates faded more
than samples in direct contact with the ozonized atmosphere,
therefore the ozone did not produce the discoloration. Methyl-
ene blue dyed and Fehling's solution deposited cuprous oxide on
the yellow portion, thus showing the presence of oxycellulose.
A thin glass shde prevented the formation of the yellow color
under it, while a quartz glass did not. The active rays of light
are thus shown to have a wave length of between 3000 and 1860.
The conclusion is drawn that ultra-violet rays act with much more
energy upon benzo colors than upon* indigo. Glass absorbs the
ultra-violet rays which attack benzo colors. Color fading is not
produced in every case by rays of the same wave length.

In an endeavor to gain an insight into the constitution of
cellulose, E. Erdmann and C. Schaefer^ examined the products
of the dry distillation of filter paper, and found that when pure
paper is heated in a copper retort until the volatile products
are completely evolved, the condensed liquid products contain
formaldehyde, furfural, maltol (CeHeOs), oxymethylfurfurol and
valerolactone. The gaseous products were found to consist mainly
of carbon monoxide, methane and hydrogen.

The results of F. Fischer and H. Niggemann* on the influ-
ence of sodium hydroxide on the distillation of cellulose and wood
is shown by the following table:

TABLE IV

Tar

Charcoal ,
Gas

100 gm. of
Cellulose

5.5%
20.0%
19 I.

100 gm. of
Cellulose
with 100 cc.
of52VNaOH

8.5%
16.0%
36 1.

100 gm. of

Cellulose
with 200 cc.
oidNNaOn

15%
15%
20 1.

100 gm. of

Cellulose

with 200 cc.

of lO^NaOH

13%

• ■ » •

39 1.

The addition of alkali caused an increase in the yield of gas and
tar and a corresponding decrease in that of the charcoal residue.
A similar influence was observed on sawdust, which yielded

1. Ber. 1910, 43, 2398; abst. J. Soc. Dyers Col. 1910, 26, 252; abst.
C. A. 1910, 4, 3223; J. C. S. 1910, 98, i, 718; J. vS. C. I. 1910, 29, 1198; Bull.
Soc. Chim. 1911, (4), 10, 445; Rep. de Chim. 1911, 11, 117; Chem. J^eiitr.
1910, II, 1304; Jahr. Chem. 1910, II, 418; Meyer Jahr. Chem. 1910,20,253.

2. Abhand. Zur Kemitnis der Kohle, 1917, 1, 176; Chem. Zentr.
1919, 90, II, 521; J. S. C. I. 1919, 38, 494-A.

CEI^LULOSE 59

16.5% of tar. The simultaneous introduction of steam or coal
gas to accelerate the removal of distillation products diminished
the yield of tar. An odor of peppermint, which was more marked
on increasing the amount of alkali, was characteristic of these
tars. They contain no paraffin hydrocarbons and are partly
soluble in petroleum spirit. By the distillation of wood with
zinc chloride, little tar and much charcoal are obtained, probably
on account of the dehydrating action of the reagent.

Action of Light and Air upon Cellulose. The action of
light and air upon cellulose has been studied but infrequently
under conditions such as would exclude all 'outside influences.
At a comparatively early time the action of sunlight and air
upon such fabrics as curtains and their gradual change to a brown
color and brittleness were noticed, but the simultaneous action
of air (oxygen) and moisture is of considerable importance and
has been observed in detail only but superficially. G. Witz^
examined cellulose in the shape of old curtains which had been
exposed to the sunlight for upwards of thirty years as well as
other forms of cellulose which had been subjected to the influence
of reflected light only. In both forms, apart from their brown
color and brittleness, dyeing with basic dyestuflfs as methylene
blue, gave characteristic reactions for oxidized cellulose. In addi-
tion to the action of sunlight and air, it must be remembered
that celluloses exposed for a considerable number of years as above,
undoubtedly were under the influence of sulfurous and sulfuric
acids from coal fire and perhaps gas light, and it is also possible,
as first pointed out by A. Girard, that the textile may have
included hydrocellulose formation which would at least partially
explain the brittleness. Cellulose under diffused light and with
moderate humidity, is but slowly affected in the open air.

Witz, in his endeavor to study the action of light with the
exclusion of air and moisture, and especially with the exclusion
of certain kinds of rays, placed the cotton under glasses which
were painted over with some of the primary colors and in this
condition the material was exposed during a whole summer to

1. Bull. ^oc. Rouen, 1883, 11, 188; abst. J. S. C. I. 1883, 2, 378; Jahr.
Chem. 1883, 1782; Wag. Jahr. 1883, 29, 1068; Tech. Chem. Jahr. 1884-5,
473; Faerb. Muster Ztg. 17, 129. See also Bull. Soc. Rouen, 1882, 416;
1883, 169; abst. Dini?l. Poly. 1883. 250, 171, 172. D. R. P. 24173; abst.
Wag. Jahr. 1883, 29, 1068. E. P. 5914, 1882; abst. J. S. C. I. 1883, 2, 412.

60 TECHNOLOGY OP CELLUIX)SE ESTERS

dry sunlight. As the result of his experiments, it was determined
that oxycellulose was formed, especially under the influence of
the blue rays, while the red and yellow rays were almost without
any chemical influence whatsoever.

According to A. Girard^ cotton is unaffected when left for
months in a sealed tube containing oxygen. Metallic salts un-
doubtedly form a powerful catalyst for the action of light, air
and moisture. Witz has been able to show that similar action
occurs where dilute solutions of ammonium chloride, copper sul-
fate, or magnesium chloride, have been used in finishing fabrics
and the fabrics thus treated exposed for a considerable time to
light. In each instance it was demonstrated that oxycellulose
had been formed as evidenced by the formation of a blue color
with methylene blue and a yellow coloration on treatment with
hot alkali. P. Jeanmaire^ has demonstrated that cellulose also
changes when iron oxides are formed within the fiber and has
proven that when a fabric is saturated with (say) iron acetate,
the tensile strength of the material is weakened in accordance
with the strength of the solution and the temperature and dura-
tion of its action. This phenomenon cannot be attributable to
the acid where acetic add has been used, in contradistinction to
the well-known action of the inorganic acids.

According to M, Pnidhomme* oxidation occurs, which nor-

1. Ann. Chim. Phys. 1881, (5), 24, 337,382;abst. Chem. News, 1881,
44, 216; J. C. S. 1882, 42, 378; Proc. U. S. Naval Inst. 1882, 8. 309; BuU.
soc. d'Encourage. 81, 176; Bull. Musee, 82, 80; Naturforscher, IS, 26; Ber.
1881, 14, II, 2834; Jahr. Chem. 1881, 985; Chem. Tech. Jahr. 1882^, 608;
Papier Ztg. 1882, 337. See also Ber. 1879, 12, 2085, 2158; abst. Jahr. rein
Chem. 1881, 9, 460. Compt. rend. 1875, 81, 1105; 1879, 88, 1322; 89, 165,
170; abst. Jahr. Chem. 1875, 786; 1879, 835, 1166; Jahr. rein Chem. 1875,
142.

2. Bull. Soc. Mulhouse, 1889, 59, 107; abst. Mon. Sci. 1889, 36, 1447;
Chem. Ztg. 1889, 13, 1605; 1890, 14, 186.

3. BuU. Soc. Mulhouse, 1891, 61, 509; Mon. Sci. 1891,38, 677; 1892,
495; abst. Chem. News, 1891. 64, 9; J. C. S. 1891, 60, 1447; J. S. C. I. 1891,
10, 834; Bull. Soc. Chim. 1892, (3), 7, 79; Compt. rend. 1891. 112, 1374;
R,ev. g^n. sci. 1891, 2, 455; Ber. 1891, 24, R, 595; Chem. Centr. 1891, II,
685; Chem. Tech. Rep. 1891, II, 123; Chem. Ztg. Rep. 1891, 15, 1024; Jahr.
Chem. 1891, II, 2816; Wag. Jahr. 1891, 37, 1115; Zts. ang. Chem. 1892, 5,
718; Tech. Chem. Jahr. 1891-2, 14, 491; Industrieblatter von Jacobsen,
1892, 262; Deut. Chem. Ztg. 1891, 218. See also H. Koechlin, Bull. soc.
ind. Rouen, 1889, 332; Bull. Soc. Mulhouse, 1889, Sept. Appendix, 39;
Chem. Tech. Rep. 1889, I, 83; Tech. Chem. Jahr. 1889-90, 12, 494; J. S. C.
I. 1890, 9, 387; Mon. Sci. 1889, 745. H. Koechlin-Baumgartner, Faerb.
Muster. Ztg. 1890, No. 23; Bayer Ind. Gew. 22, 441; Jahr. Chem. 1890,
2886; Chem. Tech. Rep. 1890, 11, 55.

CELLULOSE 61

mal oxidizing action of the air is accelerated, presumably cata-
lytically, by the presence of the iron oxides.

There is little doubt but what the so-called yellowing of
cellulose as observed in old papers and fabrics, is due primarily
to the combined action of light and air and the action of cata-
lysts. These catalysts are metallic salts, iron resinates and the
ammonia residues from the bleaching process.

The action of radium' — probably owing to the oxidation of
the oxygen of the air — considerably weakens cotton fiber. Double
refraction in some fibers has been used as a means for distinguish-
ing certain kinds of filaments. Cotton cellulose observed with
crossed nicols appears almost colorless or only slightly greyish,
while linen and ramie show a vivid play of colors.^ According
to Behrens and Herzog, the flat cotton fiber seen in the direct
light of the narrow side (edge) appears distinctly green.

A. Pauly' maintains that the double refraction permits a
conclusion to be reached as to the tensile strength of the fiber.

According to N. Gaidukow* the ultramicroscope permits the
ready differentiation of cotton from other fibers and is destined
to become a valuable auxiliary for the examination of textile fibers.

J. Schneider and G. KunzP have also made ultramicroscopic
observations of cotton filaments.

Absorption of Tannins by Cellulose. A powerful affinity
for cellulose is exerted by gallotannic acid and the tannins in
general, advantage being taken of this property in the use of the
tannins as mordants in dyeing. In this respect, tannic acid is
unlike other acids, cotton being capable of absorbing up to 10%

1. Selleger, Papier-Fabrikant, 1907, 6, 1349, 2083. See also E. Sel-
leger, Papier-Fabrikant, 1906, 4, 2213; abst. Zts. ang. Chem. 1907, 20, 452.
Kollman, Papier Ztg. 1906, 3061 ; abst. Zts. ang. Chem. 1907, 20, 452.

For data on the exposure of cotton cellulose under mercury quartz
lamp, see A. Scheurer, Bull. Soc. Ind. Mulhouse, 1910, 80, 324; abst. C. A.
1911, 5, 1998; J. S. C. I. 1911, 30, 729; Rev. g^n. mat. col. 1910. 14, 247;
Rept. Chim. 1911, 11, 38; Meyer Jahr. Chem. 1910, 20, 495.

2. Herzog, Zts. Farb. Ind. 1908, 7, 183, 218, 204, 216; abst. Chem.
Zentr. 1908, II, 547; Meyer Jahr. Chem. 1908, 18, 501; Zts. ang. Chem.
1908, 21, 2557; Chem. Ztg. Rep. 1908, 32, 436.

3. Zentr. Oesterr. ungar. Papier Ind. 1907, 321; abst. Chem. Ztg.
Repert. 1907, 31, 245.

4. Zts. Farb. Ind. 1908, 7, 251, 267; abst. Chem. Zentr. 1908, I, 1217;
1908, II, 1068; Farber. Ztg. 1907, 18, 392; C. A. 1908, 2, 3151; Jahr. Chem.
1905-8, ai, 3181; Zts. ang. Chem. 1908, 21, 393.

5. Zts. wiss. Mikr. 1908, 23, 393; abst. Chem. Zentr. 1908, I, 308.

62

TECHNOLOGY OlP CELLULOSlJ ESTERS

of its weight of tannic acid from an aqueous solution. According
to W. Gardner and T. Carter,^ cotton cellulose possesses the
power of absorbing from 30% to 32% of gallotannic acid but
no gallic acid. In the presence of a relatively small proportion
of a lower fatty acid, such as formic or acetic acid, the amount
absorbed is increased to 48-50%. They found, for instance,
that a solution of one gram per liter of tannin was absorbed in 3
hours by cellulose, as follows :

Acetic Acid per 'Liter

Tannin Absorbed

0
1
2
5
10
20

30-32%

35-36%

40-42%

49-51%

32-34% ^

S\-S27o

Little or no difference was found if formic or propionic acid was
used in equivalent amount instead of acetic acid, or polybasic
organic acids, as the following results show :

•

Quantity Absorbed in Per cent.

Tannin

32

Tannin and acetic acid

48-.50

Tannin and citric acid

19-21

Tannin and tartaric acid

Tannin and sulfuric acid

Tannin and hydrochloric acid

Tannin and sodium acetate

20-22
18-20
30-32
16-18

Dreaper and Wilson have extended this investigation to also
include the action of salts.

Other hydroxyl-containing substances show, under certain
conditions, an entirely different behavior from tannin,^ phenol
being retained. For instance, from 0.1% solutions, 10 gm. cotton
absorbed the following per cent. :

1. J. Soc. Dyers Col. 1898, 14, 143; abst. J. S. C. I. 1898, 17, 843;
Rev. mat. color. 1898, 2, 316; Mever Jahr. Chem. 1899, 9, 446.

2. Mansier, Jour. Pharm. chim. 1902, 16, 60, 116; abst. J. C. S. 1902,
82, ii, 690; J. S. C. I. 1902, 21, 1098, 1155; Rep. Chim. 1902, 2, 524; Chem.
Centr. 1902, II, 708, 769; Jahr. Chem. 1902, 238.

CELLUU)SE 63

Tannic acid

Catcchutannic acid .

Gallic acid

Pyrogallol

Phloroglucin

Protocatechuic acid

Pyrocatechin

Resorcin

Salicylic acid

Guaiacol

32

•32
0.0
4.5

24-26
0.0
0.0

45-50
0.0
0.0

From the above results it would appear that the property *
of absorption is a function of the meta position. An explanation
based merely upon capillary effect is untenable, and the instability
speaks against a chemical union, because the adsorbed material
is removable by washing with cold water. F. Kraft^ has sought
an explanation based on an assumed colloidal character for tannic
acid. If a chemical combination does exist between the cellulose
and the tannin, it must be of a very loose description. Cotton
exhibits the same attraction for tungstic acid and some of the
uranium salts, but the expense of the latter preclude their com-
mercial application at the present time as mordanting agents.

Other investigations of the absorptive capacity of cellulose
for tannin have been made by C. Koechlin,* G. Georgievics,^ W..
Dreaper and A. Wilson,* F. Blockey,^ and E. Knecht and J.
Kershaw. •

Cellulose and Dyestuflfs. Persoz, as far back as 1846,^ drew
attention to the fact that cotton absorbs aluminum from an

1. Ber. 1899, 32, 1618; abst. J. C. S. 1899, 76, ii, 472; J. S. C. I. 1899,
18, 757; Bull. Soc. Chim. 1900, 24, 399; Rev. Chim. 1899, 1, 487; Chem.
Centr. 1899, II, 169; Chem. Tech. Rep. 1899, 371; Chem. Ztg. Rep. 1899,
23, 199; Jahr. Chem. 1899, 110; Meyer Jahr. Chem. 1899, 9, 448.

2. Bull. Soc. Mulhouse, IS84, SI, 438; abst. J. C. S. 1885, 48, 208; J. S.
C. I. 1889, 8, 342; Dingl. Poly. 1884, 253, 86; Jahr. Chem. 1884, 1851; Wag.
Jahr. 1884, 30, 1138.

3. Gewerbemuseum, 1898, 8, 362; Fiirb. Ztg. 1891-1892, 3, 402; abst.
J. S. C. I. 1898, 17, 845; Chem. Centr. 1899, I, 313; Chem. Tech. Rep. 1899,
402; Chem. Ztg. Rep. 1898, 22, 242; Jahr. Chem. 1899, 105; Meyer Jahr.
Chem. 1898, 8, 490.

4. Proc. Chem. Soc. 1906, 22, 70; J. S. C. I. 1906, 25, 515; Mon. Sci.
1907, 66, 280; abst. Bull. Soc. Chim. 11X)7, (4), 2, 63; Rep. Chim. 1906, 6,
347; Chem. Centr. 19(K), I, 1621; Chem. Ztg. 1906, 30, 253.

5. Collegium, 1903, 2, 76; J. S. C. I. 1903, 22, 763; abst. Chem. Ztg.
Rep. 1903, 27, 144.

6. Jour. Soc. Dyers Col. 1892, 8, 45; Faerb. Ztg. 1891-1892, 3, 402;
J. S. C. I. 1892, 11, 129; Chem. Centr. 1892, I, 686; Chem. Tech. Rep. 1892,
I, 62; Chem. Ztg. Rep. 1892, 16, 116; Jahr. Chem. 1892, 2907; Meyer Jahr.
Chem. 1892, 2, 509; Wag. Jahr. 1892, 38, 978.

7. "Traite de Timprcssion," i846, 2, 138.

I

64 TECHNOLOGY OF C^LLUWSE ESTERS

aluminum acetate solution, especially when the aluminum is in
a state of colloidal solution as aluminum acetate.^ The investi-
gations of the action of mordants on cellulose by W. Saposch-
nikofif and W. Minajeff^ have, in the main been contradictory,
although the latter' has shown that the wall of cotton cells vary
greatly in their permeability to mordant solutions. Bowman*
established the fixation of aluminum oxide from alum solutions
and has shown that the crystalloid portion of the alum diffuses
through the exterior membrane of the cotton fiber, which there-
fore acts as a dialyzing membrane while the colloidal portion is
retained by the membrane in the insoluble state. M. Fluri* and
Rimge* have also investigated this phenomena, but not with con-
cordant results.

P. Zacharias,^ C. Liebermann,^ W. Biltz,'^ W. Suida^^^ and L.

1. Pharm. Zentralhalle, 1909, 50, 395; abst. Chem. Ztg. Rep. 1909,
33, 346; C. A. 1910, 3, 1910; Chem. Zentr. 1909, II, 142.

2. Zts. Farbenind. 1903, 2, 269; 1904, 3, 164; 1906, 4, 81; abst. J. S.
C. I. 1903, 22, 903; 1904, 23, 604; 1905, 24, 272; Rep. Chim. 1903, 3, 380;
Chem. Centr. 1903, II, 471; 1904, I, 1584; 1905, I, 906; Jahr. Chem. 1903,
1560; 1904, 1811; 1905-1908, II, 3174; Wag. Jahr. 1903, II, 523; Zts. ang.
Chem. 1905, 18, 585; Meyer Jahr. Chem. 1905, 15, 510.

3. Zts. Farbenind. 1907, 6, 236, 252, 309, 345; abst. J. S. C. I. 1907,
26, 1236; Chem. Zentr. 1908, I, 308; Jahr. Chem. 1905-1908, II, 3176; Zts.
ang. Chem. 1908, 21, 1255.

4. "The Structure of Cotton Fibre," page 435.

5. Flora, 1908, 99, 81; Naturw. Rundsch. 1909, 23, 610; abst. Bied.
Zentr. 1909, 38, 670; C. A. 1908, 2^ 3370; J. C. S. 1909, 96, ii, 338, 1046;
Chem. Zentr. 1909, I, 386; Chem. Ztg. Rep. 1908, 32, 547.

6. "Farbenchemie, Die Kunst zu drucken," 1842, 2, 1.

7. "Die Theorie der Faerbevorgaenge," 1908.

8. Ber. 1893, 32, 1574; abst. J. C. S. 1893, 64, i, 513; J. S. C. I. 1894,
13, 28; Bull. Soc. Chim. 1893, 10, 1083; Chem. Centr. 1893, II, 342; Jahr.
Chem. 1893, 610; Meyer Jahr. Chem. 1893, 3, 521; Wag. Jahr. 1893, 39,
1005.

9. Nachr. Gess. Wissensch. Gottingen, 1904, 1; Ber. 1904, 37, 1766
abst. J. C. S. 1904, 86, ii, 392; J. vS. C. I. 1904, 23, 439; Bull. Soc. Chim
1905, 34, 176; Rep. Chim. 1905, 5, 111; Chem. Centr. 1904, I, 1039; Chem
Ztg. Rep. 1904, 28, 175; Chem. Zts. 1904, 3, 783; Jahr. Chem. 1904, 99
1804; Zts. ang. Chem. 1904, 17, 1833; 1905, IB, 585; Nachr. Gess. Wissensch
Gottingen, 1905, 46; Ber. 1905, 38, 184, 2963, 4143; abst. J. C. S. 1905, 88
i, 224; BuU. Soc. Chim. 1906, 36, 436; Rep. Chim. 1906. 6, 158; Chem
Centr. 1905, I, 475; II, 524; Chem. Ztg. Rep. 1905, 29, 363; Jahr. Chem
1905-1908, II, 3151; Zts. ang. Chem. 1906. 19, 1473. See also P. Zach
arias, Ber. 1904, 37, 4387; 1905, 38, 816; Fifth Intern. Cong. Chem. 1903
II, 94; abst. J. C. S. 1905, 88, i, 74, 293; Bull. Soc. Chim. 1905, 34, 629
786; Rep. Chim. 1905, 5, HI; Chem. Centr. 1905, I, 127, 906; Jahr. Chem
1904, 99, 1804; 1905-1908, II, 3151, 3153; Meyer Jahr. Chem. 1905, 15
519; see* also Farberztg. 1901, 149, 165; Zts. physik. Chem. 1902, 39, 468
Chem. Ztg. 1902, 26, 290; Zts. Farben u. Textil-Chem. 1903, 2, 233.

10. Monatsh. 1904, 25, 1107; 1905, 26, 413; Wien. Akad. Ber. 113, 725
abst. J. C. S. 1905, 88, i, 75; J. S. C. I. 1904, 23, 1144; Bull. Soc. Chim.

CELLUW)SE 65

I/iechti and W. Suida* have attempted analyses of alizarin lakes,
but their results are inconclusive.* F. Krafft' and W. Crum,* as
well as the later work of W. MinajeflF,® have shown as the result
of examination of microscopical photographs that the fiber is
mostly dyed superficially. F. Krafft® was the first to point out
the colloidal nature of tatmic add when employed with tartar
emetic as the foundation for the application of basic dyestuflFs.
F. Erban,^ L. Vignon* and Persoz® have shown that insoluble
lead salts like those that are soluble, are retained by the fiber,
especially if the cotton be subsequently passed through a solu-
tion of the calcium salt. According to W. Elbers" and Lauber,*^

1906, 34, 437; Rep. Chim. 1905, 5, 484; Chem. Centr. 1905, I, 128, 974;
Chem. Ztg. 1904, 2S, 626; Jahr. Chem. 1904, 185; Meyer Jahr. Chem.
1905, 15, 512; Tschermak's Mitt. 1905, 23, 534.

1. Mitt. Gewerbemus. 1885, Nos. 1, 2, 3, 4; 1886, 3, 1; abst. J. S. C.

I. 1886, 5, 623; Mon. Sci. 1887, 29, 270; Chem. Ztg. Rep. 1886, 10, 11; Jahr.
Chem. 1886, 2206; Wag. Jahr. 1886, 32, 919; Chem. Tech. Jahr. 1885-1886,
3,426.

2. W. Biltz has . investigated this point for the system alizarin in
alkaline solution against ferric oxide and the relation of the composition of
the dye^lakes formed to the concentration of its components. In this case
the existence of a chemical compotmd was proven, but the behavior of
alizarin red SW towards chromic oxide was found to indicate the formation
of an absorption compound.

3. Ber. 1899, 32, 1618; abst. J. C. S. 1899, 76, ii, 472; Chem. Centr.
1899, II, 169; J. S. C. I. 1899, 13, 767; Jahr. Chem. 1899, 110; Bull. Soc.
Chim. 1900, 24, 399; Rev. Chim. 1899, 1, 487; Chem. Ztg. Rep. 1899, 23, 199.

4. Bull. Mulhouse, 1864, 34, 385; J. C. S. 1863, IS. i, 404; abst. Chem.
Centr. 1863, 927; 1864, 238; abst. Jahr. Chem. 1863, 16, 782; Wag. Jahr.
1863, 9, 615.

6. Zts. Farbenind. 1905, 4, 81; 1907, 6, 234; 1908, 7, 345; 1909, 3,
313; abst. J. S. C. I. 1907, 26, 1236; Chem. Centr. 1905, I, 906; 1908, I, 308;
Wag. Jahr. 1908, II, 458; Zts. ang. Chem. 1908, 21, 1255.

9. Ber. 1893, 32, 1618; abst. J. C. S. 1899, 76, ii, 472; J. S. C. I. 1899,
13, 751; BuU. Soc. Chim. 1900, 24, 399; Rev. Chim. 1899, 1, 487; Chem.
Centr. 1899, II, 169; Chem. Ztg. Rep. 1899, 23, 199; Jahr. Chem. 1899, 110.

7. Zts. fur Textil Ind- 1909, 13, 117; Farberztg. 1909, 20, 5, 24; abst.
Chem. Zentr. 1909, I, 598; Chem. Ztg. Rep. 1909, 33, 152; Wag. Jahr. 1909,

II, 493.

8. Rev. mat. Col. 1909, 13, 316; Bull. Soc. Mulhouse, 79, 244; abst.
C. A. 1910, 4, 386; J. C. S. 1909, 96, ii, 576; J. S. C. I. 1909, 23, 661; Bull.
Soc. Chim. 1909, (4), 5, 675; Compt. rend. 1909, 148, 1329; Rep. Chim. 1909,
9, 464; Chem. Zentr. 1909, II, 166; Chem. Ztg. 1909, 33, 720; Chem. Ztg.
Rep. 1909, 33, 424; Jahr. Chem. 1909, I, 875, 876.

9. "Traite de I'impression," 2, 126.

10. D. R. P. 101190, abst. Mon. Sci. 1899, 54, 79; Chem. Centr. 1899,
I, 1092; 1900, I, 699; Chem. Tech. Rep. 1899, 53; Cfhem. Ztg. 1899, 23, 152;
Jahr. Chem. 1899, 2206; Wag. Jahr. 1899, 45, 1062; Zts. ang. Chem. 1899,
12, 231. D. R. P. 106708; abst. Chem. Centr. 1900, I, 699; Wag. Jahr.
1899, 45, 960. E. P. 509, 1898; abst. J. S. C. I. 1899, IB, 39. E. P. 6546,
1898; abst. J. S. C. I. 1899, IB, 39. F. P. 274053; abst. Mon. Sci. 1899, 54,
42. F. P. 278376. Russ. P. 2664, 1899.

11. "Handbuch des Zeugdrucks,'' 1902, 2nd Ed., 2, 228.

66 TECHNOLOGY 01^ CELLUU)SE ESTERS

when indigo paste is applied to cellulose in the fabric the indigo
sublimates into the interstices of the fiber. W. Minajeff^ has
partially established the fact that the amount of dyestuflf ab-
sorbed is directly proportional to the concentration, no physical
absorption in general occurring, although apparently a certain
amount of absorption occurs in soaking the fiber with b-naphthol
and naphthylamin solutions. E. Justin-Mueller* and C. Schwalbe
and W. Hiemenz' have shown that in dyeing produced with azo
colors developed in the fiber the addition of oil or sulfonated oil
plays an important part in the percentage of dyestuflf absorption!
R. Haller,* C. Liebermann,^ H. Freundlich and G. Losev,' G.
von Georgievic and L. Loewy^ and G. von Georgievic,* together
with C. Weber® and W. Suida and P. Gelmo*® have made exhaus-
tive investigations."

Cellulose Solvents. No simple solvent for so-called normal
cellulose, of which cotton is the type, is at present known. By

1. Zts. Farbenind. 1905, 4, 81; 1907, 6, 234, 252, 309, 451; 1908, 7,
345; 1909, S, 313; abst. J. S. C. I. 1907, 26, 1236; Chem. Centr. 1905, I,
906; Chem. Zentr. 1908, I, 308; Wag. Jahr. 1908, II, 458; Zts. ang. Chem.
1908, ZL, 1255.

2. 6th Intl. Cong. Appl. Chem; abst. Zts. Farbenind. 1906, 5, 272;
Chem. Centr. 1906, II, 640; J. S. C. I. 1906, 2S, 532; Zts. ang. Chem. 1906.
19,852.

3. Zts. Farbenind. 1906, 5, 109; abst. Chem. Centr. 1906, I, 1469.

4. Zts. Farbenind. 1907, 6, 126; J. S. C. I. 1907, 26, 523.

5. Dingl. Poly. 1866,181, 133; abst. Jahr. Chem. 1866, 895; Zts. anal.
Chem. 1866, 5, 463; Vierteljahrsschr. pr. Pharm. 16, 446; Bull. Soc. Chim.
1866, 6, 506.

6. Zts. phys. Chem. 1907, 59, 284; abst. J. S. C. I. 1907, 26, 682;
Chem. Zentr. 1907, II, 274; J. C. S. 1907, 92, ii, 534; Biochem. Centr. 1907,
6, 373; Chem. Ztg. Repert. 1907, 31, 283; C. A. 1907, 1, 2343.

7. Monatsh. 1895, 16, 345; abst. J. C. S. 1895, 68, i, 668; Jahr. Chem.
1895, 196.

8. Monatsh. 1894, 15, 705; abst. J. C. S. 1895, 68, ii, 259.

9. Faerber Ztg. 1893, 22, 185.

10. Monatsh. 1906, 27, 225, 1193; Zts. Farbenind. 1907,6, 41; Wien.
Akad. Ber. US, lib, 997; abst. C. A. 1907, 1, 1174; J. C. S. 1906, 90, i, 445;
1907, 92, i, 231; J. S. C. I. 1907, 26, 89; Chem. Zentr. 1907, I, 853; Jahr.
Chem. 1905-1908, II, 3161, 3162; Zts. ang. Chem. 1907, 20, 771, 773.

11. Behrens, Chem. Ztg. 1903, 27, 1252. Biltz, Ber. 1905, 38, 2963;
1907, 38, 2973. Dreaper, J. S. C. I. 1894, 13, 96; Rev. Mat. Col. 1905, 9,
133. Erdmann, Chem. Ind. 1896, 19, 6. H. Freundlich, Zts. physik. Chem.
1906, 57, 385. H. Freundlich and G. Losev, Zts. physik. Chem. 1907, 59,
2^. G. von Georgievics, Chem. Ztg. 1902, 26, 129. G. von Georgievics
and Loewy, Monatsh. 1894, 15, 705; 1895, 16, 345. Gnehm and Kaufler,
Zts. ang. Chem. 1902, 15, 345. Gnehm and Roetheli, Zts. ang. Chem. 1898,
11, 482, 501. Haller, Zts. Farbcn Textil Chem. 1907, 6, 128. Heidenhaim,
Pfluegcrs Archiv. 1903, 100, 217; Chem. Centr. 1904, I, 116. Herrmann,
Farber. Ztg. 1904, 15, 218. Hucbner, J. C. S. 1907, 91, 1059, 1064, 1068,
X071. Justin-Mueller, Zts. Farben. Textil Chem. 1903, 2, 365; 1904, 3, 251;

c«i.i.uu)SS 67

solvent of a substance is understood that liquid which has a dis-
solving influence and at the same time permits the recovery of
the cellulose from the solvent without change in its material prop-
erties, especially its chemical deportment. All cellulose com-
pounds going into solution are precipitated in modified forms and
the esters prepared from these forms appear to be not derivatives
of normal cellulose, but of a form of hydrocellulose whose nature
has, up to the present, not been definitely determined. The so-
called solutions of cellulose are really colloidal solutions. The
reagents which have a dissolving influence upon cellulose may
be classified as follows:

1. Concentrated solution of zinc salts upon heating, or in
conjunction with mineral acids as hydrochloric acid. Zinc chlor-
ide, zinc bromide, zinc iodide and zinc chlorate have been pat-
ented for this purpose.

2. Ammoniacal solutions of copper salts, as the hydroxide,
carbonate and chloride, and solutions of copper hydroxide in
alkylamines.

3. Powerful mineral acids as sulfuric, hydrochloric, phos-
phoric and nitric (sp. gr. 1.52) are known to dissolve cellulose,
especially when the acid is in a concentrated form. Concentrated
solutions of mercuric chloride, bismuth chloride, stannous chlor-
ide, antimony pentachloride, stannic chloride and titanium tetra-
chloride mixed with varying amounts of hydrochloric acid. In
the latter case one can best observe the dissolving eflfect from the
fact that the cellulose fibers swell up and become translucent
before passing into solution.

4. Certain organic reaction mixtures in which the cellulose

Rev. Mat. Col. 1909. 13, 75; Zts. Farben.-Ind. 1909, 8, 93; Zts. Chem. Ind.
KoUoide. 1909. 5, 235. Kaufler, Zts. physik. Chem. 1903, 43, 686. Knecht,
Farber. Ztg. 18^. 10, 60; J. Soc. Dyers Col. 1909, 25, 194. KrafTt, Ber.
1889, 32, 1618. R. Meyer and J. Maier, Ber. 1903, 36, 2972. R. Meyer
and J. Schaefer, Ber. 1894, 27, 3355. Michaelis, Pfluegers. Archiv. 1903,
97, 634; Chem. Centr. 1903. II. 608; Beitraege, Z. Chem. Physiol, and Path-
olgie, 1906, •, 46. Minajeff, Zts. Farben.-Ind. 1907, 6, 312. de Mosen-
thal, J. S. C. I. 1904, 23, 293. Pelet-Jolivet, Bull. Mulhouse, 1909, 79,
155; Zts. Chem. and Ind. der KoUoide, 1908, 3, 275; 1909, 5, 238. Roetheli,
Dissertation, Zurich, 1898, 58. Rosenstiehl, Compt. rend. 1909, 149, 396;
Chem. Centr. 1909, II, 1504. Schmidt, Zts. Phys. Chem. 1894, 15, 60.
Suida and Hoehnel, Farber. Ztg. 1905, 5, 105. Teague and Buxton, Zts.
physik. Chem. 1907, 60, 4»4. Vignon, Rev. Mat. Col. 1897, 1, 221 ; 1909,
13, 185. Weber, Farber. Ztg. 1893, 4, 186, 201, 202, 213. P. Wilhelm,
Zts. Farbcn. Textil Chem. 1901, 4, 1901. Witt, Farber. Ztg. 1890, 1, 1.
Zacharias, Farber. Ztg. 1901, 12, 149. Zts. Farben. Textil. Ind. 1895, 4,465 .

68 TECHNOWXJY Olf CELLUIX)Sa ESTERS

dissolves with the production of esters as in the f ormylation and
acetation of cellulose, and in the preparation of cellulose ethers,
as by ethylation. In all of the above instances the cellulose may
be quantitatively recovered from this solution although constitu-
tionally altered. A so-called solution of cellulose in water may
be effected by the combined action of alkaU and carbon bisulfide.
Neither carbon bisulfide nor alkali, however, can be properly
designated as solvents. The xanthates of cellulose (viscose) be-
long to this category. According to P. Weimam^ cellulose may
be dissolved in solutions of most salts when heated under pressure.

In addition to this observation of P. Weimam, others have
recorded that upon heating concentrated solutions of metallic
salts such as zinc or magnesium chlorides with cellulose, the lat-
ter is converted either into a plastic material or passes entirely
into solution. For instance, J. Huebner and W. Pope* have
pointed out that a saturated solution of potassium iodide or
other iodides can initiate a similar change under the action of
heat or pressure, alone or together. A saturated aqueous barium-
magnesium iodide solution has a similar effect. A. Scheurer'
records that when cellulose is heated to 140° with zinc chloride,
or with tin chloride of 5° B^., the cellulose undergoes material
change. With stoicheiometrical quantities of calcium or /and mag-
nesium chloride there is but slight action, while with sodium or
potassium chlorides, potassium iodide, ammonium chloride or
barium chloride, operating under similar conditions, but little or
no change appears to occur.

Action of Cuprammonium Solutions on Cellulose. A "sol-
vent" of cellulose of a wide range of application, and of great com-
mercial importance in that an industry of artificial silk manufac-

1. KoU. Zts. 1912, 11, 41; abst. Chem. Zentr. 1912, II, 817; C. A.
1912, 6, 3516; J. C. S. 1912, 1IK2, i, 679; J. S. C. I. 1912, 31, 768. As far
back as 1858, A. Vogel (Ber. Miinchener Acad; abst. Instit. 1858, 151;
Jahr. Chem. 1858, 481) observed that lead acetate solution dissolved filter
paper.

2. J. S. C. I. 1904, 23, 404; abst. Zts. Farben u. Textil. Chem. 2, 315;
Chem. Centr. 1904, I, 1625; Chem. Zts. 1903-1904, 3, 77; Jahr. Chem. 1904.
1813; Zts. ang. Chem. 1904, 17, 777. (This article is accompanied by colored
microphotographs of cotton fiber under polarized light.) See J. Barral and
Salvetat, Ann. Chim. Phys. 1876, (5), 9, 126; Compt. rend. 1875, 81, 1189;
Chem. News, 1876, 33, 18; J. C. S. 1876, 29. 821; BuU. Soc. Chim. 1876,
25, 425; Ber. 1876, 9, 68; Mon. Sci. 1876, IB, 90; Dingl. Poly. 1876. 219,
469; Jahr. Chem. 1875, 1164.

3. Bull. Soc. Mulhouse, 1883, 53, 76; abst. Wag. Jahr. 1883, 29, 1053.

C^IXULOSE 69

ture has been founded upon the principles involved, is cupram-
monium solution. It is said that the solvent action of such
a solution was first observed by E. Schweizer^ in 1857, and
"Schweizer's Solution" (usually incorrectly spelled Schweitzer)
from that time to the present is the name that has been appUed
to cuprammonium solutions. This discovery has also been attrib-
uted to Mercer, who employed a solution of ammonia of 0.92
specific gravity, which was saturated with cupric hydroxide at
ordinary temperatures and then diluted with three volumes of
water. Mercer investigated closely the various phases of this
reaction in respect to the influence of the conditions of concen-
tration and treatment, and demonstrated that speed of solution
was retarded by the presence of salts, and that therefore the
solutions obtained by decomposing copper salts with an excess of
ammonia were much less reactive than equivalent amounts of
the piu^ hydroxide.

He also showed that the reactivity was materially decreased
by elevating the temperature, and that concordant solutions of
maximum stability were only producable when the temperature
was low and kept under strict control. He devised an interesting
method of demonstrating the solvent capacity for the cupram-
monium solutions upon cellulose, by applying a solution of cupric
nitrate to cotton cloth — preferably previously mercerized — then
immersing the cloth into a dilute solution of caustic soda. After
washing to remove the major portion of the alkali and partially
drying, the cloth was exposed to the action of gaseous ammonia,
when the treated portions of the fabric would gelatinize and
eventually pass into solution, leaving the untreated portion sub-

1. J. prakt. Chem. 1857, 72, 109. 344; Zts. Pharm. 1859, 110; Poly.
Notiz. 1859, 157; Dingl. Poly. 1859, VS2, 302; Bayer. Kunst. u. Gewerbebl.
1869. 372; Chem. Tech. Mitth. 1858-1859, 77. Compare J. Schlossberber,
J. prakt. chem. 1858, 73, 373;VierteljahrsschriftdernaturforschendenGesell-
schaft in Zurich, 1857, 2, 396. See Dingl. Poly. 1874, 213, 361; Chem.
Tech. Mitth. 1874-1875, 196. Cramer Q. prakt. Chem. 1858, 73, 1) came
to the conclusion from osmotic measurements, that ammoniacal copper dis-
solved cellulose to a true solution, while Erdmann considered it to be a very
highly hydrated gel. Cross and Bevan (Textbook of Paper Making, 8) have
expressed the view that the copper compound combines with the cellulose
to form a colloid double salt. H. Baubigny, Compt. rend. 1887, 104, 1616.
Neubauer, Zts. anal. Chem. 1875, 14, 196; abst. Poly Notiz. 1875, 256;
Chem. Tech. Mitth. 1875-1876, 141. E. Mulder, Scheik. Onderz, 3, 166;
Jahr. Chem. 1863, 16, 566. M. Rosenfeld, Ber. 1879, 12, 966. Compare
Bronnert, Fremery and Urban, D. R. P. 119230.

70 TECHNOU)GY Olf CnUMhOSU ESTERS

stantially unacted upon, although contmued action had an effect.
The preparation of the cuprammonium solution which is to
be used for dissolving the cellulose is of considerable technical
importance, and involves close attention to many seemingly im-
important details, especially when the solution is to be used for
artificial filament formation. The solutions of the cuprammonium
compounds in general attack normal cellulose but slowly, unless
the cellulose has been hydrolyzed by previous treatment with
caustic soda solution but with excess of ammonia solution proceeds
energetically, gelatinous hydrates being first formed, which finally
entirely pass into solution. It appears that solutions of pure
cuprammonium hydroxide exert a greater dissolving power than
do those solutions resulting from the decomposition of a copper
salt with excess of ammonia. The two methods in general use
at the present time for producing cuprammonium solutions are
as follows:

1. To an aqueous solution of a cupric salt is added am-
monium chloride, and then sufficient sodium hydroxide to produce
the maximum of blue precipitate. This latter is thoroughly
washed with cold or warm water upon a cloth filter, centrifugalized,
and immediately dissolved in the cold in the minimum amount
of ammonia. Before use it is carefully filtered and kept at a low
temperature until required.

2. In the second method copper, either in thin sheets or
copper shavings or turnings, is placed in a glass receptacle and cov-
ered with ammonia of 0.92 gravity. Atmospheric air is aspirated
through the container at such speed as to amount to about 40
times the volume of liquid used per hour. After six to eight
hours substantial solution takes place, the liquid having the com-
position of ammonia 10-15%, copper (calculated as CuO) 2.0%-
2.5%. In the C. Wright method,^ a solution of cuprammonium
hydroxide is obtained by piling pieces of copper loosely in vertical
iron towers, preferably arranged in series, down which water is
caused to trickle, while air mixed with ammonia is admitted from
below. A weak solution of ammonia or of cuprammonium hy-

1. E. P. 737, 1883. J. S. C. I. 1884, 3, 121; Mon. Sci. 1884, 26,
1134. J. Scoffern (U. S. P. 86103). waterproofed paper and woven fabrics
with "copperized ammonia," as far back as 1869. See E. Grimaux, Compt.
rend. Iii84, 98, 1434, Maumene, Compt. rend. 1882, 55, 223. G. Bradbook,
U. S. P. 1244463, 1919, describes a cuprammonium and casein adhesive.

CEI<I*UW)SB 71

droxide may be used instead of water. The air and ammonia
are led successively through the connected towers, and the weak
solutions thus obtained are systematically used instead of water.
The proportion of copper in the solution may be increased by
immersing copper in it and blowing air through the solution, or
the solution may be run down a tower packed with copper, air
meanwhile being forced upwards. To obtain solutions contain-
ing zinc-ammonium hydroxide, with or without the cuprammo-
nium compound, fragments of brass or other copper-zinc alloy is
used in the process instead of copper.

M. Prud'homme* prefers to use potassium instead of sodium
hydroxide. H. Pauly proposed to accelerate the solvent action
by means of the presence of scraps of platinum or by means of
an electric current. ^ Titanous and chromous salts* have been
suggested for the same purpose. According to B. Borzykowski*
an ammoniacal copper solution containing a maximum of copper
and a corresponding minimum of ammonia is produced by adding,
to an ordinary ammoniacal copper solution, aqueous solutions of
copper sulfate and caustic alkali, whereby the cupric hydroxide
dissolves as soon as formed.

In another method,^ the solvent for cellulose is prepared by

1. F. P. 344138, 1904; abst. J. S. C. I. 1904, 23, 1087; Mon. Sci.
1906, 65, 34.

2. E. P. 28631, 1897. F. P. 272718; abst. Mon. Sci. 1898, 52, 200.
D. R. P. 98642, 1897; abst. Jahr. Chem. 1898, 1370; Wag. Jahr. 1898, 44,
994; Chem. Centr. 1898, II, 911. Belg. P. 132273, 1897. In this connection
see: A. Healy, E. P. 174, 1878. M. Neumann, U. S. P. 241056, 1881. W.
Beddmghaus, E. P. 20359, 1894; abst. J. Soc. Dyers Col. 1896, 12, 25.

3. P. Spence & Sons, F. P. 449801, 1912; abst. C. A. 1913, 7, 3025;
J. S. C. I. 1913, 32, 483. E. P. 25532, 1911; abst. J. S. C. I. 1913, 32, 18.
D. R. P. 264952, 1912; abst. C. A. 1914, S, 248. F. P. 449803, 1912; abst.
J. S. C. I. 1913, 32, 483; C. A. 1913, 7, 3025. E. P. 25333, 1911; abst. J. S.
C. I. 1913, 32, 18. D. R. P. 264951, 1912; abst. C. A. 1914, 8, 248. D. R. P.
Anm. S-37390, 37391, 37392; abst. Kunst. 1913, 3, 200. Belg. P. 250442,
1912; abst. Kunst. 1913, 3, 235. Belg. P. 250441, 1912.

4. U. S. P. 1100518; 1914; J. S. C. I. 1914, 33, 746. E. P. 24996,
1912; J. S. C. I. 1913, 32, 283; Jour. Soc. Dyers Col. 1913, 29, 171; C. A.
1913, 7, 3025. F. P. 450193, 1912; J. S. C. I. 1913, 32,4&3; C. A. 1913, 7,
3025; Mon. Sci. 1914, 4, 5; Kunst. 1913, 3, 196. F. P. 420682. D. R. P.
Anm. B-65475, 1911; Kunst. 1913, 3, 60. D. R. P. Anm. 68108, 1912;
Kunst. 1913, 3, 160. Belg. P. 251118, 1912; Kunst. 1913, 3, 235.

5. Rhemische Kunstseide Fabrik. D. R. P. 231652, 1909; abst. Zts.
ang. Chem. 1911, 24, 623; Chem. Zentr. 1911, I, 770; Wag. Jahr. 1911, II,
415; Kunst. 1911, 1, 114; C. A. 1911, 5, 2737. E. P. 18342, 1909 (O. Muller);
abst. J. S. C. I. 1910, 29, 557. D. R. P. 236537, 1908; abst. C. A. 1912,
6, 1231; Wag. Jahr. 1911, II, 416; J. S. C. I. 1911, 30, 1248; Zts. ang. Chem.
1911, 24, 1499; Chem. Zeptr. 1911, II, 326; Kunst. 1911, 1, 295. F. P. 405571.

/

72 TKCHNOWXJY OF CKLLUI.OSE ESTERS

treating 1-3 parts of solid copper sulfate with 2-4 parts of a
solution of NaOH of 21° B€, and adding to the mixture 5-15
parts of aqueous ammonia of 25° B^. The solution is then cooled
to 0° and the crystals which form are separated. The liquid is
said to be sufficient for dissolving one part of cellulose, the sol-
vent being particularly applicable to the cellulose obtained from
cottonseed hulls. E. Friedrich^ replaces a portion or all of the
ammonia by amines as monomethylamine or other alkylamine,
producing soluble compoimds with cellulose. W. Traube* advo-
cates for the same purpose, aliphatic diamines as ethylene di-
amine, ethylenediaminotrimethylenediamine and tetramethylene-
diamine. M. Wassermann' advises to mix cuprous oxide with
ammonium chloride which is then dissolved in ammonia at a

1909; abst. J. S. C. I. 1910, 29, 417. D. R. P. 237816, 1910; addn. to D. R.
P. 236537; abst. C. A. 1912, 6, 1679; J. S. C. I. 1911, 30, 1248; Zts. ang. Chem.
1911, 24, 1988; Chem. Zentr. 1911, II, 1084; Wag. Jahr. 1911, II, 416; Kunst.

1911, 1, 378. D. R. P. Anm. R-26760, R-29685. Belg. P. 218118, 1909.
Aust. Anm. 5916, 1909.

1. U. S. P. 850571, 1907; abst. J. S. C. I. 1907, 26, 525. E. P. 27727,
1906; abst. J. S. C. I. 1907, 26, 405. F. P. 372002, 1906; abst. J. S. C. I.

1907, 26, 525. D. R. P. 189359, 1905; abst. Zts. ang. Chem. 1908, 21, 1194;
Chem. Zentr. 1908, I, 1119; Jahr. Chem. 1905-1908, II, 989; Chem. Ind.

1908, 31, 141; Wag. Jahr. 1908, II, 354. U. S. P. 813878, 1906; abst. J. S.
C. I. 1906, 2S, 280. E. P. 17164, 1905; abst. J. S. C. I. 1906, 25, 950. P. P.
357171, 1906; abst. J. S. C. I. 1906, 2S, 88. U. S. P. 827434, 1906; abst.
J. S. C. I. 1906, 25, 845. E. P. 17381, 1905; abst. J. S. C. I. 1906, 2S, 586.
F. P. 357172, 1905; abst. J. S. C. I. 1906, 2S, 70. D. R. P. 172264, 1904;
abst. Wag. Jahr. 1906, II, 391. D. R. P. 172265, 1904; abst. Wag. Jahr.

1906, II, 391. Aust. P. 30705. Swiss P. 35080. E. P. 6072, 1906; abst.
J. S. C. I. 1906, 2S, 1040. F. P. 364066, 1906; abst. J. S. C. I. 1906, 2S, 980.
E. P. 12842, 1906; abst. J. S. C. I. 1907, 26, 196. F. P. 366793, 1906; abst.
J. S. C. I. 1906, 26, 1091. D. R. P. 178410, 1905; abst. Zts. ang. Chem.

1907, 20, 410; Wag. Jahr. 1907, II, 400. Aust. P. 31802. E. P. 21144, 1906;
abst. J. S. C. I. 1907. 26, 1045. F. P. 400221, 1909; abst. Mon. Sci. 1911, (5),
74, 153. Can. P. 102233, 1906; 107979, 1907. Belg. P. 182289, 183058,
186471, 1905; 192529. 194741, 196219. 1906. Dan. P. 8258, 1906.

2. W. Traube, U. S. P. 1064260, 1913; abst. J. S. C. I. 1913, 32, 696;
C. A. 1913, 7, 2683; Mon. Sci. 1914, 23. E. P. 356, 1912; abst. J. S. C. I.

1912, 2^ 637; C. A. 1913, 7, 2307. F. P. 438632, 1912; abst. J. S. C. I. 1912,
31, 584; Kunst. 1912, 2. 439. D. R. P. 245575, 1911; abst. C. A. 1912, 6,
2316; J. S. C. I. 1912, 31, 532; Zts. ang. Chem. 1912, 2S, 1034; Wag. Jahr.
1912, II, 439; Kunst. 1912, 2, 176. D. R. P. 252661, 1911; addn. to D. R. P.
245575; abst. C. A. 1913, 3, 416; Zts. ang. Chem. 1912, 25, 2381; Kunst.
1912, 2, 475; C. A. 1912, 6, 2316. D. R. P. Anm. T-15850; abst. Kunst.
1912, 2, 79, 240; T-16998, addn. to T-15850; T-16544, addn. to T-15850; abst.
Kunst. 1912, 2, 340. Aust. A-10798, 1911; abst. Kunst. 1912, 2, 399.
Swiss P. 58882, 1911. Belg. P. 241976, 245575, 252661, 1912; abst. Zts.
Chem. Ind. KoU. 1912, 11, 310.

3. D. R. P. 274658, 1913; abst. C. A. 1914, 8, 3374; Kunst. 1914, 4,
234; Wag. Jahr. 1914, II, 336; Chem. Tech. Rep. 1914, 38, 394; J. S. C. I.
1914, 33, 785. Wassermann and Jaeger, Kunst. 1913, 3, 117.

CELI<UU>SB 73

low temperature, caustic alkali being then added imtil a bright
blue precipitate forms; this dissolves comparatively slowly in
the cold, and is separated from the liquid which is then used as
a cellulose solvent. It is claimed* that at least 6% NH3 must
be added to the Schweizer liquid. In the method of G. and A.
Schaefer* the copper is subjected to the action of air and ammonia
at a temperature changing alternately between — 4° and +8®,
and to the solution thus obtained the requisite amount of cupric
sulfate and alkali are added, it being stated that 8-8.5 parts of
a solution prepared in this manner containing about 8%-12% of
ammonia and 45-50 gm. copper per liter will dissolve 1 part of
cellulose. Where the cuprammonium solution is prepared by the
action of sodium hydroxide upon copper sulfate with addition
of ammonia, there is a tendency to the deposition of crystals of
sodium sulfate. This is avoided in the O. Mueller' process by
mixing the cupric salt with a solution of sodium chloride and
glycerol before adding the ammonia and caustic alkali.^ The
La Soie Artificielle* start with copper sulfacetate and sodium
carbonate.' The patented methods of E. de Haen,' E.

1. J. Wetzel. F. P. 423510, 1910; abst. C, A. 1912, 6, 2001; Mon. Sd.
1913, 79, 117. F. P. 424293, 1911; abst. C. A. 1912, 6, 2003.

2. U. S. P. 879416, 884298, 1908; abst. J. S. C. I. 1908, 27, 749; C. A.
1908, 2, 2432; Mon. Sci. 1909, 68, 28. Swiss P. 45321.

3. P. P. 451406, 1913; abst. Mon. Sci. 1913, 7; C. A. 1913, 7, 3227;
Kunst. 1913, 3, 213; J. S. C. I. 1913, 32, 596; Rev. Chim. Ind. 1913, 24, 189.

D. R. P. 192690, 1905. D. R. P. Anm. M-47935, 1912; abst. Kunst. 1913,
3, 180. Belg. P. 251128; abst. Kunst. 1913, 3, 355.

4. Example: 120 kilos, of powdered copper sulfate are stirred with
200 liters of a 1-2 per cent, solution of sodium chloride containing 2.25-3
liters of glycerol; to this are added 300 liters of ammonia, (sp. gr. 0.91,) and
the copper salt is dissolved. Then 200 liters of caustic soda (sp. gr. 1.125-1.2)
are added and 50 kilos, of cellulose finally introduced. See G. Fassbender,
Ber. 1880 13 1822.

* 5. F. p'. 437815, 1911; abst. J. S. C. I. 1912, 31, 636; Kunst. 1912, 2,
294. D. R. P. 252179; abst. Zts. Chem. Ind. KoU. 1912, 11, 310. See
Glanzfaeden Akt. D. R. P. 306107, 1918; abst. Chem. Zentr. 1918, II, 327.

6. To 200 parts of this solution, about 14 parts of cellulose are added
and allowed to steep until almost dissolved. After half an hour, 3 parts
of caustic soda in 10 parts of water are added to the mixtmie and a perfect
solution of the cellulose is thereby obtained.

7. U. S. P. 1034235, 1912; C. A. 1912, 6, 3018; Mon. Sci. 1913, 78,
110; Kunst. 1913, 3, 16; J. S. C. I. 1912, 31, 811. E. P. 27835, 1911; C. A.
1913, 7, 1972; J. S. C. I. 1912, 31, 770. E. P. 4610, 1912; C. A. 1913, 7,
2856; J. S. C. I. 1912, 31, 1075. E. P. 6408, 1912; J. S. C. I. 1912, 31, 981.

E. P. 11613, 1912; C. A. 1913, 7, 3662; J. S. C. I. 1912, 31, 1120. F. P. 436968,
1911; J. S. C. I. 1912, 31, 485; Kunst. 1912, 2, 235. F. P. 440907, 1912;
J. S. C. I. 1912, 31, 812; Kunst. 1912, 2, 353, 460. First addn. 15861, 1912,
to F. P. 440907; Kunst. 1913, 3, 53; J. S. C. I. 1912, 31, 1120. F. P. 441063,

74 TECHNOLOGY OF CKLLUW)SE ESTERS

Mertz/ J. Ludlow and D. Mosher,* W. and V. Mahler,' W. Walenn
and I. Timmis/ T. Eck,^ F. Scheyn,* A. Chaumat,^ Boettger,^ and
others' diflfer but little from the principles as above mentioned.
To increase the stability of the cuprammonium solution a small
amount of a polyhydric alcohol as glycerol or mannite,^^ grape
sugar, ^' milk sugar or cane sugar, ^* or^' an organic hydroxy com-
pound, such as potassium sodium tartrate, and a little ammonium
persulfate or other oxidizing agent may be added. J. Wetzel**
claims to materially increase the stability and keeping qualities
of a cuprammonium solution by reducing the amount of free am-

1912; J. S. C. I. 1912, 31, 812. D. R. P. Anm. H-65092, 1911; Kunst. 1912,
2, 240. D. R. P. Anm. H-56704, 1912; Kunst. 1912, 2, 300. Belg. P.
241649, 1911; 243694, 243897, 245524, 1912; Kunst. 1912, 2, 399. Holl. P.
585, 1912; C. A. 1913, 7, 3239. Holl. P. 586, 1912; C. A. 1913, 7, 3415. Con-
sult Linkmeyer, F. P. 353187.

1. F. P. 364911, 1906. Belg. P. 193002, 1906. U. S. P. 954984, 1910;
abst. C. A. 1910, 4, 1671; J. S. C. I. 1910, 29, 627. L. Boneyds, Belg. P.
189754, 1906.

2. U. S. P. 853986, 1907; abst. J. S. C. I. 1907, 26, 688.

3. Aust. Anm. A-3509, 1903. Aust. P. 18454, 1904.

4. E. P. 6029, 1891.

5. D. R. P. 240082, 1909; C. A. 1912, 6, 2169; J. S. C. I. 1911, 30,
1447; Zts. ang. Chem. 1911, 24, 2334; Zts. Chem. Ind. KoU. 1912, 10, 62;
Chem. Zentr. 1911, II, 1567; Wag. Jahr. 1911, II, 417; Kunst. 1911, 1, 454.
D. R. P. Anm. E-18037, 1912; Kunst. 1913, 3, 340, 400. D. R. P. Anm.
E-14725, 1909; D. R. P. Anm. E-14902, 1909. E. Eck and E. Bech-
tel, U. S. P. 839825, 840611, 1907. T. Eck, E. Eck and F. PoUak, Belg. P.
210025, 1908. E. Elsaesser, E. P. 113010, 1917; abst. J. S. C. I. 1918, 37,
146-A; C. A. 1918, 12, 1256. Erste Oesterreichische Glanzstoff Fabr. A. G.,
Aust. P. A-781, 1905; abst. Mon. Sci. 1910, (4), 72, 45.

6. Belg. P. 187283, 1905.

7. U. S. P. 1062222, 1913; C. A. 1913. 7, 2472; J. S. C. I. 1913, 32,
653; Mon. Sci. 1914, 4, 23; Kunst. 1913, 3, 417. E. P. 14525, 1899. F. P.
429841, 1910; J. S. C. I. 1911, 30, 1308.

8. Boettger, N. Rep. Pharm. 23, 732; abst. Jahr. Chem. 1874, 878.

9. A. DesMinieres, E. P. 2739, 1904; abst. J. S. C. I. 1904, 23, 936.
Comp. Francaise de la Soie Parisienne, F. P. 297278, 1900. Soc. Gen. Fabri-
cation des Mati^res Plastiques, Aust. P. 2739, 1899. D. R. P. 113208. E.
P. 14525, 1899.

10. Chem. Fabr. Bettenhausen Marquart and Schulz, E. P. 4872,
1909; J. S. C. I. 1909, 28, 1314. F. P. 399911, 1909; J. S. C. I. 1909, 28,
938; Chem. Ztg. Rept. 1909, 33, 472. Aust. P. 41720. Swiss P. 45290.
Belg. P. 214426, 1909. See F. Flor and E. Murman, E. P. 14184, 1902.

11. Vereinigte Glanzstoff Fabriken, Belg. P. 182386, 182455, 1905;
204557, 1907. E. P. 27707, 1907; abst. J. Soc. Dyers Col. 1909. 2S, 17.

12. Soc. anon, francaise "La Soie Artificielle," E. P. 9253, 1908; abst.
J. Soc. Dyers Col. 1909, 25, 62.

13. V. Mcrtz, U. S. P. 9549^, 1910; abst. J. S. C. 1. 1910, 29, 627; C. A.
1910, 4, 1671. F. P. 364911, 1907. Swiss P. 34760, 1906. F. P. 411592. E.
P. 1 148, 1909. Belg. P. 222298, 1910. (Brit. Cellulose Syndicate and V. Mertz.)

14. F. P. 424293, 1910; abst. C. A. 1912, 6, 2033. See also F. P. 423510.
1910; abst. J. S. C. I. 1911, 30, 615. D. R. Ai)m. B-57073.

C^LI<ULOSE 75

monia to 3%. M. Prud'homme has found* that an addition of
caustic soda increases the solvent power of cuprammonium solu-
tions for cellulose, four times the amount of copper present to
cellulose being dissolved when two molecules of alkali are present
to one molecule of copper salt. According to the Soci^t^ anonyme
*'Le Crinoid,"* that portion of the cuprammonium solution which
is in the colloid state exerts an especially energetic solvent power.
Such colloid solutions may be obtained by dialysis as well as by
treatment of copper salts with ammonia and alkalis provided
the solution contains not to exceed two parts of cellulose for each
part of cupric hydroxide in solution.

The quantities of cellulose which may be dissolved in solu-
tions without the addition of foreign substances has been var-
iously stated, variation being probably due to the preliminary
(if any) treatment to which the cotton or other form of cellulose
has been subjected. Fremery and Urban' found that ordinary
or imtreated cellulose dissolves in cuprammonium solution to the
extent of only 4%, while in the Pauly patent^ is stated that 45
gm. of cellulose dissolves in one liter of cuprammonium solution
containing 15 gm. copper per liter, the time required to eflfect
complete solution being given as eight days. Both low tem-
perature and high copper content are conducive to most rapid
and complete solution.

E. Grimaux^ has studied the dialysis of these copper solutions
and came to the conclusion that it was the non-dialyzable portion
of the solution of copper hydroxide in ammonia which acted as
a solvent for the cellulose.

All solutions of ammoniacal cupric oxide possess the defect
that on exposure to the atmosphere they readily decompose,
cupric oxide is deposited, and their solvent power toward cellu-

1. F. P. 344138, 1904; abst. J. S. C. I. 1904, 23, 1087. See Dingl.
Poly. 1872. 204, 514; Chem. Tech. Mitth. 1871-1872, 34.

2. F. P. 401741, 1902; abst. J. S. C. I. 1909, 2S, 1121. E. P. 14143,
1908; ab^ J. S. C. I. 1909, 2S, 880; J. Soc. Dyers Col. 1909, 25, 246.
U. S. P. 947715; abst. C. A. 1910, 4, 152.

3. D. R. P. 111313, 1899; abst. Wag. Jahr. 1900, 11, 448; Chem.
Centr. 1890, 11, 550. U. S. P. 646381, 657818. E. P. 6557, 1899. F. P.
278371, 286925. Aust 3636.

4. D. R. P. 98642; abst. Wag. Jahr. 1903, II, 417; Jahr. Chem. 1898,
1370; Chem. Centr. 1898, II, 911. F. P. 272718. E. P. 28631. 1897. U. S.
P. 617009

6. Compt. rend. 1884, 98, 1434; abst. Bull. Soc. Chim. 1884, 42, 156;
J. C. S. 1884, 46, 957. See also Peligot, Ann. Chim. Phys. 1861, (3), 13, 343.

76 raCHNOWXJY OF CBLI*UU>SS ESTORS

lose correspondingly diminished. The decomposition increases
with rise in temperature, whereas the solubility of the cellulose
diminishes as the temperature becomes higher. Various pro-
posals for obviating this defect have been made, such as the addi-
tion of an electro-negative insoluble metal, oxygen, ozone, and
carbohydrates and polyvalent alcohols. Glycerol, acetol, potas-
sium sodium tartrate or ammonium persulfate* have also proved
suitable.

Attention is drawn to the fact that cuprammonium hydroxide
is not as strong an alkali as sodium hydroxide. Levallois^ has
stated that the solution of cellulose in cuprammonium is optically
active, which statement is not substantiated by Bechamp.' The
solutions of cellulose in hydrochloric acid, however, aqpear to be
optically inactive.*

After the artificial filament has been forced through the
spinneret, it is precipitated or coagulated by immersion in acid
or alkaline baths, dextrin,^ diastase,* starch,^ soluble" arsenites,*

1. British Cellulose Syndicate and V. Mertz, E. P. 1148, 1909. Belg.
P. 222298; 1910; J. S. C. I. 1910, 29, 24. F. P. 411692. U. S. P. 954984;
abst. J. S. C. I. 1910, 29, 627.

2. BuU. Soc. Chim. 1885, (2), 43, 83; Ber. 1885, 18, 64; J. C. S. 1884,
4€, 1288; Compt. rend. 1884, 98, 732; 1884, 99, 431, 1027.

3. Compt. rend. 1884, 99, 1027, 1122; 1885, 100, 279, 368; Ber. 1885,
18, 113.

4. R. Willstatter and L. Zechmeister, Ber. 1913, 48, 2401 ; abst. C. A.
1913, 7, 3412; J. S. C. I. 1913, £2, 822; J. C. S. 1913, 104, i, 955; J. Soc.
Dyers Col. 1913, 29, 326; Bull. Soc. Chim. 1913, 14, 1354; Chem. Zentr.
1913 II 1209

'5. ' J. Delpedi, F. P. 437014, 1911; J. S. C. I. 1912, 31, 485; Kunst.

1912, 2, 233. See Thomas and Bona vita, F. P. 302908, 1900.

6. E. Legrand, E. P. 19001, 1912; abst. C. A. 1914, 8, 671; J. S. C. I.

1913, 32, 907; J. Soc. Dyers Col. 1913, 29, 326. D. R. P. 250357, 1911;
abst. C. A. 1913, 7, 246; J. S. C. I. 1912, 31, 1120; Kunst. 1912, 2, 319, 353;
Zts. ang. Chem. 1912, 2S, 2381; Wag. Jahr. 1912, II, 441. F. P. 445896,
1911; abst. J. S. C. I. 1912, tt, 1176. U. S. P. 1130830; abst. C. A. 1915,
9, 1123. E. P. 5154, 1913, addn. to E. P. 19001, 1912; abst. C. A. 1914, 8,
2258; J. Soc. Dyers Col. 1913, 29, 326; J. S. C. I. 1913, 32, 907. F. P.
17170, 1912, addn. to F. P. 445896, 1911; abst. C. A. 1914, 8, 822; J. S. C. I.
1913, 32, 865; Kunst. 1913, 3, 332. D. R. Anm. L-33200, 1911.

7. i;. Cuntz, F. P. 383411, 383412, 383413, 1907; abst. J. S. C. I. 1908,
27,331.

8. Comp. Fran^ais Des Applications de La Cellulose, E. P. 27878,
1910; C. A. 1912, 6, 1526; J. S. C. I. 1911, 30, 1236, 1309. E. P. 28779, 1910;
C. A. 1912, 6, 1526; J. S. C. I. 1911, 30, 1236. E. P. 11714, 1911; C. A.
1912, 6, 3183; J. S. C. I. 1912, 31, 428; Kunst. 1912, 2, 296. F. P. 422565,
1910; J. S. C. I. 1911, 30, 532; Kunst. 1911, 1, 276. F. P. 429841, 1910;
J. S. C. I. 1911, 30, 1309; Kunst. 1911, 1, 455. F. P. 440776, 1911; J. S. C. I.
1912, 31, 812; Kunst. 1912, 2^ 460. D. R. P. 262180, 1911 ; abst. C. A. 1913,
7, 416; Zts. ang. Chem. 1912, 2S, 2381; Wag. Jahr. 1912, $8, II, 443;
Kunst. 1912, 2, 399. Aust. A-4369, 1911. Swiss P. 57951; Kunst. 1913, 3,

CELLUW)SE 77

alkaline carbonates,^ or bexoses, saccbarobioses and polysaccbar-
ides.^ Sodium ricinoleate has been proposed as an addition to
soften the filaments.*

In addition to filament formation, the cuprammonium cellu-
loses have been extensively employed in the waterproofing of
textiles, and qaper as in the processes of C. Hime and J. Noad,*
A. Healey and J. Williams,* who developed the "Willesden goods,"
J. IngUs,« E. Krusche,^ A. Maltman,^ Y. Murrow,® C. Snell,i» C.
Baswitz*^ and J. Williams.** In the manufacture of incandescent

213. Belg. P. 237056, 1911; D. R. P. Anm. C-20719, 1911; abst. Kunst.
1912 2« 260.

'l. Le Crinoid Soc. Anon. E. P. 21191, 1908; abst. J. S. C. I. 1909,
2S, 1194; J. Soc. Dyers Col. 1909, 2S, 313. E. P. 22413, 1909; abst.
J. S. C. I. 1910, 29, 1053. F. P. 410827, 1909; abst. J. S. C. I. 1910, 29, 810;
Mon. Sci. 1911, (5), 74, 165. U. S. P. 980294, A. Lecoeur and P. Rudolf,
F. P. 201741. 1909. F. P. 401741, 1909. F. P. 392^9. See also A. Lecoeur.

2. P. Freidrich. Swiss P. 45764, 48576, 1909. Belg. P. 217548, 221951,
1909. D. R. P. 206883, 1907; abst. Chem. Zentr. 1909, I, 213; Papierfabr.
1909, 7, 210. Belg, P. 210489, 1908; 214932, 216802, 217548, 1909. Marquart
and Schulz, Swiss P. 45290, 1909.

3. E. Bechtel, U. S. P. 988430, 1911. U. S. P. 1066785, 1913; abst.
J. S. C. I. 1913, 30, 785; Mon. Sd. 1914, 33, 23; C. A. 1913, 7, 3031. D. R. P.
220711, 1907; abst. J. S. C. I. 1910, 29, 556; Chem. Zentr. 1910, I, 1474;
Wag. Jahr. 1910, II, 428; C. A. 1910. 4, 2209; Jahr. Chem. 1910, 427. D.
R. P. 225549, 1909; J. S. C. I. 1913, 32, 420; C. A. 1911, 5, 2176. D. R.
P. 229711, 1909; Wag. Jahr. 1911, II, 413; Kunst. 1911, 1, 74; Zts. ang.
Chem. 1911, 24, 189; Chem. Zentr. 1911, I, 279; C. A. 1911, 5, 2554. D.
R. P. 255549, 1911; abst. J. S. C. I. 1913, 32, 420.

4. C. Hime and J. Noad, U. S. P. 456821, 1891. E. P. 7715, 7716,
1889. Belg. P. 86160, 1889. F. P. 198076, 1889. D. R. P. 50936, 1889.
Can. P. 32739, 1889. Victoria P. 7278, 1889. N. South Wales P. 1859,

1889. Turkey P. 158, 1889. New Zealand P. 4095. 1889. Ital. P. Dec.
5, 1889, LII, 103. Cape of Good Hope P. Dec. 17, 1889, C. D. 28. Natal
P. Dec. 18, 1889. Tasmania P. Dec. 23, 1889, No. 780/10. S. Australia P.
1486, 1889. S. Africa Repub. P. 141, 1889. Brazil P. 813, 1889. Queens-
land P. 910, 1889. Span. P. 10241. 1889. Aust.-Hung. P. 44671, 1890.
India P. March 28 and April 24, 1890. Straits SetUements P. May 2. 6.

1890. Ceylon P. 345, 1890. Hong-Kong P. June 13, 1890. Port. P. 1539,
1891.

5. A. Healey, E. P. 3685. 1877; 185, 1878; 5054, 1894; abst. J. S. C. I.
1895, 14, 381. D. R. P. 14717, 1894; abst. Wag. Jahr. 1881, 93; Mon. Sci.
1894 44 167.

'6. ' J. Inglis, E. P. 101894, 1916; abst. C. A. 1917, 11, 542; J. S. C. I.
1916, 35, 1257.

7. E. Krusche, D. R. P. 106043; abst. Wag. Jahr. 1900, II, 449; Chem.
Centr. 1900, I, 639; Jahr. Chem. 1900, 846.

8. E. P. 104986, 1916; abst. J. S. C. I. 1917, 36, 544; C. A. 1917, 11,
2155.

9. E. P. 1063, 1874.

10. E. P. 10107, 1888.

11. E. P. 16708, 20665, 1889; abst. J. S. C. 1. 1890, 9, 1047; 1891, 10, 133.

12. E. P. 1358, 12309, 1889; 20524, 1889; abst. J. S. C. I. 1890, 9, 742;

1891. 10, 157. U. S. P. 444515, 1891. E. P. 19013. 1901; abst. J. S. C. I.
1902. 21, 1132.

78 TBCHNOI.OGY OF CEI*LUW)SB ESTERS

gas mantles from cuprammonium cellulose, the patented proc-
esses of R. Langhans,* and the work of A. Mueller,* W. Bruno'
and G. Drossbach & Co.,* may be cited. D. von Monckhoven
has proposed to utilize the cellulose for photographic films,^ but
the process has never been successfully commercially exploited.
As substitutes for rubber,*, in the waterproofing of wood, ^ as an
ingredient in cements, sizes and finishes,® to render corks imper-
meable and water-resistant,^ for artificial leather*® and bone,"
and plastic masses,** are some of the fields of usefulness which have
been proposed for the cellulose regenerated from ammoniacal
copper solutions. Attempts to combine cuprammonium cellu-
lose with natural silk and fibroin, as in the processes of E.

1. Chem. Tech. Rep. 1895. 34, II, 127. U. S. P. 672946, 1901; absf
Mon. Sci. 1901, (4), 57, 283. D. R. P. 140347; abst. Wag. Jahr. 1904, II
389; Jahr. Chem. 1903, 1013. D. R. P. 115068; abst. Wag. Jahr. 1901, I, 93

2. Zts. ang. Chem. 1906, 19, 1810; abst. C. A. 1907, 1, 355; Jahr
Chem. 1905-1908, I, 2217.

3. Zts. ang. Chem. 1906, 13, 1387; abst. C. A. 1907, 1, 481; see also
1907, 1, 355; Jahr. Chem. 1905-1908, 2217.

4. Zts. ang. Chem. 1906, 19, 1427; abst. Chem, Centr. 1906, II, 1147.
See also D. R. P. 117755, 1899; abst. Chem. Centr. 1901, I, 546.

5. Compt. rend. 1859. 48, 648; abst. Poly. Centr. 1859, 2S, 813; see
also Poly. Centr. 1858, 427. Eder's. Hand. Phot. 1896, 2, II, 344.

6. J. Gebauer, F. P. 415996; abst. Kunst. 1911, 1, 92. P. and G.
Marino. E. P. 22303, 1901. C. Steinmetz, U. S. P. 669358, 1901; abst.
Kunst. 1913, 3, 390. E. P. 21293, 1900. O. Wheeler, U. S. P. 1049955,
1913; abst. C. A. 1913. 7, 906; Kunst. 1913, 3, 218; Mon. Sci. 1913, 78, 107.

7. J. Gerlache, E. P. 8176, 1909; abst. J. S. C. I. 1910, 29, 568. H.
Monseur, E. P. 23139, 1911; abst. J. S. C. I. 1913, 32, 235. D. Whitehead
and Q. Marino. E. P. 20143, 1905; abst. J. S. C. I. 1906, 25, 1052.

8. C. Schwalbe, Zts. Chem. Ind.. der KoUoide. 1908, 2, 229; abst.
J. S. C. I. 1908, 27, 278. J. ScofiFem, E. P. 1744, 1859; 1380, 1717, 1868.
Annal. du Genie Civil, 1869, 613; Mon. Sci. 1870, 34; Dingl. Poly. 95, 95;
Chem. Centr. 1870, 34; Poly. Centr. 1869, 1596. J. Scoffem and G. Tid-
combe. E. P. 827, 1875. Sedlaczek, Kunst. 1911, 1, 143; abst. Chem. Ztg.
1912, 36, 196; Wag. Jahr. 1911. II, 143. G. Brabrook, U. S. P. 1244463.
1917; abst. J. S. C. I. 1918, 37, 15-A.

9. L. Pink, U. S. P. 1056446, 1056447, 1913. E. P. 2455, 1911. Can.
P. 133161, 1911. D. R. P. Anm. A-711, 1911. See also Nat. Drug. 1912.
10, 465.

10. R. Lissauer, U. S. P. 586907, 1897.

11. R. Reiman, U. S. P. 4^4891, 1893.

12. L. CoUardon, U. S. P. 953319, 1910; Dingl. Poly. 1872, 204, 514;
abst. J. C. S. 1872, 25, 1137. P. Isherwood, E. P. 16364, 1906. L. Jumau,
E. P. 27120. 1906. King's Norton Metal Co., T. Bayliss, H. Brownsdon
and H. Smith, E. P. 13297, 1905; 7472, 1910. Mertens & Co. and H. Jer-
osch, E. P. 18493, 1908. A. Paraf, E. P. 219, 1868. R. Seeman, E. P.
18864, 1900. Soc. Anon. Francaise la Soie Artificielle, F. P. 385083, 1907;
abst. J. S. C. I. 1908, 27, 558; C. A. 1909, 3, 1094. F. P. 385083, 1907; and
addn. 9253, 1908; abst. J. S. C. I. 1908, 27, 1057.

CEl*I*ULOSK 79

Galbert* and P. FoUet and G. Ditzler,* have in the main, been
unsuccessful.

Physical Constants of Cuprammonium Solutions. F. Don-
nan and J. Thomas' have determined at 25° the solubility of
crystalline cuprous oxide in solutions of ammonia of varying
concentrations, and have found that for a certain range of am-
monia concentration, the amount of total copper dissolved is
approximately proportional to the square root of the "free"
ammonia. From this result the conclusion is drawn that in these
solutions the cuprous-ammonium hydroxide present, is mainly of
the type (Cu.NH8)0H.

In the experiments made on the solubility of cellulose in
ammoniacal copper hydroxide and on the relationships existing
between the concentration of ammonia, copper and the quantity
of cellulose dissolved, as carried out by E. Connerade,* it is shown
that a solution of ammoniacal cuprous hydroxide prepared at
low temperatures contains — in comparison with cupric hydroxide

1. F. P. 440846, 1911; J. S. C. I. 1912, 31, 811; Kunst. 1912, 2, 333,
460. F. P. 442117, 1911; abst. J. S. C. I. 1912, Xl, 917; Kunst. 1912, 2, 347.

2. E. P. 22753, 1907; J. S. C. I. 1908, 27, 19. E. P. 21285, 1908; J. S.
C. I. 1909, 28, 87. F. P. 382859, 1907; J. S. C. I. 1908, 27, 221; C. A. 1909,
3, 1093; Mon. Sci. 1908, (4), 68, 166. F. P. 395223, 1908: J. S. C. I. 1909,
28, 307. D. R. P. 210280, 211871, 1906; abst. C. A. 1909, 3, 2630. D. R. P.
223294, 1907; addn. to D. R. P. 211871, 1906. D. R. P. 229677, 1908; C. A.
1911, 5, 2535; J. S. C. I. 1911, 30, 210; Zts. ang. Chem. 1911, 24, 183; Chem.
Zentr. 1911, 1, 274. Belg. P. 190636, 1906; 203196, 1907. Aust. P. 43640. Swiss
P. 41238, 44075, F. Beltzer, Kunst. 1912, 2, 223. B. BiUtt, Le Genie Civil,
1909, 15, 451 ; Chem. Ztg. Rept. 1910, 34, 23. H. Blackmore, U. S. P. 803391,
1905; abst. J. S. C. I. 1905, 24, 1226. H. Boistesselin and C. Gay, F. P.
403193, 1909. J. Brandenberger, D. R. P. Anm. B-62509, 1911. Chem.
Fabr. von Heyden, Belg. P. 232475, 1911. Cramer and Wiesner, Chem.
Tech. Rep. Jacob. 1871, lH, I, 66. R. Freemantie, D. R. P. 137461; Wag.
Jahr. 1903, II, 415. See Wag. Jahr. 1901, 513. J. Foltzer, Kunst. 1911, 1,
301, 390, 404, 427. See J. Foltzer, Belg. P. 189918, 1906. Fremery, Rev.
Ind. 21^ 264. La Soie Artificielle Soc. Anon. Francaise, E. P. 1573, 1912.
E. Richard, Zts. Farben Ind. 1910, 9, 361; abst. Jahr. Chem. 1910, 428.
H. Riesenfeld and F. Traube, Ber. 1905, 38, 2798; abst. Wag. Jahr. 1905,
II, 396; Jahr. Chem. 1905-1908, 987. W. Vieweg, International Congress.
London; abst. Zts. ang. Chem. 1909,^, 1119. H. Vogel, J. Appl. Chem.
Sept. 1872; abst. Am. J. Pharm. 1872, 44, 518. M. Weertz, E. P. 12422,
1910; abst. J. S. C. I. 1911, 30, 798. See also Ding. Poly. 1874, 204, 514;
abst. Chem. Centr. 1872, 827. Chem. Tech. Rep. 1872, 11, I, 105. Neues
Erfindungen unt Erfahrungen, 1874, 1, 516. C. N. 1880, 41, 284. Cosmos,
1899, 40, 450. Mon. Sci. 1908, (4), 68, 657. F. P. 436936, 1911.

3. F. Donnan and J. Thomas, Proc. Chem. Soc. 1911, 27, 213; J. C. S.
1911, 09, 1788; J. S. C. I. 1911, 30, 1250.

4. E. Connerade, Bull. Soc. Chim. Belg. 1914, 28, 176; J. S. C. I. 1914,
28, 744; C. A. 1915, 9, 861; J. C. S. 1914, 106, i, 932. A. Droste, Belg. P.
191200, 1906. E. Legrand, Belg. P. 248521, 1912.

80 T«CHNOW>GY O? CEI/I/UU>S^ ^STRRS

— a large excess of colloidal ammonium cuprous hydroxide. Ac-
cording to this investigator, the solubility of cellulose is directly
proportional to the concentration of the colloidal cuprammonium
solution. The solution of the cellulose is best brought about by the
combination of quantities of colloidal ammoniacal cuprous hydrox-
ide and water in amounts which increase to a point at which an
equilibrium exists between the liquid and solid phases. It is
alleged that the strongly hydrated colloidal complex combines
with ammonia in proportion to its concentration, which tends
to render the complex more stable. Furthermore, the coagulation
of the colloidal complex can be effected reversibly in solution.

Bouzat^ has prepared a number of crystallized cuprammonium
salts. The compound CuCl2.5NH3.'/2H20 is prepared by cooling
an ammoniacal solution of cupric chloride to — 15®, or by passing
ammonia gas into the solution at 0®; it forms small dark blue
crystals, soluble in water. In presence of a large quantity of
water, cupric hydroxide separates. On heating, the compound
CUCI2.2NH3 is formed. On standing over caustic potash in an
atmosphere of ammonia, the salt loses 1 mol. of water, forming
the compound CUCI2.5NH3.V2H2O. /

The salt CuCl2.4NH8.2H2O is produced by allowing an am-
moniacal solution of cupric chloride to evaporate at the ordinary
temperature in an atmosphere of ammonia, or by treating a con-
centrated, hot, ammoniacal solution of cupric chloride with alco-
hol, and allowing to cool. It forms dark blue crystals and has
properties similar to the above-mentioned compound.

The salt CUCI2.2NH3.V2H2O is obtained by heating an am-
moniacal solution of cupric chloride to 50® and then incompletely
precipitating with hot alcohol. It forms bluish green microscopic
crystals smelling faintly of ammonia. Like the corresponding
anhydrous salt, it is decomposed by water.

The cuprammonium sulfate CuS04.4NH8. '/2H2O can be pre-
pared by allowing an ammoniacal solution of copper sulfate to
evaporate over lime; by precipitating such a solution with alco-
hol; by allowing a similar hot concentrated solution to cool;
or by passing ammonia into such a solution. It has similar prop-

1. Ann. Chira. Phys. 1903, (7), 29, 305; abst. Chem. Centr. 1903, II,
417; J, S. C. I. X903, 22, 1045. See also J. S. C. I. 1902, 21, 932, 970, 1158.

CELLULOSE 81

erties to the chloride, CuCl2.4NH3.'/2H20, but less energetic.

The author has determined the thermo-chemical relations of
these salts, and also of the two double salts

CuS04.(NH4)2S04.6H20 and CuCl2.2NH4Cl.2H2O.

Bouzat^ has also investigated the effect of adding bases to
ammonio-cupric salts, and of adding ammonio-cupric hydroxide
to salts of these bases, by determining the resulting thermal
changes. The ammonio-cupric base displaces ammonia com-
pletely from its salts, while ammonia has no effect on the ammonio-
cupric salt. Iij_the case of potash and the ammonio-cupric salt
(or ammonio-cupric base and potassium salt) there is partition,
the potash taking the greater part of the acid; but the amount of
ammonio-cupric salt increases as the excess of ammonia present
increases. This partition is shown also by adding potash to a
solution of ammonio-cupric salt, which then acquires the power
(possessed by the base but not by its salts) of dissolving cellulose;
or by adding a potassium salt to a solution of cellulose in am-
monio-cupric hydroxide, when some of the cellulose is precip-
itated. In the case of lime (or calcium salts) there is also parti-^
tion; but when the ammonio-cupric liquor is strongly ammoniacal,
it will displace lime almost completely from calcium salts, form-
ing a considerable precipitate of lime in the liquid. The am-
monio-cupric hydroxide is thus shown to be a very strong base.

When the ammoniacal solution of cupric hydroxide in excess
of ammonia is allowed to stand over sulfuric acid until a pre-
cipitate begins to appear, the product has the composition ex-
pressed by CUO.25NH3. Bouzat* has made calorimetric measure-
ments on the neutralization by acids of the solution CUO.28NH3,
and concludes that the base is formed from copper oxide and
ammonia with slight evolution of heat, and that, when formed,
it is a strong base, much more energetic than ammonia.

Schiitzenberger and Riesler' have stated that ammoniacal
cuprous oxide absorbs, when shaken with water containing air,

1. Compt. rend. 1902, 134, 1502; abst. J. S. C. I. 1902, 21, 970. See
the researches of E. Connerade, Bull. Soc. Chim, Belg. 1914, 28, 176; Zts.
Chem. Ind. KoU. 1915, 16, 95.

2. Compt. rend. 1902, 134, 1310; abst. J. S. C. I. 1902, 21, 932; J. C.
S. 1903, 84, ii, 21; Chem. Centr. 1902, II, 185; Jahr. Chem. 1902, 068.

3. Ber. 1873, S, 678; BuU. Soc. Chim. 1873, 19, 152; 20, 145; Compt.
rend. 1873, 7G, 440, 1214; Jahr. Chem. 1873, 981.

82 TECHNO]:/)GY OP CBLLULOSE ESTBRS

twice the amount of oxygen necessary to convert it into cupric
oxide, and have accotmted for this, by assuming the formation
of hydrogen peroxide or some similar body. J. Meyer^ has pre-
pared an ammoniacal cuprous solution by adding ammoniacal
sulfate to a boiling solution of sodium sulfite without access of
air, when the reduction occurs rapidly and quantitatively. This
solution is converted quantitatively by hydrogen peroxide into
the cupric condition, so that the two substances cannot co-exist.
Moreover, when shaken up with a known volimie in excess of
moist air, it absorbs exactly the amount needed to convert it
into the cupric solution. The author considers that, Schutzen-
berger's results are due to the fact that he prepared his cuprous
salt by reducing a cupric salt with sodium thiosulfate; he thus
produced cuprous salt and sulfite, and the absorption of the ex-
cess oxygen was eflFected by the sulfite so produced. Direct ex-
periments show that the oxidation of sulfite by moist air is greatly
accelerated by the presence of cupric salts. Arsenites are not
similarly oxidized. Possibly the process of oxidation may con-
sist in the formation of a cupric peroxide, which at once oxidizes
Aore cuprous oxide (2CU2O + Oj = CU2O3 + CU2O = 4CuO),
or may oxidize sulfiu" dioxide if that be present (CujO + O2 +
SO2 = CU2O3 + SO2 = 2CuO + SOz).

In his investigations of the manufacture of cuprammonium
filaments by the Linkmeyer process,^ W. Normann' has found

1. Ber. 1902, 35, 3952; abst. J. S. C. I. 1902, 21, 154. C. Guignet has
shown (Compt. rend. 1889, 109, 528; abst J. C. S. 1889, 56, 1133) that dry
starch or flour readily absorbs cuprammonium solution, decolorizing the liquid.
Starch paste acts in an analogous manner, but the color is rapidly lost. A
deep blue compound is formed from which water and even dilute ammonia
remove only traces of copper. It retains ammonia if heated with water to
40 ^'f the solution becoming pale blue. At 80^ starch paste begins to form,
but retains cupric oxide so tenaciously that tmder microscopic examination
each starch granule is observed to be covered with a dark gray pellicle. In-
ulin behaves in a similar manner.

2. R. Linkmeyer, U. S. P. 795526, 1905; abst. J. S. C. I. 1905, 24,
887. E. P. 4755, 1905; abst. J. S. C. I. 1906, 25, 371. E. P. 4756, 1905.
F. P. 346722, 1904; abst. Wag. Jahr. 1905, II, 396; J. S. C. I. 1905, 24, 238.
D. R. P. 183153, 1904, abst. Wag. Jahr. 1907, II, 394; Zts. ang. Chem. 1907,
20, 1542; Chem. Zentr. 1907, II, 1033; Chem. Tech. Rep. 1907, n, 210;
Mon. Sci. 1909, (4), 70, 166; Jahr. Chem. 1905-1908, 988. Aust. P. 46701.
U. S. P. 796740, 1905; abst. J. S. C. I. 1905, 24, 966. F. P. 352528, 1905;
abst. J. S. C. I. 1905, 24, 967; Mat. Col. 1905, 9, 339. E. P. 6356, 1905;
abst. J. S. C. I. 1905, 24, 967. D. R. P. 169906; abst. Wag. Jahr. 1906, II,
386. Swiss P. 35434. Aust. P. 28595. U. S. P. 839013, 839014, 1906;
abst. J. S. C. I. 1907, 28, 197. F. P. 356402, 1905; abst. J. S. C. I. 1905,
24, 1300. E. P. 4761, 1905; abst. J. S. C. I. 1905, 24, 671; Wag. Jahr. 1905,

cBLi<ui*osa 83

that the coagulated thread, instead of becoming milky white as
is the case when an acid coagulating bath is used, remains blue
and perfectly transparent. This is due to the formation of a
copper alkali cellulose, by the displacement of ammonia by soda
in the cellulose compound. Cupric hydroxide dissolves to a
flight extent in concentrated soda lye giving a blue solution. If
cotton be immersed in this solution the ordinary phenomena of

II, 396. U. S. P. 842568, 1907; abst. J. S. C. I. 1909, 28, 406. E. P. 4765,
1905; abst. J. S. C. I. 1906, 2S, 371. F. P. 361061, 1905; abst. J. S. C. I.

1906, 25, 692. U. S. P. 857640, 1907; abst. J. S. C. I, 1907, 28, 808. E. P.
3649, 1906; abst. J. S. C. I. 1906, 25, 1090. U. S. P. 852126, 1907; abst
J. S. C. I. 1907, 28, 606. D. R. P. 183557; abst. Jahr. Chem. 1905-1908,
988; Wag. Jahr. 1907, II, 394; Chem. Zentr. 1907, II, 1034; Chem. Tech.
Rep. 1907, Jl, 245. D. R. P. 187313, addn. to D. R. P. 183557; abst. Jahr.
Chem. 1905^1908, 988; Wag. Jahr. 1907, II, 195, 394; Chem, Zentr. 1907,
II, 1768; Chem. Tech. Rep. 1907, 31, 423; see also E. P. 4755, 1905. U. S. P.
866371. E. P. 3566, 1906; abst. J. S. C. I. 1907, 28, 252. F. P. 353187,
1905; abst. J. S. C. I. 1905, 24, 1011. D. R. P. 184150; abst. Jahr. Chem.
1905-1908, 988; Wag. Jahr. 1907, II, 395; Chem. Zentr. 1907, II, 1034; Chem.
Tech. Rep. 1907, 31, 245. Aust. P. 35268. Swiss P. 40614 (R. Linkmeyer
and M. PoUak). U. S. P. 945559, 1910. E. P. 4104, 1909 (P. Friederich);
abst. J. S. C. I. 1909, 28, 934. U. S. P. 962769, 1910; abst. J. S. C. I. 1910,
29, 941; see also P. Friederich, D. R. P. 206883, 1907; abst. J. S. C. I. 1909,
28, 362. U. S. P. 962769, 962770, 1910; abst. J. S. C. I. 1910, 29, 941. E. P.
14112, 1909; abst. J. S. C. I. 1910, 29, 622. F. P. 404372. D. R. P. 206883;
see also P. Freiderich, Swiss P. 48679. U. S. P. 979013, 1910. U. S. P.
1000827, 1911; abst. C. A. 1911, 5, 3700. U. S. P. 1022097, 1912; abst.
Kunst. 1912, 2, 354; C. A. 1912, 8, 1675; J. S. C. I. 1912, 31, 429. F. P.
409789, 1909; abst. J. S. C. I. 1910, 29, 750. U. S. P. 1062106, 1913; abst.
J. S. C. I. 1913, 32, 653. E. P. 11700, 1909; abst J. S. C. I. 1909, 28, 1246;

C. A. 1913, 7, 2472. E. P. 1501, 1905; 4746, 1905; abst. J. S. C. I. 1906,
25, 473. F. P. 347960, 1904; abst. Mat. Col. 1905, 9, 209; J. S. C. 1. 1905, 428.
F. P. 346722, 1904; abst. Zts. ang. Chem. 1905, 28, 1108; Bay. Ind.
Gew. Blatt. 1905, 37, 367. F. P. 350889, 352530, 1905; abst. Mat.
Col. 1905, 9, 339. E. P. 6357, 1905. Swiss P. 35435. F. P. 357837, 1905;'
abst. J. S. C. I. 1906, 25, 120. D. R. P. 168830. 1904. Aust. P. 28581.

D. R. P. 175296, 1904; abst. Mon. Sci. 1908, (4), 68, 160; Zts. ang. Chem.

1907, 20, 461; Chem. Tech. Rep. 1906, 30, 334; Chem. Zts. 1906, 8, 9; Wag.
Jahr. 1906, II, 387. Aust. P. 30449. D. R. P. 183557, 1904. D. R. P.
185139, addn. to D. R. P. 175296, 1904; abst. Wag. Jahr. 1907, II, 395;
Zts. ang. Chem. 1907, 20, 1542; Chem. Zentr. 1907, II, 1039; Chem. Tech.
Rep. 1907, 31, 303. D. R. P. 185139, addn. to D. R. P. 176296, 1904.
D. R. P. 222131; abst. Wag. Jahr. 1910, II, 436; Chem. Zentr. 1910.11,51.
D. R. P. 249002, 1911; abst. Kunst. 1912, 2, 352; Wag. Jahr. 1912, II, 437.
Belg. P. 181359, 181360, 1906; 183197, 183198, 186698, 188519, 1905. Can.
P. 94977, 94978, 1905; 101114, 1906. Neues. Erfindungen und Erfahrungen
1906, 33, 130. R. Linkmeyer and M. PoUak, F. P. 350888, 1905; abst. J.
S. C. I. 1905, 24, 800; Mat. Col. 1905, 9, 309. E. P. 1501, 1905; abst. J.
S. C. 1. 1905, 24,670. F. P. 350889, 1905; abst. J. S. C. I. 1905, 24, 888.
Swiss P. 40164, 1907. See also, F. P. 347960; abst. J. S. C. I. 1905, 24, 438.
Belg. P. 181944, 181945, 1905.

3. W. Normann, Chem. Zts. 1906, 30, 47, 584; abst. Gummi. Ztg.
Celluloid Suppl. 1906, 21, 3; J. S. C. I. 1906, 25, 652; Jahr. Chem. 1905-1908,
987; Chem. Centr. 1906, II, 719; Zts. anorg. Chem. 1905, 41, 132.

84 TECHNOWGY OF CBI.LUI.OSK ESTERS

mercerization are observed, but at the same time the fiber is
colored deep blue, and the liquid is decolorized. By repeatedly
renewing the copper solution a saturation point is reached at
which the cellulose ceases to absorb more copper. The compound
can then be washed without dissociation by means of soda lye
of a certain strength, and analysis shows a ratio of cellulose to
copper in the. saturated compound corresponding to the formula
C12H20O10.CUO, or 23.15% of copper oxide. The copper-alkali-
cellulose compound is dissociated by water, pale blue copper
hydroxide being precipitated in the thread. The precipitation of a
cuprammonium solution of cellulose by substitution of the alkali re-
quires a certain concentration of the soda lye; conversely the soda
in the coagulum can be displaced if a large excess of concentrated
ammonia be employed, and the soluble ammonium compound is
i^egenerated. Consequently copper-alkali cellulose can be pro-'
duced in solutions rich in copper by adding sufficient caustic soda
lye to a solution of cuprammonium. The threads of artificial
silk coagulated in a caustic soda bath, and washed in soda lye
are deep blue in color; the copper is immediately removed by
dilute acids, and the decolorized threads retain their perfect
transparency. Additional work has been done upon this sub-
ject by W. Bonsdorff,^ G. Bodlaender and R. Fittig,* K. Koe-
lichen,' E. Berenguer,^ R. Trierenberg,* W. Minajefif,* H. Ost,^
A. Herzog,® E. Berl and A. Innes,* C. Beadle and H. Stevens,^^
F. Tiemann and C. Preusse,^^ J. Koenig and C. Krauch," C.

1. Ber. 1903, 36, 2322; J. C. S. 1902, 84, ii, 692; abst. Chem. Centr.
1904 II 942

'2. ' Zts.' physik. Chem. 1902, S9, 607; abst. J. C. S. 1902, 82, ii, 248;
Jahr. Chem. 1902, 205; Chem. Centr. 1902. I, 656.

3. Zts. Phys. Chem. 1900, 33, 129; abst. J. C. S. 1900, 78, ii, 395.

4. E. P. 10546, 1907; J. S. C. I. 1908, 27, 658; C. A. 1909, 3, 117.

5. Papierfabr. lH, 3; abst C. A. 1912, 6, 2634.

6. Zts. Farben. Ind. 1908, 7, 236; abst. J. S. C. I. 1908, 37, 851; C. A.

1910, 4, 1384.

7. Zts. ang. Chem. 1911, 24, 1892; abst. J. S. C. I. 1911, 30, 1247;
Zts. Chem. Ind. KoU. 1912, lH, 260.

8. Monatsh. fur. tex. Ind. 28, 155; Wag. Jahr. 1911, II, 417; Kunst.

1911, 1, 401, 443; Chem. Ztg. Rep. 1912, 36, 110; C. A. 1912, 6, 2171.

9. Zts. ang. Chem. 1910, 23, 987; Wag. Jahr. 1910, II, 440; Chem.
Ztg. 1910, 34, 532; J. S. C. I. 1910, 29, 687.

10. C. N. 1913, 107, 13; abst. C. A. 1913, 7, 12^; Chem. Zentr. 1913,
I, 970.

11. Ber. 1879, 12, 1768; abst. J. C. S. 1880, 38, 137; Jahr. Chem. 1879,
1027.

12. Zts. anal. Chem. 1880, 19, 269; abst. Jahr. Chem. 1880, 1147; Chem.
News, 1880, 42, 206, 218. See also Ber. 1880, 154; Chem. News, 1880, 41, 216.

CEI.I.UU)S« 85

Engler/ H. Herzog,* W. Manchot and J. Herzog,' Mohr,* C.
Wicke,* W. Jorissen," F. Haber and F. Bran,' S. Bigelow,' and
by L. Meyer and F. Binnecker.®

Applications of the Cuprammonium Celluloses. Fremery
and Urban, under the name of Pauly, in 1897 patented the first
practical process for the manufacture of artificial filaments from
cuprammonium cellulose solutions,*® but inasmuch as ordinary
cellulose dissolves but very slowly in Schweizer's reagent, and the
solution is moreover accompanied by oxidation which modifies
the cellulose molecule so that it is imfit for spinning purposes,
the process was not a commercial success until Bronnert pro-

1. Ber. 1900, 33, 1102; abst. Jahr. Chetn. 1900, 19; Chem Centr. 1900,
I, 1153, 1154.

2. Dissertation, Gott. 1901.

3. Ann. 1901, 316, 318; abst. Jahr. Chem. 1901, 1519; Chem. Centr.
1901, II, 350.

4. Lehrb. anal. Titrirmeth. 1855, 271.

5. Zts. ffir Chem. 1865, 89, 305; abst. Jahr. Chem. 1865, 265, 725;
Chem. Centr. 1865, 493; Zts. anal. Chem. 1865, 4, 424.

6. Zts. phys. Chem. 1897, 23, 667; abst. Jahr. Chem. 1897, 449; Chem.
Centr. 1897, II, 724; Maandbl. Natuurw. 21, 79.

7. Zts. phys. Chem. 1900, 34, 513; 1903, 35, 81; abst. Jahr. Chem.

1900, 190; Chem. Centr. 1900, II, 936; 1901, I, 84.

8. Zts. phys. Chem. 1898, 28, 493; abst. J. C. S. 1898, 74, il, 506; Jahr.
Chem. 1898, 246.

9. Ber. 1887, 20, 3058; abst. Jahr. Chem. 1887, 13. See also Kessler,
Jahr. Chem. 1863, 124. Harcourt, Jahr. Chem. 1864, 9.

10. U. S. P. 617009, 1899; abst. Mon. Sci. 1900, 56, 6; 650715, 1900;
abst. Rev. Chim. 1900, 3, 32. 657818, 1900; 658632, 1900; abst. J. S. C. I.

1901, 20, 38. 661214, 1900; 672350, 1901; abst. Mon. Sci. 1901, 57, 283.
691257, 1902: abst. J. S. C. I. 1902, 21, 272. 698254, 1902; abst. J. S. C. I.

1902, 21, 705; Mon. Sci. 1902, 58, 161. 705748, 1902; abst. J. S. C. I. 1903,
21, 1150; Mon. Sci. 1903, 59, 165. 804191, 1905; abst. J. S. C. I. 1905, 24,
226, 1251; Mon. Sci. 1906, 85, 69. 856857, 1907; abst. J. S. C. I. 1907, 28,
836; C. A. 1907, 1, 924; Mon. Sci. 1907, 87, 159. E. P. 28631, 1897; 6557,
1899; abst. J. S. C. I. 1900, 10, 239. 6641, 1899; abst. J. S. C. I. 1900, 10,
240. 6656, 1899. 6735, 1899; abst. J. S. C. I. 1900, 10, 344. 20630, 1899;
abst. J. S. C. I. 1900, 10, 821. 24101, 1899; abst. J. S. C. I. 1900, 10, 1105;
1902, 21, 1150; Rev. Chim. 1900, 2, 34. 4303, 1900; abst. J. S. C. I. 1901,
20, 1207. 20801, 1900; abst. J. S. C. I. 1901, 20, 1231; J. Soc. Dyers Col.
1901, 17, 295; Chem. Zts. 1901-1902, 1, 580. F. P.: 286692, 1899; abst.
Rev. Chim. 1900, 2, 175; first addn. dated Oct. 14, 1899 to F. P. 286692, 1899;
abst. Rev. Chim. 1900, 2, 444. 286726, 1899; abst. Rev. Chim. 1900, 2,
303; first addn. dated Dec. 4, 1899, to F. P. 86726, 1899. 286925, 1899; abst.
Mon. Sci. 1899, 54, 198; Rev. Chim. 1899, 1, 441. D. R. P. 111313,
1899; abst. Chem. Centr. 1900, II, 550; Wag. Jahr. 1900, II, 448. 111409;
abst. Wag. Jahr. 1900, II, 447; 111790, addn. to D. R. P. 111409. 121429,
1899; abst. Mon. Sci. 1901, 57, 283. 121430, 1899; addn. to D. R. P. 121429,
1899; abst. Mon. Sci. 1901, 57, 283. 271656, 1912; abst. C. A. 1914, 8, 2813;
Kunst. 1914, 4, 193. Belg. P. 141697, 141721, 141756, 145510, 146487,
1899; 147579, 1900; 155637, 1901. Aust. P. 3636, 6843, 11879. Swiss P.
16077, 1898. Can. P. 60705, 1898. Ind. Text. 18, 352.

86 TECHNOIX)GY OF CEI^I^UtOSK ESTERS

posed the use of celltilose hydrate mstead of cellulose as the initial
cellulosic material, and thus laid the foundation for the cupram-
monium silk industry of today.

Cuprammonium artiiScial filaments, known as "Glanzstofif,"
"Pauly SUk," "CuprateSilk," "Kuproid," "Lustracellulose," "Sole
de Hal/* and "Parisian Silk," in the trade, are produced by forc-
ing cuprammonium cellulose solutions, through glass or platinum
spinnerets into a coagulating solution, washing out the reacting
chemicals, and drying and otherwise treating the filaments thus
formed. The processes for this purpose as patented by A.
Lecoeur,^ D. Lance,* A. Lacroix, J. Sella and J. de Sauverzac,'
A. Kracht,* E. Knecht, A. Perl and P. Spence & Sons, Ltd.,*
A. Hart,' R. Homberg,^ J. Hartogs,' Hanauer Kunstseiderfab-

1. U. S. P. 863801, 1907. E. P. 8910, 1906; abst. J. S. C. I. 1906, 25,
984. F. P. 362986, 365099, 1906; abst. J. S. C. I. 1906, 25, 808, 925. D. R. P.
185294, 1906; abst. Wag. Jahr. 1907, II, 393; Chem. Ztg. Rep. 1907, 31,
303; Zts. ang. Chem. 1907, 20, 1542; Chem. Zentr. 1907, II, 1035. Aust. P.
30496. U. S. P. 863802, 1907. E. P. 16442. 1906; abst. J. S. C. I. 1907,
28, 963. F. P. 374277, 1906; abst. J. S. C. I. 1907, 28, 761; Mon. Sci. 1908,
(4), 68, 28. U. S. P. 967397, 1910. F. P. 381939, 1907; abst. J. S. C. I.
1908, 27, 221. E. P. 18936, 1907; abst. J. S. C. I. 1908, 27, 745; C. A. 1909,
3, 380. U. S. P. 980294, 1911; C. A. 1911, S, 1188; Kunst. 1911, 1, 174;
J. S. C. I. 1911, 30, 126. F. P. 410827, 1909; abst. J. S. C. I. 1910, 29, 810;
E. P. 22413, 1909. E. P. 14143, 1908; abst. C. A. 1910, 4, 108. F. P. 392868,
1907; abst. J. S. C. I. 1909, 28, 88; Mon. Sci. 1909, (4), 70, 147. E. P. 21191,
1908; (Soc. anon. LeCrinoid). F. P. 392869, 1907; abst. J. S. C. I. 1909.
28, 88. Belg. P. 189870, 1906.

2. F. P. 435156, 1910; abst. J. S. C. I. 1912, 31, 328. Belg. P. 234303,
1911. Compare Rheinische Kunstseidefabrik, Aust. Anm. A-9791, 1911.
H. Heyderhaus, A. Banhegyi and K. Glaser, F. P. 406139, 1909; abst. J. S.
C. I. 1910. 29, 417. P. Minck, U. S. P. 1317306; abst. C. A. 1919, 13, 3316.

3. F. P. 402125, 1908; abst. Mon. Sci. 1910, (4), 24, 290.

4. F. P. 355064, 1905; abst. J. S. C. I. 1905, 24, 1226; Mon. Sci. 1906,
85, 167. Belg. P. 183521, 1905.

5. E. P. 25532, 1911; abst. J. S. C. I. 1913, 32, 18; C. A. 1913, 7, 1608;
Kunst. 1913, 3, 73. F. P. 449801, 1912; abst. J. S. C. I. 1913, 32, 483. E. P.
25533, 1911; abst. J. S. C. I. 1913, 32, 18; C. A. 1913, 7, 1608; Kunst. 1913,
3, 73. F. P. 449803, 1912; abst. J. S. C. I. 1913, 32, 483. E. P. 25534, 1911 ;
abst. J. S. C. I. 1913, 32, 19; C. A. 1913, 7, 1608; Kunst. 1913, 3, 74. F. P.
449802, 1912; abst. J. S. C. I. 1913, 32, 483.

6. E. P. 18607, 1910; J. S. C. I. 1911, 30, 1448. F. P. 433013, 1911;
J. S. C. I. 1912, 31, 123; Mon. Sci. 1913, 78, 24. See E. Cruraiere, U. S. P.
9(M684. Belg. P. 194941, 1906; 205672, 206788, 1908. D. R. P. 201915,
1908; abst. Chem. Ztg. 1909, 33, 66; Zts. Chem. Ind. KoU. 1908, 3, 245.

7. U. S. P. 983139, 1911; J. S. C. I. 1911, 30, 278. D. R. P. Anm.
H-51313, 1910. D. R. P. 2,35,306, 1910; C. A. 1911, 5, 3169; J. S. C. I. 1911,
30, 1248; Zts. ang. Chem. 1911, 24, 1499; Chem. Zentr. 1911, II, 175; Wag.
Jahr. 1911, II, 418; Kunst, 1911, 1, 275. D. R. P. 237717, 1909; J. S. C. I.
1911, 30, 1248; C. A. 1912, 8, 1679; Zts. ang. Chem. 1911, 24, 1988; Chem.
Zentr. 1911, II, 922; Wag. Jahr. 1911, II, 418; Kunst. 1911, 1, 378. Belg.
P. 227722 1910.

8. U. S. P. 1119155, 1914; abst. C. A. 1915, 9, 247; J. S. C. I. 1915,

/

CELI.UW)SE 87

rik,^ G. Guadagni,^ Glanzfaden Akt. Ges.,' R. Frericks/ and also F.

34, 25. D. R. P. 237744, 1910; abst. J. S. C. I. 1911, 30, 1249; Chem. Zentr.
1911, II, 814; Wag. Jahr. 1911, II, 423.

1. U. S. P. 839825, 1907; J. S. C. I. 1907, 28, 340; C. A. 1907, 1, 791.
U. S. P. 840611, 1907; J. S. C. I. 1907, 2S, 340; C. A. 1907, 1, 792. E. P.
10164, 1907; J. S. C. I. 1907, 28, 1026; C. A. 1907, 1, 2651. E. P. 10165,
1907; J. S. C. I. 1907, 28, 888. F. P. 377325, 1907; J. S. C. I. 1907, 28. 1026.
F. P. 377326, 1907; J. S. C. I. 1907, 28, 1004; Mon. Sci. 1908, (4), 88, 29.
D. R. P. 187696, 1906; Chem.. Zentr. 1907, II, 1768; Jahr. Chem. 1905-1908,
988; Chem. Tech. Rep. 1907, », 449; Chem. Ind. 1907, 30, 451; Wag. Jahr.

1907, II, 392; Mon. Sci. 1910, (4), 72, 76. D. R. P. 220711, 1909; 221041,
1908; C. A. 1910, 4, 2732; J. S. C. I. 1910, 29, 689; Chem. Zentr. 1910, 1, 1662;
Jahr. Chem. 1910, 427; Wag. Jahr. 1910, II, 429. D. R. P. 222873, 1908;
Jahr. Chem. 1910, 427. D. R. P. 222893, 1908; addn. to D. R. P. 221041,
1908; J. S. C. I. 1910, 29, 875. D. R; P. 231693, 1906; C. A. 1911, 5, 2737;
J. S. C. I. 1911, 30, 484; Chem. Zentr. 1911, I, 770; Wag. Jahr. 1911, II, 416;
Kunst. 1911, 1, 114. D. R. P. 232873, Wag. Jahr. 1910, II, 430; C. A. 1911,
5, 2737, 3157. D. R. P. 233370, 1908; C. A. 1912, 8, 1854. D. R. P. 235219,
1909; C. A. 1911, 5, 3157; J. S. C. I. 1911, 30, 484; Zts. ang. Chem. 1911,
24, 1341; Chem. Zentr. 1911, II, 119; Wag. Jahr. 1911, II, 416; Kunst. 1911,
1, 275. D. R. P. 240242, 1908; C. A. 1912, 8, 2169; J. S. C. I. 1911, 30,
1447; Zts. Chem. Ind. KoU. 1912, 10, 62; Zts. ang. Chem. 1911, 24, 2334;
Chem. Zentr. 1911, II, 1567; Wag. Jahr. 1911, II, 417; Kmist. 1911, 1, 456.
D. R. P. 255549, 1911; C. A. 1913, 7, 1811; J. S. C. I. 1913, 32, 420; Kunst.
1913, 3, 20, 53. D. R. P. 260650, 1908; C. A. 1913, 7, 3237; J. S. C. I. 1913,
32, 748. Aust. P. 50506, 1909; Kunst. 1912, 2,-ir5. Belg. P. 199881, 199882,
1907.

2. U. S. P. 977863, 1910; J. S. C. I. 1911, 30, 19; C. A. 1911, 5, 994.
U. S. P. 978878, 1910; C. A. 1911, 5, 995. U. S. P. 979013, 1910. E. P.
1265, 1908; J. S. C. I. 1908, 27, 682. E. P. 25986, 1910; C. A. 1912, 8, 161;
J. S. C. I. 1911, 30, 1050; Kunst. 1911, 1, 416. F. P. 386339, 1908; J. S. C. I.

1908, 27, 682. D. R. P. 216669, Chem. Zentr. 1910, I, 217; Jahr. Chem.

1910, 426; Chem. Tech. Rep. 1910. 34, 23; Chem. Ind. 1909, 32, 837; Wag.
Jahr. 1909, II, 394. Aust. P. 51799, Kunst. 1912, 2, 156. Belg. P. 205243,

1908. Swiss P. 42305, 1908.

3. D. R. P. 228872, 1908; abst. C. A. 1911, 5, 2177; Zts. ang. Chem.

1911, 24, 1151; Chem. Zentr. 1911, I, 51; Kunst. 1911, 1, 34. D. R. P.
230141, 237716, 241921, being addn. to D. R. P. 228872. Aust. P. 46861.
F. P. 400321 (F. Friedrich). Swiss P. 45764. E. P. 4104, 1909. U. S. P.
945559 (R. Linkmeyer). D. R. P. 230141, 1908; addn. to D. R. P. 228872,
1908; abst. C. A. 1911, 5, 2732; J. S. C. I. 1911, 30, 1248; Zts. ang. Chem.
1911, 24, 286; Chem. Zentr. 1911, I, 364; Wag. Jahr. 1911, II, 414; Kunst.
1911, 1, 74. D. R. P. 237716, 241921; addn. thereto. F. P. 10732, addn.
to F. P. 400321 (P. Friedrich). E. P. 7617, 1909. Swiss P. 48576. U. S. P.
979013 (R. Linkmeyer). Aust. P. 47147 (P. Friedrich). D. R. P. 237716,
1908; addn. to D. R. P. 228872, 1908; abst. C. A. 1912, 8, 1679; J. S. C. I.
1911, 30, 1248; Zts. ang. Chem. 1911, 24, 1988; Chem. Zentr. 1911, II, 922;
Kunst. 1911, 1, 378. U. S. P. 962770. F. P. 404372. E. P. 14112, 1909 (R.
Linkmeyer). Swiss P. 48679 (P. Friedrich). D. R. P. 241683, 1909; abst.

C. A. 1912, 8, 2170; J. S. C. I. 1912, 31, Zts. ang. Chem. 1912, 25, 286; Wag.
Jahr. 1911, II, 418; Kunst. 1912, 2, 57. D. R. P. 241921, 1909; addn. to

D. R. P. 228872; abst. C. A. 1912, 8, 2181; Zts. ang. Chem. 1912, 25, 286.
D. R. P. 269787, 1908; abst. C. A. 1914, 8, 2251 ; Kunst. 1914, 4, 40, 96. D. R.
P. 286297, 1913; abst. C. A. 1916, 10, 1101; J. S. C. I. 1916, 35, 173. D. R.
P. Anm. 26613, 1908; 26679; abst. Kunst. 1913, 3, 140. F-28001, 28869,

1909. G-39779, 1913; abst. Kunst. 1914, 4, 384.

4. U. S. P. 729749, 1903; abst. Mon. Sci. 1903, 59, 165. D. R. P.
137461; abst. Wag. Jahr. 1903, II, 415; Chem. Zts. 1902-1903, 2, 438. Ac-

88 TECHNOLOGY OF CELLULOSB BSTRRS

G. Donnersmarck'sche Kunsteiden und Acetatwerke/ W.
Dreaper,^ G. Ditzler,' R. Adler/ J. BoulHer and J. Lafais,* G.
Boucquey,' H. Bernstein,^ A. Pellerin,^ R. Pawlikowski," Palatine
Artificial Silk Yarn Co., Ltd./^* Rheinische Kunstseide Fabrik,^^

cording to E. Rasser (Papier Fabr. 1918, 16, 621, 645; C. A. 1919, 13, 1926,
2277) textile papers and yam may be waterproofed by impregnation with
a solution of parchment clippings in cuprammonium hydroxide, followed by
removal of the copper and formation of a basic aliuninum sulfate on the
fibers by means of an aluminum soap.

1. F. P. 398424, 1909. D. R. P. 212594; abst. Chem. Zentr. 1909, II,
774; Wag. Jahr. 1909, II, 203. E. P. 1407, 1909; abst. J. S. C. I. 1910, 23,
208. Swiss P. 47395.

2. E. P. 27222, 1905. Belg. P. 196857, 1906. F. P. 373088, 1906.
E. P. 11959, 1908; J. S. C. I. 1909, 28, 791. E. P. 20316, 1908; J. S. C. I.

1909, 28, 121; J. Soc. Dyers Col. 1909, 2S, 314; C. A. 1910, 4, 827. Belg. P.
196857, 1906.

3. D. R. P. 244510, 1911; C. A. 1912, 6, 2327; Zts. ang. Chem. 1912,
25, 1034; Wag. Jahr. 1912, II, 439; Kunst. 1912, 2, 100. E. P. 9336, 1911;
abst. C. A. 1912, G, 3019; J. S. C. I. 1912, SI, 180; J. Soc. Dyers Col. 1912,

28, 120; Kunst. 1912, 2, 134. Belg. P. 225041, 226352, 1910.

4. U. S. P. 1169756, 1916; abst. C. A. 1916, lH, 973; J. S. C. I. 1916,
35, 303; Mon. Sd. 1916, 83, 78.

5. J. BouUier and J. Lafais, E. P. 16512, 1907; 15015, 1908. F. P.
392442, 1908; J. S. C. I. 1908, 27, 1201.

6. F. P. 368706, 1906; J. S. C. I. 1907, 26, 17. F. P. 376065, 1907;
Mon. Sci. 1908, 68, 87. Belg. P. 186233, 1905; 191080, 1906.

7. U. S. P. 798868, 1905; 960791, 1910; J. S. C. I. 1910, 29, 810; C. A.

1910, 4, 2574. U. S. P. 965273, 1910; C. A. 1910, 4, 2732; J. S. C. I. 1910,

29, 1105. U. S. P. 965557, 1910; J. S. C. I. 1910, 29, 1105. E. P. 849, 1911.
E. P. 15991, 1910; C. A. 1911, 5, 3622; J. S. C. I. 1911, 30, 957. F. P. 418282,
1910; Mon. Sci. 1913, 78, 86. D. R. P. Anm. B-59472, 1910. D. R. P.
248303, 1910; Kunst. 1912, 2, 240, 295; Zts. ang. Chem. 1912, 25, 1804;
C. A. 1912, 6, 3019; Wag. Jahr. 1912, II, 440. D. R. P. 254029, 1905; J. S.
C. I. 1905, 24, 1011. Swiss P. 53440, 1910; Kunst. 1912, 2, 156. Can. P.
100206, 1906. Belg. P. 227339, 1910.

8. Belg. P. 255192; abst. Kunst. 1914, 4, 16. Swiss P. 64190, 1913;
abst. C. A. 1914, 8, 2482. D. R. P. 271215; abst. C. A. 1914, 8, 2491.

9. E. P. 16629, 1910; abst. J. S. C. I. 1911, 30, 1009; C. A. 1911, 5,
3919. F. P. 417851, 1910; abst. Kunst. 1911, 1, 196. D. R. P. 235325,
1910; abst. Chem. Zentr. 1911, II, 119; C. A. 1911, 5, 3169. E. P. 17089,
1910; abst J. S. C. I. 1911, 30, 1052. F. P. 403488, 1909; abst. Mon. Sci.
1910, 73, 169; C. A. 1911, 5, 1514. D. R. P. 222624, 1908; abst. C. A. 1910,
4, 3004; Wag. Jahr. 1910, II, 260; Jahr. Chem. 1910, 427. Aust. P. 49170;
abst. Kunst. 1911, 1, 378. Swiss P. 49399. F. P. 431074, 1911; abst. J. S.
C. I. 1911, 30, 1375; Kunst. 1912, 2, 17. D. R. P. 237200, 1909; abst. C. A.
1912, 6, 1536; Chem. Zentr. 1911, II, 500; Kunst. 1911, 1, 339. D. R. P.
237240, 1909. D. R. P. 248172, 1910; abst. Zts. ang. Chem. 1912, 25, 1548;
Kunst. 1912, 2, 254; C. A. 1912, 6, 3019; Wag. Jahr. 1912, II, 440. D. R. P.
Applications P-24172, 1909; P-25543, 25760, 26509, 1910; V-4289, 1909.
Belg. P. 216341, 216546, 1909; 236204, 1911. Swiss P. 49399, 1909. Aust.
P. Application A-4926, 1911.

10. E.P.9336,1911;abst.C.A.1912.6,3019;J.S. C.I. 1912, 31, 183; J.
Soc. Dyers Col. 1912, 28, 120; Kunst. 1912, 2, 134.

11. F. P. 405571; abst. J. S. C. I. 1910, 29, 417. D. R. P. 231652,
1909; abst. C. A. 1911, 5, 2737; Chem. Zentr. 1911, I, 770; Wag. Jahr. 1911,
II, 415. D. R. P. 236537, 1908; abst. C. A. 1912, 6, 1231; Chem. Zentr.

CBLLUIX)S^ 89

Soc. anon. laSoienouvelle,^ Soc. la Sole Artificielle de Nord,* E.
Thiele and Soc. Gen. de la Sole Artificielle Linkmeyer,' Ver.
Kunstseidefabriken,* J. Vermeesch,* Consortium Mulhousien pour
la fabrication de fils/ Farb. vorm. Meister, Lucius and Briining,^

1911, II, 326; Wag. Jahr. 1911, II, 415. D. R. P. 237816, 1910; abst. C. A.

1912, G, 1679; Chem. Zentr. 1911, II, 1085; Wag. Jahr. 1911, II, 416. E. P.
18342, 1909; abst. J. S. C. I. 1910, 29, 557.

1. F. P. 366067, 1906; abst. C. A. 1907, 1, 2429; J. S. C. I. 1906, 25,
1041. U. S. P. 836620. E. P. 9254, 1906; abst. J. S. C. I. 1907, 28, 91,
262 (J. Vermecsch).

2. F. P. 379000, 1906; abst. J. S. C. I. 1907, 26, 1196. F. P. 385053.
1907; abst. Mon. Sci. 1908, (4), 68, 166; same as D. R. P. of Apr. 27, 1907.
F. P. 442019. Belg. P. 244554, 1912.

3. E. P. 15133, 1906; abst. J. S. C. I. 1906, 25. 1040. F. P. 367979;
abst. J. S. C. I. 1906, 25, 1144. U. S. P. 909257 (E. Thiele) : abst. J. S. C. I.
1909, 28, 137. E. P. 16088, 1906; abst. J. S. C. I. 1907, 26, 45. D. R. P.
179772; abst. Wag. Jahr. 1906, II, 392; C. A. 1907, 1, 2202; Zts. ang. Chem.
1907, 20, 461; Chem. Zentr. 1907, I, 1472; Chem. Tech. Rep. 1907, SA, 37.
F. P. 357837. Aust. P. 35264. E. Thiele, Belg. P. 171980, 1903; 192866,
1906. Soc. Gen. de la Soie Artificielle Linkmeyer, Belg. P. 185875, 188519,
1906. See also R. Linkmeyer, Belg. P. 181360, 1904; 181944, 183945, 183603,
186898, 1905. E. Thiele, U. S. P. 710819; abst. J. S. C. I. 1902, 21, 1393.
E. P. 8083, 1902; abst. J. S. C. I. 1903, 22, 550. F. P. 320446, 1902; abst.
J. S. C. I. 1903, 22, 25. D. R. P. 154507; abst. Wag. Jahr. 1904, II, 392;
1906, II, 391. D. R. P. 157157; addn. to D. R. P. 154507; abst. Wag. Jahr.
1904, II, 507. D. R. P. 173628, addn. to D. R. P. 154607; abst. C. A. 1907,
1, 673; Chem. Centr. 1905, I, 576, 1906, II, 900; Jahr. Chem. 1905-1908,
987; Mon. Sci. 1908, (4), 68, 160; Zts. ang. Chem. 1910, 987. Aust. P. 21119.

D. R. P. 226161; addn. to D. R. P. 154607; abst. Wag. Jahr. 1910, II, 431;
Chem. Zentr. 1910, II, 1010; Kmist. 1911, 1, 16; Jahr. Chem. 1910, 427;
U. S. P. 909257, 1909; abst. J. S. C. I. 1909, 28, 137; C. A. 1909, 3, 1090.

E. P. 15133, 1906 (E. Thiele and Soc. Gen. Art. Linkmeyer); abst. J. S. C. I.
1906, 25, 1040. F. P. 367979. Aust. P. 37119. Belg. P. 192866, 1906;
264161; abst. Kunst. 1913, 3, 357. Rev. Prod. Chim. (21), 3, 325; abst.
J. S. C. I. 1901, 20, 1 19. Zts. Farben, 1902, 73 ; abst. Wag. Jahr. 1902, II, 470.

4. D. R. P. 184510; abst. C. A. 1908, 2, 347; Chem. Zentr. 1907, II,
1035; Chem. Tech. Rep. 1907, 31, 257; Wag. Jahr. 1907, II, 391. D. R. P.
230941, 1908; abst. J. S. C. I. 1911, 30, 484; C. A. 1911, 5, 2736; Zts. ang.
Chem. 1911, 24, 479; Chem. Zentr. 1911, I, 697; Wag. Jahr. 1911, II, 941;
Kunst. 1911, 1, 91, 114. U. S. P. 986017 (F. Lehner). Aust. P. 57698;
abst. Kunst. 1913, 3, 178. Belg. P. 164907, 164908, 1902.

6. U. S. P. 836620, 1906; abst. J. S. C. I. 1907, 26, 91; C. A. 1907, 1,
603. E. P. 9264, 1906; abst. C. A. 1907, 1, 1490; J. S. C. I. 1907, 26, 252.

F. P. 365057 (Soc. Anon. La Soie. Nouvelle.). U. S. P. 850695, 1907; abst.
J. S. C. I. 1907, 26, 527; C. A. 1907, 1, 1787. F. P. 369973, 1906; abst. J. S.
C. I. 1907, 26, 319. E. P. 20408, 1906. Belg. P. 190509, 1906; 195684, 1906
(J. Vermeesch and F. Scheys). Belg. P. 188529, 1906 Q. Vermeesch and H.
Monge).

6. F. P. 290405, 290406, 1899; abst. Mon. Sci. 1900, 56, 126. Belg. P.
143669, 143570, 146201, 1899. E. P. 13331, 1899; abst. J. S. C. I. 1900, 18,
631.

7. U. S. P. 779176, 1905; abst. J. S. C. 1. 1905, 24, 129. E. P. 21988,
1904; abst. J. S. C. I. 1905, 24, 1010. F. P. 350220, 1905. D. R. P. 186387;
abst. Jahr. Chem. 1905-1908, 989; Chem. Zentr. 1907, II, 1134, 1815; Wag.
Jahr. 1907, 391; Chem. Tech. Rep. 1907, 31, 361. Aust. P. 28151. D.
R. P.190217, addn. to D. R. P. 186387. Belg. P. 180370, 1914.

90 TECHNOLOGY O? CELLULOSE ESTERS

H. Luxburg,* J. Hermans,* R. Miiller,^ J. Bemberg/ J. Foltzer
and J. Vermeesdi,** Le Crinoid See. Anon.,* F. Lehner,^ K.
Mueller, J. Schwarz and M. Scheid,* C. Muellet,* C. Mueller and
D. Wolf,^® Vereinigte GlanzstoflF Fabriken.^^ E. Bron-

1. E. P. 1407, 1909. F. P. 398424, 1909; abst. J. S. C. I. 1909, 28,
880; 1910, 29, 208.

2. U. S. P. 1034235, 1912; C. A. 1912, S, 3018; J. S. C. I. 1912, 31,
811; Mon. Sci. 1913, 78, 110; Kunst. 1913, 3, 16. E. P. 4610, 1912; J. S. C. I.
1912, 31, 1075. F. P. 440907, 1907; J. S. C. I. 1912, », 812.

3. U. S. P. 779175, 1905; abst. J. S. C. I. 1905, 24, 129; Chem. Zts.
1905 4 89 540.

'4.' D. R.P. 162866, 1900; Jahr. Chem. 1905-1908, 987; Wag. Jahr.
1905, II, 393; J. S. C. I. 1906, 25, 38. D. R. P. 174508, 1905, addn. to D. R.
P. 162866, 1900; Wag. Jahr. 1906, II, 386; C. A. 1907, 1, 951; Mon. Sci. 1908,
(4), 68, 160.

5. Belg. P. 181525, 1906.

6. U. S. P. 980294, 1911. E. P. 22413, 1909; abst. J. S. C. I. 1910,
29, 1053; C. A. 1911, 5, 2429; Kunst. 1911, 1, 34. F. P. 410827, 1909; abst.
J. S. C. I. 1910, 29, 810. Belg. P. 217312, 1909.

7. Belg. P. 153296, 1900.

8. E. P. 3725, 1890; abst. J. S. C. I. 1891, lH, 539.

9. F. P. 373429, 1907; abst. Mon. Sci. 1908, (4), 68, 83; J. S. C. I.
1907, 26, 713.

10. E. P. 5659, 1912. F. P. 443133, 1912; abst. J. S. C. I. 1912, 31,
1029' 1913 32. 133.

11. Verein. GJanzstofif-Fabriken, A. G., E. P. 1283, 1905; abst. J. S. C. I.
1905, 24, 1251. U. S. P. 806533. F. P. 351208, 1905; abst. J. S. C. I. 1905, 24,
856. D. R. P. 169567; abst. Wag. Jahr. 1906, II, 385; J. S. C. 1. 1906, 25, 775;
Mon. Sci. 1908, (4), 68, 45. See also F. P. 351206, 1905. E. P. 1284, 1905; abst.
J. S. C. I. 1905, 24, 1106. F. P. 351206, 1909; abst. J. S. C. I. 1905, 24,
855. U. S. P. 856857. D. R. P. 186766, 1904; abst. Mon. Sci. 1910, (4),
72, 76; Zts. ang. Chem. 1908, 21, 271; Chem. Zentr. 1907, II, 1767; Chem.
Tech. Rep. 1907, 31, 395; Chem. Ind. 1907, 30, 413; Wag. Jahr. 1907, 390.
See also E. P. 1745, 1905; abst. J. S. C. I. 1905, 24, 1320. F. P. 351207,
351208, 1905; abst. J. S. C. I. 1905, 24, 856; Mat. Col. 1905, 9, 503. U. S. P.
804191. Aust. P. 32377. D. R. P. 186766, 1904; abst. Chem. Tech. Rep.
1907, 31, 395; Wag. Jahr. 1907, 390; Chem. Zentr. 1907, II, 1767. D. R. P.
188113, 1905, addn. to D. R. P. 186766, 1904; abst. Mon. Sci. 1910, (4), 72,
76; Chem. Zentr. 1907, II, 1768; Chem. Tech. Rep. 1907, 31, 504; Wag. Jahr
1907, 390. E. P. 16495, 1907; abst. J. S. C. I. 1907, 26, 1004. F. P. 379935.
1907; abst. J. S. C. I. 1907, 26, 1237. D. R. P. 235134, 1906; abst. Kimsf,
1911, 1, 255; Zts. ang. Chem. 1911, 24, 1340; Chem. Zentr. 1911, II, 64.
Aust. P. 35269. Swiss P. 41109, 1907. See also D. R. P. 259816, 1910;
abst. C. A. 1913, 7, 3227; Kunst. 1913, 3, 196. E. P. 18936, 1907. E. P.
22092, 1907. Aust. P. 35272. E. P. 27707, 1907; abst. J. Soc. Dyers.
Col. 1909, 25, 17. D. R. P. 208472, 1907; abst. C. A. 1909, 3, 2052; Chem.
Zentr. 1909, I, 1370; Chem. Ztg. Rep. 1909, 216; Chem. Tech. Rep. 1909,
32, 216; Chem. Ind. 1909, 32, 211; Wag. Jahr. 1909, II, 392; Chem. Zts.
1909, 8, 1395. D. R. P. 218490, addn. to D. R. P. 208472; abst. C. A. 1910,

4, 2044; Chem. Zentr. 1910, I, 784; Jahr. Chem. 1910, 426; Chem. Tech.
Rep. 1910, 34, 135; Chem. Ind. 1910, 33, 154; Wag. Jahr. 1910, II, 427; Chem.
Zts. 1910, 9, 1836. D. R. P. 229863, addn. to D. R. P. 208472. Aust. P.
35275. F. P. 9253, addn. to F. P. 385083 (Soc, Anon. La Soie Artificielle).
Swiss P. 41554, 1907. E. P. 9268, 1908; abst. J. S. C. I. 1908, 27,
897. D. R. P. 229863, addn. to D. R. P. 208472; abst. C. A. 1911,

5, 2723; Ztg. ang. Chem. 1911, 24, 285; Chem. Zentr. 1911, 1, 364; Wag. Jahr.

cEi*i.ui/)S^ 91

nert,^ and others,^ are among the numerous investigators whose
results are described in detail in Volume IV of this present series.

1911, II, 414; Kunst. 1911, 1, 74. Aust. P. 35275. F. P. 385083 (Soc. anon.
La Soie AritficieUe). E. P. 309, 1911; abst. J. S. C. I. 1911, 30, 484. U. S.
P. 1055513; abst. J. S. C. I. 1913, 32, 422. F. P. 424621, 1911. E. P. 15700,
1910; abst. Kunst. 1911, 1, 75. E. P. 27539, 1910; abst. J. S. C. I. 1911,
30, 415. F. P. 423064. D. R. P. 239214; abst, C. A. 1912, S, 2169; Zts.
ang. Chem. 1911, 24, 2229; Wag. Jahr. 1911, 419; Kunst. 1911, 1, 456. E. P.
27600, 1910; abst. J. S. C. I. 1911, 30, 616. U. S. P. 1049201 ; abst. J. S. C. I.
1913, 32, 133. F. P. 423104; abst. J. S. C. I. 1911, 30, 615. D. R. P. 235476;
abst. Zts. ang. Chem. 1911, 24, 1499; Chem. Zentr. 1911, II, 175. E. P.
29046, 1910; abst. J. S. C. I. 1911, 30, 1051; C. A. 1912, 6, 1526. F. P.
424419, 1910; abst. J. S. C. I. 1911, 30, 740. E. P. 29246, 1910; abst. J. S.
C. I. 1911, 30, 888. F. P. 423774, 1910; abst. J. S. C. I. 1911, 30, 615. E. P.
2992, 4922, 1913; abst. J. S. C. I. 1914, 33, 72; C. A. 1914, 8, 2805. F. P.
454811, 1913; abst. J. S. C. I. 1913, 32, 865; Mon. Sci. 1914, 43; C. A. 1914,
8, 572; Kunst. 1913, 3, 356. U. S. P. 1106077; abst. J. S. C. I. 1914, 33,
859. D. R. P. 268261, 1912; abst. C. A. 1914, 8, 1668; Kunst. 1913, 3, 459.
F. P. 426089, 434621, 1911. D. R. P. 190217, addn. to D. R. P. 186257.
(Meister, Lucius and Bruening); abst. Chem. Zentr. 1907, II, 1815; Jahr.
Chem. 1905-1908, 989; Wag. Jahr. 1907, 392^ D. R. P. 231279, 1910. D. R.
P. 2365^, 1910; abst. Kunst. 1911, 1, 277; 1912, 2, 75. D. R. P. 240846,
1908; abst. C. A. 1912, 6, 2169; J. S. C. I. 1912, 31, 67; Zts. ang. Chem. 1912;
25, 47; Chem. Zentr. 1911, II, 843; Wag. Jahr. 1911, II, 421; Text. Col. 1912,
34, 71; Kunst. 1912, 2, 15. D. R. P. 274550, 1914; abst. C. A. 1915, 9, 2590,
F. P. 454011, 1913; abst. C. A. 1914, 8, 257. D. R. P. 283286, 1913; abst.
Kunst. 1915, 5, 72. D. R. P. Anm. V-9306, 9387, 9388, 1910; V-9635, 1910.
abst. Kunst. 1912, 2, 379; V-10780, 1912; abst. Kunst. 1914, 4, 100. Aust.
P. 54819; abst. Kunst. 1912, 2, 456. Aust. Anm. A-115, 1911; abst. Kunst.

1912, 2, 320; A-756, 1905; abst. Mon. Sci. 1910, (4), 72, 45; A-1677, 1913;
abst. Kunst. 1914, 4, 260; A-5148, 1910; A-9230, 9285, 1910. Belg. P. 182368,
182455, 182486, 1905; 203012, 1907; 204557, 1907. D. R. P. 208472, 1907.
Belg. P. 243387, 1910; 254219; abst. Kunst. 1913, 3, 356. Can. P. 120762,
1909. Hung. Anm. G-3210, 3227, 1911. Swed. P. 40463, 1916; abst. C. A.
1916, S, 2044. Swiss P. 53936, 1910. Kunst. 1912, 2, 100, 158, 178, 196;

1913, 3, 78, 197; 1914, 4, 137; 1915, 5, 83; Chem. Ztg. 1911, 1186.

1. E. Bronnert, U. S. P. 646351; abst. Mon. Sci. 1900, 50, 219.
646381; abst. Mon. Sci. 1900, 56, 218; Rev. Chim. 1900, 2, 304. 646799,
abst. Mon. Sci. 1900, 56, 219; Rev. Chim. 1900, 2, 351. 1023548, 1912;
J. S. C. I. 1912, 31, 485; C. A. 1912, 6, 1672; 1049201, 1912; C. A. 1913, 7,
700; J. S. C. I. 1913, 32, 133; 1055513, 1913; C. A. 1913, 7, 1608; J. S. C. I.
1913, 32, 422; 1102237, 1914; C. A. 1914, 8, 2947; T. S. C. I. 1914, 828;
1106077, 1914; C. A. 1914, 8, 3237; J. S. C. I. 1914, 33, 859. E. P. 13331,
1899; 18260, 1899; abst. J. S. C. I. 1900, IS, 659: 18884, 1899; abst. J. S. C.

I. 1900, IS, 531; 22092, 1907; abst. J. S. C. I. 1907, 26, 1275; J. Soc. Dyers
Col. 1908, 24, 118; 27539, 1910; J. S. C. L 1911,30,415; E. P. 309, 1911; J. S.
C. I. 19n, 32, 484. F. P. 278371; 292988, abst. Mon. Sci. 1900, 56, 224;
423104, 1910; J. S. C. L 1911, 30, 615; 4&4811, 1913; J. S. C. L 1913. 32,
865. D. R. P. 109996, 1899; Jahr. Chem. 1900, 843; Wag. Jahr. 1900, II,
448; Mon. Sci. 1901, (4), 57, 20. 111313, 1899; 118836, 1899; Jahr. Chem.
1901, 890; Wag. Jahr. 1901; II, 514; Mon. Sci. 1901, (4), 57, 213; 118837,
addn. to D. R. P. 118836, 1899; Jahr. Chem. 1901, 890; Wag. Jahr. 1901,

II, 514; Mon. Sci. 1901, (4), 57, 213. Aust. P. 3638, 11066. Belg. P. 143569,
1899; Bull. soc. Ind. Mulhouse, 1900, 177; Chem. Centr. 1900, II, 749; Jahr.
Chem. 1900, 843; Mon. Text. Ind. 1901, 16, 817. E. Bronnert and M. Fre-
mery, U. S. P. 1030251, 1912; J. S. C. I. 1912, 31^680; Kunst. 1912, 2, 457.
E. P. 22092, 1907; 9268, 1908; J. S. C. I. 1908, 27, 897. E. Bronnert, M.
Fremery and J. Urbain, U. S. P.: 617009, 658632, 1900. 672350, 1901;

92 TOCHNOW)GY OF CBI.I<UU)SB ESTERS

Celltilose and Hydrochloric Acid. It has for some time
been known that concentrated hydrochloric acid exerts a dissolv-
ing influence upon cellulose and that cellulose does not withstand
the action of fuming hydrochloric acid for any length of time,
but breaks down by the rupture of the fibers into a pulp that is

Mon. Sd. 1901, (4), 57, 283; 698264, 1902; J. S. C. I. 1902, 21, 706; Mon.
Sci. 1902, 58, 161; 691257, 764943, 764944; Mon. Sci. 1905, €2, 16. E. P.
28631, 1897; 13300, 1899. 1763, 1900; J. S. C. I. 1901, 20, 119; 4303,
1900;J.S. C.I. 1901,20, 1207. 20801, 1900; J. S. C. I. 1901, 20, 1231; 4303,
1901. P. P. 272718, 292988, 308715, 1901; J. S. C. I. 1902, 21, 49; Mon.
Sci. 1902, (4), 58, 37. D. R. P. 98642, Jahr. Chem. 1898, 1370; Wag. Jahr.
1903, II, 417. 115989; Wag. Jahr. 1900, II, 446. 119098, 1899; Jahr. Chem.
1901, 890; Mon. Sci. 1901, (4), 57, 213. 119099, addn. to D. R. P. 119098;
Jahr. Chem. 1901, 891; Mon. Sci. 1901, (4), 57, 213. 119230. 1900; Mon.
Sci. 1901, 900; Mon. Sd. 1901. (4), 57, 213; 125310; Wag. Jahr. 1901, II,
513; Mon. Sd. 1902, (4), 58, 130. Aust. 6150, 6064, 8596, 10263, 11066.
Bdg. P.. 147579, 1900. Can. P. 81298, 1903; 99425, 1906. E. Bronnert and
T. Schlumberger, E. P. 6858, 1898.

2. Grandquist, D. R. P. 111248, 111333; Wag. Jahr. 1903, II, 417.
G. Hager, D. R. P. 163233, 1904. A. Hdbronner and E. Vallee, D. R. P.
197250; abst. Mon. Sci. 1911, 53. F. P. 361796. Swiss P. 41005. Chem.
Fabr. von Heyden, A. G., Belg. 232475, 1911. P. Joliot, F. P. 468337,
1913. L. Leduc, H. Jaquemin and Soc. Anon, des Soieries de Maransart,
Bdg. P. 253537; abst. Kunst. 1913, 3, 356. W. Bruckner, D. R. P. 241781,
1909; addn. to D. R. P. 238361, 1909; abst. J. S. C. I. 1912, 31, 227.
Rheinische Kunstseide Fabrik Akt. Ges. E. P. 18342, 1909. F. P. 405571,
1909; J. S. C. I. 1910, 29, 417. D. R. P. 231652, 236817, 236537, 237816;
J. S. C. I. 1911, 30, 1248. E. Crumiere, U. S. P. 908754, 911868, 1909.
Compagnie Francaise des Applications de la Cellulose, Swiss P. 57951.
Aust. Anm. 4369, 1911. O. Dony-Henault, Eighth Inter. Cong. Appl.
Chem. 1912, 2, 83; C. A. 1912, 6, 3526. X. Eschalier, U. S. P. 995852. F. P.
374724, abst. J. S. C. I. 1907, 28, 821. M. Fremery and E. Bronnert,
U. S. P. 856857. See also D. R. P. 186766, 1904 (Ver. Glanzstoff Fabr.).
M. Fremery, E. Bronnert and J. Urban, U. S. P. 804191, 1905; abst. J. S. C. I.

1905, 24, 1251; see also D. R. P. 188113, 1905 (Ver. Glanzstoff Fabr.,
U. S. P. 806533, 1905, 806857, 1907). Levallois, BuU. Soc. Chim. 1885, 43,
85. L. Lilienfeld, F. P. 399460, 1909; abst. J. S. C. I. 1909, 28, 958; Chem.
Ztg. Rept. 1909, 472. E. P. 8708, 1908; abst. J. S. C. I. 1909, 28, 257.

B. Loewe, Belg. P. 238479, 1911. O. Muller and Rheinische Kunstseide
Fabrik, E. P. 18342, 1909; abst. J. S. C. I. 1910. 29, 557. F. P. 405571,
1909; abst. J. S. C. I. 1910, 29, 417. MuUer, U. S. P. 836452. E. P. 10094,

1906. F. P. 365776. D. R. P. 187947. Aust. P. 33678. Swiss P. 42306.
M. Prudhomme, F. P. 344138, 1904; abst. J. S. C. 1. 1904, 23, 1087. F. Bdtzer
Mon. Sci. 1908, (4), 68-09, 657. J. Ubertin, F. P. 444462, 1911; abst.
J. S. C. I. 1912, 31, 1120; Kunst. 1913, 3, 16. Soc. anonyme Soierres Nou-
velles de Bruxelles, Belg. P. 186098, 1905. Soc. la Sole Artificielle du Nord,
F. P. 437815, 1911. C. Wright, E. P. 737, 1883. A. Bardelli, Ital. P. 129734,
1913; abst. C. A. 1915, 9, 2316. E. Bloch-Pimentel; U. S. P. 1044434, 1912,

C. A. 1913, 7, 221. E. P. 7893, 1912, C. A. 1913, 7, 3227. British Cel-
lulose Syn. Ltd. and V. E. Mertz, U. S. P. 954984. E. P. 1148, 1909; J. S.
C. I. 1910, 29, 24. F. P. 411592, 1910; J. S. C. I. 1910, 29, 879. D. R. P.
250596, 1910; C. A. 1912, 0, 3518; Zts. ang. Chem. 1912, 25, 2382; Wag.
Jahr. 1912, II, 441; Kunst. 1912, 2, 359, 373. British Thomson-Houston
Co., E. P. 8207, 1900; Kunst. 1913, 3, 410. British Glanzstoff Manu-
facturing Co., Ltd., Kunst. 1912, 2, 218.

CEI.I.UI.OSB 93

partially soluble in the acid. With still stronger acid the effect
is more marked, especially when the solution contains some zinc
chloride, in which case considerable dissolving effect upon the
cellulose takes place.

Our knowledge concerning the solubility in fuming hydro-
chloric acid dates back to 1856, in which year A. Bechamp^ pub-
lished his observations upon the solubility of cotton in concen-
trated acids such as hydrochloric acid, after the cotton was first
converted into a pulp-like mass. In his later investigations upon
optical activity A. Bechamp^ made use of precipitation obtained
by forming a solution of cellulose in cuprammonium with acetic
acid. In general, however, the knowledge that concentrated
hydrochloric acid has a dissolving action upon cellulose has re-
mained useless for practical purposes because the fuming acid of
commerce (37% to 38% absolute HCl) at ordinary temperature
reacts only slowly and with great difficulty.

According to the patented method of R. Willstaetter,' hy-
drochloric- acid of unusually high concentrations (which, how-
ever, cannot be obtained commercially but must be made by the
evaporation of the technical varieties by the addition of hydro-
chloric acid gas at low temperatures), show an entirely different
behavior with cellulose and cellulosic bodies. He appears to have
succeeded with highly concentrated hydrochloric acids in obtain-
ing solutions of cellulose, hydrocellulose, hydrated cellulose and
oxycellulose, either from wood or from cotton cellulose, and
suitable acids such as 40.8% to 41.4% HCl, yielding solutions
containing from 12% to 15% of cellulose. According to this
chemist's investigations, the limits of practicability are well be-
yond the strength of the ordinary acids of commerce, acids of

1. Compt. rend. 1856, 42, 1210; abst. Instit. 1856, 235; Ann. 1856,
IM, 367; Jahr. Chem. 1856, 674; J. prakt. Chem. 1856, W, 449; Kunst.
1913 3 399.

'2.* Coinpt. rend. 1884, 99, 1027, 1122; 1885, IM, 279, 368; abst.
J. C. S. 1885, 28, 237, 369; Bull. Soc. Chim. 1885, 43, 661; Mon. Sci. 1885,
27, 88, 218, 311, 317; Ber. 1885, IB, R, 113, 141; Jahr. Chem. 1884, 303;
Kunst. 1913, 3, 399.

3. U. S, P. 1141510, 1915; abst. C. A. 1915, 9, 2311; Kunst. 1915, S,
240. E. P. 10605, 1914; abst. C. A. 1915, 9, 2980; J. S. C. I. 1914, 33, 859.
F. P. 471479, 1914; abst. J. S. C. I. 1915, 34,349. D. R. P. Anm. W, 42345,
1913; abst. Kunst. 1913, 3, 399, 400. D. R. P. 273800; abst. C. A. 1914, 8,
2948; Chem. Zentr. 1914, I, 1904; J. S. C. I. 1914, 33, 746. HoU. P. 1848,
1917; abst. C. A. 1917, 11, 1300. R. Willstaetter and h. Zechmeister, Ber.
1913, 46, 2401; abst. C. A. 1913, 7, 3412.

94 TECHNOI«OGY OF CEIXUU>SQ ESTERS

sp. gr. 1.199 equivalent to 38.9% HCl being required, while an
acid containing 39.5% HCl is exceptionally well suited for this
purpose.

Hydrochloric acid at low and at room temperatures ordi-
narily acts only slowly upon cellulose, primarily by hydrolyzing it.
For this reason the polyose may be precipitated into a gelatinous
elastic mass by removing the excess of HCl gas or by diluting the
solution with either water, alcohol, salt solutions or dilute acids
or alkalis, and in this condition are suitable for the production
of pure cellulose, cellulose esters and elastic substances, such as
films, sheets, or artificial filaments.^

1. The following examples are typical of canying this method into
efifect: (1) 1 part of cotton is kneaded with 12 to 15 parts of hydro-
chloric add (sp. gr. 1.209 at 15°) tmtil a homogeneous viscous liquid, without
residue is obtained. The HCl gas in excess is removed by suction and re-
covered together with some air bubbles. The solution is thereupon pressed
through small orifices, water being used as the coagulating medium. (2)
1 part of cellulose is kneaded with 8 parts of hydrochloric acid (sp. gr. 1.212
at 15°) in a kneading apparatus tmtil an almost clear viscous mass is formed,
and the mixture allowed to stand for some time to reduce the viscosity.
The coagulation of the cellulose is then brought about in any of the wdl
known ways. (3) 1 part of wood meal is stirred for one-half hour with
7 parts of hydrochloric acid (sp. gr. 1.212 at 15°) at ordinary temperature,
and then allowed to stand for one-quarter to one-half hour. The solution
is then filtered ofif from the insoluble lignin, and precipitated or coagulated.
This process is of peculiar interest in that it is stated that substantially the
entire nitrocellulose supply of Germany during the recent war was obtained
from wood pulp in a similar manner by dissolving it in Willstaetter's acid
and reprecipitating the pure cellulose, which is then nitrated.

According to R. Willstaetter and L. Zechmeister (Ber. 1913, 4€, 2401;
abst. C. A. 1913, 7, 3412; Chem. Zentr. 1913, II, 1209; J. S. C. I. 1913, 32,
822) whereas cellulose does not dissolve in ordinary concentrated hydro-
chloric add of 1.19 density, but passes into solution with acid of density
1.204, 1.209 and 1.212 at 15°, corresponding to 39.9%, 40.8% and 41.4%
HCl respectively, cotton or filter paper shaken with acid of 1.209 density
dissolves clear in a few seconds at the room temperature.

By kneading the cellulose with a 1.212 gravity acid, a 15% solution can
be obtained at room temperatures. These solutions are at first clear and
colorless but after standing for a day a slight flocculent precipitate is formed
which, upon further standing, becomes darker in color and finally a dark
brown substance separates. Grape sugar behaves in the same way. By
removing the HCl in vacuo the hydrolysis is retarded. The filtrate does not
reduce Fehling's solution and acquires no reducing power on warming. Pine
wood quickly dissolves and leaves 30% of its weight in lignin substances.
48% HBr gelatinizes cellulose, 57% acid dissolves it incompletely, whereas
with 66% acid the cellulose goes completely into solution, even at zero
degree. Concentrated hydriodic add does not dissolve cellulose, whereas 70
to 75% HP gdatinizes and quickly dissolves it. From all these solutions,
however, the cellulose can be re-precipitated, but in a changed condition.

In order to determine the amount of sugar formed, polarimetric measure-
ments were made first on solutions with glucose and concentrated hydro-
chloric acid, and it was determined that before the hydrolysis is completed

CBtI.UIX>SB 95

Similar in many respects to the above described process, is
the method of Z. Ostenberg,^ in which concentrated sulfuric acid
is added to cold ( — 10** to — 15** C.) concentrated hydro-
chloric acid until the mixed acid is of such concentration that it
will dissolve cellulose. For example, to 35% hydrochloric add
about 8 or 10% sulfuric acid is added so that the total strength
if measttfed as hydrochloric acid in dissolving power would be
about 41% to 42%. This acid will dissolve cellulose readily and
differs from the Willstaetter solvent described above in that the
latter employs hydrochloric acid only. The solution thus ob-
tained is filtered through fine mesh copper screen and "spun" by
squirting through microscopic perforations in a sheet of platinum
or acid-resisting alloy into water. The resulting filaments are
washed free from acid, bleached lightly and dried, the dried
product being easy of nitration, resulting in the formation of a
nitrocellulose of satisfactory stability and ballistic powers.^

Cellulose and Sulfuric Acid. It was in 1819 that H. Brac-

the polarimetric method gives higher values than the Fehling's Solution
method (G. Bertrand, Bull. soc. chim. 1906, (3), 3S, 1285); abst. Chem. Zentr.
1907, I, 763; J. S. C. I. 1907> 26, 60; Jahr. Chem. 1906-1908, II, 910, show-
ing that the solution contains compound sugars. W. de Coninck and A.
Raynaud (Bull. Acad. Roy. Belg. 1910, 587; abst. J. C. S. 1910, 98, i, 654;
C. A. 1911, 5, 1585; J. S. C. I. 1910, 29, 1299; Chem. Zentr. 1910, II, 1459;
Jahr. Chem. 1910, II, 417) found that on macerating filter paper with con-
centrated hydrochloric add at 28°, no reducing substance is produced, even
after forty hours. If the paper is macerated during sixty-two houfs and
the mixture then heated at'95-96° dtuing twenty minutes, it becomes brown
but the filtrate does not reduce Pehling's solution. The brownish residue
is partly soluble in ammonia and consists of humic matter. Cotton macer-
ated during forty hours in hydrochloric add shows no reduction, but after
dghty-seven hours at 28.5, and then ten minutes at 95^-96°, shows copious
reduction. It dissolves in fuming hydrobromic add at 29° in a few min-
utes and the solution blackens on keeping. Such a solution gives a slight
brownish l3lack predpitate partly soluble in ammonia on dilution, and re-
duces Pehling's solution. See A. Ldnveber, Kunst. 1918, 8, 235; C. A.
1919, 13, 1927. E. Rasser, Kunst. 1918, 8, 97, 112; C. A. 1919, 13, 1926.

1. U. S. P.' 1218954, 1917; abst. T. S. C. I. 1917, 36, 450. U. S. P.
1242030, 1917; abst. J. S. C. I. 1917, 36, 1174; C. A. 1918, 12, 223. E. P.
104173, 1917; abst. J. S. C. I. 1918, A, 37, 146; C. A. 1917, U, 1903. F. P.
484442, 1917; abst. C. A. 1918, 12. 1123. ^n a later patent (U. S. P. 1315393,
1919; abst. C. A. 1919, 13, 3035) Z. Ostenberg describes the production of
glucose by dissolving cellulose in a mixture of HCl (35%) 9 parts, HtS04,
0.6, and HaP04 (85%) 2 parts. Accordmg to T. Pritsch (E. P. 6590, 1906;
abst. J. S. C. I. 1906, 2S, 1006) paper is made resistant to water by passing
the dry sized paper through a mixture of sulfuric and hydrochloric acids
or sulfuric and nitric adds, or through hydrochloric acid or nitric acid alone.
The excess of acid is then removed, and the paper is thoroughly washed.
Writing on papers so treated cannot be removed easily by mechanical means,
and the paper is also stated to be more durable.

2. According to a modification of the Z. Ostenberg process (U. S. P.

96 TECHNOLOGY OF CBLl,UI<OSE ESTERS

«

onnot^ observed that linen dissolved in concentrated sulfuric
acid, and that if the linen was diluted with water, a clear solu-
tion resulted containing, besides sulfuric acid, another acid which
he named acide vegeto-sulphurique. When the diluted solution
was boiled for some hours a substance was produced which was
fermentable, and which he consequently considered to be glucose.

In 1844 Blondeau de CaroUes* investigated this acid, and
found that when cotton was added to the concentrated acid, it
dissolved and formed a light yellow solution which changed to
dark violet upon standing. When the solution was diluted with
cold water and neutralized with barium carbonate, the excess of
acid was precipitated as the sulfate, while the barium salt of
cellulose-sulfuric acid remained in solution; this was precipitated
from the concentrated clear solution on adding strong ethyl alco-
hol. It was found that the composition of these salts varied with

1218953, 1917; abst. J. S. C. I. 1917, 36, 450; C. A. 1917, U, 1545; Kunst.
1917, 7, 261) cellulose is dissolved in a mixture of highly concentrated hydro-
chloric acid and a concentrated inorganic add such as j>hosphoric acid,
which does not react with the hydrochloric acid, at a temperature below
50®, not less than 25% of hydrogen chloride being present in the mixture.
The method of the Zellstoflfabrik Waldhof and V. Hottenroth (Swiss
P. 76329, 1917; abst. C. A. 1918, 12, 1123. Dan. P. 23957, 1918; abst.
C. A. 1919, 13, 1390. D. R. P. 306818, 1917; abst. J. S. C. 1. 1919, 38, 131-A;
Chem. Zentr. 1918, II, 327. Swiss P. 76329, 1917; abst. C. A. 1918, 12,
1123. E. P. 132815, 1919) is somewhat similar to that above, in that a
mixture of hydrochloric and sulfuric acids is claimed as especially energetic
and efficacious as a solvent combination for cellulose, the total amount of
HCl being less than 39%. Ten parts of ordinary concentrated HCl of
density 1.19 (37.2% HCl) are mixed with one part of sulfuric acid (80%
strength), and into this mixture—which contains 32.5% HCl to 10.1% H,S04 is
thoroughly incorporated one part of cotton, the mixture being cooled mean-
while. The cellulose in a short time dissolves to a clear viscous liquid, from
which it may be obtained in filament form by expressing from nozzles into
water as the precipitating medium. Or, into 8 parts of an acid mixture of
20% HCl and 18% HjS04 is incorporated one part of cellulose by stirring,
with cooling, a clear viscous solution being obtained after 15-20 minutes
which may be precipitated either before or after filtration. According to
W. de Coninck (BuU. Acad. Roy. Belg. 1910, 587; abst. J. S. C. I. 1910, 29,
1299; Chem. Zentr. 1910, II, 1459; C. A. 1911, 5, 1585; Jahr. Chem. 1910,
II, 417) filter paper which has been subjected to the action of concentrated
hydrochloric acid for 62 hours does not yield a product capable of reducing
Fehling's solution. A product possessing cupric-reducing power is, however,
formed by the action on cotton of concentrated hydrochloric acid for 87
hours, or of fuming hydrobromic acid for 24 hours.

1. Ann. Chim. Phys. 1819, (2), 12, 185; abst. Edin. PhU. J. 1820, 2,
363; Gilb. Ann. 1819, 63, 347; J. de Pharm. 1820, 6, 416; Quart. J. Sci. 1820,
8, 386; Schw. J. 1819, 27, 328. A. TUloch, PhU. Mag. 1820, 55, 53, 118.

2. Ann. 1844, 52, 412; J. prakt. Chem. 1844, 32, 427; 33, 439; Rev.
Sci. et Ind. 16, 468; 1843, 69, 476; Berz. Jahr. 1846, 25, 547, 582; Annuaire
de Chemie, 1845, 1, 468. See M. Honig and J. Schubert, Ber. 1885, 18, 614.

cuhhxjuysn 97

the period the sulfuric acid solution of cellulose was allowed to
stand before diluting.

About the same time^ H. Fehling found the composition of
one of the barium salts to be of percentage corresponding to
C9oHi8o09oBaO(S08)2. R. Marchand* acted on Swedish filter
paper with sulfuric acid for four weeks, and obtained a lime salt,

C88H2808(S08)2CaO.

A. Bechamp' states that the substance obtained by dissolv-
ing cellulose in sulfuric acid is a dextrin-like starch dextrin — but
with a lower specific rotatory power, and that' on boiling this
with acids a sugar is formed.

It is therefore apparent that for many years it has been
recognized that concentrated sulfuric acid of certain strengths is
capable of exerting a swelling or solvent action upon cellulose and
its closely alUed products. In 1891 R. Langhans^ published his
process for the manufacture of artificial filaments of cellulose dis-
solved in sulfuric and phosphoric acids, for which purpose cellu-
lose is first subjected to a * 'purifying process*' by treatment with
an alkali and then with aqueous hydrochloric or sulfuric adds,
afterwards washing with water until neutral and finally drying
at about 40*^. The cellulose is next impregnated with a solution
consisting of aqueous phosphoric acid containing equivalent to
33% of phosphorus pentoxide and sufficient sulfuric acid so that
the combined cellulose contains 20% H2SO4, using only enough
to thoroughly saturate and impregnate the cellulose, the acid
mixture being allowed to act until the fiber begins to swell and

1. Ann. 1845, S3, 135; 55, 13; abst. Annuaire de Chemie, 1846, 2,
486; J. prakt. Chem. 1^5, 36, 62; J. de Pharm. 1845, 8, 477.

2. J. prakt. Chem. 1845, 35, 228. Terreil, J. C. S. 1873, 26, 370.

3. Compt. rend. 1856, 42, 1210; abst. Instit. 1856, 235; Ann. 1856,
100, 367; Jahr. Chem. 1856, 674; J. prakt. Chem. 1856, 69, 449; Knsut. 1913,
3,399. E. P. 8260, 1911.

4. U.S. P. 571530, 1896. D. R. P. 72572, 1891; 82857, 1893; abst.
Jahr. Chem. 1895, 1362; Wag. Jahr. 1895, il, 957. F. P. 217557, 1891.
Text. Col. 1897, 19, 317; Ind. Text. 1897, 13, 239. A. Herzheim, U. S. P.
501968, 1897. D. R. P. 86938, 1895. F. P. 252501, 1895. Belg. P. 118877,
1895, treats hydrocellulose with sulfuric acid or with cuprammonium, and
afterwards with pyroxylin solution in the manufacture of water and grease
proof paper. See also K. Hofman, D. R. P. 227198; Wag. Jahr. 1910, II,
431; Chem. Zentr. 1910, II, 1349; Kunst. 1911, 1, 16. See W. Harrison,
Jour. Soc. Dyers Col. 1912, 28, 238; abst. Zts. Chem. Ind. Koll. 1913, 12,
60; J. S. C. I. 1912, 31, 679; C. A. 1913, 7, 4077. S. Tschumanow, Zts.
Chem. Ind. Koll. 1914, 14. 321; abst. J. C. S. 1914, 106, i, 932; C. A. 1914,
8, 2971; J. S. C. I. 1914, 33, 744; Chem. Zentr. 1914, II, 617.

98 TECHNOlyOGY OF CEl,I<UU)SE KSTHRS

pass into solution. The mass is then kneaded with sulfuric acid,
and phosphoric acid added, when the dough is said to be trans-
formed into a glass-like, transparent, viscid S)rrup, suitable for
filament formation. It appears, however, that but little com-
mercial use has been made of this process.

E. Berl^ has found that cellulose or its closely allied deriv-
atives may be used for the manufacture of artificial threads,
filaments and plastic masses by treatment with sulftuic acid, if
the temperature be kept continually very low (not exceeding — 10®
C.) the sulfuric acid being 60-77% H2SO4. Under these condi-
tions, according to the patentee, the decomposing and dehydrating
action of the sulfuric acid on the cellulose is restricted so as to be
practically negligible and harmless. This advantageous influence
of low temperature must be maintained during the entire process
of coagulation, otherwise the decomposing action of the sulfuric
acid predominates, resulting in the prepared products lacking in
stability. It has been proven that the coagulation temperature
must be nearly the same as or lower than the temperature for
producing the solution to obtain products of commercial utility.*

1. E. P. 4966, 1913; abst. J. S. C. I. 1913, 32, 1063. D. R. P. 259248.
1912; abst. J. S. C. I. 1913, 32, 653. Belg. P. 253945, 1913. D. Nagy
Belg. P. 191460, 1906. S. Gwynn. U. S. P. 73322, 1868. J. Hanna, U. S. P-
19&'i82, 1877. S. Haskin, U. S. P. 488967, 1892. E. Andrews, U. S. P.
312945. 1885. F. Taylor, U. S. P. 316817, 1885.

2. As coagulants are recommended aliphatic alcohols, such as methyl
and ethyl alcohol and their aqueous solutions, solutions of sulfates (such as
ammonium sulfate), of phosphates, dilute sulfuric acid, the melting points
of which are not above — 10**. The following examples are illustrative of
carrying the process into effect :

(a) One part of cool, dry, and finely divided cotton is digested in the
kneading machine with 12 parts of 74% sulfuric acid and not above — 15°,
and then left standing for some time, when a viscous mass is obtained; the
confined air can be exhausted in vacuo and after filtration of this mass
coagulation is caused by immersion in 50% alcohol and cooled to — 20®.

(6). One part mercerized cotton is thoroughly mixed with 12 parts
70% sulfuric add in a knead,ing machine at not exceeding — 15° until it
has swollen to a viscous mass, coagulation being obtained by a 60% solu-
tion of methyl alcohol reduced to a low temperature.

(c) Hydrocellulose is digested with sulfuric acid as described above
until a homogeneous viscous mass is obtained, coagulation being brought
about by 25 'o sulftuic acid cooled almost to its freezing point.

((/) Finely divided, carefully dried wood cellulose is digested with
cooled 65% sulfuric acid until a homogeneous mass is obtained, this being
coagulated by a solution of 38.5% by weight of ammonitun sulfate cooled
to —18°.

E. Cunningham and F. Thicle (U. S. P. 637090, 1899; abst. Mon. Sci.
1900, 56, 139) have described the preparation of a synthetic gum, having
the adhesive characteristics of gum arabic, and produced by treating cellu-

cEi<i<ULOSK - 99

A. Stem has made a comprehensive study of the action of sulfuric
acid on cellulose and correlatied the work of previous investigators
in this field.^

The process of X. Karcheski, which consists in the treatment
of cloth or other textile vegetable fibers, either alone or united
with paper or a similar fibrous material by means of sulfuric acid,
in which the textile is first immersed in a bath of sulfuric acid
until the fiber has been partially dissolved,^ and a similar process
of L. Grote' have apparently not been developed commercially.

lose (lint) with sulfuric acid of not less than 1.842 sp. gr. at a temperature
not exceeding 40® F., the "cellulose tetrasulfate'* thus formed uniting with
water in the presence of potassium pyrosulfate which is also used, the sul-
furyl groups in the cellulose tetrasulfate being eliminated and arable acid
formed.

1. Proc. Chem. Soc. 1894, 186; J. C. S. 1895, 67, 74; abst. J. S. C. I.
1894, 13, 1230; Bull. Soc. Chim. 1896, (3), 16, 1081; Ber. 1895, 28, R, 462;
Jahr. Chem. 1895, 48, 1358; Meyer Jahr. Chem. 1895, 5, 145, 524; Chem.
News, 1894, 70, 267; Chem. Centr. 1895, 66, I, 29; Jahr. Chem. 1894, 47,
1132. Proc. Chem. Soc. 1904, 20, 43; J. C. S. 1904, 8S, 336; abst. Chem.
News, 1904, 89, 117; J. S. C. I. 1904, 23, 265; Bull. Soc. Chim. 1904, 32,
1175; Chem. Centr. 1904, 75, I, 934, 1405; Chem. Ztg. 1904, 28, 246; Jahr.
Chem. 1904, 57, 1161. In this connection see Proc. Chem. Soc. 1904, 20,
90; J. C. S. 1904, 85, 691; abst. Chem. News, 1904, 89, 235; J. S. C. I. 1904,
23, 557; Bull. Soc. Chim. 1904, 32, 1301; Rep. Chim. 1904, 4, 293; Chem.
Centr. 1904, 75, I, 1557; Jahr. Chem. 1904, 57, 1161. See also M. Hoenig
and S. Schubert, Monatsh. 1885, 6, 708; 1886, 7, 455; abst. Wein. Akad. Ber.
^ (2 Abth.), 737; BuU. Soc. Chim. 1886, (2), 46, 517; Ber. 1885, .18, 614;
Jahr. Chem. 1885, 38, 1376. AUihn, J. prakt. Chem. 1880, 130, 61. J. v.
Kalinowsky, J. prakt. Chem. 1845, 35, 193; J. de Pharm. 1845, 8, 309.

2. X. Karcheski, U. S. P. 137451, 1873. Refer to Chemische Fabrik
auf Aktien, D. R. P. 86938, 1895; Ber. 1896, 29, R, 610.

3. E. P. 23728, 1912; abst. J. S. C. I. 1913, 32, 1104; C. A. 1914, 8,
1346. E. Bert, Ital. P. 134462, 1913; C. A. 1915, 9, 2710.

The parchmentizing effect of sulfuric acid is probably explained from
the fact that the cellulose becomes dissolved super^cially due to the action
of the sulfuric add, this action penetrating to a certain depth in the paper.
Upon washing the treated surface the dissolved cellulose becomes precip-
itated in the interstices of the paper, as it were, and cements the individual
cellulose fibers more firmly together into an apparently homogeneous mass.
This cementation of the paper undoubtedly explains its increase in strength,
and translucent appearance. When paper thus treated is moistened it
loses its toughness and rigidity and can be considerably expanded without
rupture. If stretched tight and allowed to dry, it regains its corneous struc-
ture again. By reason of this property it finds considerable use for capping
the stoppers of bottles.

For additional data on the development of parchment and pergament
paper, see: Smith, Lond. J. Conj. S. U. 45, 177. Weinraann, Dingl. Poly.
1855, 136, 159. Bayer, Kunst. u. Gewerbebl. 1855, 365. Gaine, Dingl.
Poly. 1857, 144,« 154; Monit. Ind. 1857, No. 2152, 2336; Mech. M. V. 66,
446; Chem. Centr. 1857, 892; Pr. Mech. J. (2), 3, 175. Hofmann, Chem.
Centr. 1859, 614; Dingl. Poly. 1859, 152, 380. Bayer, Kunst. u. Gewerbebl.

1859, 297. Jennings, Rep. of Pat. 34, 391; Ann. 112, 243; Hannover Mitth.

1860, 61; Bull. soc. Encourag. I860, 690; Chem. Centr. 1860, 56; Dingl.
Poly. 1860, 155, 388; J. prakt. Chem. 1859, 78, 488. Taylor, Lond . J. N. S

100 TOCHNOU)GY 01^ C^1.1.UU)SE ESTERS

Unless the action of sulfuric acid upon cellulose be carefully
regulated as to concentration and temperature, sulfuric acid pro-
duces amyloid (mentioned elsewhere), and this fact is utilized in
the manufacture of what is known as "vegetable parchment/'
which product is obtained by a short immersion of unsized paper
in 75-85% sulfuric acid, followed by immediate thorough wash-
ing and drying. The effect of this treatment is to cause the
formation of gelatinous amyloid on the surface of the paper, ^

10, 351; J. prakt. Chem. 1859, 78, 207; Dingl. Poly. 1860, 15S, 397; Wieck's
Gwz. 1860, 250; Bayr. Kunst. u. Gewerbe. 1860, 125. Reinsch, Dingl.
Poly. 1860, 15S, 156; Wieck's Gwz. 1860. 249; Chem. Centr. 1860, 1199;
Bull. Soc. Encourag. 1860, 692; Bayer. Gewerbeztg. 1860, No. 8; Pharm.
Centralh. 1860, No. 48; Chem. Tech. Mitth. 1859-1860, 115. V. Kletzinsky,
Pharm. Centralh. 1860, 2, No. 3; Stamm's illust. Wochensch. 1860, No. 16;
Chem. Tech. Mitth. 1859-1860, 113; Dingl. Poly. 1860,156, 385; Chem. Centr.
1860, 911; Wieck's Gwz. 1860. 319. DuUo (product called Papyrine), Dingl.
1860, 158, 392; Chem. Centr. 1861, No. 2; Poly. Notiz. 1861, No. 3; Chem.
Tech. Mitth. 1860-1861, 120. Hoffmann, Ann. 1859, 112, 243; Pharm.
Centralh. 1860, 377; Dingl. Poly. 1860, 155, 388; Bayer. Kunst. u. Gewerbebl.
1860, 125; Poly. Centr. 1860, 120; Chem. Tech. Mitth. 1859-1860, 116. Ferwer.
Dingl. Poly. 1861, 159, 218; Chem. Centr. 1861, 543; Bayer. Kunst. u.
Gewerbebl. 1861, 425. Brandegger, Dingl. Poly. 1862, 163, 467; Bayer.
Kunst. u. Gewerbebl. 1862, 101 ; Chem. Centr. 1862, 830. Graham, Wieck's
Gwz. 1862, 87; Chem. Centr. 1862, 551; Phil. Mag. (4), 23, 290; Deutsch.
Ind. Ztg. 1862, 321. Vogel, Wieck's Gwz. 1862, 258; Chem. Centr. 1862,
1244. Sauerwein, Chem. Centr. 1862, 1101; Wieck's Gwz. 1862, 313. Winter,
Chem. Centr. 1863, 1595. Gaedicke, Zts. d. V. deutsch. Ingen. 1864, 345.
Jacobsen, Pharm. Centralh. 1865, No. 3; Chem. Tech. Repert. 1864, II, 29;
Industriebl. 1865, No. 1, 2, 3; Poly. Notiz. 1865, No. 5; Poly. Centr. 1865,
461; Dingl. Poly. 1865, 176, 167; Chem. Tech. Mitth. 1864-1865, 159.

1. For general discussion on the effect of sulfuric acid in dissolving
cellulose, see W. Zaenker, Kunst. 1916, 6, 17; abst. C. A. 1916, 10, 971;
Zts. ang. Chem. 1916, 29, R, 182; J. S. C. I. 1916, 35, 596. Cf. C. A. 1907,
1, 1696, 2174; 1914, 8, 1675, 2219.

The behavior of sulfuric, phosphoric and hydrochloric adds of varying
concentration towards cellulose in the form if surgeon's cotton purified by
treatment with 1% sodium hydroxide, has been studied by A. Leighton (J.
Phys. Chem. 1916. 20, 182; abst. J. C. S. 1916, HO, ii, 128, 226; J. S. C. I.
1916, 35, 464; C. A. 1916, 10, 1296). He treated one gram of cellulose with
100 cc. acid for three hours, then centrifugalized for an hour, gravimetrically.
estimating the acid retained by the cotton. Curves were plotted illustrating
the increase in absorption with increasing concentration of acid and it was
found that selective absorption is shown only at high concentration and is
most marked in the case of hydrochloric acid; with sulfuric acid it begins at
a concentration of 400 grams per liter, and it is not (detected with phos-
phoric acid. The value of the absorption expressed in grams is greatest
with sulfuric and least with hydrochloric acid. No evidence of the forma-
tion of a compound between acid and cellulose was discovered. The presence
of acid lowers appreciably the amount of water absorbed by the cotton.

For methods of testing imitation parchment papers, consult G. Schacht,
Wochbl. Papicrfabr. 1911, 42, 3632; abst. C. A. 1912, 6, 684; J. S. C. I. 1911,
30, 120G. For the action of concentrated sulfuric acid on cellulose, see L.
Sabattani, KoU. Zts. 1914, 14, 29; abst. Chem. Zentr. 1914, I. 2033; C. A.
1914. 8, 1690.

CEI*I<UIX)S^ 101

which, in appearance, resembles natural parchment. Artificial
horse hair has been prepared from certain Mexican grasses in a
somewhat similar manner.

As stated under the topic '*Mercerization/* concentrated
mineral acids under proper conditions of treatment have a mer-
cerizing action upon cellulose fibers, which by the hydrating
treatment possess an increased aflSnity for dyestuffs, acquires an
increased luster and additional strength. If the action of the
acid be prolonged, complete destruction of the fiber occurs.

Action of Zinc Chloride on Cellulose. Concentrated solu-
tions of neutral zinc chloride are capable of dissolving cellulose
only after prolonged digestion at 80® to 100°, although by first
treating the cotton with alkalis, solution occurs much more
readily and in the cold. This solution of cellulose is not a simple
phenomenon, but is attended both with hydrolysis and condensa-
tion, the former being shown by reduction of Fehling's solution
and the latter evidenced by the formation of furfural and similar
bodies obtainable by diluting the original solution and filtering
from the re-precipitated cellulose.

Cross and Bevan have observed that when experiments upon
cotton cellulose have been carefully conducted, solution and re-
precipitation may occur with a loss of not over 1% in weight of
cellulose. This phenomenon of the solution of cellulose in zinc
chloride has many industrial applications. As far back as 1884
J. Wynne and L. Powell^ dissolved cellulose in a solution of zinc
chloride, bromide or iodide, or bismuth chloride or bromide, or
mixtures of these, and then freed the solution from air by heat-
ing in a chamber connected with an exhaust pump. The cellulose
was then precipitated by squirting the solution through a small
orifice and the threads used for the production of carbon filaments
for incandescent electric lamps, insulating materials and woven
fabrics. Previous to this, Persoz^ had discovered a substitute

1. E. P. 16805, 1884; abst. J. S. C. I. 1886, 5, 172. Lane-Fox was the
first to patent electric light carbons made by carbonizing parchmentized
cellulose (zinc chloride treatment). He used a vulcanized fiber as also did
Swan, quite independently. Compare also T. Taylor, E. P. 787, 1859;
abst. Lond. Jour. Arts, 1859, 351; Poly. Centr. 1860, 207; Pharm. Centrahalle,
1860, No. 45; Dingl. Poly. 1860, 155, 397; Polyt. Notiz. 1860, 98; Chem.
Tech. Mitth. 1859-1860, 115. G. Robertson, E. P. 4630, 1877.

2. Poly. Centr. 1867. 617; abst. Chem. Centr. 1867, 448; Chem. Tech.
Rep. 1867, I, 95; D. Indztg. 1867, 5. W. Courtenay, U. S. P. 193322, 193323,
1877. H. Tiffany. U. S. P. 1226279; C. A. 1917, 11, 2155.

102 TECHNOUKJY OF CEI^I<UU)SE ESTERS

for collodion valuable to photographers, by dissolving a solution
of silk in a mixture of zinc chloride neutralized with zinc oxide.

E. Manby^ sized fabrics by treating cellulose dissolved in
zinc chloride, the finishing material being especially appUcable,
according to the patentee, in calico printing and dyeing mixed
with coloring liquids or with mordants or applied to the fabric
or yam preparatory to the dyeing process.

The so-called fiberless thread of J. Hoyne^ consists in dis-
solving cellulose in a designated solution of a zinc salt, filtering
the cellulose and passing the solution under pressure through a
thread-forming medium into a coagulating compound, which,
after washing, was dried in the usual manner.

W. Dreaper,' W. Dreaper and H. Tompkins* and H. Tomp-
kins and W. Crombie*^ have converted cellulose into hydrocellulose
either by treatment with a strong solution of sodium hydroxide
without any bleaching process, or by steeping it in a solution of
zinc chloride of 10° Tw. and then heating. The hydrocellulose
thus obtained is then dissolved in a solution of zinc chloride, pre-
ferably made distinctly acid to facilitate solution, which solution
is then forced through fine openings into a coagulating bath of
either strongly alkaline solution to which ammonium chloride or
ammonia is added to prevent precipitation of the zinc com-
pounds, or a concentrated solution of a suitable salt as sodium
sulfate, either with or without the addition of alcohol.

In the W. Werner inventions,* the process of A. de Madaillon,'

C. Mueller and D. Wolf,® and Y. Ogawa and S. Okubo,® cotton

1. B. P. 943, 1894; abst. J. S. C. I. 1895, 14, 568. See also E..P.
10466, 1894; abst. J. S. C. I. 1895, 14, 569. F. P. 308715, 1901.

2. U. S. P. 625033, 1899. E. P. 17901, 1897. D. R. P. 113, 786; abst.
Chein. Centr. 1900, II, 1043. A. Hill, B. P. 8076, 1901. F. P. 320614.

3. E. P. 858, 1908; abst. J. S. C. I. 1909, 28, 201.

4. E. P. 10i87, 17901, 1897; abst. J. S. C. I. 1898, 27, 573, 841. Belg.
P. 135251, 1898. E. P. 12259, 1911. J. Strehli, U. S. P. 717050. 1902.

5. E. P. 28712, 1904; abst. J. S. C. I. 1906, 25, 119.

6. U. S. P. 697580; abst. J. S. C. I. 1902, 21, 614. B. P. 1850, 1901;
abst. J. S. C. I. 1902. 21, 771.

7. F. P. 345012, 1904; abst. J. S. C. I. 1904, 23, 1206. F. Ahrens,

D. R. P. 216629, 1907; Mon. Sci. 1911, (5), 74, 63; Zts. ang. Chem. 1910, 23,
144; Chem. Zentr. 1910, KL, I, 71; Chem. Tech. Rep. 1909, 33, 664; Chem.
Ind. 1909, 32, 837; J. S. C. I. 1910, 29, 36; C. A. 1910, 4, 827.

. 8. U. S. P. 931634, 1909; abst. J. S. C. I. 1909, 28, 1001; C. A. 1909,
3, 2627. E. P. 6942, 1906; abst. J. S. C. I. 1906, 25, 775. E. P. 10430,
1912; abst. J. S. C. I. 1913, 32, 531. F. P. 443133, 1912; abst. J. S. C. I.
1912, 31, 1026. F. Muller, Belg. P. 211349, 1908. Swiss P. 35911.

9. Jap. P. 31374, 1917; abst. C. A. 1918, 12, 224. F. P. 489330, 1918.

\

cEi<i.ui*osS 103

cellulose is dissolved in saturated zinc chloride solution at a tem-
perature of 80*^ to 100°, the cellulose being afterwards regen-
erated by precipitation in a suitable coagulating medium.

In the well-known process of E. Brorihert^ the clean cellulose
is treated successively with a concentrated solution of caustic
alkali at a low temperature, together with an oxidizing and
bleaching agent and subsequently dissolved in concentrated zinc
chloride solution without the application of heat. A rather vis-
cous solution is thus obtained containing approximately 8% of
cellulose. The solution thus formed may either be used by itself
or combined with a solution of natural silk waste dissolved in the
usual manner in a solution of zinc chloride, the mixture being
especially applicable for printing and coating fabrics and in the
manufacture of threads. For the latter purpose, however, the
amount of silk solution in the mixture should, according to the
patentee, not exceed one-fifth that of the cellulose. The printed
or coated fabric is passed through a bath containing dilute acid
or a 10% solution of ammonium chloride and dried in a stretched

Can. P. 187349, 1918; abst. C. A. 1919, 13, 186. E. P. 122527, 1919; abst.
C. A. 1919, 13, 1764; J. S. C. I. 1919. 38, 170-A.

The essence of their invention lies in using saturated solutions
of zinc chloride and elevated temperatures, in order to reduce the
dissolving time. Whereas ordinarily, cellulose is warmed with ZnClt
solution of sp. gr. 1.8-1.88 at or below 80°, the temperature being
raised when the cellulose becomes gelatinized, this method requires several
hours to completely effect solution, and in consequence of this long period
of heating the celltdose solution is prone to become dark colored. The pat-
entees take 100 gm. ZnClj of sp. gr. 1.915 at 30°, add solid zinc chloride in
amounts so that when the solution is subsequently heated to 65°, the solu-
tion is still saturated. When the solution is raised to 100°, 5 gm. absorbent
cotton is added, complete solution resulting in less than half an hour.

In Jap. P. 31625, 1917; abst. C. A. 1918, 12, 534, Y. Ogawa, S. Okubo
and N. Satake mix a solution of cellulose in zinc chloride with a solution of
cane or grape sugar, or a mixture of starch and dextrin, the resulting mix-
ture being extruded through a very small opening in a glass nozzle into
alcohol as the precipitant, a satisfactory artificial silk, according to the pat-
entees, being thereby produced. See F. P. 489330; La Papeterie, 1919, 12,
80; Paper, 1919, 2S, 24.

1. U. S. P. 646799; abst. Mon. Sci. 1900, 56, 219. E. P. 18260, 1899;
abst. J. S. C. I. 1900, 19, 659. F. P. 292988; abst. Mon. Sci. 1900, 56, 224;
Chem. Ztg. 1900, 24, 572; Rev. Chim. 1900, 2, 111, 268, 351. D. R. P.
118836, 1899; abst. Chem. Zts. 1901-1902, 1, 186; Chem. Centr. 1901, I,
714; 1901, II, 514; Chem. Ztg. 1901, 2S, 252. Belg. P. 145281, 1899. See
also: Bull. Soc. Mulhouse, 1900, 177; abst. J. S. C. I. 1900, 19, 819, 820;
Jahr. Chem. 1900, 843; Chem. Centr. 1900, II, 740. Aust. P. 11066; abst.
Chem. Centr. 1901, I, 714. See also, Bayerisches Ind. und Gewerbe. Blatt.
1891, 23, 476; Gummi, Ztg. 1891. No. 13.

104 TECHNOLOGY O^ CELI<UI<OSE ESTERS

condition, and which does not admit of additional treatment.

Vulcanized Fiber. ^ In addition to the industrial applica-
tions of the zinc chloride solutions of cellulose for artificial fila-
ments, fiber treated with a solution of zinc chloride is known as
vulcanized fiber, the resulting gelatinous mass obtained being
manufactured into various articles, such as blocks and sheets.
The chief diflSculty encountered where large articles are obtained
in this manner, is the subsequent removal of the zinc salt, this
latter necessitating a most thorough and lengthy process of wash-
ing. The material may be rendered more waterproof by a fur-
ther process of nitration.

L. CoUardon^ manufactures a plastic material as a substitute

1. F. Taylor, B. P. 10864, 1884; abst. J. S. C. I. 1885, 4, 115; renders
vulcanized fiber pliable by submitting it to a bath of a deliquescent salt
combined with glycerol. H. Arledter (E. P. 2018, 1910; abst. J. S. C. I. 1911,
30, 205; F. P. 418584, 1910; abst. J. S. C. I. 1911, 30, 80; E. P. 16085, 1912;
abst. J. S. C. I. 1913, 32, 865) has described a process of treating cellulose
in which the air is preferably ozonized, and in which aluminum sulfate or
other parchmentizing compound is added to the mixture, the treatment
being continued until a jelly-like mass has been formed. The T. Kelley
cellulose composition for an india-rubber substitute is described in E. P.
19853, 1910; abst. J. S. C. I. 1912, 31, 83; C. A. 1912, 6, 1503. Celluvert
(G. Springer, Gummi Ztg. 1901, 15, 329; abst. J. S. C. I. 1901, 20, 602) is a
hydrocellulose impregnated with zinc chloride, first produced in the United
States in 1878, and patented in England by H. Morrow (E. P. 9319, 1885;
abst. J. S. C. I. 1885, 4, 751; U. S. P. 322629; abst. Wag. Jahr. 1885, 31, 1043).
The "elamite," of G. Robertson, E. P. 4630, 1877, is similar. A zinc chlor-
ide treated paper was patented by T. Taylor as early as 1859 (E. P. 787,
1859), Lond. Jour. Arts, 1859, 351; Poly. Centr. 1860, 207; Pharm. Centralh.
1860, No. 45; Dmgl. Poly. 155, 397; Poly. Notiz. 1860, 98; Chem. Tech. Mitth.
1859—1860 115.

2. F. P. 372584, 1906; abst. J. S. C. I. 1907, 26, 539. U. S. P. 953319,
1910; abst. C. A. 1910, 4, 1530; J. S. C. I. 1910, 29, 557. H. Stassen, Belg.
P. 254057, 1913, agglomerates cellulose materials to replace leather by zinc
chloride followed by cuprammonia. See E. Krusche, E. P. 8164, 1899;
abst. J. S. C. I. 1899, 18, 756, who prepares vulcanized fiber with cupram-
monia. Vulcanized Fibre Co., E. P. 1008, 1877. See Papier Ztg. 1905,
3183; 1908, 3330. T. Hanna, U. S. P. 196894, 196895, 1877. In the F.
Ahrens process for vulcanized fiber manufacture (Papierfabr. 1913, U, 1414;
abst. J. S. C. I. 1913, 32, 1152; C. A. 1914, 8, 1203) boiled cotton or linen
rags are beaten in presence of sodium carbonate to a long-fibered half -stuff.
The pulp is drained and washed in centrifugal machines, in which also the
short-beaten fiber-fragments are eliminated. The stuff is mixed with a dil-
ute solution of zinc chloride and formed into boards of spongy texture. Single
boards are laid flat in stonewai-e trays, covered with a concentrated solution
of zinc chloride and allowed to remain protected from the air for some hours.
The excess of liquid is drained off and the surface of the sheet is strewn with
a layer of finely powdered, fused zinc chloride, several mm. thick. When
the powder has dissolved, the action can be accelerated by slight and uni-
form heating in an electrically heated oven, in which the tem])erature at all
points can be carefully controlled. At first the temp>erature must not exceed
40°, but after an hour it may be raised to 60*'-70®. The board becomes

CEtI.UU)SE 105

for felt, leather or cork by pressing and drying a mixture of com-
minuted organic fibers as cotton, cork or wood meal in a solution
of cellulose in zinc chloride as the cementing material. In hard-
ening cotton fiber sheets or other fibrous material, H. Tiffany^
immerses in a bath of zinc chloride which softens or gelatinizes
the cellulose of the fiber, which is then electrolyzed to remove the
acid or salt retained by the fabric, the latter being then slowly
dried in order to harden.*

In the A. Parkes process' zinc iodide or nitrate have been
specified as preferable to the corresponding chloride, while in the
method of C. Mueller* zinc chlorate is advocated, especially where
the filaments are to be used in the production of incandescent
mantles. If a gelatin or celluloid substitute is to be manufactured
a hardening agent such as formaldehyde, may be added during
the boiling process, the resulting mass being treated, if necessary,
with calcium chlorate solution and afterwards rolled into fila-
ments or sheets.

Along similar lines is the process of J. StrehU,*^ whereby ma-
terials similar to vulcanized fiber, gelatinized fiber, and leatheroid
are obtained by treatment of cellulose first with zinc chloride (or
the chlorides of tin, calcium, magnesium or aluminum) in order
to render the cellulose more dense and less porous. The next
step in the process consists in incorporating some body which
tends to induce flexibility, such as sugar, glycerol and water, the

vitreous and smooth. The tray is removed, the board allowed to cool and
absorb moisture from the air, and the lye poured off and replaced by water.
The sheet gradually hardens and is allowed to dfain on a glass plate. Wash-
ing is continued in a tank of water in which the sheet is suspended on lead-
covered wire netting, and is completed in running water. The sheet is dried
slowly at 60°-100°, if necessary with the help of a vacuum. It is finally
pressed ]9at and constitutes a product which is pale yellow in color, fairly
transparent at a thickness of 1 cm. and possesses all the properties of the
best vulcanized fiber. The zinc chloride is recovered to the extent of 90% and
the fine particles of fiber from the centrifugal machines are collected in filter-
presses and used as a filling for vulcanite goods. Compare D. R. P. 216629,
1907; abst. C. A. 1910, 4, 827; Chem. Zentr. 1910, I, 71; Zts. ang. Chem.
1910, 23, 144.

1. U. S. P. 1226279, 1917; abst. C. A. 1917, U, 2155; J. S. C. I. 1917.
36,708.

2. Compare C. Cross and E. Bevan, Cosmos, 1893, 26, 288.

3. E. P. 983, 1881. D. R. P. 18413, 1882; abst. Dingl. Poly. 1882,
245, 141; Wag. Jahr. 1882, 28, 1061; Chem. Tech. Rep. 1882, 21, 1, 83; Chem.
Tech. Mitth. 1882-1883, 32, 84, 278; Chem. Ind. 1882, 5, 48.

4. E. P. 10430, 1912. F. P. 443133, 1912; abst. J. S. C. I. 1912, 31,
1026; 1913, 32, 531.

5. U. S. P. 717050, 1902; abst. J. A. C. S. X903, 26, 344.

106 TECHNOUKSY OF CEtLUWSE ESTERS

material being then heated with a fusible binding agent as resin,
gum or shellac, for the formation of thermoplastic, moldable
articles.

According to La Compagnie Francaise de la Soie Parisienne,^
elastic cellulose fibers of great tensile strength and capable of
replacing silk are obtained from solutions of cellulose in zinc
chloride or ammoniacal cupric chloride, when the separation of
the individual filaments is effected by moderately concentrated
sulfuric acid of 30-65% strength. The best results are claimed
to be obtained at the ordinary temperature with 50% acid. The
threads produced with a more dilute acid are weaker and less
pliant, while the employment of acid of higher concentration than
65% results in the partial disintegration of the product.

A. Hill* imparts to mercerized cotton yams and tissues the
plasticity necessary to enable them to receive and retain — ^like silk
fabrics — forms impressed upon them in the operations of crimping,
by treatment with a solution of cellulose in zinc chloride and
calcium chloride, the fabrics or tissues being then passed through
alcohol to precipitate the cellulose and remove the solvents.
Or, they may be coated with casein, or gelatin followed by a
formaldehyde bath to render the proteid insoluble, in some
instances increasing the water-repellent effect by a final treat-
ment with celluloid dissolved in acetone or other readily evap-
orable liquid.

Other Cellulose Solvents. According to A. Dubosc,' cellulose
readily dissolves in the thiocyanates (sulfocyanides) forming a
viscous material like collodion, which is adapted to form threads
and may be used in the manufacture of artificial silk.

In a recent patent disclosure* is described a process for the
treatment of cellulose in the production of solutions and viscous

1. F. P. 308715, 1901; abst. J. S. C. I. 1902, 21, 49. See also, C.
Suevem, Faerb. Ztg. 1900, 11, 97; abst. J. S. C. I. 1900, 19, 436. E. Bron-
nert. Bull. Soc. Ind. Mulhouse, 1900, 177; abst. J. S. C. I. 1900, 19, 819,
820; Jahr. Chem. 1900, 843; Chem, Centr. 1900, II, 749.

2. E. P. 8076, 1901. U. S. P. 705244, 1902. F. P. 320614, 1902; abst.
J. S. C. I. 1902, n, 912, 1074; 1903, 22, 42.

3. Bull. soc. ind. Rouen; Chem. Ztg. 1905, 29, 823; abst. J. S. C. I.
1905, 24, 901. Bull. soc. incf. Rouen, 33, 318; abst. Muster. Ztg. 53, 19.
BuU. soc. ind. Rouen, 1908, 36, 272; C. A. 1908, 2, 3283.

4. Manchester Oxide Co., R. Clayton, J. Huebner, and H. Williams,
E. P. 123784, 1919; abst. J. S. C. I. 1919, 38, 282-A; C. A. 1919, 13, 1637.
U. S. P. 1301652, 1919; abst. J. S. C. I. 1919, 38, 460-A; C. A. 1919, 13, 1928.

c«i.i.uix)s« 107

and gelatinous bodies, which is brought about by the treatment
of cotton and other forms of cellulose with thiocyanates. The
thiocyanates of manganese, strontium, calcium and lithium will
of themselves act satisfactorily, while in other cases best results
are obtained by employing two or more thiocyanates simultan-
eously, as by dissolving sparingly soluble thiocyanates in solu-
tions of more soluble thiocyanates or in calcium chloride — the
latter having no adverse effect on the solvent action of the thio-
cyanates for cellulose. The thiocyanate solutions may be acidi-
fied, preferably with acetic acid. The method of carrying the
process into effect is indicated by the following examples:

1. Four gm. of cotton, preferably dry, is placed in 100 cc.
of calcium thiocyanate solution of sp. gr. 1.38, the mixture is
stirred, heated to 100° and the heating continued for one hour
with agitation, the temperature being afterwards raised to 120®,
and there maintained until solution of the cellulose results.

2. Proceed as in Example 1, the solvent mixture being 100
cc. containing 70 gm. each of sodium and mercuric thiocyanate.

3. Thirty cc. of calcium chloride solution containing 86 gm.
CaCU per 100 cc. of solution is added to 70 cc. calcium thio-
cyanate solution containing 76 gm. per 100 cc. of solution. The
liquids after thorough mixing, are used as in Example 1 above.

Acetic acid of 4% strength may be added to the above.

In the process for the production of new derivatives as dis-
closed by P. Goissedet* cellulose, such as cotton, preferably in
the dry condition, or cellulose derivatives containing hydroxy!
groups, is made to react with an aliphatic or aromatic isocyanic
ester, with or without the addition of a tertiary base or bases, to
produce carbamic esters, which can be used for the same purpose
as other cellulose esters. Thus, dried cellulose may be heated
with about three times its weight of phenyl isocyanate or other
isocyanic ester, in presence of anhydrous pyridine (which promotes
the reaction and acts as a diluent), and the resulting phenylcarb-
amic ester is isolated by pouring the mass into water.

According to H. Deming* strong solutions of mercuric chlor-

1. E. P. 130277, 1919; abst. J. S. C. I. 1919, 38, 714-A.

2. J. A. S. C. 1911, 33, 1515; abst. J. S. C. I. 1911, 30, 1111; J. C. S.
1911, W, i, 771; C. A. 1911, 5, 3678; Chem. Zentr. 1911, II, 1433; Koll. Zts.
1911, 9, 200; Zts. Chem. Ind. Koll. 1912, U, 43. P. v. Weimarn (D. R. P.
275882, 1912; abst. J. S. C. I. 1914, 33, 958; C. A. 1915, 3, 378; Zts. ang.

108 TECHNOWMJY OF CEl«I,UIX>SE ESTERS

ide and bismuth chloride m concentrated hydrochloric acid fonn
splendid solvents of cellulose, even in the cold. Four parts of
stannous chloride dissolved in one part of water brings cellulose

Chem. 1914, 27, 603; Chem. Ztg. Rep. 1914, 38, 434; Wag. Jahr. 1914, II, 413)
has embodied these ideas in a patent, the essence of which is the conversion of eel-
lulosic substances first into a gelatinous or plastic condition and finally into col-
loidal solutions, by heating them under suitable conditions with solutions of neu-
tral salts, other than zinc salts, potassium and ammonium thiocyanate, potassi-
um iodide^ and potassium-mercuric or barium-mercuric iodide. When sodium
iodide, calcium bromide or iodide, or barium, calcium, strontium, or sodium
thiocyanate is used, the reactions can be carried out at atmospheric pressure.
Sodium or potassium chloride and sodium sulfate involve the use of higher pres-
sures. When "concentrated" sodium chloride solution is used, solution of the
cellulose commences at about 1 70 ° at 8 atmos. The same solvent action is obser-
ved with nitrates, acetates, and many other salts. P. von Weimam (Zts. Chem.
Ind. Kol. 1912, U, 41; abst. J. S. C. I. 1912, 30, 768; C. A. 1912,
6, 3516; J. C. S. 1912, 102, i, 679; Chem. Zentr. 1912, II, 817; Chem.
Ztg. Rep. 1913, 37, 14) has found that different kinds of cellulose (filter-
paper, pure cotton wool) can be converted into a gelatinous, plastic
condition or into a dispersoid (colloidal) solution by simple treatment with
aqueous salt solutions, if certain conditions of concentration, pressure,
temperature, and duration of action, varying according to the nature of
the salt, be maintained. The more soluble the salt and the greater its
capacity of forming hydrates, the more readily soluble (peptizable) is
the cellulose in the solution ; hence it is generally advisable to increase the
solubility by increasing the pressure or temperature, or both. In carrying
out this peptization process, a vessel is filled with water, the cellulose,
e. g., filter-paper (3 gms. per 100 cc. of water) is introduced, and a suitable
salt (lithium chloride, calcium bromide, manganese thiocyanate, etc.) is added,
while the contents of the vessel are heated. After a time the conversion of
the cellulose into a gelatinous, plastic condition begins and may be accelerated
by agitating the mixture. When the desired condition has been attained,
the heating and addition of the salt are stopped, the mixture is cooled, the
solution decanted from the precipitate deposited, and the latter washed with
water, alcohol, etc., to remove the adsorbed salt or product of hydrolysis of
the latter. The decanted solution and the wash-liquors are used instead of
water for the peptization of a further quantity of cellulose. Instead of cool-
ing and waiting for a precipitate to deposit, the mixture may be diluted with
water, and the gelatinous cellulose separated by filtration. If a dispersoid
(colloidal) solution is desired, the heating and addition of the salt are contin-
ued until the peptization is complete; from the colloidal solution, hydrated
cellulose can be recovered in different forms by means of various coagulating
agents. The hydrated cellulose prepared by this method, on account of
its high degree of dispersion, is highly reactive. With certain salts, e. g.,
sodium iodide, calcium bromide, iodide, and thiocyanate, strontium iodide
and thiocyanate, barium thiocyanate, etc., the process can be carried out at
atmospheric pressure, but with other salts, e. g., sodium, potassium and barium
chlorides, etc., increased pressure is necessary. With a concentrated solu-
tion of sodium chloride, peptization of cellulose begins at about 170^ and 8
atmospheres pressure. In order to prevent decomposition of the cellulose, as
far as possible, it is preferable to work at a moderate temperatuce and in-
crease the solubility of the salt by increasing the pressure. With saturated
solutions (at the boiling temperature under atmospheric pressure), peptiza-
tion of cellulose proceeds rapidly with lithium chloride, bromide, iodide, and
nitrate, sodium iodide, strontium iodide, and thiocyanate, calcium bromide,
iodide, and thiocyanate, barium and manganese thiocyanates, etc. Solu-

CBLlrULOSE 109

into solution when warmed to 100°, while the same salt in con-
centrated hydrochloric acid is reactive in the cold. Antimony
pentachloride, tin tetrachloride and titanium tetrachloride mixed
with a small amoimt of hydrochloric acid are also cellulose sol-
vents. Cobalt chloride, auric chloride, lu-anyl chloride, cerous
chloride and chromic chloride are less efficient. To secure a clear
solution in such cases it is usually necessary to filter the liquid
through an asbestos felt which has been washed with concentrated
hydrochloric acid as portions of the filter remain dissolved. Ac-
cording to Deming the action of bromides in acid solution is com-
plicated by the fact that hydrobromic acid has such a powerful
effect on cellulose. The decomposition of the latter by hydro-
bromic acid gas in ethereal solution with the production of brom-
methylfurfural is known.^ Concentrated aqueous hydrobromic
acid dissolves cellulose almost instantly but, however, with pro-
found decomposition. Aqueous zinc »bromide exerts a dissolving
action upon cellulose while the action is comparatively weak with
zinc fluoride. Bismuth bromide and mercuric bromide dissolved
in hydrochloric acid attack cellulose at concentrations where an
equivalent amount of hydrobromic acid would disintegrate the
fibers without dissolving them. The same is substantially true

lions of cellulose containing only about 1% of the latter set to transparent
or semi-transparent jellies on cooling, and if the jellies are left exposed to the
•air, the salts effloresce, and a skeleton jelly of hydrated cellulose is left.
With other salts, which effect peptization only on more* prolonged heating,
degradation of the cellulose to substances of lower molecular weight also
takes place. Cellulose which has been swollen by soaking in concentrated
saline solutions can be subsequently peptized much more readily than un-
treated cellulose.

1. H. Fenton and M. Gostling, Proc. Chem. Soc. 1901, 17, 119; J. C. S.
1901, 73, 807; abst. Bull. Soc. Chim. 1901, 26, 796; Rep. Chim. 1901, 1, 424;
Chem. Centr. 1901, II, 123, 426; Jahr. Chem. 1901, 838, 1494; Zts. ang.
Chem. 1901, 14. 273; Chem. Ztg. 1901, 25, 180, 507. See also M. Gostling,
J. C. S. 1903, 83, 181; abst. J. Soc. Dyers Col. 1903, IS, 69; Chem. Centr.
1903, I, 250, 629; Bull. Soc. Chim. 1903, 30, 883; Rep. Chim. 1903. 3, 224;
Chem. Ztg. 1903, 27, 102; Jahr. Chem. 1903, 1014. See also M. Conrad and
M. Guthzeit; Ber. 1886, 18, 439; 1886, IS, 2659, 2844; abst. J. C. S. 1885,
48, 746; 1887, 52, 229; Bull. Soc. Chim. 1886, 48, 10; 1887, 47, 652; Jahr.
Chem. 1885, 1745. 1746; Wag. Jahr. 1885, », 753; 1886, 32, 615. E. Win-
terstein (Zts. physiol. Chem. 1892, 17, 400; abst. J. C. S. 189B, 64, i, 127;
Chem. Centr. 1893, I, 22; Jahr. Chem. 1892, 2475) has studied the action
of dilute acids and alkalis upon cellulose prepared from various sources, and
has expressed the loss sustained by the cellulose in a series of tables. The
results obtained, in general, confirm the statements of previous observers
that cellulose is but slightly attacked by very dilute, hot mineral acids.
With alkalis (5%-10%) the cellulose is considerably dissolved, which is
confirmatory of other investigators.

110 TECHNOWGY OF CEI<WU)SH ESTERS

of zinc and mercuric iodides in HCl solutions which dissolve cellu-
lose quite readily. Lead iodide and bismuth iodide, when dis-
solved in hydriodic acid cause cellulose to pass into solution, but
the concentrated acid itself, it must be remembered, has con-
siderable solvent power. The chlorides of the alkalis and alkaline
earths will not dissolve cellulose in hydrochloric acid, one reason,
perhaps, being the fact that the salts themselves are but spar-
ingly soluble in the acid. However, solutions of calcium chloride,
calcium bromide, barium bromide, magnesium bromide, lithium
chloride and potassium chloride in formic acid or any mixture of
the latter with hydrochloric acid do dissolve cellulose, a less
decided action being obtained with solutions of lithium and cal-
cium chlorides in trichloracetic acid.

Organic acids in solution, even when moderately concentrated,
appear to have no injiuious action upon cotton cellulose. Such
non-volatile organic acids, however, as oxaUc, tartaric and citric,
when allowed to dry upon the fiber, act much in the same maimer
as an inorganic acid, especially at elevated temperatures. Acetic
acid, however, exerts no destructive action, but cellulose pre-
viously soaked in acetic acid esterifies much more readily than if
not so treated.^

E. Knecht^ has shown that portions of calico printed with

1. Chem. News, 1870, 21, 144, 156; 1884, 49, 190. C. Cross and E.
Bevan, Chem. News, 1891, €3, 66; abst. J. C. S. 1891, €0, 890; Mon. Sci.
1892, 39, 202; Chem. Centr. 1891, I, 534; Chem. Tech. Rep. 1891, I, 174;
Chem. Ztg. Rep. 1891, 15, 44; Jahr. Chem. 1891, 2181. T. Hanausek, Chem.
Ztg. 1894, IB, 441; Chem. News, 1894, 69, 174, 192; abst. Chem. Centr.
1894, I, 864; Jahr. Chem. 1894, 1132. C. Cross and E. Bevan. Chemical
Notes, Feb. 6, 1891; abst. Year Book Pharm. 1891, 91. F. and A. van den
Bosch and O. Miiller, E. P. 6942, 1906; abst. J. S. C. I. 1906, 35, 775. Belg.
P. 237056, 1911, Compagnie Francaise des Applications de la Celltdose.

2. Seventh InU. Cong. Appl. Chem. 1909; J. S. C. I. 1909, 28, 700;
abst. C. A. 1908, 2, 3403; Zts. ang. Chem. 1909, 22, 1120; Proc. Manch.
Lit. Phil. Soc. 1908, &Z, II. XXII. A. Scheurer (Bull. Soc. Ind. Mulhouse,
1904, 74, 211; abst. J. S. C. I. 1904, 23, 981) has recorded some experiments,
on the effect of oxalic, lactic, tartaric, citric, thiocyanic, o-, w-, and pyro-
phosphoric and phosphorous acids on cotton under the influence of dry and
moist heats. Solutions of oxalic acid containing 10 and 20 gm. per liter were
used, and solutions of the other acids of equivalent strength. Thiocyanic
acid had the greatest effect on the tensile strength of the cotton in a dry
atmosphere at 40°-50®, the stronger solution causing the tensile strength to
fall to less than half its original value after 72 hours; the effect of thiocyanic to
acid and steam is so small as to be negligible. Meta- and pyrophosphoric
acids, in the stronger solutions, caused a reduction of about one-third of the
tensile strength, both after three days of hot-air treatment and after one
hour's steaming. The action of phosphorous and oxalic acids was some-
what less, the reduction being from 25% to 27% in either case. Lactic,

CEI^LULOSE 111

oxalic acid and thickened with "British gum," lose their char-
acteristic properties — ^marked affinity for methylene blue and
decreased aflSnity for direct colors — ^af ter boiling for a few minutes
in dilute NaOH. No oxalic acid could be detected in the caustic
soda extract, but formic acid was found, which appears to be
formed by the decomposition of the oxalic acid, and to act upon
the cellulose in the nascent state, forming formylcellulose. Mai-
onic acid acts similarly, yielding cellulose acetate. No action was
observed With succinic or glutaric acids.

Action of Salts on Cellulose. Under the topic ''Solvents
of Cellulose," it has been shown that by the action of concentrated
neutral or acid aqueous solutions of salts at high temperatures
upon cellulose, the latter may either be converted into a plastic
or go entirely into solution. With less drastic treatment, as for
example, the simple contact of cellulose with salt solutions, a
certain aflSnity of the cellulose for various saline combinations
has been noticed. In some instances the cellulose simply ab-
sorbs the salt from the solution, which can afterwards be removed
by washing with water. In other cases the salt is fixed in the
cellulose material and is not removed by simple washing with
water. The results obtained by different workers, however, are
not concordant.

Vignon^ foimd one gram of cotton capable of retaining up
to 0.4% of the salt from a solution containing 1 gm. ammonium
chloride in 250 cc. water. He finds, however, that sodium chlor-
ide is not retained under similar conditions and this observation
agrees with that of Mansier.* According to this worker, cellu-
lose materials also retain calcium chloride. Against this latter
assertion, we have the evidence of E. Knecht,' who states that

orthophosphoric, tartaric, and citric acids, in the order named, had still less
effect on the tensile strength of the cotton, the reduction lying between 10%
and 20%. The addition of glucose to the printing mixture containing oxalic
acid diminished the destructive action of the add under the influence of hot
air or steam to a considerable extent, particularly in the former case.

T. Edison (Poly. Notiz. 1877, 32, 352; Chem. Centr. 1877, 58, 693;
Chem. News, 1877, 36, 138) has recorded that the vapor of chloral hydrate
is a solvent of cellulose.

2. Jour. Pharm. Chito. 1902, (6), IS, 60; abst. Chem. Centr. 1902,
II, 768, 769; J. C. S. 1902, 82, ii, 690; J. S. C. I. 1902, a, 1098, 1155; Rep.
Chim. 1902, 2, 624; Tahr. Chem. 1902, 238; Zts. anal. Chem. 1904, 43, 314.

3. Ber. 1888, 21, 1557, 2804; abst. Chem. Ztg. 1888, 13, 1173; Chem.
Ztg. Rep. 1888, 13, 170; J. C. S. 1888, 54, 832; J. S. C. I. 1888, 7, 621; J.

112 TECHNOI<OGY OP CELI<UlrOSE ESTERS

no aflSnity is shown by cellulose for calcium chloride.

Various cellulose materials, such as cotton fiber, have the
power of absorbing and fixing other salts, such as those of iron,^
cerium,^ copper,^ lead,* and titanium.^ It is considered* that a
small quantity of oxycellulose or other cellulose derivatives may
be responsible for the reactions recorded between cellulose ma-
terials and various metallic derivatives. The experiments of
Molisch' tend to support this view, for he finds that cellulose
after treatment with alkali, acquired increased affinity for the
absorption and fixation of iron, lead and other metallic salts. He
attributes the increased affinity not to the formation of oxycel-
lulose, but rather to the presence of small quantities of pectic
substances in the cellulose material.^ The retention of salts in
cellulose may be due not only to absorption and combination,
but also in part to capillary action."

In the above instances of the absorption and fixation of salts
in cellulose we are dealing in the main with neutral salts. The
phenomena must be regarded in a somewhat different light when

Soc. Dyers Col. 1888, 104; Bull. Soc. Chim. 1889, (3), 2, 546; Mon. Sci. 1888,
32, 1159; Chem. Ind. 1888, 11, 400; Chem. Tech. Rep. 1888, II, 32; Jahr.
Chem. 1888, 2865; Wag. Jahr. 1888, 34, 1108; Zts. ang. Chem. 1888, 1, 683;
Tech. Chem. Jahr. 1888-1889, 11, 234. See also Zts. Chem. Ind. 1887, "
165; Wag. Jahr. 1887, 33, 165.

1. Schellen, Dissertation, Strassburg, 1905, 14.

2. G. Witz, Bull. soc. ind. Rouen, 1882, 416; 1883, 11, 169; abst. J. S.
C. I. 1883, 2, 378; Faerb. Must. Ztg. 17, 129; Mon. Sci. 1883, 25, 517; 1884,
26, 1161; Jahr. Chem. 1883, 1782; Wag. Jahr. 1883, 29, 1068; Dingl. Poly.
1883, 250, 271. See also G. Witz. D. R. P. 24173. H. Schmid, Dingl. Poly.
1883,250,272.

3. Herzog, Zts. Parbenind. 1908, 1, 281. v. Cochenhausen, Zts. ang.
Chem. 1906, 19, 1987, 2024; abst. Bull. Soc. Chim. 1907, (3), 37, 491;
Chem. Zcntr. 1907, I, 188; Chem. Ztg. Rep. 1907, 31, 11; Jahr. Chem. 1905-
1908, I, 1397; Wag. Jahr. 1906, I, 539.

4. E. Knecht, Jour. Soc. Dyers Col. 1909, 25, 47. See also Frerichs,
Apoth. Ztg. 1902, 884,

5. Hibbert, Jour. Soc. Dyers Col. 1906, 22, 278; Chem. Ztg. Repert. 1906,
30, 394; C. A. 1907, 1, 242; J. S. C. I. 1906, 25, 880; Text. Col. 28, 297.

6. See Schwalbe, Die Chemie der Cellulose, 1911, 79-80,

7. See W. Massot, Zts. ang. Chem. 1909, 22, 241, 299; abst. C. A.
1910, 4, 1240; Chem. Zentr. 1909, I, 801.

8. Persoz, Traite de I'impression, 1846, 1, 312.

9. F. Goppelsroeder, "Darstellung der FarbstofTe," 1885. Zts. Chem.
Ind. KoU. 1909, 4, 94. See also R. KruUa, Zts. physik. Chem. 1909. 66,
307; abst. Chem. Zentr. 1909, I, 1956; Jahr. Chem. 1909, 120; Meyer Jahr.
Chem. 1909, 19, 28; C. A. 1909, 3, 1959; J. C. S. 1909, 96, ii, 469; BuU. Soc.
Chim. 1910, (4), 8, 489; Rep. Chim. 1909,9, 387; Zts. Chim. Ind. Kol. 1909,
4, 214; Chem. Tech. Rep. 1909, 33, 325.

CEtLUlX)SE 1 13

we consider the possibility of acid formation.^ On this view, the
neutral salt on heating would act in the sa^ie manner as an acid
salt,^ although possibly not so energetic.

Vignon has shown that a cellulose material such as cotton
(which has received a preliminary alkali treatment), absorbs mer-
curic oxide with smaller quantities of mercuric chloride from a
mercuric chloride bath. The mercuric chloride solution, in pres-
ence of cellulose under heat, appears to form mercuric oxide and
hydrochloric acid' and the oxide remains combined with the cel-
lulose. The absorption of mercuric chloride in smaller quan-
tities has also been noted by W. Schellens.* Cellidose, which has
first been soaked in a solution of aluminium sulfate or chloride
and then dried, is stated on subsequent wetting, to show an acid
reaction,^ the cellulose fiber being attacked and weakened. • Pos-
sibly a basic salt is formed and free acid liberated. A similar
formation of acid is stated to occur when the aluminium salt is
replaced by certain other compounds such as magnesium chlor-
ide.^ The fixing of metallic compoimds is most marked in the
case of salts which are readily dissociated. According to Girard*
the main reaction consists in the transformation of cellulose into
hydrocellulose by the action of acid. He considers that any car-
bonization occurring as a result of the dehydration is only an

1. J. Barral and Salvetat, Ann. Chim. Phys. 1876, (6), 9, 127; Compt.
rend. 1875, 81, 1189; abst. Chem. News, 1876, 33, 18; T. C. S. 1876, 30, i,
821; Bull. Soc. Chim. 1876, 25, 425; Mon. Sci. 1876, IB, 90; Ber. 1876, 9,
A, 68; Dingl. Poly. 1876, 219, 469; Jahr. Chem. 1875, 1164. See also Bayer
Ind. Gew. 1875, 296; abst. Dingl. Poly. 1876, 219, 182.

2. R. Schwarz, Paerb. Ztg. 1908, 19, 66, 87; abst. C. A. 1908, 2, 2168;
J. S. C. I. 1908, 27, 329; Rep. Chim. 1908, 8, 280; Chem. Zentr. 1908, I,
1502; Zts. ang. Chem. 1908, 21, 2480.

3. Vignon, Compt. rend. 1893, 116, 517, 684, 645; Bull. Soc. Chim.
1893, (3), 9, 502, 506; abst. Chem. News, 1893, 68, 49; J. C. S. 1893, 64, i,
387; J. S. C. I. 1893, 12, 948; Chem. Centr. 1893, 64, 1, 708, 844; Chem. Ztg.
1893, 17, 74; Chem. Ztg. Rep. 1893, 17, 97; Jahr. Chem. 1893, 47, 882. See
also Compt. rend. 1890, HO, 534; abst. Chem. News, 1893, 67, 145; Bull.
Soc. Chim. 1890, (3), 3, 405, 472, 851; 1891, (3), 5, 557; Chem. Ztg. Rep.
1890, 14, 56; 1891, 15, 76, 111.

4. Arch. Pharm. 1906, 243, 617; abst. Jahr. Chem. 1905-1908, II,
3183. Blondel, Zts. Farbenind. 1904, 3, 291. F. Breinl and C. Hanofsky,
Gewerbemus. 1892, 203; Chem. Ztg. 1897, 2L, 563.

5. Liechti and Suida, Gewerbemus. 1883.

6. Kielmayer, Faerberldirling, 133.

7. E. Uhler, Faerb. Ztg. 1908, 57, 1; abst. Chem. Ztg. Repert. 1908,
32, 44; C. A. 1908, 2, 1048.

8. Ann. Chim. Phys. 1881, (5), 24, 333; abst. Ber. 1881, 14, II, 2834;
Jahr. Chem. 1881, 34, 986: J. C. S. 1882, 42, 378; Proc. U. S. Nav. Inst.
1882, 8, 209; Bull. d'Enc. 81, 176; BuU. Musee. £2, 80; Naturforscher, 15, 26.

114 rncuNoioGY of ceullxose bsthks

accompanying factor, tfaongh other workers^ contend that dehy-
dration is the main factor. The weakening of the fiber may
be also due to a catalytic transference of oxygen by the salts or
the oxides separated.^ Iron, copper, and possibly aluminium
oxide act as oxygen carriers.'

Kolb^ accounts for the weakening of cellulose which occurs
when the cellulose fiber has been moistened with a salt solution
and then dried at a high temperature in a different manner. He
considers the weakening as brought about by a mechanical pro-
cess, and infers that crystals in the dried material actually cut
the fibers. With neutral salts such as sodium sulfate he finds
weakening of the fiber of the cellulose material. These observa-
ticms indicate that the formation of acid does not always accotmt
for carbonization. Against the acid formation theory the evi-
dence of ChcvrcuP is important. He has shown that a piece of
woollen fabric containing cellulose, when saturated with an amount
of hydrochloric acid corresponding to a given quantity of alum-
inium chloride, does not show destruction on heating. No hydro-
chloric acid vapors are detected on heating to 140° a cellulose
which has been previously soaked in ammonium chloride solu-
tion.* Moreover, when aluminium chloride is employed the color
of the wool is not changed, while with free hydrochloric acid the

1. Sec C. Beadle, La papeterie, 1909, 31, 69.

2. P. Sislcy, Rev. mat. Col. 1909, 13, 8; abst. C. A. 1909, 3, 1692;
Rep. Chim. 1909, 9, 280; Bull. Soc. Chim. 1909, (4), 5, 1; J. S. C. I. 1909, 28,
136.

3. Witz, Bull. soc. ind. Rouen, 1883, 11, 212.

4. J. Kolb, Bull. Mulhouse, 1868, 38, 920; Compt. rend. 1868, 68,
1024; 87, 742; Instil. 1868, 329; Ann. Chim. Phys. 1868, (4), 14, 348; Bull.
Soc. Chim. 1809, (2), 11, 431; Dingl. Poly. 1845, 85,62; 96, 321; Jahr. Chem.
18(^8,21,981.

6. Compare R. Buntrock and E. Raeuber, Text. u. Faerb. Ztg, 1903,
3. 21, 12;^; abst. Jahr. Chem. 1903, 58, 1560. T. Appleyard and T. Deakin,
J. vSoc. Dyers Col. 1902, 18, 128; Rev. mat. color. 1902, 8, 166; J. S. C. I.
nH)2, 21, 702. R. SchUler and R. Bauer, D. R. P. 212694; abst. Wag. Jahr.
imm, II, 405; Zts. ang. Chem. 1909, 22, 861. U. S. P. 917402, 1909; abst.
J. S. C. I. HKH), 28, 471. L. Cassella & Co., Zts. ang. Chem. 1909, 22, 88.
1861; ()est. Woll. Leinenind. 1909. 29, 520.

6. A. Beck. Bull. soc. ind. Rouen, 1904, 32, 351; Zts. Farbenind.
1905, 4, 49; Chem. Ztg. Rep. UKU, 28, 707. G. de Keukelaere, D. R. P.
HMM48; Knerb. Ztg. 1906. 17, 261; Chem. Ztg. 1906, 30, 405; Wag. Jahr.
HHMi, 82, II, 398; Zts. ang. Chem. 1906. 19, 1815. B. Rassow (Zts. ang.
Chem. 1911, 24, 1127; J. S. C. I. 1911. 30, 1307; C. A. 1912, 8, 684) has ex-
am tned the caiHicity of cellulose for absorbing and fixing small quantities
of mctul from dilute solutions of copper, nickel, aluminium and potassium
salts.

CEI<LUI*0SB 115

color is destroyed. A basic aluminium salt is probably precip-
itated which protects the color. The type of material employed
may influence the result obtained and in part explain the appar-
ently contradictory results of various workers. Thus, according
to Breinl and Hanofsky/ cellulose (e. g., filter paper), which has
been soaked in aluminium chloride and then dried at a high tem-
perature, evolves hydrochloric acid in small quantities. In a
comparative experiment using sheep- wool instead of cotton, prac-
tically no hydrochloric acid was evolved. Sisley,* on heating
various cellulose materials at a high temperature with sodium
chloride, finds that cotton acts in an entirely different manner to
silk and wool.

L. Liechti and W. Suida have shown in their investigation
with aluminium salts,' that the fact that a salt is basic is no
indication that it possesses powers of mordanting, the basic chlor-
ides and oxychlorides of aluminium not being mordants.

R. Haller* has studied the behavior of cotton of different
degrees of purification towards solutions of metallic salts. Repre-
sentative samples of Indian, American and Egyptian cotton were
prepared in different stages of chemical purification following
the usual industrial bleaching process. The samples were treated
at the ordinary temperature for 48 hours with solutions
of aluminium sulfate, aluminium acetate, and lead acetate.
The change in the percentage of metallic base in the solu-
tions was^ then determined in order to have an approxi-
mate measure of the absorption, and the quantity of me-
tallic base fixed by the cotton after washing was determined

1. F. Breinl and C. Hanofsky, Gewerbemus. 1892, 203; abst. Chem.
Ztg. 1897, 21, 563. See P. Bolley, Ann. 1859, lOS, 235; Kritische und ex-
perimentelle Beitraege zur Theorie der Faerberei, Zurich, 1859; Dingl. Poly.
1859, 153, 362, 431; Phil. Mag. 1859, (4), IB, 481; Chem. Centr. 1859, 30,
897; N. ^ch. phys. nat. 6, 67. J. Boeseken, G. Tergau and A. Binnendijk,
Proc. Acad. Sci. Amsterdam, 1919. 21, 893; abst. C. A. 1919^ 13, 2123.

2. Rev. Mat. color. 1909, 13, 9; abst. C. A. 1909. 3, 1692; Rep. Chim.
1909, S, 280; Bull. Soc. Chim. 1909, (4), 5, 1; J. S. C. I. 1909, 28, 136. Moeh-
lau, Ber. 1886, IS, 2914; abst. J. C. S. 1886. 50, 947; J. S. C. I. 1886, 5, 597;
Bull. Soc. Chim. 1886, (2), 48, 121; Chem. Ind. 1886, S, 254; Jahr. Chem.
1886; 39, 2201; Wag. Jahr. 1886, 32, 508. Green and R. Levy, Rev. mat.
color. 1897, 1, 378; 1898, 2, 28; abst. Meyer Jahr. Chem. 1897, 7, 473.

3. J. S. C. I. 1883, 1. 637; J. C. S. 1884, 48, 794; Chem. Ind. 1884,
7, 129; Dingl. Poly. 1884, 251, 177; Jahr. Chem. 1883, 38, 1784; Wag. Jahr.
1883, 29, 1078; Mittheil des techn. Dewer. Wien. 1883, No. 1, 3.

4. Chem. Ztg. 1918, 42, 697; abst. J. S. C. I. 1919, 38, 70-A.

116 TBCHNOWXJY OF CKI<I<UI/)SB ^TERS

by incineration. In some cases with aluminium sulfate and in
all cases with aluminium acetate, a negative absorption was ob-
served, that is, the concentration of metallic base in solution was
increased instead of decreased by the action of the cotton. Using
aluminium acetate, the negative absorption was smallest in the
case of the raw fiber and became greater as the degree of piuifica-
tion was increased. Cotton which had been boiled with lime
gave higher values than that which had been boiled with caustic
soda. Negative adsorption was most pronounced in the case of
the Eg)T)tian cotton. Using aluminium sulfate, positive adsorp-
tion was observed in all cases with the raw cotton and with those
which had been boiled with lime; on the other hand, the samples
boiled with caustic soda, also those boiled first with lime and then
with soda, and the fully bleached samples, all showed negative
adsorption, increasing generally with the degree of purification.

Lead acetate showed in all cases a large positive adsorption
increasing with the purification of cotton. The maximum adsorp-
tion in all cases, both positive and negative, appears to corre-
spond with maximum ptuification of the cotton, which is attained
by boiling first with lime and then with caustic soda, with a sour
after each boil. Treatment with bleach liquor appears to de-
crease the purity of the cellulose, at least it lowers the adsorption
values. An exceptionally large adsorption with lead acetate was
shown by the raw cottons; no doubt, the ease of wetting by the
various solutions plays a part. Adsorption does pot necessarily
run parallel with fixation of insoluble base in the £!&er. In all
the experiments with aluminium salts, there was a fixation of
alumina, even when negative adsorption values were recorded.
In the experiments with lead acetate showing high positive ad-
sorption, a large fixation was at the same time observed in the
case of the raw cottons, and the appearance suggested that the
lead oxide was combined with some of the non-cellulose constitu-
ents. After boiling, the amount of fixation of lead oxide became
smaller with increasing purification of the cotton, although the
adsorption became more marked.

Cellulose and Acids. Comparatively early in the develop-
ment of cellulose, it was recognized that even the action of diluted
inorganic acids tended to diminish the strength of the cellulose. The
destruction of the cotton in half -woollen rags by means of satura-

c«ttui/)SB 117

tion and subsequently heating with adds is said to have been
first practiced in England by G. Koeber in 1852, while the re-
moval of extraneous material from wool by the same means is
supposed to have been originated in 1854 by Isart and Frezon.
R. Penton is said to have patented this idea of Koeber in 1853.^
It was in 1868 that J. Kolb observed^ that when a sample of linen
yam is immersed in sulfuric acid of 4^ B€. strength for 25 hours
its strength is reduced from 1.25 to 0.68 kilos, and emphasized
the fact that even very diluted acids must not be allowed to dry
on the material.

When J. Barral and Salvetat* treated cotton celltdose with
5% solution of hydrochloric, nitric and boric acids at 140®, the
cellulose darkened and could readily be rubbed to a powder.
These results were confirmed and extended by A. Girard in
1875,* who described the preparation of a structureless cellulose
of greatly diminished tensile strength by immersion of cotton in
55% sulfuric acid for 12 hotu^. His analyses indicated a water-
absorption conforming to the formula, CwHjjOn. He* proposed
for this product the name "hydrocellulose," this modification
representing, in his judgment, the first stage in the breaking
down of the cellulose molecule to glucose, and saw in parchment,
a paper glued together by the superficial formation of this hydro-
cellulose. He distinguished two forms of cellulose, one which
preserved the morphological structure of the cotton filament, and
the other, which is gelatinous and without structural form, being
easily reduced to a pulverulent state by rubbing. The properties
of hydrocellulose are detailed more extensively under the topic
"Hydrocellulose," but in connection with the tendering of cellu-
lose by means of acids, the fact must be remembered that be-

1. E. P. 1891, 1853.

2. BuU. Mulhouse, 1868, 38, 922.

3. Ann. Chim. Phys. 1876, (6), S, 129; abst. Chem. News, 1876, 33,
18; J. C. S. 1876, 29, 821; BuU. Soc. Chim. 1876, 25, 425; Compt. rend. 1876,
81, 1189; Mon. Sd. 1876, 18, 90; Ber. 1876, S, 68; Dingl. Poly. 1876. 219,
469; Jahr. Chem. 1876, 1164.

4. Compt. rend. 1876, 81, 1105; 1879, 88. 1322; 89, 170: Ann. Chim.
Phys. 1881, (5), 24, 337; abst. J. C. S. 1879, 36, 911; 1882, 42, 378: Jahr.
Chem. 1876, 786; 1879, 836; 1881, 985; Proc. U. S. Nav. Inst. 1882, 8, 309;
Ber. 1879, 12, 2168; 1881, 14, 2834; Wag. Jahr. 1879, 25, 419; BuU. Soc.
Chim. 1880, 34, 607; Mon. Sci. 1879, 21, 968; Chem. News, 1881, 44, 216;
J. A. C. S. 1879, 1, 400; Jahr. rein Chem. 1875, 142; 1881, 460.

6. Ann. Chim. Phys. 1876, (6), 9, 116.

118

TECHNOLOGY OP CBIXULOSE BSTERS

sides a loss of strength, comes at the same time an increased
affinity of the cellulose for basic dyesttiffs.

This characteristic property of loss of strength and in-
creased attraction for dyestuffs, when cellulose is treated with
acids has been the subject of numerous investigations right down
to the present time, as the phenomena exhibited is of paramount im-
portance in several branches of the textile art.

L. Vignon* has made comparative examinations of the ab-
sorption of adds by cotton, wool and silk, the values found for
cotton being reproduced below. They are of interest in connec-
tion with the subsequent development of the cellulose ester art
in indicating how the preUminary treatment of the cellulose may
so affect its structure and composition .as to be reflected in varia-
tions in solubility and stability when the cellulose is afterwards
nitrated, acetated or alkylated.*

TABLE VII.— ACTION OF SULFURIC ACID ON COTTON

Kind of Fiber

400 gm. Acid 1%.

Weight

K

Ki

K,

Ki/K,

Crude silk

10.00
8.63
9.12
9.85

1.015
1.015
1.015
1.015

0.950
0.985
1.016
0.902

2.169
1.379

4!379

2.26
1.40

• • ■ •

4.85

Dressed silk

Cotton

Wool

400 gm. Acid 0.1%.

«

Crude silk

Weight

K

K,

K,

Ki/K,

9.92

10.30

9.13

9.70

0.098
0.098
0.098
0.098

0.054
0.070
0.095
0.026

1.77
1.06

'2!96

32.77
14.93

Dressed silk

Cotton

Wool

1. Compt. rend. 1906, 143, 550; Rev. mat. color, 1907, 11, 15; Bull.
Soc. Ind. Mulhouse, 1906, 76, 359; Bull. Soc. Chim. 1906, 35, 1140; Zts.
ang. Chem. 1907, 20, 1144; C. A. 1907, 1, 781; J. C. S. 1907, W, i, 102; J. S.
C. I. 1906, 25, 1038; 1907, 26, 195; Rep. Chim. 1907, 7, 91; Chem. Centr.
1906, II, 1852; 1907, I, 517; Jahr. Chem. 1905-1908, II, 3181; Chem. Ztg.
1906, 30, 1078, 1263.

2. In the above table, which is taken from Schwalbe, "Die Chemie
der Cellulose," 43, K signifies the weight in gm. of the acid in 100 gm. of
solution before the experiment; Ki the weight in gm. after the experiment;
Kf is the weight in gm. of add fixed upon 100 gm. cotton, not including the
acid soaked up. The hanks were immersed for out hour at ordinary tem-
perature in 1% and 0.1% solutions of HsS04. The cotton was thoroughly
washed with distilled water before the experiment.

CELLULOSE

119

L. Vignon has likewise shown Hhat the add absorption is also
accompanied by a certain and definite evolution of heat, the cal-
ories evolved by immersing cotton in a normal solution of acid
being shown in the following table:

TABLE VIII.— COTTON

Spun, Unbleached

Loose. Bleached

For 100 gm.

For 1 mol.

For 100 gm.

For 1 mol.

H,S04

HCl

0.40
0.38

0.65
0.60

0.40
0.36

0.65
0.58

E. BlondeF found that sulfuric acid of 55%-62% slowly
changes cellulose at ordinary temperature, so that methylene
blue produces deep shades — a characteristic of oxycellulose — the
conditions of treatment being practically the same as that de-
scribed by A. Girard for the preparation of hydrocellulose.

According to E. Grandmougin* very dark shades are pro-
duced by dyeing those spots which previously have been touched
with 5% sulfuric acid, and this is l?ome out by the results of C.
Koechlin.* The data obtained by Vetillart is not so conclusive.*

It has been found that sodium sulfate exerts a neutralizing
action on the acid with less resultant tendering of cotton, due in
all probability to the formation of acid sodium sulfate. Later
it was found that with oxalic acid, sodium acid oxalate is the
main product of the reaction between oxaUc acid and sodium
sulfate. M. Fort and F. Pickles' have applied some of the mod-
ern views of physical chemistry obtained from electric conduc-
tivity experiments with solutions of acids and salts to the tender-

1. Compt. rend. 1890, HO, 286, 909; Bull. Soc. Chim. 1890, 3, 405,
851; abst. J. C. S. 1890, 58. 563. 939; J. S. C. I. 1890, 9, 855; Mon. Sci. 189Q,
35, 412, 635; Ber. 1890, 23, R, 555; Chem. Centr. 1890, I, 591, 988; Jahr.
Chem. 1890, 272, 273; Wag. Jahr. 1890, 36, 1122; Zts. ang. Chem. 1890, 3,
278.

2. Bull. soc. ind. Rouen, 1882, 10, 438, 471.

3. Zts. Farbenind. 1907, 6, 2; abst. Chem. Zentr. 1907, I, 946; Chem.
Ztg. Rep. 1907, 31, 77; Meyer Jahr. Chem. 1907, 17, 504.

4. Bull. Soc. Ind. Mulhouse, 1888. 55, 547; Mon. Sci. 1888, 31, 509,
1885; Chem. Ind. 1888, 11, 400; 1889, 12, 15; Chem. Tech. Rep. 1888, I,
37, 71; II, 60; Chem. Ztg. 1888, 12, 375; Jahr. Chem. 1888, 2859.

5. Bull. soc. ind. Rouen, 1883, 11, 234.

6. J. Soc. Dyers Col. 1915, 31, 255; abst. C. A. 1916, 10, 2527; J. S.
C. I. 1916, 35, 38.

120 TECHNOLOGY OF CSl<tUlX)SE RSTBRS

ing of cotton, their restilts being expressed in a series of tables.
One table gives relative strengths of acids used and their invert-
ing efficiency for comparison with tendering results with sulfuric,
hydrochloric, acetic, phosphoric, trichloracetic and tartaric adds
and add sodium sulfate. Their method was to treat 5 gm. sam-
ples of cotton cdlulose with 100 cc. of a solution of a definite
normality under a reflux condenser at a temperature maintained
by a boiling water-bath.

They found that the tendering action (hydrolysis) of acids
on cellulose, like the inversion (hydrolysis) of cane sugar, is de-
pendent on the strength or dectric conductivity of the acid.
The extent of tendering varied with the strength of the add
used except in the case of trichloracetic acid, which decomposes
into HCl and glycollic add on boiling with water. In experiments
with sodium chloride, sulfate, oxalate or acetate or with zinc or
magnesium chlorides or magnesium sulfate, no considerable de-
gree of tendering was caused except by NaHSOi. Tendering was
increased by the addition of magnesium sulfate, probably by the
liberation of HGl. It was also noted that the elongation figures
are considerably effected in which the tensile strength is not.^

H. Wilkinson has found* that cellulose fibers treated with
aqueous sulfuric acid and dried without heat, although tendered
when in the acidified condition apparently regained somewhat in
strength on neutralization of the acid. Tensile strength tests
indicated:

1. Tendering action increases with length of time the add

1. From their results the following conclusions may be drawn: (1)
The addition of a salt of the same acid to a solution of an add causes re-
duced dectrolytic dissodation of the add, and also causes a corresponding
reduction in the tendering action on cotton. (2) The addition of a salt
of a weaker add to the solution of an add, produces a large amount of weak,
feebly ionized add which replaces the strong, highly ionized add, also re-
sults in a decreased tendering action upon cellulose. (3) The addition
of a ^t of a stronger add to the add solution sets up an equilibritun whereby
the total add effect (measured by electric conductivity) becomes greater
and results in an increased tendering action, depending upon how much of
the stronger acid is required to be set free to acquire equilibrium. (4) The
results of Pilkington that oxalic, dtric and tartaric acids all tender less when
padded and steamed in the presence of sodium sulfate was confirmed also
for the treatment of cotton with a hot solution of oxalic add, the soditun add
oxalate formed being separated and analyzed.

2. J. Soc. Dyers Col. 1917, 33, 148; abst. C. A. 1918, 12, 1254; J. S.
C. I. 1917, 36, 707.

«i.i.ui/>s« 121

remains on the fiber, and is greatly accelerated by heat.

2. Cotton regained in strength considerably on washing
out the acid, gain being less in those samples which had been
tendered greatest in the acidified condition.

3. Neutralization by alkaU and then washing, gave same
results as those obtained by washing only.

The action of diluted sulfuric acid upon cellulose has been
studied by A. Scheitfer^ and C. Koechlin,* who found appreciable
weakening of the fiber when the concentration of the add was
0.2% at 80® for 30 minutes, and especially after one hour's im-
mersion. E. Knecht,* as the result of boiling cotton cellulose
with dilute sulfuric add, was unable to determine whether the
add was bound physically or chemically. According to Kuehn*
and Aronstein and Schulze,* on boiling cellulose with 5% HjSOi
but 0.64% sugar (calculated on the cellulose) was formed. Kern'
found the action to be much more pronounced ^hen the cellulose
had previously been boiled with 1.25% KOH solution. In gen-
eral the results obtained in this direction have been insufficiently
. investigated in a quantitative direction, in that, in the majority
of instances, no determinations were made of the changes in the
dissolved portion, only the amount of sugar formed being es-
timated.

On boiling with 50% sulfitfic add, C. Cross, E. Bevan and
C. Smith^ observed the formation of the following products:

1. Bull. Soc. Ind. Mulhouse, 1888, S5, 364, 399, 439; abst. Mon. Sd.
1889, 33, 257; J. S. C. I. 1888, 7, 841, 843; Jahr. Chem. 1889, 2841; Chem.
Tech. Rep. 1888, II, 60, 106; Chem. Ind. 1889, 12, 40; Wag. Jahr. 1888. 34,
1099; Bull. Soc. Chitn. 1888, 50, 597.

2. Bull. Soc. Ind. Mulhouse, 1888, 55. 547; abst. Mon. Sd. 1888, 31,
509, 1385; Chem. Ind. 1888, 11, 400; 1889, 12, 15; Chem. Tech. Rep. 1888,
I, 37, 71; II, 60; Chem. Ztg. 1888, 12, 375; Jahr. Chem. 1888, 2859.

3. J. Soc. Dyers Col. 1888, 4, 104; abst. J. S. C. I. 1888, 7. 621; BuU.
Soc. Chim. 1889, 2, 846; Mon. Sci. 1888, 3^ 1459; Ber. 1888, 21, R, 708;
Chem. Ind. 1888, 11, 552; Chem. Tech. Rep. 1888, II, 101; Chem. Ztg.
1888, 12, 1173; Jahr. Chem. 1888, 2864. See also E. Mills and J. Takamine,
J. C. S. 1883, 43, 142; abst. Chem. News, 1882, 48, 299; Ber. 1883, 16, 973;
Jahr. Chem. 1883, 1784. E. Knecht (Seventh Intl. Cong. Appl. Chem.
1909; J. S. C. I. 1909, 28, 700; Proc. Manch. Lit. Phil. Soc. 1908, S2, II,
XXII; abst C. A. 1908, 2, 3403; Zts. ang. Chem. 1909, 22, 1120) has also
studied the action of oxalic acid on cellulose.

4. J. Landw. 1865, 304.

5. Zts. physiol. Chem. 1890, 14, 244.

6. Jour. Landw. 1876, 19; Zts. physiol. Chem. 1890, 14, 244.

7. Ber. 1895, 28, 1943; abst. J. C. S. 1895, 88, i, 640; Chem. Centr.
1895, II, 832; Jahr. Chem. 1895, 1350.

122

TECHNOLOGY OF CELLULOSE ESTERS

Material Taken

Furfurol

Acetic Acid

Formic Acid

Swedish filter paper

Bleached cotton

0.3%
Trace

2.7%
3.1%
5.0%

17.2%

13.2%

9.4%

American crude cotton

Of the action of sulfurous acid, little definite is known. A
Girard* ascribed the friability of fabrics saturated with solutions
of sulfur dioxide to be due to the action of sulfiuic acid formed
by the oxidation of the SO2 in the presence of water.

Although a weak acid, hydrogen sulfide under certain con-
ditions exercise a vigorous action upon cellulose. Dumas has
shown that in a wet fabric saturated with HaS, at 40°, sulfuric
acid was formed by atmospheric oxidation.^

Acid Celluloses. As referred to under the topic "Oxycellulose,"
G. Bumcke and R. Wollfenstein' have shown that our knowledge
of cellulose is primarily based upon the ease with which it changes
into dextrin and glucose, intermediate derivatives in this process
of degradation being hydrocellulose and oxycellulose. The con-
tention of G. Bumcke and R. Wollfenstein as the result of their
repeating the work of G. Witz,* H. Schmid,^ P. Richard, « L.
Vignon^ and A. NastukofF,® is that insufficient proof has been

1. Ann. Chim. Phys. 1881, (5), 24, 337; Compt. rend. 1877, 81, 1105;
1879, 88, 1322; 89, 170; Bull. Soc. Chim. 1880, 34, 507; abst. Mon. Sd. 1879,
21, 958; J. C. S. 1879, 36, 911; 1882, 42, 378; Wag. Jahr. 1879, 25, 419; Ber.
1879, 12, 2158; 1881, 14, 2834; Chem. News, 1881, 44, 216; J. A. C. S. 1879.

1, 400; Proc. U. S. Nav. Inst. 1882, 8, 309; Jahr. Chem. 1875, 786; 1879,835,
1116; 1881, 985; Jahr. rein Chem. 1875, 142; 1881, 460.

2. Compt. rend. 1846, 23, 774; Instit. No. 669, 357; abst. Berz. Jahr.
1848, 27, 42; Annuaire de Chim. 1847, 797.

3. Ber. 1899, 32, 2493; abst. J. C. S. 1899, 76, i, 852; J. S. C. I. 1899,
18, 940; BuH. Soc. Chim. 1900, 24, 620; Chem. Centr. 1899, II, 752; Jahr.
Chem. 1899, 1290; Meyer Jahr. Chem. 1899, 9, 300.

4. Bull. soc. ind. Rouen, 1882, 416; 1883, 169; abst. Wag. Jahr. 1883,
29, 1068; Mon. Sci. 1884, 26, 1161; see also H. Schmid, Dingl. Poly. 1883,
250, 271; abst. J. C. S. 1884, 46, 528.

5. Wag. Jahr. 1883, 29, 1076.

6. Wag. Jahr. 1883, 29, 1112.

7. Compt. rend. 1897, 125, 448; Bull. Soc. Chim. 1898, 19, 790; abst.
J. C. S. 1898, 74, i, 8; J. S. C. I. 1897, 16, 908; Rev. Phys. Chim. 1897-1898,

2, 21; Mon. Sci. 1897, 49, 859; Chem. Centr. 1897, II, 843; Chem. Ztg. 1897,
21, 811; Jahr, Chem. 1897, 1506. Compt. rend. 1898, 126, 1355, 1658; 127,
872; abst. J. C. S. 1898, 74, i, 620; J. S. C. I. 1898, 17, 680; Bull. Soc. Chim.
1898, 19, 810; Mon. Sci. 1898, 51, 454; Rev. g6n. sci. 1898, 9, 918; Chem.
Centr. 1898. II, 24, 972; Chem. Ztg. 1898, 22, 425; Jahr. Chem. 1898, 2265.

8. J. Russ. Phys. Chem. Soc. 1892, 24, 256; Bull. Soc. Ind. Mulhouse,
1892, 493; abst. J. C. S. 1893, 64. i, 387; J. S. C. I. 1893, 12, 516; Bull. Soc.
Chim. 1893, 10, 124; Ber. 1892, 25, R, 911; Chem. Ztg. Rep. 1892, 16, 293;
Meyer Jahr. Chem. 1893, 3, 517; Wag. Jahr. 1892, 38, 989.

CBi<i.UM>s0 123

adduced for the homogeneity of the celluloses operated upon,
while the oxycelluloses produced by different processes, and by
modifying the same process, are not always identical. While
there is practically no contention as to the direct entry of oxygen
into the cellulose molecule in the formation of the oxycelluloses,
the mechanics of the reaction is invariably complicated by the
presence of hydrolyzing processes. The *'hydralcellulose" of
these investigators is transformed by boiling with ten times its
weight of 10% aqueous NaOH into roughly two-thirds cellulose,
and one-third acid cellulose, this latter body being readily pre-
cipitated from the alkaline solution by acids.

The same phenomenon occurs when hydralcellidose is al-
lowed to stand in the cold for some time with sodium hydroxide.
Acid cellulose is distinguished from cellulose by its solubility when
freshly prepared in NaOH solutions, and from hydralcellulose
by the absence of aldehydic properties. Acid cellulose dissolves
in concentrated HCl, from which it may be recovered unaltered
from the acid solution by dilution with water or by the addition
of alkalis to neutralization.

When a HCl solution of acid cellulose is allowed to stand
for some time, or upon heating, it loses the property of precip-
itation upon dilution with water. From the fact that the solu-
tion strongly reduces Fehling's solution it is evident that hydrol-
ysis has taken place, and this occurs more readily in acid solu-
tion than does ordinary cellulose. The solubility in NaOH is
lost by acid cellulose upon drying, as well as its property of hydrol-
ysis in the presence of concentrated HCl. Dry acid cellulose
appears as a light greenish, brittle but exceedingly hard mass,
translucent like horn, and pulverizable with difficulty. When
subjected to analysis, 3.05% ash was found, and combustion gave
figures leading to the formula CseHeoOsi for the dry, and CMHesOn
for the moist acid cellulose.

C. Haeussermann^ does not agree that acid cellulose contains
carboxyl groups, and calls attention to similar products obtained

1. Zts. Schiess Spreng. 1906, 1, 305; abst. Chem. Centr. 1906, II.
1830; Jahr. Chem. 1905-1908, II, 980; Meyer Jahr. Chem. 1906. 16, 324.
See also M. Hoenig and S. Schubert, Wien. Akad. Ber. 1885, 92, II, 737;
Monatsh. 1885, «, 708; 1886, 7, 455; abst. J. C. S. 1886, 50, 44; 1887, S2, 125;
Bull. Soc. Chim. 1886, 48, 517; 1887, 47, 578; Ber. 1885, 18, R, 614; 1886,
19, R, 748; Chem. Tech. Rep. 1886, II, 218; Jahr. Chem. 1885. 1575; 1886,
1780; Wag. Jahr. 1886, 32, 610.

124 TBCHNOIXX^Y OP CEI.LUIX>SE ESTERS

from the celltilose nitrates. He is opposed to the assumption of
an acid character to the acid celluloses on account of its indifference
in the moist state to ammonia, alkaline carbonates, lime and
bar3rta water, and also on account of the fact that upon attempt-
ing dialysis in pure water, coagulation almost immediately oc-
curs. Add cellulose differs from the j3-oxycellulose of Cross and
Bevan by its insolubility in ammonia, and is not identical with
the oxycellulose of Nastuko£f, which is converted into water-
soluble compounds by treatment with dilute sulfuric add, fol-
lowed by treatment with dilute alkali. Haeussermann holds that
add cellulose is also formed by the saponification of those par-
ticular nitrocelluloses which form upon treatment of cotton by
cold nitric add of 1.473 sp. gr. As yet, acid cellulose has not
been prepared free from ash, the air-dry product, even after
repeated washing, showing 2%-2.5% of ash. Haeussermann has
shown that in the denitration of nitrocellulose filaments, the
cellulose formed is, at ordinary temperatures more or less soluble
in 10% NaOH solution and in concentrated HCl, and upon the
predpitation of such a solution by dilution with water a floccu-
lent coagulum is obtained which is completdy dissolved in 10%
sodium hydroxide solution, this being in contradistinction to the
precipitation of cellulose from a cuprammonium solution by HCl,
which gives a product insoluble in alkalis.

According to C. Schwalbe,^ apparently the same add cellu-
lose is formed when cellulose is placed in a dish and 30% aqueous
NaOH poured over it and subsequently heated to boiling. After
boiling and decanting the supernatant solution and repeating this
process several times, a dear solution results, thus indicating that
cellulose can be completely hydrolyzed.

Btmicke and Wollfenstein do not regard the formation of
acid cellulose as an oxidation process, but rather the cellulose, as
being first hydrolyzed to hydralcellulose, and this in turn forms
add cellulose under the influence of the alkali. They regard the
product recovered from cuprammonium cellulose solutions as
similar to add cellulose, the slight redudng property being as-

1. Chemie der Cellulose, p. 204. W. Hoffmeister, Landw. Versuch-
stat. 1891, 39, 461; abst. J. C. S. 1892, €2, 129; J. S. C. I. 1892, U, 452; Ber.
1893. 26, R, 497; Chem. Centr. 1892, I, 27; Chem. Ztg. Rep. 1891, 15, 317;
Jahr. Chem. 1891, 2180; Wag. Jahr. 1891, 37, 1105; Zts. ang. Chem. 1891,
4,709.

CEU*UIX>SE 125

cribed to the presence of small amounts of hydralcellulose. H.
Ditz* has described a supposed acid cellulose obtained by him
by the oxidation of cellulose with ammonitun persulfate.

Eckstroem* has obtained patent protection for the conver-
sion of wood waste into sugar, in which he assumes an acid cellu-
lose to be formed among the products of the degradation of
cellulose to sugar. He assumes the acid cellulose to be first formed,
which is then converted into dextrin and finally into grape sugar.

Bckstroem treats the wood waste or other form of cellulose
with 70% sulfuric acid at 10'*-40'' for about 20 minutes, when
the cellulose becomes converted into a thick jelly-like mass which
is alleged to be a homogenous substance oi acid reaction and con-
taining carboxyl groups, and not to possess aldehydic properties.
On boiling with water a small portion is transformed into grape
sugar, but when boiled with acids, this conversion is complete.

Amyloid.' According to E. Winterstein, amyloid is a con-

1. Chem. Ztg. 1907, 31, 833, 844, 857; abst. C. A. 1907, 1, 2941 ; J. C. S.
1907, 92y i, 129; J. S. C. I. 1907, 26, 988, 1026; BuU. Soc. Chim. 1907, (4), 2,
14d8; Chem. Zentr. 1907, II, 1606; Jahr. Chem. 1905-1908, II, 964; Meyer
Jahr. Chem. 1907, 17, 604; Wag. Jahr. 1907, II, 507; Zts. ang. Chem. 1908,
21, 1185. For the G. Pink method for the production of add derivatives
of ceUulose, see D. R. P. Anm. F-29131, F-32918; abst. Kunst. 1912, 2, 319.

2. D^ R. P. 193112, 207354. U. S. P. 970029. E. P. 18341, 1907.
F. P. 380358, 1907; abst. C. A. 1908, 2, 1642; 1909, 3, 2070; J. S. C. I. 1908,
27, 32, 514; 1910, 29, 1173; Chem. Zentr. 1908, I, 784; 1909, I, 1296; Chem.
Ztg. Rep. 1908, 32, 42; 1909, 33, 182; Wag. Jahr. 1908, II, 326; 1909, II.
228; Zts. ang. Chem. 1908, 21, 1094; 1909, 2, 599.

3. It would appear that in addition to the above described "vege-
table" amyloid, there exists a protein amyloid which gives a characteristic
carbohydrate reaction ¥rith iodine, notwithstanding its animal origin, differ-
ing from all other known products of degeneration in not being formed in
the organism in any phase of the normal or physiological Hfe, and therefore
must be looked upon as a pathological product. Amyloid — ^like hyalin — is
regarded as a modification coagulation product of the circulating proteid,
probably serum albumen, not fibrin. Detailed information concerning this
body is to be found in the writings of P. Herz (Chem. Ztg. IS, 1594; abst.
J. C. S. 1893, 64, i, 447); N. Krawkow (Centr. Med. Wiss. 1892, 145; Bied.
Ccntr. 21, 753; J. C. S. 1893, 64, i, 288; Arch. exp. Path. Pharm. 1897, 40,
195; J. C. S. 1898, 74, ii, 42); C. Neuberg (Verh. Deut. Path. Ges. 1904, p.
19; Chem. Centr. 1904, II, 1576); C. Hanson (Biochem. Zts. 1908, 13, 185;
J. C. S. 1908, a4, ii, 968); M. Mayeda (Zts. physiol. Chem. 1909, 58, 469;

i. C. S. 1909, 36, i, 274); L. Crie (Compt. rend. 1879, 88, 759; J. C. S. 1879.
B, 613); S. Kostiurina (Chem. Centr. 1887, 120; J. C. S. 1887, S2, 506);
A. Tschermak (Zts. physiol. Chem. 1895, 20, 343; J. C. S. 1895, 68, i, 255).
For amylocellulose, see E. Fembach (Compt. rend. 1904, 138, 819; abst.
T. C. S. 1904, 819; J. S. C. I. 1904, 23, 449); E. Roux (Compt. rend. 1905,
140, 440; J. S. C. I. 1905, 24, 285); J. Wolfif (Woch. f. Brau. 1906, 23, 31;
J. S. C. I. 1906, 2S, 139; Woch. f. Brau. 1906, 23, 216; J. S. C. I. 1906, 2S,
716).

For aiAylase, refer to P. Petit (Compt. rend. 1904, 138, 1231; J. S. C. I.

126 TECHNOU>GY OP CELLULOSE ESTERS

stituent of the cell wall,^ and (like starch) yields a blue coloration
with iodine, whence its name. R. Reiss^ found on digestion with
sulfuric add it yielded dextrose. It was as far back as 1846 that
J. Poumarede and L. Figuier* described their "modification sul-
furique" and called commercially "Papyrine," obtained from or-
dinary filter paper by treatment with sulfuric acid, and later
called vegetable parchment. E. Blondel,* and C. Guignet* and
others investigated the formation of amyloid from cellulose by
hydrolysis or hydration, but with conflicting conclusions.

Blondel observed that when sulfuric acid was brought to-
gether with cotton, those places where the acid came in direct
contact with the fabric gave much deeper dyeings, especially with
xylidine ponceau.

Guignet in saturating dry cotton cellulose with 50** B^. sul-
furic acid noted that the jelly-like mass which is formed without
rise in temperature is stable in the presence of an excess of the
acid, but on heating quickly passes into dextrin. After treat-
ment with water and washing until neutral, the "colloidal cellu-
lose" is said to be substantially soluble in water, and can be
nitrated without change in form.

M. Mendelsohn and E. PrankeP manufacture amyloid by
treating substances rich in cellulose, especially wood meal, with
a mixture of sulfuric add and sodium sulfate, or with sodium acid

1904, 23, 616); J. Effront (Mon. Sci. 1904, 18, 561; J. S. C. I. 1904, 23, 831);
L. Brasse, Bied. Centr. 14, 169; J. S. C. I. 1885, 4, 460); J. Effront (Compt.
rend. 1905, 141, 626; J. S. C. I. 1905, 24, 1183; Mon. Sci. 1895, 45, 541, 711;
J. S. C. I. 1896, 15, 127).

1. Ber. 1892, 25, 1237; Zts. physiol. Chem. 1892, 17, 353; abst. J. C. S.
1892, €2, i, 803; 1893, 64, i, 127; J. S. C. I. 1892, 11, 763; Bull. Soc. Chim.
1892, 5, 971; 1893, 10, 414; Chem. Centr. 1892, I. 820; Jahr. Chem. 1892,
2149; Chem. Ztg. Rep. 1892, IS, 144.

2. Ber. 1889, 21, 609; Landw. Jahr. 1889, 18, 761; abst. J. C. S. 1889,
56, 687; J. S. C. I. 1889, 8, 406; Bull. Soc. Chim. 1890, 3, 713; Chem. Centr.
1889, I, 541 ; Jahr. Chem. 1889, 2086.

3. Compt. rend. 1846, 23, 918; 1847, 25, 17; J. prakt. Chem. 1847,
42, 25; Ann. 1847, 64, 387; Rg»t Sci. 1847, 14, 68; Soc. Philom. Proc. Verb.
1846, 130; J. Pharm. 1847, (3), 11, 81; Rep. Pharm. (2), 47, 344; abst. An-
nuaire de Chim. 1847, 453; Jahr. Chem. 1847-1848, 1, 797.

4. Bull. soc. ind. Rouen, 1882, 10, 471.

6. Compt. rend. 1889, 108, 1258; abst. J. S. C. I. 1889, 8, 1001; J. C. S.
1889, 56, 847; Chem. Centr. 1889, II, 124; Jahr. Chem. 1889, 2839; Chem.
Ztg. Rep. 1889, 13, 194; Chem. Tech. Rep. 1889, 1, 145; Wag. Jahr. 1889, 35,
1180; Ber. 1889, Zt, R, 574; Mon. Sci. 1889, 33, 986; Chem. News. 1889, 60, 24.

6. D. R. P. 220634, 1908; abst. C. A. 1910, 4, 2202; J. S. C. I. 1910,
29, 777; Chem. Zentr. 1910, 1, 1476; Chem. Ztg. Rep. 1910, 34, 200; Zts. ang.
Chem. 1910, 23, 958.

CELI^UtOSE 127

sulfate, the amyloid being subsequently precipitated with water
and separated from the liquid. By proceeding in this manner
the patentees claim little or no dextrin is formed, the resulting
amyloid when fermented and saccharified yielding a spirit
nearly free from fusel oil.

In the process for producing colloidal cellulose as disclosed
by L. Lilienfeld,^ 100-200 parts of cellulose in small amounts is
added to 1000 parts of sulfuric acid of 60° B^. at I'^-S**, and after
the cellulose has become nearly transparent and homogeneous,
it is precipitated by the addition of water, washed until neutral,
and then dissolved in 5% aqueous NaOH to a 5% solution of
cellulose. By making faintly add with HCl or acetic acid, a
fine flocculent precipitate results, which, when washed with water
and dried at a low temperature gives a colloidal cellulose es-
pecially desirable for subsequent nitration or alkylation, or for
the formation of artificial filaments, either by the cupranimonium,
zinc chloride or viscose processes.

In general,^ when the action of sulfuric acid has been allowed
to proceed at relatively low temperatures and for a short period,
the products possess little or no reducing properties, but on the
other hand if the sulfuric acid has remained in contact with the
cellulose for a long time, or the solution has been allowed to rise
in temperature during the treatment, then the resulting product
acquires strong reducing properties. Long continued action of
concentrated sulfuric acid imparts to the product strong reducing
properties, grape sugar being finally obtained.

£. Plechsig' has shown that when certain conditions are
maintained, the reaction may be made quantitative, the total
amount of cellulose present being converted into grape sugar.

Hydrocellulose.^ The compound or compounds resulting

1. Aust. P. 63524. 1914.

2. For other data on amyloid, consult A. Trecul, Compt. rend. 1858,
47, 687. Schulze. Zts. physiol. Chem. 1894, 19, 38. Votocek, Zts. Zuckerind.
1902-1903, 27, 708. E. Bourquelot and H. Herissey, Compt. rend. 1900,
laO, 42, 731; 1901, 133, 302. H. Herissey, Compt. rend. 1900, 13t, 1719.
£. Hansen, Mitteil. Carlsberg Labor. 1879, 2. Beijerinck, Centr. Bakteriol.
1898, 2, (2), 213. A. Meyer, Ber. botan. Ges. 1901, 428.

3. Zts. physiol. Chem. 1883, 7, 523; Zts. deutsche Spirittisfabr. 1883,
805; abst. Ber. 1883, IS, 2508; Chem. Tech. Rep. 1883, II, 144; Jahr. Chem.
1883, 1363; Wag. Jahr. 1883, 29, 681; Tech. Chem. Jahr. 1883-1884, €, 275.

4. J. Briggs, Papierfabrikant, 1910, 8, 46; Chem. Ztg. 1910, 34, 455;
abst. J. S. C. I. 1910, 29. 622; Jahr. Chem. 1910, II, 422; Bull. Soc. Chim.
1911, 19, 60; C. A. 1910, 4, 2372. K. Berl and R. Klaye, Zts. Schiess. Spreng.

128 TECHNOWXJY O^ CELLULOSE ESTERS

from the hydrolysis of normal or tmmodified cellulose by means
of dilute acids has been termed "hydrocellulose," and appears to
be a combination of cellulose with one molecule of water and
therefore has been given the empirical formula CuHaOn. This

1907, 2. 381; abst. C. A. 1908. 2, 184; J. C. S. 1908, 94, i, 604; J. S. C. I.

1907, 26, 1157; Chem. Zentr. 1908, 1, 1381 ; Chem. Ztg. Rep. 1908, 32, 43; Jahr.
Chem. 1906-1908, II, 976. G. Buttner and J. Neumann, Zts. ang. Chem.

1908, 21, 2609; 1909, 22, 686; abst. Chem. Zentr. 1909, I, 441, 1471; C. A.

1909, 3, 1168, 1467; J. C. S. 1909, 96, i, 86, 290; Bull. Soc. Chim. 1909, 6,
879; J. S. C. I. 1909, 28, 106. C. Cross, Ber. 1911, 44, 163; abst. Kunst.
1912, 2, 14; Chem. Zentr. 1911, 1, 619; J. S. C. I. 1911, 30, 204; J. C. S. 1911,
100, i, 114; C. A. 1911, 5, 1613; BuU. Soc. Chim. 1911, 10, 1297; Rep. chim.
Pure, 1911, 11, 232. C. Cross and E. Bevan, Chem. Ztg. 1909, 33, 368;
abst. C. A. 1909, 3, 1589; J. C. S. 1909, 96, i, 290; Chem. Zentr. 1909, 1, 1471;
Bull. Soc. Chim. 1909, 6, 986; Chem. Tech. Rep. 1909, 33, 216. H. Ditz,
J. prakt. Chem. 1908, (2), 78, 343; Chem. Ztg. 1907, 31, 833, 844, 867; abst.
C. A. 1907, 1, 2941; J. C. S. 1907, 92, i, 129; Bull. Soc. Chim. 1907 (4), 2,
1468; Chem. Zentr. 1907, II, 1606; Jahr. Chem. 1906-1908, II, 964; Meyer
Jahr. Chem. 1907, 17, 604; Wag. Jahr. 1907, II, 607; Zts. ang. Chem. 1908,
21, 1186. C. Cross, E. Bevan and C. Smith, J. C. S. 1897, 71, 1001; Proc.
Chem. Soc. 1897, 160; abst. Meyer Jahr. Chem. 1897, 7, 164; J. S. C. I.
1897, 16, 691; Chem. Centr. 1897, II, 644, 614; Jahr. Chem. 1897, 1602. C.
Guignet, Compt. rend. 1889, 108, 1268; abst. J. C. S. 1889, 56, 847; Amer.
J. Pharm. 1889, Ci, 668; Mon. Sci. 1889, 33, 987; J. S. C. I. 1889, 8, 1001;
Chem. Tech. Rep. 1889, I, 146, 194; Ber. 1889, 22, 674; Wag. Jahr. 1889,
35, 1180; Chem. News, 1889, 60, 24; Jahr. Chem. 1889, 2839. H. Jentgen,
Zts. ang. Chem. 1910, 23, 1641; 1^11, 24, 11, 686; abst. C. A. 1911, 5, 1187,
1677, 3163; Bull. Soc. Chim. 1911, 10, 86; Chem. Zentr. 1911, I, 640, 1816;
J. C. S. 1911, 108, i, 116, 355; J. S. C. I. 1911, 30, 125. T, Koemer, Zts.
ang. Chem. 1908, 21, 2353; Papier Ztg. 1908, 33, 3702; abst. C. A. 1909, 3,
484. L. Mangin, Compt. rend. 1890, 110, 296, 644; abst. Ber. 1892, 2S,
R-109; Jahr. Chem. 1890, 2184; J. C. S. 1890, 58, 734. O. MiUer, Ber.

1910, 43, 3430; 1911, 44, 728; abst. J. C. S. 1911, 100, i, 17, 366; Kunst.
1912, 2, 14; C. A. 1911, 5, 1187, 2175; Chem. Zentr. 1911, I, 366, 1164; Bull.
Soc. Chim. 1911, 10, 1160, 1297; Rep. Chim. 1911, 11, 178, 323. W. Mina-
jew, Zts. Farb. Ind. 1910, 9, 66; abst. Chem. Zentr. 1910, I, 1304; Textil
Farb. Ztg. 8, 132; abst. C. A. 1910, 4, 3006; Chem. Tech. Rep. 1910, 34,
267. H. Ost and F. Westhoff, Chem. Ztg. 1909, 33, 197; abst. C. A. 1909,
3, 1394; J. S. C. I. 1909, 28, 326; J. C. S. 1909, 96, i, 210; BuU. Soc. Chim.
1909, 6, 686; Jahr. Chem. 1909, II, 385. R. Scholi, Ber. 1911, 44, 1312;
abst. Kunst. 1911, 453; C. A. 1911, 5, 3061; J. C. S. 1911, 100, i, 625; Chem.
Tech. Rep. 1911, 35, 340. C. Schwalbe, Zts. ang. Chem. 1910, 23, 1641;

1911, 24, 12, 585; abst. Kunst. 1911, 1, 452; J. S. C. I. 1911, 30, 125; C. A.
1911, 5, 1677; Chem. Zentr. 1911, I, 640; J. C. S. 1911, 100, 115. A. L.
Stem, Proc. Chem. Soc. 1894, 186; J. C. S. 1895, 67, 74; abst. Chem. News,
1894, 70, 267; Ber. 1895, 28, R, 462; Jahr. Chem. 1894, 1132; Meyer Jahr. Chem.
1896, 5, 524; Rev. g6n. sci. 1895, 6, 48. R. Oertel, Chem. Ztg. 1911, 35,
713; abst. Chem. Zentr. 1911, II, 855; J. C. S. 1911, 100, i, 607; J. S. C. I.
1911, 30, 887. By the electrolysis of cellulose in a neutral potassium chlor-
ide bath the author has succeeded in transforming it into a product which
is soluble in 10% sodium hydroxide and is probably a new hydroxy cellulose.
It can be obtained either as retaining the fibrous structure of cellulose or in
such a form that it gives a milky, colloidal solution with water. L. Vignon.
Compt. rend. 1900, 131, 530, 708; abst. C. N. 1900, 82, 255; J. C. S. 1901.
80, i, 16; Chem. Ztg. 1900, II, 1151; T. S. C. I. 1900, 19, 1102; Mon. Sci.
1900, 55, 836; Rev. g6n. sci. 1900, 11, 1152; Rev. sci. 1900, 37, II, 466;

CELLULOSB 129

is not to be confused with hydra-cellulose, which contains only,
water of hydration nor with the cellulose hydrates, the name
applied by C. Cross and E. Bevan^ to those modifications of cel-
lulose containing in addition to hygroscopic moisture which is
governed by atmospheric conditions, water of hydration which
is dependent upon the constitutional structure and is more firmly
held than ordinary hygroscopic moisture. With hydrocellulose,
water apparently enters into chemical combination with the cel-
lulose to form new derivatives. C. Schwalbe* has endeavored to
differentiate between hygroscopic moisture and water of hydra-
tion by assuming that the former is entirely expelled at 100^
while the latter is only driven oflF at the temperature of boiling
toluene. But such a distinction has, in general, been found to
be invalid.' The formation of hydrocellulose from cotton results
in structural disintegration to such an extent that the fiber may
readily be reduced to a fine powder. On accotmt of the fact that
it is much more reactive than ordinary cellulose, hydrocellulose is
of considerable importance and has been employed for the pro-
duction of the nitric and acetic esters of cellulose, as the hydro-
cellulose compounds, although less stable, are in general, more
soluble in the solvents employed. In the art of cellulose acetyla-
tioh therefore, hydrocellulose was formerly of considerable im-
portance in that on accoimt of its greater chemical reactivity
cellulose was usually transformed first into hydrocellulose as a

Jahr. Chem. 1900, 840; Chem. Centr. 1900, II, 1069, 1151; 1901, I, 440;
Bull. Soc. Chim. 1901, (3), 2S, 137. P. von Weimarn, Zts. Chem. Ind. Kol-
loide, 1912, U, 41; abst. Rev. Chim. Ind. 1913, 24, 261; Zts. ang. Chem.
1913, 26, R, 290; C. A. 1912, 6, 3516; J. C. S. 1912, 102, i, 679; J. S. C. I.
1912, 31, 768; Chem. Zentr. 1912, II, 817; Chem. Ztg. Rep. 1913, 87, 14.
E. Jandrier, Compt. rend. 1899, 128, 1407; abst. C. N. 1899, 80, 11; J. C. S.
1899, 76, i, 788; J. S. C. I. 1899, 18, 711; BuU. Soc. Chim. 1899, 21, 895;
Chem. Centr. 1899, II, 184; Jahr. Chem. 1899, 1295. C. Bay, Zur Kennt-
nis der Hydro-, Oxy-, Hydral-, und Acid cellulosen. Giessen, 1913, 87.

1. Proc. Chem. Soc. 1904, 20, 90; abst. J. S. C. I. 1904, 28, 557; Chem.
News, 1904, 89, 235; Rev. gin. sd. 1904, IS, 522; Rep. g6n. chim. 1904, 4,
293; Chem. Centr. 1904, I, 1557; J. C. S. 1904, 85, 691; Bull. Soc. Chim.
1904, 32, 1301; Jahr. Chem. 1904. 1161.

2. Ber. 1907, 40, 1347, 4523; abst. J. S. C. I. 1907, 26, 548, 1291;
Chem. Zentr. 1907, I, 1490; 1908, I, 239; C. A. 1907, 1, 1696, 2179; 1908,
2, 1043; J. C. S. 1907, 92, i, 390; 1908, 94, i, 9; Zts. ang. Chem. 1907,20,2166.

3. Chem. Ztg. 1909, 33, 197; abst. J. S. C. I. 1909, 28, 325; J. C. S.
1909, 96, i, 210; Chem. Zentr. 1909, I, 1231; C. A. 1909, 3, 1394; Zts. ang.
Chem. 1909, 22, 1856; Rep. g^n. chim. 1909, 9, 321; Bull. Soc. Chim. 1909,
6,685. Zts. ang. Chem. 1908, 21, 1321; abst. J. C. S. 1908, 94, ii, 627;
C. A. 1908, 2, 2448; BuU. Soc. Chim. 1909, 6, 58; Jahr. Chem. 1906-1908,
II, 960; Chem. Zentr. 1908, I, 239.

130 TECHNOU)GY OP CBI.LUI.OSE ESTERS

separate method and the hydroceUulose thus formed subsequently
acetylated. At the present time it is a question of considerable
legal importance in patent litigation in the acetylation of cellulose
in the presence of small amounts of catalyzers as sulfuric acid,
as to whether the entire reaction is one of hydroceUulose forma-
tion and subsequent acetylation or whether acetylation is suc-
•ceeded by partial hydrolysis, i. e,^ whether the final product
should be considered as acetylated hydroceUulose, or, more prop-
•erly, hydrolyzed acetylceUulose. From a legal point of view the
question has as yet never been adjudicated.

In the preparation of hydroceUulose according to the method
of A. Girard,^ cotton cellulose is placed at ordinary temperatures
in sulfuric acid of sp. gr. 1.463 (55.5% H2SO4) when it is with a
little swelling converted into friable ceUulose after 10 to 12 hours
immersion. When washed imder proper precautions it retains
its original fibrous state but is very friable and easUy reduced to a
powder.

According to B. ToUens* and G. Buettner and J. Neumann,*

1. Compt. rend. 1875, 81, 1105; abst. Ber. 1876, 9, I, 65; Jahr. Chem.
1875, 786; Chem. Centr. 1876, 83; J. C. S. 1876, 30, i, 696; Chem. News,
1875, 33, 10; Amer. J. Sci. 1876, (3), 11, 483; Schweizerische Wochenschrift
f. Farmacie, Jmie 2, 180; Pharm. J. and Trans. 1876-1877, (3), 7, 26; Year
Book of Pharm. 1877; Zts. des Oesterr. Apoth. Ver. 1876, 557; Chem. Tech.
Rep. 1874, U, II, 179; Industrieblatter, 1876, 164; Dingl. Poly. 1876, 219,
549. Ann. Chim. Phys. 1876, (5), 9, 116; abst. Chem. Centr. 1877, 6. Compt.
rend. 89, 170; abst. Jahr. Chem. 1879, 1116; Chem. Centr. 1879, 582; Chem.
Tech. Rep. 1879, IS, II, 180; J. C. S. 1879, 36, 911; BuU. Soc. d'Encour.
(3), 8, No. 91; Chem. News, 1881, 44, 216; BuU. de la Soc. Franc, de Phot.
1879, 2S, 318; Mondes, 49, 614; Publ. Ind. 1880, 26, 46; J. A. C. S. 1879,
400; N. C. Eng. Mech. 1880, 30, 420. Compt. rend. 1879, 88, 1322; abst.
BeA 1879, 12, II, 2085, 2158; Jahr. Chem. 1879, 835; J. de Pharm. 1879,
30, 348; J. C. S. 1879, 36, 779; Year Book Pharm. 1880, 80; Chem. Centr.
1879, 531; Mon. Sci. 1879, 958; Zts. f. d. Gesammte Brauwesen, 1879, 413;
Wag. Jahr. 1879, 2S, 419, 1099. See also Wag. Jahr. 1876, 1066; Ann. Chim.
Phys. 1881, (5), 24, 337; abst. Ber. 1881. 14, II, 2834; Jahr. Chem. 1881,985; J.
C. S. 1882, 42, 378; Proc. U. S. Nav. Inst. 1882, 8, 309; BuU. d'enc. 81, 176;

abst. BuU. Musee. 82, 80; Naturforscher, 15, 26. For the life of A. Girard, see
M. L. Lindet, BuU. Soc. Chim. 1898, (3), 20; I-XXIV, with bibliography.

2. J. Murumow, J. Sack and B. ToUens, Ber. 1901, 34, 1431; abst.
J. C. S. 1901, 80, i, 453; J. S. C. I. 1901, 20, 739; BuU. Soc. Chim. 1902, 28,
269; Chem. Centr. 1901, II, 38; Jahr. Chem. 1901, 896. See also G. Bumcke
and R. Wolffenstein, Ber. 1899, 32, 2493; abst. J. C. S. 1899, 76, i, 852; J. S.
C. I. 1899, 18, 940; BuU. Soc. Chim. 1900, 24, 620; Chem. Centr. 1899, II,
752; Jahr. Chem. 1899, 1290; Meyer Jahr. Chem. 1899, 9, 300. B. ToUens,
Ber. 1901, 34, 1434; abst. J. C. S. 1901, 80, i, 1453; J. S. C. I. 1901, 20,
269; Chem. Centr. 1901, II, 39; Jahr. Chem. 1901, 897.

3. Zts. ang. Chem. 1908, 21, 2609; abst. C. A. 1909, 3, 1168; J. C. S.
1909, 96, i, 86; J. S. C. I. 1909, 28, 105; Chem. Zentr. 1909, I, 441; Chem.
Ztg. Rep. 1909, 33, 91; Jahr. Chem. 1905-1908, II, 960; Meyer Jahr. Chem.

CBLLULOSS 131

maximum friability is attained with an acid of sp. gr. 1.52 to 1.54
but if the cotton is left in contact with the acid for too long a period
the product is jelly-like and can then be washed only with great
diiBculty. Tollens^ has prepared hydrocellulose by immersing
50 gm. of cotton in 280 gm. of sulfuric acid of sp. gr. 1.52 to 1.54
and after 12 to 14 hours immersion is first washed with water to
neutrality, finally with alcohol and ether and dried in the air.
However, G. Buettner and J. Neumann claim that when cellu-
lose is treated with dilute sulfuric acid of sp. gr. 1.453 to 1.53 a
mixttu-e is formed consisting probably of hydrocellulose and oxy-
cellulose, together with unchanged material. Under special con-
ditions (using acid of only 3% to 4% strength), however, cellulose
hydrates result of the general formula (C«Hio06)x-H20. Hydro-
cellulose of this composition, whether x = 2, 3, or 6, is a white,
sandy powder, extremely resistant towards acids and alkalis.
It is invariably not changed by boiling with dilute sulftuic acid,
but is dissolved by cold concentrated sulfuric or fuming nitric
acid and is only colored yellow on boiling with caustic potash
or soda. Like cellulose, it is soluble in an ammoniacal solution
of copper oxide. When the hydrocellulose, as prepared by the
above investigators, is treated with acetic anhydride and concen-
trated stdfuric acid added, a vigorous reaction ensues, the sub-
stance dissolves, and on dilution with water an acetyl derivative
is precipitated in white to blue opalescent flocks. This hydro-
cellulose is colored blue with zinc chloride-iodine reagent, or
iodine and potassitun iodide solution and is reduced by Pehling's
solution or ammoniacal silver nitrate. They have been unable
to corroborate Girard's statement that hydrocellulose is readily
oxidized even at 50**, for the piu-e substance in their hands re-
mained unchanged at 100°. If, however, traces of sulfuric acid
are present decomposition ensues upon warming.^

Hydrocellulose may also be manufactured commercially by

1008, 18, 195; Wag. Jahr. 1908, II, 492; Zts. ang. Chem. 1909, 22, 585; abst.
C. A. 1909, 3, 1467; J. C. S. 1909, 36, i, 290; BuU. Soc. Chim. 1909, C, 879;
Chem. Zentr. 1909, I, 147; Jahr. Chem. 1909, II, 386; Wag. Jahr. 1909,
II, 514.

1. Ber. 1901, 34, 1433; abst. J. C. S. 1901, 30, i, 453.

2. In another method recommended by A. Girard and extensively
used, cotton cellulose is first saturated with sulfuric acid, pressed or centri-
fuged untU it retains not more than 35% to 40% of its weight of liquid, al-
lowed to dry in the air and then heated preferably in a s^ed vessel for S
to 10 hours at 35 ** to 40 ^ or 3 hours to 70 ^ and finally washed with water

132 TECHNO WGY O^ CEI.I.UI.OSE ESTERS

the two methods of R. Stahmer. In the first one^ chlorine is
introduced into glacial acetic acid until the latter becomes dis-
tinctly yellow, when it is then heated to 60°-70**. The wood
cellulose is then introduced with stirring, the cellulose swelling
gradually so that it becomes necessary to use four to five times
the amount of acetic acid to the cellulose. This voluminous mass

4

after a short time again becomes thin, whereupon the resulting
thin paste is washed to neutrality and dried. The temperatiure
must not exceed 70**. It has been questioned as to whether or
not oxycellulose rather than hydrocellulose is obtained by this
method. It at least appears probable that mixtures of hydro-
cellulose and oxycellulose result. The latter also possesses, to a
larger degree, the property of friability.

Instead of glacial acetic acid, R. Stahmer^ recommends hydro-
chloric acid and potassium chlorate, 100 kilos of wood cellulose being
introduced into a steam-jacketed kettle containing agitators, with
800 to 1000 kilos of crude hydrochloric acid of 21'' B^. (33.6%
HCl), and when the mass reaches a temperature of 70**, approx-
imately one kilo of potassium chlorate is added in small portions
during the course of one to one and a half hours. After the mass
has attained a pasty consistency, it is centrifugalized, washed and

and with ether. According to H. Mork and W. Walker (J. Frank. Inst. 1907,
1$4| 136;abst. Mon.Sci. 1908, 60, 461; C. A. 1908, 3, 318), this method is
uncertain in its results and does not yield uniform products. G. Buettner
and J. Neumann also were unable to obtain a product of the same elementary
composition ' as described by Girard when using his different methods of
preparation.

1. U. S. P. 679204, 1901; abst. Mon. Sci. 1901, (4), 57. 284. F. P.
304723, 1900; abst. J. S. C. I. 1901, 20, 469; Chem. Ztg. 1901, 2S, 270; Mon.
Sci. 1900, (4), 59, 20. D. R. P. 123121, 1900; abst. J. S. C. 1. 1901, 20, 1133; Zts.
ang. Chem. 1901, 14, 905; Chem. Centr. 1901, II, 567; Jahr. Chem. 1901, 892;
Mon. Sci. 1900, (4), 59, 9; Wag. Jahr. 1901, II, 612. E. P. 19039, 1900; abst.
J. S. C. I. 1901, 20, 926. See also D. R. P. Anmel. H-53315; abst. Kunst.
1912, 2, 260. For acetylation of hydrocellulose prepared as above, see U. S.
P. 692775, 1902; abst. J. S. C. I. 1902, 2L, 356; Mon. Sci. 1900, (4), 50-59, 161.
L. Lederer, D. R. P. 118538, 1901; abst. Wag. Jahr. 1901, II, 611; Chem.
Centr. 1901, I, 712; Chem. Ztg. 1901, 25, 271; Zts. ang. Chem. 1901, U, 345.

2. U. S. P. 679203, 1901; abst. Mon. Sci. 1901. (4), 57, 284. F. P.
309759, 1901 ; abst. J. S. C. I. 1902, 21, 65; Mon. Sd. 1902, (4), 50, 170. D. R.
P. 123122, 1900; abst. J. S. C. I. 1901, 20, 1133; Mon. Sci. 1902, (4), 50, 9;
Jahr. Chem. 1903, 892, 1014; Zts. ang. Chem. 1901, 14, 905; Chem. Centr.

1901, II, 568; Wag. Jahr. 1901, II, 612. D. R. P. 137206, 1901; abst. Zts.
ang. Chem. 1902, 15, 1301; Chem. Centr. 1903, I, 107; Jahr. Chem. 1903,
1014; Wag. Jahr. 1902, 40, I, 595. Aust. P. 8171, 1902. For acetylation of
hydrocellulose prepared as above, see U. S. P. 692497, 1902; abst. J. S. C. I.

1902, 21, 362; Mon. Sci. 1902, (4), 50, 161. F. P. 308506, 1901; abst. J. S.
C. I. 1902, 21, 64; Mon. Sci. 1902, (4), 50, 159.

<

CELlrULOSE 133

■dried. This product is said to possess in a high degree, resistance
towards inorganic acids and the alkalis. The amount of potas-
sium chlorate used is intended to be insufficient for the formation
of oxycellulose, this latter reducing Fehling's solution, whereas
the described product does not do so.

A. Stem^ has shown that in the formation of hydrat-cellu-
lose, under certain conditions there is invariably a loss in weight
and not gain, as would be indicated by theory, from which he
infers that a hydrat-cellulose is not always formed, but that a
hydrocellulose occurs similar to that formed by other carbohy-
drates under comparable conditions.

A low degree of hygroscopicity is quite characteristic for the
washed and dried hydrocelluloses which form white powders, and
although their formation entails a great loss in tensile strength
there at first is no change in form, for tmder the microscope the
hydrocelluloses when reduced to a powder, still exhibit the struc-
ture of the cotton filament.

According to A. Girard,* hydrocellidoses are very sensitive
to increased temperatures and begin to distinctly blacken at 100°.
This statement of Girard is apparently due to the fact that he
washed his preparations insufficiently, so that traces of the acid
probably still remained. According to Ost,^ very pure hydro-
cellulose is quite stable at 100° and in some instances up to as

1. Proc. Chem. Soc. 1894, 186; J. C. S. 1895, 67, 74; abst. J. S. C. I.
1894, 13, 1230; Bull. Soc. Chim. 1896, (3), IS, 1081; Ber. 1895, 28, R, 462;
Jahr. Chem. 1895, 48, 1358; Meyer Jahr. Chem. 1895, 5, 145, 524; Chem.
News, 1894, 70, 267; Chem. Centr. 1895, S6, I, 29; Jahr. Chem. 1894, 47,
1132. Proc. Chem. Soc. 1904, 20, 43; J. C. S. 1904, 85, 336; abst. Chem. News,
1904, 89, 117; J. S. C. I. 1904, 23, 265; Bull. Soc. Chim. 1904, 32, 1175; Chem.
l,7S, I, -

Centr. 1904, 75, I, 934, 1405; Chem. Ztg. 1904, 28, 246; Jahr. Chem. 1904,
57, 1161. In this connection see Proc. Chem. Soc. 1904, 20j90; J. C. S. 1904,
85, 691; abst. Chem. News, 1904, 89, 235; J. S. C. I. 1904, 23, 557; Bull. Soc.
Chim. 1904, 32, 1301; Rep. Chim. ^904, 4, 293; Chem. Centr. 1904, 75, I,
1557; Jahr. Chem. 1904, 57, 1161' See also M. Hoenig and S. Schubert,
Monatsh. 1885, 6, 708; 1886, 7, 455; abst. Wem. Akad. Ber. 92 (2 Abth.),
737; Bull. Soc. Chim. 1886, (2), 46, 517; Ber. 1885, 18, 614; Jahr. Chem.
1885, 38, 1576. Braconnot, Ann. Chim. Phys. 1819, (2), 12, 185. Blondeau
de Carolles, Ann. 1844, 52, 412; J. prakt. Chem. 1844, 33, 439. Fehling, Ann.
1845, 53, 135; Marchand, J. prakt. Chem. 1845, 35, 200. Bechamp, Ann. 1856,
100, 364. AUihn, J. prakt. Chem. 1880, 130, 61.

2. Compt. rend. 1877, 88, 1322; abst. J. C. S. 1879, 36, 779; Bull.
Soc. Chun. 1880, 34, 507; Jahr. Chem. 1879, 835, 1116.

3. Zts. ang. Chem. 1906, 19, 994; abst. J. C. S. 1909, 90, i, 560; Chem.
Centr. 1906, II, 672; J. S. C. I. 1906, 25, 606; BuU. Soc. Chim. 1906, 36,
1058; Jahr. Chem. 1905-1908, II. 983; Meyer Jahr. Chem. 1906, 16, 219;
Wag. Jahr. 1906, 52, II, 484.

134 TECHNOI.OGY OP CEI*I*ULOSS ESTERS

high as 125°. This observation is corroborated by Witz/ while
Stem found that when the hydrocelluloses are absolutely free
from acid they do not turn black when heated up to 125**.^
Hydrocellulose is sharply differentiated from normal cellulose by
being colored blue with a solution of zinc chlor-iodide or with a
solution of iodine in potassium iodide, and by reducing Fehling's
solution and a solution of ammoniacal silver nitrate. Another
important characterization of the hydrocelluloses are their power
of dissolving in sodium hydroxide solutions with a marked reduc-
ing power. T^iey resemble celluloses in exhibiting a great affinity
for water, giving well defined hydrates of hydrocellulose, the ex-
tent of the hydrocellulose hydration being determined by the
degree of hydrolysis; that is, the amount of water with which
a cellulose will combine is dependent primarily upon the number
of hydroxyl groups contained therein. Hydrocelluloses are but
little changed by cold diluted adds, more so upon heating, when
a yellow discoloration first appears, followed by decomposition.
Schwalbe has determined that by boihng with 10% sodium hy-
droxide solution about 15% passes into solution. However, in 1%
hot potassium hydroxide solution Girard's hydrocellulose apparent-
ly is unaflFected, which is not in accordance with the experience of E.
von Lippman.' Maximum solution, according to A. Girard, oc-
curs at 160°,* and the undissolved residue has a decreased reduc-
ing power.** With all the hydrocelluloses, prolonged boiling will
eventually lead to complete solution of the substances or else
to a disappearance of the reducing property of the residue. W.
Vieweg* has boiled hycirocellulose prepared with hydrochloric

1. Bull. Rouen, 1882, 11, 419; 1883, 169; abst. Jahr. Chem. 1883,
1782.

2. J. C. S. 1904, 85, 336; abst. Jahr. Chem. 1904, 1161; Proc. Chem.
Soc. 1904, 43; Chem. Centr. 1904. I, 934, 1405; J. S. C. I. 1904, 23, 265;
Rev. g6n. sci. 1904, 15, 323; Bull. Soc. Chim. 1904, 32, 1175.

3. "Chemie der Zuckerarten," 1904, 3 Ed., 1519.

4. Ami. Chim. Phys. 1881, (5), 24, 366.

5. C. Schwalbe, Zts. ang. Chem. 1907, 20, 2170; Chem. Ztg. 1907, 31,
937; abst. C. A. 1908, 2, 704; Ber. 1907, 40, 1961, 4523; J. C. S. 1908, 34, i, 9;
Jahr. Chem. 1905-1908, II, 961 ; Bull. Soc. Chim, 1908, 4, 381 ; Chem. Zentr.
1908, I, 240.

6. Papier Ztg. 1907, 32, 130, 174; 1909, 34, 149; Ber. 1907, 40, 3880;
1908, 41, 3269; abst. C. A. 1907, 1, 1320; 1908, 2, 3403; J. C. S. 1907, 92,
i, 893; 1908, 84, i, 857; J. S. C. I. 1907, 26, 836, 1157; 1908, 27, 1081; BuU.
Soc. Chim. 1908, (4), 4, 902; Rep. Chim. 1908, 8, 62; Chem. Zentr. 1907,
II, 1780; 1908, II, 1584; Chem. Ztg. Rep, 1908, 32, 27, 619; Meyer Jahr.
Chem. 1907, 17, 215; 1908, 18, 506; Zts. ang. Chem. 1908, 21, 1184.

CELLULOSE • 135

acid for 15 to 20 minutes with normal sodium hydro:Sde solu-
tion and Ihen titrated back with semi-normal sulfuric acid, and
has found that upon prolonged boiling the hydrocellulose takes
unto itself alkali hydroxides. In this way he determines the
"acid number," which indicates the amotmt of alkali taken up.
C. Schwalbe, on the other hand,^ has demonstrated that cellulose
also absorbs or consumes alkali upon analogous treatment. This
determination, therefore, so far as the differentiation of the hydro-
cellulose given is inaccurate because the amount of alkaU con-
stuned apparently bears no definite ratio to the form of cellulose
or hydrocellulose operated upon.

More recently W. Vieweg,* has stated that the add number
is in no measure influenced by hydrocellulose, which statement
is diametrically opposite to the results of his earlier researches.

According to C. Cross and E. Bevan,' the residues described
by A. Stem,* and having the empirical composition of cellulose,
are no doubt products of hydrolysis and reversion, and are con-
stitutionally different from the original cellulose, but are in Ho
case identical with those described by Girard and therefore this
investigator's exhaustive account of the action of acids on cellu-
lose is not in accordance with anal3rtical determinations observed
by C. Cross and E. Bevan. They call attention to the fact that
inasmuch as cellulose is of a chemically labile and structturally
plastic character, occupying a position intermediate between the

1. Papier Ztg. 1909, 35, 691, 994. Compare A. Luck and A. Dtim- .
ford, E. P. 4769, 1896; abst. J. S. C. I. 1896, 15, 134; Chem. Ztg. 1896, 28,
652; Chem. Tech. Rep. 1896, 35, 498, who describe a process for producing
nitrocellulose in a dense powdery form, the essence of their invention being
to destroy the structure of the cotton by treatment with H2SO4 and water,
or aqueous zinc chloride, with subsequent nitration.

2. Papier Ztg. 1909, 35, 890; compare 1910, 35, 994; Wochenblatt f.
Papier Fabr. 1910, 40, 1255.

3. Proc. Chem. Soc. 1904, 20, 90; J. C. S. 1904, 05, 691; abst. Chem.
News, 1904, 00, 236; J. S. C. I. 1904, 23, 657; Bull. Soc. Chim. 1904, 32,
1301; Rep. Chim. 1904, 4, 293; Chem. Centr. 1904, 75, I, 1657; Jahr. Chem.
1904, 1161. Chem. Ztg. 1909, 33, 368; abst. C. A. 1909,3, 1589; J. C.S. 1909,
06, i, 290; BuU. Soc. Chim. 1909, (4), 6, 985; Chem. Zcntr. 1909, 00, 1, 1471.
C. Cross, E. Bevan and C. Smith, J. C. S. 1897, 71, 1005; Chem. News, 1896,
74, 177; 1807, 76, 188; abst. T. S. C. I. 1897, 16, 691; Bull. Soc. Chim. 1898,
20, 62; Chem. Centr. 1897, 60, II, 544, 614, 1028; Jahr. Chem. 1897, 1502;
Meyer Jahr. Chem. 1897, 7, 154.

4. In this connection see Proc. Chem. Soc. 1904, 20, 43; J. C. S. 1904,
05, 336; abst. Chem. News, 1904, 00, 117; J. S. C. I. 1904, 23, 265; Bull.
Soc. Chim. 1904, 32, 1175; Chem. Centr. 1904, 75, I, 934, 1405; Chem. Ztg.
1904, 20, 246; Jahr. Chem. 1904, 1161.

136 TBCHNOW)GY OP CELLULOSE BSTBRS

two exfi^me products formed from ordinary cellulose by the
action of, first, alkali hydroxide, and second, the halogen
hydradds, both in presence of water, the suggestion is made that
the terms hydra-cellulose and hydrocellulose, respectively, should
properly be retained to designate two groups of derivatives ob-
tained by processes **a*' and **b" above mentioned. Hydrocellu-
lose upon being brought in contact with concentrated potassium
hydroxide swells up and gives a blue coloration with iodine, which
it did not do previous to alkaline treatment, or at least to any
great extent.

According to B. ToUens,^ those hydrocelluloses prepared
with sulfuric acid are not colored by concentrated sodium hydrox-
ide, while those prepared with this add of high concentration form"
colloids which partially dissolve with yellow discoloration. Prom
these solutions, however, flocculent precipitates result by the addi-
tion, of hydrochloric add, and upon heating with concentrated
potassitmi hydroxide, there is obtained acetic add, oxaUc add
and acetone, whereas upon boiling with lime, iso-saccharic add
was fotmd by ToUens among the products of decomposition.
Hydrocdlulose upon heating with alkalis under pressure, forms
acetic add; and with saturated potassium carbonate solution, as
high as 14% of acetic add has been fotmd where the temperature
has been raised from 100"^ to 110°.*

On heating with alkali for eight hours in a closed vessel,
41.7% of acetic acid has been formed and this yield,, it has been
stated, may be materially increased by the addition of oxidizing
agents. With cold diluted inorganic adds hydrocelluloses axe
unusually stable, less so with hot adds. ToUens has recorded
that he was able to effect only slight solution and formation of
but littie glucose on boiling for eight hours with sulfuric acid of
3%.' Cotton cellulose is less resistant than is hydrocellulose, the^
residue of such boiling possesses, according to G. Buettner and
J. Neumann,^ giving the same elementary composition as the

1. Ber. 1901, 34, 1432; abst. J. C. S. 1901, 80, i, 453; J. S. C. I. 1901,
20, 739; Chem. Centr. 1901, 72, II, 39; Bull. Soc. Chim. 1902, 28, 269; Jahr.
Chem. 1901, 897.

2. C. Cross, E. Bevan ami J. Isaac, J. S. C. I. 1892, U, 966; abst.
Chem. Ztg. 1893, IS, 1863; Chem. Centr. 1893, €4, I, 407; Ber. 1893, 26,
R, 594; Mon. Sci. 1893, 41, 889.

3. ToUens, Ber. 1901, 34, 1433.

4. Zts. ang. Chem. 1908, 21, 2609.

CELLUU>SE 137

original material. On boiling with acids a small amount of fur-
fm-al has been detected.^ When pressure is used this resistance
to decomposition is materially reduced. As is well known, hydro-
cellulose is more readily saccharified imder pressure than is cot-
ton cellulose. This statement is corroborated from the experi-
ments of T. Koemer,* who, upon heating. 40 grams of hydrocel-
lulose prepared with 4% of sulfuric acid and fermentation, fotmd
that the fermented filtrate contained 18 grams of alcohol for each
100 grams of hydrocellulose. These results lack importance in
that no comparative value for cotton cellulose was determined
at the same time tmder comparable conditions. Girard found
that when hydrocellulose is heated to 180° for eight to ten hoiu^
with 5% sulfuric add, much carbon dioxide is evolved and ele-
mental carbon separated.

According to B. Tollens,' zinc chloride-iodide solutions react
bluish violet with hydrocellulose prepared with sulfuric add, but
the general observation has been that nearly all the hydrocellu-
loses react likewise. The color is quite fugitive against wat^
which is a point in contradistinction to those of the hydrat-cel-
luloses. Hydrocellulose reacts with fuchsine in sulfiu: dioxide
not at all or only faintly,* but due to the fact that filter paper
always contains small but variable amotmts of oxycellulose, the
content of the latter is responsible for the fact that filter paper
usually reacts with sulfur-dioxide-fuchsine. L. Vignon has stated

1. L. Vignon, Compt. rend. 1898, 12S, 1365; abst. J. C. S. 1898, 74, i,
620* J. g. C. I. 1898, 17, 680: Bull. Soc. Chim. 1898, IS, 810; Mon. Sd. 1898,
51, 464; Rev. g^n. sci. 1898, 9, 918; Chem. Centr, 1898, C9, II, 24, 972; Chem.
Ztg. 1898, 22, 425; Jahr. Chem. 1898, 2265. Cross and Bevan, Researches,
1,70.

2. Dissertation, Dresden, 1907, 36; compare Zts. ang. Chem. 1908,
21, 2357; abst. J. S. C. I. 1908, 27, 1216; J. C. S. 1908, 84,955; Chem. Zentr.
1908, 79, II, 2049; Papier Ztg. 1908, 33, 37(fe; C. A. 1909, 3, 484. See also
E. Simonsen, Zts. ang. Chem. 1898, 11, 195, 219, 962, 1007; abst. Chem.
Centr. 1898, 99. I, 808; II, 144, 1148; J. S. C. I. 1898, 17, 365, 481, 1164;
J. C. S. 1899, 78, i, 471; Bled. Centr. 1899, 28, 200; Festschrift tech. Schule,
Christiania, 1898, 22; Norsk, teknisk. Tidskr. 1895, 65; abst. Bied. Centr.
1896, 2S, 47; J. C. S. 1896, 79, 331. Papier Ztg. 1903, 28, 1787; Zts. ang.
Chem. 1903, 16, 572; abst. J. S. C. I. 1903, 22, 814. See also W. Gentzen
and L. Roth, D. R. P. 147844; abst. Chem. Centr. 1904, 75, I, 410; Chem.
Z\%. 1904, 28, 66; Wag. Jahr. 1904, 49, II, 370; Zts. ang. Chem. 1904, 17,
244. A. Classen, D. R. P. 118540; abst. Chem. Ztg. 1901, 25, 252; Wag.
Jahr. 1901, 47, II, 280; Zts. ang. Chem. 1901, 14, 348.

3. Ber. 1901, 34, 1432; abst. J. C. S. 1901, 89, i, 453; J. S. C. I. 1901,
29, 740; Bull. Soc. Chim. 1902, 28, 269; Chem. Centr. 1901, A, II, 39; Jahr.
Chem. 1901, 897.

4. C. Schwalbe, Zts. ang. Chem. 1907, 20, 2171.

138

TECHNOlrOGY OP CELI.UW)SE ESTERS

that hydrocellulose does not possess reducing properties/ whereas
Cross and Bevan have shown that in alkaline solutions reduction
takes place. According to B. ToUens,* hydrocellulose prepared
by the process of Girard is also inert toward Fehling's solution,
but H. Ost. has demonstrated' that slight reduction of cellulose
prepared with sulfuric acid of 3% results, whereas C. Schwalbe*
has proven beyond question that hydrocellulose possesses char-
acteristic reducing properties in contradistinction to the hydrat-
cellulose and pure normal or cotton cellulose. For a series of
hydrocelluloses the following values have been fotmd:

Hydrocellulose
precipitated
Hydrocellulose
Hydrocellulose
Hydrocellulose
Hydrocellulose

3%

Hydrocellulose
Hydrocellulose

3%

Hydrocellulose
of 3%

cotton with concentrated H1SO4,

byHiO

: cotton with H2SO4 of 45** B6. . . .

: cotton with HCl gas

: cotton with HjS04 of 3%

: absorbent cotton with HtS04 of

: fiiter paper with HjSb4 of 3%. .
from parchment with HsS04 of

: mercerized cotton with HsS04

Copper
Ntunber

7.9
3.9
4.0
5.6

5.2
6.2

8.7

8.8

Hygroscopic
Water

5.3
6.3
3.8
3.6

3.8
6.0
6.3

The hydrocelluloses, however, prepared by the process of
Stahmer with hydrochloric add and potassium chlorate, are said
not to possess reducing properties and not to reduce either am-
moniacal silver nitrate or Fehling's solution. The hydrocellu-
loses dissolve much more readily than ordinary cotton in cupram-
monitun solution. B. Bronnert,^ on the other hand, in his patent
application, states that solution takes place at the best but slowly

1. Compt. rend. 1898, 12S, 1355; abst. J. C. S. 1898. 74, 620; Jahr.
Chem. 1898, 2265; J. S. C. I. 1898, 17, 680; Chem. Centr. 1898, C9, II, 24;
Bull. Soc. Chim. 1898, 19, 810; Mon. Sci. 1898, SI. 454.

2. Ber. 1901, 34, 1432; abst. J. C. S. 1901, 80, i, 453; J. S . C. I. 1901,
aO, 739; Chem. Centr. 1901, II, 38.

3. Zts. ang. Chem. 1906, 19, 994; abst. J. S. C. I. 1906, 2S, 606; BuU.
Soc. Chim. 1906, 36, 1058; J.C.S. 1906,90,i,560; Chem. Centr. 1906, II, 672.

4. Zts. ang. Chem. 1907, 20, 2170; Chem. Ztg. 1907, 31, 937; abst.
C. A. 1908, 2, 704; Ber. 1907, 40, 4523; J. C. S. 1908, 94, i, 9.

5. D. R. P. 109996. See also Aus. P. 3638. Fr. P. 278371. U. S. P.
646381. E. P. 13331, 1899; abst. Mon. Sci. 1901, (4). 57, 20; Wag. Jahr.
1900, II, 448; Jahr. Chem. 1900, 843; Chem. Centr. 1900, 71, I, 231; Chem.
Ztg. 1900, 24, 426.

CEI.LUI,OSE 139

and imperfectly. C. Schwalbe, in a sample prepared by means
of 3% sulfuric acid,* found ready solubility. Hydrocellulose is
not difficultly soluole in zinc chloride-hydrochloric add mixtures,
whereas with zinc chloride solution alone without the addition
of hydrochloric acid, hydrocellulose is readily soluble, especially
in syrupy phosphoric acid. The afl&nity of hydrocellulose to-
ward dyestuflfs has been but imperfectly and inconclusively
studied. Statements available are in large part contradictory,
presumably because hydrocellulose of very different modes of
preparation have been used for the experiments, and also from
the fact that undoubtedly in many instances traces of acids were
not entirely eliminated from the hydrocellulose after formation.

G. Witz claims hydrocellulose does not dye with such basic
dyes as methyl violet or methylene blue,' whereas Ost fotmd that
hydrocellulose gives a light shade with fuchine, deeper however,
than cotton cellulose.

Hydrocellulose is often confotmded with hydrat-cellulose;
statements applying to the latter, therefore, are confusing.
Schwalbe has observed that one and the same hydrocellulose dyes
strongly with methylene blue and less powerfully with diamond
green than cotton cellulose.' Statements in general show that a
thorough investigation of the numerpus t3rpes of dyestufiPs as to
their behavior against hydrocellulose is necessary before tangible
data can be established as to their deportment in this respect.
Against oxidizing agents, however, especially of the oxygen of the
air, hydrocellulose is sensitive. Solutions of permanganate are
reduced,^ this oxidation leading to the formation of oxalic and
saccharic adds. For the detection of hydrocellulose, the dim-
inished tensile strength, potassium iodide-iodine test, the hygro-
scopidty and espedally the reducing properties may be utilized.

H. Ditz* considers it possible to distinguish the hydrocellu-
loses from oxycellulose by means of Nessler's reagent. The same

1. C. Schwalbe, Zts. ang. Chem. 1907, 2P, 2171.

2. Bull. soc. chim. Rouen, 1883, U, 220.

3. "Faerbetheorien/* page 85.

4. L. KoUmann, Zentr. f. d. Oester. Papier. Ind. 1900, 408; 1910, 709;
Papierfabr. 1910, S, 863, 890; abst. J. S. C. I. 1910, 29, 1151; Chem. Ztg.
Rep. 1910, 34, 455.

5. J. prakt. Chem. 1908, 78, 343; abst. J. S. C. I. 1908, 27, 1129;
J. C. S. 1908, M, i, 954; Chem. Zentr. 1908, II, 2000; C. A. 1909, 3, 841;
Bull. Soc. Chim. 1909, 6, 1176; Chem. Ztg. Rep. 1908, 32, 619.

140 TECHNOIX)GY OP CBIXULOSB BSTERS

applies as to reducing property, by a quantitative determination
of the reducing power when the presence of either hydrocellulose
or oxycellulose can be detected.

According to G. Buettner and J. Neumann, however,^ it is
impossible to produce by the same method of preparation, bodies
of the same elementary composition, and therefore it is impos-
sible, contrary to the contention of these authors, to determine
accurately by ultimate analysis the hydrocellulose content of a
cellulose derivative, quite apart from the fact that the ultimate
analysis does not permit of the differentiation between hydrocel-
lulose and hydrat-cellulose derivatives. However, we know
with certainty that hydrocellulose contains more water than
cotton cellulose. A. Girard's investigations conform to the for-
mula (CeHio06)i.HiO. A. Stem, on the other hand,* all^;es
to have obtained figiu'es conforming more nearly to the formula
CeHioOs, but it must be remembered that he boils the initial
material with add of 5%. H. Ost was tmable to obtain such
high figures,' his results leading to the formula (C«Hio06)6.H20.
T. Koemer* and G. Buettner and J. Neumann' have obtained
still different results. It is only upon boiling the hydrocellulose
prepared by Buettner and Neuman with dilute sulftuic acid
(one to one) that figures are found by analysis conforming to
(C6Hio06)6.HiO. As all these hydrocelluloses were prepared from
filter paper, it is natural to assume that they represent in reality
a mixture of hydrocellulose containing smaller amounts of oxy-
cellulose. The general proposition, however, has been repeatedly,
experimentally and analytically demonstrated that the hydrocellu-
loses also contain more water than normal cellulose, but the amount

1. Zts. ang. Chem. 1908, 21. 2609; Wochenblatt. 1909, 40, 17; abst.
C. A. 1909, 3, 1168; J. S. C. 1909, 98, i, 86; J. S. C. I. 1909, 28, 105; Chem.
Zentr. 1909. I. 441; Chem. Ztg. Rep. 1909, 33, 91; Jahr. Chem. 1905-1908,
II, 960; Meyer Jahr. Chem. 1908, 18, 195; Wag. Jahr. 1908, II, 492.

2. J. C. S. 1904, 85, 336; abst. Chem. News, 1904, 89, 117; J. S. C. I.
1904, 23, 265; Bull. Soc. Chim. 1904, 32, 1175; Chem. Centr. 1904, I, 934,
1405; Chem. Ztg. 1904, 28, 246; Jahr. Chem. 1904, 1161.

3. Zts. ang. Chem. 1906, 19, 994; abst. I. C. S. 1906, 90, i, 560; J. S.
C. I. 1906, 25, 606; Bull. Soc. Chim. 1906, 38, 1053; Chem. Centr. 1906,
77, II, 672; Jahr. Chem. 1905-1908, II, 983; Meyer Jahr. Chem. 1906, 18,
219; Wag. Jahr. 1906, 52, II, 484.

4. Dissertation, Dresden, 1907, 34; compare Zts. ang. Chem. 1908,
21, 2357; abst. J. S. C. I. 1908, 27, 1216; J. C. S. 1908, 94, 955; Chem. Zentr.
1908, 79, II, 2049; Papier Ztg. 1908, 33, 3702; C. A. 1909, 3, 484.

5. Zts. ang. Chem. 1908, 21, 2609; 1909, 22, 585.

CELLULOSE 141

of this water depends in a large measure upon the method of
operation and these methods have not as yet been worked out
satisfactorily.

Cotton cellulose also is capable of permanently fixing a small
amount of metal as copper from dilute solutions of cupric salts,
while the corresponding adds remain almost quantitative in
the solution. Unbleached cotton takes up relatively much,
bleached cotton less of these metals. The small amount of metal
which is nevertheless absorbed after the purification is due, accord-
ing to B. Rassow^ to the presence of oxycellulose. Cellulose
hydrate and hydrocellulose do not take up any copper from
solutions of its salts, the "copper sulfate equivalent" shotdd there-
fore be a valuable adjunct to Schwalbe's "copper equivalent" in ^
the characterization and differentiation of celluloses. Nickel sul-
fate, aluminum sulfate and potassium chloride behave towards
bleached cotton like copper salts. Artificial silks which contain
oxycellulose fix these metals better than ordinary cotton. This
fixation apparently is independent of the concentration of the
solutions, temperature and the time. Silver nitrate is reduced
by the various celluloses. R. Haller* has shown that the pres-
ence of nitrogenous matter in the lumen of the cotton fiber
accounts for the fiber being readily dyed by saffranine. The
hydrocelltdoses esterify, and especially acetylate, much more readily
than normal cotton cellulose. At 180^, as first shown by SchQt-
zenberger, hydrocellulose reacts almost quantitatively with acetic
anhydride but with profound decomposition, the pulverulent
hydrocelltdose being converted into a viscid syrup which is pre-
dpitable by water. Hydrocelltdose prepared according to the
methods of Stahmer with gladal acetic add and chlorine are
alleged to give acetyl derivatives of spedal chemical and physical
properties in that they dissolve in nitric add to a dear reddish
brown liquid from which a nitro-compound may be thrown out
by water. Hydrocelluloses prepared with hydrochloric acid and

1. Zts. ang. Chem. 1911, 2i, 1127; abst. J. Soc. Dyers Col. 1911,
27, 214; Chem. Ztg. 1911, 35, 645; abst. C. A. 1912, 6, 684; J. S. C I. 1911,
30, 1307; Chem. Ztg. Rep. 1911, 35, 340; .Meyer Jahr. Chem. 1911, 21, 514;
Wag. Jahr. 1911, 57, II, 503.

2. J. Soc. Dyers Col. 1907, 23, 167; Zts. Parbenind. 1907, 6, 125;
abst. J. S. C. I. 1907, 26, 523; Chem. Zentr. 1907, 78, II, 953; Chem. Ztg.
Rep. 1907, 31, 257; Jahr. Chem. 1905-1908, II, 3185; Zts. ang. Chem. 1907,
2Q,2085.

142 TECHNOLOGY OF CELLUU)SE ESTERS

potassium chlorate under the same conditions, however, are said
to be more difl&cultly susceptible to acetylation.

W. de Coninck has shown^ that after filter paper has stood
in ordinary hydrochloric acid for 18 hours at 28**, the liquid does
not reduce Fehling's solution, whereas after 62 hours contact,
the solution on boiling turns brown and a brownish black pre-
cipitate, partly soluble in ammonia, is formed (humus). On the
other hand, cotton, while it does no reduce Fehling's solution,
does not turn brown on boiling. In fuming hydrobromic acid it
dissolves in a few minutes with amber color, changing to black
the following day. A small amount of humus in this instance is
formed, and the liquid appreciably reduces Fehling's solution.

J. Ville and W. Mestrezat* have found that dilute hydro-
fluoric acid (5% to 30%) has little effect on cellulose, while the
more concentrated acid brings about destructive hydrolysis. By
heating on the water bath with 50% acid for six hours, a 50%
yield of dextrose is obtained.

According to the observations of R. SchoU' the reducing
properties of modified cellulose in its action toward Fehling's
solution may be shown by its behavior with certain "vat dye-
stuflFs." Flavanthrene, a yellow dyestuflf which gives a blue
"vat" on reduction, is said to be particularly suitable for these
experiments. Reduced "flavanthrene vat" prepared by boiling
0.03 gram of flavanthrene with a little dilute sodium hydroxide
and solid sodium hydrosulfite, when used to treat cellulose for
a few seconds develops a dark blue liquid.

C. Schwalbe,* who has hydrated cotton cellulose by the
action of concentrated alkalis and acids, finds there is no differ-
ence between the product of the reaction and cellulose itself in-
sofar as their reducing action on Fehling's solution is concerned.
Dilute adds hydrolyze cellulose to hydrocellulose which has a

1. Bull. Sd. acad. Roy. Belg. 1910, 587; abst. J. C. S. 1910, 98, i,
664; C. A. 1911, 5, 1685.

2. Compt. rend. 1910, ISO, 783; abst. J. C. S. 1910. 98, i. 301; C. A.
1910, 4, 2094; J. S. C. I. 1910, 29, 483; Rev. ghi. sd. 1910, 2L, 311; Bull.
Soc. Chim. 1910, 7, 372; Chem. Zentr. 1910, I, 1781.

3. Ber. 1911, 44, 1312; abst. J. S. C. I. 1911, 30, 739; J. C. S. 1911,
100, i, 626; Chem. Zentr. 1911, II, 80; C. A. 1911, S, 3061; Bull. Soc. Chim.
1911, 10, 1644; Rep. g^n. chim. 1911, U, 408.

4. Chem. Ztg. 1907, 31, 937; abst. J. S. C. I. 1907, 20, 1107; C. A.
1908, 2, 704; Zts. ang. Chem. 1907, 20, 2170; Ber. 1907, 40, 4623; J. C. S. 1908,
94, i, 9.

CELLUirOSE 143

much higher reducing power than cellulose. Vegetable parch-
ment and Chardonnet silk are both able to reduce Fehling's solu-
tion, though not so much as the hydrocellulose. According to
Schwalbe, parchment owes its reducing power to the production
of a small quantity of hydrocellulose formed while the concen-
trated acid is being washed out during the process of preparation.
On the other hand, the reducing action of Chardonnet silk is due
primarily to the production of oxycellulose by the nitric add
employed in its preparation. These oxycelluloses, moreover, are
distinguished from the hydrocelluloses by being much more
strongly colored by basic dyestuflFs. Mercerized cotton, Pauly
silk and viscose silk have scarcely any reducing action on Feh-
ling's solution.

C. Schwalbe,^ in criticising the work of G. Beuttner and J.
Neumann,^ contests their view that elementary analysis is the
best measure for the degree of re-solution in the case of hydro-
cellulose and that even if elementary analysis were sufficiently
accurate it would fail to make any distinction between hydro-
celluloses and cellulose hydrates. He contends that the cupric
reduction method, on the other hand; is characteristiqjfor hydro-
celluloses and is in actual use and practice for the determination
of the degree of hydrolysis, whereas Buettner and Neumann
state that hydrocelluloses are extremely resistant toward alkalis
and adds. It has been pointed out that their results merdy
show the residual hydrocellulose to have the same elementary
composition after boiling with adds as it had before, and do not
take into consideration account of the quantity of substance dis-
solved in the form of sugar as the result of the add treatment.
Similarly, Schwalbe contests the statement as to the resistance
of hydrocelluloses toward alkalis. It is well known that sodium
hydroxide at the boiling point dissolves a large proportion of the
hydrocellulose and that the cupric reducing power of the residue
is thereby diminished. This author quotes the following results
which he has obtained by boiling Girard's hydrocellulose with
15% sodium hydroxide solution:

1. Zts. ang. Chem. 1909, 22, 155; abst. J. S. C. I. 1909, 28, 216; C. A.
1909 3 1013

'2/ Zts." ang. Chem. 1908. 21, 2609; abst. J. S. C. I. 1909, 28, 105;
J. C. S. 1909, 98, i, 86; Chem. Zentr. 1909, I, 441; C. A. 1909, 3, 1168.

144

TECHNOLOGY OF CBLI.UU)SB ESTERS

Hydrocelliilose

Quantity of NaOH

Solution of 15%

Strength

Time of Boiling

Undts.solved
Residue

Gm.
10
10
10
10
10

Gm.
200
200
200
200
400

Min.
10
20
30
40
60

Percent.
48
42
40
37
33

The blue color produced by zinc chloride-iodine reagent on hydro-
cellulose is said to be very transient and is rapidly removed by
water, whereas the same coloration with cellulose hydrate resists
the action of water for a considerable period of time. Whereas
H. Taufs^ has shown that the action of water on cellulose at high
temperatures causes the formation of hydrocellulose, C. Schwalbe
and M. Robinoff^ found that only a chemically treated cellulose,
e. g., filter paper or a bleached cellulose, underwent marked hydrol-
ysis. Pure cellulose hydrolyzed but slowly, even at 30 atmospheres
pressure; above 150** however, the action is marked. Pure cel-
lulose was obtained by boiling pure, unbleached Egyptian cotton
with hard soap solution, washing and carefully bleaching. The
"corrected copper number" of this cellulose was 0.04. Bleaching
with h3rpochlorite solution and the subsequent add treatment
caused formation of oxycellulose as was indicated by the in-
creased copper number. Using an add concentration of 0.1%
hydrochloric add or acetic add, the copper number was 0.15.
In cold solution, cotton cellulose is hydrolyzed most effidently

1. Dingl. Poly. 1889, 273, 276; abst. C. A. 1911, 5, 1838; Jahr. Chem.
1889 2838.

'2. Zts. ang. Chem. 1911, 24, 256; abst. C. A. 1911, 5, 1838. See also
C. Schwalbe, Ber. 1907. 40, 4523, 4547; abst. J. S. C. I. 1907, 26, 1293; J. C. S.

1907, 92, i, 390; Zts. ang. Chem. 1907, 20, 1735; Chem. Zentr. 1907, I, 1490;

1908, I, 239, 1264; Jahr. Chem. 1905-1908, II, 961; Chem. Ztg. 1907, 31,
937; Bull. Soc. Chim. 1908, (4), 4, 381; Zts. ang. Chem. 1907, 20, 2166; abst.
J. S. C. I. 1908, 27, 35; Chem. Zentr. 1908, I, 239. Zts. ang. Chem. 1908,
21, 1321; abst. J. C. S. 1908, 04, ii, 627; Chem. Zentr. 1908, II, 447; C. A.
1908, 2, 2448. Zts. ang. Chem. 1909, 22, 155; abst. C. A. 1909, 3, 1013: Chem.
Zentr. 1909, I, 737. Zts. ang. Chem. 1909, 22, 929; abst. C. A. 1909, 3, 1457,
1811; Chem. Zentr. 1909, I, 1988. Zts. ang. Chem. 1910,23,2030; abst.
C. A. 1911, 5, 1187. Zts. ang. Chem. 1911, 24, 12; abst. C. A. 1912, 6, 545;
T. C. S. 1911, 100, i, 115. Zts. ang. Chem. 1911, 24, 256; abst. J. S. C. I. 1911,
30, 277. Zts. ang. Chem. 1911, 24, 1260; abst. J. C. S. 1911, 100, i, 712; Kunst.
1911, 1, 452; C. A. 1912, 6, 545; see also C. A. 1911, 5, 1187, 1677, 3153;
J. C. S. 1911, 100, i, 180.

CELI.UW>SE

145

by 4% alkali solution, a maximum copper number of 0.257 being
obtained at this concentration. They found that the solubility
of the cotton cellulose decreased with increasing concentration of
alkali up to 9% strength, when the solubility is unappredable at
ordinary temperatures. Solubility also increases with rise in tem-
perature, and above 150° it is considerable. The following table
is given as the copper numbers obtained after hydrolysis of pure
cellulose at various temperatures. It will be noted that the 4%
solution, in each case, is the most efficient.

Room Temp.

Water

Strength of Alkali Solution

1%

2%

3%

4%

5%

100** F.

135**

150**

179**

213**

0.042
0.109
0,153
0.300

0.150
0.180
0.142

0.166
0.200
0.170
0.110

0.195
0.262
0.395
0.128

0.257
0.528
0.890
0.445

0.135
0.168
0.285
0.050
0.000

Where 3% sulfuric add was allowed to act upon cellulose,
C. Schwalbe found the resulting hydrocellulose gave a copper
number of 5.2 (when made from binding twine) or 5.6 (from
filter paper). There is a sharp difference between alkali-prepared
hydrat-cellulose, and add prepared hydrocellulose. H. Jentgen^
finds for the preparation of hydrocellulose that Girard's method
is difficult of control, and prefers to distribute the add through
the cellulose by means of a solvent which does not dissodate the
add, heating the material in the presence of an excess of solvent.
Suitable solvents are gladal acetic add, ether, amyl acetate,
ethyl acetate, ethyl acetoacetate, formic add and glycerol. He
contends that the degree of formation of the cellulose into hydro-
cellulose is best shown by Schwalbe!s cupric reduction method,*
and that the formation increases with the time and temperature
of the treatment up to a certain point when sulfuric add is used.
The formation is said to be very rapid, but the hydrocellulose
tends to gelatinize on washing. The copper value of hydrocel-
lulose thereby falls generally between four and six, but higher
and lower values are occasionally obtained. Several salts of

1. Zts. ang. Chem. 1910, 23, 1541; abst. J. S. C. I. 1910, 29, 1052.

2. Zts. ang. Chem. 1910, 23, 924; abst. J. S. C. I. 1910, 29, 689.

146 TECHNOLOGY OP CELLULOSE ESTERS

strong adds with weak bases also convert cellulose into hydro-
cellulose tmder similar conditions, the action of these salts being
direct and not depending on dissociation as has often been as-
sumed. In the production of hydrocellulose the add is said to
enter into assodation with the cdlulose by adsorption, and hydrol-
ysis proceeds by the action of findy divided water on the adsorp-
tion compound, the acid acting as a contact agent. It is therefore
necessary that the acid be in a findy divided, concentrated (mole-
cular or non-ionized) condition. Where moisting is rigorously
•excluded, which is very difficult to insure, the cdlulose may be
recovered practically unchanged by washing the adsorption com-
pound,with water. Hydrocellulose prepared as above is soluble
in all the solvents of cellulose and is attacked by strong sulfuric
add in the same manner as cellulose. Strong caustic soda lye
•dissolves a portion of the hydrocellulose (generally about one-
third), the residue being mercerized and the copper value thereby
reduced. About 85% of the soluble portion is repredpitated by
add; the remainder being permanently soluble and profoundly
decomposed. In the case of hydrocellulose,. the refraction colors
of ordinary cotton cellulose in polarized light are considerably
•diminished.

In a subsequent communication^ in defining his viewpoints
ss to the fact that adds such as sulfuric add are only capable of
hydrolyzing cellulose when they are finely distributed in a mole-
•cular condition, and that ionized adds have no such action, this
author points out the following: 1st, that 1% concentrated solu-
tions of acid have practically no hydrolyzing action on cellulose;
2nd, that alcoholic solutions of adds hydrolyze only very slowly
and the rate of hydrolysis is directly influenced by the dissodated
capadty of the solvent; 3rd, that 1% solution of acid in non-
•dissociating solvents hydrolyze cellulose rapidly. In the prepara-
tion of hydrocellulose by Girard's method, where the cellulose
is steeped in a 3% solution of sulfuric add, the former must be
dried in the air before the add will act, whereby the latter be-

1. Zts.ang. Chem. 1910,23,1541; abst. C. A. 1911, 5, 1187. Zts. ang.
Chem. 1911, 24, 11; abst. J. C. S. 1911, 100, i, 116; J. S. C. I. 1911, 30, 125.
See also Schwalbe, Zts. ang. Chem. 1911, 24. 12, 1260; C. A. 1911, S, 1187.
Zts. ang. Chem. 1911, 24, 585; Kunst. 1911, 1 452; J. C. S. 1911, 100, i, 355.
See also C. Sdiwalbe, Zts. ang. Chem. 1^11, 24, 12; abst. J. C. S. 1911, 100,
i, 115.

CBUAJLOSB 14T

comes concentrated to about 30%, at which concentration sufl5-
dent molecular sulfuric acid is adsorbed by the celltdose to effect
its . disintegration. In the production of hydrocellulose it is
assumed that the adsorption compound is formed between
molecular sulfuric add and cellulose , and that water must be
present, but not in suffident quantity to cause complete ioniza-
tion of the add, and that the adsorbed add then promotes
reaction between the celltdose and the water and acts .as a
catalyst. The production of such an adsorption compound
is asstuned in ester reaction, e. g., in acetylation as a
primary phase, esterification being secondary and hydrolysis
being tertiary. Similarly, nitric add also forms adsorption
compounds with cdlulose as a primary stage and nitration is
secondary. Schwalbe, replying to the above contentation, holds
that dilute aqueous adds do have a distinct hydrolyzing action
on cdlulose, and that cellulose may be prepared by Girard's
method by steeping celltdose in add of only 0.001% concentra-
tion. If this celltdose be dried in the air the add present will
have a concentration of only 0.02% but will still hydrolyze the
celltdose. The contentions of Jentgen have repeatedly been
brought into question by Schwalbe.

The following^ are intermediate products of the hydrolysis
of cotton celltdose by means of stdfuric add:

Gmgnets cellulose^ is prepared by triturating 5 gms. of air-
dry cotton wool in a mortar with 86 cc. of 62.5% stdftuic add
for 15 minutes, digesting the mass at the ordinary temperature
for 5 hours, diluting with 176 cc. of water, filtering off on a doth
and washing the predpitate by decantation until free from add.
It gives colloidal solutions which are stable on boiling and may be
re-constituted after evaporation to dr3mess, but which are coagu-
lated by small quantities of adds and salts, also oli the addition
of alcohol. It is distingtushed by its low hydrol3rsis value
(Schwalbe) ; it is only colored blue by iodine solution in presence

1. C. Schwalbe and.W. Schulz, Ber. 1910, 43, 913; abst. J. C. S. 1910,.
, i, 301. Zts. ang. Chem. 1913, 26, 499; abst. J. S. C. I. 1913, 32, 499; C. A.

1910, 4, 1751; Jahr. Chem. 1910, C3, II. 419.

2. Compt. rend. 1889, 106, 1258; abst. Ber. 1889, 22, 574: Jahr. Chem.
1889, 42, 2839: Chem. Centr. 1889, 60, II, 124; J. C. S. 1889, SI, 847: Chem.
News, 1889, 60, 24; J. S. C. I. 1889, 3, 1001; Chem. Ztg. Rep. 1889, 13, 194;
Chem. Tech. Rep. 1889, I, 145; Wag. Jahr. 1889, 35, 1180; Mon. Sd. 1889,.
33,986.

148 TECHNOUX5Y OF CELLUU)SE ESTERS

of sulfuric acid, whereas vegetable parchment gives a blue colora-
tion direct.

Flechsig*s amyloid} is prepared by treating 5 gm. of cotton
with a cooled mixture of 30 gm. of 92% sulftuic add and 10 gm.
of water. The add is allowed to act for 1-2 hours at a tempera-
ture between 6® and 30®. The sticky mass is coagulated by
dilution and washed free from add. The washed product can be
dried at 95° without decomposition but not at 105°. It is col-
ored blue by iodine in presence of sulfuric add. It possesses
colloidal properties, but in a less pronounced degree than Guig-
net's cellulose; it has higher copper value, hydrolysis value and
solubility in alkali than Guignet's cdlulose.

Parchmentized cellulose is prepared by immersion for 10-30
seconds in 78% sulfiuic acid. The properties vary according to
whether loose cotton or filter paper is treated. Parchmentized
cotton wool, when boiled with 10% sodium hydroxide for 15
minutes, is dissoved to the extent of 70%, but filter paper sim-
ilarly treated loses only 18%. It absorbs cupric hydroxide from
Fehling's solution and the last traces are removed only with diffi-
culty by add; the hydrolysis value is high, the copper value is
relatively low. It is stained blue by iodine without the interven-
tion of sulfuric add.

Ekstrom's acid cellulose is prepared by treating 5 gm. of
cotton in a mortar with 18 gm. of 78% sulfuric add for 45 min-
utes, then diluting with 29 cc. of water and pressing the product
between doths. On stirring the residue with a little water a
colloidal solution is obtained, but with much water the product
is parchmentized. It is colored blue by iodine without sulfuric
acid. It has high copper and hydrolysis values and is completdy
soluble in alkali.

J. Briggs* has found that cellulose is converted by oxaHc add,
slowly at the ordinary temperature, more rapidly at higher tem-
peratures, partly into a hydrocellulose and partly into a compound
which is considered as an add oxalate of hydrocellulose. The
ester exhibits, even in the form of its sodium salt, a strong affinity

1. Zts. physiol. Chem. 1883, 7, 523; abst. Zts. deutsche Spiritusfabr.

1883, 805; Ber. 1883, 16, 2508; Chem. Tech. Rep. 1883, 21, II, 144; Jahr.
Chem. 1883. 36, 1363; Wag. Jahr. 1883, 29, 681; Tech. Chem. Jahr. 1883-

1884, 6, 275.

2. J. S. C. I. 1912, 31, 520; abst. J. C. S. 1912, 102, i, 539.

cELirULOSE 149

for basic dyestuflfs, as well as for the substantive dyestuflFs. Mork
has described processes for the esterification of hydr ©cellulose^
without change of form. Many methods have been devized for
the commercial acetation of hydrocellulose, either with sulfuric^

1. U. S. P. 854374, 1907; abst. J. S. C. I. 1907, 26, 713; Mon. Sci.
1907, 66, 169; C. A. 1907, 1, 2316. For the preparation of "alkali-hydro-
cellulose," see Vereinigte Kimstseidefabriken, A. G. F. P. 323475, 1902;*
abst. J. S. C. I. 1903, 20, 508. E. P. 17501, 1902; abst. J. S. C. I. 1903, 22;
817.

2. U. S. P. 692497, 1902; abst. J. S. C. I. 1902, 21, 362: Mon. Sci. 1908,
(4), S8, 161. F. P. 308506, 1901; abst. J. S. C. I. 1902, 21, 64; Mon. Sci.
1902, (4), S8, 159. U. S. P. 654988, 1900; abst. Mon. Sd. 1901, (4), 57, 98.

E. P. 11749, 1900; abst. J. S. C. I. 1901, 28, 741. D. R. P. 118538, 1899;
abst. Mon. Sd. 1901, 57, 213; Zts. ang. Chem. 1901, 14, 345; Chem. Centr.
1901, 72, I, 712; Jahr. Chem. 1901, 54, 891; Chem. Ind. 1901, 24, 330.

D. R. P. 120713, 1900; being addn. to D. R. P. 118538; abst. Mon. Sd. 1901,
57, 283; Chem. Ind. 1901, 24, 453; Zts. ang. Chem. 1901, 14, 575; Chem.
Centr. 1901, 72, I, 1219. F. P. 301749, 1900; abst. Mon. Sd. 1901, 57, 63.
U. S. P. 708456, 708457; abst. J. S. C. I. 1902, 21, 1243; Mon. Sd. 1903, (4),
60, 165. U. S. P. 999236, 1911; abst. J. S. C. I. 1911, 30, 1050. E. P. 3103,
1907; abst. J. S. C. 1. 1907, 26, 889. F. P. 374370, 1907; abst. J. S. C. I. 1907,
26, 776; Mon. Sci. 1908, 68, 84; Chem. Zts. 1907, 6, 139. F. P. 324718, 1903;
abst. J. S. C. I. 1903, 22, 620. E. P. 4886, 1902; abst. J. S. C. I. 1903, 22,
315. F. P. 316500, 1901; abst. J. S. C. I. 1902, 21, 719; Mon. Sd. 1903,
50, 53. Aust. P. 17456, 1902. D. R. P. Anm. L-15737. E. P. 22237, 1911;
abst. J. S. C. I. 1912, n, 279. F. P. 435507, 1911; abst. J. S. C. I. 1912, 31,
329. Bdg. 239564, 1911. U. S. P. 679204, 1901; abst. Mon. Sd. 1901, 57,
284. F. P. 304723, 1900; abst. J. S. C. I. 1901, 20, 469; Chem. Ztg. 1901,
25, 270; Mon. Sci. 1900, (4), 59, 20. D. R. P. 123121, 1900; abst. J. S. C. I.
1901, 20, 1133; Zts. ang. Chem. 1901, 14, 905; Chem. Centr. 1901, 72, II,
567; Mon. Sci. 1900, 50, 9; Jahr. Chem. 1901, 54, 892. E. P. 19039, 1900;
abst. J. S. d. I. 1901, 20, 926. U. S. P. 854374, 1907; abst. J. S. C. I. 1907,
26, 713: Mon. Sci. 1907, 67, 159. U. S. P. 922340, 1909; abst. J. S. C. I.

1909, 28, 671. F. P. 400652, 1909; abst. J. S. C. I. 1909, 28, 1061; Mon.
Sd. 1910, 73, 165. D. R. P. 237718, 1907; abst. Zts. ang. Chem. 1911, 24,
1988; Chem. Zentr. 1911, 82, II, 922; Chem. Ind. 1911, 34, 573; Chem. Ztg.
Rep. 1911, 35, 481. It. P. 303-136-101262, 1909. U. S. P. 734123, 1903;
abst. J. S. C. I. 1903, 22, 961; Mon. Sd. 1903, 60, 173. U. S. P. 790565,
1905; abst. J. S. C. I. 1906, 24, 686. D. R. P. 153350, 1901; abst. Zts. ang.
Chem. 1904, 17, 1697; Chem. Centr. 1904, 75, II, 625; Jahr. Chem. 1904,
57, 1168; J. C. S. 1904, 86, i, 853; Chem. Ind. 1904, 27, 538. D. R. P. 159524,
1901 ; abst. Chem. Centr. 1905, 76, II, 527 ; Zts. ang. Chem. 1905, 18, 1636 ; Jahr.
Chem. 1905-1908, II, 984; J. C. S. 1906, 90. i, 6; Chem. Ind. 1905, 28. 535.

F. P. 317007, 1901; abst. J. S. C. I. 1902, 21, 870; Mon. Sd. 1903, 60, 54.

E. P. 21628, 1901; abst. J. S. C. I. 1902, 21, 870. Aust. P. 31391. It. P.
62042, 1901. U. S. P. 953677, 1910; abst. J. S. C. I. 1910, 29, 557. U. S. P.
955082, 1910; abst. J. S. C. 1. 1910, 29, 557; Mon. Sd. 1910, 73, 131. E. P. 17036,
1909; abst. J. S. C. I. 1910, 29, 1005. F. P. 405293, 1909; abst. J. S. C. I.

1910, 29, 417; Mon. Sd. 1910, 73, 171; Chem. Ztg. Rep. 1910, 34, 75. D.
R. P. 219162, 219163, 1907; abst. Jahr. Chem. 1910, 63, I, 426; Zts. ang.
Chem. 1910, 23, 768; Chem. Ind. 1910, 33, 186; Wag. Jahr. 1910, 56, II,
433; Chem. Zts. 1910, 9, 1986, 1988. Aust. P. 45765, 1909. Hung. Anm.
N-952, July 21, 1909. Ital. P. 103978, 1909. Belg. P. 198984, 198985,
1907; 217837, 1909.

150 TECHNOUK5Y OP CELLULOSE ESTERS

or phosphoric adds;^ or iodine,* both at normal' and reduced
pressures.* Hydrocellulose benzoates,* formates' and sulfonates^
have also been described but they are not commercially manu-
factured at the present time. Water-soluble and alcohol-
soluble cellulose acetates result from the acetation of hydrocellu-
loses prepared according to Stahmer;* for the manufacture of
lakes* and the toughening of gas mantles with hydrocellulose
acetates,^® consult Volume VIII.

1. K. P. 4886, 1902; abst. J. S. C. I. 1903, 22, 315. F. P. 316500,
1901; abst. J. S. C. I. 1902, 21, 719; Mon. Sci. 1903, 59, 53. Aust. P. 17466,
1902. D. R. P. Anm. L-15737.

2. U. S. P. 679204, 1901; abst. Mon. Sci. 1901, 57, 284. F. P. 304723,
1900; abst. J. S. C. I. 1901, 2Q, 469; Chem. Ztg. 1901, 25, 270; Mon. Sci.

1900, 55, 20. D. R. P. 123121, 1900; abst. J. S. C. I. 1901, 2Q, 1133; Zts.
ang. Chem. 1901, 14, 905; Chem. Centr. 1901, 72, II, 567; Mon. Sci. 1900,
59, 9; Jahr. Chem. 1901, 54, 892. B. P. 19039, 1900; abst. J. S. C. I. 1901,
29,926.

3. K. P. 2511, 1907; abst. J. S. C. I. 1907, 28, 634; J. Soc. Dyers Col.
1907, 23, 215. F. P. 376262, 1907; abst. J. S. C. I. 1907, 28,.988; Mon. Sd.
1908, 68, 87. D. R. P. 189836, 189837, 1908; abst. Zts. ang. Chem. 1908,
21, 268; Jahr. Chem. 1905-1908, II, 983; J. C. S. 1908, 94, i, 321; Chem. Ind.
1907, 39, 617. U. S. P. 679203, 1901; abst. Mon. Sd. 1901, 57, 284; F. P.
309759, 1901; abst. J. S. C. 1. 1902, 21, 65; Mon. Sd. 1902, 58, 170. D. R. P.
123122, 1900; abst. J. S. C. I. 1901, 29, 1133; Mon. Sd. 1902, 58, 9; Jahr.
Chem. 1903, 1014; Zts. ang. Chem. 1901, 14, 905; Chem. Centr. 1901, 72,
11,568.

4. U. S. P. 1030311, 1912; abst. J. S. C. I. 1912, 31, 680; C. A. 1912,
6, 2528; Chem. Ztg. 1912, 36, 485. Can. P. 139046, 1912; abst. C. A. 1912,
6, 1526. B. P. 25893, 1912; abst. J. S. C. I. 1912, 3ll 279.

5. B. P. 22237, 1911; abst. J. S. C. I. 1912, 31, 279. F. P. 435507,
1911; abst. J. S. C. I. 1912, 31, 329. Belg. P. 239564, 1911.

6. U. S. P. 953677, 1910; abst. J. S. C. I. 1910, 29, 557. U. S. P.
955082, 1910; abst. J. S. C. I. 1910, 29, 557; Mon. Sd. 1910, 73, 131. E. P.
17036, 1909; abst. J. S. C. I. 1910, 29, 1005. F. P. 405293, 1909; abst. J. S.

C. I. 1^10, 29, 417; Mon. Sd. 1910, 73, 171; Chem. Ztg. Rep. 1910, 34, 75.

D. R. P. 219162, 219163, 1907; abst. Jahr. Chem. 1910, I, 426; Zts. ang.
Chem. 1910, 23, 768: Chem. Ind. 1910, 33, 186; Wag. Jahr. 1910, 56, II,
433 ; Chem. Zts. 1910, 9, 1986, 1988. Aust. P. 45765, 1909. Hmig. Anm. N-952,
July 21, 1909. Ital. P. 103978, 1909. Bdg. P. 198984, 198985, 1907; 217837,
1909.

7. D. R. P. 200334, 1907; abst. J. S. C. I. 1908, 27, 1130; Mon. Sd.
1911, 74, 63; Chem. Zts. 1908, 7, 909; Zts. ang. Chem. 1908, 21, 2233; Chem.
Zentr. 1908, 79, 655; Jahr. Chem. 1905-1908, 987; J. C. S. 1908, 94, i, 955;
Chem. Ind. 1908, 31, 499.

8. U. S. P. 679204, 1901; abst. Mon. Sci. 1901, 57, 284. F. P.
304723, 1900; abst. J. S. C. I. 1901, 29, 469; Chem. Ztg. 1901, 25, 270;
Mon. Sci. 1909, 59, 20. D. R. P. 123121, 1900; abst. J. S. C. I. 1901, 29,
1133; Zts. ang. Chem. 1901. 14, 905; Chem. Centr. 1901, 72, II, 567; Mon.
Sd. 1900, 59, 9; Jahr. Chem. 1901, 892. B. P. 19039, 1900; abst. J. S. C. I.

1901, 29, 926.

9. U. S. P. 692497, 1902; abst. J. S. C. I. 1902, 21, 362; Mon.
Sci. 1902, 58, 161. F. P. 308506. 1901; abst. J. S. C. I. 1902, 21, 64; Mon.
Sci. 1902, 58, 159.

10. F. P. 324718, 1903 ; abst. J. S. C. I. 1903, 22, 620.

CELLUlrOSE 151

The cellulose regenerated from any of these solutions differs
from the untreated material in being more reactive and in con-
taining a larger proportion of hydrogen and oxygen. The ele-
mentary composition agrees well with the formula (CiaHioOio).!!^©
or some mixture of this with normal celltdose. Treatment of
cellulose with acids and alkalis 3delds eventually very similar
products. Those obtained by the hydrolysis of nitrocellulose and
other cellulose esters possess analogous characteristics. There
are, however, considerable differences between celluloses which
have been treated by the different processes. Those celluloses
which have been mercerized and the alkali washed out or have
been treated into viscose and cellulose regenerated therefrom, are
not as reactive with Pehling's solution as celltdose that ^as under-
gone add treatment. The hydrate celluloses in general give off
the extra water at a temperature of 120** to 125®,^ whereas hydro-
cellulose retains its water more obstinately and at this tempera-
ture eliminates less than the untreated celltdoses.^

Action of Ozone on Cellulose. As previously stated, ac-
cording to M. Cunningham and C. Doree,' ozone in concentration
of 1% to 2% rapidly attacks cotton, forming a cellulose peroxide
and an add derivative together with some carbon dioxide, the
peroxide being decomposed at 80®. The acid may be removed
by boiling with water or digestion with dednormal alkali, the
neutral residue then obtained being an oxycellulose. The acidity

1. H. Ost and F. Wcsthoff, Chem. Ztg. 1909, 33, 197; abst. J. S. C. I.
1909, 29, 325; Chem. Zentr. 1909, 1, 1231. See also O. Hauser and H. Herz<
feld, Chem. Ztg. 1915, 39, 689; abst. C. A. 1915, 9, 3128. Compare C. A.
1908, 2, 184, 704, 1043, 1882; 1909, 3, 1013, 1108, 1457, 1811; 1910, 4, 1369;

1911, 5, 1187, 1677, 3153; 1912, 6, 546; 1913, 7, 2303; 1914, 9, 1009. See
H. Ost, Zts. ang. Chem. 1906, 19, 993; abst. Chem. Centr. 1906, II, 673;
J.^ C. S. 1906, 90, i, 560; J. S. C. I. 1906, 25, 606; BuU. Soc. Chim. 1906, 36,
1053; Jahr. Chem. 1905-1908, II, 983; Meyer Jahr. Chem. 1906, IS, 219;
Wag. Jahr. 1906, S2, II, 484.

2. For other applications of hydrocelltilose, see Heberlein & Co., F. P.
468821, 1914; abst. C. A. 1915, 9, 2315. Hide-ite Leather Co. E. P. 14527,

1912. F. P. 445279; abst. Kunst 1913, 3, 176. J. Hinde, Can. P. 77779.
H. MacFarland and R. Shoemaker, U. S. P. 1146189, 1915; abst. C. A. 1915,
9, 2432. A. Nobel & Co., D. R. P. 4410, 1878; abst. Wag. Jahr. 1879, 419;
Deut. Ind. Ztg. 1879, 171; Ber. 1879, 12, 712; Chem. Ztg. 1879, 3, 197; Dingl.
Poly. 1879, m, 188; Chem. Ind. 1879. 2, 171; Chem. Tech. Rep. 1879. I,
287; J. A. C. S. 1879. 1, 303. J. Rice, D. R. P. 279167, 1913; abst. C. A. 1915,
9, 1247; Wag. Jahr. 1914, 90, II, 405; Chem. Ztg. Rep. 1914, 39, 552; Zts.
ang. Chem. 1914, 27, 662; Chem. News, 1876, 33, 10; 1899, 99, 237; 1903, 97,
20. Erfind. u. Erfahr. 7, 625.

3. Proc. Chem. Soc. 1912, 29, 38; abst. J. S. C. I. 1912, 31, 278; J. C. S.
1912, 191, 497; C. A. 1912, 9, 1849; Chem. Zentr. 1912, 93, I, 1818; Bull.
Soc. Chim. 1912, 12, 1129. Cf. Kolb, Bull. Soc. Ind. Mulhouse, 1868, 94.

152 TECHNOLOGY OF CELLULOSE ESTERS

and amount of carbon dioxide produced dtuing treatment from
one to twenty hotu^ in duration, have been meastued and the
constants of the oxycellulose determined and compared with
typical oxycelluloses. Lignocellulose jute is not appreciably af-
fected unless moisture is present, in which case it is oxidized, giv-
ing carbon dioxide, acetic and formic acids and complex non-
volatile adds which yield fiufural. Quantitative treatment of
this progressive action of the ozone has shown that the lignin
group is rapidly attacked in the first three hours, after which the
action becomes slower, the residue being then uniformly oxidized.
The lignin reaction ceases when the loss in weight is about 33%.
Direct evidence of ozonized formation has not been obtained,
although the formation of formic and acetic acids appear to be
due to decomposition of some product formed in the first instance
by the action of ozone. In a continuation of their work on the
same hgnocellulose jute,^ the action of ozone on the more complex
tissues of wood has been examined. In the presence of moisture,
ozone rapidly attacks the wood substance, producing CO2 and
acetic compounds. As a result of the oxidation, a considerable
portion of the wood is converted into derivatives soluble in water,
the loss after twelve hoiu^ being some 40% in weight. The
water digest contains formic, acetic and other reducing acids and
yields fiufuraldehyde. The results are weU explainable by the
formulation of the hgnin groups given by Cross and Bevan,* but
do not lend weight to the coniferyl alcohol formula proposed by
Klason. The action of ozone on purified cotton cellulose fiu"-
nishes a peroxide recognized by its oxidizing action on potassium
iodide solution.' In their investigation of this question it was
found that with a high percentage of moisture a small amotmt of
peroxide alone is produced, but in air-dried material the quantity
of peroxide formed is very much greater and at the same time
soUd insoluble acid derivatives and oxycellulose result. The
amount of "active oxygen" fixed by air-dried cotton, mercerized

1. Proc. Chem. Soc. 1913, 29, 104; abst. J. S. C. I. 1913, 32, 482;
J. C. S. 1913. 103, 677; Chem. Zentr. 1913, 84, II, 246; Bull. Soc. Chim.
1913, 14, 950; Rev. g^. sci. 1913, 24, 410; C. A. 1913, 7, 2385.

2. "Researches on Cellulose." Ill, 104.

3. Proc. Chem. Soc. 1913, 29, 222; abst. J. S. C. I. 1913, 32, 695; C. A.
1913, 7, 3661; J. C. S. 1913. 103, 1347; Chem. Zentr. 1913, 84, II, 1466;
Bull. Soc. Chim. 1913, 14, 1263.

CELLULOSE

153

cotton, and lustra-cellulose after 18 hours exposure to ozone, was
0.0056%, 0.0106% and 0.0248% respectively. The peroxide is
slowly decomposed on treatment with water, hydrogen peroxide
being generated. It is also decomposed to the extent of 25%
after heating for two hours at 37® and almost entirely so after
two hours at 95®. The activity appears to soon disappear if the
material is kept in the air but persists for some weeks in a dry
atmosphere. These properties recall the * 'photographic action"
of the natural woods described by Wi RusselP and has been
shown to be due probably to the same cause, namely, the gradual
production of hydrogen dioxide.

C. Doree* has investigated the effect of the treatment witn
ozone on the breaking strength and elongation of cotton, mer-
cerized cotton and viscose silk, as shown in the following table.

The cotton yams were successively extracted with alcohol,
alcohol-ether, ether and water, then wetted out, pressed between
the cloth, opened out and hung in a chamber through which
ozonized oxygen (1.5% to 2% ozone) was continually passed.
After exposure the yarns were inunersed in water, pressed and
dried:

The effect of 2% ozone on the chemical characters of cotton
and viscose silk is shown in the following tfift>le, the copper num-

Relative Breaking Strength (B) and Elongation (E) after

Treatment with Ozone for Different Periods. (Untreated

Time

Material = 100)

of
Treat-
ment

Egyptian Cotton

Grey

Grey
Cotton

Viscose

Cotton
2/60

Silk, 120
Deniers

1/40

2/80

*

2-60
Mercerized

Hrs.

B

E

B

E

B

E

B

E

B

E

0.6

100

99

103

92

99

96

• •

• ■

106

99

1

99

84

100

84

94

103

97

104

98

90

3

91

80

88

76

82

97

92

100

86

70

6

88

78

70

65

65

82

82

94

73

54

12

53

52

44'

47

52

70

70

76

53

21

1. Phil. Trans. 1904, 197, 281; Proc. Roy. Soc. 1904, 74, 131; abst.
J. S. C. I. 1904, 23, 998; Jahr. Chem. 1904, 57, 168; Rev. g6n. sci. 1904. IS,

917

* 2. J. Soc. Dyers Col. 1913, 29, 205; abst. J. S. C. I. 1913, 32, 746;
C. A. 1913, 7, 3029. See also J. S. C, I. 1912, 31, 278; 1913, 32, 482, 695.

154

TBCHNOLOGV OP CBLLX7IX)SB BSTBRS

Cotton
Wool

Mercerized

Cotton

Wool

Mercerized

Yam 2/60

Grey

(Tension)

Viscose
Silk 120
Deniers

Nor-
mal

After
24 hr.
Ozone

Nor-
mal

After
24 hr.
Ozone

Nor-
mal

After
24 hr.
Ozone

Nor-
mal

After
24 hr.
Ozone

Loss- in weight, % .

C, per cent

Methylene blue ab-
sorption

• • • •

44.4

0.3

1.2

....

12
43.5

2.1
16.9
64

• • • ■

43.2

0.4

1.7

• ■ • •

7
43.5

3.1
24.0
57

■ • ■ •

« • • •

• • • •

• • • •

• • • »

• • •

• • •

2:3
9.6

• • •

* B • ■

44.6

1.6
3.0

• • ■ •

4.5
44.4

1.8
15.5
50

Copper number

LossinlO%KOH.

bers being determined by Schwalbe's method^ and the methylene
blue absorption by Vignon's method.* The loss of weight on
both for ten minutes with 10% solution of potassium hydroxide
was also determined:

Cellulose Peroxide. Cotton (as well as linen) fabrics which
have been bleached and acidified without the subsequent use of
an "antichlor," occasionally retain the property characteristic of
"active oxygen," in that they liberate iodine from potassium
iodide for a much longer time than is consistent with the emanat-
ing amounts of residual hypochlorites which may be present.
C. Cross and E. Bevan^ have recorded a case in which a cotton
cloth, bleached, soured and washed tmder normal conditions,

1. Ber. 1907, 40, 1347; abst. J. S. C. I. 1907, 26, 548; Zts, ang. Chem.
1910, 23, 924; abst. J. S. C. I. 1910, 29, 689. See also W. Viewee, Papier
Ztg. 1907, 32, 130, 174; 1909, 34. 149; Ber. 1907, 40, 3880; 1908, 41, 3269;
abst. C. A. 1907, 1, 1320; 1908, 2, 3403; J. C. S. 1907, 02, i, 893; 1908, 04,
i, 857; J. S. C. I. 1907, 26, 836, 1167; 1908, 27, 1081; Bull. Soc. Chim. 1908,
(4), 4, 902; Rep. Chim. 1908, 8, 62; Chem. Zentr. 1907, 7B, II, 1780; 1908,
70, ll, 1584; Chem. Ztg. Rep. 1908, 32, 27, 619; Meyer Jahr. Chem. 1907.
17, 215; 1908, IB, 506; Zts. ang? Chem. 1908, 21, 1184.

2. L. Vignon, Compt. rend. 1897, 125. 448; Bull. Soc Chim. 1898,
10, 790; abst. J. S. C. I. 1897, 16, 908; 1898, 17, 917; J. C. S. 1898, 74, i, 8;
Rev. Phys. et Chim. 1897-1908, 2, 21; Mon. Sci. 1897, 40, 859; Chem. Zentr.
1897, 68, II, 843; Chem. Ztg. 1897, 21, 811; Jahr. Chem. 1897, SO, 1506.

3. Zts. ang. Chem. 1906, 10, 2101; 1907, 20, 670; abst. J. S. C. I. 1907,
26, 44; 1908, 27, 260; Papier Ztg. 1907, 32, 87; Wochbl. Papierfabr. 1907,
38, 384; abst. C. A. 1907, 1, 1320, 2489; Chem. Zentr. 1907, 78, I, 1637;
1908, 70, II, 640; see also K. Rieth, Wochbl. Papierfabr. 1907, 38, 394. Ac-
cording to D. Zimmermann (Zts. ang. Chem. 1907, 20, 1280; abst. Chem.
Zentr. 1907, 78, I, 1537; II, 925) and E. Grandmougin (Chem. Ztg. 1908,
32, 242; abst. Chem. Zentr. 1908, 70, I, 1617), a loose combination of HCl
and cellulose is more probable, especially in view of the colloidal character of.
cellulose.

CBU.ULOS9 155

retained an add reaction and oxidizing properties (towards potas-
sium iodide) even after exhaustive washing with distilled water.
The acidity was removed or rather neutralized by washing with
hard water but the iodide reaction persisted. On the other hand,
the oxidizing property was rapidly destroyed by boiling with water
or by treatment with an "antichlor." Dry heat at 100® also
destroyed the "active oxygen" in the cloth but the fabric was
distinctly tendered. Having regard for all these circumstances, the
authors postulate the possibility of the formation of a peroxidized
derivative of cellulose under certain conditions of the industrial
bleaching process. H. Ditz,^ referring to the above opinion as ex-
pressed by Cross and Bevan, calls attention to the fact that the same
phenomenon is obtainable with an add solution of a persulfate.
This is accomplished by slowly heating cellulose for about one
and one-half hotu^ with add ammonium persulfate up to a tem-
peratiu^ of 80® and then gradually cooling. During this opera-
tion gas is evolved to an extent not observable in the absence of
the cellulose. When the product is subsequently well washed
with cold water it exhibits the same properties as the cellulose
peroxide described by Cross and Bevan. Ditz is satisfied that
the change is not due to the absorption of persulfate by the cellu-
lose, for when the latter is heated with a persulfate solution at
boiling point cdlulose exerts a powerful action on the decomposi-
tion of the salt with the evolution of oxygen and carbon dioxide

1. Chem. Ztg. 1007, 31, 833, 844»857; abst. J. Soc. Dyers Col. 1907,
23, 316: C. A. 1907, 1, 2941; Chem. Zentr. 1907, 73, II, 1606; J. S. C. I.

1907, 23, 988, 1026; J. C. S. 1907, 32, i, 829; see also J. prakt. Chem. 1908,
(2), 73, 343; abst. J. C. S. 1908, 34, i, 964; Chem. Zentr. 1907, II, 1606; 1908,
II, 2000; J. C. S. 1908, i, 954; C. A. 1909, 3, 841; Bull. Soc. Chim. 1909, 6,
1176; Chem. Ztg. Rep. 1907, 31, 833, 844, 867; 1908, 32, 619; J. S. C. I.

1908, 27, 1129; C. A. 1909, 3, 841. He fomid (J. prakt. Chem. 1908, (2),
73, 343; abst. Chem. Zentr. 1908, II, 2000; J. C. S. 1908, 34, i, 964; C. A.

1909, 3, 841; Bull. Soc. Chim. 1909, 6, 1176) that very litUe gas is evolved by
the action of hydrogen peroxide upon cellulose, with ammonium persulfate,
the reverse is the case. It appears that cellulose peroxide formed by the
persulfate method does not contain sulfuric add. Cellulose peroxide does
not evolve ammonia when boiled with lime water, but gives with Nessler's
reagent a brown coloration, becoming grey in consequence of the reduction
of the mercuric salt by the small amount of oxycellulose present in the per-
oxide. Due to the fact that it behaves towards Nessler's reagent in the
same manner as a dilute formaldehyde solution, oxycellulose is considered to
probably contain an aldehydic group. The gases evolved by the action of
ammonitun or potassitun persulfate upon ^Uulose are found to contain
carbon dioxide in addition to "active" oxygen. Compare L. Rosenthaler,.
Pharm. Central h. 1906, 47, 681; abst. J. C. S. 1906, 30, ii, 911; Chem.
Centr. 1906, H, II, 717.

156 TECHNOLOGY OP CELLULOSE ESTERS

and an irritating gas, but in these circumstances the cellulose does
not retain the properties of a peroxide. Again, when ammonium
persulfate is allowed to act on cellulose in the absence of an acid,
the products obtained show but very faintly the properties of a
peroxide. This author lays some stress on the distinct difference
between the acidity of the cellulose peroxide and the active oxy-
gen, for the former is not destroyed, like the latter, by boiling
with water for two or three minutes, and these two particular
properties are quite independent of each other. On gently heat-
ing cellulose peroxide obtained by means of ammonium persul-
fate with a 10% solution of potassium hydroxide, a golden yellow
coloration is produced, at the same time partial solution taking
place. On treating and filtering with an excess of hydrochloric
acid, almost total decoloration ensues with the formation of a
dirty white deposit. The author finds a difference between the
peroxidized cellulose under consideration and the hydralcellulose
of Bumcke and Wolffenstein^ obtained by the action of hydrogen
peroxide on cellulose in so far as it contains an acid, possibly
add-cellulose. It has been shown that the products of the action
of ammonium persulfate in the presence of sulfiuic add upon
cellulose are a peroxide, and free add, and only probably a por-
tion of imaffected cellulose. Dilute sulfiuic acid at 70° acting
alone upon cellulose, yields a product containing txaces of free
acid and a reducing body. The latter has been foimd to be
hydrocellulose, not oxycellulose. When ammonitun persulfate is
used alone, oxidized cellulose with a formation of oxycellulose and
free add results, but only traces of peroxidized cellulose. The
author's conclusions are that the sulfuric acid exerts this influence
by increasing velodty at the rate of decomposition of the am-
monium persulfate. J. Heinke^ has found that linen fiber once
peroxidized, does not lose the property of liberating iodine from

1. Ber. 1899, 32, 2493; abst. J. C. S. 1899, 76, i, 854; J. S. C. I. 1899,
IB, 940; Chem. Centr. 1899. 70, II, 752; Jahr. Chem. 1899, 52, 300, 1290;
Bull. Soc. Chim. 1900, 24, 620; Meyer Jahr. Chem. 1899, 9, 300.

2. Chem. Ztg. 1907, 31, 974; abst. J. Soc. Dyers Col. 1907, 23,
317; C. A. 1908, 2, 180; Chem. Zentr. 1907, 7B, II, 1714; Jahr. Chem. 190&-
1908, II, 961. He was able to confirm the observations of Cross and Sevan
in the case of bleached linen, where an iodine reaction persists in spite of
the most thorough washing. Heinke points out that the dry material is to
all appearance not damaged during exposure as regards decrease in tensile
strength, but a loss of strength in the material up to 50% was fotmd to take
place on boiling it in alkaline solutions.

CELLULOSE 157

potassium iodide by drjring above the normal temperature, and
shows according to the author's rather limited experimentation,
no appreciable weakening of the fiber; but on the other hand, if
the same material be treated in a warm weak solution of alkali
such as sodium carbonate, sodium hydroxide or sodium sulfide,
then the fiber and the linen become quite yellowish, while the
fiber loses at the same time about 50% in strength and is useless
for weaving piuposes. From the investigations hitherto recorded,
it would appear that the amount of "cellulose peroxide" formed
is in any case extremely small.

As stated, according to C. Doree,^ much more cellulose per-
oxide is formed by the action of ozone from ak-dry than from
bone-dry cellulose product. The "active oxygen" fixed by air-
dry cotton, mercerized cotton and lustracellulose on eighteen
hours' exposure to ozone was 0.0056%, 0.0106% and 0.0248%,
respectively. The peroxide slowly decomposes, the formation of
hydrogen peroxide on treatment with water being partiaUy de-
composed by two hotu^ heating at 37® and almost entirely so
when the temperatm^ is raised to 95®. The activity is retained
some weeks when exposed in a dry atmosphere.

However, M. Cunningham and C. Doree^ have fotmd that
1% to 2% ozone rapidly attacks cotton, forming a cellulose per-
oxide and an add derivative, together with some carbon dioxide,
the peroxide content being decomposed at 80® C. The acid
may be removed by boiling with water or by digestion with deci-
normal alkali, the neutral fiber residue then obtained being an
oxycellulose.

With lignocellulose jute no appreciable effect is observed
unless water is present, in which case it is oxidized giving carbon
dioxide, acetic and formic acids and complex non-volatile acids
that yield furfural. Quantitative measurements of the progres-
sive action of the ozone shows that the Ugnone group is rapidly
attacked in the first three hoiU"s, after which the action becomes
slower, the residue then being oxidized uniformly. The lignin

1. Proc. Chem. Soc. 1913, 29, 222; abst. J. S. C. I. 1913, 32, 695; C. A.
1913, 7, 2385. J. C. S. 1913, UB, 1347; C. A. 1913, 7, 3661. Chem, Zentr.
1913, 84, II, 1466.

2. Proc. Chem. Soc. 1912, 28, 38; abst. J. S. C. I. 1912, 31, 278; J. C. S.
1912, 101, 497; Chem. Zentr. 1912, I, 1818; C. A. 1912, 6, 1849; Bull. Soc.
Chim. 1912, 12, 1129.

158 TECHNOUX>Y OF CELLULOSE ESTERS

reactions, however, cease when the loss of weight is about 33%.

Cellulose and Oxidizing Agents.^ Although as has been pre-
viously stated, cellulose is tmusually stable against oxidation and
hydrol3rtic treatments considering the complexity of its composi-
tion, it is nevertheless profoundly changed upon prolonged ex-
posing to these influences, especially at elevated temperatiures.

In general, chlorine acts but slowly upon the fiber in the
absence of moisture, although, as noted by J. Kolb,* dyed fibers
are usually not discolored, although the cellulose may be ren-
dered brittle and friable. It would appear that Kolb had not
succeeded in entirely excluding moisttue, his observations indi-
cating hydrocellulose formation, this taking place as pointed out
by Girard in the presence of moist hydrochloric acid.

G. Hertel has developed chlorine from bleaching powder and
sulfmic acid and htmg strips of cellulose in a current of the gas.
The bleaching was found to be very effective when the chlorine
was freshly generated but when the gas was left standing for some
time it became quite ineffective, due most probably to the devel-
opment of chlorine oxides. While freshly developed HCl acts
energetically, dilution with an inert gas as COj materially inhibits
the action.'

When a strip of moist caUco is htmg in an atmosphere of
chlorine mixed with air, G. Witz* observed that after a short
time a much stronger dyeing effect with methylene blue was
produced, oxycellulose ultimately being formed. T. Leykauf,*
and subsequently Loewenthal* and C. Cross, and E. Bevan^

1. Data in this topic has been taken from the excellent work of
Schwalbe, "Die Chemie der Cellulose/' to which source acknowledgment is
due.

2. Bull. Soc. Ind. Mulhouse, 1868, 38, 914; Compt. rend. 1868, 66,
1024; 67, 742; Instit. 1868, 329; Ann. Chim. Phys. 1868, (4), 14, 348; BuU.
Soc. Chim. 1868, 9, 431; Dingl. Poly. 1868, 190, 62; 1869, 191, 321; Jahr.
Chem. 1868, 21, 981.

3. Leipziger Farberztg, 1886.

4. Bull. soc. ind. Rouen, 1882, 10, 439; 1883, 11, 176; abst. J. S. C. I.
1883, 2, 378; Mon. Sci. 1883, 25, 517; 1884, 26, 116; Dingl. Poly. 1883, 250,
271; Jahr. Chem. 1883, 86, 1782; Wag, Jahr. 1883, 29, 1068; Farb. Must.
Ztg. 17, 129.

5. J. prakt. Chem. 1840, 21, 316. Leuch's Allg. polytech. Ztg. Sept. 1840.
For data on some natural oxycelluloses, see G. de Chalmot, Ber. 1894, 27,
1489; Am. Chem. J. 1894, 16, 589; abst. J. C. S. 1894, 66, i. 399; Bull. Soc.
Chim. 1895, 14, 271; Chem. Centr. 1894, II, 148; Jahr. Chem. 1894. 47,
1146; Meyer Jahr. Chem. 1894, 4, 570.

6. Leipziger Monatsh. Textilind. 1890, 599.

7. J. S. C. I. 1890, 9, 450; Mon. Sci. 1891, 87, 156; abst. Ber. 1891, 24,

CELLULOSE 169

together with C. Schwalbe,^ found that cellulose is chlorinated by
chlorine, being still able to find chlorine in the cellulose after
washing and exposing to the air for several months. Whether
the chlorine absorption is in the cellulose or in the accompanying
pectinous and nitrogenous protoplasmic material is not quite
dear.

However, G. Witz* has convincingly demonstrated that the
change in the cellulose fiber is not entirely due to chlorination,
for samples of chlorine-impregnated calico, after saturating with
nitric acid, drying and igniting, gave no indications of the presence
of chlorine. •

In the experience of A. Franchimont,' bromine in the absence
of moisttu^, does not act upon cellulose, a chloroform solution of
bromine being without action. The nece^ity, however, should
be emphasized of the absence of moisture, otherwise HBr will be
formed, and this in ttun, results in the formation of hydrocellu-
lose and brom-methylfurfurol. So also when HBr is formed from
the bromine, oxidation by the nascent oxygen must also take
place, as in the case with chlorine. If, however, as stated by O.
Faber and B. Tollens,^ large amounts of bromine are allowed to
act upon cellulose in the presence of water, especially in the
presence of caldtun carbonate, a typical oxycellulose results.

Iodine appears to be devoid of oxidizing action, although
it is absorbed by the cellulose. J. Huebner^ has recorded that
10 gm. cotton takes up from a solution of 7.6 gm. iodine in 750 cc.
KI solution, 0.136 gm. iodine, which, however, may be readily
and completdy removed by energetic washing. Filter paper
undoubtedly bas a strong absorbent power for iodine, and accord-

R, 621; Chem. Centr. 1890, €1, II, 185; Chem. Tech. Rep. 1800, 29, I, 89;
Chem. Ztg. Rep. 1890, 14, 216; Jahr. Chem. 1890, 43, 2886; Tech. Chem.
Jahr. 1890-1891, 13, 521; Wag. Jahr. 1890, 36, 1110; Deutsche Chem. Ztg.
1890 220

' 1. bhem. Ztg. 1908, 32, 489, 521.

2. Bull. soc. ind. Rouen, 1882, 10, 446.

3. Rec. trav. Chim. Pays-Bas, 1883, 2, 91; abst. Ber. 1883, IS, 1872;
Jahr. Chem. 1883, 36. 1366.

4. Ber. 1899, 32, 2591; abst. J. S. C. I. 1899, IB, 1014* T. C. S. 1899,
7$, i, 854; Chem. Centr. 1899, 70, II, 901; Jahr. Chem. 1899, 82, 1292; Chem.
Ztg. Rep. 1899, 23, 321 ; Chem. Tech. Rep. 1899, 38, 550; Bull. Soc. Chim.
1900, 24, 621.

5. J. C. S. 1907, 91, 1072; Proc. Chem. Soc. 1907, 23, 144; Chem.
News, 1907, 98, 273; abst. J. S. C. I. 1907, 26, 866; BuU. Soc. Chim. 1908,

4), 4, 165: Rep. Chun. 1907, 7, 355; Chem. Zentr. 1907, 78, II, 752; Chem.
tg, 1907, 31, 716; Jahr. Chem. 1905-1908, II, 3171.

i

160 TECHNOLOGY OF CELLULOSE ESTERS

ing to p. Mylius^ forms a loose chemical combination with cel-
lulose similar to that with starch. Cellulose free from starch is
stained yellow to brown with iodine, but with zinc igdide or
iodine in H2SO4 a strong blue color appears. E. Flechsig^ contends
that this coloration appears only in the presence of acid.

As an oxidizing agent for cellulose, oxygen in the entire
absence of light is negative, as well preserved manuscripts from
very ancient times prove. With ozone there is no analogy, for
the latter acts very energetically upon cellulose at the same time
increasing its weight as pointed out by J. Kolb,' who exposed
unbleached dry linen yam for some weeks to the influence of a
current of ozone produced by the action of sulfuric acid upon
potassitun permanganate. G. Witz^ has also demonstrated the
oxidizing action of ozone by dyeings with methylene blue (oxycel-
lulose formation). High concentrations of hydrogen dioxide
according to G. Bumcke and R. Wolffenstein* induce energetic
hydrolysis. With elevated temperatiu"es, however, oxidizing
action takes place, Prud'homme* having recorded the ready
formation of oxycellulose upon boiling cellulose in the presence
of magnesia with concentrated hydrogen dioxide solutions.

Certain metals and metallic oxides seem to markedly intensify
the action of hydrogen dioxide upon cellulose, the oxides of iron,

1. Ber. 1895, 28, 390; abst. J. C. S. 1895, 6S, i, 313; Bull. Soc. Chim.
1895, 14, 901 ; Chem. Centr. 1895, W,I, 793; Jahr. Chem. 1895, 48, 514.

2. Zts. Physiol. Chem. 1883, 7, 523; abst. Zts. deutsche Spiritusfabr.
1883, 805; Ber. 1883, 16. 2508; Chem. Tech. Rep. 1883, 22, II, 144; Tech.
Chem. Jahr. 1883-1884, 8, 275; Jahr. Chem. 1883, 38, 1363; Wag. Jahr. 1883,
29,681.

3. Bull. Soc. Ind. Mulhouse, 1868, 38. 914; Compt. rend. 1868, 88,
1024; 87, 742; Ami. Chim. Phys. 1868, (4), 14, 348; Bull. Soc. Chim. 1869,
11, 431; abst. Dmgl. Poly. 1868, 198, 62; 1869, IM, 321; Jahr. Chem. 1868,
21, 981.

4. Bull. soc. ind. Rouen, 1883, U, 198; abst. J. S. C. I. 1883, 2, 378;
Jahr. Chem. 1883, 38, 1782; Wag. Jahr. 1883, 29, 1068.

5. Ber. 1899, S2, 2493; abst. J. C. S. 1899, 78, i, 852; J. S. C. I. 1899,
18, 940; Bull. Soc. Chim. 1900, 24, 620; Chem. Centr. 1899, II, 752; Jahr.
Chem. 1899, 52, 1290; Meyer Jahr. Chem. 1899, 9, 300.

6. Bull. Soc. Ind. Mulhouse, 1891, 81, 503; Faerb. Ztg. 1891-1892, 12;
Compt. rend. 1891, 112, 1374; Mon. Sci. 1891, 38, 677; 1892, 39, 495; abst.
Chem. News, 1891, 84, 9; J. C. S. 1891, 88, 1447; J. S. C. I. 1891, 18. 834;
Bull. Soc. Chem. 1892, 7, 79; Rev. g^. sci. 1891, 2, 455; Ber. 1891, 24, R,
595; Chem. Centr. 1891, 82, II, 685; Chem. Tech. Rep. 1891, 38, II, 123;
Chem. Ztg. Rep. 1891, 15, 1024; Jahr. Chem. 1891, 44, 2816; Wag. Jahr.
1891, 37, 1115; Zts. ang. Chem. 1892, 5, 718; Tech. Chem. Jahr. 1891-1892,
14, 491; Indbl. 1891, 262; Deutsche Chem. Ztg. 1891, 218.

CSLLULOS^ 161

aluminum and chromium appearing to act as catalysts. E.
Knecht^ mordanted cotton with chromium oxide, and upon treat-
ment of the mordanted fabric with hydrogen dioxide, found
oxycellulose readily formed. Wolffeiistein^ made similar obser-
vations with metals, specially lead.

Nitric acid may either form (a) hydrocellulose, (b) oxycel-
lulose, (c) mercerize, or (d) nitrate. The oxides of nitrogen,
however, appear to act entirely different. The gases from the
action of acetic acid upon a metallic nitrite apparently do not
form oxycellulose as judged by the methylene blue test,' but the
fumes from concentrated nitric acid weaken cotton and other
forms of cellulose.* MitscherUch* affirms that Swedish filter
paper is not attacked by HNO3 of 1.2 sp. gr. in tl\e cold. At
more elevated temperattu-es oxycellulose is formed, as has been
noted independently by several observers. Whether or not the
reaction of oxycellulose formation by nitric acid is due to the
presence of small amounts of nitrous add, as assumed by B.
Bull* for the oxidation of compound celluloses, has, as yet, not
been proven.

Cellulose may also be oxidized with chromic acid, a fact
long since known and made use of by calico printers. P. Jean-

1. J. Soc. Dyers Col. 1897, 13, 109, 131; abst. J. S. C. I. 1897, 16,
534; Jahr. Chem. 1897, SO, 1511. See also Persoz, Bull. soc. ind.
Rouen, 1882, 10, 466; Bull. Soc. Chim. 1883, 39, 620; Chem. Ind. 1884, 7,
162; Chem. Tech. Rep. 1884, 23, 1, 26.

2. D. R. P. 206566; abst. Chem. Zentr. 1909, 80, I, 967; Chem. Ztg.
Rep. 1909, 33, 152.

3. G. Witz, Bull. soc. ind. Rouen, 1883, U, 212.

4. A. Schuerer, Bull. Soc. Ind. Mulhouse, 1888, S5, 304, 364, 399, 439;
abst. J. S. C. I. 1888, 7, 841, 843; Bull. Soc. Chim. 1888, 50, 597; Mon. Sci.
1889, 33, 257; Chem. Ind. 1888, U, 556; 1889, 12, 40; Chem. Tech. Rep.
1888, 27, II, 60, 105; Jahr. Chem. 1889, 42, 2841 ; Wag. Jahr. 1888, 34, 1099.

5. GmeUn Handbuch der Chemie, 7, 585.

6. J. C. S. 1897, 71, 1090; Chem. News, 1897, 78, 249; abst. Chem.
Centr. 1897, 88, II, 733; Jahr. Chem. 1897, SO, 1507; Meyer Jahr. Chem. 1897,
7, 151. See also G. Mulder, Scheik. Onderzoek, 1846, 3, 336; abst. Ann. 1846,
88, 334; J. prakt. Chem. 1846, 38, 150. C. Cross and £. Sevan, J. C. S. 1883,
43, 22; Chem. News, 1882, 48, 240; J. S. C. I. 1884, 3, 206, 291; abst. Bull.
Soc. Chim. 1883. 38, 671; Chem. Ind. 1883, 8, 353; Chem. Tech. Rep. 1883,
22, II, 94; Dmgl. Poly. 1883, 2S0, 280; Jahr. Chem. 1883, 38. 1366, 1777;
Mon. prod, chim. 1883, 242. Sacc, Ann. Chim. Phys. 1849, (3), 25, 218; 1892,
271, 288. J. Porter, Pharm. Centr. 1849, 28, 777; abst. Jahr. Chem. 1849,
2, 474; Ann. 1849, 71, 115. J. Lindsey and B. ToUens, Ann. 1892, 287, 366.
R. Tromp de Haas and B. ToUens, Ann. 1895, 288, 296. G. Witz, Bull. soc.
ind. Rouen, 1882, 416. A. Nastjukoff, Bull. soc. ind. Rouen, 1883, 169; 1892,
483. E. Naiting, Bull. soc. ind. Rouen, 1892, 493.

162 TECHNOLOGY OP CELLUW)SE ESTERS

maire,* G. Witz^ and C. Brandt' have all employed the formation
of oxycellulose by means of chromic acid to produce dark designs
on a light background in a one-bath operation. The oxycellulose
obtained with chromic acid differs from the oxycellulose prepared
by means of nitric acid in that the latter, upon distillation, jrields
much less furfurol than the former.

- Alkaline solutions of chlorates appear* to be without action
upon cellulose. Vignon used chlorates in acid solution for oxy-
cellulose formation.

C. Brandt has observed^ that aniline black may be prevented
from turning green by over-dyeing with methyl violet, — green and
violet being supplementary to blue. This peculiar property
according to Witz, can only be explained upon the assumption that
traces of oxycellulose are also formed. •

H)q)ochlorous acid is an energetic oxidizing agent for cellu-
lose, it depending entirely upon the concentration of the bleaching
liquor as to whether the cellulose is damaged.^ The strength of
bleaching solution for maximum effect without weakening the
fiber is given as 0.2% by G. Witz,^ and 0.8% by A. NastjukoflF.'

If cotton fabric is saturated with a strong sodium hypochlorite
solution and subsequently placed in an atmosphere of CO2, an
exceedingly violent reaction takes place, as noted by A. Girard.^®
The fabric almost instantaneously loses its fibrous structure, swells
up, and ultimately becomes a thick structureless paste. C.

1. Bull. Soc. Ind. Mulhouse, 1873, 43, 334; abst. Chem. News, 1874,
29, 174; J. C. S. 1874, 27, 931; Chem. Centr. 1874, 45, 207; Chem. Tech. Rep.
1874, 13, I, 70; Dingl. Poly. 1874, 211, 403; Jahr. Chem. 1874, 27, 1199; Wag.
Jahr. 1874, 20, 852; Indbl. 1874, 133; Poly. Centr. 1874, 40, 144; Deutsche
Ind. Ztg. 1874, 96; Poly. Notizbl. 1874, 29, 85.

2. Bull. soc. ind. Rouen, 1883, 11, 208.

3. Bull. Soc. Ind. Mulhouse, 1891, 01, 496; abst. Reiman's Faer-
berztg. 1891, 3, 61, 62; Deutsche Chem. Ztg. 1891, 417; J. S. C. I. 1892, U,
33; Chem. Ind. 1892, 15, 172; Chem. Tech. Rep. 1891, 30, 63; Wag. Jahr.
1891,37,1138.

4. G. Witz, Bull. soc. ind. Rouen, 1883, 11, 202.

6. Bull. Soc. Ind. Mulhouse, 1876, 66, 441; abst. Chem. Tech. Rep.
1876, 15, I, 49; Dingl. Poly. 1877, 223, 331; Tudbl. 1877, 191; Zts. Chem.
Grossgew. 1876, 1, 204.

6. Bull. soc. ind. Rouen, 1883, 11, 206.

7. Dalichow, D. R. P. 135723. J. Thompson and J. Rickmann, D. R.
P. 30830, 32704; abst. Wag. Jahr. 1885, 31, 966.

8. Bull. soc. ind. Rouen, 1882, 10, 416.

9. Bull. Soc. Ind. Mulhouse, 1892, 62, 500.

10. Ann. Chim. Phys. 1881, (5), 24, 337, 382; abst. Tahr. Chem, 1881, 34,
985;J.C.S. 1882, 42,378.

^

CELIvUI<OSE 163

Schwalbe^ has shown that inasmuch as the product possesses a
high degree of reducing power, oxycellulose undoubtedly is present.
A. Girard* contends that the destructive action of bleaching
powder on cellulose is due to the formation of hydrocellulose —
the CO2 and h3rpochlorous acid forming HCl and this in turn
producing hydrocellulose — a view also expressed by Dumas,'
who assumed a transformation of the chlorine into HCl imder
the influence of light. In support of his contention, Girard
immersed a piece of hemp fabric in sodium hypochlorite solution
which retained its strength, but immediately disintegrated in an
atmosphere of COj.*

Calcium hypochlorite is unquestionably the most important
and widely used of the alkaline oxidizing agents for cellulose, and,
as has been pointed out, it does appreciably attack the fiber in
dilute solution, while with higher concentrations and at elevated
temperatures oxycellulose is formed. At the temperature of
boiling water disintegration is complete, and the cellulose becomes
a structureless powder devoid of tensile strength. Bearing in
mind that a sodium hypochlorite solution when heated with
cellulose produces energetic oxidation, it is difficult to reconcile
the statement of Salvetat and J. Barral* that no weakening of the
fiber results upon saturating cellulose with sodium hypochlorite
solution of 5° B6. and subsequently heating to 140°.

The action of alkaline bromine solutions is presumably analo-
gous to that of chlorine, J. Collie^ having recorded that ener-
getic action leads to the formation of bromoform among the re-
action products along with carbon tetrabromide.

The action of potassium permanganate is different from the

1. Zts. ang. Chem. 1907, 20, 2171; Chem. Ztg. 1907, 31, 937; abst. C.
A. 1908, 2, 704; J. C. S. 1908, 94, »» 9; BuU. Soc. Chim. 1908, 4, 381 ; Ber. 1907.
40, 961, 4523; Chem. Zentr. 1908, 79, 1, 240; Jahr. Chem. 1905-1908, II, 961.

2. Compt. rend. 1877, 81, 1105; Ann. Chim. Phys. 1881, (5), 24, 337,
382; abst. Jahr. Chem. 1881, 34, 985; J. C. S. 1879, 36, 911; 1882, 42, 378.

3. Traite de chimie, 1843, 6, 31.

4. According to Witz (Bull. soc. ind. Rouen, 1882, 10, 440) the COi
of the air decomposes calcium hypochlorite into calcium carbonate and
hypochlorous acid. This very unstable compound, with an odor entirely
diifferent from that of chlorine, further decomposes in the presence of organic
matter.

5. Ann. Chim. Phys. 1876, (5), 9, 126; Chem. News, 1876, 33, 18; abst.
J. C. S. 1876, 29, 821; Ber. 1876, 9, 68; Compt. rend. 1875, 01, 1189; Dingl.
Poly. 1876, 219, 469; Jahr. Chem. 1875, 20, 1164; Bull. Soc. Chim. 1876,
25 425

6.* J. C. S. 1894, 65, 262; abst. Bull. Soc. Chim. 1894, 12, 448; Jahr.
Chem. 1894, 47, 758.

164 TECHNOLOGY O^ CEttUtOSE ESTERS

other oxidizing agents above mentioned, G. Witz^ having found
that oxidation with permanganate, although resulting in the
formation of a brilliant white color, nevertheless perceptibly
weakened the cellulose fiber. While potassium ferrocyanide
scarcely attacks cellulose,* potassium permanganate has been
employed by E. Berl and R. Klaye' to prepare oxycellulose from
cellulose.

Ammonium persulfate under certain circumstances, may'
cause considerable deterioration in the strength of cotton fiber
as clearly shown by A. Scheurer,* where losses up to 40% have
been recorded.

Oxycellulose. When powerful inorganic oxidizing agents
such as chlorine, permanganates, chromic acid, chlorates and
persulfates are allowed to act in concentrated solution upon
various forms of cellulose, the latter is readily attacked and con-
verted into a brittle modification which has an increased aflfinity
for dyestujffs. In a fairly comprehensive manner. G. Witz^
subjected the conditions of origin and properties of the converted
cellulose, called "oxycellulose" by him, to a thorough investiga-
tion. He preferably prepares oxycellulose by immersing in a
solution of chloride of lime or other liquid containing free chlorine,
strips of cotton cellulose which are afterwards exposed to the air.
No exterior change in the material is apparent even under vigorous
oxidation, but it is found to be very brittle and friable and has

1. Bull. soc. ind. Rouen, 1883, 11, 211.

2. Bull. Soc. Ind. Mulhouse, 1890. 80, 311.

3. Zts. Schiess u. Sprengw. 1907. 2, 403; abst. C. A. 1908, 2, 184; J. C. S.
1908, H i, 604; J. S. C. I. 1907, 26, 1167; Chem. Zentr. 1908, I, 1381; Chem.
Ztg. Rep. 1908, 32, 43; Jahr. Chem. 1906-1908, II, 976.

4. Bull. Soc. Ind. Mulhouse, 1901, 71, 182; abst. J. C. S. I. 1901, 20,
891; Meyer Jahr. Chem. 1901, 11, 447.

6. BuU. Soc. Chim. Rouen, 1882, 10, 416, 447; 1883, U, 169, 2210;
abst. Wag. Jahr. 1883, 29, 1068; J. C. S. 1884, 46, 628; J. S. C. I. 1883, 2, 378;
Mon. Sci. 1883, 25, 517; 1884, 26, 1161; Dingl. Poly. 1883, 2S0, 271; Jahr.
Chem. 1883, 36, 1782; Farb. Must. Ztg. 17, 129. F. von Goppelsroeder
alleges (Dingl. Poly. 1884, 254, 42; Chem. Ind. 1884, 8, 14; abst. Jahr. Chem.
1884, 37, 1833, 1845; J. C. S. 1886, 48, 208; J. S. C. I. 1884, 3, 518, 519)
that, in confirmation of the results of Witz and Schmidt, that when cotton
saturated with a solution of potassium nitrate or chlorate or sodium chloride,
either neutral or alkaline, is placed in contact with platinum foil and a current
passed through, the cotton at the points touched by the positive wire have a
greater affinity for certain dyes, just as though mordants had been applied, so
that it was found possible to produce designs of a darker shade on a lighter
backgrotmd when dyeing with methylene blue, aniline green or fuchsine»
Turkey red or indigo blue.

CELLULOSE 165

lost considerable of its strength when strong solutions of bleaching
powder have been used. In this case the oxycellulose is obtain-
able as a clear, voluminous, water-insoluble powder.

The oxycellulose of Witz is quite free from chlorine, as shown
by analysis. The structureless and brittle nature of oxycellulose
caused a marked tendering of the cotton fiber when it is present in
considerable quantities.

Oxycellulose as prepared by Witz is stable at 100° in vacuum,
but exposed to dampness and air rapidly turns pale yellow, in
which condition it is partially soluble in alkalis. The fabric,
however, remains pale yellow and does not turn white as is the
case when partially prepared oxycellulose is treated with alkalis
or alkaline earths. When brought in contact with steam the
yellow color gradually turns to a brown. If spots of oxycellulose
have been formed during the bleaching operation they then turn
brownish yellow if much oxycellulose is contained in them and
the strength of the fabric sniffers correspondingly. However,
upon immersing oxycellulose in boiling water no change in color
occurs, while the water remains colored. However, if a small
amoimt of caustic soda is contained in the water, the yellowish
brown color immediately appears and a similar weakening of the
fabric results as when exposed to steam. By immersion in a
boiling 5% solution of sodium hydroxide, a vivid yellow is imme-
diately produced analogous to that of chromate solutions, this
color being reproduced in a lesser degree by means of caustic
soda. This phenomenon is not shown by treatment with ammo-
nium hydroxide.

The reduction of alkaline copper tartrate (Fehling's solution)
is most characteristic. After treatment with boiling caustic soda
solution, the reducing power is considerably decreased, from
which it appears that the reducing property is due to the presence
of a substance or substances which can be extracted by alkalis.
The hot alkaline extract, however, possesses a reducing power
which rapidly disappears.

The affinity to hold basic dyestuffs, specifically methylene
blue, either before or after the alkaline washing is very pronounced
and characteristic, while with diphenylamine blue there is little
or no attraction. With cold decinormal sodium hydroxide solu-
tion, the oxycellulose of Witz is but slightly colored. However,

166

TECHNOU)OY 01^ CHtLUU)SE ESTERS

there, occurs an appreciable observable chemical action, because
the solution becomes brown on boiling, while even on standing the
original light amber color turns to brown in the course of a few
days.

The addition of hydrochloric acid to the freshly prepared
alkaline extract causes a precipitation of voluminous flakes which,
after careful washing are readily dyed by a cold solution of basic
dyestuffs as methylene blue, methyl violet or rhoduline heliotrope.
It would appear therefore that a secondary or subsidiary substance
accompanies the oxycellulose proper, this latter material being
insoluble in boiling water, not discolored by ammonium, and
destroyed by alkaline solutions. The Witz oxycellulose proper
is insoluble in both weak and concentrated sodium hydroxide.

According to V. Zanotti^ the shells of nuts contain com-
pounds which yield xylose and dextrose, and whose constitution
is very different from that of cotton cellulose. He found that
when cellulose prepared from purified cotton wool was oxidized
by (a) hydrochloric acid and potassium chlorate, (b) chromic and
sulfuric acids, (c) potassium permanganate and sulfuric acid,
**oxycelluloses" of the following compositions were obtained:

Ash

Carbon

Hydrogen

Oxygen

Furf uraldehyde

Cellulose

Oxycellulose, by difference,

a

b

c

0.15

0.50

0.30

43. 6C

42.96

42.52

6.60

6.52

6.56

49.74

50.52

50.92

0.8Q

3.05

1.90

45.20

26.05

39.92

54.80

73 . 95

60.08

Action of alkalis indicated that these substances are really
mixtures of cellulose and hydrocellulose with their oxidation and
decomposition products.

A. Franchimont^ has examined the oxycellulose as submitted
by Witz to the esterification process, but found that by treatment of
cellulose with an equal weight of fused zinc chloride and four
times its weight of acetic anhydride at a temperature somewhat

1. Annuario Soc. Chim. Milano, 1899, I, 27; abst. J. C. S. 1899, 78, i,
851; Chem. Centr. 1899, 1, 1209; Jahr. Chem. 1899, 52, 1288.

2. Compt. rend. 1879, 89, 712; abst. Bull. soc. ind. Rouen, 1882,
ID, 448; 1883, 11, 230; Rec. Trav. Chim. 1883, 2, 239.

CKLI^ULOSE 167

above one hundred degrees, a reaction occurs and the oxycellu-
lose dissolves. Upon pouring this solution into a large volume of
water, the ester precipitated out in amorphous white flakes. When
washed with water until neutral and dried at a moderate tempera-
ture it has been found that cold alcohol dissolves from it a sub-
stance having a semblance to impure oct-acetyl-diglucose ;
while under the influence of heat a portion dissolves which is
redeposited upon cooling. By exhaustion with boiling amyl
alcohol, the latter also dissolves a portion which is re-precipi-
tated upon cooling. The greater portion, however, is insoluble
in this or other solvents but is soluble in highly concentrated
acetic acid. The product of maximum esterification, when dried
presents the same physical phenomena as the acetyl-celluloses
obtained by the process of Schuetzenberger; i. e., the ability of
transforming into a strong jelly when dissolved under heat in a
comparatively large quantity of nitrobenzene and then allowed to
cool.

G. Witz* has observed that oxycellulose exerts a powerful
attraction for certain inorganic compounds and has proven that
vanadium in the form of chloride may be withdrawn by oxy-
cellulose from aqueous solutions containing some microscopic
proportion, as one-billionth of the element.

The investigations of Witz also lead to the assumption that
oxycellulose arises from cellulose by the direct admission of oxygen
but no proof was given for the homogeneity of the. cellulose oper-
ated upon and as shown by Witz, the oxycelluloses obtained by
him by different processes were not identical, especially diverging
in their composition as found upon analysis, from 42%-44.2%
carbon.

The formation of oxycellulose, according to the microscopic

1. Bull. soc. ind. Rouen. 1882, 10, 416; abst. Dingl. Poly. 1883, 250,
271; Jahr. Chem. 1883, 1782; G. Witz and F. Osmond (Bull. Soc. Chim. 1886,
45, 309; abst. J. C. S. 1886, 50, 923; Bull. soc. ind, Rouen, 1886, 14, 30; J. S.
C. I. 1886, 5, 546; Ber. 1886, 19, 318; Jahr. Chem. 1886, 39, 1493; Wag. Jahr.
1886, 37, 362) employ oxycellulose to detect and determine vanadium
quantitatively in small traces, claiming a sensitiveness of one-millionth mgm.
per liter. The test is performed by immersing strips of oxycellulose in the
solution containing the vanadium salt for 8 hours at 15^. The strips are
then washed, dried at 40°, and i>rinted with the usual aniline black mixture,
to which however, no vanadium compound has been added. The color is then
developed in the oxidation chamber during a given period and the amount of
vanadium in the solution examined is estimated by the depth of black obtained.
The presence of 0.5-1 cc. of a mineral acid, as also the presence of ammonium
oxalate entirely prevents the fixation pf vanadium on the fiber.

168 TECHNOW)GY OP CELLULOSE ESTERS

investigations of Vetillart,^ as shown by diminution of the width
and length of fibers showed an average extent of 12.5%. While
according to Permetier^ the oxidized fibers do not swell up like
ordinary cotton when brought in contact with cuprammonium
solutions.

According to L. Vignon' oxycellulose may be prepared by
treating purified cotton with a boiling solution of one per cent.

1. Bull. soc. ind. Rouen, 1883, U, 234. The process of C. Kellner,
(E. P. 5420, 1890; 24542, 1902. F. P. 326313. U. S. P. 773941, 1904; abst.
J. S.C.I. 1890, 9, 821; 1903, 22, 817; 1904. 2S, 1159) is very similar to that of A.
Nodon, (F. P. 453111. Belg. P. 253427, 1913. D. R. P. 251268; abst. Rev.
Chim. Ind. 1913, 24, 263; C. A. 1913, 7, 310; Wag. Jahr. 1912, 58, II, 634;
Chem. Zentr. 1912, 83, II, 1321; Chem. Ztg. Rep. 1912, 36, 587; Ztg. ang.
Chem. 1912, 25, 2512; Kunst. 1912, 2, 379) who preserves and strengthens
cellulosic materials by an electric treatment in the presence of saline solu-
tions. The material is only superficially sattu'ated with the solution, the
current being passed for a long time that the action may penetrate to the
center. Aqueous solutions of sodium sulfate, sodium chloride or zinc chloride
are specified.

2. Bull. soc. ind. Rouen, 1883, 11, 236. C. Smith, J. C. S. 1894,
65, 472; Chem. News, 1894, 69, 236; abst. J. S. C. I. 1894, 13, 537; Ber. 1894,
27, R, 513; Chem. Centr. 1894, 65, I, 1152; Chem. Ztg. 1894, 18, 674; Jahr.
Chem. 1894, 47, 1133; Meyer Jahr. Chem. 1894, 4, 570; Jahr. organ. Chem.
1894, 2, 220, has contributed interesting observations upon the "celluloses"
of esparto and the cereal straws, and the (1) ultimate composition, and (2)
amount of fiu^ural obtained on boiling with aqueous HCl (1.06 relative
density) determined. These "celluloses" are considered by the author to be
oxycelluloses, and as they are widely distributed in nature, their physiology
was studied. A systematic course of observations was therefore underftiken
on the germination and growth of the barley plant in relation to the com-
position and constitution of its permanent tissue. The observation has been
made that, by germination in the dark and growth of the sprouts (etiolated)
until the endosperm is nearly exhausted, there is considerable increase in
furfural-yielding constituents with no pentosan reaction, which was considered
proof of the presence of oxycellulose.

3. Compt. rend. 1897, 125, 448; Bull. Soc. Chim. 1898, 18, 790; abst.
Chem. News, 1897, 76, 194; J. C. S. 1898. 74, i, 8; J. S. C. I. 1897. 16. 908;

1898, 17, 917; Mon. Sci. 1897, 49, 859; Rev. Phys. Chim. 1897-1898,2, 21;
Chem. Centr. 1897, 68, II, 843; Chem. Ztg. 1897, 21,811; Jahr. Chem. 1897,

50, 1506.

Compt. rend. 1898, 126, 1658; Bull. Soc. Chim. 1898, Id, 857; abst. Chem.
News, 1898, 78, 146; J. C. S. 1898, 74, i, 619; J. S. C. I. 1898, 17, 794; Mon.
Sci. 1898, 51, 527; Chem. Centr. 1898, 69, II, 1246; Jahr. Chem. 1898, 51,
1378.

Compt. rend. 1898, 127, 872; Bull. Soc. Chim. 1899, 21, 597; Chem.
News, 1899, 79, 35, J. C. S. 1899, 76, i, 242; J. S. C. I. 1899, 18, 81; Mon. Sd.

1899, 53, 75; Rev. Chim. 1899, 1, 132, 338; Rev. Phys. Chim. 1899, 3, 80;
Chem. Centr. 1899, 70, I, 24; Chem. Ztg. 1898, 22, 1049; Jahr. Chem. 1898,

51, 1378. Compt. rend. 1899, 128, 1038; Bull. Soc. Chim. 1899, 21, 600;
abst. Chem. News, 1899, 79, 240; J. C. S. 1899, 76, i, 560; J. S. C. I. 1899,
18, 579; Rev. Chim. 1899, 1, 293, 338; Rev. Phys. Chim. 1899, 3, 27; Chem.
Centr. 1899, 70, I, 1162; Chem. Ztg. 1899, 23, 404; Jahr. Chem. 1899, 52,
1294.

Compt. rend. 1900, 131, 509; Bull. Soc. Chim. 1901, 25, 130; abst.

CElvI^ULOSE 169

potassium hydroxide, then a one per cent, solution of hydro-
chloric acid in the cold followed by final treatment in a cold
sodium carbonate solution. The fiber thus obtained is treated
with hot 5% aqueous potassium chlorate to which a small amount
of hydrochloric acid has been added, the liquid then being heated
for an hoiu- and the modified cotton thus obtained dried. The
oxycellulose is obtained in the form of short brittle fibers which
turn yellow upon heating.

Hemp was treated with two successive baths of one per cent,
sodium carbonate for 30 minutes at the boiling temperattu-e,
followed by one per cent, caustic soda under the same conditions,
the material being dissolved to a blackish liquid which when
treated with hydrochloric acid, then water, and finally with
alcohol and dried at 70° to 80°, produced a relatively white and
brilliant, flocculent product. It was found that purified hemp
was much more difficultly attacked than cotton when subjected
to oxidation. In the oxidation of flax and ramie, both of these
textiles behaved similar to cotton and gave a yield of 65%-75%.
The four oxycelluloses thus produced by him were found to react
strongly with Pasteur's liquid and in the fixation of basic coloring

Chem. News, 1900, 82, 169; J. C. S. 1900, 78, i, 589; J. S. C. 1. 1900, 13, 1039;
Mon. Sci. 1900, 55, 782; Rep. Chim. 1901, 1, 102, 130; Rev. Phys. Chim. 1900,
4, 467; Chem. Centr. 1900, 71, II, 811; Jahr. Chem. 1900, 53, 849.

Compt. rend. 1900, 131, 530; BuU. Soc. Chim. 1901, 25, 133; abst. Chem.
News, 1900, tt2, 169; J. C. S. 1900, 78, i, 629; J. S. C. I. 1900, 13, 1045; Mon.
Sci. 1900, 55, 782; Chem. Centr. 1900, 71, II, 811, 891; Chem. Ztg. 1900, 24, 819,
847; Jahr. Chem. 1900, 53, 849; Meyer Jahr. Chem. 1900, 13, 321.

Compt. rend. 1900, 131, 558; BuU. Soc. Chim. 1901, 25, 135; abst. Chem.
News, 1900, 10, 208; J. C. S. 1900, 78, i, 628; J. S. C. I. 1900, 13, 1102; Mon.
Sci. 1900, 55, 784; Rep. Chim. 1901, 1, 103, 130; Chem. Centr. 1900, 71, II,
948; Chem. Ztg. 1900, 24, 905; Jahr. Chem. 1900, 53, 844. Compt. rend.
1900, 131, 708; BuU. Soc. Chim. 1901, 25, 137; abst. Chem. News, 1900, 82,
255; J. C. S. 1901, 80, i, 16; J. S. C. I. 1900, 13, 1103; Mon. Sci. 1900, 55,
835; Rep. Chim. 1901, 1, 130; Chem. Centr. 1900, 71, II, 1151; Chem. Ztg.
1900, 24, 999; Jahr. Chem. 1900, 53, 840. Compt. rend. 1903, 138, 818;
BuU. Soc. Chim. 1903, 21, 509, 511 ; abst. Chem. News, 1903, 87, 227; J. C. S.
1903, 84, i, 461; J. S. C. I. 1903, 22, 646; Mon. Sci. 1903, 59, 380; Chem.
Centr. 1903, 74, 1, 1081; Chem. Ztg. 1903, 27, 372, 392; Jahr. Chem. 1903, 56,
1017.

Compt. rend. 1903, 138, 969; BuU. Soc. Chim. 1903, 23, 513; abst. Chem.
News, 1903, 87, 251; J. C. S. 1903, 84, i, 461; J. S. C. I. 1903, 22, 646; Mon.
Sci. 1903, 53, 444; Chem. Centr. 1903, 74, I, 1176; Chem. Ztg. 1903, 27, 437;
Jahr. Chem. 1903, 53, 1014. L. Vignon and F. Gerin, Compt. rend. 1900,
131, 688; BuU. Soc. Chim. 1901, 25, 139; abst. Chem. News, 1900, 82, 219;
J. C. S. 1900, 78, i, 629; J. S. C. I. 1900, 13, 1103; Mon. Sci. 1900, 55,833;
Rep. Chim. 1901, 1, 103, 130; Chem. Centr. 1900, 71, II, 1069; Chem. Ztg. 1900,
24, 932; Jahr. Chem. 1900, 53, 843.

170 TECHNOlrCX5Y OF CELLUlrOSE ESTERS

materials Vignon has determined the absorbing power of the
oxycelluloses with respect to safranin and methylene blue. He
concludes that oxycellulose obtained from the oxidation of cotton,
hemp, flax and ramie gives substantially the same products upon
oxidation, the numerous discrepancies between the qualities of
the oxycelluloses being relatively small and explained away
either by the condition of the physical state characteristic to
every textile material, or by the condensations of the molecule
(CeHio05)n, which varies greatly in the different textile materials.

The oxycellulose of Vignon, when treated with potassium
hydroxide solution is partially dissolved, giving a golden yellow
solution. When dried at the ordinary temperature, a white,
amorphous powder results containing 3.5% of water, which it
loses at 110°. It has the same composition as cellulose, but
differs from it in heat of combustion and in the ease with which
it forms furfuraldehyde. It is soluble to the extent oi 0.396
gm. per liter in hot water, and is insoluble in alcohol, ether,
chloroform, benzene, acetone or CS2. The yellow solution upon
treatment with alkalis readily becomes brown upon standing, and
may be re-precipitated by acids or solutions of the chlorides of
potassium, sodium, barium or calcium. Hydrochloric acid dis-
solves it partially, nitric acid completely, and it is carbonized
by sulfuric acid. Fehling's solution is reduced, and a pink color-
ation is given with Schiff's reagent.

I. Frankenburg and C. Weber^ prepare a-oxycellulose by
scouring cotton waste with 2.5% caustic soda, then immersing in
a bleaching solution of sp. gr. 1.03. After 12 hours the cotton is
removed, washed in acidulated water and finally disintegrated by
treatment with a boiling solution of 20% hydrochloric, sulfuric
or oxalic acids, or by impregnation with strong solutions of
aluminium, magnesium or zinc chlorides, with subsequent steam-
ing.

A patent was issued in 1887 to C. Lundholm and J. Sayers*

1. E. P. 12367, 1893 ; abst. J. S. C. 1. 1894, 13, 725. D. R. P. 77826; abst.
Chem. Ztg. 1894, IS, 2()44; Wag. Jahr. 1894, 40, 1096. R. Alder (Can. P.
154062, 1914; abst. C. A. 1914, 8, 2269) has described a plastic composite of
ammonia, an albuminous substance and oxycellulose.

2. E. P. 6399, 1889; abst. Wag. Jahr. 1890, 36, 546; J. S. C. I. 1890,
9, 414. L.Lloyd, J. Soc. Dyers Col. 1910, 26, 273; abst. J. S. C. I. 1910. 29,
1450; J. V. Falkenstein and A. Boehm (E. P. 72,38, 1892; abst. J. S. C. I.
J893, 12, 547; Chem. Ztg. 1893, 17, 1417; Chem. Teqh. Rep. 1893, 32, II, 272.

CHI.I*ULOS^ 171

for employment, — instead of nitrocellulose for the manufacture of
explosives — the a-oxycellulose of Cross and Bevan. Their
explosive comprises a combination of nitrated oxycellulose,
either alone or mixed with an oxidizing agent, and with or without
any carbonaceous matter or camphor in a suitable solvent for
consolidating the explosive, the camphor being subsequently
partially removed from the explosive.

B. Tollens* has shown that both hydrocellulose and all crude
oxycellulose preparations contain unaltered cellulose. From the
action of alkalis upon these bodies Tollens concludes that the
true products of reaction (e. g. celloxin) are combined with the
cellulose somewhat after the manner of esters. The author
divides the cellulose group, therefore, into fotu" classes:

(a) Celluloses.

(b) Hydrated Celluloses, i. e., hydrocelluloses and hemicel-
luloses, bodies which are non-reducing, but readily hydrolyzed
to reducing compounds.

(c) Celluloses with acid, i. e., carboxyl groups; this class
including the pectins.

(d) Celluloses with both acid (carboxyl) groups and aldhydic
or ketonic groups; this class including the oxycelluloses which are
cupric reducing bodies.

The more highly oxidized classes, **c" and "d" are distinguish-
able from "a" and "b" by elementary analysis, the ratio of H
and O being 1 : 8 to 9 instead of 1 : 8 as in the ''a** and "b" classes.

0. V. Faber and B. Tollens* have examined oxycellulose
prepared in various manners by heating with milk of lime for

D. R. P. 70067; abst. Ztg. ang. Chem. 1893, 8, 465; Chem. Centr. 1893, €4,
II. 1016; Chem. Ztg. 1894, IS, 1089; Chem. Tech. Rep. 1893. 32, 272; Wag.
Jahr. 1893, 3S, 426; Ber. 1893, 26, 958. Jahr. organ. Chem. 1893, 1, 262;
Tech. Chem. Jahr. 1893-1894, 16, 165; Meyer Jahr. Chem. 1893. 3, 366,
prepare nitrocellulose for smokeless powder from cellulose which has been
oxidized to oxycellulose by treatment with potassium permanganate and
nitric acid, which also renders the nitrocellulose amorphous.

1. Ber. 1901, 34, 1434; abst. J. S. C. I. 1901, 20, 740; J. Soc. Dyers Col.
1901, 17, 238; J. C. S. 1901, 80, i, 453; Bull. vSoc. Chim. 1902, 28, 269; Chem.
Centr. 1901, 72, II, 39; Jahr. Chem. 1901. 54, 897.

2. Ber. 1899, 32, 2589; abst. J. S. C. I. 1899, 18, 1014; J. C. S. 1899, 76, i,
864; Jahr. Chem. 1899, 52, 1292; Chem. Ztg. Rep. 1899, 23, 321; Chem. Tech.
Rep. 1899, 38, 550; Bull. Soc. Chim. 1900, 24, 021. For natural oxycelluloses,
consult G. de. Chalmot, Amer. Chem. J. 1894, 16, 589; Ber. 1894, 27, 1489;
T. C. S. 1894, 66, i, 399; Bull. Soc. Chim. 1895, 14, 271; Chem. Centr. 1894,
65, II, 148; Jahr. Chem. 1894, 47, 1146; Meyer Jahr. Chem. 1894, 4, 570;
Jahr. organ. Chem. 1894, 2, 221.

172 TECHNOLOGY OF CELLULOSE ESTERS

several hours on the water bath. In this way the oxidized portion
of the product, termed by them "celloxin," was broken down
into soluble products from which isosaccharic acid and dihydroxy-
butyric acid were separated with calcium salts.

J. Murumow, J. Sack and B. ToUens^ have extended and
expanded this series of observations to an oxycellulose prepared
by the addition of potassium chlorate and hydrochloric add accord-
ing to the method of Vignon, and have found that the soluble
products are identical in this case with those isolated by Faver
and ToUens, and the insoluble residue likewise possessed all the
properties of unaltered cellulose.

A. Nastukoff^ has oxidized Swedish filter paper with (1)
calcium h)rpoclilorite solution,^ (2) permanganate solution fol-
lowed after 36 hours by the introduction of sulfm* dioxide gas and
finally the addition of weak and lukewarm sulfuric acid. The
products in both cases appeared to be laevo-oxycelluloses. By
heating these on the water bath with ten volumes of sulfiuic acid
solution of 5%, washing and reheating with a similar volume of
10% sodium carbonate solution, a new class of oxycelluloses
characterized by ready solubility in water were obtained in 60-

1. Ber. 1901, 34, 1427; abst. J. S. C. I. 1901, 20, 739; J. Soc. Dyers
Col. 1901, 17, 238; J. C. S. 1901, 80, i, 453; Bull. Soc. Chim. 1902, 28, 269;
Chem. Centr. 1901, 72, II, 38; Jahr. Chem. 1901,54, 896. J. Porter, Pharm.
Centr. 1849, 20, 777; Ann. 1849, 71, 115; Amer. J. Sci. (Sill.), 1850, (2), 9, 20;
Chem. Gaz. 1849, 469; Jahr. Chem. 1849, 2,474. S. Zeisel and M. Stritar, Ber.
1902,35, 1252; abst. J. C. S. 1902, 82, ii, 363; J. S. C. I. 1903,22,642; Bull.
Soc. Chim. 1902, 28, 863; Rep. Chim. 1902, 2, 408; Chem. Centr. 1902, 73, I,
1076; Chem. Ztg. Rep. 1902, 26, 124; Jahr. Chem. 1902, 55, 1052; Zts. ang.
Chem. 1902, 15, 736. B. Bull, J. C. S. 1897, 71, 1090; Chem. News, 1897.
78, 249; abst. Chem. Centr. 1897, 68, II, 733; Jahr. Chem. 1897, 50, 1507;
Meyer Jahr. Chem. 1897, 7, 151.

2. J. Russ. Phys. Chem. Soc. 1900, 32, 543; 1901, 33. 310, 678; Ber. 1900,

33, 2239; 1901, 34, 719, 3589; abst. Chem. News, 1902, 86, 306; J. C. S. 1900,
78, i, 540; J. S. C. I. 1900, 13, 733; 1901, 20, 63, 573; J. Soc. Dyers Col. 1901,
17, 122; Bull. Soc. Chim. 1901, 26, 123, 557; 1902, 28, 130, 481; Rep. Chim.
1901, 1, 414; 1902, 2, 189; Chem. Centr. 1900, 71, II, 430; 1901, W, I. 99.
932; II, 335, 1263; Chem. Ztg. Rep. 1900, 24, 258; 1901, 25, 122, 353; Jahr.
Chem. 1900, 53, 844; 1901, 54, 897, 898; Meyer Jahr. Chem. 1901, 11, 441;
Zts. ang. Chem. 1900, 13, 1083.

3. H. Moore (J. Soc. Dyers Col. 1915, 31, 180; abst. J. S. C. I. 1915,

34, 1008; C. A. 1915, 9, 3365) has also studied the action of calcium and
sodium hypochlorite of varying concentration upon cotton yam, methylene
blue being employed to estimate the amount of oxycellulose formed. The effect
of moderate additions of acid was to decrease the amount of oxycellulose
and not increase it, as might reasonably be expected. Upon addition of
alkali to the bleach, a minimum amount of oxycellulose is produced at a
definite concentration of caustic soda. Permanganate solutions gave similar
results.

CHLLUU)S^ 173

80% 3deld. The oxycellulose resulting from the action of the chlo-
ride of lime required to be heated with acid for three hours while
that from the permanganate oxidation for one hour only. A small
quantity of sugar was formed during this acid hydrolysis, and a
larger quantity if the time of heating was prolonged. A hydra-
zone resulted — possibly mannose-hydrazone. The alkaline hy-
drolysis need be continued for only ten to thirty minutes at a
temperature of 70°-100°. For the new soluble oxycelluloses the
name 7-oxycellulose has been proposed, it being considered
entirely different to the class already distinguished by the prefix
j8.^ The properties are briefly as follows:

The aqueous solution when dilute is opalescent or milky and
yellow in transmitted light, is readily filterable, and does not
alter on standing or when heated. More concentrated solutions
(5%-10%) resemble glycerol or viscose, and when dried in a desic-
cator or over a water bath, both deposit silky transparent scales or
plates. The addition of various metallic salts of adds or alcohol
induces precipitation. When precipitated by an acid, the solu-
bility greatly diminishes as the substance dries, but is restored by
the action of warm soditmi carbonate solution. If washed with
almost any dilute add the oxycdlulose becomes insoluble once
more and \his cycle may be indefinitely repeated. Drying at
110°, however, does not permanently destroy the solubility.
This 7-oxycdlulose reduces Fehling's solution when heated,
and forms a yellow hydrazone which is insoluble if prepared
from the insoluble oxycellulose, but like it, becomes soluble by
the action of alkali. Its solutions also become yellow and
opalescent and deposit lustrous, golden colored scales. Iodine
produces no coloration. The pentosan reaction does not take
place, and the ash has an alkaline reaction.

7-Oxycellulose in its soluble form would appear to be the
sodium salt of a soluble add which when dried becomes an insol-
uble anhydride or lactone.

According to A. NastukoflF,* the oxycellulose soluble in ammo-

1. J. C. S. 1883, 43, 22; Chem. News. 1882, 46, 240; abst. J. S. C. I.
1884, 3, 206, 291; Bull. Soc. Chim. 1883, 39, 671; Chem. Ind. 1883, 6, 353;
Chem. Tech. Rep. 1883. 22, II, 94; Dingl. Poly. 1883, 250, 280; Jahr. Chem.
1883, 38, 1366, 1777. Mon. prod. chim. 1883, 242.

2. Bcr. 1901, 34, 3689; J. Russ. Phys. Chem. Soc. 1901. 33, 678; J. Soc.
Dyers Col. 1902, IB, 16; abst. Chem. News, 1902, 86, 306; J. S. C. I. 1902, 21,
63.

174 TECHNOLOGY OF CELI<UU)SB ESTERS

nia which is obtained by boiling cellulose with nitric acid of 1.3
sp. gr., is termed jS-oxycellulose, Cross and Bevan obtaining a 3deld
of only 30% from cotton, the remainder being oxidized to oxalic
acid.

0. V. Faber and B. ToUens^ obtained a yield of 70%, and by
the method of NastukofF a jrield of 90% is claimed. For the
preparation of this /3-oxycellulose the author takes a quantity
of nitric acid of sp. gr. 1.3, equal only to 2.5 times the weight of
the cellulose, and heats for one hour on the water bath. By
this method a yield of 90% of oxycellulose which is completely
soluble in boiling ammonia is obtained. Where larger propor-
tions of acids are used, lower 3delds are said to result, correspond-
ingly larger quantities of oxalic acid being produced. This
author has also found that /3-oxycellulose combines with barium
to form a salt containing about 5% of barium. On the other hand
7-oxycellulose prepared with bleaching powder gives a barium
salt containing only about one per cent, of barium. The various
iS-oxycelluloses and its salts are hard, while the 7-compounds are
brittle. On evaporating solutions of sodium salts with 7-oxy-
cellulose, lustrous films result which are easily detached from the
glass whereas solutions of /3-oxycellulose salts leave no such films.
It is true, however, that by evaporation in a desiccator films are
formed, but they are entirely different. The salts of /3-oxycel-
lulose decrease considerably in solubility after drying at 80° to

1. Ber. 1899, 32, 2589; abst. J. S. C. I. 1899, 28, 1014; J. C. S. 1899,
78, i, 854; Chem. Centr. 1899, 70, II, 901; Jahr. Chem. 1899, S2, 1292; Chem.
Ztg. Rep. 1899, 23, 321; Chem. Tech. Rep. 1899, 38, 550; Bull. Soc. Chim.
1900, 24, 621. B. Scholl (Ber. 1911, 44, 1312; abst. J. C. S. 1911, 180, i,
525; J. S. C. I. 1911, 30, 739; Bull. Soc. Chim. 1911, 10, 1644; Rep. Chim.
1911, U, 408; Chem. Zentr. 1911, 82, II, 80; Chem. Ztg. Rep. 1911, 35, 340;
Kunst. 1911,1,453), has devised the following simple experiment to demon-
strate the reducing properties of cellulose. The sp>ecimen to be tested is
digested for a few seconds with a dilute aqueous solution of flavanthrene
(D. R. P. 136015, 138119, 139C33. 139^35, 140573, 141355, 142963. Scholl,
Ber. 1903, 38, 3436; 1907, 40, 1692; 1910, 43, 346; abst. J. C. S. 1904, 88, i,
110; 1907, 92, i, 540), dilute sodium hydroxide solution and solid sodium
hjrposulfite. After washing, the yellow dye is developed by exposing the
fabric to the air for a few minutes, or by treatment with hy|>ochlorite solution.
By heating the fabric to boiling with 2N NaOH solution the blue color is
restored. The length of time required for the reduction depends upon- the
amount of hydro-cellulose and oxycellulose present in the original specimen.
Oxycelluloses give an immediate blue color, but when the oxycelluloses are
removed by previous boiling with caustic soda solution, a longer time is re-
quired for the development of the blue color, and the alkaline extract produces
the coloration more rapidly than does pure alkali. The pyranthrones or
anthraquinoneazines may replace the flavanthrene.

CELLULOSE 175

110° whereas the solubility of the salts of 7-oxycellulose are not
appreciably affected by this treatment.

R. Oertel* has prepared oxycellulose by treating cellulose in a
neutral 15% solution of potassium chloride which was subsequently
subjected to electrolysis. The cellulose is gradually attacked,
being ultimately entirely transformed into soluble products.
When from 60% to 70% of the cellulose has been dissolved, the
residue of oxycellulose is found to be entirely soluble in cold 10%
NaOH solution, while still further treatment )rields an oxycellu-
lose giving a stable colloid solution with water.

The "copper values" of the oxycellulose products as deter-
mined by C. Schwalbe's method* were unduly high, increasing
with the degree of treatment, a maximum of 39.5 being recorded.
The copper value was found not always to be in direct relationship
with the solubility in sodium hydroxide. The furfiural value of
the oxycellulose prepared by electrolysis was 1.7%, the solubility
of ordinary cotton being less than one per cent., while the ftuiural
value is insufficiently definite to serve for the definite character-
ization of oxycellulose. When subjected to H. Ost*s viscosity
test,* oxycellulose showed the minimum value at an early stage.
The susceptibility of oxycellulose to acid hydrolysis (Schwalbe's
"hydrolysis-difference value**) is high, being 12.12 as compared
with 2.18 for normal cellulose.

When saccharified by 70% sulfuric acid according to the

1. Chem. Ztg. 1911, 35, 713; abst. J. C. S. 1911, UO, i, 607; J. S. C. I.
1911, 30, 8S7; Chem. Zetitr. 1911, 32, II, 855. Zts. ang. Chem. 1913, 26, I,
246; abst. C. A. 1913, 7, 2302; J. C. S. 1913, 104, i, 594; J. S. C. I. 1913, 32,
595; .Chem. Zentr. 1913, 84, I, 2110; Chem. Ztg. Rep. 1913,37,273; Kunst.
1913, 3, 330; Wag. Jahr. 1913, 59, II, 543.

2. Ber. 1907, 40, 1347; Wochenbl. Papierfabr. 38, 2535; abst. C. A.
1907, 1, 1696, 2179; J. C. S. 1907, 92, i, 390; J. S. C. I. 1907, 26, 548; BuU.
Soc. Chim. 1908, 4, 1533; Rep. Chim. 1907, 7, 318; Chem. Zentr. 1907, 78, I,
1490; Chem. Ztg. Rep. 1907, 31, 302; Jahr. Chem. 190&-1908, II, 961; Meyer
Jahr. Chem. 1907, 17, 215; Zts. ang. Chem. 1908, 21, 265.

3. Ztg. ang. Chem. 1911, 24, 1892; abst. C. A. 1912, 6, 684; J. C. S.
1911, 100, i, 838; J. S. C. I. 1911, 30, 1247; Chem. Zentr. 1911, 82, II, 1519;
Chem. Ztg. Rep. 1911, 35, 620; Meyer Jahr. Chem. 1911, 21, 220; Wag. Jahr.
1911, 57, II, 428. The method of oxycellulose estimation devised by G.
KiU (J. Chem. Ind. Tokyo, 1917, 20, 138; abst. J. S. C. I. 1917, 36, 868;
C. A. 1917, U, 2405) differs from Schwalbe's method in that it is not applicable
to the determination of injury that may occur in the various treatments of
cellulose as in bleaching. Compare E- Jandrier, Compt. rend. 1899, 128,
1407; Bull. Soc. Chim. 1899, 21, 895; abst. Chem. News, 1899, 80, 11; J. C. S.
1899, 76, i, 788; J. S. C. I. 1899, 18, 711; Rev. Chim. 1899, 1, 338; Chem. Centr.
1399, 70, II, 184; Chem. Zt^. 1899, 23, 517; Jahr. Chem. 1899, 52, 1296.

176 TECHNOLOGY OI^ CELLUI/>SB ESTBRS

method of H. Ost and L. Wilkening,^ oxycellulose yields at the
most only about 90% of the quantity of dextrose obtainable from
cellulose. This would indicate that one in ten of the dextrose
residues in the oxycellulose molecule is in the modified or oxidized
condition. On acetylation, using zinc chloride as a catalyst
and steeping the material for some days in glacial acetic acid
prior to acetylation, oxycellulc^ was found to be much more
readily esterified than cellulose, the product containing a greater
proportion of acetone-soluble ester, and this portion was fotmd
to possess a lower laevo-rotatory power. On acetolysis according
to Ost's method, oxycellulose yields only 20%-31% of crys-
tallized cellobiose acetate^ as compared with 40% from cellulose.
Elementary analysis of oxycellulose as carried on by this author,
showed C. 43.8% and H. 6.30%, from which is concluded that
oxycellulose prepared by his process is an oxidized derivative of •
hydrolyzed cellulose and not a homogenous product, probably
varying in the degree of modification in both directions. Hy-
drolytic modification of the cellulose in the production of the
oxycellulose is indicated by the low viscosity of its solutions and
the cupric-reducing power, the high proportion of acetate soluble
in acetone and the low rotatory power of the normal acetic ester.
The oxidized modification is indicated by an increased cupric-
reducing power as compared with hydrocellulose, the low com-
bined acetic add in the acetic ester indicating suppression of
hydroxyl groups, invariably accompanied by a low yield of
dextrose on saccharification and a low 3deld of cellobiose on
acetylation. W. Bancroft and R. Currie' have conducted
experiments to ascertain to what extent the properties of oxy-
cellulose or the oxycelluloses differ when prepared by the action of
nitric acid, permanganate, chloric add and bleaching powder
on cellulose, and the results obtained afford no evidence for the

1. Chem. Ztg. 1910, 34. 461; abst. C. A. 1910, 4, 1888; J. C. S. 1910,
98, i, 365; J. S. C. I. 1910, 29, 688; Bull. vSoc. Chim. 1911, 10, 61; Chem.
Zentr. 1910, 81, I, 2074; Jahr. Chem. 1910. M, II, 420; Meyer Jahr. Chem.
1910, 20, 318; Wag. Jahr. 1910, 56, II, 392; Ztg. ang. Chem. 1910, 23, 1534.
See E. Nolting and Rosenthal, Bull. st)c. ind. Rouen, 1883, 10, 170, 239.
C. Kurz, Zts. Farb. Textilchem. 1902. 1, 46; J. S. C. I. 1902, 21, 405; Rep.
Chim. 1902, 2, 15; Chem. Centr. 1902, 73, I, 956; Chem. Ztg. Rep. 1902, 20,
79; Jahr. Chem. 1902, 55, 1600; Wag. Jahr. 1902, 48, II, 562.

2. See Vol. 8 of this work.

3. J. Phys. Chem. 1915, 19, 159; abst. C. A. 1915, 9, 964; J. C. S. 1915.
108, i, 76; J. S. C. I. 1915, 34, 274.

CEI.I.UI.OSB 177

assumption of the existence of three different oxycelluloses. Ac-
cording to these authors the substance described as a-oxycellu-
lose is apparently unchanged cellulose more or less contaminated
with certain products of degradation. Except in regard to the
degree of normal j8- and 7-oxycellulose appear to be the same.
None of the above oxidizing agents give a completely oxidized
product, and it is doubtful therefore whether a pure oxycellulose
has as yet been obtained. The reducing action on Fehling's
solution is considered as not characteristic of oxycellulose, but
more probably due to other products of the oxidation reaction.
Experiments with a number of metallic mordants are recorded
and indicate that these are not absorbed to any large extent.

A mixture of oxycellulose, made for example by treating
cellulose with dilute nitric acid, and albuminous matter such as
casein or glutin, may form into a plastic mass with the aid of
ammonia.^ The mass after being precipitated by means of acid
is hardened, for example by means of formaldehyde, and then
dried at 60 °-80 °. This composition is claimed to be advantageous
in the manufacttu-e of artificial silk.

R. IVIiiller^ has found in connection with a process for bleach-
ing cotton and linen by immersion in an alkaline aqueous solution
through which a current of air or oxygen is passed, that the pres-
ence of small quantities of other metal compoimds, as, for instance,
only 0.5% of cobalt oxide, causes the oxidation of fibrous mate-
rials to oxycellulose. The alkaline solutions mentioned as being
especially suitable in this instance are the alkali hydrates, carbon-
ates, chlorates and silicates. C. Kurz^ proposes the use of oxycellu-
lose in calico printing for the production of body colors -in place
of viscose. The oxycellulose is prepared by treating cotton with
alkaline permanganate, the product thus obtained being allowed
to stand in contact with fairly strong caustic soda for several

1. Naamlooze Venootschap Hollandsche Zijde Maatschappij, E. P.
4521, 1913; abst. C. A. 1914, 8, 2497; Kunst. 1914, 4, 194. Gross and Bouchary
(F. P. 487070, 1912) have described a process for the manufacture of oxalic
acid and oxycellulose.

2. E. P. 9369, 1910; abst. J. S. C. I. 1911, 30, 82; see also F. P. 414821,
1910; abst. J. S. C. I. 1910, 29, 1200.

3. Zts. Farb. Textilchem. 1902, 1, 46; J. Soc. Dyers Col. 1902, IS,
143; abst. J. S. C. I. 1902, 21, 405; Rep. Chim. 1902, 2, 15; Chem. Centr.
1902, 73, I, 966; Chem. Ztg. Rep. 1902, 26, 79; Jahr. Chem. 1902, 55, 1600;
Wag. Jahr. 1902. 48, II, 562; Rev. gen. mat. Col. 1901.

178 TECHNOLOGY OF CELLULOSE ESTERS

days, after which it is diluted with water and the oxycellulose
precipitated by the addition of mineral acid and washed.

For printing, the oxycellulose paste is thickened with albumin
and gum tragacanth, printed on and steamed. Zinc chloride may
also be added to the printing color.

In the process for removing stains from textile fabrics caused
by -oxycellulose, the Bleachers Association Limited and A. Benja-
min and R. Hiibner,^ boil the textile fabrics for twenty minutes in
a solution prepared by mixing 20 liters of a halogen containing
about 17% of titanous chloride with one thousand liters of water.
The material is then washed and if desired, soured with hydro-
chloric acid after which it is again washed. Upon dyeing fabrics
thus treated with, for example, direct cotton dyestuflfs, even
dyeings are obtained while spots on parts which before the treat-
ment with the titanous salt, were "tender" owing to the presence
of oxycellulose in them, are, it is stated, very much stronger.
Instead of titanous chloride, other titanous salts may be employed
but this is the only one at present commercially available.

It has pointed out^ that in one case at least the increased
affinity which oxycellulose usually shows for basic coloring mat-
ters such as methylene blue, does not necessarily furnish a con-
clusive proof of its presence. More reliable results, in his estima-
tion, are obtained by utilizing the property of oxycellulose to
reduce Fehling's solution. For this purpose the material to be
tested is first treated in such manner as to remove the substances
used in finishing and then digesting on the water bath for fifteen
minutes with a ten per cent. Fehling's solution and well rinsed
with water. When oxycellulose is present the fiber is stated to
be colored red.

W. Harrison' has reviewed the work of G. Witz,* A. Nastukoff,*^

1. E. P. 17653, 1902; abst. J. S. C. I. 1902, 31, 1328; Chem. Ztg. 1903,
27 1259

2. Zts. dffentl. Chem. 1909, 524; abst. J. Soc. Dyers Col. 1910, 17, 69.

3. J. Soc. Dyers Col. 1912, 28, 359; abst. J. S. C. I. 1913, 32, 17;
Meyer Jahr. Chem. 1912, 22, 508. A process for Uie manufacture of salts-
free oxycellulose, has been described by R. Adler in D. R. Anm. A-25211;
Chem. Zentr. 1919, II, 387.

4. Bull. soc. ind. Rouen, 1883, U, 188; abst. J. S. C. I. 1883, 2, 378;
Mon. Sci. 1883, 25, 517; 1884, 26, 116; Dingl. Poly. 1883, 250, 271; Jahr.
Chem. 1883, 38, 1782; Wag. Jahr. 1883, 28, 1068. Farb. Must. Ztg. 17, 129;
Tech. Chem. Jahr. 1884-1885, 473.

5. J. Russ. Phys. Chem. Soc. 1900, 32, 643; 1901, 33, 310, 678; Ber.
1900, 33, 2239;1901, 34, 719, 3589; abst. Chem. News, 1902, 88, 306; J. C. S.

cBu<xji*os® 179

E. Berl and R, l^aye,^ and O. von Faber and B. Tollens,* and
concludes that none of the tests described by them, nor those of
Vetillart' and H. Ditz/ are capable of distinguishing between
oxycellulose and hydrocellulose. He asserts that the evidence
available apparently indicates that the« different forms of oxycel-
lulose and hydrocellulose are absorption compounds of peptized
cellulose and the products of hydrolysis of cellulose. The dyeing
properties, therefore, depend mainly upon the colloidal state of
the cellulose portion, the reducing properties being due to the
products^ of hydrolysis. If this is so, it therefore would appear
probable that the absorbed reducing substances are of an aldehy-
dic nature in hydrocellulose and of an acidic nature in oxycellulose.
For the detection of reducing substances (oxycellulose or hydro-
cellulose) in fabrics, the author recommends a reagent prepared
by adding silver nitrate to sodium thiosulfate solution with
vigorous stirring, and then adding sodium hydroxide so as to
obtain a liquid containing silver nitrate one per cent, sodium
thiosulfate fotu- per cent, and sodium hydroxide four per cent.
If the material be boiled in this solution and then steamed, the
portions containing oxycellulose or hydrocellulose are stained.
The effect is said to be enhanced if the material be heated with a
one per cent, solution of phenylhydrazine in glacial acetic add
and then washed thoroughly with dilute acetic acid before treating

1900. 78, i, 540; J. S. C. I. 1900, 13, 733; 1901, 20, 63, 673; T. Soc. Dyers Col.

1901, 17, 122: BuU. Soc. Chim. 1901, 26, 123, 557; 1902, 28, 130, 481; Rep.
Chim. 1901. 1, 414; 1902, 2, 189; Chem. Centr. 1900, 71, II, 430; 1901, 1%
I, 99, 932; II, 335, 1263; Chem. Ztg. Rep. 1900, 24, 258; 1901, 25, 122, 353;
Jahr. Chem. 1900, 53, 844; 1901, 54, 897, 898; Meyer Jahr. Chem. 1901, 11,
441; Zts. ang. Chem. 1900, 13, 1083.

1. Zts. Schiess-Spreng. 1907, 2, 381, 403; abst. C. A. 1908, 2, 184;
J. C. S. 1908, 84, i, 504; J. S. C. I. 1907, 26, 1157; Chem. Zentr. 1908, 78,

1, 1381; Chem. Ztg. Rep. 1908, 32, 43; Jahr. Chem. 1905-1908. II, 976.

2. Ber. 1899, ^ 2589; abst. J. S. C. I. 1899, 28, 1014; J. C. S. 1899,
76, i, 854; Chem. Centr. 1899, 70, II, 901; Jahr. Chem. 1899, M, 1292; Chem.
Ztg. Rep. 1899, 23, 321; Chem. Tech. Rep. 1899, 38, 550; Bull. Soc. Chim.
1900 24 621.

'3. 'buII. soc. ind. Rouen. 1883, U, 234, 934.

4. Chem. Ztg. 1907, 31, 833. 844, 857; abst. C. A. 1907, 1, 2941 ; J. C. S.
1907, 82, i, 129; J. S. C. I. 1907, 26, 988, 1026; BuU. Soc. Chim. 1907, (4),

2, 1468; Chem. Zentr. 1907, 78, II, 1606; Jahr. Chem. 1905-1908, II, 964;
Meyer Jahr. Chem. 1907, 17, 504; Zts. ang. Chem. 1908, 21, 1185; reproduced
J. prakt. Chem. 1908, (2), 78, 343. In this connection see also h. Meyer,
Chem. Ztg. 1907, 31, 902; abst. C. A. 1908, 2, 180; Chem. Zentr. 1907, 78,
II, 1607: Jahr. Chem. 1905-1908, II, 964. C. Councler, Zts.Forst. u.Jagd-
wesen. 2#, 427. I/. Meyer, Zts. Forst. u. Jagdwesen, 28, 428.

180 TKCHNOlrOGY OF CEI*LULOSE_HSTERS

with the silver solution, but excess of the latter must be avoided.
In conjunction with the observations of Harrison, it is main-
tained by L. Lloyd ^ that the reaction of Ditz is entirely reliable
when carried out as follows : The cotton is boiled with water, about
one-fifth the volume of Fehling's solution is added and the vessel
suspended for about half an hour in boiling water; the cotton is
then removed from the solution and well washed with water.
With material which gives by tensile strength tests a five per cent,
tendering, a faint pink deposit is observable on the material
Increase in the amotmt of oxycellulose will in some cases also
result in the precipitation of cuprous oxide in the liquid. By
appl3dng the reaction as above given the author claims to be able
to prove the formation of oxycellulose by the action of ammonia
and metallic salts upon cotton in a moist atmosphere at 50^.

A. Knaggs* in working upon the test as devised by E. Knecht'
to determine whether cotton has been mercerized or not and
obtained by dyeing the sample in a weak solution of benzopur-
piuin, foimd that upon carefully reducing with titanous chloride,
the shade on mercerized material appears bluish red just before
the dyestuff is all destroyed, whereas upon unmercerized cotton
the color is bluish violet. In some cases this reduction is found
unnecessary for when strong hydrochloric acid is added drop by
drop to the dilute dye-bath in which the samples of mercerized
and immercerized cotton are lying, the shade of the unmercer-
ized piece becomes blue at the time when the mercerized sample
appears a bright red color.

This difference is not attributable to alkali remaining in the
mercerized material for this may be treated with acid until the
shade becomes blue and then returned to the dye-bath when the
red shade will reappear. In respect to oxycellulose it has been
found that when for instance a piece of cotton spotted with
bleaching powder or other agent capable of producing oxycellu-
lose is rinsed in acid and finally with water it will be dyed a deep
shade with benzopurpurin. However, upon placing in the acid so

1. J. Soc. Dyers Col. 1910, 26, 273; abst. C. A. 1911, 5, 1843; J. S. C. I.
1910, 29, 1450; Meyer Jahr. Chem. 1910. 20, 487.

2. J. Soc. Dyers Col. 1908, 24, 112; abst. J. S. C. I. 1908, 27, 442;
Chem. Ztg. Rep. 1908, 32, 315.

3. J. Soc. Dyers Col. 1908, 24, 67, 68; abst. J. S. C. I. 1908, 27, 400;
Chem. Ztg. Rep. 1908, 32, 272; Wag. Jahr. 1908, 54, II, 467.

CELLULOSE 181

that the shade becomes blue and then rinsing in water until the red
color on the ordinary cotton reappears, those parts which have
been converted into oxycellulose are said to remain a blue-black
in color.

According to G. Kita,^ the method of estimating oxycellulose
suggested by H. Nishida* and consisting in treating with a known
quantity of methylene blue solution and then titrating the excess
of dyestufF not fixed by the oxycellulose with titanium chloride
is untrustworthy, because the quantity of dyestuflF fixed is in-
fluenced by the degree of saponification of the substance under
examination and by other factors, and furthermore there is no
proportionality between the color of the oxycellulose and the
amount of methylene blue absorbed. Though it may be con-
veniently used in certain special instances, this method is not con-
sidered applicable in the same broad way, as Schwalbe's copper
value for the determination of the damage caused by various
treatments of cellulose.

M. Saget' has called attention to the fact that the diminu-
tion in strength which occurs in cream-tinted linen on bleaching,
depends to a large extent upon the method used for cream-tinting,
and is due primarily to the formation of oxycellulose during the
latter process. This oxycellulose, however, cannot be detected
in a chemical manner as the linen itself is yellow and contains
impurities, but may be determined by measuring the strength of
the fiber on steaming and on treatment in an alkaline bath.
The presence or absence of chlorine in a fiber is not of necessity
indicative of the strength of the material. Linen which has been
partially converted into oxycellulose tenders under the influence
of rain and sunlight.

Acetolysis and Octa-Acetylcellobiose. Decomposition of
cellulose to cellobiose first caused by Skraup and his pupils by
means of acetic acid anhydride in the presence of sulfuric acid
is the process called acetolysis, and is of especial importance in this
connection because as a result of the investigations in this direction,

1. J. Chem. Ind. Tokyo, 1917, 20, 138, 219; abst. J. S. C. I. 1917, 26,
868* C. A. 1917 ^"1. 2405.

' 2.* kiinst'. 1914, 4, 266; abst. C. A. 1914, 8, 3236; Zts. ang. Chem. 1914,
27, II. 605.

3. J. Soc. Dyers Col. 1914, 30, 331; abst. C. A. 1915, 9, 1394; J. S. C. I.
1914, 33| 1151; Zts. ang. Chem. 1915, 28, 1, 71.

182 TBCHNOI.OGY OF CELI.XJI.OSE BSTBRS

much has been revealed as to the mechanism of the process of
acetylation and hydrolysis.

Z. Skraup/ in repeating the work of Franchimont, fomid
that when cellulose is treated with sulfuric acid and acetic add
anhydride, if low temperatures and small quantities of sulfuric
add are used, the products are more complicated than when these
precautions are not observed.

What was at first considered to be a pentacetylhexose was
afterwards^ shown to be a cdlobiose octacetate, of crystalline
structure, and melting at 227°-228°, and yielding upon saponifi-
cation a biose, cellobiose. By the action of hydrochloric add on
the acetyl derivative, an acetochloro compound results, from
which, by replacing the chlorine by acetyl, a new acetyl com-
pound was obtained of m. pt. 200°, isomeric with the product
mentioned above. A heptaacetylchlorocellobiose, formed by
the action of HCl on heptacetylcellobiose, mdted at 178°.'

1. Ber. 1899, 32, 2413; abst. J. C. S. 1899, 78, 852; Jahr. Chem. 1899,
1288; J. S. C. 1. 1899, IS, 941 ; Chem. Centr. 1899. 70, II. 752; Bull. Soc. Chim.
1900, (3). 24,619. W. Hoffmeister. Landw. Versuchstat, 1891, 39, 461; abst.
J. S. C. I. 1892, U, 452; J. C. S. 1892, 62, 129; Ber. 1893, 26, R, 497; Chem.
Centr. 1892, 63, I, 27; Chem. Ztg. Rep. 1891, 15, 317; Jahr. Chem. 1891, 44.
2180; Wag. Jahr. 1891, 37, 1105; Zts. ang. Chem. 1891. 4, 709.

M. Hoenig and S. Schubert, Monatsh. Chem. 1885, 6, 708; 1886, 7, 455;
abst. J. C. S. 1886, SO, 44; 1887, 52, 125; Bull. Soc. Chim. 1886, 46, 517; 1887.
47, 578; Ber. 1885, IS, R, 614; 1886, IS, R. 748; Chem. Tech. Rep. 1886, 25,
II. 218; Jahr. Chem. 1885, 3S, 1575. 1576, 1577; 1886, 39, 1780; Wag.
Jahr. 1886. 32, 610.

2. Z. Skraup and J. Koenig, Ber. 1901, 34, 1115; J. S. C. I. 1901, 20,
740; J. C. S. 1901, SO, i, 370; Jahr. Chem. 1901, 878; Chem. Centr. 1901, I,
1197; J. Soc. Dyers Col. 1901, 16, 85, 203.

3. Z. Skraup and J. Koenig, Monatsh. 1901, 22, 1011; abst. Centr.
1902, 75, 183; J. S. C. I. 1902, 21, 144. Compare K. KeUermann and I. Mc-
Beth, Centr. Bakt. 1912, 34, II, 485; Chem. Zentr. 1912, S3, II, 856; C. A. 1912.
6, 1763. H. Pringsheim, Zts. physiol. Chem. 1912, 7S, 266; abst. C. A. 1912,

6, 2632; J. C. S. 1912, 102, ii, 587; J. S. C. I. 1912, 31, 531; Bull. Soc.
Chim. 1913, 14, 398; Chem. Zentr. 1912, S3, II, 538; Meyer Jahr. Chem.
1912, 22, 254. For acetochlorglucose and acetochlorgalactose, see Z. Skraup
and R. Kremann, J. C. S. 1902, S2, i, 135; Monatsh. Chem. 1901, 22,
1037; abst. J. S. C. I. 1902, 21, 144; BuU. Soc. Chim. 1902, (3). 2S,
928; Monatsh. 1902, 22, 375; abst. Bull. Soc. Chim. 1902, (3), 2S, 482;
J. S. C. I. 1901, 20, 513. For other carbohydrate acetates, see /3-acetobrom-

falactose, alphaglucosepentacetate, E. Fischer and E. Armstrong, Ber. 1901,
4, 2885; 1902, 35, 833. 3153; abst. Sitzungsber. Akad. Wiss. Ber. 1901,

7, 123; J. S.C.I. 1901,20, 1151; 1902.21, 1302; J. C.S. 1901. 7S, i. 189; 1902,
SO, i, 746; Chem. Centr. 1901. I, 679; II. 981; 1902. I. 758; Jahr. Chem. 1901,
847; 1902. 1005; Bull. Soc. Chim. 1902, (3), 2S, 128, 524; 1903, (3), 30, 691;
Rep. Chim. 1902, 2, 241. cr-Acetochlorlactose, /3-heptacetobrommaltose,
E. Fischer and E. Armstrong, Ber. 1902, 35, 841. 3153. Heptacetochlormal-
tose. E. Fischer and E. Armstrong. Ber. 1901, 34, 2895; 1902, 35, 840. 3153.
/3-Methylmaltosideheptacetate, E. Fischer and E. Armstrong, Ber. 1901, 34,

CELLULOSE 183

A large number of these interesting derivatives have been prepared,

2895. /3-Phenolmaltoside, E. Fischer and E. Armstrong, Ber. 1902, 3S, 3153.
/9-Phenolmaltosideheptacetate, E. Fischer and E. Armstrong, Ber. 1902, 3S,
3153. ^-Acetobromglucose, W. Koenigs and E. Knorr, Ber. 1901, 34, 962;
abst. J. S. C. I. 1902, 21, 196; J. C. S. 1902, 82, i, 135; Chem. Centr. 1902, I,
302; Kept. Chimie, 1901, 1, 470; Bull. Soc. Chim. 1902, (2), 28, 317. /3-Aceto-
chlorglucose, A. Colley, Compt. rend. 1870, 70, 401; 71, 436; abst. J. C. S.
1873. 26, 1612; Jahr. Chem. 1870, 841; Ber. 1870, 3, 212; 1871, 4, 933; Bull.
Soc. Chim. 1870, 14, 58; 1873, 13, 406. /3-Acetochlorlactose, Z. Skraup and
R. Kremann, Monatsh. Chem. 1901, 22, 375; abst. J. S. C. I. 1901, 28, 513;
J. C. S. 1901, 80, i, 506; Zeit. ang. Chem. 1901, 14, 371; Chem. Centr. 1901,
II, 194; Bull. Soc. Chim. 1902, (3), 28, 482; Kept. Chimie, 1901, 1, 438; Jahr.
Chem. 1901, 846. a-Acetonitroglucose, A. Colley, Compt. rend. 1873, 78,
436; abst. J. C. S. 1873, 27, 612; Bull. Soc. Chim. 1873, (2), 13, 406; Ber. 1873.
8, 197; Jahr. rein. Chem. 1873, 1, 114. Arabic acid-nitrile-tetracetate, A.
Wohl, Ber. 1893, 26, 732; See also Ber. 1891, 24, 993; Jahr. Chem. 1891, 2171;
abst. J. C. S. 1893, 84, i, 292; Wag: Jahr. 1893, 33, 867; BuU. Soc. Chim.
1893, 10, 792; Minuni Jahr. organ. Chem. 1893, 251; Jahr. Chem. 1893. 859.
Arabinose tetracetate, xylose tetracetate, W. Stone, Am. Chem. J. 1893, 15,
653; abst. Jahr. Chem. 1893, 852; Ber. 1894, 27, R, 83; Jahr. organ. Chem.
1893, 1, 251, 253. Cellose /3 octacetate, L. Maquenne and W. Goodwin, Bull.
Soc. Chim. 1904, (3), 301, 854; abst. J. C. S. 1904, 88, i, 799; Chem. Centr.
1904, II, 644; Jahr. Chem. 1904, 1149; Kept, de Chim. 1905, 5, 55; Rev. Sci.
1904, (5), 2, 181; Rev. g^n. sci. 1904, 15, 668. Erythrite tetracetate, G.
Griner, BuU. Soc. Chim. 1893, (3), 3, 218; Compt. rend. 1893, 118, 723; 117,
553; abst. J. C. S. 1893,84, i, 450; Jahr. Chem. 1893, 660; Jahr. organ. Chem.
1893, 1, 27; Ber. 1893, 28, 314, 773, 931 ; Mon. Sd. 1893, 952; Chem. News, 87,
193, 289; Jahr. Chem. 1893, 3, 130. a-Ethylmaltosideheptacetate. Foerg,
Monatsh. Chem. 1902, 23, 44; Wien. Acad. Ber. 110, IIB, 1054; abst. J. S. C. I.
1902, 21, 506; J. C.S. 1902,82,1. 347; Zeit. ang. Chem. 1902, 14, 1210; Chem.
Centr. 1902, 1, 861; Jahr. Chem. 1901, 877; Rept. Chim. 1902, 2, 203; Bull. Soc.
Chim. 1903, (3), 30, 335. d-Fructose-pentacetate, E. Erwig and W. Koenigs,
Ber. 1890, 23, 672; abst. J. C. S. 1890, 58, 732; Bull. Soc. Chim. 1890, (3), 8, 12;
A-Fructose-tetracetate, F. Jaeger, Zts. Kryst. 1908, 45, 539; abst. J. C. S.
1908, 34, i, 413; C. A. 1908, 2, 2076; Rep.de Chimie, 1908, 266, 417; Bull. Soc.
Chim. 1909, (4), 8, 326. Galactonic acid lactone-chlorhydrin-triacetate, O.
Ruff and A. Franz, Ber. 1902, 35, 943; abst. Chem. Zentr. 1902, I, 858; Jahr.
Chem. 1902, 888; Rept. de Chim. 1902, 2, 372; Bull. Soc. Chim. 1902, (3),
28, 524. Galactonic acidrnitrile-pentacetate, A. Wohl and E. List, Ber.
1897, 30, 3101 ; abst. J. S. C. 1. 1898, 17, 170; J. C. S. 1898, i, 168; Chem. Centr.
1898, I, 372; Bull. Soc. Chim. 1898, 20, 289. /3-Galactose-pentecetate, E.
Erwig and W. Koenigs, Ber. 1889, 22, 2207; 1890, 23, 672; abst. J. S. C. I.
1889,8,718,994; 1890,3,637; J.C. S. 1889,58,952,991. 1131; 1890, 58, 732;
Chem. Centr. 1889, 80, 748; Jahr. Chem. 1889, 1692, 2041; 1890, 2132; Bull.
Soc. Chim. 1890, (3), 3, 12, 24; 4, 517, 557. Gluconic acid ethyl ester-pentace-
tate, F. Volpert, Ber. 1886, 13, 2621; abst. J. C. S. 1887, 52, 127; Jahr. Chem.
1886, 1379; Chem. Ind. 1886, 351; BuU. Soc. Chim. 1887, (2), 47, 775. Glu-
conic acid lactone-tetracetate, tetracetyl-d-gluconolactone), C. Paal and F.
Hoemstein, Ber. 1906, 33, 1361; abst. J. C. S. 1906, 30, i, 400, 802; Chem.
Centr. 1906, II, 1182; Bull. Soc. Chim. 1907, (4), 2, 1281. Glucose diacetate
and triacetate, S. Acree and J. Hinkins, Afti. Chem. J. 1902, 28, 370; abst.
J. C. S. 1903, 84, i, 218; Chem. Centr. 1903, I, 76; Jahr. Chem. 1902, 1013;
J. A. C. S. 1903, 25, R, 78, 130; Bull. Soc. Chim. 1904, (3), 32, 191. Glucose
tetracetate, C. Istrati and h. Edeleanu, Chem. Ztg. Rep. 1892, 18, 102; abst.
Bull. Soc. Sci. Fiz. Bucuresci, 1, 46; J. C. S. 1892, 82, 1293; Chem. Centr. 1892,
I. 624; Jahr. Chem. 1892. 2448. Glucose tetracetate, D. Law, Chem. Ztg. 1908,
32, 365; abst. J. C. S. 1908, 34, 321; Zeit ang. Chem. 1908, 21, 1317; Chem.

184 TECHNOLCXJY OF CELLULOSE ESTERS

and their reactions and physical constants carefully investigated.

Zentr. 1908, I, 1831; Bull. Soc. Chim. 1909, (4), 6. 157. Glucoseamin-triace-
tate-bromhydrin, M. Hamlin, J. A. C. S. 1911, 33, 766; abst. C. A. 1911, S,
2643;J.C.S. 1911,100,1, 529; Chem. Zentr. 1911, II, 443; Rept. Chimie 1911,
II, 374; Chem. Ztg. Rep. 1911, 35, 369; BuU. Soc. Chim. 1912. (4), 12, 83.
/3-Glycose pentacetate, A. Franchimont, Ber. 1879, 12, 1938; Compt. rend.

1879, OS, 711; abst. J. C. S. 1880, 38, 158; Jahr. Chem. 1879, 832; Jahr. rein
Chim. 1879, 7, 501; Mon. Sci. 1879, 1250; Chem. News, 1879. 40, 264. Gly-
curonic acid lactone-bromhydrindiacetate (diacetylbromoglycuronic lactone),
C. Neuberf and W. Neimann, Zts. physiol. Chem. 1905, 44, 114; abst, J.
C. S. 1905, 88, i, 412; Chem. Centr. 1905, I, 1086; Bull. Soc. Chim. 1905, 34,
(4), 993. Inosite hexabenzoate, L. Maquenne, Bull. Soc. Chim. 1887,
48, (2), 54; Compt. rend. 1887, 104, 1719; abst. J. C. S. 1887, 355, 459, 908;
Chem. Ind. 1887, 10, 443; Ber. 1887, 20, 478, 696; Mon. Sci. 1887, 871; Chem.
News, 1887, 56, 23, 279. Inosite hexacetate, C. Tanret, Bull. Soc. Chim.
1895 (3), 13, 261; Compt. rend. 1895, 120, 228; abst. Jahr. Chem. 1896,
1303; T. Pharm. Chim. (6), 1, 228; Mon. Sci. 1895, 44, 306; Rev. g6n. sci.
1895, «, 438. Inosite pentacetate. H. MuUer, J. C. S. 1907, 01, 1780; abst.
C. A. 1908, 2, 796, 1001; J. S. C. I. 1907, 26, 1293; Chem. Zentr. 1908. 1, 268;
Bull. Soc. Chim. 1908, (4), 4, 904; Chem, News, 1907, 96, 243; Rept. de
Chim. 1908, 8, 177. Isomeric lactose octoacetates, C. Hudson and J. John-
son, J. A. C. S. 1915, 37, 1270; abst. Chem. Zentr. 1915, II, 321. Lactose
mono- and di-acetate, Demole, Ber. 1879, 12, 1935; Bull. Soc. Chim. 1879,
(2), 32, 489; abst. Arch. phys. Nat. (3), 2, 408; Jahr. Chem. 1879, 857; J. C. S.

1880. 38, 29; Jahr. rein Chem. 1879, 7, 498; Chem. News, 1879. 40, 156; 1880.
41, 48. Lactose octoacetate, A. Herzfeld, Ber. 1880, 13, 265; abst. J. C. S.
1880, 38, 619; Chem. Centr. 1890, 757; Jahr. Chem. 1880, 1011; 1882, 880;
Bull. Soc. Chim. 1181, (2), 35, 250. Levosine acetate, C. Tanret, Bull. Soc.
Chim. 1891, (3), 5, 724; Compt. rend. 1891, 112, 293; abst. J. S. C. 1. 1891, 10,
473; J. C. S. 1891, 60, 661; Jahr. Chem. 1891, 2177; Tech. Chem. Tahrb, 1891,
14, 273; Mon. Sci. 1891, 312; Chem. News, 1891, 63, 119; 1891, 64, 61; Rev.
g€n. sci. 1891, 2, 91. Lichenine triacetate, Husemann and Hilger, Die
Pflanzenstoffe, 2d Ed. 129. Maltose octoacetate, A. Herzfeld, Ann. 1883,
220, 215; Ber. 1895, 28, 440; abst. J. S. C. I. 1883, 2, 482; J. C. S. 1883, 43,
652; Jahr. Chem. 1883, 1099, 1363; Wag. Jahr. 1883, 679; Ber. 1883, R, 2672;
Bull. Soc. Chim. 1884, (2), 42, 34, 533. Maltose-monoacetate, H. Yoshid^,
Ber. 1881, 14, 365; abst. J. C. S. 1881, 40, 568; Jahr. Chem. 1881, 984; Chem.
News, 1881, 43, 29. Mannite hexacetate, Franchimont, Ber. 1879, 12, 2059;
abst. J. C. S. 1880, 38, 104; Jahr. Chem. 1879, 598; Jahr. rein Chem. 1879.

7, 503; Bull. Soc. Chim. 1880, (2), 34, 354. Melibiose octacetate, C. Scheibler
and H. Mittehneier, Ber. 1890, 23, 1438; see also Ber. 1889, 22, 1678, 3118;
abst. J. S. C. I. 1889, 8, 718; 1890, 9, 311, 815; J. C. S. 1889, 56, 953; 1890.
58, 226, 1085; Jahr. Chem. 1889, 2058; 1890, 2146; Bull. Soc. Chim. 1890, 4,
613, 515; 1891, 5, 714; Wag. Jahr. 1889, 35, 943; 1890, 36, 945. 3-Methyl-
glucose-tetracetate, Koenigs and Knorr, Ber. 1901, 34, 966; abst. J. S. C. I.

1902, 21, 196; J. C. S. 1902, 82, i, 135; Chem. Centr. 1902, I, 302; BuU. Soc.
Chim. 1902, (2), 28, 317; Rept. Chimie, 1901, 1, 470. Mucicacid tetracetate.
L. Maquenne, Bull. Soc. Chim. 1887, 48, (2), 719; abst. J. C. S. 1888, 54,
676; Jahr. Chem. 1887, 1777; Ber. 1888, 21, R, 186; Chem. News, 1888, 57,
161. Quercite acetate, F. Homann, Ann. 1878, 190, 282; see also Ber. 1875,

8, 1039; abst. J. C. S. 1878, 34, 399; Jahr. Chem. 1877, 535; 1875, 799; Ber.
1875, 8, 1039; 1879, 11, 252; Bull. Soc. Chim. 1876, (2), 25, 302. a-Quinite-
diacetate, L. Brunei, Bull. Soc. Chim. 1903, (3), 29, 131, 231; Compt. rend.
1902, 135, 1055; 1903, 136, 383; abst. J. C. S. 1903, 84, i, 157, 338; Chem. Centr.

1903, I, 233, 58;3, 711, 970; Jahr. Chem. 1902, 1344; 1903, 1116; Chem. News,
87, 16; 88, 70; Rept. de Chim. 1903, 3, 129, 227, 205, 277. Saccharic acid-
ethylester- tetracetate, A. Baltzer, Ann. 1869, 149, 237; see also Naturf. Ges.

CELLULOSE 185

L. Maquenne and W. Goodwin,^ preparing cellobiose by a

Ziirich, 1867, 303; Zts. Chem. 4, 219; abst. Jahr. Chem. 1868, 644; Bull. Soc.
Chim. 1868, (2), 10, 2^3. Scillite hexacetate, J. Mueller, Ber. 1907, 40,
1821; abst. C. A. 1907, 1, 2109; J. C. S. 1907, 92, i, 482; Chem. Zentr. 1907,
II, 51; Kept, de Chim. 1907, 7, 364; Bull. Soc. Chim. 1908, (4), 4, 1509. Sor-
bite hexacetate, C. Vincent and B. Delachanal, Compt. rend. 1889, 109j
676; abst. J. S. C. I. 1890, 9, 311; J. C. S. 1890, 58, 21; Jahr. Chem. 1889,
1352; Ber. 1891, 23, 24; Chem. News, 1889, 59, 120; 60, 258. Sucrose octoace-
tate, A. Herzfeld, Ber. 1880, 13, 267; abst. J. C. S. 1880, 38, 619; Chem.
Centr. 1890, 757; Jahr. Chem. 1880, 1011; 1882, 880; BuU. Soc. Chim. 1881,
(2), 35, 250. Xylan monoacetate, R. Bader, Chem. Ztg. 1895, 19, 55; abst. J.
C. S. 1896, 70, i, 335; Jahr. Chem. 1895, 1297; Ber. 1895, 28, 427. Xylite
pentacetate, G. Bertrand, Bull. Soc. Chim. 1891, (3), 5, 556, 740; abst. J. S. C. I.
1891, 10, 716; J. C. S. 1892, 62, 28, 29; Ber. 1891, 24, R, 530, 567. Heptaceto-
bromlactose, menthol-maltoside, menthol-maltoside-heptacetate, E. and H.
Fischer, Ber. 1910, 43, 2530; abst. C. A. 1910, 4, 3234; J. C. S. 1910, 98, A, i,
716; Chem. Zentr. 1910, II, 1456; Rept. Chimie, 1911, 11, 108; Chem. Ztg.
Rep. 1910, 534; Bull. Soc. Chim. 1911, (4), 10, 702. Manneo-tetrose-tetra-
dekacetate, mannino-triose-hendekacetate, C. Tanret, Bull. Soc. Chim. 1902,
27, (3), 947; Compt. rend. 1902, 134, 1686; abst. J. S. C. I. 1902, 21, 1033;
J. C. S. 1902, 82, i, 661; Chem. Centr. 1902, II, 347, 1177; Rev. g6n. sci.
1902, 13, 701; Jahr. Chem. 1902, 1031; Mon. Sci. 1902, (4), 14, 621; Chem.
News, 1903, 87, 142; Rev. Sci. 1902, (4), 18, 52. /3-Glucose pentacetate,
lactose tetracetate, glucose di- and triacetate, Schuetzenberger and Naudin,
Bull. Soc. Chim. 1869, (2), 12, 204; abst. J. C. S. 1872, 25, 366; Chem. Centr.
1869, 681; 1871, 740; Jahr. Chem. 1869, 760; Zts. Chem. 1869, 264; Ber.

1869, 163, 556. Mannite acetate, P. Schuetzenberger, Ann. Chim. Phys.

1870, (4), 21, 256. Glycogen triacetate, P. Schuetzenberger, Ann. 1871,
100, 80; Ann. Chim. Phys. 1870, (4), 21, 235; abst. J. C. S. 1872, 25, 366;
Chem. Centr. 1871, 740. Sucrose acetate, Schuetzenberger and Naudin,
Compt. rend. 1869, 68, 814; abst. Bull. Soc. Chim. 1869, (2), 12, 107, 204,
206; 1868, (2). 10, 128; reproduced in Ann. 1871, 160, 80; Chem. Centr. 1869,
681; Jahr. Chem. 1869, 750; Zts. Chem. 1869, 264; Ber. 1869, ^63, 556.

1. Bull. Soc. Chim. 1904, (3), 31, 854; abst. J. C. S. 1904, 86, i, 799;
Chem. Centr. 1904, II, 645; Jahr. Chem. 1904. I, 1149. According to H.
Fenton and M. Gostling, various forms (J. C. S. 1898, 73, 554; 1899, 75, 423;
1901, 79, 361, 807; abst. Chem. News, 1898, 77, 282; 1899, 79, 124; 1901,
83, 92, 272; J. S. C. I. 1899, 18, 404; Bull. Soc. Chim. 1899, 22, 782; 1901,
26, 341, 796; Rep. Chim. 1901, 1, 424; Chem. Centr. 1898, 69, II, 181, 421;
1899, 70, I, 877, 1162; 1901, 72, I, 679, 775; II, 123, 426; Chem. Ztg. 1898,
22, 493; 1899, 23, 225; 1901, 25, 108, 507; Jahr. Chem. 1898, 51, 1312; 1899,
52, 2176; 1900, 53, 1442; 1901, 54, 838, 1494; Meyer Jahr. Chem. 1898, 8,
202; 1899, 9, 181; 1901, 11, 223; Zts. ang. Chem. 1901, 14, 273) and H.
Fenton (Proc. Chem. Soc. 1901, 17, 166; abst. Chem. News, 1901, 84, 7;
J. S. C. I. 1901, 20, 757; Rep. Chim. 1901, 1, 515; Chem. Centr. 1901, 72,
II, 405; Chem. Ztg. 1901, 25, 591; Jahr. Chem. 1901, 54, 840) of "cellulose"
(such as filter paper and cotton) give considerable yields of the chloro- or
bromo-derivatives of methylfiu-fural when they are heated with dry hydrogen
chloride or bromide dissolved in an appropriate solvent. It was fiu-ther
shown that the formation of the bromo-derivative in any notable quantity
is indicative of the presence of a ketohexose nucleus or grouping, and tiie exis-
tance of one or more such groupings in "cellulose" was consequently inferred.
Recent experiments indicate that the same observations apply also to the
cA/oro-derivative.

After treatment of cellulose in this manner with dry hydrogen chloride
and complete removal of the methylfurfural derivative by washing repeatedly

186 technoi.cx;y o^ cellulose esters

modification of Skraup's process, obtained two octacetyl deriva-
tives, one melting at 228°-229° and the other melting at 196° and
instantly converted into the first form by heating with acetic
anhydride and sulfuric acid. Skraup^ subsequently prepared
the acetochloro derivative directly from cellulose, but was unable
to obtain a biose from the acetyl modification with melting point
of 200°. E. V. Hardt-Stremayr* found that the acetates of Ma-
quenne and Goodwin and of Skraup are identical, the true melting
point being 196°.

In the method of F. Klein,' for the preparation of cello-

with ether, a dark brown residue is left, which, in the case of filter paper,
still shows a fibrous structure and amounts to about 90% of the material
taken. If this residue is digested with warm water, a solution is obtained
which gives all the reactions of dextrose. It is strongly dextro-rotatory, and
with phenylhydrazine acetate, on heating, yields glucosazone (m. p. 204**-
206**. N = 15.83, theory requiring 15.64 percent.). On evaporating the
solution to small bulk in a vacuum and adding alcohol, a syrup is at once
precipitated, which solidifies on standing, and the solution continues to de-
posit crystalline crusts after a time. Mannose appears to be excluded from
the fact that phenylhydrazine gives no precipitate in the cold even after
standing for several hours.

Fifty grams of Swedish filter paper were treated in the manner above
described, the solvent used being carbon tetrachloride, and the resulting
chloromethylfurfural estimated by weighing the crystals. The residue was
then extracted with water, and the dextrose estimated by means of Pehling's
solution. The results gave chloromethylfurfural 3.1 gm., and dextrose 1.57
gm. At first sight, therefore, it would appear that the methylfurfural de-
rivative is produced in excess. But it is found that when dextrose is treated
in the same manner, a considerable portion is destroyed, leaving a black
residue. A blank experiment was made with 5 gm. of dextrose under exactly
similar conditions, with the result that the carbon tetrachloride extract
weighed only 0.01 gm., and the residual sugar 2.2 gm. If it be assumed that
the dextrose resulting from the action on cellulose is destroyed to a similar
extent, the calculated amount of this sugar produced in the first experiment
mentioned would be 3.54 gm. This, it will be seen, is approximately the
quantity required (3.86 gm.) on the assumption that the chloromethylfur-
fural and dextrose are produced in equal molecular proportions (144.5:180).

These facts app>ear to be of special interest in relation to the work of
Skraup and Konig (Bcr. 1901, 34, 1115), in which it is stated that the cellu-
lose acetate obtained by the action of acetic anhydride and concentrated
sulfuric acid on filter paper is an octo-acetyl biose, and that this on hydrolysis
yields "cellose." C12H22O1,.

1. Monatsh. 1905, 26, 1415; abst. J. C. S. 1906, 90, i, 67; Jahr. Chem.
1905—1908 II 929

2. Wien. Akad. Ber. 116, 2-b, 3; Monatsh. 1907, 28, 63; abst. J. C. S.
1907, 92, i, 389; Chem. Zentr. 1907, I, 1570; J. S. C. I. 1907, 26, 482; BuU.
Soc. Chim. 1908, (4), 4, 4; Jahr. Chem. 1905-1908, II, 922; C. A. 1907, 1,
2179. See also Hardt-Strcmayr, Wicn. Akad. Ber. 116, Il-b, 13; abst.
Jahr. Chem. 1905-1908, II, 922.

3. Zts. ang. Chem. 1912, 25, 1409; abst. J. S. C. I. 1912, 31, 713; Chem.
Zentr. 1912, 83, 1196; Chem. Tech. Rep. 1912, 36, 532; Kunst. 1912, 2, 311;
C. A. 1913, 6, 2303; J. C. S. 1912, 102, i, 679. For pentaisovaleryl-, pentalauryl-.

CEI.I.ULOSE 187

biose octacetate, 10 gm. of cellulose are treated with 50 gm.
of a mixture containing 80% of acetic anhydride and 20% of
sulfuric acid, with special precautions to avoid local rise of tem-
perature in the early stages. Subsequently the temperature may
be raised to 35° or even 60° in order to accelerate the action.
After 2-4 days the liquid sets to a mass of crystals; it is then
diluted with glacial acetic acid and poured into a liter of water.
The dried precipitate is recrystallized from three times its weight
of 96% alcohol, the crystals forming long needles or leaflets.
With proportions less than 3.5% of sulfuric acid or more than 30%
no crystallization of the octacetate is obtained. Hydrocellulose
gives the same results as cellulose and is more easily manipulated.
The highest yield of cellobiose octacetate obtained is 60% of the
weight of cellulose, or about 30% of the theoretical quantity.
Although not more than about one-third of the monose groups of
cellulose are obtained in the form of cellobiose octacetate, the
evidence is quite in accordance with the view that all these groups
are combined in the same manner. The by-products are of two
kinds: acetylated cellulose dextrins and products soluble in water
of the nature of mixed acetosulfuric esters. The acetates obtained
from the alcoholic mother-liquors from the crystallization of the
cellobiose octacetate, having specific rotations from -[-11° to
+34,° are doubtless intermediate products of the breakdown of
the cellulose molecule. The regular rise in the rotatory power and
percentage of combined acetic acid, in these fractionated dextrin
acetates, makes it almost certain that acetolysis proceeds in a
regular series of steps. The products soluble in the aqueous
liquors after precipitating the dextrin and cellobiose acetates
have not been fully investigated; in certain circumstances, these
water-soluble products amount to 40% of the weight of the cel-
lulose, and their properties suggest that they are probably aceto-
sulfates either of cellobiose or of dextrose. The experimental
methods of investigating the various products of acetolysis include
observation of melting point, hygroscopic moisture, specific

pentapalmityl-, pentastearyl-, i>entacarbomethoxy-, tetracetylbenzoyi-, tetra-
acetysalicyl-, glucose, and heptaacetylbenzoylccllobiose, see G. Zemplen and E.
Laszio, Ber. 1915, 4S, 915-26; abst. C. A. 1915, 9, 2251. For data on Cell-
ulase. see H. Huler, Zts. ang. Chem. 1912, 25, 250; abst. C. A. 1912, 6, 3516.
de Bary, Bot. Zts. 1886, 377. M. Ward, Ann. Bot. 1888, 2, 319. Schellenberg,
Flora, 1908, 9S, 257. Brown and Morris, J. C. S. 1890, 57, 453. Green,
PhU. Trans. 1887, 39, 179. C. Yllner, Zts. ang. Chem. 1912, 25, 103.

188 TECHNOLOGY OF CELLULOSE ESTERS

rotatory power in chloroform solution, combined acetic acid,
cupric reducing power and solubility of the free dextrins obtained
on saponification. The combined acetic acid is best determined
by hydrolysis with a mixture of equal volumes of sulfuric acid
and water and titration of the volatile acid. Alkaline saponifi-
cation with N/2 alcoholic sodium hydroxide for 12-18 hoiu*s must
be resorted to when it is desired to investigate the free dextrins;
the acetic acid thus found is 1 %-3% higher than by acid hydrolysis.
For the isolation of the free dextrins soluble in water, saponifi-
cation with baryta water is more convenient. The melting
points of the dextrin acetates are very doubtful and range
about 100®; cellobiose octacetate alone melts sharply, at 222®; the
combined acetic acid is 70.4%, and [a]D = +41.7®.

H. Ost and T. Katayama^ acetylated cellulose, hydrocellu-
lose, and alkali-cellulose both in presence of zinc chloride and of
sulfuric acid, under similar conditions, the resulting acetates
being examined as regards solubility in alcohol, acetone, and
chloroform, and the dissolved fractions tested for rotatory power
and acetic acid content. In the first series of experiments, 5
gm. of the cellulose were acetylated at 70° with 25 gm. of
acetic acid, 25 gm. of acetic anhydride, and 2.5 gm. of zinc
chloride; the acetates obtained from hydrocellulose and alkali-
cellulose, after like periods, contained larger percentages soluble
in acetone than the acetates of cellulose; in each case the percentage
soluble in acetone increased with the period of acetylation, indi-
cating hydrolysis. Both hydrocellulose and alkali-cellulose were
completely esterified within two hours, while the cellulose re-
quired 20 hours. After 65 hours treatment, the acetates from
cellulose contained 21.7 and 22.5% soluble in acetone, while after
2 hours the esters from hydrocellulose contained 18.9% and
after 20 hours 32.8%, and those from alkali-cellulose after 2 hoiu^'
treatment 27.1% soluble in acetone. These acetone-soluble
portions gave films which were either very brittle or non-elastic.
In the second series of experiments the same quantities were
used, but the zinc chloride was replaced by 0.5 gm. of sulfuric
acid and acetylation was carried out at the ordinary temperature;

1. Zts. ang. Chem. 1912, 25, 1467; abst. J. S. C. I. 1912, 31, 713; Jour.
Ind. Eng. Chem. 1912, 4, 701; Kunst. 1912, 2, 311; Chem. Tech. Rep. 1912.
36, 485; Wag. Jahr. 1912, 11, 660; C. A. 1913, 6, 2303; Chem. Zentr. 1912,
II, 1199.

CELLULOSE 189

in these experiments only cellulose and hydrocellulose were
used, and the ester mixtures from these appeared identical after
48 hours; the percentages soluble in acetone were 20.0 and 24.8,
respectively. The specific rotatory power of the fractions soluble
in chloroform from cellulose and hydrocellulose varied between
—20.5 "" and —21 . 1 '', and from alkali-cellulose from — 21 ° to —22 "" ;
the figures for the corresponding portions soluble in acetone were
—17.3 to —17.8°, and —21.8°. The acetic acid content of the
chloroform- and acetone-soluble fractions agreed in all cases with
that of cellulose triacetate, except that of cellulose acetylated in
presence of zinc chloride for 65 hours, when it was slightly higher.
In the third series of experiments, cellulose and hydrocellulose
were acetylated in presence of sulfiuic acid at 70°; in this case
more than half the product was soluble in alcohol, and the re-
mainder completely soluble in acetone; when 1 gm. of sulfuric
acid was used instead of 0.5 gm., the products were almost com-
pletely soluble in alcohol, and consisted principally of cellobiose-
octa-acetate; under suitable conditions this ester is converted into
a-dextrose-penta-acetate, of m. p. 112.°

E. Ejioevenagel^ has shown that acetolysis occurs in the
presence of many contact substances besides sulfuric acid, in
the presence of acetic anhydride, and has intimately studied the
effect of acetic anhydride upon benzolacetone in the presence
of ferric chloride.

G. Zemplen* found that when cellulose and hydrocellulose

1. Zts. ane. Chem. 1909. 22, 281; abst. Chem. Ztg. 1909, 31, 104;
J. C. S. 1911, 100, i, 179. See also "Dissertation on the Hydrolytic and
Acetolytic Breaking up of Cellulose under the influence of Different Contact
Substances," Heidelberg, 1911. W. Schleimann, "Cellobiose and the
Acetolysb of Cellulose," Ztg. ang. Chem. 1912, 2S, 771; Ann. 1911, 378, 366;
abst. BuU. Soc. Chim. 1911. (4), 10, 1346; C. A. 1911. 5, 1276; Chem. Zentr.
1911, 1, 807; J. S. C. I. 1911, 30, 126.

2. Zts. physiol. Chem. 1913. 85, 180; abst. J. S. C. I. 1913. 32, 651;
J. C. S. 1913. 104, i. 708; C. A. 1913, 7, 3836; Chem. Zentr. 1913 II. 426.
For bromacetoceUobiose. iodoacetocellobiose and hepta-acetylcellobiose.
see Fischer and G. Zemplen. Ber. 1910, 43, 2536; abst. J. C. S. 1910, 98, i,
718. According to G. Bertrand and M. Holderer (Compt. rend. 1909, 149,
1385; abst. J. S. C. 1. 1908, 27, 102; cellose Z. Skraup and J. Koenig, Ber. 1901,
34, 1115; Monatsh. Chem. 1901, 22, 1011; J. S. C. I. 1901, 20, 740) a biose
produced by the partial hydrolysis of cellulose, is not hydrolyzed by maltase
and sucrase. After contact, however, with an aqueous maceration of Asper-
gillus niger for about three days at 37° C, pure cellose is entirely trans-
formed into dextrose. Emulsin and trehalase also hydrolyze it, but these
diastases are not obtainable in suifident purity to form definite conclusions
from their action. The authors conclude in favor of the existence of a dias-

190 TECHNOLOGY O^ CELLULOSE ESTERS

are subjected to acetolysis preferably under the conditions de-
scribed by Klein, both yield practically the same amount (50-55%)
of cellobiose octacetate. According to his results, amyloid is not
identical with hydrocellulose, and hydrolysis by 70% sulfuric
acid, even after prolonged action does not extend to thejcello-
biose groups, for the final product yielded no dextrose pentacetate
as the result of the acetolysis.

H. Ost^ found by the action of dilute sulfuric acid upon
cellulose, that hydrocellulose is very readily formed, but not
more than about one-half of the cellulose can be made to undergo
total hydrolysis to dextrose by this means. Moreover, there
appear to be no intermediate products (dextrins) between hydro-
cellulose and dextrose when cellulose is hydrolyzed by dilute adds.
According to the author's experiments, neither cellulose nor hydro-
cellulose become perfectly anhydrous when dried at 100^-105®;
the sample should be heated slowly up to that temperature and
finally dehydrated at 120°-125°. Between that temperature
and 130** or even 140^, purified cotton cellulose remains white
and suffers no fiuther loss of weight, but certain samples of
hydrocellulose are slightly decomposed by heating at 125**-130**.

Hydrocellulose is less hygroscopic than cellulose. When
both substances are corrected for the hygroscopic moisture ex-
pelled at 120,** elementary analysis fails to show any difference
between cellulose and hydrocellulose. The quantity of water
combining with the cellulose in this first stage of hydrolysis falls
within the limits of analytical error. When cellulose is hydrolyzed
by means of strong sulfuric acid, it forms the acid esters of a
series of cellulose dextrins, which by heating at 120°, after dilution,
may be almost quantitatively resolved into dextrose. Any
"amyloid" precipitated by dilution must again be treated with
strong sulfuric acid before it can be completely hydrolyzed.
Sulfuric acid of 70% strength is a better reagent for the "sulf-
olysis" of cellulose than the more concentrated acid. When
cellulose is acetylated by a mixture containing sulfuric acid as a

tase, cellase, distinct from maltase. For the partial hydrolysis of tunicate
cellulose, see the topic "Animal Celluloses."

1. Ann. 1913, 398, 313 ; abst. J. S. C. 1. 1913, 32, 784; Kunst. 1913. 3, 352;
C. A. 1913, 6, 3836; J. C. S. 1913, IM, i, 446, 833, 1148; Chem. Zentr. 1913,
II, 2035; Ber. 1913, 46, 2995. See also Ost, Zts. ang. Chem. 1912, 2S, 1996;
abst. Kunst. 1913, 3, 330.

cBi<i^xJU)SE 191

catalyst, the solution on further standing» loses its viscosity and
a range of dextrin acetates is produced, terminating in cellobiose
octacetate and dextrose pentacetate. These hydrolyzed products
contain more combined acetic acid than cellulose triacetate.

The author has investigated the most favorable conditions
for the total acetolysis of cellulose to dextrose acetates. The
best results are obtained with a mixture of equal parts of acetic
anhydride and glacial acetic acid containing 10 gm. of sul-
furic acid per 100 cc. Cellulose is digested with about 11 times
its weight of such a mixture at 18^-20® for 4-6 months. From
the reaction-product a certain amount of cellobiose acetate crys-
tallizes out; the liquid is poured into water and the dried preci-
pitate is extracted with ether; the insoluble matter contains cello-
biose acetate and the acetates of intermediate dextrins. The
former separates on crystallization from 70% alcohol, while the
dextrin acetates are precipitated from the mother liquors by water.
The ethereal extract of the precipitate and the ethereal extract
of the portion of the reaction product soluble in water contain
the dextrose acetate; a portion of this crystallizes out as pentace-
tate and further quantities of pentacetate may be prepared by
subsequent acetylation of the residual s)mips with mixtiu'es con-
taining only traces of sulfiu*ic acid. Of crystallized products,
cellobiose and dextrose acetates, 60.6% of the theoretical quantity
have been obtained from cellulose, but the residual syrups con-
taining acetates soluble in ether but not crystallizable, bring the
total yield of simple products to over 92% of the theoretical.
These residual s)rrups are identical with those obtained in the
acetylation of dextrose, and the author concludes that the cellu-
lose molecule is entirely composed of dextrose residues.

He claims^ the total hydrolysis of cellulose to dextrose has
only been accomplished by way of its esters. After conversion
into the sulfuric ester, cellulose may be completely resolved by
"sulfolysis," by heating the solution with water at 120°, into
its constituent hexose groups. In an analogous manner a similar
resolution may be effected by "&cetolysis" after conversion into
the acetate. Hydrolysis of the cellulose complex must take place
by the oxygen atoms, which unite the hexose residues by lactonic

1. Chem. Ztg. 1012, 36, 1099; abst. J. S. C. I. 1912, 31, 980; Kunst.
1912, 2, 412; Jour. Soc. Dyers, 1912, 28, 369.

192 TECHNOLOGY O^ CELLULOSE ESTERS

linkages, taking up each one molecule of water and fonning two
hydroxyl groups. Thus the 3 mn hydroxyls of a cellulose mole-
cule made up of mn dextrose residues will become on hydrolysis
n (3m + 2) hydroxyls, and a dextrin which may be produced,
composed for instance, of 10 dextros^ residues, will contain, not
30, but 32 hydroxyls, while the biose will contain 4 and the monose
5 hydroxyls per Cc unit. This progressive hydrolysis can only be
detected by elementary analysis in its later stages, but it is more
sharply indicated by the increase in the combined acetic acid in
the esters.

Thus cellulose triacetate contains 62.5% of acetic acid, the
acetate of a dextrin, C60H102O512 (with 32 hydroxyls) contains
64.4%, cellobioseoctacetate contains 70.8%, and dextrose penta-
cetate 76.9%. Cellulose may be converted into dextrose pentace-
tate in the following manner: 5 gm. of cellulose, 25 cc. of acetic
anhydride, 25 cc. of acetic acid and 5.5 gm. of sulfuric acid are
digested at 40°-45° for two days. The product is poured into
water when it has reached a stage when a minimum precipitation
(bioseacetate and humus matters) thereby results. The aqueous
solution is exhausted with ether, which extracts a syrupy mixture
of various acetates of dextrose. When this mixtiu*e is re-acety- 1 ^

lated in the cold by acetic anhydride with only traces of sulfiu*ic
acid, a very large yield of pure dextrose- ot-pentacetate, melting at
112°, is obtained.

According to J. Boeseken, J. van den Berg and A. Kerstjens^
the acetylation of carbohydrates of high molecular weight requires
a catalyst which forms an unstable compound with the hydroxyl
group. Thus sulfuric, hydriodic, hydrobromic, and hydrochloric
acids are active in the order named, corresponding with the order
of stability of their compounds with the hydroxyl group. Of the
catalysts examined, only hydrobromic acid, hydriodic acid, and
acetyl iodide are comparable with sulfiu^ic acid. The primary
function of the catalyst is to act as a common solvent of the car-
bohydrates and the acetic anhydride, and the rate of acetylation
is limited by the rate of diffusion of the acetylating mixture in the
carbohydrate, which is much slower than the actual acetylation.
The difference in the rates of acetylation of cellulose and starch

1. Rec. Trav. Chim. Pays-Bas, 1916, 35, 320; abst. J. S. C. I. 1916,
%S, 464; Zts. Chem. lud. KoU. 1917, 21, 160; J. C. S. 1916, HO, ii, 466.

CELLULOSE 193

is probably due to the difference in the surface exposed,
and the influence of catalysts on both reactions is approx-
imately of the same order. The relative surface of colloidal car-
bohydrates is probably approximately measured by the velocity
of acetylation, because this depends on the diffusion of the acetyl-
ating mixture in the carbohydrates. The chemical reaction
consists of a succession of processes of acetylation and hydrolysis
(or acetolysis). It is doubtful whether mono- and di-acetates of
cellulose have ever been obtained directly since if the reaction is
stopped before the cellulose has all dissolved, the acetate in
solution is the triacetate, and the undissolved cellulose contains
practically no combined acetic acid. If the general formula of
the polyglucoses is written (C6Hi206)n — (n-l)H20, n becomes
lower as the molecule is hydrolyzed, and the acetyl number in-
creases gradually from 62.5 (for cellulose triacetate) to 77 (for
dextrose pentacetate). A proportional figure for the degree of
acetolysis is obtained by assuming that the carbohydrate molecule
(C«Hi20fl)„ — (n-l)H20 combines with (3n + 2) molecules of acetic
acid, forming the triacetate of molecular weight (162n + 18) +

1000 (3n + 2)

(3n + 2)42. The acetyl number is then — tz — , ^^ from

^ ^ ^ 48n + 17

which n can be calculated. It gives the average number
of dextrose groups in the products of hydrolysis. It is probable
that as long as the acetyl number is about 62.5, the cellulose has
only split into groups of approximately equal size, without forming
simple molecules such as cellobiose acetate or dextrose pentace-
tate; otherwise there would be a large proportion of the product
soluble in alcohol and etlier. When the acetyl number begins to
exceed 62.5, n increases very rapidly with time, indicating pro-
found acetolysis of the molecule.

E. Boiu-quelot and M. BrideP find cellobiose or cellose to be
isomeric with gentiobiose and maltose. It is dextrogyrous with
multiple rotation reaching 34° at stability. One mgm. cellobiose
precipitates 1.38 mgm. Cu. It is hydrolyzed by emulsin or
better by an enzyme, cellobiase, whose specificity has been de-

1. Compt. reiid. 1919, 168, 253, 701, 1016; abst. C. A. 1919, 13, 1209,
1486, 2010. G. Bertrand and M. Holderer, Ann. inst. Pasteur, 1910, 24,
180; Bull. Soc. Chim. 1910, 7, 177; abst. C. A. 1910, 4, 1870, 1994, 3240.
Compt. rend. 1910, 150, 335; abst. C. A. 1910, 4, 1994.

194 TECHNOlrOGY OP CELLU1.0SE KST^RS

termined by Bertrand and Holderer. To each of two solutions of
glucose containing 30 to 50 gm. respectively, in 100 cc. H2O, one
gm. of emulsin was added and the synthesizing reaction allowed
to proceed at ordinary temperature to equilibrium, when, after
convenient dilution, top yeast was added to destroy the remaining
glucose. This being done, the solutions were filtered, evaporated,
to dryness imder reduced pressure, and found to be 15.7® and
15.9° respectively, showing the reactions to have been the same.
From these residues some gentiobiose with a rotation of 10.2**
was removed, showing that other sugars with a higher rotation
than 15° were mixed with the gentiobiose. If the residue, 42
gm.^ is dissolved in 60 cc. H2O and 40 cc. absolute alcohol added
a voluminous precipitate is formed. The liquid is decanted and
the residue taken up at boiling, first with 100 cc. 95% alcohol,
then with 200 cc. 90% alcohol. This last solution was decanted
and after 15 days primed by rubbing the walls of the beaker with
a rod to which adhered traces of cellobiose chemically prepared.
The crystals produced showed the exact microscopic appearance
of chemically prepared cellobiose and a multirotation of 12.06°,
25.74°, and 30.50° after 4 minutes, and stabilization, respectively,
one mgm. precipitated 1.389 mgm. Cu, and 1. gm. treated with
3% sulfuric acid gave 1.07 gm. reduced sugar. It, therefore,
appears established that gentiobiase, cellobiase and glucosidase
exercise simultaneously their synthesizing action in a solution of
glucose.

Hydrolysis and Saccharification. The study of the hydrolysis
of cellulose has engaged the attention of chemists for over a cent-
ury, as far back as 1797. A. Fourcroy and Vauquelin* having
published a memoir upon this subject, which twenty-two years
later was made the basis of an investigation by H. Braconnot.'
The interest in the problem is due not only to the possible economic
utilization of the resulting products, but also to the theoretical

1. Cf. C. A. 1919, 13, 1209, line 20.

2. Ann. Chira. Phys. 1797, (1), 23, 186, 203; Nicholson J. 1797, I, 385;
Trommsdorff, J. Pharm. 1797, 6, 172, 189.

3. Ann. Chim. Phys. 1819, (2), 12, 172; abst. Dingl. Poly.
1820, 1, 312; 1827, 25, 81; Gilb. Ann. 1819, €3, 348; Edin. Phil. J. 1820, 2,
363; J. de Pharm. 1820, 6, 416; Quart. J. Sci. 1820, 8, 386; Schw. J. 1819,
27, 328. Tilloch, Phil. Mag. 1820, 55, 53, 118. See also Nancy. Trav.
Soc. Sci. 1819-1823, 66; Gilb. Ann. 1822, 70, 389; Giom. Arcad. 1820, 6, 277;
Quart. J. Sci. 1820, 9, 392.

CELI.UI.OS^ 195

importance of the reactions as possibly furnishing a satisfactory
solution of the structure of the cellulose complex, for the products
obtained were crystalline and hence readily purified in contra-
distinction to cellulose, which in all forms is amorphous.

The work of Braconnot was followed by that of J. Amould,^
M. Pettenkofer,^ Tribouillet,' Pelouze/ G. Melsens,* F. Varren-
trapp,* A. Payen,^ H. Ludwig,® H. Tauss,® J. Matheus,^*^ C. Amos
and W. Anderson, ^^ J. Poumarede and L. Figuer,^* as well as,

1. Compt. rend. 1854, 39, 807; Dingl. Poly. 1854, 134, 219; Poly. Notiz.
1855, 31; Wag. Jahr. 1855, 1, 221; Instit. 1854, 366; Arch. ph. Nat. 27, 331.
See also TribouiUet, Mon. Ind. 1854, 908; Dingl. Poly. 1854, 134, 316; Poly.
Centr. 1855, 21, 128; Wag. Jahr. 1855, 1, 221. Melsens, Genie. Ind. 1855,
106; abst. Dingl. Poly. 1855, 138, 426.

2. Bayer Kunst. u. Gewerbebl. 1855, 136; Dingl. Poly. 1855,138, 387;
Poly. Centr. 1855, 21, 955; Poly. Notiz. 1855, 10, 161; Wag. Jahr. 1855, 1,
222; Poly. Centr. 1855, 21, 955; Pharm. Centr. 1855, 26, 557.

3. Mon. Ind. 1854, 1908; Dingl. Poly. 1854, 134, 316; Poly. Centr.
1855, 21, 128; Wag. Jahr. 1855, 1, 221 ; Compt. rend. 1854, 39, 980.

4. Compt. rend. 1859, 4S, 327, 1027; abst. Mon. Sci. 1859-1860, 2, 86,
131; Poly. Centr. 1859, 25, 976; Dingl. Poly. 1859, 151, 394; Jahr. Chem.
1859, 12, 533; J. pharm. 1859. 35, 209; Instit. 1859,49;Rep. Chim. Pure,l,272.
See also Weil, Compt. rend. 1859, 4S, 1027. Payen, Dingl. Poly. 1855, 138,
58. W. Stein, Poly. Centr. 1855, 21, 429. A. Hofmann and Redwood,
Pharm. J. Trans. 14, 556; 15, 28; Chem. Soc. Quart. J. 1855, 8, 120. Robinet,
J. Pharm. (3), 27, 191. Campani, Cimento, 2, 210. Rabourdin, J. Pharm.
(3), 28, 68; Vierteljahrschr pr. Pharm. 5, 406; Jahr. Chem. 1854, 7, 797.
Walz, N. Jahr. Pharm. 3, 217. H. Ludwig, Arch. Pharm. (2), 82, 22; Pharm.
Centr. 1855, 28, 512. Bordier, Dingl. Poly. 1855, 138, 387.

5. Genie industr. 1855, 106; Dingl. Poly. 1855. 138, 426; Wag. Jahr.
1855, 1. 221 ; Poly. Centr. 1856, 22, 873.

6. Mitth. f. Gewerbever. des Herzogthums, 1865, 70; Dingl. Poly. 1866,
181, 233; Wag. Jahr. 1866, 12, 466; Braunschweig. 1866, 73; Deut. Ind. 1866,
366; Poly. Centr. 1866, 32, 1150.

7. Compt. rend. 1867, 84, 1167; Dingl. Poly. 1867. 185. 308; Chem.
Centr. 1868, 13, 20; Jahr. Chem. 1867, 952, 953; Mon. Sci. 1868. 10, 322;
Poly, Centr. 1867, 33, 1351. See also- Payen, Ann. Chim. Phys. 1866. (4),
7, 382; Zts. Chem. 1866, 334. Bachet and Marchard, Jahr. Chem. 1866, 19,
663; Van Tieghem, Compt. rend. 1863, 58, 963; abst. Jahr. Chem. 1863, 18,
565; Chem. Centr. 1863, 34, 950.

8. Zts. f. deutsche Landwirthe. 1855, 192; Dingl. Poly. 1855, 138, 80;
Poly. Centr. 1855, 21, 1085; Poly. Notiz. 1855, 10, 286; Wag. Jahr. 1855,
1 223.

9. Dingl. Poly. 1889. 273, 276; 1890, 278, 411; abst. Chem. News,

1890, O, 169; J. S. C. I. 1889. 8, 913; Mon. Sci. 1890, 55, 164; Ber. 1889, 22,
R. 769; Chem. Centr. 1889. 80, II, 444; Chem. Ind. 1889, 12, 514; Chem. Tech.
Rep. 1890, II, 105; Jahr. Chem. 1889. 42, 2838; Wag. Jahr. 1889. 35, 1; Apoth-
ker Ztg. 1890, 232; J. S. C. I. 1890, 9. 883; Mon. Sci. 1891, 38, 1264; Ber.

1891. 24, R, 277; Chem. Centr. 1890, tt, II, 187; Jahr. Chem. 1890, 43, 2189,
2873; 1891, 44, 2811; Wag. Jahr. 1890, 38, 1148.

10. Dingl. Poly. 1893, 287, 91; abst. Jahr. Chem. 1893, 48, 647.

11. Mechanics Mag. 1866, 341; abst. Dingl. Poly. 1867, 184, 308; Jahr.
Chem. 1867, 20, 953. Chaudet and Delamure-Debouteville, F. P. 123556,
1878; abst. Chem. Ind. 1878, 1, 421 ; Mon. Sci. 1879, 21, 1042.

12. Compt. rend. 1846, 23, 918; 1847, 25, 17; abst. J. prakt. Chem.

196 T^CHNOlrOGY OI^ CElrtULOSB ESt^R^

J. Sacc/ F. Schulze,2 H. Mohl,^ E. Fremy* with TerreiP and Urbain,«
F. Bente,7 J. Erdmann,* A. Stutzer,^ H. Kolbe,^^ Flechsig," G.

1847, 42, 25; Berz. Jahr. 1849; 28, 340; Jahr. Chem. 1847-1848. 1, 797; Rev.
Sci. 1847, 14, 68; Ann. 1847, 64, 387; Annuaire de Chim. 1847, 453; J. Pharm.
1847, (3), 11, 81 ; Rep. Pharm. (2), 47, 344;Soc. Philom. Proc. Verb. 1846, 130.

1. Ann. Chim. Phys. 1849, (3), 25, 218; abst. Jahr. Chem. 1849, 2, 473,
688, 704; J. prakt. Chem. 1849, 46, 430; Pharm. Centr. 1849, 20, 235; Chem.
Gaz. 1849, 274. See also J. Sacc, Ann. Chim. Phys. 1849, (3), 27, 473; J.
prakt. Chem. 1850, 49, 296; Pharm. Centr. 1850, 21, 91; Jahr. Chem. 1849.

2, 704; J. Pharm. 1849, 16, 293.

2. Chem. Centr. 1857, 28, 321; Jahr. Chem. 1857, 10, 491. See also
Mitscherlich, Berl. Acad. Ber. 1850, 102; Ann. 1850, 75, 305; J. prakt. Chem.
1850, 50, 144; Pharm. Centr. 1850, 21, 385; Chem. Gaz. 1851, 61; Instit.
1850, 228; Jahr. Chem. 1850, 3, 541. E. Schulze, Ber. 1890, 23, 2579; abst.
J. C. S. 1890, 58, 1456; Chem. Centr. 1890, 61, 1, 650; J. S.C. I. 1890,13,1051.

3. Flora, 1840, 23, 609, 625; Ann. Sci. Nat. 1841, 15, 38.

4. Compt. rend. 1859, 48, 202, 862; 1876, 83, 1136. N. J. Pharm. 35, 81 ;
abst. Rep. Chim. Pm-e, 1859, 1, 269; Compt. rend. 1859, 48, 325, 360, 667,
862; J. Pharm. 35, 321, 401; abst. Inst. 1859, 121, 151; Rep. Chim. Pure, 1859,
1, 357, 433; Pharm. Vierteljahr. 9, 221; N. J. Pharm. Inst. 1859, 357; Rep.
Chim. Pure, 1859, 1, 602; Chem. Centr. 1860. 4; Compt. rend. 1859, 49, 561;
Jahr. Chem. 1859, 12, 529, 530, 532, 533, 534, 537, 540; Bull. Soc. Chim.
1877, 28, 174; Ber. 1877, 10, 90.

5. Compt. rend. 1868. 66, 456; Bull. Soc. Chim. 1868, 9, 436; Ber. 1877,
10, 90; J. pharm. Chim. 1868, 7, 241; abst. Chem. Centr. 1868, 39, 616; Jahr.
Chem. 1868, 21, 762.

6. Compt. rend. 1882, 94, 108; Ann.sci.nat. 1882, (6), 13, 353; abst.
J. C. S. 1882, 42, 708; J. S. C. I. 1882, 1, 113; Bull. Soc. Chim. 1882, 37, 409;
Jahr. Chem. 1882, 35, 1150.

7. Ber. 1875, 8, 476; Landw. Versuchstat. 1876, 19, 164; abst. Bull.
Soc. Chim. 1876, 25, 278; Chem. Centr. 1875, 46, 392; Chem. Tech. Rep. 1875,
14, I, 16; Dingl. Poly. 1875, 217, 235; Jahr. Chem. 1875, 28, 785; Wag. Jahr.
1875, 21, 1045; Jahr. rein Chem. 1875, 3, 382.

8. Ann. 1866, 138, 1; Ann. Suppl. 1867, 5, 223; abst. Bull. Soc. Chim.
1866, (2), 6, 340; 1868, (2), 10, 295; Chem. Centr. 1866, 37, 401; 1868. 39,
395; Jahr. Chem. 1867, 20, 672, 738; Zts. Chem. 1868, 155, 245; J. Pharm. (4),

3, 478. Jahr. rein Chem. 1875, 3, 382.

9. Ber. 1875, 8, 575; abst. Bull. Soc. Chim. 1876, 25, 471; Jahr. Chem.
1875, 28, 822. A. Stutzer, D. R. P. 215273, 1908; Pap. Ztg. 1909, 34,
3758; abst. C. A. 1910, 4, 628; Chem. Zentr.'1909, 80, II, 1783; Chem. Ztg.
Rep. 1909, 33, 606; Wag. Jahr. 1909, 55, I, 291. F. P. 402871, 1909; abst.
J. S. C. I. 1909, 28, 1323. Des. Deut. Naturforscher und Aerzte Sept. 1909;
abst. Zts. ang. Chem. 1909, 22, 1999; J. S. C. I. 1909, 28, 1162; Bull. Soc,
Chem. 1910, (4), 6, 222; Jahr. Chem. 1909, 62, II, 387; Meyer Jahr. Chem.
1909, 19, 323.

10. J. prakt. Chem. 1880, (2), 21, 443; 22, 112; abst. Oest. Ung. W. u.
Agr. Ztg. 11, 241; J. C. S. 1880, 38, 520; 1881. 40, 212; Bull. Soc. Chim. 1880,
34, 96; Ber. 1880, 13, 1142, 1759; Chem. Centr. 1880, 51, 358, 501; Chem.
Tech. Rep. 1880, I, 19, 444; Chem. Ztg. 1880, 4, 488; Jahr. Chem. 1880, 33,
1063; Jahr. rein Chem. 1880,8,369; Wag. Jahr. 1880, 28, 454; Zts. Chem.
Grossgewerbe, 1860, 5, 119, 135, 151, 308.

11. Zts. physiol. Chem. 1883, 7, 523; abst. Ber. 18a3, 16, 2508; Chem.
Tech. Rep. 1883, 22, II, 144; Jahr. Chem. 1883, 36, 1363; Wag. Jahr. 1883,
29, 681; Tech. Chem. Jahr. 1883-1884, 6, 275; Zts. Deut. Spiritusfabr. 1883,
805.

CfiLI.UWSE 197

Mulder,* F. Hoppe-Seyler,^ T. Thomsen/ F. Koch,* A. Ihl,« M.
Singer,* and others^ previous to 1895. Notwithstanding the

1. Scheik. Onderzoek, 2, 76; abst. J. prakt. Chem. 1844, 32, 336;
Ann. 1841, 39, 150.

2. Ber. 1871, 4, 15; abst. J. C. S. 1871, 24, 226; Chem. Centr. 1871,
42, 84; Jahr. Chem. 1871, 24, 476; Bull. Soc. Chim. 1871, 15, 98; Chem.
News, 1871, 23, 131. See G. Foch, Chem. Ztg. 1913, 37, 1221. R. McKee,
Paper, 1919, 25, 25, 34,

3. J. prakt. Chem. 1879, 127, 146; abst. Ind,. Blatter 1879, 402; Archiv.
Pharm. 9, 557; J. C. S. 1879, 36, 613; J. S. C. I. 1883, 2, 89; BuU. Soc. Chim.
1880, (2), 33, 494; Ber. 1879, 12, 1012; Chem. Centr. 1879, 50; Dingl. Poly.
1879, 233, 413; Jahr. Chem. 1879, 32, 896; Jahr. rein Chem. 1879, 7, 503;
Wag. Jahr. 1879, 25, 1155. See also Scheibler, Ber. 1873, 6, 612; abst. Jahr.
Chem. 1873. 26, 829.

4. Pharm. Zts. Russ. 25, 619, 635, 651, 667, 683, 699, 730, 747, 763;
abst. Ber. 1887. 20, 145; Wag. Jahr. 1887, 33, 1.

5. Chem. Ztg. 1885, 9, 231, 451, 485; 1887, 11, 19; abst. Chem. News.
1885, 51, 114; J. C. S. 1885, 4S, 694; 1887, 52, 534; J. S. C. I. 1887, 6, 306;
Ber. 1885, 18, 128; 1887. 20, 77 R; Chem. Centr. 1885, 56, 761; Chem. Ind.
1888, 11, 188; Chem. Tech. Rep. 1885, 24, I, 258; II, 17; 1887, 26, II, 329;
Dingl. Poly. 1887, 266, 597; Jahr. Chem. 1887, 40, 2642; 1885, 38,
1977; 1886, 39, 1971. See also H. Molisch, Monatsh. Chem. 1886, 7, 198; abst.
Jahr. Chem. 1886, 39, 1971, 2172; Dingl. Poly. 1886, 261, 135.

6. Monatsh. 1882, 3, 396; abst. J. C. S. 1882, 42, 1122; J. S. C. 1. 1882,
1, 404; 1883, 2, 89; Ber. 1882, 15, 2272; Chem. Tech. Jahr. 1883, 22, I, 243;
Chem. Ztg. 1882, 6, 603, 813; Wag. Jahr. 1882, 28, 1060; Akad. Wissensch.
Wein, 1882, 100; Tech. Chem. Jahr. 1892-1893, 5, 212.

7. T. Seliwanoff, Ber. 1887, 20, 181; abst. J. C. S. 1887, 52, 459; Bull.
Soc. Chim. 1887, .(2), 48, 135; Ber. 1887, 20, 181; Chem. Ztg. 1887, 11, 1486;
Jahr. Chem. 1887, 40, 2301; Landw. Ver.-Stat. 34, 414. See also Chem. Ztg.
1885, 9, 231. C. Wurster, Ber. 1887, 20, 808, 3195; abst. J. C. S. 1887, 52,
620; J. S. C. I. 1887, 6, 565; Chem. Ind. 1888, 11, 90; Chem. Tech. Rep. 1887,
26, I, 188; II, 350; Jahr. Chem. 1887, 40, 2467; Industriblatter, 1887, 119.
E. Siegle, J. prakt. Chem. 1856, 69, 148; Poly. Centr. 1856, 22, 206; Wag.
Jahr. 1856, 2, 226. Roy. Ann. Soc. Linn. Paris. 1826, 219; Jour. f. oeken
Chem. 1, 215. Baer, Physikal. Lexicon, 1859, 6, 849; Wag. Jahr. 1859, 5, 401.
Koemer, Diss. Dresden, 1907; Zts. ang. Chem. 1908, ^ 2353. Gottlieb, J.
prakt. Chem. 1883, (2), 28, 385. Harpf, Pap. Ztg. 1891, 1845. Chudiakow,
Landw. Jahr. 1894, 23, 391. Giltay and Anderson, Jahr. Wiss. Bot. 1894,
26, 643. Hansen, Medd. Carlsberg Labor. 1881, 2. Iwanowsky, Bot.
Centr. 1894, 58, 344. Pederson, Pap. Ztg. 1890, 422.

For data on obtaining ethyl alcohol from sulfite solution as in wood pulp
manufacttu-e, consult, E. Haegglund, Pulp Paper Mag. 15, 1125, 1157; E.
Hendrick, Met. Chem. Eng. 1918; Papers Makers Monthly, 1918, 56, 136;
Paper, 22, No. 4, p. 13. A. White and J. Rue, Paper Makers Monthly, 1917,
55, 109, 146; Met. Chem. Eng. 1917, 9, 182. G. Stlele, Worlds Paper
Trade Rev. 66, No. 25, p. 12. E. Oman, Pap. Fab. 13, 534. V. Krieble,
Paper, 23, No. 23, p. 153; Pulp Paper Mag. 17, 116.

Paper Makers Monthly, 1918. 56, 136, 230, 235, 238, 359. Can. Chem.
J. 2, 211. Paper, 21, No. 17, p. 16, 30; No. 18, p. 13; No. 19, p. 11; No. 20,
p. 15. V. Krieble, Paper, Ann. Conv. No. 1919, 23, 153; abst. J. S. C. 1. 1919, 38,
571-A F. Storer, Bull. Bussey Institution, 1900, 2, (9) ; abst. J. S. C. I. 1901,
20,822. G.Pradel,F. P. 385015, 1907; abst. J. S. C. I. 1908, 27, 516. G.
Mezzadroli, Boll. Chim. Farm. 1918, 57, 360-62; abst. J. S. C. I. 1919, 38,
50-A. F. La Forge, U. S. P. 1288429, 1918; abst. J. S. C. I. 1919, 38, 154-A.
R. Kocher, E. P. 107219, 1916 (appl. No. 7339 of 1916); abst. J. S. C. I.
1917, 36, 973. H. Landmark, First Addn. dated May 20, 1914 to F. P.

198 TECHNOLOGY OF CELLULOSE ESTERS

extensive nature of this pioneer work, but little real progress had
been made toward establishment of the data accumulated upon a
firm commercial manufacturing basis.

The most complete study of the saccharification of cellulose
published up to that time is contained in a series of papers by E.
Simonson in 1898/ who embodied his results in a patent.^ He
worked only on wood cellulose with the objective of the manufac-
tvat of industrial ethyl alcohol,^ and found the most favorable
conditions for the saccharification of 40 gm. of celluose to be a 2
hours digestion at 6-8 atmospheres pressure with 1080 cc. of 0.5%
sulfuric acid, longer digestion causing a serious destruction of
sugar. His results are epitomized in the following two tables,
in which table 10 shows the amounts of (/-glucose formed with sul-
furic acid of varying concentrations after four hours treatment
under the pressures stated:

456871, 1913. Q. S. C. I. 1913, 32, 1063); abst. J. S. C. I. 1915, 34, 488.
Chem.-Ztg. 1915, 39, 98-99; abst. J. S. C. I. 1915, 34, 275. F. P. 456871. 1913;
abst. J. S. C. I. 1913, 32, 1063. T. Norton, U. S. Cons. Reps. Nov. 1911;
abst. J. S. C. I. 1911, 30, 1466. F. Kressmann, J. I. E. C. 1915, 7, 920-923;
abst. J. a C. I. 1915, 34, 1221. J. I. E. C. 1914, 6, 625-630; abst. J. S. C. I.
1914, 33, 1914. Junien, Bull. Assoc. Chim. Sucr. 1914, 31» 500-501; abst.
J. S. C. I. 1914, 33, 213. E. Hagglund. J. prakt. Chem. 1915, 91, 368-364;
abst. J. S. C. I. 1915, 34, 975.

1. Zts. ang. Chem. 1898, 12, 195, 219, 962, 1007; 1903, IB, 572; Pap.
Ztg. 1903, 28, 572, 1787; J. C. S. 1896, 70, i, 331; 1899, 76. i, 471; J. S. C. I.
1898, 17, 365, 481; 1898, 17. 1164; Chem. Centr. 1898, 69, I, 808; II, 144,
1140; Zts. ang. Chem. 19tt3, 16, 572.

2. D. R. P. 92079, 1894; abst. Chem. Centr. 1897, 68, II, 559; Wag. Jahr.
1897, 43, 978. E. P. 10762, 1895; Ber. 1897, 29, 1035; Chem. Centr. 1896,
670; Chem. Ztg. 1896, 20, 887; Pap. Ztg. 1896, 21, 460. Norsk teknisk Tids-
krift, 1895, 65. SeeSwed. P. 28551, 1907. Zts. ang. Chem. 1898, 11, 219; abst.
J. S. C. I. 1898, 17, 365, 481. See also Ann. 1819, 12, 172; Dingl. Poly.
1820, 1, 312; 1827. 25, 81; la'H, 134, 219, 316; 1856, 136, 187; 1855,138, 79,
80, 426; 1859, 151, 394; 1866, 181, 233; 1867, 185, 308; 1889, 273, 276; 1893,
287, 91. Wag. Jahr. 1855, 1, 200, 220; 1856, 2, 225, 242; 1859, 5, 40, 401.
Zts. f. Spirit. Ind. 1883, (7). Lindsay, Inaug. Dissertation, 1891.

3. See "Cellulose as a Polysaccharide," J. Briggs, J. S. C. I. 1909, 28,
340; abst. C. A. 1909, 3, 1589; Bull. Soc. Chim. 1909, (4), 6, 1028; Rep. Chim.
1909, 9, 370; Chem. Zentr. 1909, 80, II, 270; Chem. Ztg. Rep. 1909, 33, 257,
313; Jahr. Chem. 1909, 62, II, 382; Meyer Jahr. Chem. 1909, 19, 217; Zts.
ang. Chem. 1909, 22, 2300. Lassar-Cohn, AUg. Produktenzeit. 8, 1; Chem.
Zentr. 1918, 89, II, 778; C. A. 1919, 13, 3034.

CEtl^ULOSE

199

TABLE XVI.— CELLULOSE TO GLUCOSE.

Pressure in
Atmospheres

Sulfuric Acid

0.15%

0.3%

0.45%

0.6%

1.3

2.1

2.7

4.0

6.0

8.0

9.0

10.0

12.0

14.0

• • • ■

• • • ■

• • • •

■ ■ • •

21.5
30.5

• • • •

35.0
38.4
20.0

2.5
6.6
9.3
16:4
28.0
38.4
43.1
36.6

• • ■ «

• • • ■

2.7

8.6

11.3

■ • • •

30.7
45.0

• • • •

30.0

• • • •

• • • •

3.1
10.6
12.6
20.3
43.9
33.3

• • • •

18.0

■ • • •

• • ■ ■

TABLE XVII .—CELLULOSE TO GLUCOSE (2.7 ATMS. PRESSURE)

Hours

Percentage of Sugar, with Sulfuric Acid of

0.3%

0.45%

0.6%

4
6
8

9.3
11.3
12.6

11.3
13.6
15.3

12.6
15.0
17.4

From the best of his experiments (an exceptional case), he
claims to have obtained 45% of sugar and 44% of residue, which
residue upon fiuther treatment yielded 27% of sugar, but he does
not appear to have corroborated this experiment by duplicating
the work. He was the first to determine the factors which
influence the hydrolysis of cellulose, and these are (a) pressure,
(b) amount of water present, (c) length of time for maximum
sugar formation, and (d) correct acidity. On a semi-manufac-
turing scale he determined the most favorable conditions to be as
follows: The cellulose in the form of fine sawdust is mixed with
0.5% sulfuric acid in the ratio of wood to liquid 1 to 4, and is heated
in an autoclave for 15 minutes at a pressure of 9 atmospheres,
the sugar being then extracted from the residue. The sugar was
not separated as such, but used directly after neutralization for
the production of alcohol by fermentation. Yields of alcohol
equivalent to 25 gallons of absolute alcohol per ton of dry sawdust
are stated to have been obtained. It is usual in the hydrolysis
of cellulose with sulfuric acid on the industrial scale, not to recover

200 TECHNOLOGY OI^ CELLULOSE ESTERS

as such the sugar formed, but to ferment it directly into ethyl
alcohol, the conditions under which the hydrolysis is carried out,
influencing of course, the nature of the sugar formed and the ulti-
mate yield of alcohol obtained.

The results of Simonsen — admittedly the most reliable —
have been called in question by Koemer,^ who has pointed out
that Simonsen's yields of sugar were determined only by the
cupric reducing power of the extracts, which is open to criticism.
Furthermore Simonsen's extracts were not completely fermentable.
Koemer, working along similar lines, obtained a yield of 12-18%
of alcohol from wood cellulose corresponding to (say) 26% of
dextrose. From "hydrocellulose" was obtained 18% alcohol,
but the source of the hydrocellulose is not stated. Simonsen and
Koemer conducted their researches, bearing in mind the utili-
tarian side of the question, and their work therefore, as has been
pointed out by J. Briggs, lacks "the scientific value of a contri-
bution to the theory of the constitution of the cellulose aggregate."
The yield of alcohol theoretically possible from 100 gm. dry cellu-
lose is 56.9 gm. and as under the most favorable conditions not
over 25% of the theoretical quantity has been obtained by the
simple hydrolysis of cellulose, it appears probable that of the
entire cellulose complex, only a portion is capable of hydrolysis
and conversion into fermentable sugar.

Braconnot and many of his successors proceeded by employ-
ing sulfuric acid of such a concentration that its first action in
the cold is one of solution due to esterification. A. Stem^ has

1. Ztg. ang. Chem. 1908, 21, 2353; Pap. Ztg. 1908, 33, 3702; C. A.
1909, 3, 484; J. S. C. I. 1908, 27, 1216; Bull. Soc. Chim. 1908, (4), S, 230; Mon.
vSci. 1909, 70, 326; Chem. Zentr. 1908, 79, II, 2049; Chem. Ztg. Rep. 1909,
32, 692; Jahr. Chem. 1905-1908, II, 179; Meyer Jahr. Chem. 1909, IS, 392;
Wag. Jahr. 1909, 54, II, 339. vSee also L. Roth and W. Gentzen, D. R. P.
147844; abst. Zts. ang. Chem. 1903, IS, 244; Chem. Centr. 1904, 75, I, 410;
Jahr. Chem. 1904, 57, 878; Chem. Ztg. 1904, 2S, 66; Wag. Jahr. 1904, 50,
II, 370; Mon. Sci. 1909, 70, 327. See Aktiebolaget Ethyl, U. S. P. 1042332,
1050723, 1912. F. P. 446717, 446718, 1912; abst. J. S. C. I. 1912, 31, 1075;
1913 32 133 192 377.

*2. *Proc. Chem. Soc. 1894, 186; J. C. S. 1895, S7, 74; abst. J. S. C. I.
1894, 13, 1230; Bull. Soc. Chim. 1896, (3), IS, 1081; Ber. 1895, 28, R, 462;
Jahr. Chem. 1895, 48, 1358; Meyer Jahr. Chem. 1895, 5, 145, 524; Chem.
News, 1894, 70, 267; Chem. Ccntr. 1895, SS, I, 29; Jahr. Chem. 1894, 47,
1132. ProL\ Chem. Soc. 1904, 20, 43; J. C. S. 1904, 85, 336; abst. Chem.
News, 1904. 89, 117; J. S. C. I. 1904, 23, 265; Bull. Soc. Chim. 1904, 32, 1175;
Chem. Centr. 1904, 75, I, 934, 1405; Chem. Ztg. 1904, 28, 246; Jahr. Chem.
1904, 57, 1161. In this connection see Proc. Chem. Soc. 1904, 20, 90; J. C. S.

CElrLUI.OSE 201

pointed out that in this manner the acid-sulfuric esters of a series
of dextrin-like bodies are formed which on prolonged boiling in
presence of dilute sulfuric acid are gradually hydrolyzed to dextrose.
Stem has fractionated these esters and determined the cupric
reducing and specific rotatory power of each fraction, the series
chemically being analogous to the maltodextrin series of starch
products. The "cellulose sulfuric acids*' of Stem are non-re-
ducing bodies, and the yields of barium cellulose sulfates from
which all his deductions were made, never accounted for as much
as half of the original cotton cellulose operated upon. J. Lindsey
and B. Tollens^ isolated 3.5% of crystalline dextrose from wood
cellulose by this method, and Ernest^ obtained about 4% of a
dextrase S3anp from ramie cellulose in the same manner.

G. Eckstrom' records a conversion of 55%-75% of dextrose
by heating the cellulose in an autoclave for 0.5-5 hours at a pressure
of from 3 to 8 atmospheres. In oj3taining alcohol from waste sulfite

1904, 85, 691; abst. Chem. News, 1904, 89, 235; T. S. C. I. 1904, 23, 557;
BuU. Soc. Chim. 1904, 32, 1301; Rep. Chim. 1904, 4, 293; Chem. Centr. 1904,
75, 1, 1557; Jahr. Chem. 1904, 57, 1161. See also M. Hoenig and S. Schubert,
Monats^. 1885, S, 708; 1886, 7. 455; abst. Wein. Akad. Ber. 92, (2 Abth.)
737; Bull. Soc. Chim. 1886, (2), 46, 517; Ber. 1885, IS, 614; Jahr. Chem. 1885,
38, 1576. Braconnot, Ann. Chim. Pnys. 1819, (2), 12, 185. Blondeau de
Carolles, Ann. 1844, 52, 412; J. prakt. Chem. 1844, 33, 439. Fehling, Ann.
1845, 53, 135; Marchand, J. prakt. Chem. 1845, 35, 200. Bechamp, Ann.
1856, 100, 364. AllihnJ. prakt. Chem. 1880, 130, 61.

1. Ann. 1891, 207, 341; Ber. 1892, 25, 322; Zts. ang. Chem. 1892, 5,
154.

' 2. Zts. Zuckerind. 1906, 30, 270; abst. J. S. C. I. 1906, 25, 388; J. C. S.
1906, 90, i, 401; Rep. Chim. 1906, S, 404; Ber. 1906, 39, 1947; Chem. Centr.

1906, 77, I, 1581; Chem. Ztg. 1906, 30, 155; Zts, ang. Chem. 1907, 20, 455;
Jahr. Chem. 1905-1908, II, 958. H. Berger and A. Ernest, Ber. 1907, 40,
4671; abst. Wag. Jahr. 1907, 53, II, 230. See Stora Kopparbergs Bergslags
Aktiebolag, F. P. 402331, 1909; abst. J. S. C. I. 1909, 28, 1221; Wochenbl.
Papierfab. 1909, 40, 4265; Pap. Ztg. 1909, 43, 1682.

3. U. S. P. 970029. E. P. 18341, 1907; abst. J. S. C. I. 1908, 27, 514;
1910, 29, 1173; C. A. 1908, 2, 1642; Chem. Zentr. 1908, 79, I, 784; Chem.
Ztg. Rep. 1908, 32, 42; Wag. Jahr. 1908, 54, II, 326; Zts. ang. Chem. 1908, 21,
1094. F. P. 380358, 1907; abst. J. S. C. I. 1908, 27, 32. Belg. P. 201746,

1907. U. S. P. 1035086, 1042332, 1046160, 1912; 1050723, 1913; 1087356.
1087743, 1087744, 1914; abst. J. S. C. I. 1912, 31, 912, 1075; 1913, 32, 103,
192; 1914, 33, 349. E. P. 6741, 1910; abst. J. S. C. I. 1911, 30, 504. F. P.
402331, 1909; abst. J. S. C. I. 1909, 28, 1221. D. R. P. 193112, 1906; Chem.
Zentr. 1908, 79, I, 784; 1909, I, 1296; Chem. Ztg. Rep. 1908, 32, 42; Jahr.
Chem. 1905-1908, II, 861; 1909, 62, 344; 1910, S3, II, 419; Wag. Jahr. 1908,
54, II, 326; Ztg. ang. Chem. 1908, H, 1094. D. R. P. 207354, 1907; Pap.
Ztg. 1908, 33, 386; 1909, 34, 1682; 1910, 35, 649, 690, 2519; Chem. Ztg. 1909,
32, 182; 1910, 34, 223; Wochenbl. Papierf. 1910, 41, 638; Pap. Fab. 1910, 8,
238, 582; Svensk kemisk. Tidskrift 1909, Pt. 7; Zts. Chem. Ind. KoU. 1908,
3, 47; C. A. 1909, 3, 2070; Chem. Zentr. 1909, 80, I, 1296; Wag. Jahr. 1909,
II, 55, 228; Zts. ang. Chem. 1909, 22, 599.

202 TECHNOLOGY O^ CEl^I<UI.OSE ESTERS

lyes, he^ adds a catalyzer to the liquid before fermentation to
oxidize the liquor, which is then aerated.

H. Ost* and with W. Wilkening* first dissolve the cellulose
in strong sulfuric acid of 65%-72% strength for a few hours at room
temperature to change it into soluble dextrins, which are subse-
quently converted into dextrose by diluting the mixture with
water until it contains 2%-3% H2SO4 and 0.2%-0.5% of cellulose
and boiling for 5-8 hours; or for 2 hours in an autoclave at 120**.
Whereas they compute that theoretically 100 gm. of water-free
cellulose gives 111.1 gm. dextrose; in several instances they actu-
ally obtained 100 gm. Working along similar lines, only hydroly z-
ing with dilute sulfuric acid, R. Willstaetter and L. Zechmeister^
obtamed 56%-83%.

Hydrofluoric acid has been employed in the hydrolysis of
proteins^ and cellulose* (in the form of filter paper), using a lead
vessel to carry out the reaction. It was found that HF up to
30% concentration had but little action, but with acid of 40%-50%

1. Swed. P. 34624, 1912; abst. C. A. 1914, 8. 1669.

2. Ber. 1913, 4S, 2995; abst. J. C. S. 1913, 104, i, 1148; C. A. 1914, 8,
120; J. S. C. I. 1913, 32, 822, 1062; Bull. Soc. Chem. 1914, (4), 16, 95; Chem.
Zentr. 1913, 84, II, 2035; Chem. Ztg. Rep. 1913, 37, 624. For the utilization of
sisal waste in the production of alcohol, see Tropical Life, 1917, 13, 155;
Bull. Agric. Intell. 1918, 9, 988; J. S. C. I. 1918, 37,677-A. Chem. Ztg. 1912,
36, 1099; abst. J. S. C. I. 1912, 31, 713, 980; Chem. Ztg. Rep. 1913, 37, 68.
Ann. 1913, 388, 313; abst. J. S. C. I. 1913, 32, 784; Bull. Soc. Chim. 1913,
(4), 14, 1262. WiUstaetter and Zcchmeister, Ber. 1913, 46, 2401; abst. BuU.
Soc. Chim. 1913, (4), 14, 1354. Ost and Wilkening, Chem. Ztg. 1910, 34,
401; abst. Chem. Zentr. 1910, 81, 1, 2074.

3. Chem. Ztg. 1910, 34, 461; abst. C. A. 1910, 4, 1888; J. S. C. I. 1910,
29, 688; J. C. S. 1910, 98, i, 364; Bull. Soc. Chim. 1911, (4), 18, 61; Chem.
Zentr. 1910, 81, I, 2074; Jahr. Chem. 1910, 63, II, 420; Meyer Jahr. Chem.
1910, 20, 318; Wag. Jahr. 1910, 56, II, 392; Zts. ang. Chem. 1910, 23, R,
1534. See also, Flechsig, Zts. Physiol. Chem. 1883, 7, 913.

4. Ber. 1913, 46, 2401 ; abst. C. A. 1913, 7, 3413; J. C. S. 1913, 184, i,
955; J. S. C. I. 1913, 32, 822; Bull. Soc. Chim. 1913, (4), 14, 1354. Hydro-
chloric acid has been patented for purposes of cellulose hydrolysis as far back
as D. R. P. 11836, 1880; abst. Wag. Jahr. 1881, 27, 818.

5. L. Hugouneng and A. Morel, J. pharm. chim. 1908, 99, 486;
Compt. rend. 1908, 146, 1291; 147, 212; 1909, 148, 236; Bull. Soc. Chim.
1908, (4), 3, 612, 1146; abst. C. A. 1908, 2, 2397; 1909, 3, 662, 1039; J. S. C. I.
1908, 27, 764; Rev. Chim. 1908, 8, 409; Chem. Zentr. 1908, 79, II, 332; Jahr.
Chem. 1905^1908, II. 4498, 4501; Meyer Jahr. Chem. 1908, IB, 236, 239.
See also Compt. rend. 1906, 142, 1426. P. Schuetzenberger, Ann. Chim.
Phys. 1879, (5), 16, 334.

6. J. Ville and W. Mestrezat, Compt. rend. 1910, 150, 783; abst. C.
A. 1910, 4, 2094; J. C. S. 1910, 98, i, 301; J. S. C. I. 1910, 29, 483; Bull.
Soc. Chim. 1910, (4), 7, 362, 1064; Rep. Chim. 1910, 18, 281; Chem. Zentr.
1910, 81, I, 1781; Jahr. Chem. 1910, 63, II, 419; Meyer Jahr. Chem. 1910,
20, 253, 318; J. d'Orlowsky, Belg. P. 226890, 1910.

CEi<lrUi«OSE 203

concentration action is more vigorous, and a rapid destruction
of the cellulose soon sets in, the mixture assuming a brown color.
With 50% acid concentration there is obtained an average of 41
gm. glucose per 100 gm. cellulose, when the process is carried on
for 6 hours. They observe on heating glucose with 50% HF that
the sugar is gradually destroyed and 53.5% of it disappears when
the heating is continued for six hours. This observation may
account for the relatively small yield of glucose obtained in the
hydrolysis of cellulose as compared with the possible theoretical
yield, on the assumption, of course, that the main product of
hydrolysis is glucose.

A. Ernest^ in hydrolyzing various cellulose materials such
as ramie and cellulose from sugar beet, found only dextrose in the
hydrolyzed product. On the other hand, on the assumption
that all the sugar formed is dextrose, the conversion to alcohol
in practice is small, and according to E. Hagglimd,* considerable
amounts of pentoses may be found in the final product.

A. Claessen' has made an exhaustive technical study of this.

1. Zts. Zuckerind. 1906, 30, 270; abst. J. S. C. I. 1906, 25, 388; J. C. S.
1906, 90, i, 401; Rep. Chim. 1909, 6, 404; Ber. 1906, 39, 1947; Chem. Centr.
1906, 77, I, 1581; Ztg. ang. Chem. 1907, 20, 455. See also A. Ernest and H.
Berger, Ber. 1907, 40, 4671; abst. Wag. Jahr. 1907, 53, 11, 230.

2. J. prakt. Chem. 1915, 91, 358; abst. C. A. 1915, 9, 3127; J. C, S. 1915,
100, i, 629; J. S. C. I. 1915, 34, 883; Biol. Chem. Zts. 1915, 09, 181.

3. U. S. P. 700616, 1902; abst. J. S. C. I. 1902, 21, 867; Mon. Sci.
1902, 50, 190. U. S. P. 825808, 1906; abst. J. S. C. I. 1906, 25, 771; Chem.
Zts. 1906, 5, 495; C. A. 1907, 1, 116; Mon. Sci. 1907, 07, 55. U. S. P. 696800,
1902; Re. 12108, 1903; abst. J. C. S. I. 1902, 21, 630; 1903, 22, 706; Mon. Sci.
1902, 50, 190. U. S. P. 654518, 1900; Re. 12069, 1902; abst. J. S. C. I. 1903,
22, 153; Chem. Ztg. 1900, 24, 693; Mon. Sci. 1902, 50, 13. U. S. P. 695795.
1902; abst. J. S. C. I. 1901, 20, 734; 1902, 21, 630; Mon. Sci. 1902, 50, 190.
U. S. P. 707903, 1902; abst. J. S. C. I. 1902, H, 1190; Mon. Sci. 1903. 59,
111. U. S. P. 1101061, 1914; abst. J.S. C. I. 1914,33, 761. E. P. 258,259,
1900; abst. J. S. C. I. 1900, 19, 364, 1028. E. P. 4199. 1901 ; abst. J. S. C. I.
1901, 20, 734. E. P. 12588. 1901; abst. J. S. C. I. 1901, 20, 1008. E. P.
22709, 1905; abst. J. S. C. I. 1906, 25, 898. F. P. 365595, 1906; abst. C. A.
1907, 1, 2429; J. S. C. I. 1906, 25, 1000; Mon. Sci. 1907, 07, 99. F. P. 295847;
abst. J. S. C. I. 1901, 20, 1008; 1902, 21, 358; Mon. Sci. 1901. 57, 41. F. P.
448496. 1912; abst. J. S. C. I. 1913, 32, 441. D. R. P. 111868, 1899; abst.
Wag. Jahr. 1900, II, 288; Chem, Centr. 1900, II, 608; Chem. Ztg. 1900, 24,
524;Zts.ang.Chem. 1900, 13, 651; Jahr. Chem. 1900,53,809. D. R. P. 118540,
1900; Wag. Jahr. 1901, II, 280; Chem. Ztg. 1901, 25, 252; Zts. ang. Chem. 1901,
14, 348; Jahr. Chem. 1901, 54, 844. D. R. P. 118542, 1900; Wag. Jahr. 1901,
II, 281; Chem. Centr. 1901,1, 716; Chem. Ztg. 1901,25,249; Zts. ang. Chem.
1901, 14, 348. D. R. P. 118543, 1900; Wag. Jahr. 1901, II, 282; Chem. Centr.
1901, 1, 716; Chem. Ztg. 1901, 25, 249; Zts. ang. Chem. 1901, 14, 349. D. R. P.
118544, 1900; Wag. Jahr. 1901, II, 282; Chem. Centr. 1901, 72,1, 716; Chem.
Ztg. 1901, 25, 249; Zts. ang. Chem. 1901, 14, 349; Jahr. Chem. 1901, 54, 844.
D. R. P. 121869, 1900; Wag. Jahr. 1901. II. 282; Chem. Ztg. 1901, 25, 571;

204 TECHNOI.OGY O^ CEl<I*UWSE BSt^RS

problem, employing, in general, sulfur dioxide in the gaseous or
liquid state as the hydrolyzing material. He uses also a mixture
of 0.2% H2SO4 with 20% SO2 dissolved in water. The reaction
is carried out in a current of air and the material heated to a temp-
erature of 120°-145° for one hour at a pressure of 6-7 atmospheres.
When this process was attempted on an industrial scale many
were the difficulties which were encountered, but it is of particular
interest since it was the beginning of this industry in the United
States for the production of ethyl alcohol from wood. In 1903
the United States patent rights for the Ckiessen process were
acquired by a firm in Chicago, Illinois, and after experimentally
demonstrating this process to its satisfaction, erected a plant at
Hattiesburg, Miss, at a cost of about $250,000 to operate on
long-leaf pine saw mill waste. This plant was substantially a
failure because of the number of mechanical and technical diffi-r
culties, the chief of which were as follows:* (a) the length of time
necessary to hydrolyze the wood was found to be 4-6 hours; (b)
the large quantity of acid needed; (c) the action of the acid and
water in the rotatingdigesterreduced the wood to a very fine powder,
and formed much sulfuric acid which acted upon the sugar and
other substances present to form gums and caramels, and so made
the complete extraction of the sugar from the residue both unduly
tedious and expensive; (d) the digester was lead lined, and the
buckling and breaking of the lining necessitated repairs after every
two or three "cooks," which proved a great source of delay and
expense. A. Claessen* found technical difficulties in dealing with
cellulose materials containing tannic and gallic acids, such as oak,
chestnut, and in a lesser degree the poplar and beech. Gallic
acid appears to be always formed on hydrolysis of these woods,
which materially interferes during the subsequent fermentation
of the sugars. The trouble was finally overcome by the addition

Zts. ang. Chem. 1901, 14, 788. D. R. P. 123911. 1900; Wag. Jahr. 1901, II,
283; Chem. Centr. 1901, 72, II, 1032; Chem. Ztg. 1901, 2S, 940; Zts. ang.
Chem. 1901, 14, 1144. D. R. P. 161644; abst. J. S. C. I. 1905, 24, 1078;
Wag. Jahr. 1905, II, 338; Chem. Centr. 1905, 7S, II, 660; Chem. Ztg.
1905, 29, 772; Zts. ang. Chem. 1905, IS, 1567. Zts. Verein Zuckerind, 1900,
589; 1901, 348, 351, 754; 1907, 57, 206, 525; abst. Meyer Jahr. Chem. 1907,
17, 375, 376. Can. P. 77979, 81207, 84014. Belg. P. 139919, 1898; 142335,
1899.

1. Chem. Trade J. & Chem. Engr. 1918, 63, 231.

2. U. S. P. 825808, 1906; abst. J. S. C. I. 1906, 25, 771; C. A. 1907, 1,
16; Mon. Sci. 1907, 67, 55.

of a ferric salt to the liquid after hydrolysis. In the French
modification of the Claesseii process,^ the by-products are said
to have value as a cattle food.

M. Ewen and G. Tomlinson* who were associated with the
Claessen process, began experimenting along new lines in order
to remedy the defects of the. Hattiesburg plant. Instead of
using an aqueous solution of sulfur dioxide, they passed the gas
into the digester along with steam, which furnished therefore,
both the heat and moisture required. Somewhat later however,
Ewen and Tomlinson abandoned the use of SO2 and were granted
a patent' covering the use of sulfuric acid as the catalytic agent.
This patent and the process patented by E. Simonson* disclose a*

1. F. P. 365595, 1906, abst. C. A. 1907, 1, 2429; J. S. C. I. 1906, 25,
1000; Mon. Sci. 1909, 67, 99.

2. U.S. P. 763472, 1904 ; abst. J. S. C. 1. 1904, 23, 797. Belg. P. 220462,
1909. F. P. 343006, 1904, abst. J. S. C. I. 1904, 23, 797, 994. E. P. 30072.
30073, 1912; abst. J. S. C. I. 1914, 33, 132, 156. U. S. P. 1032440 to 1032450,
1912; abst. J. S. C. I. 1912, 31, 832, 833. U. S. P. 938308, 1909; abst. Chem.
Ztg. Rep. 1909, 659; Zts. ang. Chem. 1909, 22, 2462; Pap. Ztg. 1910, 35,
262; J. S. C. I. 1910, 29, 38; C. A. 1910, 4, 381. U. S. P. 1032391, 1032392,
1912; abst. J. S. C. I. 1912, 31, 762, 832; C. A. 1912, S, 2863. F. P. 408229,
1909; abst. J. S. C. I. 1910, 29, 586. G. Tomlinson, ''Wood Waste as a Source
of Ethyl Alcohol," Chem. and Met. Eng. 1918, 19, 552; J. S. C. I. 1918, 37,
71 1-A ; 274-R. Orljavacer Chemische Fabrik, F. P. 357432, 1905; abst. J. S. C.

I. 1906, 25. 117. J. d'Orlowski, F. P. 405187, 1909; abst. J. S. C. I. 1910,
29, 230. F. P. 343006, 1904; abst. J, S. C. 1. 1904, 23, 994. E. P. 10664, 1904;
abst. J. S. C. 1. 1905, 24, 808. R. McKee, U. S. P. 1273392, 1284739, 1284740;
1918; abst. J. S. C. I. 1918. 37, 600-A; 1919, 3S, 71-A. E. P. 120520, 1918;
abst. J. S. C. I. 1918, 37, 780-A. Paper, 1919, 24, 584; abst. C. A. 1919. 13,
1927. E. P. 24589, 1909; abst. J. S. C. I. 1910, 29, 710. G. Foth (Chem.
Ztg. 1913, 37, 1145, 1221. 1297; Zts. Spirit. Ind. 1913, 36, 161, 485, 497,
595; Deut. Essigind. 17, 481; abst. C. A. 1914, 8, 1343; Chem. Zentr. 1913,
84, Ilrl831; Wag. Jahr. 1913, 59, II, 431; Zts. ang. Chem. 1913, 2$, I, 519;

II, 432), found 0.5% by weight of fusel oil in alcohol by this process, with
oidy traces of methyl alcohol and no acetone. For the preparation of xylose
from com cobs, see C. Hudson and T. Hardifig, J. Am. Chem. Soc. 1917,
39, 1038; 1918, 40, 1601; abst. J. S. C. I. 1917, 36, 730; 1918, 37, 778-A.
B. LaForge and C. Hudson. J. Ind. Eng. Chem. 1918, 10, 925; J. S. C. I.
1919, 38, 86-A. K. Munroe, J. Am. Chem. Soc. 1919, 41, 1002; abst.
J. S. C. I. 1919, 38, 550-A; C. A. 1919, 13, 2036. For production of alcohol
from peat, refer to G. Pradel, E. P. 5128, 1907; J. S. C. I. 1908, 27, 416.

3/ U. S. P. 938308, 1909; abst. J. S. C. I. 1910, 29, 38; Mon. Sci. 1910,
73, 87. F. P. 408299. 1909; abst. J. S. C. I. 1910, 29, 586. Can. P. 146794,
1913; abst. C. A. 1913, 7, 2137.

4. D. R. P. 92079, 1894; abst. Chem. Centr. 1897, 68, II, 559; Wag.
Jahr. 1897, 43, 543, 978. In the T. Wagner process (U. S. P. 1261328, 1918;
abst. J. S. C. I. 1918, 37, 410A,) the fermented sugar-containing liquor resulting
from the hydrolysis of cellulosic material is concentrated, after the distillation
of the alcohol, the concentrated product containing more than 30% of reducing
sugars (calculated as dextrose) and approximately 25%-35% of water.

See R. Ruttan, J. S. C. I. 1909, 28, 1290; abst. C. A. 1910, 4, 637; Chem.
Zentr. 1910, 81, I, 1393; Zts. ang. Chem. 1910, 23, 860; Jahr. Chem. 1909,

206 TECHNOLOGY OF CELLUU>SE ESTERS

rexnarkable identity as to ideas. They erected a plant at George-
town, South Carolina for the demonstration of their process,
which plant was later acquired by a powder company, and has
been intermittently operated up to the present time.^

On an industrial scale, cellulose in the form of sawdust may
be converted first to sugar and finally to alcohol in the following
manner. Sawdust from several sawmills is brought by the aid

62, 99; Wag. Jahr. 1909, 55, II. 368; Chem. Ztg. Rep. 1909. 33, 59. Comp.
Industrielle des Alcools de I'Ardeche, F. P. 391057, 1908; E. P. 26619. 1908;
abst. J. S. C. 1. 1908, 27, 1 126; 1909. 28, 998. F. P. 358696. 1905; abst. J. S. C. I.
1906. 25, 277. F. Gallagher and I. Pearl. Eighth Intl. Cong. Appl. Chem.
1912. 13, 147; J. S. C. I. 1912. U, 870. H. Fenton, J. S. C. I. 1901, 2t, 757.
J. Teeple, J. Ind. Eng. Chem. 1913. 5, 680; abst. C. A. 1914. 8, 1665. R.
BfLuers and B. ToUens, Ber. 1903. 36, 3306; abst. Chem. Centr. 1903, 84,
II, 1167; J. C. S. 1904. 8S, i. 16; J. S. C. I. 1903, 22, 1151; Bull. Soc. Chim.
1904. (3). 32, 1104; Jahr. Chem. 1903. 58, 1011. R. Hauers, Dissertation,
Gottingen 1902. J. Koenig, D. R. P. 265483; abst. Chem. Zentr. 1913, 84,
II. 1535; Chem. Ztg. Rep. 1913, 37, 587; Wag. Jahr. 1913, 59, II, 348; Zts.
ang. Chem. 1913, 28, 653. E. P. 8006, 1914; abst. J. S. C. I. 1915, 34, 901;
C. A. 1916, 18, 75. V. Omelianski (Compt. rend. 1897,125, 1131; Arch, des
Sc. biolog. 1900. 7, 411; Chem. Centr. 1900, 71, I, 918) in studying the prod-
ucts of the fermentation of cellulose, fermented pure paper in the presence of
calcium carbonate at a temperature of about 35** for 13 months. The prod-
ucts obtained from 3.473 gm. of paper were: acetic series of acids, 2.24 gm.;
COj, 972 gm.; and hydrogen, 0.014 gm. The acids were chiefly acetic and
butyric, with small quantities of valeric. Higher alcohols- and odoriferous
products were also formed but not isolated. No methane was detected.

1. Several years ago western capital erected a plant at Port Hadlock,
Washington, on Puget Sound, for the production of ethyl alcohol and cattle
food from sawdust obtained from mills at Seattle, Tacoma, Everett, Anacortes,
and Port Blakeley. The plant was equipped with 6 digesters of the same size
and type as those that were developed in France by the Compagnie Indus-
trielle des Alcohols de I'Ardeche. These digesters consist of steel cylinders,
2V2 m. in internal diam. by 2V» m. in length, through which are placed 22
tubes, 160 mm. in diam. The outside of each of a tube head has a flanged
boiler steel jacket, one to receive the live steam from the boiler and the other
to take off the condensed steam, the heating being indirect, the idea being to
save steam by means of the indirect heating. Sawdust and enough water
are added through a manhole into the space between the tubes to raise the
moisture content to about 45%. Anhydrous sulfiu- dioxide was then added,
and the mixture was cooked at 75-100 lbs. pressure. The cost of conversion
was excessive because of the very rapid corrosion of the digesters, the long
time necessary to heat indirectly, and because the sulfurous acid gas leaked
from the digester into the stream space, thereby preventing the use of the
low pressiu-e steam. In addition, the extraction equipment was inefficient
and out of date, though the buildings of the plant were excellent and expen-
sive, and much of the equipment was imported from France at a large cost.

The extracted sawdust—which had only from 50%-60% of the sugar
formed extracted from it — was mixed with Hawaiian molasses, and was put
on the market as a cattle food. It was necessary to dry the extracted material
down to about 12% moisture in order to prevent decay, and this caused trouble
because of explosions of dust in the driers. In addition, the plant was situa-
ted about 80 miles from a railway, which greatly increased transportation
charges. These facts coupled with the very poor design and equipment —

CEI.I.UI.OSE 207

of belts to a central factory, and is there distributed between
several digesters in which the acid hydrolysis is to be carried out.
These digesters are of a spherical shape 12 feet in diameter, with
steel plate construction and lined with a special acid-resisting
brick. After the digester has been charged with sawdust, sul-
furic acid is added until the acid constitutes about 0.5% to l%on
the wood, calculating on the dry weight. The vessel is then

especially digester and extraction equipment — ^were no doubt the prime
reasons which caused the failure of this plant.

" The alcohol company subsequently disposed of the Georgetown plant,
and the company was reorganized, a considerable amount of foreign capital
being introduced. A large plant for the production of 5,000 gallons of ethyl
alcohol per day was erected at Fullerton. At this plant from 25%-28% of the
anhydrous wood is rendered soluble, and of this amount 80% can be converted
into fermentable sugar, though to accomplish this requires most careful
control. It is hkely that a greater percentage will be obtained by the use of
dilute acids. For the present, therefore, a conversion yielding 20%-22% of
fermentable sugars, or from 10%-11 % of ethyl alcohol corresponding to a max-
imum of, say, 36 gallons of 96% alcohol per dry ton, represents the immediate
goal. On a large scale the actual average yields have hardly exceeded half
of this amount, so that there is a wide margin for improvement.

An excellent description of the process and of the plant employed is
given in a paper on "By-Products of the Lumber Industry," issued by the
U. S. Dept. of Commerce, from which the following details are taken. The
sawdust is conveyed on a belt from several sawmills to the alcohol plant, and
lifted into storage bins by means of an elevator. From the storage bin it is
distributed to four digestors as required for charging. These digesters are
of spherical shape, 12 ft. in diam. They are of steel-plate construction and
are lined with acid proof brick. After a digester is charged with sawdust,
diluted sulfuric acid is added until it constitutes about 0.6%-!% of the weight
of the dried wood. The digestion is then slowly rotated by means of a worm
gear by direct steam. The pressure gradually rises to 120 lbs. and a maximum
temperature of 336° F. is reached. The total time of digestion, including
charging, heating up, cooking, blow-off, and discharge, is about one hour.

After complete digestion the digester is discharged, and the wood, now
known as "hydrolyzed" wood, is carried by belt conveyors to the diffusion
batteries, in which the soluble constituents of the mass are extracted with hot
water, in the same manner as in tannin-extract manufacture and in sugar
extraction. The product of the digester contains more water than the raw
material — which often contains 60% water — owing to the addition of the
dilute sulfuric acid and to the condensation of steam used for the heating.
After extraction the washed residue, consisting of tmchanged sawdust, is
conveyed to compressors, where the water contained is reduced to about
55%. It is afterwards burnt as fuel, and is sufficient for the generation of
all the steam and power required in the plant.

The Uquor from the diffusion battery, known as wood liquor, contains
sulfuric acid, sugar, and other organic compounds, and is next hydrolyzed with
milk of lime in tanks fitted with agitators. It then flows into a storage tank.
It is fiuther clarified by decantation, and after cooling is pumped into the
fermenting vats. Yeast grown in wood liquor is added, after which fermen-
tation proceeds. The fermented liquor is then distilled in stills for the pro-
duction of rectified alcohol. The alcohol thus produced is of a high grade,
and is reported to contain only traces of fusel oil, esters, and ethers. When
properly piuified, it differs in no respect from the ordinary grain alcohol.

208 TOCHNOI<OGY Ot CELLXJlvOSE ESTERS

slowly rotated by means of a worm-gear while steam is used for
heating, the maximum temperature reached being 120°. The
time of charging, heating up, cooking, blowing off and dischar-
ing is about one hour. After the hydrolysis, the acid liquor con-
taining the sugar, is passed through diffusion batteries in order to
remove unchanged wood and to separate the soluble portion.
The insoluble residue of practically unchanged sawdust is conveyed
to hydraulic presses where its water content is reduced to 55%
by pressure alone. The mother liquor from the diffusion batteries
is neutralized with lime in tanks fitted with stirrers, it is further
clarified by decantation and after cooling is pumped into fer-
mentation vessels. Yeast which has grown in wood liquor is
added, and the fermentation allowed to proceed. The fermented
liquor is finally distilled in column-stills for the production of
concentrated alcohol.

A. de Posnansky and L. Spassky^ first ptuify their cellulose
material before attempting hydrolysis, and extract the material
with dilute alkaline solution to remove resins and tannins. Next,
in order to remove lignin, they heat with a dilute solution of calcium
bisulfite for two hours and follow this by an acid treatment.
The purified material is hydrolyzed with a dilute solution of
hydrochloric, sulfuric or hydrofluoric acids, saccharification

At the Fiillerton plant it was estimated in 1913 that if a monthly capacity of
100,000 gallons had been reached, the cost would not have exceeded 21 cents
per gallon, as against 30 cents, the cost of grain alcohol at American distil-
leries in 1913. But since the summer of 1916 the plant has been running
i continuously, taking advantage of the high prices ruling.

The quality of the product at FuUerton was reported upon as one of the

purest cologne spirits that had come under the observation of the analyst.

I If the cost of production should be higher than in 1913, then the fact that

I alcohol from either grain or molasses is more than double the price of that

year, would still leave the advantage in favor of the product from wood waste.

As the sugars used in wood alcohol can be used for feeding animals, as is done

with cane molasses, there would seem to be great possibilities here. In the

I same paper a short account is also given of the manufacture of alcohol from

I sulfite liquor, in which similar reactions take place as those already described.

This process has been introduced on a large scale in Sweden, and at three
paper mills in that country about a million and a quarter gallons of alcohol are
obtained per annum from sulfite liquor, and the process is also being worked
in the United States.

1. L. Spassky, F. P. 451268, 1913; abst. J. S. C. I. 1913, 32, 620;
C. A. 1913, 7, 3187; Mon. Sci. 1914, 81, 42. A. de Posnansky and L. Spassky,
F. P. 459593, 1912; abst. J. S. C. I. 1913, 32, 1167; C. A. 1914, 8, 2637. Swiss
P. 61410, 1912; 63563, 1913; abst. C. A. 1914, 8, 2276. A. de Posnansky, F. P.
464502, 468188; 473925, 1913; abst. J. S. C. I. 1914, 33, 497, 978; 1915, 34,
729; C. A. 1914, 8^ 3215.

1

CELLUW)Se 209

being complete after three hours. The alkaline and bisulfite
treatments as well as the acid hydrolysis are all carried out at
140°. The volatile acids present are removed by distillation tmder
reduced pressure, the residual sugar solution being finally neu-
tralized and extracted with alcohol.

F. Gallagher^ in hydrolyzing sawdust distils off any vola-
tile products present such as turpentine, in the first stages of the
heating. He also allows the volatile products formed during the
hydrolysis to escape continuously, or intermittently, while main-
taining the pressure. He claims to obtain by this procedure a
greater yield of sugar and a liquid more suitable for the fermen-
tation process.

The bisulfite treatment referred to above for removal of
lignin and other compounds, gives a liquor containing small
quantities of sugar. In the preparation of wood pulp for paper
manufacture, an enormous quantity of these waste sulfite liquors
are formed and many schemes have been suggested for their
utilization.'

■

A •preliminary treatment of crude cellulose materials by
means of chlorine has been suggested.' The cellulose, without
washing, is digested with 1% of its weight of sulfuric acid for
30 minutes under a pressure of 9 kilograms. It has also been sug-
gested in the case of straw* to heat under pressure with water.
The solution obtained is employed for the extraction of a second
quantity of straw. Each portion is extracted twice under pres-

1. U. S. P. 1056161. 1913; 1091327. 1914; abst. J. S. C. I. 1913. 32,
441; 1914, 33, 497. F. GaDagher and H. Mork, U. S. P. 1037185. 1056162,
1056163, 1913. E. P. 400, 14939. 1913; abst. J. S. C. I. 1913, 33, 441, 1166;
1914, 33, 801; C. A. 1912, S, 3340. F. Gallagher and H. Mork, U. S. P.
1033064, 1912; abst. J. S. C. I. 1912, 31, 833. E. Gazagne and R. Demuth,
F. P. 477077, 1914; abst. J. S. C. I. 1916, 35, 613.

2. H. Landmark, Chem. Ztg. 1915, 39, 98; abst. J. S. C. I. 1915, 34,
275. A. Frohberg, Wochenbl. Papier-Fabr. 1913, 44, 4432; abst. J. S. C. I.
1913, 32, 1152. J. Koenig, J. Hasenbaeumer and M. Braun, Zts. ang.
Chem. 1913, 2$, 481; abst. J. S. C. I. 1913, 32, 939. Holzverkohlungs Indus-
trie A. G. Belg. P. 254945, 256353, 1913.

3. Standard Alcohol Co. U. S. P. 1032443, 1032444, 1032449, 1032450,
1033064, 1912; 1056162, 1913; 1096030, 1914; abst. Mon. Sci. 1914, 81, 139.
F. P. 452920, 462921. 453129, 460085, 1913; abst. J. S. C. I. 1912, 31, 833;
1913, 32, 441. 761, 833; 1914, 33, 37; C. A. 1914, 8, 3215. D. R. P. 279991,
1913; abst. C. A. 1915,9,2124. Aust. P. 71273, 1916; abst. C. A. 1916, 10,
2497. Swed. P. 41072, 1916; abst. C. A. 1916, 10, 2612. Norw. P. 27188, 1916;
abst. C. A. 1916, 10, 3172.

4. W. GUes and F. Norris, U. S. P. 918997, 1909; abst. J. S. C. I. 1909.
20, 638; C. A. 1909, 2, 1795; Mon. Sci. 1909, 71, 142.

210 TECHNOLOGY OF CELLUlrOSE ESTERS

sure, first with a solution from a previous extraction, and secondly
with water. The united solutions are acidified, and when sac-

«

charification is complete, are neutralized and fermented.

An important advance was made by R. Willstaetter and
L. Zechmeister^ in 1913. They found that fuming hydrochloric
acid of a specific gravity of 1.209-1.212 at 15 °C., (containing
41% concentration of acid) was capable of hydrolyzing cellulose
in the cold. One part of cellulose in the form of cotton was added
to seven parts of concentrated hydrochloric acid. In a very short
period the cotton had dissolved. When water was added to the
solution after it had stood for a short period, the cellulose was
precipitated quantitatively. If however, the concentrated solu-
tion of the cellulose be allowed to stand for two days and then
diluted, no cellulose is precipitated, but instead an optically
active solution is obtained. The solution, moreover, has strong
reducing properties when tested with Fehling's solution. It is
claimed dextrose is formed to the extent of 95%-96% of the possible
theoretical conversion. The concentrated hydrochloric acid
solution containing the dissolved cellulose is optically inaotive at
first, but after an hour, a slight rotation is observable. The
rotatory power then gradually increases and becomes constant
at the end of 24-48 hours, the actual number of hours depending
on the concentration of the hydrochloric acid. The rotation
figure does not increase regularly from zero to its maximum, but
rises for the first few hours, then remains practically constant for
a short period and finally increases again until the maximum is
reached. These changes are interpreted on the assumption
that an intermediate compound is formed at an early stage dimng
the hydrolysis.

According to these workers, cellulose in other forms such as
filter paper, or pine wood, may also be hydrolyzed by very concen-
trated hydrochloric acid (specific gravity 1.2). In the case of
pine wood a 30% residue of lignin substances is obtained. Con-
centrated hydriodic . acid is less reactive, and with the latter
heating is necessary in order to dissolve the cellulose. Hydro-
bromic acid (specific gravity 1.78), concentration (66%), behaves

1. Ber. 1913, 46, 2401; abst. J. S. C. I. 1913, 32, 822; J. C. S. 1913.
104, i, 955; C. A. 1913, 7, 3413; Bull. Soc. Chim. 1913, (4), 14, 1354; Chem.
Zentr. 1913, 84, II, 1209.

CKlrLXJI.OSE 211

in a manner similar to hydrochloric acid (41%), the hydrobromic
acid dissolving the cellulose even at 0°. With hydrofluoric acid
of 70%-75% strength a similar action takes place.

In view of R. Willstaetter and L. Zechmeister's work con-
cerning the action of concentrated hydrochloric acid on cellu-
lose in the cold, it is of interest to refer to H. Fenton's experi-
ments* in which he treats cellulose (Swedish filter paper — 50
gm.) with dry hydrogen chloride dissolved in an inert solvent
(carbon tetrachloride). He obtains 3.1 gm. of chloromethyl-
furfuraland 1.57 gm. of dextrose. According to Fenton the two
latter compounds are probably produced in equa-molecular pro-
portions initially, but part of the dextrose formed is destroyed
during the heating. Similar reactions take place with hydrogen
bromide. The formation of these halogen derivatives point to
the presence of a ketohexose nucleus or grouping in the cellulose
complex.

R. Willstaetter and L. Zechmeister, in their hydrolysis with
concentrated hydrochloric acid, identified their products solely
by means of optical activity determinations and copper reduction
figures. They did not, however, prove the quantitative yield to
dextrose by actual isolation of the dextrose or a derivative of the
sugar. H. Ost,* regards their results, especially with the higher
concentrations of cellulose, as improbable. According to M.
Cunningham' the products of hydrolysis of cellulose are not iden-
tified by the rotation constants of the hydrolyzed solution, and
in support of this view adduces the following reasons. Widely
different t)rpes of cellulose such as cotton and esparto-cellulose
give identical optical rotation data on hydrolysis, but the ultimate
products necessarily have divergent constituents. In addition,
it is known that concentrated hydrochloric acid produces con-
stitutional changes even in the simple hexoses — large fluctuations
in optical activity accompanying slight variation in the strength

1. Proc. Chem. Soc. 1901, 17, 166; abst. J. S. C. I. 1901. 2t, 757; Chem.
News, 1901, 84, 7; Rep. Chira. 1901, 1, 515; Chem. Centr. 1901, 72, II, 405;
Chem. Ztg. 1901, 2S, 591; Jahr. Chem. 1901. 54, SAO.

2. Ber. 1913, 46, 2995; abst. J. C. S. 1913, 104. i, 1148; C. A. 1914,
8, 120; J. S. C. I. 1913, 32, 1062; Bull. Soc. Chim. 1914, (4), Ifi, 95; Chem.
Zentr. 1913, 84, II, 2035; Chem. Ztg. Rep. 1913, 37, 624. Chem. Ztg. 1912,
3S, 1099; abst. J. S. C. I. 1912, 31, 713, 980; Ann. 1913, 398, 313; J. S. C. I.
1913, 32, 784.

3. J. C. S. 1918, 113, 173; abst. C. A. 1918, 12, 1379; J. S. C. I. 1918,
37, 236-A; Ann. Rep. Soc. Chem. Ind. 1918, 3, 127, 149.

212

tECHNOU)GY O^ CElrLUW)SE EStERS

of acid. Cellulose under the action of concentrated hydrochloric
acid forms esters of polysaccharoses containing acidic hydroxyl
groups. Cunningham failed to isolate dextrose from the solution.

F. Gallagher and I. PearP have made a series of experi-
ments on the hydrolysis of sawdust from long-leaf pine wood
screened through a 10-mesh sieve. The proportion of sulftuic
acid used was 1 f>er cent, of the dry weight of wood, the proportion
of liquor was 3:1, the maximum pressure was 135 lb. per sq. in.,
maintained for 30 minutes, and the total duration of the treatment
was about 70 minutes. The digested material was extracted
with water, evaporated to a density of 1.045 and fermented.
Subsequent hydrol)rsis of the residue gave a fiuther yield of fer-
mentable sugars. The following table illustrates some of the

results obtained:

TABLE VII.— HYDROLYSIS OF PINE WOOD

Material

Total
Ex-
tract

Re-
ducing

Ma-
terial

Fer-
mentable
Sugars

Ratio of
Ferment-
able
Sugars to

total
Extract

Cellulose

Before' After
Diges- Diges-
tion tion

1

a. Long leaf pine sawdust. . .

b. Residue from (a)

c. Residue from (b)

d. Bleached cotton

Per

cent.

22.0

6.3

2.8

3.1

4.5

17.7

7.5

Per

cent.

19.3

4.7

1.7

1.6

2.8

16.0

4.3

Per
cent.
11.8
3.0
1.6
1.4
2.5
6.3
3.8

Per
cent.
0.53
0.47
0.67
0.44
0.55
0.36
0 51

Per Per
cent. cent.
54.0 52.0
52.0 42.0

e. Residue from (d)

f . Bleached soda wood pulp .

g. Residue from (f)

Other investigators who have contributed to this subject
include Mitscherlich,* Neumann,^ Voerkelius,* G. Foth,* R. v.

1. Eighth Intl. Cong. Appl. Chem. 1912, 13, 147; abst. J. S. C. I. 1912,
31, 870, C. A. 1912, 6, 3013.

2. D. R.P. 72161; abst. Mon. Sci. 1905, 63, 823; Ber. 1894, 27, 149;
Wag. Jahr. 1893, 39, 1063; Zts. ang. Chem. 1893, S, 732. U. S. P. 284319.
1883

3. "Critical Study of the Hydrolysis of Cellulose from Wood." Diss.
Dresden, 1910.

4. Wochenbl. Papierfabr. 1911, 42, 854; abst. C. A. 1911, 5, 2942;
Chem. Ztg. Rep. 1911, 35, 852.

5. Chem. Ztg. 1913, 37, 1145, 1221, 1297; abst. C. A. 1914, 8, 1343;
Chem. Zentr. 1913, 84, II, 1831; Wag. Jahr. 1913, 59, II. 431; Zts. ang. Chem.
1913, 2$, I, 519; II, 432; Zts. Spirit. Ind. 1913, 36, 161, 485, 497, 595; Deut.
Essigind. 17, 481.

CBLI^ULOSB 213

Demuth,^ C. Schwalbe and W. Schulz,* Societe anonyme **Origo",'
H. Wallin/ W. Cohoe,'^ T. Koeraer/ F. Zimmer,^ H. Ruediger,*
W. Gentzen and L. Roth,® and G. Zemplen.^"

Patent protection for carrying these ideas into eflfect, have
been granted to E. Bouchard-Praceiq,^^ A. Boemen,^^ H. Berg-
strom/3 E. Tillberg," and others."

Cellulose Hydrates. Alkali Cellulose. The action of alkalis
on cellulose is much diflferent from that of acids. Whereas the
milder alkalis such as soap, borax, and sodium phosphate have no
action upon cellulose, nor has ammonia under ordinary circum-

1. Zts. ang. Chem. 1913, Ifi, 786; abst. C. A. 1914, 8, 1343; Chem.
Zentr. 1914, 85, 1, 924; Wag. Jahr. 1913, 59, II, 432.

2. Ber. 1910. 43, 916; abst. J. C. S. 1910, 38, i, 301; C. A. 1910, 4,
1751; J. S. C. I. 1910, 29, 688; Chem. Zentr. 1910, 81, I, 1781; Jahr. Chem.
1910,83,II,419;MeyerJahr. Chem. 1910,28,253; Zts. ang. Chem. 1910, 23,
1244.

3. D. R. P. 204058; abst. J. S. C. I. 1909, 28, 35; Chem. Zentr. 1903,
79, II, 1900; Chem. Ztg. Rep. 1908, 32, 671; Jahr. Chem. 190^1908, II, 179;
Wag. Jahr. 1908, 54, II, 327; C. A. 1909, 3, 686.

4. Swed. P. 26825, 1907; Norw. P. 18687, 1908; Chem. Ztg. Rep. 1919,
251;Pap.Fab. 1910,8,311; Pap. Ztg. 1910,35,669,649,690, 1110, 1387,2118.

5. J. S. C. I. 1912, 31, 513; abst, C. A. 1912, S, 3329; Chem. Zentr.
1912, 83, II, 1074; Chem. Ztg. Rep. 1912, 36, 485.

6. Zts. ang. Chem. 1908, 21, 2353; Sci. Amer. 1909, 67, 238; Pap.
Ztg. 1908, 33, 3707; C. A. 1909, 3, 484; J. S. C. I. 1908, 27, 1216; BuU. Soc.
Chim. 1908, (4), 6, 230; Mon. Sci. 1909, 70, 326; Chem. Zentr. 1908, 79, II,
2049; Chem. Ztg. Rep. 1909, 32, 692; Jahr. Chem. 1905-1908, II, 179; Meyer
Jahr. Chem. 1908, IS, 392; Wag. Jahr. 1909, 54, II, 339.

7. Mitteil. d. landw. Inst. kgl. Univ. Breslau, 1902, 2, 245.

8. Chem. Ind. 1905, 28, 547; abst. Chem. Centr. 1905, 76, II, 1697.

9. D. R. P. 147844, 1901; abst. Mon. Sci. 1905, 63, 71; 1909, 71,
327; Chem. Centr. 1904, 75, I, 410; Chem. Ztg. 1904, 28, 66; Jahr. Chem.
1904, 57, 878; Wag. Jahr. 1904, 50, II, 370; Zts. ang. Chem. 1903, 16, 244.

10. "Sugar and Alcohol from Wood," Budapest, 1910.

11. F. P. 393336; abst. J. S. C. I. 1909, 28, 103; Meyer Jahr. Chem.
1909, 19, 420; Zts. Spiritsmd. 32, 237.

12. Zts. ang. Chem. 1908, 21, 2355; E. P. 16262, 1904; abst. J. S. C. I.
1905, 24, 808; Chem. Ztg. 1905, 29, 1234; Chem. Zts. 1905, 4, 354.

13. Pap. Fabr. 1909, 7, 506, 507, 1314; 1910, 8, 506; 1912, 10, 677;
Svensk Papperstidning, 1904, Pt. 10, 116.

14. Swed. P. 25283, 1907. See Segerfelt, Svensk Kemisk Tidskrift,
1911, 149. Hofer, AUg. Fischereiztg. 1906, n. No. 4.

15. Stova Kopparbergs Bergslags, Aust. P. 41479, 1909. See also,
Stutzer, Pap. Ztg. 1910, 35, 3930. Klason, Pap. Fabr. 1909, 7, 27; Tek.
Tidskr. Afd. Kemioch Bergsvetenskap, 1893, 49; 1908, Pt. 7. Willstaetter,
Ber. 1913, 46, 2401; Klein, Pap. Fabr. 1914, 12, 630. Mattheus, Pap. Fabr.
1910, 8, 532. Krause, Chem. Ind. 1906, 29, 217; Pap. Ztg. 1907, 32, 1100.
Key-Aberg, Svensk Papperstidning, 1914, 45. Tomlinson, Chem. Ztg. Rep.
1909, 659. Ost, Chem. Ztg. 1910, 34, 461. Krause, Chem. Ind. 1903, 29,
217. Hoenig, Pap. Fabr. 1912, 10, 103. Akt. Ges. "Ethyl," Swed. P.
34624» 1912.

214 TECHNOUXJY OF «I^I^ULOSE ESTERS

stances, L. Vignon has pointed out,^ that if cotton is heated under
pressure with concentrated aqueous ammonia, or with ammonia
combined with calcium chloride, a nitrogenous compound is ob-
tained if the temperature is raised to 200*^, while the cellulose —
unchanged in external appearance — ^behaves toward acid dyes
like the animal fibers.

On the other hand, dilute alkaline hydroxides or lime do not
adversely effect the fiber, if during the operation air be rigidly
excluded. In the presence of air, however, and at high temper-
atures, oxycellulose readily forms, with consequent tendering of
the fiber. Non-recognition of this fact is apt to give rise to diffi-
culties in bleaching, and care therefore must be exercised in boil-
ing cotton with lime or alkali under pressure, to ensure the sub-
stantial absence of air or other sources of oxygen. At the ordinary
temperature cellulose appears to be adversely effected by caustic
soda, the oxidation appearing to increase with increase in concen-
tration of the alkali.

With alkaline hydroxides of high concentration, cellulose
undergoes both a physical and chemical change, a fact observed
as far back as 1844 by J. Mercer, a calico printer of Lancashire,
England, and to him science is chiefly indebted for the first clear
statement of the observable phenomenon which occurs when cotton
cellulose is treated with concentrated alkaline hydroxides, sulfuric
acid or zinc chloride.^ Mercer followed up the subject only

1. Compt. rend. 1891, 112, 487, 623; abst. Chem. News, 1891, ^,
163, 285; J. C. S. 1891, 60, 662; J. S. C. I. 1891, 10, 694; Bull. Soc. Chim
1891, 5, 472, 474, 557; Mon. Sci. 1891, 37, 415, 533; Ber. 1891, 24, R, 259
Chem. Centr. 1891, €2, I, 683, 898; Chem. Tech. Rep. 1891, 30, 1, 38; Chem
Ztg. Rep. 1891, 15, 76, 111; Jahr. Chem. 1891, 44, 2814, 2824; Wag. Jahr
1891. 37, 1124; Deut. Chem. Ztg. 1891, 109; Centr. Textilind. 1891, 90
Indbl. 1891, 109. L. Vignon and h. Cassela & Co., D. R. P. 57846; abst
Chem. Centr. 1892, €3, I, 80; Chem. Ind. 1891, 14, 560; Chem. Tech. Rep
1891, 30, II, 119; Wag. Jahr. 1891, 37, 1121; Zts. ang. Chem. 1891, 4, 560
Indbl. 1891, 382; Tech. Chem. Jahr. 1891-1892, 14, 485. French Patent
206007, 1890; abst. Mon. Sci. 1891, 37, 229; D. R. P. Anm. C-3408, abst
Mon. Sci. 1891, 38, 1003.

2. The discovery was apparently the outcome of an experiment carried
out by Mercer in connection with his investigations of the theory of solution,
his object being to induce a partial separation of different hydrates of caustic
soda by filtering its solution through cotton. For this purpose a filter com-
posed of six folds of cotton was made, but a solution of caustic soda poured
into the filter was found to pass through very slowly and to lose in strength
as the result of the act of filtration. At the same time the cotton cloth used
as a filter was found to have undergone an extraordinary change, having become
translucent, contracted in both dimensions, and thickened.

CElrlrU1.0SE 215

intermittently, and it was not until six years later that he embodied
his ideas in patent form.^ After demonstrating that upon treat-
ment of cotton with strong caustic soda solution, the cellulose
swelled up, shrunk greatly, and became more transparent, he
endeavored to more closely examine the phenomenon by measur-
ing the density of the alkali before and after it had been in contact
with the cellulose, and found that it decreased from 1.30 to 1.25.
As the result of his investigations it was fotmd that (a) sulfuric
acid and zinc chloride acted similarly under certain conditions,
while (b) warming the alkali solution retarded the action, and
cooling accelerated it. Best results were obtained by Mercer when
working with sodium hydroxide solutions of 20°-30° B^. density
the firmness of the threads increasing in the ratio of 13 to 22. It
was also found that the action of the alkali upon the cellulose
increases proportionately with the concentration of the NaOH.

Mercer came to the conclusion that a definite compound
results from the action of concentrated alkali upon cellulose, and
that the compound formed is represented by the formula
CiiHaoOio-NaaO, which is, in tiun, decomposed by water into a
hydrated cellulose C12H20O10.H2O and NaOH. This latter formula
nearly corresponds to the increase in weight (4.5%-5.5%) of the
cotton after treatment. He considered that at 100° this water of
hydration is liberated along with the hygroscopic moisture, but is
reabsorbed when the fabric is again exposed to the air. He was
also aware of two other changes brought about by this alkaline
treatment, i. e., the greater tensile strength of the treated fabric,
and secondly a considerable increase in affinity for coloring
matters, especially the organic dyestuffs.

J. Gladstone next investigated the change in the minute
structure of the cotton cell when induced by treatment with alkali^

1. E. P. 13296, 1860; Dingl. Poly. 1850, 121, 438; 1851, 122, 318; Jahr.
Chem. 1851, 4, 747; Rep. Patent Invent. 1851, 358; Practical Mech. Jour.

1851, 115; Deutsche Muster Ztg. 1851, I. No. 6.

For German claim to priority of discovery of the action of alkali on
cellulose, see Polytechnische Ztg. published by Leuchs & Co. Jan. 28, 1847.

2. J. C. S. 1853. 5, 17; Phil. Mag. 1853, 5, 313; Chem. Gaz. 1^52;
Dingl. Poly. 1852, 124, 158; J. prakt. Chem. 1852, 56, 247; Jahr. Chem.

1852, 5, 823. See also W. Griine, Must. Ztg. 1851; abst. Poly. Notizbl.
1852, 7, 20. Varrentrap, Poly. Notizbl. 1853, 8, 268.

Gladstone's method of examination consisted in immersing 20 gm.
hanks of cotton in caustic soda solutions of various concentrations, expressing
the alkali, and repeatedly washing the cellulose with alcohol to remove the

216 TOCHNOLOGY Olf CELLULOSE ESTERS

while W. Crum^ eactracted with alcohol cotton which had been
treated with strong caustic potash, in order to remove the excess
of reagent. The fiber thus extracted gave up to water the whole
of the potash in combination, which was determined and found
to agree with the formula (C6Hio06)2KOH — that is, it contained
but half as much alkali as Mercer's product. This formula, has since
been the subject of much criticism. However, Crum and Glad-
stone together established that with solutions of sodium hydroxide
of strengths exceeding 10% of NaOH when brought in contact
with cellulose at ordinary temperatures, changes were induced as
above indicated, and as the result of a defiinite reaction (under
identical concentration and temperature conditions), and that
this compound of cellulose and alkali is not firmly fixed, as is seen
by the fact that decomposition results even upon washing with
cold water, the alkali remaining unchanged, and the cellulose
going to a hydrated form. Upon treatment with alcohol instead
of water, but half of the alkali is liberated.

In 1901 E. Thiele published his investigations, and in the
main, corrobrated the composition of alkali-cellulose as determined
by Mercer and Gladstone, and further showed that in the inter-

NaOH. After vacuum drying the amount of soda retained was estimated
either by noting the increase in weight of the cotton, or by washing out the
soda with water and determination of the alkalinity. From the results of
these experiments he concluded "it appears that lignine is capable of forming
a combination with soda, the proportion of the alkali varying with the strength
of the solution employed, but in no instance exceeding one atom, and this
compound is decomposed by water, being resolved into its original com-
pounds."

1. J. C. S. 1863, 16, 1, 404; Man. Lit. PhU. Soc. 1863-1864, 6, 186; abst.
Chem. News, 1862, 5, 319; Chem. Centr. 1863, 34, 927; 1864, 35, 238; Chem.
Tech. Rep. 1863, 2, II, 25; Jahr. Chem. 1863, 16, 782; Wag. Jahr. 1863, 9,
615.

Crum examined cotton fiber before and after mercerization, and found
that the action of the alkali was to cause the flattened fiber to assume the
round, solid form of ripe cotton. While at the same time the central opening
is decreased in size, if not completely obliterated. He considered the con-
traction of the mercerized fibers to be due to the twisting of the fiber under
the influence of the alkali, and is increased by mercerizing, so that there is
consequent shortening of it sufficient to account for the shrinking in length
and breadth, and the thickening of any fabric submitted to the process.
Diagonal lines were sometimes observed in the ripe, treated fibers giving the
impression of a spiral structure, but these evidently are due to the creasing
or corrugating effect of extreme twisting.

C. O'Neill (Text. Col. 187G, 1, 325) carried on experiments with twenty
individual New Orleans cotton filaments, and measured the contraction in
length and the increase of strength of each filament after treatment with
caustic soda of sp. gr. 1.250. The contraction amounted to 139/996 or about
15%, and the strength increased from 138 to 154 grains, or nearly 12%.

CEtLULOSB 217

action of the latter with carbon bisulfide whereby viscose is formed,
the alkali-cellulose appears to play the rdle of an alkali alcoholate.^
He described a cellulose hydrate obtained with concentrated
aqueous ammonia, which is distinguished from the other cellulose
hydrates in possessing a greater elasticity and resiliency.

The next year^ appeared the patented process of the Vere-
inigte Kunstseidefabriken for producing stable alkaline solutions
of cellulose hydrate by dissolving the hydrate in a 3%-40% (some
range) solution of NaOH. This firm proposed to impregnate
cotton goods with cellulose hydrate which are then passed through
a weak acid bath whereby the cellulose hydrate is precipitated
upon and between the fibers of the fabric, forming, after washing,
a solid, lustrous finish.

C. Cross and E. Bevan had previously made the observation'
that the hydrated modification of cellulose affords a ready means
for preparing the cellulose benzoates. By treatment of the alka-
line solution with benzoyl chloride,* these derivatives may readily
be formed, and are soluble in glacial acetic acid, from which solu-

1. Zts. Parb. Text. Chem. 1902, 73; Chem. Ztg. 1901, 25, 610; abst.
J. C. S. 1901, 80, i, 634; J. S. C. I. 1901, 20, 890; Chem. Centr. 1901, 72,
II, 405; Jahr. Chem. 1901, 54, 889; Meyer Jahr. Chem. 1901, 11, 446; Wag.
Jahr. 1901, 47, II, 514. See also E. Thiele, U. S. P. 710819, 1902; abst.
J. S. C. I. 1902, a, 1393. U. €. P. 750502, 1904. E. P. 8083, 1902; abst.
J. S. C. I. 1903, 22, 550. D. R. P. 133427; abst. Chem. Ztg. 1902, 26, 971;
Chem. Zts. 1903, 2, 438; Wag. Jahr. 1902, 4S, II, 469. D. R. P. 134312; abst.
Mon. Sci. 1904, 0, 104; Chem. Ztg. 1902, 26, 852; Chem. Zts. 1903, 2, 438; Jahr.
Chem. 1902, 55, 1053; Wag. Jahr. 1902, 48, II, 470. D. R, P. 154507; abst.
Chem. Centr. 1904, 75, II, 1179; Chem. Ztg. 1904, 28. 962; Chem. Zts. 1905,4,
534, 540; Jahr. Chem. 1905-1908, II, 988; 1910, 63, II, 427; Wag. Jahr.
1904, 50, II, 391; Zts. ang. Chem. 1904, 17, 1864. D. R. P. 157157; abst.
Chem. Centr. 1905, 76, I, 576; Chem. Ztg. 1905, 29, 11; Chem. Zts. 1905, 4,
540; Jahr. Chem. 1905^1908, II, 987, 988; 1910, 63, II, 427; Wag. Jahr.

1904, 50, II, 392; Zts. ang. Chem. 1905, 18, 434. Belg. P. 162701, 171980.
F. P. 320446. Aust. P. 21119.

2. E. P. 17601, 1902; abst. J. S. C. I. 1903, 22, 817. F. P. 323475;
abst. J. vS. C. I. 1903, 22, 508; Mon. Sci. 1903, 53, 128. D. R. P. 155744;
abst. Chem. Centr. 1904, 75, II, 1678; Chem. Ztg. 1904, 28, 1113; Chem. Zts.

1905, 4, 249; Wag. Jahr. 1904, 50, II, 385; Zts. ang. Chem. 1905, 18, 197.

3. Chem. News, 1890, 61, 87; abst. Chem. Centr. 1890, 61, I, 584;
Chem. Ztg. Rep. 1890, 14, 58. Chem. Ztg. 1909, 33, 368; abst. C. A. 1909, 3,
1589; T. C. S. 1909, 96, i, 290; Bull. See. Chim. 1909, 6, 985; Chem. Zentr.
1909, 80, I, 1471. H. Ost. and F. Westhof, Chem. Ztg. 1909, 33, 197; abst.
C. A. 1909, 3, 1394; J. S. C. I. 1909, 28, 325; J. C. S. 1909, 96, i, 210; Zts.
ang. Chem. 1909, 22, 1856; Chem. Zentr. 1909, 80, I, 1231; Jahr. Chem.
1909, 62, II, 385; Rep. Chim. 1909, 9, 321; Bull. Soc. Chim. 1909, 6, 685; Wag.
Jahr. 1909, 55, II, 514.

4. Ber. 1886, 19, 3218; abst. J. C. S. 1887, 52, 228; Bull. Soc. Chim,
1887, 47, 427; Jahr. Chem. 1886, 39, 1426.

218

TECHNOLOGY OP CELLULOSE ESTERS

tions they may be recovered by precipitation with water. It was
pointed out that a noteworthy property of these hydrated cellu-
loses is that they are assimilable by microscopic organisms, i. e.,
that they form an excellent nidus for moulds.

In order to shed further light upon the subject of the com-
bination of cellulose with alkali, W. Vieweg^ immersed purified
cotton dried at 90**, in caustic soda of varying strengths. After
the cellulose had stood in contact with the NaOH for two hour
periods, the alkali was titrated, and from the diminution in the
strength of the latter, the amotmt of alkali entering into combina-
tion with the cellulose was calculated. The amounts found to
have been taken up are shown in the following table:

TABLE XIX.— ACTION OF CAUSTIC SODA ON CELLULOSE

Concentration: Gm. NaOH in

Gm. NaOH taken up by

100 cc. Lye

100 Gm. Cellulose

0.4

0.4

2.0.

0.9

4.0

2.7

8.0

4.4

12.0

8.4

16.0

12.6

20.0

13.0

24.0

• 13.0

28.0

15.4

33.0

20.4

35.0

22.6

40.0

22.5

According to Vieweg therefore, the absorption of caustic
soda rises rapidly until the concentration of the lye reaches 16%,
when the absorption remains constant up to a strength of lye of
24%. It then rises and becomes constant again at 35%
strength. The amount of caustic soda taken up from the 16%
lye is about 13%, and this figure corresponds to the compound
(C6Hio05)2NaOH isolated by Gladstone by extracting cotton,

1. Papier Ztg. 1907, 32, 130, 174; 1908, 34, 149; Ber. 1907, 40, 3876;
1908, 41, 3269; ab.st. C. A. 1907, 1, 1320; 1908, 2, 3403; J. C. S. 1907, 92, i.
893; 1908, 94. i, 857; J. S. C. I. 1907, 26, 836, 1157; 1908, 27, 1081; Bull. See.
Chim. 1908, 4, 902; Rep. Chim. 1908, 8, 62; Chem. Zentr. 1907, 78, II, 1780;
1908, 79, 11, 1584; Chem. Ztg. Rep. 1908, '32, 27, 619; Meyer Jahr. Chem.
1907, 17, 215; 1908, 18, 506; Ztg. ang. Chem. 1908, 21, 1184; Wochenbl.
Papierfabr. 1907, 38, 1890. See also W. Herbig, Zts. Text. Ind. 1900-1901,
4, 785; abst. Chem. Centr. 1901, 72, II, 1115; Jahr. Chem. 1901, 54, 890.
See W. Vieweg, D. R. Anm. 7215, 1907.

CELLULOSE 219

which had been steeped in strong caustic soda, with alcohol. On
the other hand, the amount of caustic soda taken up from a lye
exceeding 35% in strength would correspond about to an alkali
cellulose having the composition (C6Hio06)2(NaOH)2. From the
results thus obtained it is certain that in mercerizing, chemical
action takes place, for an adsorption or a distribution of caustic
soda between water and cellulose would not take place in mole-
cular proportions in such widely different concentrations
(16%-24%, 35%-40%).

The author further points out that cellulose which has been
treated with caustic soda solutions beyond a certain strength has
acquired after washing in water, then in acetic acid and again in
water, the property of absorbing more caustic soda from a dilute
solution of the latter than the same cotton untreated.

Vieweg foimd* that from ll%-24% solutions of sodium
hydroxide, cellulose takes up an amount of alkali sufficient
to form the compound CwHisOioNa, and if the results are
plotted the curve obtained is discontinuous, the point of
discontinuity corresponding with the formation of this compound.
He has also shown that the higher the degree of mercerization the
greater the capacity for absorption of sodium hydroxide, more
being taken up at lower than at higher temperatures.

The views of Vieweg are not shared by O. Miller who has been
tmable to substantiate Gladstone's formula for mercerized cel-
lulose,^ in that he finds the percentage of sodium hydroxide in
mercerized cellulose increases with the concentration of the alka-
line solution. He has shown' that if cellulose is dried for stx
hours at 95°, treatment with concentrated sodium hydroxide
solution at 10° indicates practically no alteration in weight.
As the result of criticisms recently made by C. Cross* and

1. Ber. 1908, 41, 3269; abst. J. S. C. I. 1908, 27, 1081.

2. Ber. 1907. 40, 4903; 1908, 41, 4297; abst. J. S. C. 1. 1909, 28, 37;
Chem. Zentr. 1908, 79, I, 453; 1909, 80, I, 273; J. C. S. 1909, 96, i, 13; 1908,
94, i, 78; J. Russ. phys. Chem. Soc. 1905, 37, 361; Bull. Soc. Chim. 1907,
2, 141; Chem. Ztg. Rep. 1908, 32, 82; Jahr. Chem. 1905-1908, II, 962; Meyer
Jahr. Chem. 1908, 18, 506; Wag. Jahr. 1907, 53, II, 507.

3. Ber. 1910, 43, 3430; abst. C. A. 1911, 5, 1187; J. C. S. 1911, 100, i,
17; J. S. C. I. 1911, 30, 18; J. vSoc. Dyers Col. 1911, 27, 10; Bull. Soc. Chim.
1911, 10, 1150; Rep. Chim. 1911, 11, 178; Chem. Zentr. 1911, 82, I, 355;
Chem. Ztg. Rep. 1911, 35, 35.

4. Ber. 1911, 44, 153; abst. C. A. 1911, 5, 1513; J. C. S. 1911, 100, i,
114; BuU. Soc. Chim. 1911, 10, 1297; Rep. Chim. 1911, U, 232; Chem. Zentr.

220 TECHNOLOGY OF CELLULOSE ESTERS

C. Schwalbe/ upon the accuracy of the investigations of Miller, he

1911, 80, 1, 619; Kunst. 1912, 2, 14; J. S. C. I. 1911, 30, 204.

5. Ber. 1911, 44, 151; abst. C. A. 1911, 5, 1613; J. C. S. 1911, 100, i,
114; BuU. Soc. Chim. 1911, 10, 1297; J. S. C. I. 1911, 30, 204; Rep. Chim.
1911, U, 232; Chem. Zentr. 1911, 80, 1, 619; Kunst. 1912, 2, 14. C. Schwalbe,
(Zts. Chem. Ind. KoU. 1908, 2, 229; abst. J. S. C. I. 1908, 27, 278; Chem.
Zentr. 1908, 79, I, 1216; Chem. Ztg. Rep. 1908, 32, 204; Zts. ang. Chem,
1908, 21, 1377) records a case in which cotton cloth was beaten in a paper-
maker's beater for several hours until it was converted into a gelatinous
cellulose hydrate. When this was dyed with Benzopurpurin lOB it was
colored a bluish black instead of the normal red color of the dyestuff.
• Congo Red and Benzopurpurin 4B, on the other hand, did not show the
blackening. The abnormal reaction was finally traced to the presence of
colloidal copper in the pulp, derived from the bronze knives of the beater.
Benzopurpurin lOB is sensitive to copper and forms a blue copper compound.
As C. Schwalbe has pointed out (Zts. ang. Chem. 1909, 22, 197; abst. J. S.
C. I. 1909, 28, 216; C. A. 1909, 3, 1143; BuU. Soc. Chim. 1909, 6, 662; Rep.
Chim. 1909,9,490; Chem. Zentr. 1909, 80, I, 840; Chem. Ztg. Rep. 1909,33,
120; Jahr. Chem. 1909, 82, II, 386; Wag. Jahr. 1909, 55, II, 514) it U necessary
to emphasize the difference between hydrolysis and hydration in the case of
cellulose, although under certain conditions both may occur simultaneously.
The hydrocelluloses, products of hydrolytic action, are generally character-
ized by free carbonyl groups which reduce Fehling's solution. The cellulose
hydrates may be produced, with or without simultaneous hydrolysis, whenever
cellulose is subjected to the action of alkalis, adds, or salts which exert a
swelling or solvent influence in presence of water. According to Cross, hydra-
tion may take place in presence of water by mechanical action alone. Besides
the cellulose hydrates artificially produced from the normal cellulose (anhy-
dride), other types exist in nature which have never attained the dehydrated
and polymerized condition of a normal cellulose. These imdeveloped types
are sometimes included in the group of "hemicelluloses." The hydrated
celluloses differ widely in their proi>erties, but a high hygroscopic moisture is
common to aU; the hydrocelluloses on the other hand are distinguished by an
abnormally low moisture-content. Some of the hydrates, e. g., mercerized
cotton, possess high tensile qualities, others, e. g., the artificial silks, are
mechanically deficient. These two groups also differ widely as regards their
solubility in alkalis. Under certain conditions, the hydrated celluloses are
resistant to esterifying influences to which the normal cellulose responds. All
the hydrated celluloses are characterized by a diminished resistance to hydrol-
ysis by acids, to an extent proportional to their "degree of hydration." Many
methods have been proposed for the determination of the "degree of hydra-
tion" of a given cellulose: Vieweg measures the absorption affinity towards
sodium hydroxide. Cross and Bevan utilize the thio-carbonate reaction and
measure the viscosity of the product, Hiibner uses a colorimetric method with
solutions of zinc chloride of different strengths, while Knecht measures the
absorption of benzopurpurin tmder standard conditions. All these methods
are open to objections, and the author has devized a method based on the
increased susceptibility to hydrolysis by acids. The proceditfe is as follows:
The "copper value" (cupric-reducing value) of the sample is first determined
on 3 gm. of the substance in the manner previously described (see J. S. C. I.
1907, 26, 648). Another portion of the finely chopped substance is then
boiled with a standard quantity of sulfuric acid of 6 per cent, strength, for
15 minutes witti constant stirring. The acid is neutralized and the prescribed
quantity of Fehling's solution is added without separating the hydrolsrzed
fiber from the liquid. In this way a second "copper value" is obtained, and
the difference between the two measures the hydrolysis which has taken place
and which is proportional to the "degree of hydration" of the original cellulose.

C^LLUI^OS^

221

has gone over his work again, ^ and made further determinations
in which precautions were taken to recover any cellulose lost in
the lye. The results calculated on dry weights were: mercerized
product, 99.6%; fibers, etc. recovered from the alkali after neu-
tralization, 0.26%; loss, 0.14% of the original cellulose taken.

Whereas Vieweg has shown that in mercerization the adsorp-
tion is greater, the greater the alkali concentration, J. Briggs^ points
out that an increased adsorption capacity is characteristic of
Some of the more typical results are indicated in the following table.
TABLE XX.— ACTION OF ALKAU ON CELLULOSE

Cotton wool

Ditto mercerized with 8 per cent.

soda lye

Ditto mercerized with 16 per cent.

soda lye

Ditto mercerized with 24 per cent.

soda lye

Ditto mercerized with 40 per cent.

soda lye ,

"Glanzstoflf" silk

Viscose silk A

Viscose silk B

Viscose silk C

Chardonnet silk

Girard's hydrocellulose

Mitscherlich wood pulp, tmbleached
Ritter-Kellner wood pulp unbleached

Copper

Copper

Hygro-

Value

Value

Differ-

scopic

after

before

Moisture

Hydrol-

Hydrol-

ence

ysis

ysis

Per cent.

6.1

3.3

1.1

.2.2

7.7

3.2

0.9

2.3

10.7

5.0

1.3

3.7

11.3

6.1

1.2

4.9

12.1

6.6

1.9

4.7

9.8

12.8

1.5

11.3

10.7

14.0

1.9

12.1

10.2

14.5

3.0

11.5

11.0

16.6

2.9

13.7

11.4

17.7

4.1

13.6

3.6

6.6

5.7

0.9

• • • •

4.4

2.4

0.9

• • • •

3.5

2.8

2.7

In their investigations on mercerized cellulose, A. Fraenkel and P.
Priedlaender (Mitt. k.k. Tech. Gew. Mus. 1898, 326) found the luster effects
are not obtained unless the action of water is associated. Their results
showed that usiQg a cotton with a breaking strain of 358 gm. and an elas-
ticity of 21 mm. elongation, mercerization with caustic soda of 35 '^ B€.
gave an average breaking strain of 548 gm. and an elongation of 40 mm.
Where cold 10% alcoholic soda was used, the breaking strain registered 618
gm. and elongation 28 mm., whereas when the alcoholic soda was hot, the
^gures obtained were 720 gm. and 33 mm. respectively.

1. Ber. 1911, 44. 728; abst. C. A. 1911, 5, 2175; J. C. S. 1911, 100, i,
355; J. S. C. I. 1911, 30, 413; BuU. Soc. Chim. 1911, 10, 1297; Rep. Chim.
1911, U, 323; Chem. Zentr. 1911, 82, 1, 1164; Kunst. 1912, 2, 14.

2. Chem. Ztg. 1910, 34, 455; Zts. Chem. Ind. Koll. 1911, S, 67; abst.
C. A. 1910, 4, 2372; J. S. C. I. 1910, 29, 622; BuU. Soc. Chim. 1911, 10, 60;
Chem. Zentr. 1910, 81, I, 2075; Jahr. Chem. 1910, €3, II, 422; Zts. ang.
Chem. 1910, 23, 1389.

222 TECHNOLOGY OP CELLULOSE ESTERS

hydrated celltdoses generaDy, by whatever method the hydration
may have been induced, and that the increase in adsorption may,
in strictly comparative cases, be taken as a measure of the "degree
of hydration." He also shows that small differences in the degree
of hydration may be measured on a magnified scale by determin-
ing the adsorption of the alkali in alcoholic media, instead of in
aqueous solutions. The percentage of sodium hydroxide adsorbed
by cellulose from 2 per cent, solutions is very much greater in
alcoholic media, and it increases with the alcoholic strength. The
author finds that maximum adsorption of 14-15 per cent, of
sodium hydroxide, calculated on the dry weight of the cellulose,
are recorded in the case of artificial silks in presence of 93 per cent,
alcohol of approximately N/2 alkalimetric strength. By working
in 93 per cent, alcohol, it is possible to show differences in the
degree of hydration of cellulose fibers which have been hydrated
by mechanical means only in the papermaker*s beating engine.

H. Wichelhaus and W. Vieweg^ hold the view that in mer-
cerized cellulose only the cuticle of the fiber is removed* is incor-
rect. By comparing the esters of nitric and benzoic acids derived
from natural and mercerized cellulose the change is shown to be
chemical in character. The yield of benzoate obtained from 100
parts of cellulose by the action of benzoyl ghloride and NaOH,'
is given as follows:

TABLE XXI.— BENZOYLATION OF CELLULOSE

«

Yield, before
Mercerizing

Yield, after
Mercerizing

Cotton

Flax

112
121

139
137

Again, although the percentage of nitrogen in the nitrates

1. Ber. 1907, 40, 441; abst. C. A. 1907, 1, 1266, 1621; J. C. S. 1907, 92,
i, 186; J. vS. C. I. 1907, 26, 195; Rep. Chim. 1907, 7, 179; Biochem. Centr.
1907, 6, 90; Chem. Zentr. 1907, 78, I, 800; Chem. Ztg. Rep. 1907, 31, 186;
Jahr. Chem. 1905-1908, II, 962; Meyer Jahr. Chem. 1907, 17, 215; Wag.
Jahr. 1907, 53, II, 411; Ztg. ang. Chem. 1907, 20, 1537.

2. A. Fraenkel and P. Friedlaender, Mitt. K. K. Tech. Gewerbemus,
1898, 326; abst. J. S. C. I. 1898, 17, 839; Chem. Centr. 1899, 70, 1, 191 ; Chem.
Ztg. 1898, 22, 670; Jahr. Chem. 1899, 52, 1298; Meyer Jahr. Chem. 1898, 8,
484.

3. C. Cross and E. Bevan, Chem. News, 1890, 81, 87; abst. Chem.
Centr. 1890, 81, I, 584; Chem. Ztg. Rep. 1890. 14, 58. Chem. Ztg. 1909, 33,
368; abst. C. A. 1909, 3, 1589; J. C. S. 1909, 98, i, 290; Bull. Soc. Chim. 1909,
8, 985; Chem. Centr. 1909, 80, I, 1471.

CELLULOSE 223

derived from cotton and from flax both before and after mercer-
ization is practically constant (13%), the products obtained are
different in that the nitrate from the mercerized product gives
a much higher solubiUty in ether-alcohol, a statement which
repeatedly has been proven.

C. Beadle and H. Stevens^ have conducted an investigation
as to the influence of temperature on the absorption of water and
sodium hydroxide from aqueous NaOH solutions containing from
1% to 25% NaOH using regenerated cellulose, the particular
form employed being a monofil of 360 denier made by the cupram-
monium process. It was found that for any given temperature
between 5° and 40° a maximum hydration takes place, these
maxima being greater the lower the temperature; the maxima for
0° however, falls below that for 5°. Similarly, with regard to the
absorption of NaOH, in which case maximum absorption at 5°,
12°, 20°, 30° and 40° takes place in 9%, 11%-12%, 12%-14%,and
14% NaOH respectively, the maximum amounts of NaOH
absorbed being 256, 162, 112, 82, and 78 parts respectively per
100 parts regenerated cellulose.

According to a recent process,* cotton textile or spinners*
raw cotton materials are treated with caustic alkali of strength
below that which produces the effects of mercerization, whereby
the material is improved in elasticity and extensibility. A suit-
able caustic lye may contain 9% caustic soda but the strength
may be varied somewhat and the treatment carried out between
15° and 50°.

E. Heberlein claims' that transparent effects on cotton
fabrics are produced by subjecting the goods to the action of a
caustic alkali solution of at least 15° B^. (sp. gr. 1.109), washing
and then treating with sulfuric acid of at least 50.5° B€. (sp. gr.
1.498), both treatments being carried out at a temperature below
0°. The order of the treatments may be reversed, and the two
treatments may be repeated alternately; one of the reagents may
be caused to react only in places to produce pattern effects, and

1. Eighth Intl. Cong. Appl. Chem. 1912, 13, 25; abst. C. A. 1912, 6,
3013; J. C. S. 1912, 102, i. 947; Chem. Ztg. 1912, 36, 1222.

2. Fine Cotton Spinners' and Doublers' Assoc., M. Cunningham and
C. Cross, E. P. 131212, 1918; abst. J. S. C. I. 1919, 38, 759-A.

3. E. Heberlein, U. S. P. 1265082, 1918; abst. J. S. C. I. 1918, 37,
461-A; C. A. 1918, 12, 1703; Ann. Rep. Soc. Chem. Ind. 1918, 3, 159.

224 TECHNOLOGY O? CELI^UU)SE ESTERS

the fabrics may preferably be treated under considerable tension.

L. Vignon/ E. Grandmougin,* R. WolfFenstein and G. Bumcke*
are among others who have studied this subject, but there are
many important points yet to be cleared up before our knowledge
in this field may be regarded as satisfactory.

Mercerization. After Mercer secured patent protection in
England in 1850,* apparently little was done towards its commer-

1. Compt. rend. 1900, 131, 708; Bull. Soc. Chim. 1901, 2S, 137; abst.
Chcm. News, 1900. 82, 265; J. C. S. 1901, 80, i, 16; J. S. C. I. 1900, 19, 1103;
Mon. Sd. 1900, 55, 835; Rep. Chim. 1901, 1, 130; Chem. Centr. 1900, 71,
II, 1151; Chem. Ztg. 1900, 24, 999; Jahr. Chem. 1900. 53, 840.

2. Chem. Ztg. 1908, 32, 241; abst. Chem. Zentr. 1908. 79, I. 167;
Jahr. Chem. 1905-1908. II, 969. Compare K. Haupt, Faerb. Ztg. 25, 173.
P. Thies. Faerb. Ztg. 25, 196; Chem. Zentr. 1914, 85, II, 824.

3. Ber. 1901. 34, 2415; abst, J. C. S. 1901, 80, i. 582; J. S. C. I. 1901,
20, 925; Bull. Soc. Chim. 1902, 28, 368; Rep. Chim. 1902, 2, 46; Chem. Centr.
1901, 72, II. 529; Jahr. Chem. 1901, 54, 888.

For the reparation of cellulose and its derivatives, the following scheme
has been suggested :

A. Celluloses.

B. Hydrated celluloses (Hydrocellulose).

(a) reducing (hydral -cellulose).

(b) reducing and with carbonyl groups.

(c) with carbonyl groups (acid cellulose), and not reducing.

(d) not reducing, and without carbonyl groups (lactone form).
F. Seibert and J. Minor (Paper, 1919, 24, 1007; abst. C. A. 1919, 13,

2440; J. S. C. I 1919, 38, 713-A) record that in the course of the prolonged
beating of unbleached sulfite pulp chemical changes occur which are shown
by a progressive increase in the "copper value" of the pulp. This increase is
attributed to hydrolysis and oxidation of the cellulose owing to the hydration
of the fiber and its prolonged exposure to the air, and does not take place to
the same extent when the fiber is rapidly cut up, for instance, in a Jordan
refiner. A break in the regularity of the increase in the copper value is noted
immediately after the addition of a basic dyestuff , at which point a sharp
fall in the copper value takes place, but the loss is again made up by further
changes occurring during the subsequent beating. The influence of basic
dyestuffs is accounted for by their chemical reaction with the lignin. During
the process of washing after bleaching there is a progressive decrease of the
copper value, showing that the removal of soluble oxidizable products by
washing takes place more rapidly than the formation of such products due to
the beating; when washing is stopped the copper value begins to increase.
The copper value increases considerably during the process of bleaching, but
the increase does not correspond with the quantity of bleach liquor tmtil a
large excess of bleach liquor has been used. The loss of weight of the pulp
apparently varies directly with the amount of bleach liquor used, but it is not
excessive even when the proportion of bleach liquor is high. A distinct
advantage in the quality and feel of the paper is derived from the use of a
substantial amount of bleach liquor and the loss of strength of the paper is
barely appreciable. On the other hand with a large excess of bleach liquor,
sufficient to increase the copper value of the pulp to an abnormal extent,
especially if kept warm, the destruction of the fibers is very pronounced.

4. E. P. 13296, 1850; Dingl. Poly. 1851, 121, 438; Jahr. Chem. 1851,
4, 747; Rep. Patent Invent. 1851, 358; Practical Mech. Jour. 1851, 115.

CBLLXJLOSB 225

dal exploitation. It is recorded, however, that a French concern
offered Mercer the sum of two hundred thousand dollars for the
purchase of his patent rights which in those days was an immense
sum of money. If this be true, it is indicative of the importance
which at that time was attached to his discovery. In spite of
the many advantages of this process, it has attained a firm indus-
trial footing in the textile trade only within recent years, due
primarily to the surface contraction which was then considered
inevitable, and which materially increased the cost of the product.
Mercers patent was followed by those of J. Mayer-Rauschenbach,^
J. Sachs,* C. LightoUer and J. Longshaw,* E. Fremy and A.
Urbain,^ W. Lukacs,* and the P. and C. Depoully patents issued in
1883.* In the years 1894,^ 1895,8 1896,® 1897,i« 1898,^* as well as

1. E. P. 340, 1887.

2. E. P. 2966, 1880.

3. E. P. 5713, 1881.

4. E. P. 1816, 1882.
6. E. P. 3103, 1883.

6. E. P. 28696, 1883; 8642, 1884; 15140, 1885; 6533, 1895. D. R. P.
30966, 1884; 37658, 1885. See also E. P. 5838, 1884, A. Prinz and E. Quelltnalz.

7. W. Kay and Thornliebank Co. E. P. 19388, 20308, 1894. Com-
pare also E. Goodwin, E. P. 22566, 1892; 16698, 1893.

8. G. Ormondroyd, E. P. 20786, 1895.

9. E. P. 8235, 1896; J. Weiss. E. P. 16840, 1896; D. R. P 128284,
1896, P. Bernhardt. E. P. 19428, 1896; D. R. Anm. 12196, 1896; D. R. P.
134449, 1897, J. Schneider. E. P. 19633, 21253, 21942, 1896, A. Liebmann.
E. P. 23741, 1896, A. Xiebmann and W. Kerr. E. P. 28499, 1896, A
Green. E. P. 28870, 1896; D. R. P. 112773, 1896; 133456, J. Bemberg. D.
R. P. 120576, 1896, G. Dietrich and O. Seyfert. E. P. 29504, 1896, Salis,
Schwade and Co. and A. Bins and R. Boral. E. P. 29832, 1896, Farbwerke
vorm. Meister, Lucius & Bruning. D. R. P. 109607, 1896, F. Sheuclen.

10. E. P. 3218, 1897; P. P. 269138, 1897, A. Bonbon. E. P. 5350, 1897;

D. R. P. 98182, 1897; 113458, 1899; 118429, 1900; F. P. 264396, 1897. U. S. P.
679426, 1900, M. Beck. E. P. 5573, 27020, 1897; D. R. P. 99337, 1896, F.
Bayer & Co. E. P. 6122, 1897, W. Kay, and Thornliebank Co. E. P. 7093,
1897; D. R. P. 102672, 1896, Kleinewefers Sohne. E. P. 9056, 1897,

E. Crepy. F. P. 265009, 1897, Compagnie parisienne des couleurs d'aniline.

D. R. P. 109937, 1897; F. P. 269550, 1897, Soc. F. Vanoutryve& Co. E. P.
10784, 11313, 1897, Meister, Lucius, & Briining. E. P. 15169, 16746, 1897,
M. Sharp. F. P. 269380, 1897, A. and H. Pinel. E. P. 17397, 1897, H. Lowe.

F. P. 267459, 1897, DoUfus, Mieg. & Co. E. P. 23268, 1897, G. Douglas.

E. P. 25948, 1897, J. Hill. E. P. 26247, 1897; D. R. P. 100796, 1897;

F. P. 270437, 271509, 1897; 276526, 1898, H. David. D. R. P. 95482, 1897,
P. Dosne. D. R. Anm. 5109, 1897; F. P. 263912, 1897, Kahnert. E. P.
27435, 1897, J. Dean, J. Knowles and H. Barker. E. P. 29613, 1897; D. R.
P. 102103, 1897; U. S. P. 610619, 1898; F. P. 272994; Swiss P. 14961, 1897,
A. Wyser, E. P. 30142, 1897; U. S. P. 646787, W. and H. Aykroyd. U. S. P.
612189, 1897, A. Birch. U. S. P. 608194, 1897, J. Greenwood. D. R. Anm.
9620, 1897; 10798, 1898; D. R. P. 120344. 1898; F. P. 268971, 1897; 424247,
1911, E. Friedrich. D. R. P. 95904, 1897; 100701; F. Mommer & Co. D.
R. P. 98968, 1897. U. Ungnad.

11. E. P. 626, 1898, F. Cloth. E. P. 1839, 1898, G. Oldham. E. P.

226 TECHNOLOGY OP CELLULOSE ESTERS

1899,^ 1900,^ especially in the latter year, and the early part of

2307, 1898, H. Lowe. E. P. 2915, 1898, G. Douglas. E. P. 4067, 4556, 1898,
G. Hamilton. E. P. 7317, 1898; D. R. P. 109285, 1899, A. Ashworth. E. P.
7687, 1898, H. Gassner. E. P. 7688, 1898; D. R. P. 109431, 141623, T.
Schiefner. E. P. 9885, 1898, J. Hope. E. P. 10246, 1898; D. R. P. 100796,
1897; 107378, 1898; U. S. P. 618399, 1898; F. P. 276941, 1898; H. David.
E. P. 10708, 10709, 1898; D. R. P. 177241, 1903, W. Hall. E. P. 10943, 1898,
J. and G. Lord. E. P. 12379, 1898; D. R. P. 103328, 1898; 118270, 118271,
1900; 120602, 1899; F. P. 290498, 1899; B. Cohnen. E. P. 12669, 1898, L.
Van Westrum. E. P. 13953, 1898, P. Marshall. E. P. 13495, 1898, D, Hors-
burgh. E. P. 14472, 1898, Cassela & Co. D. R. P. 40506, 156402, 196741;

D. R. Anm. 51392. 1910, C. Haubold. E. P. 14917, 1898, J. Nelson. E. P.

16823. 1898, J. Kleinewefers Sohne. E. P. 22101, 1898; D. R. P. 108653, 1898,
W. and H. Aykroyd. E. P. 23135, 1898, T. and W. Caldwell, and E. Johns-
tone. U. S. P. 616709, 1898; Re. 9885, 1898; D. R. P. 106596, 118061, 1898,
N. Istomin. E. P. 23325, 1898, B. Ermen. D. R. P. 101813, 108107, 109431,

1898. T. Schiefner and Getzner, Mutter & Co. E. P. 24433, 1898, F. Davis and
A. Liebmann. D. R. P. 107379. 108766, 108881, 1898, H. Krissmanech & F.
Auderieth. E. P. 24784, 1898, J. Wood. D. R. P. 114192, 1898; F. P.
264546, 1897; 277031, 1898, Soc. Anon. Blanchiment, Teinture et Impression.

E. P. 25881, 1898, F. Gros and P. Bourcart. U. S. P. 643781, 1898, R. Sub-
renat. E. P. 26728, 1898, B. Cohnen. D. R. P. 111370, 1898. J. Ashton and
E. Kayser. E. P. 27361, 1898, W. Kay and the Thornliebank Co. D. R.
P. 116029, 1898, C. Gadd. U. S. P. 607150, 1898, C. Wichelt and A. Jones.

1. E. P. 54. 1899, H. Aykroyd. E. P. ^9, 1899; D. P.. P. 102017,
1897; 109756, 1898, T. Schiefner. E. P. 1079, 1899, S. Schwabe & Co. and
Boral. Robin and Kymer. E. P. 2211. 1899, F. Holland and J. Jackson.
E. P. 2708, 1899, H. Newell. E. P. 3914, 1899. S. Wood and Park House
Dyeing Co. E. P. 4170, 4773. 1899, T. Pickles. E. P. 5469. 1899; D. R. P.
110633, 117249, 1899, Badische Anilin u. Soda Fab. E. P. 5703, 1899, C.
Fischer. E. P. 6249, 1899, G. Tagliani. E. P. 6769. 1899. G. Kershaw and
A. Seeley. E. P. 9452, 1899; 20519. 1906; U. S. P. 628669, 1898, A. MiUer.
E. P. 9937, 24163, 1899, J. Copley. E. P. 10936, 1899; U. S. P. 656319, 1899;
J. Copley, P. Marshall and R. Heaton. E. P. 11509, 1899; U. S. P. 634362,
1899; F. P. 287998, 1899, P. MarshaU. E. P. 10943, 1899; U. S. P. 648275,
1899; F. P. 297067, 1900; D. R. P. 119331, 1899, J. Lord. E. P.
13514, 17642, 1899, G. Grandage. E. P. 14032, 1899,- B. Cohnen. E. P.
14329, 1899, P. Jeanmaire. F. P. 287793, 1899, W. Neuhoff. E. P. 14932,

1899, E. Brown. E. P. 15397, 1899, T. Robinson. E. P. 16782, 1899; D. R.
P. 106593, 1897; 127161, 1899; A. Romer and E. Holken. E. P. 18260,
1899, E. Bronnert. E. P. 19936, 1899, R. Brandts. E. P. 20011, 1899, F.
Gartner. E. P. 21162, 1899, A. Boyeux. E. P. 21192, 1899, F. Cochrane.

E. P. 21488, 1899; U. S. P. 645698, 1899, L. Weldon. E. P. 22095, 1899, D.
Crowther. E. P. 22292, 1899, A. Wyser. E. P. 23098, 1899; D. R. P. 110508,

1898, W. Herschmann. E. P. 23695, 1899, E. Price. E. P. 24188, 1899;
U. S. P. 608033, 1897, J. Ecob. E. P. 9521, 19273, 24397, 1899; 2699, 12327,
12580, 1900; F. P. 287924, 1899; 307800, 312957, 1901; D. R. Anm. 21633,
1909, J. Dolder. E. P. 25638, 1899; F. P. 295677, 1899, E. Simon. E. P.

25703. 1899, M. Sharp. U. S. P. 648115, 1899, G. Remsen. U. S. P. 650442,

1899, F. Stelter. U. S. P. 655546. 1899, W. Denn* U. S. P. 617561, 1897;
786264, 1899, H. Butterworth. D. R. P. 113704, 113457, 113374, 1899;

F. P. 306197, 1900, Andemacher Textilwerk. D. R. P. 119149, 1899. J.
Belger. D. R. P. 112916, 1899, E. Kruse.

2. E. P. 156, 1900, J. EmpseU and E. Firth. E. P. 459, 1900. R.
Brandts. E. P. 1577, 1900, O. Isherwood. E. P. 1736, 1900; U. S. P. 657705,

1900, W. Macconnel. E. P. 2699, 11436, 12327, 12580, 1900, J. Dolder. E. P.
5416, 1900, H. Keams. E. P. 3466, 1900, R. Turner, E. P. 5409, 1900, C. Jack-

CELLULOSE 227

1901,* 1902* and 1903' progress in the art was especially rapid.

son. E. P. 7189, 1900; D. R. P. 112741, 1899; 119137, 1900; F. P. 290665,.
1899; U. S. P. 734333, 1900, P. Jeanmaire. E. P. 8230, 1900, F. Hasslacher.
E. P. 8654, 1900; D. R. P. 122750, 1900; F. P. 300601, 1900, O. Kopp and

E. Usuelli. E. P. 9505, 1900, J. Ross and J. Schneider. E. P. 11077, 1900;
W. Crompton and W. Horrocks. D. R. P. 131134, 131228. 1900, E. Schaef-
fler. D. R. P. 122488, 1900, F. Klein. D. R. P. 123445, 1900; F. P. 316963,
1901; 4010(H, 1909, R. Hahn. E. P. 12454, 1900, C. Lavel. E. P. 12650,^
1900; H. Brassard. D. R. P. 120302, 1900, A. Schmidt. D. R. P. 119737,
1900, F. Deissler. E. P. 14283, 1900; F. P. 302887, 1900; U. S. P. 682494,
1900; F. Reichmann and C. Lagerquist. D. R. P. 118359, 119427, 1900,
Esser and Scheider. E. P. 15329, 1900, J. Obermaier. D. R. P^ 122863,^

1900, C. Schulze. E. P. 16161, 1900, F. Johnson. E. P. 19937, 1900; D. R. P.
131704, 135695, 1900; 134968, 1901 ; U. S. P. 661649, 1900; F. P. 306139, 1900,

F. Shuman. E. P. 20136, 1900; U. S. P. 657293, 1900. J. Morgan and W.
Menzies. E. P. 20377, 1900, F. Gilli. E. P. 21397. 1900, F. Simons. E. P.
23470, 1900; D. R. P. 158272, 1900; F. P. 300693, 1900, M. Frings. U. S. P.
669721, 1900; 685889, 722064, 1901. C. Weichelt. D. R. P. 119333, 1900,.
A. Kunow. D. R. P. 117255, 1900; D. R. P. 102548, 1897; O. Hoffmann.
F. P. 305662, 1900, F. Simons. F. P. 267079, 1900, F. Reichmann. F. P.
305237, 1900, J. Decode.

1. E. P. 1374, 1901; D. R. P. 119736, 123822, 1900; F. P. 301640, 30164U
1900; U. S. P. 755765, 1902, P. Hahn. E. P. 2697, 1901, J. Dolber. E. P.
3568, 1901, F. Shuman. E. P. 5655, 1901. F. Konitzer. E. P. 6644, 1901,
Badische Anilin u. Soda Fab. E. P. 7480, 1901, K. Weldon. E. P. 8076,

1901, A. Hill. E. P. 12476, 1901; 25445, 1906, T. Pickles. E. P. 17735,
1901, J. Gebauer. E. P. 18728, 1901, C. Reichenbach. E. P. 19566, 1901 ;
F. P. 306826, 1901. U. S. P. 694109, 1901. D. R. P. 143612, 1901, A. Romer.
E. P. 20394, 1901, J. Pearsons. E. P. 21646, 1901, P. Bourcart. E. P.
22996, 1901, Pearson. E. P. 19089, 23181, 1901. U. S. P. 760694, 1903.

D. R. P. 152337, 1903, T. Pratt. D. R. P. 129974, 1901, P. Schmidt and E.
Price. D. R. P. 144428, 1901; M. Sarfet. D. R. P. 141132, 1901; F. P.
308117, 1901, J. Ecob. F. P. 309244, 1901, BufTaud and Robatel.

2. E. P. 2202, 1902, J. Pearson. E. P. 2524. 1902, J. Schneider. E. P.
3376, 1902, G. Mueller. E. P. 6931, 1902, T.French. E.P.6894, 1902,J.Dutton.

E. P. 13217, 1902. J. Spenle. E. P. 13982, 1902, Lang, Bridge & Wood. E. P.
14675, 1902. J. Klauder. E. P. 14525, 1902, Calico Printers Assoc. E. P.
19734, 1902. E. Scott. E. P. 24302. 1902, W. Knowles. E. P. 25163, 1902,
J. Nasmith. E. P. 20672, 1902; F. P. 324848, 1902. R. ChevoUeau. F. P.
322028, 1902, Beltzer and Thiebaut. F. P. 324076, 1902, L. Brettonniere.

3. E. P. 894, 1903, P. Edlich. E. P. 5249, 1903, J. Spenle. E. P.
10255, 1903; U. S. P. 680131, 1901 ; D. R. P. 128647, 1900; 166807, 1904; W.
Crompton and W. Horrocks. E. P. 20959, 1903, T. de Naeyer. E. P. 9683,
1903; D. R. P. 157323. 1903; F. P. 333078, 1903, L. Cippolina. E. P.
7872, 1903; D. R. P. 127002, 1900; F. P. 331012, 1900, C. Jackson and

•E. Hunt. D. R. P. 156434, 1903, E. Kruse. D. R. P. 149140, 19a3, H.

Gordon. D. R. P. 156402, 1903; 196741,205962, 212900, 1907; C. Haubold.

For the effect of traces of iron in mercerized cotton, see L. Lefevre and

E. Blondel, Rev. mat. Color. 1909, 13, 313; abst. C. A. 1910, 4, 386; Chem.

Ztg. Rep. 1909, SS, 597. K. HaerUing, KoU, Zts. 1919, 25, 74.

A silky luster resembling that imparted by mercerization may be given
to cotton cloth by means of what is known as a calender finish, the method being
called the "Schreiner finish." This is accomplished by passing the cloth
between rollers under heavy pressure, one of the rollers being engraved with
obliquely set lines ruled from 125 to 600 to the lineal inch. The effect is ta
produce a great number of parallel flat surfaces on the doth, which causes it
to acquire a high luster. By previously heating the rollers, the finish may be

228 TECHNOLOGY OP CELLULOSE ESTERS

H. Lowe made a distinct advance in mercerization/ and followed
this up in 1900^ with basic improvements.

He clearly showed that in mercerizing cotton piece goods under
tension, in addition to obtaining the recognized advantages of
mercerizing (increased strength and aflfinity for coloring matters),
that the tension imparted a permanent luster tg the goods. This
discovery of Lowe did not receive the financial support which its
intrinsic value merited, and meeting with no encouragement he
allowed his patent rights to elapse. In the interem, R. Thomas
and E. Prevost,' who had been working along similar lines with
Egyptian cotton, and apparently oblivious to the previous work of
Lowe — also recognized that a permanent luster was obtainable
and took out patents in various coimtries.*

As soon as this product had been placed upon the market
wide-spread interest was aroused, and a demand created which
h£is not abated but increased to the present day. For some
time mercerization w£is confined to yam, but afterwards it was
recognized that piece goods could also be satisfactorily treated.
Litigation upon the validity of the Thomas and Prevost patents
was carried to adjudication in several countries, and were annuled
on the grotmds of prior disclosure in Lowe's patent specification,
and this adversely effected the patents issued after 1889, many
of which were allowed to lapse. ^

The temperature at which mercerization should be carried
on is a question of considerable moment, Mercer recommending
16° as the best temperatm-e for conducting the process. Rise in
temperature during alkaline impregnation is deleterious to the
result, while material reduction in temperature is apt to impart
a harsh feel to the finished goods. With lower temperattires

made permanent and quite simulate mercerized cotton. See L. Schreiner,
E. P. 7637, 1895; 3113, 6315, 1899; 2157, 1900; D. R. P. 113343, 112076,
1899. S. Jones, U. S. P. 1316958, 1919; J. S. C. I. 1919, 38, 897-A.

1. E. P. 20314, 1889; 4452, 1890; 17397, 1897; 2307, 1898.

2. E. P. 4452, 1900. J. Weiss, U. S. P. 586750, 1897.

3. R. Thomas and E. Prevost, E. P. 18040, 1895; 20714, 1896; 9517,
14201, 1897. D, R. P. 85504, 1895; 97664, 1898, addn. to D. R. P. 85564,
129883, 1900; F. P. 259625, 1896.

4. The E. Heberlein patents are, E. P. 27529, 1898; 4528, 1907; E. P.
4683, 1909. See also, Heberlein & Co., E. P. 108671, 1917; abst. J. S. C. I.
1918, 37, 297-A. U. S. P. 624800, 1899.

5. E. P. 4452, 1890; 18040, 1895; 20714, 1896; 9517, 14201, 1897. D.
R. P. 85565, 1895; 97664. D. R. Anm. 21427, 1898; 44213, 1908. F. P.
168742; 246244, 1895; 399904, 1909. A. Hawley, P. Crossland, F. Dixon,
E. P. 132647, 133441, 1918,

CBLLULOSE

229

mercerization may be carried on with less concentrated alkaline
Nations. Thomas and Prevost patented the application of
artificially cooled caustic soda for this purpose,^ maintaining that
the process may be carried on economically and eflSciently with
caustic soda of 15°-18° Tw. At the present time, however, re-
frigeration is seldom employed except to regulate the rise of
temperature of the caustic soda when acting upon the cellulose.

Mention is made in the specification of Mercer and elsewhere
in literature as to other efficient agents sulfuric acid,^ caustic
potash, zinc chloride,* etc.* for producing this result, but they
have little or no interest from a commercial point of view in this
connection.

The time required for mercerization has been recognized
from the first as being of very short dtu-ation — ^in fact may be
measiu-ed by seconds. E. Knecht* carried out some interesting
experiments with American cotton yam to shed light on this point,
the skeins after immersion being inmiediately neutralized and then
dyed in 1% Benzopurpurin, the results obtained being indicated
in the following table.

TABLE XXII.— MERCERIZATION OF COTTON

Immersion Time
in Alkali

Shrinkage
Per cent.

Amount Dyestuff
Taken Up
Per cent.

5

10
20
40
60
180

15.7
17.4
25.0
25.0
25.0
27.4

3.24
3.62
3.80
3.89
3.91
4.10

As will be observed, the above figures indicate the major
portion of the reaction takes place during the first five seconds.

A permanent luster may be obtained on cotton by various
means without tension, but none of the processes have as yet been

1 E P 9517 1897

2. M. Rauschenbach, E. P. 340, 1867. C. Brodbeck, E. P. 18119,
1890. K. Schreiner and K Grunert. D. R. P. 312087, 1916.

3. E. Bronnert, E. P. 18260, 1899.

4. J. Schneider. E. P. 19428, 1896, used sodium and potassium
sulfidies. W. Hall, E. P. 10708, 1898, used both alkali and acids. For mercer-
izing and bleaching simultaneously, see J. Copley, E. P. 24163, 1899.

5. J. Soc. Dyers Col. 1908, 24, 68, 112; Chem. Ztg. 1908, 32, 272;
Ztg. ang. Chem. 1909, 22, 243, 249; Lehne Faerb. Ztg. 1908, 276.

230 TECHNOLOGY OF CELLULOSE ESTERS

coinmerialized. Meister, Lucius and Bruening^ add a strong
solution of sodium silicate to the alkali, while Bayer and Co.^ add
a half volume of glycerol to one of caustic soda. The merceri-
zation of loose cotton' entails too much waste to make it a pajdng
proposition although many processes* have been devised for this
purpose. G. Tagliani* mercerizes cotton piece goods on one
side only by padding the side of the fabric with strong caustic
soda by means of an engraved steel cylinder/ but the process is
restricted to printed goods.

H. Lange,^ E. Hanausek,® J. Huebner alone,^ and with
Pope^^ and F. Teltscher" as well as others have sought the cause
of the increased luster of cotton mercerized under tension,** but
there is much lack of harmony in their results.

*'When viewed under the microscope in reflected light the
irregular surface of the cotton fiber is seen at the points at which
the light is reflected, to exhibit a strong luster, and the same holds
good for cotton which has been mercerized without tension.

1. E. P. 10784, 11313, 1897. D. R. P. 78601, 1897. D. R. P. 97664,
1898; Chem. Centr. 1898, 69, II, 1110. D. R. P. 103041, 1896; Chem. Centr.
1899, 70, II, 550.

2. E. P. 27020, 1897.

3. Lowe, E. P. 17397, 1897.

4. Gros and Boucart, D. R. P. 124135. 1898; F. P. 283587, 1898;
U. S. P. 677450, 1899. H. Brassard, D. R. P. 124856, 1900; U. S. P. 670098,
1901. J. Schmidt, D. R. P. 138893, 1901. C. Reichenbach, D. R. P. 129843,
1901; E. P. 18728, 1901. P. Boucart, D. R. P. 145582, 1901; E. P. 21645,
1901. T. Schiefner, D. R. P. 141623, 1901. J. Kleinewefers Sohne, D. R. P.
181927, 1905; F. P. 403724, 1909. E- Steiner, F. P. 364965, 1906. Heber-
lein & Co., D. R. P. 214512, 1907; E. P. 4528, 1907; F. P. 375068, 1907.
C. Ahnert, D. R. P. 209428, 1907; 225704, 1909. J. Copley, E. P. 12551,
1910. J. Robson, U. S. P. 975074. 1910.

5. E. P. 6249, 1899; D. R. P. 107916, 1897; F. P. 287814, 1899.

6. For hydrolyzing cellulosic materials, see Testrup and Wet Carbon-
izing, Ltd. E. P. Appl. 19389, 1918. For hydrated cellulose, see J. DeCew,
Belg. P. 256401, 1913; U. vS. P. 1140799, 1915; abst. J. S. C. I. 1915, 34, 711.

7. Faerb. Ztg. 1895-1896, 441; 1898, 197, 234. For mercerizing imder
pressure, refer to C. Ahnert, D. R. P. 181927, 204512, 209428. For mercer-
izing in a vacuum, see Societe Meyer Freres, F. P. 270670.

8. Dingl. Poly. 1897. 306, 19; 1898, 307, 180.

9. J. S. C. I. 1909, 28, 228; abst. J. Soc. Dyers Col. 1911, 27. 126.

10. J. S. C. I. 1904, 23, 404; Jour. vSoc. Dyers Col. 1903, li, 139. See
their E. P. 2758, 1904; abst. J. vS. C. I. 1905, 24, 85. D. R. P. 167930. 1904;
177166, 1905. E. P. 6384, 1904; 2993, 1905; D. R. P. 177166, W. Mather,
J. Huebner and W. Pope.

11. J. S. C. I. 1909, 28, 641; abst. C. A. 1910, 4, 1241; Bull. Soc. Chim.
1910, 8, 59; Chem. Zentr. 1909, 80, II, 1284; Jahr. Chem. 1909, 62, II, 383.

12. In a "Manual of Dyeing," Knecht, Rawson, Lowenthal, 1910, 1,
37, the explanation of the phenomenon of mercerization is given, as above
quoted.

CELLULOSE 231

In yam, however, but more especially in the piece, this luster
is not apparent, because the irregular reflecting surfaces of
the fibers disperse the reflected light in every direction and the
impression produced in the eye is that of a dull or lusterless siuiace.
The same holds good for cotton mercerized without tension.
But if a large proportion of the fibers in a piece of calico are caused
to lie in the same plane — e. g., by passing the piece through a
heated calender, a lustrous or glazed siuiace results. The effect
is not permanent because the fibers have not been set by the treat-
ment, and on being moistened with water r6snm€ their previous
irregular positions, which results in the disappearance of the luster.
But if cotton yam is mercerized under tension, it acquires, while
saturated with the caustic soda, a gelatinous, and to some extent
plastic condition, so that the fibers, whUe becommg rounded and
more translucent (and in this respect more like silk in structure),
are drawn out and stretched, and become set in this position by
the subsequent washing. We have consequently in the finished
yam a large proportion of stretched and straightened fibers, with
•a more or less round section lying parallel to each other, as in the
case of spun silk, so that the inherent luster of the fiber becomes
visible to the naked eye."

The mercerizing finish may be made more permanent
by various after treatments. P. Krais^ with the Bradford
Dyers Association' and M. . Petzold,' have advocated the
use of nitrocellulose dissolved in amyl acetate, similar proc-
esses having been described by J. Bemberg,* E. Mueller,^

1. E. P. 18742, 1904. U. S. P. 834913, 1906. D. R. P. 212695. 1905;
abst. J. S. C. I. 1905, 24, 887; 1909, 28, 653; Text. Rec. 1907, 32, 100; Text,
u. Faerb. Ztg. 1906, 4, 165.

2. D. R. P. 212696, 1903; Belg. R 182834, 1905. R. Ritter, D. R. P.
210499, 1907. W. Yates, E. P. 27693, 1907; D. R. P. 224343, 1908.

3. D. R. P. 224806, 225282, 1907; 211506, 216622, 1908; Chem. Ztg.
Rep. 1909, 664. H. Akyroyd and P. Krais, D, R. Anm. 6850, 1899; U. S. P.
667849, 1899. Compare J. WUde, D. R. P. 110184. J. Ashwell, D. R. P.
181466. J. Matter, D. R. P. 215045. Fischer and Rosenfelder, F. P. 285955;
D. R, P 113928

4. D. R. P. 198480, 1904. E. During, D. R. Anm. A-18422. E.
Schelling, F. P. 424434, 1911. D. Habel, D. R. P. 230669, 1909. M. Schuetze,
D. R. P. 128475. M. Kohl, D. R. P. 237835, 1910. M. Wunchmann, D. R.
P. 212263, 1908; 220484, 1909. G. Capron, D. R. P. 117733. F. P. 306837.
P. Wolf, D. R. P. 235661, 1908. H. Gassner, D. R. P. 113929. W. Hersch-
mann, D. R. P. 110508.

5. D. R. P. 222777. 1909. A. Martin, D. R. P. 218774, 1908. H.
Kearas, D. R. P. 138222, 1900. P. Hahn, D. R. P. 219838, 1908; D. R. Anm.
47637, 1909; 52445, 1910. F. P. 405551, 1909. E. P. 28329, 1910. H. Muller,

232 TECHNOUXJY OF CELLULOSE ESTERS

M. Petzold/ L. Chischin,* and F. Bayer and Co.,' in which
the cellouse nitrates are combined with amyl formate
and similar solvent combinations. The use of cellulose
acetate for this purpose, either alone,* or combined with other
cellulose esters^ has been patented by Lilienfeld. Viscose,*
albumen,^ resins,^ stearine,' and other bodies have been brought
forward from time to time as applicable for this purpose. ^^

D. R. P. 228042, 1909. H. Schubert, D. R. Anm. 25102, 1906.

1. D. R. Anm. 26083, 1910. O. Venter, D. R. P. 203745, 211566. 1907.
A. Palmer, E. P. 20645. 1909. L. WaUach. D. R. P. 202789, 1907. Akt.
Ges. Rothes Meer, D. R. P. 182937. 1906. A. Keller-Dorian. D. R. P. 185835^
1905. A. Bernhardt. D. R. P. 233514, 1909. J. Eck & Son, D. R. P. 144695;
197589. 1906; 232568, 1910.

2. D. R. Anm. 12045. 1903. J. Matter, D. R. Anm. 39012. 1909;
42356. 1910; D. R. P. 215045. 1908. M611er-Holtkamp. D. R. P. 207813,
217022, 1907. J. Palmer, U. S. P. 765398, 1904. H. Schubert, D. R. Anm.
25102, 1906. G. de Keukelaere, D. R. P. 223925, 1909.

3. D. R. P. 122351, abst. Wag. Jahr. 1901. II. 530; Chem.Ztg. 1901,
650. Zts. ang. Chem. 1901. 835; Jahr. Chem. 1901. 1417. D. R. P. 195315, abst.
Wag. Jahr. 1908. 54, II. 416; Chem. Zentr. 1908. 79, I, 1103; Chem. Ztg.
Rep. 1908. 32, 180.

4. L. Lilienfeld. U. S. P. 1031616. 1912; abst. J. S. C. I. 1912. 31, 770;
C. A. 1912, 6, 2687. E. P. 11354. 1909; abst. J. S. C. I. 1910. 29, 752. E. P.
18193. 1909. abst. J. S. C. I. 1910. 29, 575. E. P. 13100. 1910; abst. J. S. C. I.
1911. 30, 533. F. P. 408370. 1910; abst. J. S. C. I. 1910. 29, 624. First Add.
No. 12469. dated April 13. 1910, abst. J. S. C. I. 1910, 29, 1299. Second
Add. dated June 11, 1910; abst. J. S. C. I. 1910. 29, 1371. Aust. P. 29b. 4642-
10. June 21. 1909. U. S. P. 888516. 1908; abst. J. S. C. I. 1908, 27, 683;
C. A. 1908. 2, 2866. U. S. P. 904269. 1908; abst. J. S. C. I. 1908, 27, 1202.

E. P. 4597, 1906; abst. J. S. C. I. 1907, 26, 146. E. P. 592, 1907, abst. J. S. C.
I. 1908. 27, 73; C. A. 1908. 2, 2018. E. P. 14483. 1903; abst. J. S. C. I. 1903,
22, 1345. D/ R. P. 176664. 1903; abst. ^ts. ang. Chem. 1907. 20, 461. D. R.
P. 169782, 1904; 182773. 1904; abst. Zts. ang. Chem. 1907. 20, 2090. D. R.
P. 182773. 1904; 196315. 1905; 185456, 1906.

5. D. R. P. 175664, 1903; abst. Wag. Jahr. 1906, 52, II, 444; Zts. ang.
Chem. 1907, 20, 461.

6. A. Fielding-, E. P. 9849, 1903; abst. J. S. C. I. 1904, 23, 439. For
"mercerized paper." see Sci. Amer. 1917, 629.

7. E. Duering. D. R. P. 206901. 1907; abst. Chem. Ztg. Rep. 1909. 33,
512; Zts. ang. Chem. 1909. 22, 609. 217679. abst. Chem. Zte. Rep. 1910, 34,
67; Wag. Jahr. 1910. 56, II. 479; Zts. ang. Chem. 1910, d, 336. 218566,
1908; abst. Chem. Ztg. Rep. 1910, 120; Wag. Jahr. 1910, II, 479. See C.
Rumpf, D. R. P. 220349, 1907; abst. Chem. Ztg. Rep. 1910, 34, 180; Wag.
Jahr. 1910. 56, II. 481. D. R. Anm. 22188. 1907; 26012. 1908. W. Ader-
holdt. D. R. P. 235701. 1908; abst. Chem. Ztg. Rep. 1911. 35, 340; Wag. Jahr.
1911,57,11.468.

8. C. Goedtler, D. R. P. 110029. 1898; abst. Chem. Ztg. 1900. 24, 272;
Wag. Jahr. 1900. 46, II. 461 ; Zts. ang. Chem. 1900, 13, 323.

9. R. Huebner and J. H. Riley Co., E. P. 7972, 1908; abst. J. S. C. I.

1909, 28, 520. J. Huebner, D. R. P. 226521. 1909; abst. Chem. Ztg. Rep.

1910. 34, 540; Wag. Jahr. 1910. 56, 1, 484.

10. Grossmann Bros. F. P. 293983, 1899.

CELLULOSE 233

The production of crepe effects, as by the processes of P.
and G. Depoully,^ Heilmann,* Schwabe' and others/ Jtogethej;
with the moreening process of J. Bmpsall and E. Firth* are other
commercial ramifications of this art. Sizing may be combined
with lustering;* printing and creping may take place together;^
but usually in these combination processes the chemicals recovered
are so low that the method is unduly expensive, notwithstanding
the saving in labor by a combination of operations.

From observations of i partially mercerized cotton cloth, J.
Lester* believes the mercerization process in the individual fila-
ments goes on progressively from the periphery to the center.
J. Huebner* and C. Beadle and H. Stevens^® have studied the
effect of addition of NaCl to NaOH used in mercerizing. The
former found that when sodium chloride is present the shrinkage
is lessened, the affinity for dyestuffs diminished, and the degree
of luster impaired as compared with results under directly compar-
able conditions when no NaCl was added to the lye. The latter
show that the proportion of NaOH absorbed by the cellulose
becomes greater in the presence of NaCl, and that the addition
of other soluble salts alters the hydration and NaOH absorption
to a marked degree.

1. E. P. 28696, 1883; 8642, 1884; 15140, 1885; 5533, 1895; D. R. P.
30966, 1884; 37658, 1885.

2. Heilmann & Co., D. R. P. 83314, 1895; abst. Wag. Jahr. 1895, 41,
987; Zts. ang. Chem. 1896, 9, 26.

3. Schwabe & Co., D. R. P. 29504, 1897.

4. Wuerttemberg Kattun Manufaktur Heidenheim, D. R. P. 89977,
1895. Neunkirchner Druckfabriks, D. R. P. 101915.

5. J. Empsall and E. Firth, E. P. 156, 1900; abst. J. Soc. Dyers Color,
1901 17 71 78.

'6. 'e. Heberlein, E. P. 27529, 1898. J. Bolder, E. P. 19273, 1899.

7. W. Kay and Thomliebank Co. E. P. 19388, 20308, 1894; 6112, 1897.
Salis, Schwabe & Co. D. R. P. 29504, 1896. Badische Anilin & Soda Fahrik,
E. P. 5469, 1899; 45.34, 1900.

8. J. S. C. I. 1909, 28, 230; abst. C. A. 1910, 4, 1240; Chem. Zentr.
1909, 80, I, 1836; Jahr. Chem. 1909. 82, II, 1064; Wag. Jahr. 1909, 55, II,
413; Zts. ang. Chem. 1909, 22, 1038.

9. J. S. C. I. 1909, 28, 228; Chem. Ztg. 1908. 32, 220; Chem. Zentr.
1909, 80, I, 1836. J. Huebner, J. S. C. I. 1908, 27, 105; Proc. Manch. Lit.
Phil. Soc. 1908, 52, 2; abst. C. A. 1908, 2, 1187; 1347; Chem. News, 1908,
97, 10; Proc. Chem. Soc. 1907, 23, 304; Bull. Soc. Chim. 1908, 4, 1660; Rep.
Chim. 1909, 9, 238; Chem. Zentr. 1908, 79, I, 1097; Chem. Ztg. 32, 220;
Jahr. Chem. 1905-1908, II, 3185; Meyer Jahr. Chem. 1908, 18, 505; Wag.
Jahr. 1908, 54, II, 467; Zts. ang. Chem. 1908, 21, 87, 1760.

10. Eighth Intl. Cong. Appl. Chem. 1912, 13, 25; abst. C. A. 1912, 6,
313; J. C. S. 1912, 102, i, 947; Chem. Ztg. 1912, 38, 1222.

234 TECHNOIXKJY OF CELLULOSE ESTERS

I. Nakata^ has demonstrated experimentally that the strength
•f cotton yam under the mercerizing treatment is materially
diminished and then increased again by thoroughly washing with
water. He finds the mercerization process is most effective if
the boiled yam contains moisture to the extent of 75% on the dry
yam.

A. Dubosc* has described a combination lustering treatment,
the cloth being mercerized under tension in NaOH in the usual
manner, squeezed, and while still under tension is passed into a
solution containing 100 parts of 30% copper sulfate solution,
100 parts ammonia and 300-400 p^s of water. When the doth
appears brilliant and gelatinous it is again mercerized in 15^ B6.
NaOH, washed, acidified and rinsed.

The preparation of alkali cellulose by such methods as those
described by H. Eggert' and E. Block-Pimentel* are more properly
considered imder the section ** Viscose'* in another volume of this
series.*^ Flax* and jute^ may also be mercerized.

Cellulose Condensations. According to La Sole Artificielle^
a new condensation product of cellulose results by treating it

1. J. Chem. Ind. Tokyo, 1917, 20, 1224; abst. C. A. 1918, 12, 998; J. S. C.
I. 1918, 37, 203-A.

2. Sealed Note, No. 674; Bull. Soc. Ind. Rouen, 41, 337; abst. C. A.
1914, 33, 2951. H. Lange, Chem. Ztg. 1903, 27, 692, 735; abst. J. S. C. I.
1903, 22, 1242; Wag. Jahr. 1903, 49,447. W. Herbig, Zts. TextiHnd. 1899-
1900, 3, 671.

3. Kunst. 1913, 3, 381; abst. C. A. 1914, 8, 244. G. Lanzendorf^,
E. P. 21869, 1904. A. RUey, E. P. 11818, 1905. B. Beresin, E. P. 699&,
1906

4. E. P. 7893, 1912. See E. P. 10851, 1904, F. Holtkamp, Moeller
and E. Bucholz. E. P. 25445, 1906; T. Pickles. E. P. 4251, 1907; A. Silver-
wood and J. Taylor.

5. For early work on alkali cellulose, see Sachs, Sitz. Ber. Wien. Akad.
1859, 1; Mangin, Compt. rend. 1892, 113, 1069; Bull. Soc. bot. France, 1888,
35, 421. Hoppe-Seyler, Ber. 1870, 4, 15. See also, Ind. rubber, 1897, 14,
102.

6. E. Fremy and V. Urbain, E. P. 1816, 1882. D. R. P. 22370, 1882;
abst. J. S. C. I. 1883, 2, 276.

7. W. Lukacs, E. P. 3103, 1883.

In the process of S. Jones (U. S. P. 1316958, 1919; abst. C. A. 1919,
13, 3020) mercerization of cotton fibers woven with artificial silk formed of
viscose is effected without injury to the viscose silk by subjecting the composite
fabric to the action of a solution formed of alcohol 5.7% and 60° Tw. NaOH
solution 94.3%.

8. E. P. 9196, 1915; abst. C. A. 1916, 11, 3159. F. P. 477655, 1914;
abst. J. S. C. I. 1916, 35, 597. X. EschaUer, E. P. 25647, 1906; abst. J. S.
C. I. 1907, 26, 1292. F. P. 374724, 1906; abst. J. S. C. I. 1907, 26, 821;
Mon. Sci. 1908, 69, 29.

CELLULOSE 235

with trioxymethylene in the presence of ferric chloride or of
organic acids, with or without dehydrating agents such as alum
or calcium chloride. The product is stated to weigh more than
the original cellulose and to liberate formaldehyde on hydrolysis.

Where cellulose is treated with ferric chloride and formalde-
hyde and dried under high vacuum, trioxymethylene is produced,
the condensation product being formed upon stoving. This
product is said to possess greater resistance to water than the
original cellulose.

The process of E. Block-Pimental is similar.*

W. Vieweg has given a detailed description of the formalde-
hyde-cellulose of E. Blumer,^ who allows a mixture of dilute
alkali hydroxide of 5° B6. strength and formaldehyde to act upon
starch or cellulose for some hours in the cold, when it is heated
for a short time, the product washed with water, and then with
dilute acetic acid, the material being finally dried around 50°.

Cellulose and Benzene. In 1902 A. Nastukoff^ described
a compotmd obtained by the action of benzene upon a sulfuric
add solution of cellulose, which was at first considered as a tetra-
phenylcellulose, but subsequently was foimd to contain sulfur.
The product, which when dried at the ordinary temperature in
a desiccator corresponds to a tetraphenylcellulose plus two mole-
cules of SO2 with various amounts of water, was found to readily
nitrate and sulfonate. Upon dry distillation of this compound,

1. U. S. P. 1234720, 1917; abst. J. S. C. I. 1917, 36, 1044; C. A. 1917,
U, 2611. In an example of carrying the process into effect as shown in the
patent, cellulose is treated with formaldehyde in the presence of ferric chlor-
ide, alum or calcium chloride, the material being then dried in a vacutlm as
much as possible, and after desiccation is heated in an oven. In the first
phase of the reaction trioxymethylene is formed, which thereuiKMi reacts
with the cellulose in the presence of the ferric salt. The treated product is
said not to lose its original appearance or strength, while resistance to aqueous
liquids or water is materially increased. To 486 parts of cellulose, 90 parts
of triox)mie^ylene is employed. See this vol., p. 420.

2. D. R. P. 179590; abst. Papier Ztg. 1907, 32, 309, 398; Chem. Ztg.
1907, 31, 85; C. A. 1907, 1, 1319; J. S. C. I. 1907, 26, 1066; Chem. Zentr.
1907, 78, 1, 383; Wag. Jahr. 1906, 52, II, 79; Zts. ang. Chem. 1907, 20, 1246;
Jahr. Chem. 1905-1908, II, 948. A. Nodon (E. P. 6668, 1913; abst. C. A.
1914, 9, 2935; Kunst. 1915, 5, 215. F. P. 453111; abst. C. A. 1914, 8, 248;
Kunst. 1913, 3, 314) strengthens and renders cellulose rot-proof by super-
ficial impregnation with a solution of a salt as sodium chloride, or zinc chlor-
ide, followed by the prolonged passage of an electric current. Either period-
ically-reversed or alternating ciurents may be used.

3. J. Russ. Phys, Chem. Soc. 1902, 34, 231, 505; abst. J. C. S. 1902,
82, i, 362, 747; Chem. Centr. 1902, 73, I, 1277; II, 576; Chem. News, 1903,
88, 255; J. S. C. I. 1902, 21, 1302; Zts. Farben u. Textchem. 1, 633; abst
Chem. Centr. 1903, 74, I, 139.

236 TECHNOLOGY OF CELLULOSE ESTERS

toluene is obtained as the main product, while 45% benzoic acid
is yielded upon oxidation with potassium or sodium permanganate.^

By varying the method of treatment of the cellulose in sul-
furic acid with benzene, the product has been prepared so as to
contain but a small amount (0.43%) of sulfur and this has been
termed j8-phenyldesoxyn to distinguish it from the former material,
to which the name phenyldesoxyn was given. It appears to be
derived from cellulose by the replacement of three hydrogen by
three phenyl groups. With toluene, xylene and cumene, corres-
ponding desoxjrps result, which upon oxidation with permanganate
forms tolyl-, xylyl- and cumyl-desoxyn and yields 20% of tere-
phthalic, 4% terephthalic and 25% of trimellitica acid, and pyro-
mellitic acids respectively. Prehnitic or meUophanic acids could
not be found. In each of these four instances, carbonic and oxalic
(about 15%) adds are also formed. The cellulose residue in each
case appears to enter the benzene nucleus in the para position rela-
tive to methyl. It has been f otmd that dextrose, like cellulose, also
combines with bens^ene, forming apparently a compound in which
three hydroxyl groups have been replaced by three phenyl radicles.

Cellulose and Phenol. It has been known for some time^
that hard, soluble resinous products result upon the condensa-
tion of certain cai-bohydrates with phenols, and G. Mauthner*
has obtained patent protection for such a process. According to
his method liquid condensation products result when cotton is con-

1. J. Russ. Phys. Chem. Soc. 1907, 39, 1109; Zts. Farb. Ind. 1907, 6^
701; abst. Chem. Zentr. 1907, 78, I, 820; J. C. S. 1907. 92, i, 413; J. S. C. I.
1907, 26, 282; C. A. 1908, 2, 1274; Jahr. Chem. 1905-1908, II, 1427; Zts.
ang. Chem. 1907, 20, 1782. Compare E. P. 28638, 1902; abst. J. S. C. I.
1903, 32, 414; Chem. Ztg. 1904, tt, 435. F. Ephraim, Ber. 1901, 34, 2780;
abst. J. C. S. 1901, 80, i, 688; Bull. Soc. Chim. 1902, 28, 150; Chem. Centr.
1901, 72, II, 1008; Jahr. Chem. 1901, 54, 1271. For glucose phenyldesozine^
see A. Nastukoff and J. Kotjukow, Bull. Soc. Chim. 1909, (4), 6, 579; 1913,
(4), 13, 102; Jour. Russ. Phys. Chem. Soc. 1912, 44, 1152; abst. Chem. Zentr.
1913, I, 19. F. Fischer and W. Schneider, J. S. C. I. 1920, 39, 225-A.

2. C. Councler, Ber. 1895; 28, 24; abst. J. C. S. 1895, 68, i, 164; Bull.
Soc. Chim. 1895, 14, 898; Chem. Centr. 1895, 66, I, 481; Jahr. Chem. 1896,
48, 1294.

3. D. R. P. 247181; abst. Zts. ang. Chem. 1912, 2S, 1600; Chem.
Zentr. 1912, 83, II, 74; Chem. Ztg. Rep. 1912, 36, 332; Wag. Jahr. 1912,
S8, 11, 99; Friedlaender, 1910-1912, 10, 1056. See also D. R. P. 220582;
abst. Zts. ang. Chem. 1910, 23, 957; Chem. Zentr. 1910, 81, I, 1473; Chem.
Ztg. Rep. 1910, 34, 228; Wag. Jahr. 1910, 56, II, 586; Friedlaender, 1910-12.
10, 1060. D. R. P. 222512; abst. Zts. ang. Chem. 1910, 23, 1740; Chem. Zentr.
1910, n, II, 122; Chem. Ztg. Rep. 1910, 34, 298. D. R. P. 234806; abst.
Zts. ang. Chem. 1911, 24, 1336; Chem. Zentr. 1911, 82, II, 118; Chem. Ztg.
Rep. 1911, 35, 299; Wag. Jahr. 1911, 57, I, 5; Friedlaender, 1910-1912, 10,.
1058.

CELLULOSE 237

densed with phenol in the presence of mineral acids. For in-
stance, by heating a mixture of one kilo of phenol and 100 gm.
sulfuric acid with 350 gm. of cotton to 150-200°, a product is
obtained useful in the preparation of lacquers, varnishes and for
the impregnation of porous materials. Various products from
liquid to plastic masses result by varying the proportion of react-
ing constituents, and the temperature and time of heating.

Hemi-Celluloses. The cotyledons of Lupin seeds contain
cell-wall constituents which are easily soluble in dilute mineral
acids and which are known as hemi-celluloses, the seeds of Lu-
pinus hirsutus contain a considerable quantity of this material.
After the removal of the fat from the disintegrated seeds and
separation of the protein substances by means of caustic soda,
a powder is obtained which resembles starch flour, and consist-
ing about 90% of hemi-celluloses.^ According to N. Castoro*
there is no evidence that the hemi-celluloses of seed shells are
drawn again into metabolic processes and these substances can-
not, therefore, be called "reserve celluloses/' Structurally, the
hemi-celluloses are different from the fibrous celluloses, usually
occurring in parenchyma cells. By hydrolysis they are resolved
into crystalline monoses.

According to H. Buler' an examination of the literatiu-e on
the cellulose-cleaving enzymes, celluloses or cytases, leads to the
conclusion that if the group of reserve-carbohydrates or "hemi-
celluloses" be excl{ided, no case of the fission of pure cellulose
by the action of enzymes secreted either by fungi or higher
plants, has as yet been recorded. On the other hand, there is
abundant evidence at hand of the breaking down of true cellulose
due to the action of living bacteria in fungi.* In general the
study of the action of enzymes upon cellulose is complicated

1. E. Schulze and N. Castoro, Zts. physiol. Chem. 1902, 37, 40; 1903,
39, 318; abst. Chem. Centr. 1903, 74, I, 18; J. S. C. I. 1903, 22, 169; Jalir.
Chem. 1902, 55, 1064; 1903, 56, 1014; J. C. S. 1903, 84, i, 152, 793; BuU.
Soc. Chem. 1903, 30, 664.

2. Zts. physiol. Chem. 1906, 49, 96; abst. C. A. 1907, 1, 250; Chem.
Centr. 1906, 77, II, 1441; J. C. S. 1906, 90, ii, 884; 'Bull. Soc. Chim. 1907,
2, 542; Biochem. Centr. 1906, 5, 760; Jahr. Chem. 1905-1908, II, 965.

3. Zts. ang. Chem. 1912, 25, 250; abst. Chem. Zentr. 1912, 83, I,
1229; J. S. C. I. 1912, 31, 224; C. A. 1912, 6, 3517; J. C. S. 1912, 102, i, 327.

4. C. YUner, Zts. ang. Chem. 1912, 35, 103; abst. J. S. C. I. 1912, 31,
122; Chem. Zentr. 1912, 83, I, 1211; J. C. S. 1912, 102, i, 163; C. A. 1912, 6,
1224.

238 TECHNOLOGY OF CELLULOSE ESTERS

owing to the insolubility of the substratum. The author there-
fore has carried on his investigations with the soluble **cellulose-
dextrins" derived from cellulose by the action of sulfuric acid.^

The hemi-celluloses as complex carbohydrates are structur-
ally different from the fibrous celluloses, differ in physiological

1. For additional data concerning hemicellulose and the pentosans*
refer to E. Allen and B. Tollens, Ann. 1890, 260, 289. R. Bauer, Ann. 1888*
24S, 140; Landw. Versuchstat. 1893, 38, 191. S. Bey, Zts. klin. Med. 1900,
39, 305. G. Bertrand, Compt. rend. 1892, 111, 1492. G. Bertrand, Bull.
Soc. Chim. 1891, (3), 5, 546. C. Browne and B. Tollens, Ber. 1902, 3S, 1457.
G. de Chalmot, Ber. 1893, 26, 387, 791; abst. Chem. Centr. 1893, I, 1009;
Jahr. Agric. Chem. 1895, 197; Ber. 1894, 27, 422, 2722; Amer. Chem. J.
1894, 16, 218, 229. G. de Chalmot, Amer. Chem. J. 1894, IS, 276; 1895, 16»
689. C. Counder, Jahr. Agri. Chem. 1894, 638; Chem. Ztg. 1897, 21, 2.
Duering, Jour. Landw. 1897, 45, 79. Elfert, Bibliotheca botan. 1894, part 30.
E. Fischer, Ber. 1894, 27, 2486. G. Fownes, Ann. Chim. Phys. 1846, (3),
17, 460. E.Flint and B. Tollens, Landw. Versuchstat. 1893,42.381. G.
Fraps. Amer. Chem. J. 1901, 25, 601; abst. Chem. Centr. 1901, 72, II, 324.
P. Garros, Bull. Soc. Chim. 1894, U, 595; abst. Chem. Centr. 1894, 65, II,
317. R. Gans and B. Tollens, Ann. 1888, 249, 245. F. Goetze and Pfeififer,
Landw. Versuchstat. 1896, 47, 59. L. Gruenhut, Zts. anal. Chem. 1901, 40,
542. A. Guenther and Tollens, Ber. 1890, 23, 1751. R. Hauers and B.
Tollens, Ber. 1903, 36, 3306. A. Herzfeld, Ber. 1895, 28, 440. W. Herzfeld,
Zts. Ver. Ruebenzucker-Ind. 1897, 604. W. Hoffmeister, Landw. Jahr.
1889, IB, 767; Landw. Versuchstat. 1897, 48, 401. R. Jaeger and E. Junger,
Ber. 1902, 35, 4440; 1903, 36, 1222. Johnson, Jahr. Agrik. Chem. 1896, 197.
K. Katsuyama, Ber. 1902, 35, 669. H. Kiliana and F. Koehler, Ber. 1904,
37, 1210. Krueger and Tollens, Zts. Ver. Ruebenzuckerind. 1896, 21.
E. Kraft, Chem. Centr. 1902, 73, II, 482. E. Kroeber, Jour. Landw. 1901,
48, 357; 1902, 49, 7. Kroeber, Rimbach and Tollens, Zts. ang. Chem. 1902,
15, 477, 508; Zts. physiol. Chem. 1902, 36, E. v. Lippmann, Ber. 1887, 20,
1001. E. V. Lippmann, Ber. 1881, 14, 1509. C. Lintner and G. Duell,
Zts. ang. Chem. 1891, 4. 538; Chem. Centr. 1891, 62, II, 799. L. Maquenne,
Compt. rend. 1889, 109, 573. W. MaxweU, Amer. Chem. J. 1890, 12, 51;
Landw. Versuchstat. 1889, 36, 15. F. Mann, M. Kriiger and B. Tollens,
Zts. ang. Chem. 1896, 9, 33. A. Muntz, Compt. rend. 1882, 94, 453; 1886,
HO, 624; Ann. Chim. Phys. 1882, (5), 26, 121 ; 1887, (6), 10, 566. E. Salkowski,
Zts. physiol. Chem. 1892, 35, 240; 1901, 54, 162. A. Schoene and B. Tol-
lens, Jour. Landw. 1901, 48, 349. E. Schulze, E. Steiger and W. Maxwdl,
Zts. physiol. Chem. 1890, 14, 227; abst. Jahr. Chem. 1889, 42, 2087. C.
Schulze and B. Tollens, Ann. 1892, 271, 60; 1892, 271, 55; Landw. Versuch-
stat. 1892, 40, 367. E. Schulze. Ber. 1891, 24, 2277; Zts. physiol. Chem.
1892, 16, 387; 1894, 19, 38; Ber. 1889, 22, 1192; 1890, 23, 2579; Landw.
Jahr. 1892, 21, 72; 1894, 23, 1; Chem. Ztg. 1895, 19, 1465. A. Schoene and

B. Tollens, J. Landw. 1901, 49, 21; abst. Chem. Centr. 1901, 72, I, 1098.

C. Scheibler, Ber. 1873, 6, 612; 1868, 1, 58, 108. E. Schulze and E. Steiger*
Ber. 1887, 20, 290; Landw. Versuchstat. 1889, 36, 9; 1892, 41, 207. T.
Seliwanoff, Chem. Centr. 1889, 60, I, 549. P. SoUied, Chem. Ztg. 1901, 25»
1138. E. Steiger, Ber. 1886, 19, 827; Zts. physiol. Chem. 1887, 11, 373.
J. Stoklasa, Zts. Zuckerind. 1889, 23, 291, 387; Just. Jahr. 1899, II, 181.
E. Steiger and E. Schulze, Ber. 1890, 23, 3110. E. Stone, Ber. 1890. 23,
2576; 1895, 28, 1006. E. Subaschow, Zts. Ver. Ruebenzucker-Ind. 1896*
270. H. Suringar and Tollens, Jour. Landw. 1896, 44, 355. B. Tollens.
Ber. 1896, 29, 1202; 1903, 36, 221; Ann. 1890, 260. 289; 1892, 271, 60. B.
Tollens and Krueger, Zts. Ver. Rubenzucker-Ind. 4o, 480. B. Tollens* Jour.

CELLULOSE 239

function, and by hydrolysis are readily resolved into the crystal-
line monoses. As a class, the hemi-ceUuloses are less distinctly
characterized, and much more heterogeneous than the normal
celluloses.

C. Stine^ has patented a detonator charge consisting of
nitrated hemi-cellulose with a primer containing an initial deto-
nating composition.

Ash. Cellulose btuns quietly with a luminous, smoky flame,
leaving from 0.5%-2% of residue as ash, the major portion of
which is usually silica, and half of the remainder alumina and
iron oxide. In natural unpurified cotton, the ash has been stated
as 0.2%-0.5%, and this amount may readily be reduced to less
than 0.05% by careful purification. It has frequently been as-
serted that the silica found in cellulose has a distinct structural
function in carrying out the life processes of the cell, and exists
— ^in part at least — as organic silicon compounds. B. v. Ammon,*
A. Grimaldi,' P. Thenard,* A. Landenberg* and W. Lange," who
have carefully investigated this subject from various angles, ar-
rived independently at entirely negative conclusions.^ Although
the natural ash of cellulose seldom exceeds 2%, in some siliceous
plants it may rise as high as 30%.®

Landw. 1896, 44, 171. F. Ullik. Chem. Centr. 1894, II, 31. E. Votocek,
Zts. Zuckerind. 1899, 2S, 229. B. Welbel and S. Zeisel, Monatsh. 1895, 16,
283. S. Wdser and A. Zeitschek, Pflueg. Arch. 1902, 93, 98; abst. Jahr.
Chem. 1903, SS, 1007. H. Wheeler and B. Tollens, Ann. 1889, 254, 351.
W. Windisch and R. Hasse, Wochenschr. Brauerei, 1901, IB, 493. C.
Wittmann, Botan. Centr. 1901, 87, 373. J. Widsoe and B. Tollens, Ber.
1900, 20, 132. K. Yoshimura, Coll. Agric. Tokio, 1895, 2, 207. V. Zanotti,
Annuario See. chim. Milano, 1889, 27; abst. Chem. Centr. 1899, 70, 1, 1209.

1. U. S. P. 1313650, 1919; abst. J. S. C. I. 1919, 38, 742-A; C. A. 1919,
13, 2763. H. Timpe and J. Jurgens, E. P. 25400, 1910.

2. Dissertation. Cologne, 1862; abst. Jahr. Chem. 1862, 140.

3. Polli, AnnaU, 1870, SI, 109; Gazz. Chim. Ital. 1872, 2, II, 110;
abst. Ber. 1872, 5, 437.

4. Compt. rend. 1870, 70, 1412.

5. Ber. 1872, 5, 568; abst. Chem. News, 1872, 26, 36; J. C. S. 1872,
2S, 910; BuU. Soc. Chim. 1872, 18, 271; Jahr. Chem. 1872, 25, 795.

6. Ber. 1878, 11, 822; abst. Chem. News, 1879, 38, 47; J. C. S. 1878,
34, 682; Chem. Centr. 1878, 49, 458; Jahr. Chem. 1878, 31, 948; Jahr. rein
Chem. 1878, 6, 48.

7. They conducted their experiments upon the Equisetum or horse-
tail species, characterized by an ash high in silica, in which they endeavored
to determine the presence of organic silicon compounds analogous to the
corresponding carbon compounds. They showed that the functions of var-
ious plants were not disturbed by cultivation in silica-free soil.

8. As distinguished from mechanically contained dirt, not entering
into the structure of the plant.

240 TECHNOUX>Y OF CELLULOSE ESTERS

Producing Amorphous Cellulose for Subsequent Nitration.
According to the process of I. Kitsee,^ "amorphous cellulose"
may be produced "by applying an oil or fatty substance to a
portion of the stuiace of a fibrous material and then subjecting
the material to nitration, whereby only the parts which are not
protected with the oily substances are nitrated." In the more
rational process of L. Guiguet,* guncotton and nitrocellulose for
smokeless powders, may be preferably formed from a cellulose
precipitated from a fairly thin solution; e. g., in the form of fila-
ments, thus allowing the cellulose to be obtained in a more or
less homogeneous state and practically free from impurities.

In the English patent of the Dynamite Manufacturing Co.,'
a process for the nitration of cotton is described according to which
the cellulose before esterification is converted into a fine and im-
palpable powder and placed in the loose form in sulfuric acid.
The cellulose is allowed to remain in contact with this acid for
some time, then washed with pure water and dried; or the powder
may be dissolved in a mixture of sulfuric acid with water, and
then precipitated by mixing with a large volume of water and
finally dried. The celluloses treated by either of the above de-
scribed methods become after drying, fine impalpable powders.

The process of the Dynamit A. G.* for the treatment of
cellulose for facilitating the formation of nitrocellulose is similar,
in that the cellulose as cotton is first swelled with sulfuric acid
of 40° to 49° B^. or with concentrated solution of zinc chloride,
then washed to neutrality and dried in the usual manner.

The observation is worth recording that those who have
worked with amorphous celluloses in the finely divided condition
as above, have found a proneness to fume off in the nitrating

1. U. S. P. 767822, 1904; abst. J. S. C. I. 1904, 2S, 880; Mon. Sci.
1905, 62, 16. This amorphous ceUulose (I. Kitsee, U. S. P. 806348, 1905;
abst. J. S. C. I. 1906, 25, 28) is said to be excellent as an insulating material.
The process of insulating consists in moistening one side of the strips with
some solvent for the cellulose, moistening also the wire, and then, by means
of rollers, enclosing the wire in the strips of cellulose.

2. E. P. 30075, 1913. F. P. 464028, 1913; abst. J. S. C. I. 1914, 33,
376; C. A. 1914, 8, 3122. See P. Girard, F. P. 438131, 1911; addn. 15399,
1912.

3. E. P. 2519, 1878. See also J. Huetter, D. R. P. 3867, 1878; abst.
Dingl. Poly. 1879, 232, 188.

4. D. R. P. 4410, 1878; abst. J. A. C. S. 1879, 1, 303; Dingl. Pcrfy.
1879, 232, 188; Chem. Centr. 1879, 50, 720. See Gocher Oehmuhle Gebr.
van den Bosch, Belg. P. 190009, 1906.

CRLLUIX>SB 241

mixture, coupled with an unusually low 3deld, due to large amounts
of cotton going into solution or suspension in the nitrating fluid.

In the process of J. KaUivoda and A. Boehm,^ one part of per-
manganate of potash is dissolved in ten parts of water and the
solution cooled to 12° to 14°, when two to three parts of com-
minuted cellulose is added and the paste stirred. The reaction
is considered completed when the gas evolution stops. This
mass is washed until neutral and the residue mixed with one part
of nitric acid of 1.3 sp. gr. and left for 12 hours. The mixture
is then heated to 40°-70° on the water bath until the manganese
has gone into solution as manganese nitrate and the amorphous
cellulose separated as sediment. The solution is then decanted
and the manganese recovered as permanganate, while the cellu-
lose is washed until entirely neutral, ground, pressed to 30%-^0%
of water and dried. It is then nitrated in the customary manner
and used as smokeless powder.

The invention of A. Luck and A. Dumford^ relates to the
production of nitrocellulose in a dense powdery form, which, ac-
cording to the patentees, may be produced by employing a cotton
or other form of cellulose whose structure has been destroyed,
which is converted into a powder and then nitrated. The cellu-
lose is first treated with "solvents," as sulfuric acid and water;
zinc chloride in aqueous solution; or zinc chloride in HCl and
water, the cellulose being afterwards separated from its solution
in a hydrated state in the form of gelatinous granules. Prom
sulfuric acid or zinc chloride, the cellulose is precipitated by merely
diluting with water. It is recommended to keep the solution in
a constant state of agitation during the precipitation process,
and that the solution be largely diluted with water in order to
obtain the gelatinous granules in a finer state. The precipitate
is washed, and dried with constant stirring in order to facilitate
the formation of a dense powder.

Lignocelluloses (Jute and Wood).^ Lignocellulose^ has

1. D. R. P. 70067; abst. Wag. Jahr. 1893, 39, 426; Chem. Centr. 1893,
€4, II, 1015; Zts. ang. Chem. 1893, 6, 465; Ber. 1893, ^ 598.

2. E. P. 4769, 1895; abst. Chem. Centr. 1896, 67, I, 1150; J. S. C. I.
1896, IS, 134.

3. "Lignose" has also been applied as a trade name for an explosive
described by Trutzschler-Falkenstein (Deutsche Ind. Ztg. 1875, 375; abst.
Wag. Jahr. 1875, 21, 532; Chem. Tech. Rep. 1876. 14, I, 217), and consist-
ing of nitroglycerol and wood fiber.

4. For detailed development of the lignocelluloses, consult : £. Kabsch,

•242 TECHNOLOGY OF CELLULOSE ESTERS

already been referred to as one of the three groups into which
compound celluloses may be divided. In addition to comprizing

Jahrb. wiss. Bot. 1863, 3, 357. Raspail, J. Scien. d'observat. II, p.
415. Autenrieth and Bayrhammer, Berz. Jahresber. 1822, I, 107.
Bracoiinot, Ann. Chim. phys. 1819, (2), 12; Gilbert's Annal. 1819,
^, 347. Payen, Compt. rend. 1838, 7, 1052; 8, 51 and 169; 1839, S,
149; Ann. sc. nat. (2), 1839, II, 21; Mem. sur les devdoppements des vege-
taux, p. 271. Baumhauer, J. prakt. Chem. 1844, 22, 210; Berzelius Jahr.
1846, 25, 585. Promberg, Berz. Jahr. 1845, 24, 462. Chevandier, Ann.
Chim. Phys. 1844, (3), 10, 129; Compt. rend. 1845, 20, 138. Petersen and
Schoedler, Ann. 17, 142. Mulder, Physiol. Chem. 1844, p. 209, 475. Pou-
marede and L. Figuier, Compt. rend. 1846, 23, 918; J. prakt. Chem. 1847,
42, 25; Berz. Jahr. 1849, 28, 340. Sacc. Ann. Chim. Phys. 1849, (3), 25,
218. F. Schulze, Chem. Centr. 1857. 321; Jahr. Chem. 1857, 491. Mohl,
Flora, 1840. Fremy, Compt. rend. 48, p. 202, 862. Fremy and Terreil,
Compt. rend. 1868, 00, 456; Bull. soc. chim. 1868, p. 436; Ber. chem. Ges.
1877, 10, 90. Fremy and Urbam, Compt. rend. 1882, 34, 108; Ann. sc. nat.
1882, (6), 13, 353. Fremy, Compt. rend. 1876, 83, 1136. Erdmann, Lieb.
Ann. 138, p. 1; Suppl. Vol. V, p. 233. F. Bente, Ber. chem. Ges. 1875, 8,
476; Landw. Vesuchstat. 1876, 19, 164. A. Stutzer, Ber. chem. Ges. 1875,
8, 575. Runge, Pogg. Ann. 1834, 31, 65. Tiemann and Haarmann, Ber.
chem. Ges. 1874. 7, 608. Schapringer, Dingl. poly. J. 1865, 178, 166. Wies-
ner, Karstens bot. Unters. 1866, I, 200. T. Thomsen, J. prakt. Chem. 19,
p. 146. F. Koch. Pharm. Ztg. Russland, 1886, 2S; Ber. chem Ges. 20, Ref.
145. Wheeler and Tollens, Lieb. Ann. 1889, 254, 304. Allen and Tollens,
Lieb. Ann. 1890, 280, 289. Hoppe-Seyler, Zeits. phys. Chem. 1888, 13, 84.
G. Lange, Ibid. 1889, 14, 15, 283. M. Singer, Sitzungsber. Wien. Akad. 1882,
85, 1,.345. Czapek, Zeits. phys. Chem. 1899, 27, 141, concerning "Hadromal."

E. Gottlieb, J. prakt. Chem. 1883, 28, 385. R. Otto, Bot. Centralbl. 1901,
88, 210, 331. Henneberg, Lieb. Ann. 146, p. 130. Holdefleiss, Landw. Jahr-
buecher, Suppl. Vol. I, 1877. E. Kern, J. fuer Landwirtsch. 1877. Tollens
and Suringar, Zeits. ang. Chem. 1896, 712, 742. F. Buehler, Chem. Centr.
1903, I, 1051. R. Bader, Chem. Ztg. 1895, p. 856. M. Potter, Annals of
Botan. 1904, 18, 121. Czapek, Ber. bot. Ges. 1899, 17, 166. Baltzer, Just
Jahresber. 1873, 295. Cross and Bevan, J. C. S. 1883, I, 19; Ber.
chem. Ges. 1880, 13, 1998; J. C. S. 1889, 55, 199; Pharm. J. Trans. 1884.
III. 570; Ber. chem. Ges. 1895. 28, II, 1940; 1891, 24, 1772; 1894, 20,
2520. Lindsey and Tollens, Lieb. Ann. 1891, 267, 370. H. Tauss, Dingl.
poly. J. 2Z3, 286; 1890, 276, 411. T. SeliwanofT, Chem. Centr. 1889, I, 549.
G. Bertrand, Compt. rend. 1899, 129, 1025. Kimoto, Agric. Coll. Tokio,
1902, p. 253. H. Wheeler and B. Tollens, Ber. chem. Ges. 1889, 22, 1046. Dra-
gen dorflF, Analyse d. Pfl. 1882, p. 87, 90, 93. Schippe. Dissert. Dorpat, 1882;
Just. Jahresb. 1882, I, 95. Winterstein. Zeits. physiol. Chem. 1893, 17, 381.
R. Bader, Chem. Ztg. 1895, 19, 55. Johnson, Am. Chem. J. 1896, 18, 214.
Hoffmeister, Landw. Jahrbuecher, 1888, 17, 259. Tollens, J. Landw. 1896.
44, 171. Okamiu^, Landw. Versuch. 1894, 45, 437. Councler, Forstl.
Blaetter, 1889, p. 307; Chem. Ztg. 1892, 16, 1719. Lange, Zeits. physiol.
Chem. 1889, 14, 15, 283. Streeb, Chem. Centr. 1893, II, 184. C. Macule,
Verhalten verholz. Memb. gegen KMn04 Habilitationsschrift, Stuttgart,
1901. L. de Lamarliere, Rev. Gen. Bot. 1903, 15, 149. Singer, Sitz. Ber.
Wien. Akad. 1882, 85, (1), 349. HoflFmeister, Land,w. Jahrbuecher, 1888, 17,
260. Nickel. Bot. Centr. 1889, 38, 754. Allen and Tollens, Lieb. Ann.
1891, 267, 304. Lmdsey and Tollens, Lieb. Annal. 1891, 267, 341. Anony-
mous, Dingl. poly. J. 216, 372. T. Hartig, Jahr. f. Foerster, 1861, I, 263.

F. V. Hoehnel, Sitz. Ber. Wien. Akad. 1877, 76, (I), 527. J. Wiesner, Wien.
Akad. 1878, 77, (I), 60. Ihl, Chem. Ztg. 1885, p. 266. L. Schaeffer, Ber.
-chem. Ges. 1869, II, 91. Niggl, Flora, 1881, 545. v. Baeyer, Lieb. Annal.

CELLULOSE 243^

a large portion of all woody tissue, lignocelltilose is contained in
vegetable fibers such as jute, straw and esparto grass. The fol-

140. Mattirolo, Zeits. wiss. Mikrosk, 1885, II, 354. Ihl, Chem. Ztg. 1890,
14, 1571. Lubavin, Ber. chem. Ges. 1869, II, 99. E. and H. Erdmann,.
Ber. chem. Ges. 1899, 32, II, 1213. T. and D. Tomassi, Ber. chem. Ges.
1881, 14, II, 1834. H. Molisch, Ber. botan. Ges. 1886, IV, No. 7. F. Runge,
Pogg. Ann. 1834, 31, 65. Tangl, Flora, 1874, 239. Molisch, Verhandl.
zool. bot. Ges. Wien, 1887, p. 30. Wuerster, Ber.' chem. Ges. 1887, p. 808.
Nickel, Farbenreakt. der Kohlenstofifverbindungen, 2nd Ed. 1890, p. 51.
Hegler, Flora, 1890, p. 33; Botan. Centralbl. 1889, 38, 616. A. Piutti, Gazz.
chim. ital. 1898, 28, II, 168. Ihl, Chem. Ztg. 1890, 14, 1571. EUram, Chem.
Centr. 1896, II, 99. E. Senft, Monatsh. Chem. 1904, 25, 397. Ihl, Chem.
Ztg. 1890, 1907. E. Covelli. Chem. Ztg. 1901, 25, 684. A. Kaiaer, Chem.
Ztg. 1902, 26, 335. Seliwanoff, Bot. Centr. 1891, 45, 279. Nickel, Chem.
Ztg. 1887, p. 1520; Bot. Centr. 1889, 38, 753. Czapek, Zeits. phys. Chem.
1899, 27, 153. H. Tauss, Chem. Centr. 1889, II, 445; 1890, II, 187. IhU
Chem. Ztg. 1889, 432, 560; 1891, 201. Hancock and Dahl, Ber. chem. Ges.
1895, 28, 1558. van Ketel, Beihefte bot. Centr. 1897, 423. Reinitzer,
Zeitschr, phys. Chem. 1890, 14, 466. Czapek, Zeits. phys. Chem. 1899, 27,.
154. Molisch, Ber. bot. Ges. 1886, 4, 301. M. Potter, Ann. of Bot. 1904,
18, 121. Lewakowsky, Just Jahresber. 1882, I, 422. Hancock and Dahl,
Ber. chem. Ges. 1895, 28, II, 1558. Schorler, "Isis," 1894. Berthold, Pro-
toplasmamechanik, ^. 39. T. Morawski, Chem. Centr. 1888, II, 1630.
Benedikt and Bamberger, Monatsh. Chem. 1890, U, 260. A. Herzog, Chem.
Ztg., 1896, 20, 461. A. Cieslar, Mitteil. forstl. Versuchwes. Osterr. 1897„
No. 23; Chem. Centr. 1899, I, 1214. Zetsche, Bot. Centr. 1897, 70, 206.
F. V. Faber, Ber. botan. Ges. 1904, 22, 177. Boodle, Ann. of Bot. 1902,
18, 180. Devaux, Soc. Linnaenne Bordeaux, April 22, 1903. Molisch, Sitz.
Ber. Wien. Akad. June. 1881, Vol. 84. Sadebeck, Just Jahresber. 1887, II,
514. Molisch, Wien. Akad. 1879, 1, p. 80, No. 1, 2. Belohoubek, Bot Centr.
1884; Just. Jahresber. 1884, I, 176, II, 399. Tschirch and A. WiU,
Arch. Pharm. 1899, 237, No. 5, 369. Lange, Flora, 1891, p. 393. A. Nathan-
sohn, Jahrb. wiss. Bot. 1898, 32, 671. Schellenberg, Jahrb. wiss. Bot. 1896,
20, 236. Warburg, Ber. bot. Ges. 1893, U, 425. Sonntag, Landw. Jahrb.

1891, 21, 839; Ber. bot. Ges. 1901, p. 138; Jahrb. wiss. Bot. 1903, 30, 71.
For data on cork substance (Suberin) consult: Payen, Compt. rend. 1868,.
80, 509. Haberlandt, Oest. botan. Zts. 1874, 24, 229. K. Kuegler, Arch.
Pharm. 1884, 222, 217. Chevreul, Ann. Chim. Phys. 1807, (1), 82, 323;
1815, 08, 141; Schw. Jour. 1816, 18, 323. Brandes, Schw. Jfour. 1821, 32,
393. Fremy and Urbam, J. Pharm. Chim. 1882, (5), 5, 113. F. Czapek,.
Biochemie der Pflanzen, 1905, 1, 574. O. Doepping, Ann. 1843, 45, 286.
Van Wisselingh, Arch, neerland, 1888, 12, Part 1; 1893, 28, 305; Justs botan.
Jahr. 1888, I, 689; Verhandl. d. Akad. Amsterdam, 1892; Chem. Centr.

1892, II, 516. F. Flueckiger, Arch. Pharm. 1890, 228, 690. E. Gilson, La
Cellule, 1890, 8, 87. F. v. Hoehnel, Sitzungber. Wien. Akad. 1877, 78, I,
527. L. Brugnatelli, Crells Ann. 1787, 1, 145. B. la Grange, Ann. Chim. Phys.
1797, (1), B, 42. M. V. Schmidt, Monatsh. 1904, 25, 302. C. Istrati and A.
Ostrogovich, Compt. rend. 1899, 128, 1581. Siewert, Zts. ges. Naturwiss.
1867, 30, 129. Braeutigam, Pharm. Centralh. 1898, 30, No. 23. Thoms,
Pharm. Centralh. 1898, 30, 699. C. Correns, Sitzungsber. Wien. Akad.
1888, 07, 658. L. Petit, Compt. rend. Biol. 1903, 55. 31; Botan. Literaturbl.
1903, 280. A. Zimmermann, Zts. wiss. Mikr. 1902, 10, 525. G. Lagerheim,
Zts. wiss. Mikr. 1902, 10, 525. A. Bayer, Ber. 1872, 5, 1096. Kleeberg.
Ann. 1891, 283, 285. Caro, Ber. 1892, 25, 939. Moehlau and Kahl, Ber.
1898, 31, 251. E. Drabble and M. Nierenstein, Biochem. Jour. 1907, 2,.
No. 3; Collegium, 1907, 179; Chem. Centr. 1907, II, 79.

244

TECHNOLOGY OF CELLULOSE ESTERS

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CBLLULOSE 245

lowing table gives comparative data relating to, various cellulose
materials.^

The fiber of the jute, which is derived from two species of
plants, Corchortcs capsularis and C, olitorius (nattu-al order Til-
iaceae), is a simple tissue and is not subject to such various mod-
ifications as wood. It is, therefore, a more favorable subject for
the preliminary study of the nattu'e of lignocellulose.^

The plants of the Corchorus species are annuals.' The seeds
are sown in April or May and grow to a height of 8-15 feet and
have long, straight, cylindrical stems, V» to '/4 inch in thickness.
The fiber is located between the bark and the central woody
cylinder of the stem, and is surrotmded by a gummy product
consisting mainly of pectoses. Flowering takes place in August
or September. The fiber is freed from other material by the
well known process of retting. The stems, tied in bundles, are
immersed in pits containing water and allowed to remain tmtil
fermentation of the gummy matter is completed, this process
lasting from 7 to 30 days, the length of time depending on the
age of the plants, temperature of the water and other conditions.
The material is inspected at intervals during the retting treatment
in order to ascertain when the fiber separates most readily. This
examination is necessary, since if the fermentation be allowed to
proceed too far, a weak fiber deficient in luster results. If, on

1. H. Mueller, "Pflanzenfaser." The figures given for jute and wheat
straw include pectic matter; for esparto and bamboo, include protein and
pectic matter; and under lignin for different woods, also include pectic matter.

2. A. Hantzsch and K. Schniter, Ber. 1887, 20, 2033; abst. J. C. S.
1887, S2, 925; BuU. Soc. Chim. 1888, 4$, 211; Jahr. Chem. 1887, 40, 1343.
C. Cross, E. Sevan and Barnes, Papierfabr. 1909, 7, 155. C. Cross and E.
Bevan, J. S. C. I. 1908, 27, 1129; 1892, 11, 966; abst. Mon. Sci. 1893, 41,
889; Ber. 1893, 26, R, 594; Chem. Centr. 1893, 64, I, 407; Chem. Ztg. 1892,
16, 1863. C. Cross, E. Bevan and C. Beadle, Ber. 1893, 26, 2521; abst.
Chem. News, 1893, 68, 225, 235; J. C. S. 1894, 66, i, 63; Bull. Soc. Chim.
1894, 12, 442; Chem. Centr. 1894, 65, I, 23; Jahr. Chem. 1893, 46, 885;
Meyer Jahr. Chem. 1893, 3, 515; Wag. Jahr. 1893, 39, 975. E. Chorley
and W. Ramsay, J. S. C. I. 1892, 11, 395, 872; abst. Chem. Centr. 1893, 64,
I, 189; Chem. Ztg. 1893. 17, 653, 1709; Jahr. Chem. 1892, 45, 2897, 2898.
J. Collie, J. C. S. 1894, 65, 262; abst. Chem. News, 1894, 68, 81; Bull. Soc.
Chim. 1894, 12, 1448; Ber. 1894, 27, R, 417; Chem. Centr. 1894, 65, I, 579;
Jahr. Chem. 1894, 47, 758; Jahr. organ. Chem. 1894, 2, 11. P. Sestini, Gazz.
chim. ital. 1880, 10, 240, 355; abst. Chem. News, 1880, 42. 271; J. C. S. 1880.
38, 538, 865; Ber. 1880, 13, 1877; Jahr. Chem. 1880, 33, 1026; Jahr. rein
Chem. 1880, 8, 488.

3. E. Goulding and W. Dunstan, "Cotton and other Vegetable Pibers,"
131, 135. See Raspail, Jour, scienc. d'observat. 2, 415. Autenrieth and
Bayerhammer, Berz. Jahr. Chem. 1822, 1, 107.

246 TECHNOWXJY OF CELLUi:X)SB ESTERS

the other hand, the fermentation process is not allowed to pro-
ceed far enough a gummy product results. When the retting is
completed, the bundle is unfastened and the bast fiber removed
from the wood and freed from cortex, hand labor being employed
in these processes. The washed, separated fiber is dried in the
sim or preferably in the shade. The dried material is made up
into bundles, sorted according to quality and color, and finally
packed by hydraulic presses into bales for export.

The jute fiber is from 5 to 12 feet long and of a light yellow
color with a pronounced luster. According to E. Goulding and
W. Dunstan,^ each strand is composed of a large number of ul-
timate fibers from 2 to 5 mm. long and 0.02 to 0.25 mm. in diam-
eter. A transverse section of a filament of jute reveals from 8 to
20 ultimate fibers. This length of fiber in the case of flax or
hemp is 25 to 40 mm., which difference accoimts for the struc-
tural inferiority of jute as compared with other fibers.^

Jute is weaker than flax or hemp and less durable. It may

1. A specimen of "extra fine" Calcutta jute gave the following results
upon analysis: moisture, 9.6%; ash, 0.7%; loss on a-hydrolysis, 9.1%; loss
on /5-hydrolysis, 13.1%; cellulose, 77.7%.

2. Many plants of the natural orders Malvaceae and Tiliaceae yield
bast fibers which resemble lignified jtite fiber and are capable of replacing
it in manufacture. The same method of purification is employed as with
jute. The following plants have been used as jute substitutes: Abution
species (yield the so-called China jute). Hibiscus species (of which the
Hibiscus cannabinus is grown in considerable quantities and yields a fiber
called "Bimlipatam jute'0> Other important plants of this species are
Hibiscus abelmosckus and Hibiscus esculentus (also known as "Okra/' "Awk-
raw" or "Bhindi"); Hibiscus guineensis (also known as "Ramo"); HibiS'
cus lunariifolius (also known as "Ramma"); Hibiscus quinquelobus (also
known as "Kowe," "Corwey," "Nassim" and "West African jute"); Hibis-
cus rostdlatus; Hibiscus sabdariffa (also known as "Rama") ; Hibiscus squamo-
sus; Hibiscus tiliaceus (also known as "Ba£Foodo julo"). In addition, plants
of the following species give fibers which may act as jute substitutes: Honck-
enya fidfolia (natural order Tiliaceae) also known as "Naptmti," "Potepo"
or "Bolobolo;" Sida species (natural order Malvaceae), {S. carpinifolia, 5.
rhombifolia and S. urens); Triumfetta (natural order Tiliaceae), (T. cordifolia
and T. rkomboidea); Urena species (nattu^ order Malvaceae) (also known
as "Na fen fe," "subwe," "Akeiri," (Urena lobata is known in Brazil as "Ara-
mina fiber), anotiier plant of this species which yields a jute substitute is
Urena sinuata (known also as "Rama"). Cellulon, made from wood pulp
(Board of Trade J. April 25, 1918; J. S. C. I. 1918, 37, 203-R), is a substitute
for jute of a different type. The pulp is conducted over drums the stuiaces
of which are divided into parallels corresponding to the number of the yam
to be produced. The roving, which consists of a solid mass of cellulose, is
taken from the drum by a special apparatus and then twisted (finished or
twined) on a spinning machine. In the Scherbach process a mixture of
pulp and cotton waste or wool is spun. The pulp, or mixtures containing
pulp, is obtained in fiber form by squeezing the material under high pres-
sure through small holes in plates.

CBLI<UIX>SE 247

readily be dyed and is capable of combining directly with basic
dyestufFs. Jute on bleaching becomes weak and brittle, and even
soaking in water causes deterioration. It may be readily bleached
with dilute potassium permanganate after the fiber is first washed
with dilute alkali, although the process is imduly expensive.
The more usual hypochlorite bath is employed in practice, when
bleaching is resorted to. Bleaching tends to produce a soft prod-
uct with a high luster. The process in presence of water, tmless
carefully conducted, weakens the fiber^ Bales of jute, especially
if the moisture content be high, often deteriorate during trans-
port, the deterioration being most marked in the center of the
bale, the action being considered as due to bacteria.

Jute, compared with cotton cellulose, shows a higher ratio
percentage of carbon and hydrogen to oxygen.

C

H

O

Liimocellulose (jute)

46.0-47
44.4

6.8-6.1
6.4

47.2-47.9
49.3

Cotton cellulose

It is impossible to fix any definite empirical formula, owing
to the variations in composition which are encountered. Even
the conditions under which the fiber is grown influences its com-
position to a marked extent. However, the higher ratio percent-
age of carbon and hydrogen to oxygen in lignocellulose (jute), as
compared with the ratio in cotton cellulose, would indicate that
the relation of cellulose to lignocellulose may be represented by
supposing dehydration to have taken place in the case of the
latter. This representation is in agreement with the view of
Sachsse. On physiological groimds this worker suggests that
lignocellulose is a product of the metabolism of cellulose. C.
Cross and E. Bevan* favor this view. From extended researches
on jute, they conclude generally that lignification is a result of
the gradual modification of cellulose, in which the products formed
remain combined with the parent substance. •

Jute cellulose is considerably more reactive than normal cel-

1. "Cellulose," p. 178. For the action of chlorine on lignocellulose,
see C. Cross and E. Bevan, Chem. News, 1888, 58, 215; 1891, 64, 63; J. C. S.
1889, 55, 199; abst. J. C. S. 1892, 62, 129; J. S. C. I. 1891, 10, 786; Ber. 1889,
22, R, 62, 348; Jahr. Chem. 1888, 41, 2326; 1889, 42, 2106.

248 TECHNOLOGY OF CELLULOSE ESTERS

lulose.^ It combines with chlorine to form a well defined, yellow,
chlorinated derivative which answers to certain characteristic
tests. One of these consists in treating the chlorinated fiber
with sodium sulfite, when a magenta coloration is obtained.
Aniline salts in aqueous solution color the jute fiber a deep golden
yellow. Ferric chloride produces a brownish green color. Solu-
tions obtained by mixing ferric chloride and potassium ferricyan-
ide in equimolecular proportions, stain the fiber a deep blue color,
and as much as 50% of the weight of pigment may be absorbed.
Salts of nitraniline also produce a characteristic reaction. When
jute is treated with a hot solution of p-nitraniline (2 cc.) in hydro-
chloric acid (100 cc.) a deep blood-red stain is rapidly produced.
Other substances, such as many of the soluble aromatic dye-
stuffs, also color the jute. Iodine is rapidly absorbed by jute
and the fiber stained a deep brown color. With alkylsulfonic
acids, a red or blue color is obtained,* depending upon the amotmt

1. Sachsse, "Chemie u. Physiologic der Farbstoffe, Kohlenhydrate u.
Proteinsubstanzen/' Leipzig, 1877. For data concerning a jute substitute
called "Cellulon," see Paper, 1917, 22, No. 13, p. 19; Paper Makers Monthly,
1918, 56, 168.

2. See "Lignone Reactions and Constitution," C. Cross and E. Bevan,
J. Soc. Dyers and Col. 1916, 32, 136; abst J. S. C. I. 1916, 35, 628; Year book
Pharmacy, 1891, 91., They have found that with hydroxylamine, the max-
imum conbination in the case of jute lignocellulose corresponds to 0.18% of
nitrogen fixed. With phloroglucinol and hydrochloric acid, it is confirmed
that the color reaction only accounts for a fraction of the total combination.
The major reaction is attributed to a diketo-cyclohexene group in the Ugnone
complex, while the color reaction is accounted for by the presence of a frac-
tional quantity of an aldehydic group, probably a derivative of hydroxyfur-
fural. Higher results than are afforded by the standard method are obtained
by drying down an excess of a solution of phloroglucinol in dilute hydrochloric
acid in presence of the lignocellulose, exposed to the air for a period of four
days. Both the phenol and the acid are thereby concentrated on the fiber;
in this way a figure of 8.9% was obtained with a specimen of wood meal
showing 6.84% after 16 hours by the standard method. Determinations were
also made with pyrogallol by the air-drying process and the fixation of 7.6%
on the wood lignocellulose was recorded. Jute digested with strong (33%)
hydrochloric acid for six days at ordinary temperature lost 17% by weight;
this was mainly confined to the furfural-yielding constituent (/3-cellulose)
which passed into the add solution with a loss of about one-third of its fur-
fural yield. The hydrolyzed solution contained 3% of acetic acid on
the original fiber, and the fiber residue after oxidation with chromic add in
presence of dilute sulfuiic add yielded 6% more; thus the effect of the t^^eat-
ment was a considerable increase in the total yield of volatile add. The
action of ethereal hydrogen chloride on the jute fiber was also mainly con-
fined to the /3-cellulose, but no volatile acid was obtained in the extract.
Oxidation of the lignone complex in the lignocellulose by chromic add in
presence of dilute sulfuric acid, yidds for the main part, simple adds, acetic,
oxalic, and carbonic, in proportions varying with the quantity of chromic

CELLULOSE 249

of reagent used. The aromatic sulfonic acids induce the same
reaction. Naphthalenesulfonic acid gives a blue color, while
anthracenesulfonic acid produces a deep red color. With ben-
zenesulfonic acid an intense deep blue color results.

Jute fiber in presence of a solution of phloroglucinol in hydro-
chloric acid (density 1.06) assumes a reddish violet color,* the
color reaction, however, accounting for a fraction only of the total
combination. In a quantitative study of this reaction, C. Cross
and E. Bevan found that a considerable time (16 hours) was
required to obtain maximum combination. With hydroxylamine

add and the strength of the sulfuric add. By the indpient roasting of ligno-
cellulose and cellulose the authors have isolated maltol (methylhydroxypyrone)
and suggest from this that the pyrone configuration is represented in some
portion of the constitutional structtu-e of these bodies. C. Schwalbe and E.
Becker (Zts. ang. Chem. 1919, 32, 126;abst. J. S. C. I. 1919,38,408-A) have
blade comparative examinations of flax, hemp and spruce, utilizing the
scutching wastes, consisting mainly of partides of flax and hemp woods ("sprit"
or "sheave"). These were analyzed according to Schwalbe's scheme. The
ash was free from manganese. The fat and wax were estimated in two ways
with different results, viz., by extraction with ether, followed by alcohol,
and by extraction with a mixture of equal volumes of alcohol and benzene.
It would appear that alcohol alone is capable of extracting certain substances
other than fat, wax, and resin. In both materials the cholesterol test for
resin was positive. Attempts to estimate the lignin according to Kdnig's
method by dissolving out the cellulose with sulfuric add did not give very
reliable results. The following method with preliminary disintegration of
the structure by hydrolysis gave concordant values, but too great reliance
should not be placed on their interpretation: 1 gm. of substance was moist-
ened with strong hydrochloric add (sp. gr. 1.19) in a stoppered bottle and
heated for some time; the stopper was then removed and the material in the
bottle dried on the water bath. The hydrolyzed product was collected on
an asbestos filter, washed, and the material, together with the asbestos, was
digested with 50 cc. of 72% sulftuic add at the ordinary temperature for
1-2 days. The residue was collected in a Gooch crudble, dried, weighed,
ignited, and the lignin calculated by difference. Pectin was estimated by
von Fellenberg's method (J. S. C. I. 1917, 36, 1190) by means of the
methyl alcohol produced on heating with dilute acids. Pentosans were
estimated from the furfural value according to Tollens and Krober, the
phlorogludde predpitate being afterwards extracted with alcohol to give the
methylfurfural value, the results of which, however, were somewhat variable.
Cdlulose was estimated by Sieber and Walther's modification of Cross and
Bevan's method (J. S. C. I. 1913, 32, 974), and since the cellulose retained
the greater portion of the pentosans, these Were deducted from the cellulose
results. A substantial amount of acetic add was formed on distillation with
dilute sulfuric add according to Schorger's method. The anal3rtical results
are summarized in the table below, together with the values of spruce wood
for comparison. It is to be noted, however, that the woody portions of
flax and hemp show a doser similarity to the dicotyledonous woods than to
coniferous woods, particularly as regards their high content of pentosans and
the substantial yield of acetic acid. The sum of the proximate constituents
calculated from the analytical results amounts to considerably over 100%
and the authors propose to reject the direct lignin values, substituting for
them the average value of 20%-21% which has been established for the

250

TECHNOI.OGY OI^ CELLULOSE ESTERS

they found the reaction to be incomplete, corresponding to but
wood of foliage trees, and permits of accurate generalizations.

Ash

Wax, Fat and Resin:

(a) Ether extract

(b) Alcohol extract

(c) Sum of (a) and (b)

(d) Alcohol-benzene extract

Methyl value

Pectin (according to von Fellenberg) . . . .

Acetic acid (Schorger's method)

Protein, N X 6.25

Furfural

Pentosan

Methylpentosan

Cellulose containing pentosan

Cellulose corrected for pentosan

Lignin (residue from 72% sulfuric acid) . .

Calculated on Dry Substance

•

Flax

Hemp

Spruce

Sprit

Sprit

Wood

1.40

1.20

1.00

1.38

1.20

0.6

1.31

1.95

0.38

2.69

3.15

0.98

2.34

2.23

• • ■ •

2.68

2.55

2.33

2.68

0.98

0.14

4.79

4.04

1.6

2.70

2.85

1.2

13.81

13.03

■ • « •

23.59

22.15

11

0.47

0.51

• • • •

62.99

71.13

60

46.35

50.52

53

23.77

30.13

30

1. See A. Wheeler (Ber. 1907, 40, 888; Chem. News, 1907, 95,299
Jour. Soc. Dyers Col. 1907, 23, 214; Chem. Zentr. 1907, 78, II, 186; Jahr
Chem. 1905-1908, II, 965; see also E. Grandmougin, Ber. 1907, 40, 2453
abst. Jahr. Chem. 1905-1908, II, 966, who uses p-nitraniline hydrochloride
J. Hertkorn (Chem. Ztg. 1902, 36, 632; abst. J. S. C. I. 1902, n, 725, 1041
J. C. S. 1902, 82, ii, 632; Rep. Chim. 1903, 3, 16; Chem. Centr. 1902, 73, II
481 ; Jahr. Chem. 1902, 55, 1052) has pointed out that not only does amy!
sulfuric acid give a red or blue coloration with ligneous matter according to
the quantity of the reagent used, but all the alkyl sulfuric acids and the
aromatic sulfonic acids give the same coloration, notably the higher mem-
bers of the series. Naphthalene sulfonic acid gives a blue coloration, while
anthracene sulfonic acid produces a deep red with ligneous matter, cellulose
giving no coloration under the same conditions. By heating benzene with
sulfuric acid till sulfurous acid is evolved, a reagent is produced, which gives
an intense blue with wood-pulp. Cellulose is also slightly colored by this
reagent. A. Backe, Compt. rend. 1910, 150, 541; 151, 78; abst. C. A. 1910,
4, 624, 1509, 2936; J. C. S. 1910, 98, i, 225, 544; J. S. C. I. 1910, 29, 447,
970; Bull. Soc. Chim. 1910, 7, 1064; Chem. Zentr. 1910, 81, I, 1387, 1647;
Jahr. Chem. 1910, 63, 1371, 1696; Wag. Jahr. 1910, 56, II, 309. E. Erdmann and
C. Schaefer, Ber. 1910, 43, 2398; abst. C. A. 1910, 4, 3223; J. C. S. 1910,
98, i, 718; J. S. C. I. 1910, 29, 1198; Bull. Soc. Chim. 1911, 10, 445; Rep.
Chim. 1911, 11, 117; Chem. Zentr. 1910, 81, II, 1304; Jahr. Chem. 1910,
63, II. 418; Meyer Jahr. Chem. 1910, 20, 253. R. Benedikt and M. Bam-
berger, Monatsh. 1890, U, 260; abst. Chem. News, 1892, 65, 21; J. C. S. 1890,
58, 1474; J. S. C. I. 1890, 9, 1156; Bull. Soc. Chim. 1891, 5, 535; Ber. 1890,
23, R, 649; Chem. Centr. 1890, 61, II, 608; Chem. Zts. 1890, 14, 872; Jahr.
Chem. 1890, 43, 2555; Wag. Jahr. 1890, 36, 1156; Zts. ang. Chem. 1890, 3,
741. C. Cross, E. Bevan and J. Briggs, Ber. 1907, 40, 3119; abst. Chem.
News, 1907, 96, 40; J. C. S. 1907, 92, i, 750; J. S. C. I. 1907, 26, 941; BuU.
Soc. Chim. 1908, 4, 903; Rep. Chim. 1907, 7, 450; Chem. Zentr. 1907, 78,
II, 1362; Jahr. Chem. 1905-1908, II, 966; Wag. Jahr. 1907, 53, 506; Zts. ang.
Chem. 1908, 21, 1184; Biochem. Centr. 1907, 6, 513.

CELLULOSE 251

0.18% of nitrogen fixed. The major reaction is attributed by
them to be due to a diketocydohexene group in the lignone com-
plex, while the color reaction is accounted for by the presence of
a very smaU quantity of an aldehydic group — ^probably a deriv-
ative of hydroxjrfurfural. Jute contains 3 to 4% of methoxyl
group as estimated by Zeisel's method.

When exposed to the action of hydrolyzing agents, jute is
partially resolved into soluble bodies, furfuraldehyde having been
fotmd among the products of decomposition. C. Cross and E.
Bevan in treating jute with 33% hydrochloric acid for six days
at ordinary temperature, find a loss of 17% in the weight of the
fiber. This is mainly confined to the furfural-yielding constitu-
ents which pass into the acid solution with the loss of about one-
third of its furfural yield. The hydrolyzed solution contains 3%
of acetic acid on the original fiber, and the residue, after oxidation
with chromic acid in presence of sulfuric acid, yields a further
6% of acetic acid. On boiling with dilute alkaline solutions (3
to 4% caustic soda) at high temperatures (140°-180°), the jute
is resolved into cellulose and bodies of an acetic nature. Among
the latter is acetic acid as well as complex adds erf high molecular
weight. However, using an elevated temperature and concen-
trated alkaline solutions in excess, the molecule is completely
broken down, the degradation products being mainly acetic and
oxalic acids. Small proportions of carbon dioxide, methane and
carbon monoxide also are produced.

Nitric add acts on jute fiber with the oxidation of the lig-
none portion, leaving behind a residue of cellulose. The reac-
tion, however, requires nitrous acid for its completion, since in
the presence of urea the action is a simple hydrolytic one. In
the destructive oxidation with nitric acid, the main products ob-
tained are oxalic and acetic acids.* The chloro-compound formed

1. W. Thorn, Dingl. Poly. 1873, 210, 24; abst. Chem. News, 1874,
29, 218; J. C. S. 1874, 27, 297; Bull. Soc. Chim. 1874, 21, 92; Mon. Sci. 1874,
IS, 99; Chem. Centr. 1873, 44, 744, 763; Chem. Tech. Rep. 1873, 12, II,
140; Jahr. Chem. 1873, 26, 1016; J. prakt. Chem. 1873, 116, 182; Wag. Jahr.
1873, IS, 428; Poly. Centr. 1873, 39, 1427; Hannover. Wochenblatt f. Handel
u. Gewerbe, 1873, 391. J. Lifschtitz and Chem. Pabrik Grtinau, Landshoff
and Meyer, D. R. P. 69807; abst. Zts. ang. Chem. 1893, 6, 465; Chem. Centr.
1893, 64, II, 1015; Chem. Ztg. 1893, 17, 1213; 1894, 18, 1089; Chem. Tech.
Rep. 1893, 32, II, 272; Wag. Jahr. 1893, 39, 427; Ber. 1893, 26, R, 921; Mon.
Sci. 1893, 42, 200; Meyer Jahr. Chem. 1893, 3, 366. F. Tiemann and W.
Haarmann, Ber. 1874, 7, 608; abst. Chem. News, 1874, 30, 3; Ann. Chim.

252 TECHNOWXJY OF CELLULOSE ESTERS

from jute is a well defined substitution product. About one-half
of the chlorine which reacts in the case of jute, appears as hydro-
gen chloride, thus indicating the probable absence of secondary
reactions. The product after washing can be purified by pre-
cipitation from alcohol. It is apparently pure, since it has not
been resolved into other substances by fractional precipitation or
by fmlher chlorination. By treatment with suitable reagents,
such as sodium sulfite solution, the chlorinated complex is broken
down, leaving behind a residue of cellulose. A fiuther examina-
tion of the chlorinated compotmd indicates a relationship with
the polyhydric aromatic phenols. Reduction yields a tridiloro-
p)rrogallol. This latter reaction indicates a relation between jute
lignocellulose and the tannins. The presence of groups related
to the tannin complex in jute lignocellulose probably accoimts
for the ready absorption of various dyes, since these groups may
retain their mordanting power in the complex.

The lignocellulose molecule is considered by C. Cross^ to
consist of cellulose combined with aromatic groupings. The lig-
nocellulose complex is composed of two or more celluloses (a-
cellulose and /3-cellulose) in union with a lignone group and may
be represented thus:

CO o o q_.

HC AcH.(CH,.CO)^HC ACH.CH^H.CH<(_ l^g^
CHa CO

This formula, it is claimed, accounts for the quantitative action
of chlorine on cellulose, and the resolution by bisulfite. The
production of acetic acid in many of the reactions (hydrolysis
and oxidation) which involve a breaking down of the molecule
may be explained by this formula. It also takes into considera-
tion the presence of CHsO and OH groups, and is in agreement

Phys. 1874, (6), 3, 327; BuU. Soc. Chira. 1874, 22, 386; Compt. rend. 1874.
78, 1366; Mon. Sci. 1874, 1€, 577; Chem. Centr. 1874, 45, 356; Jahr. Chem.
1874, 20, 519, 888; Berl. Akad. Ber. 1874, 333; Pharm. J. Trans. (3), 4, 996;
Proc. Roy. Soc. 1874, 22, 398; Poly. Centr. 1874, 40, 989; Jahr. rein Chem.
1874, 2, 399, 490.

1. J. Soc. Dyers Col. 1914, 30, 346; abst. J. S. C. I. 1914, 33, 1201;
C. A. 1915, 9, 1393. For action of dilute nitric acid on lignocellulose, consult
C. Cross and E. Bevan, Ber. 1891, 24, 1772; abst. J. C. S. 1891, 00, 1001;
T. S. C. I. 1891, 10, 831; Chem. News, 1891, 63, 210; Chem. Centr. 1891.
02, I, 969. For products of dry distillation of Juniperus oxycedrus, and
other coniferae, consult R. Huerre, J. Pharm. Chim. 1919, 19, 33, 65; abst.
C. A. 1919 , 13, 1369.

CELLULOSE 253

with the results obtained on oxidation of ligxiocellnlose by ozone. ^
The chemical treatment of jute indicates that the lignocellu-
lose or bastose is composed of a more resistant a-cellulose and
a less resistant /3-cellulose. The a-cellulose comprizes oxidized
radicals, while the /3-cellulose contains methoxy groups. The
a-cellulose is estimated by boiling the jute fiber for five minutes
with a 1% solution of caustic soda and then washing the insol-
uble portion free from alkali, drying and weighing. The /3-cel-
lulose may be determined as follows: The sample is boiled for
one hour with 1% alkali (caustic soda) and then treated as in
the case of the a-cellulose.

By heating jute or cellulose to a temperature of 100-200°,
3-hydroxy-2-methyl-y-p)rrone (maltol) is fotmd among the prod-
ucts formed:

• H H

CO o

\=/

OH CH,

It has been suggested that the pyrone configuration represents
some portion of the structxu'e of lignocellulose.

Jute fiber is dissolved by the same solvents that attack cellu-
lose and it is to be noted that these solvents are not able to bring
about any resolution into fractions of different composition.
Jute also deports, itself like cellulose on nitration, the nitro-jutes
being described elsewhere in detail in this work.

A preferential break-down of the lignocellulose molecule is
possible by the action of various chemicals,' the chlorination
method yielding the highest percentage of cellulose residue.
This is probably due to the absence of any important secondary
reactions which oxidize the cellulose complex.

A somewhat similar method has been proposed by H. Miiller,
which consists in alternately treating the material with cold

, 1. C. Doree and M. Cunningham, J. C. S. 1913, 103, 677; abst. C. A.
1913, 7, 2385; J. S. C. I. 1913, 30, 482; BuU. Soc. Chim. 1913, 14, 950; Chem.
Zentr. 1913, 84, II, 246. For the jute substitute of C. Rich, see D. R. P.
308214.

2. See C. Schwalbe, Zts. ang. Chem. 1918, 31, 193; abst. J. S. C. I. 1918,
37, 686-A. J. Lawrence, Met. Chem. Eng. 1917, IS, 416; J. S. C. I. 1917,
3S, 383, 543. For chemical constitution of fir, M. Mueller and O. Heigis,
D. R. P. 284681, 1914; abst. J. S. C. I. 1915, 34, 1048; Chem. Zentr. 1915,
S$, II, 112; Zts. ang. Chem. 1915, 28, II, 351.

264

TECHNOLOGY OF CELLULOSE ESTERS

bromine water, followed by an alkaline solution such as aqueous
ammonia. It is usually necessary to repeat this action several
times. As compared with the dilorination method, the results
are generally somewhat lower. By treatment with aqueous sul-
fites or bisulfites at elevated temperatures under pressure, the
lignone complex is removed, but there is also some attendant
hydrolysis of the furfural yielding cellulose. Other methods
which involve the breaking down of a portion of the cellulose as
well as the lignone, are (a) Schultze's method using nitric acid
and potassium chlorate at the room temperature, or (6) heating
at a temperature of 60° with a 5% to 10% solution of nitric acid,
or (c) digestion of the jute with alkali sulfite or bisulfite.

Woods from various sources which have been freed from
such extraneous materials as resins, tannins, etc., have approx-
imately constant composition, the carbon content of the separated
and purified wood being in general, higher than that of normal
cellulose, as will be seen from the following analyses by E. Gott-
lieb i^

TABLE XXVI.— COMPOSITION OF WOOD

Wood

Composition

Percentage
Ash

C

H

N

O

Oak

50.16
49.18
48.99
49.06
48.88
50.36
60.31

6.02
6.27
6.20
6.11
6.06
5.92
6.20

43.45
43.98

0.37
0.57
0.50
0.57
0.29
0.28
0.37

Ash

Hornbeam

Beech

44.
0.09

31

44.17

Birch

0.10
0.05
0.04

44.67
43.39
43.08

Fir

Pine

Wood is the lignified tissue of perennial stems, and in con-
sequence its lignocellulose content is probably modified to a greater
extent than is the case with jute. The chemistry of lignocellu-
lose has therefore been developed in the main from the study of
simple tissues such as those of the jute fiber.

Wood lignocellulose closely resembles jute lignocellulose in
many of its reactions. On distillation with dilute hydrochloric

1. J. prakt. Chem. 1883, (2), 136, 385; abst. Chem. News, 1884, 4$»
115; J. C. S. 1884, 46 477; Bull. Soc. Chim. 1884, 42, 12; Mon. Sd. 1884,
26, 128; Ber. 1883, 16, 3064; Chem. Ztg. 1883, 7, 1695; Jahr. Chem. 1883,
36, 1773.

cELLUi:x)SE 255

acid considerable quantities of furfiu-aldehyde are obtained in
both cases. It has been shown also by Benedikt and Bamberger
that a methoxy group is present, the amount varying slightly
with the species of wood, and ranging between 4% to 6% of
methoxy group. On account of the slight variation in the CH«0
content it has been proposed to utilize this approximate content
in estimating mechanical wood pulp in unknown mixtures.^
Wood is resolved into acetic and other acids of low molecular
weight by treatment with suitable reagents. By processes in-
volving hydrolysis with acids or alkalis, acetic acid is produced
in amounts up to 10%. By drastic treatment with alkalis, con-
siderable quantities of acetic acid are obtained, together with
oxalic add. By heating sawdust or wood chips with twice its
weight of caustic potash and caustic soda at 240°-250° for one
hour the main product obtained is oxalic acid. One part of
cellulose will yield, imder these conditions, 1.2 parts of oxalic
acid. 2

The action of chlorine on wood lignocellulose yields similar
products to those obtained with jute fiber, except in the case of
coniferous woods. These latter give a somewhat different color

1. R. Benedikt and M. Bamberger, Monatsh. 1890, U, 267; abst.
Chem. News, 1892, 65, 21; J. C. S. 1890, 58. 1474; J. S. C. I. 1890, 9, 1156;
BuU. Soc. Chim. 1891, 5, 535; Ber. 1890, 23, R, 649; Chem. Centr. 1890,
€1, II, 608; Chem. Ztg. 1890, 14, 872; Jahr. Chem. 1890, 43, 2555; Wag.
Jahr. 1890, 36, 1166; Zts. ang. Chem. 1890, 3, 741.

2. A. von Hedenstrdm, Chem. Ztg. 1910, 34, 613; 1911, 35, 853; abst.
C. A. 19U, 5, 3729; J. C. S. 1911, 112, i, 767; Mon. Sci. 1912, 76, 345; Chem.
Zentr. 1911, 82, II, 748; Zts. ang. Chem. 1911, 24, 2085. See also L. Gay-
Lussac, Ann. Chim. Phys. 1829, 41, 398; Edinb. J. Nat. Geogr. Sci. 1830,
1, 384; Erd. J. tech. Chem. 1829, 6, 387; Phil. Mag. 1829, 6, 367; Pogg. Ann.
Phys. 1829, 17, 171, 528; Quart. J. Sci. 1829, 2, 414; Schweiger's J. 1830,
58, 87. F. Hoppe-Seyler, Zts. physiolog. Chem. 13, 77. Capitaine and von
Hertling, D. R. P. 84230; abst. Chem. Centr. 1896, 67, I, 184; Ber. 1895,
28, R, 1080; Wag. Jahr. 1895, 41, 547; Zts. ang. Chem. 1895, 8, 675; Jahr.
Chem. 1895, 48, 1148. Elektrochemische Werke, G. m. b. H., D. R. P. 144150;
abst. Wag. Jahr. 1903, 4$, II, 8; Chem. Centr. 1903, 74, II, 777; Chem. Ztg.
1903, 27, 901; Zts. ang. Chem. 1903, 16, 924; Chem. Zts. 1904, 3, 166, 277.
C. Graebe and H. KraflFt, Ber. 1906, 3S, 794. For the production of methyl
alcohol from residual products of sulfate cellulose manufacture, see H. Berg-
strom, F. P. 433168, 1911. U. S. P. 1129542, 1915; abst. J. S. C. I. 1912,
31, 123; 1915, 34, 349. Papierfab. 1909, 8. 970; 1912, 10, 251; J. S. C. I.
1908, 27, 1037; 1909, 28, 37, 162; 1912, 31, 278. H. Tiemann (J. Frank.
Inst. 1919, 188, 27; abst. C. A. 1919, 13, 2118) has investigated the com-
position and structure of wood, and those factors which affect its drying.
Analyses are recorded of the internal stresses which occur in wood as mois-
ture is lost, and the wood passes from the green condition to the perfectly
dry state.

256

TECHNOLOGY OF CBLLULOSB ESTERS

reaction with sodium sulfite, especially in concentrated solution.

E. Heuser and C. Skioldebrand^ have prepared lignin from
spruce wood sawdust, previously extracted by ether, by hydro-
lyzing the cellulose with 42% HCl according to the method of
Willstatter and Zechmeister. Two treatments with the strong
HCl left the lignin apparently free from cellulose, giving a yield
of 33.12% of dry lignin on the dry wood substance. The lignin
contained, in the air-dry state, 9.25% of moisture and 0.485%
of ash; it yielded no furfural on distillation with HCl, but showed
a Cu value of 12.90% by Schwalbe's method. The methyl value
according to Zeisel's method was 6.77%. This lignin was de-
structively distilled and the results are compared in the following
table with those obtained from the raw wood and wood cellulose
by Klason:

1

Charcoal

Tar

Acetone

Methyl alcohol.
Acetic add

CO2

CwHm

CO

CH4

Spruce

Cotton

Wood

Lignin

Wood

Cellulose

Cellulose

37.81

38.82

34.86

60.641

8.8

4.16

6.28

13.00

0.20

0.07

0.13

0.19

0.96

0.07

0.90

3.19

1.39

2.79

1.09/

56.50

67.87

62.90

9.60)

1.72

1.53

1.56

2.00

32.55

36.37

32.42

50.90

9.23

4.23

3.12

37.60)

%

by weight

on dry

ash-free

substance

%

by volume
on

the gases

In the distillation of the lignin, charring began at 270° and the
reaction was most intense at 400°-450°; gas was still produced
up to 627°. As in the case of wood and cellulose, the reaction
was exothermic. The formation of CO2 per unit of time was
largest at the beginning of the gasification and then fell off rapidly.
The lignin is distinguished from the other materials by the large
production of CH4 and CO and the small production of CO2;
thus the heating value of the gas from lignin is very high. In a
similar way the yield of charcoal and tar is very high in the
case of the lignin as compared with the other materials. As
regards the yield of CH3OH the result was disappointing, as it
should have been three times as much as that obtained from

1. Zts. ang. Chem. 1919, 32, I, 41; abst. C. A. 1919, 13, 2769; J. S. C.
I. 1919, 38, 216-A.

CISI.LULOSE 257

raw wood; this deficiency is attributed to the breaking up of the
methoxyl groups into gases, owing to the higher temperature
employed.

If the lignin be digested with dilute HCl under steam pressure,
larger yields of CHsOH can be obtained than by destructive dis-
tillation. The acetone also is probably derived from the same
groups and the relative yield is low for the same reason; the
acetone produced by the distillation of wood cellulose may be
derived from the methylpentosans. Acetic acid is formed from
the lignin, but only to the extent of one-third of the amount
produced from the raw woo^. Acetic acid is derived both from
the cellulose and the lignin and in larger quantities from the
former than from the latter; the absence of furfural-yielding
> groups from the lignin precludes the pentosans as the source of
the acetic acid.

P. Waentig and W. Gierisch^ have determined the degree
of lignificatibn of vegetable fibers by measuring the action of
chlorine under specified conditions upon fibers containing lignin,
it appears to be possible to determine the degree of lignification.
The material to be chlorinated is placed in a small U-tube with
ground-in stoppers, which is connected with an absorption ves-
sel charged with 10% hydrochloric acid, through which the current
of chlorine is passed and becomes saturated with moisture before
entering the reaction tube. The outlet of the latter is connected
with a Second U-tube containing calcium chloride to retain the
moisture from the reaction tube. The apparatus is weighed
before the chlorination and again after the excess of chlorine has
been removed by means of a current of air, and the percentage
chlorine absorption is calculated from the increase in weight.
Pine wood freshly ground to a powder gave in duplicate deter-
minations chlorine values of 43.7 and 43.2. When treated by
Willstatter and Zechmeister's method of hydrolysis with hydro-
chloric acid and subsequent extraction with alcohol and ether,
this pine wood yielded 28% of lignin free from chlorine and ash.
On chlorination as described, this lignin showed a chlorine value
of 143.0. Finely ground rye straw showed a chlorine value of
30.5, and when hydrolyzed by the method of Willstatter and
Zechmeister, left 22.4%, residue containing 1.81% chlorine and

1. Zts. ang. Chem. 1919, 32, 173; abst. J. S. C. I. 1919, 38, 530-A.

258

TECHNOLOGY O^ CELLULOSE ESTERS

13.05% of ash, corresponding with 19.1% of lignin. This had
a chlorine value of 144.7, which was almost the same as that of
pine wood lignin. From a comparison of the chlorine values of
lignified fibers with those of the isolated lignins it appears prob-
able that the "lignin" is relatively unchanged in the hydrolytic
process. The specific action of chlorine makes it a more suitable
reagent than alkalis or acids for the oxidation or decomposition
of fibers.

The following analyses of wood are recorded by W. Dore:^

Red-
wood

Yellow
Pine

Sugar
Pine

Live
Oak

Blue
Gum

Loss at 160" C

%

8.53
0.29
4.14
0.80
7.84
47.58
27.62

%

8.98

2.02

1.36

1.54

10.47

48.38

23.60

%
9.84

2.56

1.71

1.98

9.13

48.67

23.23

%

7.72

0.30

4.00

.3.52

7.15

47.52

13.59

%
10.12

0.06

2.24

1.81

12.25

51.48

13.28

Benzene extract

Alcohol extract

Water-soluble

Soluble in l%NaOH....
Cellulose

Lignin

96.80

96.35

97.12

83.80

91.24

The benzene and alcohol extracts were determined by extracting
the dried wood (in the form of sawdust) for 6 hours successively
with benzene and alcohol. The wood was then dried again and
boiled for 3 hours with water to obtain the water-soluble con-
stituents, and next boiled for 1 hour with 1% sodium hydroxide
solution. The washed wood remaining after these treatments
was, while still moist, transferred to a flask and the cellulose
determined by a modification of Cross and Bevan's method.
The chlorination was carried out in vacuo; the air was exhausted
from the flask and chlorine then admitted slowly, the rate being
judged by bubbling the gas through a wash-bottle. The flask
was cooled in a bath of water and the flow of chlorine stopped
when the saturation point was reached as indicated by the gas
almost ceasing to bubble through the wash-bottle. Lignin was
determined by Konig's method; in the case of the hard woods
this method appeared to fail as shown by the low results ob-
1. J. Ind. Eng. Chem. 1919, U, 556; abst. J. S. C. I. 1919, 38, 496-A.

cEi^i^uLOSE 259

tained. Cutin was not found in appreciable amount.

Four methods have recently^ been investigated for the esti-
mation of the lignin by the destruction of the cellulose, viz., by
heating under a pressure of 6-7 atmospheres for-6-7 hours with
1% hydrochloric acid; by treating the wood at the ordinary tem-
perature with 72% sulfuric acid; by treating the wooi with
fuming hydrochloric acid, sp. gr. 1.21; and by the action of
gaseous hydrogen chloride. According to the last method, 1 gm.
of wood meal which has been extracted by alcohol-benzene, is
mixed with 6 cc. of water and treated with gaseous hydrogen
chloride, with cooling, until a thin fluid is obtained. After stand-
ing for at least 24 hoiu-s to complete the hydrolysis of the cellu-
lose the residual lignin is collected in a Gooch crucible and the
weight of ash-free residue ascertained. In the case of deciduous
woods the hydrochloric acid methods gave rather more consistent
results than the sulfuric acid method. The composition of the
lignins obtained ranged between the limits C = 67.31%-71.35%
and H = 5.07%-7.80%. For the estimation of hemi-celluloses, 4
gm. of wood powder is heated with 200 cc. of 0.4% sulfuric acid for
4-5 hours under different pressm-es, viz., 0.5-0.75 atm. for alder,
ash and poplar, 1 atm. for beech and willow, 2.25-2.5 atm. for
birch and fir, and 3.5 atm. for pine wood. The extract is neutral-
ized with calcium carbonate and the cupric reducing value deter-
mined; it is then fermented and the fermentable sugar X 0.9 is
calculated as hexosans, while the dissolved pentosans are cal-
culated from the difference between the pentosans in the original
material and in the residue from hydrolysis. The results ob-
tained in general showed that the total pentosan of the coniferous
woodswaslow(10%-12% on the dry substance) as compared with
the foliage woods (22%-26%). The lignin of the coniferous woods
was high (28%-29%) as compared with the foliage woods (20%-
26%) . As regards the hemi-celluloses, the coniferous woods showed
small quantities of pentosans (8%-9%) and large quantities of hex-
osans yielding fermentable sugars (about 13%), while the foliage
woods showed large quantities of pentosans (15%-23%) and only
small quantities of hexosans (3%-6%). The pure cellulose (cor-
rected for pentosans) ranged between 39% and 45% for all the

1. J. Koenig and E. Becker. Zts. ang. Cheni. 1919, 32, 155; abst. J. S.
C. I. 1919, 38, 530-A.

260 TECHNOLOGY OF CElrlrULOSE ESTERS

woods, with the exception of poplar, which showed 47%-49%.
Analyses were made of the sugars produced by the hydrolysis of
the hemi-celluloses of the woods. In the extracts from coniferous
woods, xylose and dextrose were present in nearly equal propor-
tions (21%-26%of the total reducing sugars) ; small quantities of
galactose and large quantities of mannose were also found, pine
woods being particularly rich in mannan. In the extracts from
foliage woods (beech and birch) xylose was the main constituent,
the dextrose was approximately the same as in coniferous woods,
the quantity of galactose was small, and that of mannose very
much smaller than in coniferous woods. The waste liquors from
sulfite wood pulp contain fermentable sugars equivalent to 4%-5%
of the wood, also hemi-celluloses, since the sugars may be increased
to 12%-14% by the hydrolysis of the liquors with sulfuric acid.
Experiments on the utilization of sulfite liquor in fodder have
given encouraging results, the main points to be noted being
that the liquor must be completely neutralized with calcium car-
bonate and lime to a faintly alkaline reaction; it must also be
strongly aerated, for instance, by trickling over galvanized wire
netting, and it must be evaporated at a temperature which will
avoid the caramelization of the sugars. The dry basis of the
fodder may be brewers' grains and hay meal, also bran, malt
germs, or beet slices. 100-120 kilos of the dry fodder may be
mixed with a cub. m. of liquor containing 120-130 kilos of dis-
solved solids. Provided it be neutralized and aerated, fermented
spent wash from the sulfite liquors may be used. The sulfite
fodder is readily eaten (e, g., by sheep) and the soluble constitu-
ents, including the lignin, show a high percentage of assimilation.

0. Kress, S. Wells and V. Edwardes^ have recently given an
account of all the species of American woods which have been
tested in the Forest Products Laboratory, showing weights per
solid cub. ft. lengths of ultimate fibers, yields of pulp by sul-
fite and sulfate process, bleaching qualities, character and uses of
pulps. The more important species of coniferous woods are:
Black spruce {Picea ntariana), excellent for sulfite and sulfate
pulps; blue spruce (P. parryana), ditto; Engelmann spruce (P.
eyigelmanni) ditto, also for mechanical pulp; red spruce (P. rubens),
ditto; length of fiber, 3.7 mm.; Sitka spruce (P. sitchensis), ex.

1. Paper, 1919, 24, 914; abst. J. S. C. I. 1919, 38, 713-A.

CBLI^UU)SE 261

cellent for sulfite and sulfate, length of fiber 3.5 mm., mechanical
pulp slightly greyish; white spruce (P. canadensis), the standard
sulfite pulp wood of America, sulfate pulp of highest quality,
mechanical pulp excellent, fiber length 2.8 mm.; Alpine fir (Abies
lasiocarpa)y excellent sulfite, sulfate and mechanical pulps, equiv-
alent to spruce; Amabalis fir {A, amabalis), sulfite pulp fair
strength, sulfate excellent, mechanical excellent strength, slightly
greyish; balsam fir {A. balsamea), all pulps excellent, almost as
good as spruce; grand fir (A, grandis), sulfite pulp fair strength,
other pulps equivalent to spruce; noble fir {A. nobilis), sulfite
pulp poor strength, sulfate good, mechanical excellent; red fir,
{A. magnified), sulfite pulp good but hard to bleach, sulfate pulp
good, mechanical fair; white fir {A, concolor), all pulps good;
Douglas fir (Pseudotsuga taxifolia), sulfite pulp poor color, few
uses, sulfate pulp fairly strong; hemlock {Tsuga canadensis), sul-
fite pulp fair, sulfate good, mechanical fair; Western hemlock
{Tsuga heterophylla), sulfite and sulfate pulps good, mechanical grey-
ish; tamarack {Larix laricina), sulfite pulp strong but difficult to
bleach — coarse, sulfate pulp good, mechanical fair; Western larch
{Larix occidentalis) ditto; jack pine {Pinus divaricata), sulfite pulp
useless, sulfate good, mechanical rather poor; lodgepole pine {P.
murrayyana), sulfite good, sulfate excellent, mechanical good but
pitchy; longleaf pine {P. palustric), sulfite unsuitable, sulfate good.
The other varieties of pine are practically useless for sulfite pulps,
but give excellent or good sulfate pulps; white pine (P. strobus)
and yellow pine (P. ponderosa), give mechanical pulps of medium
quality

The color reactions of wood with various chemical reagents
in HCl solution are oftei^ characteristic, and have been summar-
ized by F. Czapek^ as follows:

In the destructive distillation of woods the products formed
are very similar to those from jute lignocellulose. This subject
has been worked out in great detail for wood, on account of the
commercial importance of the products. The chief compounds
distilling over are methyl alcohol, acetone and acetic acid. It is
considered probable that the primary products are methyl alco-

1. F. Czapek, "Biochemie der Pflanzen," Jena, 1905, 567; Ber. bot.
Gcs. 1899, 17, 166; Zts. physiol. Chem. 1899, 27, 153; abst. J. C. S. 1899.
7$, i, 560; Chem. Centr. 1899; 70, I, 692; Jahr. Chem. 1899, S2, 1300; Chem.
Tech. Rep. 1899^38, 103; Apotheker Ztg. 1899. 322.

262

TECHNOLOGY OF CKI^LULOSE ESTERS

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CELLULOSE 263

hoi, acetic acid, furfuraldehyde and pyrogallol derivatives, and

1 . Pogg. Ann. Phys. 1834, 31, 65. See also J. prakt. Chem. 1850, 51, 95 "

2. Wien. Akad. Ber. 1878, 77, I, 60; abst. Dingl. Poly. 1878, 22T
397; J. C. S. 1878, 34, 612; Jahr. Chem.. 1878, 31, 1086; Zts. anal. Chem. 1878,

17, 511. See also R. v. Wagner, Dingl. Poly. 1878, 228, 173; J. prakt. Chem.
1851, 52, 451 ; J. C. S. 1878, 34, 397. A. Kielmeyer, Dingl. Poly. 1878, 227, 584.

3. Chem. Ztg. 1885, 9, 266; abst. Chem. Tech. Rep. 1885, 24, II. 263;
Wag. Jahr. 1885, 31, 1054; Indbl. 1885, 102.

4. L. Schaeffer (Ber. 1869, 2, 91; abst. Chem. News, 1870, 21, 58;
Bull. Soc. Chim. 1869, 12, 313; Jahr. Chem. 1869, 22. 485). M. Niggl. Chem.
Ztg. 1887, 15, 201, 289, 563; abst. J. S. C. I. 1887, 6, 306; 1888, 7, 51; 1889,
8, 421, 640, 914, 1012; 1890, 9, 418, 555, 770; 1891, 10, 165, 575, finds the
reaction heightened in the presence of /3>naphthol. For color reactions of
starch with naphthol, thymol, cresol, guaiacol, catechol, orcin, resorcin,
phloroglucin, see A. Ihl, Chem. Ztg. 1887, 11, 19; abst. J. C. S. 1887, 52, 534;
Jahr. Chem. 1887, 40, 2460.

5. Flora, 1881, 545.

6. Zts. wiss. Mikro. 1885, 2, 354.

7. Chem. Ztg. 1890, 14, 1571; abst. J. S. C. I. 1891, 10, 165; Ber.
1891, 24, R, 220; Chem. Centr. 1890, 61, II, 1028; Jahr. Chem. 1890, 43,
2554. N. Lubavin, Ber. 1869, 2, 99; abst. Chem. News, 1869, 20, 129; Jahr.
Chem. 1869, 22, 623.

8. Ber. 1899. 32, 1213; abst. J. C. S. 1899, 76, i, 621; T. S. C. I. 1899,

18, 604; Bull. Soc. Chim. 1899, 22, 717; Chem. Centr. 1899, 70, 1, 1247; Jahr.
Chem. 1899, 52, 2057.

9. T. and D. Tomassi, Ber. 1881, 14, 1834; abst. J. C. S. 1882. 42,
245; Jahr. Chem. 1881, 34, 1229; Jahr. rein Chem. 1881, 9, 266.

10. Ber. botan. Ges. 1886, 4, 301; Dinpl. Poly. 1886, 261, 135; Zts. anal.
Chem. 1887, 26, 258; abst. Chem. News, 1888, 57, 71; J. C. S. 1886, 50,
1088; 1887, 52, 692; J. S. C. I. 1886, 5, 508; Chem. Centr. 1887, 58, 366;
Jahr. Chem. 1886, 39, 2172; Wag. Jahr. 1886, 32, 891; Pharm. Centralh.
1886, 28, 718.

11. Flora, 1874, 239.

12. Sitz. Ber. Wien. Akad. 1882, 85, 349;Monatsh. 1882, 3, 395; abst.
J. C. S. 1882, 42, 1122; J. S. C. I. 1882, 1, 404; 1883, 2, 89; Ber. 1882, 15,
2272; Chem. Tech. Rep. 1883, 22, I, 243; Dingl. Poly. 1882, 246, 487; Wag.
Jahr. 1882, 28, 1060. For the action upon cellulose of iodine, with either
sulfuric acid, calcium chloride, aluminium chloride or phosphoric acid, see
Erfind u. Erfahr. 1897, 24, 511.

13. Dmgl. Poly. 1886, 261, 135; Zts. anal. Chem. 1887, 26, 258; abst.
Chem. News, 1888, 57, 71; J. C. S. 1886, 50, 1088; 1887, 52, 692; J. S. C. I.

1886, 5, 608; Chem. Centr. 1887. 58, 366; Jahr. Chem. 1886, 39, 2172; Wag.
Jahr. 1886, 32, 891 ; Pharm. Centralh. 1886, 28, 718.

14. Ber. 1886, 19, 3217; 1887, 20, 808; abst. J. C. S. 1887, 52, 620;
T. S. C. I. 1887, 6, 565; Bull. Soc. Chim. 1887, 48, 76; Chem. Centr. 1887,
58, 735; Jahr. Chem. 1887, 40, 2467; Wag. Jahr. 1887, 33, 1178; Papier Ztg.

1887, 599, 666, 748; Zts. Chem. Ind. 1887, 2, 25.

15. Farbenreakt. der Kohlenstoffverb. 1890, 51; Botan. Centr. 1889,
38, 754; Chem. Ztg. 1893, 17, 1209, 1243; abst. J. S. C. I. 1890, 9, 904; 1893.
12> 869; 1894, 13, 423; Ber. 1889, 22, R, 841; 1893, 26, a31; Chem. Centr.
1889, 60, II, 197; 1893, 64, II, 736; Jahr. Chem. 1889, 42, 2523; 1893, 46,
1889. Refer to C. Cross. E. Bevan and J. Briggs. Ber. 1907, 40, 3119; Chem.
Ztg. 1907, 31, 725; abst. T. S. C. I. 1907, 26, 941, 942; C. Cross and E. Bevan,
J. Soc. Dyers Col. 1916, 32, 135. J. S. C. I. 1893, 12, 105.

16. Flora, 1890, 33; Botan. Centr. 1889, 38, 616.

17. Gazz. chim. Ital. 1898, 28, 168; abst. J. C. S. 1899, 76, ii. 340;

2G4 TECHNOLOGY OF CELLULOSE ESTERS

methoxy derivatives. If it is true, as has been stated, that the

J. S. C. I. 1899, 18, 76; Chem. Centr. 1899, 69, II, 990; Jahr. Chem. 1898,
51, 1377.

18. Chem. Ztg. 1890, 14, 1707; abst. J. S. C. I. 1891, 10, 165; Ber.
1891, 24, R, 47; Chem. Centr. 1891, 62, I, 212; Jahr. Chem. 1890, 43, 2555.

19. Sitzber. Naturf. Ges. Univ. Jurjew, Dorpat, 1895, 11, 117; abst.
Chem. Ztg. Rep. 1896, 20, 164; Chem. Centr. 1896, 67, II, 99. E. Senft,
Monatsh. 1904, 2S, 397; abst. J. C.S. 1904,86, ii, 595; J. S. C. I. 1904, 23,
685; Bull. Soc. Chim. 1905, 34, 238; Chem. Centr. 1904, 75, I, 373; Jahr.
Chem. 1904, 57, 1130.

20. Chem. Ztg. 1890, 14, 1571; abst. J. S. C. I. 1891, 10, 165; Ber.
1891, 24, R, 220; Chem. Centr. 1890, 61, II, 1028; Jahr. Chem. 1890, 43,
2554.

21. Chem. Ztg. 1902, 26, 335; abst. J. C. S. 1902, 82, ii, 434; J. S. C. I.
1902, 21, 725; Rep. Chim. 1902, 2, 352; Chem. Centr. 1902, 73, I, 1176;
Jahr. Chem. 1902, 55, 1052.

22. Zts. Farb. Textilind. 1906, 5, 317; abst. J. C. S. 1906, SO, i, 754;
Chem. Centr. 1906, 77, II, 1761 ; Jahr. Chem. 1905-1908, II. 2703.

23. In this connection see also, T. Seliwanoff, Botan. Centr. 1891, 45,
279; Jour. Russ. Phys. Chem. Soc. 1889, 21, I, 85. E. CoveUi, Chem. Ztg,
1901, 25, 684. H. Tauss, Dingl. Poly. 273, 286; 1890, 276, 411; Chem.
Centr. 1889, 60, II, 445; 1890, &, II, 187. W. Hancock and O. Dahl, Ber.
1895, 28, 1558. v. Ketel, Beihefte Botan. Centr. 1897, 423. F. Reinitzer,
Zts. physiol. Chem. 1890, 14, 466. G. Lange, Zts. physiol. Chem. 1889, 14,
15. V. Grafe, Monatsh. 1904, 25, 987. S. Schapringer, Dingl. VdLy. 1865,
176, 166. V. Hohnel, Sitzungber. d. Wiener Akad. 1877, 76, I, 527. H.
Blau, Pharm. Post, 1905, 38, 752. E. Senft, Monatsh. 1904, 25, 397. E.
Grandmougin, Zts. Farben Textilchem. 1906, 5, 321; Ber. 1907, 40, 2453;
J. C. S. 1907, 92, ii, 588. Hegler, Flora, 1890, 73, 33; Botan. Centr. 1889,
38, 616. T. Morawski, Bayer Ind. u. Gewerbebl. 20, 641; Chem. Centr.
1888, 59, 1630. R. Combes, Bull. Soc. Pharmacol. 1906, 13, 293. Lewa-
kowsky, Justs Botan. Jahrb. 1882, 1, 422. A. Wheeler, Ber. 1907, 40, 1888;
abst. J. C. S. 1907, 92, ii, 511. The constitutional relationship of the lignin
of coniferous wood to coniferyl alcohol, HO.CeH3(OCH,).CH:CH.CHjOH,
has previously been developed by P. Klason, Ark. Kemi. Min. o. Geol. 1917,
6, 21, pp.; Chem. Zentr. 1919, 90, I, 92; abst. J. S. C. I. 1919, 38, 570-A
(see J. S. C. I. 1898, 17, 63). The separation of the carbohydrates from the
salts of ligninsulfonic acids in the spent sulfite liquors may be effected by
precipitation with calcium chloride after first precipitating the sulftu'ic acid
by barium chloride. The calcium ligninsulfonate from fir wood has a com-
position^ represented by the formula, C4oH440i8S2Ca, which maybe expressed
as 1 mol. of coniferyl alcohol (C10H12O3) -j- 3 mols. of hydroxyconiferyl alco-
hol (CsoHmOiz) -fl mol. CaCSOaH), 2-3 mols. H2O. By the boiling point
method the value of 916 was determined for the molecular weight of the
ligninsulfonate, allowance being made for the degree of dissociation; it is
readily soluble in water and nearly insoluble in alcohol. Naphthylamine
ligninsulfonate is obtained by treating the calcium salt with naphthylamine
hydrochloride; it is a yellowish sandy powder almost insoluble in water.
After the precipitation of the calcium or barium ligninsulfonate from the
sulfite liquor, a further precipitate may be obtained with naphthylamine
hydrochloride. This latter salt has the formula, CsoHboOhSsNi, and would
correspond to a lignin of the formula C2«H2«Os, containing 12.3% CHsO,
whereas the calcium salt corresponds to a lignin of the formula, C4oH«Oij,
containing 17% CH3O. The original lignin might be regarded as being com-
posed of equal molecules of both. The molecule apparently contains a
benzene nucleus substituted in the 1.3.4-positions. On destructive distil-
lation the lignhi yielded h^'^c of phenols. The author favors the hypothesis

CELLUUDSE ' 265

destructive distillation of cellulose does not yield methyl alcohol,
it would appear that this product probably comes from the
lignone grouping in the distillation of wood.^

When wood is digested with a boiling aqueous solution of
stannous chloride, a small quantity of a compound or compounds
closely related to lignocellulose is formed.^ This product is ob-
tainable in a crude form by extracting the stannous chloride solu-
tion with benzene or ether, a second extraction being carried out
with boiling ligroin. The product separates from the petroleum
upon cooling, and may be further purified by crystallization from
ether and formation of bisulfite derivative. The yield of purified
product is l%-2%of the weight of the wood. Czapek considers
this material as a definite compound, to which he ascribes the
name of hadromal. It has a melting point of 75°-80°, and is
closely allied to compounds containing the vanillin group. Had-
romal, according to subsequent workers,' is a mixture of vanillin
methylfurfural and pyrocatechol.

W. Cross and B. Tollens* have corroborated the work of

that the Hgnin of fir wood consists of condensed forms of more or less methyl-
ated cinnamic alcohols and allied aldehydes and acids, and the general type
of substitueilts shows a relationship to protocatechuic acid, to which resins
and tannins are also related. It is not improbable that lignin may be present
in the wood in t e form of a glucoside, and it may be built up from the
pentoses.

1. P. Klason, G. von Heidenstam, O. Fagerlind and E. Norlin, Arkiv.
Kem. Min. Geol. 1908. 3, 1; No. 5, 1; No. 6, 1; No. 10, 1; abst. J. C. S. 1908,
94, i, 717; C. A. 1908, 2, 3280, 3281; 1909, 3, 1810; J. S. C. I. 1908, 27, 1080;

1909, 28, 132; Chem. Zentr. 1908, 79, II, 1302, 1303; 1909. 80, I, 109; 11,
1178; Chem. Ztg. Rep. 1908, 32. 252. 270, 602; Wag. Jahr. 1908, 54, I, 5;
II, 20; Zts. ang. Chem. 1909, 22. 1205. In investigating the products ob-
tained from the dry distillation of cellulose obtained from various sources,
the authors have shown that the velocity of this reaction begins to become
considerable at about 270°, at which temperature the dry distillation of cel-
lulose becomes an exothermic process, the heat of the reaction being about
6% of the heat of combustion of cellulose. The gases evolved during the
distillation have a heating value of about 3.5% of the heat of combustion
of the cellulose, and include hydrogen and aromatic hydrocarbons. Acetic
acid is formed during this dry distillation, beech and birch celltilose yielding
a larger amount of this acid per unit weight than either cotton, fir, or pine,
cellulose.

2. F. Czapek, Zts. physiol. Chem. 1899, 27, 154; abst. J. C. S. 1899,
7G, i, 560; Bull. Soc. Chim. 1909, 22, 685; Chem. Centr. 1899, 70, I, 692;
Chem. Tech. Rep. 1899, 38, 103; Jahr. Chem. 1899, S2, 1300; Apotheker Ztg.
1899, 322. Brown and Tollens, Ber. 1902, 35, 1457.

3. Sitzber. Wien. 1904, 113, 253. For determination of the reducing
power of cellulose with permanganate, see h. Kollmann, Chem. Ztg. Rep.

1910, 34, 455; abst. J. Soc. Dyers Col. 1910, 28, 251; J. S. C. I. 1910, 29,
1151; Zts. oester. Papier Ind. 1909, 408; 1910, 709.

4. Jour. Landw. 1911, 59, 185; abst. Chem. Zentr. 1911, 82^ II, 970;
C. A. 1912, 6, 2599; Zts. ang. Chem. 1911, 24, 1660.

266 TECHNOLOGY OF CELLULOSE ESTERS

Cross and Bevan, that fonnyl and acetyl groups undoubtedly
exist in lignin, and are split off hydrolytically.

Other forms of lignocellulose are glycolignose, the substance
of fir woods, ^ and glycodrupose, the substance of the stony con-
cretion of pears.*

Wood Pulp.' The preparation of wood pulp as an interme-
diate product in the manufacture of paper is, of course, a very
important industrial process. The coniferous woods, such as the
pine, fir and spruce, are the main raw materials employed. Di-
cotyledenous trees as poplar, and practically all soft woods, when
available, can be employed equally as well for this purpose.'

1. J. Erdmann, Ann. 1866, 138, 1; 1867, Suppl. 5, 223; abst. Bull. Soc.
Chim. 1866, G, 340; Jahr. Chera. 1866. 19, 672; Chem. Centr. 1866, 37, 401;
Zts. Chem. 1866. 245; J. Pharm. (4), 3, 478.

2. F. Bente, Ber. 1875, 8, 476; abst. J. C. S. 1876, 29, 421; BuU. Soc.
Chim. 1876, 25, 278; Chem. Centr. 1876, 46, 392; Chem. Tech. Rep. 1875,
14, I, 116; Dingl. Poly. 1876, 217, 235; Jahr. Chem. 1875, 28, 785; Jahr.
rein Chem. 1875, 3, 382; Wag. Jahr. 1875, 21, 1045.

3. For general information on this subject, consult: E. P. 2316,
1884; abst. J. S. C. I. 1885, 4, 242. Papier Ztg.; Chem. Trade J. 9,
107; abst, J. S. C. I. 1891, 18, 786. No. 772, Foreign Office Annual Series;
abst. J. S. C. I. 1890, 9, 906. Papier Ztg. 1894, 938; abst. J. S. C. I. 1884,
3, 495. Dingl. Poly. 1883, 249, 23, 124, 302; abst. J. S. C. I. 1883, 2, 421.
Moniteur Industriel; abst. J. S. C. I. 1896, 15, 610. Papier Ztg. 1896, 21,
(37), 1183; abst. J. S. C. I. 1896, 15, 579. Board of Trade Journal, May
1896, 601; abst. J. S. C. I. 1896, 15, 371. Board of Trade Journal, Jan. 1896,
40; abst. J. S. C. I. 1896, 15, 57. Canadian Gazette of September 26th;
abst. J. S. C. I. 1895, 14, 998. Moniteur Official de Commerce of February
14th; abst. J. S. C. I. 1895, 14, 320. Bulletin of the French Chamber of
Commerce at Montreal; Board of Trade Journal; abst. J. S. C. I. 1895, 14,
204. Bulletm du Musee Commercial 1893; Board of Trade Journal; abst.
J. S. C. I. 1894, 13, 674. Board of Trade Journal; abst. J. S. C. I. 1893, 12,
875. Reports Consuls of the U. S. A., May 1893, 123-128; abst. Mitscherlich
Patent, J. S. C. I. 1893, 12, 701; J. S. C. I. 1893, 12, 793. Chem. Trade
J.; J. S. C. I. 1892, 11, 174; abst. J. S. C. I. 1893, 12, 778. Board of Trade
Journal; abst. J. S. C. I. 1893, 12, 1074. Board of Trade Journal; abst.
J. S. C. 1. 1893, 12, 635. Pharm J. 1893, 5 (July 1 ) ; abst. J. S. C. 1. 1893, 12, 619.
Foreign Office Annual Series, 20, 13; abst. J. S. C. I. 1897, 16, 1053. Toronto
Globe, Oct. 7, 1898; U. S. Cons. Reps. ; abst. J. S. C. 1. 1899, 18, 84. Eng. and
Mining J. 1898, 66, 514; abst. J. S. C. I. 1899, 18, 63. Foreign Office
Annual Series, No. 2062, April 1898; abst. J. S. C. I. 1898, 17, 507. For-
eign Office Annual Series, No. 2161; abst. J. S. C. I. 1898, 17, 813. Papier
Ztg. 1898, 23, (55), 2027; abst. J. S. C. 1. 1898, 17, 788. Papier Ztg. 1898, 23,
(19), 687; abst. J. S. C. I. 1898, 17, 688. U. S. Cons. Reps., Feb. 1899,
530; abst. J. S. C. I. 1899, 18, 313. U. S. Cons. Reps., Feb. 1899, 322;
abst. J. S. C. I. 1899, 18, 186. Foreign Office Annual Series, No. 2299,
June 1899; abst. J. S. C. I. 1899, 18, 720. Papier Ztg. 1899,24,(68),
2625; abst. J. S. C. I. 1899, 18, 853. Toronto Monetary Times, 2nd
December; Board of Trade Journal; abst. J. S. C. I. 1893, 12, 79. Indus-
tries, abst. J. S. C. I. 1893, 12, 190. Chem. Trade J.; abst. J. S. C. I. 1893,
12, 79. Scient. American, 76, (23), 358; abst. J. S. C. I. 1897, 16, 576.
3ull. de I'Assoc. des Chim. dQ Sucr. et de Dist. 1396, 14, 456; abst. J. S,

CELLULOSE 267

Wood pulp is prepared either by mechanical or chemical
processes, the latter being more deep-seated in their action than
the former. In the mechanical treatment, only water soluble

C. I. 1897, 16, 58. Wood Pulp, 1896, 1, (3), 61-64; abst. J. S. C. I. 1896, 15,
833. Comm. Intelligence, May 19, 1900; abst. J. S. C. I. 1900, 19, 575.
U. S. Consular Report for June, page 386; J. S. C. I. 1892, 11, 720. Prakt.
Handbuch der Papierfabr. 1896, 42, 1633-34; abst. J. S. C. I. 1896, 15, 610.
Cons. Rep. May 16, 1903; abst. J. S. C. I. 1903, 22, 768. Board of Trade
Journal, Dec. 26, 1901 ; abst. J. S. C. I. 1902, 21, 84. Board of Trade Jour-
nal, May 14, 1903; abst. J. S. C. T. 1903, 22, 666. U. S, Cons. Reps., Aug.
12, 1902; abst. J. S. C. I. 1902, 21, 1166. Foreign Office Annual Series, No.
2749; abst. J. S. C. I. 1902, n, 514. Comm. Intelligence, Nov. 21, 1901;
abst. J. S. C. I. 1901, 20, 1161. Foreign Office Annual Series, No. 2690;
abst. J. S. C. I. 1901, 20, 958. Papier Ztg. 1901, 26, (62), 233; abst. J. S. C. I.
1901. 20, 925. Papier Ztg. 1901, 28,' (31), 1159; abst. J. S. C. I. 1901, 20,
739. Board of Trade Journal, Nov. 22, 1900, 426; abst. J. S. C. I. 1900,
19, 1165. U. S. Cons. Reps., Aug. 1900; abst. J. S. C. I. 1900, 19, 870.
U. S. Cons. Report, July 1900; abst. J. S. C. I. 1900, 19, 789. U. S. Cons.
Reps.. March 1900, 404; abst. J. S. C. I. 1900, 19, 388. Tiraar's Rundschau,
3, (43), 497-99; abst. J. S. C. I. 1900, 19, 166. Papier Ztg. 1899, 24, (81),
3162; abst. J. S. C. I. 1899, 18, 1047. Board of Trade Journal, March 9,
1905; abst. J. S. C. I. 1905, 24, 300. U. S. Cons. Rep. No. 2179, Feb. 9,
1905; abst. J. S. C. I. 1905, 24, 254. U. S. Forest Service Circular, No. 44,
abst. J. S. C. I. 1904, 28, 164. Board of Trade Journal, Dec. 21, 1905;
abst. J. S. C. I. 1906, 25, 37. Chem. and Drug. 1905, 07, 871-872; J. S. C.
I. 1901, 20, 734, 1008; abst. J. S. C. I. 1905, 24, 1329. Board of Trade Jour-
nal, June 22, 1905; abst. J. S. C. I. 1905, 24, 758. Wochenbl. f. Papierfab.
1904, 35, 3941, 3942; abst. J. S. C. I. 1905, 24, 148. U. S. Cons. Reps. No.
2058, Sept. 17, 1904; abst. J. S. C. I. 1904, 23, 958. Board of Trade Journal.
Feb. 25, 1904; abst. J. S. C. I. 1904, 23, 280. Wochenbl. f. Papierfabr. 1904,
35, (3), 162-163; abst. J. S. C. I. 1904,^^ 23, 127. Pulp and Paper, Nov.,
1908; abst. J. S. C. I. 1908, 27, 1129. Board of Trade Journal, March 2§,
1908; abst. J. S. C. I. 1908, 27, 352. Board of Trade Journal, Sept. 26,
1907; abst. J. S. C. I. 1907. 28, 1063. Report of Annual Meeting, J. S. C. I.
1910. 29, 858. Papierfabr. 1910, 9, 61-64; abst. J. S. C. I. 1910. 29, 230.
Paper Making, 1909, 28, 279; abst. J. S. C. 1. 1909, 28, 850. Paper Making, 191 1,
30, 376; abst. J. S. C. I. 1911, 30, 1248. Papierfabr. 1910. 8, 996; abst.
J. S. C. I. 1910, 29, 1245. Board of Trade Journal, Aug. 4, 1910; abst. J. S.
C. I. 1910. 29, 1004. Board of Trade Journal, May 15, 1913; abst. J. S. C. I.
1913, 32, 530. Board of Trade Journal, June 11, 1914; abst. J. S. C. I. 1914,
33, 745. /Bull. Imp. Inst. 1914, 12, 42^44; abst. J. S. C. I. 1914, 33, 477. '
Bull. Imp. Inst. 1914, 12, 44-45; abst. J. S. C. I. 1914, 33, 477. Consular
Reports, No. 115; abst. J. S. C. I. 1914, 33, 915. Paper Makhig, 1916,
35, 10-11; abst. J. S. G. I. 1916, 35, 172. Board of Trade Journal, Jan.
27, 1916^ abst. J. S. C. I. 1916, 33, 192. U. S. Comm. Rept. No. 277, Nov.
27, 1915; abst. J. S. C. I. 1916, 35, 108. J. Roy. Soc. Arts, 1915, 84, 132;
abst. J. S. C. I. 1916, 35, 39. U. S. Commerce Report, No. 169; abst. J. S.
C. I. 1915. 34, 867. U. S. Commerce Report. No. 181, Aug. 4, 1915. abst.
J. S. C. r. 1915, 34, 867. Bull. Imp. Inst. 1916, 14, 163-167; abst. J. S. C. I.
1916, 35, 1008. Board of Trade Journal. Feb. 17, 1916; abst. J. S. C. I.
1916, 35, 302. Bull. Imp. Inst. 1917. 15, 1-7; abst. J. S. C. I. 1917, 38,
1004. BuU. Agric. Intell. 1918, 9, 1-8; abst. J. S. C. I. 1918, 37, 226-R.
Bull. Imp. Inst. 1918, 18, 16-24; abst. J. S. C. I. 1918, 37, 601-A. U. S.
Comm. Rep. Oct. 1, 1918; abst. J. S. C. I. 1918, 37, 476-R. Board of Trade
Journal. July 18, 1918; abst. J. S. C. I. 1918, 37, 321-R. U. S. Com. Rep.
Mar. 11, 1919; abst. J. S. C. I. 1919. 38, 171-R. Foreign Office Annual

268 TKCHNOLOGY OF CELLUl,OSE ESTERS

constituents are ren^pved, the pulp affer treatment containing
upwards of 30% of lignin. Such a wood pulp, owing to the im-
purities present, is unsuitable for many purposes, for example,
the preparation of good paper. The dark color of the pulp may
be reduced by bleaching, but even after excessive treatment, it
is difficult to obtain a product which will retain its white color
indefinitely.

In the mechanical process^ the wood is cut into lengths of
1-4 feet. The outer bark is then removed and the wood ground
to a fine state of division by forcing the blocks against revolving
grindstones by the aid of hydraulic pressiu*e. In some processes
the wood is steamed before grindmg. During the grinding, water
flows slowly over the wood and carries off to a pit the finely
divided fibrous material as it is produced.^ The larger particles
are removed by forcing the liquor through a series of wire sieves
or strainers.' By grinding "wet" a comparatively long fiber
wood pulp is obtained, dry grinding being only resorted to when
an especially fine product is required. The larger portions which
resist grinding may be converted into wood pulp by a chemical
treatment at a comparatively low temperature.*

J. van Wessem,^ in preparing mechanical wood pulp from

Series, No. 2337, 1899; abst. J. S. C. I. 1899, 18, 876. Foreign Office Annual
Series, No. 2317, July 1899; abst. J. S. C. I. 1899, 18, 793. Foreign Office
Annual Series, No. 2450, June 1900; abst. J. S. C. I. 1900, 19, 703. Foreign
Office Annual Series, No. 2401, April 1900; abst. J. S. C. I. 1900, 19, 481.
Foreign Office Annual Series, No. 2471, July 1900; abst. J. S. C. I. 1900,
19, 798. Foreign Office Annual Series, No. 2490, July 1900; abst. J. S. C. I.
1900, 19, 799. Foreign Office Annual Series, No. 2879; abst. J. S. C. I. 1902,
21, 1208. Foreign Office Annual Series, No. 2879; abst. J. S. C. I. 1902,
21, 1257. Foreign Office Annual Series, No. 3014: abst. J. S. C. I. 1903, 22,
892. Wochenbl. f. Papierfabr. 1904. 35, 2530-2531 ; abst. J. S. C. I. 1904,
23, 879. Foreign Office Annual Series, No. 3037; abst. J. S. C. I. 1903, 22,
980. Foreign Office Annual Series, No. 3040; abst. J. S. C. I. 1903, 22,
980. Foreign Office Annual Series, No. 3412; abst. J. S. C. I. 1905, 24, 758.
Foreign Office Annual Series, No. 2659; abst. J. S. C. I. 1901, 20, 864.
vSwedish Board of Trade Announcement; abst. J. S. C. I. 1916, 35, 108.

1. G. Dunstan, "Cotton and Other Fibers," 216.

2. M. Adam, E. P. 17846, 1915; abst. C. A. 1917, 11, 1902. In this
connection compare E. P. 2018, 1910; 17714, 20220, 1911; 17427, 1912;
abst. C. A. 1913, 7, 415, 890; 1914, 8, 416.

3. M. Lamort, E. P. 332, 1911; abst. J. S. C. I. 1911, 30, 798. B.
Loomis, F. P. 454137, 1913; abst. J. S. C. I. 1913, 32, 865. U. S. P. 1052675,
1913; abst. J. S. C. I. 1913, 12, 28,3.

4. A. Anderson and C. Vig, Norw. P. 28771, 1918; abst. C. A. 1918,
12, 2686. A. Anderson, U. S. P. 1068092, 1913; abst. J. S. C. I. 1913, 32,
864. See H. de Chaume and G. Pinard-Martineau, Belg. P. 192074, 1906.

5. E. P. 117086, 1918; abst. C. A. 1918, 12, 2248. D. Francke, D. R.
P. 24924, 188S. F. P. Oct. 13 and Dec. 21, 1881; abst. Wag. Jahr. 1883.

, 1123. U. S. P. 295868.

CELLULOSE 269

sawdust and wood waste, grinds in presence of water, the water
amounting to 60% of the weight of the wood, while the hdkt
generated during the grinding causes 30% of this added water to
evaporate. The wood is passed through a crusher to a sorting
machine, where it is graded with other woods. By the aid of a
screw-conveyor the crushed wood from which the coarser material
has been removed, is then groimd in presence of a regulated
amount of water. The ground material, after subjection to hy-
draulic pressure, is rolled and packed for export.

To obtain a plastic material from the wet wood pulp, it is
treated as follows:^ Part of the water is first removed from the
pulp by draining or by a hydroextractor, the partly dry material
being then mixed with a powdered, gelatinous substance, such
as gum or starch, and heated in a closed vessel at 75°-100°. The
resulting pulped material is plastic and may be rolled or pressed
into any desired shape. In M*. Porter's patent,* to the wet wood
pulp mixed with a small proportion of tough fibers, is added china
clay, talc, aluminium resinate (to waterproof) and a binding
material, such as albumin and gelatin. The mixture is moulded
and dehydrated by heat.

To prepare a product of higher purity than that obtainable
by mechanical means and also in order to remove the lignocellu-
lose, it is necessary to subject the wood to chemical treatment.
The soda process gives a high grade product largely used for book
paper. The sulfate or KrafFt process gives a strong fiber and is
used for wrapping paper, and other purposes. It is usually un-
bleached. The sulfite process gives a pulp which is employed
largely in the preparation of newspapers.^

In the soda process,* the wood in 4 feet lengths, with the bark

1. H. Jackson, E. P. 11946, 1917; abst. J. S. C. I. 1918. 37, 63-A.
C. Clark, U. S. P. 927950, 927951, 1909; abst. J. S. C. I. 1909, 28, 905. C.
WeUberg, U. S. P. 981042, 1911; abst. J. S. C. I. 1911, 30, 204.

2. E. P. 8184, 8325, 1909; abst. J. S. C. I. 1910, 29, 416, 483. J.
Fuller, U. S. P. 40659, 1863. M. Porter, E. P. 8325, 1909; addii. to E. P.
8184, 1909; abst. J. S. C. I. 1910, 29, 416, 483.

3. A. Smith, J. S. C. I. 1916. 35, 281; abst. C. A. 1916, 10, 2402. F.
Dobson. E. P. 27188, 1912; abst. J. S. C. I. 1914, 33, 20. Addn. to E. P.
3181, 1911; abst. J. S. C. I. 1912, SQL, 225. F. P. 439286, 1912; abst. J. S. C.
I. 1912, n, 225.

4. E. and T. Kittelson, Swed. P. 40894, 1916; abst. C. A. 1916, 10,
2637. A. Behr, D. R. P. 28219; 31548, 1883; abst. Dingl. Poly. 1885, 255,
111; J. S. C. I. 1885, 4, 241; Papier Ztg. 1884, 1436. E. Berghoff, D. R. P.
160651, 1904; Bled. Tech. Chem. Jahr. 1904, 27, 558. M. Faudel. Dingl. Poly.

270 MCHNOI/)3Y O? C«UI^UI*OSE SSTBRS '

removed, is digested in a solution of caustic soda 0,5%-A% at a
temperature of 160®-206® in large digesters, and at a pressure of
10-15 atmospheres for about four hours. Superheated steam is
preferably used for heating in order to maintain a high concen-
tration. The alkaline liquid may be heated by circulating it
through external heaters, the latter being heated by steam, which,
as it condenses in the coil is retimied to the boiler.^ The heaters
are in two or more sections and may be connected by valves with
any of the digesters so that the tmits can be operated independ-
ently. During the heating, the alkali in the liquor is gradually
neutralized for about 4r-4V» hours. Then for approximately
half an hour, no further alkali is destroyed, although the heating
is continued. After this period fmther alkali is neutralized, the
higher the temperature of digestion, the sooner this stop in the
neutralization of the alkali occurs. At this stage the material
has undergone sufficient heating.

Another method of determining the rate of digestion is to
periodically test a sample of the alkaline liquor with slight excess
of sulfuric acid. When the neutralized liquor is boiled a precip-
itate is formed, which in successive testings up to a certain stage,
gradually diminishes in bulk. When this precipitate at succes-
sive testings no longer continues to diminish in bulk, the diges-
tion of the wood is considered as completed. During the alkali
digestion the material constituents, sap, lignocellulose, acids, etc.,
are dissolved by the caustic soda and pass into solution. After
digestion the whole mass is blown out of the digester by its own
pressure, the caustic liquor drawn off, and the cellulose washed
with weaker and weaker alkaline liquids, and finally with water
tmtil neutral.

Wood in the form of sawdust or shredded material may,
before the soda treatment, be leached out in an acid or neutral
solution* in order to obtain a final product with firm and flexible

1876, 219, 428; abst. J. C. S. 1876, 30, 231. B. Blackmann. U. S. P. 369836,
630634, 530635; Pap. Ztg. 1895, 20, 1376, 2152. J. Pfiel, E. P. 11489, 1911;
abst. J. S. C. I. 1912, 31, 584.

1. A. Cellulosepatenter, E. P. 4278, 1915; abst. C. A. 1916, 10, 2299.
D. R. P. 288018, 1915; abst. J. S. C. I. 1916, 35, 356. Bock, Pap. Ztg. 1892.
17, 555. H. Bucherer, Pap. Ztg. 1905, 30, 1350.

2. A. Deiss and C. Fournier, F. P. 403518, 1909; abst. C. A. 1911, 5,
1514. First addn. dated Sept. 2, 1909, to F. P. 403518, 1909; abst. J. S. C.
I. 1910, 29, 556. E. P. 23625, 1909; abst. J. S. C. I. 1910, 29, 1101. D. R.
P. 235852; abst. C. A. 1912, 6, 1365; J. S. C. I. 1910, 29, 84. U. S. P. 967001,

CEIXUlrOSE 271

fibers. This operation is usually carried out in an open vessel or
in elongated tanks into which the liquid is sprayed.^ This treat-
ment is usually repeated until the wood has lost nearly half its
original weight.

For this preliminary treatment gaseous nitrogen oxide or
nitrous acid may be employed efficiently.* Nitric acid, hydrogen
peroxide, sodium peroxide or other oxidizing agents in a concen-
tration of 0.5%-l% also may be used. When the acid treatment
is completed the cellulose material is digested with an alkaline
solution, some oxycellulose being formed during these treatments.
C. Cross' finds that even hard woods in the form of waste, as
fragments, chips, shavings, etc., can be economically treated with
nitric acid to produce a good cellulose. The economy of the pro-
cess is eflfected by a recovery of the by-products formed during
the acid decomposition. These products consist in the main of

1910; abst. J. S. C. I. 1910, 29, 1063. P. Sparre, D. R. P. 237081, 1910;
abst. C. A. 1912, 6, 1526, 1989; Zts. ang. Chetn. 1911, 24, 1583; Chem. Zentr.

1911, II, 411. F. P. 420640, 1910; abst. J. S. C. I. 1911, 30, 279. E. P.
29118, 1909; abst. J. S. C. I. 1911, 30, 80.

1. Z. Ostenberg, U. S. P. 1220778; abst. C. A. 1917, 11, 1749. See
also Z. Ostenberg, U. S. P. 1218954, 1242030 E. P. 104173; F. P. 484442,
under the topic "Cellulose and Hydrochloric Acid." A. Mitscherlich, D. R.
P. 1078, 8674; abst. Chem. Ind. 1878, 1, 318. F. Cyster, Paper, 1916, 16,
No. 22, p. 13; C. A. 1915, 9, 3129. For the preparation and spinning of
threads from strips of paper, see A. Lemveber, E. P. 10530, 1902; F. P. 320529,
1902; abst. J. S. C. I. 1903, 22, 25, 737.

2. C. Schwalbe, E. P. 29991, 1909. F. P. 410460, 1909; abst. J. S. C. I.
1910, 29, 810; 1911, 30, 416. In this manner, according to the patentee,
the ligneous matter can be rendered similar to cotton, and is suitable for the
manufacture of explosives, artificial silk and celluloid. E. P. 19142, 1910;
abst. J. S. C. I. 1910, 29, 1299. E. P. 18199, 1914; abst. J. S. C. I. 1916, 34,
956. D. R. P. 282050, 1913; abst. J. S. C. I. 1916, 34, 656; C. A. 1915, 9,
2312. D. R. P. 204460, 1907; abst. J. S. C. I. 1908, 27, 1220. Papierfab-
rikant, 1911, 9, 1522; abst. J. S. C. I. 1912, 31, 121. Wochenbl. Papierfab.

1912, 43, 1454; abst. J. S. C. I. 1912, 31, 631. Zts. ang. Chem. 1908, 21,
302; abst. J. S. C. I. 1908, 27, 243. Zts. ang. Chem. 1918, 31, 50, 57; abst.
J. S. C. I. 1918, 37, 365 A. Compare D. R. P. 259691, 279622, 280317,
283199, 288720. Aust. P. 69136. U. S. P. 1153970, 1201535.

3. E. P. 409, 1894; 8544, 8545, 1904; abst. J. S. C. I. 1905, 24, 288,
340. U. S. P. 807250, 1905; abst. J. S. C. I. 1906, 25, 34. F. P. 351048,
1905; abst. J. S. C. I. 1905, 24, 908. C. Cross (E. P. 104032, 1916; abst.
J. S. C. I. 1917, 36, 383; C. A. 1917, 11, 1902) has described a process wherein
lignified materials, such as paper pulp or textiles, are treated with a solution
containing 0.2%-0.5% hydioxylamine or hydroxylamine acedite in order to
restore their color or to make them capable of resisting discoloration under
the influence of atmospheric exposure. In E. P. 8544, 8545, 1904, cellulose
or hemi-cellulose of short cellular structure obtained from cotton-seed hulls
is hydrolyzed with four or five times its weight of l%-3% sulfuric acid. The
solution is filtered and neutralized with barium carbonate or chalk. After
filtration, the solution is evaporated until the sugar crystallizes.

272 TECHNOLOGY OF CELLULOSE ESTERS

oxalic and acetic acids. To 1 part of wood, 3 parts of 10%
nitric acid is added and the temperature raised to 80°, this
^temperature being maintained by the heat generated in the
reaction. When the reaction is completed the soluble por-
tion is removed by draining and pressing the wood, this solution
being worked up for oxalic and acetic acids. The cellulose ma-
terial still contains non-cellulose constituents and these are re-
moved by a subsequent alkaline treatment, followed by bleaching
where a very pure product is required. This cellulose can be
nitrated with nitric acid of sp. gr. 1.5 without any sulfuric acid,
and when washed after nitration the washings are utilizable as
the 10% acid for the treatment of further quantities of wood.

Resinous and gummy substances may be extracted by hot
water before the chemical treatment.^ These extraneous mat-
ters may also be removed by steaming in the absence of air.*
It has also been suggested to remove them by a retting process
by means of a ferment derived from African esparto grass,* the
process being carried out, preferably, in a vacuum.

The efficiency of the soda process is enhanced by the addi-
tion of small quantities of certain metallic substances to the solu-
tion, mercury being especially suitable.* In one process the
boiler is filled with a dilute solution of mercuric chloride (0.001 N),
and after mercury has been deposited, the solution is run off.
The boiler is then used to greater advantage for the treatment
of wood by the usual soda method. This deposition of mercury
is repeated every fourteen days. In this process the soda lye

1. B. Loomis. U. S. P. 1052675, 1913; F. P. 454137, 1913; abst. J. S.
C. I. 1913, 32, 283. 865. U. S. P. 1122404, 1914; abst. J. S. C. I. 1915, 34,
222. In this method the material is treated in a closed vessel, first with
hot water and then with a dilute alkaline solution, which is circulated at
gradually increasing temperatures through the material, a heater, and a
separator in which the matters removed from the material are separated by
floating or deposition. The cleansed material is subsequently digested with
alkali to reduce it to pulp.

2. C. Schwalbe, D. R. P. 203230, 1907; abst. C. A. 1909, 3, 714; Zts.
ang. Chem. 1908, 21, 2556; Chem. Zentr. 1908. 79, II, 1842; Chem. Tech.
Rep. 1908, 32,^94; Wag. Jahr. 1908, 54, II, 377; J. S. C. I. 1908, 27, 1173.

3. A. Deiss, E. P. 23625, 1909; abst. J. Soc. Dyers Col. 1910, 2S. 252;
J. S. C. I. 1910, 29, 1101. F. P. 403518. 1909; abst. J. S. C. I. 1910, 29, 84.

4. Aktiebolaget Cellulosa, E. P. 116288, 1917; abst. J. S. C. I. 1918,
37, 651-A; C. A. 1919, 13, 73. Compare also, E. P. 6652, 1912; abst. C. A.
1913. 7, 3025; J. S. C. I. 1912. 32, 284. F. P. 441186. 1912; abst. J. S. C. I
1912. 31, 812. R. Biltz, F. P. 155014, 1883.

CBLI.UU)SE 273

used is about 6% concentration and must be sulfiur-free.

An important objection ^o the soda treatment is the fact
that noxious gases are evolved dining the boiling, and are due,
to a large extent, to the atmospheric oxygen present in the boiler
combining with decomposition products of the wood. It has been
proposed^ on this account to replace the air by carbon dioxide
or nitrogen.

The soda process is comparatively expensive owing to the
large amount of alkali required, the high consumption of fuel
and the short life of the vessels in which the reaction is carried
out.^

After the soda treatment and the removal by washing of free
alkali from the cellulose material, the latter is bleached. This
process is carried out either by the action of chlorine gas, bleach-
ing powder or by electrolytic methods.' When the bleaching
treatment is completed the wood pulp is washed with dilute acid
or alkali.^ The bleaching is preferably performed in a rotating

1. O. Dietrich, D. R. P. 201259, 1907; abst. T. S. C. I. 1908, 27, 1037;
Zts. ang. Chem. 1908, 21, 2233; Chem. Zentr. 1908, 79, II, 1074. W. Burton,
U. S. P. 959307. F. Buehler, D. R. P. 94467; abst. Chem. Ind. 1903, 28,
138; Wag. Jahr. 1903, 49, II, 543.

2. V. Drewson, U. S. P. 492196, 505755, 1893; 730439, 1903; 1309863,
1310509; abst. J. S. C. I. 1903, 22, 817. U. S. P. 731290, 1903; abst.
J. S. C. I. 1903, 22; 876. U. S. P. 789416, 789417, 789418, 1905; abst. J. S.
C. I. 1905, 24, 633. U. S. P. 789887, 1905; abst. J. S. C. I. 1905, 24, 1028.
F. P. 344692, 1904; abst. J. S. C. I. 1904, 23, 1233. U. S. P. 853943, 1907;
abst. J. S. C. 1. 1907. 28, 713. U. S. P. 996225, 1911 ; abst. J. S. C. 1. 1911, 30, 950.
U. S. P. 1229422, 1917; abst. J. S. C. I. 1917, 38, 923. U. S. P. 1283113,
1283114, 1917; abst. C. A. 1919, 13, 187; J. S. C. I. 1919, 38, 71-A. U. S. P.
1298476, 1298477, 1298478. 1298479, 1298480, 1298481, 1919; abst. J. S. C. I.
1919, Uj 459-A; C. A. 1919, 13, 1764, 1765. U. S. P. 1303176, 1303177, 1919;
abst. J. S. C. I. 1919. 38, 507-A. E. P. 5156, 1911; abst. J. S. C. I. 1912,
31, 184. F. P. 344692, 1904; abst. J. S. C. I. 1904, 23, 1233.

3. F. Stewart, U. S. P. 811523, 1906; 923088, 1909; 1017023, 1018994,
1912; abst. J. S. C. I. 1906, 25, 226; 1909, 28, 737; 1912. 31, 352; 1913, 32,
669. In F. P. 465732, 1913; abst. J. S. C. I. 1914, 33, 589, the raw material
is digested with an oxidizing agent, e. g., dilute nitric add, chromic acid or
a mixture of dilute nitric acid and hydrochloric acids under a steam pres-
sure of 4-5 atmos. for 10-30 mins. then drained, washed and neutralized
with a 5%-10% solution of sodium hydroxide Mrith which it is boiled for 5-^30
mins. The pulp is bleadied with ordinary bleach liquor which is grad-
ually brought to the boiling point, a small quantity of dilute nitric acid being
then added. The cellular matter of the plants is separated by this process
from the fibers and may be collected for use as a filling material.

4. A. de Vains and J. Peterson, E. P. 19099, 1913; HoU. P. 2395, 1918;
abst. C. A. 1915, 9, 377; 1918, 12, 2686. U. S. P. 1106994, 1914; abst. J. S.
C. I. 1914, 33, 916. F. P. 449497, 1912; abst. J. S. C. I. 1913, 32, 482.

274 TECHNOI.OGY OF CELLULOSE ESTERS

drum, for a period of several hours, using concentrated liquors.*

In C. Kellncr's process,^ the cellulose material after the soda
treatment, is exposed to the action of chlorine and hypochlorous
acid, generated at the anode during the electrolysis of brine, the
lignocellulose, pectocellulose and other impurities being oxidized
and converted into water-soluble or alkali-soluble compounds;'

1. F. Kcttlet)rook, E. P. 3181, 1911; abst. J. S. C. I. 1912, 31, 225.
Compare C. Cross and E. Bevan, E. P. 1548, 1883; abst. J. S. C. I. 1883,
2, 541. Carpenter and Schulze, D. R. P. 7830(5; abst. Wag. Jahr. 1895,
41, 1027; Jahr. Chem. 1895, 48, 1357; addn. to D. R. P. 71942; abst. Ber.
1896, 28, 260; Wag. Jahr. 1894, 40, 1060; Jahr. Chem. 1894, 47, 1135. C.
Clark, D. R. P. 214000; abst. Wag. Tahr. 1909, 55, II, 506; Chem. Ztg. Rep.

1909, 33, 597; Zts. ang. Chem. 1909, 22, 2438. U. S. P. 927950, 927951 ; abst.
J. S. C. I. 1909, 28, 905; Pap. Fabr. 1909, 8, 1082; Pap. Ztg. 1909, 34, 3390.

2. E; P. 24542, 1902; J. S. C. I. 1903, 22, 1145. F. P. 326313, 1902;
abst. J. S. C. I. 1903, 22, 817. U. S. P. 773941; abst. J. S. C. I. 1904, 23,
1159. D. R. Anm. 4724, 1886; Pap. Ztg. 1885, 10, 233. U. S. P. 542932,
1859. E. P. 4960, 5053, 6951, 6993, 15930, 15931, 1890; 12970, 12971.
1891; abst. J. S. C. I. 1890, 9, 819; 1891, 10, 380, 566, 944, 1022. Aust. P.
33685, 56889, 1891. See E. Ritter and C. Kellner, U. S. P. 328812, 329214>
329215, 1885. Aust. P. 20024, 31730. F. P. 157754; abst. Mon. Sci. 1884.
26, 768. Belg. P. 62746. Ital. P. 16316.

3. B. Johnsen and R. Hovey, J. S. C. I. 1918, 37, 132-T; Paper, 1918.
21, 36; abst. C. A. 1918, 12, 1250, 1598. In this connection refer to, E.
Heuser, Woch. Papierfabr. 1913, 44, 2209; abst. J. S. C. I. 1913, 32, 695.
E. Heuser and T. Blasweiler, Papier Ztg. 1918, 43, 593, 613; Chem. Ztg.
Rep. 1918, 42, 108; abst. J. vS. C. I. 1918, 37, 574-A. E. Heuser and A.
Haug, Zts. ang. Chem. 1918, 31, 99, 103, 166, 172; abst. J. S. C. I. 1918,
37, 365-A, 650-A. Sec also, J. S. C. I. 1914, 33, 71. E. Heuser and R. Sie-
ber, Zts. ang. Chem. 1913, 26, 801 ; abst. C. A. 1914, 8, 1343, 2059. E. Heuser
and C. Skioldebrand, Zts. ang. Chem. 1919, 32, 41; abst. J. S. C. I. 1919, 38,
215-A. See also, J. S. C. I. 1913, 32,822. R. Sieber and L. Walter, Papier-
fabr. 1913, 11, 1179; abst. J. S. C. I. 1913, 32, 974; C. A. 1914,8, 1202.
A. Schorger, J. Ind. Eng. Chem. 1917, 9, 556, 561, 748; abst. C. A. 1917, U,
2218, 2542; J. S. C. I. 1917, 36, 867, 1003; Ann. Rep. S. C. I. 1917, 2, 144.

A. Dean and G. Tower, J. Amer. Chem. Soc. 1907, 29, 1119; abst. J. S. C. I.
1907, 26, 988. B. ToIIens,Zts. ang. Chem. 1898, U, 337; abst. J. S. C. I.
1898, 17, 3(>5, 481, 682. B. ToUens and R. Dmochowski, J. Landwirtschaft,

1910, 58, 1 ; abst. Chem. Zentr. 1910, 81, II, 246. B. ToUens and Krober, J.
Landw. 1901, 48, 357; 1905, 53, 13. Lange, Zts. physiol. Chem. 1910, 14,
15, 217. J. Koenig and E. Rump, Untcrs. Z. Niihr. Genussm. 1914, 28,
177; abst. C. A. 1915, 9, 815. H. Wisliccnus, Zts. Chem. Ind. Kol. 1910,
6, 1. H. Wisliccnus and M. Kleinstucck, Zts. Chem. Ind. Kollojd, 1910,
6, 17, 87; abst. J. S. C. I. 1910, 29, 268. P. Klason, Chem. Ztg. 1903, 27,
585; abst. J. S. C. I. 1903, 22, 826. Svcnsk Pap. Tid. 1916, 129. Papier.
Ztg. 1908, 33, 3779; abst. J. S. C. I. 1908, 27, 1219; 1909, 28, 37. Papier-
fabrikant, 1909, 7, Fest-und Auslandsheft, 26, 627, 671, 701, 795; abst.
J. S. C. I. 1909, 28, 100. Wochenbl. Papierfabr. 1910, 41, 464, 541; abst.
J. S. C. I. 1908, 27, 1080: 1910, 29, 343. Papierfabr. 1910, 8, 1285; abst.
J. S. C. I. 1911,30,79. Pulp and Paper Mag. 1918, 16, 1015, 1037; abst.
J. S. C. I. 1919, 38, 38-A. vSee also J. S. C. I. 1916, 35, 172, 832.
P. Klason and H. Mcllquist, Papierfabrikant, 1913, 11, 145; abst. J. S.
C. I. 1913, 32, 227. vScc also, J. S. C. I. 1910, 29, 343. P. Klason and

B. Scgerfelt, Papierfabrikant, 1911, 9, 1039; abst. J. S. C. I. 1911,

CELLULOSE 275

the caustic soda formed at the cathode is utilized for the purifica-
tion of further quantities of wood. The brine may with advan-
tage be replaced by other chlorides as magnesium chloride.^

A very pure cellulose product is obtained from wood pulp
which has been purified by the soda process by the following sup-
plementary treatment. The wood pulp is first bleached for sev-
eral hours with an aqueous solution containing 2%-8% chlorine,
the resulting product being then heated under pressure with a
solution of sodium carbonate for several hours. The resulting
cellulose is washed free from alkali and aerated. ^

Impurities retained in wood pulp after the soda treatment

30, 1145. R. Benedikt and M. Bamberger, Chem. Ztg. 1891, 15, 221-
222. Compare, Mittheil. k. k. Techn. Gew. Museums, 1888, 18, 66-67; 1889,
9-14; Jahresber. d. Wiener Handelsak. 1890, 159. J. S. C. I. 1888, 7,
863-64; 1889, 8, 574, 735, 925; 1890, 9, 659, 1156; 1891, 10, 163, 576. Mon-
atsh. 1890, 11, 260-67; Chem. Ztg. 1889, 13, 872, 1087; Monatsh. 1890,
U, 84; Chem. Centr. 1&57, 28, 321; J. S. C. I. 1890, 9, 659; 1889, 8, 735,
925, 1156. J. Koenig, Zts.- Unters. Nahr. u Genussm. 1906, 12, 385; abst.
J. S. C. I. 1906, 25, 1069. Chem. Ztg. 1912, 36, 1101; abst. J. S. C. I. 1912,

31, 980. See also J. S. C. I. 1910, 29, 688; 1912, 31, 427. J. Koenig and
E. Becker, Zts. ang. Chem. 1919, 32, 155; abst. J. S. C. I. 1919, 38, 530-A.
J. Koenig, J. Hasenbaumer and M. Braun, Zts. ang. C)iem. 1913, 26, 481 ;
abst. J. S. C. I. 1913, 32, 939.

1. J. Lifschuetz and Chem. Fab. Gruenau, Landshoff and Mayer,
D. R. P. 60233, 69807; abst. Wag. Jahr. 1892, 38, 1020; 1893, 39, 427; Ber.
1892, 25, 298; 1893, 26, 921; Chem. Centr. 1893, 64, II, 1015; Zts. ang.
Chem. 1892, 5, 154; 1893, 6, 465; Jahr. Chem. 1892, 45, 2899; Meyer Jahr.
Chem. 1893, 3, 366; Chem. Tech. Rep. 1893, 32, II, 272; Mon. Sci. 1893, 42,
200.

C. Ellis has described (U. S. P. 1311215) a binder composed of strongly
acid sulfite cellulose liquor solids in a non-fluent form, soluble in water,
stable on exposure to air while the solids are in the dried condition, and
becoming gradually insoluble when subjected to a protracted exposure to
air in the presence of moisture. U. S. P. 1311216, a binder, is composed of
solid, oxidized constituents of waste sulfite cellulose liquor which has its
normal acidity reduced about one-half. U. S. P. 1311217, sulfite cellulose
liquor, is partially neutralized, then evaporated to a solid mass and comminuted.
U. S. P. 1311218, normally acid sulfite cellulose liquor is treated with a quan-
tity of alkaline substance insufficient to neutralize the liquor, and the prod-
uct is evaporated by atomizing in the presence of oxygen to form a solid
binder. U. S. P. 1311219, an acid binding agent, is prepared by dissolving
the desiccated solids of sulfite cellulose liquor in water, the composition
being characterized by having a viscosity at least 10% lower than that of
ordinary concentrated sulfite cellulose liquor of the same density. U. S. P.
1311220, a dry mixture of acid solids of sulfite waste liquor and lime. U. S.
P. 1311211, briquettes or other moulded articles, are made by incorporating
atomized, dried, slightly oxidized, water-soluble solids of sulfite cellulose
liquor, moulding and converting the solids of the binder into an insoluble
form. U. S. P. 1311222, dried, powdered sulfite cellulose liquor solids, are
incorporated with an agent capable of rendering them insoluble, a water-
proofing agent, water, and a material to serve as a filler, and then shaped.

2. A. Berglind, E. P. 114456, 1917; abst. J. S. C. I. 1918, 37, 296-A.

276 TKCHNOIXXxY OF CELLULOSE ESTERS

may also be removed by oxidation with a very dilute solution of
a manganate or permanganate, the oxidation product being
washed out with sulfurous acid.

The alkali remaining after the removal of the wood pulp
which has been subjected to the soda treatment, is evaporated
in multiple-eflfect evaporators. The dried residue is ignited and
afterwards extracted with water. The aqueous solution of soditmi
carbonate obtained is treated ynth lime, and the recovered caus-
tic soda solution employed for the treatment of further quantities
of wood. The disposal of the lye may also be carried out thus:
The liquid is evaporated to 28°-32° B^. gravity, the concentrated
liquor then passing directly to the so-called "blach-ash furnace,"
where it is burned with the addition of coal. **Black-ash*' results.
The hot gases are used to heat the boilers, which provide a por-
tion of the steam for the plants. Sodium carbonate is recovered
from the black ash by lixiviation. Acetone can be obtained from
the soda lye as follows: The soda liquor to which some extra
caustic soda is added, is evaporated to 35** B€, To 2 tons of
this liquor 1 ton of lime is added and a dry, easily handled solid
is said to result, but in the writer's experience, it is a very trouble-
some material to handle. This solid, known by the name of
"calignate,** is then fed into a horizontal, cylindrical, rotating,
retort and subjected to a maximum temperatiu-e of 480°, when
a destructive distillation occiu-s. On a manufacturing scale, from
1 ton of waste liquor 24 lbs. of acetone is said to be obtained, in
addition to 12 lbs. of methyl alcohol and 6 lbs. of methylethyl-
ketone. This process, up to the present time, has not passed
beyond the experimental stage.

Sometimes the caustic soda is partly replaced by sodium
sulfate and the process is then known as the "sulfate process."
The waste lye obtained in the process, when evaporated and
ignited, gives in addition to sodium carbonate, considerable
amounts of sodium sulfide.

In the preparation of wood pulp by the sulfite process, the
wood is heated for several hours at a temperatiu-e of 120°-155°
with an aqueous solution of sodium, calcium, or magnesium sul-

H. Simpson and G. Mackirdy, E. P. 8817, 1887; abst. J. S. C. I. 1888, 7,
451. J. VanWessem, E. P. 117086, 1918; abst. J. S. C. I. 1919, 38, 496-A.
R. Pictet and G. Brelaz. D. R. P. 26331, 1883; abst. Wag. Jahr. 1884, SO,

1147.

CKi.Luix>SB 277

files or a mixture of these salts, the heating being effected by the
aid of steam admitted through coils. The digester in which the
reaction mixture is contained has a special lining of acid-resisting
tile. There are two principal methods in which this digestion
is practically carried out.^ In the R. Mitscherlich process' a
comparatively low temperature (115°-120°), and a pressure of
2.5-4 atmospheres, is employed. The time of heating is 24-48
hours, and a strong fiber cellulose is obtained. In the Ritter-
Kellner process the temperatiu-e is raised to 140°-155°, the heat-
ing being preferably cairied out with live steam for a period of
8-16 hours (pressure 4-6 atmospheres). In the initial stages of
the heating in both processes when the temperature is about 70°,
the digester is opened for a short period to allow air expelled from
the pores of the wood to escape.' Dimng the pressure-boils, the
non-cellulose constituents of the wood are attacked, and are con-
verted into soluble products.

The preparation of alkali sulfite on a large scale is carried
out as follows: A tower about 60 feet high and 6 feet diameter
is divided into about 30 sections by means of gratings* These
segmental compartments are packed with limestone or magnesite.
A bat'ery of such towers is usually erected. From the top,
water flows slowly down the tower, sulfur dioxide enters at the
bottom and is forced upwards. A portion of the sulfur dioxide
is absorbed by the water but the exit gases from the top of the
tower still contain sulfur dioxide, and this gas is led to the base
of a second tower and the process repeated. The sulfur dioxide
dissolves in the water to sulfurous acid, which then attacks the
limestone or magnesite and the corresponding sulfite is formed.

Instead of using limestone or other mineral packed in a
tower, a liquid or an emulsion may be employed. In a recent

1. J. Bcveridge, J. S. C. I. 1916, 35, 563; abst. C. A. 1916, 10, 2799.
E. P. 2872, 1891; 14105, 1892; abst. J. S. C. I. 1892, U, 176; 1893, 12, 779.
For cymene production from sulfite cellulose, see T. Ortenblad, Teknisk
Tidsk. 1918, 8; Papierfabr. 1918, 16, 717; C. A. 1919, 13, 2276.

2. D. R. P. 4178, 4179, 1878; abst. Dingl. Poly. 1883, 249. 23. E. P.
11816, 1884; abst. J. S. C. I. 1885, 4, 649; Dingl. Poly. 1876, 22i, 479; abst,
Chem. Tech. Mitth. 1875, 255; Dingl. Poly. 1884, 2SI, 262. U. S. P.
284319, 1883; abst. Dingl. Poly. 1884, 251, 262; Papier Ztg. 1884, 1. See
A. Tilgham, E. P. 385, 1867; 2924, 1886. U. S. P. 70485, 1867; 92229, 1869.

3. C. Schwalbe, Wochbl. Papierfabr. 44, 2786; Papierfabr. U, 1095;
abst. C. A. 1914, 8, 245. F. Cohn, Pap. Ztg. 1884, 9, 1929. M. Coulon
and R. Godeffroy, D. R. P. 88299; abst. Ber. 1896, 29, 888; Wag. Jahr.

1896, 42, 1027. S. Ferenczi, Pap. Ztg. 1897, 22, 3575, 3647, 3679.

278 TlSCHNOLOGY OF CELLULOSE ESTERS

patent^ is described an apparatus in which milk of lime is placed
in a tower or vessel divided vertically into a series of compart-
ments with connecting tubes between the divisions for the pas-
sage of sulfur dioxide. C. Schwalbe^ disintegrates the wood with
calcium sulfite lye without heating under pressure. The wood is
soaked for 3-5 hours at 70°-100° in a solution of calcium sulfite
containing about 3% by weight of SO2. The lye is then drawn
off and gaseous sulfur dioxide injected until the acid content in
the wood is doubled. The lye still present is then washed out
and the material steamed.

With ammonium sulfite lyes containing excess of free ammonia
a higher pressure can be developed than with soda lyes.' The
ammonium sulfite lye may be regenerated by driving off the free
ammonia, collecting the condensate in water, and treating this
with sulfurous acid. For the treatment of pine wood a satisfac-
tory composition of lye is: — 3%-3.5% sulfur dioxide and 1.7%-2%
ammonia. The wood is digested for ten hours at a temperature
of 165° at a pressure of 10-12 atmospheres. A yield of 65%
unbleached cellulose from the pine wood is claimed by operating
in this manner.

C. Harnist* treats the crude cellulose successively or alter
nately with ammonia (or other alkaline solution) and sulfur di-

1. A/S Themes Mek. Voerkstad, Norw. P. 27202, 1916; abst. C. A.
1916, 10, 3141. For methods of determining the purity of wood cellulose,
consult, E. Richter, Wochbl. Papierfabr. 1912, 43, 1631; 1913, 44, 1776;
abst. C. A. 1912, 6, 2524; J. S. C. I. 1912, 31, 530; 1913, 32, 594. Eighth
Int. Cong. Appl. Chem. 1912, 13, 233; abst. J. S. C. I. 1912, 31, 530. 869.

2. D. R. P. 282050, 1913; abst. C. A. 1915, 9, 2312; abst. Chem. Zentr.
1915, 86, I, 411; Chem. Ztg. Rep. 1915, 39, 77; Zts. ang. Chem. 1915, 28,
224. H. Fleck, Pap. Ztg. 1884, 9, 1804. R. Gans, E. Stone and B. Tollens,
Ber. 1888, 21, 2148; abst. J. C. S. 1888, 5i, 1051); J. vS. C. I. 1888, 7, 595;
Bull. Soc. Chim. 1889, 1, 746; Jahr. Chem. 1888, 41, 2309. For method of
manufacture of wood pulp from California "Redwood" tree, see E. P. 8817,
1887.

3. J. and A. Rosenblum, G. de Gottinan, L. Brech and E. Tyborowski,
E. P. 5552, 1911 ; abst. J. S. C. I. 1912, 31, 329; C. A. 1912, 6, 2529. F. P.
460472, 1913; abst. J. S. C. I. 1914, 33, 19. A. de Vains and J. Peterson,
E. P. 19099, 1913; abst. J. S. C. I. 1914, 33, 746. F. P. 449497, 1912; abst.
J. S. C. I. 1913, 32, 482.

4. F. P. 477895, 1914; abst. C. A. 1916, 10, 1433. A. Gawalowski,
Pap. Ztg. 1899, 24, 3112. R. Gentzcn and L. Roth, D. R. P. 147844, 1901;
abst. Wag. Jahr. 1904, 50, II, 370; Chem. Centr. 1904, 75, I, 410; Chem.
Ztg. 1904, 28, 66; Zts. ang. Chem. 1904, 17, 244; Jahr. Chem. 1904, 57, 878;
Chem. Ztg. 1904, 28, 66. J. Lifschuetz, D. R. P. 60233; abst. Ber. 1892,
25, 298; Chem. Centr. 1893, 64, II, 1015; Zts. ang. Chem. 1892, 5, 154; Jahr.
Chem. 1893, 3, 366.

CELLUU)SE 279

oxide. Compressed or liquefied atnmonia and sulfur dioxide can
also be used.

Purified cellulose fiber can also be obtained from wood chips ^
by boiling under pressure with water in presence of 10% calcium
oxide and 2%-4% of finely divided sulfur. The chips are washed
and disintegrated or partly separated into a fibrous condition by
means of a beating machine or hollander, subsequent boiling
with soda ash eliminating the sulfur. This treatment is followed
by washing and drying. The resulting fiber still contains 0.3%-
0.4% of sulfur.

J. Hasenbaumer^ claims that a very pure cellulose may be
obtained from fir, pine and beech by a combination of the alkali
and sulfite processes, on account of the fact that the resulting
mother liquors are more readily utilized. By the action of dilute
alkali followed by that of dilute acid the advantages of both the
soda and sulfite treatments are obtained. The resulting lye is
free from large excess of soda or sulfite and it is claimed can be
utilized as a fodder.^ The wood is digested for 5-6 hours at 2-3
atmospheres pressure with 4-5 times its volume of aqueous am-
monia (concentration 3%-5%), or soda (concentration l%-2%).
When ammonia is used it is recovered from the waste lye. In this
process 3%-5% of resin and l%-2% of tannic acid are recovered
from coniferous wood. The wood residue is then digested for 6-8
hours at 1-2 atmospheres pressure with five times its volume of
dilute sulfuric acid (concentration about 0.5%). The hemi-cel-
luloses are dissolved and the residual lye contains considerable
amounts of sugar. This mother liquor is mixed with the liquors
from the alkaline digest and the mixture poured over hay or ab-

1. V. Drewsen, U. S. P. 996225; abst C. A. 1912, 6, 2;il5; J. S. C. I.
1911, 30, 950. E. P. 5157, 1911; abst. J. S. C. I. 1912, n, 184. D. R. P.
67889; abst. Wag. Jahr. 1893, 39, 1060; Ber. 1893, 26, 559. E. Goldschmidt,
D. R. P. 97935, 1897; Chem. Centr. 1898, 69, II. 616; Pap. Ztg. 1898. 23,
2664. h: Gottstein. Wochenbl. Pap. 1905, 36, 1390, 1616, 1779; Zts. ang.
Chem. 1905, 18, 983. C. Grabowski, Aust. P. 44713, 1894.

2. J. Hasenbaumer, M. Braun and J. Hoenig, Zts. ang. Chem.
1913, 26, 481; abst. C. A. 1914, 8, 420. E- Kirchner, Das Papier, 1907. 3,
615; Wochenbl. Papicrfabr. 1904, 35, 3411; 1910, 41, 1995; abst. J. S. C. I.
1904, 35, 3411; 1910, 29, 873. A. Frank, Papier Ztg. 1896, 21, 354; abst.
J. S. C. I. 1896, 15, 370; Papier Ztg. 1913, 38, 136. E. P. 13286, 1886; abst.
J. S. C. I. 1887, 6, 735.

3. J. Koenig, Zts. Nahr. Gcnussm. 1916, 31, 171; abst. J. S. C. I.
1916. 35, 960. A. Harpf, Pap. Ztg. 1891, 16, 1726, 1788, 1844, 1908, 1964,
2026, 2094. 2155; 1892, 17, 792. 1089, 1121. 1525, 1557, 1643; Zts. ang. Chem.
1898. 11, 875. 925. 1169; Chem. Centr, 1899, 70, I. 313.

280

TECHNOLOGY OF CELlrUIvOSE ESTERS

sorbed by dry grain. When lime, followed by sulfuric acid is
used, the insoluble gypsum formed has no injtu'ous action in the
fodder mixture. When soda is used it is necessary to follow up
with hydrochloric acid in the acid treatment, and the resulting
sodium chloride does not reduce the food value of the fodder.
The lignin which still remains in the cellulose is removed by
oxidizing with a bleaching agent. If spinning fibers are required,
the strength of the reagents and the pressure and time of the
alkali and acid boils are diminished.

Many suggestions have been put forward for the utilization
of the aqueous lye from the sulfite process,^ but hitherto there has
been but little success in this direction. During the sulfite treat-
ment, 45%-55% of the wood is converted into soluble constitu-
ents. The spent sulfite lye containing the soluble material from
the wood has hitherto been mainly regarded as a waste product,
and allowed, after neutralization, to flow away.

According to analyses by H. Seidel of the Ritter-Kellner
waste liquors, the latter average 11.4% solids. The dried residue
obtained on evaporation has the approximate ash-free compo-
sition of — carbon = 53.7%, hydrogen = 5.2%, sulfur = 8.8%
and oxygen = 32.3%. A more detailed analysis of various waste
liquors has been given by C. Hoffmann.^

TABLK XXX.— ANALYSIS OF WASTE SULFITE LIQUOR

Total solids

Loss on ignition

Ash

Total sulfur

Free sulfur dioxide. .
Sulfite radical (SO3) .
vSulfate radical (SOO
Oxygen consumed . .

Grams per Liter

• 1

2

3

4

5

82

88

85

93

92

68

75

• • ■

81

• • ■ •

14

13

16

12

• « • ■

• • ■ •

■ ■ • •

• ■ • ■

• • • •

9.2

2.6

2.2

2.9

2.6

3.8

7.3

7.9

6.7

1.2

3.8

4.1

5.4

4.8

2.7

1.9

52

52

50

60

• • • •

1. H. Seidel and L. Hanak, Mitt. d. k. k. Tech. Gew. Mas. N. F. 1897.
7, 119. 283; 1898, 368; Rev. Gen. Mat. Color. 2, 370; abst. J. S. C. I. 1898.
17, 178. 596, 844. 86,3. 1043; 1900, 19, 1033; Chem. Centr. 1899, 70, I, 312;
Zts. ang. Chem. 1898, U, 1054; Pap. Ztg. 1898. 23, 75. H. Seidel, D. R. P.
99682, 1897; Zts. ang. Chem. 1900, 13, 951. 1307; Pap. Ztg. 1900, 2S, 3295,
3371; J. S. C. I. 1900. 19, 1033. See also Dissertation, Goettingen, 1892.
J. Lindsey and B. ToUens. Ann. 1891, 267, 341; abst. Ber. 1892, 25,
322; Zts. ang. Chem. 1892, 5, 154. A. Pictet, E. P. 121723. 1918; abst. J. S.
C. I. 1919. 38, 298-A.

2. "Praktische Handbuch der Papier Fabrikation," 1897. C. Hoff-

CELLULOSE 281

The sulfite lye usually has a specific gravity of about 1.05
and contains considerable quantities of the deliquescent calcium
salt of lignonsulfonic acid.^ In addition, there is present sugar,
resins, tannins, gummy matter, xyloneandsomevolatileacids (main-
ly acetic) . The sugar content of the waste liquor before evaporation
averages l%-2.5%, about 70% of which is dextrose, the remainder
being mainly mannose and galactose. As a general rule, the
higher the temperatm-e during the digestion of the wood with the
bisulfite, the greater the amount of sugar formed.* To obtain
alcohol' from this liquid it is first freed from fatty acids and
sulftu' dioxide by vacuum distillation, although this is not essen-
tial. This distillation may be carried out on the residual waste
liquors or may be previously done during the digestion of the
wood.* The waste liquor is next neutralized with lime, the pre-
cipitated calcium salts and parts of the organic matter removed
by filtration, and the filtered liquid treated with a special yeast
cultivated for the purpose, the solution meanwhile being aerated.

mann, Pap. Ztg. 1896, 21, 2483.. D. R. P. 128213 is by M. Hoffmann.
Papier Ztg. 1902, 27, 817; 1905, 30, 3374; abst. J. S. C. 1. 1902, 21, 602; 1905,
24, 1250. A. Staempfli, D. R. P. 309969, 1918; abst. J. S. C. 1. 1919, 38, 283-A.

1. M. Hoenig and J. Spitzer, Monatsh. Chem. 1918, 39, 1; abst. J. S.

C. I. 1918, 37, 502-A. E. Hoehn, Pap. Ztg. 1887, 12, 245. J. Juergensen,

D. R. P. 73718, 1892; Ber. 1894, 27, 445; Wag. Tahr. 1894, 40, 50; Chem.
Centr. 1894, 05, I, 1168; Zts. ang. Chem. 1894, 7, 188; Jahr. Chem. 1894.
47, 1136. Gore, Pap. Ztg. 1903, 28, 1282; Dingl. Poly. 1907, 302, 427.
Ociterreichische Ver. Chemische u Metallwgische Produktion, D. R. P.
25485, 1882; abst. Wag. Jahr. 1884, 30, 1151.

2. E. Simonsen, Norsk, teknisk Tids. 1895, 65; abst. J. C. S. 1896,
70, i, 331. W. Kerp and P. Woehler, Pap. Fab. 1909, 7, 45, 1131; Pap. Ztg.
1909, 34, 3286; 1910, 35. 1932; Chem. Centr. 1909, 80, II, 710. A. Klein,
Zts. ang. Chem. 1907, 20, 610; Pap. Ztg. 1905, 30, 3965; 1906, 31, 167, 474.
4286; Wochenbl. Papierfabr. 1909. 40, 240; Chem. Ztg. 1906, 30, 1259.

3. T. Koemer, Zts. ang. Chem. 1908, 21, 2353; abst. J. C. S. 1908,
34, i, 955; J. S. C. I. 1908, 27, 1216. See also E. Simonsen, J. S. C. I. 1898,
17, 365, 481, 1164. A. Classen. J. S. C. I. 1900, 18, 1028. P. Nicolardot,
F. P. 476696, 1914; abst. J. S. C. I. 1916. 35, 613. In the treatment of
sawdust, or other material containing cellulose with the object of producing
alcohol and organic by-products, the vapors which escape when the digesters
are opened are condensed in contact with alkaline-eaith carbonates, which
retain the acids but allow aldehydes, etc.. to pass. The large proportion of
organic acids remaining in the liquor in the digesters, which hinders the
fermentation of the dextrose, is almost entirely removed by vacuum distilla-
tion. The acid vapors are absorbed in milk of lime in large receivers acting
as vacuiun accumulators.

4. A. and E. Lederer. F. P. 464608. 1913; abst. J. S. C. I. 1914. 33,
478. B. Newlands. E. P. 16510. 1906; abst. J. S. C. I. 1907, 26, 835; C. A.
1907. 1, 2515. H. Krause. Chem. Ind. 1906. 28, 217; abst. Chem. Centr.
1906. 77, I, 1851 ; J. S. C. I. 1906, 25, 495. K. Kraut, Pap. Ztg. 1886, U,
1419.

282 TECHNOLOGY OF CELLULOSE ESTERS

The fermentation takes about five days, the alcohol formed is
separated by distillation. It is claimed that this process of pro-
ducing alcohol is very cheap and can rival the production of alco-
hol from food products. As the fermentable sugar content of
the waste lye is small, the production of alcohol, therefore, does
not solve the problem of tlie utilization of the sulfite lye.

H. Seidel proposes the use of waste sulfite liquor, under the
name of lignorosin, as an assistant in mordanting wool with
bichromate, to replace tartar emetic or lactic acid.

As to its use as a reducing agent the following example may
be cited: 10 grams 1.1-di-nitronaphthalene, 800 cc. water, 20
cc. waste sulfite lye, 20 gm. sodium bisulfite, 38° B6., and 20 gm.
soda lye, 30° B€. are heated on a water bath until complete solu-
tion results. The greenish blue solution obtained is acidified
with hydrochloric acid and boiled until free from sulfur dioxide.
The dyestuff is then precipitated with alcohol. It dyes wool dark
violet and silk violet-grey from an acid bath. The reducing
power of the sulfite liquor renders the color somewhat fugitive.

Waste sulfite lye may be employed in the indigo vat. The
following directions give the method of working according to H.
Seidel and L. Hanak : 2283 kilos indigo 80% (ground witli soda
lye — 1 part indigo, 3 parts water), 3.75 kilos slaked lime, 2.5
kilos calcined soda, and 10 kilos sulfite liquor 28° B€. are brought
to 62.5 liters with water and heated with direct steam until a
reaction suddenly begins at 75°. The vat is then made up to
500 liters and the diluted liquid treated with 10 kilos sulfite lye,
3.75 kilos lime and 2.5 kilos of calcined soda. The subsequent
working is the same as when glucose is employed. The sulfur
content of the evaporated lye is but 6%-8% and mainly present
in organic combination. It is difficult to recover this sulfur
economically. It has also been proposed to recover the sodium
salts. ^

In V. Drewsen's method^ the waste sulfite lye is heated with

1. E. Rinman, Swcd. P. 33084, 1910; abst. C. A. 1913, 7, 700. U. S. P.
1017320, 1912; abst. J. S. C. I. 1912, 31, 279. U. S. P. 1202317, 1916; abst.
J. S. C. I. 1916, 35, 1215. D. R. P. 2^5752, 1914; abst. J. S. C. I. 1915, 34,
1139. Ver. Zellstoff u Papierchem. Dec. 5, 1914; abst. Chem. Ztg. 1915,
39, 99; abst. J. S. C. I. 1915, 34, 274. vSee also J. S. C. I. 1912, 31, 274.

2. V. Drewseti, D. R. P. 67889, 1891; Bcr. 1893, 26, 558; Pap. Ztg.
1893, 18, 128(J. V. Drcwsen and L. Dorenfcldt, U. S. P. 620751. 726036,
1899; Chem. Ztg. 1899, 23, 276. K. Lehmann, Pap. Ztg. 1893, 18, 1924,
1956, 1989, 2025, 2057, 2089, 2122, 2153.

c^LLui^osE 283

caustic lime under a pressure of six atmospheres. The calcium
mono-sulfite formed in the reaction is converted into the soluble
bisulfite compound by means of sulfurous acid. The cost of this
process, however, is said to be high.

When the sulfite lye, as separated from the cellulose
material, cannot be utilized in this condition or when it is
inconvenient to run large amounts of it to waste, then the only
alternative is to evaporate the liquid, the evaporation being
preferably carried out in vacuo. When the moisture content of
the residue is about 50%, the material may be used as a fuel
direct; it is then subjected to dry distillation, with recovery of
good charcoal from the retort and of organic products from the
distillate. The residual material in the evaporation may, on the
other hand, be mixed with an equal weight of sawdust and made
into briquettes.^ This fuel has a calorific value of about 60% of
that of an average coal.^ H. Seidel neutralizes the sulfite liquor
with lime, saturates the solution with carbon dioxide and then
concentrates in vacuum evaporators or in a multiple-effect ap-
paratus.

The evaporated material is of a gummy nature (owing to
the presence of calcium salts of the lignonsulfonates) and contains
only relatively small quantities of nitrogen, potash or phosphate,
and therefore is unsuitable as a manure from the standpoint of
fertilizing efficiency. Owing to the gummy and plastic nature of
the material, it has been utilized as a substitute for resins and
gums. It is also a possible sizing material, but with only limited
application in this direction. The material may be used as a
source of oxalic acid but its employment is met by the compe-
tition from sawdust, which yields oxalic acid more economically.

Owing to the great bulk of water (90%) present, it is expen-
sive to obtain the solid residue by evaporation. A process has
been developed by E. Oman in which the expense of removing
the water, in cold countries such as Sweden, may be reduced by

1. R. Strehlenert, Chem. Trade J.; J. Ind. Eng. Chem. 1916, 8, 1070.
Can. P. 190864, 1919; abst. C. A. 1919. 13, 1764. Papierfabr. 1913, U,
645, 666; abst. J. S. C. I. 1913, 32, 652. See "Literature of Sulfite-cellulose
Spent Liquors," M. Mueller, Berlin, 1911, 114 pages.

2. Engineering, 1916, 177. A. Leonhardt, D. R. P. 34420, 1885;
abst. Wag. Jahr. 1885, 31, 1043; 1886, 32, 938. C. Liesenberg, D. R. P.
37882, 1886; abst. Wag. Jahr. 1888, 34, 1178; Chem. Centr. 1887, 58, 132;
Pap. Ztg. 1887, 12, 398.

284 TECHNOU>GY OF CEI.I.UI.OSK KSTl^RS

40%. This is brought about by freezing out the water. In this
way four-fifths of the total water can be readily removed and the
residue worked up for organic constituents. A method of recov-
ering lignon sulfonates by salting out has also been proposed by
E. Oman.^

Another possible use of spent sulfite lye is in connection with
the leather industry. Hide powder will absorb about 20% of
dry sulfite residue.^ In W. Dickerson's patent' waste sulfite lye
is used "for the manufacture of a tanning extract. The lye is
digested with an electrolyte such as sodium chloride, which is
capable of gelatinizing the liquid or of converting it into a mobile
fluid when concentrated. Treatment of the lye with 1% of ben-
zoyl chloride in a weak alkaline solution is said to separate the
tannins in the form of a white powder.

The soda and sulfite treatments give a wood pulp suitable
for most purposes, especially if a bleaching treatment has been
carried out. The average composition of the piu-ified wood pulp
prepared by the various chemical methods is approximately the
same, being carbon 50%, nitrogen 6% and oxygen 44%. The
wood pulp is, for example, suitable for paper manufacture and it
may be used as an absorbent of nitroglycerol in the preparation
of gelignite.* If required, however, for the preparation of yam,

1. E. P. 103479, 103480, 103822, 1917; abst. J. S. C. I. 1918, 87, 407-A»
541-A, 573-A. E. P. 103649, 103650, 103651, 103652, 103653, 103654, 103655.
1917; abst. C. A. 1917, U, 1749; J. S. C. I. 1918, 37, 121 A, 146 A. 461 A.
U. S. P. 1130192, 1915; abst. J. S. C. I. 1915, 34, 419. E. P. 1145, 1914;
abst. J. S. C. I. 1914, 33, 348. F. P. 467466, 1914; abst. J. S. C. 1. 1914, 33, 828.
Chemikerversammlung, Stockholm, May 28-29, 1915; Chem. Ztg. 1915, 39,
820; abst. J. S. C. I. 1916, 35, 172.

2. See D. R. P. 75351; abst. Wag. Jahr. 1894, 40, 1061; 86651; abst.
Zts. ang. Chem. 1896, 9, 343; 93944; 93945, abst. Wag. Jahr. 1897, 44, 1066,
1067; 122489; abst. Zts. ang. Chem. 1901, 14, 808; 183415; abst. Wag. Jahr.
1907, 53, II, 603; 194872; abst. Wag. Jahr. 1908, 54, II, 487. J. Graham.
E. P. 5365, 5366, 5367, 5368, 1882. D. R. P. 23718, 1882; abst. Dingl.
Poly. 1884, 2SL, 70; Papier Ztg. 1883, 434; Wag. Jahr. 1884, 30, 247.

3. U. S. P. 1043303, 1912; abst. J. S. C. I. 1912, 31, 1160. C. Meyer.
Aust. P. 1210, 1889. E. Morterud, Wochenbl. Papierfabr. 1907, 38, 1056
Pap. Ztg. 1906, 31, 3819; 1907, 32, 296.

4. Here it serves the double purpose of absorbing the nitroglycerol
and reducing the temperature of explosion. It should be free from acid and
foreign substances, especially metallic particles, and should contain but little
resin. The moisture should be under 10%, and should absorb nitroglycerol
readily. For the preparation of adhesives from sulfite liquor, see E. P. 2924,
1866; 6652, 1912; 304, 1913. For cellulose briquettes, compare Belg. P.
133967, 1898; 254944, 1913. The J. Jurgens and H. Timpe plastic of cellu-
lose and aluminates is described in Belg. P. 228578, 1910.

CELLUWSE 285

nitrocellulose, cellulose xanthate, various plastic films of artificial
silk, further purification is expedient, as there are impurities pres-
ent which impair its use in the preparation of these products.^

To take a particular example, wood-cellulose from the sul-
fite process, gives a lower yield on nitration, as compared with
the yield from purified cotton. The nitration product also has
a lower ignition temperature and a greater solubility in ether-
alcohol.* According to Klemm, one of the chief difficulties in
obtaining uniformity from wood cellulose, lies in the different
structures of the cells of the spring and autunm growths, and it
is suggested that wood grown in tropical regions would afford
more tmiform results under chemical treatment.

Wood pulp is composed of cellulose of varying degrees of
piurity, together with some incrusting matter, resins, gums and

1. E. Opfermann, E. Priedmann and Akt. Ges. f. Maschinenpapier-
fabrikation, D. R. P. 219085, 1910; abst. Wag. Jahr. 1910. 56, II, 427; Chem.
Zentr. 1910, U, I, 978; Chem. Tech. Rep. 1910. 34, 135; Chem. Ind. 1910,
33, 154; Chem. Zts. 1910, 9, 2031; C. A. 1910. 4, 2044; Jahr. Chem. 1910.
63, 429. F. P. 402462. 1909; abst. J. S. C. I. 1909, 28, 1270. E. Schauffel-
bergcr, U. S. P. 1282636, 1917; abst. J. S. C. I. 1919. 38, 9-A. E. P. 113494,
1917; 124676, 1918; abst. J. S. C. I. 1918, 37, 2033; 1919. 38, 367-A. Can.
P. 187949, 1918; abst. C. A. 1919. ll 1149. F. P. 402462. 1909; abst. J. S. C.
I. 1909, 28, 1270; Mon. Sci. 1911, 74, 164. E. P. 10604, 1909; abst. J. S. C.
I. 1910, 29, 269.

2. K. Nitzelnadel (Wochbl. Papierfabr. 1912, 43, 3488; abst. J. S. C. I.
1912, 31, 964; C. A. 1913. 7, 257) has prepared nitrocellulose from various
samples of sulfite wood pulp, bleached and unbleached, also from straw
cellulose. These materials contain higher proportions of non-cellulose impur-
ities than the cotton ordinarily employed in the nitrocellulose industry;
straw pulp also possesses the disadvantage of not being readily wetted by
liquids. The nitration experiments showed that sulfite wood pulp yields prod-
ucts containing at least as much N as those prepared from cotton; the products
from straw cellulose were generally rather poorer in N. The solubility in
ether-alcohol of the nitrocellulose prepared from these celluloses was gen-
erally over 40% ; in one case only was it as low as 13%. The films obtained on
evaporating the solutions were inferior to those from solutions of nitrated
cotton. The stability tests, performed according to Will's method, showed
that these nitrocelluloses were sufficiently stable to satisfy official specifica-
tions; the products from straw cellulose showed the lowest stability. The
ignition temperature, according to Kast's test, was in general somewhat
lower than for nitrated cotton, but all the nitrocelluloses prefMured from
wood fiber showed temperattu-es of ignition well above the specified mini-
mum limit of 180°; the products from straw cellulose tended to fall below
this limit. The yields of nitrocSlulose from sulfite wood pulp were lower
than those obtained from cotton; straw cellulose gave the lowest yields.
His conclusions are in favor of the use of wood cellulose as a raw material
in the nitrocellulose industries, but considers straw cellulose unsuitable. The
disadvantages of wood cellulose, as compared with cotton, are the lower
yields, the lower ignition temperattu-e of the products, and the greater solu-
bility in ether-alcohol.

286 TECHNOLOGY OF CKLLUWSE ESTERS

quinoline-like compounds.^ A process has been patented to im-
prove the wood pulp so as to make it more suitable for special
purposes, as for the preparation of highly nitrated gun-cotton.*
The wood cellulose is freed from incrusting matter by further
chemical treatment using any of the known processes. The ma-
terial is then reduced to a high degree of mechanical division in
a special disintegrator. The chemical action must not be too
drastic .or the cellulose itself may be attacked. If the latter oc-
curs appreciable amounts of oxycellulose are formed during the
subsequent bleaching operations. In such cases, where oxycel-
lulose is present it is difficult to obtain a stable highly nitrated
cellulose. In addition, the solutions made for the production of
artificial filaments have too low a viscosity and are also unsuit-
able for artificial filament formation.* Overbleached cellulose can
be detected by its reducing action, the reducing power being ex-
pressed in the so-called copper number, and for a cellulose to be
suitable for nitration the copper number must be low. Abso-
lutely pure cellulose has no reducing power.* The risk of ob-

1. R. Sieber, Paper, 1915. 16, 13; abst. C. A. 1915, 9, 3128. Schriften
des Vereins der Zellstoff-u. Papierchem. 9, Zts. ang. Chem. 1916, 29, R,
429; abst. J. S. C. I. 1916, 35, 1151. See also J. S. C. I. 1909, 28, 438.

2. Zellstoflf-fabrik Waldiiof, (E. P. 336, 1891; abst. J. S. C. I. 1892,
11, 180; Mon. Sci. 1892, 40, 166). This process seeks to obviate the lack of
uniformity which wood pulp often has, and at the same time to remove all
incrusting and extraneous material. This is accomplished by chemical treat-
ment, aided by a high degree of mechanical subdivision of the purified pulp,
the latter being accomplished by means of a disintegrating apparatus on
the order of a carding or tearing machine. The disintegrator consists of
two rings or discs carried on separate shafts placed in line with one another
and rotating in opposite directions at a speed of about 1500 revolutions per
minute. These ^ discs carry pins so adjusted that the pins on one disc pass
between the pins of the other, the cellulose being introduced through a cen-
tral orifice in one of the discs is centrifugally thrown, and thus becomes
uniformly comminuted. The material is passed through the machine a suffi-
cient number of times, until a sample, after nitrating, washing^ and drying,
has the requisite fineness.

3. C. Piest, Zts. ang. Chem. 1913, 26, 24; abst. Kunst. 1913, S, 92;
C. A. 1913, 7, 1284; Papierfabr. 1914, 12, 860; J. S. C. I. 1914, 33, 856.
Mountsing, D. R. P. 189735; abst. Wag. Jahr. 1907, S3, II, 499; Chem. Ztg.
Rep. 1907, 31, 536; Zts. ang. Chem. 1908, 21, 270. F. Muellner etal.. D. R.
P. 96467, 1897; Pap. Ztg. 1898. 23, 687; 1062, 1218; abst. Wag. Jahr. 1898,
44, 1108; Chem. Zcntr. 1898, 69, I, 1183; Chem. Ztg. 1898, 22, 300; Zts. ang.
Chem. 1898, U, 378; Jahr. Chem. 1898, 51, 398, 1373. See A. Mitscherlich,
E. P. 12927, 1893; abst. J. S. C. 1. 1894, 13, 834. C. Ekman, E. P. 20036, 1893;
abst. J. S. C. I. 1894, 13, 1085. Zellstofffabrik Waldhof and V. Hottenroth,
Swiss. P. 77322, 1918; abst. C. A. 1918, 12, 2248; addn. to Swiss P. 76329; abst.
C. A. 1918 12 1123.

4. C. Schwalbc, Ber. 1907, 40, 1347; abst. Chem. Centr. 1907, 78,
I, 1490; Chem. Ztg. Rep. 1907, 31, 302; C. A. 1907, 1, 1696, 2179; J. C. S.

CELLULOSE 287

taining oxycellulose can be considerably reduced by employing
alkali carbonate instead of caustic alkali, and alkali sulfite in the
final purification process. In addition, a less drastic bleaching
is required. A suitable concentration of lye is 0.5% to 2% with
a boiling of 3-6 hours at a pressure of 2-3 atmospheres.^

An impurity usual' y present in wood pulp prepared by the
ordinary chemical methods is a small quantity of resin, pitch and
o!ly matter. The resin content is usually less in bleached than
in unbleached wood pulp. The soda process, on account of the
more drastic chemical action, gives a purer product from the
point of vi2w of resin content than sulfite wood pulp, the resin in
the former type being but 0.05%. In the R. Mitscherlich process^

1907. 92, i, 390; J. S. C. I. 1907, 26, 548; Jahr. Chem. 1905-1908, II, 961;
Zts. ang. Chem. 1908, 21. 265. M. Mueller and E. Meyer, D. R. P. 112449;
abst Wag. Jahr. 1900, 46, II, 529; Chem. Centr. 1900, 71, II, 827; Chem.
Ztg. 1900, 24, 674; Dingl. Poly. 1902, »?, 750. A. Nettl, Aust. P. 1576,
1888. Compare W. Normann, Chem. Ztg. 1906, 30, 584; abst. Chem. Centr.
1906, 77, II, 719; Zts. ang. Chem. 1906, 18, 993; abst. Chem. Centr. 1906,
77, II, 673.

1. Refer to "Alcohol from Wood Waste," U. S. Consulate Report,
Nov. 1911; abst. J. S. C. I. 1911, 30, 1466. F. Raschig (E. P. 11668. 29696,
1912. F. P. 441419, 1912; abst. J. S. C. I. 1912, 31, 845; 1913, 32, 254.
abst. J. S. C. I. 1913, 32, 454) prepares potassium, sodium and ammonium ;
nitrate explosives by adding thereto the dry residue from the lyes obtained
in the manufacture of cellulose by the sulfite process. D. Newbaecker,
D. R. P. 110972, 1899; abst. Wag. Jahr. 1900, 46, II, 315; Chem. Ztg. 1900, 24,
570; Zts. ang. Chem. 1900, 13, 674; Chem. Zts. 1902, 1, 191. J. Novak,
D. R. P. 74030, 1893; Ber. 1894, 27, 474; Pap. Ztg. 1894, 19, 1169; Wag.
Jahr. 1894, 40, 1061.

2. W. Herzberg, Papier Ztg. 1906, 31, 3819; Mitt. Materialprufung-
samt. 22, 180; abst. Chem. Centr. 1905, 76, I, 1286; Mitt. Koenig. tech.
Versuchs, 1890, 13, 132; abst. 1904, 22, 180; abst. J. S. C. I. 1890, 9, 112,
1068; 1891, 10, 661; 1897, 16, 350; 1901, 20, 739; 1905, 24, 453. Papierfabr.
1911, 9, 914, 948; abst. J. S. C. I. 1911, 30, 1049. See also Sitz. d. poly.
Gesellsch. Berlin, 1882; Papier Ztg. 1884, 432; Ber. 1887, 20, 808; J. S. C. I.
1887, 565; 1891, 10, 576. A. Mitscherlich, D. R. P. 4178, 4179, 1878. E. P.
1548, 1883; Ber. 1879, 12, 395; Papier Ztg. 1883, 8, 343, 718, 750, 824, 893,
932, 934, 999, 1029, 1425, 1469, 1498, 1529, 1633, 1670, 1705; 1884, 9, 213,
249. 285, 1715, 1763, 1801. It should be noted that D. R. P. 4178 is iden-
tical with Sachs, D. R. P. 3912, 1875. D. R. P. 34420, 1885; 54206, 1890;
72161, 1891; 72362, 1891; 82498, 1893; 86651. 1895; 93944, 1896; abst. Ber.
1891, 24, 343; 1894, 27, 149, 221; 1895, 28, 869; 1897, 29, 452; Pap. Ztg.
1893, 18, 3222; 1894, 19, 272; 1895, 20, 2716; 1896, 21, 1848; 1897, 22, 3074,
3148. D. R. P. 169408, 169409, 1903; abst. Wag. Jahr. 1906, 52, II, 546;
Chem. Ztg. 1906, 30, 489; Zts. ang. Chem. 1907, 20, 368. D. R. P. 220066,
1908; abst. Pap. Ztg. 1906. 31, 1732; 1893, 18, 1673; 1896, 21, 2344, 2850;
Wag. Jahr. 1910, 56, II, 527; Chem. Zentr. 1910, 81, I, 1309; Chem. Ztg.
Rep. 1910, 34, 180; Zts. ang. Chem. 1910, 23, 959. Aust. P. 112, 1894; 2945,
1897. For history of work of Mitscherlich, see Paper, 1916, 18, No. 18, p.
17. In this connection compare R. Kuhn, Pap. Ztg. 1895, 20, 120, 248, 466,
500, 562, 663, 727, 822, 952, 983, 1083, 1147, 1351, 1445, 1547, 1870.

288

TECHNOLOGY OF CELLULOSE ESTERS

the resin is usually 0.3%-0.5%. This latter figure is approxi-
mately constant for different sulfite samples and does not appear
to depend on the method by which the process is carried out.

The following table shows the amount of resin obtained by
W. Herzberg, from various types of ptuified wood pulp.

TABLE XXXI.— RESINS IN WOOD PULP.

-

Per cent.

Mitscherlich cellulose, unbleached

Mitscherlich cellulose, bleached

Ritter Kellner cellulose, unbleached....

Ritter Kellner cellulose, bleached

Sulfite process, unbleached

0.58
0.44
0.69
0.46
0.72
0.43
0.04
0.03

Sulfite Drocess. bleached

Sodium sulfite, unbleached

Sodium sulfite, bleached

The resin in the above celluloses is separated, for estimation,
by extraction with ether.

The differences in the physical condition of wood pulp ob-
tained in various methods and from different types of wood may
produce nitrocelluloses with widely varying physical properties.
To secure uniform products from different woods A. Luck and E.
Dumford^ destroy the physical structure of the wood before nitra-
tion. This is brought about by first treating the cellulose material
with known solvents so as to effect solution. Such solvents as
aqueous sulfuric acid, zinc chloride in hydrochloric acid or caustic
soda, carbon bisulfide and water are advocated. The cellulose is
separated in a hydrated form in the usual way after freeing from
traces of solvent. A compact powdery material is then obtained
which, on nitration and purification, is said to give a dense,
granular nitrocellulose.

P. Girard* purifies wood pulp by subjecting it to the action

1. E. P. 4769, 1895; abst. J. S. C. I. 1896, IS, 135. H. Opl, D. R. P.
75351, 1893; Ber. 1894, 27, 836. Reid. Dingl. Poly. 1886, 261, 379; J. S. C. I.
1886, 5, 273; Wag. Jahr. 1886. 984. A. Sparre, D. R. P. 237081, 1911; abst.
Zts. Chem. Ind. KoU. 1912, 10, 111; Wag. Jahr. 1911. 57, II, 600; Chem.
Zentr. 1911, 82, II, 411; Chem. Ztg. Rep. 1911, 35, 481; Ztg. ang. Chem.
1911, 24, 1583.

2. F. P. 44.3897; abst. Kunst. 1913, 3, 15. Many of the essential ideas
of this process are to be found in E. P. 1454, 1860, L. Obert, J. Vasseur and
A. Houbigant. E. Steiger and E. Schulze, Ber. 1890, 23, 3110; abst. J. C. S.
1891, 60, 33; Jahr. Chem. 1890. 36, 2188. B. ToUens and W. Stone, Ber.
1888, 21, 1572; abst. J. C. S. 1888, 54, 808; J. S. C. I. 1888, 7, 611.

CELLULOSE 289

of solvents which do not attack the cellulose, but which dissolve
the other products. It is claimed that the resulting product is
equal to the more expensive forms of cellulose obtained from
cotton and other sources. The extracted materials such as resin,
etc., can be regained from the solvent by evaporation. The sol-
vents used are methyl, ethyl, or amyl alcohols, acetone, carbon
tetrachloride, chlorine derivatives of ethane or ethylene, as for
example, trichloroethylene, either singly or in combination, or
when mixed with 5%-10% of formaldehyde solution. The use
of formaldehyde has two purposes: it acts as an antiseptic and
causes a matting together of the substance that is being extracted.
The water appears to preserve the porosity of the mass so that
the solvent penetrates into the structure of the wood.

V. Drewsen has described a process of refining sulfite^ or
sulfate'^ wood pulp for nitrating purposes, the invention relating
especially to the refining or purification of wood pulp produced
from pine, spruce, or similar suitable wood, by either the caustic
soda or sulfate process or sulfite or acid process, to secure a re-
fined pulp of low caustic potash solubility with minimum loss of
the original wood pulp material.

In carrying this process into effect the original wood pulp
is preferably partially bleached with chlorine water so as to con-
siderably change some of the colored compounds, thus giving the
wood pulp a grayish yellow or yellowish tinge, the colored material
being removed by a cooking process with sodium carbonate or
sodium hydroxide.

The pulp, after this treatment, has a considerably reduced
caustic potash solubility and is said to be sufficiently light in
color to be used without serious objection for some nitrating pro-
cesses. If desired, however, the treated pulp may he given a
second bleaching action with a relatively small proportion of
bleaching powder solution to still further improve its color without

1 . U. S. P. 12831 14, 1918. C. Rosenhain, Deutsche Industrieztg. 1875,
502; Chem. Centr. 1877, 48, 103; Dingl. Poly. 1876, 220, 81. H. Spindler,
Chem. Ztg. 1897, 21, 302.

2. U. S. P. 1283113, 1918. A. Ullmann, Aus. P. 3043, 1890. E.
Unger and R. Jaeger, Ber. 1903, 36, 1222; abst. Chem. Centr. 1903, I, 1194;
J. C. S. 1903, S4, ii, 456. B. Wagner, D. R. P. 188428, 1906; abst. Pap. Ztg.
1907, 32, 3356; Wochenbl. Papierfab. 1907, 38, 3519; Wag. Jahr. 1907, 53,
I, 10; Chem. Ztg. Rep. 1907, 31, 491.

290 TECHNOLOGY OF CELLULOSE ESTERS

undesirably increasing its percentage of caustic potash solubility.

Wood pulp^ contains about the same (91%-92%) quantity
of cellulose. Mitscherlich and Ritter-Kellner sulfite pulps con-
tain the smallest amount of pentosans and roda pulp the most.
There, however, is not much difference in the lignin content of
the pulp. Sulfite pulps yield about 0.7% ether-extract and soda
pulps about 0.2%.

The development of this art from a practical point of view,
is clearly set out in the work of A. Frank, ^ M. Elb,' C. Eckman,*
L. Dorenfeldt,*^ F. Ahrens,^ T. Knoesel,^ A. Kumpfmiller," M.

1. C. Schwalbe, Zts. ang. Chem. 1918, 31, 50; abst. J. S. C. I. 1918,
37, 365-A; C. A. 1918, 12, 2439. C. Weilberj;, U. S. P. 981042; J, S. C. I.
1911, 30, 204. F. Wendenberg, D. R. P. 32329; Pap. Ztg. 1886, U, 188.

2. D. R. P. 40308, 1880; abst. Wag. Jahr. 1887, 33, 1177. Aust. P.
646, 1887; Bcr. 1887, 20, 667; Dingl. Poly. 1888. 268, 4^5; 276, 58; Zts. Papier-
zeugung Vcrbrauch, 1888, 2, 733; Wochenbl. Papierfabr. 1904, 35, 3338;
Pap. Ztg. 1886, 11, 541, 1387; 1887, 12, 137, 1170, 1765, 1782, 1823; 1889.
14, 123, 3a3, 1091, 1488, 1556; 1890, 15, 1398; 1891, 16, 1813; 1892, 17, 791;
1904, 29, 2465, 3368. See D. Frank, E. P. 5532, 1882; abst. J. S. C. I. 1882,
1, 244. Forbes, U. S. P. 510168; Dingl. Poly. 1896, 300, 50.

3. D. R. P. 166947, 1905; abst. Wag. Jahr. 1906, 52, II, 547; Jahr.
Chem. 1905-1908, II, 973. Aust. P. 23146, 1905; abst. Chem. Centr. 1906.
77, I, 801; Pap. Ztg. 1906. 31, 152. D. R. P. 173686, 1905; abst. Pap. Ztg.
1906, 31, 3180; Chem. Centr. 1906. 77, II, 924. X. Zawadski and E. Meyer,
D. R. P. 45951, 1888; Ber. 1889, 22, 75; Pap. Ztg. 1889, 14, 388.

4. E. P. 20036, 1893. D. R. P. 81643. 1893. Aust. P. 569, 1894;
3229. 1899; Ber. 1896, 28, 71 1 ; Pap. Ztg. 1895, 20, 2524; Chem. Ztg. 1895, 19,
605; Pap. Ztg. 1896, 21, 2218, 2609, 3247. Wochenbl. f. Papierfab. 19(M,
35, 461; abst. J. S. C. I. 1904, 23, 265. G. Eichelbaum, D. R. P. 96316,
1897; Pap. Ztg. 1898, 23, 1404; abst. Chem. Centr. 1898, 69, I, 1288. Erste
Oesterreichische Sodafabrik, Aust. P. 2336, 1899.

5. D. R. P. 113435; abst. Wag. Jahr. 1900, 46, II, 530; Chem. Centr.
19(X), 71, II. 702; Chem. Ztg. 19(K), 24, 762; Jahr. Chem. 1900, 53, 848; 1901.
54, 899; 106021; 1898; abst. Wag. Jahr. 1899, 45, 1063; Chem. Centr. 1900,
71, 636; Zts. ang. Chem. 1899. 12, 1161; Jahr. Chem. 1900,53, 848; 122489,
1898; abst. Wag. Jahr. 1901, 47, II, 591 ; Chem. Centr. 1901, 72, II, 248; Chem.
Ztg. 1901, 25, 6,31; Zts. ang. Chem. 1901, 14, 808; 129227, 1900. Aust.
P. 3807. 4602, 5(K)2, 1898; abst. Pap. Ztg. 19a). 25, 384, 2916; Wag. Jahr.
1902, 48, II, 569; Chem. Centr. 1902, 73, I, 686; Chem. Ztg. 1902, 26, 233;
Papier Ztg. 1903, 28, (7), 215; abst. J. S. C. I. 1903, 22, 160. A. Denison
and H. Palmer, U. S. P. 49(K)00. D. R. P. 73924; Dingl. Poly. 1894, 292,
123; Wag. Jahr. 1894, 40, 1059.

6. Zts. ang. Chem. 1895, 8, 41; Chem. Centr. 1895, 66, I, 569; Ber.
1895, 28, 238; Pap. Ztg. 1895. 20, 562; 1905, 30, 1539; Chem. Zts. 1905, 4,
40. L. Abraham. Aust. Anm. A-5635, 1909; D. R. P. 224411; Pap. Ztg.
1910, 35, 2140; Wochenbl. Papierfabr. 1910, 41, 1 111, 2613; Wag. Jahr, 1910,
56, II, 454; Chem. Zcntr. 1910, 81, II, 614. Dresel, D. R. P. 5891. Duerr
& Co., D. R. P. 71942. 1893; abst. Ber. 1894, 27, 220; Pap. Ztg. 1894. 19,
76; Wag. Jahr. 1894, 40, 1060; Jahr. Chem. 1894, 47, .1135. B. Diamond,
V. S. P. 938128, 1909; D. R. P. 216798, 1907; abst. Chem. Ztg. Rep. 1909,
33, 607. 624; Wag. Jahr. 1909. 55, I. 492; Chem. Zentr. 1910. 81, 1, 213; Chem.
Ztg. Rep. 1909, 33, 670; Zts. ang. Chem. 1910. 23, 227; Jahr. Chem. 1910, 63,

CELLULOSE 291

Hoenig,^ B. Philippi,^ J. Robeson,' J. Schwager,^ D. Stewart,*

I, 362.

7. Chem. Ztg. 1902, 26, 2?9; Chem. Centr. 1902, 73, I, 955; Pap.
Ztg. 1903, 28, 288; Wochenbl. Papierf. 1907, 38, 1293, 2542; 1908, 33, 3276;
1908, 40, 4049; 1909, 40, 1603; abst. J. S. C. I. 1909, 28, 671. F. Zenk, Pap.
Ztg. 1894, 19, 688, 699, 733, 796, 893, 928, 961. A. Zimmermann, Pap.
Ztg. 1897, 22, 947.

8. D. R. P. 81338, 1894; Ber. 1896, 28, 686; Chem. Centr. 1895, 06,

II, 472; Pap. Ztg. 1895, 20, 2030, 2072. Chem. Ztg. 1910, 34, 19; abst. J. S.

C. I. 1911, 30, 19. vSee also D. R. P. 194127; abst. Wag. Jahr. 1908, 54, I,
506; Chem. Zentr. 1908, 79, I, 1124; Chem. Ztg. Rep. 1908, 32, 139. D. R.
P. 194744; abst. Wag. Jahr. 1908, 54, I, 506; Chem. Ztg. Rep. 1908, 32, 145.

D. R. P. 194745; abst. Wae. Jahr. 1908, 54, 1, 506; Chem. Zentr. 1908, 79, 1, 1 124;
Chem. Ztg. Rep. 1908, 32, 135. D. R. P. 196390; abst. Wag. Jahr. 1908,

54, I, 506; Chem, Zentr. 1908, 79, I, 1352; Chem. Ztg. Rep. 1908, 32, 239.
D. R. P. 197160. D. R. P. 197587; abst. Wag. Jahr. 1909, 55, II, 287; Chem.
Zentr. 1908, 79, I, 1819; Chem. Ztg. Rep. 1908, 32, 287. D. R. P. 201052.
abst. Wag. Jahr. 1908, 54, I, 506; Chem. Ztg. Rep. 1908, 32, 632. D. R. P.
202393, 204470. D. R. P. 206743, abst. Wag. Jahr. 1909, 55, I, 514; Chem.
Ztg. Rep. 1909, 33, 107. D. R. P. 206743, abst. Wag. Jahr. 1909, 55, I,
514; Chem, Ztg. Rep. 1909, 33, 107. D. R. P. 206999, abst. Wag. Jahr. 1909,

55, I, 514. D. R. P. 207355, 208373. D. R. P. 83438, 1894; Ber. 1896,
28, 1030; Pap. Ztg. 1896, 21, 236; Wag. Jahr. 1895, 41, 746; Zts. ang. Chem.

1896, 9, 25; Jahr. Chem. 1895, 48, 1356. D. R. P. 183415, 1905; Aust. P.
5849, 1894; Chem. Zentr. 1907, 78, II, 109; Wochenbl. Papierfabr. 1907,38,
1402; Pap. Ztg. 1907, 32, 2046; Chem. Ztg. Rep. 1907, 31, 243. D. R. P.
189177. 1904; abst. Wag. Jahr. 1907, 53, I, 8; Chem. Ztg. Rep. 1907, 31,
491; 176722; abst. Chem. Ztg. Rep. 1907, 31, 109; 195286; abst. Wag. Jahr.
1908, 79, I, 5; Chem. Ztg. Rep. 1908, 32, 176; 199279, abst. Chem. Zentr.
1908, 79, I, 1118; Pap. Ztg. 1907, 32, 3356; Wochenbl. Papierfabr. 1907,38,
3019. D. R. P. 194872, 1906; 183415; Chem. Zentr. 1908, 79, I, 1118; Pap.
Ztg. 1908, 33, 896; Chem. Ztg. Rep. 1908, 32, 255; Wochenbl. Papierfab.

1908, 39, 1306. D. R. P. 207776, 1906; Papierfabr. 1909, 7, 293; Pap. Ztg.

1909, 34, 986; Chem. Ztg. Rep. 1909, 33, 195. D. R. P. 216284, 1907; abst.
Chem. Ztg. Rep. 1909, 33, 627, 631; Pap. Ztg. 1909, 34, 3716; Wag. Jahr.
1909, 55, II, 507; Chem. Zentr. U)09, 80, II, 2108; Chem. Ztg. 1909, 33. 631.
D. R. P. 203648. 1906; Aust. P. 40657, 1906; Chem. Zentr. 1908, 79, II,
1834; Pap. Ztg. 1908, 33, 3564; Chem. Ztg. 1908, 32, 1036; Wochenbl. Papier-
fabr. 1909, 40, 260. U. S. P. 940394, 1909; Chem. Ztg. Rep. 1909, 33, 648;
Pap. Ztg. 1910, 35, 300. T. KomdorfT, D. R. P. 32696, abst. Wag. Jahr.
1885, 31, 1192; Pap. Ztg. 1886, U, 259. Knoeselmehl, D. R. P. 128213;
Chem. Ztg. 1902, 26, 229; 1903, 27, 21; 1904, 28, 38; Chem. Centr. 1902, 73,
I, 955; Pap. Ztg. 1903, 28, 288; 1905, 30, 1539; 1904, 29, 3367; Chem. Zts.
1905, 4, 40; Zts. ang. Chem. 1904, 17, 1788. D. Kempe, Aust. P. 3962,

1897. G. Katz, D. R. P. 149461, 1903; abst. Wag. Jahr. 1904, 50, II, 533;
Pap. Ztg. 1904, 29, 800; Chem. Ztg. 1904, 28, 217; Zts. ang. Chem. 1904,
17, 535; Jahr. Chem. 1904, 57, 1104. O. Karr, U. S. P. 762139; Pap. Ztg.
1904 29 2726.

'l. *D. R. P. 132224, 1901; abst. Wag. Jahr. 1902, 48, II, 600; Chem.
Centr. 1902, 73, II, 174; Chem. Ztg. 1902, 26, 611. 152236; abst. Wag. Jahr.
1904, 50, II, 514; Chem. Ztg. 1904, 28, 648; Zts. ang. Chem. 1904. 17, 1256.
Aust. P. 7325, 1901; 12970, 1902; 31862, 1906; Pap. Ztg. 1902, 27, 2162.
J. Hough, U. S. P. 931608, 945394, 1910; J. S. C. I. UK)9, 28, 1148; Pap.
Ztg. 1904, 34, 2787. J. Hanson, E. P. 12261, 1885; abst. J. vS. C. I. 1886,
5, 614; Pap. Ztg. 1887, 12, 352. E. Haenisch and M. vSchroder, D. R. P.
36721, 1886; abst. Dingl. Poly. 1886, 262, 418; Wag. Jahr. 1886, 32, 267;

292 TECHNOLOGY OP CISLLUl,OSE ESTERS

E. Trainer,^ J. VogeP and other investigators in this field.

Chem. Centr. 1887, 58, 159; Bied. Tech. Chem. Jahr. 1886-87, 3, 109.

2. D. R. P. 195643, 1904; abst Chem. Zentr. 1908, 79, I, 1232; Pap.
Ztg. 1908, 33, 1210; Wag. Jahr. 1908, 54, II. 557; Chem. Ztg. Rep. 1908,

32, 169. D. R. P. 211348, 1905; abst. Pap. Ztg. 1909, 34, 2294; Wag. Jahr.
1909, 55, II, 563; Chem. Zentr. 1909, 80, II, 400; Chem. Ztg. Rep. 1909,

33, 447. G. Pictet, D. R. P. 26331, 1883; 41703, 1887; abst. Wag. Jahr.
1884, 30, 1147; 1888, 34, 398; Pap. Ztg. 1884, 9, 562. E- Pollacsek, Aust. P.
967, 985, 1524, 1898. Pissier, E. P. 12762, 1887. A. Selkirk, E. P. 11848,
1888; abst. J. S. C. I. 1888, 7, 864,

3. E. P. 17956, 1908. Aust. P. 42479, 1909. U. S. P. 851378, 851381;
J. S. C. I. 1909, 28, 1052; Chem. Ztg. 1907, 31, 312; Pap. Ztg. 1910, 35, 300.
E. Rinman, D. R. P. 222302, 1909; abst. Pap. Ztg. 1910, 35, 1726; Wochenbl.
Papierfab. 1910, 41, 1869; Papierfabr. 1910.8,536; Wag. Jahr. 1910, 56, II,
453; Chem. Zentr. 1910, 81, II, 52; Chem. Ztg. Rep. 1910, 34, 299; Zts. ang.
Chem. 1910, 23, 1390. P. Remy, D. R. P. 90798, 1896; abst. Pap. Ztg.
1897, 22, 426; Wag. Jahr. 1897, 43, 10; Chem. Ztg. 1897, 2L, 229.

4. D. R. P. 53043, 1889; 58599, 1890; 87678. 1895; 96434, 1897; 115256,
1900; 128903, 1901; 148331; abst. Wag. Jahr. 1890,36,600; 1891,37,868;
1896, 42, 790; 1901, 47, II, 311; 1902. 48, I, 519; Chem. Ztg. 1896, 20, 726;

1902, 26, 410; Jahr. Chem. 1898, 51, 172; Chem. Centr, 1898, 69, II, 458;
Zts. ang. Chem. 1901, 14, 94; 1902, 15, 314; Ber. 1890, 23, 159; Pap. Ztg.

1903, n, 2075, 2183.

5. U. S. P. 909343, 1909. Aust. P. 40528, 1907; Chem. Ztg. Rep. 1909,
33, 175. U. S. P. 923088, 1909; abst. J. S. C. I. 1908, 28, 737. J. Stanley,
U. S. P. 9681278. E. P. 29087, 1910r abst. J. S. C. I. 1911, 30, 951. D.
Sparre, D. R. P. 237081; abst. Wag. Jahr. 1911. 57, 500; Chem. Zentr. 1911,
82, II, 411; Chem. Ztg. Rep. 1911, 35, 481; Zts. ang. Chem. 1911, 24, 1583.
A. Schweinberg, Aust. P. 14423, 1902. W. Schacht. D. R. P. 122171, 131108;
abst. Wag. Jahr. 1901, 47, II, 590; 1902, 48, II, 566; Chem. Ztg. 1901, 25,
707; 1902, 26, 462. Papier Ztg. 1901, 26, (^), 3143; abst. J. S. C. I. 1901,
20, 1230.

1. D. R. P. 136322. 1900; 140542. 140862, 144819, 1902; 161675, 1903;
181126, 1905; 197195, 202132, 1906. Aust. P. 36847; Pap. Ztg. 1902, 27,
3478; 1903, 28, 86, 1332, 1942, 3086, 3478; 1905. 30, 2582; 1907, 32, 994;
1908, 33, 3238; Wochenbl. Papierfabr. 1907. 38, 1307; 1908, 39, 2539, 3466;.
Zts. ang. Chem. 1908, 21, 1194; Chem. Zentr. 1908, 79, I, 1595; II, 1389;
1907, 78, II, 109; Pap. Fabrik. 1907, 641. E. Trippe, D. R. P. 133312, 1901;
abst. Wag. Jahr. 1902, 48, II, 568; Chem. Centr. 1902, 73, II, 410; Chem.
Ztg. 1902. 26, 737; Zts. ang. Chem. 1902, 15, 765.

2. D. R. P. 215273; Pap. Ztg. 1906, 31, 1278, 1314, 1355; 1907. 32,
961, 1010, 1054. 1098; 1908, 33, 3855, 3890, 3931; 1909, 34, 3; Wochenbl.
Papierfabr. 1907,38,881, 958; 1909, 40, 857, 930, 1110; Chem. Centr. 1906,
77, I, 1853; Zts. ang. Chem. 1910, 23, 116; Chem. Ztg. 1909, 33, 1187. C.
Voight, D. R. P. 33235, 40693, 1886; abst. Wag. Jahr. 1888, 34, 1091.
Verein f. Chemische Industrie, D. R. P. 25485, 31747; abst. Wag. Jahr.
1884, 30, 1151; 1885. 31, 1038.

For early history of utilization of pulp, see E. P. 2481, 1801, Koop.
E. P. 5041, 1824, Lambert. E. P. 13979. 1852, Coupier and Mellier. E. P.
2219, 185.3, Poole. E. P. 1942, 1853, U. S. P. 6854, 1854, Watt and Burgess.
E. P. 2172, 1854, Mellier. E. P. 2488. 18^. Cashellain. E. P. 135, 1855,
Johnson. E. P. 836, 1855, Cowlev and Sullivan. E. P. 2019, 2315, 1855,
Fraser. U. S. P. 12361. E. P. 4671, 1857, Houghton. U. S. P. 16202.
Falser and Rowland. E. P. 1997, 1859, Collyer. E. P. 1507, 1861, Watt.
E. P. 1822, 1861, Henry. E. P. 2351, 1861, Grantham. E. P. 408, 467,
1863, Clark. E. P. 112, 1866. Stevens. E. P. 167, 1868, Fyfe. E. P. 1050.
1868, Baumann. E. P. 2793, 1868. E. P. 3392, 1870, Walsh. E. P. 748.

CEI.I.UI.OSE 293

H
Wood Pulp for Esterification. In the conflict which has so

1870, E. P. 3139, 1870, Ruck. E. P. 3148, 1870, Wrigley. E. P. 1871,

1871, Richardson. E. P. 279, 1871, Annandale. E. P. 1422, 1871, Newton.
U. S. P. 119224, Eaton. E. P. 257, 1872; D. R. P. 933, Ungerer. E. P. 1851,

1872, V. Baerle. E. P. 2147, 1872, Biyth and Southly. E. P. 695, 863,

1873, Lee. E. P. 2956, 1874, Tiffany.

See also: A. Aberg, U. S. P. 691091, 1902; abst. J. S. C. I. 1902, 21, 272.

J. Abom, E. P. 8964, 1894; abst. J. S. C. I. 1894, 13, 824. Aflenzer-Graphlt-

und Talksteingewerkschaft, D. R. P. 277385, 1913; abst. J. S. C. I. 1915,

34, 173. E. Ahlfors and H. Helin, Papier-Fabrikant, 1909. 7, 287-289; abst.

J. S. C. I. 1909, 28, 438. A. Ahlin, Papier Ztg. 1902, 27, (33), 1178; 1908, 33,

1181-1182; J. S. C. 1. 1902, 21, 134; abst. J. S. C. I. 1902, 21, 718; 1908, 27,

517. Akt.-Ges. f. ZeUstoff-und Papierfabr. D. R. P. 309551, 1916; J. S. C.

I. 1919, 38, 218-A. J. Aktschourin, E. P. 18191, 1911; abst. J. S. C. I. 1912,

31, 871; see F. P. 433424, 1911; abst. J. S. C. I. 1912, M, 225; U. S. P.

1169592, 1915; abst. J, S. C. I. 1916, 35, 303. E. Allen and B. Tollens, Ann.

1890, 280, 289-306; abst. J. S. C. 1. 1891, 10, 473. S. Allen, U. S. P. 253656, 1882;

abst. J. S. C. I. 1882, 1, 116, J. Almond and S. Andrews, E. P. 24600 1898;

abst. J. S. C. I. 190, 1$, 67. E. Altmann, Chem.-Ztg. 1911, 35, 979; abst.

J. S. C. I. 1911, 30, 1154. P. Ammon, Paper-making, 1909, 28, 437; abst.

J. S. C. I. 1909, 28, 1269. J. Annandale, F. P. 345044, 1904; abst. J. S. C. I.

1904, 23, 1159; see E. P. 26012, 1903; abst. J. S. C. I. 1904, 23, 1040; E. P.

14558, 1889; abst. J. S. C. I. 1891, 10, 62. E. Applegarth, E. P. 2832, 1890;

abst. J. S. C. I. 1891, 10, 268. C. D. Aria, E. P. 8981, 1888; abst. J. S. C. I.

1889, 8, 565. G. Archbold, Ber. 1883, 18, 350; abst. J. S. C. I. 1883, 2, 295.

H. Arledter, F. P. 418584, 1910; abst. J. S. C. I. 1911, 30, 80. E. P. 20395,

1911; abst. J. S. C. I. 1912, 31, 981, U. S. P. 1153883, 1915; abst. J. S. C. I.

1915, 34, 1087; U, S. P. 1048123, 1912; abst. J. S. C. I. 1913, 32, 81. E. P.

2018, 1910; abst. J. S. C. I. 1911, 30, 205. L. Atwood, U. S. P. 698428,

1902; abst. J. S. C. I. 1902. 21, 788. A. Audibert, F. P. 403151, 1909; abst.
J. S. C. I. 1909, 28, 1323. C. Bache-Wug, E. P. 944, 1914; abst. J. S. C. I.

1914, 33, 417. U. S. P. 1084244, 1914; abst. J. S. C. I. 1914, 33, 198. U. S.

P. 1240920, 1917; abst. J. S. C. I. 1917, 38, 1174. U. S. P. 903679, 1909;
abst. J. S. C. I. 1909, 28, 381. C. BadoU, F. P. 382439, 1907; abst. J. S. C.
I. 1908, 27, 244; F. P. 392750, 1908; abst. J. S. C. I. 1909, 28, 38. A. Badoil
and J. Valadon, F. P. 338477. 1903; abst. J. C. S. I. 1904, 23,677. L.
Baekeland, U. S. P. 1160362, 1915; abst. J. S. C. I. 1915, 34, 1244. U. S. P.
1160365, 1915; abst. J. S. C. I. 1915. 34, 1245. A. Baker and J.
Jennison, Paper and Pulp, Jan. 1910; Sindall and Heckford, Paper
Trade Review, Oct. 7, 1904; abst. J. S. C. I. 1914, 33, 284. J. Barker, G.
Sheolin and F. Barker, U. S. P. 693215, 1902; abst. J. S. C. I. 1902, 21, 362.
A. Barthelemy, F. P. 369657, 1906; abst. J. S. C. I. 1907, 28, 220. C. Bartsch,
Papierfabrikant, 1911, S, 23; J. S. C. I. 1911, 30, 414, 887. T. Bates, abst.
J. S. C. I. 1918, 37, 457-R. J. Baudisch, Papier Ztg. 1891. 16, 2414-2415;
J. S. C. I. 1888, 7, 863; 1889, 8, 574, 1891, 10, 576; 1892, 11, 464. F. Bau-
mann, D. R. P. 22177, 1882; abst. J. S. C. I. 1883, 2, 359. F. Bayer & Co.,
E. P. 10729, 1907; abst. J. S. C. I. 1908, 27, 138. D. R. P. 283107, 1913;
abst. J. S. C. I. 1915, 34, 729. F. P. 385944, 1908; abst. J. S. C. I. 1908,
27, 707. C. Beadle, U. S. P. 1286502, 1918; abst. J. S. C. I. 1919, 38, 131-A;
E. P. 116005, 1917; abst. J. vS. C. I. 1918, 37, 409-A. Paper and Pulp, 1905,
10, 297-301; abst. J. S. C. I. 1905, 24, 633. C. Beadle and H. Stevens,
Chem. News, 1907, 95, 193; abst. J. S. C. I. 1907, 28, 548; Chem. News,
1914, 109, 302-304; abst. J. S. C. I. 1914, 33, 745; Paper-making, 1914, 47,
397-403; J. S. C. I. 1913, 32, 1103; abst. J. S. C. I. 1914, 33, 545; Papermaker,
1913, 45, 150-157; abst. J. S. C. I. 1913, 32, 1103; Eighth Int. Cong.
Appl. Chem. 1912, 13, 25; 1912, Sect. Via Orig., Comm. 13, 265;
abst. J. S. C. I. 1913, 32, 174. Eighth Int. Cong. Appl. Chem. 1912, Sect.

294 TECHNOLOGY OF CELLULOSE ESTERS

recently closed, while by far the major portion of the cellulose

VlaOrig. Comm. 13, 39-45; abst. J. S. C. I. 1912, 31, 870; abst. J. S. C. I-
1909, 28, 1015; J. S. C. I. 1913, 32, 217. W. Beaumont, E. P. 24904, 1898;
abst. J. S. C. I. 1899, 18, 392. E. Belani, Der Papierfabrikant, 1908, 6,
604-605; abst. J. S. C. I. 1908. 27, 707. J. Bell, abst. J. S. C. I. 1894. 13,
117. J. Beltzer, Bull. Soc. Chim. 1910, 7, 294^300, 361-367; abst. J. S. C.
I. 1910, 29, 690. J. Bennett and W. Appleyard, E. P. 9716, 1899; abst.
J. S. C. I. 1899, 18, 782. W. Benso and B. Jirotka, E. P. 26824, 1911; abst.
J. S. C. I. 1913, 32, 421. A. Berge, Bull. Soc. Chim. Belg. 1906, 20, 168-159;
abst. J. S. C. I. 1906, 25, 912. E. Bergerhoff, D. R. P. 279411, 1914; abst.
J. S. C. I. 1915, 34, 419; D. R. P. 160651, 1903; 163070, 1904; abst. J. S. C.
I. 1905, 24, 1028; 1906, 25, 37. A. Berget, U. S. P. 683836; Papier Ztg.
1901, 26, (92). 3427; abst. J. S. C. 1. 1902,21,64. F.Berguisand E. Hagg-
lund, D. R. P. 311933. 1917; abst. J. S. C. I. 1917, 36, 760-A. A. Bergoo,
Papierfabrikant. 1912. 10, 419-422; abst. J. S. C. I. 1912, 31, 427. D. Ber-
tram and S. Milne, E. P. 8275, 1899; abst. J. S. C. 1. 1900, 19, 552. G. Bertrand,
Compt. rend. 1898, 127, (2), 124-127; 1899, 126, 762, 842 and 984; Bull.
Soc. Chim. 1898, 15, 592; abst. J. S. C. I. 1898, 17, 936. P. Billon, F. P.
363279, 1906; abst. J. S. C. I. 1906, 26, 865. H. Bh-d, E. P. 16375. 1892;
abst. J. S. C. I. 1893, 12, 461. R. Birkholz. U. S. P. 787971. 1905; abst.
J. S. C. I. 1905, 24, 558. A. Bloxam, E. P. 116604, 1917 (Appl. No. 11536,
1917); abst. J. S. C. I. 1918, 37, 461-A. A. Boake and G. Roberts. E. P.
8840, 1888; abst. J. S. C. I. 1889, 8, 565. L. Bohm, E. P. 14035. 1900; abst.
J.S. C. I. 1900, 19, 1034. U. S. P. 875315. 1907; abst. 1908, 27, 178. J.
Bonar, E. P. 8214, 1911; abst. J. S. C. I. 1912, 31, 428. E. Bosaeus. Kemi-
och Bergvetenskap, 1910, Part 3; Papierfabrikant, 1910, 8, 737-739, 767-
770; J. S. C. I. 1910, 29, 343; abst. J. S. C. I. 1910, 29, 1052. G. Boulais
and P. Lefevre, F. P. 465534, 1913; abst. J. S. C. I. 1914, 33, 608. D. Bowack,
R. Heald and A. Davis, Aynsome Annual, 1911, 3, 62-75; World's Paper
Trade Rev. 1911; abst. J. S. C. I. 1912, 31, 582. P. Boy, F. P. 350117, 1904;
abst. J. S. C. I. 1905, 24, 1169. C. Brand, U. S. Dep't Agric. Bureau of
Plant Industry, Circular No. 82, August 31, 1-19; abst. J. S. C. I. 1912,
31, 120. C. Brand and J. Merrill, U. S. Dep't Agric. Bull. No. 309, Nov.
4, 1915, 1-27; abst. J. vS. C. I. 1916, 35, 417. C. Braun, D. R. P. 261848,
1912; abst. J. S. C. I. 1913. 32, 823; D. R. P. 279517, 1913; abst. J. vS. C. I.
1915,34,419. J. Briggs, World's Paper Trade Rev. 1911; Papierfabrikant,
1911, 9, 1340-1341; abst. J. S. C. I. 1911. 30, 1374. A. Brin, E. P. 15720,
1892; abst. J. S. C. I. 1893, 12, 858. A. and L. Brin, E. P. 4953, 1887; abst.
J. S. C. I. 1888, 7, 33. H. Bristol, Papierfabr. 1911, 9, 309-312; abst. J. S.
C. I. 1911, 30, 413. C. Brodbeck, E. P. 23598, 1895; abst. J. S. C. I. 1897.
16, 327. O. Brune, D. R. P. 310554, 1917; abst. J. S. C. I. 1919, 38, 357-A.
C. Bullard, Eighth Int. Cong. Appl. Chem. 1912, Sect. Via. Qng. Comm. 13,
77-82; abst. J. S. C. 1. 1912. 31, 869. J. Burby, F. P. 444703. 1912; abst. J. S.
C. I. 1912, 31, 1075; U. S. P. 1029848, 1912; abst. J. S. C. I. 1912, 31, 680.
T. Burgess, U. S. P. 693684, 1902; abst. J S. C. I. 1902, 21, 494. W. Bur-
ton, D. R. P. 220912. 1909; abst. J. S. C. I. 1911, 30, 80. F. Bushbridge.
U. S. P. 789792, 1905; abst. J. S. C. I. 1905. 24, 633. E. P. 25075, 1903;
abst. J. S. C. I. 1904, 23, 677. F. P. 342265. 1904; abst. J. S. C. I. 1904.
23, 949. W. Caldwell, E. P. 15,332, 1893; abst. J. S. C. I. 1894, 13, 1085.
W. Callender. E. P. 20346, 1900; abst. J. S. C. I. 1901. 20, 831. T. Carlson,
Kemi och Bergsvetcn.skap, 1910, (l);Wochenbl. Papierfabr. 1910, 41, 551-
552; abst. J. S. C. I. 1910, 29, 343. J. and F. Carmichael, F. P. 329107,
1903; abst. J. S. C. I. 1903, 22, 1012. O. Carr, U. vS. P. 762139, 1904;
1089691, 1914; abst. J. S. C. I. 1904, 23, 725; 1914, 33, 417. H. Carriere,
F. P. 329445, 1903; abst. J. S. C. I. 1903, 22, 1062. B. Cataldi, E. P.
101475, 1916 (Appl. No. 12862 of 1916); abst. J. vS. C. I. 1917, 36, 1232.
B. Cawthorn and J. Cornett, E. P. 2923, 1894; abst. J. S. C. I. 1895, 14,

ci5i.i,ui.osB 295

nitrated and acetated in the Entente countries was some form of

18S. J. De Cew, J. S. C. I. 1907, 28, 561. W. Chaplin, F. P. 449943,
1912; abst. J. S. C. I. 1913, 32, 482. L. Chaptal and J. Gaisset, F. P.
446^^82, 1912; abst. J. S. C. I. 1913, 32, 133. F. Cheesbrough, E. P. 9694,
1889; abst. J. S. C. I. 1890, 9, 321. C. Classen, B. P. 9579, 1908; abst.
T. S. C. I. 1909, 28, 363. A. Clark, E. P. 3240, 1883; abst. J. S. C. I. 1884,
3, 190; E. P. 11557. 1884; abst. J. S. C. I. 1884, 3, 645. F. Clark, School
of Mines Quarterly, S, 162-177; abst. J. S. C. I. 1888, 7, 497. G.
Clark, U. S. P. 696314, 1902; abst. J. S. C. I. 1902, 21, 635. M. Cline and
T. Thickens, Eig'it'i Int. Con^. Appl. Chem. 1912, Sect. VI*, Orig. Comra.
13, 83-99; abst. J. S. C. I. 1912, 31, 869. M. Cram, J. Ind. En?. Chem.

1914, €, 896; abst. Chem. Zentr. 1915, I, 860. T. Cobley, E. P. 3599, 1883;
abst. J. S. C. I. 18^, 3. 328. W. Cohoe, U. S. P. 985725 and 985726, 1911;
abst. J. S. C. I. 1911. 30, 441. E.* P. 23573, 1910; abst. J. S. C. I. 1912.

31, 86. J. Colby. D. R. P. 157763, 1902; abst. J. S. C. I. 1905, 24, 633.
J. Comett, E. P. 14191, 1893; abst. J. S. C. I. 1893, 12, 859. M. Coulon,
Millheil, des k. k. Tech. ' Gew.-Museums, 2, 28-34; abst. J. S. C. I.
1888. 7, 843. P. Couper, E. P. 2774, 1905; abst. J. S. C. I. 1905, 24, 1215.
F. P. 361005, 1905; abst. J. S. C. I. 1906, 25, 556. E. P. 9942 and 20355,
1913; abst. J. S. C. I. 1914, 33, 478. G. Craighill and G. Kerr, U. vS. P.
817960, 1906; abst. J. S. C. I. 1906. 25, 494. W. CroU, U. S. P. 1165323,

1915, renewed May 20. 1915: abst. J. S. C. I. 1916, 35, 250. E. P. 121318.
1918; abst. J. S. C. I. 1919, 38, 31-A. W. Cross, Ber. 1910, 43, 1526-1528;
abst. J. S. C. I. 1910, 29, 750. W. Curtis, E. P. 4945, 1898; abst. J. S. C. I.
1898, 17, 789. A. CurtLs and A. H. White. U. S. P. 1181967, 1916; ab.st.
J. S. C. I. 1916, 35, 686. G. Gushing, U. S. P. 788633, 1905; abst. J. S. C.
I. 1905, 24, 633. C. Dahl, U. S. P. 296935, 1884; E. P. 11150, 1888; abst.
J. S. C. I. 1889, 8, 814. A. Dassonville, F. P. 387104, 1908; abst. J. S. C. I.
1908, 27, 817. First addition dated Sept. 3, 1908 to F. P. 387104, 1908
(J. S. C. I. 1908. 27, 817); abst. J. S. C. I. 1909, 28, 241. E. Davies and
H. Goodfellow. E. P. 3288, 1896; abst. J. S. C. I. 1896, 15, 554. W. Decker.
U. S. P. 928247. 928248. 928249 of 1909; abst. J. S. C. I. 1909, 28, 958.

E. P. 26762, 1909; abst. J. S. C. I. 1910, 29, 148. E. P. 15269. 1909; abst.
J. S. C. I. 1910, 29, 269. J. Desmarest, E. P. 26260, 1901; abst. J. S. C. I.
19a3, 22, 109. G. Devimcux, F. P. 409034, 1909; abst. J. S. C. I. 1910,
29, 751. R. Dietz, Zts. ang. Chem. 1905, 18, 647-653; abst. J. S. C. I.
1905, 24, 557. W. Digby, Electrochem. and Metall. Ind. 1907, 5, 178-182;
abst. J. S. C. I. 1907, 26, 712. J. Dohan, U. S. P. 865168, 1907; abst. J. S.
C. I. 1907, 26, 1 107. H. and A. von Donnersmarck-Beutel, F. P. 353997, 1905;
abst. J. S. C. I. 1905, 24, 1081. C. Doree and M. Cunningham, Chem.
Soc. Proc. 1913, 29, 104-105; J. S. C. I. 1912, 31, 278; abst. J. S. C. I. 1913.

32, 482. B. Donier. E. P. 8638. 1911; abst. T. S. C. I. 1911, 30, 1376;
U. S. P. ia38730. 1912; abst. J. S. C. I. 1912, 31, 981. C. Doughty, U. S.
P. 775525, 1904; abst. J. S. C. I. 1904. 23, 1233. W. Dreaper, J. Soc. Dyers
Col. 1912. 28, 178-179; abst. J. S. C. I. 1912, 31, 485. F. Dubrot,

F. P. 396647, 1908; abst. J. S. C. I. 1909, 28, 597. L. Dulfus, E. P. 3780,
1884; abst. J. S. C. I. 1885, 4, 242. L. Echegut, F. P. 359550, 1905; abst.
J. S. C. I. 1906, 25, 388. EgorofT and A. Remmer, F. P. 410835, 1909;
abst. J. S. C. I. 1910, 29, 811. E. Eichhom, F. P. 322177, 1902; abst. J. S.
C. I. 19a3, 22, 315. R. Eichmann, D. R. P. 184991, 1906; abst. J. S. C. I.
1908, 27, 244. G. Ekstrom, Papierfabrikant, 1910, 8, 582; abst. J. S. C. I.
1910, 29, 810. U. S. P. 10958:}0, 1914; abst. J. S. C. I. 1914, 33, 659.
C. Ellis, U. S. P. 1311595, 1919; abst. J. S. C. I. 1919, 38, 678-A. R. Em-
bree, U, S. P. 1203511, 1916; abst. J. S. C. I. 1916, 35, 1257. C. Esser,
U. S. P. 836069, 1906: abst. J. S. C. I. 1907, 26, 112. E. P. 9589, 1901;
abst. J. S. C. I. 1901, 20, 8:30. L. Evans, E. P. 19808, 1905; abst. J. S. C.
I. 1906, 25, 950. H. Falk, Papierfabrikant, 1909, 7, 469-474; J. S. C. I.

296 TECHNOLOGY OF CELLULOSE ESTERS

short fiber cotton immense quantities of wood pulp were esterified

1908, 27, 1037; abst. J. S. C. I. 1909, 28, 622. H. Falke, Farb. Ztg. 1894, 5,
97-100, 113-116; abst. J. S. C. I. 1894, 13, 399. Faraand, Wochenbl.
Papierfab. 1909, 40, 4449-4460; abst. J. S. C. I. 1910, 29, 147. A. Faust,
E. P. 21737, 1900; abst. J. S. C. I. 1901, 20, 496. J. Feldschmid, abst.
J. S. C. I. 1913, 32, 975. J. Ferrand, U. S. P. 774982, 1904; abst. J. S. C.

I. 1904, 23, 1233.. F. P. 327046. 1902; abst. J. S. C. I. 1903, 22, 879. A.
Fest, U. S. P. 1218638, 1917; abst. J. S. C. I. 1917, 36, 451. A. von Festy.

E. P. 7428, 1899; abst. J. S. C. I. 1899, 18, 942. F. Finiels, F. P. 440329,
1911; abst. J. S. C. I. 1912, 31, 812. F. Fischer and H. Niggemann, Ges.
Abhand. zur. Kenntnis der Kohle, 1917, 1, 176-183; Chem. Zentr. 1919,
90, II, 521; abst. J. S. C. I. 1919, 38, 494. E. Fleury, E. P. 11103, 1906;
abst. J. S. C. I. 1907, 26, 712. E. Foley, U. S. P. 1154851, 1915; abst.
J. S. C. I. 1915, 34, 1086. F. La Forge and C. S. Hudson, J. I. E. C. 1918,
10, 925-^27; abst. J. S. C. I. 1919, 38, 86-A. J. Forshaw, E. P. 1292, 1914;
abst. J. S. C. I. 1914, 33, 1197. E. Fox, E. P. 20664, 1897; abst. J. S. G. I.
1898, 17, 944. G. Frankforter, J. Ind. Eng. Ghem. 1911, 3, 4-10; abst.
J. S. G. 1. 1911, 30, 1304. W. Freeman, F. P. 471620, 1913; abst. J. S. G. 1. 1915.
34, 419. E. P. 28929, 1913; abst. J. S. G. 1. 1915, 34, 488. Frohberg, Wctehenbl.
Papierfabr. 1911, 42, 668-669; abst. J. S. G. I. 1911. 30, 352; Wochenbl.
Papierfabr. 1910, 41, 1602-1606; abst. J. S. G. I. 1910, 29, 688; Wochenbl.
Papierfabr. 1910, 41, 1179-1182; abst. J. S. G. I. 1910, 29, 556; Wochenbl.
Papierfabr. 1913, 44, 3699-3601; abst. J. S. G. I. 1913, 32, 974; Ghem. Ztg.

1914, 38, 126; abst. J. S. G. I. 1914, 33, 857. K. Fromherz, Z. physiol.
Ghem. 1906, 50, 209-240; Ghem. Zentr. 1907, 1, 643-645; J. S. G. I. 1905.
24, 212; 1903, 22, 114; abst. J. S. G. I. 1907, 26, 339. A. Gagdeois, U. S.
P. 848361, 1907; abst. J. S. G. I. 1907, 26, 483. F. P. 360158, 1905; abst.
J. S. G. 1. 1906. 25, 441. First addition 3823, to F. P. 306276, 1900; abst. J.
S. G. I. 1905, 24, 344. E. and W. Gelinek, E- P. 5178, 1893; abst. J. S. G. I.
1893, 12, 858. G. Gemmell, abst. J. S. G. I. 1890, 9, 165. D. Gtaj-Tenua,

F. P. 357374, 1905; abst. J. S. G. I. 1906, 25, 88. R. Godeffroy, Mitt. k. k.
techn. Gew. Museum, 1891, 295; 1888, 18, 62; 1889, 9; abst. J. S. G. I. 1892,

II, 464. G. Goessmann, E. P. 10535, 1901; abst. J. S. G. I. 1902, 21, 362.
J. Goode, E. P. 18157, 1901; abst. J. S. G. I. 1903, 22, 109. A. Gorz, E. P.
12096, 1898; abst. J. S. G. 1. 1898, 17, 944. L. Gottstein, Zts. ang. Ghem. 1905,
18, 983-984; abst. J. S. G. I. 1905, 24, 748. O. Goy, E. P. 5339. 1903; abst.
J. S. G. I. 1903, 22, 817. A. Grand jean, E. P. 22566, 1894; abst. J. S. G. I.
1896, 15, 132. E. Grandmougin, Ber. 1907, 40, 2453; J. S. G. I. 1907, 26,
633; J. S. G. I. 1906, 25, 912; abst. J. S. G. I. 1907, 26, 775. H. Green.
U. S. P. 1206777, 1916. Renewed AprU 24, 1916; abst. J. S. G. I. 1917. 36,
80. M. Griffin, Paper and Pulp, 1905. 10, 492-496; abst. J. S. G. I. 1905,
24, 937; J. S. G. I. 1890, 9, 453. G. Gunn, E. P. 23947, 1908; abst
J. S. G. I. 1909, 28, 541. B. Haas, Papierfabrikant, 1910, 8, 74-78, 150-
152, 177-178, 197-201; abst. J. S. G. I. 1910, 29, 415. H. Haddan. E. P.
7495. 1885; abst. J. S. C. I. 1886, 5, 435. H. Hadfield, Paper-Making,

1915. 34, 206; abst. J. S. G. I. 1915, 34, 830; B. Hafner and F. Krist. F. P.
383776. 1907; abst. J. S. G. I. 1908. 27, 415. E. P. 24503. 1907; abst. J. S.

G. I. 1908, 27, 1033. C. Hagemann, E. P. 18470. 1891 ; abst. J. S. G. 1. 1892. 11,
1026. G. Hahnle. U. S. P. 1026577. 1912; abst. J. S. G. I. 1912, 31, 584.
W. Hall. E. P. 12502, 1888; abst. J. S. G. I. 1889, 8, 814. U. S. P. 802754,
1905; abst. J. S. C. I. 1905, 24, 1185. U. S. P. 802755, 1905; abst. J. S. G. I.
1905. 24, 1185. R. Hamilton and I. G. Hamilton, E. P. 1433, 1889; abst. J. S.
G. 1. 1890, 9, 211. W. Hancock and O. Dahl, Ber. 1895, 1588; J. S. G. 1. 1895,
14, 897. E. Hanausek, Ztschr. f. Nahrungmittelrentersuch u. Hygiene, 1887,
1, 153; abst. J. S. G. I. 1887, 6, 840. E. Hanausek and R. Zaloziecki, Ghem.
Ztg. 1905, 39, 3^; abst. J. S. G. I. 1905, 24, 101. T. Hanausek, Papier-
fabrikant, 1911, 9, 14(>4-1465; abst. J. S. G. I. 1911, 30, 1446. W. Hargreaves,

CELLULOSE 297

— ^mainly nitrated — especially in Germany, a large portion of

Dept. Chem., S. Australia, Bull. No. 1, 1916. pp. 1-56; abst. J. S. C. I. 1917,
36, 27. H. Havik, Papierfabrikant, 1912, 10, 859-861; abst. J. S. C. I. 1912,
31, 768. J. Heden, D. R. P. 212838, 1908; abst. J. S. C. I. 1909, 28, 1001.
W. Hellwig, U. S. P. 1121099, 1914; abst. J. S. C. I. 1915, 34, 25. E. P.
28489, 1911; abst. J. S. C. I. 1912, 31, 1075. F. P. 451957, 1912; abst. J. S.
C. I. 1913, 32, 653. D. R. P. 229390, 1909; abst. J. S. C. I. 1911, 30, 278.
W. Hellwig and F. Herrmann, E. P. 28489, 1911; abst. J. S. C. I. 1912, 31,
1075. G. Herbein, F. P. 486771, 1918; abst. C. A. 1919, 13, 1909. J. Hert-
korn, Chem. Ztg. 1902, 26, (55), 632; abst. J. S. C. I. 1902, 21, 1041.
L. Herz, E. P. 24131, 1908; abst. J. S. C. I. 1909, 28, 1271. F. P.
397576, 1908; abst. J. S. C. I. 1909, 28, 811. D. R. P. 220424, 1909;
abst. J. S. C. I. 1910, 29, 751. U. S. P. 1039941, 1912; abst. J. S. C. I. 1912.
31, 1027. F. P. 422490, 1910; abst. J. S. C. I. 1911, 30, 533. U. S. P.
1041791, 1912; abst. J. S. C. I. 1912, 31, 1075. E. P. 25255, 1911 and 19334,
1912; abst. J. S. C. I. 1912, 31, 1176. First addition dated Nov. 6, 1911,
to F. P. 422490, 1910; J. S. C. I. 1911, 30, 533; abst. J. S. C. I. 1912, 31,
485. R. Herzog and F. Horth, Z. Physiol. Chem. 1909, 60, 152-154; Z.
anal. Chem. 1896, 35, 344; abst. J. S. C. I. 1909, 28, 667. G. Heyl-Dia,
E. P. 2610, 1899; abst. J. S. C. I. 1899, 18, 602. G. Hibbert, E- P. 25040,
1894; abst. J. S. C. I. 1896, 15, 291. E. P. 6897, 1887; abst. J. S. C. I.
1888, 7, 398. A. Hmzke, U. S. P. 702556, 1902; abst. J. S. C. I. 1902, 21,
986. U. S. P. 1303314; abst. C. A. 1919, 13, 1928. F. Hiorth. E. P. 15995,
1890; abst. J. S. C. I. 1891, 10, 157. P. Hoering, E. P. 21328, 1911; abst.
J, S. C. I. 1912, 31, 1027. W. Hoffmeister, Landw. Jahrb. 17, 239;
abst. J. S. C. I. 1888, 7, 620. H. Hoffmann, Papier Ztg. 1907, 32, 2558;
abst. J. S. C. I. 1907, 26, 942.- M. Holaubek, F. P. 353730, 1905;
abst. J. S. C. I. 1905, 24, 1079. T. Holmes, U. S. P. 704259, 1902; abst.
J. S. C. I. 1902, 21, 1093. M. Honig, Chem. Ztg. 1912, 36, 88^-890; abst.
J. S. C. I. 1912, 31, 768. G. Horteloup, F. P. 327136, 1902; abst. J. S. C. I.
1903, 22, 879. F. P. 331176, 1903; abst. J. S. C. I. 1903, 22, 1145, 1146.
E. P. 26149, 1903: abst. J. S. C. I. 1904, 23, 268. E. P. 26150. 1903; abst.
J. S. C. I. 1904, 23, 500. W. Hoskins, U. S. P. 770463, 1904; abst. J. S. C.
I. 1904, 23, 990. U. S. P. 1226333, 1917; abst. J. S. C. I. 1917, 36, 708.
W. Hough, U. S. P. 903859, 1908; 931608, 1909; abst. J. S. C. I. 1908, 27,
1212; 1909, 28, 1148. F. P. 406514, 1909; abst. J. S. C. I. 1910, 29, 483.
G. C. Howard, U. S. P. 997064, 1911; abst. J. S. C. I. 1911, 30, 951. U. S.
P. 1057151, 1913; abst. J. S. C. I. 1913, 32, 421. U. S. P. 1258568, 1918;
abst. J. S. C. I. 1918, 37, 264-A. E. P. 20220, 1911; abst. J. S. C. I. 1912,
31, 812. C. Hudson and T. Harding, J. A. C. S. 1917, 39, 1038-1040;
abst. J. S. C. 1. 1917. 36, 730; J. A. C. S. 1918, 40, 1601-1602; J. S. C. I. 1917,
36, 730; abst. J. S. C. I. 1918, 37, 778 A. E. Hudson and H. Merriam, U. S.
P. 1303321, 1919; Appl. Feb. 7, 1917; abst. J. S. C. I. 1919, 38, 494-A.
Hughes, F. P. 320162, 1902; abst. J. S. C. I. 1903, 22, 42; U. S. P. 691771;
abst. J. S. C. I. 1902, 21, 362. J. Hughes. U. S. P. 691770 and 691771,
1902; abst. J. S. C. I. 1902, 21, 362. W. Huntington, U. S. P. 709488, 1902;
abst. J. S. C. I. 1902, 21, 1345. R. Hutchison, E. P. 7112, 1893; abst. J. S.
C. I. 1893, 12, 780. T. Hutchmson and United Railway and Trading Co.,
E. P. 20267, 1907; abst. J. S. C. I. 1909, 28, 106. G. Huth and J. Bertram
and Son, Ltd., E. P. 21962, 1899; abst. J. S. C, I. 1900, 19, 370. A. Ihl, Chem.
Ztg. 1890, 14, 34, 67; abst. J. S. C. I. 1890, 9, 418. E. Imhaus, F. P. 355245,
1905; abst. J. S. C. I. 1905, 24, 1185. J. Irwin, U. S. P. 1250106, 1917;
abst. j: S. C. I. 1918, 37, 120-A. H, Jackson, U. S. P. 1083102 and 1083213,
1913; abst. J. S. C. I. 1914, 33, 132. E. P. 25051, 1910; E. P. 6019, 1911;
abst. J. S. C. I. 1912, M, 225. E. P. 4996, 1904; abst. J. S. C. I. 1905, 24,
149. First addition (dated May 15. 1912) to F. P. 435090. 1911; abst. J. S.
C. I. 1912, a, 1075. E. P. 12933, 1911; abst. J. S. C. I. 1912, 31, 636.

298 TECHNOLOGY OP CELLULOSE ESTERS

which was first purified by solution in concentrated hydrochloric

S. Jacques, E. P. 30579, 1897; abst. J. S. C. I. 1898. 17, 944. J. Jardine,
U. S. P. 1143401, 1915; abst. J. S. C. I. 1915, 34, 831. E. P. 18371, 1913;
abst. J. S. C. I. 1914, 33, 1006. J. Jardine and T. Nelson, F. P. 475981,
1914; abst. J. S. C. I. 1915, 34, 1245. ^E. P. 18371, 1913; abst. J. S. C. I.
1914, 33, 1006. Jensen and Son, E. P. 6831, 1900; abst. J. S. C. I. 1901,20,
602. S. Jentsch, Zts. ang. Chem. 1918, 31, 72; abst. J. S. C. I. 1918, 37, 365-A.

B. Jirotka, D. R. P. 288320, 1914; abst. J. S. C. I. 1916, 35, 542. E. P. 15105,
1911; abst. J. S. C. I. 1912, 31, 67. B. Johnsen, Papierfabr. 1913, 11, 979-
980; abst. J. S. C. I. 1913, 32, 863; abst. J. S. C. I. 1918, 37, 129-T. J.
Johnson, E. P. 5160, 1883; abst. J. S. C. I. 1884. 3, 495. E. P. 7511, 1884;
abst. J. S, C. I. 1885, 4, 363. J. Johnson, E. P. 24503, 1893; abst. J. S. C.
I. 1894, 13, 1216. W. Johnson, U. S. P. 733969. 1903; abst. J. S. C. I. 1903,
22, 961. G. WUdridge. E. P. 9517. 1900; abst. J. S. C. I. 1901, 20, 603.

E. Jones, U. S. P. 696822, 1902; abst. J. S. C. I. 1902, 21, 635. A. Jouve,

F. P. 359452, 1905; abst. J. S. C. I. 1906, 25, 389. J. Juel and E. Ryan,
E. P. 2349, 1891; abst. J. S. C. I, 1891, 10, 566. P. Justice, E. P. 8983,
1903; abst. J. S. C. I. 1903, 22, 1011. A. Kaiser, Chem. Ztg. 1902, 26,
(31), 355; abst. J. S. C. I. 1902. 21, 725. A. Kalmann, E. P. 3656, 1901;
abst. J. S. C. I. 1902. 21, 422. W. Kershaw, E. P. 12682, 1896; abst. J. S.

C. I. 1897, 16, 696. F. Keyes, E. P. 4309, 1900; abst. J. S. C. I. 1901, 20,
62. W. Keys, E. P. 1517, 1890; abst. J. S. C. I. 1890, 9, 541. W. Kilby,
Chem. Ztg. 1910, 34, 1077-1078, 1091-1093; abst. J. S. C. I. 1910, 29, 1265;
Chem. Ztg. 1915, 39, 212-214, 261-265, 284-285. 307-308, 350-352; J. S.
C. I. 1910, 29, 1052 (Wallin and Ekstrdm); J, S. C. I. 1915, 34, 275 (Und-
mark); J. S. C. I. 1913, 32, 652; 1915, 34, 274 (Strehlenert and Rinman);
abst. J. S. C. I. 1915, 34, 1085. A. Kiraer, F. P. 353538, 1905; abst. J. vS.
C. I. 1905. 24, 1028. E. P. 8206, 1905; abst. J. S. C. I. 1906, 25, 132. F. P.
first addn. dated Oct. 1905 to F. P. 353538 (J. S. C. I. 1905. 24, 1028); abst.
J. S. C. I. 1906, 25, 388. J. Kitsee, U. S. P. 775829, 1904; abst. J. S. C. I.
1904, 23, 1233. A. Klein, Paper-Making. 1907, 28, 180-181; abst. J. S. C.
I. 1907. 26, 482; Papierfabrikant, 1914. 22, 601-603, 634-636; J. S. C. I.
1910, 29, 810, 1052. 1265; 1913, 32, 652; 1914, 33, 307; abst. J. S. C. I. 1914,
33, 1201. P. Klemra. Wochcnbl. Papierfabr. 1909, 40, 3973-3976; abst.
J. S. C. I. 1910,29, 16; Wochenbl. Papierfabr. 1911, 42, 967-968; abst. J. S.

C. I. 1911, 30, 413. J. Klinsch, E. P. 15529, 1899; abst. J. S. C. I. 1900,
19, 682. The Kellner-Partington Paper-Pulp Co., Ud.. E. P. 15783, 1895;
abst. J. S. C. I. 1896, 15, 668. A. Knopf, E. P. 13255. 1900; abst. J. S. C. I.
1901, 20, 926. E. P. 13269, 1902; abst. J. S. C. I. 1903, 22, 646. E. Kolb,

D. R. P. 189882. 1905; abst. J. S. C. I. 1908. 27, 244. L, Kollmann, Papier-
fabrikant. 1911, 9, 845-851; abst. J. S. C. I. 1911. 30, 949. C. KoUner.

E. P. 20225, 1891; abst. J. S. C. I. 1893, 12, 461. H. Krause. Chem. Ind.
1906, 29, 217-227; abst. J. S. C. I. 1906, 25, 493. O. Kress, J. I. E. C. 1916,
8, 883-886; abst. J. S. C. I. 1916, 35, 1105. O. Kress and C. Textor, J. I.
E. C. 1918, 10, 268-270; abst. J. S. C. I. 1918, 37, 296-A. O. Kress and
S. Wells, U. S. P. 1266957, 1918; abst. J. S. C. I. 1918. 37, 543-A. R. Kron,
E. P. 2560, 1910; abst. J. S. C. I. 1911. 30, 80. F. P. 381462, 1907; abst.
J. S. C. I. 1908. 27, 178. V. Kucss. E. P. 20911, 1909; abst. J. S. C. I.
1910, 29, 1053. F. P. 394494, 1908; abst. J. S. C. I. 1909, 28, 257. E. P.
29480, 1909; abst. J. S. C. I. 1910, 29, 751. F. P. 409614, 1909; abst. J. S.
C. I. 1910, 29, 752. A. Kuhn, Papierfabr. 1914, 11, Fest-heft, 53-60; abst.
J. S. C. I. 1914. 33, 744. C. Kurtz-Hahnle, K. P. 26019. 1911; abst. J, S.
C. I. 1912, 31, 1176; U. S. P. 1026577. 1912; abst. J. vS. C. I. 1912, 31, 584.
W. Ladd and M. Keen, U. S. P. Re. 1449, 1863. S. Lagermarck and W.
Sverdrup. U. S. P. 1161696. 1915; abst. J. vS. C. I. 1916. 35, 39. H. Lake,
E. P. 7774, 1902; abst. J. S. C. I. 1903, 22, 646; E. P. 210. 1896; abst.
J. S. C. I. 1897, 16, 630; E. P. 20145, 1892; abst. J. S. C. I. 1893. 12, 462;

J

CEI.LUI.OSE 299

acid by the process of Wilstaetter, as detailed on page 93.

E. P. 11484, 17227, 1888; abst. J. S. C. I. 1888, 7, 864; 1889, 8, 209; E. P.
1808, 1887; abst. J. S. C. I. 1887, 6, 380; E. P. 15188, 1884; abst. J. S. C. I.

1885, 4, 243; E. P. 6376, 1884; abst. J. S. C. I. 1884, 3, 496. W. Lake,
E. P. 6534, 1901; abst. J. S. C. I. 1902. 21, 362; E. P. 12346, 1884; abst.
J. S. C. I. 1885, 4, 242. U. S. P. 683836; abst. J. S. C. I. 1902, fl, 64. L.
LamgviUe, U. S. P. 475062, 1892. E. P. 13847, 1892; abst. J. S. C. I. 1892,
11, 935; E. P. 18519, 1893; abst. J. S. C. I. 1894, 13, 170. A. Lannoye,
E. P. 7872, 1913; abst. J. S. C. I. 1914, 33, 132. F. P. 457006, 1913; abst.
J. S. C. I. 1913, 32, 1063. C. Lee, U. S. P. 701271, 1902; abst. J. S. C. I.
1902. 21, 1092. A. Lefebvre, U. S. P. 1277737, 1918; abst. J. S. C. I. 1918,

37, 687-A. Legrand, Papier fabrikant. 1910, 9, 32-33; abst. J. S. C. I. 1910,
29, 208. Lehmann, Papier Ztg. 1904, 29, 3562; abst. J. S. C. I. 1904, 23,
1233. J. Lester, J. S. C. 1. 1902, 21, 380; abst. J. S.C.L 1905, 24,171. G. Light-
foot, Advisory Council of Sci. and Ind., Bull. No. 11, 1919; J. S. C. 1. 1917,36,
27; abst. J. S. C. I. 1919, 38, 356-A. J. Lindsey and B. Tollens, Ann. 267,
341; Landw. Vers.-Sta. 13, 222; Chem. Soc. J. 55, 213; J. S. C. I. 1892,
U, 835; Zts. ang. Chem. 1892, 154-158; abst. J. S. C. I. 1893, 12, 287.
V. Litchauer, Centr. fiir oesterr. Papier Industrie, 1918, 23; Paper, 1919, 23,
646-62; abst. C. A. 1919, 13, 1016. A. Little, Amer. Inst. Chem. Eng.. Jan. 12,
1912; Met. and Chem. Eng. 1916. 14, 133-135; J. S. C. I. 1914, 33, 71;
U. S. P. 1092221, 1914; J. S. C. I. 1914, 33, 477, 563; abst. J. S. C. I. 1916,
35, 301. L. Litynski, A. Rodakiewiez and F. Kurowski, E. P. 16996, 1898;
abst. J. S. C. I. 1899. 18, 763. F. Long, U. S. P. 702142. 1902; abst. J. S.
C. I. 1902, 21, 986. E. P. 3178, 1902; J. S. C. I. 1902, 21, 1092. W. Long-
ley, E. P. 19250, 1905; abst. J. S. C. I. 1906, 25, 845. J. Lorimer, E. P.
16765, 1886; abst. J. S. C. I. 1887, 6, 508; E. P. 16780, 1886; abst. J. S.
C. I. 1887, 6, 608. J. Lundberg, U. S. P. 1257290, 1918; abst. J. S. C. I.
1918, 37, 238-A. D. R. P. 284628, 1914; abst. J. S. C. I. 1915. 34, 1048.
A. Luttringer, Papierfabr. 1913, U, 884-886; abst. J. S. C. I. 1913, 32, 822.
P. Magnier and A. Brangier, E. P. 12241, 1899; abst. J. S. C. I. 1900. 19,
165. U. S. P. 695673. 1902; abst. J. S. C. I. 1902. 21, 632. J. Makin,
E. P. 5626. 1886; abst. J. S. C. I. 1891, 10, 157. N. Malcolmson, E. P.
28163, 1908; abst. J. S. C. I. 1910. 29, 147. G. Mallary, E. P. 8862, 1887;
abst. J. S. C. I. 1888, 7, 639. C. Marchand, U. S. P. 1155256. 1915; abst.
J. S. C. 1. 1915, 34, 1087. E. Marks. E. P. 12311 1, 1917; abst. J. S. C. I. 1919,

38, 216-A. R. Marr. U. S. P. 1166848, 1916; abst. J. S. C. I. 1916, 35, 250.
M. Marsden, U. S. P. 781612, 1905; abst. J. S. C. I. 1905, 24, 208; U. S.
P. 1165689, 1915; abst. J. S. C. I. 1916, 35, 260. G. MarshaU, U. S. P.
982379, 1911; abst. J. S. C. I. 1911, 30, 278. H. Martinson. U. S. P. 708058,
1902; abst. J. S. C. I. 1902, 21, 1345. T. Marusawa, U. S. P. 1244525, 1917;
abst. J. S. C. I. 1918, 37, 6-A. A. Masson and R. vScott, E. P. 26501. 1898;
abst. J. S. C. I. 1899, 18, 1150. H. Maste, U. S. P. 480334, 1892; J. A. C. S.
1892, 14, 297. Matheus. Papierfabr. 1911, 9, 1375-1376; abst. J. S. C. I.
1911, 30, 1374; Papierfabr. 1911, 9, 93-95; abst. J. S. C. I. 1911, 30, 204.
J. Mathieu, E. P. 2767, 1899; abst. J. S. C. I. 1900, 19, 370. H. Mayr,
Handbuch der Papierfabr. (4), 1896, 1592-96; abst. J. S. C. I. 1896, 15,
468. H. McCormack and E. McMuUen, U. S. P. 1196708. 1916; abst. J. S.
C. I. 1916, 35, 1009. A. McDougall, E. P. 4569, 1885; abst. J. S. C. I.

1886, 5, 676. I. McDougaU, E. P. 1349 and 3257, 1883; abst. J. S. C. I.
1888, 7, 451. J. T. M'Dougall, E. P. 3257, 1883; abst. J. S. C. I. 1884, 3,
190. J. T. and J. M'Dougall, E. P. 1795, 1886; abst. J. S. C. I. 1887, 6,
146. J. McLaughlin, U. S. P. 706441, 1902; abst. J. vS. C. I. 1902, 21, 1150.
A. McQuade, E. P. 26811, 1898; abst. J. S. C. I. 1899, 18, 392. W. McRae,
U. S. P. 1151490, 1915; abst. J. S. C. I. 1915, 34, 1008. E. P. 26043, 1911;
abst. J. S. C. I. 1912, 31, 769. W. McRae and N. Malcolmson, E. P.
26043, 1911; abst. J. vS. C. I. 1912, 31, 769; E. P. 14871, 1911; abst. J. S.

300 TECHNOI.OGY OF CEI.I.ULOSE ESTERS

Either the wood pulp was first made into paper — as in the

C. I. 1912, a, 769; F. P. 452989, 1912; abst. J. S. C. I. 1913, 32, 748-
Meister, Lucius and Briining, F. P. 373182, 1906; abst. J. S. C. I. 1907»
26, 606. E. P. 5342, 1906; abst. J.^S. C. I. 1907, 317. J. Melchers, U. S. P.
1162797, 1915; abst. J. S. C. I. 1916, 35, 108. C. Mdhardt, D. R. P. 279102
1913; abst. J. S. C. I. 1915, 34, 276. R. Menzies, U. S. P. 714216. 1902;
abst. J. S. C. I. 1903, 22, 42; E. P. 28, 1902; abst. J. S. C. I. 1903, 22,
109. J. MerriU, U. S. P. 1145498. 1915; abst. J. S. C. I. 1915, 34, 867.
R. Menzies, C. Cross and J. Bevan, E. P. 6840, 1885; abst. J. S. C. I.
1886, 5, 321. E. MUlard, U. S. P. 1244116, 1917; abst. J. S. C. I. 1918.

37, 6-A. M. Mills, U. S. P. 729953, 1903; abst. J. S. C. I. 1903, 22, 817.
S. Milne, E. P. 14070. 1914; abst. J. S. C. I. 1915, 34, 867; E. P. 2420,
1903; abst. J. S. C. I. 1904, 23, 335; E. P. 28611, 1903; abst. J. S. C. I.
1905, 24, 102. F. P. 478063, 1915; abst. J. S. C. I. 1916, 35, 1106.
C. Milts, U. S. P. 691958; abst. J. S. C. I. 1902, 21, 362. A. Monin.
F. P. 366112, 1906; abst. J. S. C. I. 1906, 25, 1064. K, Monroe, J. A.
C. S. 1919, 41, 1002-1003. LaForge and Hudson, J. S. C. I. 1919, 38,
86-A; Hudson and Harding, J. S. C. I. 1918, 37, 778-A; abst. J. S. C. I.
1919, 39, 550-A. Montanus, Wochenbl. Papierfabr. 1904, 35, 2832-3 ; abst. J. S.
C. I. 1904, 23, 947. H. de Montessus, Papier Ztg. 1907, 32, 1534r-5; abst. J. S.
C. I. 1907, 28, 633. H. de Montessus de BaUore, F. P. 322921, 1902; abst.
J. S. C. 1. 1903, 22, 437. G.Moore, U. S. P. 1207978, 1916; abst. J. S. C. 1. 1917,

38, 132. O. Moore, U. S. P. 695754, 1902; abst. J. S. C. I. 1902, 21, 635.
W. Moore, E. P. 118291, 1917; abst. J. S. C. I. 1918, 37, 575-A. K. Morch.
U. S. P. 1160942, 1915; abst. J. S. C. I. 1915, 3i, 1245. E. Morterud, U. S.
P. 883328, 1908; abst. J. S. C. I. 1908, 27, 466; U. S. P. 1299597, 1919;
abst. J. S. C. I. 1919, 38, 459-A; D. R. P. 286074, 1913; abst. J. S. C. I.

1916, 35, 173. M. Miiller and O. Heigis, D. R. P. 284681, 1914; abst.
J. S. C. I. 1915, 34, 1048. L. deNaeyer, E. P. 12461, 1895; abst. J. S. C. I.
1896, IS, 554. D. Nagy, D. R. P. 180847, 1905; abst. J. S. C. I. 1907, 28,
1064. W. Nanson, Paper-making. 1916, 35, 371-374; abst. J. S. C. I. 1917,

38, 131. B. Nase, U. S. P. 1061316, 1913; abst. J. S. C. I. 1913, 32, 652.
T. Nash, U. S. P. 1140181, 1915; abst. J. S. C. I. 1915, 34, 656. E. P. 6876,
1914; abst. J. S. C. I. 1914, 33, 640. A. Navarre, Ind. Electrochim. 1890,
3, 4^51; abst. J. S. C. I. 1900, 19, 267. P. Nebrich, E. P. 16403, 1904;
abst. J. S. C. I. 1904, 23, 949. F. P. 345827, 1904; abst. J. S. C. I. 1905,

24, 40. J. Nef, O. F. Hedenburg and J. W. E. Glattfield, J. A. C. S. 1917,

39, 1683-1652 (see J. S. C. I. 1908, 27, 31; 1910, 23, 1264); abst. J. S. C. I.

1917, 38, 1022. J. Neil, F. P. 442850, 1912; abst. J. S. C. I. 1912, 31, 1027.

E. Nemethy, F. P. 373721, 1906; abst. J. S. C. I. 1907, 28, 713. M. Ner-
son, F. P. 403023, 1908; abst. J. S. C. I. 1909, 28, 1323. A. Neuberger,
Papier Ztg. 1903, 27, (3), 70-71; abst. J. S. C. I. 1903, 22, 159. E. Neu-
bauer, Zts. ang. Chem. 1912, 25, 2155-2159; abst. J. S. C. I. 1912, 31, 1026.
A. Newell and R. J. Marx, E. P. 2865, 1915; abst, J. S. C. I. 1915, 34, 1138;

F, P. 477995, 1915; abst. J. S. C. I. 1916, 35, 1009. P. Newton, E. P. 2046,
1888; abst. J. S. C. I. 1889, 8, 209. E. Nickel, Chem. Ztg. 1883, 17, 1209;
abst. J. S. C. I. 1893, 12, 869; Chem. Ztg. 1883, 17, 869; J. S. C. I. 1893.
12, 869; abst. J. S. C. I. 1894, 13. 423. H. Nishida, J. I. E. C. 1916, 8,
1096-1100; abst. J. S. C. I. 1917, 38, 27. Nodon, Bretonneau, and D'Alton-
Shee, Rev. Prod. Chim. 1, (13), 196; abst. J. S. C. I. 1899, 18, 63.
le Normant des Vamnes and A. Regmouf de Vains, F. P. 347925, 1904;
abst. J. S. C. I. 1905, 24, 454; U. S. P. 818206, 1906; abst. J. S. C. I. 1906,

25, 494. E. P. 505, 1905; abst. J. S. C. I. 1906, 25, 494. V. Nunez. Papier-
fabr. 1914, 12, Fest-heft, 41-44; abst. J. S. C. I. 1914, 33, 744. J. Nussbaum
and W. Ebert, Papierfabr. 1907, Parts 24 and 25; abst. J. S. C. I. 1907, 28,
1063. F. Oliver, Brit. Med. Jour., April 13, 1918; abst. J. S. C. I. 1918.
37, 246-R. D. Otto, E. P. 11651, 1884; abst. J. S. C. I. 1885, 4, 415. H.

CEI.LU1.0SE 301

method of the Westphalische Anhaltische SprengstofF Aktiengessel-

Parker, E. P. 6219, 1906; ahst. J. S. C. I. 1907, 28, 220. F. P. 365866, 1906;
abst. J. S. C. I. 1906, 25, 1001. E. P: 22718, 1905; abst. J. S. C. I. 1906,
2S, 232; E. P. 76, 1902; abst. J. S. C. I. 1902, 21, 870. U. S. P. 808614,
1905; abst. J. S. C. I. 1906, 25, 88; U. S. P. 693896, 1902; abst. J. S. C. I.
1902, 21, 494. von Possanner, Papierfabr., Pest und Atislandsheft, 1912,
m, 60-1; abst. J. S. C. I. 1912, 31, 713. R. Pearson, abst. J. S. C. I. 1917,
36, 631. R. Pearson and J. S. Stoneham, E. P. 26573, 1908; abst. J. S.
C. I. 1910, 29, 17. N. Pederson, E. P. 119028, 1918; abst. J. S. C. I. 1919,
38, 760-A. V. de Perini, F. P. 370547, 1906; abst. J. S. C. I. 1907, 26, 262;
U. S. P. 831621, 1906; abst. J. S. C. I. 1906, 25, 1040; E. P. 20006, 1906;
abst. J. S. C. I. 1907, 26, 1087. S. Persichetti, F. P. 318660, 1902; abst.
J. S. C. I. 1902, 21, 1467. J. Persoz, Rev. Gen. Mat. Col. 1911, 15, 40-3;
abst. J. S. C. I. 1911, 30, 278. L. Peufaillit, first addition dated Jan. 31.
1911 to F. P. 413097, 1910; abst. J. S. C. I. 1912, 31, 428. E. P. 22869,
1910; abst. J. S. C. I. 1911, 30, 1307. F. P. 413097, 1910: abst. J. S. C. I.
1910, 29, 1101. L. Peufaillit and A. Leblanc, F. P. 415188, 1910; abst.
J. S. C. I. 1910, 29, 1245. H. Heifer, E. P. 27587, 1903; abst. J. S. C. I.
1905, 24, 149; F. P. 338330, 1903; abst. J. S. C. I. 1904, 23, 620. J. Pficl,
U. S. P. 1058898, 1913; abst. J. S. C. I. 1913, 32, 531. F. P. 431044, 1911;
abst. J. S. C. I. 1911, 30. 1375. S. Phillips, J. Soc. Arts, 1905, 53, 700-717;
abst. J. S. C. I. 1905, 24, 633. S. Pitt, E. P. 9509, 1884; abst. J. S. C. I.
1885, 4, 464. Poore, B. Appl. 17278, July 15; J. S. C. I. 1919, 36, 557-A.
von iPossanner, Wochenbl. Papierfabr. 1911, 42, 1157-8; J. S. C. I. 1911.
30, 278; abst. J. S. C. I. 1911, 30, 483. R. Preston and T. Thomley. E. P.
2743, 1894; abst. J. S. C. I. 1895, 14, 183. P. Priem, U. S. P. 997144, 1908;
abst. J. S. C. I. 1908, 27, 1220. W. Raitt, E. P. 16488, 1915; abst. J. S.
C. I. 1916, 35, 1009; E. P. 15779, 1912; abst. J. S. C. I. 1913, 32, 785.
F. P. 453307, 1913; abst. J. S. C. I. 1913, 32, 786; Paper-making, 1907,
24, 606-508, 539-541; abst. J. S. C. I. 1908, 27, 35; Indian Forest Reports,
1912, 3, Part 3, 1-37; J. S. C. I. 1912, 31, 870; abst. J. S. C. I. 1912, 301,
1025; Eighth Int. Cong. Appl. Chem. 1912, Sect. Via Orig. Comm. 13, 219-
232; abst. J. S. C. I. 1912, 31, 870. C. Ramsey, E. P. 1834, 1889; abst.
T. S. C. I. 1890, 9, 211. G. Rayner, F. P. 453307, 1912; abst. J. S. C. I. 1913,
32, 785. H. Reed, U. S. P. 1310713, 1919; abst. C. A. 1919, 13, 2443. J.
Readmann and G. Gemmell, abst. J. S. C. I. 1893, 12, 1005; Chem. Tr. J.,
July 22, 1893, 51. R. Redmayne, E. P. 927, 1891; abst. J. S. C. I. 1892,
11, 176. T. Reid, abst. J. S. C. I. 1886, 5, 273, 349; E. P. 9774, 1884;
abst. J. S. C. I. 1885, 4, 507. P. Reinicke, F. P. 388748, 1908; abst. J. S.
C. I. 1908, 27, 956. J. Remington, D. A. Bowack and P. W. Davidson,
Aynsome Annual, 1911, 3, 5-11; World's Paper Trade Rev. 1911; abst.
J. S. C. I. 1912, 31, 582. J. Remington, D. Bowack and B. Dixon, World's
Paper Trade Review, 1909, 51, 6-8; abst. J. S. C. I. 1909, 28, 540. G. Rich-
mond, Philipp. J. Sci. 1906, 1, 433-462; abst. J. S. C. I. 1906, 25,
863; Philipp. J. Sci. 1906, 1, 1075-1084; abst. J. S. C. I. 1907, 26, 274;
Philipp. J. Sci. 1910, 5, 233-255. SindaU, J. S. C. I. 1907, 1157. Raitt, J. S.
C. I. 1908, 27, 35; J. S. C. I. 1906, 25, 863; 1907, 26, 274, 941; abst. J. S.
C. I. 1910, 29, 1450. B. Roberts, Appl. 17547, July 14; J. S. C. I. 1919,
38, 557-A. C. Roberts, U. S. P. 954209, 1910; abst. J. S. C. I. 1910, 29, 556.
R. Roe, U. S. P. 783137, 1905; abst. J. S. C. I. 1905, 2i. 288. F. Roeckner and
R. Roeckner, E. P. 9126, 1892; abst. J. S. C. I. 1893, 12, 461. H. Rogers, E. P.
19376, 1890; abst. J. S. C. 1. 1891, 10, 1022. W. Ruth, U. S. P. 781097, 1905;
abst. J. S. C. I. 1905. 24, 208. R. Ruttin, J. S. C. I. 1898, 17, 365, 481, 1164;
1900, 19, 1028; 1901, 20, 734, 1008; abst. J. S. C. I. 1909, 28, 1290. C.
SahlstrSm and E. Parr, E. P. 14943, 1892; abst. J. S. C. I. 1893, 12, 825.
Sandberg and G. K. Sundblad, E. P. 24126, 1912; abst. J. S. C. I. 1913, 32,
279. H. Sanguinetti, E. P. 16245, 1904; abst. J. S. C. I. 1905, 24, 856.

302 TECHNOLOGY OF CELLULOSE ESTERS

schaft — and after tearing into small pieces was nitrated in centri-

H. Sanguinetti and P. H. Sanguinetti, E. P. 9682, 1898; abst. J. S. C. I. 1899,
18, 602. E. Savage, U. S. P. 710014, 1902; abst. J. S. C. I. 1902, 21, 1345.

B. Saylor, U. S. P. 1004473, 1911; abst. J. S. C. I. 1911, 30, 1207. F. P.
428678, 1911; abst. J. S. C. I. 1911, 30, 1156. O. Schmidt, Papier Ztg.
1901, 2S, (13), 475-^77; abst. J. S. C. I. 1901, 20, 382. H. Schmolka, E. P.
21222, 1900; abst. J. S. C. I. 1901, 20, 496. L. Schopper, E. P. 27948, 1907;
abst. J. S. C. I. 1908, 27, 588. E. Schreiber, D. R. P. 197983, 1907; abst.
J. S. C. I. 1908, 27, 708. F. Schreyer, F. P. 431044, 1911; abst. J. S. C. I.
1911, 30, 1375. R. Schuehmacher, F. P. 373327, 1907; abst. J. S. C. I.
1907, 26, 713. E. Schuricht, D. R. P. 20139, 1882 (addn. to D. R. P. 5427,
1878); abst. J. S. C. I. 1883, 2. 188. C. Schwalbe, Verein deut. Chem. Sep.
1918; Zts. ang. Chem. 1918, 31, 193-4; abst. J. S. C. I. 1918, 37, 685-A.
G. Sellergen, Paper-Making, 1907, 26, 231; abst. J. S. C. I. 1907, 26, 633.
W. vSembritzki, Papier Ztg. 1908, 33, 872; abst. J. S. C. I. 1908, 27, 466.

D. Sharpe, U. S. P. 694678, 1902; abst. J. S. C. I. 1902, a, 494, C. Shartle,
U. S. P. 1173748, 1916; abst. J. S. C. I. 1916, 35, 465. J. Shorrock, E. P.
15956, 1888; abst. J. S. C. I. 1889, 8, 914. H. Simonin, F. P. 407844, 1909;
abst. J. S. C. I. 1910, 29, 647. J. Simons and S. Smith, E. P. 10259, 1890;
abst. J. S. C. I. 1891, 10, 566. G. Sinclaire, E. P. 6441, 1893; abst. J. S. C.
I. 1893, 12, 779. R. Sindall, abst. J. S. C. I. 1918, 37, 167-R; Report to
Indian Govt., Rangoon, March, 1906; abst. J. S. C. I. 1907, 26, 1157; Pam-
phlet 1900, 1-15; abst. J. S. C. I. 1900, 19, 843. Readmann and Gemell,
J. S. C. I. 1893, 12, 1005; J. S. C. I. 1896, 15, 239. M. Singer, Dingier, 246,
487; 1879, 233, 413; abst. J. S. C. I. 1883, 2, 89. E. Slack, Techn. Com-
mittee Canadian Paper and Pulp Assoc.; Pulp and Paper Mag. 1919, 17,
265-270; abst. J. S. C. I. 1919, 38, 356-A. B. Smart, Papier Ztg. 1909,

34, 923-924; abst. J. S. C. I. 1909, 28, 438. A. Smith, abst. J. S. C. I. 1916,

35, 281. W. Smith, E. P. 19150, 1909; abst. J. S. C. I. 1910, 29, 1152. Soc.
Anon. Le Camphre, F. P. 462681, 463879, 1912; abst. J. S. C. I. 1914, 33, 430;
Soc. anon. "Mirabet," F. P. 355852, 1905; abst. J. S. C. 1. 1905, 24, 1252. SDc.
anon, pour la Fab. des Pates a Papier de lin et succedanes, F. P. 365046, 1906;
abst. J. S. C. I. 1906, 25,- 950. Soc. Haemers et van Den Baviers, first
addition dated Aug. 31, 1906 to F. P. 373668, March, 1906, J. S. C. I.
1907, 26, 713; abst. J. S. C. I. 1907, 26, 775; F. P. 373668, 1906, abst. J. S.

C. I. 1907, 26, 713. C. Solbrig, Papier Ztg. 1906, 31, 3770; abst. J. S. C. I.
1907, 26, 338. I. Soraas; U. S. P. 1297028, 1919; abst. J. S. CI. 1919, 38,
358-A; U. S. P. 1268774, 1918; abst. J. S. C. I. 1918, 37, 543-A. H. Spiccr,

E. P. 120086, 1917 (appl. 15467, 1917); abst. J. S. C. I. 1919, 38, 8-A. C.
Springer, E. P. 8073, 1885; abst. J. S. C. I. 1886, 5, 435. O. vStaflford, E. P.
119040, 1918 (appl. 14708/18), Int. Conv. vScpt. 10, 1917; abst. J. S. C. 1. 1919,
38, 215-A. O. Stage, U. S. P. 1279604, 1918; appl. 14318; abst. J. S. C. I.
1919, 38, 8-A. N. Statham, U. S. P. 1298594, 1919; J. S. C. I. 1919, 38,
459-A. F. Stehle, E. P. 10716, 1895; abst. J. S. C. I. 1896, 15, 371. A.
Steinschneider, Zts. ang. Chem. 1909, 22, 1410-1411; J. S. C. I. 1909, 28,
324; abst. J. S. C. I. 1909. 28, 904. A. Stern. Proc. Chem. Soc. 1894, (142),
186-187-P; abst. J. S. C. I. 1894, 13, 1230. C. vStcward, H. D. Hall and H.
Beadle. E. P. 116005, 1917; abst. J. S. C. I. 1918. 37, 409-A. W. Stocks,
E. P. 25303, 1910; abst. J. S. C. I. 1911, 30, 1375. W. Stone and W. H.

• Test. Amcr. Chem. J. 1893, 15, 195; J. S. C. I. 1890, 9, 748; abst. J. S. C. I.
1893, 12, 618. J. Strachan, abst. J. S. C. I. 1919, 38, 102-R. E. Strange,
J. H. Carle and A. A. Longsdon, E. P. 27738, 1903; abst. J. S. C. I. 1904, 23,
1207. E. Streeb, Mitth. aus den k. tech. Versuchstat. zu Berlin, 1893, U,
23; abst. J. S. C. I. 1893, 12, 1053. F, vStromer, D. R. P. 21398, 1882; abst.
J. S. C. I. 1883, 2, 295. A. Stutzer, Wochenbl. Papierfabr. 1911, 42, 4956;
abst. J. S. C. I. 1912, 31, 121; Chem. Ztg. 1910, 34, 1352; J, S. C. I. 1909,
28, 1162; abst. J. S. C. I. 1911, 30, 18; Zts. ang. Chem. 1909, 22, 1999-2005;

^ CELLULOSE 303

fugals, or else was purified by solution in HCl, extruded through

abst. J. S. C. I. 1909, 28, 1162. H. E. Surface, U. S. Dept. Agric. Bull-
No. 80, Aug. 31. 1914, 1-63; abst. J. S. C. I. 1914, 33, 1151. H. Surface
and R. E. Cooper, U. S. Dept. Agric. Bull No. 72. May 29, 1914, 1-26;
abst. J. S. C. I. 1914, 33, 857. E. Sutermeister, Pulp and Paper Mag. 1919,
17,215-218,243-246,263-264,289-292; abst. J. S. C. 1. 1919, 38, 356.A; Eighth
Int. Cong. Appl. Chem. 1912, Sect. Via Orig. Comm. 13, 265-69; abst.
T. S. C. I. 1912, 31, 869; Papierfabr. 1914, 12, 898-900; abst. J. S. C. I. 1914,
33, 857. H. Tartar. J. Ind. Eng. Chem. 1916, 8, 226-228; Ekstroms. J. S.
C. I. 1910, 29, 810; abst. J. S. C. I. 1916, 35, 483. C. Taylor and H. K.
Cook, U. S. P. 1181553, 1916; abst. J. S. C. I. 1916, 35, 686. C. Tennant-
Lee, F. P. 345632, 1904; abst. J. S. C. I. 1905, 24, 40. J. Thickens, U. S.
Dept. of Forests Bull.; Papierfabr. 1914, 12, 275-281; abst. J. S. C. I. 1914,
33, 1202. W. Thompson, E- P. 18169, 1890; abst. J. S. C. I. 1892, 11, 175.
W. Thorner, Zts. Unters. Nahr. und Genussmittel, 1902, 5, (7), 304^05;
abst. J. S. C. I. 1902, 21, 641. E. TUlberg, F. P. 385270, 1907; abst. J. S.

C. I. 1908, 27, 634. O. Tingberg, E. P. 6491, 1912; abst. J. S. C. I. 1912,
31, 812. J. Tompkins, E. P. 3472, 1886; J. S. C. I. 1886, 5, 435. T. Tor-
rance and J. Hervell, E- P. 13587, 1893; abst. J. S. C. I. 1893, 12, 946. H.

. Turner, U. S. P. 772192, UK)4; abst. J. S. C. I. 1904, 23, 1110. W. Uraphcrs-
ton. E. P. 13024, 1892; abst. J. S. C. I. 1893, 12, 461. E. Valenta, Chem.
Ztg. 1904, 28, 502-503; abst. J. S. C. I. 1904, 23, 686. J. Van Wessem, E-
P. 117086, 1918; abst. J. S. C. I. 1919, 38, 496-A. F. Veitch and J. L. Mer-
rill, U. S. Dept. Bureau of Chem., Bull. No. 159, Jan. 18. 1913, 28 pp.; abst.
J. S. C. I. 1913, 32, 358. H. Vessier and A. Wilbaux, E. P. 14859. 1881;
abst. J. S. C. I. 1885, 4, 686. L. Vidal, Papierfabr. 1910, 8, 1042-1045;
abst. J. S. C. I. 1910, 29, 1298. J. Vogel, Papierfabr. 1911, 9, 438-140;
abst. J. S. C. I. 1911, 30, 532; Papier Ztg. 1907, 32, 961-962; 1010-1012,
1054, 1098-1099; see also J. S. C. I. H)06, 25, 555; abst. J. S. C. I. 1907, 26,
482. N. Vrooman and R. Kirkland, U. S. P. 689934, 1901; abst. J. S. C. I.
1902. 21, 271; U. S. P. 703682, 1902; abst. J. S. C. I. 1902, 21, 1036. P.
Waentig and W. Gierisch, Zts. ang. Chem. 1919, 32, 173-175; J. S. C. I.
1913, 32, 822; abst. J. S. C. I. 1919, 38, 530-A. A. Wahlstrom, U. S. P.
771403, 1904; abst. J. S. C. I. 1904, 23, 1011. C. Waite and J. E. Heden.
U. S. P. 1249287, 1917; abst. J. S. C. I. 1918, 37, 53-A. G. Walker, abst.
J. S. C. I. 1911, 30, 934. W. Walker, abst. J. S. C. I. 1913, 32, 389. R.
Wallace and G. Reynaud, F. P. 394234, 1907; abst. J. S. C. I. 1909, 28, 255.
J. Wallberg and J. Ullgren, E. P. 2685, 1896; abst. J. S. C. I. 1896, 15, 372.
G. Walsh, Paper-Making. 1917, 36, 283-285; abst. J. S. C. I. 1917, 36, 1091.
J. Walton. E. P. 16113, 1886; abst. J. S. C. I. 1887, 6, 223. H. Wandrowsky,

D. R. P. 309630, 1918; abst. J. S. C. I. 1919, 38, 28.3-A. J. Warren and F.
A. Cloudman, E. P. 11610, 1887; abst. J. S. C. I. 1887, 6, 736. R. Wasicky.
Papierfabrikant, 1918, 16, 212-213; Zts. ang. Chem. 1918, 31, Ref. 371;
abst. J. S. C. I. 1919, 38, 131-A. H. Watson and J. S. Watson, E. P.
16928, 1890; abst. J. S. C. I. 1891, 944. D. Wells, J. I. E. C. 1913, 5,
906-907; abst. J. S. C. I. 1913, 32, 1102; U. S. P. 1269350, 1918; abst. J. S.
C. I. 1918, 37, 575-A; U. S. P. 1268193, 1918; abst. J. S. C. I. 1918, 37,
453-A. W. Wentworth and A. B. Larchar, U. S. P. 912339 and 912340,
1909; abst. J. S. C. I. 1909, 28, 541. F. Werle, E. P. 16281, 1904; abst.
J. S. C. I. 1905, 24, 40. Van Wessen, E. P. 122812, June 25 (10681, 1918);
abst. J. vS. C. I. 1919, 38, 484-A. A. Westad and E. Haag, U. S. P. 1309207,
1919; abst. J. S. C. I. 1919, 38, 678-A. C. Wcygang. E. P. 12299, 1891;
abst. J. S. C. I. 1892, 11, 711-A. A. Wheeler, Ber. 1905. 38, 2168-69; abst.
T. S. C. I. 1905, 24, 748; Ber. 1907, 40, 1888-1890; abst. J. S. C. I. 1907.
26, 633. A. White, U. S. P. 1197983, 1916; abst. J. S. C. I. 1916, 35, 1106.
A. White and J. Rue, Tech. Assoc, of Pulp and Paper Ind. N. Y., Feb. 7,
1917; Met. and Chem. Eng. 1917, 16, 182-186; abst. J. S. C. I. 1917, 36,

s

304 TECHNOIX)GY OP CELLUlrOSE ESTERS

small orifices into water as the precipitating medium, and these

383. J. White, E. P. 24381. 1901: abst. J. & C. I. 1902, a, 493; E. P.
3091. 1899; abst. J. S. C. I. 1900. IS, 370. E. P. 17022, 1891; abst. J. S. C
I. 1892. 11, 935. Widsoe and ToUens. Ber. 1900. 33, (1). 132-143; abst.
J. S. C. I. 1900, IS, 160. H. Wigger, E. P. 14563. 1889; abst. J. S. C. I. 1890.
S, 819. M. WUbuschewitsch. E. P. 27950. 1909; abst. J. S. C. I. 1911, 30,
80. F. Williams, abst. J. S. C. I. 1913. 30, 457. B. WUliamsoa. U. S. P.
1025356, 1912; abst. J. S. C. I. 1912. 31, 532. I. Willstatter and L. Zech-
meister, Ber. 1913. 46, 2401-2412; abst. J. S. C. I. 1913. 32, 822. F. Wolesky,
Papier Ztg. 1896, 21, (18), 563; abst. J. S. C. I. 1896. 15, 370; Ber. Osterr.
Ges. z. Forder d. Chem. Ind. 1894, 16, 119; abst. T. S. C. I. 1895. li, 72.
H. Wrede, Papierfabr. 1909. 7, (Fest und Auslandsh). 43-46; abst. J. S. C. I.
1909. 28, 811; Wochenbl. Papierfabr. 1911. 42, 582-584; abst. J. S. C. I.
1911, 30, 278. A. Wright, E. P. 12903, 1887; abst. J. S. C. I. 1888, 7, 640.
C. Wurster. Ber. 1887. 20, 808-810; abst. J. S. C. I. 1887. 6, 565; Papier Ztg.
1903. 28, (46), 1608-1609; abst. J. S. C. 1. 1903, 22, 824; abst. J. S. C. I. 1903,
22, 817; U. S. P. 690506. 1902; abst. J. S. C. I. 1902. 21, 271; U. S. P. 690505,
1902; abst. J. S. C. I. 1902, 21, 271. T. Young and J. Pettigrew, Jr.. E. P.
14735 and 14998, 1884; abst. J. S. C. I. 1885, 4, 364. D. R. P. 280476, 1914;
abst. J. S. C. I. 1915. 34, 488. F. Zacharias, Papierfabrikant. 1912, 10,
65-70, 98-99, 132-135, 168-170, 195-198, 222-226. 253-257. 274-277. 301-
303, 333-337, 362-365, 391-i394, 423-426. 452-455. 502-504; D. R. P. 117380,
1900; abst. J. S. C. I. 1912. 31, 582. C. Ziegelmeyer. Papier Ztg. 1918, 42,
1855-1856; Zts. ang. Chem. 1918, 31, 174-175; abst. J. S. C. I. 1918. 37,
408-A. A. Zimmermann, J. Roy. Soc. Arts, 1912, 01, 69-81; abst. J. S. C.
I. 1912. 31, 1197; E. P. 3963, 8359 and 13746, 1913; abst. J. S. C. I. 1914,
33, 348. O. Zimmermann and G. Hagemann, E. P. 10326. 1894; abst. J. S.
C I. 1895, 14, 676. F. Zweigler, Papierfabrikant, 1912, 10, 1364r-65; abst.
J. S. C. I. 1913, 32, 18. Anon., Pap. Ztg. 1916. IS, 1446. 1447. F. Abra-
ham, Gerberei-Technik, 1913, No. 11, 12; Collegium. 1913, 11. 599; J. S.
C. I. 1913, 32, 1079. H. Achenbach. D. R. P. 286601, 1914; Add. to D. R.
P. 252412, 1911; Nor. P. 23689, 1913; abst. C. A. 1916, 10, 2148; Papir J.
1913, 1, 30. F. Ahrens, Zts. ang. Chem. 1895, 8, 41; abst. J. S. C. 1. 1895,
14, 503. Chem. Zts. 1903, 2, 743; abst. Chem. Centr. 1903, 74, II, 812.
Pap. Ztg. 1905, 30, I. 1539; Chem. Zentr. 1905, 76, I, 700; Chem. Zts. 1905.
4, 40; J. S. C. I. 1905. 24, 343. Aktiebolaget Ethyl. Sweden, F. P. 446717,
446718, 1912; abst. Chem. Ztg. Rep. 1913, 37, 116; J. S. C. I. 1913. 32, 133,
377; C. A. 1913, 7, 1972, 2115. Nor. P. 24757, 1914; 27613, 1917; abst.
Papir J. 1914, 2, 263; C. A. 1917, 11, 1903; Pulp Paper Mag. Can. 1917, 15,
765, 788. Aktiebolaget Ethyl and G. Ekstrom, Aust. P. Anm. 940, 1913;
Swed. P. 35232, 1912. Aktieselskabet Sulfitspirit, Hoi. P. 1763. 1917; Nor.
P. 25927, 1915; abst. Papir J. 1915, 3, 190; C. A. 1917, 11, 1300; Pulp and
Paper Mag. Can. 1917, 15, 541. M. Albersheim, D. R. P. Anm. K. Albert
and L. Behrend. D. R. P. 250275. 1911; abst. Chem. Zentr. 1912, 83, II,
779. H. Alt, Farber Ztg. 1899, 10, 303; abst. Wag. Jahr. 1899, 45, 972.
W. Appelius. J. Amer. Leather Chem. Assoc. 1915. 10, 202; Ledertechn.
Rundschau, 1915. 7, 17; J. S. C. I. 1915, 34, 501. W. Appelius and R.
Schmidt. Ledertechn. Rundschau. 1914. €, 225; Zts. ang. Chem. 1914, 27,
691; Collegium, 1914, 706; J. Amer. Leather Chem. Assoc. 1914. S, 64; J. S.
C. I. 1915. 34, 189. O. Arlt. D. R. P. 128213. 1898; abst. Chem. Zentr.
1902, 73, I, 446; Chem. Ztg. 1901, 26, 229; Pap. Fabr. 1905. 3, 785; J. Auer-
bach, Chem. Ztg. 1913. 37, 906. D. Aufhauser. Zts. ang. Chem. 1912, 25,
74. B. Bache-Wiig, D. R. P. 129326, 1901; abst. Chem. Centr. 1902. 73,
I, 740. G. Badermann, Zts. ang. Chem. 1910, 23, 1216; J. S. C. I. 1910,
29, 874. Badische Anilin & Soda Fabrik, D. R. P. 222191, 1900; 265536,
1912; abst. Chem. Ztg. Rep. 1910, 34, 271; Wochenbl. Papfabr. 1910, 41,
2612; Chem, Zentr. 1910, 81^ I, 1998. L. Bakeland, U. S. P. 1Q57319, 1913;

CELlrULOSE 305

coarse filaments made into rovings and nitrated as such, in much

abst. J. S. C. I. 1913, 82, 428; C. A. 1913, 7, 1796; Paper Trade J. 1913, 57,
No. 20, 46. G. Banthier, J. Gasbel. 1914, 57, 32, 55; J. S. C. I. 1914, 33,
129; C. A. 1914, 8, 1344. G. Bantlin, J. Gasbel. 1914, 57, 32; Chem. Zentr.

1914, 85, I, 923; C. A. 1914, 8, 1344. K. Earth, Pap. Ztg. 1890, 15, 667.
J. Bates, Pulp, Paper Mag. Can. 1917, 15, 553. H. Becker and F. Gross,
Ledertechn. Rundschau, 1914, 6, Oct. 22; abst. Collegium, 1915, 106; J. S.
C. I. 1915, 34, 501. H. Bennett, Shoe and Leather Rep. 1912, 104, 31;

C. A. 1912, €, 1383. E. Bergerhoflf, D. R. P. 160151. 1903; abst. Bied. Tech.
Chem. Jahr. 1904, 558; Chem. Zentr. 1905, 76, I, 1576. H. Bergstrom,
Jemkontorets Annaler, 1909, 691; Papier Fabr. 1909, 7, 506, 607; 8, 970;
J. S. C. I. 1909, 28, 1162; Zts. ang. Chem. 1910, 23, 1823. D. R. P. 290680,
1914; Nor. P. 27849, 1914; abst. C. A. 1917, 11, 888; Pulp, Paper Mag. Can.
1917, 15, 809. Pap. Fabr. 1912, 10, 359; J. S. C. I. 1912, 31, 381; C. A.

1912, 6, 2528. Pap. Fabr. 1914, 12, 1040; abst. Zts. ang. Chem. 1915, 28,
47; J. S. C. I. 1915, 34, 487; C. A. 1915, 9, 149; Chem. Trade J. 1915, 57,
208; Papier J. 1914, 2, 389. H. Bergstrom and B. Lindquist, Swed. P.
33333, 1910; abst. C. A. 1913, 7, 1288. J. Beveridge, J. S. C. I. 1916, 35,
563; Paper, 1916, 18, No. 16, 17; C. A. 1916, 10, 2799. D. Bibb, U. S. P.
1158364, 115a365, 1158266, 1915; Nor. P. 27881, 1917; abst. J. S. C. I. 1915,

34, 1119; Pap. Fabr. 1917, 5, No. 13, 111. B. Blackman, U. S. P. 369530,
369634, 369836, 530635, 1895; abst. Pap. Ztg. 1895, 20, I, 1376; II, 2152.

D. Hanson, U. S. P. 1330632, 1920. D. R. P. 266122, 1912; abst. J. S. C. I.

1913, 32, 1104; C. A. 1914, 8, 822. K. Bloesch, Russ: Privilegium, 558,
1898; abst. Chem. Ztg. 1898, 23, 320. J. Briggs, Chem. World, 1914, 2,
346; C. A. 1914, 8,i204; Paper Makers Brit. Trade J. Ann. No. 1913-1914,
66; Paper 1913, 13. No. 11. 21. E. Bruck, Chem. Ztg. 1892, 95, 1782; abst.
T. S. C. I. 1893, 12, 460. L. Brunet, F. P. 459069, 1912; abst. C. A. 1914,
8, 2805; J. S. C. I. 1913. 32, 1153. O. Bryant, Pulp. Paper Mag. Can. 1915,

13, 139; Paper, 1915, 15, No. 26, 15. H. Bucherer, Pap. Ztg. 1905, 30, I,
1350; Zts. ang. Chem. 1904, 17, 31. W. Buddens, Pap. Ztg. 1891, IS, 1813.
J. Buisson, F. P. 442809, 1912; abst. Chem. Ztg. Rep. 1912, 36, 69; J. S.

C. I. 1912, 31, 1120. F. P. 449350, 1912. F. Byrom, E. P. 24196, 1914;
abst. J. S. C. I. 1915, 34, 1063; C. A. 1916, 10, 1610. T. Carlson, Pap.
Fabr. 1909, 7, 587. Pap. Ztg. 1910, 35, II, 2117. Carpenter and Schulze,

D. R. P. 78306, 1894; Add. to D. R. P. 71942; abst. Ber. 1896. 28, 260.
Chemische Fabrik Floersheim, D. R. P. 247119, 1910. Chemische Fabrik
Griinan, Landshoff and Meyer, D. R. P. 48269, 1888; abst. Pap. Ztg. 1889,

14, 2310. Chem. Fabrik K. Kopper and F. Kammer, D. R. P. 114401,
1899; abst. Chem. Zentr. 1900, 71, II, 1046. Chemische Industrie und Han-
dels Ges. D. R. P. 248055, 1910; abst. J. S. C. I. 1912, 31, 999. P. Claes,
Belg. P. 244151, 1912. A. Claflin, J. Amer. Leather Chem. Assoc. 1912,
7, 154; abst. Zts. ang. Chem. 1912. 25, 1932; C. A. 1912, 6, 1383. A. Clas-
sen, D. R. P. 161644, 19a3; abst. Chem. Zentr. 1905, 76, II, 560. M. Cough-
lin, U. S. P. 1103267, 1914; 1217157, 1917; abst. J. S. C. I. 1914, 33, 931;
1917, 36, 512. M. Coughlin and C. Sweet, U. S. P. 1114119, 1114120, 1914;
abst. C. A. 1914, 8, 3858; J. S. C. I. 1914. 33, 1152, 1153; Paper, 1914, 15,
No. 7, 24, 32. C. Cross and E. Bevan, E. P. 1548, 1883; abst. J. S. C. I.
1883, 2, 541. A. Cushraan, J. S. C. I. 1911, 30, 211. J. DeCew, U. S. P.
1010122, 1911; 1155708. 1915; Nor. P. 26293, 1915; abst. J. S. C. I. 1912,
31, iS9; 1915. 34, 1244; Papir J. 1915, 3, 262; Paper Maker Brit. Trade J.

1915, 43, 332. J. DeCew, U. vS. P. 1203856. 1916; abst. J. S. C. I. 1916,

35, 1257; C. A. 1917, 11, 100; Paper Makers Monthly J. 1916, 54, 212. F.
Detsinyi, Aust. P. 10t)87, 1898; abst. Pap. Ztg. 1898. 23, I, 950. Deutsche
Saduyn Gesellschaft, Wochenbl. Papfarb. 1910. 41, 3847. B. Diamond,
U. S. P. 938128. 94a394; E. P. 5206. 1909; D. R. P. 216798, 222193, 1909; abst.
J. S. C. I. 1909, 28, 1239; Zts. ang. Chem. 1910, 23, 1390; Chem. Ztg. Rep.

306 TECHNOU)GY OP CELLULOSE ESTERS

the manner that Memphis Star and other comparatively long fiber

1909. 33, 607, 624; Wag. Jahr. 1909, 55, I, 492. W. Dickerson, E. P. 7438,
1910; abst. J. S. C. I. 1911, 30, 438. U. S. P. 1043303, 1912; abst. Paper
Trade T. 1913, 57, No. 2, 42; Wochenbl. Papfabr. 1912, 44, 4796; J. S. C. I.

1912, al, 1140. J. Amer. Leather Chem. Assoc. 1914, 9, 489; J. S. C. I.
1914, 33, 1163. U. S. P. 1059716, 1913; abst. J. S. C. I. 1913, 32, 531; C. A.

1913, 7, 2115. Paper, 1917, IS, No. 20, 19; No. 21, 17. R. Dieckmann and
E. Hagglund, Chem. Ztg. 1916, 40, 581; C. A. 1917, 11, 1544. L. Doren-
feldt, E. P. 11974, 1898; D. R. P. 122489, 1898; Aust. Privilegium, 4602,
1898; Pap. Ztg. 1898, 23, 652; 1900, 26, I, 2602; Chem. Centr.|1900, 71,
II, 248; J. S. C. I. 1898, 17, 788; 1899, 18, 702. D. R. P. 113435, 1898;
129227, Aust. Privilegium, 3807, 1898; abst. Pap. Ztg. 1900, 25, II, 2916;
Chem. Centr. 1900, 71, II, 702; 1902, 73, I, 686. Zts. ang. Chem. 1901, 14,
82. V. Drewsen, E. P. 2629, 1892; abst. J. vS. C. I. 1893, 12, 461. Durr
& Co. D. R. P. 71942, 1893; abst. Ber. 1894, 27, 220. W. Eitner, Gerber,
1911, 37, 227, 241, 255; 1913, 39, 43, 57; abst. J. S. C. I. 1911, 30, 1269;
1913, 32, 229. C. Ekmann, E. P. 20036, 1893; D. R. P. 81643, 1893; abst.
Ber. 1896, 28, 711; Pap. Ztg. 1896, 21, I, 2218, 2609, 3247; J. S. C. I. 1894,
13, 1085; 1896, 15, 735; Aust. Privilegium, 569, 1894. C. Eckman, D. R. P.
109951, 1899; E. P. 189, 1899; Aust. P. 3229, 1899; abst. Pap. Ztg. 1900,
25, 797; J. S. C. I. 1899, IS, 1150. G. Ekstrom, Svensk. Kem. Tid. 1909,
No. 7; Pap. Ztg. 1910, 35, II, 2519. Pap. Fabr. 1910, 8, 582; abst. J. S. C.
I. 1910, 29, 810; Chem. Ztg. 1910, 34, 223; Wochenbl. Pap. Fabr. 1910, 41,
638; E. P. 6741, 1910; Can. P. 132717, 1911; abst. J. S. C. I. 1911, 30, 504.
Swed. P. 34623, 1912; abst. C. A. 1914, 8, 1669. Can. P. 142290, 1912;
abst. C. A. 1914, 8, 2251; Paper, 1914, 14, No. 22, 20. U. S. P. 1042332,
1912; Can. P. 142288, 1912; abst. J. S. C. I. 1912, 31, 1075; Papir, 1912,
10, No. 9, 16. U. S. P. 1046160, 1912; Can. P. 142289, 1912; abst. J. S.
C. I. 1913, 32, 103; C. A. 1913, 7, 677; Paper, 1912, 10, No. 9, 16. U. S. P.
1050723, 1913; Swed. P. 34624, 1912; Can. P. 142287, 1912; abst. J. S. C. I.

1913, 32, 192; C. A. 1913, 7, 889; 1914, 8, 1669. vSwed. P. 33876; abst.
Chem. Ztg. 1913, 37, No. 31, 32. Svensk. Pap. Tid. 1913, 2258; Papir T.

1914, 298; Pap. Ztg. 1910, 35, 3244; 1913, 38, 2258. Pap. Ztg. 1914, »,
269; Wochenbl. Papfabr. 1914, 45, 825. U. S. P. 1098561, 1098562, 1914:
Can. P. 142285, 142286, 1912; abst. J. S. C. I. 1914, 33, 785; C. A. 1914,
8, 2803. Swed. P. 35706, 1912; abst. Pap. Fabr. 1914, 12,727. Pulp, Paper
Mag. Can. 1915, 13, 68; C. A. 1915, 9, 1114. Paper J. 1914, 2, 298. U. S. P.
1139507, 1915; Can. P. 142542, 142,543, 1912; abst. J. S. C. I. 1915, 34, 729;
C. A. 1914, 8, 2251, 2803; 1915, 9, 1825. U. S. P. 1087356, 1914; abst.
Chem. Ztg. 1914, 38, 25; J. S. C. I. 1914. 33, 349; C. A. 1914, 8, 1346. M.
Elb, D. R. P. 166947, 1905; Aust. P. 23046, 1905; abst. Pap. Ztg. 1906,

31, I, 215; Chem. Centr. 1906, 77, I, 801. D. R. P. 173686, 1905; abst.
Pap. Ztg. 1906, 31, II, 3180; Chem. Centr. 1906, 77, II, 924. C. Ellis,
U. S. P. 1042538, 1912; abst. J. S. C. I. 1912, 31, 1120. U. S. P. 1057416,
1912; abst. J. S. C. I. 1913, 32, 482; C. A. 1913, 7, 1806; Pulp, Paper Mag.
Can. 1912, 10, 372. U. S. P. 877414, 1908; abst. Chem. Ztg. Rep. 1908,

32, HI; J. S. C. I. 1908, 27. 177. U. S. P. 1223158, 1917; abst. J. S. C. I.
1917, 36, 593; C. A. 1917, 11, 1903; Pulp. Paper Mag. Can. 1917, 15, 741.
U. S. P. 1068084, 1913; abst. J. S. C. I. 1913, 32, 829. U. S. P. 1119500,
1914; abst. J. S. C. I. 1915. 34, 82. Erste Oesterreichische Sodafabrik, Aust.
P. 2336, 1889. Farbenfabriken vorm F. Bayer & Co., D. R. P. 264920.
265167, 1912. Farbwerke Friedricbsfeld, P. Remy, D. R. P. 90798, 1896;
abst. Pap. Ztg. 1897, 22, I, 426; J. S. C. I. 1897, 16, 630. Feldmiihle Papier
und Zellstoffwerke, D. R. P. 307087. 307663. 1918; abst. J. S. C. I. 1920,
39, 16-A. S. Fercnczi, Pap. Ztg. 1897, 22, 3575, 3647, 3679; abst. J. S. C. 1.
1898, 17, 264. J. Landw. 60, 183; abst. Zts. ang. Chem. 1912, 25, 2088.
A. Fcst, U. S. P. 1218638, 1917; C. A. 1917, 11, 1545; Pulp, Paper Mag. Can.

CELL,UW)SE 307

cottons are hand or pot nitrated at the present day for the prep-

1917, 15, 677; Paper, 1917, 20, No. 11, 22. P. Fittica, Pap. Ztg. 1902, 27,
II. 3144. G. Forrester, Paper, 1912, 6, No. 11, 15. H. Fosse, Ber. Pharm.
Ges. 1915, 25, 303; abst. J. S. C. I. 1915, 34, 1261. A. Foster, U. S. P.
1320043, 1919; abst. J. S. C. I. 1919, 38, 959-A. G. Foth, Zts. Sptritusind,
1910, 589; abst. Chem. Ztg. 1911, 35, 35; C. A. 1911, 5, 1970.' Chem. Ztg.
1913, 37, 1221. A. Frank, E. P. 13286, 1886; abst. J. S. C. I. 1887, 6, 735.
Aust. P. 646, 1887. Pap. Ztg. 1904, 29, II, 2465; 1906, 31, II, 3322. D. R.
P. 40308, 1886; abst. Ber. 1887, 20 667; Pap. Ztg. 1887, 12, 1170. Pap.
Ztg. 1887, 12, 1765, 1782, 1832; 1888, 13, 531; abst. Dingl. Poly. 1888, 26S,
485; 1890, 276, 58. Pap. Ztg. 1889, 14, 1488. Pap. Ztg. 1910, 35, I, 145.
Pap. Ztg. 1889. 14, 383, 1488, 1556. Das Papier, 1907, 2, 134. Wochbl.
Papierfabr. 1907, 38, 3199. A. Frank and E. Lehmann, Pap. Ztg. 1904,
29, II, 3368; Wochenbl. Papfabr. 19(H, 35, 3338. W. Freeman, U. S. P.
1175422, 1175423, 1175424, 1175425, 1175426, 1916; abst. C. A. 1916, 10,
1434; J. S. C. I. 1916, 35, 533. A. Gansser, Collegium, 1909, 360; 1912,
482; 1914, 324; Zts. ang. Chem. 1913, 26, 528; Chem. Ztg. Rep.

1913, 37, 442; J. S. C. I. 1914, 33, 654; C. A. 1915, 9, 535. A. Gawalowski,
Pap. Ztg. 1899, 24. 3112; E^ Gewerkschaft, D. R. P. 200210, 1907; abst.
Chem. Ztg. 1908, 32, 478; Pap. Ztg. 1908, 33, II, 2014. Swed. P. 23464,
1906; abst. Chem. Ztg. Rep. 1908, 32, 82. D. R. P. 246289, 1908. D. R. P.
252439, 1908; abst. Zts. ang. Chem. 1912, 25, 2359; C. A. 1913, 7, 416. G.
Gianoli, U. S. P. 1063428, 1913, abst. J. S. C. I. 1913, 32. 760. E. Gold-
Schmidt, D. R. P. 97935, 1897; abst. Chem. Centr. 1898, 69, II, 616; Pap.
Ztg. 1898, 23, 2664. Chem. Ztg. 1898, 22, 374; J. S. C. I. 1898, 17, 790.
L. Gottstetn, Wochenbl. Papfabr. 1905, 36, I, 1390, 1616, 1779; abst. Pap.
Ztg. 1907, 26, 1. 828; abst. J. S. C. I. 1901, 20, 495. Chem. Ztg. 1914, 38,
804. Pap. Ztg. 1889, 14, 1556. Pap. Ztg. 1906, 31, 952; abst. Zts. ang.
Chem. 1906, 19, 293. Wochenbl. Papierfabr. 1912, 43, 4329. Chem. Ztg.

1914, 38, 804. O. Goy, Zts. ang. Chem. 1913, 23, 602; Landw. Vers. Sta.
1913, 82, 1; C. A. 1913, 7, 4023. B. Graetz, D. R. P. 211479, 1912; Chem.
Ztg. Rep. 1914, 38, 175; J. S. C. I. 1914, 33, 471. D. R. P. 280455, 1913;
abst. J. S. C. I. 1915, 34, 540. Swiss P. 73107, 1916; Dan. P. 21889, 1917;
abst. C. A. 1917, 11, 100; Pulp, Paper Mag. Can. 1917, 15, 741. P. Grempe,
Wochenbl. Papfabr. 1912, 43, 3417. L. Griffin, D. R. P. 69874, 1892; abst.
Ber. 1893, 26, 905. Paper Trade J. Conv. No. 1911; Paper Maker Brit.
Trade J. 1911, 17, 55. Pulp, Paper Mag. Can. 1906, 4, 75. F. Gross. D. R.
P. Anm. 38003, 1912. U. S. P. 1154762, 1915; abst. J. S. C. I. 1915, 34,
1139, 1155; C. A. 1915, 9, 3378. G. Grosser, Technikum, 1912, 20, 166;
Chem. Ztg. 1913. 37, 442; Collegium, 1912. 510. 557; 1913, 479. O. Grothc,
U. S. P. 1087911, 1914; abst. C. A. 1914, 8, 1357; J. S. C. I. 1914, 33, 349.
Paper Trade J. 1915, 60, 52. Nor. P. 25315, 1915; abst. Papir J. 1915, 3,
37. W. Gunther, D. R. P. 255853, 1910; abst. J. S. C. I. 1913, 32, 284;
C. A. 1913, 7, 1869. W. Gunther, F. P. 457159, 1913; abst. C. A. 1914, 8,
2018. W. Haage, D. R. P. 228721, 1908; abst. Chem. Zentr. 1911, 82, II,
1789; Pap. Ztg. 1911. 36, 67; C. A. 1911, 5, 2177. A. Haeffner, U. S. P.
1231153, 1917; abst. Paper, 1917,20, No. 21, 23; Paper Making. 1917, 36,
238; Pulp, Paper Mag. Can. 1917, 15, 1031 ; Paper Makers Monthly J. 1917.
55, 277. E. Hagglund, Chem. Ztg. 1916, 40, 433; C. A. 1915, 9,
2925; 1916, 10, 2636; J. S. C. I. 1916, 35, 832. Pulp, Paper Mag. Can,
1917, 15, 1125, 1157. 1185; Paper, 1917. 21, 11; No. 17, 16; No. 18, 13; No.
19, 11, 20; No. 20, 15. Pap. Fabr. 1916, 14, 353. A. Harpf, Dingl. Poly.
1892, 286, 84, 112. H. Harpf, Zts. ang. Chem. 1898, 11, 875, 925, 1169;
Chem. Centr. 1899, 70, 313. W. Harrocks, and J. Tullis. E. P. 18332, 1914;
abst. J. S. C. I. 1915, 34, 1063. Hartmanh, Pap. Ztg. 1895, 20, 822, 952,
1084; 1896, 21, 764; 1899, 24, 1667. A. Harvey, Leather World, 1917, 9, 73.
A. Haussner, Dingl. Poly. 1890, 275, 577, 276, 49; 277, 118, 174, 211; Jahr.

308 TECHNOU)Gy OF CELLULOSE ESTERS

aration of high class water- white pyroxylin lacquers for the protec-

Chem. 1890, 43, 2876. J. Hedalen, Pulp. Paper Mag. Can. 1916, 14, 176;
Paper, 1916, IS, No. 17, 15; C. A. 1916. 10, 2403. M. Hedden. U. S. P.
1130817, 1915; abst. J. S. C. I. 1915, 34, 419; C. A. 1915, 9, 1115. E. Hen-
drick, Met. Chem. Eng. 1918, IS, 360; abst. Paper Makers Monthly J. 1918,
56, 136; Paper, 22, No. 4, 13. Hoesch & Co., E. P. 21994, 1911; F. P.
434943, 1911; Belg. P. 239604; Hung. P. Appl. 4348, 1911; abst. J. S. C. I.

1912, 31, 351, 696. H. Hofer, AUgem. Fischerei Ztg. 1908, U, 71. AUgem.
Fischerei Ztg. 1915, No. 20, 21; Pap. Ztg. 1916, 41, 1; C. A. 1916, IS, 1432.*
C. Hofmann, Pap. Ztg. 1896, 21, II, 2483. M. Honig, E. P. 18265, 1896;
abst. J. S. C. I. 1896, 15, 819. Russ. Privilegium, 953, 1898; abst. Chem.
Ztg. 1899, 23, 319. U. S. P. 727798, 1903; D. R. P. 132224, 1901; Aust.
P. 7325, 1901; Pap. Ztg. 1902, 27, II, 2162; Chem. Centr. 1902, 73, II, 174;
J. S. C. I. 1903, 22, 753. D. R. P. 152236; Aust. P. 12970, 1902; abst. Pap.
Ztg. 1903, 29, II, 2226; Wag. Jahr. 1904, 50, II, 514. Aust. P. 31862, 1906;
Add. to Aust. P. 7325. F. P. 413849, 1910; Aust. P. Appl. 3325, 1910,
Hung. P. Appl. 3806, 1910; Chem. Ztg. Rep. 1910, 34, 251; Zts. ang. Chem.
1910, 33, 499; J. S. C. I. 1910, 29, 1121. E. I*. 7066, 1910; abst. C. A. 1911,
5, 2989. D. R. P. Anm. H. 56968, 1912; Aust. Anm. A. 1511; Add. to Aust.
P. 43742. U. S. P. 1080970, 1913; abst. C. A. 1914, 8, 591. J. S. C. I. 1912;
31, 768; Chem. Ztg. 1912, 36, 880; C. A. 1912, 6, 3517; Paper, 1912, 9, No.
1, 29; Paper-Maker, Brit. Trade J. 1915, 497. W. Hoskins, U. S. P. 1226333.
1917; abst. C. A. 1917, 11, 2153; Pulp, Paper Mag. Can. 1917, 15, 741.
W. Hough, E. P. 19116, 1909; abst. C. A. 1911, 5, 1839. W. Hough, U. S.
P. 931608; abst. Pap. Ztg. 1909, 2787; Pulp, Paper Mag. Can. 1910, 8, 48.
H. Hurt, U. S. P. 1075916, 1913; 1147245, 1915; abst. C. A. 1913, 7, 4095;
1915, 9. 2465. J. S. C. I. 1913, 32, 1079; 1915, 34, 915; Paper Trade J.

1913, 58, 44. E. Hutchins, Paper, 1913, 13, No. 3. 17; No. 4, 15; No. 5, 17;
C. A. 1913, 7, 2855. International Association of Leather Trade Chemists,
Enke, Stuttgart, 1910, 1, 689; 1911, 3, 15. A. Jabs, D. R. P. 287015, 1912;abst.
J. S. C. I. 1916, 35, 103. F. Jedlica, Collegium, 1913, 489. A. Jemberg,
U. S. P. 1221058, 1917; abst. C. A. 1917, 11, 1750; J. S. C. I. 1917, 36, 561;
Pulp, Paper Mag. Can. 1917, 15, 719. F. Jurgensen, F. Niesz and G. Giim-
bel, D. R. P. 73718, 1892; abst. Ber. 1894, 27, 445. A. Katz, D. R. P.
149461, 1903; abst. Pap. Ztg. 1904, 29, I, 800; Wag. Jahr. 1904, 50, II, 533,
Kausch, Kunst. 1913, 3, 112, 127. H. Kayser, Wochenbl. Papfabr. 1908,
39, 2201. Pap. Ztg. 1910, 35, 768. D. Kerape, Aust. Privilegium 3962.
1897; Swed. P. 8422, 1897; abst. Chem. Ztg. 1898, 22, 26. F. Kcnnard.
U. S. P. 1138118, 1915; abst. C. A. 1915, 9, 1691; J. S. C. I. 1915, 34, 656;
J. Ind. Eng. Chem. 1915, 7, 1008. L. Kern, D. R. P. 278492, 1914; abst.
Pap. Ztg. 1914, 39, 2500; J. S. C. I. 1915, 34, 240. Wochenbl. Papfabr.

1915, 46, 278; C. A. 1915, 9, 1086. W. Kerp and P. Wohler, Pap. Ztg. 1913,
38, 3063; Arbeit. Kais. Gesundh. 32, 120. G. Kerschaw, Pulp, Paper Mag.
Can. 1915, 13, 111. Z. Kertesq, Chem. Ztg. 1916, 40, 945; abst. C. A. 1917,
12, 1040; Paper Maker and Brit. Trade J. 1917, 52, 36; Pulp, Paper Mag.
Can. 1917, 15, 236. 306; Paper Makers Monthly J. 1917, 55, 49; Paper,
1917, 19, No. 17, 15. P. Kestner, D. R. P. Anm. 46236, 1910. W. Kiby,
Chem. Ztg. 1910, 34, 1077. 1091; C. A. 1911, 5, 785; J. S. C. I. 1910. 29,
1265. Chem. Ztg. 1915, 39. 212, 261, 284, 350; abst. C. A. 1915, 9, 2311;

1916, )0, 116; Paper, 1915, 17, No. 15, 12. A. Kielmeyer, Farber Ztg. 1899,
34; abst. Wag. Jahr. 1899, 45, 972. E. Kirchner, Das Papier, 2, pt. B, C.
122, 126. I. Kitsee, U. S. P. 942207, 1909; abst. J. S. C. I. 1910, 29, 83;
C. A. 1910, 4, 668. A. Kjaer & Co., Nor. P. 276;i7, 1917; abst. C. A. 1917,
U, 1902; Pulp and Paper Mag. Can. 1917, 15, 741. P. Klason, Pap. Ztg.
1909, 34, I, 1315; Pap. Fabr. 1909. 7, 445; Zts. ang. Chem. 1909, 22, 1423.
Wochenbl. Papfabr. 1909, 40, 2668; Pap. Fabr. 1909, 7, 26, 671, 701, 795;
J. S. C. I. 1909, 28, 1000; Pap. Ztg. 1910, 35, 2116; Pulp, Paper Mag. Can.

CELlrULOSE 309

tion of silverware. For the manufacture of pyroxylin artificial

1910, 8, 185; Paper, 1911, 3, No. 2, p. Pap, Ztg. 1910, 35, 375, 451, 731.
Pap. Pabr. 1916, 14, 657, 739. Svensk Pap. Tid. 1916, 13, 115; 1917, 20,
176. Svensk Pap. Tid. 1917, 20, 176. P. Klason and Segerfeld, Svensk.
Kem. Tidskrift. Paper, 1914, 13, No. 18, 18; C. A. 1914. 8, 1345. A. Klein,
Pap. Ztg. 1909, 34, I, 227; Wochenbl. Papfabr. 1909, 40, 240. Papfabr.

1914, 12, 601, 639; abst. J. S. C. I. 1914, 33, 1201; Paper, 1914, 14, No. 22,
15; No. 23, 16; No. 24, 22; No. 25, 17. O. Knight, U. S. R 1143714, 1915;
abst. J. S. C. I. 1915, 34, 830; Paper Trade J. 1915, 61, No. 3, 50; Paper,

1915, 17, No. 2, 18. T. Knoesel, Pap. Ztg. 1898, 23, I, 1503. Wochenbl.
Papfabr. 1908. 39, 3276; 1909, 40, 4049; C. A. 1909, 3, 484, 1083. D. Landw.
Presse, 1902, No. 4; Chera. Ztg. 1902, 26, 229; Chem. Zentr. 1902, 73, I,
955; Pap. Ztg. 1903, 28, I, 288; J. S. C. I. 1902, 21, 489. Pap. Fabr. 1904,
2, 759; 1905, 3, 1914. D. Landw. Presse, 1902, No. 4, 63; 1905, No. 4, 13;
Chem. Ztg. 1902, 26, 329; 1903, 27, 21; 1904, 28, 38; Chem. Zentr. 1902,
73, I, 955; Pap. Ztg. 1903, 28, I, 288; 1905, 30, I, 1539; 1904, 29, II, 3367;
Wochenbl. Papfabr. 1905, 33; Pap. Fabr. 1904. 2, 759; 1905, 3, 1714; Chem.
Zts. 1905, 40; Zts. ang. Chem. 1904, 17, No. 47; Wochenbl. Papfabr. 1908,
38, II, 2542; F. P. 423562, 1910; abst. J. S. C. I. 1911, 30, 638. Pap.
Ztg. 1911, 36, 2193. Holzstoff Ztg. 1913, 20, 775. Zts. Sauerstoff Stick-
stoff Ind. 1912, 4, 65. A. Knopflmocher, E. P. 102608, 1916; abst. Paper
Makers Monthly J. 1917, 55, 259; J. S. C. I. 1917, 36, 589. R. Kolkwitz,
Wochenbl. Papierfabr. 1907, 38, 1998, 2289. Ber. Botan. Ges. 1912, 30, 9.
R. Kolkwitz and Pritzkow, Chem. Zentr. 1908, 79, II, 2048; Wochenbl.
Papfabr. 1908, 39, 332. Mitt. Prufungsamt. Wasser u Abwasser. 1909, 10,
173, 1116; abst. C. A. 1909, 3, 1661, 1662. J. Konig, Zts. Nahr. Genussm.
1913, 26, 273; Chem. Zentr. 1913, 84, II, 1700. U. S. P 1128154, 1915;
F. P. 469768, 1914; D. R. P. 284715, 1914; abst. C. A. 1916, 10, 76; J. S.
C. I. 1915, 34, 47, 299; Paper, 1914, 15, No. 22, 17. Nor. P. 26029, 1915;
Swed. P. 40438, 1916; abst. C. A. 1916, 10, 2045; Papir J. 1915, 3, 203.
Zts. Nahr. Genussm. 1916, 31, 171; abst. Papir J. 1916, 4, 187; Zts. ang.
Chem. 1916, 29, 379; C. A. 1916, 10, 3114; J. S. C. I. 1916, 35, 960. Zts.
ang. Chem. 1906, 19, 750. Chem. Ztg. 1887, 11, 1111. Pap. Ztg. 1887,
12, 770. Zts. ang. Chem. 1906, 19, 750. T. KorndorflF, D. R. P. 32696;
1886; abst. Pap. Ztg. 1886. 11, 1419. G. Krause. U. S. P. 1213887, 1917,
abst. J. S. C. I. 1917, 36, 329. H. Krause, Chem. Ind. 1906, 29, 217; Pap.
Ztg. 1907, 32, I, 1100; J. S. C. I. 1906, 25, 493. W. Krep and P. Wohler,
Arbeit. Kais. Gesundh. 1909, 23, 120; Chem. Zentr. 1909, 62, II, 710; Pap.
Fabr. 1909, 7, 45, 1135; Pap. Ztg. 1909, 34, 3286; 1910, 35, 1932; J. S. C. I.
1909, 28, 1001; C. A. 1910, 4, 443. E. Kressel, U. S. P. 1225825, 1917;
abst. C. A. 1917, 11, 2255; J. S. C. I. 1917, 36, 730. F. Kruger. Mon. Sci.
1905, 63, 801; Farben Ztg. 1906, 11, 237. A. Kuhn, Wbchenbl. Papfabr.

1916, 47, 2139, 2179, 2233, 2270; abst. J. S. C. I. 1917, 36, 639; Chem. Ztg.
Rep. 1917, 41, 148; Paper, 1917, 20, No. 24, 13; Pulp Paper Mag. Can. 1917,
15, 857, 1009. R. Kuhn, Pap. Ztg. 1895, 20, 1083, 1351, 1445. A. Kumpf-
miller, D. R. P. 203648, 1906; abst. C. A. 1909, 3, 714; J. S. C. I. 1908, 27,
1174. Aust P. 40657, 1906. D. R. P. 183415, 1905; abst. Wag. Jahr. 1907,
53, II, 503; Chem. Zentr. 1907. 78, II, 109; Wochenbl. Papfabr. 1907, 38,
1402; Pap. Ztg. 1907, 32, I, 2046; Chem. Ztg. Rep. 1907, 31, 243. D. R.
P. 203648, 1906; abst. Chem. Zentr. 1908, 79, II, 1834; Pap. Ztg. 1908, 33,
ri, 3564; Chem. Ztg. 1908, 32, 1036; Wochenbl. Papfabr. 1909, 40, 260;
J, S. C. I. 1908. 27, 1174; C. A. 1909, 3, 714. Aust. P. 40657, 1906. D.
R. P. 194872, 1906; abst. Chem. Zentr. 1908, 79, I, 118; Pap. Ztg. 1908,
33, I, 896; Chem. Ztg. Rep. 1908, 32, 255; Wochenbl. Papfabr. 1908, 39,
1306; J. S. C. I. 1908, 27, 562. D. R. P. 207776, 1906; abst. Pap. Fabr.
1909, 7, I, 293; Pap. Ztg. 1907, 32, I, 986; J. S. C. I. 1909, 28, 484; C. A.
1909, 3, 2072. D. R. P. 216284, 1907; abst. J. S. C. I. 1909, 28, 1324; Chem.

310 TECHNOU)GY OF CElrlrULOSE ESTERS

leathers and nitrocellulose waterproofing compositions, it is

Ztg. Rep. 1909, 33, 627; Pap. Ztg. 1909, 34, II, 3716; C. A. 1910, 4, 1114.
U. S. P. 939394, 1909; abst. C. A. 1910, 4, 527. Chem. Ztg. 1910, 34, 1352;
J. S. C. I. 1911, 30, 19; C. A. 1911, 5, 2944. D. R. P. 189177, 1904; abst.
Pap. Ztg. 1907, 32, II, 3356; Chem. Zentr. 1908, 79, I, 1118; Wochenbl.
Papfabr. 1907, 38, 3049; Wag. Jahr. 1907, S3, I, 8. Aust. P. 40657, 1906.
See D. R. P. 176722, 195286, 199279. A. Kumpfmiller and E. Schultgen,
D. R. P. 81388, 83438, 1894; abst. Ber. 1895, 28, 685; 1896, 28, 1030. Aust.
Privilegium, 5849, 1894. H. Landmark, Nor. P. 21848, 1911; Swed. P.
35500, 1911; Ledertechn. Rundschau, 1912, 4, 308; Pap. Ztg. 1911, 36, 3706;

1913, 3063; C. A. 1914, 8, 2278; Paper, 1913, 13, No. 11, 23. F. P. 474336,
1914; abst. J. S. C. I. 1915, 34, 1005. E. P. 7090, 1915; abst. J. S. C. I.
1916, 35, 372; C. A. 1916, 10, 2813. Tid. Kemi. Farm. Terapt 1916, 9,
No. 1, 2. F. P. 456871, 1913; Nor. P. 23673, 1912; abst. J. S. C. I. 1913,
32, 488, 1063; C. A. 1914, 8, 822; Papir J. 1913, 1, 15; Paper, 1914, 13, No.
18, 17. Nor. P. 24562, 1914; abst. Tidschrift, 1914, 4, 222; Papir J. 1914,
186. Papir J. 1914, 2, 63; Pulp Paper Mag. Can. 1914, 12, 267. Papier
Ztg. 1915, 40, 495, 519; Wochenbl. Papfabr. 1915, 46, 834; 843. Chem.
Ztg. 1915, 39, 98; J. S. C. I. 1915, 34, 275; C. A. 1915, 9, 2709; Paper, 1915,
16, No. 11. 18. U. S. P. 1236948, 1917; abst. C. A. 1917, 11, 2963; J. S.
C. I. 1917, 36, 1092. Papir J. 1916, 4, 279; Pulp and Paper Mag. Can.
1917, 15, 88, 101. Nor. P. 28147, 1917; abst. Papir. J. 1917. 5, 173. Lassar-
Cohn, Pap. Ztg. 1911, 36, 677. Chem. Ztg. 1914, 38, 657; abst. J. S. C. I.

1914, 33, 639; Paper, 1914, 14, No. 17, 23. D. R. P. Anm. 36157, 1913.
R. Laufman, Ledertechn. Rundschau, 1914, 6, Oct. 22; abst. Collegium,

1915, 106; J. S. C. I. 1915, 34, 501. Chem. Ztg. 1917, 41, 273, 286; abst.
J. S. C. I. 1916, 35, 563. A. and E. Lcderer, F. P. 464608, 1913; abst. J. S.
C. I. 1914, 33, 478. E. Lehmann, D. R. P. 128661, 1900. 169880. 1905;
abst. Pap. Ztg. 1906, 31, II, 2548. D. R. P. 282950, 282951, 1912;'Nor. P.
24561, 1913; abst. C. A. 1915, 9, 2590; J. S. C. I. 1915. 34, 656; Wochenbl.
Papfabr. 1915, 46, 1178; Pap. Fabr. 1915, 13, 314; Papir J. 1914, 2, 185.
C. Leisenberg, D. R. P. 37882, 1880; abst. Ber. 1887, 20, 30; Pap. Ztg. 1887,

12, 398. H. Leonhardt, D. R. P. 34420, 1885. K. Leschly-Hansen, Papir
J. 1917, 5. L. Lichtenstein, Chem. Ztg. Rep. 1912, 36, 658. Farber Ztg.
1913, 24, 442; Chem. Zentr. 1913, 84, II. 2181; C. A. 1914. 8, 2064. H.
Liese. E. P. 1832. 1911; abst. J. S. C. I. 1911, 30, 1441. Lindhardt, Zentr.
Oesterr-Ung. Paperind. 1905, 13; abst. Zts. ang. Chem. 1905, IS, 983. J.
Lindsey and B. ToUens, J. C. S. 1889. 55, 213; Ber. 1893. 26, 322; J. S. C.
I. 1892. 11, 835. Thesis. Gottingen 1891; Zts. ang. Chem. 1892. 5, 154;
J. S. C. I. 1893. 12, 287. A. Little. Pap. Fabr. 1907, 5, 649. E. Ljungbergl
Affars varlden, 1912, 133; Pap. Ztg. 1912, 36, 337. 490. K. Loffl. Seifenseder.
Ztg. 1915. 42, 431; abst. C. A. 1916, 10, 1443. K. Lorcntz. Seifensieder
Ztg. 1916. 43, 400, 501; Zts. ang. Chem. 1916. 29, 445; J. S. C. I. 1916. 35,
1163. F. Loveland. J. Amer. Leather Chem. Assoc. 1912, 7, 368; 1913. 8,
128; abst. J. S. C. I. 1913. 32, 373. O. Luhrs, D. R. P. Anm. L. 34995.
1912. A. Lucrssen, Zts. Hyg. 58, 121; abst. J. S. C. I. 1908. 27, 1220. J.
Luke. Nor. P. 20138, 1915; abst. Pap. Fabr. 1915, 3, 215. Mackay and
Miller. J. S. C. I. 190i). 28, 1183. R. McKee. Pulp, Paper Mag. Can. 1915,

13, 165. C. Marchand, U. S. P. 1155256. 1915; Can. P. 163400, 1915; abst.
C. A. 1915. 9, 2980, 3358; J. S. C. I. 1915. 34, 1087. Paper Trade J. 1916,
62, 201; Paper. 1916, 17, No. 23, 24. Maschinenbauanstalt Golzern. D. R.
P. 69892, 1893; abst. Ber. 1893. 26, 973; Pap. Ztg. 1893, 18, 1280. W.
Massot. Zts. ang. Chem. 1906, 19, 177. W. Mathcsius, Chem. Ztg. 1913.
37, 625. Matheus. Pap. Fabr. 1910, 8, 532; abst. Zts. ang. Chem. 1910.
23, 1584; Pap. Fabr. 1911. 9, 1407. 1435; abst. C. A. 1912, 6, 1365; J. S. C. I.
1911. 30, 1375, 1446; Pulp Paper Mag. Can. 1912, 10, 5*; Paper 1912, 6, No.
5, 16. R. McKcc, U. S, P. 1273392. 1918; abst. C. A. 1918, 12, 1926. C.

CELlrUIvOSe 311

not as essential that the cellulose-either in the form of a

Melhardt, D. R. P. 148275. 1903; abst. Pap. Ztg. 1904, 29, I, 574; Wag.
Jahr. 1904, 50, I, 6. H. Messow, D. R. P. 297075, 1915; abst. J. S. C. I.
1917, 3G, 873. L. Meunier, F. P. 466196, 1913; abst. J. S. C. I. 1914, 33,
604. A. Mitscherlich, D. R. P. 4178, 4179, 1878; 72161, 1891; E. P. 1668,
1882; 12927, 1893; abst. Ber. 1879. 12. 395; 1894, 27, 149; J. S. C. I. 1883,
2, 700; 1894, 13, 834; Pap. Ztg. 1893, IS, 3222; 1896, 21, 2349, 2850. Aust.
Privilegium, 112, 1894. E. P. 12566, 1884; 11372, 1890; abst. J. S. C. I.
1885, 4, 550; 1891, 10, 787. E. P. 1655, 1884; abst. J. S. C. I. 1885, 4, 549.
D. R. P. 72161, 1891; E. P. 12927, 1893. D. R. P. 72362, 1891; abst. Ber.

1894, 27, 221; Pap. Ztg. 1894, 19, 272. D. R. P. 82498, 1893; abst. Ber.

1895, 28, 869; Pap. Ztg. 1895, 20, II, 2716. Aust. Privilegium, 112, 1894.
D. R. P. 86651, 1895; Add. to D. R. P. 82498, 1893; abst. Ber. 1897, 29,
452; Pap. Ztg. 1895, 20, 466, 529; 1896, 2L II, 1848, 2349, 2850. D. R. P.
93944, 93945, 1896; abst. Pap. Ztg. 1897, 22, II, 3074, 3148; Chem. Centr.
1897, 68, II, 1126. D. R. P. 169408, 169409, 1904; abst. Pap. Ztg. 1906.
31, I, 1732; Wag. Jahr. 1906, 53, II, 546; Wochenbl. Papfabr. 1906, 37,
1847, 1848. Holzzellstoffabrikation 1907. 19. D. R. P. 4179, 1878; E. P.
1668. 1882. D. R. P. 41780 1878. 54206, 1890; Add. to 34420, 1885; abst.
Ber. 1891, 24, 343. D. R. P. 220066, 1908; abst. J. S. C. I. 1910, 29, 483.
235965. 1911; abst. Pap. Ztg. 1911, 36, 2077; Pap. Fabr. 1911, 9, 825; J. S.

C. I. 1911, 30, 1051. Pap. Ztg. 1896, 21, 2349, 2850. W. Moeller, Collegium,

1913, 489; 1914, 153, 319; abst. C. A. 1914, 8, 2082; J. S. C. I. 1914, 33, 365,
654; Ledertechn. Rundschau. 1910, 2, 73; Pulp Paper Mag. Can. 1914, 12,
468; Paper, 1914, 14, No. 19. 18. C. Monnet, Collegium, 1913, 224; abst.
Zts. ang. Chem. 1913, 31, 646; C. A. 1913, 7, 3856; J. S. C. I. 1913, 32, 616.
H. Moore and R. Wolf, U. S. P. 1103216, 1110454, 1914; abst. C. A. 1914,
8, 3119; J. S. C. I. 1914, 33, 859, 1006; Pulp Paper Mag. Can. 1914, 12,
470, 533; Paper, 1914, 15, No. 4, 22. E. Morterud, U. S. P. 833936, 1906;

D. R. P. 180168. 1905; Aust. P. 638, 1905; abst. C. A. 1907, 1, 2204; Wochenbl.
Papfabr. 1907, 38, 1056; Pap. Ztg. 1906, 31, II, 3819; 1907, 32, I, 296. M.
MuUer, Wochenbl. Papfabr. 1908. 39, 1484. D. R. P. 241282, 1910; abst.
C. A. 1912, 6, 2170; J. S. C. I. 1912, 31, 123; Wochenbl. Papfabr. 1911, 42,
4864. D. R. P. 262473, 1912. Wochenbl. Papfabr. 1914, 45, 2276,
abst. C. A. 1914. 8, 3119. P. Muller. E. P. 7324, 1913; abst. J. S. C.
I. 1914, 33, 478; Paper, 1914, 14, No. 13, 23. Belg. P. 255636, 1913. F.
Mullner, D. R. P. 96467, 1897; abst. Chem. Centr. 1897, 68, I, 1183; Pap.
Ztg. 1898, 23, 687, 1062, 1218. E. Murbe, Swed. P. 41542, 1916; abst.

C. A. 1917, 11, 535. D. R. P. 293394. 1914; abst. J. S. C. I. 1916, 35, 1106.

D. R. P. 297440, 1914; abst. J. S. C. I. 1917, 36, 870. Necas, Pulp Paper
Mag. Can. 1913, 11, 599; Paper 1913, 12, No. 10, 20. E. Nemethy, Zentr.
Oesterr-Ung. Papicrind, 19a3, No. 18; Pap. Ztg. 1904, 28, 1897. E. Nere-
sheimer. Die Wasserwirtschaft, 6, 2; Wasser Abwasser, 1914. 7, 408, C. A.

1914, 8, 1178. A. Nettl, Aust. Privilegium, 1576, 1888. D. R. P. 52491,
1889; abst. Ber. 1891. 24, 102. A. Nicolle, F. P. 425991, 1910; abst. J. S.
C. I. 1911, 30, 951. P. Nitsche, Wochen. J. amg. Chem. 1912, 43, 4045; abst.
Zts. ang. 'Chem. 1912, 25, 2058; C. A. 1913, 7, 528; J. S. C. I. 1912, 21, 1000.
T. Norton, J. S. C. I. 1911, 30, 1466; World's Paper Trade Rev. 56, 1236;
C. A. 1912, 6, 929. J. Novak, D. R. P. 74031, 1893; abst. Ber. 1898, 27,
474; Pap. Ztg. 1894, 19, 1196. Oesterreichischer Verein fur Cellulosefab-
rikation, D. R. P. 104359, 1898; abst. Chem. Centr. 1899, 70, II, 1077. Oes-
terreichischer Verein fur Celluldsefabrikation, D. R. P. 180768; abst. Pap.
Ztg. 1907, 32, I, 948. E. Oman, Svensk Pap. Tid. 1916, 19, 143. Tekn.
Tid. 1916, 46, 6; Pap. Fabr. 1916, 14, 256. 273, 291, 306, 485, 509. 584; J. S.
C. I. 1916, 35, 832; C. A. 1916, 10, 2637. Pap. Fabr. 1915. 13, 534, 553;
abst. Zts. ang. Chem. 1915, 28, 5(>4; J. S. C. I. 1916, 35, 172; C. A. 1916,
10, 3158, Chem. Ztg. 1915, 39, 820; abst. J. S. C. I. 1916, 38, 172; C. A.

312 TECHNOLOGY OF CELLULOSE ESTERS

cellulose as cotton, or a lignocellulose as wood pulp, should

1916, 10, 3158; Paper, 1916, 18, No. 1, 22. F. P. 481917, 1917; abst. pulp
Paper Mag. Can. 1917, 15, 1197. U. S. P. 1130192, 1915; E. P. 1145, 1914;
F. P. 467466, 1914; Can. P. 154165, 1914; abst. C. A. 1914, 8, 2805; 1915.
9, 1319, 1843; J. S. C. I. 1914, 33, 348; 1915, 34, 419; Pulp, Paper Mag. Can.

1914, 12, 282; Paper, 1914, 14, No. 8, 20; 1915, IS, No. 6, 19. E. P. 103649,
103650, 103651, 103652, 103653, 103654, 103655, 106493, 1917; abst. C. A.

1917, 12, 1749; Pulp Paper Mag. Can. 1917, 15, 719, 924. G. Onsager, E. P.
24738, 1913; abst. J. S. C. I. 1915, 34, 25; Chem. Trade J. 1915, 5S, 355;
Paper, 1914, 15, No. 21,21; 1915, IS, No. 7, 12. Opitz and Kayser, Wochenbl.
Papfabr. 1908, 39, 1299. C. Opl, D. R. P. 75351, 1893; abst. J. S. C. I.
1895, 14, 976. Paeszler, Chem. Ztg. 1906, 30, 1000; 1912, 36, 812; J. S. C.
I. 1912, 31, 736. Chem. Ztg. 1914, 38, 974; abst. J. S. C. I. 1915, 34, 189;
Paper Trade J. 1915, 01, No. 13, 50. J. Parker, Collegium, 1912, 611; Chem.
Ztg. 1913. 37, 6; C. A. 1914, 8, 839. E. Partington, Pap. Ztg. 1904, 29, II,
2686. F. Patch, Paper, 1914, 15, No. 11, 21. Phelps and McRae, J. S. C.
I. 1913, 32, 389. E. Phelps, The Paper Mill, 32, 19; Pap. Ztg. 1909, 34,
726. W. PhUippi, D. R. P. 195643, 1904; 211348, 1905; F. P. 369608, 1906;
abst. Chem. Zentr. 1908, 79, II, 1232; 1909, 80, II, 400; Pap. Ztg. 1908, 33,
I, 1210; 1909. 34, II, 2294; Wag. Jahr. 1908, 54, II, 557; J. S. C. I. 1907, 26,
106; C. A. 1909, 3, 2640. Aust. P. Anm. 1821, 1909; abst. Chem. Ztg. Rep.
1909, 33, 447. D. R. P. 254866, 1910; F. P. 448064, 1912; Pap.
Fabr. 1913, 11, 102; J. S. C, I. 1913, 32, 438, 439. R. Pictet,
D. R. P. 26331, 1883. R. Pictet and G. Brelaz, E. P. 9509. 1884;
abst. J. S. C. I. 1885, 4, 464. M. Platsch. D. R. P. 286210, 1911. U. S. P.
1054141, 1913; E. P. 19600, 1912; F. P. 447578, 1912; abst. J. S. C. I. 1913,
32, 284, 823; C. A. 1913, 7, 1415. Nor. P. 26028, 1915; abst. Papir J. 1915.
3, No. 15, 203. M. Platsch and Hoesch & Co., F. P. 455059, 1913; Norw.
P. 26296, 1915; abst. J. S. C. I. 1913, 32, 864; Pap. Ztg. 1914, 39, 1988; Papir
J. 1915. 3, 262. E. Pollacsek. Aust. Privilegium, 967, 1898, Aust. Privileghim,
967, 1524, 1898. Aust. Privilegium, 985, 1898. D. R. P. 264783, 1912;
266401, 1913. F. P. 462429, 1913; U. S. P. 1133499. 1915; Nor. P. 24349,
1914; abst. J. S. C. I. 1914. 33, 248. 746; 1915. 34, 488; C. A. 1915. 9, 1391;
Papir J. 1914, 2, 138; Tidskrift, 1914, 4, 191. Pap. Ztg. 1914. 39, 1616.
H. Polz, Pap. Ztg. 1913, 38, 3064; Wochenbl. Papierfabr. 1913, 44, 4611.
A. Pritzkow. Eng. Record, 1910. 62, 468; C. A. 1911, 5, 1144; Paper, 1912.
7, No. 1, 23. Mitt. Prufgsamt. Wasser. u Abwassrt. 1911. 119; Chem.
Zentr. 1911, 82, II, 1455. H. Proctor and S. Hirst, J. S. C. I. 1909, 28r
293; Zts. ang. Chem. 1909, 32, 1566; C. A. 1909, 2395. J. Puring,
U. S. P. 1185604, 1916; abst. C. A. 1916, 10, 1939; J. S. C. I. 1916, 35, 747.
A. Raaz, Farber Ztg. 1898, 9, 245; abst. J. S. C. I. 1898, 17, 923. W. Ramsay,
Zts. ang. Chem. 1906, 19, 833; Chem. Ztg. 1906, 30, I, 431. F. Raschig,
U. S. P. 1056366, 1056367, 1913; E. P. 2069. 11568, 29696, 1912; F. P. 440625,
447419, 1912; abst. J. S. C. I. 1913, 32, 454. 845. H. Reed, U. S. P. 1217218,
1917; abst. J. vS. C. I. 1917, 36, 503; C. A. 1917, U, 1545. A. Reilley, U. S.
Com. Repts. No. 276, Nov. 24, 1917, 755. B. Reinitzer, Pap. Ztg. 1911,
36, 2882, 2913; Zts. ang. Chem. 1911, 24, 1851; J. S. C. I. 1911,- 30, 1206;
Oesterr. Chem. Ztg. 15, 61; C. A. 1912, 6, 1480. P. Remy, D. R. P. 90798,
Pap. Ztg. 1897, 22, 426; J. S. C. I. 1897, 16, 630.' A. Richter, D. R. P. Anm.
R, 31311. 1910. D. R. P. 275832, 1910; abst. Pap. Ztg. 1914, 39, 2021;
J. S. C. I. 1914, 33, 1043. A. Richter and L. Dunbar, U. S. P. 1213414.
1213415. 1917; abst. C. A. 1917, 11, 888. E. Rinman, D. R. P. 269994,
1913; abst. J. S. C. I. 1914, 33, 346. Wochenbl. Papfabr. 1915, 46, 990;
Chem. Ztg. 1915, 39, 99; J. S. C. I. 1915. 34, 274; Pap. Ztg. 1915, 40, 559.
574; C. A. 1915, 9, 2709; Pai)er 1915, 16, No. 9, 11; Pulp, Paper Mag. Can.

1915, 13, 337. Nor. P. 2G603, 1914; Swed. P. 42108, 1917; Papir J. 1916,

CELLULOSE 313

be as thoroughly and exhautively purified, as some of nitro-

4, 47; C. A. 1917, 11, 2153; Pulp Paper Mag. Can. 1917, 15, 741. J. Robeson.
ErP. 17956. 1908; Aust. P. 42479, 1906; abst. Pap. Ztg. 1905, 30, I. 266;
C. A. 1910. 4, 669. U. S. P. 833634. 1906; E. P. 22887, 1906; abst. J. S. C.

I. 1906, 25, 1115; 1907, 26, 340; C. A. 1907. 1, 498. U. S. P. 851378. 851379,
851380, 851381. 1907; abst. J. S. C. I. 1907, 26, 634; C. A. 1907. 1, 1640.
E. P. 17956. 17957. 17958, 1908; U. S. P. 851378, 851379, 851380, 851381,
1909; Aust. P. 42479, 1909; Chem. Ztg. 1907, 31, 312; Pap. Ztg. 1910, 35,
300; J. S. C. I. 1909, 28, 1052. U. S. P. 947101, 1909; 947128, 1910; abst.
C. A. 1910, 4, 652. J. Robeson, Aust. P. 42479. Paper, 1911, 8, No. 9,
63. U. S. P. 1013614, 1912; D. R. P. 238119, 1907; Pap. Ztg. 1913, 38, 1221;
C. A. 1912, 6, 591, 1592. U. S. P. 1069031, 1913; abst. J. S. C. I. 1913,
32, 864. U. S. P. 1069029, 1069030, 1069031; 1075856, 1075857, 1913;
abst. J. S. C. I. 1913, 32, 864, 869, 1070. J. Rogers, Paper Trade Rev.
1904, 31, No. 12. P. Rohland, Farber. Ztg. 1913, 24, 401; Pap. Ztg. 1913,
38, 3522. Chem. Ztg. 1913, 37, 754. Biochem. Zts. 1912, 46, 374; abst.
J. S. C. I. 1912. 31, 1119. Zts. ang. Chem. 1913, 80, 174; Chem. Zentr.
1913, 84, I, 1858. Rosenblatt and M. Rosenband, Chem. Ztg. 1909, 33,
921. Rosenthal, Pap. Ztg. 1914, 39, 1007; Wochenbl. Papfabr. 1914, 45,
1847; Chem. Ztg. 1914, 38, 126. Sachs-Bankges, Quellmalz & Co., D. R.
P. 158497, 1906; 186652, 1907. E. Sandberg and G. Sundblad, E. P. 24125,
1912; abst. J. S. C. I. 1913, 32, 279; C. A. 1914. 8, 1346. A. Sander. Fort.
Chem. 1911, 4, 300. J. Saxl and L. Oberlander. D. R. P, 63042, 1891; abst.
Zts. ang. Chem. 1892, 5, 382. C. Schall, D. R. P. 194127, 194744, 194745.
196390, 197160, 197587, 201052, 202393. 204470. 206743, 206999, 207355,
208373; abst. Zts. ges. Wasserwirtsch, 1909. 9, 147. H. Schild, Pap. Ztg.
1900, 25, I, 1725; II, 1125. 2456; Jahr. Chem. 1900, 53, 15. J. Schlauf,
Paper Maker Brit. Trade J. 1911, 42, 55. A. Schmidt, U. S. P. 1136723,
1915; abst. C. A. 1915, 9, 1526. H. Schmidt, D. R. P. 86542, 1895; abst.
Ber. 1896, 29, 452. S. Schmidt-Nielsen, Papir J. 1916, 4, 17. H. Schnar-
mann, Pap. Ztg. 1897, 22, II, 3679. F. Schneider, Pap. Ztg. 1910, 35, 1902;
Zts. Hyg. 1907, 121; Pap. Fabr. 1909, 7, 34; Zts. ang. Chem. 1909, 22, 655.
Collegium, 1912, 678. F. Schneider and G. Graf, D. R. P. Anm. Sch. 36744,
1910; abst. Pap. Fabr. 1911. 9, 827. R. Schorr, Eng. Min. J. 1910, 88, 451;
C. A. 1910, 4, 1369. H. Schrieb, Pap. Ztg. 1888, 12, 1489; 1889, 14, 1576.
1875. Zts. ang. Chem. 1890, 3, 675. Pap. Ztg. 1906, 30, 1111; Zts. ang.
Chem. 1906, 19, 1302. Chem. Ztg. 1907, 31, 1133,-1157; abst. Zts. ang.
Chem. 1907, 20, 1986. F. Schulte. Ledertechn. Rundschau, 1914, 6, 129;
abst. C. A. 1914, 8, 2637; J. Amer. Leather Chem. Assoc. 1914, 9, 335. G.
Schutz, D. R. P. Anm. Sch. 39465, 1911. J. Schwager, Pap. Ztg. 1903, 28,

II, 2075, 2183. C. Schwalbe. Wochenbl. Papfabr. 1910, 41, 2354; Zts. ang.
Chem. 1910. 23, 1080, 1537; J. S. C. I. 1910, 29, 1052; Pap. Ztg. 1910, 35,
2004; C. A. 1911, 5, 196. Koll. Zts. 1909, 5, 129. C. Schwalbe and H.
Grim, Wochbl. Papfabr. 1913, 44. 3251; C. A. 1913, 7, 3837. J. Scott,
Paper Maker Brit. Trade J. 1914, 47, 395; abst. C. A. 1914, 8, 2620. Paper
Maker Brit. Trade J. 1911, 42, No. 3, 401; Wasser Abwasser, 1911, 4, 540.
B. Segerfeld, Pap. Ztg. 1910, 35, 2518, 2558. H. Seidel, Mitth. Tech. Gew.
Mus. 1897, 7, 119; abst. J. S. C. I. 1898, 17, 178. Zts. ang. Chem. 1900,
23, 1307; Pap. Ztg. 1900, 25, II. 3295; J. S. C. I. 1900, 19, 1033. Rev. gen.
mat. Col. 1898, 2, 370; abst. J. S. C. I. 1898, 17, 1048; Pap. Ztg. 1898, 23,
II, 2812; Chem. Ztg. 1898, 665. Farber Ztg. 1899, 10, 68. Mitt. Techn.
Gew. Mus. 1900, 10, 158; abst. J. S. C. I. 1900, 19, 896. H. Seidel and L.
Hanak, Mitt. Techn. Gew. Mus. 1898. 8, 337; abst. J. S. C. I. 1898. 17, 863.
H. Seidel and h. Hanak, Mitt. Techn. Gew. Mus. 1898, 8, 337; abst. J. S. C.
I. 1898, 17, 863. H. Seidel and J. Pollak, Farber Ztg. 1899, 10, 321; abst.
Wag. Jahr. 1899, 49, 972. W. Seoibritzki, Wochenbl. Papfabr. 1908. 39,
658, 2866; Chem. Ztg. Rep. 1908, 32, 221; J. S. C. I. 1908, 27, 466, 915;

314 TECHNOLOGY OP CELLULOSE ESTERS

cellulose used for lacquers and in the Tabrication of artificial

Pap. Ztg. 1908, 33, 872; C. A. 1908, 2, 484, 1885, 3463; Pulp, Paper Mag.
Can. 1908, 6, 257. Pap. Ztg. 1908, 33, I, 872; Wochenbl. Papfabr. 1908,
39, 2866; J. S. C. I. 1908, 27, 915; C. A. 1908, 2, 3403. Shelvin and Small,
U. S. P. 880247, 1908; abst. Chem. Ztg. Rep. 1908, 32, 347. E. Siebner,
Chem. Ztg. 1913, 37, 1057. Simonson, Swed. P. 28551, 1907. R. Sindall,
Paper Makers Monthly J. 1911, 39, 401; Pap. Ztg. 1912, 36, 300; Pulp Paper
Mag. Can. 1912, 10, 59. F. Small, J. Amer. Leather Chem. Assoc. 1913,
8, 62; Zts. ang. Chem. 1913, 26, 670. B, Smart, Swed. P. 31956, 1909;
abst. C. A. 1912, 6, 2316. L. Sody, Chem. Ztg. 1913, 37, 442; abst. Col-
legium, 1912, 529; J. Amer. Leather Chem. Assoc. 1912, 7, 373; J. S. C. I.

1912, 31, 737. SoUbrig, Pap. Fabr. 1907, 5, 5. K. Sorge and A. Weiskopf,
Chem. Ztg. 1913, 37, 7. H. Spatz, D. R. P. 159377, 1903; abst. Wag. Jahr.
1905, 51, I, 379; Pap. Ztg. 1905, 30, 1054. H. Spindler. Chem. Ztg. 1897,
21, 302. A. Splittgerber, Wasser u Gas. 1914, 243, 268, 290, 313; Wasser
Abwasser, 1914, 7, 24; C. A. 1915, 9, 376. D. Stewart, Aust. P. 40528,
1907; U. S. P. 909343, 1909; abst. Chem. Ztg. 1909, 33, 175. Stora Koppar-
bergs Aktiebolag, F. P. 402331, 1909; abst. J. S. C. I. 1909, 28, 1221;
Wochenbl. Papfabr. 1909, 40, 4265; Pap. Ztg. 1909. 43. 1682. D. R. P.
256964; abst. Pap. Ztg. 1913, 37, 768; Pap. Fabr. 1913, 11, 342; J. S. C. I.

1913, 32, 421; C. A. 1913, 7, 2472. R. Strehlenert, U. S. P. 1149420, 1915;
D. R. P. 266096, 1912; Can. P. 151445, 1913; Nor. P. 24140, 1912; Swed.
P. 34941, 1912; abst. C. A. 1914, 8, 572; J. S. C. I. 1913, 32, 1104; 1914,
34, 957; Paper, 1915, 17, No. 2, 19; Paper Trade J. 1916, 03, 64; Pap. Fabr.
1913, 9, 666. Pulp, Paper Mag. 1913, 11, 452; abst. C. A. 1913, 7, 3022.
vSvensk Kem. Tid. 1913, 25, 78; Pap. Fabr. 1913, 11, 645, 666; C. A. 1913,
7, 2471; J. S. C. I. 1913, 32, 652; Pulp, Paper Mag. Can. 1913, 11, 778; 1914,
12, 46; Paper, 1913, 12, No. 9, 18; Chem. Ztg. Rep. 1913, 37, 605; Wochenbl.
Papfabr. 1913, 44, 414,2. Pap. Ztg. 1914, 39, 414. Papir J. 1916, 4, 269;
abst. Pulp, Paper Mag. Can. 1917, 15, 88, 101; Papir J. 1917, 5, 14; abst.
Pulp, Paper Mag. Can. 1917, 15, 449. Paper Trade J. 1917, 45, 36; Paper
Makers Monthly J. 1917, 55, 284; Pulp Paper Mag. Can. 1917, 15, 1073.
J. I. E. C. 1916, 8, 1070. Nor. P. 27637, 1917; abst. Pulp, Paper Mag. Can.
1917, 15, 789. Svensk Pap. Tid. 1917, 20, 128, No. 12, 144; No. 13, 158.
Papir J. 1917, 5, 101; abst. Pulp, Paper Mag. Can. 1917. 15, 764. A. Stutzer,
W. Landw. Presse, 1902, 29, 725; Chem. Ztg. Rep. 1902, 20, 327; J. S. C. I.
1903, 22, 42. Chem. Ztg. 1910, 34, 1167; J. S. C. I. 1910, 29, 1370; Wochbl.
Papfabr. 1910, 41, 4148; C. A. 1911, 5, 1335. Pap. Ztg. 1911, 35, 5; Jahr.
Chem. Techn. 1913, II, 501. D. R. P. 215273, 1908; abst. Pap. Ztg. 1909,
34, II, 3758; Chem. Zentr. 1909, 80, II, 1783. Zts. ang. Chem. 1909, 22,
1999; abst. C. A. 1910, 4, 107; J. S. C. I. 1909, 28, 1162; Pap. Ztg. 1909,
34, II, 3210, 3251; Wochenbl. Papfabr. 1909, 40, 107. F. P. 402871, 1909;
abst. J. S. C. I. 1909, 28, 1323. Chem. Ztg. 1910, 34, 1352; abst. C. A.

1911, 5, 2946; J. S. C. I. 1911, 30, 18. D. Landw. Presse 1902, No. 63.
J. S. C. I. 1913, 32, 1165. Wochenbl. Papfabr. 1913, 42, 2685; Landw. Ztg.
1913, 02, 139; C. A. 1913, 7, 4037; Pulp, Paper Mag. Can. 1913, 11, 769;
Paper, 1913, 11, No. 8, 22. D. R. P. 256658, 1911; abst. Zts. ang. Chem.

1912, 25, 1752; J. S. C. I. 1912, 31, 871. Pap. Ztg. 1911, 30, 3450.
D. R. P. 236035, 1909; abst. Pap. Fabr. 1911, 9, 858; C. A. 1911, 5, 3622.
Pap. Ztg. 1911, 30, 3738; Wochenbl. Papfabr. 1911, 42, 4956; C. A. 1912,
0, 1850; J. S. C. I. 1912, 31, 121. D. R. P. 246658, 1911; abst. C. A. 1912,
0, 2529. Sudcnburger Maschinenfabrik u Eisengisserei, D. R. P. 219204,
266909, 1912. A. vSweinburg. Aust. P. 14423, 1902. J. Szamek, D. R. P.
130665, 1901; abst. Bicd. Chem. Tech. Jahr. 1901, 590; Chem. Centr. 1902,
73, I, 1082. H. Tartar, J. Ind. Eng. Chem. 1916, 8, 226; abst. J. S. C. I.
1916, 35, 483; C. A. 1916, 10, 1268; Paper. 1916, 17, No. 26, 14. A. Taver-
nier and C. Oulman, F. P. 359239, 1905; D. R. P. 186775, 1906; abst.

CEI.LULOSE 315

filaments, or for transparent thermoplastic celluloid compounds.

Wochenbl. Papfabr. 1907, 38, 3048; Chem. Zentr. 1907, 78, II, 1276; J. S.
C. I. 1906, 35, 365. F. P. 413152, 1910.; abst. J. S. C. I. 1910, 29, 1095. W.
Teas, U. S. P. 916057, 1909; abst. J. S. C. I. 1909, 28, 432. C. Thorne,
U. S. P. 1076078, 1912; D. R. P. 291854, 1913; Nor. P. 26445. 1915; abst.
C. A. 1917, 11, 1546; Papir J. 1916, 4, 22; Pulp Paper Mag. Can. 1917, 15,
677. Pulp Paper Mag. Can. 1916, 13, 173; abst. C. A. 1915, 9, 1390. B.
Tilghman, E. P. 2924, 1866; U. S. P. 70485, 1867; 92220, 1869. E. TiUberg,
Swed. P. 25283, 1907. E. Trainer, D. R. P. 130322, 140542, 140862, 144819.
161675; abst. Chem. Centr. 1902, 73, II, 410; Pap. Ztg. 1902, 27. II, 3478;
1903, 28, II, 1942, 3086; 1905, 30, II, 2582; Wag. Jahr. 1903, 49, 16, 162;
1905. 51, I, 19; Wochenbl. Papfabr. 1903. 34, 2658; Pap. Fabr. 1903, 1,419;

1905, 3, 1557. D. R. P. 239675, 1909; Zts. ang. Chem. 1912, 24, 2335;
C. A. 1912, 6, 2169. D. R. P. 181126, 1905; abst. Pap. Ztg. 1907, 32, 994;
Wochenbl. Papfabr. 1907, 38, 1307; J. S. C. I. 1907, 26, 1272. Pap. Fabr.

1907, 641. Pap. Ztg. 1907, 32, 994; Chem. Zentr. 1907, 78, II, 109. D. R.
P. 197195, 1906; Aust. P. 36847, 1908; abst. J. S. C. I. 1908, 27, 708; Chem.
Zentr. 1908, 79, I, 1595; Pap. Ztg. 1908. 33, I, 1516; Zts. ang. Chem. 1908,
21, 2539; C. A. 1908, 2, 2301. D. R. P. 202132, 1907; abst. Chem. Zentr.

1908, 79, II, 1389; Wochenbl. Papfabr. 1908, 39, 3238; J. S. C. I. 1908, 27, •
1173; C: A. 1909, 3, 491. D. R. P. 283931, 1911 ; abst. C. A. 1915, 9, 2591.
U. S. P. 974001, 1910; abst. J. S. C. I. 1910, 29, 1365. and W. Haage, U. S.

P. 969504, 1910; abst. J. S. C. I. 1910, 29, 1365. W. Trippe, E. P. 8088.
1901; abst. J. S. C. I. 1901, 20, 741. D. R. P. 133312, 1901; abst. Chem.
Centr. 1902, 73, II, 410. G. Turk. D. R. P. 115607, 1899; abst. Wag.
Jahr. 1900, 46, II, 530. H. Ullmann, Aust. Privilegium, 3043, 1890. F.
Ulzer and H. Seidel, Mitt. Techn. Gew. Mus. 1896, 6, 186. Voerkelius,
Wochenbl. Papfabr. 1911, 42, 853. J. Vogel, Zts. ang. Chem. 1906, 19,
748, 750; 1907, 20, 786; Wochenbl. Papfabr. 1907, 38, 780, 881, 958; Pap. ^
Ztg. 1906, 31, 1278, 1314, 1355; 1907, 32, 961, 1010, 1054, 1098; Chem.
Zentr. 1906, 77. I, 1853. Pulp Paper Mag. Can. 1907, 5, 142. Wochenbl.
Papfab. 1906, 37, 1612; Pap. Ztg. 1906, », 1278. 1314, 1355; J. S. C. I.

1906, 25, 555. Pap. Ztg. 1908, 33, II, 3855, 3890, 3931; Wochenbl. Papfabr.

1909, 40, 847. 930; Zts. ang. Chem. 1909, 22, 49; J. S. C. I. 1909, 28, 158;

C. A. 1909, 3, 1196; Pulp. Paper Mag. Can. 1909, 7, 289. Pap. Ztg. 1909,

34, I, 3; abst. Zts. ang. Chem. 1910. 23, 116; Chem. Ztg. 1909. 33, 1187.
Pap. Ztg. 1911. 35, 1547; abst. C. A. 1912. 6, 803. Pap. Fabr. 1911, 9,438;
abst. J. S. C. I. 1911, 30, 532; C. A. 1911, 5, 2520. K. Voitel. Rauch Staub.
1912. 2, 252; Wasser Abwasser 1913. 6, 144; C. A. 1913. 7, 692. B. Wagner.

D. R. P. 188428. 1906; abst. Pap. Ztg. 1907, 32, II, 3356; Wochenbl. Papfabr.

1907, 38, 3579; Wag. Jahr. 1907, 53, I, 10. W. Walker, J. S. C. I. 1913,
32, 389; Chem. Eng. 1913, 17, 246. J. S. C. I. 1913, 32, 389; Paper, 1913,
11, No. 9, 21. J.Wallin. D.R. P. 246708, 1908; abst. C. A. 1912.2569. Nor. P.
18687, 1908; abst. Chem. Ztg. Rep. 1909, 33, 251; Pap. Ztg. 1910, 35,
No. 16; Chem. Zentr. 1912. 83, I. 1871; Pulp Paper Mag. Can. 1912. 10,
358. Pap. Ztg. 1910. 35, 1588, 2519; Wochenbl. Papfabr. 1909. 40, 4253.
Pap. Ztg. 1912. 36, 1283. Pulp Paper Mag. Can. 1913. 11, 526. J. Walsh.
U. S. P. 1178979, 1916; abst. J. S. C. I. 1916. 35, 636. R. von Walther,
D. R. P. 262468, 1912; abst. J. vS. C. I. 1913, 32, 827. M. Webster, Pap.
Ztg. 1889, 14, 1312. A. Wegelin. Akt. Gcs. f. Russfabrikation. F. P. 474819.
1914; abst. J. S. C. I. 1915. 34, 1118. F. Weld. J. Lindsey. W. Schnelle and
B. Tollen.s. Ber. 1890. 23, 2990; ab.st. J. vS. C. I. 1891, 10, 156. R. Weldert.
Gesund. Ing. 1909. 32, 72.3; Chem. Ztg. Rep. 190^). 33, 617; Pap. Ztg. 1910.

35, 300. F. Wellensick. D. R. P. 266998, 1913; abst. J. S. C. I. 1914, 33,
39. J. Welsh, U. S. P. 1175853; abst. Paper, 1916, 18, No. 2, 14. E. Wer-
necke, D. R. P. 201372. 1907. H. Wichelhaus. Chem. Ind. 1895. 18, 51;
Pap. Ztg. 1895, 20, 1180; Chem. Ztg. 1895, 19, 40. H. Winter, Ledertechn.

316 TECHNOI/)GY OF CELLULOSH ESTERS

As S. Wells and V. Edwardes have pointed oiit,^ the woods of
the deciduous trees are considerably inferior to those from con-
iferous trees as raw materials for the manufacture of cellulose
suitable for nitration. The inferiority is based mainly on the
high percentage of pentosans in the cellulose and on the extreme
shortness of the fibers of the former group. In the manufacture
of wood cellulose the most difficult point to meet in the specifica-
tion is that which requires a solubility in 10% potassium hydrox-
ide solution not exceeding 7%. Soda wood pulp manufactured
from jack pine in the imbleached condition, prepared by rapid
digestion by severe treatment, came within the limits of specifi-
cation, but after bleaching, the amount of matter soluble in caustic
alkali was increased to an abnormal extent, so that the specifica-
tion could not be met when more than 5% of bleaching powder
was employed. That amount, however, is quite inadequate for
bleaching a soda wood pulp, so that the authors recommend the
use of soda pulp only in the unbleached condition, and consider
the caramelized brown coloring matters as probably innocuous
for explosives manufacture. Sulfite pulp, on the other hand,
does not form products soluble in caustic alkali as the result of
moderate bleaching, but it contains a large amount of such mat-
ters originally. By digesting sulfite pulp with* weak caustic soda
under mild conditions, matters soluble in alkali are removed, but
the pulp suflFers a loss of about 25% in weight. Sulfite pulp so
treated is suflftciently piu"e to pass the nitration tests without
bleaching, but if a good color be required it may be bleached
satisfactorily with 4% of bleaching powder. Batches both of
soda pulp and piuified sulfite pulp in the form of craped sheets
have been submitted to nitration with distinctly satisfactory re-
sults. The sheets nitrated evenly, yielding products with high
solubility in ether-alcohol, and a high nitrogen content. The

Rundschau. 1913, 5, 161; abst. Zts. ang. Chem. 1913, 26, 646. A. Winthol,
D. R. P. 287016, 1913; abst. J. S. C. I. 1916, 35, 103. F. Wolesky, Pap.
Ztg. 1914, 39, 1008. L. Woodrop. U. S. P. 1221259, 1917; abst. J. S. C. I.
1917, 38, 540. J. Yocum and A. Faust, J. Amer. lyeather Chem. Assoc., 1911,
6, 537; J. S. C. I. 1912, 31, 36; Collegium, 1912. 227; Chem. Ztg. 1913, 37,
115. Zawadski and Meyer, D. R. P. 45951, 1888; Aust. Privilegium, 1210,
1889; abst. Ber. 1889, 22, 75. A. Ziegler, D. R. P. 105669, 1897; abst.
Chem. Ztg. 1900, 25, I, 154.

1. Paper, 1919, 23, 180; abst. J. S. C. I. 1919. 38, 603-A; C. A. 1919,
13, 3012.

CEi.i.uu)S« 317

sulfite pulp gave a little trouble in the wringers on account of
the clogging of the holes. The nitrocellulose from the wood
pulp occupied more space in the boiling tubs than that from
cotton but it was ground in half the time in the hollanders. The
wood pulp product was not so easily dehydrated as that from
cotton. It was less viscous than nitro-cotton and a saving of
10% in solvent was recorded. Yields of nitrocellulose from wood
pulp in the laboratory showed 150%, as compared with 160%-
165% from cotton. ^

W. Baker* has called attention to the fact that waxy and
resinous impurities present in wood pulp tend to form yellow
compounds on nitration which have an adverse influence on the sta-
bility. The yellow compounds are partly eliminated by prolonged
boiling with water, preferably with the addition of a little sodium
carbonate. The presence of hydrocellulose or oxycellulose in the
wood pulp is also highly deleterious from the point of view of

1. As a result of the investigation, material that met the specifica-
tions for cotton was thus obtained from both soda and sulfite pulps. Fifty
pound batches, together with one of sulfate pulp, were sent to the Picatinny
Arsenal, where the nitrating investigations on wood pulp are being conducted
by the Ordnance Department. Runs were made using the factory nitrating
apparatus with acid mixtures found by the Arsenal stafif to be very success-
ful with wood pulp and the product carried through the regular steps used
in the plant and run into powder of several calibers.

Contrary to expectations, the soda and treated sulfite sheets nitrated very
evenly with a high solubility in ether-alcohol and a high nitrogen content.
The solubility of the sulfate pulp was not so good but it seems probable that,
with a few trials, this fault can be remedied.

The soda and sulfate pulps wrung easily, but trouble to some extent
was experienced with the sulfite on account of plugging of the holes of the
wringer.

In the boiling tubs the weight of the nitrocellulose contents were re-
duced by 40% on account of the greater volume taken by wood pulp over
that of an equal weight of cotton.

In the pulping operation, however, wood pulp was reduced in half the
time taken for cotton with a corresponding decrease in power and increase
in capacity.

The poaching treatment was also cut in half, due to the greater acces-
sibility of the interior of the fiber canals of wood pulp to water in comparison
with the very fine canals of cotton.

It was found to take longer in the wringers to wring wood pulp to the
same moisture content, probably due to the relatively larger volume of the
fiber canals.

More time or pressure also was necessary in the dehydrating presses.

In mixing, wood pulp was found to be less viscous and a saving of 10%
in solvent was possible.

In the graining presses no difference was noticeable except that due to
the difference in viscosity.

2. ^p and Paper Ind. 1918, 45.

318 TECHNOIvOGY OF CElrlrUI^OSE ESTERS

Stability, and the products of the chlorine bleach are very detri-
mental. The mineral constituents of the pulp, especially the
silica, should be reduced to a minimum. Vegetable wax and
resins present a resistance to the uniform penetration of the
nitrating acids which is inimical to successful nitration; for this
reason the ether-extract of the cellulose should not exceed 0.4%.
The physical condition of the cellulose is of the greatest impor-
tance; the texture and length of fibers should be as uniform as
possible. The yield of nitrated product is considerably reduced
by the presence of modified cellulose which is soluble in the
acids. For this reason bleached soda pulp gives results greatly
inferior to sulfite pulp. The suitability of a pulp from this point
of view may be determined by the loss of weight when boiled
with a 10% solution of potassium hydroxide. Samples of wood
pulp specially manufactured in Germany for the preparation of
explosives have been examined and nitrated on the large scale,
and the nitrocellulose obtained was in every respect equal to sim-
ilar products prepared from cotton.

C. Schwalbe and A. Schrimpff ^ have examined a variety of
wood celluloses — Mitscherlich cellulose, Ritter-Kellner cellulose,
soda cellulose, aspen cellulose — were compared with paper and
cotton wool as regards suitability for making guncotton. The
chemical properties before nitration were determined. After
nitration, solubility, stability, nitrogen content, etc., were esti-
mated. All the wood celluloses yielded stable nitro products,
but the nitrogen contents were lower, solubilities higher, yields
lower, and nitric acid consumption higher than with cotton
wool under the same conditions. To obtain the same nitrogen
content a stronger nitric acid is necessary. Specifications for cel-
luloses for nitration should include limits for moisture, ash, por-
tion soluble in alcohol and ether, lignin, oxycellulose. Absence of
chlorine compounds and a good absorptive power for nitrating
acids are prescribed.

They have also^ made comparative nitration experiments
with cotton and a series of typical wood celluloses. The com-
mercial wood pulps were transformed into thin sheets of paper,

1. Zts. Schiess. Sprcngst. 1919, 14, 41; abst. Chem. Zentr. 1919. 90,
II. 622; J. S. C. I. 1919, 38, 55r)-A.

2. Zts. ang. Chem. 1914, 27, 662; abst. J. S. C. I. 1915, 34, 152; C. A.
1915, 9, 715. See also O. Witt, Chem. Ztg. 1914. 38, 120.

CBLLULOSE 319

m

which were dried at 95 '^-100° before nitration. The highest
nitrate obtained from cotton contained 13.46% N, the highest
from wood cellulose 13.34%. It was found possible to prepare
from wood pulp a nitrocellulose with a solubility of 5%-6% in
ether-alcohol. Stabilization by digestion with water imder pres-
sure produced a change in the constitution of the nitrocellulose
such that its solubility in ether-alcohol was materially increased;
the ordinary technical method of stabilization was therefore
adopted. No difficulty was experienced in removing the unstable
products from the nitrocelluloses prepared from wood pulp; after
suitable treatment these gave results conforming with the official
specification by Bergmann and Junk's test, and were at least as
stable as the cotton nitrocelluloses. In the nitration of thin paper,
success depends on the structure of the latter: overbeaten fibers
give bad results. In pulping nitrocotton, traces of copper,
amounting in some cases to 0.050%-0.058%, may be absorbed
from the beater-knives, but without appreciable effect upon the
stability test. In celluloid manufacture, the product is some-
times bleached after nitration and pulping; this operation was
found to eliminate unnitrated cellulose and had a slight effect
on the nitrogen-content, varying in either direction according to
the origin of the material. Unstable sulfuric esters can be elim-
inated by boiling with dilute acid; 1% hydrochloric acid gave
better results than dilute sulfuric acid, causing no decomposition
of the nitrocellulose, and leaving a product of lower solubility and
somewhat greater stability.

K. NitzelnadeP has prepared nitrocellulose from various sam-
ples of sulfite wood pulp, bleached and unbleached, also from
straw cellulose. These materials contain higher proportions of
non-cellulose impurities than the cotton ordinarily employed in
the nitrocellulose industry; straw pulp also possesses the disad-
vantage of not being readily wetted by liquids. The nitration
experiments showed that sulfite wood pulp yields products con-
taining at least as much nitrogen as those prepared from cotton;
the products from straw cellulose were generally rather poorer in
nitrogen. The solubility in ether-alcohol of the nitrocellulose

1. Wochenbl. Papierfabr. 1912, 43, 3488; abst. J. S. C. I. 1912. 31,
954; Zts. Schiess Spreng. 1912, 7, 257, 301, 339, 3^, 409; abst. C. A. 1913,
7, 257, 892; J. S. C. I. 1912, 31, 954; Chem. Zentr. 1912, 83, II, 157; Chem.
Tech. Rep. 1912, 36, 507; Wag. Jahr. 1912, 58, 1, 438.

320 TECHNOLOGY OF CBLLULrOSE ESTERS

prepared from these celluloses was generally over 40%; in one
case only was it as low as 13%. The films obtained on evapor-
ating the solutions were inferior to those from solutions of nitrated
cotton. The stability tests, performed according to Will's method,
showed that these nitrocelluloses were sufficiently stable to sat-
isfy official specifications; the products from straw cellulose showed
the lowest stability. The ignition temperature, according to
Kast's test, was in general somewhat lower than for nitrated
cotton, but all the nitrocelluloses prepared from wood fiber showed
temperatures of ignition well above the specified minimum limit
of 180°; the products from straw cellulose tended to fall below
this limit. The yields of nitrocellulose from sulfite wood pulp
were lower than those obtained from cotton; straw cellulose gave
the lowest yields. The author's conclusions are in favor of the
use of wood cellulose as a raw material in the nitrocellulose in-
dustries, but he considers straw cellulose unsuitable. The disad-
vantages of wood cellulose, as compared with cotton, are the lower
3aelds, the lower ignition temperature of the products and the
greater solubility in ether-alcohol. Commenting on the above,
Klemm points out that one of the chief difficulties in preparing
nitrated derivatives from wood cellulose lies in the different struc-
ture of the cells of the spring and autumn growths, and it is pos-
sible that woods grown in tropical regions would afford more uni-
form results under chemical treatments.

In the process of W. v. Ruckteschell,^ wood fiber is boiled
with potash and with dilute nitric acid, and after drying is then
considered in proper condition for nitration. The Zellsto£fabrik
Waldhof^ purify lignin by treatment with calcium sulfite solu-
tion, bleaching with calcium hypochlorite, washing with dilute
caustic potash solution and purifying with alcohol. The last
treatment, although it is said to leave the lignin practically resin-
free, is unduly expensive.

In another more recent method,' wood in any form is first
treated with Schweizer's reagent, then with liquid ammonia,

1. E. P. 4349, 1886. The product is chiefly for use in actuating the
gas engine described in E- P. 15475, 1885.

2. D. R. P. 64878; abst. Wag. Jahr. 1892, 38, 371; Ber. 1893, 26, 78;
Zts. ang. Chem. 1892, 5, 706.

3. D. Whitehead and Q. Marino, E. P. 20143, 1905; abst. J. S. C. I.
1906, 25, 1052; Chem. Zts. 1906, 5, 572.

CEI.I.ULOSB 321

being finally washed free from alkali with water and dried.
For bleaching the lignin, treatment with SO2 gas is specified. P.
Girard^ eliminates resins, gums and other non-cellulose products
in wood by extracting the wood pulp in the .disintegrated or sheet
form with a volatile solvent which, while not attacking the lignin
portion, readily dissolves the resins. Solvents specified as suit-
able are alcohols, acetone, carbon tetrachloride and the chlori-
nated derivatives of ethylene and ethane. The solvents are
preferably employed in conjunction with 5%-10% of commercial
aqueous formaldehyde. The essence of the C. Classen process*
is to first dry the wood pulp, which is then rolled up tightly or
compressed, and the products then comminuted in a wood-work-
ing machine. In this manner, it is alleged, an entirely uniform
product especially suitable for esterification is obtained.

In the nitration of wood cellulose to a product especially
applicable for the manufacture of celluloid, K. Schonlau' takes
wood cellulose, manufactured either by the sulfite or sulfate pro-
cesses, which is first bleached and then treated in a beating engine
with a mixture of water and oil of turpentine to remove the res-
ins and other incrusting matters. The cellulose is then made
into a cellulose wadding formed of thin layers, which is dried at
a moderate temperature and is then suitable for nitration.

V. Edwardes* has described a process whereby vegetable
fibrous materials such as wood-chips are treated with acid sulfite
liquor, the fibrous material being separated from the liquor and
treated with a 0.5%-2% solution of NaOH under a pressure of
at least ten pounds per square inch, and at a temperature of at
least 115°. In this manner, it is claimed, a cellulose especially
suitable for nitration is obtained.

W. Baker^ has called attention to the fact that substances
foreign to normal cellulose are undesirable in cellulose for con-
version into cellulose nitrates because of their interference with
(1) the stability of the resulting nitrate, (2) the adaptability to
a specific use and (3) the yield of finished products. The stability

1. F. P. 443897, 1912; abst. J. S. C. I. 1912, », 1120; Kunst. 1913,
3, 15.

2. Swiss P. 71591, 1916; abst. C. A. 1916, 10, 1791.

3. F. P. 469484, 1914; abst. J. S. C. I. 1915, 34, 24.

4. ^U. S. P. 1310694, 1919; abst. C. A. 1919. 13, 2443.

5. Tech. Assoc. Pulp and Paper Ind. 1918, 45; abst. C. A. 1919, 13,
3012.

322 TECHNOU)GY OF CELLULOSE ESTERS

of the resulting nitrates is decreased by the presence in the cellu-
lose of vegetable waxes and resinous substances, hydro- and oxy-
cellulose, lignins^ and bleach residues. Vegetable wax and res-
ins and intercellular matter interfere with the successful nitration
of the cellulose by the present rapid processes of nitration, due
to the fact that the absorption of the nitrating acids is retarded
and the uniformity of the nitration is interfered with. The phys-
ical condition of the cellulose also exerts an influence upon the
resulting nitrocellulose as well as upon the success of the process
of nitration.

H. Schwarz has described^ experiments made in Germany on
the use of wood cellulose which showed that conifer woods, coji-
taining on the average 0.4% to 0.5% of ash and about 8% to
10% ofwater, are the most suitable for this purpose, while soft
woods, such as poplar and beech, yield inferior products. In pre-
paring the wood the outer bark, dirt, etc., are removed, and the
wood cut into sections about 1 m. long and 5 cm. thick, and
these are shredded, while the harder parts (knots) are ground in
a mill. The soda process gives a product which dissolves to
some extent in the subsequent acid treatment, and is difiicult to
bleach, but, apart, from the lower yield, the cellulose obtained
by this process does not differ materially from that obtained by
the sulfite-cellulose process.

The Ritter-Kellner method of direct boiling proved cheaper
and yielded a cellulose which was softer and absorbed acid more
readily than the product obtained by the Mitscherlich sulfite
process. It was specified that suitable wood cellulose should
weigh from 18 to 22 gm. per sq. m., should be in flocks of 5 to 10
cm. in size, free from small particles, dust, knots, and vegetable
impurities. It should absorb acids readily (35 to 40 mins. per
charge), and should be white and free from bleaching agent
(chlorine).

The permissible limit for ash was fixed at 0.6%; fat and rosin,
0.5%; water, 6%; and wood gum (alkali-soluble constituent of
cellulose), 2.5%. When nitrated it should not become pasty, and
must not become more than pale yellow (not brown). It should
be free from lignin. Cellulose and cellulose wool intended for

1. Oesterr. Chem. Ztg. 1919, 22, 50, 57; abst. T. S. C. I. 1919,
a02-A.

c^i,i,ui,osE 323

the mantif acture of smokeless powder must have been made from
well-seasoned wood and be free from knots. After boiling and
washing the unbleached cellulose should give, at most, a slight
rose coloration in the phloroglucinol test. It should be bleached
in the cold with a not too concentrated solution, washed, and dried
at a temperature not exceeding 110°-120°. In 1915-1916 cel-
lulose wool was only used as a partial substitute for cotton wool,
but subsequently it was used alone.

Nitrated wood cellulose is usually chemically purer than cot-
ton celltilose. It consumes somewhat less acid in nitration, and
there is less risk of ignition. The opening of the compressed balls
in the powder factory is more readily effected, and with less loss
(dust) than in the case of the cotton product. It is also dried
more rapidly, and there is less loss in washing the nitrocellulose,
while the last traces of absorbed acid are removed more easily.
On the other hand, wood cellulose is more voluminous than cotton
cellulose, so that the nitration charge is reduced by about 10%.
The adherent (as distinguished from the absorbed) acid requires
longer washing to remove, and the absorptive capacity for acid
is less than with cotton cellulose. On the whole, according to
Schwartz, the advantages outweigh the disadvantages.

Nitrated wood pulp forms a separate topic in this volume
called **Nitro-lignin,** where are described the various methods
for nitration of lignocellulose and the industrial applications of
the nitrated lignocelluloses.

According to the patented process of W. Stevenson,^ bleached
sulfite wood pulp is used as the cellulose basis in the manufacture
of acetylcellulose. A mixture of sulfite cellulose, 1 part; glacial
acetic acid, 2.8; acetic anhydride, 4.0, and zinc chloride, 0.2 part,
is digested at 60°-70° C. for 7-8 hours. ^

In the writer's hands, acetated lignin is not a satisfactory
product for the replacement of acetated tissue paper for aeroplane
dopes, or more especially for the uninflammable continuous

1. E. P. 13e029, 1917; abst. J. S. C. I. 1919, 3S, 714-A.

2. According to the patent specification, zinc chloride is employed as
catalyst, the acetylating bath being composed of, 1 k. bleached sulfite paper
pulp, 2.8 k. glacial acetic acid, 4. k. acetic anhydride (strength not stated),
and 200 gm. zinc chloride. These are thoroughly mixed and allowed to stand
at 60**-70°. "I thus obtain my precipitate, which is thoroughly washed
and dried in a temperattu'e of 100°-120°. The precipitate is easily dissolved
in pure acetone to form a transparent solution."

324 TECHNOlrOGY Olf CElrLUU)SE ESTERS

photographic films. In tensile strength, tenuity and viscosity of
solutions it is decidedly inferior to acetated filter paper. The
clarity and solubility of acetated lignocellulose is satisfactory.
The acetated celluloses are described in Volume VIII of this series.
Cellulose Carbamates. Recently there has been brought to
the attention of chemists an apparently new class of cellulose
derivatives. For some time it has been known that alcohols
and phenols act upon the aliphatic or aromatic isocyanates, there-
by producing esters of the alkyl- or aryl-carbamic acids.

^N — R^ /NHR^

R — OH + CC = O = C<

% \OR

P. Goissedet^ has found that this reaction can be applied to
cellulose and to its derivatives containing hydroxyl radicals.
When, for instance, phenyl isocyanate is allowed to act upon
cellulose in the presence of tertiary bases the cellulose is trans-
formed into phenyl carbamic esters, which the patentee claims
can be applied to the same uses as the cellulose esters.

This product may be prepared by heating together one part
of dried cotton with 3 parts of phenyl isocyanate diluted with
dry pyridine, the amount of pyridine employed being about G
times the weight of the cellulose us^d. The mass is stirred at
about 120° for from 12 to 24 hours, during which time the cotton
fibers gradually disappear leaving a colloidal solution from which
the insoluble cellulose phenyl carbamic ester is precipitated by
water. At the same time small amounts of diphenyl urea are
formed which are separated from the ester by a solvent for tlie
diphenyl urea, as petroleum ether.

The ratio of pyridine to cellulose may vary within compar-
atively wide limits. The former apparently aids in the reaction
in addition to acting as a desirable diluent. Due to the fact
that the process may be carried out in the presence of tertiary
bases either singly or intermixed, products may be obtained having
a wide range of solubility in the usual cellulose ester solvents.
In general, the longer the esterifying materials are allowed to
act upon the cellulose, the greater is the solubility in a given
solvent or solvent mixture.

Cellulose derivatives of sulfinic acid have been described by

1. E. P. 130277, 1919.

CBLI<UU)SE 325

»
Knoll & Co.^ and are obtained by bringing cellulose, hydro-
cellulose or oxycellulose in contact with sulfinic acid and organic
anhydrides. In the presence of the necessary amounts of suit-
able solvents, the cellulose goes into solution in the form either
of sulfur-contained or sulfur-free cellulose derivatives.

Animal Celluloses. Compounds of the aggregate compo-
sition of cotton cellulose have been described, resulting from the
isolation of certain bodies from the mantle of Ascidia and other
invertebrates by extended hydrol)rtic treatment. Such residues
have been investigated by C. Schmidt,* M. Berthelot,' Schaefer,*
C. Loewig and A. Koelliker,'^ and A. Franchimont,' from which

1. D. R. P. 180666, 1905; abst. Chem. Centr. 1907, 78, I, 773.

2. Ann. 1846, 54, 318; J. prakt. Chem. 1846, 38, 433. This product
was discovered by Schmidt in 1846, and distinguished from cellulose and
named "timicin" by Berthelot.

3. Compt. rend. 1858, 47, 227; Ann. Chim. Phys. 1859, 56, 149; Rep.
Chim. Pure, 1859, 1, 69; J. prakt. Chem. 1859, 7$, 371; Pharm. Centr. 1858,
29, 675. M. Berthelot and G. Andre, Compt. rend. 1890, HO, 925; abst.
Chem. News, 1890, tt, 253; J. C. S. 1890, 58, 937; Bull. Soc. Chim. 1890, 4,
230; Jahr. Chem. 1890, 43, 284. See also R. Schiitze, Mitth. pharm. Inst.
Erlangen, 1889, 2, 280; abst. Chem. Centr. 1889, €0, II, 588; Jahr. Tierchem.

15, 328. A. Franchimont, Compt. rend. 1879. 89, 711, 713, 765; Ber. 1879,
12, 1938; abst. Chem. News, 1879, 40, 264; J. C. S. 1880, 38, 233; Jahr. Chem.
1879, 32, 832; Fuerth, Vergl. Chem. Physiol, d. nied. Tiere, 1903, 467.

4. Ann. 1871. 160, 312; abst. Chem. News, 1872, 25, 107; J. C. S.
1872, 25, 309; Bull. Soc. Chim. 1872, 17, 371; Jahr. Chem. 1871, 24, 789.
See Dumas. Edwards, Boussingault and Payen, Compt. rend. 1846, 22, 581;
Ann. Sci. nat. 1846, 238. Schlossberger, J. prakt. Chem. 1858, 73, 374.

5. J. prakt. Chem. 1846, 37, 439; Compt. rend. 1846, 22, 38; abst.
Annuaire de Chim. 1847, 3, 694; Ann. Sci. nat. (3), 5, 193; Berz. Jahr. Chem.
1848, 27, 685. E. Schulze, Zts. physiol. Chem. 1892, 16, 387, 427; abst.
J. C. S. 1892, 62, 907; J. S. C. I. 1892, 11, 49; Bull. Soc. Chim. 1892, 8, 491;
Ber. 1892, 25, R, 434; Chem. Centr. 1892, 63, I, 700; Chem. Ztg. Rep. 1892,

16, 215; Jahr. Chem. 1891, 44, 2208; 1892, 45, 2138; Ber. 1891, 24, 2277;
abst. Chem. Centr. 1891, 62, 11, 472. R. Gans and B. ToUens, Ann. 1888,
249, 218; abst. J. S. C. I. 1888, 7, 595; Bull. Soc. Chim. 1889, 1, 746; Ber.
1888, 21, 2148; Chem. Tech. Rep. 1888, 27, II. 289; Jahr. Chem. 1888, 41,
2309; Wag. Jahr. 1888, 34, 954. E. Winterstein, Ber. 1893, 26, 362; Zts.
physiol. Chem. 18, 43; abst. J, C. S. 1893. 64, 380, 497; J. S. C. I. 1893, 12,
702; Bull. Soc. Chim. 1893, 10, 699; Chem. Centr. 1893, 64, I, 602, II, 218;
Jahr. Chem. 1893, 46, 880; Meyer Jahr. Chem. 1893, 3, 236; Jahr. Tierchem.

1893, 23, 67.

6. Compt. rend. 1879, 89, 711. 713, 755; abst. Ber. 1879, 12, 1938;
Chem. News, 1879, 40, 264; J. C. S. 1880, 38, 233; Jahr. Chem. 1879. 32,
832; Jahr. Tierchem. 1879, 9, 52. W. Stone and B. ToUens, Ann. 1888, 249,
259; abst. J. C. S. 1889, 56, 480; J. S. C. I. 1888, 7, 511; Ber. 1888, 21, 1572;
Jahr. Chem. 1888, 41, 2459. F. Hoppe-Seyler, Ber. 1894, 27, 3329; abst.
J. C. S. 1895, 68, i, 166; BuU. Soc. Chim. 1895, 14, 765; Chem. Centr. 1895.
66, I, 393; Jahr. Chem. 1894, 47, 1131; Meyer Jahr. Chem. 1894, 4, 289; Jahr.
organ. Chem. 1894, 2, 894. E. Salkowski, Ber. 1894, 27, 497, 925, 3325;
abst. J. C. S. 1894, 66, i, 222; 1895, 68, i, 166; J. S. C. I. 1894. 13, 411; 1895.
14, 376; Bull. Soc. Chim. 1894. 12, 1051; 1895, 14, 698; Chem. Centr. 1894,
65, I, 624; 1895, 66, I, 328; Jahr. Chem. 1894, 47, 2344; Meyer Jahr. Chem.

1894, 4, 288; Jahr. organ. Chem. 1894, 2, 221.

326 TECHNOI.OGY OP C^I.LUU)SE ESTERS

it appears that the sugar obtained as the product of hydrolysis
is similar €b or identical with the dextrose obtained from certain
vegetable celluloses. Cellulose has also been identified as a con-
stituent of oemeba and other protozoa, the investigations of W.
Halliburton^ on the investing membrane of Ophrydium versatile
indicating such matrix to consist primarily of a cellulose similar
to those of the tunicates. R. Virchow^ also found cellulose in
degenerated human spleen.

As E. Abderhalden and G. Zemplen have emphasized' that
the mere obtaining of dextrose from tunicin and similar animal
bodies does not necessarily establish its identity with vegetable
cellulose. Further proofs of the identity or close relationship
have been adduced by these investigators, who have found that,
(1) by the action of acetic anhydride in the presence of sulfuric
acid an acetyl compound (octacetylcellobiose) was obtained, with
the same melting point, solubility, composition, and optical activ-
ity as the product similarly obtained from filter paper; (2) the
osazones of the cellobiose are also identical, (3) by saponification

1. Quart. J. Micr. Sci. 1885, 25, 173, 445; abst. J. Roy. Micr. Soc.
1885 5 222

'2.' Compt. rend. 1853, 37, 492, 860; abst. Pharm. Centr. 1853,
24, 768; Jahr. Chem. 1853, 6, 592; J. prakt. Chem. 1854, €1, 59.
Cellulose does (Peligot, Compt. rend. 1858, 47, 1037; Ann. Chim.
phys. 1860, (3), 58, 83; abst. Rep. Chim. Pure, 1859, 1, 234; Chem.
Centr. 1860, », 341; Jahr. Chem. 1858, 11, 574) not (G. Staedeler.
Ann. 1859, HI, 28; abst. Rep. Chim. Pure, 1859, 1, 569; J. Pharm. (3), 3S,
229; Chem. Centr. 1859, 30, 705; Jahr. Chem. 1859, 12, 598; J. prakt. Chem.
1859, 78, 169) occur in the skin of silk worms; and does (H. Ambronn,
Mitt. zool. Station Neapl. 1890, 9, 475; abst. Jahr. Tierchem. 20, 318; J.
Roy. Micro. Soc. 1890, 704) not (F. Schulz, Zts. physiol. Chem. 1900, 9,
475; abst. J. C. S. 1900, 78, ii, 292; Bull. Soc. Chim. 1901, 26, 32; Chem.
Centr. 1900, 71, I, 729; see also Krawkow, Zts. Biol. 11, 177; Zander, Pflii-
ger's Archiv. 66, 545) occur in the shield of Os sepia.

3. Zts, physiol. Chem. 1911, 72. 58; abst. J. C. S. 1911, 100, i, 525; C. A.
1912, 5,3081; Bull. Soc. Chim. 1912, 12, 524; Chem. Zentr. 1911, 82, II, 625;
Meyer Jahr. Chem. 1911, 21, 264.

For the constituents of the tissues of fungi, refer to E. Winterstein,
Zts. physiol. Chem. 1894, 19, 521; 1895, 21, 134. E. Schulze, Ibid. 1894,18,
711. R. Reiss, Landw. Jahr. 18, 711. Braconnot, Jour, de physique, 1811,
73. Payen, Ann. Sci. nat. (2), 2, 21. A. Doepping, Ann. 1844, 52, 106.
C. Richter, Sitzungsber. Akad. Wiss., Wien, 83, 1, 494. Fueisting, Botan. Ztg.
1868, 661. W. Hoffmeister, Landw. Jahr. 1888, 239. J. Schlossberger,
Ann. 1844, 51, 207. Naegeli and Loew, J. prakt. Chem. 1878, 125, 403.
A. Brown, J. C. S. 1886, 49, 432; 1887. 51, 643; Ber. 1886, 19, R, 463. E.
Gilson, Ber. botan. Ges. U. 441 ; Compt. rend. 1895, 120, 1000. J. Dreyfus,
Zts. physiol. Chem. 1894, 18, 358. V. Fleschig, Zts. Physiol. Chem, 7, 525.
L. Mangin, Compt. rend. 1893, 118, 816. T. Araki, Zts. physiol. Chem.
1895, 20, 504.

c^LLUi^osE 327

of the acetyl compound by means of barium hydroxide in the
cold, crystallized cellobiose was obtained.

So far as aware, no attempts have been made to esterify these
bodies into the corresponding nitrates and acetates.

Esparto. Esparto grass, Stipa^ macrochloa {tenacissima),
grows wild in Spain, Portugal, Greece, and various districts in
Northern Africa, especially in the Algerian area.* It grows
readily on sandy ferruginous soils and large crops are obtained
without artificial cultivation. The grass attains a height of
three to four feet, has a narrow cylindrical stem coated with stout
hairs, the haulms being 0.3 to 0.5 mm. long and 1 to 1.5 mm.
thick. The bast fibers are grouped together. The cuticular and
bast fibers examined microscopically are seen as narrow cylinders
with pointed ends. The Spanish type of esparto is considered
one of the best for cellulose production. Other types employed
for paper making, etc., are known by the termsT Northern African,
Oran, Tunis, Arzen, Gabes and Sfax. A grass known as: Tripoli
esparto {Imperata cylindrica P. B.) is very similar to esparto, and
gives a 40% yield of cellulose.^

The grass is pulled during dry summer weather, tied into
bundles and packed by hydraulic presses into bales for export.
Before conversion into pulp, the grass is subjected to a mechanical
purification. The bales are opened and the loose fibers having
been cut up into suitable lengths, are spread on wire netting sup-
ported in frames. Impurities, such as clay or sand, pass through
the sieves. The grass is also hand-picked and other foreign mat-
ter removed, this stage of the process being known as *'dry pick-
ing."' The preliminary cleaning is readily carried out also by
the aid of machinery in which the crude fiber is agitated.

The cuticle of esparto grass contains a wax of industrial im-
portance.* In the process of dusting of the grass prior to its
conversion into paper pulp, a portion of this cuticular wax is me-
chanically removed, another portion being recovered during the

1. E. Goulding and W. Dunstan, "Cotton and Other Vegetable Fibers,"
219.

2. F. Vignolo-Lutati, VInd. Chim. 1913, 13, 17; abst. J. S. C. I. 1913.
32, 228; C. A. 1913, 7, 3413.

3. Thorpe, Djctionary Applied Chemistry, article "Esparto," 2, p. 348.

4. C. Cross and D. Russell, F. P. 395250, 1908; E. P. 8268, 1908;
abst J. S. C. I. 1909, 28, 372; C. A. 1909, 3, 2392.

328 TI5CHNOI.OGY OF CEI.I.UI.OSE ESTERS

subsequent chemical treatment to which the material is exposed.

The grass is next heated with caustic soda at a pressure of
10-50 lbs. for five hours, the amount of caustic soda required
being approximately one-quarter of the weight of esparto treated.
After removal of mother liquor and thorough washing of the
residual cellulose fiber, the latter is again spread out and hand
picked (wet picking) to remove any portions which have been
incompletely boiled. In the newer press-pAte system the bleached
pulp is passed through a series of strainers or knotters. The sub-
sequent working up of the cellulose pulp from esparto is similar
to that described under jute or wood pulp.

With modifications in the alkali treatment, various materials
in addition to esparto may be utilized in the preparation of cel-
lulose pulp.^ Among the materials which have been so employed
are plants generally,^ the fiber of Ulex europens (ajonc),' rhea,*
ramie, '^•^ gorse,' hemp,® hop runners,' com stalks,^® com pith,^^

1. O. Silberrad, F. P. 434709, 1911; abst. J. S. C. I. 1912, 31^ 279.
E. P. 28193, 1910; abst. J. S. C. I. 1912, 31, 67; C. A. 1912, 6, 1534.

2. C. Kellner, E. P. 24542, 1902. F. P. 326313, 1902; abst. J. S. C. T.
1903, 22, 817, 1145. For comprehensive analyses of fibers, consult Bull.
Imp. Inst. 1917, 15, 7; abst. C. A. 1917, 11, 3443; J. S. C. I. 1917, 3S, 1003.

3. G. Horteloup, E. P. 26149, 26150, 1903; 21505, 1905; abst. J. S.
C. I. 1904, 23, 266, 500; 1906, 25, 441. F. P. 327136, 1902; 331176, 1903;
347353, 1904; abst. J. S. C. I. 1903, 22, 879, 1145; 1905. 24, 344; Mon. Sci.
1903, 59, 195. He proposed to nitrate the cellulose from Ulex Europens
for the manufacture of artificial silk, celluloid and guncotton. H. Davoine
(F. P. 470606, 1914; abst. J. S. C. I. 1914, 33, 172) advocated the nitration
of Hedychium coronarium for the same piuT>ose.

4. W. Cordner, E. P. 13846, 1899; abst. J. S. C. I. 1900, IS, 734;
Kunst. 1913, 3, 390; U. S. P. 654691, 654951, 654952, 1900.

5. J. Rossi, Manchester Guardian, May 7, 1919; abst. J. S. C. I. 1919,
38, 188-R.

6. P. Birkenstock, U. S. P. 949643, 1910; 1004974, 1911; abst. C. A.
1910, 4, 1106; 1912, 6, 300. F. P. 404037, abst. Mon. Sci. 1911. 75, 154; F. P.
434416. 1911; abst. J. S. C. I. 1912, 31, 328. He purified the material by
first boiling in sodium sulforicinate and NaOH, washing, then steeping in
dilute mineral acid, and finally bleaching.

7. A. Bouret and A. Verbrese, E. P. 24768, 1898; abst. J. S. C. I.
1900, 19, 42. For data on cocoanut fiber, see H. Matthes, Ber. 1908, 41,
400; abst. J. C. S. 1908, 94, ii, 2;^6. H. Matthes and F. Streitberger, Ber.
1907, 40, 4195; abst. J. C. S. 1907, 92, ii, 991. H. Matthes and Muller,
Zts. Nahr. Genussm. 1906, 12, 159. J. Koenig, Ber. 1908, 41, 46. J. Tor-
rilhon. U. S. P. 496075, 1893. F. P. 196095, 1889.

8. C. Hengst, E. P. 13056, 1888; abst. J. S. C. I. 1889, 8, 478; 1890,
9, 325; Wag. Jahr. 1890, 36, 546; Zts. ang. Chem. 1890, 3, 247; Tech. Chem.
Jahr. 1889, 12, 165; Chem. Tech. Rep. ;890, 29, I. 222; Chem. Ztf. 1890.
14, 408; Jahr. Chem. 1890, 43, 271 ; Proc. U. S. Nav. Inst. 1889, IS^ 497.
Paper Maker, 1919, 57, 152; J. Ind. Eng. Chem. 1919, 11, 479; C. A. 1919,

CELLULOSE 329

vegetable pith such as from com stalks, waste vegetable fiber/
sugar cane megass/'* straw/ flax straw, bamboo,^ and cocoanut

13, 1390. R. Sherwood, U. S. P. 40577, 1863. G. Sellers, U. S. P. 40576,
1863. W. Woodbridge, U. S. P. 39981, 1863.

9. C. Midler and D. Wolf, F, P. 443133; E. P. 5659, 1912; abst.
J. S. C. I. 1912, 31, 1029; 1913, 32, 133. D. R. P. 256351; abst. C. A. 1913,
7, 1982; Wag. Jahr. 1913. 58, II, 442; Chem. Zentr. 1913, 84, I, 867; Chem.
Ztg. Rep. 1913, 37, 116; Zts. ang. Chem. 1913, 28, 175. The bast sheath
or fibrous material stirrounding the pith of hop runners is separated from
the woody and other matter with which it is associated, being then boiled
in sodium carbonate and soft soap with an addition of caustic soda up to
5%. By this process the bast sheath is loosened from the ligneous portion
and can readily be separated by peeling. The fibrous raw material thus
obtained is then bleached, washed and dried, when it is in condition for
nitration. According to the patentee "the product thus, obtained is ready
for direct use" for filament formation, and "artificial silk thus produced has
a flexibility hitherto possessed only by natural silk, and textile goods made
of this fiber cannot be distinguished from pure silk."

10. Sci. Amer. 1905, 82, 505. For making yarn from kapok fiber, see
J. de Saint-Rene and J. Tissier, E. P. 27303, 1910.

11. Engineering, 83, 9. Consult the topic, "Nitrates of the Carbo-
hvdrates "

1. I. Herz, U. S. P. 1041791, 1912; abst. C. A. 1912, 6, 3518; J. S. C. I.
1912. 31, 1075; E. P. 23255, 1911; 19334, 1912; abst. J. S. C. I. 1912, 31,
1176; F. P. 422490, 1910; abst. J. S. C. I. 1911, 30, 533.

2. R. Lhuilier and L. Maurice, F. P. 405684, 1909; abst. J. S. C. I.
1910, 28, 417; Mon. Sci. 1911, 75, 148. The cellulosic material is preferably
packed in iron baskets which can be immersed in boilers, lifted out and
transferred to other boilers without unloading. The chemical treatments
consist of a digestion, at the boiling temperature or otherwise, in a solution
of an alkali carbonate, followed by a bleaching operation by means of an
alkaline solution of an alkali hypochlorite. The digestion with sodium car-
bonate is best effected with a "battery" of three boilers in order to obtain
a systematic exhaustion of the liquors.

3. V. Drewsen, U. S. P. 853943, 1907; abst. J. S. C. I. 1907, 28, 713;
C. A. 1907, 1, 2191.

4. V. Drewsen, U. S. P. 731290, 1903; 789416, 1905; abst. J. S. C. I.
1903, 22, 876; 1905. 24, 633.

5. E. Heuser and A. Haug, Zts. ang. Chem. 1918, 31, 166; abst. J. S. C. I.
1918, 37, 365-A. 650-A; C. A. 1918, 12, 2439. In their process the crude cellulose
prepared by the chlorination method with the use of caustic soda contained
only 0.35% of ash, whereas that prepared with the use of sodium sulfite con-
tained 1.1%. The yield was 54.60% of crude cellulose with furfural value
13.30%, equivalent to 22.34% of xylan. Hence the calculated yield of true
cellulose was 42.97%. The original straw had furfural value 15.4, equivalent
to 25.62% of xylan on the dry and ash-free basis; thus 47.32% of the original
xylan remained in the cellulose. The proportion of xylan remaining in the
cellulose varies inversely as the yield of cellulose and is a function of the
concentration of the caustic soda solution used for extracting the chlorinated
products. For instance, the furfural value of 13.3 was found when a 1%
solution of caustic soda was employed; with a 2^'c solution the furfural value
of the crude cellulose fell to 10.4, and with a 3*^7 solution to 9.3. The fur-
fural value of commercial straw cellulose also varies with the yield and with
the severity of the chemical treatment; it may reach 18^' c- Most of the
xylan may be removed from the crude straw cellulose preparations by re-
peated extraction with 6% caustic soda solution, but it has not been found

330 TECHNOLOGY OF CEl.LUU)SB ESTERS

shell/ all of which have been nitrated and whose nitric esters are
described in Part III of this volume.

T. Knosel, in the preparation of cellulose from vegetable
fibers replaces 25% of the caustic soda in the soda boil by sodium
carbonate, and largely dilutes the lye so that it amounts to 5-10
times the weight of the fiber. The boiling is carried out at at-
mospheric pressure for four hom^, the separated material next
bleached using two-thirds the amount of the bleaching material
employed in the ordinary process and the washed fiber again
boiled with alkali. In this latter case the boiling solution only

possible to reduce the furfural value of the cellulose below 1.95% in this
manner. Attempts to remove the whole of the xylan by extraction before
chlorination as well as afterwards, led to a similar result, and a fully extracted
preparation from commercial bleached straw pulp stiU gave 2.02% of fiu*-
fur^l. Commercial bleached straw 'cellulose shows a "copper value" of 3.0;
unbleached straw cellulose, on the other hand, has a "copper value" of 0.94-
0.99, and bleached straw cellulose which has beeniully extracted until the
furfural value is reduced to the limit of 2.0% shows a "copper value" of only
0.61-0.78. Moreover, by further bleaching and the production of oxycel-
Itilose, the "copper value' of this product may be increased to 15.5 without
any effect on its furfural value. Hence it is concluded that straw cellulose
does not correspond to a special type of "natural oxycellulose," but is an
ordinary cellulose similar to that of cotton qr wood, strongly contaminated
with a pentosan and modified by bleaching under industrial conditions m
such a way that the commercial pulp contains a substantial amount of oxy-
cellulose. The only outstanding question is the nature of the residual 2%
of furftu^l which cannot be eliminated by extraction of the purified cellulose.
On hydrolysis with 1% stilfuric add at 136** for half an hour, this furfural-
yielding residue is divided half in the hydrolyzed liquid and half in the hydro-
cellulose. An examination of the liquid and the preparation of the benzoate
and osazone, m. pt. 160**-180** C, suggested the presence of xylose, and it
is probable that the residue in question consists merely of a trace of xylan,
equivalent to less than 1% of furfural, which is obstinately retained by the
cellulose, while 1.0-1.5% of furfural may be attributed to the cellulose
itself, just as in the case of cotton cellulose. Hydrolysis with 72% stilfuric
acid followed by digestion of the diluted liquid at 120° C. for 2 hours, accord-
ing to the method of Ost and Wilkening, was carried out on the purified
straw cellulose. The results were compared with those obtained with pure
dextrose, observations being made of cupric-reducing power, polarization,
yield of alcohol by fermentation, and the m. pt. of the osazone. These were
all in close agreement and afforded satisfactory evidence that the resolution
of straw cellulose to dextrose is practically complete and that its constitution
corres]>onds with that of cotton cellulose. A. Lyman, U. S. P. 40696, 1863.
A. Tait, U. S. P. 40728, 1863.

6. T. Knosel, F. P. 435895, 1911; abst. J. S. C. I. 1912, 31, 381. D.
R. P. 252411, 1910; abst. Wag. Jahr. 1912, 59, II, 549; Chem. Zentr.
1912, 83, II, 1710; Chem. Ztg. Rep. 1912, 36, 610; Zts. ang. Chem. 1912,
27 2384' C. A 1913 7 416.

1. 'Germain, F. P. 192181, 1888; abst. Mon. Sci. 1889, 33, 507. Used
as an explosive after treatment. Cf. J. Dypowski and Societe Textile du
Centre, F. P. 486323; abst. C. A. 1919, 13, 1936. C. Schwalbe, D. R. P.
309555, 1917; abst. J. S. C. I. 1919, 38, 295-A.

cdi.i.ui.osB 331

contains 0.5%-1.0% of sodium carbonate. In a recent French
patent^ a method is described for the production of cellulose from
various types of fibrous materials. The chemical treatment con-
sists in boiling with alkali carbonate followed by a bleaching opera-
tion by means of alkali hypochlorite solution. The alkali diges-
tion is carried out in a battery of 3 boilers in order to obtain a
systematic exhaustion of the liquors.

It has also been suggested to replace the soda by ammonia.^
The fiber is boiled under pressure in an alkali solution containing
ammonia, animal fat and soap, washed and subsequently treated
with a boiling solution containing in addition, vegetable oil, oleic
acid and boric acid or a borax compound.

According to a method patented in France,' vegetable fibers
may be converted into cellulose as follows: The cleaned material
is submitted to a preliminary drying in order to render the cellu-
lose more resistant in the subsequent treatment, after which the
fibers are placed in a tank with a false bottom formed of an iron
grid which acts as a positive electrode. Sufficient water (slightly
acid) is placed in the tank to cover the fiber. A negative elec-
trode is fixed in the upper portion of the tank in contact with the
water, through which a current of 0-5 ampere at 2 volts is passed,
and this, it is claimed, accelerates the action of the pectase on
the pectoses present, these later being converted into soluble
compounds. The ciurent is then turned off and the material
treated with dilute alkali (0.5 kilos of alkali per 100 kilos of fiber),
the liquid meanwhile being agitated by air. By this method of
treatment the fatty and resinous matter and the chlorophyll are
removed. The cellulose is next bleached and washed with alkali
and finally with water. The residue consists of a pure cellulose
quite suitable for paper manufacture. Cellulose may also be
obtained from various vegetable materials such as maize stems,
by first removing the water-soluble constituents and then treat-
ing the moist material with nitric oxide and steam. An alternative

1. L. Dewolf-Wante, F. P. 458289, 1913; abst, J. S. C. I. 1913, 32,
1063. Holl. P. 1538, 1916; abst. C. A. 1916, 10, 3167. Societe Darrasse
Freres and L. Dupont, E. P. 123326, 1919; abst, C. A. 1919, 13, 1478. A.
Angell, U. S. P. 219668, 1879.

2. R. Rol?erts, U. S. P. 1062187, 1913; abst. J. S. C. I. 1913, 32, 653;
C. A. 1913, 7, 2476; Can. P. 150728, 1913; abst. C. A. 1913, 7, 4079.

3. C. Tanquerel, F. P. 383099, 1907; abst. J. S. C. I. 1908, 27, 352;
Mon. Sci. 1908, 63, 166; C. A. 1909, 3, 1093.

1

332 TECHNOLOGY OF CELlrULrOSE ESTBRS

«

process consists in treatment with a mixture of nitric oxide and
chlorine. The purified fiber is washed, neutralized and again
washed.^

The sulfite process is not directly applicable to esparto or
material such as straw, on account of the silica present. The
latter, it is claimed,* hindering the penetration of the liquor into
the fiber. Silica, however, may be removed by treating the crude
material for several hours with a 1.5% solution of hydrofluoric
acid. The cellulose material after this treatment is washed with
water until free from acid, and heated with 4-5 times its weight
of liquor (containing 3.5% available sulfur dioxide). The yield
of cellulose from straw will average about 42%.

On boihng with solution of aniline salts, esparto cellulose
develops a rose color. It fxulhermore reacts with Fehling's solu-
tion, salts of phenylhydrazine, and magenta sulfurous acid solu-
tion, indicating the presence of active CO groups.' The fiber is
slowly oxidized by dry air at 100°, becoming discolored in the
process. With iodine dissolved in potassium iodide, a greyish
brown color is obtained, while with zinc chloride and iodide a
bluish violet stain is produced.

The carbon percentage of esparto cellulose varies from 41-
42.4 and the hydrogen content from 5.4-5.8. An exception to
this is recorded by C. Cross and E. Bevan for a particular esparto
cellulose which gave the following results: Carbon 44.68%, hy-
drogen G.1G%.* the yield of furfural being 12.5%. From these

1. F. Stewart, U. S. P. 845378, 1907; abst. J. S. C. I. 1907, 2S, 548;
C. A. 1907, 1, 1071. See U. S. P. 811523, 1906; abst. J. S. C. I. 1906, 25,
226. Cellulose is obtained from the stems of maize and similar plants by
removing the water-soluble constituents, leaving the stalks in a divided and
absorptive condition, and then treating the material when moist, either with
nitric oxide and steam, or with a mixture of nitric oxide and chlorine, subse-
quently washing, neutralizing, and again washing the cellulose.

2. R. Dietz, Zts. ang. Chem. 1905, 18, 648; abst. Chem. Centr. 1905,
76, I, 1676; J. S. C. I. 1905, 24, 557; Jahr. Chem. 1905-1908, II, 971.

3. Cross and Bevan, Cellulose, p. 84.

4. C. Cross and E. Bevan, J. C. S. 1918, 113, 182; abst. J. S. C. I.
1918, 37, 236-A; C. A. 1918, 12, 1380. They have recently (J. Soc. Dyers
Col. 1919, 35, 70; abst. J. S. C. I. 1919. 38, 249-A) investigated raffia, a
complex tissue composed of a true epidermis or cuticle and underlying sder-
enchyma, the cells of which are sufficiently elongated to rank as fibers; under
most chemical treatments the two tissues exhibit a joint resistance. The
material showed: moisture, S%-^%, ash 2.7 ^,y;; on boiling with 1% caustic
soda solution the loss was 16.8% in 5 minutes and 24.3% in 60 minutes.
The attack by aqueous caustic soda was not, however, sufficiently specific
to afford a pure preparation of cellulose by the chlorination method. On the

CEi.LUU)S« 333

figures it appears that the composition of esparto cellulose cor-
responds to that of a normal cellulose containing 30% of fur-
furoid constituent. Esparto cellulose resembles oxycellulose
rather than normal cellulose. Although it is generally assumed
that the furfuroid grouping in esparto is of pentosan configura-
tion, there is no direct proof that such is the case, and the experi-
mental work of C. Cross and E. Bevan throw doubt on the ac-
cepted *'furfuroid-pentose" relationship of esparto cellulose. They
find that simple treatments so modify the constitution of the com-
plex that the total yield of furfural is reduced to a large degree.
Treatment at 15°-20° with 17.5% sodium hydroxide gives 84.14%
of resistant cellulose with a furfural value of 4, and 15.86% of a
hydrolyzed product with a furfural value of 26. The total furfural
value is reduced from 12.5 to 7.48. With dilute sulfuric acid treat-
ment a reduction in fiuiural value is also obtained. The fixation of
SO4 groups, according to C. Cross and E. Bevan, indicates the
reactivity of oxygen of basic function in excess of that which

other hand, a preliminary treatment with alcoholic caustic soda broke down
the resistance of the cutocellulose ester and subsequent chlorination yielded
42% of cellulose. The loss of weight with alcoholic soda was considerable:
39.94% with 2% NaOH and 46.7% with 5% NaOH. The residue after
saponification was readily chlorinated, the lignone groups of the sclerenchyma
fibers being attacked and the ultimate fibers, 2 mm. in length, being sep-
arated. The ratio of HCl formed to chlorine combined with the lignone was
approximately 2:1. The isolated cellulose yielded 5.2% of furfural, as com-
pared with 8% for the crude raffia. From the soaps of the alkaline hydrol-
ysis, 11 %-12% of a fatty acid and 6%-7% of a resin acid, the sodium salts of
which are insoluble in alcohol, were separated. The fatty acid had a com-
position corresponding to the formula CnHjjOs, with one COOH and one OH
group; iodine value (Wijs), 13.6%. The resin acid contained 68.4% of car-
bon and 10.0% of hydrogen. On fusion with aqueous sodium hydroxide at
260 ^-SOO® C. the separation of the fat constituent occurred with less modi-
fication, its lower acid value being held to indicate a higher molecular weight;
the cellulose on the other hand, was profoundly decomposed with formation
of volatile acids. Conversion into viscose, benzoylation and acetylation of
the raffia gave mixed reactions of no sharply differentiated character. Nitra-
tion^ gave results indicating profound oxidation of the fat and resin com-
ponents. The lignin reactions of raffia are considerably suppressed; it does
not combine with phloroglucinol and reduces permanganate only to a lim-
ited extent. Certain effects of nitric acid are specific: a mixture of 36 parts
of glacial acetic acid and 2 parts of nitric acid to 5 of raffia at 96° C. gave
the fat-resin complex in solution in a form showing minimtun modification.
Dilute aqueous nitric acid product a structural cleavage between the cuticle
proper (40%) and the sclerenchymatous tissue (60%). The cuticle proper
closely resembles that of apple peel. The general characteristics of raffia
is that of an ester of fatty and resin acids with an oxidized modification of
cellulose in intimate association with a lignoceUulose ether. A purple reac-
tion with ferric chloride, which is intensified by alkaline saponification, ap-
pears to be a characteristic of the complex tissue.

334 TBCHNOI.OGY OF CHLLUWS^ ESTERS

characterizes the alcoholic-hydroxyls of a hexose configuration.

Cellulose Filters. In addition to the ordinary filter paper,
advantages of the use of cellulose as a filtering substance in sugar
and other industries have been described by A. Aulard,^ the ad-
vantages of wood pulp being that it is easily washed; gives a
siurface which is completely homogeneous as contrasted with the
fibrous mesh of the cloth filter; the first liquid to come through a
clean filter is as clear as the last; and varying thicknesses of pulp
as needed for different liquids to be filtered may be easily ad-
justed. Data as to thicknesses of mat used and rapidity of filtra-
tion are given.

In the Prade system for the cellulose clarification of wines,*
there is provided a closed cylindrical vessel inside of which are
two concentric cylinders of filter-mass (cellulose) and held in
place by perforated partition's. The whole is so arranged that
the liquid filters through the inner and outer cellulose layers into
the annular space between them.

An acid-resisting material intended more • particularly for
filtering gases containing acids in suspension, is prepared by heat-
ing cotton or similar fabric out of contact with air, to a temper-
ature of from 200°-350° for from a few minutes to a week, accord-
ing to the temperature employed. Cotton cloth weighing 350 gm.
per square meter and having a tensile strength of 2300 kilos per
meter, when heated to 300°-400° for periods of from 10 minutes
to one hour, showed a loss of weight of from 68% to 76%, the
tensile strength being reduced to 30-35 kilos per meter. The
material retains its flexibility.'

Siemens and Halske* have described a diaphragm particu-
larly suitable for use in chlorine-alkali electroljrtic cells with hor-
izontal electrodes, which is made from a mixture of powdered
cement and cellulose, or material containing cellulose, mixed to
a pulpy mass with water. The diaphragms thus produced are
said to be strong and somewhat pliable, and to possess excellent
porosity, the latter property being varied by the amount of con-

1. Orig. Com. Eighth Intern. Cong. Appl. Chem. 1912, 2S, 489; abst.
C A. 1913 7 3045.

2. F. P. 319029, 1902; abst. J. S. C. I. 1903, 22, 224.

3. Metallbank & Metallurgische Ges., F. P. 456524, 1913; abst. J. S.
C. I. 1913, 32, 1094; C. A. 1914, 8, 1860. D. R. P. 275662, 1913; abst. C. A.
1915, 9, 133; Chem. Ztg. Rep. 1914, 38, 418; Zts. ang. Chem. 1914, 27, 539.

4. D. R. P. 307471, 1916; abst. J. S. C. I. 1918, 37, 741-A.

cELi.ui.osje 335

tained cellulose. They possess the advantage of cheapness over
the Billiter asbestos diaphragms. M. Sussmann^ has patented
the use of a special cellulose powder to be used as an absorbent
for the electrolyte of secondary batteries, made by comminuting
filter paper, which is purified by successive boilings in dilute sul-
furic acid, caustic potash and alcohol.

Cellulose Plastics and Aggregates. In the plastic composi-
tion of P. Defaucamberge,^ cellulose is mixed with the natiu-al
latex of rubber in the presence of viscose. Thus the physical
properties of elasticity, tenacity and non-conductivity for elec-
tricity found in Para rubber are enhanced and made more re-
sistant by the presence of the cellulose.

Heat-insulation is produced by H. MacFarland and R. Shoe-
maker' by cooking the fibrous portions of Zostera marina in 2%
NaOH solution, separating the soluble substances and treating
the fibrous residue with sulfuric acid, using the gummy product
thus formed as a binder for the cellulosic portion.

In the soft-soldering or coating of metals, the composition
when made up in stick or paste form is squirted into tubes made
of cellulose, as the latter leaves practically no residue on burning
away.*

The W. Freeman cellulose plastic* composition is produced
by hydrolyzing cellulose with an alkaline solution, drying it, mix-
ing the dry fiber with magnesium oxide, and causing the whole
to set by adding a solution of magnesium chloride. C. Ellis*
produces a fibrous plastic composition by means of cellulose ag-
glutinated together by the solids precipitated from acid sulfite-
cellulose waste liquor. A. and M. Weiser^ soften and mould

1. E. P. 22053. 1893; abst. J. S. C. I. 1895, 14, 370.

2. U. S. P. 943658. 1909; Can. P. 121286, 1909; abst. Kunst. 1911, 1,
216. The plastic mass of F. Ahrens (D. R. P. 216629; Pap. Ztg. 1909, 34,
4008; Chem. Zentr. 1910, 81, I, 71; Chem. Ztg. Rep. 1909, 33, 664; Zts.
ang. Chem. 1910, 23, 144) is composed of cellulose made plastic by means of
zinc chloride.

3. U. S. P. 1146190; abst. C. A. 1915, 9, 2432. See U. S. P. 1139305,
1916; abst. C. A. 1915, 9, 1691.

4. A. Rosenberg, E. P. 23300, 1912; abst. J. S. C. I. 1913, 32, 1115.

5. U. S. P. 1183446, 1916; abst. J. S. C. I. 1916. 35, 734. Compare E.
P. 17624, 1904; abst. J. S. C. I. 1905, 24, 893.

6. U. S. P. 1246806, 1917; abst. J. vS. C. I. 1918, 37, 53-A.

7. Swiss P. 77143, 1918; abst. C. A. 1918, 12, 2248; Kunst. 1918, 8,
214. For the artificial sponge manufacturing process of P. Raabe, see Bel^.
p. 261288, 1913; abst. Kunst. 1914, 4, 393.

336 T^CHNOI^OGY Olf CElyIyUU)SE ESTERS

cellulose without the addition of a binder by means of high pres-
sure. The cellulose absorbent pad of J. Grant, ^ and the artificial
leather composition of J. Hofmeier^ are similar.

A. Hill' has devised a process for applying a cellulose to the
fibers of a hydrated cellulose fabric, precipitating the cellulose,
washing out the solvent, and then coating the fibers with a pro-
teid in solution, as albumen. By this means, it is claimed, arti-
ficial leathers may be produced which may be printed upon as in
calico printing.*

D. Hennequin^ manufactures washers for bottle capsules and
stoppers from a sheet of cellulose, to each side of which is cemented
a layer of vegetable parchment, which is then varnished. "Arti-
ficial wool"® and "excelsior,"^ prepared from cellulose, have also
been described.

In a recent process,* plastic masses are described which may

1. E. P. 8499. 1913.

2. E. P. 12023, 1885.

3. U. S. P. 705244, 1902.

4. A cleansing compound for teeth has been patented by G. Richter
and J. Wilowski (D. R. P. 236619, 1910; abst. Zts. ang. Chem. 1911, 24,
1533; Chem. Zentr. 1911, II, 327; C. A. 1912. 6, 11; Wag. Jahr. 1911, 57,
II, 143; Chem. Ztg. Rep. 1911, 35, 390) made by dissolving acid halides in
an indifferent viscous solution of cellulose, which solidifies upon exposure
to the air. The acid halides then decompose, and dissolve the tartar on the
teeth.

5. E. P. 7083, 1911. See A. Deiss and C. Foumier, Belg. P. 213988.
215784, 215985, 218996, 1909.

6. C. Villedieu, F. Lebert and A. Coumbray, F. P. 459406, 1912; abst.
J. vS. C. I. 1913, 32, 1153; Kunst. 1914, 4, 116. F. P. 17916, addition to F. P.
459406; abst. Kunst. 1914, 4, 155.

7. A. Borzner, U. vS. P. 1165062, 1915; abst. J. S. C. I. 1916. 35, 250;
Chem. Ztg. Rep. 1914, 38, 241; Kunst. 1914, 4, 194.

8. Naamlooze Venootschap Hollandsch Zijde Maatschappij, E. P.
4521, 1913; Belg. P. 256046, 1913; abst. Kunst. 1914, 4, 77. In the manu-
facture of "simili" silk (J. Debourg, F. P. 427113, 1910; U. S. P. 1018850.
1912; abst. J. S. C. I. 1911, 30, 1050; Chem. Ztg. Rep. 1912. 35,^9), fibers,
such as flax, hemp, ramie, nettle, are packed in shallow circular trays which
are stacked one above the other in a cage. The cage is lowered into an
autoclave which is heated by a perforated steam-coil passing around the
outside of the cage and terminating in a vertical portion passing through
holes in the center of the trays, up the axis of the autoclave. The fibers
are first digested in a solution of sodium carbonate of about 0.5% concen-
tration for two hours under a pressure of 2-3 atmospheres. The liquor is
drained off and replaced by one containing, per 1000 liter of water: 108 kilos of
slaked lime, 5.25 of sodium bisulfite, 5.5 of sal ammoniac, 0.56 of sodium
peroxide and 5.75 of magnesium salt. The fibers are again heated for two
hours, washed, acidified and washed. The treated fibers are carded, combed
and spun according to their natiu-e. For the "celloyam" of A. Kube Co.,
see Svensk Papperstidning, 1918, 523; abst. C. A. 1919, 13, 515. For "paper
yam" sec World's Paper Trade Rev. 67, No. 8, p. 8. For the simili silk of

c^LLui^os^ 337

be formed by means of employing certain carbohydrates which
are completely soluble in albumen in the presence of ammonia,
but which, after drying or precipitation of the mass with acid
without further treatment, lose this capacity of dissolving in
water. The patentees find that certain oxycelluloses satisfy these
conditions, especially those which are produced by the action of
dilute nitric acid on cellulose. Such oxycelluloses are said to be
completely soluble in dilute ammonia, but become insoluble upon
heating the solution to 60°-80°. Valuable plastics are said to
be produced by combining such oxycelluloses with ammoniacal-
soluble albuminous bodies (glutins and casein), to which pigments
and filling materials may be added. ^

Pergamyn, perhaps better known as grease-proof imitation
parchment paper, is prepared from strong Mitscherlich sulfite
wood pulp by beating it until it acquires a gelatinous consistency.
H. Hofmann,^ who has studied the formation of pergamyn under
various conditions, finds that the original pulp and the pergamyn
both yielded equal quantities of water-soluble constituents and
both contained pentosans and methylpentosans upon hydrolysis.
He also found that when sulfite wood pulp was heated in a drying
oven it suffered a progressive chemical change, and that upon
subsequent hydrolysis with acid it yielded increased quantities
of sugar (xylose), proportional to the degree and duration of the
heating. The degradation of the sulfite wood cellulose by heat
was scarcely perceptible after heating for 4 hours at temperattu^es
below 90°, but became definite and distinct at temperatures be-
tween 90° and 100°. Other pulps such as straw, raw wood, and
rye, suffered no change at 100°.^^ Tests for determining the

G. Ragot. refer to Belg. P. 185671, 185672, 1905. For "celloyam," consult
A. Leinveber, Kunst. 1918, 8, 2.34; E. P. 10530, 1902; F. P. 320529, 1902;
abst. J. S. C. I. 1903, 22, 25, 757. Textilose, Belg. P. 256019, 1913; abst.
Kunst. 1914, 4, 75.

1. Vereinigte Koln Rottweiler Pulverfabriken. Belg. P. 129882, 1897.
produce a dense cellulose by beating ordinary cellulose until it hydrates to
a point where it becomes structureless, then eliminating the water, adding
other ingredients and moulding the dried finished product.

2. Inaugural Dissertation, Gottingen, 1906; Papier Ztg. 1906, 31,
4190, 4331; abst. J. S. C. I. 1907, 26, 110; Zts. ang. Chem. 1907, 20, 746;
Wochbl. Papierfabr. 1907, 38, 1137; C. A. 1907, 1, 485, 2179; Gew. Bl.
Wuert. 1901, 53, 348; World's Paper Tr. Rev. 69, 78. Compare Poly. Centr.
1860, 26, 56, 207, 911, 1199. E. P. 12023. .1885.

3. For rdsum^ of recent progress in the industrial applications of
cellulose, see A. Klein, Papier Ztg. 1906, 31, 4286; Woch. Papierfabr. 38,

338 TECHNOWGY O^ CELLUI/>SB SSTORS

grease-proof properties of pergamjm have been described.*

CeUulith.^ According to G. Springer, Brunswig's celltilith
is produced by grinding wood pulp in a paper beater until an
apparently homogeneous mass, free from every trace of wood
fiber, is obtained. This pulp is then drained from the bulk of
its moisture by allowing it to run into a vat provided with a bot-
tom of metallic boards, where it is subsequently dried, either in
the air or in rooms having a temperature of about 40®. The
product contracts greatly and finally forms a solid mass of the
hardness of horn, which is sold under the above name. The
material is not waterproof.' It has a sp. gr. of about 1.5, is not
inflammable, can be worked with tools like wood or horn, and is
very resistant to oils, fats, alcohols and petroleum. It is said to
be applicable as a substitute for horn or ebonite and to be used
for buffing and polishing wheels.*

Bacterial Action on Cellulose Materials. It is a well known
fact that when cotton is stored in a moist warm atmosphere it

1813; abst. C. A. 1907, 1, 2492; Chem. Zentr. 1907, 78, I, 381; Chemu Ztg.
1906, 30, 1259; Zts. ang. Chem. 1907, 20, 610. F. Bdtzer. Rev. g^n. chim. 1909,
13,20.

1. C. Bartsch, Mitt. K. Materialpruef. 1915. 33, 441; abst. J. S. C. I.
1916, 35, 923; C. A. 1917, 11, 1748; Chem. Zentr. 1916, 87, I, 1279. See
Vereinigte K6hn-Rottweiler Pulverfabriken, E. P. 18930, 1897.

2. For "Cellulite," see Proc. Amer. Pharm. Assoc. 1900, 48, 787.
For Xylolith, consult A. Fraass, Belg. P. 234005, 1911. H. MacParland and
R. Jay (E. P. 8004, 1915; abst. C. A. 1916, 10, 2970) convert the cellulose
of eel grass into a structureless mass by acid and alkaline treatment, and this
is compressed into sheets.

3. D. R. P. 3181, 1878, waterproofing being increased bv nitrating
the vulcanized fiber. J. S. C. I. 1901, 20, 602; Gummi Ztg. 15, 329 (G.
Springer). Neues Erfind. Erfahr, 1899, 28, 125; Pharm. Centralh. 1900. 41,
333; Cosmos, 1900, 42, 384; La Nature, 1900, 28, 11, 119; U. S. Consular
Report, No. 64, p. 461.

4. In the process of the Vereinigte Koe^ n-Rottweiler Pulverfab. (E.
P. 18930, 1897; abst. Chem. Ztg. 1899. 23, 10; J. S. C. I. 1898. 17, 65) is
described a method of producing a hard, dense, homy material from fibrous
cellulose without the use of mechanical pressure, a solvent or of a cementing
material, in which ordinary cellulose either in the natural or purified state
is taken and beaten in water tmtil the fibrous structure of the cellulose has
been entirely destroyed. After removal of a portion of the water by pressing
until 60%-90% remains, the paste is moulded into any desired form and left
to dry either in the open air or at a temperature of about 40''. In the process
of drying, the cellulose condenses and shrinks up into a hard mass of 1. 4-1.5
sp. gr., and in this condition may be worked with tools. This "cellulith"
can be used for imitation ivory, horn, wood or lapis. See H. Arledter. E. P.
16085. 1912; abst. C. A. 1914, 8, 247; J. S. C. I. 1913, 22, 865; E. P. 684,
1913; abst. J. S. C. I. 1913, 32, 865. See E. P. 2018, 1910; abst. J. S. C. I.
1911, 30, 205; C. A. 1911, 5, 2947. E. P. 6677, 1914; abst. C. A. 1915, 0,
2588; J. S. C. I. 1915. 34, 793. D. R. P. 237474, 1910; abst. J. S. C. I. 1911.
30, 1058; C. A. 1912, 6, 1990; Chem. Ztg. Rep. 1911, 35, 481.

c«i.i,ui.os^ 339

often deteriorates. The fibers become brittle and a large amount
of fine, dust-like cotton results. This material is unsuitable for
the production of a stable nitrocellulose. It is also kno\ni that
when moist jute is baled, the fiber may be damaged "heart
damage." In extreme cases the fiber is completely disintegrated
and under slight pressure, breaks down to a fine dust.^ The
cause of these changes with cotton and jute is bacterial. The
fermentation set up is not necessarily due to imptuities, since
even cellulose in a piu'e form is capable of being attacked by
bacteria when a suitable culture food is present. The subject
of the action of bacteria will be considered from the aspect of
attack on cellulose or cellulose material generally, rather than
from the view of bacterial action on cotton solely.

The resolution of the cellulose complex into simpler mole-
cules may be brought about not only by the usual chemical
hydrolyzing and oxidizing agents, but also by bacterial action.
E. Mitcherlich,* in 1850, observed the bacterial decomposition of
crude potato cellulose. Hoppe-Seyler' found that Swedish filter
paper in presence of river mud was changed completely into sol-
uble or gaseous products. In 1886 he put forward the view that
the cellulose is first changed by hydration into a fermentable
carbohydrate and that this latter breaks down to carbon dioxide
and methane.

C«HioOb + H2O2 = CcHiaOe — ^ 3C02 + 3CH4.
The presence of hydrogen is assumed to be derived from acetic
acid, which may be formed as an intermediate product. In the
breaking down of the cellulose molecule by the aid of bacteria,
no intermediate compounds have been isolated. The main prod-
ucts identified by V. Omelianski* are methane, hydrogen, carbon

1. C. Cross and K. Sevan, Researches on Cellulose, III, 128.

2. Bcr. Berlin. Akad. 1860, 102; Ann. 1850, 75, 305; J. prakt. Chem.
1850, 50» 44; J. de Pharm. 1851, 19, 145; Chem. Gaz. 1851, 61; Instit. 1850,
228; Jahr. Chem. 1850, 3, 541; Pharm. Centr. 1850, 21, 385.

3. Zts. physiol. Chem. 1886, 10, 200, 401; abst. J. C. S. 1886, 50,
677, 932; Ber. 1886, .19, 766, 879; Jahr. Chem. 1886, 39, 1873; Wag. Jahr.

1886, 32, 1036. For the estimation of hydrogen in methane, see Zts. physiol.
Chem. 1887, 11, 257; abst. Chem. Ind. 1887, 10, 362; Chem. Tech. Rep.

1887, 28, II, 257; Chem. Centr. 1887, 58, 1166.

4. Compt. rend. 1897, 125, 970, 1131; abst. Jour. Chem. Soc. 1898,
74, i, 291; J. S. C. I. 1898, 17, 60, 171; 1900, 19, 679; BuU. soc. chim. 1898,
(3), 19, 203, 204; Chem. Centr. 1898, 89, I, 269; 1900, 71, I, 918; Chem.
Ztg. 1897, 21, 1057; Jahr. Chem. 1897, 50, 2800; Arch, des Soc. Biolog. St.
Petersb. 7, 411.

340 TECHNOWGY OF CEI.LUU)SE ESTERS

dioxide, acetic and butyric acids, as well as valeric acid in smaller
amounts, and a trace of some unidentified higher alcohols.

Although so many workers have obtained crude cultures
which were capable of acting on cellulose to give definite decom-
position products,^ yet W. Omelianski was the first to isolate the
bacteria and to study the decomposition quantitatively.^ He
demonstrated that pure Swedish filter paper is attacked by cer-
tain anaerobic bacteria obtained from river mud, maniu^e or sew-
age deposits. The fermentation process is very slow compared
with ordinary alcoholic fermentations, and it is best carried out
at 35° C. in presence of calcium carbonate. The incubation
period, before gas is evolved, varies from one week to several
months. During fermentation, fatty acids are formed and these
gradually dissolve part of the calcium carbonate present. The
cellulose is gradually changed into soluble constituents, and at
the end of thirteen months a residue was obtained which was
only 3.6% of the weight of the cellulose originally present.

There are at least two different types of bacteria capable of
converting cellulose into these simple degradation products. In
both cases carbon dioxide is formed, but one type of bacteria
gives hydrogen while the other gives methane. Normally, the
methane fermentation occurs, but if the vitality of the methane-

1. E. Diirin, Compt. rend. 1876, 83, 128, 355; abst. Jour. Chem. Soc.
1877, 31, 106; Chem. News, 1876, 34, 63; Mon. Sci. 1876, IB, 862; Ber. 1876,
9, 1430, 1446; Chem. Tech. Rep. 1876, 15, II, 129; Jahr. Chem. 1876, 29,
947; Zts. Chem. Grossgewerbe, 1876, 1, 135; J. de Pharm. 1876, 24, 290,
356. See also L. Pasteur, Compt. rend. 1876, 83, 176; Chem. Centr. 1876,
47, 663; Chem. Tech. Rep. 1876, 15, II, 129; Mon, Sci. 1876, IB, 862.

2. V. Omelianski, Compt. rend. 1895, 121, 653; abst. Jom-. Chem.
Soc. 1896. 70, H, 202; J. S. C. I. 1896, 15, 129; Biederm. Centr. 25, 501; Chem.
Centr. 1895, 66, II, 1166; Jahr. Chem. 1896, 49, 2013. For the action of
Mucor boulard on starch and cellulose, see Soc. Franc, des Distilleries d
rindo Chine, F. P. 459634, 459815, 1912; abst. J. S. C. I. 1913, 32, 1167;
C. A. 1914, 8, 3215. Arch, biolog. St. Petersb. 7, 411; abst. Chem. Centr.
1900, 71, I, 918; Jour. Chem. Soc. 1900, 78, ii, 493; J. S. C. I. 1900, 19,. 679;
Jahr. Chem. 1900, 53, 842; Meyer Jahr. Chem. 1900, 10, 246; Centr. f.
Physiol. 1900, 14, 33. Centr. Bakt. Parasilenk. 1906, 15, ii, 673; abst.
Chem. Centr. 1906, 77, I, 1034; J. C. S. 1906, 90, ii, 188; Rep. Chim. 1906,
6, 187; Meyer Jahr. Chem. 1906, 16, 270; Biochem. Centr. 1906-1907, 5,
494. Centr. Bakt. Parasitenk. 1904, 11, 369; abst. Jour. Chem. Soc. 1904,
86, ii, 278; Rep. Chim. 1904, 4, 379; Chem. Centr. 1904, 75, II, 825; Jahr.
Chem. 1904, 57, 2126; Zts. ang. Chem. 1904, 17, 566, 1556. F. Czapek,
Beitr. chem. Physiol, u. Pathol, 1, 538; 2, 557; 3, 47; abst. Chem. Centr.
1902, 73, 1, 532; II, 1068; J. C. S. 1902, 82, ii, 280; 1903, 84, ii, 35, 168; Bull.
Soc. Chim. 1903, (3), 30, 440, 526, 1278; Chem. Zts. 1902-1903, 2, 343; Jahr.
Chem. 1902, 55, 1936.

CEI.I.UI,OSE

341

producing organism is reduced or destroyed by previously warm-
ing the inoculant, the hydrogen fermentation occurs. The bacilli
which bring about the two different types of fermentation are
very similar morphologically.

The following table shows Omelianski's results from two ex-
periments.^

Hydrogen
Fermentation

Methane
Fermentation

Cellulose:
Quantity taken

3.4743 gm.
0.1272gm. (3.6%)

-
2.0815 gm.

Undecomposed residue

Fermentation products:

Volatile organic acids

Carbon dioxide

0.0750 gm. (3.6%o)

3.3471 gm. (96.4%)

2.0065gm. (96.4%)

2.2402gm. (64.5%;)

0.9722gm.) ,28 ao/^
0.0138gm. P^-^/^^

1.0223gm. (49.1%,)

Hydrogen or methane

Total products of fermentation .

3.2262gm.

2.0273 gm.

S. Trotman* has called attention to the communication of
S. Penticost,' on a pink discoloration sometimes caused in cotton
cloth by the formation of pseudo-mauveine. Trotman has
investigated a similarly appearing case which was due to an
entirely different cause, i. e., mould. The goods upon storing
for two weeks, gave a faint pink color, microscopical examination
disclosing mould which readily developed on starchy matter,
particularly in the presence of organic acids, but could not be
grown upon gelatin.

The particular bacteria regarded by P. van Tieghem* and

1. Chem. Ztg. 1902, 28, 133; abst. Centr. Bakt. Parasitenk. 1902, 8, ii,
193, 225. 257. 289, 321, 353, 385; abst. J. C. S. 1902, 82, ii, 468; Chem.
Centr. 1902, 73, I, 732, 887, 945, 1068; J. Russ. Phys. Chem. Soc.
1902, 34, II, 7; Chem. News, 1901, 84, 220; J. S. C. I. 1902, 21, 418; Bull.
Soc. Chim. 1902. (3), 28, 853; Rep. Chim. 1902, 2, 311, 450; Chem. Ztg. 1902,
28, 133; Jahr. Chem. 1902, 55, 1987; Biochem. Centr. 1902-1903, 1, 157; Arch,
d. Sci. Biol. 9, No. 3.

2. J. S. C. I. 1909, 28, 1237; abst. C. A. 1910, 4, 1241; Chem. Zentr.
1910, 81, I, 1396. Zts. ang. Chem. 1910, 23, 757; J. Soc. Dyers Col. 1910,
28,32.

3. J. S. C. I. 1909, 28, 1180; abst. C. A. 1910, 4, 672; Chem. Zentr.
1910 81« I 778.

'4. Bull. soc. botan. 1877, 24, 128; 1879, 25; Compt. rend. 1879, 88,
205; 8S, 6, 1102; abst. Chem. News, 1879. 39, 103; J. C. S. 1880, 38, 334;
Mon. Set. 1879, 2i, 296; Ber. 1879. 12, 2087; Chem. Tech. Rep. 1879. 18,

342 t]SCHNOI.OGY OI^ C^LtrUWS^ ESt^RS

others as' the specific ferment of cellulose, namely Bacillus amylo-
bacteria, sis not capable, according to Omelianski, of decomposing
cellulose. Pure cultures of the special bacteria employed by the
latter worker are obtained by the method of selective cultures.*
To Swedish filter paper and chalk contained in flasks, is added a
solution containing the following media, which acts as food for
the bacteria: Potassium and ammonitmi phosphates, magnesium
sulfate, a small quantity of gum-arabic and a trace of river-mud.
The flask is then hermetically closed and kept at 30°-35° C.
Fermentation sets in after a definite interval. The progress of
the fermentation is followed by changes which occur in the appear-
ance of the cellulose material. The filter paper first becomes a
yellowish color; a transparency and gelatinous stage is reached
later, and finally the greater portion of the paper is changed into
a soluble condition. Portions of the chalk are also dissolved by
the fatty acids formed, and pass into solution as calcium acetate
and calcium butyrate. The bacteria remains attached to the
small portion of unattacked paper which remains. From the
organisms collected on the filter paper, the bacillus is obtained
by heating for five minutes to 90°, and then cooling to 37^.
These operations of heating followed by cooling are repeated sev-
eral times. Further cultivations on potatoes are necessary.
There is difficulty in obtaining the cellulose-decomposing bac-
teria in a pure state, as they cannot be isolated by the usual pro-
cedure, since they do not grow on solid media. The method of
accumulation is usually employed in the elimination of foreign
bacteria. The ferment is G-7 /* long and 0.2-0.3 m broad. It
forms round spores with a diameter of 1 /a.

W. Oechsner de Coninck,^ treated filter paper in a similar
manner to Omelianski, but uses a simpler food media. He em-
ploys potassium phosphate and ammonia nitrate with a small
proportion of slime or mud. Fermentation starts in four days
and proceeds in a manner similar to that recorded by Omelianski.
Among the resulting products he identified propionic acid. A

79; Jahr. Chem. 1879, 32, 1016; Wag. Jahr. 1879, 25, 817; Jahr. rein
Chem. 1879, 7, 570; Zts. f. Spiritusind. 1879, 329; Zts. Chem. Grossgewerbe,
1879 4 23 146 154.

'l.' Compt. reiid. 1895, 121, 653; abst. Jour. Chem. Soc. 1896, 70, ii,
202; J. S. C. I. 1896, 15, 129; Bied. Centr. 25, 501; Chem. Centr. 1895,
66, II, 1166; Jahr. Chem. 1896, 49, 2013.

2. Compt. rend. soc. biol. 1916, 79, 166; abst. C. A. 1917, 11, 54.

CELI.UI.OSS 343

cellulose decomposing organism has also been described by H.
Hutchinson and J. Clayton^ and others.* A. Herzen has found
aerobic organisms capable of destroying cotton and linen.'

The property possessed by cellulose of resisting the action of
most bacteria is utilized in the removal of the natiu-al impurities
of cotton cloth. B. Levine* found that bacterial treatment

1. J. Agric. Sci. 1919. 9, 143; abst. J. S. C. I. 1919, 38, 381. For
data on the deterioration of paper and cellulose by fungi, refer to P. See,
Compt. rend. 1917, 164» 230; abst. C. A. 1917, U, 1041; J. S. C. I. 1917,
36 449.

2. H. Pringsheim, Zts. physiol. Chem. 1912, 78, 266; 80, 376; abst.
J. C. S. 1912, 102, ii, 587; J. S. C. I. 1912, 31, 631; C. A. 1912. 6, 2632; BuU.
Soc. Chim. 1913, (4), 14, 398, 468; Chem. Zentr. 1912, 83, II, 638; Meyer
Jahr. Chem. 1912, 22, 178. 269. See also van Iterson, Centr. f. Bak. u. Para-
sitenk. 11, €89; abst. Chem. Centr. 1904, 75, I, 1338. He exposed cellulose
to the action of bacteria for varying lengths of time, and when the decompo-
sition became too vigorous, an antiseptic was added. This checks the devel-
opment of gas but allows the action of the endoenzymes to continue. After
a short period of action of these it is possible to show the presence of cello-
biose and dextrose in the degradation products.

3. Compt. rend. soc. biolog. 41, 140; abst. Her. 1891, 24, 163; Jahr.
Chem. 1891, 44, 2331. See Dudaux, Ibid. 41, 163. C. v. Iterson, Centr.
Bakt. 1904, 11, 689; Kon. Akadem. Amsterdam. 1903, 807; Chem. Centr.
1904, 75, I, 1338. H. Pringsheim and M. v. Markatz (Zts. physiol. Chem.
1919, 105, 173; abst. J. S. C. I. 1919, 38, 694-A) have found that diastase
is without action on a dextrin prepared from cellulose. Extracts prepared
from the stomach, intestines and pancreas of oxen were also unable to de-
compose the dextrin, from which it is concluded that the hydrolysis of cellu-
lose in the digestive system of these animals is caused by bacteria. For the
"Decomposition of Cellulose by the Anaerobic Organism, -Spirochaeta cyto-
phaga," see H. Hutchinson and J. Clayton, J. Agric. Sci. 1919, 9, 143.

4. J. Ind. Eng. Chem. 1916, 8, 298; abst. C. A. 1916. 10, 1273; J. S.
C. I. 1916, 35, 687; Chem. Zentr. 1918, 8S, I, 492; Sci. 1915. 41, 543. J.
Hebden, J. Ind. Eng. Chem. 1914, 6, 714; abst. J. S. C. I. 1914, 33, 959;
C. A. 1914, 8, 3632. According to Hebden, the yellowing of bleached cotton
cloth on steaming or diuing storage is due to imperfect removal of alcohol-
soluble and nitrogenous impurities. B. Levine confirms Hebden with regard
to the importance of the nitrogenous impurities, but finds that the ether-
soluble impurities have an equally injurious action, whereas the yellowing
is not connected in any way with the presence of the alcohol-soluble con-
stituents. Laboratory experiments with different species of bacteria (Bac.
amylolylicus, Bac. fimi, Bac. bibulus, Bac. carolovarus and Ba^. sublilis, Ehren-
berg) in a nutrient solution containing 1 gm. each of dipotassium phosphate
and magnesium sulfate and 2 g^. each of sodium chloride, ammonium sul-
fate, and calcium hydroxide per liter, showed that the nitrogenous substances
and ether-soluble impurities of cotton can be efficiently removed by bacterial
action. The bacteria mentioned converted starch sizing only to dextrins
and had little action on the alcohol-soluble impurities. Samples of cotton
cloth purified by bacterial action and then bleached, showed no yellow color-
ation when subjected to steam at a pressure of 10 lbs. per sq. in. for 45 mins.
Preliminary trials on a large scale for the purification of paper-making stock,
cotton yam, and cotton cloth by bacterial treatment, previous to bleaching,
have given promising results, the material being incubated with the bacteria
culture for periods ranging from 72 down to 24 hotu-s. See also C. Cross,
E. Bevan and J. Briggs, J. S. C. I. 1908, 27, 260.

344 TECHNOLOGY OF CELLULOSE ESTERS

f

might be employed to remove impurities from mitreated cotton.
A. Deiss has described^ a means of obtaining a special anaerobic
ferment derived from African esparto, which is capable of destroy-
ing certain impurities in such raw cellulose material as crude
hemp, com bast, rice, cotton, jute, etc. The fiber is also
disintegrated and in a suitable condition for further purification
in order to obtain pure cellulose.

The development of mildew^ or colored spots' on cotton
goods requires the presence of starchy and nitrogenous material
as food for the fungi.* The growth is not due to a direct attack
on the cellulose complex. Moulds, however, will grow on pure
nitrocellulose suspended in water, provided the requisite mineral
matter is present and the material placed in the dark.*

The possibility of the decomposition of cellulose in the diges-

1. E. P. 23625, 1909; abst. C. A. 1911, 5, 2429. A. Deiss and Four-
nier, F. P. 403518, 1909; abst. C. A. 1911. 5, 1514; J. S. C. I. 1910, 29, 84;
Mon. Sci. 1910, 73, 168, 447; 406722, 1909; abst. C. A. 1911, 5, 1662; Mon.
Sci. 1910, 73, 174; D. R. P. 235852; abst. C. A. 1912, S, 1365; Chem. Zentr.
1911, 82, II, 328; Wag. Jahr. 1911, 57, II, 500; Zts. ang. Chem. 1911, 24, 1498.
For the fermentation of cellulose giving methane, see Bull. Union des Phjrsi-
cians, 1918, 71. P. van Tieghem, Bull. soc. botan. 1877, 24, 128; 1879,
25; Compt. rend. 1879, 38, 205; 1879, 89, 5, 1102; abst. Chem. News, 1879,
39, 103; J. C. S. 1880, 38, 334; Mon. Sci. 1879, 21, 296; Ber. 1879, 12, 2087;
Chem. Tech. Rep. 1879, 18, 79; Jahr. Chem. 1879, 32, 1016; Wag. Jahr.
1879, 25, 817; Jahr. rein Chem. 1879, 7, 570; Zts. Spiritusind. 1879, 329;
Zts. Chem. Grossgewerbe, 1879, 4, 146, 154. V. OmeUanski,, Compt. rend.

1897, 125, 970, 1131; Arch, des Soc. Biolog. St. Petersb. 7, 411; J. C. S.

1898, 74, i, 291; J. S. C. I. 1896, 15, 129; 1898, 17, 60, 171; 1900, 19, 679;
Bull. Soc. Chim. 1898, 19, 203, 204; Chem. Centr. 1898, 69, I, 269; 1900,
71, I, 918; Chem. Ztg. 1897, 21, 1057; Jahr. Chem. 1897, 50, 2800. N.
Kessener, D. R. P. 290126, 1914; abst. Chem. Zentr. 1916, 87, I, 350; Chem.
Ztg. Rep. 1916, 40, 102; Zts. ang. Chem. 1916, 29, 127; J. S. C. I. 1916, 35, 486.

2. For this reason mildew does not appear as often on white and
colored cloth, as when in the grey (unbleached) condition, which, being sized
is much more prone to this defect. When cotton is thoroughly scoured,
therefore, there remains only traces of nitrogenous products, and this scarcity
of nitrogenous food makes it difficult for the organisms to thrive. An im-
perfectly scoiu-ed cotton may contain as much as 0.5% of nitrogen, equivalent
to 3.25% albuminoid bodies, and such cottons are readily attacked by moulds.

3. S. Trotman, J. Soc. Dyers Col. 1910, 26, 32; abst. C. A. 1910, 4,
1393; J. S. C. I. 1909, 28, 1238; Chem. Zentr. 1910, 81, I, 1396; Zts. ang.
Chem. 1910, 23, 757.

4. E. Knecht (J. Soc. Dyers Col. 1905, 21, 189; abst. J. S. C. I. 1905,
24, 841; Biochem. Centr. 190.^1906, 4, 416; Chem. Ztg. Rep. 1905, 29, 235;
Meyer Jahr. Chem. 1905, 15, 510; Lehne's Faerberztg. 1905, 16, 313; Leip-
ziger Faerberztg. 1905, 54, 375; Zts. ang. Chem. 1906, 19, 303, 1476) has
shown that human saliva has a peculiar and distinct action upon cotton
cellulose, and that when a piece of bleached calico has previously been sat-
urated with saliva, it will absorb considerably more substantive dyestuffs
than untreated cotton. On account of the fact that the saliva loses this power
after boiling, the effect has been ascribeditoTthe ptyalin present.

5. T. Bokomey (Chem. Ztg. 1896, 20,«985; abst. J. C. S. 1898, 64,

CELLULOSE 345

live organs of some animals has often been suggested. It
is assumed that the cellulose is converted into soluble substances
which are assimilated by the animal organism. ^'^•'•*'*'® According to

ii, 39; Chem. Centr. 1897, 68, I, 30; Jahr. Chetn. 1896, 49, 1031) showed
that the bacterial growth is rapid, and a considerable quantity of the vege-
table growth accumulates round the masses of cellulose nitrate. He claims
that cellulose itself cannot act as a food supply, and it seems probable that
if glycerol is present cellulose nitrate is no longer made use of.

1.' Celltdose-dissolving Enzyme in Snail Liver, W. Biedermann and P.
Moritz, Pflueger's Archiv. 1898, 73, 219; abst. J. C. S. 1899, 76, ii, 166;
Chem. Centr. 1898, 69, II, 1214.

2. H. Lohrisch, Digestion of Crude Fiber and Cellulose by Man and
Animals, Zentr. ges. Physiol. Path. Stoffwechsels. 21, 801; abst. C. A. 1908,
2, 562. Absorption and Nutritive Value of Cellulose and Hemicellulose in
Man, Zts, exper. Path. 5, 478; abst. C. A. 1909, 3, 1434. Digestion of Cel-
lulose by Dogs, Zts. physiol. Chem. 69, 143; abst. J. C. S. 1910, 98, ii, 1083;
C. A. 1911, 5, 936; Chem. Zentr. 1910, 81, II, 1829.

3. Cellulose Digestion, W. Ellenberger, et al., Zts. physiol. Chem. 1915,
96, 236; abst. C. A. 1916, 10, 916; J. C. S. 1916, tWj i, 588. W. Grimmer and A.
Scheunert, Berl. Tierarztl. Wochenschr. 1910, 26, reprint; Zentr. Biochem.
Biophys. 10, 71; abst. C. A. 1910, 4, 2531; J. C. S. 1910, 98, ii, 554; Chem.
Zentr. 1910, 81, I, 1625. Digestion of Cellulose in, and Ferments of, the
Caecum, A. Scheunert, Zts. physiol. Chem. 1906, 48, 9; abst. J. C. S. 1906, 90,
ii, 463; Chem. Centr. 1906, 77, II, 62. Solubility of Cellulose in Saliva of
Sheep, A. Scheunert, Berl. Tierarztl. Wochenschr. 1910, 26, reprint; abst.
C. A. 1910, 4, 2531; J. C. S. 1910, 98, ii. 521. "Cellulose Digestion and the
Estimation of Cellulose by the Methods of Lange and Simon and Lohrisch,"
A. Scheunert and E. Lotsch, Zts. physiol. Chem. 1910, 65, 219; abst. C. A.
1910, 4, 2312; J. C. S. 1910, 98, ii, 464; J. S. C. I. 1910, 29, 555; Chem. Zentr.
1910, SL, I, 1851; Jahr. Chem. 1910, 63, II, 421; Zts. ang. Chem. 1910, 23,
1389. Cellulose Digested by Dog? A. Scheunert and E. Lotsch, Biochem.
Zts. 1909, 20, 10; abst. C. A. 1910, 4, 64, 2531; J. C. S. 1909, 96, ii, 905;
Chem. Zentr. 1909, 80, II, 1265. Digestion of Cellulose in Domestic Ani-
mals, A. Scheunert, H. Lotsch and W. Grimmer, Berl. Tierarztl. Wochen-
schr. 1909, 26, 5, 113; abst. C. A. 1910, 4, 2169, 2530; J. C. S. 1910, 98, ii, 520;
Chem. Zentr. 1910, 81, I, 1625; Jahr. Chem. 1910, 63, II, 420.

According to S. Acree (Pulp and Paper Mag. 1919, 17, 569; abst. J. S.
C. I. 1919, 38, 677-A), very serious losses may be caused by the rotting of
wood in stacks. Calculated on the basis of equal volumes of sound and
rotten woods, a loss of 75% of wood substance has been recorded after 12
months. A block of sound spruce wood contains 58% of its weight of cel-
lulose; in a similar block of rotten wood only 13%-14% of cellulose was found,
equivalent to a loss of 76% of the original cellulose. The methoxyl group,
from which wood alcohol is formed, has been destroyed to the extent of 75%;
the acetic acid group, 80%; the pentosan, 77%, and the methylpentosan,
65%. These constituents had been converted into gases and soluble sub-
stances; the matter soluble in hot water had increased by 146%. The fungi
and bacteria infect the stacks in certain parts. Some of them get through
into the (mechanical) pidp and growths of red or black patches appear in
the pulp is inferior in color and strength to that made from soimd pulp.
Estimates made at pulp mills indicate losses of wood amounting to 5%-10%
through rotting, and in addition, losses of strength in the pulp of 10%-20%,
or in some cases even 50%. The fungus of "red rust" has been isolated and
studied in the form of cultures.

4. H. Weiske and T. Mehlis, Digestion of Cellulose by Geese, Landw.
Versuchst. 21, 411; abst. Jour. Chem. Soc. 1878, 34, 905; Chem. Centr. 1878,

346 TECHNOLOGY Oi^ CELLULOSE ESTERS

I. Dreyfus/ however, certain organisms such as Polyporus,
Agaricus campestris, Bacillus subtilis, pus bacilli and Aspergillus
glaucus, contain cellulose.

W. Tappeiner* analyzed the gases from the intestines of her-
bivorous animals, and found them to consist of carbon dixoide and
methane with smaller quantities of hydrogen. To test if organ-
ized ferments brought about the decomposition of cellulose, he
placed pure cellulose, in the form of absorbent cotton or pulp of
the finest vellum paper, with a food medium (1% meat extract).
He sterilized the mixtiu'e and then added a small quantity of
pancreas extract of bovine origin. A vigorous fermentation set
in and carbon dioxide and methane were evolved in some experi-
ments. In others the gases evolved were carbon dioxide and
hydrogen. In control-experiments where the pancreas extract
was absent no gas was evolved.*

E. Knecht* and J. Huebner* have observed that bleached

49, 504; Jahr. Chem. 1878, 31, 987.

5. Nutritive Value of Cellulose, N. Zuntz, Pflueger's Archiv. 49, 477,
483; Bied. Centr. 1892, 21, 88; abst. J. C. S. 1893, 64, ii, 22; Ber. 1891, 24,

• R, 837; Chem. Centr. 1891, 62, II, 383; Jahr. Chem. 1891, 44, 2258; 1892,
45, 2193; Meyer Jahr. Chem. 1892, 2, 281. See also A. Mallevre, Pflueger's
Archiv. 49, 460; abst. J. C. S. 1893, 64, ii, 21; Mon. Sci. 1891, 37, 76; Ber.
1891, 24, R, 836; Chem. Centr. 1891, 62, II, 381; Chem. Ztg. Rep. 1891,
15, 197; Jahr. Chem. 1891, 44, 2258. von Henneberg and Pfeiflfer, Jour,
f. Landwirtschaft, 1890, 38, Part 2. W. von Tappemer, Zts. f. Biol. 24,
118. N. Zuntz and Lehmann, Landw. Jahr. 1889, 41, 153. A. von Werther,
Zts. d. Ver. f. Ruebenzuckerind. 1886, 426. Pfeiffer and Lehmann, Jour,
f. Landw. 1886, 239. J. Munk and T. Rosenheim, Verhandlungen der
physiolog. Ges. Berlin, Feb. 27, 1891.

6. Celltdose Digestion by Enzymes, E. Newcombe, Botan. Centr.
1898, 73, 105; Annals of Bot. 1899, 13, 49; abst. J. C. S. 1900, 78, ii, 99;
Chem. Centr. 1899, 70, II, 129; Chem. Ztg. Rep. 1898, 22, 72; 1899, 23,
102; Jahr. Chem. 1899, 52, 2590; Meyer Jahr. Chem. 1899, 9, 2^.

1. Zts. physiol. Chem. 1893, 18, 358; abst. J. C. S. 1894, 66, "ii, 24; Chem,
Centr. 1893, 64, II, 941; Jahr. Chem. 1893, 46, 879; Chem. Ztg. Rep. 1893,
17, 271.

2. Amer. J. Sci. 1883, (3), 26, 404; Ber. 1882, 15, 999; abst. Chem.
News, 1884, 50, 260; J. C. S. 1882, 42, 985; Bull. Soc. Chim. 1882, 38, 44;
Chem. Ztg. 1882, 6, 494; Jahr. Chem. 1882, 35, 1202; Bied. Centr. 13, Part 4.

3. C. Beadle and H. Stevens, J. S. C. I. 1909, 28, 1018; abst. C. A.
1910, 4, 482, 1100; Paper Trade J. (4), 50, 62; Bull. Soc. Chim. ISffo, 8, 523;
Rep. Chim. 1910, 10, 112; Chem. Zentr. 1910, 81, I, 779; Jahr. Chem. 1909,
63, II, 383; Wag. Jahr. 1909, 55, II, 527; Zts. ang. Chem. 1910, 23, 852.
For the decomposition of cellulose in the presence of bacteria, see E. Meusel,
Ber. 8. 1215, 1356, 1653; Compt. rend. 1875, 81, 95; abst. Chem. News,
1875, 32, 204; 1876, 33, 262; J. C. S. 1876, 29, 189, 413; Jahr. Chem. 1876,
28, 172, 898; Jahr. rein chem. 1875, 3, 20.

4. J. Soc. Dyers Col. 1905, 21, 189; abst. J. S. C. I. 1905, 24, 841;
Biochem. Centr. 1905-1906, 4, 416; Chem. Ztg. Rep. 1905, 29, 236; Meyer

calico which is saturated with saliva absorbs more coloring mat-
ter than untreated calico. If the saliva is previously boiled its
eflfect is lost. Diastase has also an action, but to a less degree.^
Knecht assumes that an enzyme ptyalin in the saliva is the active
principle. The solution of the vegetable cell walls dtuing ger-
mination is attributed to a special ferment (cytase),* by J. Grliss.

The conversion of the cellulose into soluble compounds is
probably brought about by destructive fermfiats present in the
digestive tract. H. Bierry and J. Giaja' obtained from the
alimentary tract of various invertebrates certain enzymes which
were capable of hydrolyzing cellulose and polysaccharides. V.
Hofmeister^ introduced freshly mown grass enclosed in a suitable
apparatus into the rumen of a sheep. In three days he found
that 78.4% of the 21.6% of fiber present in the grass had been
removed. Experiments were carried out comparing the solvent
action of gastric juices and liquid manures on grass-fiber. The
gastric juices dissolved 78.8%, while an equal amount of the liquid
maniu-e dissolved only 3.5% of the fiber. The amount of hay
dissolved by gastric juice, is proportionate to the amount of the
latter solvents present. The solvent action of gastric juice ndxed
with glycerol and saliva from various glands on cellulose, was
also investigated. The greatest amount of fiber dissolved (80.4%)

Jahr. Chem. 1905, 15, 510; Lehne's Faerberztg. 1905, 16, 313; Leipziger
Faerberztg. 1905, 54, 375; Zts. ang. Chem. 1906, 19, 303, 1475.

5. J. Huebner, J. S. C. I. 1908, 27, 105; Proc. Manch. Lit. Phil. Soc.
1908, 52, 2; abst. C. A. 1908, 2, 1187, 1347; Chem. News, 1908, 97, IQ;
Proc. Chem. Soc. 1907, 23, 304; BuU. Soc. Chim. 1908, 4, 1060; Rep. Chim.
1908, 8, 238; Chem. Zentr. 1908, 79, I, 1097; Chem. Ztg. 1908, 32, 220;
Jahr. Chem. 1905-1908, II, 3185; Meyer Jahr. Chem. 1908, 18, 505; Wag.
Jahr. 1908, 54, II, 467; Zts. ang. Chem. 1908, 21, 87, 1760.

1. Scheurer, Bull. Soc. Ind. Mulhouse, 1903, 73, 320; abst. J. S. C. I.
1904, 23, 57;.Moii Sci. 1903, 59, 704; Chem. Ztg. 1903, 27, 772.

2. Wochenschrift f. Brauerei, 1895, 12, 1257; J. Landw. 43, 379;
abst. J. C. S. 1896, 70, ii, 669; J. S. C. I. 1896, 15, 464; Chem. Centr. 1895,
86, I, 787; 1896, 67. I, 313; Chem. Ztg. Rep. 1895, 19, 71; 1896, 20, 48;
Jahr. Chem. 1895, 48, 2681 ; 2701 ; J. Landw. 1896, 43, 379. Wochenschrift
f. Brauerei, 1902, 19, 243; abst. J. C. S. 1902, 82, i, 713; J. S. C. I. 1902, 21,
715; Chem. Centr. 1902, 73, I, 1277; Jahr. Chem. 1902, 55, 1989; Wag.
Jahr. 1902, 48, II, 410.

3. Biochem. Zts. 1912, 40, 370; abst. C. A. 1912, 6, 2116; J. C. S. 1912,
102, ii, 657; J. S. C. I. 1912, U, 561; Bull. Soc. Chim. 1913, 14, 331; Chem.
Centr. 1912, 83, II, 199.

4. Arch. Wiss. Prakt. Thierheilk, 1881, 7, 169; abst. Bied. Centr. 1881,
669; abst. J. C. S. 1882, 42, 237.

348 TECHNOLOGY OF CELLULOSE ESTERS

«

occurred in the experiment where mixed saliva was employed.

Experiments with sheep by ]?. Lehmann^ with a Pettenkofer
respiration apparatus, indicated that cellulose as a food was equal
to starch material, as far as increase in the production of lean
meat was concerned; cellulose, however, was much inferior as a
fat producer. O. Kellner, et al.,^ carried out a very detailed ex-
perimental study of the assimilation of cellulose by herbivorous
animals. He concluded that straw cellulose, from which the
lignone constituents had been removed, has a nutritive value equal
to that of starch as far as flesh formation was concerned.

In the breaking down of cellulose in the digestive tract, it
is probable that compounds other than methane, hydrogen, car-
bon dioxide and fatty acid were formed. These intermediate
decomposition products have probably a large nutritive value.
They are assimilated in this stage by the animal organism.*

Analjriical Examination of Cellulose Raw Materials/ 1. Gen-

1. Lehmann, Exper. Stat. Record, 1895, 7, 235; Land. Jahr. 1895,
24, 117; J. C. S. 1896, 70, ii, 262.

2. Landw. Versuchs-Stat. 1900, 53, 1474; abst. J. C. S. 1900, 78, ii,
566; Chem. Centr. 1900. 71, 1, 992, 994.

3. G. Lusk, Amer. J. Physiol. 1911, 27, 467; abst. J. C. S. 1911, 100,
ii, 311; Chem. Zentr. 1911, 02, I, 1227. A. deBary, Ann. Sd. Nat. Botan.
1863, (4), 20, 1. Bot. Ztg. 1886, 44, 377, 393, 409, 433, 449, 465. J. Beh-
rens, Centr. Bak. Para, u Infektion. 1898, 4, II, 514, 547, 577, 636, 700,
739. M. Berthelot, Compt. rend. 1889, 109, 841. Bertrand, Gabriel and
M. Holderer, Ann. I'Inst. Pasteur, 1910, 24, 180. E. Bourqudot, Bull. soc.
Mycol. 1893, 9, 230. J. Choukevitch, Ann. I'Inst. Pasteur, 1911, 2S, 247
P. Deherain, Ann. Agronom. 1884, 10, 385. A. Distaso, Compt. rend. soc.
Biol. 1911, 70, 995. U. Gayon, Compt. rend. 1884, 98, 528. Mem. soc.
Sci. Phys. et Nat. Bord. 1884, (3), 1, LI. LVII. Ber. Verter K6nig. Sach.
1859, 104. A. Hebert, Ann. Agronom. 1892, 18, 536. J. Henneberg, Zts.
Biol. 1885, 21, 613. K. Kellerman and I. McBeth, Centr. Bak. Para, u In-
fektion. 1912, 34, II, 485. W. von Knieriem, Zts. Biol. 1885, 21, 67. Leh-
mann, Franz and J. Vogel, J. Landw, 1889, 37, 251. Macfayden, Allan and
F. Blaxall, Trans. Jenner Inst. Prev. Med. 1899, (2), 162, R, 186. W.
Nylander, Bull. Soc. Bot. 1865, 12, 395. W. Omelianski, Centr. Bak. Para,
u Infektion. 1902, 8, II, 193. 225, 257, 289, 321, 353, 385; 1904, 11, II, 369,
12, II, 33; 1906, 15, II, 673. L. Popoff, Pfliiger's Archiv. 1875, 10, 113.
J. Reiset, Compt. rend. 1856, 42, 53. H. Schellenberg, Flora, 1908, 98. 257.
T. Schloesing, Compt. rend. 1889, 109, 835. Ann. Agronom. 1892, 18, 5.
A. van Senus, Jahr. Gahr. Organ. 1890, 1, 136. E. Smith, Sd. 1902, 15,
405. A. Trecul, Compt. rend. 1865, 61, 156; 432; 1867, 05, 521. L. Tulasnc,
Ann. Sci. Nat. Bot. 1854, (4), 2, 77. H. Ward, Ann. Bot. 1888, 2, 319;
1898, 12, 565. H. Weiske, Zts. Biol. 1870, 6, 456; 1888, 24, 553. Chem.
Centr. 1884, 55, 385. K. Weiske, B. Schulze, and Flechsig, Zts. Biol. 1886,
22, 373.

4. This topic in its entirety has been contributed by J. F. Briggs,
Research Chemist, British Cellulose & Chemical Manufacturing Co.

It will be remembered that this author's contributions cover the entire
domain of cellulose and cellulose derivatives as indicated by the following:

cEUUUi^osE 349

eral Discussion: The chemical constitution of all plant struc-
tures capable of serving as raw materials for the cellulose
industries varies within sufficiently narrow limits to admit of
one general scheme of analytical investigation. Nevertheless,
within these narrow qualitative limits there remains room
for wide variations in quantitative relationships among certain
well defined types. Close conformity to chemical type is a
strong characteristic of all species in the vegetable world.
The constitutional units of the plant structiu-e may be
grouped under three main complexes: the Cellulose complex,
the Lignin complex and the Cutin complex. Depending
on these complexes as colloids in the natural state, there are
factors such as moisture, mineral matters, etc., which move
with them, but in addition to these there is a whole range of
transitory components and localized deposits, such as sugars, tan-
nins, resins, coloring matters, proteins, etc., which from the pres-
ent point of view may be dismissed as non-constitutional or
adventitious and, though frequently important and valuable in
themselves, they have no significance in the valuation of cellu-
lose raw materials. Such components are often conveniently
classed together under the general denomination of "extractives,**
and sometimes it is convenient to express analytical results cal-
culated on the material free from moisture, ash, fat and extrac-
tives.

The components of the main constitutional complexes may

J. Briggs, "Cellulose as a Polysaccharide," J. S. C. I. 1909, 2S, 340. "Ab-
sorption of Sodium Hydroxide by Cellulose Hydrate," Chem. Ztg. 1910,
34, 455. "Hydration of Cellulose in the Beating Process and Nature of
Cellulose Hydrates," Papierfabrikant, 1910, S, Fest u. Auslandsheft, p. 46.
"Tendering of Linen in Presence of Copper," J. S. C. I. 1911, 30, 397.
"Microscopic Details of Certain Wood Pulps," World's Paper Trade Review,
1911; abst. J. S. C. I. 1911, 30, 1374. "Action of Oxalic Acid on Cellulose,"
J. S. C. I. J912, 31, 521. "Acid Tendering of Nitro Artificial Silks," Faeber.
Ztg. 1913, 24, 75. "Cellulose Esters of Benzoic Acid," Zts. ang. Chem.
1913, 26, 255. "System of Paper Testing," Papierfabrikant. 1914, 12,
Fest u. Auslandsheft, 25. "Bleaching of Linen and Cotton Textiles," J. S.
C. I. 1916, 35, 78. "The paper Mill Chemist in War Time," J. S. C. I.
1916, 35, 798. "Progress in the Analysis of Cellulose and Cellulose Deriv-
atives," Analyst, 1915, 40, 107. (With R. Balston) "Manufacture of Solu-
ble Acetylized Cellulose Derivatives," E. P. 10243, 1903. (With C. Cross and
E. Bevan) "CeUulose Acetosulfates," Ber. 1905, 38, 1859, 3531. "Xantho-
genic Esters of Starch," Chem. vSoc. Trans. 1907, 91, 612. "Color Reactions
of Lignocelluloses," Ber. 1907, 40, 3119. "Phloroglucinol Absorption of
Lignocellulose. Estimation of Ground Wood Pulp," Chem. Ztg. 1907, 31,
725. "Chloramine Reactions of Proteins (Flax Bleaching)," J. S. C. I.
1908, 27, 260. "Fibrous CeUulose Acetates," J. Soc. Dyers Col. 1908, 24, 189.

350 TSCHNOI.OGY O^ CEI.I.UI.OSE ESTERS

be regarded as existing in many stages of molecular aggregation,
condensation or polymerization, manifested as components of
inferior and superior resistance to hydroljrtic agencies. A classi-
fication in this sense has been suggested by J. Kdnig and E.
Rump/ who proposed the prefixes *'proto" for the components
of least resistance removable by boiling with water under pres-
sure, "heuM** for those of intermediate resistance removable by
boiUng with dilute mineral acids imder pressiu-e, and "ortho" for
those of superior resistance. This is a very convenient nomen-
clature applicable both to the cellulose and lignin complexes,
but the divisions are purely arbitrary and only capable of defin-
ition in terms of the conditions of time, concentration and tem-
perature which govern the actual percentages of material re-
moved by hydrolysis.

The Cellulose Complex. In the widest sense of the word,
the cellulose complex may be defined as comprizing all the poly-
saccharide carbohydrates which form an essential portion of the
structure of the plant and which yield cupric reducing sugars on
hydrolysis with acids. From this definition starch woidd be
excluded, functioning as stored-up sugar and belonging rather to
the circulatory system than to the plant structiu-e. The poly-
saccharides fall into two main groups: the Pentosans, yielding
pentose sugars on hydrolysis, and the Hexosans, yielding hexose
sugars; normal cellulose itself being the most resistant of the hex-
osans. The definition of **Cellulose" in a narrower sense is a
question around which much controversy has been waged. The
cellulose complex comprizes superior and inferior members of the
hexosan and pentosan groups, some of which become detached
in the processes of isolation and purification. With this circum-
stance in view, cellulose may be defined as the resistant residue
from a series of carefully regulated process of attrition by methods
of selective extraction, oxidation and hydrolysis, sufficient to
effect the complete removal, in the mildest possible manner, of
the other constitutional complexes, together with all adventitious
and extractive matters. Those members which succumb to the
most careful treatment belong to the group of hemicelluloses,
while the resistant residue is the purified cellulose, itself a com-

1. Zts. Nahr. u. Genussmittel, 1914, 28, 188; abst J. S. C. I. 1915,
34, 1203; C. A. 1916, 9, 816.

cBi.i<ULOSB 351

plex product which may comprize both hexosan and pentosan
members and divisible into a-cellulose (more resistattit) and j8-
cellulose (less resistant). The degree of resistance of any of the
members, however, is in no case absolute, but only relative. De-
gradation of substantial portions of the j8-cellulose and of smaller
portions of the a-cellulose takes places more or less in the manu-
facture of cellulose by industrial processes, according to the
severity of the treatment required for purification, and indeed,
can hardly be avoided even in anal3rtical processes in the lab-
oratory. This conception »f cellulose as itself a complex residue
from purification introduces the necessity of admitting variations
in nature and composition according to the species of plant from
which the cellulose was derived. These variations due to species
follow well defined classifications, and we have to deal with natural
t3rpes represented, for example, by cotton cellulose, flax cellulose,
the cellulose of grasses (straw and esparto) and the cellulose of
woods, which last are again naturally subdivided into woods of
coniferous and deciduous or broad-leafed types.

Further, any analytical definition of cellulose must conform
to some ideal of technical utility, the first object of such being
the establishment of an analytical basis for the control of the
processes of production, by afifording a comparison between the
total amotmt of cellulose present in the material and that realiz-
able on the industrial scale imder the limitations imposed by
conmiercial conditions. The practical problem in this sense is to
determine for any given plant material the maximum yield of
purified cellulose possessing all the physical and chemical qual-
ities recognized as characteristic of the species of the optimum.
The second object of technical utility is the characterization of
natural variations of chemical type, in order that the cellulose
may be properly placed in the chemical groups to which it belongs
and its commercial value from a chemical point of view estimated.
In any method for estimating cellulose it is necessary to eliminate
those inferior members of the cellulose complex which, from a
technical point of view, are not entitled to rank either with the
a-cellulose or the /3-cellulose. The method of this exclusion can
only be empirically established as a controlled process of hydrol-
ysis, because the hemicelluloses are only differentiated from their

352 TECHNOLOGY OF CELLULOSE ^STERS

celluloses by their inferior resistance to hydrolysis. In the ab-
sence of any generally agreed specification some authorities have
considered it advizable to omit any intentional hydrolytic treat-
ment for the elimination of hemicelluloses, rel)dng only on what
occurs unavoidably in the process of removing the hgnin. In
such cases the yield of cellulose would be high, but the presence
of inferior constituents in the cellulose would have to be reckoned
with. Other authorities, on the other hand, notably J. Konig,^
have gone so far in the elimination of hemicelluloses as virtually
to destroy the quality of the cellulose. In such cases the yield of
cellulose is low and may even be lower than the commercial yield,
thereby defeating the technical utility which is the object of the
analytical estimation.

For an account of the nature and relative proportions of the
various hemicelluloses in the two main classes of woods, refer-
ence may be made to a publication by J. Konig and E. Becker,^
who have described the analysis of the mixtures of sugars pro-
duced by the hydrolysis of the hemicelluloses by dilute mineral
acids. The hemihexosans yield dextrose, mannose and small
quantities of galactose and the hemipentosans yield exclusively
xylose. These analyses also show that the coniferous woods con-
tain substantial quantities of mannan, while the hemicelluloses
of broad-leafed woods consist principally of xylan.

In the present scheme of analytical discussion the constituent
described by the older authorities under the name of ''wood
gum," extracted from plant materials by digestion with 5%
sodium hydroxide in the cold is intentionally passed over, first
because the extraction of hemicelluloses by this treatment is not
complete and has no quantitative significance, and secondly be-
cause the extract undoubtedly comprizes a portion of the lignin.
On similar grounds of indefinite constitution the application of
the term "pectose" or "pectin" to the structiu^al components of
cellulose raw materials is also avoided, the substances originally

1. Zts. Nahr. u. Genussmittel, 1903, 6, 774; abst. J. C. S. 1903, M,
ii, 764; Rep. Chim. 1904, 4, 19; Chem. Centr. 1903, 74, II, 1147; Chem. Ztg.
1903, 27, 614; Chem. Zts. 19a3-1904, 3, 481; Jahr. Chem. 1903, S€, 1015.
Zts. Nahr. u. Genussmittel, 1906, 12, 3&5; abst. J. C. S. 1906, 90, ii, 906;
J. vS. C. I. 1906, 25, 1069; Rep. Chim. 1907, 7, 46, 93; Chem. Centr. 1906,
77, II, 1529; Chem. Ztg. 1906. 30, 1159; Chem. Zts. 1907, 6, 143; Jahr. Chem.
190.^1908, II, 968; Zts. aiig. Chem. 1907, 20, 543.

2. Zts. ang. Chem. 1919. 32, 155.

CBLI<UU)SE 353

designated tinder that name being more appropriately character-
ized as hemicelluloses.

The Lignin Complex. The chemical constitution of this
most characteristic component of woody substance still awaits
a convincing elucidation. The only investigators who have at-
tempted to give approximate and speculative accounts of its con-
stitutional structure are C. Cross and E. Bevan^ on the one hand,
and P. Klason* on the other. Both authorities are agreed as to
the presence of an aromatic or hydroaromatic nucleus to which
many of the particularly striking color reactions of lignin are to
be referred. This portion of the complex shows relationships
and analogies to the tannins, with catechol as an ultimate deriv-
ative; lignin, in fact, has been described as a kind of insoluble
tannin. Lignin reacts as an unsattu'ated compotmd; it is readily
oxidizable, combines with halogens to form characteristic prod-
ucts, with nitrousiacid to form bright yellow nitroso compotmds,
and with sulfurous acid or bisulfites to form sulfonic adds. With
caustic soda, on heating, soluble sodium salts of definitely acid
derivatives are formed. All these reactions are actually utiUzed
to convert lignin into a soluble form and liberate the cellulose,
but only that depending on the combination with halogens is of
general analytical significance, both for qualitative and quanti-
tative purposes. By this reaction a perfectly clean and complete
separation of the lignin from the cellulose complex is attained
with the minimum of hydrolytic attack on the latter.

Lignin is not a carbohydrate and contains no alcoholic hy-
droxyl groups capable of esterification. It is condensed rather
than hydrolyzed by strong mineral acids which break down the
cellulose complex completely into soluble products, and this re-
sistance forms the basis of an analytical method for the estimation
of hgnin as an insoluble residue.

The Methoxyl group is a characteristic function of the lignin
complex, capable of exact determination in the form of methyl
iodide by Zeisel's method. The quantity of lignin, however, can-

1. J. Soc. Dyers Col. 1916, 32, 135; abst. J. S. C. I. 1916, 35, 628;
C. A. 1916, 10, 2303.

2. "Beitrage zur Kenntniss der chemischen Zusammensetzung des Pich-
tenholzes," Berlin, 1911. Ark. Kemi. Min. o. Geol. 1917, 6, 21; abst. J. S.
C. I. 1919, 38, 570-A. Svensk. Kem. Tidskrift. 1917, 29, 5, 47; abst. C. A.
1917, U, 2482. Cf. C. Schwalbe and E. Becker, Zts. ang. Chem. 1919, 32,
155, 229.

354 TECHNOU)GY OI^ CEI<I<UU)SE ESTERS

not be calculated from the methoxyl value because this differs
in different types of lignin. M. Honig and J. Spitzer,* for in-
stance, have detected in the same wood, lignins differing greatly
in the percentage of methoxyl group combined. T. von Fellen-
berg^ considers that the methoxyl group is characteristic of "pec-
tin" as well as of lignin, and has proposed a method for the sep-
arate estimation of the two types of methoxyl, that from pectin
being liberated by dilute acids and that from lignin only by strong
adds. Although this distinction has been endorsed by C. G.
Schwalbe,' who applies it for the estimation of * 'pectin" in woods
and other plant structures, its justification and utility have not
been demonstrated, and the vague definition of "pectin," as ap-
plied to these materials, probably covers only the more readily
soluble hemihexosans and hemipentosans, together with the lignin
combined with them.

The Acetic Acid group, which is regarded as the source of the
pyroligneous acid formed by the destructive distillation of wood,
is a characteristic component of woody, i. e., lignified, plant tis-
sues generally, and may consequently be classed as an adjtmct
of the lignin complex rather than of the cellulose. It is, however,
liberated by the mildest hydrolytic treatments, even by digestion
with steam, and has never been definitely localized as attached
to either of the major complexes when these are separated. The
actual quantity of acetic acid obtainable on hydrolysis is variable
according to the chemical pre-treatment of the raw material,* and
it may be assumed that under certain circumstances part of the
acetic acid must be derived from other groups not only of the lig-
nin, but also of the cellulose. In this sense the precise constitu-
tional significance of the acetic add group remains ill-defined;
nevertheless, by adopting standard conditions of hydrolysis, the
yield of acetic acid may be established as an anal3rtical constant
of specific importance.*

The Cutin Complex. The cutin complex composes the ex-

1. Monatsh. 1918, 39, 1; abst. J. S. C. I. 1918, 37, 502-A.

2. Mitt. Lebensmittelunters. u. Hyg. 1916, 7, 42; abst. J. C. S. 1916.
HO, ii, 351; C. A. 1916, 10, 2772.

3. Zts. ang. Chem. 1919, 32, 1, 125.

4. C. Cross and E. Bevan, J. Soc. Dyers Col. 1916, 32, 135; abst
J. S. C. I. 1916, 35, 628.

5. A. Schorger, J. Ind. Eng. Chem. 1917, 9, 656, 561; abst C. A. 1917,
U, 2218; J. S. C. I. 1917, 36, 867; Ann. Rep. Soc. Chem. Ind. 1917, 2, 144.

cKi.LUU)se 355

tertial cuticular covering of all plants. This region ranges in
dimensions from bulky masses, represented by cork, to mem-
branes of infinite thinness. All cuticular tissues, fulfilling the
nattu^ function of water repulsion, namely that of keeping suflft-
dent moisture in and excess of water out, show an exudation of
free fat, fatty acid or wax, which is determined by simple extrac-
tion with solvents. When this free fat is removed, there remains
the parent complex, the cutin proper, which appears to be com-
posed of cellulose esters of fatty and resin acids. ^ This complex
is closely associated with the complexes of the lignocellulose, but
the nature of the association, whether constitutional or merely
mechanical, is not known. The cutin ester resists most of the
ordinary chemical treatments, but it is saponified and broken
down into its components by alcoholic sodium hydroxide. A
method for the estimation of cutin has been recommended by
J. Konig,^ based on its insolubility in cuprammonium reagent or
in acid zinc chloride solution, but the satisfactory application of
this method is somewhat difficult, since it involves the previous
removal of the lignin without attacking the cutin. C. G. Schwalbe'
has stated that if the structural complexes of the plant material
be first broken down by heating with hydrochloric acid so as to
obtain a friable powder, the quantity of free. fat, wax or resin
extractable by volatile solvents is very considerably increased, in
some cases doubled.

2. Qualitative and Preliminary Examination. Tests for
Lignification. — One of the first steps in the examination of a raw
material is to obtain an idea of the extent of lignification and to
ascertain whether the lignified structure is general or local. The
most useful test for this purpose is the phloroglucinol-hydrochloric
acid reagent, which gives an intense crimson stain with raw lignin,

1. C. Cross and E. Bevan, J. Soc. Dyers Col. 1919, 35, 70; abst. J. S.
C I. 1919 38* 249- A,

2. Zts. Nahr. u. Genussmittel, 1906, 12, 385; abst. J. C. S. 1906, SO,
ii, 905^1. S. C. I. 1906, 25, 1069; Rep. Chim. 1907, 7, 46, 93; Chem. Centr.
1906, 77, II, 1629; Chem. Ztg. 1906, 30, 1159; Chem. Zts. 1907, 6, 143; Jahr.
Chem. 1905-1908, II, 968; Zts. ang. Chem. 1907, 20, 543.

3. Zts. ang. Chem. 1919, 32, I, 125. In this connection refer also to
A. Besson, Chem. Ztg. 1917, 41, 346. Lindner, Zts. ang. Chem. 1919, 32,
56. C. Schwalbe. Papierfabr. 1908, 6, 551. Zts. ang. Chem. 1918, 31, 193.
C. Schwalbe and W. Schtilz, "Ueber die Aufschlieszung pflanzlicher Roh-
stoflFe mittels Salzsaure," 1917, p. 25; Chem. Ztg. 1918, 42, 229; abst. Zts.
ang. Chem. 1918, 31, 125. G. Testone, Staz. sperim. agarar. ital. 50, 97;
abst. Chem. Zcntr. 1918, 83, II, 865. D. R. P. 309555, 1917.

356 TECHNOI/>GY 01^ CBI^LUI<OSE EStBRS

but is by no means to be relied upon with materials which have been
chemically treated. The reagent is most economically prepared
by dissolving 0.5 gm. of phloroglucinol in 50 cc. of water and then
adding 50 cc. of strong conmiercial hydrochloric acid. The ma-
terial to be examined is steeped in a little alcohol and then covered
with an equal volume of the phloroglucinol reagent. The maxi-
mum color is developed in a few minutes, but appears more
slowly if no alcohol be used. It is not advizable to mix alcohol
with the original reagent, as sometimes reconmiended, since its
keeping properties are thereby impaired. Lignin gives charac-
teristic colors with a large number of aromatic amines and phe-
nols, the bright yellow stain developed on treatment with solu-
tions of aniline salts being largely employed. A test much in
favor with certain workers is Maule's reaction, according to
which the material is steeped for a few minutes in potassium
permanganate, washed, decolorized with 12% hydrochloric acid,
again washed and treated with a little ammonia solution. Lignin
then shows a deep red coloration. The most characteristic and
delicate test for lignin, whether raw or as a residue after chemical
treatments, is the chlorine-sodium sulfite reaction.

Alkaline Hydrolysis. The method originally introduced by
C. Cross and E. Bevan^ for the preliminary classification of fibrous
raw materials still affords useful general indications. The ma-
terial is boiled with 1% solution of sodium hydroxide (a) for five
minutes, (j8) for one hour, the volume of the liquid being kept
constant. The results are quantitatively expressed as loss of
weight of the fibrous residue calculated on the dry substance.
The indications of this test cannot be defined in terms of any
particular constituents of the material. The loss in the short
period of 5 minutes may be held to comprize mainly extractive
matters in general, sugars, starch, resin, tannins, etc., and this
figure serves to afford a zero point from which to measture the
indications of the longer treatment. The difference between the
two may be taken as a measure of the readily hydrolyzable com-
ponents of the major constitutional complexes and comprizes the
inferior hemicelluloses, together with the lignin associated with
them. It must be remembered, however, that the separations

1. "Miscellaneous Vegetable Fibers," C. Cross, Reports of Colonial
and Indian Exhibition^ 1886.

CHLUUWS^ 357

are not sharp or specific, and that what is measured is in fact a
certain region on the curve indicating the rate of hydrolysis of
the entire material.

Chlorination and Isolation of Ultimate Fibers. The elegant
reaction discovered and applied by C. Cross and E. Bevan for
the quantitative estimation of cellulose may be utilized in its
qualitative application for the isolation of the ultimate fibers,
vessels and cells which compose the masses or strands of raw
plant tissues. In the majority of cases the cohesion of these con-
stituent elements can only be broken down by the removal of
the lignin, and Cross and Sevan's chlorination reaction effects
this in the most complete and simplest manner. The manipula-
tion follows closely the lines indicated for the quantitative esti-
mation of celltdose {q. v,) but the preliminary disintegration of
the material need not be so complete for the present purpose.
Nevertheless, in the case of massive materials such as wood, it
is necessary to afford free exposiu-e to the chlorine gas by shredding,
rasping, shaving, or otherwise opening up the tissues before the
chemical treatment. After chlorination, the chlorolignin com-
potmd is decomposed and extracted by boiling with 2% sodium
sulfite sofution, the action of which for qualitative purposes may
be considerably accelerated by the addition of a little caustic
soda to the boiling solution. With a little mechanic^ assistance,
the material falls apart into its constituent elements composed of
substantially pure cellulose and the felted mass is collected on a
cotton filter, washed, pressed, and preferably kept in the moist
state for microscopical examination.

Examination of Cellulose Fibers, Certainly in those in-
dustries which utilize cellulose in virtue of its structural proper-
ties, the microscopic characteristics are fundamental, and are
not to be neglected in those industries which only regard cellulose
as a chemical raw material. The microscopical identification of
cellulose fibers for the diagnosis of species is a specialized branch
of study which is outside the present subject, but in any case it
is important to ascertain the structiuul homogeneity or hetero-
geneity of the pure cellulose prepared from the material. Thus
it is necessary to establish the presence or absence of fibers of
abnormal development, the density and thickness of the cell
walls and the relative proportions of fibrous and non-fibrous ele-

358 TECHNOWXJY OF C^I.LtJI*OSE ESTERS

ments. All these are contributory factors which may considerably
influence the uniformity of the chemical reactions in industrial
applications with pure cellulose as a basis. The chemical reac-
tivity of a mass of cellulose which is not structurally homogeneous
is governed by the reaction velocity of its most resistant mem-
bers and in so far as this is dependent on processes of diffusion
and other physical factors, a knowledge of the microscopic struc-
tiu-e is of great importance.

The cellulose carefully prepared by the chlorination process
should be completely free from lignin, but in many cases the cutin
complex is but little attacked by the operations described. If
now the preparation be treated with cuprammonium solution
(Schweizer's reagent), the cellulose is rapidly dissolved, leaving
the cuticular elements in the form of an insoluble residue. The
microscopic examination of this residue may afford confirmatory
evidence of identification and, if the quantity is substantial it
will have to be taken into account from an industrial point of
view.

J, Quantitative Methods. Moisture. The exact determina-
tion of hygroscopic moisture in cellulose materials has been in-
vestigated and discussed by M. Renker.^ The problem is simplest
in the case of pure or approximately pure cellulose, but becomes
increasingly complicated in the case of materials containing high
proportions of unsaturated oxidizable constituents, such as lignin
or resins, or of volatile essential oils. Renker proposes as the
basic standard of hygroscopic moistm^ the loss in weight sus-
tained on exposure in a vacuum desiccator over phosphorus
pentoxide at a temperature not exceeding 35° C. imtil constant
weight is attained. Equilibrium, however, is reached only slowly,
and an exposure of at least 20 hours is required.

For practical purposes, among which may be included all
industrial applications, as well as the formulation of a dry weight
basis for the calculation of the results of other analytical factors,
the ordinary method of drying in a steam-heated oven at 98 °~
105° C. to constant weight has been generally accepted and for-
mally approved.' The time of heating required ranges from 4
to 6 hours. It is important that the dried sample be placed in

1. "Ueber Bestimmungsmethoden dcr Cellulose," Berlin, 1909.

2. Ver. der Zellstoff und Papier Chemiker, Hauptversammlung, 1909,
133.

CELLULOSE 359

a weighing bottle with close-fitting stopper before removing from
the oven and be allowed to cool in the desiccator before weighing,
as dried cellidose is extremely hygroscopic.

It has been remarked that the errors and the difficulty of
arriving at a constant dry weight increase the further the com-
position of the material is removed from that of pure cellidose.
In dealing with materials rich in resin and volatile oils the method
of distillation with a hydrocarbon may be adopted and has the
additional advantage that a large sample is used for the deter-
mination. This method is advocated by C. G. Schwalbe.^ Fifty
to one htmdred gm. of the shredded material are placed in a
tin-lined copper distillation flask and covered with about 200 cc.
of petroleum of suitable boiling point. The liquid is boiled and
after one-fourth or one-third of the hydrocarbon has distilled,
the whole of the moisture will have passed over into the receiver.
This is so constructed that the volume of the aqueous layer can
be accurately read off after the separation is complete by allow-
ing the water to settle out from the petroleum distillate in the
graduated lower portion of the receiver. A. Besson* has de-
scribed an improved form of distillation vessel and receiver for
tiie estimation of moisture in this manner.

Oil, Fat, Wax and Resdn. For the estimation of these con-
stituents the only method is by extraction with volatile organic
solvents in a Soxhlet or equivalent continuous extraction appa-
ratus, an operation requiring at least six hours.

The amotmt of fatty or resinous matter varies with the nature
of the solvent employed. Ether is the solvent most generally
and conveniently used, but it is also the one which gives the
lowest yield of extractive matter. C. G. Schwalbe' recommends
exhaustive extraction with ether, followed by extraction with
absolute alcohol. The alcoholic extract may, however, contain
other matters besides the true fat, wax and resin groups, and

1. Zts. ang. Chem. 1908, 21, 400» 2311; abst. C. A. 1908, 2, 1885, 2448;
1909, J, 406; J. C. S. 1908, 34, ii, 627; J. S. C. I. 1908, 27, 294; Bull. Soc. Chim.
1908, 4, 633; 1909, 6, 58; Chem. Zentr. 1908, 79, 1, 1336; II, 447; Jahr. Chem.
1905-1908, II, 960; Meyer Jahr. Chem. 1908, 18, 604; Wag. Jahr. 1908,
S4, II, 492. Zts. ang. Chem. 1919, 32, 125. "Die Chemie der Cellulose,"
1911, 612.

2. Chem. Ztg. 1917, 41, 346; abst. J. S. C. I. 1917, S6, 671. Schwciz.
Apoth. Ztg. 1917, 55, 69; abst. C. A. 1917, U, 1613.

3. Zts. ang. Chem. 1919, 32, 125,

360 TECHNOU)GY OI^ CELLULOSE ESTERS

may include substances soluble in water. An alternative method,
also favored by Schwalbe and less tedious than the double ejctrac-
tion, consists in extracting the material with a mixture of equal
volumes of alcohol and benzene. This mixture is to be preferred
because the influence of the benzene may be expected to prevent
the extraction by the alcohol of the water-soluble substances
referred to above.

Whatever solvent be employed, the material should be thor-
oughyl dried in the air before extraction; drying in the oven is to
be avoided as the heating tends to render some of the resins
insoluble.^ Schwalbe has indicated that the results of extraction
with volatile solvents are largely subject to the factor of penetra-
tion and has shown that if the structure of the material be com-
pletely broken down by a preliminary treatment with hydro-
chloric acid, a very much larger quantity of fat or resin is extracted
by volatile solvents than in the case of the raw material. This
process, however, requires further standardization.

Aqueous Extract. Various plant materials contain various
percentages of constituents soluble in cold or hot water. While
this factor is easily demonstrable, it is distinctly diflScult in quan-
titative application. The groups soluble in cold water comprize
sugars, tannins, coloring matters, etc., while those soluble in hot
water include starch, pectin and some of the nitrogenous matters.
The principal difficulty encountered in the quantitative estima-
tion of these groups is the mechanical difficulty of effective pene-
tration, even when the material is thoroughly prepared by crush-
ing or rasping. To facilitate penetration, the operation should
be carried out on material which has been freed from fat and resin
by extraction with volatile solvents, but even then the resistance
of the cutin layer to water persists almost tmimpaired.

A further complication occurs with regard to extraction with
hot water owing to the fact that the process does not halt at
simple extraction, but extends to the hydrolysis of the more
sensitive constituents of the major complexes. Thus, while over-
coming the difficulty of defective penetration the loss of substance
by conversion into soluble products of hydrolysis is continuous
with the duration of boiling. The time of boiling with water

1. C. Schwalbe and W. Schulz, Chem. Ztg. 1918, 42, 229; abst. C. A.
1918, 12, 2253, 2450; J. S. C. I. 1918, 37, 382-A.

CELLULOSE 361

must therefore be limited and specified and should not exceed a
period of three hoiu^. The loss of weight is determined after
drying the residual material in the oven and is calculated on the
dry raw material.^

Alkaline Hydrolysis. The processes of a-hydrolysis and /?-
hydrolysis, carried out as described on page 356 in a quantitative
manner, afford important information on the general quality of
a raw material, but the treatment is not suflSciently specific for a
quantitative measure of any characteristic group of constituents.
It is possible, however, to effect a complete isolation of the cellu-
lose by digestion with caustic soda solution under pressure in an
autoclave, and this method is often adopted in the laboratory,
not so much for an analytical determination of the total cellulose
present, as for studying the best conditions of treatment in indus-
trial working. The yield of cellulose thus obtained represents
the practical yield under the conditions adopted and is always
considerably less than the theoretical yield obtained by analytical
methods. The amount of this difference depends on the severity
of the treatment necessary to liberate the cellulose from the lig-
nin, during which the j8-cellulose components are progressively
hydrolyzed.

The concentration of the caustic soda solution employed for
this digestion ranges from 2% to 4% of NaOH and the temperature
from 130® to 170® C, corresponding to pressures of 25 to 95 lbs.
per sq. in. This test digestion is generally accompanied by peri-
odical determinations of the quantity of sodium hydroxide neu-
tralized by the acidic products of the hydrolysis, mainly lignic
and acetic acids, together with lactonic acids derived from the
carbohydrates when high temperatures have been employed. The
procedure usually adopted is to draw off portions of the alkaline
liquor at stated intervals during the digestion and to estimate by
titration the total soda after evaporation and incineration of one
part of the sample, using methyl orange, and the **free" soda
directly in another part of the sample, using phenolphthalein as
indicator. The decrease in the ratio of **free'' to total soda is a
measure of the progress of the reaction, and when the difference
between consecutive samples becomes small and constant the end

1. A. Schorger, J. Ind. Eng. Chem. 1917, 9, 556, 561; abst. C. A. 1917,
11, 2218; J. S. C, I. 1917, 36, 867; Ana, Rep. Sgc. Chem. lad. 1917, 2, 144,

362 TECHNOLOGY O^ CBLI<UU)SB BSTERS

of the digestion is indicated^ except in special instances.

Cellulose. The classical chlorination reaction of Cross and
Bevan has been almost unanimously adopted as the basis of all
the analytical methods for the quantitative estimation of cellu-
lose in raw and partly purified materials, but, although the agree-
ment in principle is general, the actual manipulation has been
variously modified by individual workers. The treatment con-
sists in exposure of the moist material to an atmosphere of chlor-
ine gas and the subsequent decomposition and extraction of the
chlorinated lignin by boiling sodium sulfite solution.

The difficulties of the process arie all traceable to mephanical
obstacles, that is, the resistance of the denser colloidal tissues to
the penetration of the gas. For this reason the removal of the
lignin is only rarely completed in one operation, and it is neces-
sary to repeat the alternate chlorination and extractions with
sulfite tmtil the residual cellulose no longer shows a perceptible
coloration during the treatment. Thus any deficiency in mechan-
ical disintegration has to be made good by chemical attrition, and
it may easily happen that serious chemical losses of cellulose may
occur by excessive exposure to the attack of the chlorine.

It is imderstood, therefore, that before making the analyses
the sample must be suitably prepared by mechanical means ac-
cording to its nature, in order to present the minimum resistance
to the penetration of the gas, for instance, by crushing and open-
ing out any hard portions or, in the case of woods, by taking thin
shavings or fine raspings.

The chemical manipulations may be described according to
two different schemes although, as mentioned above, several
variations are possible.

(a) Cross and Bevan' s method. This original scheme di£Fers
from most of those which have subsequently been proposed in
that the raw material is previously submitted to a chemical pre-
paration before exposure to the chlorine gas. This pre-treatment
consists in boiling the raw material for one horn* with a 1% solu-
tion of sodium hydroxide ; that is to say, it undergoes the /3-alkaline
hydrolysis. One effect of this is to eliminate the gummy colloidal
carbohydrates included under the general term of "hemicellu-
loses," comprizing hemihexosans and hemipentosans, and to ex-
clude them ab initio from the cellulose definition. A certain

c^i<LUi/>s^ 363

amount of misapprehension has arisen on this point owing to the
fact that the yield of "cellulose" is lowered by the alkaline pre-
treatment and higher values are obtained by its omission,^ but it
may be contended that carbohydrates which cannot survive the
simple process of /3-hydrolysis are not entitled to rank as cellu-
lose and are more correctly eliminated at the start than at a later
stage. Incidentally the alkaline treatment removes the portion
of the lignin which is associated with the hemi-celluloses and con-
siderably faciUtates the chlorination of the remainder by opening
up the harder tissues to the access of the gas. Thus the chemical
pre-treatment supplements the mechanical preparation and re-
duces the number of chlorinations required to arrive at a pure
product.

Cross and Bevan's manipulation is adapted for deaUng with
relatively large samples of the raw material, for instance, not
less than 5 gm. nor more than 10 gm. of the air-dry substance.
The sample is first covered with a 1% solution of sodium hydrox-
ide and the liquid is boiled for exactly one hour (Cross and Bevan
specify half an hour) under a reflux condenser. The residue is
collected on a cotton cloth filter, washed with hot water and
pressed. It is then teased out and treated in a closed bottle with
a current of washed chlorine gas. The bottle should be immersed
in a freezing bath and the duration of the first chlorination should
not exceed one hour. The object of these precautions is to re-
strict the hydrolyzing action of the hydrochloric acid which is
formed in large quantities in the first chlorination treatment; in
fact, if more than a single chlorination is required in any case,
it is better to limit the duration of the first to half an hour. After
chlorination, the material is quickly treated with a solution of
sulftu'ous acid or a sulfite and washed to neutrality on the cotton
filter. The substance is then transferred to a 2% solution of
sodium sulfite in which the characteristic crimson coloration is
developed, and the liquid is boiled for about half an hour. The
fiber, now largely liberated, is again coj^eded on the filter, washed,
pressed and subjected to a second chlorination of shorter duration,
followed by a second extraction of the chlorinated lignin with hot
sulfite solution.

With loose fibers, such as jute, hemp, etc., a single treatment

1. M. Renker, "Bestinunungsmethoden."

364 TECHNOI^OGY OP CEI^I^UI^OSE ESTERS

is sufficient to remove all the lignin and with denser materials the
number of chlorinations required depends on the perfection of the
preliminary preparation. The purified cellulose is finally bleached
with highly dilute sodium hypochlorite or permanganate, soured,
washed and weighed after drying in the oven.

(b) Sieber and Walter* s Method, It is to be noted that the
chemical pre-treatment with boiling alkali according to the method
described above, is only recommended in the case of raw plant mate-
rials in order to remove hemi-celluloses and so-called **pectins." In
the case of partially purified materials, such as commercial wood
celluloses, which have already undergone fairly severe hydrolytic
treatments, the alkaline hydrolysis is not legitimate. The ten-
dency in recent times has been (wrongly, in our opinion) to omit
the alkaline pre-treatment even in the case of raw materials, in-
cluding that of raw wood. This omission affords a slightly in-
creased yield of cellulose as it leaves in a portion of the hemi-
cellulose. The method described by R. Sieber and L. Walter^
in its application to wood is representative of this other scheme
of procedure and has received endorsement by various workers.*

By this method all the operations are performed in a porce-
lain Gooch crucible having a perforated porcelain plate fitting
loosely inside the bottom. This plate is stitched between two
pieces of fine cotton fabric and the cotton is trimmed off round
the edge to fit tightly in the bottom of the crucible. The raw
wood material is very finely powdered by means of a rasp and
sifted so that the portion which passes through a 75-mesh sieve
but not through a 100-mesh is taken for the analysis. This fine
mechanical subdivision considerably facilitates the chemical re-
actions but necessitates the employment of relatively small quan-
titiefs for the analysis. Not more than 1 gm. of the air-dry pow-
der is weighed out into the previously dried and tared Gooch
crucible, which is then suspended in hot alcohol in order to ex-
tract the resin. The alcohol is washed out with hot water on the
suction pump and the contents of the crucible are partially dried

1. Papierfabr. 1913, 11, 1179; abst. J. S. C. I. 1913. 32, 974; C. A.
1914, 8, 1202; Zts. ang. Chem. 1914, 27, II, 311. Cf. A. Dean and G. Tower,
J. A. C. S. 1907,29, 1119.

2. B. Johnsen and R. Hovey, J. S. C. I. 1918, 37, 132-T; Paper, 1918,
21, 136; abst. C. A. 1918, 12, 1250, 1598; Ann. Rep. Soc. Chem. Ind. 1918,
3, 134. See also C. Schwalbe and E. Becker, Zts. ang. Chem. 1919, 32, 1, 230.

C^Ei^i^ULOS^ 365

by passing a current of dry air through the mass. Afterwards
the crucible is connected with a supply of washed chlorine gas,
which is passed through the cake of moist wood meal for the re-
quired time. When the treatment is finished the material is
treated with sulfurous acid, washed and the crucible is suspended
in a bath of hot sodium sulfite solution (3%) in which it is digested
for one hour. All these operations are performed consecutively
without removing the material from the Gooch crucible; all the
filtrations are assisted by the suction pump, but care must be
taken not to suck the wood powder down to a hard cake against
tlie filter plate. The alternate chlorination and digestion treat-
ments are repeated until the lignin reaction is no longer indicated.
With suitably powdered wood the purification of the cellulose
may be effected with four chlorinations, lasting respectively for
20, 15, 15 and 10 minutes.

The cellulose prepared by the chlorination process from the
majority of raw plant materials is not a homogeneous substance
and is not to be regarded as chemically equivalent to purified
cotton cellulose. It is a complex of a- and j3-celluloses contain-
ing both hexosan and pentosan constituents.

Furfural Value or Pentosans. The polysaccharides of pen-
tosan constitution are important members of the cellulose com-
plex and, like the hexosans, may be represented as groups pre-
senting various degrees of resistance to hydrolytic attack, and
although a portion of these constituents is eliminated with the
hemi-celluloses, a residue of the more resistant types remains not
only in the cellulose prepared by chlorination, but also to some
extent in that purified by industrial processes.

The quantitative measurement of pentosan groups is based
on the condensation reaction induced by aqueous hydrochloric
acid on the pentose molecule whereby furfural is produced. The
reaction has been developed into an analytical method of con-
siderable accuracy by B. ToUens and his colleagues, and a com-
plete description of the conditions to be observed is given by^W.
Kroeber.^ These conditions must be accurately followed, as the

1. J. Landw. 1901, 4S, 357; 48, 7; abst. J. C. S. 1901, 80, i, 371; ii. 288;
J. S. C. I. 1901, 20, 396; Chem. Centx. 1901, 72, I. 477, 1119; Jahr. Chem.
1901, 54, 885. 886; Zts. anal. Chem. 1908, 47, 520. vSee also W. Kroebcr,
C. Rimbach and B. ToUens, Zts. ang. Chem. 1902, 15, 477, 508; abst. J. C.
S. 1902, 82, ii, 637; J. S. C. I. 1902, 21, 875; Rep. Chim. 1902, 2, 475; Ch*n.
Centr. 1902, 73, II, 76; Jahr. Chem. 1902, 55, 1049, 1050.

36G TECHNOU)GY OP CELLUl^OSE ESTERS

method in its quantitative application is substantially empirical.

A suitable quantity of the air-dry material, chosen so that
the weight of furfural phloroglucide to be obtained shall not ex-
ceed 0.3 gm., is placed in a distillation flask of about 350 cc.
capacity fitted with a dropping funnel and connected with a con-
denser. The material is covered with 100 cc. of 12% hydro-
chloric acid (sp. gr. 1.06) and the liquid is heated slowly at first
and then distilled at such a rate that 30 cc. of the add distils in
10-15 minutes. The drops of distillate are allowed to fall into
the receiver through a small filter to remove traces of volatile
fats. After 30 cc. of distillate has been collected, the same quan-
tity of fresh acid is introduced through the dropping funnel and
the distillation is continued at the same rate with repeated addi-
tions of acid so that the volume of liquid in the flask remains
substantially constant. Alternatively the dropping funnel may
be so adjusted that fresh acid is continually dropping into the
flask as fast as the distillate is driven off. Care must be taken to
wash down with fresh acid any particles of the material thrown
on to the side of the flask and protection should be provided to
prevent the overheating of the walls of the flask; a shallow bath
of fusible metal may be used for heating. When 360 cc. of dis-
tillate has been collected, the whole of the furfural should have
come over and a drop of the distillate should no longer show a
red spot when tested with aniline-sodium acetate reagent. The
entire distillate is then treated with a solution of pure phloro
glucinol, free from diresorcinol, in 12% hydrochloric acid, the
quantity of phloroglucinol used being double the weight of the
expected furfural. The mixture is stirred, made up to 400 cc.
with 12% hydrochloric add and set aside to stand over night.
The amorphous greenish black predpitate is collected in a tared
Gooch crudble fitted with an asbestos pad and washed with 150
cc. of cold water in such a way that the cake is not completely
drained until the washing is completed. It is then dried for four
hours in the oven at 100° C. and weighed in a well closed weigh-
ing bottle, as the dried phloroglucide is extremely hygroscopic.
The weight of the phloroglucide is then expressed in terms either
of furfural or pentosans by the application of factors given by
Kroeber as follows:

(a) For weight of phloroglucide "w" between 0.03 and

cBLLUi^osR 367

0.300 gm., the following formula is to be used:

Furfural = (w -f 0.0052) X 0.5185
Pentosan = (w -|- 0.0052) X 0.8866

(b) For weight of phloroglucide **w*' less than 0.03 gm.
Furfural = (w -f 0.0052) X 0.5170

Pentosan « (w -f 0.0052) X 0.8949

(c) For weight of phloroglucide **w" above 0.300 gm.

Furfural = (to -f 0.0052) X 0.5180
Pentosan ^ {w + 0.0052( X 0.8824

A more rapid method for the precipitation of the furfural
phloroglucide has been described by K. Boddener and B. Tol-
lens,^ whereby the precipitate is formed in hot solution instead
of cold. Three hundred cc. of the acid distillate are treated with
phloroglucinol (double the calculated quantity +0.15 gm.) also
dissolved in 12% hydrochloric acid. The volume is then made
up to 400 cc. with 12% hydrochloric acid and the liquid is heated
to 80°-85° C, then allowed to stand at the ordinary temperature
for V/i-2 hours. It is then filtered off in the Gooch crucible,
'washed with 150 cc. of water, dried for 4 hours in the water oven,
placed in a weighing bottle, cooled in the desiccator and weighed.
The phloroglucide thus obtained has a different composition from
that precipitated in the cold and the factor for calculating to
furfural is 0.571.

Methylpentosan. A minor portion of the phloroglucide pre-
cipitate consists of the methylfurfiu-al derivative which may be
separated by extracting the weighed precipitate of total phloro-
glucides with warm 95% alcohol according to the method of W.
EUett and B. Tollens.* The extraction is made in an apparatus
resembling a Soxhlet apparatus in which the Gooch crucible con-
taining the precipitate is suspended, as described by M. Ishida
and B. ToUens.' The passage of the alcohol is continued until
the extract flows through practically colorless, which takes only
a short time. The residue, consisting of furfural phloroglucide,
is dried and weighed back, the difference in weight being reck-

1. J. Landw. 1910, 58. 232; abst. C. A. 1911, 5, 736; J. S. C. I. 1911,
30, 242; Chem. Zentr. 1911, 82, I, 127.

2. Zts. Ver. Zuckerind. 1905, S5, 19; Ber. 1905, 38, 492; abst. J. C. S.
1905, 88, ii, 210; J. S. C. I. 1905, 24, 212; Bull. Soc. Chim. 1906, 36, 619;
Chem. Centr. 1905, 76, 1, 834; Chem. Ztg. Rep. 19a5, 29, 48, 75; Jahr. Chem.
1905-1908, II, 957; Zts. anal. Chem. 1909, 48, 166; Zts. ang. Chem. 1905,
18 1541.

3. J. Landw. 1911, 58. 261; abst. C. A. 1911, 5, 2508; J. C. S. 1911,
100, ii, 645; J. S. C. I. 1911, 30, 1181; Chem. Zentr. 1911, 82, II, 794.

368 TECHNOLOGY OK CELLULOSE ESTERS

oned as methylfurfural phloroglucide. The corrected value for
furfural phloroglucfde is calculated according to Kroeber's for-
mula (above) and the methylfurfural phloroglucide is calculated
to methylpentose by a formula given by W. Mayer and B. Tol-
lens^ for fucose where **w" is the weight of phloroglucide in
milligrams.

Mgrms. Methylpentose = 2.6595 W — 0.01226 W«+0.586
Methylpentosan = Methylpentose X 0.89.

Acetic Acid Group. It has been noted that the quantity of
acetic acid obtainable from lignified materials is subject to var-
iation according to the method of treatment employed. Con-
sequently, when applying this factor as a characteristic of species,
it is desirable that the conditions of hydrolysis should be as sim-
ple as possible and strictly defined. E. Schorger* has described
the following procedure, which has been adopted for the exami-
nation of woods: 2 gm. of the powdered raw material are boiled
under a reflux condenser with 100 cc. of 2.5% sulfuric acid for
3 hours. The volume of the liquid is then made up to 250 cc.
and an aliquot portion of the filtered hydrolyzed solution is dis-
tilled under vacuum. The volatile acid in the distillate is titrated
with standard sodium hydroxide and calculated in terms of acetic
acid; it will, however, include a minor proportion of formic acid.

Methozyl Group. This factor is estimated by the classical
method of Zeisel, as described by R. Benedict and M. Bamber-
ger,' and modified by G. Gregor,* whereby the material is com-
pletely broken down by boiling with concentrated hydriodic
acid and the methoxyl converted into methyliodide, which is
absorbed in alcoholic silver nitrate solution and decomposed into

1. Ber. 1907, 40, 2434, 2441; abst. C. A. 1907, 1, 2562, 3062; 1908, 2,
674; J. C. S. 1907, 92, ii, 586; J. S. C. 1. 1907, 26, 781; Bull. Soc. Chim. 1908,
4, 435, 464; Rep. Chim. 1907, 7, 3«9, 426; Chem. Zentr. 1907, 7S, II. 301,
302, 745; Jahr. Chem. 1905-1908, II, 858; Meyer Jahr. Chem. 1907, 17,
135; Zts. anal. Chem. 1908, 47, 322; Zts. ang. Chem. 1908, 21, 28.

2. J. Ind. Eng. Chem. 1917, 9, 556, 561; abst. C. A. 1917, 11, 2218;
J. S. C. I. 1917, 36, 867; Ann. Rep. Soc. Chem. Ind. 1917, 2, 144.

3. Monatsh. 1890, U, 260; abst. Chem. News, 1892, S5, 21; J. C. S.
1890, 58, 1474; J. S. C. I. 1890, 9, 1156; Bull. Soc. Chim. 1891, 5, 535; Ber.
1890, 23, R, 649; Chem. Centr. 1890, 61, II, 608; Chem. Ztg. 1890, 14, 872;
Jahr. Chem. 1890, 43, 255; Wag. Jahr. 1890, 36, 1156; Zts. ang. Chem. 1890,
3, 741; Zts. anal. Chem. 1891, 30, 636.

4. Monatsh. 1898, 19, 116; Wien. Akad. Ber. 1117, 140; abst. T. C. S.
1898, 74, ii. 490; J. S. C. I. 1898, 17, 609; BuU. Soc. Chem. 1899, 22, 191;
Chem. Centr. 1898, 69, II, 510, 831; Chem. Ztg. Rep. 1898, 22, 149; Jahr.
Chem. 1898, 51, 841; Oest. Chem. Ztg. 1898, 1, 253, 288.

CELLULOSE ' 369

silver iodide, and after drying, the material is carefully weighed.

The apparatus comprizes a special distillation flask of about
50 cc. capacity, having a long neck capable of serving as a reflux
air-cooled condenser. Two side tubes are fused into the neck,
about 20 cm. apart, the lower one serving for the introduction of
a slow current of CO2 gas and the upper one for the discharge
of the methyl iodide vapors. A CO2 generator (marble and hydro-
chloric acid), delivering gas through washing vessels containing
silver nitrate solution in the first and strong sulfuric acid in the
second, is attached to the lower branch of the distillation flask,
while the upper branch is attached to a U-shaped gas-washing
bulb tube containing a few cc. of a 10% solution of potassium
carbonate and arsenious acid. ' The U-tube is suspended in a
beaker of water heated at 50°-60° C. This solution absorbs
vapors of hydriodic acid and iodine which may be carried over,
while the COj containing the methyl iodide vapors passes through
into two absorption flasks, the first of which contains 50 cc. and
the second 25 cc. of an alcoholic solution of silver nitrate, pre-
viously standardized with AT/lO-thiocyanate, and containing a
few drops of nitric add. The silver solution is prepared by dis-
solving 17 gm. of silver nitrate in 30 cc. of water and diluting to
one liter with absolute alcohol.

A quantity of the material- which will yield about 0.1-0.2 gm.
of silver iodide is placed in the distillation flask with 20 cc. of
hydriodic acid of sp. gr. 1.70, which represents the aqueous solu-
tion of the acid of constant boiling point of 127** C. The current
of CO2 is adjusted at a slow-rate and the acid is caused to boil
gently. The zone of condensation in the long neck of the flask
should be maintained at about one-third of its total length and
no hydriodic acid should distil over. Ebullition and passage of
COj gas should be continued for at least 3 hours or imtil no fur-
ther precipitate is obtained on inserting a test-tube containing,
alcoholic silver solution in the place of the absorption flasks.
When the operation is completed the clear liquid in the first
absorption flask is decanted off into a 250 cc. gauged flask, the
precipitate is washed several times with cold water and the wash-
ings are added to the bulk of the liquid in the 250 cc. flask. The
contents of the second absorption flask are also added and the
whole is mad^ up to 250 cc. and filtered through a dry paper

370 TECHNOU)GY OK. CELLULOSE ESTERS

into a dry receiver. For the titration of the excess of silver
nitrate, 100 cc. of the filtrate are treated with nitric add and
ferric sulfate, then titrated in the usual way with iV/10 thio-
cyanate.

An alternative procedure in which the titration in the pres-
ence of alcoholic liquids is avoided is as follows: The absorption
flasks are charged with alcoholic silver nitrate without the addi-
tion of nitric acid. The methyl iodide then forms a double com-
pound of silver nitrate and iodide. After the distillation is com-
plete the contents of the absorption flasks are mixed together
and the alcohol is distilled off. Nitric acid is then added, the
double salt is decomposed by boiling and the excess of silver
nitrate is titrated with thiocyanate without filtering off the silver
iodide, which does not interfere with the accuracy of the titration.

The silver iodide found is usually calculated in terms of the
methyl group (CHj) expressed on the dry weight of raw material,
but it must bfe understood that only groups containing methoxyl
are determined by this method. A novel method of estimating
the methyl iodide by means of pyridine, forming the methiodide
of a quaternary base has been described by J. Hewitt and W. J.
Jones. ^

Lignin. The direct estimation of the lignin as a residue
depends on the total hydrolysis and removal of the cellulose com-
plex. This may be effected either by sulfuric acid of 72% con-
centration or by hydrochloric acid of 42% concentration (1.21
sp. gr.). J. Konig and E. Becker* have investigated compar-
atively four different methods for the estimation of lignin in this
manner. In all cases the previous removal of the resin, etc., by
extraction with alcohol-benzene is necessary. The sulfuric add
method does not give such concordant results as the hydrochloric
acid methods and the latter are therefore to be preferred. One
of these, the method of R. Willstatter and L. Zechmeistcr* re-
quires a solution of hydrochloric acid gas in concentrated hydro-
chloric acid saturated at 0° C; the concentration is thereby
raised to 42%. A modification of the method of H. Krull in

1. J. C. S. 1919, 115, 193; abst. C. A. 1919, 13, 1438.

2. Zts. ang. Chem. 1919, 32, I, 155.

3. Ber. 1913, 4S, 2401; abst. C. A. 1913, 7, 3413; J. C. S. 1913, Iti,
i, 955; J. S. C. I. 1913, 32, 822; Bull. Soc. Chim. 1913, U, 1354; Chem. Zcntr.
1913, 84, II, 1209.

cEi.irUi.osE 371

which hydrochloric acid gas is used is described by K5nig and
Becker as follows: One gram of wood powder which has been
extracted with alcohol-benzene to remove resins is moistened with
6 cc. of water in a wide, thick-walled test-tube smd hydrochloric
acid gas is conducted into the mass, while cooling in an ice-bath,
imtil no further change is apparent and the mass is converted
into a thin, deeply colored fluid. The liquid is then allowed to
stand for at least 24 hoiu^ to complete the hydrolysis until
cellulose can no longer be detected by microscopic examination,
after which it is diluted with water and the lignin residue is col-
lected in a Gooch crucible, washed and dried. The dry weight
of lignin is corrected by incineration and weighing the ash.

In all these operations it is an important point of the manipu-
lation to avoid the formation of a thick paste in which particles
of the original material are enclosed by gelatinized cellulose and
protected from the complete action of the acid.

Chlorine Absorption. P. Waentig and W. Gierisch^ have
proposed to measure the degree of lignification by the quan-
titative estimation of the amount of chlorine fixed by the hgnin
when the finely powdered material is treated with an excess of
the moist gas. The material is placed in a small U-tube with
grotmd glass stoppers, which is connected on the inlet side with
a supply of chlorine gas and a gas-washing vessel charged with
10% hydrochloric acid. Attached to the exit side is a second
U-tube charged with calcium chloride which serves to retain the
moisture carried over from the reaction tube. The apparatus is
weighed before and after the passage of the chlorine gas and the
quantity of chlorine fixed, both as lignin chloride and hydro-
chloric acid, is found by the increase in weight after sweeping
out the excess of chlorine. The quantity of lignin in the material
is then calculated by assuming a chlorine factor for pture lignin
of 144.

Phloroglucinol Absorption. This indirect method for the
estimation of lignin groups was devised by C. Cross, E. Bevan
and J. Briggs,* and depends on the determination of the quantity
of piu^ phloroglucinol absorbed by the lignified material from a
solution of definite concentration in the presence of aqueous

1. Zts. ang. Chem. 1919. 32, 173; abst. J. S. C. I. 1919, 3S, 530-A.

2. "Textbook of Papermaking/' 4th Edition, London, 1916, p. 397.

372 TECHNOLOGY OF CELLULOSE ESTERS

hydrochloric add. The following are the solutions required:

(a) Standard phhroglucinol solution, 2-5 gm. of purest
crystallized phlorogludnol are dissolved in 250 cc. of water and
the solution is made up to 500 cc. with hydrochloric acid of com-
mercial strength.

(b) Formaldehyde solution. 1 cc. of commercial 40% "for-
malin** is added to a mixture of 250 cc. of commercial hydrochloric
acid with 250 cc. of water.

(c) Aqueous hydrochloric acid. Equal volumes of commer-
cial hydrochloric add and water.

Two grams of the finely divided raw material are dried in the
oven and weighed; the dry weight is corrected for ash and the
material is placed dry in a dry flask together with 40 cc. of the
standard phlorogludnol solution. The flask is allowed to remain
corked, for at least 16 hours at the ordinary temperature. The
time factor for the test is regulated according to the resistance
to penetration of the material. After the absorption is complete,
the phlorogludnol solution is filtered off through a plug of glass
wool and 10 cc. are withdrawn for the titration of the excess of
phlorogludnol. This liquid is diluted with 20 cc. of the aqueous
hydrochloric acid, heated in a water-bath to 70® C. and titrated
with formaldehyde solution in small quantities at a time. After
each addition of formaldehyde the flask must be returned to the
water-bath for two minutes to allow the precipitate to form.
Towards the end of the titration smaller quantities of formalde-
hyde solution are added, namely, 0.1-0.2 cc., but the period of
two minutes should be allowed each time. The end point is
indicated by spotting a drop of the liquid on a piece of newspaper,
on which the phloroglucinol forms a pink stain, and the titration
is finished when no trace of pink is shown after rapidly drying the
spot. The difference between the titer of the original phloro-
glucinol solution and that of the filtered product indicates the
weight of phlorogludnol absorbed by the material. This is cal-
culated as a percentage of the corrected dry weight which is ex-
pressed as the phlorogludnol absorption value and may be referred
to a standard wood meal containing 28% of lignin and showing
a phlorogludnol value of about 8%.

Examination of Isolated Cellulose, Celluloses isolated by
industrial processes may be examined by methods dosely sim-

cui^i^utosE 373

ilar to those enumerated for the raw materials with only com-
paratively slight modifications, as enumerated herein.

The estimations of moisture, ash, fat or resin are carried out as
already described.

ResidiMl Lignin, The examination for residual lignin may
be performed in various wajrs. The malachite green test has
been devised by the chemists of the British War OflSce for the
purpose of detecting traces of lignin residues which are localized
or irregularly distributed throughout the mass of ptuified cellu-
lose and depends on the selective attraction or mordanting action
of the lignin towards basic dyestuffs. The reagent is prepared
by dissolving 0.1 gm. of the pure basic dyestufif in hot water and
diluting to 500 cc. then adding to this solution one containing
50 cc. of commercial 40% formalin and 1 gm. of sodium bisulfate
and diluting to one liter with water. Three grams of the cellulose
are heated with 300 cc. of the malachite green-formaldehyde solu-
tion in the boiling water-bath for ten minutes. At the end of
that time 25 cc. of a dear solution of bleaching powder at a con-
centration of 20 gm. per liter are added to the colored liquor.
The excess of dyestuff is thereby destroyed and the cellulose is
allowed to steep for a further five minutes in the hot liquid.
The liquid is then filtered off and the residual cellulose is rinsed,
pressed and examined. In this way any specks or fibers of lig-
nified material show up as bright green particles against a white
cellulose background, and the quantity may be estimated by in-
spection or by comparison with a standard material.

The best method of testing for traces of lignin when the
distribution is general rather than localized is by applying the
chlorination reaction and noting the amount of pink color devel-
oped after transferring the chlorinated fiber to a solution of sodium
sulfite suJBSciently strong to neutralize the acidity developed on
the fiber. The comparison may also in this case be made with a
standard preparation of cellulose similarly exposed to chlorine gas
and developed with sodium sulfite in a separate dish. The acidity
produced by chlorination under standard conditions may be
titrated and employed as a meastu'e for comparing the sample
with a standard cellulose similarly chlorinated.

Pure Cellulose, The pure cellulose contained in a sample
of commercial cellulose may also be estimated by the chlorination

374 TECHNOLOGY OP CELLUWSE ESTERS

reaction carried out, with all the precautions previously described
for raw materials, on the crude cellulose after the extraction of
the fat and resin with volatile solvents. The procedure is the
same as that indicated in the case of raw materials with the ex-
ception that the preliminary hydrolysis with boiling 1% sodium
hydroxide should be omitted when dealing with a cellulose which
has been isolated by industrial chemical processes.

Bleaching Test. A. Baker and J. Jennison^ have recom-
mended the following standard bleaching test for commercial
samples of sulfite wood celluloses: Ten grams of air-dry cellulose
are suitably disintegrated, for instance, by beating up with water
and draining to a known degree of moisture. The requisite
quantity of standardized bleaching powder solution, selected so
that only a slight excess shall remain tmused at the end of the
test is diluted in a wide mouth stoppered bottle with water suffi-
cient to bring the total quantity of liquid used for the 10 gm.
of cellulose up to 160 cc. The temperature of the liquid in the
bottle is then adjusted at exactly 105** F. (41® C.) and the moist
cake of cellulose is dropped in. The cellulose is thoroughly dis-
integrated by shaking the bottle and the whole is digested at
100** F. (38** C.) for two hours. At the end of that time the pulp
is poured on a Buchner filter so as to form a cake of uniform
thickness; it is there washed, drained, pressed and subsequently
dried. The filtrate and washings are made up to a tmiform bulk
of 2 liters and the excess of bleach liquor contained therein is
ascertained by titration. In this way the consumption of bleach-
ing powder, the color of the bleached sheet and the loss of weight
are recorded.

a-Cellulose and fi-Cellulose. The separation of a-cellulose
and /3-cellulose in a commercial pulp or crude cellulose isolated from
lignified raw materials can only be made on arbitrary rather than
on scientific lines. The inferior members of the cellulose complex
present in such preparations may comprize not only those con-
stituents of the original /S-cellulose which have siu^ved the pro-
cesses of isolation and purification but also newly formed com-
pounds of inferior type which have been produced by the de-
gradation, by hydrolysis or oxidation, of the a-cellulose as the

1. J. S. C. I. 1914, 33, 288; abst. C. A. 1914. 8, 2944; Zts. ang. Chem.
1915, 28, II, 224.

CBLlrULOSB 375

restilt of the unavoidable destructive action of the ch*emicals em-
ployed and, in quantity, depending on the severity of these
processes.

The method worked out in the laboratory of Cross and Bevan
for the separation of the more resistant from the less resistant
components has been described by H. Jentgen^ as follows: Ten
grams of the air-dry cellulose of known dry weight are macerated
and thoroughly stirred up to a tmiform paste with 50 cc. of sodium
hydroxide solution of 17.5% strength (sp. gr. 1.2) for exactly half
an hour at the ordinary temperature. The mixture is then diluted
with 50 cc. of water and the fluid is immediately poured on to a
Buchner funnel with a fine cotton filter doth. It is sucked as
dry as possible with the pump and washed with successive quan-
tities of 50 cc. each of water, draining thoroughly after each wash-
ing. The washed residue of resistant a-cellulose is soured with
dilute acetic acid, then washed with hot water and dried in the
oven and weighed. The alkaline filtrate and washings, amount-
ing to about 1 liter, is acidified without delay with a slight excess
of acetic acid and heated in the water-b^th until the flocculent
precipitate of gelatinous j3-cellulose coagulates. This is then
filtered off hot on a folded filter of fine cambric, washed with
boiling water, scraped off the filter into a flat dish, dried at 100°
C. and weighed. Only a minor portion generally of the less re-
sistant cellulose is re-precipitated by acid in this manner and the
remainder, calculated by difference, is classed as 7-cellulose, con-
sisting mainly, of components of the j3-cellulose which have been
hydrolyzed to permanently soluble products.

Pentosans. The pentosan (**furfuroid") groups present in
commercial celluloses are estimated exactly in the same manner
as that described for the raw materials. There appears to be no
reason for regarding the pentosan groups of vegetable tissues in
any other light than the other polysaccharides of the cellulose
complex. Some belong to components of the **hemi-cellulose*'
type and are removed in the purification of the cellulose. Others
are of the /S-cellulose type and are to be accepted and valued as
integral components of the commercial cellulose according to its
species, while other members of the pentosan group are only

1. Kunst. 1911. 1, 165; Wag. Jahr. 1911. 57, II. 426; Zts. ang. Chem.
1911.24,1341.

376 TECHNOLOGY OF CELLULOSE ESTERS

slightly, if *at all, less resistant than the a-cellulose itself. The
proportion of pentosan groups remaining in the purified cellulose
depends first on the species of raw material from which it was
derived and secondly on the severity of the processes employed
in its isolation. Thus, cellulose carefully prepared by the chlor-
ination treatment in the laboratory will contain a more sub-
stantial portion of the original pentosan groups than cellulose of
the same variety prepared commercially by manufacturing proc-
esses.

Alkaline Hydrolysis. Various modifications of Cross and
Sevan's method of j3-hydrolysis described under the section de-
voted to raw materials have been proposed and adopted in the
examination of isolated and purified celluloses. It is obvious that
some such test is desirable in the case of cellulose, but the inter-
pretation of the results is far more difficult than in the case of
raw materials. Any cellulose, even though it has been isolated
by digestion with caustic soda will always yield a further quan-
tity of soluble matter when it is again subjected to an alkaline
treatment.

The loss of substance by hydrolysis of a commercial cellu-
lose with boiling sodium hydroxide solution may fall under sev-
eral heads: (1) The previous ptuification of the cellulose may
have been defective and a portion of the loss in the alkaline
hydrolysis test may be due to the further removal of original im-
pimties. (2) The cellulose may be a variety which is rich in
components of the /S-cellulose or pentosan type and the hydrol-
ysis by attrition of these less resistant groups may be continued
almost indefinitely. (3) The previous industrial purification, if
it be of an acid character as in the bisulfite process, may have
modified even the a-cellulose so that it has become particularly,
susceptible to the attack of alkaline hydrolytic agencies. (4)
If the cellulose has been bleached a similar susceptibility may
have been induced by the oxidation of the fiber.

Thus the results of the test, as applied to purified and bleached
cellulose may represent the sum of a number of complex factors,
and it may be said that the function of this test is to call attention
to the existence of certain divergences from type without, how-
ever, indicating the cause of such abnormalities.

The procedure adopted in the United States is based on some

CELLULOSE ' 377

investigations made by E. Parker.^ About 2 gm. of cellulose
of known dry weight are covered with 100 cc. of a 10% solution
of potassium hydroxide and the liquid is boiled for three hours
without loss of water by evaporation, care being taken, however,
to avoid local overheating and exposure of the cellulose above
the surface of the liquid. At the end of the operation the cel-
lulose is collected in a Gooch crucible, washed, soured, washed
again and dried in the oven. The percentage loss of weight is
calculated on the dry substance.

According to the modification of the test prescribed by the
British War Office, 3 gm. of the cellulose, previously extracted
with ether, are covered with 300 cc. of a 3% solution of sodium
hydroxide and boiled gently for one hour, the manipulation being
otherwise the same as described above.

Modified Celltdose. An important section of the ana-
l3rtical chemistry of cellulose is concerned with the determina-
tion of what may be called the * 'chemical condition*' of cellulose.
Interest in this aspect has grown up with the development of
the chemical industries which employ purified cellulose as their
raw material, as it became recognized that two specimens of cel-
lulose of similar origin and purified apparently in a similar man-
ner are not necessarily chemically equivalent.

Owing to its complexity cellulose is a very sensitive organism
and its integrity is liable to modification by the cumulative effect
of almost every agency to which it has been exposed. The
analytical problem then is to determine in what sense and to
what degree such modification has taken place. The results may
be used for comparing a modified cellulose with a normal speci-
men of the same type in order to establish the optimum charac-
teristic of the species, or else for comparing various t)rpes of cel-
lulose with a standard type, for which cotton cellulose is adopted
by general consent.

The chief modifications to be recognized are those due to
hydration, oxidation, acid hydrolysis and "depolymerization."^

Hydrated Celltdose. It is recognized that cellulose is cap-

1. J. Phys. Chem. 1913, 17, 219; abst. C. A. 1913, 7, 2302; J. C. S.
1913, 102, i, 594; J. S. C. I. 1913, 32, 419; Bull. Soc. Chim. 1913, 14, 863;
Chem. Zentr. 1913, 84, I, 1727.

2. J. Briggs, "Recent Progess in the Analysis of Cellulose and Cel-
lulose Derivatives," Analyst, 1915, 40, 114. A comprehensive and exhaus-
tive r^sum^.

378 TECHNOLOGY OI^ CELLULOSE ESTERS

able of existing in various stages of colloidal activity which, in
their relation to water, may be described as degrees of hydration,
sometimes termed degrees of **mercerization.*' It was formerly
held that cellulose formed loose combinations with water, con-
stituting definite hydrates to which it was attempted to assign
formulas in molecular terms. A distinction was made between
hygroscopic moisture and water of hydration, which were sup-
posed to be expelled at different temperatures corresponding to
a difference in the nature of the tmion. These views, however,
have been modified, and it is necessary now to regard the phe-
nomenon of hygroscopicity merely as a manifestation of hydra-
tion, both belonging to the same order of adsorption phenomena
common to the colloidal condition.^ In the presence of an excess
of moisture, whether in the form of atmospheric aqueous vapor
or of liquid water, an adsorption equilibrium is set up between
the cellulose and the surrounding medium, and the proportion of
water fixed in the cellulose depends on its colloidal development.
In this sense, all celluloses, including even the normal cotton
cellulose, are hydrated, but the degree of hydration is capable
of modification over a very wide range by chemical or mechanical
treatments.

Thus hydration being a colloidal adsorption phenomenon, the
degree of- hydration may be measured analytically by estimating
the relative adsorption capacity of the cellulose for various chem-
ical substances under strictly standardized conditions.

Several tests of this nature have been described, one of the
most useful qualitative indications being the blue adsorption com-
pound which cellulose of a high degree of colloidal hydration
forms with iodine. So-called vegetable parchment in which the
cellulose has been converted into a colloid condition by the action
of sulfuric acid gives the blue coloration directly with a solution
of iodine in potassium iodide. Less modified forms of cellulose
adsorb in a minor degree and a sensitizing agent must be added
to the iodine solution before the blue stain can be developed.
The sensitizing agent may be sulfuric acid or zinc chloride of a
certain concentration or in general any liquid which has a vigorous
hydrating action on cellulose. The test lends itself admirably to
microscopic manipulation, and it may be utilized in two wajrs:

1. Papierfabr. 1910 (Kestheft), 8, 46; abst. J. S. C. I. 1910, 29, 874.

cEi<i<ui.osE 379

(1) With a constant concentration of the sensitizing agent, to
identify those forms of cellulose which are more susceptible than
others to the hydrating agencies, that is to say, those celluloses
which already exist in a more highly hydrated condition will be
stained blue by a reagent which will merely color the less hydrated
modifications red. (2) With cellulose of any degree of hydra-
tion, to determine the concentration of sensitizing agent which
is required to effect the transition from the red to the blue iodine
coloration.

F. Vetillard^ employs the iodine in a separate solution from
the sensitizing agent and steeps the cellulose on a microscope
slide in a drop of a saturated solution of iodine in 1% potassium
iodide solution. The excess of iodine solution is absorbed with bib-
ulous paper and the preparation is mounted in a sensitizing re-
agent consisting of a mixtiu'e of 3 parts by volume of concentrated
sulfuric acid, 2 of glyx^erol and 1 of water.

W. Herzberg* prefers to use zinc chloride as a sensitizer, and
combines the iodine in the same solution. Herzberg's reagent is
made with 20 gm. of zinc chloride dissolved in 10 gm. of water,
and this solution is then mixed with a solution made up with 2.1
gm. of potassium iodide, 0.1 gm. of iodine and 5 gm. of water.

J. Hiibner* describes various methods of applying the iodine-
zinc chloride reagent at different concentrations in order to ascer-
tain the degree of hydration (mercerization) of a fibrous cellulose,
all of which are based on the development of the blue adsorption
compound with more or less ease according to the initial degree
of hydration existing. Thus it is possible to determine with cer-
tainty whether a given sample of cotton has been mercerized or
not, and it is possible,' within certain limits, to determine with
what concentration of alkali the mercerizing effect was produced.

E. Knecht^ has devized a method having a similar object,
based on the increased adsorption of substantive dyestuffs by

1. "Etudes siir les Fibres textiles/' 1876, 28. 29.

2. "Papierprufung," Berlin. 1902, p. 65.

3. J. S. C. I. 1908, 27, 105; Proc. Manch. Lit. Phil. Soc. 1908, 52, 2;
abst. C. A. 1908, 2, 1187. 1347; Chem. News, 1908, 97, 10; Proc. Chem. Soc.
1907.23,304; BuU. Soc. Chim. 1908. 4, 1660; Rep. Chim.-1908, S, 238; Chem.
Zentr. 1906. 79, I. 1097; Chem. Ztg. 1908, 32, 220; Jahr. Chem. 1905-1908.
II. 3185; Meyer Jahr. Chem. 1908, 18, 505; Wag. Jahr. 1908, 54, II. 467;
Zts. ang. Chem. 1908. 21, 87, 1760.

4. J. Soc. Dyers Col. 1908, 24, 67; J. S. C. I. 1908, 27, 400; abst.
Chem. Ztg. Rep. 1908. 32, 272; Wag. Jahr. 1908. 54, II. 467.

380 TECHNOI.OGY OF CElrWUDSE ESTERS

hydrated cellulose, the cellulose to be examined being dyed, to-
gether with a standard sample of cellulose, in the same bath of
Benzopurpiu-in 4-B. After the dyeing, the depth of the shades
may be compai'ed and the relative amotmts of dyestuffs fixed on
the fibers may be estimated by titration with titanous chloride.

C. Schwalbe^ also uses an adsorption method to give what
he calls the hydration copper value of the cellulose which is based
on the relative quantity of cupric hydroxide adsorbed by the cel-
lulose from Fehling's solution in the cold.

W. Vieweg* proposes for the same purpose to meastu-e the
adsorption of caustic soda by dry cellulose from a 2% solution of
sodium hydroxide imder standard conditions and J. Briggs' has
shown that the adsorption of sodium hydroxide from a solution
in 93% alcohol takes place on a magnified scale and that a simple
and convenient method for estimating the degree of hydration,
however, produced, may be based empirically on the adsorption
of alkali from a 2% solution of sodium hydroxide in 93% alcohol
at the ordinary temperature.

A method based on the rate of hydrolysis with boiling dilute
sulfuric acid was proposed by C. Schwalbe,* but it cannot be ad-
mitted that the hydrolysis value so found stands in a stifiSdently
direct relation to the degree of hydration as generally tmderstood.

A hydrated cellulose parts with the whole of its water of
hydration when heated above 100° C, for instance, up to 120**
C, and then acquires the composition of anhydrous cellulose cor-
responding to the empirical formula CeHioOs. The colloidal con-
dition or structure on which its degree of hydration depends is
only partially affected by such temporary dehydration. On re-
exposure the cellulose still shows the characters imparted to it
by its hydration, though in a modified degree, and does not re-

1. "Die Chemie der Cellulose," Berlin, 1911. p. 634.

2. Chem. Ztg. 1908, 32, 329; Zts. ang. Chem. 1908, 21, 87, 865; abst.
C. A. 1908, 2, 1883; J. S. C. I. 1908, 27, 418; Bull. Soc. Chim. 1908, 4, 1467;
Chem. Zentr. 1908, 79, T, 1617, 2025; Wag. Jahr. 1908, 54, II, 493.

3. Chem. Ztg. 1910, 34, 455; abst. C. A. 1910, 4, 2372; J. S. C. I. 1910,
29, 622; Bull. Soc. Chim. 1911, lO, 60; Chem. Zentr. 1910, ti, I, 2075; Jahr.
Chem. 1910, 63, II, 422; Zts. ang. Chem. 1910, 23, 1389; Zts. Chem. Ind.
Koll. 1911,3,57.

4. Zts. ang. Chem. 1908, 21, 400, 401, 1321, 2311; abst. C. A. 1908,
2, 1885, 2448; 1909, 3, 406; J. C. S. 1908, 94, ii, 627; J. S. C. I. 1908, 27,
294; Bull. Soc. Chim. 1908, 4, 633; 1909, 8, 58; Chem. Zentr. 1908, 79, I,
1336; II, 447; Jahr. Chem. 1905-1908, II, 960; Meyer Jahr. Chem. 1908,
18, 504; Wag. Jahr. 1908, S4, II, 492.

c^i^i.ui.osE 381

turn to its original condition. For instance, mercerized cotton
is characterized by a strongly increased adsorption capacity for
substantive dyestuffs. If the cotton, after being mercerized, be
dried by heat before dyeing, the adsorption capacity is distinctly
less than if it be dyed directly af t^r mercerizing, but it is always
considerably greater than that of the original unmercerized cot-
ton. In quantitative tests, therefore, it is not a matter of indif-
ference whether the cellulose to be tested be dried in the oven or
not, and a standard procedure in this respect must be adopted.

Ozycellulose and Hydrocellulose. Cellulose modified by oxi-
dizing agents of hydrolyzing acids acquires cupric reducing . prop-
erties owing to the formation or opening up of free carbonyl groups.
Neither oxycellulose nor hydrocellulose can be described in terms
of definite compounds; they merely indicate the sense in which
the cellulose complex has suffered modification, in degrees which
appear capable of infinite variation.

Oxycellulose and hydrocellulose must be assumed to differ
in the mode of formation of the open carbonyl groups which
characterize them. In the case of oxycellulose there appears to
be a definite oxidation of alcoholic hydroxyls into aldehydic car-
bonyl radicals, such an action being equivalent to an increase in
tjie balance of acidity in the groups of the cellulose complex. In
the case of hydrocellulose no such acidification takes place and
an analogy may be drawn with the hydrolytic fission which takes
place in the hydrolysis of starch and other polysaccharides with
the formation of cupric-reducing dextrins.

Estimation of Copper Value. The degree of modification in
either sense is measured by estimating the cupric-reducing value
of the celluloses with Fehling's solution, the "copper value" being
calculated as the number of grams of copper reduced from Fehl-
ing's solution by 100 gm. of cellulose. The method has been
standardized by C. Schwalbe,^ who investigated very thoroughly
the munerous sources of error which make it somewhat difficult
to obtain strictly comparable results. The purity of the chem-

1. "Die Chemie der Cellulose," p. 625. Zts. ang. Chem. 1910, 23,
924; abst. C. A. 1912, S, 159; J. S. C. I. 1910, 29, 689; BuU. Soc. Chim. 1910,
S, 943; Chem. Zentr. 1910, 81, II, 339; Chem. Ztg. Rep. 1910, 34, 335; Jahr.
Chem. 1910, 63, II, 1135; Wag. Jahr. 1910, 58, 499. Zts. ang. Chem. 1914,
27, 667; abst. C. A. 1915, 9, 712; J. S. C. I. 1915, 34, 23; Wag. Jahr. 1914.
€0, II. 408. Ber. 1907, 40, 1347; abst. Chem. Zentr. 1907, 78, 1, 1490.

382 TBCHNOLOOY OI^ CELLUWSE ESTBRS

icals used for making up the Fehling's solution must be carefully
controlled and contact with rubber or cork stoppers and other
organic matters, including filter paper, must be avoided from
start to finish. The flask in which the cellulose is boiled with
the Fehling's solution is provided with a surface-condenser sus-
pended in the neck and the glass shaft of a mechanical stirring
apparatus passes through the center of the condenser. A weighed
quantity of the air-dry cellulose equivalent to 2-3 gm. of dry
substance is placed in the boiling flask with 250 cc. of water and
the liquid is heated to the boil while stirring continuously. Mean-
while, 50 cc. each of Fehling's copper sulfate and alkaline tartrate
solutions are separately heated to boiling, mixed at the boil and
'added to the boiling water and cellulose in the flask, using 50 cc.
of boiling water to rinse the vessels. When the total mixture
has again come to the boil it is boiled for exactly fifteen minutes.
The flask is quickly removed and about 1 gm. of kieselguhr sus-
pended in water is added and shaken round in order to coagulate
any finely suspended cuprous oxide. The cellulose is then rapidly
filtered off on a Budmer funnel with double paper filter and thor-
oughly washed with boiling water. The cuprous oxide deposited
in the cellulose and on the filter is dissolved in nitric acid and
estimated by the electrolytic method. It is extremely important,
during the boiling, to keep the cellulose constantly stirred and
completely submerged in the boiling liquid. The electrolytic
determination of the copper is somewhat inconvenient in a tech-
nical laboratory; moreover, cupric hydroxide is deposited by ad-
sorption on the cellulose together with the cuprous oxide and
cannot be washed out. A more convenient and rapid method
whereby the cuprous oxide alone is determined by titration has
been indicated by E. Hagglund,^ and consists in treating the cel-
lulose on the filter with 100 cc. of a boiling solution of ferric sul-
fate strongly acidified with sulfuric acid. This solution contains
50 gm. of ferric sulfate and 200 gm. of sulfuric acid per liter, and
is previously freed from any ferrous salt by adjustment with per-
manganate. The cuprous oxide is immediately dissolved and
reduces an equivalent amount of ferric salt to the ferrous con-
dition, the quantity thus reduced being titrated in the filtrate.

1. Papierfabr. 1919, 17, 301; abst. Chem. Zentr. 1919, 90, IV, 296;
J. S. C. 1. 1919, 38, 894-A; C. A. 1919, 13, 3009.

CBLLUI.OSB 383

The following copper values have been quoted by Schwalbe for
various specimens:

Surgical cotton wool 1 .64 to 1.8

Mercerized bleached Egjrptian cotton 0.9 to 1.6

"Glanzstoflf" artificial silk 1.1

Hydrocellulose up to 6.2 to 5.8

Parchment paper 4.2

Bleached sulfite wood-pulp 3.9

Oxycellulose may show any number up to about 16.0

Schwalbe's complete prescription is so complex that many
attempts have been made to simplify its details; nevertheless,
it must be conceded that all the precautions which he prescribes
are well founded in fact.

The following procediu"e has been adopted for technical pur-
poses by the British War OflRce: 12.5 cc. each of Fehling's cop-
per sulfate and alkaline tartrate solutions^ are mixed in a conical
flask fitted with an air condenser and the liquid is heated for five
minutes in a boiling water-bath. If the solution shows no spon-
taneous precipitation of cuprous oxide it is considered to be good,
and 50 cc. of boiling water and 1 gm. of cellulose are added. The
flask is again heated for 15 minutes in the boiling water-bath,
the contents are then inunediately filtered off on a Buchner fun-
nel. The cellulose is washed with boiling water, then with a
10% solution of Rochelle salt and lastly with boiling water. The
whole is incinerated, the copper oxide is dissolved in nitric acid
and estimated volumetrically by the iodide method. Here again
it may be remarked that the ferric sulfate method is greatly to
be preferred both for simplicity and accuracy. It must be noted
that copper values determined by boiling for 15 minutes are never
to be compared with those determined by heating in the boiling
water-bath for the same length of time. The effect of the numer-
ous sources of error is much smaller in the latter method, but at
the same time the copper values themselves are also very much
lower. It should also be noted that according to the English
method the copper values are calculated in terms of cuprous
oxide and not of metallic copper.

The estimation of the copper value is the most definite meas-
lu-e for the diagnosis of the chemical condition of the cellulose in

1. The Pehlins^ copper solution contains 69.28 gm. of crystallized

?ure copper sulfate and 1 cc. of pure sulfuric acid in one liter. The Alkaline
'artrate solution contains 350 gm. of Rochelle salt and 100 gm. of sodium
hydroxide in one liter.

384 TECHNOLOGY OF CELLULOSE ESTERS

numerical terms which is available. The purest bleached cotton
of the highest commercial quality shows a copper value consider-
ably less than 1, but commercial specimens with copper values
between 1 and 2 are fairly common. The latter values already
indicate a distinct amount of chemical modification of the cellu-
lose as the result of injudicious bleaching, although this modifica-
tion may not have gone so far as perceptibly to lower the tensile
strength. With more profound modification the copper value in-
creases and a rapid loss of tensile strength and durability of the
fiber is observed. Nevertheless, the absolute value of the cupric-
reducing power is not a direct measure of the loss of quality, and
a given degree of structural disintegration in the sense of hydro-
cellulose will correspond with a far lower copper value than a
similar degree of modification in the sense of oxycellulose. More-
over, structural weakness may be induced by agencies which do
not develop a corresponding increase in the copper value, for
instance, excessive boiling with caustic soda lyes or exposure to ^

dry heat to the point of scorching. It is necessary, therefore^ to
pay attention to other diagnostic details before a complete ac-
count can be given of chemically modified celluloses.

For the distinction between oxycellulose and hydrocellulose 1

the copper value does not suffice, and it is necessary to have re- *

course to qualitative tests.

As was remarked before, these modifications of cellulose are
characterized by free carbonyl groups which are probably dif-
ferent in origin. In both cases the carbonyl groups are soluble
in boiling caustic soda solution with the formation of yellow
products. In the case of oxycellulose, however, the products
formed with boiling dilute (normal) sodium hydroxide are char-
acterized by a transient intensely golden yellow color, which sub-
sequently diminishes and becomes brownish in shade. In the
case of hydrocellulose the coloration is less intense and brown-
ish yellow from the beginning. Boiling sodium hydroxide gradually
hydrolyzes and dissolves the carbonyl groups of these modified cellu-
loses so that the copper value of the residue after treatment is con-
siderably lowered and possibly reduced to normal proportions. The
tensile strength, however, is not restored and the residue cannot be
described as normal cellulose, although substantially free from
cupric-reducing groups. Such modified and subsequently treated

CElrLULOSE 385

cellulose is characterized by its very low viscosity (see below) . Oxy-
celltilose may also be differentiated from hydrocellulose in the fact
before mentioned, that the oxidation of certain groups disturbs
the balance of basic and acidic hydroxyls and increases the acidity
of the cellulose molecule. This increased acidity of the oxidized
cellulose confers on it the property of increased affinity for dye-
stuflF bases, so that basic dyestuifs are more readily fixed on the
oxidized fiber than on the normal fiber, whereas hydrocellulose
possesses no such increased affinity. This property forms the
basis of the methylene blue test for oxycellulose which, however,
since it depends on a contrast of colors, can only be of service
when the oxidation of the fiber is localized.^

Viscosity. The viscosity of solutions of fully purified cellu-
lose is held to be a measure of the chemical quality of the cellulose
in the sense that solutions of modified celluloses are extremely
deficient in "body." The relation between viscosity and quality
has long been recognized in the artificial silk industry, but it
holds good only within restricted limits and with many reserva-
tions. In the manufacttu'e of viscose it is established that the
viscosity of the xanthate varies with every chemical modification
which the cellulose has tmdergone; nevertheless, chemical quality
is only one of the factors which influence viscosity, and the rela-
tions of the cellulose to the solvent is certainly another factor.
Hence in comparing viscosities it is important that the composi-
tion of the solvent be absolutely constant and that the purity
of the cellulose be complete; the presence of small residues of
lignin, by affecting the solubility, makes the test tmsatisfactory.

The viscosity test in cuprammonium solution was first de-
scribed as a quantitative method by H. Ost,* and has subsequently
been investigated and developed by the research department of
the British War Office at Woolwich into a standard test b)i which
the chemical quality of a purified cellulose may be numerically
recorded.

The greatest care must be taken in making up the cupram-
monium solvent in order to have a liquid of constant comparison
and free from salts. The reagent is prepared from carefully pre-

1. J. Briggs, J. S. C. I. 1916, 35, 79; abst. C. A. 1916; 10, 1098.

2. Zts. ang. Chem. 1911, 24. 1892; abst. C. A. 1912, S, 684; J. C. S.
1911, 100, i, 838; J. S. C. I. 1911, 30, 1247; Chem. Zentr. 1911, 02, II, 1518;
Chem. Ztg. Rep. 1911, 35, 520; Wag. Jahr. 1911, 57, II, 428.

1

386 TECHNOLOGY OF CELLULOSE ESTERS

cipitated and thoroughly washed cupric hydroxide, free from
basic copper sulfate, dissolved in concentrated ammonia solution.
The composition must be checked by analysis and the solution
must show copper (as Cu) equal to 10 gm. per liter within
0.15 gm. on either side. According to another prescription the
cuprammonium reagent must contain 12 gm. per liter of copper.
The anunoniacal strength of the solution determined by distillation
must be 200 gm. of NHj per liter, within 5.0 gm. on either side.

In preparing and manipulating the solution of cellulose in
this reagent every precaution must be taken to protect the solu-
tion from the action of light and air, as these cause a rapid lower-
ing of the viscosity owing to the oxidation of the dissolved cellu-
lose. For this purpose the air must be completely evacuated
from the bottle in which the solution of cellulose is prepared as
soon as the cellulose and cuprammonium reagent have been
introduced.

A quantity of air-dry cellulose, previously extracted with
ether if necessary, equivalent to exactly 2 gm. dry weight is
introduced into 100 cc. of the reagent contained in a stout glass
bottle of 150 cc. capacity from which the air is then immediately
evacuated. The contents of the bottle, including a few glass
beads, are then shaken until the cellulose is finally dissolved.
The bottle is then fitted with another rubber stopper through which
pass two glass tubes, one to the bottom of the bottle and the other
only through the cork. The latter is adapted to reach to the
bottom of a standard straight viscosimeter tube and when the
bottle is inverted the transference of the cellulose solution to
the viscosimeter is effected with a minimum exposure of the
liquid to the air and without agitation. The viscosimeter tube,
closed at the bottom, has a total length of 30 cm. and an internal
diameter of 1 cm.; it is divided by graduations exactly 5 cm.
apart and must be filled to within 3 cm. of the top. It is kept
in a dark box in which the temperature is maintained constant at
20 ** C. Steel balls, Vie in. in diameter, are introduced through
a special releasing tube which passes through a rubber cork in
the mouth of the viscosimeter tube and the time of fall through
a path of 15 cm. indicated by the graduation marks is noted by
means of a chronometer.

The absolute viscosity of the cellulose solution may be cal-

•^ •

CELLULOSE 387

culated in C. G. S. units by a modification of Stokes' formula
worked out by S. Sheppard,^ which corrects for the retardation
due to the walls of the viscosimeter tube. A simpler procedure
is to work with standardized viscosimeter tubes which have been
calibrated with pure castor oil, the absolute viscosity of which
is known (rj' = 9.65 Woolwich standard). The viscosity of the

1. J. Ind. Eng. Chem. 1917, 9, 523; abst. C. A. 1917, U, 114, 1778;
J. C. S. 1917, 112, ii, 359; J. S. C. I. 1917, 36, 670. S. Zeisel and M. Stritar
(Ber. 1902, 35, 1252; abst. J. S. C. I. 1902, 21, 642) have described the fol-
lowing method for the determination of cellulose.

In the presence of nitric acid the non-cellulose of wood is oxidized rapidly
by potassium permanganate in the cold, and completely converted into prod-
ucts soluble in dilute ammonia. It is true that in this, as in all oxidation
processes, a large portion of the cellulose — about 30% — 7 is also converted
into oxycellulose, which is insoluble in the above solvent, but which may be
extracted by boiling with 10% soda lye. The error thus involved is quite
small, but it can be estimated by extraction and allowed for. At the same
time, this and other oxidation processes are accompanied by the conversion
of some of the cellulose — at most 4% — ^into soluble products. The estima-
tion is carried out as follows: About 1-1.5 gm. of the crude, finely divided
substance (e. g., oak-wood raspings) is macerated with dilute nitric acid,
and a 3% solution of permanganate is run in, 1 cc. at a time, stirring, and
cooling, until the red color persists for half an hour. This operation occupies
about two hours; the excess of permanganate and the precipitated oxide
are removed 6y sulfurous acid, and the residue is filtered off, washed, and
then treated for 45 minutes at 60° C. with a 2.5% solution of ammonia,
being finally washed with water, alcohol and ether. The results agree very
well with those which it requires 15 days to obtain by the Schidze-Henne-
berg process — extraction of the wood with water and alcohol, and prolonged
oxidation with potassium chlorate dissolved in nitric acid. The yield of
cellulose from oak-wood amounted to 37.2%, the product containing 0.5%
of methoxyl. Experiments made with Schulze's original chlorate process
invariably gave very much higher yields, but the presence of 5% or more
of methoxyl in the cellulose obtained, indicated that the conversion was far
from complete.

The author's researches also show that the hemicelluloses, particularly
the mannoso-cellulose of the ivory nut, are completely converted into sol-
uble products by permanganate, which is not the case with chlorate mixtures.
This process, therefore, is adapted for the direct estimation of cellulose in
its narrower sense, i. e., the dextroso-celluloses. See also Ann. Chim. anal.
S, 77; abst. Bied. Centr. 1902, 31, 863; J. S. C. I. 1903, 22, 321. For addi-
tional information on this subject, consult, C. Cross and E. Bevan, Zts.
Farbenind. 1912, U, 197; abst. J. C. S. 1912, 102, ii, 1105. Eighth InU.
Cong. Appl. Chem. 1912, 13, 101; abst. J. S. C. I. 1912, 31, 870. R. Dmo-
chowski and B. Tollens, J. Landw. 1910, 58, 21; abst. J. C. S. 1910, 98, i\,
655. A. Gregoire and E. Carpiaux, Bull. Soc. Chim. Beige, 1910, 24, 217;
abst. J. C. S. 1910, 98, ii, 661. P. Klason, Chem. Ztg. 1903, 27, 585; abst.
J. S. C. 1. 1903, 22, 826. J. Konig, Zts. Nahr. u. Genussm. 1903, 6, 769;
abst. J. C. S. 1903. 84, ii, 764. Zts. Nahr. u. Genussm. 1906, 12, 385; abst.
J. C. S. 1906, 90, ii, 905. Ber. 1908, 41, 46; abst. J. C. S. 1908, 94, ii, 236.
J. K6nig and F. Hiihn, Zts. Farbenind. 1911, 10, 297, 326, 344, 366; 1912,
U, 4, 17, 37, 57, 77, 102, 209; abst. J. C. S.-1912, 102, ii, 1005. H. Matthes,
Ber. 1908, 41, 400; abst. J. C. S. 1908, 94, ii, 236. O. Simon and H. Loh-
risch, Zts. physiol. Chem. 1904, 42, 55; abst. J. C. S. 1904, 88, ii, 787.

388 TECHNOlrOGY OP CBLLULOSe BSTBRS

cellulose solution is then calculated by the simple proportional

formula

fi ^ T(S — SO
V T'(S ~ S'l)

in which rj is the absolute viscosity of the cellulose solution

Tj' is the absolute viscosity of castor oil

T is the time of fall in the solution

T' is the time of fall in castor oil

S is the density of the steel ball (7.65)

S' is the density of the cellulose solution

S'l is the density of castor oil (0.96).
The method gives fairly satisfactory results with duplicate
determinations if the conditions are rigidly maintained, but the
interpretation of them must be made with some caution. In the
case of high viscosities the differences between similar samples of
cellulose may be extraordinarily great, while in the case of low
viscosities considerable differences between two samples of cellu-
lose may be recognized by other methods without any sufficiently
perceptible difference in viscosity. Thus, in the case of cellulose
modified by hydrolysis or oxidation, the viscosity values are uni-
formly extremely low, but the different degrees of modification
such as would be recognizable easily by tensile tests or cupric
reducing values, are barely indicated by the viscosity test.

On the other hand, the viscosity method is often the only
test which will indicate modification of cellulose which has been
brought about in such a way that the product does not reduce
Fehling's solution; for instance, cellulose which has been modified
by prolonged dry heating above 100° C, cellulose which has been
modified by the action of caustic soda at excessively high tem-
peratures in the purification process, or oxycellulose and hydro-
cellulose from which the cupric-reducing, free carbonyl groups
have been largely or wholly removed by digestion with caustic
alkalis. All these forms of modified cellulose, when the modifica-
tion has not proceeded far enough visibly to affect their tensile
strength may be revealed by their abnormally low viscosity values.
It may reasonably be inferred that with certain reservations
a relationship exists between the viscosity of the solutions, the
state of polymerization of the cellulose, and its tensile strength,
but the conditions of the relationship have never been syste-
matically worked out.

CHAPTER II.

STARCH.

Origixi and Transformations of Starch.^ Starch has, as yet,
not been prepared artificially, and but little progress has been
made in this direction notwithstanding the multiplicity of inves-
tigators who have engaged themselves with this problem.

Chlorophyl, which plays such an essential part in the character-
istic ftmction of "assimilation'' in all green plants, i. e., the ab-

1. For general information on the subject of starch, see C. O'SuUivan,
J. Chem. Soc. 1886, 70; Chem. Ne^s, 1885, 52, 203. E. vSchulze and Prank-
fort, Ber. 18d4, 28, 64. Naegeli, Die Staerkekoemer, 1858, 378, 535. Bur-
gerstein, Ber. hot. Ges. 1900, 18, 180. J. Thresh, Pharm. J. Transact. 1884,
798. Weizmann, Arch. Pharm. 1886, 909. A. Petermann, Centr. Agr.-
chem. 1878, 869. Balland, Just. Jahr. 1897, II, 85. Sudakoff, Just. Jahr.
1879, I, 399. G. Baumert and K. Halpem, Arch. Pharm. 1893, 231, 641.
Pellett and Liebschutz, Compt. rend. 1880, 90, 1363. Loebe, Jahr. Agr.-
chem. 1890, 443. Lehmann and Mori, Arch. Hyg. 1889, 257. Meissl and
Boecker, Monatsh. Chem. 1883, 4, 349.. J. Moser, Centr. Agr. chem. 1879» 388.
Balland, Compt. rend. 1901, 132, 1061. L. Jahne, Centr. Agric. chem. 1881,
106. Hannamann, Jahr. 1885, I, 75. Chodat and Chuit, Just Jahr. 1888,
I, 57. Beckurts, Arch. Pharm. 1894, 231, 687. C. Hopkins, Smith and
East, J. Amer. Chem. Soc. 1903, 23, 1166. C. Brisseau-Mirbei, Elemens
de phys. veget, 1815, I, 185. Raspail, Annal. scien. nat., March 1826; Mem.
soc. d'hist. nat. 1827, 3, 17. Caventou, Ann. Chim. Phys. 1826, (2), 31, 337.
Guibort, Ann. Chim. Phys. 1829. (2), 40, 183. R. Guerin-Varry, Compt. rend.
1836, 2, 116; Ann. Chim. Phys. 1836, (2), 41, 66. Candolie, Physiologic,
dcutsch V. Roeper, 1833, 1, 149. J. Fritzsche, Pogg. Ann. 1834, 32, 129;
Ann. 1836, 37. 114. Biot, Compt, rend. 1844, 18, 795. Ehrenberg, J. prakt.
Chem. 1850, 49, 490. Marcet, Ann. Chim. Phys. 1827, (2), 30, 27. Payen,
Compt. rend. 1836, 3, 224; Ann. Chim. Phys. 1836, (2), 01, 355; 1837, (2), 45,
255; Annal. sci. nat. 1838, 5. Colin and G. de Claubry, Schw. Jour. 1815,
13, 453. Strohmeyer, Gilb. Ann. 1815, 43, 146. Nasse, Schw. Jour. 1812,
4, 111. J. Schrader, Schw. Jour. 1812, 4, 108. Vogel, Gilb. Ann. 1812, 42,
125; Schw. Jour. 1812, 5, 80. Gehlen, Schw. Jour. 1812, 5, 32. Davy,
Elem. d. Agrikult. Chem. 1814, 146. T. Saussure, Gilb. Ann. 1815, 49, 129;
Schw. Jour. 1819, 27, 323. Braconnot, Ann. Chim. Phys. 1833, (2), 52, 290.
Biot and Persoz, Ann. Chim. Phys. 1833, (2), 52, 72. Payen and Persoz,
Ann. Chim. Phys. 1833, 53, 73; 1835, 00, 441. A. Meyer, Untersuchungen
ueber die Staerkekoemer, 1895, 78-79. A. Fembach, Compt. rend.
1904, 138, 428. Naegeli, Die Staerkekoemer, 1858; Botan. Zts. 1881, 633. A.
Schimper, Botan. Zts. 1880, 881; 1881, 185. A. Meyer, Botan. Zts. 1881,
841. A. Dodel, Flora, 1892, 267. A. Bmz, Flora, 1892, 34. Belzung, Annal.
sd. nat. 1891, (7), 13, 1. Koningberger, Botan. Centr. 1892, 49, 47. C.
Acqua, Malpighia, 1893, 7, 393. J. Salter, Jahr. wissen. Botan. 1898, 32,
127. L. Buscalioni, Nuov. Giom. bot. Ital. 1891, 23, 45; Just Jahr. 1891,
I, 489. H. Fischer, Botan. Centr. 1902, B, 12, 226; Ber. botan. Ges. 1903,

390 TECHNOLOGY OF CELlrULOSK ESTERS '

sorption of carbon dioxide from the air and its decomposition in
the chlorophyl corpuscles with the evolution of oxygen, was in-

21, 107. Meyer. Botan. Ztg. 1881, 844. H. Fischer, Cohns. Beitr. z. Biolog.
1898, S, 79. Ber. botan. Ges. 1903, 22, 107. H. Kraemer, Botan. Gaz.
1902, 34. O. Buetschli, Verhandl. natur-med. Verein, Heidelb. 1893, 5, 89;
Botan. Centr. 56, 150; Naturw. Rundsch. 1893, S, 357; Verhandl. Heidelberf,
1897, 5, 457; Botan. Centr. 1896, 6S, 213. H. Rodewald and A. KatteiS,
Zts. physik. Chem. 1900, 33, 579; Berl. Akad. 1899, 24. 62. C. Scheibler,
Ber. 1869, 2, 170. Rodenwald, Landw. Versuchst, 1895, 45, 201; Zts. physik.
Chem. 1900, 33, 540, 593. Rothert, Ber. botan. Ges. 1897, 15, 234. E. Ott,
Oesterr. botan. Zeits. 1899, 39, 313. S. Schubert, Monatsh. Chem. 1884,
5, 472. Hoppe-Seyler, Ber. 1870, 4, 15. Lippmann, J. prakt. Chem. 1861,
83, 51. V. Syniewski, Ann. 1899, 309, 282. Ambronn, Ber. saechs Ges. d.
Wiss, 1891, 28. Mauch, Chem. Centr. 1902, 73, I, 1199. F. Musset, Chem.
Centr. 1896, 97, 703. Tollens, J. Landwirtsch. 1873, 375. A. v. Asboth,
Chem. Ztg. 1887, U, 147; Jahr. Agri. Chem. 1887, 406; Ber. 1888, a, 454.
C. Lintner, Zts. ang. Chem. 1888, 1, 232. Zulkowski, Ber. 1880, 13, 1398;
1890. 23, 3295. Lassaigne, Ann. Chim. Phys. 1833, (2), 53, 109. Leroy and
Raspail, Schw. Jour. 1833, 9S. 179. H. Stokes, Chem. News, 1887, 56, 112.
Meineke, Chem. Ztg. 1894, 19, 157. E. Schaer. Pharm. Centralh. 1896, 37,
540. E. Heintz. Jahr. Agr. Chem. 1879, 499. E. Puchot, Ber. 1876, 9,
1472. J. Gruess, Jahr. wissen. Botan. 1896, 26, 379. C. Roberts, Chem.
Centr. 1894, 65, II, 147. Mylius, Ber. 1887. 20, 688. F. Hale. Amer. Chem.
J. 1902, 28, 438. C. Lonnes, Zts. anal. Chem. 1894, 23, 409. F. Kues-
ter, Ann. 1894, 283, 360; Ber. 1895, 28, I, 783. C. Meineke. Chem.
Ztg. 1894, 18, 157; Chem. Centr. 1894, 65, I, 525. Mylius, Zts. physiol.
Chem. 1887, 11, 306; Ber. 1895, 28, 385. E. Rouvier, Compt. rend. 1892.
114, 128. 749; 1893, 117, 281. 461; 1894, 118, 743; 1895, 120, 1179; 1897, 124,
565. F. Seyfert, Zts. ang. Chem. 1888, 1, 15. H. Stokes. Chem. News.
1887, 56, 212; 1888, 57, 183. F. Musset, Pharm. Centralh. 1896, 37, 556.
E. Sonstadt, Chem. News, 1873, 28, 248. PeUet, Mon. Sci. 1877, 7, 988.
Bondonneau. Compt. rend. 1877. 85, 671. C. Harz, Chem. Centr. 1898, 69,
I, 1018. Roberts, Chem. Centr. 1894, 65, II, 147. H. Friedenthal,
Centr. Physiol. 1899, 13, 55. Andrews and Goettsch. Chem. Centr. 1902,
73, II, 1035. G. Kruess and E. Thiele, Zts. anorg. Chem. 1894. 7, 52. A.
Lachman, J. Amer. Chem. Soc. 1903, 25, 50. H. Beckurts and W. Freytag.
Pharm. Centralh. 1886, 27, 231. A. Michael, Amer. Chem. J. 1884, 5, 359.
Z. Skraup, Ber. 1899, 32, II. 2413. F. Pregl, Sitzber. Wien. Akad. 1902,
lib, 881. Syniewski, Chem. Centr. 1902, 73, II, 986. C. J. Lintner, Zts.
ang. Chem. 1890, 3, 546. J. Habermann, Ann. 1874, 172, 11. A. v. Asboth,
Chem. Centr. 1892, 63, II, 867. W. Syniewski, Ber. 1897, 30, 2416; 1898,
31, 1791. A. Gris, Bull.-soc. Bot. 1860, 7, 876. A. Meyer, Arch. Pharm.
1883, 21, No. 7-8; Ber. Deut. Bot. Ges. 1886, 4, 337; 1887, 5, 171. E. Rus-
sow, Sitz. Ber. Dorpater Natiu"forsch-Ges. 1884. 7, P. 1. U. Kreusler and P.
Dafert, I.andw. Jahr. 1884, 13, 767. Dafert, Landw. Jahr. 1886. 15, 259;
Sitzber. Niederrhein. Ges. Bonn, 1885, 337; Ber. Deut. Bot. Ges. 1887, 5,
108. A. Beutell and Dafert, Chem. Ztg. 1887, U, 136. A. Tschirch, Ber.
Deut. Bot. Ges. 1888, 6, 138. C. Overhage. Just Jahr. 1888, I, 745. Y.
Shimoyama, Dissert. Strassburg, 1886; Just Jahr. 1866, II, 315; Botan. Centr.
1887. 32, 6. Pellet, Compt. rend. 1880. 90, 1293. Levallois, Compt. rend.
1881, 93, 281. Saito, Bot. Centr. 1901, 88, 125. H. v. Mohl, Bot. Ztg.
1859, 225. Naegeli. Botan. Mitteil, 1863, 387, 415. A. Meyer. Bot. Ztg.
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Syniewski, Ann. 1899, 309, 282. E. Bourquelot. Compt. rend. 1887, 104,
71, 177. Lintner, J. prakt. Chem. 1886, 34, 378. J. Ford, Chem. Centr.
1904, 75, II, 645. H. Ost, Chem. Ztg. 1895, 19, 1501. A. Wrowlewski, Ber.

, STARCH 391

vestigated as far back as 1690 by de la Hire/ followed by Bonnet,*
Priestly,' Senebier,* de Saussure,^ and H. von Mohl;* the latter

1897, SO, II, 2108; Chem. Ztg. 1898, 22, 375. K. Zulkowski, Ber. 1880, 13,
1398. V. Syniewski, Ber. 1897, SO, 2415; 1898, 31, 1791. F. Schulze, J.
prakt. Chem. 1848, 44, 178. L. Bondonneau, Ber. 1875, 8, 438; Compt. rend.
1875, 80, 671; 81, 972, 1210. Beijerinck, Centr. Bakt. 1896, II, 697. Mua-
cuius, Compt. rend. 1870, 70, 857; Ber. 1870, 3. 430; 1874, 7, 824; Bull. Soc.
Chim. 1874, 22, 26. W. Naegeli, Ann. 1874, 173, 218. Bruecke, Sitzungsber.
Wien. Akad. 1872, 4S, Abt. 3. Lintner and Duell,-Ber. 1893, 26, 2533; 1895,
28, 1522. P. Salomon, J. prakt. Chem. 1883, 28, 82. L. Schulze, J. prakt.
Chem. 1883, 28, 311. C. Schiebler and H. Mittelmeier, Ber. 1890, 23, 3060.
Ost, Chem. Ztg. 1895, 19, 1500. F. AUihn, Zts. f. Ruebenzuckerind. 1883,
50. F. Allihn, J. prakt. Chem. 1880, 22, 46. G. Rolfe and Defren, J. Amer.
Chem. Soc. 1896, 18, 869. C. Lintner and G. Duell, Ber. 1895, 28, 12.
Flourens, Compt. rend. 1890, 110, 1204. Musculus, J. prakt. Chem. 1883,
28, 496. J. Effront, Mon. Sci. 1887, 29, 513. G. Rolfe and H. Geromanos,
J. Amer. Chem. Soc. 1903, 25, 1003, 1015. H. Dierssen, Zts. ang. Chem.
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1898, 22, 401. Zulkowski, Chem. Centr. 1888, 59, II, 1060. Zulkowski and

B. Franz, Oestrr. Gess. Forder. Chem. Ind. IS, 120; abst. Chem. Centr. 1894.
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1899, 12, 849. Pfeiifer and ToUens, Ann. 1881, 210, 295. Mylius, Ber.
1887, 20, 694. F. Salomon, J. prakt. Chem. 1882, 25, 348; 1882, 26, 324;
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493905, 1893. W. Adamson, E. P. 381, 1875. J. Kelly, E. P. 17260, 1887;
abst. J. S. C. I. 1889, 8, 204. A. Cajot, E. P. 18732, 1890. L. Briant and W.
Walker, E. P. 23748, 1892. T. Milligan, E. P. 12910, 1900; abst. J. S. C. I.

1900, 19, 1027. C. Eckman, E. P. 8331, 1901. F. Planchon, E. P. 4956,
1908. C. Hervey, E. P. 20484, 1908. J. D'Orlowski, F. P. 405187, 1909;
abst. J. S. C. I. 1910. 29, 230. H. Alschech, F. P. 405711, 1909; abst. J. S.

C. I. 1910, 29, 440. H. Cambron, F. P. 447845, 1912; abst. J. S. C. I. 1913,
32, 248. T. Calow & Co. D. R. P. 3S54, 1878. Leinhass and Huelsenberg,

D. R. P. 15531. Belhias, D. R. P. 160975. M. Drucker, D. R. P. 16430,
1881. Klopfer, D. R. P. 187590. Kandler. Aust. P. 32974, 1907. See also
D. R. P. 22716, addn. 24942, 1883. 26521, addn. 32256, 1884. 16373,
addn. 36850, 1885. 34031, addn. 43943, 1887. 38397, addn. 39043, 1886.
45080, addn. 70505, 1891. 50442, addn. 57049, 1890. 52578, addn. 68620,
1892. 68074, addn. 70248, 1893. For production of starch in U. S. see T.
Wagner, J. S. C. I. 1909, 28, 343. W. Kaufmann. J. S. C. I. 1910, 29, 527.
C. Chandler, J. S. C. I. 1900, 19, 617. Oil, Paint and Drug Rep. Aug. 7,
1911; abst. J. S. C. I. 1911, SO, 1080. For the production of starch in Ger-
many see Chem. Ztg. 1890, 14, 305; abst. J. S. C. I. 1890, 9, 526. Board of
Trade J. 1900, 715; abst. J. S. C. I. 1901, 29, 85. For the production of
starch in Damascus, Tiu"key, see Foreign Office Annual Series No. 2832;
abst. J. S. C. I. 1902, 21, 1004. For production of starch in Egypt, see
Board of Trade J. Oct. 10, 1901; abst. J. S. C. I. 1901, 20, 1046.

1. Mem. de I'Acad. 1690.

2. "Usage des Feuillcs," 1754.

3. Phil. Trans. 1772.

4. "Experiences sur Taction de la lumiere solaire," 1788.

5. "Recherches chimiques sur la Vegetation," 1804.

6. 'Unters. ueber die Anatom. VerhiUtnisse des Chlorophylls," Botan.
Zts. 1859, 225.

392 TECHNOLOGY OP CELLULOSE ESTERS

drew attention to the almost universal occurrence of starch grains
in chlorophyl granules, and pointed out — in no hazy way — ^that
starch grains were secondary formations within the corpuscles.
These observations in general, were confirmed and extended by
J. Schrader,* C. Kirchoff,* A. Payen,' J. Biot and J. Persoz,*
G. Guerin-Vary and M. Chevreul,* Dubrunfaut,' Mayet,^ V.
Jacquelain," A. Bechamp,' N. de Saussure,^® F. Raspail,^* O.
Masche,^* C. Jessen,*' E. Lippmann,^* W. Delffs," H. Dragen-

1. Schweig. Jour. 1812, 4, 108.

2. Schweig. Jour. 1815, 14, 385, 389. See also, Schweig. Jour. 4, 108.
3r Ann. Ghim. Phys, 1834, 56, 337; 1836, O, 365; DingL Poly. 1846.

102, 323; Compt. rend. 1846, 22, 687; 1861, 53, 1217; 1865, O, 512. Ann.
Chim. Phys. 1865, (4), 4, 286; Bull. Soc. Chim. 1865, 3, 470; Rep. Chim. appl.
1862, 4, 36; J. Pharm. (4), 1, 363; Vierteljahrschr. prakt. Pharm. 25, 221;
Dingl. Poly. 1862, 1G4, 144; 1865, 178, 69; Jahr. Chem. 1861, If, 717; 1865,
18, 597; Chem. Centr. 1865, 38, 845. A. Payen and J. Persoz, Ann. Chim.
Phys. 1833, (2), 53, 73; abst. J. Chim. med. 1833, 9, 417; Pogg. Ann. Phys.
1834, 32, 174; Berz. Jahr. Chem. 1835, li, 281.

4. Ann. Chim. Phys. 1833, (2), 52, 72; Mus. His. Nat. Nouv. Ann.

1833, 2, 109; Ann. 1833, 8, 209; Acad. Sci. Mem. 1835, 13, 437; Pogg. Ann.

1834, 32, 160; Schweig. Jour. 1833, 88, 163.

5. L'Institut, 1833, 1, 101; Ann. Chim. Phys. 1834, 58, (2). 226; J.
prakt. Chem. 1834, 3, 329; J. de Pharm. 1834, 20, 690; Ann. 1836, 13, 71;
Ann. Chim. Phys. 1834, (2), 57, 108. Ann. Chim. Phys. 1836, (2), 88, 32; Ann.
1836, 17, 261. L'Inst. 1835, 3, 157; Ann. Chim. Phys. 1836 (2), 81, 66; J.
prakt. Chem. 1835, 5, 19; 1836, 7, 205; Compt. rend. 1836, 2, 116. M.
Chevreul, Mus. Hist. Nat. Nouv. Ann. 1834, 3, 239; J. prakt. Chem. 1834,
2, 382; Ann. 1835, 18, 216.

6. Ann. Chim. Phys. 1847, (3), 21, 178; Compt. rend. 1847, 25, 308;
1849, 29, 51; Pharm. Centr. 1848. 19, 10; 1849, 20. 643; Jahr. Chem. 1847-
1848, 1, 793; 1848, 2, 464; J. prakt. Chem. 1847, 42, 425; Annuaire de Chim.
1848, 4, 260.

7. J. de Pharm. 1847, (3), U, 81; abst. Pharm. Centr. 1847, 18, 393;
Dingl. Poly. 1847, 184, 107; Jahr. Chem. 1847-1848, 1, 794. Eisner's Chem.
Tech. Mitth. 1846-48, 1, 116; Annuaire de Chim. 1848, 4. 359.

8. Ann. Chim. Phys. 1840, (2), 73, 167; 1843, (3), 8, 266; Compt. rend.
1839, 7, 916; L'Inst. 1843, 172; abst. Berz. Jahr. Chem. 1842, 21, 326; 1845,
24, 457; J. prakt. Chem. 1843, 30, 477.

9. Compt. rend. 1854, 39, 653; L'Inst. 1854, 338; J. prakt. Chem.
1855, 84, 38; Pharm. Centr. 1854. 25, 863; Jahr. Chem. 1854, 7, 622. Compt.
rend. 1856, 42, 1210; Ann. Chim. Phys. 1856. (3), 48, 468; L'Inst. 1856, 234;
Ann. 1856, 188, 364; Jahr. Chem. 1856, 9, 670; J. prakt. Chem. 1866, 89,
447. See also, L. Soubeiran, Jr.. J. Pharm. (3), 25, 89, 175; abst. Jahr.
Chem, 1864, 7, 621. J. J. Field, Pharm. J. Trans. 14, 263; abst. Jahr.
Chem. 1854, 7, 621. O. Maschke, J. prakt. Chem. 1854, KL, 1; abst. Pharm.
Centr. 1854, 25, 337; Jahr. Chem. 1854, 7, 621.

10. Phil. Trans. 1819, 29; Ann. Chim. Phys. 1819, (2), 11, 379; Gilb.
Ann. 1820, 84, 113; Giom. Arcad. 1819, 4, 227; J. de Pharm. 1819. 5, 448;
Schweig. J. 1819, 27, 301; TrommsdorflF, N. J. d. Pharm. 1820, 4, St. 2, 112.

11. Ann. Sci. nat. 1825, 8, 224, 384; 1826, 7, 325; Quart. J. Sci. 1826,
21, 176; 1827, 1, 496; Soc. Philom. N. Bull. 1826, 155; BuU. Sci. Math. 1826,
8, 333. 361; 1827, 8, 200, 204. 264.

12. J. prakt. Chem. 1852, 58, 400; 1854, 81, I; abst. Pharm. Centr.

STARCH 393

dorff,* J. Wiesner,* A. Pamintzin,^ F. Flueckiger* and Fittig,*
and especially by K. Naegeli® and Cramer.^

1852. 23, 609; 1854, 25, 337; J. de Pharm. 1854, 25, 237; Jahr. Chem. 1852,
5, 657; 1854, 7, 621.

13. Pogg. Ann. 1859, lOe, 497; 1860, 100, 361; 1864, 122, 482; Rep.
Chim. Pure, 1869, 1, 432; Vierteliahrschr. prakt. Pharm. 9, 77; Chem. Centr.
1865, 30, 128; Jahr. Chem. 1859. 12, 544, 545; 1864, 17, 571. J. prakt. Chem.
1868, 105, 65; abst. Jahr. Chem. 1868, 21, 763; Wag. Jahr. 1868, U, 458.

14. J. prakt. Chem. 1861, 83, 51; abst. Chem. News, 1862, 5, 98; Chem.
Centr. 1861, 32, 859; Dingl. Poly. 1861, 102, 450; Poly. Centr. 1862, 20,
349" Wag. Jahr. 1861. 7 359.

'l5. jahr. Ver. Naturk. 1859-1860, 28, 28; Pogg. Ann. 1860, 109, 648;
J. de Pharm. 1860, 30, 336.

1. Pharm. Zts. Russ. 1862, 1, 41; 111. Deut. Gewerbeztg. 1862, 283;
Schweizer Zts. Pharm. 7, 158; Rep. Chim. Appl. 1863, 5, 186; Chem. News,
1863, 7, 51; J. Landw. 1862, 7, 206, 211; Wilda's Landw. Centr. 1862, 317;
Chem. Centr. 1862, 33, 523; Chem. Tech. Rep. 1862, 1, II, 85; Dingl. Poly.
1864, 171, 468; Jahr. Chem. 1862, 15, 631; Wag. Jahr. 1862, 0, 406; Zts. anal.
Chem. 1862, 1, 489.

2. Dingl. Poly. 1868, 190, 154; Jahr. Chem. 1868, 21, 986; Wag. Jahr.
1868, U, 460; Poly. Centr. 1869, 35, 284; D. Ind. Ztg. 1868, 464.

3. A. Pamintzin and J. Borodin, St. Petersb. Acad. Sd. Bull. 1868,
12, 113; Ann. Sci. nat. 1867, 8, 348; Bot, Ztg! 1867, 25, 385. Heidelberger
Jahrb. der Litteratur, 1869, 226.

4. Pharm. Zts. Russ. 1868, 7, 399. J. C. S. 1871, 24, 543; Arch.
Pharm. 1871, 145.

5. Ueber die Konstitution der sogenannten "Kohlenhydrate," Tue-
bingen, 1871.

6. Botan. Mitth. 1863, 387, 415; Sitzungsber. mathem-physik. Klasse
der k. B. Akad. Wiss. Miinchen, 1881, 391; Botan. Ztg. 1881. 39, 633. In
Bied. Centr. 1882, 186; abst. J. C. S. 1882, 42, 761, K. Naeglt contributes a
paper on the growth of starch grains by intussusception, ill which he denies
the correctness of the work of A. Schjmper (Bied. Centr. 1881, 195, 479;
Botan. Ztg. 1880, 38, 881; 1881, 39, 185; Ann. Sci. nat. (Bot.) 1880-1881.
11,256, 265; Quart. J. Micro. Sci. 1881, 2L, 291; abst. J. C. S. 1881, 40, 1061.
See also K. Naegeli, Flora, 1856. No. 3S-41. Vierteliahrschr. prakt. Pharm*.
0, 256; Instit. 1863. 263; abst. Jahr. Chem. 1857, 10, 493; 1859, 12, 544;
1863, 18, 571. L. Melsens, Acad. Sci. Bull. 1856, 23, II, 663; Instit. 1857,
161; abst. Jahr. Chem. 1857, 10, 493. Compare also, W. Naegeli, Ann.
1874, in, 218; abst. Chem. News, 1874, 30, 229; J. C. S. 1875, 28, 55; Poly.
Centr. 1874, 40, 1297; Chem. Centr. 1874, 45, 809; Jahr. Chem. 1874, 27,
878; Jahr. rein chem. 1874, 2, 176; Wag. Jahr. 1874, 20, 653. J. Boehm
Sitzber. k. Akad. Wien, 1856, 22, 179; Sitzber. k. Akad. der Wiss. 1874, 89,
76; 1876, 73. Wiener Anzeiger, 1874, U, 47; 1876, 13, 12; Landw.
Versuchstat. 1879, 23, 123; abst. Chem. News, 1877, 38, 242; J. C. S. 1876,
29, 952, 953. Ber. 1876, 9, 123; 1877, 10, 1804; abst. J. C. S. 1878, 34, 84;
1879, 38, 551 ; Chem. Centr. 1875, 48, 202, 207, 217, 233, 248; 1876, 47, 109,
473, 488; 1878, 49, 53, 684; Jahr. Chem. 1876, 29, 861; 1877, 30, 924; 1878,
31, 944; Jahr. rein chem. 1876, 4, 375. Botan. Ztg. 1883, 41, 33, 49; abst.
Jahr. Chem. 1883, 38, 1390; J. C. S. 1883, 44, 820; Chem. Centr. 1883, 54,
317. He employed for the first time the now well-known method of detecting
minute starch granules by successive treatment with caustic potash and iodine.

7. "Pflanzenphysiologische Untersuchungen," 1858. According to P.
K6gel (Biochem. Zts. 1919, 95, 313; abst. J. C. S. 1919, 118, i, 471; J. S. C. I.
1919, 38, 738- A) keto-enol changes probably play an important r61e in the
photosynthesis of formaldehyde and sugar. See A. Schimper, Bied. Centr
1881, 479; J. C. S. 1881, 1061 ; Botan. Zts. 1880, 881 ; 1883, Nos. 7-10; 1885, 738]

394 TECHNOLOGY OF CELLULOSE ESTERS

It was in 1862 when J. Sachs* showed that starch grains do
not o^cur in etiolated chlorophyl granules, and that their forma-
tion in normal corpuscles is dependent upon exposure to light.^
Although adducing no experimental data to back him up, he
assumed that starch grain formation only takes place when the
assimilating organs are supplied with carbon dioxide. Godlewski
substantiated his assumption.

It was next determined' that the volume of oxygen exhaled
by assimilating organs is approximately equal to the carbon di-
oxide absorbed, a proportion which favors the assumption that
a carbohydrate has been formed, as according to the equation :

GCO2 + 5H2O = CeHioOa + 6O2

The work of N. Pringsheim,^ J. Wiesner,^ C. Kraus,® L.

1. Botan. Ztg. 1862, 20, 365; 1864, 289. Botan. Centr. 1884, 19, 35;
Arbeit Botan. Inst. Wuerzburg, 1884, 3, 1. Chem. Centr. 1884, 55, 945;
J. C. S. 1885, 48, 831 ; Ann. Landw. 1862, 33, 181, 406; Jahr. Chem. 1884, 37,
1433. He apparently was the first to suspect there is a distinct relation be-
tween the starch granules and the processes of assimilation. He established
the fact that the appearance of starch in the chlorophyl granule is induced
by, and is dependent upon, the action of light of sufficient intensity, and that
the green coloring matter of the chloroplast is essential to the production of
this autochthonous starch as it is for the decomposition of carbon dioxide,
for the decolorized chloroplasts of an etiolated plant have not this power, so
long as they remain colorless, to produce starch within their substance.
Sachs for the first time clearly formulated the proposition that the production
of starch in the chlorophyl granule is directly connected with assimilation, and
that when plants are confined in the dark the starch disappears from their
chloroplasts, to again reappear when the plants are once more illuminated.
This is indicative of a daily periodic change in green leaves, the starch which
is formed in the chloroplast in the daylight hours being wholly or partially
redissolved and removed from the leaf during the night, to supply the constant
demands of the growing parts of the plant.

2. Flora, 1873, 378; Arbeiten d. bot. Instit. Wuerzburg, 1874, 1, 343.
W. Pfeffer (Monatsh. d. Berliner Akad. 1873, 784. Botan. Ztg. 1871, 29, 319;
1872, 30, 425, 449, 465. Belgique Horticole, 1872. 22, 248; 1873, 23, 119;
J. C. S. 1872. 25, 1107; Ann. Phys. Chem. 1783, 148, 86; Chem. News, 1873,
27, 133; Jahr. Chem. 1871, 24, 186; 1873, 26, 167) proved that when plants
are placed in air entirely free from CO2, no starch was formed in the chloro-
plasts even when the plants were exposed to intense light for prolonged per-
iods. Godlewski found that previously formed starch completely disappeared
from the chloroplasts under these conditions, and on the other hand, that
starch formation within these bodies could be materially accelerated by in-
creasing, within certain limits, the amount of carbon dixoide in the air around
the plant. These results materially strengthened the earlier conclusions of
Sachs that autochthonous starch formation and assimilation go hand in hand.

3. J. Boussingault, Compt. rend. 18(31, 53, 862; Ann. Sci. nat. (Bot.),
1862, 16, 5; Pharm. J. Trans. (2), 3, 479; Ann. Chim. Phys. 1862. (3), 66,
295; Mon. Sci. 1861, 3, 621 ; Rep. Chim. appl. 1861, 3, 449; Jahr. Chem. 1861,
14 73.3.

4. Monatsh. d. Berl. Akad. 1874, 628; 1875. 745; 1879, 632. J. Bot.
1875, 4, 114; Bot. Soc. Trans. 1876, 12, 258; Bot. Ztg. 1879, 37, 789, 811;

STARCH 395

Pfaiindler,^ F. Kromayer^ and C. TimiriazefP shed but littie ad-
ditional light. However, it has long been known that starch
granules only grow and increase in size when they are in contact
with protoplasm and are exposed to sunlight at a favorable tem-
perature and in the presence of sufficient carbon dioxide. The
formation of starch in plants, therefore, must be regarded pri-
marily as a product of assimilation, and may be assumed, in
addition to the carbohydrate reaction expressed aboye, to be
possible of occurrence in somewhat like the following manner.
A. Bayer,* reasoning from the point that carbohydrates may be
oxidized to aldehydes, propounded that formaldehyde is the im-
mediate product of assimilation, and by its condensation, poly-
merizes six times to glucose, and from this to its anhydride, which
is starch. As S. Vines^ has pointed out, if this be so, then the
primary function of chlorophyl in plants is merely the decompo-
sition of carbon dioxide to carbon monoxide and oxygen.

T. Bokomy® rather corroborates the above; and using Spiro-
gyra as the material for the investigation, concluded that starch
is formed from methylal. He was imable to observe any forma-
tion of starch in the absence of light, but when the Spirogyra was
immersed in dilute methylal in sunlight abundant starch forma-
tion took place. According to Bokomy, glycol and glycerol can

Ann. Mag. Nat. Hist. 1880, 5, 62; Jahr. Botan. 1879-1881, 12, 2&S; 1882,
13, 377. See also Conrad, Flora. 1872.

5. Entstehung des Chlorophyls, Wien, 1877.

6. Flora, 1875, 58, 155, 206, 232, 253, 268, 346, 365, 381, 489.

1. Ann, 1860, 115, 37; abst. Chem. News, 1860, 2, 310; Rep. Chim.
Pure, 1861, 3, 28; Chem. Centr. 1860, 31, 851; Jahr. Chem. 1860, 13, 531.

2. Arch. Pharm. 1861, 156, 164; Chem. Centr. 1861, 32, 393; Jahr.
Chem. 1861, 14, 738.

3. Compt. rend. 1877, 84, 1236; 1890, HO, 1346. Ann. Sci. nat. (Bot.)
1885, 2, No. 2; Chem. News, 1886, 53, 180. J. C. S. 1874, 27, 285; 1877,
32, 635; 1885, 48, 714; 1886, 50, 626. Ann. Chim. Phys. 1877, (5), 12, 355.
Ber. 1873, 6, 1212; 1885, 18, R, 286; 1886, 19, R, 355; Jahr. Chem. 1873,
26, 168; 1877, 30, 196; 1883, 36, 1397; 1885, 38, 1797.

4. Ber. 1870, 3, 63; abst. J. C. S. 1871, 24, 331; Jahr. Chem. 1870, 23,
897.

* 5. J. C. S. 1878, 33, 376; Chem. News, 1878, 37, 190; abst. Ber. 1878,
11, 1263; Jahr. Chem. 1878, 31, 939.

6. Ber. botan. Ges. 1888, 6, 116; 1891, S, 1 a3 ; Landw. Versuch-Stat.
1889, 36, 229; abst. Chem. News, 1891, 64, 17; J. C. S. 1889, 56, 67; 1891,
60, 1539; J. S. C. I. 1893. 12, 281; Ber. 1892, 25, R, 471; Chem. Centr. 1888,
59, 858; 1891, 62, 120; Chem. Ztg. Rep. 1889, 13, 312; 1891, 15, 167; Jahr.
Chem. 1889, 42, 2,084; 1891, 44, 2179, 2206. Chem. Ztg. 1896, 20, 1005;
abst. J. C. S. 1898, 74, ii, 41; J. S. C. I. 1897, 16, 154; Chem. Centr. 1897,
" , I, 177; Jahr. Chem. 1896, 49, 1020.

396 TECHNOUKJY OF CEI.LULOSE ESTERS

also form starch.^'* The methylal in the presence of sodium hy-
drox3rmethyl sulfonate and dipotassium phosphate, when aUowed
to remain in carbon dioxide-free air but exposed to light, after
five days showed considerable quantities of starch, the sodium
hydroxymethyl sulfonate being split up into sodium sulfite and
formaldehyde, and this in turn, condensed and became converted
into starch.

J. Boehm, in his work on the formation of starch in chloro-
phyl granules,' pointed out that light of any intensity sufficient
to enable green plants to decompose carbon dioxide, effects also
the transfer of starch from the leaves to the chlorophyl granules,
and that in direct stmshine, transfer of recognizable amounts of
starch in chlorophyl granules from the stems to the leaves, takes
place in 10-15 minutes. It is obvious that experiments on the
formation of starch in chlorophyl granules consequent on direct
assimilation of carbon dioxide can only be made with plants per-
fectly free from starch, or with detached leaves free from starch.
From his experiments on plants of PhosccUus muUiflorus, the con-
clusion is drawn* that the statement that the starch of chlorophyl
grains is in all cases a product of the intrinsic S3mthesis from CO2
and water, is fallacious. His work leads to the following two
conclusions: (1) the formation of starch in chlorophyl grains is
in many cases the result of a metamorphosis of bodies not intrinsic
to the cells in which this conversion takes place, but liberated
elsewhere by the plant; and, (2) that the process of conversion is
entirely independent of the action of light.- In this connection,

1. Compare, K. Miyake, Bot. Mag. Tokyo, 1900, 14, 158; Botan.
Centr. 1901, 85, 389; Bied. Centr. 1902, 31, 753; J. C. S. 1903, 84, ii, 96.
E. Mer, Compt. rend. 1891, 112, 248, 964; abst. J. C. S. 1891, 80, 604; Chem.
Centr. 1891, 82, 1, 509; Chem. Ztg. Rep. 1891, 15, 154.

2. A. Mayer, Botan. Ztg. 1886, 697, 713; abst. J. C. S. 1887. 52, 460;
Chem. Centr. 1887, 58, 6.

3. Sitzber. k. Akad. Wien, 1856, 22, 179; Sitzber. k. Akad, der Wiss.
1874, 89, 76; 1876, 73. Wiener Anzieger, 1874, U, 47; 1876, 13, 12.
Landw. Versuchstat. 1879, 23, 123; abst. Chem. News, 1877, 38, 242; J. C. S.
1876, 29, 952, 953; Ber. 1876, 9, 123; 1877, 18, 1804; abst. J. C. S. 1878, 34,
84; 1879, 38, 551; Chem. Centr. 1875, 48, 202,-207, 217, 233, 248; 1876, 47,
109, 473, 488; 1878, 49, 53, 684; Jahr. Chem. 1876, 29, 861; 1877, 38, 924;
1878, 31, 944; Jahr. rein chem. 1876, 4, 374. Botan. Ztg. 1883, 41, 33,
49; abst. Jahr. Chem. 1883, 38, 1390; J. C. S. 1883, 44, 820; Chem. Centr,
1883, 54, 317.

4. Ber. 1877, 18, 1804; abst. J. C. S. 1878, 34, 84. Bied. Centr. 1883.
212; 1884, 316; abst. J. C. S. 1883, 44, 820; 1884, 48, 1250. Zts. gesammte
Brauwesen, 1883, 76.

STARCH 397

reference is- directed to the work of L. Schnlze,* R. Sachsse,^ E.
Ebermayer,' O. Boettger/ J. Baranetzky* and Bouillon-Lagrange
and Vauquelin.'

G. Bellud^ tried the effect of the presence of various sub-
stances in order to determine whether the production of starch
under the influence of sunlight and subsequent reconversion at
night, is to be properly regarded as a physiological or a chemical
change. It was found that chloroform and ether vapor destroy
chlorophyl and prevent the transformation of starch during sun-
light, and that the function of chlorophyl was also diminished
by the presence of 002. Saccharification of starch proceeds in
the dark. From the above, it would appear that the phenomena
is a physiological change.^ The presence of organic adds as

1. J. prakt. Chem. 1883, 136, 311; abst. Chem. News, 1884, 49, 70;
J. C. S. 1884, 46, 284; Bull. Soc. Chim. 1884, 42, 292; Ber. 1883, IS, 1364;
Chem. Tech. Rep. 1883, 22, II, 133; Chem. Ztg. 1883, 7, 1552; Jahr. Chem.
1883, 36, 1366; Wag. Jahr. 1883, 29, 671; Zts. deut. Spiritusfabr. 1883, 1022.

2. Leipziger Naturf. Ges. Ber. 1877, 30; abst. Chem. News, 1879, 39,
264; Chem. Centr. 1877, 48, 732; Chem. Tech. Rep. 1878, 17, I, 297; Jahr.
Chem. 1877, 39, 898; Jahr. rein chem. 1877, 5, 175; Zts. Chem. Grossgew.
1877 2. 588.

3. "Physiologische der Pflanzen," Berlin, 1882, 1, 194.

4. Dingl. Poly. 1873, 210, 79; abst. Jahr. Chem. 1873, 26, 962.

5. "Die Staerke umbildenden Fermente in den Pflanzen,'' Leipzig,
1878

6. BuU. Pharm. 3, 54, 395. A. Schimper, Bot. Ztg. 1880, 881; 1881,
186; Ann.Sci.nat. (Bot.) 1880-1881, U, 256, 265; Quart. J. Micro, Sd. 1881,
21, 291; J. C. S. 1881, 40, 1061; Bied. Centr. 1881, 195, 479. His work upon
the development of the starch granule in plants was classical. He carried
our knowledge a step further by indicating how closely the shape of the
starch granule is dependent upon the shape of the chlorophyl body which
gives rise to it, and upon the position it occupies with regard to the chloro-
phyl-body during its development. He demonstrated that in aU parts of the
plant in which starch is being deposited, either as reserve- or transitory-
starch, the starch granules in process of development are not surrotmded
inunediately by ordinary protoplasm, but are contained in, or attached to,
peculiar spherical or spindle-shaped refrangible corpuscles. These are the
starch-forming corpuscles or amyloplasts, which are casually related to the
deposition of the starch granules in the non-chlorophyllous parts of the plant,
just as are the chlorophyl bodies on the other hand, in the green assimilating
cells. As indicating the close analogy existing between the amyloplasts and
the chloroplasts as regards structure, development and starch-producing
function, it was observed that amyloplasts may, under favorable conditions
of light, actually be converted into chlorophyl corpuscles capable of assim-
ilating in the usual manner, and that, in fact, this conversion goes on normally
and regularly in the development of the plant organ.

7. Ann. chim. farm. 1887, (4), 5, 217; Staz. sperim. agrar. 14, 77;
Gazz. chim. ital. 1888, IS, 77; abst. J. C. S. 1887, 52, 1136; Chem. Centr.
1887, SO, 572; 1888, 59, 671, 977; Jahr. Chem. 1887, 40, 2285; 1888, 41, 2348.

8. See G. Bonnier and L. Mangin, "Recherches sur Taction chloro-
phyllienne," Ann. Sci. nat. (Bot.) 1886, 3 (7), 5; Compt. rend. 1884, 99,

N

398 TKCHNOI<OGY OP CEI^I.UI/)SE ESTERS

citric/ renders the action of diastase on starch in the plant more
rapid. G. Carboni' estimates the amount of starch formed by
blanching the leaves with KOH and absolute alcohol, then im-
mersing in a satiu-ated solution of iodine, and judging by the
depth of color produced. '•*'^'*'^

E. Laiurent® plunged etiolated shoots of potato plants in which
the reserve material was exhausted, and in which no trace of
starch could be found, into solutions of different organic compounds
in the dark. Starch was formed from only glycerol, dextrose,
levulose, galactose, saccharose, lactose and maltose.*'^^' It would
appear"'^*'*' that salt has a distinct influence (inhibitory in large

160; 1885, 100, 1092, 1303; 1886, 102, 123; France Soc. Bot. Bull. 1885, 32,
204, 368; abst. J. C. S. 1886, 50, 387; Ber. 1885, IS, R, 387; 1886, 19, 107;
Jahr. Chem. 1884, 37, 1431; 1885, 38, 1787, 1796; 1886, 89, 1807.

1. W. Detmer, Jenaische Sitzber. 1881, 22; Bot. Ztg. 1883, il, 601;
abst. Bied. Centr. 1882, U, 110; J. C. S. 1882, 42, 640. Zts. physiol. Chem.
7, 1; abst. Bied. Centr. 1883, 12, 71; 1884, 13, 69; Chem. News, 1884, 50, 35;
J. C. S. 1882, 42, 881; 1883, 44, 631; 1884, 46, 917, 1063. 1402; Ber. 1882, 15,
2924; Chem. Centr. 1882, 53, 46; Jahr. Chem. 1882, 35, 1233. See also P.
Deherain and L. Maquenne, Ann. Agronom. 7, 385; 12, 526; Compt. rend.

1885, 100, 1234; 101, 887, 1020; 1886, 103, 167; abst. Chem. News, 1885, 52,
47; 1886, 54, 237; J. C. S. 1882, 42, 639; 1885, 48, 927; 1886, 50, 170, 273,
1062; 1887, 52, 172; Ber. 1885, IS, R, 387, 711; Jahr. Chem. 1885, 38, 1788;

1886, 39, 1801.

2. Revista de Vitisoltura ed Enologia Italiana, 9, 13; Ann. Agronom.
U, 85, 236; J. C. S. 1885, 47, 683, 1004.

3. O. KeUner, Landw. Jahr. 1879, 243; Bied. Centr. 1879. 8, 671;
abst. J. C. S. 1880, 38, 279, 731; Chem. Centr. 1879, 50, 744, 761; Jahr. Chem.
1879, 32, 887. Versuchstat. 1885, 32, 57. O. KeUner, Y. Mori and M.
Nagaoka, Zts. physiol. Chem. 1890, 14, 297; abst. J. C. S. 1890, 58, 281;
Ber. 1891, 24, R, 532; Chem. Centr. 1890, 01, I, 909; Jahr. Chem. 1889, 42,
2285; Wag. Jahr. 1890, 38, 1011; Zts. ang. Chem. 1890, 3, 408.

4. O. Eberdt, "Origin and Development of Starch Grains," Prings-
heim's Jahr. 1891, 22, 293.

5. K. Goebl, "Beitraege zur Morphologic u. Physiologic des Blattes,"
Bot. Ztg. 1882, Nos. 22-25. •

6. Callot, Crell's Chem. J. 5, 140.

7. E. Bruecke, Wien. Akad. Ber. 1873, (3), 65, 126; J. C. S. 1873, 26,
394, 395; Bull. Soc. Chim. 1873, 20, 86.

8. "Recherches cxperimentales sur la formation d'amidon dans les
plantes," Brussels, 1888. Botan. Ztg. 1886, 151. Ann. Agronom. 14, 273;
abst. J. C. S. 1888,54, 1126.

9. Hebert, Bull. Assoc. Chim. 1897, 14, 1003; abst. J. S. C. I. 1897, 16,
623. Ann. Agron. 17, 97; abst. J. C. S. 1891, 60, 1285.

10. R. Kayser, "Ueber Vorkommen von Rohrzucker und einigen seiner
Umwandlungsproducte im Organismus des Pflanzen." Landw. Versuchs-
Stat. 1883,29,461.

11. P. Usage, Compt. rend. 1891, 112, 672; abst. J. C. S. 1891, 60,
856; Ber. 1891, 24, R, 372; Chem. Centr. 1891, 62, I, 833; Jahr. Chem. 1891,
44 2206.

12. P. Lesage, Compt. rend. 1891, 112, 891; abst. J. C. S. 1891, 60,
1133; Chem. Centr. 1891, 62, I, 1063.

13. P. Lesage, Compt. rend. 1891. 113, 373; abst. J. C. S. 1892, 62, 92.

STARCH 399

amounts) on general starch formation in chlorophyllian organs.^

Carbohydrates migrate out of leaves much more quickly
when on the plant, than when cut off and laid in water. Whereas
in spring and summer all starch disappears in 1-2 days, in winter
the process requires 7-14 days. W. Saposchnikoff^ was able to
determine the rate of formation of carbohydrates in leaves by
first determining the amount originally present, and the rate of
migration allowed for. Then the amotmt of carbohydrates
formed (in grams) per square meter of leaf smiace per hour, was
determined for a series of days of varying climatic changes.'
According to A. Meyer* and E. Acton,^ the percentage of starch
formation in a given period is augmented by the addition of
glucose, cane sugar, glycerol and inulin. The splitting oflF of
water is said to be necessary.

J. Griiss,^ in determining the time required under varying
conditions of germination for starch granules to spread in the
bud-sheath and appear in the calyptra (which in the quiescent
stage is free from starch), found that oxygen was necessary for
starch formation, which only begins at a few degrees above 0°.
At low temperatures the growth of the granules appears very
limited.^®

1. H. Pick, Ann. Agron. 10, 274; Botan. Centr. IS, 281, 314, 343, 376;
J. C. S. 1884, 46, 1402.

2. Ber. bot. Ges. 1889, 7, 258; 1890, 8, 233; 1891, S, 293; Just's Bot. Jahr.
1889, 1, 25; J. C. S. 1891, 60, 762; Chem. Centr. 1889, 00, II, 371; 1891, 02,
I, 93; 1892, 03, I, 320; Dingl. Poly. 1890, 275, 428; Jahr. Chem. 1889, 42,
2083; 1890, 43, 2794; 1891, 44, 2205; 1892, 45, 2156.

3. J. Reinke, Ber. bot. Ges. 1881, 2144; Just's Bot. Jahr. 1881, 1,
141, 395; Ber. 1881, 14, 2144; Pharm, J. Trans. (3), IS, 268; abst. J. C. S.
1882. 42, 243; 1885, 48, 182; Bull. Soc. Chim. 1887, 37, 378; Chem. Centr.
1884, 55, 220; Jahr. Chem. 1881, 34, 1006; 1884, 37, 1429, 1438. See also O.
Low and T. Bokomy, Ber. 1881, 14, 2508; abst. Jahr. Chem. 1881, 34, 1006.

4. Bot. Ztg. 1881, 841; 1886, 81, 697, 713. Ber. bot. Ges. 1891, S,
238; Pringsheim's Jahr. 1890, 21, 520; Bied. Centr. 1882, U, 396; J. C. S.
1882, 42, 1122; 1886, 50, 902. Ann. Agron. 12, 209.

5. Proc. Roy. Soc. 1890, 47, 150; abst. J. C. S. 1890, 58, 818, 1021;
J. S. C. I. 1890. S, 634; Chem. Centr. 1890, 01, I, 168; Jahr. Chem. 1889, 42,
2084; 1890, 43, 2170; Naturw. Rundsch. 4. 594. Cf. A. Meyer, Bot. Ztg.
1886, 81, 105, 129, 145; abst. Ann. Agron. 12, 209; J. C. S. 1886, 50, 902.

6. Wochen. f. Brauerei, 1897, 14, 321, 409, 487; abst. J. S. C. I. 1897,
10, 691; Chem. Centr. 1897, 08, II, 363, 665, 903; Wag. Jahr. 1897, 44, 917;
see also F. Reinitzer, Wochen. f. Brauerei, 1897, 14, 486; abst. Chem. Centr.

1897, 08, II, 903.

7. Wochen. f. Brauerei, 1898, 15, 81, 269; 1899, 10, 519; abst. J. S. C. I.

1898, 17, 479; 1899, 18, 1042; Mon. Sci. 1900, 55, 527, 532; Chem. Centr.
1898, 09, I, 785; II, 42; Jahr. Chem. 1898, 51, 1332. 2688.

8. A. Marcacci, Staz. sper. agr. ital. 18, 618; abst. J. C. S. 1891, 00,
357; Bied. Centr. 1890, IS, 792. Atti. Soc. Toscana Sci. Nat. 1890, 7, 28;
Jahr. Chem. 1890. 43, 2152.

400 TECHNOLOGY OP CELLULOSE ESTERS

H. Brown and G. Morris/ in repeating the experiments of
J. Boehm* and A. Meyer,' found that the chlorophyl granules
form starch both by assimilation and by a process of elaboration
from certain nutritive solutions of sugars. Inasmuch as the usual
phyto-histological function of starch is as a reserve nutritive
material (corresponding to fat in the animal organism), when
needed it is rendered dialyzable by means of an enzyme such as
diastase, and thereby converted into readily diffusable sugars.*'**'
There is no doubt but what imder favorable climatic conditions,
the plant is favored with the elaboration of more assimilable
material than is necessary to enable it to perform its normal
ftmctions, and the accumulation of excess is manifested by the
deposition of this water-insoluble compound, as a quickly liquidat-
able asset in time of need. Starch, therefore, is only called upon

1. H. Brown and T. Glendinning, J. C. S. 1902, 81, 388; Chcm. News.
1902, 8S, 129; abst. J. vS. C. I. 1902, a, 419; Chem. Centr. 1902, 7J, I, 775,
1065; Jahr. Chem. 1902, S5, 231.

H. Brown and J. Heron, J. C. S. 1879, 3S, 596; Chem. News, 1879, 89,
284; 1880, 4JL 22; Ann. 1879, 139, 165; abst. Ber. 1879, 12, 1477; Jahr.
Chem. 1879, 32, 838; Jahr. rein Chem. 1897, 7, 507.

H. Brown and J. Millar, J. C. S. 1899, 75, 315; Chem. News, 1899, 7S,
79, 80; abst. J. S. C. I. 1899, IB, 159; Bull. Soc. Chim. 1899, 22, 795, 797,
798; Chem. Centr. 1899, 70, I, 674, 1108; Jahr. Chem. 1899, 52, 1276, 1279.
Trans. Guiness Research Lab. 1903, 1, 79; abst. J. S. C. I. 1904, 25, 137.

H. Brown and G. Morris. J. C. S. 1885, 47, 527; 1880, 55, 449; 1890,
57, 458, 489; 1895, 57, 309; Chem. News, 1885, SI, 308; 1886, 53, 37; 1889.
59, 295; 1890, ^ 201; 1895, 71, 123; abst. Bull. Soc. Chim. 1890, 4, 682;
1891, 5, 543; 1896, 16, 1006; J. S. C. I. 1885, 4. 682; 1880. 8, 716; 1895, 14,
288; Ann. 1885, 231, 72, 109, 125; Ber. 1885, 18, R. 615; 1889. 21, R, 740;
1890, 23, R, 502; 1895, 28, R, 642; Chem. Centr. 1889, 90, II, 124, 285; 1890,
91, I, 1006; II, 149; 1895, 69, I, 849; Jahr. Chem. 1885, 38, 1757; 1889. 42,
136, 2063; 1890, 43, 2174; 1895. 48, 1335.

H. Brown, G. Morris and J. Millar. J. C. S. 1897, 71, 109; Chem. News.
1897, 75, 42, 43; abst. J. S. C. I. 1897, 16, 166; Bull. Soc. Chim. 1897, 18, 936,
937; Chem. Centr. 1897, 68, 1, 366, 367, 584, 585; Jahr. Chem. 1897, 50, 1623,
1526.

H. Brown and S. Pickering, J. C. S. 1897, 71, 783; Chem. News. 1897.
75, 295, 296; abst. J. S. C. I. 1897, 16, 624; Bull. Soc. Chim. 1897, 18, 1062.
1190; 1898, 20, 450; Chem. Centr. 1897, 68, II, 169, 464; Jahr. Chem. 1897.
50, 225, 1459.

2. Sitzber. d. k. Akad. Wien, 1856, 22, 479; 1876, 73. Ber. 1877. 10,
1804. Bot. Ztg. 1883, 33, 49. Zts. gesammte Brauw. 1883, 76.

3. Bot. Ztg. 1881, Nos. 51, 52; 1885, Nos.. 27-^32; 1886, 105. 129, 145.
697, 713; Ann. Agron. 12, 209; abst. J. C. S. 1886, 50, 902; 1887. 52, 460;
Chem. Centr. 1887, 58, 6.

4. O. Kohlrausch, Zts. Ver. Riibenzuckerind. 1885, 35, 344; abst. Bied.
Centr. 1885, 14, 349; J. C. S. 1885. 48. 1021; Wag. Jahr. 1885, 31, 763.

5. J. Habermann, Ann. 1874, 172, 11; abst. J. C. S. 1874. 27, 1077;
Chem. Centr. 1874, 45, 374; Jahr. Chem. 1874, 27, 879.

6. A. Dastre, Compt. rend. Soc. Biol. 1894, 46, 375. A. Dastre and
N. Floresco, Compt. rend. Soc. Biol. 1895, 47, 669.

STARCH 401

when assimilation ceases. These authors are of the opinion that
cane sugar is probably the first polysaccharide to be S3mthesized,
and may be regarded as the initial material for all the metabolic
changes which occur in the plant. As a temporary reserve ma-
terial, it accumulates in the sap at a time when the processes of
assimilation are at their maxima. When the degree of concen-
tration reaches a certain limit, then the chloroplasts commence
to elaborate starch.*'*''**

As the result of a study of the action of Hght on chlorophyl,
H. Wagner^ suggests that the formation of starch, sugars and
other carbohydrates in the green leaf may be initiated by the
photo-oxidation of chlorophyl and subsequent elaboration of the
aldehyde produced by the condensation (of oxidized chlorophyl)
rather than by the direct photo-synthesis of carbon dioxide and
water.*

As the conclusion to an elaborate investigation of the col-
loidal properties of starch in relation to its constitution,^ £.
Fouard has modified some of the views of H. Brown and G.
Morris* on the fimctions of starch in relation to the living plant.
As the result of an examination of the mineral constituents of
starch,* disclosing the existence of add and basic phosphates
primarily, and by virtue of the action of add and basic salts
u|x>n the coagulation of starch solution as pointed out by A.

1. R. Chodat, "Transformation of Chlorophyll-grains into Amyliferous
Leudtes/' Arch. Sd. Phys. nat. 1889, 22, 602; 1890, 23, 559; Geneve Soc.
Phys. Mem. 1890-1893, No. 62, 63.

2. A. Wigand, "Das Protoplasma als Perment-organismus,*' Marburg,
1888.

3. A. Wohl, Ber. 1890. 23, 2084; abst. J. C. S. 1890, S3, 1085; J. S. C.

I. 1890, 9, 957; Chem. Q^tr. 1890, 61, II, 338; Chem. Tech Rep. 1890, 29,

II, 99; Jahr. Chem. 1890, 43, 2143; Wag. Jahr. 1890, 36, 825.

4. E. Belzung, "Pormation of Starch-grains and Chlorophyll-bodies,"
Ann. Sd. nat. (Hot.) 1891, 13, 5. Cf. also Bull. Prance Soc. Bot. 1885, XI,
374; 1886, 33, 199, 483. Ann. Sd nat. (Bot.) 1887, 5, 179; Rev. Sd. 1887,
49, 788. J. Bot. 1887. 1, 86, 97; 1891, 5, 5; 1895. 9, 33, 41, 61, 101, 134,
137 181

' 5. Proc. Roy. Soc. 1914, 97, B, 386; abst. C. A. 1914, 9, 3451; J. C. S.
1914. 199, i. 561. See also G. Ciamidan and P. Silber, Ber. 1911, 44, 1280.

6. J. Cuboni, "Researches sue la formation de Tamidon dans les
feuilles de la vigne," Archives Italiennes de Biologic, 1886, 7, 209.

7. Compt. rend. 1906, 142, 796, 1163; 1907, 144, 501, 1368; 1908, 149,
285, 930, 980; 147, 813, 931; 1909, 149, 502, 978; abst. J. S. C. I. 1909. '
433. BuU. Soc. Chlm. 1909, 5, 828; abst. J. S. C. I. 1909, 29, 898.

8. Loc. dt.

9. See H. Brown and S. Pickering, loc. cit.

\

402 TECHNOLOGY OI? CELLULOSE ESTERS

Fembach,* and A. Fembach and J. Wolff,* and also of the fact
that the vegetable cell contains juices of variable reaction, it
would appear plausible that the phosphatic content of the starch
plays an important part in the migration of starch in the vegetable
organism.'*'*'*

A. Urspnmg^ has investigated the formation of starch in the
leaves of Phaseolus multtflarus, etc., at different positions of the
spectra of the sun and moon under the rays of different electric
lights, and finds that the extreme limits of wave-length within
which starch is formed are 760 /x and 330 /x. Synthetical processes
of the types occurring in plants, may also in some cases be effected
by the aid of the quartz-mercury lamp.^ The following reac-
tions have been studied from this point of view, and carried out
through ultra-violet light:

CO + O :;^ CO2: CO -f H2 Z^.

H.CHO: XCH2O Z^ (CH20)x: Ha + O :^ H2O.

Formamide has been obtained by exposing a mixture of CO and
NHs to ultra-violet light, ^'^^-^ii*.

1. Ann. Brass, et Dist. 1908, 11, 481. Chem. Ztg. 1908, 32, 1068;
abst. J. S. C. r. 1908, 27, 1169.

2. Compt. rend. 1906. 143, 363, 380; 1907, 145, 80, 261; abst. J. S. C.
I. 1906, 25, 898; Rep. Chim. 1908, 8, 61, 89.

3. C. Wehmer, "Zur Kohlenhydrat-Natur der Formose," Ber. 1887.
20, 2614; abst. J. C. S. 1888, 54, 40; Bull. Soc. Chim. 1888, 49, 712; Jahr.
Chem. 1887. 40, 2248.

4. W. Spring, Bull. Cong. Chim. Pharm. Liege, 1905, 1, 229. Bull.
Soc. Belg. 1910,24, 112.

5. L. Roos and E. Thomas, Compt. rend. 1892. 114, 593; abst. Chem.
News, 1892, 05, 167; J. C. S. 1892, 02, 908; J. S. C. I. 1892, 11, 627; Ber.
1892, 25, R, 387; Jahr. Chem. 1892, 45, 2156.

6. W. Hardy, Zts. physik. Chem. 1900, 33, 326; abst. J. C. S. 1900,
78, ii, 396; Chem. Centr. 1900, 71, 1, 898, 1196; Jahr. Chem, 1900, 53, 35, 36.

7. Ber. bot. Ges. 1917, 35, 69; abst. J. C, S. 1917, 112, i, 504; C. A.
1917, 11, 3301.

8. D. Berthelot and H. Gaudechon, Compt. rend. 1910, 150, 1690;
151, 316; abst. J. C. S. 1910, 38, i, 543; C. A. 1910, 4, 2408; J. S. C. I. 1910.
20^904; Chem. Zentr. 1910, 81, II, 558, 876, 1038; Jahr. Chem, 1910, 03,
I, 639; II, 362, 380. J. Pharm. et Chim. 1910, (7), 2, 5. Compt. rend. 1913,
150, 68; abst. C. A. 1913, 7, 1484; J. C. S. 1913, 104, ii, 90; J. S. C. I. 1913,
32, 160; Chem. Zentr. 1913, 84, I, 694.

9. H. Le Chatelier, Compt. rend. 1909, 149, 250; abst. J. C. S. 1909.
90, ii, 721.

10. J. Duclaux, Compt. rend. 1905, 140, 1544. Jour. Chim. Phys.
1907, 5, 29, 40, 45; 1909, 7, 413; Rev. g6n. sci. 1910, 21, 141; abst. J. C. S.
1905 88 ii 511.

11. J.'Perrin, Compt. rend. 1903, 137, 564; Jour. Chim. Phys. 1904, 2,
601; 1905, 3, 50; abst. J. C. S. 1905, 88, ii, 138. f

12. O. Loew, Ber. 1887, 20, 141, 3039; abst. J. S. C. I. 1887, 0, 446;

STARCH 403

M. Mercadante* is authority for the statement that the
starch in cells of the medulla and medullary rays may be trans-
formed into gum without any change of aspect or form, for he
finds that gum appears in the cells contemporaneous with the
starch, the latter occupying the center of the cellular mass, while
the gum forms concentric layers outside of it in the interior of
the cells.^

The behavior of starch as a protective colloid towards col-
loidal silver has been examined in detail by A. Gutbier and E.
Weingaertner,' solutions obtained by reduction with hydrazine
and with sodium hyposulfite being found similar in prop-
erties although the latter reacts more rapidly. According to
this author the coagulating influence of electrolytes diminishes in
the order: sulfiuric acid, barium chloride, magnesium sulfate, am-
monium carbonate, sodium hydroxide in the case of the solutions
reduced by hydrazine; and barium chloride, sulfuric acid, mag-
nesium sulfate, sodium carbonate and sodium hydroxide for solu-
tions reduced by sodium hyposulfite.

In general, those electrol3rtes which accelerate the ageing of
starch solutions increase the rate of coagulation, while those
which retard the coagulation of piure starch solutions have a sim-
ilar influence on silver starch solutions. The protective action
of starch solution prepared at 100° and at 120° is practically the
same, although the stabiUty of dilute silver solutions is somewhat
greater from starch solutions obtained at the higher temperature.

E. Jentys* considers the substance of starch grains to cpnsist
of a mixtture of colloids composed of reducing sugar and aromatic
substances related to the tannins but glucosidic in character.
The stratified starch grains present in chloraplastids, leucaplas-
tids, etc., are of varying composition in different portions of the

J. C. S. 1887, 52, 459; Jahr. Chem. 1887, 40, 2247. Bull. Soc. Chim. 1888,
49, 712. See also C. Wehmer and B. ToUens, Ber. 1886, 19, 2134, 2614.
Ann. 1888, 243, 334.

1. Gazz, chim. ital. 1876, 6, 97; abst. J. C. S. 1877, 31, 104; Ber. 1876,
9, 681; Jahr. Chem. 1876, 29, 866; Chem. News, 1876, 33, 205.

2. B. ToUens, Ber. 1886, 19, 2134; abst. J. C. S. 1886, 50, 1006; Jahr.
Chem. 1886, 39, 1621.

3. KoU. Chem. Beih. 1913. 5, 211;.abst. J. C. S. 1913, 104, ii, 1034;
C. A. 1914. 8, 1225; J. S. C. I. 1914, 33, 46; Chem. Zentr. 1914, 85, I, 1333.

4. Bull. Akad. Sci. Cracow, 1907, 203; abst. J. C. S. 1907, 92, i, 589;
abst. C. A. 1907, 1, 2313; J. C. S. 1907, 92, i, 589; Chem. Zentr. 1907, 78,
II, 687; Jahr. Chem. 1905-1908, II, 933.

404 TECHNOIX)GY OF CELLULOSE BSTBRS

granules. Stratification is the result of separation from a liquid
mixtture of carbohydrates and tannin-like substances. O. Tre-
boux/ in his experiments with numerous varieties of Pomoidea»
Prunoidea and Spiraeoidea has shown that all of them are able to
produce starch from sorbitol. None of these plants, however,
are able to utilize mannitol and dulcitol as compared with sugars
and glycerol, the production of starch from sorbitol being always
much more vigorous.

According to V. Griessmayer,* the coating surrounding the
starch granules does not consist of a compound present in the
imaltered granule, but is the result of change of the starch. This
substance may be obtained by the action of acid pepsin on starch
and is convertible into dextrin and finally into saccharine com-
pounds. This amylodextrin is separable with difficulty tmless it
crystallizes in sphaero-crystals, these crystals acting on polarized
light in the same manner as starch crystals, only the dark cross
is diagonal rather than orthogonal.

In studying the changes in starch granules dtuing germina-
tion, R. Wh)rmper' made longitudinal sections of wheat grains
through the embryo or germ, and transversely through the mid-
dle of the grain. Microscopical examinations of the moistened
sections were made periodically, and the following conclusions
arrived at. There appears to be no general relation between the
size of starch granules and the ease with which they are attacked
by diastase ; although with mineral acids and wet and dry heat,
almost invariably the larger granules of any one starch succumb
more quickly to attack than smaller granules of the same kind.

In studying the formation of starch by mould fungi, F. Boas*
found in experiments with Aspergillus niger and PenicilUum glau-
cum cultivated in solutions of sucrose, dextrose, levulose, or dex-
trin containing ammonium salts, the liquid after some time ac-
quired the property of yielding with iodine a blue coloration which

1. Ber. deut. Bot. Ges. 1909, 27, 428, 507; abst. J. C. S. 1910, 9t,
ii, 61; Chem. Zentr. 1909, 80, II, 1479; 1910, SL, I, 189; Jahr. Chem. 1909,
62, II, 370.

2. Ann. 1871, 100, 40; Bied. Centr. 1887, 16, 190; abst. J. C. S. 1872.
25, 72; 1887, 52, 686; Chem. News, 1879, 40, 180; J. S. C, I. 1887, 6, 446.

3. Seventh Intl. Cong. Appl. Chem. 1909; abst. J. S. C. I. 1909, 20,
806; Zts. ang. Chem. 1909, 22, 1248; C. A. 1910, 4, 1821.

4. Woch. Brau. 1917, 34, 47; abst. Biochem. Zts. 1917, 71, 308; J. S.
C. I. 1917, 36, 1285; C. A. 1917, 11, 2216, 2816.

STARCH 405

vanished on warming. The substance colored blue by iodine was
also observed in the mycelial cell walls of the moulds. Under
the influence of diastase the liquids lost their power of reacting
with iodine. Alcohol precipitated the starch-like substance from
solution in a flocculent form. The formation of this substance is
attributed to the influence of a free acid liberated in consequence
of the assimilation of the nitrogen of the ammonium salts by
the moulds, for similar results were obtained in sugar solutions
and in beer wort treated with free tartaric, phosphoric, or sulfuric
acids.

Occurrence of Starch. At some period of growth starch is
j>resent in all plants, and is said to be fotmd in most of the parts.
It is found in larger amounts in some famiUes than in others, being
especially abtmdant in the seeds of all the Leguminosae, in the
stems of various species of Sagus and Cycas, in the roots of many
plants of the natural orders Euphorbiaceae and Zinziberaceae, and
in the tubers of the potato, artichoke, cassava and canna.

Starch is especially found as a reserve material stored up in
the seeds, pith and stems, but it is still a debatable question as to
whether the starch fotmd in the leaves, sap and those portions of
the plant outside the ''reserve organs," is identical with the starch
of these organs. Certain microchemical reactions would indicate
there is a difference.

Starch is also found in varying amounts in the same parts
of the plant at different periods of the 24 hours. In general, it
Occurs in the green leaves and associated with chlorophyl with
which it is intimately identified during the day time, the propor-
tion varying as to the climatic conditions of the particular day,
especially the intensity of the sunlight and the moisture present
in the atmosphere. It appears to be present in largest amounts
toward the close of the day, and is at a minimum in the morning.
Abtmdant evidence has accumulated that at night the starch
tmdergoes a transformation into a dialyzable or soluble form, and
in this condition is transported from one part of the plant to the
other. Whether this soluble form is a sugar has not been definitely
ascertained.

Starch has also been fotmd in the pith of shrubs and in ligno-
cellulose tissue, but whether present here in a transitory condi-
tion or as a permanent resting place is not clear. Although starch

406 TECHNOUXJY OP CELI.UI<OSE ESTERS

is not known to be an animal product, there appears, in certain
pathological processes, to be a relation between starch and glyco-
gen, especially in the liver. It is present in some fungi.^

Molectilar Weight of Starch. The absolute molecular weight
of starch is unknown, but undoubtedly is very high. Represent-
ing the formula as (CcHioOb)^, according to H. Brown and G.
Morris^ by the use of Raoult's method of molecular weights deter-
mination, n is 200 for soluble starch, i. e., it has a molecular
weight of 32400. T. Pfeiffer and B. Tollens' arrive at the value
of n = 2, obtained from the composition of some sodium and potas-
sium salts. The investigations of C. O'SuUivan* lead to the con-
clusion that n is not less than 72. Independently, R. Sachsse*
and W. Naegeli* have proposed 6n + H2O as the formula, while
F. Mylius,' Salomon,* and others,* have arrived at different for-
mulas. According to 0*Sullivan,**^ we may be assured that the

1. E. Bourquelot, J. Pharm. Chim. 1891, (5), 24, 197; abst. J. C. S.
1892 €2 230.

'2. 'Chem. News, 1888, 57, 196; J. C. S. 1889, 55, 462; abst. Bull. Soc.
Chim. 1890, 4, 731; Ber. 1888, 21, R, 595; 1891, 24, R, 723; Chem. Centr.
1889, 60, II, 122. 285; Jahr. Chem. 1888, 41, 119; 1889, 42, 136.

3. Ann. 1881, 210, 295; Bied. Centr. 1882, U, 775; abst. J. C. S. 1883.
44, 307; Chem. News, 1882, 45, 78; Bull. Soc. Chim. 1882, 38, 206; Jahr.
Chem. 1881, 34, 980.

4. J. C. S. 1879, 35, 783; Chem. News, 1879, 40, 236, 288; abst. Bull.
Soc. Chim. 1879, 32, 493; Jahr. Chem. 1879, 32, 845.

5. Leipziger naturf. Ges. Ber. 1877, 30; abst. Chem. News, 1879, 39,
264; Chem. Centr. 1877, 4S, 732; Chem. Tech. Rep. 1878, 17, I, 297; Jahr.
Chem. 1877, 30, 898; Jahr. rein Chem. 1877, 5, 175; Zts. Chem. Grossgew. 1877,
2 588.

6. Ann. 1874, 173, 218; abst. Chem. News, 1874, 30, 229; J. C. S. 1875.
28, 55; Poly. Centr. 1874, 40, 1297; Chem. Centr. 1874, 45, 809; Jahr. Chem.
1874, 27, 878; Jahr. rein Chem. 1874, 2, 176; Wag. Jahr. 1874, 20, 663.

7. Ber. 1887, 20, 694; abst. J. C. S. 1887, 52, 568; J. 8. C. I. 1887, «,
563; Bull. Soc. Chim. 1887, 48, 461 ; Jahr. Chem. 1887, 40. 2263. L. Wacker. .
Ber. 1908, 41, 266; 1909, 42, 2675; abst. J. S. C. I. 1909, 28, 898; Chem. News.
1908, 37, 143; J. C. S. 1908, 94, i, 135; 1909, 96, i, 633; Chem. Zentr. 1908.
79, I. 989; 1909. 80, II, 567; Jahr. Chem. 1905-1908, II, 840. Cf. J. Traube,
Ber 1897 30 272

' 8. Ber.' 1883, 16, 2509; J. prakt. Chem. 1883, 136, 82; abst. J. C. S.
1884, 46, 36; Bull. Soc. Chim. 1884, 42, 292; Jahr. Chem. 1883, 36, 1366.

9. V. Syniewski, Ann. 1900, 309, 282; 1902, 324, 212, 260; abst. J. C. S.
1903, 84, i, 68, 69; J. S. C. I. 1902, 21, 1341; Jahr. Chem. 1902, 55, 1034. H.
Rodewald, Zts. physik. Chem. 1897, 24, 193; 1900. 33, 593; abst. J. C. S.
1898, 74, ii, 61; 1900, 78, i, 477; Bull. Soc. Chim. 1898, 20, 4; Chem. Centr.
1897, 68, II, 1068; 1900, 71, II, 180; Jahr. Chem. 1897, 50, 189; 1900. 53,
830. C. Lintner and G. Dull, Chem. Ztg. 1893, 17. 1340; Ber. 1893, 26,
2533; abst. J. C. S. 1894, 66, i, 5; J. S. C. I. 1894, 13, 53; Bull. Soc. Chim.
1894. 12, 439; Chem. Centr. 1894, 65, I, 22; Jahr. Chem. 1893, 46, 891.

10. Thorpe Diet. Chem. 1914, 5, 155, 161, 165.

STARCH 407

molecular weight of starch is certainly not less than C24oH4oo02oo*

J. Sarasin^ has made careful examination of the products of
decomposition of cellulose and starch by heat, the results obtained
indicating that /-glucosan is an intermediate product in the break-
ing down process and that this material when distilled under
reduced pressure gives the same products as do starch and cellu-
lose. These two compounds are thus considered to be polymerides
of /-glucosan, to which the author ascribes the following formula:

HO.HC CHOH

[C O

HC O CH

I 2

H,C — O — CH.OH

and he considers that it is the ring 2 which opens, giving two free
valences for the polymerization, since among the products of de-
composition of starch and cellulose 2: S-dimethylfurfttfan is fotmd.

By the action of heated malt extract upon starch, V. Sy-
niewski found* that starch solution after 216 hours was converted
into a product like the maltodextrin of Brown and Mbrris, achro-
odextrin II of Lintner, and the maltodextrin of Ling and Baker.
The author calls this *'Grenzdextrin II,*' of a molecular formula'
C36He203i. In the carbinol hydrolysis of starch, amylodextrin re-
sults on heating starch paste in an autoclave at 140°. This
author assumes that nine glucose residues make up the amylogen
complex C64H90O45 of starch are connected by nine carbonyl link-
ages of three different kinds, viz., three a-linkages connecting the
three maltose residues to a central Grenzdextrin I. (Cig) residue,
three jS-linkages which connect the three glucose components of
this Grenzdextrin I residue, and three 7-linkages which connect
the glucose components of the three maltose residues.

The potato-starch molecule is regarded as being made up of
four amylogen complexes, and its formula is C216H360O180. In this
molecule each amylogen complex is connected with the others by
six carbinol anhydride linkages, three operating between Grenz-
dextrin I. residues (d-carbinol bonds), and three between maltose
residues (w-carbinol bonds) . The malto-carbinol bonds are hydro-
lyzed by heatng with water at 140°; all other hydrolyzes, with

1. Arch. Sci. phys. nat. 1918, (4), 46, 5; abst. J. C. S. 1918, 114, i, 375;
C. A 1918 12 2187

'2. Ann.' 1902,' 324, 212; abst. J. S. C. I. 1902, 21, 1341; Bull. Acad.
Sci. Cracow, 1902, 441; J. C. S. 1903, 84, i, 69; Jahr. Chem. 1902, 55, 1034.

408 TECHNOLCX5Y OF CEI<LUU)SE BSTERS

malt extracts in different ways, act upon the various carbonyl
linkages. The two (Cis) components of Grenzdextrin II. and the
two glucose components of dextrinose are united by the d-carbinol
bonds, and these resist to the end.

Starch Iodide. The so-called ''iodide'' of starch has been
the subject of much investigation and considerable controversy.
Since its discovery by F. Stromeyer,* an unusually extensive lit-
erature has arisen, N. Blondlot,^ A. Bechamp,' J. Pohl,* R.
Fresenius,*^ E. Duclaux,* B. Brukner,^ F. Kuester,* V. Griess-
mayer," J. Personnel® and E. Baudrimont,^* consider it to be a
mixture of starch with iodine or a solution of the latter in the
former, while E. Rouvier," A. Payen," J. Fritzsche,** L. Bondon-

1. Thorpe, Diet. Chem. 1914, 5, 158. Gilb. Ann. 1815, 43, 146.

2. Ann. Chim. Phys. 1855. (3), 43, 225; abst. J. pharm. chim. 1855,
28, 45; Jahr. Chem. 1855, 8, 679. See Leroy and Raspail, Schw. Jour. 1833,
€8 179.

3. J. pharm. chim. 1855, (3), 27, 406; 28, 303; Jahr. Chem. 1855, 8,
679. Bull. Soc. Encour. 1862, 187; abst. Dingl. Poly. 1862, i6S, 67; Jahr.
Chem. 1862, V, 577; Zts. anal. Chem. 1862, 1, 466; Chem. Tech. Rep. 1862,
1, II, 89.

4. J. prakt. Chem. -1861, 83, 38; Zts. anal. Chem. 1862, 1, 84; Jahr.
Chem. 1861, 14, 715.

5. Ann. 1857, 102, 184; Zts. anal. Chem. 1862, 1, 84.

6. Compt. rend. 1872, 74, 533; Ann. Chim. Phys. 1872, (4), 25, 264;
Abst. J. C. S. 1872, 25, 299, 687; Jahr. Chem. 1872, 25, 770. See "Traite de
Microbiologic," 1899, 2, Chapt. 15, 22-25.

7. Monats'^. Chem. 1883, 4, 889, 906; abst. J. C. S. 1884, 48, 575; J.
Pharm. chim. 1885, (5), 12, 236.

8. Ann. 1895, 283, 360, 376; Ber. 1895, 28, 783; abst. J. C. S. 1895,
68, i, 199; Bull. Soc. Chim. 1895, 14, 704; Ber. 1895, 28, R, 280; Jahr. Chem.
1895 48 514 515.

'9. 'Ann. 1871, 160, 40; abst. Chem. News, 1871, 24, 265; J. C. S. 1872,
25, 272; BuU. Soc. Chim. 1872, 17, 60; Chem. Centr. 1871, 42, 636; Jahr.
Chem. 1871, 24, 789. See also Zts. f. ges. Br. 1878, 394. J. prakt. Chem.
1893, 156, 225; abst. J. C. S. 1893, 64, i, 684; Ber. 1893, 26, R, 801; Chem.
Centr. 1893, 64, II, 681 ; Jahr. Chem. 1893, 46, 894.

10. Bull. Soc. Chim. 1861, 3, 71; J. pharm. chim. 1861, (3), 30, 49.
Bull. Soc. Chim. 1866, 5, 454; J. pharm. chim. 1866, (4), 3, 94. Compt. rend.
1872, 74, 617; abst. Jahr. Chem. 1872, 25, 771.

11. Compt. rend. 1860. 51, 825; Bull. Soc. Chim. 1860, (1), 1, 246; abst.
Rep. Chim. appl. 1860, 2, 392; Mon. Sci. 1861, 3, 266; Jahr. Chem. 1860,
13, 501; Zts. Chem. 1861, 27.

12. Compt. rend. 1892, 114, 128, 749, 1366; 1893, 117, 281, 461; 1894,
118, 743; 1895, 120, 1179; 1897, 124, 565; abst. J. C. S. 1892. 02, 578, 801,
1171; J. S. C. I. 1897, 16, 475; Jahr. Chem. 1892, 45, 2468; 1B93, 46, 893;
1894, 47, 1338; 1895. 48, 197; 1897, 50, 1516.

13. Compt. rend. 1865, 61, 512; Ann. Chim. Phys. 1865, (4), 4, 286;
Bull. Soc. Chim. 1865, 3, 470; abst. Chem. Centr. 1865, 36, 845; Jahr. Chem.
1865, 18, 597.

14. Pogg. Ann. 1834, 32, 1^; Ann. 1834, 12, 287.

STARCH 409

neau,' P. Guichard,* E. Sonstadt,' H. Pellet/ E. Schar,* T.
Gobley,* F. Goppelsroeder/ C. Harz* and H. Friedenthal* con- •
sider it to be a chemical compound of starch and iodine. The
amount of iodine found has varied all the way from 3.2% to 19.6%,
and formulas deduced varying over a correspondingly wide range.

F. Kuester has shown^® that the amount of halogen in starch
iodide varies continuously with the concentration of the iodine
solution with which it is in equilibrium, and, rejecting the for-
mulas of F. Mylius,^* H. Friedenthal,** considers the blue sub-
stance to be a solid solution of iodine in starch. While Mylius
maintains that the presence of hydriodic acid or an iodide is not

1. Compt. rend. 1877, 85, 671, 673; BuU. Soc. Chim. 1877, (2), 2S,
452; abst. J. C. S. 1878, 34, 22; Chem. News, 1877, 36, 195; J. pharm. chim.
1878, (4), 27, 121; Jahr. Chem. 1877, 30, 899. Other investigations in the
starch group are, Compt. rend. 1875, 80, 671; abst. J. C. S. 1875, 28, 629.
Compt. rend. 1884, 98, 153; abst. J. C. S. 1884, 46, 927. Dingl. Poly. 1874,
213, 172. Bull. Soc. Chim. 1874, 21, 147. Bull. Soc. Encour. 1893, 849;
abst. J. S. C. I. 1894, 13, 750. Rep. anal. Chem. 14, 222; abst. J. S. C. I.
1885, 4, 541.

The Bondonneau feculometer is described in Dingl. Poly. 1874, 212, 172;
abst. J. C. S. 1875, 28, 385. V. Bondonneau and A. Forct, E. P. 986, 1887;
abst. J. S. C. I. 1888, 7, 335. D. R. P. 42519; abst. Ber. 1888, 21, R, 335;
Wag. Jahr. 1888, 34, 848.

2. Rep. Chim. Pure, 1863, S, 115, 278; abst. Chem. Centr. 1863, 34,
844; Jahr. Chem. 1863, 16, 569. See M. Guichard. Chem. News, 1868, 18, 6.

3. Chem. News, 1873, 28, 248; abst. J. C. S. 1874, 27, 352; Amer.
Chemist, 1874, 4, 396; Jahr. Chem. 1873, 26, 828; Jahr. rein chem. 1873,

I, 115.

4. Bull. Soc. Chem. 1867, 7, 147; Mon. Sci. 1877, IS, 988; abst. Chem.
Centr. 1867, 38, 1008; Zts. Chem. 1867, 352; Jahr. Chem. 1867, 20, 838;
1877 30 898

5. ' Pharm. Centralh. 1896, 37, 540; abst. J. C. S. 1897, 72, 454; Ber.
1896, 29, R, 1157; Chem. Centr. 1896, 67, II, 661; Deut. Chem. Ztg. 1896,

II, 355; Jahr. Chem. 1896, 49. 1023.

6. Dingl. Poly. 1844, 92, 128; J. Chim. med. 1844, 10, 121 ; J. pharm.
chim. 1844, (3), S, 299; Annuaire de chim. 1845, 1, 315.

7. Pogg. Ann. Phys. 1863, 109, 57; abst. Jahr. Chem. 1863, 16, 670;
Rep. Chim. Pure, 1863. 5, 615; Zts. anal. Chem. 1863, 2, 157; Vierteljahrschr.
prakt. Pharm. 13, 236.

8. Alcohol, 1898, 116; abst. Chem. Ztg. Rep. 1898, 22, 86; Chem. Centr.

1898, 69, 1, 1018; Jahr. Chem. 1898, 51, 1355.

9. Centr. Physiol. 1899, 12, 849; abst. Chem. Centr. 1899, 70, I, 924;
J. C. S. 1899, 76, i, 851; Jahr. Chem. 1899, 52, 1271.

10. Ann. 1895, 283, 360, 376; Ber. 1895, 28, 783; abst. J. C. S. 1895,
68, i, 199; Bull. Soc. Chim. 1895, 14, 704; Ber. 1895, 28, R, 280; Jahr. Chem.
1895 48 514 515.

11. 'Ber! 1887, 20, 688; 1895, 28, 385; Zts. physiol. Chem. 1887, U,
306; abst J. C. S. 1887, 52, 568; T. S. C. I. 1887, 6, 563; BuU. Soc. Chim.
1887, 46, 461 ; Jahr. Chem. 1887, 40, 2263.

12. Centr. Physiol. 12, 849; Chem. Centr. 1899, 70, I, .924; J. C. S.

1899, 76, i, 851; Jahr. Chem. 1899, 52, 1271.

410 TECHNOLOGY OF CELLULOSE ESTERS

essential to the formation of starch iodide, F. Seyfert,* J. Toth,*
F. Hale' and H. Stocks* contend HI or an alkaline iodide is essen-
tial, as well as small amounts of water.

If starch and iodine chemically unite, the compoimd is readily
dissociated,* and for this reason chemists have preferred to em-
ploy physico-chemical methods, such as depression of the freezing
point ;• osmotic pressure measurement of starch iodide;' vapor
pressure of iodine in starch solutions and the partial coefficient of
iodine between starch solutions and chloroform;^ electric conduc-
tivity;® while M. Katayama*^ used a tintbmetric method.

Analogous to the blue color produced by starch with iodine,
are cholalic acid** and lanthanum acetate,*^ while the blue color is

1. Zts. ang. Chem. 1888, 1, 15, 126; abst. J. C. vS. 1888, 54, 1050, 1134;
J. S. C. I. 1888, 7, 350; 1889, 8, 295; Ber. 1888, 21, R, 298; Chem. Centr.
1888, 59, 324, 502; Chem. Ind. 1888, 11, 159; Chem. Ztg. Rep. 1888, 12, 30;
Jahr. Chem. 1888, 41, 2577, 2578; Wag. Jahr. 1888, S4, 839, 840. Cf. also
A. V. Asboth, Chem. Ztg. 1887, U, 785; abst. J. C. S. 1887, 52, 868; J. pharm.
chim. 1888, (6), 17, 116; J. S. C. I. 1887. 6, 608; Ber. 1887. 20, R, 483; Chem.
Tech. Rep. 1887, 26, II, 330; Jahr. Chem. 1887, 40, 2464.

2. Chem. Ztg. 1891, 15, 1523, 1583; abst. Jahr. Chem. 1891, 44, 2179.

3. Amer. J. Sci. (Stlliman). 1902, 463, 379; Amer. Chem. J. 1902, 28,
438; abst. J. S. C. I. 1902, 21, 1040; J. C. S. 1902, 82, i, 533; 1903, 84, i, 151;
Bull. ?oc. Chim. 1902. 30, 325; Chem. Centr. 1902, 73, II, 26; Jahr. Chem.
1902, 55, 243, 1038; Zts. anorg. Chem. 1902, 31, 100.

4. Chem. News, 1887, 56, 212; 1888, 57, 183; abst. J. C. S. 1888, 54,
126, 668; Ber. 1888, 21, R, 479; Chem. Tech. Rep. 1887, 26, II, 280; Chem.
Ind. 1888, 11, 159.

5. G. Barger and E. Field. J. C. S. 1912, 101, 1394: abst. C. A. 1913,
7, 330; Bull. vSoc. Chim. 1913, 14, 3; Chem. Zentr. 1912,88,11. 1520; Chem.
Ztg. 1912, 36, 1240.

6. H. Friedenthal, Centr. Physiol. 1899, 13, 54; abst. J. C. S. 1899, 76,
i, 851; Chem. Centr. 1899, 70, I, 924; Jahr. Chem. 1899, 52, 1271.

7. H. Rodewald and A. Kattein, Sitzber. preuss. Akad. Wiss. 1899,
628; Zts. physik. Chem. 1900, 33, 586; abst. J. C. S. 1900. 78, i, 79, 477;
J. S. C. I. 1899, 18, 1062; Chem. Centr. 1899, 70, II, 419; 1900, 71, II, 180;
Jahr. Chem. 1899, 52, 1271; 1900, 53, 829.

8. L. Andrews and H. Goettsch, J. Amer. Chem. Soc. 1902, 24, 865;
abst. J. C. S. 1903, 84, i, 10; Chem. Centr. 1902, 73, II, 1035; Rep. Chim.
1902, 2, 422; Jahr. Chem. 1902, 55, 1037.

9. M. Padoa and B. Savare, Gazz. chim. ital. 1906, 36, i, 313; Atti
R. Acad. Lincei. 1905, (5), 14, i, 467; abst. J. C. S. 1905, 88, i, 416; Bull. Soc.
Chim. 1906, 36, 760; Chem. Centr. 1906, 77, II, 108; Jahr. Chem. 1905-
1908, II, 946.

10. Zts. anor. Chem. 1907, 56, 209; abst. J. S. C. I. 1907, 26, 1289;
C. A. 1908, 2, 749; J. C. S. 1908, 94, i, 9; Chem. Zentr. 1908, 79, I. 239; Jahr.
Chem. 1905-1908. I, 1496.

11. F. Mylius, Ber. 1887, 20, 683; 1895, 28, 388; abst. J. C. S. 1887,
52, 606, 982; 1895, 68, i, 313; Bull. vSoc. Chim. 1887, 48, 461; 1888, 49, 58,
834; 1895, 14, 901; Chem. Centr. 1887, 58, 5,39; 1895, 66, I, 793; Jahr. Chem.
1887, 40, 2333; 1895. 48, 514.

12. F. Kuester, Zts. physik. Chem. 1895, 16, 156; abst. J. C. S. 1895.
68, i, 313, 322; Bull. 3oc. Chim. 1898, 16, 649; Ber. 1895, 28, 720. 783; Chem.

St ARCH 411

inhibited or modified by the presence of chloral hydrate,^ tannin,*
many phenols,' egg albumen* and acacia or malt extract or silver
nitrate.^ W. Harrison* considers that in the case of starch an
adsorption compound is formed similar to the purple of Cassius,
and attempted to prepare colloidal blue iodine solutions. C.
Tomlinson^ states that on heating iodide of starch, in all cases the
blue color disappears at the temperature of boiling water, although
according to S. Pickering* the temperature at which the color
disappears varies with the intensity it possessed before heating.
A. Clementi* finds that the velocity of decoloration is propor-
tional to the amount of furfural liberated, and inversely propor-
tional to the amount of iodine present, and -that the decoloration
is aided by the presence of certain proteins such as albumins,
globulins, albuminates and phosphoproteins. Starch iodide may
also be produced by means of iodine monochloride or iodine mono-
bromide.^®

In the presence of a metalhc iodide, starch is colored blue
by a much smaller quantity of iodine, than when iodides are
absent. ^^ In fact, an aqueous solution of iodine may be added
to a solution of starch until the liquid is yellowish without the

Centr. 1895. 66, I, 656, 1113; Jahr. Chem. 1895, 48, 514, 515. W. Biltz,
Ber. 1904, 37, 719; abst. J. C. S. 1904, 86, II, 339; BuU. Soc. Chim. 1904, 32,
1235; Chem. Centr. 1904, 75, 1, 1001; Jahr. Chem. 1904, 57, 98.

1. E. Schaer, Pharm. Centrsah. 1896, 37, 540; abst. J. C. S. 1897,
72, i, 454; Ber. 1896, 29, R, 1157; Chem. Centr. 1896, 67, II, 661; Deut. Chem.
Ztg. 1896, 11, 355; Jahr. Chem. 1896, 49, 1023.

2. E. Heintz, Jahr. Agri. Chem. 1879, 499.

3. Such as pyrocatechin, hydrochinon, resorcin, pyrogallol, but not
phenol.

4. E. Puchot, Ber. 1876, 9, 1472; Compt. rend. 1876, 83, 225; abst.
J. C. S. 1877, 31, 107; Chem. News, 1876, 34, 72; BuU. Soc. Chim. 1877, 27,
138; Jahr. Chem. 1876, 29, 1032; Zts. anal. Chem. 1876, IS, 460.

5. Amer. J. Sci. 1894, 147, 422; abst. J. C. S. 1894, 66, i, 398; Chem.
Centr. 1894, 65, II, 147; Ber. 1894, 27, R, 602; Jahr. Chem. 1894, 47, 105.

6. J. Soc. Dyers Col. 1911, 27, 84; 1916, 32, 40; Chem. Soc. Proc.
1910, 26, 252; abst. J. C. S. 1916, 109, i, 251; J. S. C. I. 1910, 29, 1335; 1911,
30, 534; 1916, 35, 321; C. A. 1911, 5, 2769; 1912, 6, 18.

7. Phil. Mag. 1885, (5), 20, 168; abst. J. C. S. 1886, 50, 328.

8. Chem. News, 1880, 42, 311; Zts. anal. Chem. 1882, 21, 125; Jahr.
Chem. 1880, 33, 1214.

9. Arch. Farm. Sperim. 1915, 20, 258; abst. J. C. S. 1916, HO, ii, 400;
J. S. C. I. 1916, 35, 909; C. A. 1916, 10, 67.

10. H. Beckurts and W. Freytag, Pharm. Centralh. 1886, 27, 231;
Chem. Centr. 1886, 454; J. C. S. 1886, 50, i, 783; Ber. 1886, 19, R, 415; Chem.
Ind. 1887, 10, 27; Chem. Tech. Rep. 1886, 25, II, 332; Jahr. Chem. 1886,
39, 1911; Wag. Jahr. 1886, 32, 302.

11. C. Lonnes, Zts. anal. Chem. 1894, 33, 409; abst. J. C. S. 1894,
u, 475; Ber. 1895, 28, R, 27; Jahr. Chem. 1894, 47, 104.

412 TECHNOLOGY OP CELLULOSE ESTERS

development of any blue color. ^ The addition of a very small
amomit of KI, however, will induce the reaction Solutions of
starch in zinc chloride or other chloride, upon standing do not
respond to this reaction, the starch meanwhile having been
converted into dextrin.*

As A. Lachmann has observed,' the purity of the solvent
modifies the color and the sensibility of the reaction to a con-
siderable extent. According to N. Castoro,* amylopectin reacts
blue with iodine in the same manner as starch. The recent work
of H. Bordier* has shown that sunlight exerts a powerful decol-
orizing action on starch iodide, and suggests the explanation lies
in the conversion of I to HI under the influence of sunlight.

In a critical investigation of the subject, h- Berczeller* shows
that KI is not necessary for the formation of the starch-I com-
plex, whose inhibition temperature is about one degree above that
of pure starch, and that starch takes up more iodine at a lower
than at a higher temperature. The adsorption equilibrium be-
tween starch and iodine takes place more rapidly in dilute than
in concentrated solutions.

When an excess of iodine is added to starch paste in the
presence of a large quantity of water, the iodide of starch separates
as a dark colored powder, which upon washing out with water
and drying, gives an amorphous metallic appearing powder. In
the dry condition it is stable.

Starch iodide is precipitated from solutions by means of strong
acids, ^ which in the presence of various salts assumes different

1. C. Meineke, Chem. Ztg. 1894, 18, 167; abst. Chem. Centr. 1894,
65, 1, 525; Chem. News, 1894, 69, 241; J. C. S. 1895; 68, i, 79; Ber. 1894, 27,
R, 206; Chem. Tech. Rep^ 1894, 33, I, 286; Jahr. Chem. 1894, 47, 2402.

2. F. Musset, Pharm. Centralh. 1896, 37, 687; Chem. Centr. 1896,
67, II, 703; abst. J. C. S. 1897, 72, i, 456; Jahr. Chem. 1896, 48, 1024; Wag.
Jahr. 1896, 42, 774.

3. J. A. C. S. 1903, 25, 60; abst. J. C. S. 1903, 84, ii, 283; Chem. News,
1903, 88, 307; Rep. Chim. 1903, 3, 121; Chem. Centr. 1903, 74, I. 617; Jahr.
Chem. 1903, 56, 324.

4. Gazz. chim. ital. 1909, 39, i, 603; abst. J. C. S. 1909, 96, i, 634;
C. A. 1911, 5. 619; J. S. C. I. 1909> 28, 898; Rep. Chim. 1910, 18, 40; Chem.
Zentr. 1909, 88, II, 974; Jahr. Chem. 1909, 62, II, 374.

5. Compt. rend. 1916, 163, 205, 291; abst. J. C. S. 1916, 118, i, 630;
J. S. C. I. 1916, 35, 962; C. A. 1916, 18, 2669; 3016; Mon. Sci. 1916, 83, 239.

6. Biochem. Zts. 1917, 84, 37, 106; abst. J. C. S. 1918, 114, i, 101, 131;
J. S. C. I. 1918, 37, 133-A; C. A. 1918, 12, 1264.

7. See G. Kruess and E. Thiele, Zts. anor. Chem. 1894. 7, 52; abst.
J. C. S. 1894, 66, ii, 445; Chem. News, 1894. 78, 197; Ber. 1894, 27, R, 719;
Chem. Centr. 1894, 65, II, 580; Jahr. Chem. 1894, 47, 392. A. Meyer. Bot.
Ztg. 1896, 23. J. Gruess. Jahr. wiss. Mikr. 1896, 26, 379.

STARCH 413

colors* and is colored yellow by bromine,' which color, however,
may be washed out by water. On account of its strong disin-
fectant properties, starch iodide has been proposed^ as a topical
application to wounds. It is also alleged to possess strong bac-
tericidal properties.

Starch iodide paper — made by soaking filter paper in starch
solution containing an iodide — has been used to detect ozone.*
C. Storm* has given a method for its preparation.

Starch Esters. Of the organic esters of starch, the formate
and acetate appear to be fairly definitely characterized. As de-
scribed by J. Traquair,* starch formate is a white powder, sub-

1. A. Vogel. N. Rep. Pharm. 1873, 22, 349; abst. Jahr. Chem. 1873,
2«, 829; J. C. S. 1874, 27, 708; Bull. Soc. Chim. 1873, 20, 492. Cf. J. Pharm.
Chim. 1866, (4). 2, 72.

2. For additional information consult, C. van Deventer, Chem. Centr.
1888, 59, 424. Pohl, J. prakt. chem. 1861, 83, 35; abst. Jahr. Chem. 1861,
14, 716. Vogel, Jahr. Chem. 1873, 26, 829. J. Duroy, Compt. rend. 1860,
51, 1031; J. pharm. chim. 1861, 39, 94. B. Bruckner, Monatsh. 1883, 4, 889,
906; abst. J. C. S. 1884, 46, 576; Akad. Wien. 1883, 88, Pt. 1. Schoenbein,
Jahr. Chem. 1861, 14, 716. Guichard, Jahr. Chem. 1863, 16, 569. Tomlin-
son, Phil. Mag. 1885, 20, 168. Goppelsroeder, Jahr. Chem. 1863. 16, 670.
Fresenius, Ann. 1857, 102, 184. Mylius, Ber. 1887, 20, 691; Proc. Chem.
Soc. 1910, 26, 252. H. Geubel, Jahr. pr. Pharm. 1852, 24, 337; abst. Jahr.
Chem. 1852, 5. 657. Blondonneau, Bull. Soc. Chim. 28. 452. Duclaux, Zts.
Chem. 1871, 7, 702. Seifert, Jahr. Tierchem. 1888, 18, 21. Rouvier, Ber.
1892, 25, 501 ; Compt. rend. 1897. 124, 565. Fritzsche, Ann. 1834, 12, 287.
A. Girard, Ann. Chim. Phys. 1887, (6)> 12, 275. Pickering, Zts. anal. Chem.
1882, 21, 125. Mylius, Ber. 1893, 28, 389. Kuester, Ann. 1894, 283, 370.
Priedenthal, Chem. Centr. 1899, 70, 1, 1162. R. Kemper, Archiv. d. Pharm.
1862, 162, 253; abst. Jahr. Chem. 1863, 16, 571. Franchimont, Rec. Trav.
Pays-Bas. 1883, 2, 92. J. Lassaigne, Ann. Chim. Phys. 1833, (2), 53, 109;
Jour, Chim. med. 1851, (3), 7, 180. C. Lownes, Zts. anal. Chem. 1894, 33,
409. M. Magnes-Lahrens, J. pharm. chim. 1849, (3), 19,243; 1851, (3), 21,
13. C. Naegeli, Instit. 1863, 263. F. Pisani, Compt. rend. 1856, 43, 1118;
J. prakt. Chem. 1857, 70, 382. A. Potilitzin, Ber. 1880, 13, 2400; Jahr.
Chem. 1880, 33, 246. C. Schonbein, J. prakt. Chem. 1861, 84, 385; Chem.
Centr. 1862, 33, 239. H. Rodewald and A. Kattein, Sitzungber. Akad. Wiss.
Berlin, 24, 628; Chem. Centr. 1899, 70, II, 419; J. S. C. I. 1899, 18, 1062.
J. Soubeiran, J. pharm. chim. 1852, (3), 21, 329. A. Vogel, N. Rep. Pharm.
1873, 22, 349; 1875, 25, 565.

3. A. Lumiere, Compt. rend. 1917, 165, 376; abst. J. S. C. I. 1917, 36,
1061; C. A. 1918,12, 189.

4. C. Daubeny. J. C. S. 1867, 20, 1; Chem. News, 1866, 14, 246; Brit.
Assoc. Repts. 1866, 37; abst. Jahr. Chem. 1867, 20, 181; Zts. anal. Chem.
1867 6 208.

'b! C. Storm. J. Ind. Eng. Chem. 1909, 1, 802; abst. J. S. C. I. 1910,
29, 177; Chem. Zentr. 1910, 81, I, 1896; C. A. 1910, 4, 514. BoU. Chim.
farm. 1914, 53, 736; abst. C. A. 1916, 10, 1970.

6. J. S. C. I. 1909, 28, 290; abst. Zts. ang. Chem. 1909, 22, 2346;
Bidl. Soc. Chim. 1909, (4), 6, 1152; Chem. Zentr. 1909, 80, 1, 1987; C. A.
1909, 3, 1602, 2070.

414 TBCHNOI.OGY OF CELLUI.OSE ESTHRS

stantially soluble in water, and lacking the characteristic starch
appearance,^ as well as the typical chemical reactions.

Starch acetate* was first prepared in 1870,' and subsequently
investigated by h- Schulze,* A. Michael,^ Z. Skraup and H. Ham-
burger,* D. Law,^ F. Pregl,* K. Zulkowsky,* J. Traquair,'® C.
Cross and E. Bevan,** A. Kldiaschwili,^' and W. de Conick and
A. Raynaud,^' the organic esters of cellulose and starch being

1. Compare U. S. P. 778173, 1904; B. P. 9868, 1902; abst. J. S. C. I.
1903, 22, 1008; J. Soc. Dyers, 1903, IS, 275; Chem. Ztg. 1903, 27, 862.

2. See E. Worden, Kunst. 1913, S, 61; abst. C. A. 1913, 7, 1633; Zts.
ang. Chem. 1913, 26, II, 320.

3. Ann. Chim. Phys. 1870. (4), 21, 235; abst. Chem. Centr. 1871, 42,
568. Reproduced Ann. 1871, 160, 74; abst. Chem. Centr. 1871, 42, 740;
J. C. S. 1872, 25, 66.

4. J. prakt. chem. 1883, 136, 324; abst. Chem. Centr. 1884, S5, 217;
Jahr. Chem. 1883, 36, 1366; J. C. S. 1884, 46, 284; Bull. Soc. Chim. 1884,
42, II, 292; Jahr. Chem. 1883. 36, 1366.

5. Amer. Chem. J. 1883-1884, 5, 359; abst. J. C. S. 1884, 46, 420;
Bull. Soc. Chim. 1884, 42, II, 354; Jahr. Chem. 1883, 36, 1366.

6. Ber. 1899, 32, 2413; abst. J. S. C. 1. 1899, 18, 941 ; Chem. Centr. 1899,
70, II, 752; Jahr. Chem. 1899, 51, 1288; J. C. S. 1908, 04, 321.

7. Chem. Ztg. 1908, 32, 365; abst. J. C. S. 1908, 04, 321; BuU. Soc.
Chim. 1909, (4), 6, 157; Zts. ang. Chem. 1908, 21, 1377; Chem. Zentr. 1908,
70, I, 183; Jahr. Chem. 1905-1908, 11, 55.

8. Wien. Akad. Ber. 1901, 110, Il-b, 881; Monats^. Chem. 1901,22,
1049; J. C. S. 1902, 02, 135; J. S. C. I. 1902, 21, 129; BuU. Soc. Chim. 1902,
(3), 20, 929; Chem. Centr. 1902, 73, 1, 182; Jahr. Chem. 1901, 54, 880.

9. Wien. Akad. Ber. 1880, 72, II, 384f Ber. 1880, 13, 1395; 1890, 23,
3295; Chem. Centr. 1880, 51, 613; Jahr. Chem. 1880, 33, 1005. Monatsh.
Chem. 1905, 26, 1420. J. C. S. 1891, 60, 165; Chem. Centr. 1888, 50, 1060;
J. C. S. 1889, 56, 116. K. Zuhlkowsky and B. Franz, Ber. oesterr. Ges. zur
Foerderung d. chem. Ind. 1894, 16, 120.

10. J. S. C. I. 1909, 20, 288; abst. Zts. ang. Chem. 1909, 22, 2346; BuU.
Soc. Chim. 1909, (4), 6, 1152; Chem. Zentr. 1909, 00, I, 1989; Jahr. Chem.
1909, 02, 378. For reactions of starch with acetic anhydride, see P. Schut-
zenberger, Ann. Chim. Phys. 1870, (4), 21. 235; abst. Chem. Centr. 1871.
42, 668; Ann. 1871, 160, 74; J. C. S. 1872, 25, 366; abst. Chem. Centr. 1871,
42, 740.

11. C. Cross, E. Bevan and J. Briggs, Jour. Soc. Dyers Col. 1907, 23,
250. C. Cross, E. Bevan and J. Traquair, Chem. Ztg. 1905, 20, 527; Wag.
Jahr. 1905, 51, II, 197; Chem. CenU. 1905, 76, II, 36.

12. J. Russ. Phvs. Chem. Soc. 1905, 37, 421; abst. Brewers Jour. 1905,
41, 688; J. S. C. I. 1905, 24, 1246; Jahr. Chem. 1905-1908, II, 954; Chem.
Centr. 1905, 76, II, 1029; J. C. S. 1904, 06, i, 798. Compare also Z. Skraup,
E. Geinsperger, E. v. Knaffl-Lenz, F. Menter and H. Sirk, Monats''\ 1905,
26, 1415; abst. J. C. S. 1906, 00, i, 67; J. S. C. I. 1906, 25, 43; BuU. Soc.
Chim. 1906, 36, 591; Chem. Centr. 1906, 77, II, 655; Jahr. Chem. 1906-1908,
II, 929. J. Boeseken, J. van den Berg and A. Kerstjens (Rec. trav. chim. Pays-
Bas, 1916, 35, 320; abst. J. C. S. 1916, 100, i, 308; C. A. 1917, 11, 39) have
found that the velocity of acetylation of starch is less than that of oeUulose,
hydriodic acid being the best catalyst. In the case of sulfuric acid, an in-
crease in the amount of acid used produces an acceleration in esterification,
but not to an extent proportional to the amount of catalyst employed.

13. Bull. Acad. Roy. Belg. 1911, 213. 335; abst. J. C. S. 1911, 100, 423;
Chem. Zentr. 1911, 02, II, 855; C. A. 1911, 5, 2443. For the hydrolyzing

STARCH 415

described in detail in Volume VIII of this series already published.

As the result of the researches of C. Cross and J. Traquair
on the partial acetylation of starch,^ certain patents have been
issued to them^ and W. Wotherspoon' for the manufacture of a
starch acetate intended for textile purposes and known under the
commercial name of "Feculose/' for which many technical uses have
been pointed out by the inventors* and by F. Farrell.* K, Militz*
and'F. Bayer & Co.,' together with W. Dixon/ have also investi-
gated the technical side of these products.

The benzoylation of starch in the hands of C. Cross," E.

action of formic acid on starch, see W. Oechsner de Conick, Bull. Acad
Roy. Belg. 1910, 515, 586; abst. C. A. 1911, 5, 394; J. C. S. 1910, », 654;
Chem. Zentr. 1910, 81, II, 1459. See also L. Schulze, J. prakt. Chem. 1883,
136, 324; I. Frankhausen, Dingl. Poly. 1887, 266, SaS. For the preparation
of soluble starch by heating with dilute acetic acid, see E. Blumer, D. R. P.
137330, 1901; abst. Chem. Centr. 1901, 72, I, 306; Jahr. Chem. 1903. 56,
1006; Zts. ang. Chem. 1903, 16, 90. F. P. 322206, 1902; abst. J. S. C. I.
1903, 22, 310. H. P. 10872, 1902. Aust. P. 14886, 1904. Farbenfabriken
vorm. F. Bayer & Co., D. R. P. 200145; abst. Jahr. Chem. 1905-1908, II, 941.

1. C. Cross, E. Bevan and J. Traquair, Chem. Ztg. 1906, 29, 527;
abst. J. C. S. 1905, 88, i, 611. J. Traquair, J. S. C. I. 1909, 28, 288; abst.
Zts. ang. Chem. 1909, 22, 2346; Bull. Soc. Chim. 1909, (4), 6, 1063; C. A.
1909, S, 2070. J. S. C. I. 1910, 29, 323; abst. Bull. Soc. Chim. 1910, (4), 8,
1160. See also J. Traquair, J. S. C. I. 1910, 29, 323; 1912, 31, 1016.

2. E. P. 9868, 1902;abst. J. S. C. 1. 1903, £L 1008; Mon. Sci. 1904, 60, 37.
U. S. P. 778173, 1904; abst. J. S. C. I. 1905, 24, 98. See also J. Traquair,
J. S. C. I. 1909, 28, 288; 1910, 29, 323; 1912, 31, 1016.

3. F. P. 334164, 1903; abst. J. S. C. I. 1904, 23, 29. D. R. P. 182658,
1903; abst. Zts. ang. Chem. 1907, 20, 1781; Mon. Sci. 1909, 70, 77. Belg. P.
171743, 1903. Aust. P. 27352, 1907. For additional commercial applications
of the starch acetates, refer to F. Bayer & Co., D. R. P. 200145. Swiss P.
39840, 1907. Aust. P. 37386. 1909. J. Boeseken, J. v. den Berg and A.
Kerstjens, Rec. trav. chim. 1916, 35, 320; abst. J. C. S. 1916, IM, i, 308.
Staier, U. S. P. 1144073; abst. C. A. 1916, 9, 2313. A. Strut ers, E. P.
27479, 1912. H. Wheelwright, U. S. P. 1196888, 1916; abst. J. S. C. I. 1916,
35, 1009.

4. J. S. C. I. 1909, 28, 288; abst. Zts. ang. Chem. 1909, 22, 2346;
Bull. Soc. Chim. 1909, (4), 6, 1162. J. S. C. I. 1910, 29, 323; abst. Zts. ang.
Chem. 1910, 23, 1824; Bull. Soc. Chim. 1910, (4), 8, 1161.- Pharm. Jour. No.
2379, 680; abst. Merck's Rep. 1909, 18, 179; Mon. Sci. 1910, 72, 605.

5. J. Soc. Dyers Col. 1908, 24, 323; abst. Zts. ang. Chem. 1909, 22,
221; J. vS. C.I. 1909,28, 19.

6. U. S. P. 941159, 1909; abst. J. S. C. I. 1909, 28, 1322; C. A. 1910,
4, 626.

7. E. P. 25274, 1907; abst. J. S. C. I. 1908. 27, 761. F. P. 383902,
1907; abst. J. vS. C. I. 1908, 27, 415. D. R. P. 200146, 214244, 1909. Aust.
P. 37386, 1909. Swiss P. 39840, 1907.

8. E. P. 27491, 1911; abst. J. S. C. I. 1913, 32, 214; C. A. 1913, 7,
1789.

9. C. Cross and E. Bevan, J. C. S. 1893, 26, 837; Chem. News, 1890,
61, 87. C. Cross, E. Bevan and R. Jenks, Ber. 1901, 34, 2496. C. Cross
and E. Bevan, Ber. 1901, 34, 1514; J. C. S. 1901, 80, i, 452; Chem. Centr.
1901, 72, II, 94; Jahr. Chem. 1901, 54, 891.

416 TECHNOI.OGY OP CELLULOSE ESTERS

Bautnann,^ O. Hauser and H. Muschner,* and of H. Ost and F.
Klein' have thrown considerable light upon some angles of car-
bohydrate chemistry, but the starch benzoates have, as yet, ac-
quired no technical significance.

Starch forms compounds with tannic acid.*

Action of Enzymes on Starch. The action of saliva upon
different kinds of starch has been investigated by Lefberg and
Georgieski,* who found that potato starch is converted into sugar
more easily than wheat starch, while com starch occupies an
intermediate place. Soluble starch was found to behave the
same as potato starch.

Ptyalin also converts starch into sugar in the presence of
impure gastric juice, • but the action is suspended in pure gastric
juice, to again become active in the duodenum. Diastase is com-
pletely deprived of its power of converting starch to sugar by HCl
or pure gastric juice. According to E. Boin-quelot,^ when starch
has been heated with water at a definite temperature and then
cooled down to the ordinary temperature, the saliva acts only
on that portion of the starch which has undergone hydration.
He found that the hydrating action of water begins at about
35°, increase somewhat irregularly up to 74°, beyond which an
increase of temperature exerts no appreciable effect.

W. Biedermann has shown* that dilute, boiled starch solu-
tion can be hydrolyzed with comparative rapidity by saliva, but
that upon boiling the latter, hydrolysis ta^es place only after a

1. E. Baumann. Ber. 1886, Id, 3218; abst. J. C. S. 1887, 52, 228; Jahr.
Chem. 1886, 39, 1426.

2. Zts. ang. Chem. 1913, 26, 137; J. S. C. I. 1913, 32, 357; Chem.
Zentr. 1913, 84, I, 1412; J. Dyers and Col. 1913, 29, 194; Kunst. 1913, 3,
330; C. A. 1913, 7, 2854; J. C. S. 1913, 104, i, 363.

3. Zts. ang. Chem. 1913, 26, 437; J. S. C. J. 1913, 32, 823; Kunst.
1913. 3, 331; C. A. 1913, 7, 3661; J. C. S. 1913, 104, i, 1043; Chem. Zentr.
1913 85 II 1293.

4. ' J. V. Kaimowsky, J. prakt. Chem. 1845, 35, 201.

6. J. Russ. Phys. Chem. Soc. 1876, No. 1; abst. J. C. S. 1876, 30, 398;
BuU. Soc. Chim. 1876, 25, 393.

6. T. Defresne, Compt. rend. 1879, 89, 1070; abst. Chem. News, 1880,
41, 22; J. C. S. 1880, 38, 330; J. pharm. chim. 1880, (5), 1, 168; Jahr. Chem.
1879, 32, 1019.

7. Compt. rend. 1887, 104, 71, 177; abst. Chem. News, 1887, 55, 81,
94; J. C. S. 1887, 52, 354, 355; Ber. 1887, 20, R, 109, 143; Jahr. Chem. 1887,
40, 2265, 2319. J. pharm. chim. 1891, (5), 24, 197; abst. J. C. S. 1892, 62,
230.

8. Fermentforschung, 1916, 1, 474; abst. C. A. 1917, U, 1436; J. C. S.
1917, 112, i, 62; J. S. C. I. 1917, 36, 230; Chem. Zentr. 1916, 87, II, 496.

J

STARCH 417

much longer period of contact. As pointed out by C. Gessard^
and I. Wolff, ^ serums can be prepared which inhibit the action
of malt extract upon starch, the maximum inhibition being 70%,
as determined by the amount of maltose produced. At 50** the
inhibitory effect is but half that at 20**. M. Bial* and F. Roeh-
mann^ have shown that human blood serum and lymph serum
contain an enzyme capable of converting starch into dextrin,
maltose and glucose.*^

Lepetit, Dollfuss & Gansser* convert starch into partially or
completely soluble products by means of pancreas or pancreatic
extract.

A. Dobroslavine,^ M. Maercker,* W. Watson,' F. Musculus
and J. de Mering,^® A. Lea," E. Bourquelot," have shown that, in

1. C. Gessard. Compt. rend. 1906, 142, 641; Compt. rend. Soc. Biol.
1906, 61, 425; abst. J. C. S. 1906, 90, ii, 373.

2. C. Gessard and J. Wolff, Compt. rend. 1908, 146, 414; abst. J. C. S.
1908 S4« i 379.

3. Pflueger's Archiv. 1892, 52, 137; 1893, 53, 157; 54. 72; abst. J. C. S.
1893, 54, ii, 333, 581; Ber. 1892. 7S, R, 647, 912; 1893, 26, R, 412; Chem.
Centr. 1892, 63, II, 82. 1021; Jahr. Chem. 1892, 45, 2369; 1893. 46, 1999.

4. Ber. 1892, 25, 3654; Pflueger's Archiv. 1893, 53, 157; abst. J. C. S.
1893, 64, i. 187; ii, 333; 1895. 68, ii, 52; J. S. C. I. 1893, 12, 336; Bull. Soc.
Chim. 1893. 10, 413; 1895, 14, 694; Ber. 1892. 25, R, 647; 1894, 27, 3251;
Chem. Centr. 1893, 64, I, 350; Jahr. Chem. 1892, 45, 2363, 2466; 1894, 47,
2332.

5. The author finds that 100 gm. of potato starch when mixed with 5
liters of water, and after cooling, 1 liter of bullock's blood serum and 100 cc.
of 10% alcoholic solution of thymol added, that after 24 hours at 32°, glucose
and acroodextrin are the chief products formed. He claims erythrodextrin
is not a mixture of starch and acroodextrin, as stated by A. Schifferer, N.
Zts. Rub. Zucker. Ind. 1892. 29, 167; abst. J. S. C. I. 1893, 12, 368.

6. F. P. 466275, 466276. 1913; abst. C. A. 1915, 9, 724; J. S. C. I. 1914,
33, 590. D. R. P. 286050, 1913; abst. C. A. 1916, 10, 254; Chem. Zcntr. 1915,
86, 1, 211; Chem. Ztg. Rep. 1915, 39, 263; Zts. ang. Chem. 1915, 28, II, 402.
See O. Nasse, Pflueger's Archiv. 1877, 14, 473; 15, 471; abst. J. C. S. 1877.
32, 503; Jahr. Chem. 1878, n, 1034.

7. Bull. Soc. Chim. 1876. 26, 452; J. Russ. Phys. Chem. Soc. 1876, 8,
I, 57; abst. J. C. S. 1877, n, 453.

8. Landwirthschaftliche Versuchs-Stationen 23, 69; Miinch. Natur-
forscher Vers. 1877, 222; abst. J. C. S. 1878, 34, 969; Ber. 1877, 10, 2234;
Chem. Centr. 1878. 49, 559; Jahr. Chem. 1877, 30, 900; 1878, 31, 1035. For
the action of enzymes upon starches of different origin, see H. Sherman. F.
Walker and M. Caldwell. J. A. C. S. 1919. tt, 1123; abst. C. A. 1919, 13,
2297.

9. J. C. S. 1879. 35, 539; Pharm. J. Trans. (3), 9, 987; Chem. News,
1879, 39, 226; abst. Ber. 1879. 12, 1217; Jahr. Chem. 1879, 32, 958.

10. Zts. physiol. Chem. 1877, 1, 395; 1878. 2, 420; abst. Jahr. Chem.
1877. 30, 1024; 1878. 31, 994. Compt. rend. 1879, 88, 87; abst. Bull. Soc.
Chim. 1879. 31, 105; Chem. News. 1879, 39, 64; J. C. S. 1879, 36, 370; Ber.
1879, 12, 379, 672, 700; Jahr. Chem. 1879, 32, 1077.

11. J. Physiol. 1890. 11, 226; Proc. Roy. Soc. 1890, 47, 192; abst. J. C.

418 TECHNOLOGY OP CELLUlrOSH ESTERS

general, the products of enzymatic action on starch are maltose,
a reducing, unfermentable dextrin, and a small amount of dex-
trose. Ungelatinized starch is tmacted upon by ptyalin, hmt at
a temperature slightly below the gelatinizing point the starch is
dissolved, the action being most pronounced when the ferment is
allowed to act upon the starch at a temperature of 60**.

Enzymes capable of dissolving starch have not only been
observed in the pancreatic juice, ^ but in the small intestine, liver,*
and in many other animal tissues,^ including those of blood^ and
of fish.^ Of the bacteria, the Bacilltis macerans,* Mucor boulard,''
Bacterium burdigalenes^ Bacillus huiyricus,^ Bacillus amylobacter,

S. 1890, 58, 536; Chem. Centr. 1890, 61, 1, 1069; Jahr. Chem. 1890, 43, 2266.
12. Compt. rend. 1886, 104, 71, 177; abst. Chem. News, 1887, 5S, 81,
94; J. C. S. 1887, 52, 354, 355; Ber. 1887, 20, R, 109, 143; Jahr. Chem. 1887,
40, 2265, 2319.

1. H. Brown and J. Heron, J. C. S. 1879, 35, 598; Zts. Chem. Gross-
gewerbe, 1879, 6, 153, 254, 259; Chem. News, 1879, 3S, 284; 1880, 41, 22;
42, 63; 1881, 43, 154; Ann. 1879, 139, 165; Ber. 1879, 12, 1477; Chem. Tech.
Rep. 1879, 8, II, 163; Jahr. rein Chem. 1879, 7, 507; Jahr. Chem. 1879,
32, 838; Zts. ges. Brauw. 14, 442.

2. Wittich, Pfliigers Arch. f. Physiol. 1872, 6, 181; 1873, 7, 28; abst.
J. C. S. 1872, 25, 1105; 1873, 26, 515; Bull. Soc. Chim. 1873, 20, 414. C.
Bernard, Compt. rend. 1877, 85, 519; abst. J. C. S. 1878, 34, 82; Bull. Soc.
Chim. 1879, 31, 136; Jahr. Chem. 1877, 30, 980. M. Abeles, Jahr. Thier.
1876, 6, 271 ; Medizin. Jahrbiicher, 1876, 225.

3. W. EUenberger and V. Hofmeister, Jahr. Thier. 1882, 12, 501;
Archiv, wiss. Prakt. Thierheilkunde, 1882, 8, 91 ; abst. J. C. S. 1882, 42, 1119.
V. Paschutin, Jahr. Thier. 1871, 1, 304. Centr. med. wiss. 1870, 561, 577;
1872, 97; Archiv. Anat. Physiol, 1871, 305; 1873, 382; abst. J. C. S. 1873,
26, 1064; Bull. Soc. Chim. 1873, 20, 310; Jahr. Chem. 1870, 23, 907; 1872,
25, 934; 1874, 27, 1057; Zts. anal. Chem. 1872, 11, 464; 1874, 13, 104.

4. E. Bimmerman, Pfliigers Arch. f. Physiol. 1879, 20, 201 ; abst. J. C.
S. 1880. 38, 677; Ber. 1879, 12, 2168; Jahr. Chem. 1879, 32, 959. P. Plosz,
and E. Tiegel, Pfliigers Arch. f. Physiol. 1873, 7, 391; abst. J. C. S. 1873, 26,
1245.

5. C. Ricket, Jahr. Thier. 1884, 14, 359. C. Kruckenberg, Unter,
Phys. Inst. Heidelberg, 1, 2.

6. H. Pringsheim and F. Eissler, Ber. 1913, 46, 2959; 1914, 47, 256;
abst. J. C. S. 1913, 104, i, 1156; 1915, 108, i, 108, 382; J. S. C. I. 1913, 32,
985; C. A. 1914, 8, 118; 1915, 9, 83. See also E. Moreau, Ann. Falsif. 1911,
4, 65; abst. J. S. C. I. 1911, 30, 439. H. Pringsheim and A. Langhans, Ber.
1912, 45, 2533; abst. J. C. vS. 1912, 102, i, 832; J. S. C. I. 1912, 31, 1001. F.
Schardinger, Zentr. Bakt. Parasitenk. 14, ii, 772; IS, 161; 1908, 22, ii, 98;
1911, 29, 188; abst. J. C. S. 1911. 100, i, 181; J. S. C. I. 1909, 28, 153; 1911,
30, 439; Chem. Zentr. 1908, 79, I, 68; 1911, 82, 1, 874.

7. Soc. d'Exploit des Proc. H. Boulard, E. P. 25406, 1913; abst. J. S.
C. I. 1914, 33, 659; C. A. 1915, 9, 1223. F. P. 464601, 1913, 477927. 1914;
abst. J. S. C. I. 1914, 33, 497; 1916, 35, 1170.

8. H. Joucla, F. P. 474948, 1914; 478972, 1915; abst. J. S. C. I. 1915,
34, 1107; 1916. 35, 1172; C. A. 1916. 10, 2274.

9. A. Villiers, Compt. rend. 1891, 112, 435, 536; 1891, 113, 144; abst.
J. C. S. 1891, 60, 1446; J. S. C. I. 1891. 10, 474. 717; Chem. News, 1891, 63,
284; 64, 74; Bull. Soc, Chim. 1891, 5, 468, 470, 546; Ber. 1891, 24, R, 272,
319, 734; Jahr. Chem. 1891, 44, 2336,

STARCH 419

Bacillus suaveolens^ and Bacillus amylozymicus^ all possess this
property when in contact with starch under favorable conditions.
Certain organisms, bacteria, enzymes and moulds are appar-
ently able to secrete a product having the power of dissolving
starch, as indicated by the researches of A. Fitz,^ A. Aulard,*
S. Benni,'^ J. Kjeldahl,' V. Marcano,^ J. Sanguinetti,^ A. Sclavo
and B. Gosio,» and G. Bouchardat.^^ The latter by the hydrol-
ysis of starch obtained ethyl, propyl and butyl alcohols and
acetates. In general, the nature of the dissolution products has
been but imperfectly studied. According to J. Wortman,^^ A.
Fitz,^2 V. Marcano,^' U. Gayon and E. Dubourg,^* R. Atkinson ^^

1. P. Selivanoff, J. Russ. Phys. Chem. Soc. 1889, 21, 27; abst. J. C. S.
1889,58, 1132.

2. J. Wortmann, Zts. Physiol. Chem, €, 287; abst. J. C. S. 1883, 40,
930; Mon. Sci. 1883, 25, 45; Ber. 1882, 15, 2269; Jahr. Chem. 1882, 35, 1247.
Bot. Ztg. 1890, 48, 582, 597, 617, 633, 657; abst. J. C. S. 1891, 88, 856; Chem.
Centr. 1890, 81, II, 821 ; Dixigl. Poly. 1892, 283, 284; Jahr. Chem. 1892, 45,
2823. See also A. Stutzer and A. Isbert, Zts. physiol. Chem. 1887, 12, 73;
abst. J. C. S. 1888, 54, 170; Ber. 1888, 21, R, 541; Chem. Centr. 1887, 58,
1661 ; Jahr. Chem. 1887, 40, 2322.

3. Ber. 1876, 9, 1348; 1877, 10, 276. 2226; abst. J. C. S. 1877, 31, 226;
Chem. News, 1877, 35, 105; 1878, 37, 161; Bull. Soc. Chim. 1876, 28, 473;
1877, 28, 24; 1878, 29, 472; Chem. Tech. Rep. 1876, 15, I, 128, 130; Jahr.
Chem. 1875, 28, 885; 1876, 29, 343, 950.

4. Proc. Seventh Inter. Cong. Appl. Chem. 1909, Sect. VI-B; abst.
J. S. C. I. 1911, 30, 234; C. A. 1911, 5, 1969.

5. Russ. P. 1198, 1898; abst. Zts. Spiritusind. 1900. 23, 276; J. S. C. I.
1900, 19, 836; Mon. Sci. 1899, 54, 145; Chem. Centr. 1899, 70, 1. 784; Chem.
Tech. Rep. 1899, 38, 481; Chem. Ztg. 1899, 23, 203; Jahr. Chem. 1899, 52,
1272.

6. Resume du Compt. rend, des Travaux du Laboratoire de Carls-
berg, 1879; abst. Zts. ges. Brauwesen, 1880, 49; Dingl. Poly. 1880, 235, 379;
J. C. S. 1880, 38, 562; 1881, 40, 115; Bied. Centr. 1880, 9, 689; Chem. CenU.
1880, 51, 73; Jahr. Chem. 1880, 33, 1122; Wag. Jahr. 1880, 28, 624.

7. Compt. rend. 1882. 95, 345, 856; abst. J. C. S. 1882, 42, 1311;
Chem. News, 1882, 48, 122, 254; J. pharm. chim. 1882, (5), 7, 168; Ber. 1882,
15, 3089; Chem. Tech. Rep. 1883, 22, II, 44; Jahr. Chem. 1882, 35, 1236;
Wag. Jahr. 1882, 28, 800.

8. Ann. Inst. Pasteur, 1897, 11, 264; abst. La Biere, 5, 49; J. S. C.
I. 1897, 18, 626; Chem. Centr. 1897, 88, I, 998.

9. Bied. Centr. 1891, 20, 419; abst. J. C. S. 1891, 80, 1284; Arch. Ital.
Biol. 14; Staz. sperim. agrar. ital. 19, 540; Jahr. Chem. 1890, 43. 23a3.

10. Compt. rend. 1874, 78, 1145; abst. J. C. S. 1874, 27, 883; Mon.
Sd. 1874, 18, 653; Ber. 1874, 7, 657, 746; Chem. Tech. Rep. 1874, 13, I, 51;
Jahr. Chem. 1874, 27, 950; Wag. Jahr. 1874, 20, 661. See also E. P. 768,
1858.

11. Zts. Physiol. Chem. 8, 287; abst. J. C. S. 1883, 40, 930; Mon. Sci.
1883. 25, 45; Ber. 1882, 15, 2269; Jahr. Chem. 1882. 35, 1247.

12. Ber. 1876, 9, 1348; 1877. 10, 276, 2226; abst. Chem. News, 1877.
35, 105; 1878. 37, 161; BuU. Soc. Chim. 1876, 28, 473; 1877. 28, 24; 29, 472;
Chem. Tech. Rep. 1876, 15, 1. 128, 130; Jahr. Chem. 1875, 28, 885; 1876, 29,
343 950

'l3. Compt. rend. 1882, 95, 345, 856; J. pharm. chim, 1882, (5), 7, 168;

420 TECHNOLOGY OF CKLLXJWSE ESTERS

and J. Takamine,^ investigations have not conclusively gone be-
yond the statement that sugar, sugars and dextrin are among
the products of transformation. It would appear that some
gums of the arabin and bassorin group contain a starch-splitting
enzyme.*

It has long been known that com, either malted or raw, as
well as some other grains, contains an enzyme capable of dissolv-
ing starch to produce glucose as a final product.' Its action
upon starch is not as vigorous as on dextrose, while maltose is
rapidly converted into dextrose.*

As yet, no exhaustive work has appeared as to the diflferences
in action between moulds and enz3mies upon carbohydrates.

Formaldehyde and Starch. F. Beltzer^ has given a summary

abst. Chem. News, 1882, 46, 122, 254; J. C. S. 1882. 42, 1311; Ber. 1882, IS,
3089; Chem. Tech. Rep. 1883, 22, II, 44; Jahr. Chem. 1882, 3S, 1236; Wag.
Jahr. 1882, 2S, 800.

14. Compt. rend. 1886, 103, 885; abst. Chem. News, 1886, S4, 273;
J. C. S. 1887, 52, 171; J. S. C. I. 1887, S, 144; Bull. Soc. Chim. 1887, 47,
649; J. pharm. chim. 1886, (5), 14, 567; Mon. Sci. 1886, 2S, 1441; Ber. 1887,
20, R, 13; Chem. Tech. Rep. 1886, 2S, II, 87; Chem. Ztg. Rep. 1886, 10,
269; Der Biefbrauer, 1886, 566; Industriebl. 1887, 118; Jahr. Chem. 1886, 39,
1884.

15. Proc. Roy. Soc. 1881, 31, 523; 32, 299; Chem. News, 1880, 41, 169;
abst. J. C. S. 1881, 40, 1059; J. pharm. chim. 1882, (5), 5, 157; Mon. Sd. 1882,
24, 7; Ber. 1881, 14, 2287; Chem. Centr. 1880, Sl 278; Chem. Tech. Rep.
1880, Id, I, 90; Jahr. Chem. 1880, 33, 1134; 1881, 34, 985; Wag. Jahr. 1880,
26,629.

1. E. P. 5700, 17374, 1891; abst. J. S. C. I. 1891, 10, 1019; 1892, U,
1022. P. P. 214033, 216840, 1891; abst. Mon. Set. 1892, 40, 91, 266; 1894.
44, 591. D. R. P. 79763; abst. Ber. 1895, 28, R, 578; Chem. Centr. 1895.
06, I, 1128; Chem. Tech. Rep. 1895. 34, I, 92; Wag. Jahr. 1895, 41, 908.
D. R. P. 84588; abst. Ber. 1896, 29, 194; Chem. Tech. Rep. 1896, 35, 60;
Chem. Ztg. 1896, 20, 156; Wag. Jahr. 1896, 42. 907. See also Chem. News,
1898, n, 137; 1901, 84, 23. Jahr. Chem. 1891, 44, 2745; 1895, 48, 2696; Meyer
Jahr. Chem. 1894, 4, 450; 1896, 6, 363; 1897, 7, 352. U. S. P. 562103, 1896.

2. O'Sullivan, J. C. S. 1891, 59, 1061; abst. J. S. C. I. 1892, 11, 48;
Ber. 1892, 25, R, 370; Jahr. Chem. 1891, 44, 2212; Chem. Centr. 1892, 63, 1.
137.

3. L. Cuisinier, D. R, P. 37923, 1884. E. P. 1820, 1886. F. P. 171958,
1885; abst. J. C. S. 1887, 52, 354; J. S. C. I. 1887, 6. 375; Mon. Sci. 1886, 28,
718, 840; Ber. 1887, 20, 128; Chem. Centr. 1886, 57, 614; Chem. Tech. Rep.
1884, 23, II, 118; 1887, 26, I, 77, 172; II, 194; Jahr. Chem. 1886, 39, 1782,
2143, 2144; 1887, 40, 2660; Wag. Jahr. 1886, 32, 611.

4. R. Geduld, Wochenschrift f. Brauerei, 1891, 8, 620; abst. J. S. C. I.
1892, 11, 627; Chem. Centr. 1891, 62, II, 323; Dingl. Poly. 1892, 285, 184,
211; Jahr. Chem. 1892, 45, 2823. C. Lintner, Zts. f. ges. Brau. 1892, 15,
123; abst. J. C. S. 1893, 64, i, 4; J. S. C. I. 1892, U, 1021; Chem. CenU.
1892, 63, 1, 740; Jahr. Chem. 1892, 45, 2466; Wag. Jahr. 1892, SI, 878.

5. Eighth Intl. Cong. Appl. Chem. 1912, 7, 7; abst. C. A. 1912, 6,
3185; 1913, 7, 551; J. S. C. I. 1912, 31, 868; Kunst. 1912, 2, 442; Wag. Jahr.
1912, 58, II, 445; Zts. ang. Chem. 1913, 26, II, 303.

STARCH 42 1

of the action of formaldehyde upon starches. In the process of
E. Blumer,^ a mixture of dilute alkali hydroxide (5° B€,) and for-
maldehyde is allowed to act upon starch for some hours, when
it is heated for a short time, and the product then washed with
water until no odor of formalin can be detected, then with dilute
acetic acid, and finally dried carefully at a low temperature (not
over 50°).

In the method of A. Classen,^ formalin and starch are mixed
and heated in a closed vessel to 100°-120° for 5-6 hours, after
which the product is removed and treated as above indicated.
It finds a use therapeutically as a topical application to wounds
on accotmt of the antiseptic action due to the constant liberation
of formaldehyde.'

According to H. Maggi and G. Woker,* the dialysate from a
mixture of starch and formaldehyde has properties of a solution
of dextrin and the simpler carbohydrates. A precipitate pro-
duced by the addition of alcohol to such a dialysate re-dissolves
in water, and slowly reverts to dextrin upon standing. Woker*^
has also shown that diastase can behave as a peroxydase or
catalase, and that solutions of starch and glycogen suffer hydrol-
ysis when exposed to relatively large amounts of formaldehyde,

1. D. R. P. 179590. 1904; abst. J. S. C. I. 1907, 26, 1066; Chem. Zentr.
1907, 78, I, 383; Chem. Ztg. Rep. 1907, 31, 27; Jahr. Chem. 1905-1908, II,
948; Wag. Jahr. 1906, 52, II, 79; Zts. ang. Chem. 1907, 20, 1246; Friedlaender,
8 917

2. A. Classen, D. R. P. 92259. 1896; abst. Chem. Centr. 1897, 88, II,
456; Chem. Ztg. 1897, 21, 539; Jahr. Chem. 1897, 50, 1516; 1898, 51, 1242; Wag.
Jahr. 1897, 43, 623. D. R. P. 94628, 1896; abst. Chem. CenU. 1898, OS, I,
295; Chem. Ztg. 1897, 21, 1004. D. R. P. 99378, 1899; abst. Chem. Centr.
1899, 70, I, 160; Chem. Ztg. 1898, 22, 963; Jahr. Chem. 1898, 51, 124; Wag.
Jahr. 1898, 44, 559.

3. D. R. P. 94282, 1896; abst. Chem. Centr. 1898, 09, 1, 229; Chem. Ztg.
1897. 21, 963; Jahr. Chem. 1897, 50, 1645; Wag. Jahr. 1897, 43, 623; Fried-
laender, 0, 1129. E. P. 1144, 1897; abst. J. S. C. I. 1897, 10, 459. The
combination of formaldehyde with starch has been called "amyloform,''
while that with dextrin has been named "dextroform." For additional data
on amyloform and glutols, see A. Classen. Therap. Monatsh. 1897, U, 33;
Muench. med. Wochschr. 44, 307; abst. Chem. Centr. 1897, 78, I, 395, 939.
C. Schleich, Therap. Monatsh. 1897,11, 97; abst. Chem. Centr. 1897, 78, I,
715. A. Gottstein, Therap. Monatsh. 1897, 11,95; abst. Chem. Centr. 1897,
78, 1, 715.

4. Ber. 1918, 51, 790; abst. J. C. S. 1918, 114, i, 375; C. A. 1918. 12, 700.
Cf. G. Woker, J. S. C. I. 1916, 35, 1268. M. Jacoby, Ber. 1919, 52, 558;
abst. J. S. C. I. 1919, 38, 508-A. W. v. Kaufmann and A. Lewite, Ber.
1919, 52, 616; abst. J. vS. C. I. 1919, 38, 508-A. W. Biedermann, Ferment-
forsch. 1916, 1, 474. T. Wohlgemuth, Biochem. Zts. 1919. 04, 213.

5. Ber. 1916. 49, 2311; abst. J. C. S. 1917,112, i, 61, 62, 447,485;
C. A. 1917, 11, 2090, 3259.

422 TECHNOLOGY OF CELLULOSE^KSTERS

although the aldehyde is more pronounced as a prototype of a
peroxydase than of diastase. Although formalin is a powerful
enzymatic toxic, a 2-5% solution of it appears to accelerate the
action of diastase.^

According to V. Syniewsky,' when potato starch is left for
two months in the presence of 40% solution of formaldehyde, a
mobile, opalescent fluid results which must be regarded as a
definite compound, but, however, has not been isolated in the
pure state, due to the fact that upon evaporation and heating,
formaldehyde is volatilized. If this solution is diluted with water
formaldehyde gradually separates and the iodine reaction of the
solution passes from brown to blue. Inasmuch as the product
remaining in solution when the blue reaction has been reached
can be precipitated by alcohol, it would appear to be a product
of the hydrolysis of starch.

Starch and Heat. When in an entirely anhydrous condition,
starch may be heated to a temperature Of 155°-160** without
undergoing any apparent change. At higher temperatures it be-
comes dextrinated and darkens in color. However, when ordinary
air-dried starch is heated to 150°-160° it readily decomposes,
giving rise to a number of products, of which dextrin and reducing
sugars predominate. The action varies within comparatively
wide limits, depending upon the kind and purity of the starch
heated. In the E. Nowak process' the starch is rendered slightly
alkaline before being subjected to the heat treatment.

S. Schubert has recorded* that a microscopic examination of
starch granules at 160° shows the presence of gas bubbles, which
increase when the temperature is raised to 175°; that this altera-
tion of the starch granule by heat converts the granulose into
soluble starch and dextrin, while the cellulosic layers are only

1. Zts. ges. Brauw. 1908, 31, 161; abst. J. C. S. 1908. 34, i, 606; Chem.
Zentr..l908, 79, i, 1834; C. A. 1908, 2, 2881; J. S. C. I. 1908, 27, 461; Jahr.
Chem. 1905-1908, II, 948; Meyer Jahr. Chem. 1908, 18, 392; Wag. Jahr.
1908 54 II 191.

'2. ' Aiin. 1902, 324, 201; abst. J. C. S. 1903, 84, i, 68; Bull. Acad. Sci.
Cracow, 1902, 435; J. S. C. I. 1902, 21, 1341; Chem. Centr. 1902, 73, II,
986, 1248; Jahr. Chem. 1902, 55, 1039.

3. E. P. 22542, 1903; abst. J. S. C. I. 1904, 23, 32; Chem. Ztg. 1905,
29,203.

4. Ber. 1884, 17, 479; Monatsh. 1884, 5, 472; abst. J. C. vS. 1885, 48,
368. Oesterr-ung. Zts. Zucker. Ind. Landw. 1910, 39, 411; abst. Chem.
Zentr. 1910, 81, II, 688; J. C. S. 1911, 100, ii, 75.

STARCH 423

attacked at higher temperatures. When starch which has been
subjected to a high temperature is treated with water, the soluble
starch, dextrin and other products of decomposition are dissolved,
while the insolilble matter that is left, is an organized residuum
having the structure of the original granule, and soluble in hot
water.

In experiments to ascertain the temperature at which starch
suffers the maximum loss in weight without decomposition, F.
Dafert^ found that at 120° the loss was 11.31%; 105M17°,
10.89%; 100** in vacuum, 11.9%; in but the first case was the
starch changed, and then only slightly. When starch and cellu-
lose are heated^ gradually imder a pressure of 12-15 mm., the
fraction distilling between 200^-300° amotmts to about 45% of
the original, and consists of an oily crystalline mass, from which
crystals have been separated corresponding to the laevoglucosan
of C. Tanret.* By dry distillation at atmospheric pressure,
starch yields water, carbon dioxide, gaseous hydrocarbons, acetic
and homologous acids, and empyreumatic oil, and leaves a porous
charcoal.

It has been shown**^ that by heating purified starch or cellu-
lose in an atmosphere of pure and dry hydrogen, as much as 95%
of methane can be obtained. This when chlorinated to methyl
chloride, the latter hydrolyzed to methyl alcohol, and this par-
tially oxidized, produces formaldehyde — a sort of reversible syn-
thesis. O. Loew* has observed that formalin and lime water

1. Landw. Jahr. 1885, 837; 1886, 259; Ber. hot. Ges. 1887, 108; Bied.
Centr. 1886, IS, 133; Chem. Centr. 1887, 58, 567; abst. J. C. S. 1886, 50,
527; 1887, 52, 1143.

2. Compt. rend. 1918, 1(6, 38; abst. J. C. S. 1918, 114, i, 59; J. S. C. I.
1918, 37, 49-A; C. A. 1918, 12, 804, 2187.

3. Compt. rend. 1894, 119, 158; abst. J. C. S. 1894, 66, i, 564; Chem.
CenU. 1894, 65, 11, 360; Jahr. Chem. 1894, 47, 112; Chem. Ztg. Rep. 1894,
18, 194; Ber. 1894, 27, R, 665; Bull. Soc. Chim. 1894, 11, 949; Mon. Sci.
1894, 43, 7,17; Chem. News, 1894, 70, 72, 282; Rev., g^n. sci. 1894, 5, 552;
Jahr. organ. Chem. 1894, 2, 219.

4. W. Bone and D. Jerden, J. C. S. 1897, 71, 41; 1901, 79, 1042; abst.
Chem. News, 1896, 73, 151; 74, 268; J. S. C. I. 1901, 20, 696; Bull. Soc.
Chim. 1898, 18, 986; Chem. Centr. 1897, 68, I, 24, 582; 1901, 72, II, 394,
576; Jahr. Chem. 1901, 54, 570.

5. W. Bone and H. Coward, J. C. S. 1908, 93, 1197; 1910, 97, 1975;
1909, 98, 20, 265; abst. J. S. C. I. 1908, 27, 1143; 1910, 29, 744; Bull. Soc.
Chim. 1909, 6, 874, 1355; 1911, 10, 566; Chem. Zentr. 1908, 79, II, 763; 1909,
80, I, 350; 1910, 81, II, 442; Jahr. Chem. 1905-1908, II, 78.

6. J. prakt. Chem. 1886, 141, 321; Ber. 1887, 20, 141, 3039; 1889, 22,
475, 478; abst. J. C. S. 1887, 52, 459; 1889, 56, 581; J. S. C. I. 1887, 6, 446;

424 TECHNOLrOGY OF CELLULOSE ESTERS

yield a sweet syrup, called by him formose; or with magnesium
oxide, a product called methose. Later, E. Fischer showed this
formose and methose to be complex mbctures containing a-acrose.^

On distilling dry starch with lime* in the proportion of 1-4,
acetone, mesityl oxide, isophorone boiling at 207°, and various
acetone condensation bodies result. When distilled with Mn02
and dilute H2SO4, formic acid, furfural and CO2 result. Dis-
tilled with HCl and MnOj, there is formed — among other things —
trichloracetaldehyde and pentachlor-porpionicaldehyde.

Soluble and Modified Starch* In recent years a class of
**thin boiling" or ''modified*' starches have been used in the
treatment of textiles, which support their claim for recognition on
the fact that they are of low viscosity and can be prepared readily
without tedious preliminary heat treatment.-

The Casein Co. of America' modify starch by treatment
first with oxalic acid followed by ammonia when the action has
proceeded to the desired point. When the viscosity has reached
a predetermined value after the neutralization, the product is
dried and is then ready for the market. L. Cerf,* by the use of
persulfates; Arabol Manufacturing Co. with sulfocyanides;* and

1889, 8, 297; Bull. Soc. Chim. 1888, 49, 712; 1890. 3, 709, 712; Chem. Centr.
1887, 58, 229; 1889, €0, T, 465, 466; Jahr. Chem. 1887, 40, 2247; 1889, 42,
2034. A. Butlerow, Ann. 1861, 120, 295; Compt. rend. 1861, », 145; abst.
Bull. Soc. Chim. 1861, 2, 84; Instit. 1861, 260; Rep. Chim. Pure, 1861, 3,
404; Chem. Centr. 1861, 32, 686; Jahr. Chem. 1861, 14, 647; Zts. Chem.
1861, 462.

1. E. Fischer and J. Tafel, Ber. 1887, 20, 2568; abst. J. C. S. 1888,
54, 39, 358; J. S. C. I. 1888, 7, 128; 1889, 8, 296; Bull. Soc. Chhn. 1888, 49,
359, 972; J. pharm. chim. 1889, (5), 20, 411; Chem. Centr. 1887, 58, 1491;
Jahr. Chem. 1887, 40, 1283. E. Fischer, Ber. 1890, 23, 386, 2114; abst.
J. C. S. 1890, 58, 466, 1223; J. S. C. T. 1890, 9, 527, 958; BuU. Soc. Chim.

1890, 3 891; J. pharm. chim. 1890, (5), 22, 376, 401; Chem. Centr. 1890, 81,
I, 640; II, 430; Jahr. Chem. 1890, 43, 2116, 2130.

2. V. Horvat, Rad. jugost. akad. 75, 187; abst. J. C. S. 1887, 52, 460;
Chem. Centr. 1887, 58, 38; Jahr. Chem. 1887, 40, 2262.

3. U. S. P. 1053719, 1913; abst. C. A. 1913, 7, 1287; Kunst. 1913, 3,
256. F. P. 454456, 1913; abst. Chem. Ztg. Rep. 1913, 37, 577. E. P. 4203.
1913; abst. C. A. 1914. 8, 2804; J. S. C. I. 1913, 32, 302.

4. U. S. P. 698632, 1902; abst. J. S. C. I. 1902, 21, 784; Mon. Sci.
1902 58 190.

'5. ' D. R. P. 180830; abst. Chem. Zentr. 1907, 78, II, 200; Chem. Ztg.
Rep. 1907, 31, 108; Jahr. Chem. 1905^1908, II. 2940; Wag. Jahr. 1907. 53, II.
213; Zts. ang. Chem. 1907, 20, 1781. D. R. P. 221797; abst. Chem. Zentr. 1910,
81, I, 2002; Chem. Ztg. Rep. 1910, 34, 250; Jahr. Chem. 1910, 83, IT, 410;
Wag. Jahr. 1910, 56, II, 259; Zts. ang. Chem. 1910, 23, 1248. Aust. P. 29738.
39015. E. P. 7705, 1905; abst. J. S. C. I. 1906, 25, 944. U. S. P. 918925.
1907; abst. Chem. Ztg. Rep. 1909, 33, 272. F. P. 365161. 1906; abst. Mon.
Sci. 1907, 87, 99. F. P. 394167, 1908; abst. Mon. Sci. 1909, 71, 146. E. P.

STARCH 425

others^ by employing perborates accomplish a similar result, ac-
companied by a whitening of the product through the bleaching
action of the per-salt. Gaseous HCl in the hands of F. Frary
and A. Dennis;* oxalic add as manipulated by H. Dierssen;'
sulfur dioxide under pressure;* treatment with alkaline perman-
ganates,'^ or less often with chromic acid.* Ozone does not act
upon starch.^

The methods of P. Bean,® and the apparatus of A. Lenders'
should also be mentioned.

The "thin boiling" starches as perfected by C. Duryea^® and

17887, 17888, 1908; abst. J. S. C. I. 1909, 28, 996; J. Soc. Dyers Col. 1909,
2S 283. Aust. P. 39015.

1. StoU & kopke, D. R. P. 199753; abst. Chem. Zentr. 1908, 73, II,
651; Chem. Ztg. Rep. 1908, 32, 391; Jahr. Chem. 1905-1908, II. 941; Wag.
Jahr. 1908, 54, II, 190; Zts. ang. Chem. 1908, 21, 1805. D. R. P. 202229;
abst. Chem Zentr. 1908, 73, TI, 1478; Chem. Ztg. Rep. 1908, 32, 568; Chem.
Zts. 1909, 8, 1139; Jahr. Chem. 1906-1908, II, 941; Wag. Jahr. 1908, 54,
IT, 191. E. P. 30390, 1909; abst. J. S. C. I. 1910, 29, 1200. F. Fritische,
E. P. 1351, 1908; abst. J. S. C. I. 1908, 27, 869; C. A. 1909, 3, 600. U. S. P.
910524, 1909. StoU & Kopke, Aust. P. 37835, 37836, 40449, 42647.

2. J. Ind. Eng. Chem. 1915, 7, 214; abst. C. A. 1915, 9, 1132; J. S. C.

I. 1915 34, 440.

3.' Zts. ang. Chem. 1903, 16, 122; Mon. Sci. 1903, 59, 779; abst. J. C.
S. 1903, 84, i, 321; J. S. C. I. 1903, 22, 312; Rep. Chim. 1903, 3, 201;Chem.
Centr. 1903, 74, 1, 698; Jahr. Chem. 1903, 56, 995; Wag. Jahr. 1903, 49, II, 216.

4. W. Thomson and J. Morrice, E. P. 21973, 1906; abst. J. S. C. I. 1907,
26, 980. U. S. P. 951666; abst. J. S. C. I. 1908, 27, 444; Chem. Ztg. Rep.

1910, 34, 200.

5. O. Bredt & Co.. D. R. P. 149588; abst. Chem. Centr. 1904, 75, I,
976; Chem. Ztg. 1904, 28, 329; Jahr. Chem. 1906-1908, II. 941; 1904, 57,
1153; Wag. Jahr. 1904, 50, II, 222; Zts. ang. Chem. 1904, 17, 935. D. R. P.
156148; abst. Chem. Centr. 1905, 76, 1, 643; Chem. Ind. 1904, 27, 704; Chem.
Ztg. 1904, 28, 1236; Jahr. Chem. 1905-1908, II, 940; Wag. Jahr. 1904, 50,

II, 223; Zts. ang. Chem. 1905, 18, 349. Aust. P. 20714, 1905. E. P. 22370,
1903; abst. J. S. C. I. 1904, 23, 29; J. Soc. Dyers Col. 1904, 20, 38.

6. E. Harz, Bdheft. z. Botan. Centr. 1905; Woch. f. Brau. 1905, 22,
721; abst. J. vS. C. I. 1905, 24, 1315.

7. E. Gonip-Besanez, Mitt. Phys. Med. vSoc. 1869, 1, 13; Chem. News,
1863, 8, 222; J. pharm. Chim. 1859, 36, 65; Ann. 1859, 110, 103; 1863, 125,
207; abst. Rep. Chim. Pure, 1858-1859, 1, 408.

The process of L. Koenig (E. P. 9674, 1894; abst. J. S. C. I. 1894, 13,
824) deodorizes and bleaches amylaceous materials such as starch, by means
of ozone.

8. J. Text. Inst. 1915, 4, 223; abst. J. S. C. I. 1916, 35, 107; C. A.
1916, 10, 392.

9. U. S. P. 948512, 948513, 1159591, 1159592, 1168516, 1191324.
1193274, 1223406; abst. J. S. C. I. 1910, 29, 367; 1915, 34, 1265; 1916, 35, 937.

10. E. Duryea, U. S. P. 172099, 345417, 346418, 375737. H. Duryea,
U. S. P. 12846, 300700, 301436. W. Duryea, U. S. P. 22789, 42358, 263030,
312341, 312342, 320430, 320431, 340705. C. Duryea, U. S. P. 643323, 658105,
696949. E. P. 2459, 1900; 11442, 1901; 11801, 1907; abst. J. S. C. I. 1900.
19, 455; 1901, 20, 1127. F, P. 380680, 1907; abst. J. S. C. I. 1908, 27, 32;

1911. 30,789.

426 TECHNOLOGY* Ol^ CELLULOSE ESTERS

W. Nivling,* are obtained by careful treatment of raw starch for
some hours with a dilute mineral acid, preferably sulfuric, then
washing to neutrality and drying. They have had a wide sale
in the United States, especially for the stiffening of textiles and
for laundry purposes.

According to O. Schmerber,* starch oxidized with potassium
permanganate gives a paste more fluid and transparent than that
which is obtained from the same starch in the ordinary state.
On standing, permanganate oxidized starch becomes opaque, but
reassumes its transparency when heated. E. Dollfus and F.
Scheiu'er* find that the starch paste appears to be closely related
to soluble starch. W. v. Siemens* also piuifies starch with per-
manganate. Siemens & Halske* and F. Hermite* oxidize and
thin starch by electrolysis of a solution of sodium or magnesium
chlorides, starch so produced being very clear and white. C.
Lintner^ mentions that the course of thinning agents on starch,
such as the permanganates, can be followed by testing with
iodine solution, as is done in the process of converting starch into
diastase, the colors obtained with iodine at successive stages of
such action with potassium permanganate being blue-violet,
violet-red, and reddish brown. At the final stage of oxidation,
no color is produced. The products obtained are gummy sub-
stances which are differentiated from the dextrins by their reac-
tions and by their yielding a precipitate with basic lead acetate and
with barium hydroxide. On boiling they expel CO2, and slightly
reduce Fehling's solution. C. Gerber uses hydrogen peroxide,®

1. U. S. P. 1153244, 1153245, 1191216, 1236002, 1918. E. P. 10866,
1916. Can. P. 164541.

'2. Bull. Soc. Ind. Mulhouse, 1896, 238; abst. J. S. C. I. 1896, 15, 649.

3. BuU. Soc. Ind. Mulhouse, 1896, 241 ; abst. J. S. C. I. 1896, IS, 649.

4. E. P. 2597, 1893. Aust. P." 19777, 1905. D. R. P. 70012, 1892;
97565; abst. J. S. C. I. 1894, 13, 34; 1896, 15, 366. C. Siemens, Dingl. Poly.
1842, 84, 390; 1864, 172, 232; Bull. Soc. Ind. Mulhouse, 1893, 363. Zts.
f. Spiritsind. 1893, 253; 1898, 21, 59; abst. J. S. C. I. 1898, 27, 257.

5. O. Witt, assignor to Siemens & Halske, E. P. 244.55, 1895. D. R. P.
88447, 1895. U. S. P. 798509; Chem. Ind. 1909, 32, 68; J. S. C. I. 1896, 15,
366; 1905, 24, 1024. Chem. Ind. 1909, 32, 68. Cf. Soc. des Produits Amy-
laces, Swiss P. 32790, 1904, who also purify starch electrically.

6. E. P. 1061, 1892; abst. J. S. C. I. 1893, 12, 168. E. Hermite and A.
Dubosc, D. R. P. 70275; Zts.f. Spiritsind. 1893, 262, 409, 417. E. Hermite,
E. Paterson and C. Cooper, E. P. 12906, 1889; abst. J. S. C. I. 1890, 19, 878.

7. Zts. ang. Chem. 1890, 3, 546; abst. J. C. S. 1891, €0, 637; Ber. 1890,
23, R, 701; Chem. Centr. 1890, CI, II, 690; Jahr. Chem. 1890, 43, 2151; Wag.
Jahr. 1890, 36, 819.

8. Compt. rend. 1912, 154, 1543; abst. J. C. S. 1912, 102, i, 538; J. S.
C. I. 1912, 31, 654. Bied. Centr. 1913, 42, 265; Compt. rend. Soc. Biol-

STARCH 427

and A. v. Asboth^ and A. Fembach and J. Wolff,* H2O2 and am-
monia, obtaining by this action a thin starch paste from which
soluble starch (amylodextrin) may be precipitated by alcohol, the
amomit approaching, in extreme instances, 80% of the original
product. In all these treatments, the viscosity is considerably
attenuated, and the solubility in water increased. Hence the
name "soluble" starches.

0. Durieux' claims that hydrogen peroxide does not hydrolyze
starch prepared by Fembach's method at ordinary temperature,
and the same is true of colloidal solutions of iron or of mixtures of
these two. Ferric chloride alone, also has no action, but in con-
junction with H2O2, hydrolysis takes place, which increases with
fhe quantity of ferric chloride used.*

Z. Gatin-Gruzewska*^ has followed the course of the oxida-
tion and hydrolysis of starch by hydrogen peroxide, and finds that
hydrolysis and oxidation take place simultaneously, the final
products being maltose and oxalic acid. The constituents of
starch — amylopectin and amylose — are acted upon in a different
manner by hydrogen peroxide (as they are by diastase). In the
case of both, dextrins are formed as intermediate products. With
amylopectin, the attack on the micellae appears to be simul-
taneous; in that of amylose, successive.

F. Urech® has studied the rate of oxidation of starch by
means of Fehling's solution, P. Petit,^ oxidation by means of

1911. 70, 139, 391. 547. 724, 726. 728; J. C. S. 1913. 104, i, 781. Compare,
P. Bergh and H. Neuberger, U. S. P. 1133914, 1915; abst. J. S. C. I. 1915,
34, 567.

1. Chem. Ztg. 1892, ]i6, 1517, 1560; abst. J. C. S. 1893, 64^ i, 384;
Chem. Centr. 1892. 03, II, 867; Jahr. Chem. 1892, 4S, 2467.

2. Compt. rend. 1904, 138, 1217; 1905, 140, 1067. 1547; Seventh Intl.
Cong. Appl. Chem. 1909, VI-B, 124; abst. J. C. S. 1905, 88, i, 312, 574, 624;
1911, 100, i, 356.

3. Bull. vSoc. Chim. Belg. 1913, 27, 90; abst. J. C. S. 1913. 104, i. 445;
C. A. 1913, 7, 3562; J. S. C. I. 1913. 32, 440; Chem. Zentr. 1913, 84, I. 1870.

4. C. Neuberg and S. Miura, Biochem. Zts. 1911. 30, 37; abst. J. C. S.
1911, 100, i. 935; C. A. 1912, 0,374; Bull. Soc. Chim. 1912. 12, 692; Chem.
Zentr. 1911, 82. II, 1605. C. Gerber, Compt. rend. 1912. 154, 1543; abst.
J. C. S. 1912. 102, i, 538; J. S. C. I. 1912, 31, 654; BuU. Soc. Chim. 1912, H,
988; Chem. Z^ntr. 1912, 83, II, 244; Meyer Jahr. Chem. 1912. 22, 430.

5. Compt. rend. 1908. 140, 540; 1909, 148, 578; abst. J. C. S. 1908.
04, i, 320; 1909, 00, i, 209; J. S. C. I. 1909, 28, 376; C. A. 1909, 3, 1410;
1910, 4, 3082; Chem. Zentr. 1909. 80, 1. 1231; Jahr. Chem. 1909. 02, II. 377.

6. Ber. 1884. 17, 495. 1539; abst. J. S. C. I. 1884, 3, 451; J. C. S. 1884,
40, 574. 1112; Jahr. Chem. 1884, 37, 1403.

7. Compt. rend. 1892, 114, 1375; 1897, 125, 355; 1905, 141, 1247;
abst. J. C. S, 1892, 02, 1171; 1906, 30, i, 67; J. S. C. I. 1897, 10, 1028. For

428 TECHNOW)GY OF CBLI.UU)SE ESTERS

nitric acid, and some other of the inorganic acid compounds.

Many of the processes put forward from time to time for
the formation of modified starches, are applicable for the manu-
facture of soluble starch, by allowing the process to continue
until the stage of water misdbility has been reached. It is cus-
tomary to treat the starch with a mineral acid,-care being taken
that the add concentration and temperature is so controlled that
loss of starch by dextrin formation is reduced to the minimum.

T. Bayley^ and F. Vimeisel* use sulfuric add, the former of
7%-8% strength, and the latter of l%-2% add, at a temperature of
50°-55® until conversion is complete. W. Angele,' R. Chapin*
and O. Foerster,* employ hydrochloric add, while phosphoric,*
hydrofluoric, chloric,' phosphotungstic,* and formic adds® have
been advocated for this purpose. It has been shown that with
dry starch and gaseous HCP® at temperatures within 20^-100®,

treatment of starch with aluminum or ferric chlorides, see D. R. P. 217336 ;
abst. Wag. Jahr. 1910, 5€, II, 259; Chem. Zentr. 1910, 81, II, 492; Chem. Ztg.
Rep. 1910, 34, 46; Zts. ang. Chem. 1910, 23, 910. The thin boiling starch
of T. Breyer, is described m U. S. P. 881104, 881105, 1908; abst. Chem. Ztg.
Rep. 1908, 32, 300. For the non-gelatinizable starch of B. Herstein, U. S. P.
982673, 1911; abst. J. S. C. I. 1911, 30, 301; Chem. Ztg. Rep. 1911, 35, 181.
A. Leulier, J. pharm. chim. 1918, 18, 291; abst. C. A. 1919, 13, 915; J. S. C.
I. 1919, 38, 86-A. M. Witlich, Kunst. 1912, 2, 62. Otto Bredt & Co., U. S.
P. 769061, 1904. T. Breyer, U. S. P. 881104, 1908. A. Lenders, U. S. P.
1306291. 1919; abst. J. S. C. I. 1919, 38, 593-A. E. Blumer, E. P. 10872,
1902; F. P. 322206, 1902; D. R. P. 137330; Aust P. 14886, 1904; abst. J. S.
C. I. 1903, 22, 310. C. Hervey, E. P. 20484, 1908; abst. J. S. C. I. 1909, ^
1157. Casein Co., E. P. 4203, 1913. W. andS. Elbom and A. Board, E. P.
16997, 1913; abst. J. S. C. I. 1914, 33, 935.

1. E. P. 20930, 1893; abst. J. S. C. I. 1894, 13, 1082.

. 2. E. P. 12020, 1898; abst. J. S. C. I. 1899, iS, 697. Aust. P. 2023,

1900. Rev. Prod. Chim. 2, 273; abst. J. S. C. I. 1900, 19, 548. Pap.

Fab. 1909, 7, 335; abst. J. S. C. I. 1909, 28, 439. L. and F. Vimeisel, K.

Trobach and A. Cords, D. R. P. 33189, 1884; abst. Wag. Jahr. 1885, 31, 659.

3. E. P. 5617, 1893; abst. J. S. C. I. 1894, 13, 265. D. R. P. 4702,
1878; 15354, 16221, 1880; abst. Wag. Jahr. 1881, 27, 679; 1882, 28. 682.

4. J. Ind. Eng. Chem. 1914, 6, 649; abst. J. C. S. 1914, 108, ii, 739;
C. A. 1914, 8, 3401.

5. Chem. Ztg. 1897, 21, 41 ; abst. J. S. C. T. 1897, 18, 251 ; J. C. S. 1898.
74, i, 61; Chem. Centr. 1897, €8, I, 408; Jahr. Chem. 1897, 50, 1518.

6. G. Rivat, F. P. 433726, 1910; abst. J. S. C. I. 1912, 31, 245; J. Soc.
Dyers Col. 1912, 28, 84.

7. A. Ashworth, E. P. 19720, 1901; abst. J. S. C. I. 1902, 21, 1288;
J. Soc. Dyers Col. 1902, 18, 274; Chem. Ztg. 1903, 27, 104. F. Mirow, D.
R. P, 273235, 1913; abst. J. S. C. I. 1914, 33, 761; Wag. Jahr. 1914, 80, II,
460; Chem. Zentr. 1914, 85, 1, 1720; Chem. Ztg. Rep. 1914, 38, 289; Zts. ang.
Chem. 1914, 27, 387; C. A. 1914, 8, 2825.

8. K. Huppert, Zts. physiol. Chem. 1893-1894, 18, 247.

9. N. Welwart, Chem. Ztg. 1907, 31, 126; abst. J. S. C. I. 1907. 28,
216; Chem. Zentr. 1907, 78, I, 1467.

10. F. Frary and A. Dennis, J. Ind. Eng. Chem. 1915,^ 7, 214; abst.
J. C. S. 1916, HO, i, 202; C. A. 1915, 9, 1132; J. S. C. I. 1915, 34, 440.

StARCH - 429

for a given acidity there is a definite temperature range within
which heating for 30 minutes will convert starch into the soluble
variety. At higher temperatures the starch is rapidly converted
into dextrin. It has also been determined that for a given tem-
perature, range of acidity within which a soluble starch is pro-
duced is well defined, and that the use of larger quantities of acid
result in the formation of dextrin, while with a smaller amount,
the starch fails to become soluble.

E. Kunz is authority for the statement that the action of
HF is but one-seventeenth as great as HCl in the preparation of
soluble starch.^ Heat alone may be used for its preparation,* a
temperature of 140° for 3 hours at 2.5 atmospheres pressing giv-
ing excellent results.* When the starch is heated with the acid
in the form of vapor^ a lower temperature, it is claimed, may be
employed, and less danger of the formation of dextrins.^

Hypochlorites* or chlorine,^ the action being facilitated by
the presence of catal)rtic agents such as the salts of cobalt, copper,
iron, manganese and nickel, form the novelty claims of recent
patents.^ The duration of treatment is governed by the desired
solubility, complete solubility in hot water being claimed after
three to four hours heating at 60°. Copper sulfate in connec-

1. Zts. Spiritusind. 1915. 3S, 295; abst. J. C. S. 1916, HO, i, 202;
Chem. Zentr. 1915, 87, II, 783; C. A. 1915, 9, 3375. Cf. E. Deussen, Zts.
anorg. Chem. 1905, 44, 300, 408; abst. J. C. S. 1905, 88, ii, 311; J. S. C. I.
1905, 24, 440, 496; Chem. Centr. 1905, 76, I, 1208, 1298; Jahr. Chem. 1905-
1908 I 1441 1442.

2.' P. Thomas, Ann. de la Brass. 5, 267; abst. J. S. C. I. 1902, 21, 1033.

3. A. Fielding, E. P. 20488, 1906; abst. J. vS. C. I. 1907, 26, 980.

4. W. Browning and J. Barlow, U. S. P. 773469, 773783, 1904; abst.
Mon. Sci. 1905, 63, 65. E. P. 19499, 1903; abst. J. S. C. I. 1904, 23, 795;
J. Soc. Dyers Col. 1904, 20, 200. F. P. 336903. 1903; abst. J. S. C. I. 1904,
23, 449; J. Soc. Dyers Col. 1904, 20, 84.

5. F. Fol, D. R. P. 119265, 1901; abst. Wag. Jahr. 1901, 47, II, 275;
Chem. Centr. 1901, 72, I, 924; Chem. Ztg. 1901, 25, 413; Mon. Sci. 1901.
57, 217; 1905, 63, 820. Aust. P. 6251, 1901.

6. A. and H. Haake, U. S. P. 813647, 1906; abst. J. S. C. I. 1906, 25,
276. E. P. 885, 1903; abst. J. S. C. 1. 1903, 22, 754; F. P. 326286, 1902; abst.
J. S. C. I. 1903, 22, 812. D. R. P. 114973, abst. Wag. Jahr. 1900, 46, II, 371.
Aust. P. 26366, 1906.

7. H. Kindscher, D. R. P. 149588, 168980; abst. Wag. Jahr. 1904, 50,
II. 222; 1906, 52, II, 223; Chem. Centr. 1904, 75, I, 976; 1906, 77, I, 1514;
Chem. Ztg. 1904, 28, 329; 1906, 30, 304; Zts. ang. Chem. 1904, 17, 935; 1907,
20, 364; Jahr. Chem. 1904, 57, 1153; 1905-1908, II, 721, 941; Mon. Sci. 1908,
68,47.

8. A. Paira and Administration der Minen von Buchsweiler Akt. Ges.
E. P. 9370, 1909; abst. J. S. C. I. 1909, 28, 950. F. P. 402060, 1909; abst.
Mon. Sci. 1912, 77, 176.

430 THCHNOLOGY OF CEI.LULOSE ESTERS

tion with the injection of a ctirrent of air is said to admit of
soluble starch being produced in an hour at a temperature not
exceeding 40^-50®.^ E. Flick* hastens the time of action by the
use of nascent oxygen liberated from persulfates, in the presence
of small amounts of aluminium, iron or zinc chlorides.' The
'*Societe Trust Chimique" also make use of this method.* The
use of aluminium chloride,* is claimed to prevent or at least
retard, the extraction of objectionable nitrogenous matter.*

The soluble starch of R. Ansarge^ comprizes the addition of
borax, zinc white and stearin, that of C. Perkins* of borax, salt
and wax. Others use ozone, ^ sodium thiosulfate and aluminium
salts, ^® or sulfonated fatty acid (Turkey red oil),^^ the latter making
a smoother preparation, and one which penetrates textiles more
easily.

The soluble starch of K. Zulkowski^* is based upon the ob-
servation that glycerol at 190° is capable of dissolving 6% of
powdered starch and converting it into a soluble modification.

1. J. Dufour, Ann. Agronom, 12, 297; Bull. Soc. Vaudoise de Sci. Nat.
21, No. 93; abst. J. C. S. 1886, 50, 903; Arch. ph. Nat. (3), 1886, 15, 439;
Jahr. Chem. 1886, 39, 1809.

2. E. P. 25121, 1909; abst. J. S. C. I. 1910, 29, 444; J. Soc. Dyers Col.
1910, 26, 133. F. P. 406084, 1909; abst. Mon. Sci. 1911, 75, 150. D. R. P.
217336, 1910; abst. Wag. Jahr. 1910, 56, II, 259; Chem. Zentr. 1910, 81, I,
492; Chem. Ztg. Rep. 1910, 34, 46; Zts. ang. Chem. 1910, 23, 910; Chem.
Zts. 1910, 9, No. 1729. Aust. P. 50004, 1911. Swiss P. 50220, 1909.

3. T. Myers, E. P. 23554, 1896; abst. J. Soc. Dyers Col. 1896, 12, 237.

4. D. R. P. 134301, 1901; abst. Zts. ang. Chem. 1902, 15, 1019; J. S.
C. I. 1902, n, 1288; Wag. Jahr. 1902, 48, II, 300; Chem. Centr. 1902, 73,
II, 836; Chem. Ztg. 1902, 27, 901; Jahr. Chem. 1902, 55, 1037; Chem. Zts.
1903 2 281

'5.* Soc. Anon. Alliance Industrielle, E. P. 8514, 1900; abst. J. S. C. I.
1901, 20, 492; Chem. Ztg. 1901, 25, 780; Mon. vSci. 1902, 58, 162.

6. J. S. C. I. 1905, 24, 358. See also B. Federer, Chem. Ztg. 1903, 27,
925; abst. J. S. C. I. 1903, 22, 1142.

7. E. P. 586, 1897; abst. J. S. C. I. 1897, 16, 928. See also W. Zwick,
E. P. 12326, 1884; abst. J. S. C. I. 1885, 4, 237. D. R. P. 29975, 1884; abst.
Wag. Jahr. 1885, 31, 969.

8. U. S. P. 1149216, 1915; abst. C. A. 1915, 9, 2722.

9. E. Eckland, U. S. P. 1000726, 1911; abst. J. S. C. I. 1911, 30, 1130;
Chem. Ztg. Rep. 1911, 35, 454.

10. W. D'Rohan, U. S. P. 1248092, 1917; abst. C. A. 1918, 12, 298.

11. E. Weingaertner, U. S. P. 984330, 1911; abst. C. A. 1911, 5, 1534.

12. Ber. 1880, 13, 1395; abst. J. C. S. 1880, 38, 865; Chem. News, 1877,
35, 8; 1882, 45, 130; Bull. Soc. Chim. 1881, 36, 271; J. pharm. chim. 1880, 2,
494; Chem. Tech. Rep. 1878, 17, 1, 298; Jahr. Chem. 1880, 33, 1005. Oesterr.
Ges. Chem. Ind. 10, 2; abst. Chem. Centr. 1888, 59, 1060; J. C. S. 1889, 56,
116; Jahr. Chem. 1888, 41, 2322. Ber. 1890, 23, 3295; abst. J. C. S. 1891,
60, 165; J. S. C. I. 1891, 10, 56; Bull. Soc. Chim. 1891, 6, 679; Jahr. Chem.
1890, 43, 2151.

STARCH 431

«

This may readily be prepared by heating potato starch with
glycerol at 180°-190*^ for one-half hour, or for a longer time with
rice starch, the solution, after being allowed to cool down to 120°,
is poured into a large volume of alcohol, and the soluble product
washed with cold water and dried. ^

A continuous process has been evolved* in which the starch
is passed over a heated surface, the temperature and time of
contact of starch with the heat being so adjusted as to give a
water-soluble final product.

According to C. Tanret,' when soluble starch is prepared by
J. Wolff's method,* a sparingly- soluble product is also formed
resembling the amylocellulose of L. Maquenne and E. Roux.*
This apparently is not a single substance, as shown by fractional
precipitation with alcohol of its aqueous solution.^

A. Reychler^ has subjected the results of E. Fouard* on the

1. F. Aspinall, E. P. 9106, 1903; abst. J. S. C. I. 1904. 23, 618.

2. U. S. P. 578666. 1897; 785216, 1905; 984483, 1911; 1207177, 1916;
abst. J. S. C. I. 1906, 25, 998; 1917. 36, 156. E. P. 5844, 1896; 5574, 1904;
10216, 1906; 3004, 3414. 3415, 1910; 9082, 1912; abst. J. S. C. I. 1896, 15,
605; 1905, 24, 144; 1910, 29, 1468; 1913. », 788. F. P. 343614, 1904; 365834,
1906; 442619; abst. J. S. C. I. 1904, 23, 1038; 1906, 25, 998; 1912, », 788.

D. R. P. 88648, 147896. 158861, 166259, 227430. Aust. P. 21431, 1905;
24085, 1906; 56825, 56861. 56862, 1912; 63956, 1914. See also E. Oeser,

E. P. 19549, 1899.* Aust. P. 52338, 1912.

3. Compt. rend. 1909. 148, 1775; abst. J. C. S. 1909, 96, i, 556; C. A.
1909, 3, 2676; J. S. C. I. 1909, 28, 847; BuU. Soc. Chim. 1909, 5, 902; Rep.
Chim. 1909, 9, 256; Chem. Zentr. 1909, 80, II, 592, 1637; Jahr. Chem. 1909,
62, II, 374; Wag. Jahr. 1909. 55. II, 226; Zts. anj?. Chem. 1909, 22, 2346.

4. Compt. rend. 1905, 140, 14a3; abst. J. C. S. 1905, 88, i, 510; Chem.
Centr. 1906, 76, II, 121; Jahr. Chem. 1905-1908, II, 938.

5. Compt. rend. 1905, 140, 1303; abst. J. C. S. 1905, 88, i, 511; Chem.
News, 1906, 91, 279; J. S. C. I. 1905, 24, 630; Bull. Soc. Chim. 1905, 33, 723;
Rep. Chim. 1905, 5, 318; Chem. Centr. 1905, 76, II. 121, 314; Chem. Zts.
1906, 5, 10; Meyer Jahr. Chem. 1905, 15, 410; Biochem. Centr. 1905-1906,
4, 138, 380; Tech. Chem. Jahr. 1906, 28, 274. .

. 6. F. Musculus, Compt. rend. 1874, 78, 1413; abst. J. C. S. 1874, 27,
1077, 1174; Chem. News, 1874, 30, 20; Ann. Chim. Phys. 1874, (5), 2, 386;
J. pharm. chim. 1874, 20, 39; Ber. 1874, 7, 824; Chem. Tech. Rep. 1874, 13,
II, 152; Dingl. Poly. 1874, 214, 407; Jahr. Chem. 1874, 27, 881; Jahr. rein
Chem. 1874, 2, 177; Wag. Jahr. 1874, 20, 651; 1875, 21, 771; Amer. Chemist,
1875, 5, 192; Springm. Musterztg. 1875, 113.

7. Bull. Soc. Chim. Belg. 1909, 23, 378; abst. J. S. C. I. 1909, 28, 1216;
J. C. S. 1909, 96, ii, 977; Chem. Zentr. 1909, 80, II, 2140; J. Chim. Phys.
1909, 7, 497, 362; 1910, 8, No. 1.

8. Compt. rend. 1907, 144, 501; 1908, 146, 286, 978; 147, 931; 1909,
148, 502; Bull. Soc. Chim. 1909, 5, 828; abst. J. C. S. 1907, 92, i, 391, 677;
1908, 94, i. 138, 503, 953; 1909, 96, i, 13, 209; J. S. C. I. 1907, 26, 832; 1908,
27, 238, 635, 1215; 1909, 28, 433, 898; Chem. Zentr. 1907, 78, I, 1029; II,
391; 1908, 79, I, 1264; II. 1098, 2000; 1909, 80, I, 68, 644, 1091, 1987; II,
974; Jahr. Chem. 1905-1908, II, 937, 939, 940.

432 TECHNOLOGY OF CELlrUlrOSE ESTERS

absorption of certain bases by soluble starch to careful analysis,
and finds that the reactions between soluble starch and bases
take place according to Guldberg and Waage's law of mass action,
and are therefore chemical in nature. He considers these starch
compounds as similar to alcoholates.^ E. Fouard, however, has
shown* that the addition of alkalis to solutions of the various
polysaccharides cause a progressive alteration in the optical
rotatory power, usually explained by the gradual neutralization
of their acid groups, since definite chemical compounds are pre-
cipitated by the addition of a large excess of alcohol. He ap-
parently has demonstrated* that the progressive * 'solubilization**
of colloidal starch by alkalis is accompanied by a corresponding
change in the rotatory power of the solution — a change which
appears quantitative. His conclusion is that the action of alkalis
upon starch is a process of subdividing the granules of the col-
loid to a high degree, at the same time modifying them optically,
and being fixed by them in a variable proportion. This extremely
complex phenomenon is neither purely chemical or entirely phys-
ical, but rather an intramolecular change.

Whereas the term "soluble starch** and "amylodextrin** have
been employed as synonymous, A. Wroblewski* restricts the for-
mer to the first decomposition product of starch which gives a
blue coloration with iodine and does not reduce Fehling's solu-
tion. Amylodextrin is more properly to be regarded as a decom-
position product of soluble starch; iodine colors it reddish brown
and it somewhat reduces Fehling's solution.

W. Syniewski* has examined the soluble starch obtained by

1. J. Kraus, Ann. Agronom, 12, 540; abst. J. C. S. 1887, 52, 173;
Chem. News, 1887, 55, 69.-

2. BuU. Soc. Chim. 1909, 5, 828; abst. J. C. S. 1909, 98, i, 699; J. C. S.
1909, 96, i, 13, 209; Chem. Zentr. 1909, 80, I, 68, 644, 1091, 1987; II, 974;
Jahr. Chem. 1905-1908, II, 937, 939, 940.

3. Compt. rend. 1909, 148, 502; abst. J. C. S. 1909, 98, i, 209; Chem.
Zentr. 1909, 80, II, 974; Jahr. Chem. 1905-1908, II, 939, 940. See also Erste
Triester Reisschal-Fabriks Akt. Ges. E. P. 4719, 1908. F. P. 387736, 1908;
abst. J. S. C. I. 1908, 27, 854, 938.

4. Ber. 1897, 30, 2108; Chem. Ztg. 1898, 22, 375; abst. J. C. S. 1898,
74, i, 8; 1899, 76, i, 324; J. S. C. I. 1897, 16, 1028; 1898, 17, 778; BuU. Soc.
Chim. 1898, 20, 302; Chem. Centr. 1897, 68, II. 842; 1898, 69, II, 19; Jahr.
Chem. 1897, 50, 1518; 1898, 51, 1353; Wag. Jahr. 1897. 43, 788.

5. Ber. 1897, 30, 2415; 1898, 31, 1791; abst. J. C. S. 1898, 74, i, 61.
551 ; J. S. C. I. 1897, 16, 1029; 1898, 17, 778; Bull. Soc. Chim. 1898, 20, 367;
1899. 22, 223; Chem. Centr. 1897, 68, II. 1107; 1898, 69, II, 421; Jahr. Chem
1897, 50, 1518; 1898, 51, 1354.

STARCH 433

treating ordinary starch with sodium peroxide, which was found
to be insoluble in water, but when washed with water, alcohol
and ether and carefully dried, gave numbers indicating a deriv-
ative of soluble starch with the elements of water removed.
When treated with baryta water a product of the composition
Ci8H260i6(C2H30)7 was formed upon acetylation, and an analogous
benzoyl compound was also isolated. Soluble starch could not
be regenerated by hydrolysis of the acetyl derivative. By HCl
inversion, an amotmt of glucose equivalent to 99.3% was ob-
tained on the asstunption that soluble starch has the formula
C18H82O16. The invertive action of water under pressure on sol-
uble starch is hght, but a freshly prepared malt extract acting
at 65° for 90 minutes produced 82.7% of maltose.

Microscopic Appearance of Starch. When examined micro-
scopically, starch granules appear to be made up of a series of
distinctly stratified concentric or eccentric layers, the outer ones
being usually wider and denser than those nearer the center or
hilum, the latter appearing as a dark spot. Often two or more
nuclei appear in the same granule, being usually each surrounded
with concentric circles. In all starch granules, the outer layer
is of oldest growth, the granule increasing in size from without
inwards. For this reason the successive layers as the center is
approached are softer and less compact. Inasmuch as these layers
vary greatly in thickness, the individual granule gradually changes
from the original spherical to an oval or ovoid form.

A. Schimper^ finds that inasmuch as the shape and size of
the starch grains in plants depends to a large extent on their situa-
tion in the chlorophyl cells, it follows that if the latter are of
well arranged form, the starch granules are disengaged freely and
attain regular forms and normal size, while if the former are mis-
shapen the latter have not the freedom of movement and are
smaller. He considers starch grains as consisting of radial crys-
talline aggregates (sphaerocrystals), differing, however, from or-
dinary crystals by their power of swelling, and are more properly
termed crystalloids — occurring in aggregates only.

Chemical Properties of Starch. Starch (when the granules

1. ,Bot. Ztg. 1880, 881; 1881, 185; 1883, Nos. 7-10; 1886, 738; Bied.
Centr. 1881, 479; J. C. S. 1881, 40, 1061; Ann. Sci. nat. 1880-1881, 11, 256,
266; abst. Quart. J. Micro. 3ci. 1881, », 291.

434 TECHNOI.OGY OF CELLUIyOSE ESTERS

are unbroken) is absolutely insoluble in cold water,^ alcohol, ether,
chlorofprm or other solvent. Air-dried starch usually contains
about 18% of moisture, but this amount may vary within quite
wide limits, depending upon the hygrometric state of the atmos-
phere. According to F. Ullik,* starch has a great affinity for water,
which varies according to the nature of the starch. Potato
starch which, when dried at 120° was found to contain 12.1%
water, was weighed out in amounts corresponding to 20 gm. of
the air-dry substance, and mixed with an equal weight of water,
when the following increments in temperature were observed :

Increase in Tem-
perature.

1. Anhydrous starch (dried at 120°)

2. Starch dried at 90**

3. Starch dried over cone, sulfuric acid ....

4. Air dried starch

13.8**

12.0**

8.8**

3.0**

The gain of water which these samples showed were: (2) 0.85%,
(3) 2.6%, (4) 12.1%. He also has established that starch which
has been exposed in an atmosphere saturated with moisture at
a temperature of 16°-20° contains about 37% water, and that
no rise in temperature on mixing with water occurs. The mois-
ture in starch may be determined by means of organo-magne-
sium compounds, especially magnesium methyl iodide as first
suggested by H. Hibbert and J. Sudborough,' and extended by
T. Zerewitinoff.*

The moisture present in starch may be entirely driven off
by exposure in a current of dry air at a temperature of 105**, in

1. W. Wicke, Fogg. Ann. 1859, 108, 359; abst. Rep. Chim. Pure,. 1860,
2, 42; Jahr. Chem. 1859, 12, 544.

2. Zts. f. d. gesammt. Brauw. 1891, 565; abst. J. S. C. I. 1893, 12,
281; J. C. S. 1892, 62, 1066; Chem. Centr. 1892, 63, I, 250, 432; Dingl. Poly.
1892, 285, 184, 211; Jahr. Chem. 1892, 4S, 2820.

3; J. C. S. 1904, 85, 933; abst. Chem. News, 1904, 89. 19; J. S. C. I.
1904, 23, 77; Rep. Chim. 1904, 4, 144; Chem. Centr. 1904, 75, I, 402; Jahr.
Chem. lOOi, 57, 817.

4. Ber. 1907, 40, 2123; 1908, 41, 2233; 1910, 43, 3590; Zts. anal. Chem.
1911, 50, 680; abst. J. S. C. I. 1907, 26, 646; 1908, 27, 839; 1911, 30, 107,
1233; C. A. 1908, 2, 2810; 1911, 5, 1285; 1913, 7, 2390; J. C. S. 1907, 02, ii,
509; 1908, 04, i, 593; 1911, 100, i, 101; 1912, 102, ii, 1026; Chem. Zcntr. 1907.
78, II, 97; 1908, 7$, II, 445; 1912, 83, II, 1401.

STARCH 435

which condition it is very hygroscopic^ in a moist atmosphere.

The specific gravity of air-dried starches vary within com-
paratively wide limits, due primarily to the varying amounts of
moisture contained therein. Anhydrous starches, however, have
not identical gravities, anhydrous potato having a gravity of 1.65
and anhydrous arrowroot, 1.565.

In determining the action of ultra-violet rays upon starch,
L. Massol* exposed solutions of starch of 0.2%-l .0% concentration
at 10 cm. distance to the action of a mercury vapor quartz lamp.
The starch gradually lost the property of giving a blue solution
with iodine. It is to be noted that the rate of transformation
increases on decreasing the concentration and acidifying medium.
As the result of the exposure the solutions acquire reducing power,
and the starch is less precipitable with alcohol. It appears the
reducing substances formed consist of, or contain maltose. Ac-
cording to others,' the treated solution acquires an acid reaction,
and contains dextrins, dextrose, pentoses and formaldehyde.

When starch solutions are exposed for some hours to X-rays
of moderate penetrating power,* the opacity and viscosity of the
solut'ons are m^kedly diminished, and there is a partial conver-
sion to soluble starch and dextrin. Dextrin under similar con-
ditions is not convertible into dextrose. The effect is attributed
to a direct action upon the starch molecule, either by the X-rays
or by the secondary rays which they produce. In investigating
the electric transport of starch, W. Hardy^ and F. Bottazzi** are

1. W. Nossian, J. prakt. Chem. 1861, 83, 42; abst. J. Pharm. Chim.
1861, 40, 158; Chem. Centr. 1861, 32, 815; Jahr. Chem. 1861, 14, 714; Wag.
Jahr. 1861, 7, 359.

2. Compt. rend. 1911, 152, 902; 1912, 154, 1645; abst. J. C. S. 1911,
100, i, 356; 1912, 102, i, 538; J. S. C. I. 1911, 30, 503; C. A. 1911, 5, 2095;
1912, 6, 2421; 1913, 7, 430; Chem. Zentr. 1911, 82, I, 1686; Chem. Ztg. 1911,
35, 453; Meyer Jahr. Chem. 1911, 21, 528; Wag. Jahr. 1911, 57, II, 310.

3. J. Bielecki and R. Wurmser, Compt. rend. 1912, 154, 1429; abst.
J. C. S. 1912, 102, i, 538; J. S. C. I. 1912; U, 599; C. A. 1912, 6, 2082, 2916;
Biochem. Zts. 1912, 43, 154; Chem. Zentr. 1912, 83, II, 243, 1274; Meyer
Jahr. Chem. 1912, 22, 431.

4. H. Colwell and S. Russ, Proc. Phys. Soc. 1912, 24, 214; Le Radium,
1912, 9, 230; J. C. S. 1912, 102, i, 608; C. A. 1912, 6, 2863; Chem. Zentr.
1912, 83, II, 705.

5. J. physiol. 1905, 33, 251; abst. J. C. S. 1906, 90, i, 121; Biochem.
Centr. 1906-1907, 5, 41; Chem. Centr. 1906, 77, I, 688; Jahr. Chem. 1905-
1908, II, 4528.

6. Atti. R. Acad. Uncei, 1909, 18. ii, 87; abst. J. C. S. 1909, 96, i, 700;
C. A. 1910, 4, 342; Chem. Zentr. 1909, 80, II, 167; Jahr. Chem. 1909, 63, II,
379.

436 TECHNOLOGY OF CElrLUIX)SE BSTORS

not in accord. According to the former, glycogen and starch are
relatively isoelectric hydrosols. When solutions of glycogen and
starch are subjected to a field of about 5 volts per cm. (0.1 milli-
ampere), both move toward the anode, only traces migrating
toward the cathode. In the presence of small proportions of
mineral acid, alkalis or salts, starch behaves like protein or gela-
tin in acid solution in that it migrates towards the cathode, and
in alkaline solution towards the anode. In the presence of neu-
tral salts no migration is observed. W. Loeb* claims the effect
of the silent electric discharge on starch solution is to produce
hydrolysis. W. Baily* has studied the optical properties of
starch, while W. Hartley' has investigated the absorption spec-
trum.

Anhydrous starch has been prepared by the distillation of or-
dinary starch with a mixture of anhydrous benzene and absolute
alcohol, using Young's method of fractionation.* Dehydration is
complete when the boiling point of the alcohol-benzene binary
mixture (68.25**) becomes constant.

F. Sestini claims* that when bread crust is heated in a tube,
furfural begins to form at 110°-115®, whereas if heated in the
open, furfural formation does not commence until 150° is reached.
Gridkoff was unable to detect furfural by the distillation of cellu-
lose with dilute sulfuric acid, but when starch is heated dry at
about 200® or in the presence of acid at about 100°, a noticeable
yield of furfural results. When heated with aniline, only dex-
trin is formed,® while glycerol does not attack starch even at 200°.
C. Husson^ unsuccessfully endeavored to synthesize albumin by

1. Biochem. Zts. 1912, 46, 121; 1914. €0, 286; abst. C. A. 1913, 7,
476; 1914, 8, 1746; J. C. S. 1912, 102, i, 947; 1914, 106, i, 500; BuU. Soc.
Chim. 1913, 14, 1076; Chem. Zentr. 1912, 63, II, 2063.

2. Phil. Mag. 1876, (5),2, 123; abst. J. C. S. 1877, 31, 294; Jahr. Chem.
1876, 29, 147.

3. J. C. S. 1887, 51, 59; abst. Chem. News, 1886. S4, 270; J. S. C. I.
1887, 6, 285; J. pharm. chim. 1888, 50, 120, 524; Ber. 1887, 20, R, 174; Jahr.
Chem. 1887, 40, 350.

4. W. Atkins and E. Wilson, J. C. S. 1916, 107, 916; abst. J. S. C. I.
1915, 34, 818; C. A. 1915, 9, 2473; Zts. ang. Chem. 1915, 21, II, 618.

5. L'Orosi, 1898, 21, 109; Chem. Centr. 1898, II, 182; J. S. C. I. 1808,
17, 861; J. C. S. 1899, 76, i, 103; Jahr. Chem. 1898, 51, 2265.

6. H. Schiff, Ber. 1871, 4, 908; abst. J. C. S. 1872, 2S, 150; Chem.
News, 1871, 24, 300; Jahr. Chem. 1871, 24, 798; Zts. Chem. 1871, 14, 725.

7. Compt. rend. 1872, 75, 549; abst. J. C. S. 1873, 26, 46; Bull. Soc.
Chim. 1872, 18, 453; Ber. 1872, 5, 830.

STARCH 437

the action of nitrogen iodide on starch. R. Rother^ has studied
the influence of starch on the solubility of albumen.

Various starches have been found to vary as to their gelatin-
izing temperatures. According to M. Nyman,* when rye starch
is mixed with water and gradually heated, it gelatinizes at 57°;
barley at 58**, and wheat starch at 59°. The gelatinizing point
was taken as being the temperature at which the starch grains
ceased to polarize light when examined imder the micropolari-
scope. Working with a slight modification of the method of
Francis and Smith,' the gelatinization temperatiu-e of com starch
was foimd to vary between 64.1 °-7 1.1°, although concordant
results were readily obtained for a given variety.*

It has been found^ that potato starch contains 0v06% of chem-
ically combined phosphorus which can not be removed by extrac-
tion with dilute acid, either as free or combined phosphoric acid.
The analyses of phosphorous content in starch as made by A.
Thomas® is considered to support the view that it is in chemical
combination.

A. Rakovski,^ has contributed a series of papers on the ab-
sorption of salts dissolved in water by starch, including NaOH,*

1. Pharm. J. Trans. 1873. (3), 3, 644; abst. J. C. S. 1873, 26, 919; Jahr.
Chem. 1873, 26, 828.

2. Zts. Nahr. Genussm. 1912, 24, 673; abst. J. C. S. 1913, UM, ii, 160;
J. S. C. I. 1913, 32, 40; C. A. 1915, 7, 665.

3. J. Ind. Eng. Chem. 1916, 8, 509; abst. C. A. 1916, 10, 2995; J. S. C.
I. 1916, 35, 750.

4. A. Dox and G. Roark, J. A. C. S. 1917, 39, 742; abst. J. C. S. 1917,
111, ii, 276; C. A. 1917, 11, 1763; J. S. C. I. 1917, 36, 560. - .

5. J. Northrup and J. Nelson, J. A. C. S. 1916, 38, 472; abst. J. C. S.
1916, 109, i, 373; C. A. 1916, 10. 766.

6. Biochem. BuU. 1914, 3, 403; abst. J. C. S. 1915, 108, ii, 6; C. A.
1914, 8, 3801. According to A. Fernbach (Compt. rend. 1904, 138, 428;
abst. J. C. S. 1904, 86, i, 294; J. S. C. I. 1904, 23, 330; Chem, Centr. 1904;
7$, I, 819; Jahr. Chem. 1904, 57, 1150) when potato starch is levigated, two
kinds of granules — ^the heavy and the light — are obtained. Both contain
phosphorus, a higher percentage in the light granules (0.158-0.226% PsO»)
as against 0.138-0.178% in the heavy granules.

7. J. Russ. Phys. Chem. Soc. 1911, 43, 170; 1912, 44, 686, 1722; 1913,
45, 13; abst. J. C. S. 1911, 100, ii, 470; 1912, 102, ii, 743; 1913, 104, ii, 114,
303; C. A. 1912, 6, 2348, 2876; 1913. 7, 1121, 2144, 2880; Chem. Zentr. 1911,
82, 1, 1478, 1479; 1912, 83, 1, 568; II, 667; 1913, 84, I, 586, 1384, 1808.

8. A. Rakovski, J. Russ. Phys. Chem. Soc. 1913, 45, 7; Zts. Chem. Ind.
Koll. 1913, 12, 128; abst. J. S. C. I. 1913, 32, 440; C. A. 1913, 6, 2876; 1914,
7, 2880; J. C. S. 1913, 102, ii, 302; Bull. Soc. Chim. 1913, 14, 787; Chem.
Zentr. 1913, 84, 1, 1384, 1806.

438 TECHNOLOGY OF CEI.I.UU)SE ESTERS

ammonia/ and cupric hydroxide.^ It has been fomid that the
absorption of sodium hydroxide from aqueous solutions by potato
starch is increased by the presence of sodium or potassium salts
of organic or inorganic acids, the effect being greater the higher
the concentration of the salt. Slight absorption of ammonia
from aqueous solutions by starch is practically unaffected by the
presence of ammonium chloride. Whereas strongly dissociated
alkalis are absorbed in considerable proportions, the feebly dis-
sociated ammonia is slight, and falls virtually to zero in the pres-
ence of the strongly dissociated barium hydroxide. The heats
of combustion per gm./mol. for constant volume and constant
pressure are: for cellulose, 678; starch, 677.5. The heats of form-
ation are 231.0 and 231.5 respectively.*

It has been shown* that a solution of potato starch frozen
to a solid mass and then melted, yields a coagulum nearly free
from mineral matter. In fact, the starch may be completely
*'demineralized*** by heating a 1% paste in an autoclave for 2-3
hours at 130®, cooling, decanting the supernatant opalescent
liquid from a slight sandy residue, and then freezing in a mould
of pure nickel. On melting the solid block of ice, the floccufent
residue was found to contain less than 0.02% of ash. They have
found* that starch desiccated by drying in vacuo over phosphorus
pentoxide, becomes soluble in cold water through the formation
of dextrins. When desiccation has been carried so far that not

1. A. Rakovski. J. Russ. Phys. Chem. Soc. 1911, 44, 586; Zts. Chem.
Ind. Koll. 1912, 11, 51; abst. J. S. C. I. 1912, 31, 891; C. A. 1912, 6, 2348;
J. C. S. 1912, 102, ii, 743; BuU. Soc. Chim. 1912, 12, 1411; Chem. Zentr.
1912, 83, II, 668.

2. A. Rakovski, J. Russ. Phys. Chem. Soc. 1914, 46, 246; abst. J. C. S.
1914, 106, ii, 434; C. A. 1914, 8, 2512; Bull. Soc. Chim. 1914, 16, 868.

3. F. Stohmann and H. Langbein, J. prakt. Chem. J891, 152, 336;
1892, 153, 305; abst. J. C. S. 1892, 62, 4, 764; Chem. News, 1894, 70, 121.
294; J. S. C. I. 1891, 10, 1020; BuU. Soc. Chim. 1892, 8, 303; Ber.
1891, 24, R, 881; 1892, 25, R, 126, 496; Jahr. Chem. 1892, 45, 369, 373.

4. G. Malfitano and A. Moschkoff, Compt. rend. 1910, 150, 710; abst.
J. S. C. I. 1910, 29, 506; J. C. S. 1910, 98, i, 301; C. A. 1910, 4, 1556; Chem.
Zentr. 1910, 81, 1, 2074; Jahr. Chem. 1910, 63, II, 408.

5. G. Malfitano and A. Moschkoff, Compt. rend. 1910, 151, 817; abst.
J. S. C. I. 1910, 29, 1402; J. C. S. 1910, 98, i, 817; C. A. 1911, 5, 1345; Chem.
Zentr. 1911, 82, I, 17; Jahr. Chem. 1910, 63, II, 407; Wag. Jahr. 1910, 56,
II, 257. See also G. Malfitano, Compt. rend. 1904, 139, 1221; 1906, 143,
400; Rev. g6n. sci. 1908, 19, 614; J. C. S. 1906, 90, i, 804; Chem. Centr.
1906, 77, II, 1312; Jahr. Chem. 1905-1908, II, 939.

6. G. Malfitano and A. Moschkoff, Compt. rend. 1912, 154, 443; abst.
J. S. C. I. 1912, 31, 245; J. C. S. 1912, 102, i, 240; C. A. 1912, 6, 1552; Bull.
Soc. Chim. 1912, 11, 773; Chem. Zentr. 1912, 83, I, 1103.

STARCH 439

only water of hydration is evolved, but also water of constitution
proceeding from the decomposition of the molecule, then the sol-
ubility diminishes. So-called "crystals" of starch, when exam-
ined microscopically,^ although resembling crystals of dextrose,
are not crystalline in form. These particles of starch have not
the polyhedric form, neither do they exhibit the phenomena of
birefringence.*

Many of the starches exhibit well marked acidic properties,
especially rice starch. When the latter' is allowed to remain in
contact with sodium, potassium or barium hydroxides, it is found
that there is a considerable diminution of the titer of the alkali —
less so with ammonia. The absorbed alkali can again be extracted
with water. The diminution of the alkali titer is accompanied
by the formation of an equivalent quantity of sodium hydrogen
carbonate. Potassium and sodium chlorides, sulfates and phos-
phates are all absorbed by starch. More copper acetate than
sulfate is absorbed. Zinc and copper are taken up from ammo-
niacal solutions of the sulfates, the copper product being relatively
stable, water extracting ammonia but no appreciable amount of
copper from it.*

J. Groll* has found that reversible transfonnations of starch
into erjrthroamylose may take place, giving a red or violet color
with I-KI solution, when the starch solution is treated with methyl,
ethyl or octyl alcohols, ethyl ether or chloroform, in various con-
centrations. If sodium cholate or saponin is added to these solu-
tions, transformation into erythroamylose becomes irreversible,
this being ascribed to a surface tension effect.

As the result of dialyzing solutions of soluble starch, precip-

1. Bull. Soc. Chim. 1912, (4), U, 606; Compt. rend. 1913, 156, 1412;
abst. J. C. S. 1912, 102, i, 608; 1913, 104, i, 593; J. S. C. I. 1913, 32, 619;
C. A. 1912, $, 2875.

2. G. Malfitano and A. Moschkoff, Compt. rend. 1913, 156, 1681;
abst. J. C. S. 1913, 104, i, 707; C. A. 1913, 7, 2937; Chem. Zentr. 1913, 84,
II 492 493.

3.' E. Demoussy, Compt. rend. 1906, 142, 933; abst. J. C. S. 1906,
90, i. 401; J. S. C. I. 1906, 25, 489; Rep. Chim. 1906, 6, 312; Chem. Centr.
1906, 77, I, 1654; Jahr. Chem. 1905-1908, II, 933. See J. Ford and J. Guth-
rie, J. C. S. 1906, 89, 76; abst. J. S. C. I. 1906, 25, 228; Bull. Soc. Chim.
1906, 36, 1293; Chem. Centr. 1906, 77, I, 314, 990; Jahr. Chem. 1905-1908,
II, 923; Chem. News, 1905, 92, 1293.

4. W. Bate, E. P. 23703, 1903: abst. J. S. C. I. 1904, 23, 944.

5. Arch, neerland. physiol. 1918, 2. 319; abst. J. C. S. 1918, 114, i,
292; C. A. 1918, 12, 485; J. S. C. I. 1918, 37, 134-A.

440 TECHNOWXJY OF CBLLUUDSE BSTERS

itating the solution left in the dialyzer by alcohol and a trace of
NaCl, E. Clark^ concludes that soluble starch carries associated
with it certain amounts of dextrins with reducing properties, and
that it can only be freed from these by dialysis or precipitation.
A. Fembach prepares a pure soluble starch by slowly pouring
weak aqueous solutions of starch (2%) into a large excess of pure
acetone, the flocculent precipitate after exhausting with acetone,
being dried at low temperature in a vacuum. This starch is com-
pletely soluble in cold water, its solution giving a very pure blue
color with iodine.*

In investigating the colloidal properties of starch in reference
to its constitution, E. Fouard' has observed that in preparing a
collodion-dialyzed starch solution as previously indicated, the
rotatory power diminishes, at first rapidly, then more slowly, and
finally approaches asymptotically to the rotatory power for. a
maltose solution, the change being reversable, so that the
rotation again increases on neutralization. From this the infer-
ence is drawn that starch is simply a condensation of maltose of
var)ring degrees of complexity.* The production of lactic acid
from starch* is a well-known industry .•

L. Maquenne has shown that starch paste slowly reverts to
amylocellulose,^ but this action has been shown to be reversible
between the temperatures of 0°-150°.^ At higher temperatures

1. J. Biol. Chem. 1910, 7, 46; abst. J. C. S. 1910, 96, i. 544. Biochem.
Bull. 1, 194; abst. C. A. 1912, 6, 1161.

2. Eighth Intl. Cong. Appl. Chem. 1912. 13, 131; Compt. rend. 1912.
155, 617; abst. J. C. S. 1912, 102, i, 832; J. S. C. I. 1912. 3RI, 892; C. A. 1912.
6, 3339; Bull. See. Chim. 1913, 13, 86; Chem. Zentr. 1912. 83, II. 1812;
Meyer Jahr. Chem. 1912, 22, 429.

3. Compt. rend. 1907, 144, 501, 1366; 1908, 146, 285, 978; 1908, 147,
813, 931; 1909, 146, 502; abst. J. S. C. I. 1907, 26, 832; J. C. S. 1907, 92, i.
391; 1908, 94, i, 138, 503, 953; 1909, 96, i, 13, 209.

4. A. Claflin, T. S. C. I. 1897. 16, 516; abst. J. C. S. 1899, 76, i, 12;
Chem. Centr. 1897, tt, II, 338; Jahr. Chem. 1897, 50, 1223.

5. W. McLauchlan, Seventh Intl. Cong. Appl. Chem. 1909; abst. J. S.
C. I. 1909, 28, 734.

6. W. Hoffmann, Zts. Spiritusind. 1913, 36, 71; abst. J. S. C. 1. 1913,
32, 303; Deut. Essigind. 1913, 17, 102; C. A. 1913, 7, 2647; Chem. Zentr.
1913, 84, 1, 131 1 ; Zts. ang. Chem. 1913, 26, II. 371 ; Wag. Jahr. 1913. 59, II. 363.

7. Compt. rend. 1903, 137, 88, 658, 797, 1266; abst. J. C. S. 1903, 84,
i, 679; 1904, 86, i, 17, 227, 228. 294, 800; Bull. Soc. Chim. 1903, 29, 218;
Rep. Chim. 1904, 4, 102, 177; Chem. Centr. 1903, 74, II, 757; Jahr. Chem.
1903, 56, 1005.

8. Compt. rend. 1904. 138, 1356; 1905, 140, 440, 943. 1259; 1903, 142,
95; abst. J. C. S. 1904, 86, ii, 625; 1905. 88, 262, 328, 624; J. C. S. 1908. 99,
i, 235; J. S. C. I. 1904, 23, 675; 1905. 24, 285, 507, 630; 1906. 25, 130.

STARCH 441

•

the amylocellulose liquefies and on cooling forms a starch paste
which is colored blue by iodine. The statement of Naegeli that
the skeleton-like substance obtained from starch by treatment
with dilute acid is amylodextrose has been corroborated by Griess-
mayer.*

In 1856 H. V. Payr observed* the action of tin chloride upon
starch. When chloroform is added to a solution of starch in tin
chloride and allowed to remain at rest for several months, the
starch is wholly converted into dextrin. When starch paste is
treated with chloroform a soluble modification is formed, similar
to that resulting from treatment with mineral acids as HCl, and
upon heating such a mixture, the starch after some time passes
entirely into solution, which upon cooling, separates as a fine
precipitate.

When starch is shaken with 100 times its weight of 15%
aqueous chloral hydrate an almost clear but viscous solution re-
sults, which is not colored blue with elemental iodine or an iodine
solution in chloral hydrate.

Tannin immediately induces precipitation from starch paste
or from soluble starch, the product being soluble in boiling water,
from which it is again deposited upon cooling.

The sp. gr. of potato starch will average 1.60' to 1.65;* wheat
starch, 1.643,* and air-dried starch 1.53-1. 54.'

Starch Paste. This may readily be prepared by the methods

1. V. Griessmayer, Allgem. Brauer. u. Hopfenztg, 26, 147; abst. J. S.
C. I. 1887, 6, 446; Bied. Centr. 1887. 16, 190; J. C. S. 1887, S2, 686.

2. J. prakt. Chetn. 1856, 69, 425; Sitzber. k. k. Akad. Wiss. 21,
269; abst. J. pharm. chim. 1857, 31, 318; Chem. Centr. 1856, 27, 858; Jahr.
Chem. 1856, S, 672.

3. O. Saare, Zts. Spiritusind. 7, 550; abst. Chem. News, 1885, 51,
297; J. C. S. 1885, 48, 618; Chem. Tech. Rep. 1884, 23, I. 251; Chem. Ztg.
1884, 8, 934; Jahr. Chem. 1884, 37, 1654.

4. H. Rodewald, Landw. Versstat. 1894, 45, 201; abst. J. C. S. 1895,
68, i, 165; Chem. Centr. 1895, 66, I, 76; Jahr. Chem. 1894, 47, 1137.

5. H. Rodewald and A. Kattein, Zts. physik. Chem. 1900, 33, 590;
abst. J. C. S. 1900, 78, i, 79, 477; J. S. C. I. 1899, 28. 1062; Chem. Centr.
1899, 70, II, 419; 1900, 71, II, 180; Jahr. Chem. 1899, 52, 1271; 1900, 53, 829.

6. E. Parrow, Ellrodt and F. Neumann, Zts. Spiritusind. 1907, 30,
432; abst. J. S. C. I. 1907, 26, 1103; Chem. Zentr. 1907, W, II, 1606; Jahr.
Chem. 1905^1908, II, 932; Wag. Jahr. 1907, 53, II, 217. For bleaching of
starch, see A. Holste, E. P. 30390, 1909; abst. J. S. C. I. 1910, 29, 1200.
For action of glycerol on starch, see K. Zulkowsky, Ber. 1880, 13, 1395; abst.
J. C.S. 1880,38,865; Monatsi. 1905, 26, 1420; Akad. Wien. 1880, 72, II Abth.
384. K. Zulkowsky and B. Franz, Ber. Oesterr. Gess. zur Foerderung. Chem.
Ind. 1894, 16, 120.

442 TECHNOLOGY OP CELLULOSE ESTERS

of C. Higgins,^ C. Ekman,^ or G. Gastine.' In the former, starch
is digested with water and a digesting agent at a temperature just
below its gelatinizing point, until it is converted into white dex-
trin as indicated by a violet reaction with iodine. The temper-
ature is raised and the mass kept liquid for a short time, after
which it is neutralized with alkali and allowed to cool to a soft
semi-fluid mass. In the second method, rice starch is heated
with dilute mineral add at a temperature not exceeding 35^, and
then neutralized with a base as calcium carbonate or magnesium
oxide. In the Gastine process, potato starch is heated with a
trace of mercuric iodide, stirred, poured into boiling water, allowed
to settle and the supernatant liquid used. The keeping proper-
ties of the paste may be increased by the addition of a drop of
mustard oil,^ a trace of mercuric chloride,^ or a small amount of
alkali, as sodium hydroxide." The amount of alkali to be added
is insuflicient to have any influence when the starch solution is
used as an indicator in iodometric titration, yet efifectually pre-
vents bacterial decomposition of the starch solution.

In determinations requiring the use of a very delicate iodine
solution — such as the estimation of sulfurous acid in wines — ^the
end-point of the titration is often not clear cut when using or-
dinary starch paste. According to L. Mathieu,^ the soluble
starch described by A. Fembach and J. Wolff,* affords greater
precision in titration than any other. In the preparation of this

1. E. P. 19021, 1898; 1885, 1900; abst. J. S. C. I. 1899, U, 59. U. S.
P. 642330, 1900. Rev. Prod. Chim. 16, 244; abst. J. S. C. I. 1900, IS, 1126.

2. U. S. P. 742174, 1903; abst. J. S. C. I. 1903, 22, 1252; Mon. Sci.
1904, 61, 38. E. P. 8331, 1901; abst. J. S. C. I. 1902, 21, 358; Chcm. Ztg.
1902, 26, 811. See M. Brauer, D. R. P. 262501, 273311; abst. J. S. C. I.
1914, 33 747.

*3. 'buII. Soc. Chim.. 1888, 56, 172; abst. J. C. S. 1889. 56, 73; Chem.
News, 1888. 58, 245; Ber. 1888, 21, R, 802; Chem. Centr. 1888. 59, 1240;
Chem. Ind. 1888, 11, 561; Chem. Tech. Rep. 1888, 27, II. 265; Jahr. Chem.
1888, 41, 2519; Zts. anal. Chem. 1889, 28, 339.

4. A. Hirschberg. Arch. Pharm. (2), 150, 44; abst. Chem. Centr. 1872.
43, 492; J. C. S. 1873, 26, 100; Jahr. Chem. 1872, 25, 782.

5. R. Lansdale, E. P. 1803, 1875.

6. Pollitz, Zts. ang. Chem. 1917, 30, I, 132; abst. J. C. S. 1917. 112,
ii. 499; C. A. 1918, 12, 666.

7. Ann. Chim. Analyt. 1911, 16, 51; abst. J. S. C. I. 1911. 30, 399.
Bull. Assoc, chim. Sucr. Dist. 1910, 27, 1166; abst. J. C. S. 1910, 36, ii, 747;
C. A. 1910, 4, 2617; Chem. Zentr. 1910, 81, II, 685; Jahr. Chem. 1910, 63, I.
496.

8. Compt. rend. 1907. 144, 645; J. C. S. 1907, 92, i, 750. 1012; J. S.
C. I. 1907, 26, 833, 938; Rep. Chim. 1908, 8, 61, 89; Chem. Zentr. 1907, 78,
I, 1339; Jahr. Chem. 1905-1908, II, 924, 938, 943.

STARCH 443

material, starch is allowed to remain in contact with dilute HCl
(1: 1000) for some time, then washed with distilled water and
dried at 30°, followed by several hours' heating in an oven at or
above 100°. The acid treatment removes alkalis and alkaline
earths and converts neutral into acid phosphates, while during
the subsequent dry heating, gradual conversion into soluble starch
takes place. It is said that this material keeps indefinitely in the
dry state, and is converted into paste by boiling in 100 volumes of
distilled water and filtering the solution thus obtained. It is said
that this solution is very sensitive to iodine, giving a sharp change
from colorless to pure blue, and conversely. These investigators
state^ that when starch paste is made neutral to methyl orange by
the addition of sulfuric acid and then heated at 120°, its viscosity is
greatly diminished, but if disodium hydrogen phosphate be added
to the neutralized paste directly before heating, the viscosity is
increased and becomes equal to that of the original paste, when
the quantity of the salt added is equivalent to 2.5 times that of
the equivalent of the acid. The effect of sodium hydroxide in
retarding the liquefaction of starch paste is much more marked
than that of Na2HP04. It appears therefore, that the liquefac-
tion of neutralized starch paste is partly due to the transforma-
tion of the secondary phosphates present in the starch into primary
phosphates; that it is not affected by the addition of salts neutral
to methyl orange, but is retarded by the addition of salts alkaline
to this reagent, and checked altogether by traces of free alkali.

A. Fembach and J. Wolff have also shown* that when 5%

1. A. Fernbach and J. Wolff. Compt. rend. 1906, 143, 380; abst. J. C. S.
1906, $0, i, 804, Ann. Brass. 1906. 361 ; J. S. C. I. 1906, 2S, 898; Chem. Centr.
1906, 77, II. 1046; Jahr. Chem. 1905-1908, II, 4786. See also Compt. rend.
1906, 143, 380; 1907, 145, 261; abst. J. S. C. I. 1907, 26, 938. J. Wolff and
A. Ferabach. Compt. rend. 1903, 22, 1302; Bull. Soc. Chim. 1904, 31, 766;
Chem. Centr. 193. 74, II, 1451; Jahr. Chem. 1903. 56, 1912.

2. A. Fernbach. Woch. Brau. 1900, 17, 24; Ann. Brass. 1899; abst.
J. S. C. I. 1900, 13, 260; Compt. rend. 1904, 138, 428; J. S. C. I. 1904, 23,
330; Compt. rend. 1906. 142, 285; Zts. Bierbr. 1906, 349; Ann. Brass. 1906,
12; Woch. Brau. 1906, 23, 159, 160; abst. J. C. S. 1906. 90, i, 3271; J. S. C. I.
1906, 25, 192; Rep. Chim. 1906, 6, 187; Chem. Zts. 1907. 6, 40, 266; Jahr.
Chem. 1906-1908, II, 4670; Wag. Jahr. 1906, 52, II, 339, 350. Eighth InU.
Cong. Appl. Chem. 1912, Via, 592; abst. J. S. C. I. 1912, 31, 892. A. Fem-
bach and M. Schdn. BuU. Soc. Chim. 1912, 11, 303; abst. J. S. C. I. 1912,
31, 402. A. Fembach and J. Wolff. J. Fed. Inst. Brew. 1904, 10, 216; abst.
J. S. C. I. 1910, 29, 616; Seventh Intl. Cong. Appl. Chem. 1907; abst. J. S.
C. I. 1909, 28, 847; Compt. rend. 1907, 145, 80; abst. J. S. C. I. 1907, 26, 833;
Compt. rend. 1903, 137, 718; Bull. Soc. Chim. 1904, 31, 766; abst. Chem.

444 tkchnoux;y of cei*i.ui.ose hsters

starch paste is treated with a few drops of neutral HjOj and am-
monia and placed at a temperature of 70°-75°, rapid liquefaction
occurs, the liquid attaining the viscosity of water in about 15 min-
utes. Ferrous sulfate or copper sulfate also attenuate the vis-
cosity, but a longer time is required.

As M. Samec alone, ^ and with S. Jendc,^ and F. v. HoefFt,*
have shown, aging or retrogression of a starch solution is accom-
panied by a well-marked irreversible diminution in viscosity; the
final viscosity of a 1% solution being of the order of that of
molecular-disperse (true) solutions; electric conductivity of the
solution increases; the addition of HCl reduces the initial vis-
cosity of the solution and retards the subsequent decrease in viscos-
ity; the stabilizing action varies according to the concentration
of the acid.

From a comparison of the behavior of ordinary and phos-
phorus-free starches,* it would appear that initial changes pro-
duced by alkalis as seen in the starch solutions, are — at least in
great measure — due to the action of the alkali upon the phosphoric
acid* groups in the starch molecule. Further action results in
the combination of the alkali with other groups in the starch
molecule, and in the peptonization of the starch. It is claimed'
that by the action of 0.125 N potassium hydroxide, it is possible
to separate starch into two fractions, one of which does, and the

Centr. 1903. 74, II, 1457; Jahr. Chcm. 1903. 56, 1912; Compt. rend. 1905,
140, 95; abst. J. S. C. I. 1905. 24, 144. Compt. rend. 1905. 140, 1067, 1403;
abst. J. S. C. I. 1905, 24, 508.

1. Kolloidchem. Beihefte. 1912. 4, 132; abst. J. S. C. I. 1913, 32, 102;
C. A. 1913, 7, 3767; J. C. S. 1913. 104, i, 17; Chem. Zentr. 1913, 04, I, 632;
Meyer Jahr. Chem. 1912, 22, 430.

2. KoU. Chem. Beihefte. 1915, 7, 137; abst. J. C. S. 1915. 108, i, 941;
J. S. C. I. 1915, 34, 1264; C. A. 1916. 10, 289. See also G. Malfitano and
A. Moschkoff. Compt. rend. 1910. 150, 710; 151, 817; abst. J. €. S. 1910,
98, i, 301, 817; C. A. 1911, 5, 1345; J. S. C. I. 1910, 29, 1402; Chcm. Zentr.
1911, 82, I, 17; Jahr. Chem. 1910, 63, II, 407; Wag. Jahr. 1910. 56, II. 257.

3. Koll. Chem. Beihefte. 1913, 5, 141; abst. J. S. C. I. 1913. 32, 954;
C. A. 1914, 8, 837, 1602; J. C. S. 1913, 104, i, 1155. See also C. Tanret,
Compt. rend. 1909, 148, 1775; abst. C. A. 1909, 3, 2676; J. C. S. 1909, 96,
i, 556; J. S. C. I. 1909. 28, 847; Bull. Soc. Chim. 1909, 5, 310, 823; Rep. Chim.
1910, 10, 66; Chem. Ztg. 1909, 33, 837; Jahr. Chem. 1909, 62, II. 374; Wag.
Jahr. 1909, 55, II. 226.

4. M. Samec, Koll. Chem. Beihefte, 1916, 8, 33; abst. J. C. S. 1916.
109, i, 308; C. A. 1917, 11, 312.

5. M. Samec, KoU. Chem. Beihefte, 1911, 3, 123; 1912. 4, 132; 1914,
6, 23; Intern. Zts. Phys.-chem. Biol. 1914, 1, 173; abst. J. C. S. 1912, 102,
ii, 144; 1913, 104, i, 17, 1155; 1914, 166, i, 930; J. S. C. I. 1914, 33, 760.

STARCH 445

other does not contain phosphoric add, either free or combined.

The properties of *'demineralized*' starch prepared by the
methods of Wolff and Pembach/ and G. Malfitano and A. Mosch-
koff,^ correspond to a solution of ordinary aged starch as described
above, there being many facts known in strong confirmation of
the view that the characteristic properties of starch as exemplified
in starch paste are due to the presence of amlophosphoric add
or analogous complex compoimd,* probably of the type R.CH2O.-
P0(0H)2. As a generahty, the formation of soluble starch is
accompanied by a reduction in size of the starch molecule.*

As F. Schardinger has shown,^ specific microbes act upon
starch paste with the production of soluble substances similar to
dextrin. The action of the same organism {Bac. macerans) tmder
identical conditions, differs according to the kind of starch used,
potato being entirely, arrowroot largely, and wheat and rice stardi
difficultly dissolved.

Processes for the coloring* and perfuming^ of starch pastes for
selective purposes have been patented.

The value of a starch paste from a technical point of view,
rests upon a determination of the gelatinizing temperature,* vis-
cosity adhesion and resistance,' and power of gelatinization. ^®

Manufacture of Starch. The amount of starch obtainable

1. C. Tanret, Compt. rend. 1909, 148, 1776; abst. C. A. 1909. 3, 2676;
J. C. S. 1909, 36, i, 566; J. S. C. I. 1909, 28, 847; BuU. Soc. Chim. 1909, 5,
310, 823; Rep. Chim. 1910, 10, 66; Chem. Ztg. 1909, 33, 837; Jahr. Chem.

1909, 82, II, 374; Wag. Jahr. 1909, 5S, II, 226.

2. Compt. rend. 1910, 150, 710; 151, 817; abst. J. C. S. 1910, 98, i,
301. 817; J. S. C. I. 1910, 29, 606; Chem. Zentr. 1910, 81, 1, 2074; Jahr. Chem.

1910, 63, II, 408.

3. M. Samec. Koll. Chem. Beihefte, 1912, 4, 132; abst. J. S. C. I. 1913,
32, 102; C. A. 1913, 7, 3767; J. C. S. 1913, 104, i, 17; Chem. Zentr. 1913, 84,
I, 632; Mayer Jahr. Chem. 1912, 22, 430.

4. F. Drittler. U. S. P. 847658, 847986, 1907. E. P. 7705, 1906; abst.
J. S. C. I. 1906, 25, 601.

6. Zentr. Bakt. Par. 1908, II Abt. 22, 98; 1911, II Abt. 29, 188;
abst. J. S. C. I. 1909, 28, 153; 1911, 30, 439; J. C. S. 1909, 96, ii, 82; 1911,
100, i, 181; Chem. Zentr. 1909, 80, 1, 68; 1911, 82, II, 874.

6. J. Thompson, E. P. 596, 1883.

7. F. Norfolk, U. 5. P. 480669, 1892. W. Marshall, U. S. P. 890624,
1908.

8. C. Francis and O. Smith, J. Ind. Eng. Chem. 1916, 8, 509; abst.
J. S. C. I. 1916, 35, 750; C. A. 1916, 10, 2995.

9. A. Binz. Flora, 1892, 34. Dissertation in Miinchen. A. Binz and
T. Marx, Chem. Ind. 1909, 32, 167; abst. J. S. C. I. 1909, 28. 422; C. A. 1910,

4, 2219; Chem. Zentr. 1909, 80, 1, 1609; Jahr. Chem. 1909, 62, II. 375.

10. A. Dox and G. Roark, J. A. C. S. 1917, 39, 742; abst. J. S. C. I.
1917, 36, 560; C. A. 1917, tl, 1763. A. Meyer, KoU. Chem. Beihefte. 1913,

5, 1; abst. J. C. S. 1913, 104, ii, 848; C. A. 1914. 8, 1226.

446 TECHNOLOGY OF CELLULOSE ESTERS

from a given area of ground depends upon, the nature of the
starch-produdng plant cultivated; the percentage of starch con-
tained therein; and the yield per acre. Whereas wheat contains
some 55% of starch, and potatoes but 20%, yet twice as much
potato starch can be obtained per acre as wheat stardh, due to
the fact that the yield per acre is 65 as to 13. Different var-
ieties of the same species vary greatly in starch content. Or-
dinarily potato contains but 13% of starch, but in Germany by
the careful selection and propagation of species, aided by suit-
able fertilization, the percentage of starch has been raised from
13% to 20% and even higher. The yield of starch is also gov-
erned by the age of the raw material, conditions of harvesting and
exposure of raw material to extremes of heat and cold.

Over-ripe potatoes have been found to contain less starch,
the loss being 3.2%-10%.* Barley exposed to moist weather so
as to sprout, has been found to have lost 10% in starch content.
Generally diseased potatoes contain less starch than normal ones,
which is explained by the fact that the fungus attack converts
some starch into sugar. Potatoes grown with highly nitrogenous
manures are found to be more readily susceptible to attack by
fungus. Freezing potatoes diminishes their starch content, the
accepted explanation being that freezing converts a portion of
the starch into sugar. The yield of starch is, of course, governed
by the mechanical processes to which the raw material is sub-
jected, as washing, defective machinery, or insufficient settling.

Wheat, potatoes, com and rice are the usual raw materials
from which starch is extracted, although cassava,* manioc,' to-
bacco leaves,* horse chestnut,^ arrowroot,* mulberry,' locust

1. E. Kramer, Bied. Centr. 1881, 717; abst. J. C. S. 1882, 42, 242.

2. Board of Trade Jour. May 26, 1904; abst. J. S. C. I. 1904, 23, 036.
Fiji. Bull. Imp. Inst. 1909, 7, 271; abst. J. S. C. 1. 1909,28, 1265. F.Perkins,
U. S. P. 1020655, 1020656, 1912; abst. J. S. C. I. 1912, 31, 453. E. Riboud
and C. Ahnert, F. P. 462451, 1913; abst. J. S. C. I. 1914, 33, 327.

3. H. Milligan and A. Board, E. P. 5269, 1911; abst. J. S. C. I. 1912,
31, 331. F. Strumberg, F. P. 472772, 1914; abst. J. S. C. I. 1915, 35, 504.
F. Norfolk, U. S. P. 480669, 1892. J. Dubiel, U. S. P. 493689, 1893. A.
Lenders, E. P. appl. 5512, 1919. U. S. P. 1305291 ; abst. C. A. 1919.13, 2143.

4. H. Miiller-Thurgau, Landw. Jahr. 1880, 8, 168; 1882, n, 751, 828;
1885, 14, 485, 851, 909; abst. J. S. C. I. 1886, 5, 169.

5. C. Cross and E. Bevan, Ber. 1909, 42, 2198; abst. J. S. C. I. 1909.
28, 806. C. Cross and J. Remington, E. P. 1035, 1899; abst. J. S. C. I. 1899,
18, 1038. Aust. P. 2186, 1900. L. Weil, E. P. 3217, 1901; abst. Chem. Ztg.
1902, 26, 587.

6. J. Macdonald, J. S. C. 1. 1887, 6, 334 ; abst. Jahr. Chem. 1887, 40, 2662.

7. H. Brunet, E. P. 2083, 1880.

STARCH 447

beans,^ beets,* cocao,' bread fruit,* apples,^ bananas,^ and others,'
have been some of the sources from which it has been proposed
to extract starch commercially. The starch from arrowroot, cas-
sava and manioc are articles of commerce. Wheat which was
formerly extensively used, has now been almost entirely replaced
by potatoes, com and rice. Com is used almost exclusively in
the United States, potatoes in Europe and rice in England.

Starch as an industry is concerned with production for three
distinct purposes, i. e., (a) for laundry purposes; (b) for edible
purposes, as in the manufacture of com, arrowroot and tapioca
starches; (c) as a size, dressing, or stiffening or filling material
for paper, thickening of mordants in calico-printing, and the pre-
paration of glucoses and syrups.

The history of starch is very ancient, although but little
definite was known as to its composition until the commencement
of the eighteenth century. The earlier processes of manufacttue
of starch in the United States* and in England,® are now mainly
of historical interest, although many of the mechanical devices

1. A. Pinel, E. P. 13508, 1914; abst. J. S. C. I. 1915, 34, 43.

2. J. Peklo, Bied. Zentr. 1911, 40, 386; abst. J. C. S. 1911, IM, ii, 763;
C A 1912 $ 3205.

3. P. Trojanowsky, Arch. Pharm. (3), 10, 32; abst. J. C. S. 1877, 32,
363; Jahr. Chem. 1877, 30, 937; Dingl. Poly. 1877, 223, 650.

4. Bull. Imp. Inst. (Suppl. to Board of Trade J. 1904, 2, 28); abst.
J. S. C. I. 1904, 23, 553.

5. G. Warcoilier, Compt. rend. 1905, 141, 405; abst. J. C. S. 1905,
88, ii, 753; J. S. C. I. 1905, 24, 981; Chem. Centr. 1905, 7$, II, 1266.

6. H. Waterman, Chem. Weekblad, 1915, 12, 552; abst. J. C. S. 1915,
108, i. 630; C. A. 1915, 9, 2775.

7. W. Burton, E. P. 1160, 1866. W. Buttenshaw, West Ind. Bull.
1904, 5, 1; abst. J. S. C. I. 1904, 23, 672.

8. U. S. Patents, 563, 2000, 7850, 13340, 17710, 22460, 26084, 27130,
28278, 40693, 44405, 56356, 63754, 65664, 66121, 67514, 67515, 67516, 68294,
73259, 81888, 87607, 89510, 116597, 135904, 137911, 137912, 140141, 141442,
145213, 151085, 158104, 169054, 174587, 181751, 202832, 214910, 225149,
227583, 230344, 231528, 233124. 234119, 234680, 235053, 241554, 245340,
245663, 248973, 250335, 253923, 254029, 254063, 257108, 259732, 263958,
270210, 270894, 272324, 276806, 278490, 280044, 284983, 285901, 294530,
294531, 307366, 319315, 329701, 332439, 337490, 354409, 363235, 374346,
406559 491234 596265

9.' English Patents, 565, 872, 971, 997, 1377, 2370, 1855; 482, 496,
1661, 1748, 2533, 1856; 238, 617, 1226. 1235, 2801, 3001, 1857; 335, 452,
1076, 1325, 1932, 1858; 1640, 1980, 2006, 2077, 2256, 2564, 1859; 148, 611,
1050, 1181, 1454. 3038. 1860; 358, 940. 2162, 2456. 2903, 3138. 1861; 42, 1717,
3284, 3314, 1862; 2839, 1863; 782, 1624, 1957. 1864; 88, 1319, 1865; 2924,
1866; 82. 83. 2941. 3171. 1868; 933. 1897, 1869; 2102. 3956, 1872; 2007, 2307.
1875; 2370. 2694. 3236. 3517, 1876; 1492. 1968. 3226. 4501, 1877; 823, 1879;
340, 884, 937, 2631, 1880; 3314, 1881; 236, 1591, 2014, 4224, 4277, 1882;
4146, 1883; 3101, 1885; 3304, 5270, 6285, 1887; 24511, 1894.

448 TECHNOWXJY OF CBl.I*ULOSE ESTERS

evolved, have come down to the present time with but compar-
atively unimportant modifications.

The manufacture of starch from wheat and com, may be
subdivided into the older fermentation or "sour** process, and the
Martin or non-fermentative process, the latter giving the higher
yield from a raw product of the same starch percentage.

. In the older method, the kernel was used either whole or
ground, more often in the former condition, being steeped in water
for some days, where a process of * Vetting*' or decomposition
takes place whereby the grain becomes much swollen and soft,
the water being periodically renewed to wash away the soluble
portions dissolved out. The swollen grain is then placed in bags
and submitted to pressiu-e until ruptured, the water which is
expressed, being milky from starch, is run off into settling tanks
for the starch to subside. The apparati of F. Kimball,* F. Mat-
thiessen,^ H. Humphrey,' A. Atkinson,* J. Schuman,* E. Roat,*
J. Tonkin^ and A. Murdoch* were used for this purpose. This
alternate pressing and adding fresh water was repeated until
nothing more was extracted (the expressed water was not milky),
when the filtrates were combined in order to make a more homo-
geneous product, and run into cisterns where it was allowed to
repose for from 10 to 30 days, depending upon the season of the
year. During this period of subsidence fermentation sets in,
which is accelerated by the addition of some of the sotu* liquid
from a previous batch. Fermentation gradually frees the starch
grain from its enveloping glutinous capsule, the latter becomes
softened and passes more or less into solution, and completely
loses its sticky and elastic properties. J. Jeffries separates by
means of rotating reels,® C. Meyer*® aids disintegration of the gluten

1. U. S. P. 275340, 1883.
- -2. U. S. P. 273572. 1883. F. Matthiessen and A. Be*T, U. S. P. 257959,
1882. F. Mattiessen and E. Quimby, U. S. P. 257958, 1882.

3. U. S. P. 231804, 1880. U. S. P. 250362, 1881.

4. U. S. P. 253337, 1882: abst. J. S. C. I. 1882, 1, 115.

5. U. S. P. 316404, 316405, 316406, 318307, 318308, 320400, 320401.
320402, 334090, 341282, 341283. 344410, 344411, 344412, 345926, 346320,
345927 379034.

6.' U. S. P. 254157, 254158, 254239, 2W240, 1882.

7. U. S. P. 258265, 1882.

8. U. S. P. 717699, 717700, 1903; abst. J. S. C. I. 1903, 22, 153. A.
Murdoch and Improved Process Manufacturing Co.. E. P. 319, 1903.

9. J. Jeffries, U. S. P. 1007782. 1007783, 1007784. 1007785, 191 1; abst.
J. S. C. I. 1911, 30, 1401. U. S. P. 1134615, 1915.

10. E. P. 1146, 1894; abst. J. S. C. I. 1895, 4, 55; Chem. Ccntr. 1895.
66, I, 941.

STARCH 449

by adding to the wash water a small percentage of chlorine, K.
Peche^ introduces specific bacteria, while H. Frasch^ manipulates the
process at a temperature below freezing, making the final separa-
tion by means of a perforated cylindrical corrugated iron drum.^

In the earlier stages of fermentation the natural occurring
sugars of the grain, as well as any dextrin resulting from the
action of the diastase upon unbroken starch grains, are converted
into alcohol, and this oxidized into acetic acid. This fermentative
process is continued until sufficiently far advanced to admit of
the starch granules being separated in a state of comparative
purity. The fermentation should, as far as possible, be confined
to the acetic, lactic and butyric ferments, and actual putrefac-
tion avoided as much as possible, due to the possibility of the
starch granule being attacked and passing into water-soluble
products. It is advizable to periodically agitate the mass during
the fermentation process in order to equalize the action as far as
possible.

As soon as the fermentation or ripening has progressed to
the desired stage, the supernatant liquid is withdrawn and dis-
carded, fresh water admitted, the contents well stirred and then
allowed to settle until the liquid is clear, when it is again with-
drawn. This is repeated until no more coloring matter is re-
moved. After the final decantation, the starch will be found to
have subsided in layers of different size particles of varying pur-
ity, the bottom layer being the purer. These layers are now
roughly removed with a shovel and transferred to different vats,
where they are agitated with water and passed through sieves of
varying mesh. The processes of S. Gaunt,* E. Wilhelm,^ C.
Tremain,« V. Taschl,^ W. Rochteschel,^ T. Mueller,^ L. MoreP",

1. D. R. P. 292864, 1914; abst. J. S. C. I. 1916, 35, 937; Chem. Ztg.
Rep. 1916, 40, 275; Zts. ang. Chem. 1916, 29, 359.

2. U. S. P. 717184, 1902; abst. J. S. C. I. 1903, 22, 153; Mon. Sci. 1903,
59, 110; Chem. Zts. 1903. 2, 375.

3. G. Baugue, F; P. 424131, 1910; abst J. S. C. I. 1911, 30, 287; Mon.
Sci. 1912, 77, 116.

4. U. S. P. 638707, 1899; 664257, 664258, 664250, 664260. 1900.

5. U. S. P. 243024, 1881.

6. U. S. P. 300165, 1888.

7. U. S. P. 1057685. 1913. E. P. 15258, 1912; abst. J. S. C. I. 1913, 32,
125. P. P. 446008, 1912; abst. J. S. C. I. 1913, 32, 125.

8.1U. S. P. 538794, 1895.

9. ^T. Mueller and J. Decastro, U. S. P. 273128, 1883.
lO.f Addn. 285, dated March 25, 1902, to F. P. 300237, 1900; abst. J. S.
C. I. 1903, 22, 106.

450 TECHNOU)GY OF CBI*I.UU)SE ESTERS

A. Graves,^ W. Allen' and W. Booth* give details of this portion
of the process.*

The utilization or disposal of this refuse water is an impor-
tant item in connection with the manufacture ofs tarch, especially
as to its liability to pollution when passed into streams and in-
terfering with the potability of the water.^ G. de Claubry* pre-
cipitates with milk of lime and a tannin solution, and uses the
sludge for manure; MarkF precipitates with lime. Other pro-
posals are^ -to neutralize with soda and evaporate, or precipitate
with alum; to extract the alcohol from the product after neutral-
ization;' Burggraf*® distributes it over meadow land in the raw
state as a fertilizer, and Maercher*^ records definite results in sup-
port of the idea. R. Schuetze,^' H. Schreib,** h. Seelos.^* B.
Steckel*^ and others" have also put forth suggestions.

After the starch has settled in the purifying vats, the super-
natant water is decanted, and this process repeated until the
wash water shows practically no total solids, indicating all the
water soluble material has been removed from the starch sub-
stance. In this process N. and J. Bloch*^ uses a hoUander with
fine mesh screen, and T. Blumenthal*^ has described a continuous
system of washing, which is said to greatly reduce the time of
purification. The starch is then either removed from the vats
by means of wooden shovels as in the manual method of C.

1. U. S. P. 246671, 248734, 250143, 251574, 1881 ; 256315. 1882; 2703(H.
1883:362502, 1887.

2. U. S. P. 257318, 257319, 257320, 1883.

3. E. P. 3188, 1857. W. Booth and A. Bell, U. S. P. 256630, 1882.

4. I. Palmer, U. S. P. 222527, 1879; 304851, 1884; 346602. 1886.

5. Anon. Dingl. Poly. 1877, 225, 394; abst. J. C. S. 1877, 32^ 943.

6. Dingl. Poly. 1837, 63, 465; 1841, 80, 399.

7. ' Dingl. Poly. 1874, 214, 225.

8. vSce Dingl. Poly. 1838. 68, 406.

9. J. Naylor, U. S. P. dated March 7, 1803.

10. Dingl. Poly. 1835, 56, 464.

11. Zts. Landw. Central. Prov. Sachsen, 1876, 7.

12. Undw. Vers. St. 33, 197; abst. J. S. C. I. 1886, 5, 612.

13. Zts. ang. Chem. 1888, 1, 694; abst. J. S. C. I. 1889. 8, 127. Chem.
Ztg. 1890, 14, 1323; 1891. 15, 1864.

14. Zts. f. Hyg. 1899, 31, 469; abst. Zts. Untersuch. Nahr. u. Genussm.
1900, 7, 503; J. S. C. I. 1900, 13, 916; Chem. Centr. 1899, 70, II, 158.

15. D. R. P. 74359, abst. Woch. f. Br. 1896, 276.

10. C. Peifke, Zts. Spiritusind. 1884, 219; Chem. Tech. Rep. 1884, 23,
I, 277. D. R. P. 25740 (second addn. to 15741). Chem. Ind. 1884, 7, 237.
Zts. Spiritusind. 1888, 373; 1894, 324. Mitth. ges. Starke, 1890, 92; 1891, 140.

17. D. R. P. 4262, 1878.

18. D. R. P. 10579, 1880; abst. Wag. Jahr. 1880, 26, 636.

^ARCH 451

Black^ or the mechanical process of D. Wilder,^ or else stirred up
with water to a thin magma and allowed to flow over starch
planes' where the starch deposits by gravity into a compact
mass.^ H. Holden removes the impurities from the liquor by
entanglement in a voluminous froth produced by the injection of
air, the froth being carried over into a separate receptable.* In
the Verley method* nitrogenous and other impurities are elim-
inated by suspending the starch in water to form a milk of about
12^ B^., then agitating with a small portion of alkaline hypochlo-
rite and allowing to stand for several hoursJ"^®'^®'^^"'*''^**^^'"**^** S.
Aston *• advocates the use of fine cylindrical sieves for the final
starch separation, while other mechanical devices have been pat-
ented for this purpose by R. Sherman,^" G. Luthy^* and more
recently by W. Bartholomew and C. Leary.^*

Irrespective of the method of transference of the starch, it

1. U. S. P. 1131318, 1915.

2. U. S. P. 1102376, 1914.

3. Davenport Glucose Manufacturing Co., E. P. 6166, 1885; abst. J. S.
C. I. 1885, 4, 542.

4. O. Steppacher, U. S. P. 1094175, 1914.

5. H. Holden, U. S. P. 1221990, 1917; abst. J. S. C. I. 1917, S6, 607.

6. F. P. 330914, 1902; abst. J. S. C. I. 1903, 22, 1097; Mon. Sci. 1904,
a, 135; 1906, €5, 39; 1909, 71, 27.

7. G. Kandler, Aust. P. 32974, 1908.

8. P. Grimm, U. S. P. 258265, 261445, 264688, 296000, 303930, 3^634,
440262.

9. E. Kesztler, Zts. Spiritusind. 1902, 25, 249; abst. J. S. C. I. 1902,
21, 982. Aust. P. 4538, 1901.

10. H. Lafferty, E. P. 9431, 1886; abst. J. S. C. I. 1886, 5, 542.

11. M. Maercker, Landw. Versuch-Stat. 22, 69; abst. J. C. S. 1878, 34,
969. Landw. Stat. 1879. 23, 69. Bied. Centr. 1880, 501 ; abst. J. C. S. 1880,
38, 915. Zts. Spiritusind. 1883, 371, 391, 409, 501, 503; 1886, 204; 1887, 50.
Zts. anal. Chem. 1885, 24, 617. Maercker, Handbuch der Spiritusfabrikation,
VI Aufl. 1894. M. Maercker, P. Behrend and A. Morgan, Vers.-Stat. 1880,
25, 107.

12. W. Wiesebrock, E. P. 2208, 1885; abst. J. S. C. I. 1885. 4, 358.

13. F. Moll, D. R. P. 35482, 1885. J. Moll, Bot. Instit. Wiirzburg,
1878, 1, II, 105.

14. A. Parks, E. P. 8893, 1891; abst. J. S. C. I. 1891, 10, 844.

15. E. Root, U. S. P. 254239, 254240, 1882; abst. J. S. C. I. 1882, 1, 157.
U. S. P. 264157, 254158, 1882; abst. J. S. C. I. 1882, 1, 157.

16. F. Stiker, U. S. P. 270260, 320430, 327035, 327345.

17. F. and E. Verbiese, F. P. 361534, 1905. F. P. addn. dated June 5,
1905 to F. P. 361634, 1905; abst. J. S. C. I. 1906, 25, 947.

18. T. Wagner, U. S. P. 816624, 1906. E. P. 2242, 1906; abst. J. S. C.
I. 1906, 25, 1229.

19. F. P. 452395, 1912; abst. J. S. C. I. 1913, 32, 707.

20. U.S. P. 1147899, 1915.

21. U. S. P. 346820, 1886.

22. U.S. P. 1211385, 1917.

452 TECHNOI.OGY OF CELLUI^OSE ESTERS

is next placed in canvas lined wooden boxes, 48 by 12 by 6 inches
deep, where it is drained or dried into a compact mass. In the
processes of J. Berrigan,^ R. Wilson,* J. Foulis,' Gautron,* G.
Hennig,*^ W. Jaeger-Koenkendorf,*^ G. Kerr,^ F. Melkersman,^
N. MiUer,» M. Moll,*^ C. Rudolph,ii R. Schrader,i* delaTouche^'
and others,** the final separation is made by means of a centrifuge,
which not only removes more water, but causes the starch to
more firmly compact — ^which usually is desirable. When the
maximum of moisture has been removed, the starch is taken from
the box or centrifuge, and is cut into cubes of 4 to 5 inches on
a side. In one method the cubes are placed upon porous bricks
to absorb more water, and in such a manner that the under sur-
face of the starch does not become hard and homy. Of the many
methods which have been devized for this preliminary drying
process, those of H. Neuberger and F. Bergh," Harburger
Starke-Fabrik,*6 J. Lyman," W. Liess and M. Maher,*^ W. Len-
ders,*^ C. Haug and H. Magnuson,*° E. Gudeman,** C. Drumm,'*
Drumm & Co.,*' O. Beusterien** and A. Baroody*^ appear to be the

1. U. S. p. 994497, 1911; abst. J. S. C. I. 1911. 30, 914.

2. E. P. 10956, 1894; abst. J. S. C. I. 1895, 14, 590.

3. D. R. P. 35260, 1885.

4. Dingl. Poly. 1863, 169, 315.

5. Zts. Spiritusind. 1883, 526; 1884, 4.

6. D. R. P. 43550, 1888; abst. Zts. Spiritusind. 1888, 283; Wag. Jahr. •
1888, 34, 590.

7. U.S. P. 471614, 473511.

8. U. S. P. 195718, 1877.

9. U. S. P. 235001, 1880.

10. D. R. P. 33677. 1885.

11. D. R. P. 18712, 1881; abst. J. S. C. I. 1882, 1, 416; Wag. Jahr. 1882,
2S, 684 ; 1883. 29, 670. D. R. P. 19593, 1882; addn. to D. R. P. 18712, 1881 ;
abst. J. S. C. I. 1882, 1, 464.

12. U. S. P. 757778, 1904; abst. J. S. C. I. 1904. 23, 554.

13. Dingl. Poly. 1850, 118, 236; Mon. Ind. 1850, 1494.

14. Anon, le Technologiste, 1859, 32; abst. Poly. Centr. 1859, 25, 1697;
Dingl. Poly. 1860, 155, 237.

15. U. S. P. 1(M7831. 1912; abst. J. S. C. 1. 1913, 32, 102; C. A. 1913,
7, 914; Chem. Ztg. Rep. 1913, 37, 250.

16. F. P. 376767, 1907; abst. J. S. C. I. 1907, 26, 980. Aust. P. 45188.
1910. F. Th6rl, U. S. P. 990929. 1911. E. P. 9931, 1907; abst. J. S. C. I.
1907, 26, 980. D. R. P. 206763.

17. U. S. P. 721314, 1903; Mon. Sci. 1903. 59, 101.

18. U. S. P. 284447, 1883. W. Lies, U. S. P. 275394, 1883.

19. U. S. P. 1223406 1917; abst. J. S. C. I. 1917. 36, 607.

20. U. S. P. 1162771, 1915.
91 U S P 789127 1905

22! d'. R. p. 217335, 1908; abst. J. S. C. I. 1910. 29, 710; Wag. Jahr.
1910, 56, II, 258; Chem. Zentr. 1910, 81, 1, 492; Chem. Ztg. Rep. 1910, 34, 46.

23. E. P. 5260. 1884.

24. E. P. 12624, 1895.

25. U. S. P. 844911, 1907.

STARCH 453

most meritorious.* H. and R. Littmami^ compress the starch
into spheres. A novel method of compacting has been put for-
ward,' which consists in dropping the starch through a zone of
steam and hot air which superficially gelatinizes the starch and
causes it to adhere into lumps.*

At the conclusion of this preliminary drying, the starch con-
tains from 25% to 30% of water. The remaining moistitre may
be removed by placing the starch in wagons having foraminous
sides,* or in trays with cloth bottoms,* and subjecting to a heat
of 45®-55°, until the desired moisture content is reached, the
drying being carried on at atmospheric pressure, or, as in the
processes of E. Passburg' and L. Maische,* under partial vacuum.
C. Vidal® and C. Pope*^ dry under hydraulic pressure, the latter
at 500 pounds per square inch.^*"^* The Banque du Radium^ bleach
and preserve the finished starch by placing the flour on a travel-
ing band which passes beneath a quartz plate fitted in a chamber

1. M. Petersen, E. P. 11416, 1899; abst. J. S. C. I. 1899, 18, 776. U. S.
P. 649210 1900.

2. E. P. 1651, 1905. See also E. P. 1661, 1879; 12624, 1895.

3. H. Neuberger and F. Bergh, U. S. P. 1047831, 1912.

4. W. Lake, E. P. 4967, 1885.

6. L. Bauer, U. S. P. 1035302, 1912; abst. J. S. C. I. 1912, 31, 1089.
F. P. 13984 1912.

6. N.'Vagn. E. P. 5225, 1905; abst. J. S. C. I. 1906, 25, 86.

7. D. R. P. 28971, 1884.

8. D. R. P. 23355, 1882; abst. J. vS. C. I. 1884, 3, 113.

9. E. P. 1661, 1879. D. R. P. 6969, 1879.

10. U. S. P. 595408, 1897.

11. H. Benoist. F. P. 425430, 1911; abst. J. S. C. I. 1911, 30, 914. H.
Benoist and L. GraiUot, F. P. 373174, 1907; abst. J. S. C. I. 1907, 26, 704.

12. F. Wiesebrock, D. R. P. 34950, 1885. U. S. P. 312592, 312593,
333908, 346003. E. P. 2208, 1885.

13. Wever, Zts. Spiritusind. 1892, 9. Landw. Centr. f. Prov. Posen,
1892 311.

14. C. Schongart, D. R. P. 13678, 1880.

15. E. Perkins, U. S. P. dated Sept. 16, 1810. U.S. P. 815373, 1906;
abst. J. S. C. I. 1906, 25, 385.

16. J. Merrill, U. S. P. 1183097, 1916; abst. J. S. C. I. 1916, 35, 858.

17. R. Johnson, U. S. P. 227537, 1880; 323425, 1885.

18. J. Hundhausen, U. S. P. 603447. 1898. E. P. 22918, 1895; abst.
J. S. C. I. 1896, 15, 887. D. R. P. 80922, 1894. Zts. Spiritusind. 1895, 225.

19. J. Gorlt, D. R. P. 23590, 1882.

20. G. Full, U. S. P. 260188, 1882.

21. C. Fehrmann, D. R. P.- 29600, 1884. Dingl. Poly. 1885, 256, 35;
abst. J. S. C. I. 1885. 4, 356.

22. L. Bauer, U. S. P. 583783, 1897; 1035302, 1912; abst. J. S. C. I.
1912,31,1089. 1061720, 1912; abst. J. S. C. I. 1913, 32, 669. 1099276,1914.
1101071, 1914; abst. J. S. C. I. 1914, 33, 801. 1161826, 1915; abst. J. S. C. I.
1916, 35, 134. 1175113, 1175114, 1916; abst. J. S. C. I. 1916, 35, 482. L.

454 TBCHNOWX5Y OF CELI^UtOSK ESTJgRS

containing an arc lamp, a Geissler tube, a mercury \rapor lamp, or
other source of ultraviolet or similar rays.^"*' J. Harley ^^ dries starch
in an atmosphere charged with steam, the claim being that the
starch is rendered less brittle." If the starch is to be powdered
("depulverized") before being offered for sale, the methods of P.
Dreesbach,** J. Benoid" or W. Bust'* may be used. Starch for
nitration or acetation must be free from oil. This may be re-
moved by chloroform,** ligroin or carbon tetrachloride extraction.*®
In Martin's process, flour instead of the whole grain is em-
ployed, the first operation being kneading into a stiff dough as
in bread-making, when it is allowed to remain at rest until the
mass becomes thoroughly and uniformly saturated with moisture.

Bauer and T. Speck, V. S. P. 986M0, 986541, 1911; abst. J. S. C. I. 1911, 30,
503.

23. Corn Products Refining Co., F. P. 445289, 1912; abst. J. S. C. I.
1912, 31, 1089.

24. Sudenburger Maschinenfabr. and Hisengiesserei A. G., D. R. P.
261259, 1912; abst. J. S. C. I. 1913, 32, 837.

25. F. P. 428969, 1910; abst. J. S. C. I. 1911, 30, 1276.

1. M. Blumenwitz, Uhland Mach. Construe. 1874, No. 11, 173.
Bohmer, D. R. P. 22332, 1882. A. Buttner and C. Meyer, D. R. P. 34031,
1884. D.'R. P. 45080, 1888; 52578, 1889; 61659, 1891; 68074, 1892; 69808,
1892. W. Gintl, Dingl. Poly. 1874, 214, 221. J. Habrich, D. R. P. 29985,
1884. F. Kochlin, Dingl. Poly. 1851, 120, 364. G. Lindenmeyer, Dingl.
Poly. 1868, 109, 131. E. Nussbaum, E. P. 15700, 1907. H. Rodewald, Vers.-
Stat. 1894, 45, 201. R. Sclimidt, Dingl. Poly. 1863, 109, 257; 1865, 177, 116.
Schonn, Dingl. Poly. 1870, 195, 469. A. Winton, Zts. ang. Chem. 1888, 1,
273. Zts. Spiritusind. 1888, 188; 1889, 326, 361; 1890, 289, 368; 1894,
51, 391.

2. J. Hurty, U. S. P. 395977, 1889.

3. H. Wiegand, U. S. P. 392389, 1888.

4. J. Van Deinse and M. Reiseger, U. S. P. 444127, 1891.

5. J. Rubiel, U. S. P. 493089, 1893.

6. J. Ostenburg, U. S. P. 447790, 450492, 1891.

7. A. Moffatt, U. S. P. 541941, 545128, 1895.

8. J. O'Neill, U. S. P. 584399, 1897.

9. U. S. P. 50i)512 1893.

10. J. arid F. Firmcnich, U. S. P. 200380. 1882. J. and G. Firmenich,
U. S. P. 560699, 1896.

11. C. Gordon, U. S. P. 596058, 1897.

12. A. Osborn, U. S. P. 746369. 1903.

13. C. Tyler, U. S. P. 1013337, 1912; 1157738, 1915; abst. J. S. C. I.
1915, 34, 1220. 1190690, 1916.

14 U S P Re- 1123 1883

is! M.^Holauljek, F. P. 353730, 1905; abst. J. S. C. I. 1905, 34, 1079.

16. U. S. P. 1186893, 1186894, 1916; abst. J. S. C. I. 1916, 35, 860.

17. U. S. P. 867235, 1907. E. P. 14205-A, 1906.

18. U. S. P. 1046261 1912.

19] g! Hertel and G. Hornung, D. R. P. 220850, 220851, 1909; abst.
T S C. I. 1910 29 649.

20. E. Carez and Soc. Gen. du Maltose, E. P. 3606, 1890.

STARCH 455

This requires from 30 to 60 minutes, depending upon the surround-
ing temperature. For the separation of the starch from the
gluten the dough is placed in a wooden trough containing a rec-
tangular frame which mechanically oscillates. Above the trough
fine jets of water impinge upon the dough which is mechanically
kneaded, the wash water running away into settling cisterns,
where the starch is allowed to subside. The dough before wash-
ing is subdivided into small balls for convenience in extracting
the starch, washing being continued until substantially only the
gluten remains, and until the wash water runs nearly clear.
Should any particles of gluten become detached and mingle with
the wash water, they are caught by a trap arrangement.

The purification of the starch is effected in much the same
manner as previously described by means of repeated decanta-
tions. Martin improved upon his original process, by supplant-
ing washing with pure water, by washing with dilute sodium
hydroxide solution. While this does give a better product, much
experience and care is required to keep the proper alkalinity at
the various stages of the washing process. In starch produced
in this manner, excellent results are obtained by drying in the
R. Wilson apparatus. ^~^

In W. Uhland's apparatus the grain is first fed through a
hopper to a pair of crushing rollers together with dilute alkali,*
where it falls into a mixing chamber provided with a pair of re-
volving beaters.® The pure starch obtained is separated from
the crude by mechanical means.*® In the block process of drying,
he" mechanically removes the yellowish layer which forms upon
starch blocks during the drying process.*^

1. E. P. 10956 1894.

2. G. Pereire, F. P. 3^3110, 1903; abst. J. S. C. I. 19a3, 22, 1301.

3. J. Grossfeld, Zts. Untcrs. Nahr. Genussm. 1915, 29, 51; abst. Zts.
ang. Chem. 1915, 28, 223 R; J. S. C. I. 1915, 34, 676.

4. O. Frobcrg, U. S. P. 1158040, 1915.

5. C. Moore, U. S. P. 1010761, 1912.

6. J. Hilton, E. P. 25242, 1894; abst. J. S. C. I. 1895, 14, 376.

7. C. Tyler, U. S. P. 1013337, 1912.

8. E. P. 4256, 1883.

9. E. P. 425, 1905: abst. J. S. C. I. 1905, 24, 629.

10. E. P. 14428, 1900; abst. J. S. C. I. 1901, 20, 916.

11. E. P. 23866, 1897.

12. U. S. P. 725180, 19a3; abst. J. S. C. I. 1903, 22,642. 784450, 1905;
abst. J. S. C. I. 1904, 23, 795. 860068, 1907. F. P. 338792, 1903; abst.
J. S. C. I. 1904, 23, 795. 348992, 1904; abst. J. S. C. I. 1905, 24, 629. D.
R. P. 26521, 36250, 37231, 40922, 79245, 79961, 126203, 135312, 159088,

456 TECHNOWXJY OP CEl,I.Ul,OSE ESTERS

W. Jebb.^-» W.Klopfer,^0'ii A. Anderson," A. Hoyt/»-« C.
Moore,"'" F. Kaehl,** J. Loiselet,i» A. Schumann,*^ H. Vivien,"
A. Boemer,** S. LiUie,^' and F. Klopfer** are, among others,** the

159351, 174624, 251907. 1911; abst. J. S. C. 1. 1913,32, 41. 267199. 1911;
abst. J. S. C. I. 1914, 33, 36. Aust. P. 9150, 1902; 14885. 1904; 24086,
25506, 1906; 29068, 1907; 59129, 1913.

1. J. Jebb, U. S. P. 270439, 1883.

2. T. Jebb and A. Bennett, E. P. 3366, 1880.

3. T. and W. Jebb. U. S. P. 239171, 241666, 243269, 243270, 249056,
256221, 258070.

4 E P 386 1881

5! W. Jebb, U. S. P. 263525. 320361, 347611. 347612.

6. W. Jebb, E. P. 995, 1882; abst. J. S. C. I. 1882, 1, 376. E. P. 4209,
1882.

'7. W. Jebb, E. P. 4948, 1885; abst. J. S. C. I. 1885, 4, 748. E. P.
4954, 1885; abst. J. S. C. I. 1885. 4, 748. E. P. 4956, 6139, 1885.

8. W. Jebb. E. P. 508, 1886.

9. W. Jebb, D. R. P. 17815. 1881; abst. J. S. C. I. 1882, 1, 242.

10. U. S. P. 929861. 1909; abst. J. S. C. I. 1909. 28, 999. 1013497, 1912;
abst. J. S. C. I. 1912, 31, 144. E. P. 11159, 1907; abst. J. S. C. I. 1907, 2$,
1289. E. P. 19726, 1908; abst. J. S. C. I. 1909, 28. 379.

11. F. P. 394802, 1908; abst. J. S. C. I. 1909, 28, 379. D. R. P. 200774.
Aust. P. 38297 1909.

. 12.* U. vS.'p. 707892, 1902; 1035829 to 1035842, 1912; abst. J. S. C. I.
1912, 31,944.945. 1129440. 1915. E. P. 13353, 1902; abst. J. S. C. I. 1902,

21, 1189. 18946. 18949. 18950. 1912; abst. J. S. C. I. 1912, 31, 944, 945.
F. P. 321842, 1902; abst, J. S. C. I. 1902. 21, 1189.

13. U. S. P. 709544. 1902; abst. J. S. C. I. 1902, 21, 1288. 710461,
1902; 1148453, 1148454. 1915; abst. J. S. C. I. 1915, 34, 917.

14. E. P. 9790, 1915; abst. J. S. C. I. 1915, 34, 702.

15. F. P. 479236, 1915; abst. J. S. C. I. 1915, 34, 1029. Aust. P. 76153,
1915.

16. U. S. P. 1016761. 1016762, 1912; abst. J. vS. C. I. 1912, 31, 245;
1166801, 1915; abst. J. S. C. I. 1915, 34, 1157. 1224951, 1917; abst. J. S. C.
I. 1917, 36, 607.

17. E. P. 22655. 1909; abst. J. S. C. I. 1909, 28, 1123. E. P. 530, 1914;
abst. J. S. C. I. 1914. 33, 1217.

18. D. R. P. 155562, 1903; abst. J. S. C. I. 1905, 24, 629.

19. U. S. P. 702571, 1902; abst. J. S. C. I. 1902, 21, 982.

20. E. P. 5459. 5460. 1887; abst. J. S. C. I. 1888, 7, 334, 335.

21. E. P. 16827, 1886; abst. J. S. C. I. 1888. 7, 41.

22. E. P. 16262, 1904; abst. J. S. C. I. 1905, 24, 808. F. P. 345370,
1904; abst. J. S. C. I. 1904. 23, 1229.

23. U. S. P. 1014311. 1023257. 1038397, 1912.

24. U. S. P. 1013497 1912.

25! H. Barker. E. P. 4741, 1889; abst. J. S. C. I. 1889. 8, 633. Im-
proved Process Manufacturing Co., F. P. 328293. 1903; abst. J. S. C. I. 1903,

22, 957. G. Goldbeck, Chera. Ztg. 1915, 39, 680; 1916, 40, 829; abst. J. S.
C. I. 1915, 35. 1065; 1916. 35, 1169. J. Keil, E. P. 17444. 1897; abst. J. S.
C. I. 1897, 16, 927. H. Keil and R. Stoltenhoff. E. P. 6778. 1888; abst.
J. vS. C. I. 1889. 8, 298. H. Longsdon and J. Mahon, E. P. 11089, 1907. W.
Midgley, U. S. P. 319598, 1885; Re- 10722, 1886. J. Poison and J. Harley, E. P.
2703, 1883; abst. J. S. C. I. 1884. 3, 113. U. S. P. 285067, 1883. S. Spitzer.
IJ. vS. P. 329229, 1885; 361788, 1887; 386363, 1888. E. P. 4181, 1890; abst.
J. S. C. I. 1890, 9, 7,>4. H. Sulman and E. Berry, E. P. 2138, 1887; abst.
J. S. C. I. 1887, 6, 375. C. Tolhurst and A. Goldthwaite. U. S. P. 707985,
707986, 1902; abst. J. S. C. I. 1902, n, 1190. H. Vuylstcke, E. P. 21344,
1894.

STARCH 457

more important of those who have suggested improvements upon
the basic process as outlined above. C. Dobrin^ has called at-
tention to the fact that the seeds of different sorghums contain
about 60% of starch and has devised a process for its extraction.

Manufacture of Starch from Potatoes. In the earlier days
of starch manufacture, considerable quantities were produced in
the United States and Great Britain from potatoes, but in France
and Germany — especially the latter country — ^more attention has
been paid to the development of the potato from the view-point
of starch producing, and, as has been previously stated, the Ger-
mans by cross-fertilization, selection of species and fertilization,
have been able to raise the average starch content of these tubers
from 25%-40%. In these two latter countries not only is the
home market supplied, but large quantities are annually ex-
ported in normal times. The earlier processes developed in Ger-
many* and in France,' are advancements primarily due to agri-
cultural chemical research.

As the result of the examination of 61 varieties of potatoes,
X. Raab* found the total solids to vary from 16%-34%, and the
starch content from 9%-26%.* . In a series of comparative tests
on the cultivation of potatoes, in which thirty-seven varieties
were examined, H. Nitykowski* found the yield to vary from
9697 k. per 5000 sq. m. to 4167 k. per 5000 sq. m.^ Tables for
the calculation of the relation between the quantity of starch in
potatoes and their relative density have been prepared.* F.

1. Zts. Spiritusind. 1897, 20, 418; abst. J. S. C. I. 1898, 18, 59.

2. The following are German Patents on the manufacture of potato
starch: 528, 2686. 10242, 10497, 10899, 11404, 13279, 15428, 16373, 17470,
19754, 20344, 21358. 21786, 21889, 22622, 22716. 24312. 24502, 24629. 25755.
26115, 26202, 28277, 28356, 28401, 29025, 33625. 35693. 36569, 45284, 52781,
56558.

3. F. P. 62285, 62618, 62759, 68271, 68368, 69065, 70176, 70223, 70771,
75542. 77064, 77660. 78826, 79195, 79644, 80194, 81176, 81213, 82059, 85604,
86843, 87622, 88227, 90985, 106658, 114381, 114927, 116114.

4. T. C. S. 1872, 25, nil; abst. Chem. Centr. 1872, 43, 424; N. Jahr.
Pharm. 37, 204; Jahr. Chem. 1872, 25, 804.

5. A. Fesca. Dingl. Poly. 1868, 187, 435; Wochenbl. preuss. Ann.
Landw. 1867, No. 48; Poly. Notizbl. 1868, 23, 97; Poly. Centr. 1868. 34,
696; Wag. Jahr. 1868, 14, 454.

6. Dingl. Poly. 1883, 248, 381 ; abst. J. C. S. 1884, 46, 134; Jahr. Chem.
1883, 36, 1745; Wag. Jahr. 1883, 29, 668.

7. O. Abesser, Zts. Landw. Centr. Provinr Sachsen, 1874, 204.

8. F. Heidepriem. Landw. Vers. Stat. 1877, 20, 1; abst. J. C. S. 1877,
32, 233; Bull. Soc. Chim. 1878, 29, 92; Chem. Tech. Rep. 1877, 16, I, 363;
Jahr. Chem. 1877, 30, 1208.

458 TECHNOUXJY OF CBLLUtOSR ESTERS

Lankow^ claims that potatoes may be preserved without first
being subdivided, by freezing, thawing, pressing and drying, and
that a material rich in sugar is produced by freezing slowly for
a long time, and one high in dextrin and starch by freezing rapidly.'

The manufacture of potato starch on the Continent com-
prises the distinct operations of steeping, washing, disintegrating,
removal of the starch, purification, washing, draining and drying,
either centrifugally or in the air.'

Potatoes which have been raised on heavy ground are cov-
ered with adherent dirt so tenaciously that simple washing is not
sufficiently energetic treatment to remove the dirt, and they are
given a preliminary soaking in clear water for several hours,* and
then washed in a hollow revolving cylinder, the periphery of
which is composed of heavy wire of large mesh, in order to admit
of the softened dirt running out.* This cylinder is partly
immersed in a trough of water, revolving slowly, the friction of
the potatoes rubbing against each other being sufficient to effect-
ually remove all extraneous impurities. The operation is con-
tinuous, the potatoes being fed in at one end, and emerging
cleaned at the other, where they fall into a rasping* or grating
machine,^ where the starch cells are ruptured, and a critical step

1. E. P. 1048, 1905; abst. J. S. C. I. 1906, 24, 1182.

2. E. Schulze, Ber. 1874, 7, 1047; abst. Chem. Centr. 1874, 45, 645;
Chem. Tech. Rep. 1874, 13, II, 144; Dingl. Poly. 1874, 214, 339. J. prakt.
Chem. 1883, 136, 311; abst. J. C. S. 1884, 46, 284. Zts. Spiritusind. 1883.
1037; 1884, 109; 1887. 12; 1888, 341. Chem. Ztg. 1891, IS, No. 29; Zts.
Spiritusind. 1894, No. 18. E. Schulze and Barnieri, Vers. -Stat. 1878, 21, 63.
E. Schulze, J. Barbiere and Engster, Landw. Vers.-Stat. 21, 63; 27, 357.

E. Schulze and E. Eugster, Vers.-Stat. 1882, 27, 357; abst. Zts. Spiritusind.
1883, 25. E. Schulze and M. Maercker, J. Landw. 1872, 52. E. Schulze and
SeliwanoflF, Vers.-Stat. 1887, 34, 403.

3. B. Fricker, Zts. Spiritusind. 1885, 76, 120. D. R. P. 39144. 1886.
Verein der Spiritus-Fabr. D. R. P. 286106, 291307, 291308; abst. J. S. C. I.
1916, 35, 192; 1919, 38, 595-A. v. Eckcnbrecher, Zts. Spiritusind. 1888, 16;
1894, 33, 210; 1895, 27. H. Czubata, Bied. Centr. f. Landw. 1880, I, 472.
See C. Putsche translation of A. Dubief, "Starchmeal from Potatoe," 1831.

F. Anthon, Dingl. Poly. 1859, 154, 69. Zts. Spiritusind. 1893, 375. Andrew.
Dingl. Poly. 1843, 87, 396.

4. G. Gerson, Zts. Spiritusind. 188,3, 723; 1884, 57; abst. Chem. Tech.
Rep. 1885. 24, I, 178; Chem. Ztg. 1885, 9, 602; Jahr. Chem. 1883. 38, 1726.

5. Cbampannois, Dingl. Poly. 1867, 183,351; 188, 193; J. Fabricantes
de Sucre. 1867, Jan. 3d; Bull. Soc. d 'Encouragement, 1867, 390.

6. C. Steffen. E. P. 24035, 1906; abst. J. S. C. I. 1907, 28, 883. F. P.
368002, 1906; abst. J. S. C. I. 1906, 25, 1230. Addn. dated Dec. 12, 1906,
to F. P. 368002, 1906; abst. J. S. C. I. 1907, 28, 710. Aust. P. 37417, 1909;
41706, 1910.

7. H. Tryller, D. R. P. 242168, 1910; abst. J. S. C. I. 1912. 31, 505;
Wag. Jahr. 1912, 58, II, 339; Chem. Zentr. 1912. 83, I, 388; Chem. Ztg. Rep.
1912, 38, 61; Zts. ang. Chem. 1912, 25, 924; C. A. 1912. 8, 2190.

STARCH 459

in the process is to be asstired that the highest possible percentage
of cells are ruptured, since it is from these only that the starch
granule is removed.^

In order to separate the starch from the coarser bits of fiber,
the pulp is washed with water over brass sieves of varying de-
grees of fineness, and the coarser portions retained on the sieve.
Several forms of apparatus have been designed for this purpose,*
the object being to completely exhaust the pulp in the shortest
possible time with the minimum amount of wash water. A slight in-
crease in starch is obtainable by grinding the pulp after rasping,
factory practice indicating an increase of starch by 7%-10%.'
As the starchy liquor comes from the sieves, it usually contains
some fine sand which was not separated during the washing of
the potatoes, and was too fine to be held back by the sieves.
The starch liquor is therefore run into large tanks provided with
agitators, where the solution is vigorously stirred, and allowed
to remain at rest just long enough to allow the sand particles to
deposit, when the liquor is run off into other containers and the
impure starch allowed to subside.*

After several washings, sometimes in slightly alkaline water,

1. h. Gunther. Zts. Spiritusind. 1884, 93. D. R. P. Dec. 24, 1880.
Zts. Spiritusind. 1886, 126. D. R. P. Jan. 25, 1881. E. Wollny, Saat und
Pflege der Landw. Kulturpflanzen, 1885, 141. Porschungen Gebiete der
Agrikulturphysik, 1891, 14, 286. Volkers, Dingl. Poly. 1840, 76, 213. P.
Stohmann, Wag. Jahr. 1859, 5, 328. Zts. anal. Chem. 1870, 9, 275. W.
Snell, Dingl. Poly. 1844, 93, 281. Schattenmann, Dingl. Poly. 1863, 130,
72; Mon. Ind. 1853, No. 1789. J. Nessler, Dingl. Poly. 1871, 200, 342. G.
Neuhauss, Zts. Spiritusind. 1886, 464. O. Lorenz, Prakt. Machinconstr.
1883, 311, 323. Zts. Spiritusind. 1894, 77; 1896, 88. Dingl. Poly. 1846,
101, 426. J. Hannay, Dingl. Poly. 1877, 223, 548; Chem. News, 1876, 34,
155. L. Foissey, Zts. Spiritusind, 1895, 159.

2. H. Werner, "Die Aufbewahrung der Kartofifel. Kartoffelbau, 1895,
3 Ed. 170. Dingl, Poly. 1845, 97, 1158. Dingl. Poly. 1877, 22S, 394.

3. H. Eichhorn, Ann. Phys. Chem. 1852, 87, 227. F. Cloez, Dingl.
Poly. 1874, 211, 397; abst, J. C. S. 1874, 27, 1015; Bull. Soc. d'Enc. 1873,
553. A. Clerget, Dingl. Poly. 1846, 99, 71. v. Canstein, Bied. Centr. 1878,
1,368. A.Baudry,I.aFeculerie(Compiegne). 1892, 11. D. R. P. 85889, 1895.

4. B. Dietzell, Dingl. Poly. 1869, 193, 233. B. Frank, Zts. Spiritusind.
1896, 136. B. Frank and F. Kriiger, Arbei. Deut. Landw. Ges. 1894, II.
Zts. Spiritusind. 1896, 1. B. Frank and Sorauer, Deut. Landw, Ges. 1892.
F. Heine, Zts. Spiritusind. 1883. E. Habn, Zts. Spiritusind, 1894, 154. F.
Holdefleiss, Landw. Jahr. 1877, €, I Suppl. 107. See Homung and Scheibner,
"Neues Einmietungsverfahren ftir Riiben und Kartoffeln mit selbstthatiger
VentilaUon," Berlin, 1891. Huck, Dingl, Poly. 1846, 102, 361. J. Hunger-
buhler. Vers. Stat. 1886, 32, 387. H. Karsten, Vers. Stat. 1865, 7, 490.
E. Kramer, Bied. Centr. 1881, 717; abst. J. C. S. 1882, 42, 242. Oest. Landw.
Centr. 1891, 11. U. Kreusler, Landw. Jahr. 1886, 15, 309. U. Kreusler and
P. Dafert, Landw. J. 1894, 767. Krocker, Dingl. Poly. 1^49, 112, 143; Byz.
Jahr. 1848, 27, 391; Ann. 1846, 58, 212.

460 TECHNOLOGY OF CELLULOSE ESTERS

the purified starch solution is passed through a fine wire sieve
and allowed to settle until the supernatant liquid is entirely-
dear, which is then decanted, the siuiace of the starch scraped
in order to remove a yellowish layer, and the mass finally divided
into cubes and allowed to dry.^ The economic disposal of the
large amount of wash water in connection with the manufacture
of potato starch has been critically studied by M. de Leeves,*
J. Halmi,* G. Foth* and W. Kette-Jassen.*

In the process of R. Goldschmidt and J. Hasek,* the rasped
potato is agitated in a centrifugal with dilute mineral acid until
the liquors which run away are free from starch. The solid residue
remaining is then reduced to a paste by the addition of a mineral
acid if dextrin is required, or if not, is dried, grotmd, silted and
boiled, the starch being used as such or converted into amylaceous
products.^

Recently H. Ducomet and A. Girard* have published the
results of work on the utilization of rotten potatoes in the manu-
facture of starch, in which they find that spoiled potatoes are
suitable, provided decomposition has not been carried very far.
According to their observations, even when the tubers are in a

1. J. Lemmon, Zts. Spiritusind. 1883. 139; Agricultural Gaz. 1883,
Jan. 8. F. LiidersdorflF, Dingl. Poly. 1841, 79, 313. G. Marek, Jahr. Deut.
Landw. 1892, 7, 208. C. Marx, Schweiggers J. 1829, 5S, 478. A. Morgen,
Deut. Landw, 1879, 533. F. Nobbe, Vers. Stat. 1865, 7, 451. W. Paulsen.
Zts. Spiritusind. 1895, 405. E. Pott, Wiener Landw. Ztg. 1875, 168. E.
Ring, Deut. Landw. Presse, 1891, No. 22, 205.

2. Zts. Landw. Centr. Ver. Sachsen. 1876, No. 7, 171.

3. Viziigyi Kozlem^nyek, 1916, 6, 1; Bull. Agric. Intell. 1916, 7, 736;
J. S. C. I. 1916, 35, 1126; C. A. 1917, 11, 2518.

4. G. Foth, Zts. Spiritusind. 1911, 34, 25; abst. J. S. C. I. 1911. 30,
147; Wag. Jahr. 1911, 57, II, 393; Zts. ang. Chem. 1911, 24, 649, 1548.

5. Zts. Spiritusind. 1883, 662. Bled. Centr. 1884, 122; abst, J. C. S.
1884, 24, 948. Wochenschr. der P. rek. Ges. 1884, No. 4; abst. J. S. C. I.
1884, 3, 575; Bied. Centr. 1884. 13, 355; Chem. Ztg. 1884, 8, 862; Chem.
Tech. Rep. 1884, 23, I. 183. D. R. P. 7518, 1879; 10033. 1879; 10836, 1879.

6. U. S. P. 755479. 1904; abst. J. S. C. I. 1904. 23, 449. F. P. 331061.
1903; abst. J. S. C. I. 1903, 22, 1142. Aust. P. 19064. 35059.

7. A. Girard, Compt. rend. 1887, 104, 1629; abst. J. C. S. 1887, 52,
868. Anon. Dingl. Poly. 1883. 248, 381; abst. J. S. C. I. 1883, 2, 419. Zts.
Spiritusind. 19, 385; abst. J. S. C. I. 1896, 15, 913. Rahm, Zts. Spiritusind.
1891, 73. C. Sajo, Oest. Landw. Wochenbl. 1896, No. 24, 185. F. Schertler,
"Die Anwendung des spec. Gewichts als Mittel zur Werthbestimmung der
Kartoffeln, Cerealien und Hiilsenfruchte." Wien. A- Hartleben, 1873. W.
vSchultze, Dmgl. Poly. 1871, 202, 86. A. Semplowski. Zts. Pflanzenkrank-
heiten, 1895. 5, 203.

8. Compt. rend. I'Acad. Agric. France, 1917, 3, 761; Bull. Agric. Intell.
1917, 8, 1191; J. S. C. I. 1917, 36, 1283; C. A. 1918. 12, 1708.

STARCH 461

deliquescent state, the starch is still undecomposed, and only at
a later stage does the starch undergo liquefaction. It is therefore
advizable to collect all potatoes attacked by damp rot, whether
caused by frost, mildew or otherwise, and extract the starch,
which, after pioper purification, is fit for consumption by man
or beast. The period during which spoiled potatoes can be kept
for treatment may be considerably prolonged by covering them
with water and renewing this from time to time.^ The decom-
position of starch during fermentation has been investigated by
M. Delbriick.2

In order to remove the peculiar odor which sometimes at-
taches itself to potato starch, treatment of the crude starch with
chlorine has been found satisfactory.^ The M. Hansen process
for potato starch manufacture,* is by bacterial fermentation in
the absence of air. Methods of starch manufacture from potato
peelings^ and sweet potatoes® have been described. The relative
tenacity of potato starch has been reported upon by G. Whewell'
and W. Thomson.^ The contributions of O. Saare® in this field

1. E. Snell, Dingl. Poly. 1844, 93, 387. G. Vibrans, Zts. Spiritusind.
1883, 160. D. R. P. 57342. 1890. C. Weigelt, O. Saare and L. Schwab,
Arch. f. Hygiene, 1885, III, 1. Dingl. Poly. 1843. 90, 314. Zts. Spiritusind.
1885, 279; 1895, 294. L. Giinther, Zts. Spiritusind. 1886, 248.

2. Zts. Spiritusind. 1892, 95; abst. J. S. C. I. 1893, 12, 169. Zts, Spir-
itusind. 1894, 141.

3. C. HeUfrisch, E. P. 24456, 1895; abst. J. S. C. I. 1896, IS, 284.
C. Schaub, Bied. Centr. 1884, 285; abst. J. C. S. 1884, 46, 1234. Mitth. ges.
vStarke. 1890, 37.

4. D. R. P. 281830, 1912; abst. J. S. C. I. 1915, 34, 727; Chem. Zentr.
1915, 86, II, 412; Chem. Ztg. Rep. 1915, 39, 116; Zts. ang. Chem. 1915, 28,
133.

5. E. Borras and Soc. Anon. Borras, E. P. 100675, 1916; abst. J. S.
C. I. 1916, 35, 860. E. P. 5099, 1915; abst. C. A. 1916, 10, 2416, 2649. F.
P. 478185. 1915; abst. J. S. C. I. 1916, 35, 1126.

6. C. McDonnell, S. Carolina Exp. Sta. 1908, Bull. 136, 7; abst. J. S.
C. I. 1909, 28, 1265; C. A. 1908, 2, 2464.

7. J. C. S. 1879, 36, 570; Chem. News, 1879, 39, 134.

8. Chem. News, 1879, 39, 122.

9. Zts. Spiritusind. 1883, 174, 482, 543, 898, 1021, 1056; 1884, 18, 191,
216, 331, 550, 595, 762; 1885, 56, 156, 231, 240, 249, 454; 1886, 200, 476, 511,
519, 527; 1887, 2, 37, 41, 53, 60, 213, 296, 304, 320, 331; 1888, 6, 8, 13, 135,
144, 160, 301, 361, 377, 385, 391; 1889, 30. 33. 35, 137, 157, 306; 1890, 6, 13,
14; 15, 21, 59, 68, 89, 91, 102, 114, 119, 132, 147, 182, 189, 287, 295, 343, 352;
1891. 8. 11, 12, 15. 153. 237, 253, 259, 276. 291; 1892, 1, 10, 26, 34. 41. 42,
216, 311, 319. 327, 335, 343, 404, 550; 1893, 7, 50, 237. 269; 1894, 6, 8. 11,
13, 42, 49, 59; 1895, 13. 238, 349, 387, 405; 1897, Suppl. II, 4; 1898, 21, 437;
1902, 25, 44, 479; 1903, 26, 436. Mitth. ges. Starke. 1890, 3. 5, 6, 15, 83,
104, 181, 182. J. S. C. I. 1884, 3, 527; 1885, 4, 236; 1897, 16, 544, 623; 1899,
18, 155, 1038; 1902, 21, 265, 1401; 1903, 22, 1153. Ann. Agron. 16, 471;
abst. J. C. S. 1891, 60, 358. Dmgl. Poly. 1885, 255, 209; abst. J. C. S. 1885,
48. 618.

462 tKCHNOLOGY OF CELLULOSE KSTERS

have been extensive and varied, and covered a number of years.

Rice Starch. Although rice contains upwards of 80% of
starch — an amount which surpasses that contained in any other
raw material suitable for the preparation of starch/ — ^the cells and
starch granules contained therein are so intimately s^sociated by
means of a thin but highly resistant layer of gluten, that the sep-
aration on a commercial scale cannot be effected by the simple
processes which are used where potatoes or wheat is the raw
farinaceous material.* On account of the smallness of the gran-
ules, rice starch possesses a firmness wanting in the other
starches, so that in practical laundry and textile finishing operations
a much higher luster is to be obtained with rice than by the use of
the other starches. As soon as the difficulties in manufacture
were understood and overcome, an impetus was given to its pro-
duction in England, where at present it is carried on to a con-
siderable extent.

The early method of manufacture as patented by O. Jones,'
is with unimportant modifications, the process in use at the present
day/ The rice is first softened in a dilute solution of soditmi
hydroxide for a 24 hour period of maceration, the mass being
occasionally stirred. The liquor is decanted and the rice washed
once or twice with fresh alkali water, allowed to drain, and then
crushed or ground to flour between millstones. In France the
softened rice is sometimes treated with an equal weight of 2%
phosphoric acid to dissolve the gluten not acted upon by the
alkali.^ The flour thus obtained is again treated with caustic
soda solution, being repeatedly agitated during 24 hours, and
then left for a period of about 72 hours for the starch granules to
settle. The portion first deposited comprises fibrous matter car-
rying but little starch, followed by a distinct layer of nearly all of

1. M. Adlung. Deutsche Industxiertg. 1876, 142, 228; abst. Dingl.
Poly. 1876, 221, 58; J. C. S. 1876, 30, 675; Industriebl. 1876, 173; Bayer,
Ind. u. Gewerbebl. 1876, 142; Chem. Tech. Rep. 1876, IS, I, 266; Jahr.
Chem. 1876, 29, 1 136.

2. M. Adlung, Dingl. Poly. 1876, 221, 543; 1877, 224, 304; abst. J. C.
vS. 1877, 32, 363; Jahr. Chem. 1877, 30, 1207; Wag. Jahr. 1876, 22, 703.

3. E. P. 8488, 1840.

4. For general statement of progress in the manufacture of rice starch,
see J. Hundhausen, Chem. Ztg. 1897, 21, 777; Wag. Jahr. 1897. 43, 781;
Zts. Spiritusind. 1897. L. Hanemann, Chem. Ztg. 1897, 21, 982; abst. J. S.
C. I. 1898, 17, 58.

5. J. Jean & Co., F. P. 350370, 1904; abst. J. S. C. I. 1906, 25, 191;
Mon. vSci. 1900, «5, 127; 1907, 67, 44.

STARCH 4G3

the starch, gluten and other insoluble material. The water is
again run off, the starch stirred up with a large bulk of water,
and after allowing the fibrous matter to subside while the starch
is still in suspension (requiring about an hour), the aqueous por-
tion with the major part of the starch still in suspension, is
drawn off, passed through fine, silk sieves, and this process re-
peated several times, until the fibrous material is substantially
removed from the starch granule.

In the process of W. Berger* the sodium hydroxide is replaced
by sodium carbonate; in that of J. Colman,* rice is mixed with
wheat refuse, the mass allowed to ferment for 10-15 days, after
which the starch is separated by washing and sifting, as described
above. H. Ransford' first submits the rice to the usual steeping
operation, and then introduces a pressure of some 20 lbs. per sq.
in. for the purpose of disintegrating the gluten and assisting in
its removal. H. Kiel and R. Stoltenhoff* employ a vacuum for
the same purpose. According to Leconte and Co.* best results
are obtained by subjecting the starch in the steeping liquid to the
action of an electric current which coagulates the impurities and
gives the starch an unusual whiteness.® The manufacture of rice
starch in Germany is given in detail in a series of articles by J.
Berger.' In the method of H. Mack,^ which has been used com-
mercially in Germany, air under pressure is blown into the alkaline
solution and rice, much of the impurities being carried away in
the large amount of froth produced, and the rice, so it is claimed,
is softened much quicker.

Y. Tanaka' has studied the hydrolysis of glutinous rice by
diastase, and finds that the granules and products do not differ

1. E. P. 9013, 1841.

2. E. P. 9166, 1841.
3 P P 603 18t53

4! K P. 6778, 1888^abst. J. S. C. I. 1889, 8, 298. See Rehe, E. P.
10359 1884.

' 5. U. S. P. 704349, 1902; abst. J. S. C. I. 1902, 21, 1033. E. P. 2294,
1901; abst. J. S. C. I. 1902, 21, 130. Aust. P. 7973, 1902.

6. Societe des Produits Amylaces, Aust. P. 19613, 1905.

7. Chem. Ztg. 1890, 14, 1440. 1571; 1891, IS, 843; abst. J. S. C. I.
1891, 10, 152, 154, 781; Jahr. Chem. 1890, 43, 2883; 1891, 44, 2772.

8. Dingl. Poly. 1885, 256, 35. D. R. P. 30256, 1884; abst. Wag. Jahr.
1885, 31, 657. Cf. C. Fehrmann, D. R. P. 29600; abst. Wag. Jahr. 1885, 31,
659.

9. J. Ind. Chem. 1912, 4, 578; abst. J. S. C. I. 1912, 31, 832; J. C. S.
1913, 104, i, 446; 1912, 6, 3035; Chem. Zentr. 1913, 84, I, 309.

464 TECHNOI^OGY OF CELLUI^OSB KSTERS

in appearance under the microscope from that of ordinary rice
starch, nor does it contain Naegeli's amylodextrin, erylhrodex-
trin or "albuminoids."^ It probably contains a larger propor-
tion of amylopectin than ordinary starch, or at least some anal-
ogous constituent yielding a dextrin hydrolyzed slowly by diastase.

According to E. Demoussy^ rice starch demineralized by
hydrochloric acid and washed until free from chlorides, exhibits /

properties of a weak acid comparable with carbonic acid and in
this respect resembles some of the other carbohydrates.' It
forms compounds with metallic hydroxides, ammonia and the
alkali carbonates, which are dissociated by water. It is also
capable of absorbing small quantities of neutral salts, i. e., sodium
and potassium chlorides, potassium sulfate and copper acetate.

It has been foimd* that the ratio between starch and dex-
trose in pure rice starch is 93.2: 100. To trace out the cause of
this discrepancy, Sostegni examined the insoluble residue ob-
tained in the degradation of the starch molecule by unorganized
ferments. A mixture of fatty acids was obtained containing a
proportion of carbon less than that required for palmitic or oleic
acid.

The influence of various salts at tenth-normal concentration
on the rate of liquefaction of rice starch at 70° has been studied,^
using the method of F. Warth and D. Darabsett. It has been
claimed® that starches from different varieties of rice can be dis-
tinguished by fractional liquefaction at varying temper.atures.
In carrying out the test, one gram of material prepared in a
state of fine subdivision by digestion with 1% KOH for 24 hours,
is stirred with 70 cc. water and maintained at the desired tem-

1. R. Atkinson, Chem. Sake. Brew. 1882, 2; Chem. News, 1881, 44,
230; J. C. S. 1882, 42, 432; Ber. 1881, 14, 2287; Jahr. Chem. 1881, 34, 986,
1308.

2. Compt. rend. 1906, 142, 933; abst. J. S. C. I. 1906, 25, 489; abst,
J. C. S. 1906, 90, i, 401; J. S. C. I. 1906, 25, 489; Rep. Chim. 1906, 6, 312;
Chem. Centr. 1906, 77, I, 1654; Jahr. Chem. 1905-1908, II, 933.

3. J. Ford and J. Guthrie, J. C. S. 1906, S9, 76; Chem. News, 1905,
92, 300; abst. J. S. C. I. 1906, 25, 228; Bull. Soc. Chim. 1906, 36, 1293; Chem.
Centr. 1906, 77, I, 314, 990; Jahr. Chem. 1905-1908, II, 923.

4. L. Sostegni, Gazz. chim. ital. 1885, IS, 376; abst. J. C. S. 1886, 50,
221; 1888, 54. 126; J. pharm. chim. 1886, 13, 130; Ber. 1885, 13, 103; Jahr.
Chem. 1885, 38, 1756.

5. B. Viswanath, T. Row and P. Ayyangar, Mem. Dept. Agric. India,
6, No. 5, 160; abst. J. S. C. I. 1916, 35, 858; C. A. 1916, 10, 2996.

6. F. Warth and D. Darabsett, Mem. Dept. Agric. India, Chem.
Series, 1914, 3, 135; abst. J. S. C. I. 1914, 33, 433; C, A. 1914, 8, 2080.

STARCH . 465

perature for one hour. The starch liquefiable is converted into
a paste, in which insoluble starch granules remain suspended.
The cooled liquid is then treated for two hours with 10 cc. of
malt extract at 30°, at which temperature no appreciable erosion
of the starch granules occur. An aliquot portion of the filtered
solution hydrolyzed with HCl, the dextrose determined by Feh-
ling's solution; and a permanganate titration of the cuprous
oxide; while the amount of starch liquefied at a given temperature
is also ascertained. Characteristic curves for the various var-
ieties of rice starch are obtained by plotting the percentage
liquefaction against temperature.

Corn Starch. The manufacture of starch from com (maize)
is confined principally to the United Btates, where within the
last twenty years it has developed to large proportions, and is
controlled in a large measure by a single concern. Excellent
articles on the details of this process have been given by G. Arch-
bold* and more recently by W. Kaufmann,^ the former giving
details of the construction and operation of a plant of 1000 bushels
per day capacity. The amount of starch in the com used aver-
ages about 55% and is known as No. 4.'

In nearly all the processes of manufacture, advantage is
taken of the fact that the kernel is surrounded by two distinct
albuminoids, one of which is soluble in water, while the other re-
quires a dilute alkali to cause it to pass into solution. Primarily,
the process comprises the extraction of these nitrogenous bodies
from the com in such a manner that the starch, in passing through
the various purification processes, is freed from those bodies
liable to induce fermentation or acidification which tends to
injuriously affect the final product.

The method generally employed is that known as the sulfur
dioxide process, and consists first in steeping the whole grain in
immense vats with about 1% aqueous sulfur dioxide at a tem-

1. J. S. C. I. 1887, 6, 80, 189; 1902, 21, 4; abst. Chem. Centr. 1887,
58, 452; 1902, 73, I, 605; Chem. Tech. Rep. 1887, 2$, 11, I90; Rep. Chim.
1902, 2, 214; Jahr. Chem. 1887, 40, 2663; 1902, 55, 1034; Wag. Jahr. 1887,
33, 871; Zts. Chem. Ind. 1887, 1, 263; 2, 103.

2. J. S. C. I. 1910, 29, 527; abst. Chem. Zentr. 1910, 81, II, 250; Jahr.
Chem. 1910, 83, II, 412; Zts. ang. Chem. 1910, 23, 2012.

3. The Manufacture of Corn Starch in the United States, J. Kriegner,
Dingl. Poly. 1895, 295, 39; abst. J. S. C. I. 1895, 14, 287; Zts. Ver. Riiben-
zuckerind. 1893. 3; Chem. Centr. 1895, 86, I, 565.

466 .TECHNOLOGY OF CELLUWSE ESTERS

perature of about 130° F. for 2-4 days, the material meanwhile
being kept in circulation. After draining, the softened com is
conveyed to the crushing miUs, where it is decorticated and par-
tially groimd, then diluted with water and passed on to the de-
germinator. This is a long V-shaped tank, equipped with a
screw conveyor at the bottom, and skimming arrangement at the
top. The starch, endosperm and glutinous matter pass on, while
the lighter oil-bearing sperm floats and is removed by the skim-
mer. This latter is cooked with live steam and hydraulically
pressed, there exuding com oil, and leaving an oil cake which is
used as cattle food. The heavier than water portion is then
screened by means of a vibrating copper sieve, the coarser material
reground and re-treated as above, while the finer particles, either
with or without being again treated, are run over a series of
tables, runs or baffles where the starch separates and deposits bjr
gravity, the glutinous and other imptuities running away. The
"green" starch which has been deposited in the tables is shoveled
into the breakers — ^wooden vats provided with agitators — ^where
water is introduced, and in which it is usual to introduce a small
amount of caustic soda. After repeating the foregoing process,
the now nearly purified product is mn into settling tanks with a
relatively large bulk of water, where, after subsidence, the water
is withdrawn, the product washed several times with agitation,
and finally dried in a manner previously described.

In the F. Baines process^ the raw grain is first heated with
5-15 times its weight of water in a closed vessel at a temperature
of 85°-95°. The J. Wildsmith method* is somewhat similar.
The SO2 process is due primarily to L. von Wagner.' W. Sage*
precipitates the soluble products from the manufacture of com
starch by agitating the liquors with lime, transferring to a settling
tank, drawing off the supernatant liquor, forcing the sediment
into a press, and drying the pressed product.*

For the application of starch in the preparation of writing

1. E. P. 18258, 1891. S. Bensaude uses manioc roots for starch pro-
duction in E. P. 15896, 1886.

2. E. P. 4146, 1883.

3. E. P. 4758, 1886; abst. J. S. C. I. 1886, 5, 330. Dingi. Poly. 1884,
250, 173; J. C. S. 1884, 46, 528; J. S. C. I. 1884. 3, 323. Sec also L. von
Wagner, Handbuch der Starkefabrikation, Weimar, 1875.

4. U. S. P. 1187392, 1916; abst. J. S. C. I. 1916, 35, 858; C. A. 1916.
10, 2160.

5. ^Anon. Dingl. Poly. 1880, 238, 488; abst. J. C. S. 1881. 40, 330. A.
Riche, J. pharm. chim. 1880, 1, 137; Chem. Tech. Rep. 1880, 19, 1, 233.

STARCH 467

papers, consult H. Wrede^ who has made exhaustive experiments.

Action of Diastatic Ferments on Starch. It has been known
for a long time that certain enzymes exert a most powerful action
on gelatinized starch as well as on some varieties of starch in the
raw or natural state. Of these ferments, in point of activity is
the diastase of malted barley, in addition to the saliva and pan-
creatic juice mentioned in a preceding topic.

In general, if the action of a solution of any one of these fer-
ments on starch paste be observed, the first effect is complete
liquefaction with the almost immediate formation of a limpid
liquid. The iodine test applied at this point will show the pres-
ence of soluble starch. The next stage in the process is the
saccharification of the soluble starch. This is indicated by the
disappearance of the blue color first produced by the iodine,
giving place to a reddish brown color indicating the presence of
erythro-dextrin, which m turn is transformed into acroodextrin.
Coincidentally with the disappearance of the starch is observable
the appearance of sugars in an analogous ratio.

Diastase does not act upon non-gelatinized starch in the
cold,' a statement which Kjeldahl holds does not apply to all the
starches. According to C. O'Sullivan,' this is probably due to
some condition of the starch connected with the degree of ripe-
ness of the material from which it was obtained. The action and
the products of diastase on starch paste has been the subject of
repeated investigation, but as yet the periphery of the subject
has apparently been but touched.

According to A. Fembach and J. Wolff,* extracts of barley
convert the most resistant dextrins into maltose; the change being
much slower than with malt extract. When the temperature is
raised to 45° the action is incomplete and a residue of a stable

1. Wochenbl. Papierfabr. 1912, 43, 1004; Zts. Spiritusind. 1913, 36,
467; J. S. C. I. 1912, 31, 381; 1913, 32, 974; C. A. 1912, 6, 2526; 1913, 7, 2114.

2. H. Brown and J. Heron, J. C. S. 1879, 35, 696; Chem. News, 1879,
39, 284; 1880, 41, 22; abst Ann. 1879, 19S, 165; Ber. 1879. 12, 1477; Jahr.
Chem. 1879, 32, 838; Jahr. rein Chem. 1879, 7, 507.

3. J. C. S. 1876. 29, 478; 1876, 30, 133; Chem. News, 1876, 33, 218;
abst. Bull. Soc. Chim. 1877, 27, 81; Ber. 1876, 9, 650, 949; Chem. Centr.
1876, 47, 664; Jahr. Chem. 1876, 29, 837, 838, 1147; Wag. Jahr. 1876, 22,
717; Bayer. Bierbrauer, 1876, 91; Mon. Sci. 1876, IS, 1218.

4. Compt. rend. 1907, 145, 80, 261; abst. J. C. S. 1907, 92, i, 750;
C. A. 1907, 1, 2419, 2498; J. S. C. I. 1907, 2$, 833; Biochem. Centr. 1907, 6,
637, 800; Chem. Zentr. 1907, 78, II, 614, 997; Jahr. Chem. 1905-1908, II,
924, 943, 4670.

4G8 TECHNOLOGY OF CELLULOSE ESTERS

dextrin remains. Moreover^ the diastatic liquefaction of starch
is subject to the same influences as liquefaction under presstu-e.*
This is corroborated by the work of Z. Wierzchowski,' A. Schif-
ferer* and E. v. Sigmond.^ M. Pauletig^ has incubated solutions
of the various starches with diastase from diflferent sources and
draws the conclusion that diastase hydrolyzes starch from cereals
more readily than starch from the Leguminosae. S. Kende has
found^ that the soaps of the higher fatty acids inhibit the degrad-
sion by diastase of starch and glycogen, the action differing from
the ordinary action of ferment inhibitors in that the soap does not
act directly on the enzjrme, but on the substance with which it
forms apparently an adsorption compound.^

When diastase from ungerminated barley acts at 50° on a
solution of soluble starch, hydrolysis proceeds until at the end

1. Ann. Inst. Pasteur, 1904, 18, 165; abst. J. C. S. 1904, 86, i, 374;
J. S. C. I. 1904. 23, 449; Rep. Chim. 1904, 4, 131, 125; Chem. Centr. 1904,
7S, II, 47; Jahr. Chem. 1904, 57, 2134. Compt. rend. 1907, 145, 261, 263;
abst. J. C. S. 1907, 92, i, 1012. A. Fembach and M. Schoen, Bull. Soc.
Chim. 1912, 11, 303; abst. J. C. S. 1912, 102, i, 336; J. S. C. I. 1912, 3aL,'402.

2. J. Ford, J. S. C. 1. 1904, 23, 414; abst. J. C. S. 1904, 85, 980; 1904, 8€,
ii, 452; Chem. News, 1904, 89, 247; Rep. Chim. 1904. 4, 462; Chem. Centr.
1904, 75, II, 645, 825; Jahr. Chem. 1904, 57, 1152, 2125.

3. Biochem. Zts. 1913, 56, 209; abst. J. C. S. 1913, 194, i, 1255; C. A.
1914, 8, 1028; J. S. C. I. 1913, 32, 1026; Chem. Zentr. 1913, 84, II, 2142.

4. Inaug. Dissertation, Keil, 1892; abst. Neue. Zts. Riib. Zuck. Ind.
1892, 29, 167; J. S. C. I. 1893, 12, 368; Jahr. Chem. 1892, 45, 2842; Zts.
Spiritusind. 1892, 313, 345; Pharm Centralh. 1893, 507; J. C. S. 1893, 64, i,
127; Chem. Centr. 1892, 63, II, 339; Chem. Tech. Rep. 1893, 32, II, 105;
Chem. Ztg. Rep. 1892, 16, 336; Meyer Jahr. Chem. 1892, 2, 403; Tech. Chem.
Jahr. 1892-1893, 15, 301 ; Wag. Jahr. 1892, 38, 874.

5. Wochensch. f. Brau. 1897, 14, 412; abst. J. S. C. I. 1897, 16, 817;
J. C. S. 1898, 74, i, 398; Zts. Spiritusind. 1897, 29, 261; Chem. Centr. 1897,
68, II, 614; Chem. Tech. Rep. 1897, 36, 531; Jahr. Chem. 1897, 59, 1520;
Tech. Chem. Jahr. 1897-1898, 29, 260; Wag. Jahr. 1897. 43, 791, 928.

6. Zts. physiol. Chem. 1917, 199, 74, abst. J. C. S. 1917, 112, i, 670;
C. A. 1918, 12, 159.

7. Biochem. Zts. 1917, 82, 30; abst. J. C. S. 1917, 112, i, 615.

8. V. Koudeka, Allgem. Zts. Bierbrau u Malz fabr. 1916, 44, 71; Zts.
ges. Brauw. 1916, 39, 222; J. S. C. I. 1917, 36, 399. G. Krabbe, Pringsheim's
Jahr. wiss. Bot. 1890, 21, 520; abst. Bied. Centr. 29, 61; J. C. S. 1891, 69,
605; 1892, 62, 92; Jahr. Chem. 1891, 44, 2739; Chem. Tech. Rep. 1890, 29,
I, 79. C. Krotke, Dingl. Poly. 1872, 294, 241; abst. J. C. S. 1872, 25, 937;
Chem. Tech. Rep. 1871, 19, I, 101; Jahr. Chem. 1872, 25, 1022. P. Lindner,
Zts. ges. Brauw. 1907, 39, 109; Wochenschr. Brau. 1907, 24, 278; Chem.
Zentr. 1907, 78, II, 169; J. S. C. I. 1907. 26, 706. A. Ling, Brit. Assoc.
Report, 1903, advance sheet; abst. J. S. C. I. 1903, 22, 1058. J. Fed. Inst.
Brewing, 1903, 9, 446; abst. J. S. C. I. 1903. 22, 1204; J. C. ST 1904, 86, i.
658. Seventh Internl. Cong. Appl. Chem. 1909; abst. J. S. C. I. 1909, 28,
731. J. Int. Brew. 1911. 17, 570; abst. J. S. C. I. 1911, 39, 1328. A. Ling
and J. Baker, Proc. Chem. Soc. 1895, 3; abst. J. S. C. I. 1895. H, 175. F.
V. Mering, Zts. Phys. Chem. 1881, 5, 185; abst. J. C. S. 1882, 42, 749; Chem.

STARCH 469

of 1-1.5 hours maltose, unaltered dextrin and glucose are formed.'

F. Musculus states^ that when diastase dissolves starch paste
at 70°-75°, the product consists of one molecule of sugar and two
molecules of dextrin, and that when the reaction reaches this

Tech. Rep. 1881, 20, 1, 30; Zts. d: Spiritusfabr. 1881, 206. T. Moreau, Ann.
Soc. Roy. med. et mat. 64; abst. Woch. f. Bran. 1905, 22, 37, 49, 72; J. S. C.
I. 1905; 24, 204.

1. J. Baker, J. C. S. 1902, 82, 1177; abst. J. S. C. I. 1902, 21, 1087.
J. Baker and H. Hulton, Chem. Soc. Trans. 1914, 105, 1529; abst. J. S. C. I.
1914, 23, 760. Analyst, 1917, 42, 351. J. Wolff, J. prakt. Chem. 1857, 71,
86; DinRl. Poly. 1857, 145, 451. Compt. rend. 1905, 141, 1046; abst. J. C.
S. 1906, 92, i, 66. Ann. Chim. Anal. 1905, 10, 389; abst. J. C. S. 1905, 88,
ii, 866; 1906, 90, ii, 500; Woch. f. Brau. 1906, 23, 31, 316; J. S. C. I. 1906,
25, 139, 716; Ann. de la Brasserie, 1907; Wochenbl. Brauer, 1908, 27. F. P.
360091, 1905; abst. J. S. C. I. 1906, 25, 437. J. WolflF and A. Fernbach,
Compt. rend. 1903, 137, 718; abst. J. S. C. I. 1903, 22, 1302; J. C. S. 1904,
86, i, 211. Compt. rend. 1904, 138, 49, 818; 139, 1217. Compt. rend. 1905,
140, 1403; abst. J. C. S. 1905, 88, i, 510. Compt. rend. 1906, 143, 363; abst.
J. C. S. 1906, 90, i, 803. Compt. rend. 1907, 144, 645; abst. J. C. S. 1907,
92, i, 482. J. Wolflf and E. Roux, Compt. rend. 1905, 141, 1046; abst. J. S.
C. I. 1906, 25, 34. C. Lintner, J. prakt. Chem. 1886. 34, 378; 1887, 36, 481;
1890, tt, 91. Zts. ang. Chem. 1888, 1, 232; 1890, 3, 546; abst. J. C. S. 1889,
56, 316; 1891, 60, 537. Brauer and Malzerkalender, 13, 83; abst. J. S. C. I.
1890, 19, 402. Wochenschr. f. Brauer, 9, 245; abst. Jahr. Chem. 1892, 45,
2465; Zts. ang. Chem. 1892, 5, 263; Chem. Centr. 1892, 63, I, 623. Zts. gps.
Brauw. 1892, 15, 123; abst. J. S. C. I. 1892, 11, 1021. Ber. 1895, 28, 1522.
Chem. Zts. 1897, 21, 737, 752; abst. J. S. C. I. 1897, 16, 1028. Zts. ang.
1898, U, 725; abst. J. S. C. I. 1898, 17, 878. Zts. Nahr. Genussm. 1907, 14,
205; 1908, 16, 509; abst. J. C. S. 1907, 92, ii, 823; 1908, 94, ii, 1077. Zts.
ges. Brauw. 1907, 30, 109; abst. J. S. C. I. 1907, 26, 281. Zts. ang. Chem.
1912, 25, 1177; abst. J. S. C. I. 1912, 31, 653. C. Lintner and G. Diill, Zts.
ang. Chem. 1891, 4, 537. Zts. ges. Brauw. 1892, 15, 145; abst. Zts. ang. Chem.
1892, 5, 263; Chem. Centr. 1892, 63, 263; Jahr. Chem. 1892, 45, 2464. Chem.
Ztg. 1893, 17, 1340; abst. J. C, S. 1894, 66, i, 5; J. S. C. I. 1894, 13, 53; Bull.
Soc. Chim. 1894, 12, 439; Ber. 1893, 26, 2531; Chem. Centr. 1894, 65, I,
22; Jahr. Chem. 1893, 46, 891. Zts. ges. Brauw. 17, 339; abst. Jahr. Chem.
1894, 47, 1140. Zts. f. ges. Br. 1895, 18, 153. M. Baswitz, Ber. 1878, 11,
1443; 1879, 12, 1831; abst. J. C. S. 1878, 34, 903; 1880, 38, 132; Jahr. Chem.
1878. », 1034, 1155; 1879. 32, 836; Chem. Tech. Rep. 1878, 17, II, 60.
M. Battegay, Farber. Ztg. 1912, 23, 133; abst. J. S. C. I. 1912, 31, 427; C.
A. 1913. 7, 1794; Chem. Zentr. 1912, 83, I, 1934. W. Biltz, Ber. 1913, 46,
1532; abst. J. S. C. I. 1913, 32, 619; J. C. S. 1913, 104, i, 707; C. A. 1913, 7,
2702; Chem. Zentr. 1913, 84, II, 31. A. Board and A. Ling, E. P. 19391.
1909; abst. J. S. C. I. 1910. 29, 1174; C. A. 1911, 5, 2299. F. Braunbeck.
E. P. 25595, 1906; abst. J. S. C. I. 1907. 26, 984; C. A. 1907, 1, 2647. A.
Bryant and C. Miner, Eighth Inter. Cong. Appl. Chem. 1912, 13, 57; J. C.
S. 1913. 104, i, 832; C. A. 1912, 6, 3035.

2. Ann. Chim. Phys. 1860, (3), 60, 203; Compt. rend. 1860, 50, 785;
abst. Chem. News, 1860, 1, 287; Mon. Sci. 1859-1860, 2, 710; J. pharm.
chim. 1860, 37, 419; Rep. Chim. appl. 1860, 2. 140; Instit. 1860, 147; Chem.
Centr. 1860, 31, 602; Dingl. Poly. 1860, 158, 424; Jahr. Chem. 1860, 13,
502; Wag. Jahr. 1860, 6, 335; Zts. Chem. 1860, 3, 379. Compt. rend. 1862,
54, 194; abst. Rep. Chim. Pure, 1862, 4, 148; Dingl. Poly. 1862, 164, 150;
Jahr. Chem. 1861, 14, 148; Zts. Chem. 1862, 5, 169.

4?0 TECHNOLOGY Oi^ CELLUU)SE ESTERS

stage no further action takes place. A. Payen asserts* that more
.than 50% of the solid matter dissolved by the reaction is sugar,
and affirms' that four samples taken from an operation in the
space of 4.5 hours contained 8% to 26% of sugar on the total
solids dissolved.' Schwarzer* agrees with F. Musculus* and F.
Musculus and D. Gruber* in finding equivalent amounts of dex-
trin and sugar in solution, but differs from him in supposing that
dextrin is first formed and then sugar, and that the action ceases
when definite equivalent proportions are produced. He main-
tains less sugar is formed at 65° than at lower temperatures.

1. Ann. Chim. Phys. 1865. (4), 4, 286; abst. Chem. News, 1865, U,
209; Bull. Soc. Chim. 1865, 3,470; J. pharm. chim. 1865. 1, 363; Chem. Centr.
1865. 36, 845; Dingl. Poly. 1865, 178, 69; Jahr. Chem. 1865, 18, 697; Vier-
teljahrsch. pr. Pharm. 25, 221.

2. Ann. Chim. Phys. 1866, 7, 382; abst. Jahr. Chem. 1866. 19, 662;
Zts. Chem. 1866, 9, 334.

3. L. Cuisinier, U. S. P. 311646, 1885. E. P. 14271, 1884; 7788, 1885;
1820, 1886. D. R. P. 37923. abst. J. C. S. 1887, 52. 354; J. S. C. I. 1885,
4, 237; 1886, 5, 331; 1887. 6, 375; Mon. Sci. 1886, 28,. 840; Ber. 1887, 20,
R, 128; Chem. Centr. 1886, 57, 614; 1887, 58, 292; Chem. Ind. 1887, 10,
322; Chem. Tech. Rep. 1886, 25, I, 44; 1887, 26, I, 77, 172; II, 103, 194;
Chem. Ztg. Rep. 1886, 10, 35; 1887, 11, 214; Dingl. Poly. 1887, 65, 325;
Jahr. Chem. 1887, 40, 2660; 1888, 41, 2807; Wag. Jahr. 1886, 32, 611; Rev.
Brass. 1887. No. 651; Zts. Spiritusind. 1887, 10, 223; 679, N. Zts. Ruben-
zuckerind. 1886, 16, 32. H. Pottevin, Compt. rend. 1898, 126, 1218; abst.
J. S. C. I. 1898, 17, 590. Ann. Inst. Pasteur, 13, 665; abst. Chem. Centr.
1899, 70, II, 644; J. S. C. I. 1899, 18, 1145. Woch. f. Brau. 1899,16, (48),
641; abst. J. S. C. I. 1900, 19, 162. S. Pratt, U. S. P. 524651, 1894. E. P.
3302, 1893; abst. J. S. C. I. 1893, 12, 940. H. Brown, G. Morris and E.
Moritz, E. P. 1809. 1890; abst. J. S. C. I. 1891, 10, 265. H. van Laer, J.
Fed. Inst. Brew. 1900, 6, (3), 162; abst. J. S. C. I. 1900, 19, 457. BuU. Soc.
Chim. Belg.* 1907, 2X, 8; 1911, 25, 249, 393; 1912, 26, 18; abst. J. S. C. I.
1907, 26, 161; 1911, 30, 1024, 1465; 1912, 30, 197; J. C. S. 1912, 102, ii, 35.
Bull. Acad. Roy. Belg. 1910, 611. 707; 1911. 795; abst. J. C. S. 1910, 98,
ii, 839; 1911, 100, ii, 28, 478; 1912, 102, ii, 148; J. S. C. I. 1912, 31,
245; Chem. Zentr. 1912, 83, I, 483. A. Fembach and J. Wolflf. Compt. rend.
1906, 142, 1216; abst. J. S. C. I. 1906, 25, 648; J. C. S. 1906, 90, i, 484;
Chem. Centr. 1906. 75, II, 229; Chem. Zts. 1907, 6, 266; Jahr. Chem, 1905-
1908 II 924.

'4. ' J. prakt. Chem. 1870, 109, 212; abst. Chem.News, 1870, 23, 22;
Bull. Soc. Chim. 1870, 14, 400; Chem. Centr. 1870, 41, 295; Industriebl.
1870, 154; Chem. Tech. Rep. 1870, 9, I, 36; Dingl. Poly. 1870,198,321;
Jahr. Chem. 1870, 23, 854; Wag. Jahr. 1870,16,447; Bayer. Bierbrauer,
1870, 128; Poly. Notizbl. 1870, 25, 321; Poly. Centr. 1870, 36, 844.

5. Ann. Chim. Phys. 1860, (3), 60, 202. Compt. rend. 1860, 50, 785;
1862, 54, 194; 1869. 68, 1267; 1870, 70, 857; 1874, 78, 1413; 1879, 88, 612;
abst. J. C. S. 1879, 36, ii, 518; Bot. Ztg. 1879, No. 22, 345. Bied. Centr.
1881, 355; abst. J. C. S. 1881, 40, 888. J. prakt. Chem. 1883, 136, 496; abst.
J. C. S. 1884, 46, 574. Ann. Chim. Phys. 1885, (6), 4, 177. Ber. 1892, 25,
519. F. Musculus and J. de Mering, Bull. Soc. Chim. 1879, 31, 105; abst.
J. C. S. 1879, 36, 370. Zts. Phys. Chem. 1881, 5, 122.

6. Compt. rend. 1878, 86, 1459; abst. J. C. S. 1878, 34, 778. BuU.
Soc. Chim. 1878, 30, 54; Ber. 1879, 12, 287; Jahr. Chem. 1878, », 924.

STARCH 471

C. O'Sullivan* demonstrated that the sugar so produced was not
dextrose but maltose, and that the methods used in estimating
the dextrose was wrong. He has also shown that dextrose and
maltose are the invariable products of the transformation, and
that by continuing the action, the whole of the dextrin can be
converted into maltose.

F. Musculus states* that the saccharification of starch paste
with diastase ceases when half the matter in solution is sugar.
He attributes his original impression that but one-third was con-
verted into sugar to the varying structure of the starch granules,
the coating of one variety ofiFering a greater resistance to the
action of the diastase than that of another. L. Bondonneau holds'
that the action is not a splitting-up of the starch aggregate, but
that the starch molecule passes through the following four mod-
ifications: amylogen, a-dextrin, /S-dextrin and 7-dextrin, before it
arrives at the end-product, glucose. A. Petit* mentions the pres-
ence of a fermentable sugar soluble in alcohol as a constituent of
the transformation products, and without action upon FehUng's
solution.

C. O'Sullivan* has apparently conclusively proven when
working under clearly defined conditions, that maltose and dex-
trin are the only products of the action, although he pointed out
the presence of a body which gave a reduction with copper oxide
equivalent to 9%-10% of dextrose.® He also has shown that solu-

1. J. C. S. 1872, 25, 581; 1876, 30, 137; abst. Chem. News, 1876, 33,
218; Bull. Soc. Chim. 1877, 27, 81; Mon. Sci. 1876, 18, 1218; Ber. 1876,
9, 650, 949; Chem. Centr. 1876, 47, 564; Jahr. Chem. 1876, 29, 837, 838,
1147; Wag. Jahr. 1876, 22, 717; Bayer. Bierbrauer, 1876, 91.

2. Bull. Soc. Chim. 1874, 22, 32; abst. Chem. News, 1874, 30, 20;
J. C. S. 1874, 27, 1077, 1174; J. pharm. chim. 1874, 20, 39; Ber. 1874, 7,
R, 824; Chem. Tech. Rep. 1874, 13, II, 152; Jahr. Chem. 1874, 27, 881.

3. Compt. rend. 1875, 81, 1212; abst. Chem. News, 1875, 32, 281;
33, 18; J. C. S. 1876. 29. 365; Bull. Soc. Chim. 1876, 25* 2; J. pharm. chim.
1876, 23, 34; Ber. 1876, 9, 61, 69; Jahr. Chem. 1875. 28, 789.

4. Bull. Soc. Chim. 1875. 24, 519; abst. Chem. News, 1876, 33, 10;
Ber. 1875, 8, 1595; Chem. Tech. Rep. 1875, 14, II, 82; Jahr. Chem. 1875,
28 788

5.' J. C. S. 1876. 30, 125; 1879. 35, 770; abst. Chem. News, 1876, 33,
218; 1879. 40, 236, 288; Bull. Soc. Chim. 1877. 27, 81; 1879, 32, 492; Ber.
1876. 9, 650, 949; Chem. Centr. 1876. 47, 564; Wag. Jahr. 1876. 22, 717;
Bayer Bierbrauer, 1876, 91; Jahr. Chem. 1876, 29, 837, 841, 1147; 1879,
32,845.

5. A. LebedeflF. BiocVem. Zts. 1908, 9, 392; abst. J. C. S. 1908, 94,
i. 321; C. A. 1909, 3, 188; Bull. Soc. Chim. 1908. 4. 1575; C? em. Zentr. 1908,
79, I. 1712. J. Ford, J. S. C. 1904. 85, 980; 1905, 86, ii, 452; J. S. C. I. 1904,
23,414, 875; abst. Chem. News, 1904, 89, 247; Rep. Chem. 1904, 4, 462;

472 TECHNOLOGY OF CElrLULOSB ESTERS

ble starch is the first prcxiuct of the action/ and has concluded
that it is possible only one dextrin exists.

F. Musculus and D. Gruber^ regard starch as a polysaccharide
containing at least five times the group C12H20O10, and when this
is acted upon by diastase or dilute acids it is broken down with
hydration into maltose, and a dextrin containing a C12H20O10
group less than starch; furthermore, that this dextrin is broken
down in the same manner, maltose and a dextrin containing a
C12H20O10 group less than the previous one, and so on through a
series until finally the solution contains only maltose.

M. Maerker^ believes that at 60° four molecules of starch
yield three molecules of maltose and one of dextrin, while at 65**
less maltose is formed. H. Brown and J. Heron* have elim-
inated out of the possible varying proportions of maltose and
dextrin indicated by C. O'SuUivan, eleven distinct transformation
products. It is the judgment of A. Herzfeld* that erythro- and
acroo-dextrins are without reducing power on copper solution,
and calls attention to the presence of a substance among the
transformation products which appears to hold a position between
dextrin and maltose, and which he proposes the name malto-
dextrin. While H. Brown and G. Morris^ confirm the presence

Chem. Centr. 1904, 75, II, 645, 825; Jahr. Chem. 1904, 57, 1152, 2125.
Analyst, 1904, 29, 277; abst. J. S. C. I. 1904. 23, 414, 953. J. Ford and J.
Guthrie, J. vS. C. I. 1905, 24, 605; abst. Chem. Centr. 1905, 76, II, 544; Jahr.
Chem. 1905-8, II, 942; Meyer Jahr. Chem. 1905, 15, 410. S. Vines,
Brit. Assoc. Reports, 1891, 697; Annals of Botany, 1891, 409.

1. O'SuUivan, J. C. S. 1879, 35, 770; abst. Chem. News, 1879, 40,
236, 288; Bull. Soc. Chim. 1879, 32. 493; Jahr. Chem. 1879, 32. 845.

2. Bull. Soc. Chim. 1878, 30, 54; Compt. rend. 1878, 86, 1459; abst.
J. C. S. 1878, 34, 778; Ber. 1879, 12, 287; Jahr. Chem. 1878, 31, 924.

3. Landw. Vers.-Stat. 23, 69; Munich Naturforscher Vers. 1877, 222;
abst. J. C. S. 1878, 34, 969; Ber. 1877, 10, 2234; Chem. Centr. 1878. 4S,
559; Jahr. Chem. 1877, 30, 900; 1878, 31, 1035.

4. J. C. S. 1879, 35, 596; abst. Chem. News, 1879, 39, 284; 1880, 41,
22; Ann. 1879, 109, 165; Ber. 1879, 12, 1477; Jahr. Chem. 1879, 32, 838;
Jahr. rein Chem. 1879, 7, 507.

5. Ber. 1879, 12, 2120; 1885, 18. 3469; abst. Chem. News, 1880, 41,
92; 42, 96; 1883, 48, 194; J. C. S. 1880, 38, 310, 866; 1881, 40, 1024; 1886, 50,
221; Bujl. Soc. Chim. 1880, 34, 538; Chem. Tech. Rep. 1879, 18, II, 74;
1880. 19, I, 232; Jahr. Chem. 1879, 32, 837; 1885, 38, 1758.

6. J. C. S. 1885, 47, 527; 1889, 55, 449; 1890. 57, 458, 489; 1895, 67,
309; abst. Chem. News. 1885, 51, 308; iaS6, 53, 37; 1889, 59, 295; 1890,
61, 201; 1895, 71, 123; Bull. Soc. Chim. 1890, 4, 682; 1891, 5, 543; 1896, 1$,
1006; J. S. C. I. 1885, 4, 682; 1889, 8, 716; 1895, 14, 288. Ber. 18&5, 18, R,
615; 1889, 22, R, 740; 1890, 23, R, 502; 1895, 28, R, 642; Chem. Centr. 1889,
60, II, 124, 285; 1890, 61, I, 1006; II, 149; 1895, 66, I, 849; Ann. 1885, 231,
72,109, 125; Jahr. Chem. 1885, 38, 1757; 1889, 42, 136, 2063; 1890, 43, 2174;
1895, 48, 1335.

STARCH 473

of malto-dextrin, but find that the physical constants point to it
as a mixture of maltose and dextrin. They conclude^ that the
dextrins are metameric rather than polymeric.

A new angle to this subject has been brought out by C.
Lintner and G. Diill,* who have isolated a body which they term
isomaltose, which is less fermentable and soluble in alcohol than
maltose, and which is completely transformed into maltose by
diastase. G. Morris and J. Wells,' and E. Moritz* have subse-
quently described a whole series of amyloins or malto-dextrins
among which they describe as restricted starch conversions, and
assert that isomaltose is an amyloin in which the maltose portion
largely predominates. The above statements are contended by
A. Schifferer.*

It has been found by A. Fembach and J. Wolff* that at a
temperature of 50°, starch is almost completely converted into
maltose by the action of malt extract, while the second phase of
the reaction, i. e., the transformation of the dextrin into maltose
is accelerated by the addition of acid until the liquid is neutral
to methyl orange. These statements are corroborated by L.
Brasse.^

L. Maquenne and E. Roux* hold that the optimum reaction

1. J. C. S. 1889, 55, 462.

2. Zts. ang. Chem. 1892, 5, 263; Zts. ges. Brauw. 1892, 15, 145; abst.
J. C. S. 1893, 64, i, 51; J. S. C. I. 1892, li» 766, 1021; Ber. 1892, 25, R, 576;
Chem. Centr. 1892, 63, 1, 886; Jahr. Chem. 1892, 45, 2464.

3. Trans. Inst. Brew. 1892, 5, 133; abst. J. C. S. 1894, 66, i. 223;
Chem. Centr. 1892. 63, II, 222; Tech. Chem. Jahr. 1892-1893, 15, 306; Wag.
Jahr. 1892, 38, 887; Wochenschr. f. Brauerei, 1892, 886; Zts. ges. Brauw.
1892, 419.

4. Trans. Inst. Brew. 1891, 4, 141; abst. Zts. ges. Brauw. 1891, 14,
199, 222; Chem Centr. 1891, CO, I, 324; Wag. Jahr. 1891, 37, 974; Tech.
Chem. Jahr. 1891-1892, 14, 260; Jahr. Chem. 1891, 44, 2765.

5. Inaug. Dissertation, Basel.

6. Compt. rend. 1906, 142, 1216; abst. J. C. S. 1906, 90, i, 484; J. S.
C. I. 1906, 25, 648; Chem. Centr. 1906, 75, II, 229; Chem. Zts. 1907, 6, 266;
Jahr. Chem. 1905-1908, II, 924.

7. Compt. rend. 1884, W, 878; 1885, 100, 454; abst. J. C. S. 1885, 48,
499. Ann. Agronom. 12, 200; abst. J. C. S. 1886. 50, 827.

8. Compt. rend. 1905, 140, 1303; abst. Chem. News, 1905, 91, 279;
J. C. S. 1905, 88, i, 511; J. S. C. I. 1905, 24, 630; Bull. Soc. Chim. 1905, 33,
723; Rep. Chim. 1905, 5, 318; Chem. Centr. 1905, 76, II, 121, 314; Chem.
Zts. 1906. 5, 10; Meyer Jahr. Chem. 1910, 15. 410; Biochem. Centr. 1905-

1906, 4, 138, 380; Tech. Chem. Jahr. 1905, 28, 274. Compt. rend. 1906,
142, 124, 1059; abst. J. C. S. 1906, 90, i, 327, 547; J. S. C. I. 1906, 25, 192;
Ann. Chim. Phys. 1906, (8), 9, 179; Rep. Chim. 1906, 6, 174; Chem. Zts.

1907, 6, 266; Jahr. Chem. 1905-1908, II. 4670; Wag. Jahr. 1906, 52, II, 225.
I,. Maquenne, Compt. rend. 1903, 137, 85, 658, 797, 1266; abst. J. C. S.

474 THCHNOIX)GY OF CELLULOSE ESTERS

at which amylase acts on various kinds of starch is that of exact
neutrality. Starch solutions, and solutions of amylase from malt
are usually alkaline, so that su£Bcient mineral acid must be added
for exact neutralization. E. Fouard^ and A. Reychler* in the
main agree that the action of bases upon starch appears to be
to disintegrate the complex starch molecules with the formation
of a simple CeHioOg group, which then reacts with the base, so
that in the reversible reaction, disintegration and re-formation of
complex molecules occur.'

The conversion of starch by diastase is hastened by the
presence of carbon dioxide and citric acids, and retarded by the

1903, 84, i, 679; 1904, 86, i, 17, 18, 227. 800; BuU. Soc. Chim. 1903, 29, 1218;
Rep. Chim. 1904, 4, 57, 102, 131, 177; Chem. Centr. 1903, 74, II, 767; 1904,
75, I, 361, 467; Chem. Zts. 1903-1904, 3, 642; Jahr. Chem. 1903, 56, 1005;
Wag. Jahr. 1904, 50, II, 224; Chem. News, 1903, 87, 90; 1903, 88, 269, 305.

1904, 89. 59, 101 ; L. Maquenne, A. Fernbach and J. WolflF, Compt. rend.
1904, 138, 49; abst. J. C. S. 1904, 86, i, 228.

1. Bull. Soc. Chim. Belg. 1910, 24, 105; abst. J. C. S. 1910, 98, i, 225;
C. A. 1910, 4, 2104; Chem. Zentr. 1910, 81, 1, 1006. Cf. Compt. rend. 1908,
147, 931; 148, 502; abst. C. A. 1910, 4, 842; J. C. S. 1909, 96, i. 13, 209, 699;
Bull. Soc. Chim. 1909, 5, 828; Chem. Zentr. 1909, 80, I, 68, 644, 1091, 1987;
II, 974.

2. Bull. Soc. Chim. Belg. 1909, 23, 378; abst. J. C. S. 1909, 96, ii, 977;
C. A. 1910, 4, 270; J. S. C. I. 1909, 30, 1216; Chem. Zentr. 1909, 80, II, 2140.

3. B. Viswanath, T. Row and P. Ayyangar, Mem. Dept. Agric. India,
Chem. Series, 4, No. 5, 160; abst. J. S. C. I. 1916, 35, 858; C. A. 1916, 10,
2996. C. Scheibler, Zts. anal. Chem. 1869, 8, 473; Ber. 1869, 2, 170; abst.
Ann. Landw. 1869, 182; Deut. Indztg. 1869, 203; Ind. u. Gewerbebl. 1869,
181; Chem. News, 1869, 19, 297; Bull. Soc. Chim. 1869, 13, 92; Poly. Centr.
1869, 35, 749; Poly. Notizbl. 1869, 24, 338; Dingl. Poly. 1869, 192, 504;
Jahr. Chem. 1869, 22, 949; Wag. Jahr. 1869, 15, 387. C. Scheibler and H.
Mittelmeier, Ber. 1890, 23, 3060, 3295, 3473; 1891, 24. 301; 1893, 26, 2930;
abst. J. C. S. 1891, 60, 33, 165, 284; J. S. C. I. 1890, 19, 1140; 1891, 20, 378.
A. Herzfeld, Bied. Centr. 1880, 9. 347; 1881, 10, 203; abst. J. C. S. 1880, 50,
866; 1881, 52, 1024. Ber. 1879, 12, 2120; 1885, 18, 3469; abst. J. C. S. 1880,
50, 310. J. Ducreux, E. P. 11896, 1904. F. P. 425714, 1911; abst. J. S. C.
I. 1911, 30, 974. Addn. dated Jan. 30, 1912 to F. P. 425714, 1911; abst.
J. S. C. I. 1912, 31, 742. A. Dobroslavine, J. Russ. Phys. Chem. Soc. 1876,
8, I, 57; abst. Bull. Soc. Chim. 1875, 26, 452; J. C. S. 1877, 32, i, 463. A.
Boidin, E. P. 16589, 1905; abst. J. S. C. I. 1906, 25, 861 ; E. P. 8447, 1909; abst.
J. S. C. I. 1909, 28, 1265. Swiss P. 53952, 1910. Compt. rend. 1906, 143,
511 ; abst. J. C. S. 1906, 90, i, 933; Chem. News, 1906, 94, 232; Chem. Centr.
1906, 75, II, 1563; Jahr. Chem. 1905-1908, II, 4786; Wag. Jahr. 1905, 52, II,
225. H. Sherman, School of Mines Quart. 1896, 17, 356; abst. J. S. C. I.
1896, 15, 832. H. Sherman and J. Baker, J. A. C. S. 1916, 38, 1885; abst. J.
S. C. I. 1916, 35, 1076; J. C. S. 1916, 109, i, 767. H. Sherman and J. Wal-
ker, J. A. C. S. 1917, 39, 1476; abst. J. S. C. I. 1917, 36, 974. H. Sherman
and P. Punnett, J. A. C. S. 1916, 38, 1877; abst. J. S. C. I. 1916, 35, 1075.
H. Sherman and M. Schle^inger, J. A, C. S. 1913, 35, 1784: abst. J. C. S.
1913, 104, i, 1400.

^tARCH 475

presence of phenol/ and other aromatic hydroxy compounds.

Takadiastase developed by J. Takamine,* and investigated
by A. Hill* has been used in the determination of starch, as in
the methods of C. Revis and H. Burnett/ and W. Davis and A.
Daisch.* F. Ando^ proposes to saccharify starch by koji-diastase.

Action of Acids on Starch. According to the earlier work
of M. Berthelot/ C. Brunner/ Couverchel/ J. Daniell/" J. Doe-
bereiner/i J. Emmet/^ j. Fritzsche/' J. Gottlieb/^ Mayet,"^ L.
Melsens," E. Monier/^ F. Musculus/* Oswald/' A. Payen/® J. Per-

1. W. Detmer, Bied. Centr. 1883, 12, 71; abst. J. C. S. 1883. 44, 631;
Chem. News, 1884, SO, 35; Zts. physiol. Chem. 7, 1; Ber. 1882, 16, 2924;
Chem. Centr. 1882, 53, 46; Jahr. Chem. 1882, 35, 1233. Ber. Bot. 1893. 149.

2. U. S. P. 975656, 1910. U. S. P. 991560. 1910; abst. J. S. C. I. 1910,
29, 1468; C. A. 1911, 5, 801, 2299, 2576.

3. Compt. rend. 1901, 133, 244; abst. Jahr. Chem. 1901, 54, 1782;
Chem. News, 1901, 84, 23.

4. Analyst, 1915, 40, 429; abst. J. S. C. I. 1915, 34, 1109; J. C. S. 1915.
108, ii, 845; C. A. 1916, 10, 226.

5. J. Agric. Scl. 1914, 6, 152; abst. J. C. S. 1914, 106, ii. 588; J. S. C.

1. 1914, 33, 657. Zts. ang. Chem. 1914, 27, I. 116; abst. Wag. Jahr. 1914,
60, II, 249; C. A. 1914, 8, 722, 2836.

6. Eighth Inter. Cong. Appl. Chem. 1912, Sect. VI-B, Orig. Comm.
14, 13; abst. J. S. C. I. 1912, M, 946; J. C. S. 1913, 104, i, 919; C. A. 1913,
6, 3097.

7. Mem. Soc. Biol. 1857, 4, 77; Brown-Sequard, J. de Physiol. 1869.

2, 577; J. prakl. Chem. 1859, 76, 371; J. de Pharm. 1858, 34, 293; Nuovo
Cimento, 1859, 10, 383; Compt. rend. 1858, 47, 227. Mem. Soc. Biol. 1857,
4, 112; Ann. 1858,106, 117.

8. Pogg. Ann. 1835, 34, 319; abst. Berz. Jahr. Chem. 1837, 16, 211,
213; Ann. 1835, 14, 303.

9. J. Pharm. 1821, 7, 267; Ann. Chim. Phys. 1831, 46, 147; Erdmann's
J. Tech. Chem. 1831, U, 215; Flora, 1834, 17, 273, 289; Mem. Savans Etrang.
1832, 3, 206; Pogg. Ann. Phys. 1831, 32, 398.

10. Ann. Chim. Phys. 1819, 10, 219; Quart. J. Sci. 1819, 6, 32; N. J.
Pharm. 1820. 4, 182.

11. Schw. J. 1812, 5, 281.

12. (Sm.) Amer. J. Sci. 1837, 32, 140; J. prakt. Chem. 1837. 12, 120;
Berz. Jahr. Chem. 1837, 1$, 275; Bibl. Univ. 1837, 11, 172.

13. N. Ann. Sci. Nat. Bot. 10, 161. Pogg. Ann. 1834, 32, 129; Ann.
1834, 12, 287. Oken, Isi.s, 1836, Col. 731.

14. Ann. 1844, 52, 121; abst. Berz. Jahr. 1846, 25, 551.

15. N. J. Pharm. 1847, 11, 81; J. prakt. Chem. 1847, 40, 435; abst.
Jahr. Chem. 1847-1848, 1, 794; Chem. Centr. 1847, 18, 393.

16. Inst. 1857, 160, 161; Acad. Sci. Bull. 1856, 23, II, 663; abst. Jahr.
Chem. 1857, 10, 493.

17. Compt. rend. 1858, 46, 425; J. prakt. Chem. 1858, 73, 479; abst.
Jahr. Chem. 1858, 11, 632; Dingl. Poly. 1858, 147, 452; Chem. Gaz. 1858,
140; Poly. Centr. 1858, 24, 624; Wag. Jahr. 1858, 4, 415.

18. J. pharm. chim. 1860, 37, 419; Chem. Centr. 1860, 31, 602; abst.
Chem. News, 1860, 1, 287; Compt. rend. 1860, 50, 785; abst. Mon. Sci. 1859-
1860, i 710; Rep. Chim. appl. 1860, 2, 140; Instit. 1860, 147; Dingl. Poly:
1860, 158, 424; Jahr. Chem. 1860. 13, 502; Wag. Jahr. 1860. 6, 335.

19. N. Br. Archi V. d. Pharm. 1844, 40, 166; abst. Berz. Jahr. 1846, 25, 550.

47G TECHNOU)GY OF CELLUU)SIS ESTERS

soz,^ E. Scharling,* C. Schmidt,* P. Schuetzenberger* and K.
Ventske/ it had been shown that by heating starch with dilute
acids, the simplest expression of the starch molecule combines with
one molecule of water to form glucose:

CeHioOs + H2O = CflHiiOe

Moderately concentrated hydrochloric acid at room tem-
perature, converts starch after a few days into a water-soluble
modification without materially changing its microscopic appear-
ance.^ This material is apparently identical with the soluble
starch prepared by the action of malt extract upon starch pasted
Continued action of 12% HCl in the cold produces amylodextrin.*
Boiling dilute acids first convert starch into soluble starch, then
into dextrin and maltose, intermediate products of undetermined
constitution (amyloins) being also formed.' The higher the tem-
perature and the longer the period of reaction, causes a complete
conversion to take place.*® This effect is best brought about by
the employment of dilute acid.** Dilute nitric,** formic,*' oxalic,**

20. Compt. rend. 1846, 23, 487; 1847, 24, 87; 1869, 48, 775; abst. Jahr.
Chem. 1859, 12, 530, 539, 545, 563. J. pharm. chim. 1846, 10, 460; 1859, 35,
106. Rep. Chim. Pure, 1858-1859, 1, 233.

1. Compt. rend. 1843, 17, 1067.

2. Ami. 1842, 42, 272.

3. Ami. 1844, 51, 31. N. Br. Arch. Pharm. 19, 195; abst. Berz. Jahr.
Chem. 1846, 25, 564; Annuaire de Chimie, 1845, 1, 318.

4. Compt. rend. 1865, 61, 485; abst. Bull. Soc. Chim. 1866, 5, 291;
Zts. Chem. 1866, 9, 16; Chem. Centr. 1865, 36, 1036; J. prakt. Chem. 1866.
97, 250; J. pharm. chim. 1865, 2, 376; Jahr. Chem. 1865, 18, 594; Ber. 1869,
2, 163, 556.

5. J. prakt. Chem. 1842, 25, 65; 1843, 28, 101.

6. E. Preuss, Zts. Spiritusind. 1904, 27, 478; abst. J. S. C. I. 1904, 23,
1228; Wag. Jahr. 1904, 50, II, 226.

7. C. Lintner, J. prakt. Chem. 1886, 142, 378; abst. Chem. News,
1886, 54, 298; J. C. S. 1887, 52, 165; Bull. Soc. Chim. 1888, 49, 834; Ber.
1886. 19, R, 842; Jahr. Chem. 1886, 39, 1886. H. Brown and G. Morris.
J. C. S. 1889, 55, 450; Chem. News, 1889, 59, 295; Ber. 1889, 22, R. 740;
Chem. Centr. 1889, 60, II, 124, 285; Jahr. Chem. 1889, 42, 136, 2063; J. S.
C. I. 1889, 8, 716.

8. Naegeli, "Beitrage z. Kenntniss d. Starkegruppe."

9. H. Brown, G. Morris and E. Moritz, E. P. 1809. 1889; abst. J. S. C.
I. 1891, 10, 265.

10. F. Allihn, J. prakt. Chem. 1880, 130, 46; abst. Dingl. Poly. 1883.
250, 534; J. C. S. 1881, 40, 149, 770; 1884, 46, 721 ; J. S. C. I. 1884, 3, 323;
Bull. Soc. Chim. 1881, 35, 224, 442; Ber. 1880. 13, 1761; 1883. 16, 2920;
Jahr. Chem. 1883, 36, 1622, 1745.

11. L. Thorne and E. Jeffers, Seventh Inter. Cong. Appl. Chem.
1909; abst. J. S. C. I. 1909, 28, 731; C. A. 1910, 4, 1697; Zts. ang. Chem.
1909, 22, 1274.

12. Dextrin-Automat Ges., D. R. P. 286362, 1912; abst. J. S. C. I.

STARCH ' 477

lactic/ and phosphoric acids^ produce the same result. The re-
sults of W. de Coninck,' A. Roessing,* A. Daisch,^ and S. Harvey'
give experimental details. Hydrofluoric^ and hydriodic acids/
have been used for this purpose to a limited extent only.

E. Parow^ has studied the rapidity of conversion of potato
starch by dilute sulfuric acid, as measiured by the relative pro-
portions of dextrose and dextrin in the extract under varying

1916, 35, 63; Chem. Zentr. 1915, 86, II, 515; Chem. Ztg. Rep. 1915, 39, 326;
Zts. ang. Chem. 1915, 28, 476. W. Oeschner de Coninck and A. Raynaud,
Rev. gen. Chim. Pure, Appl. 1910, 14, 169; abst. J. C. S. 1912, 102, i, 73.
A. Doroschewsky and A. Rakowsky, J. Russ. Phys. Chem. Soc. 1907, 39,
427; Chem. Zentr. 1907, 78, II, 1325; J. C. S. 1907, 92, i, 678; J. S. C. I. 1907,
26, 1154. A. Doroschewsky, A. Rakowsky and A. Bardt, J. Russ. Phys.
Chem. Soc. 1908, 40, 932; abst. J. C. S. 1908. 94, i, 767. A. Seyberlich and
A. Trampedach, J. C. S. 1887, 52, 792; abst. Chem. Centr. 1887, 58, 346.
U. S. P. 337448. E. P. 8000, 1885. F. P. 165906, 1885. D. R. P. 37236,
39573; abst. J. S. C. I. 1886, 5, 453; 1887, 6, 46; Chem. Tech. Rep. 1886,
25, 1, 112; 1887, 26, II, 195; 1888, 27, II, 171; Wag. Jahr. 1887, 33, 874.

13. J. Prankhauser, Ann. Agronom, 12, 340; Der Bund (Berne), 37,
126; abst. J. C. S. 1886, 50, 1061.

14. O. V. Friederichs, Arkiv. for Kemi. Min. och Geol. 1913, 5, No. 2,
3; abst. Chem. Zentr. 1914, 85, I, 660, 762; J. S. C. I. 1914, 33, 327, 328.

1. W. de Coninck and A. Raynaud, Bull. Acad. Roy. Belg. 1911, 438;
abst. J. C. S. 1911, 100, i, 770, 771; C. A. 1911, 5, 2443, 2753, 3353, 3636;
Chem. Zentr. 1911, 82, I, 1816; II, 272, 273, 855.

2. H. Endemann, Bied. Centr. 1884, 568; abst. J. C. S. 1885, 48, 104.
E. P. 6176, 1882. D. R. P. 24041; abst. Industbl. 1884. 47; J. S. C. I. 1883,
2, 388; 1884, 3, 114; Ber. 1884, 17, R, 61; Chem. Ind. 1883, 6, 338; Chem.
Tech. Rep. 1883, 22, II, 144; Wag. Jahr. 1883, 29, 672.

3. Bull. Acad. Roy. Belg. 1910, 516. 586, 848; abst. J. C. S. 1910, 98,
i, 655; 1911, 100, i, 181. W. de Coninck and A. Raynaud, Bull. Acad. Roy.
Belg. 1911, 213, 235; abst. I. C. S. 1911, 109, i, 423; Bull. Soc. Chim. 1911,
9, 586; abst. J. C. S. 1911, 100, i, 607. H. Wilmot, E. P. 18358, 1894; abst.
J. S. C. I. 1895, 24, 879; Chem. Centr. 1896, 67, 1, ?31.

4. Zts. Offentl. Chem. 1903, 9, 133; 1904, 10, 61, 277; abst. Chem.
Centr. 19a3, 34, I, 1378; 1904. 35, I, 1177, II, 855; J. S. C. I. 1903, 22, 886;
1904, 23, 563, 953; J. S. C. I. 1904, 86, ii, 298. Chem. Ztg. 1905, 29, 867;
abst. J. S. C. I. 1905, 24. 979; J. C. S. 1905, 88, i, 684.

5. J. C. S. 1914, 105, 2053, 2065; abst. J. S. C. I. 1914, 33, 934; C. A.
1915, 9, 196; Bull. Soc. Chim. 1915, 18, 138, 139; Zts. ang. Chem. 1915, 28,
II, 340.

6. Analyst, U, 221; abst. J. C. S. 1887, 26, 125; Ber. 1887, 20, R, 76.

7. F. Malinsky, Zts. Spiritusind. 1899, 22, 240; abst. J. S. C. I. 1899,
18, 1037. D. R. P. 103592; abst. Chem. Centr. 1899, 70, II, 892; Chem.
Ztg. 1899, 23, 724; Jahr. Chem. 1899, 52, 404; Wag. Jahr. 1899, 45, 725.

8. W. de Coninck and A. Raynaud, Bull. Soc. Chim. 1911, 9, 586;
abst. J. S. C. I. 1911, 30, 914; C. A. 1911, 5, 2443, 2753. 3353, 3636; Chem.
Zentr.1911, 82, 1, 1816; II, 272, 273, 855; J. C. S. 1911, 100, i, 770, 771.

9. E. Parow, Zts. Spiritusind. 1905, 28, 121; 1906, 29, 51; abst. J. vS.
C. I. 1905, 24, 450; 1906, 25, 225; Bied. Centr. 1905, 34, 546; J. C. S. 1905,
88, i, 684. E. Parow, Ellrodt and F. Neumann, Zts. Spiritusind, 1907, 30,
430; abst. J. S. C. I. 1907, 26, 1103. E. Parow and F. Neumann, Zts. Spir-
itusind. 1907, 30, 561; abst. J. C. S. 1908, 94, ii, 543; Chem. Zentr. 1908, 79,
I, 557.

478 TECHNOW)GY OP CELLUI^OSE ESTERS

conditions and tabulated his results. B. Tollens^ found in the
products of hydrolysis of potato starch with 8% sulfiuic acid,
dextrose, at best only traces of mannose and no galactose.'

As a summary of the work of A. Berge,' C. O'SuUivan,*
F. Musculus and D. Gruber,* L. Bondonneau,* F. Salomon,^ R.
Sachsse,® L. Schulze,* L. Sostegni,^® A. Seyberlich and A. Trampe-

1. Ber. 1873, 6, 1390; abst. J. C. S. 1874, 27, 245, 565; Chem. Centr.
1873. 44, 648. Ber. 1883, 16, 921. Ber. 1906, 39, 2190; abst. J. C. S. 1906,
90, i, 560. Zts. ver. Deut. Zuckerind, 1906, 664; abst. J. S. C. I. 1906, 25,
771. G. Topf, Zts. anal. Chem. 1887, 26, 137.

2. H. V. Vogel, Schw. J. 1812, 5, 80; Ann. Chim. Phys. 1812, tt, 148;
Gilb. Ann. 1812, 42, 123; Nicholson J. 1812, 33, 274. A. Vogel, Ber. 1871,

4, 140; abst. J. C. S. 1871, 24, 226; Chem. News, 1871, 23, 179; Jahr. Chem.

1871, 24, 201.

3. D. R. P. 47572, 1888; abst. Ber. 1889, 22, 616; Wag. Jahr. 1889,
35, 874; Chem. Tech. Rep. 1889, 28, II, 59; Dingl. Poly. 1889, 274, 563;
Jahr. Chem. 1889, 42, 2759. Belg. P. Feb. 4, 1890. E. P. 9320, 1888; 7272,
1891; abst. J. S. C. I. 1889, 8, 633; 1892, 11, 448. Bull. Assoc. Belg. Chim-
istes, 10, ^4; abst. J. S. C. I. 1897, 16, 548. See also Soc. Anon. La Sac-
charification, F. P. 207361; abst. Rev. chim. ind. 1891, 2, 20; Mon. Sci.
1891, 37, 448. C. Pope, U. S. P. 570183, 585285.

4. J. C. S. 1872, 25, 579, 581; 1876, 30, 478; 31, 125; 1879, 35, 772;
abst. Chem. News, 1872, 25, 250; 1876, 33, 218; 1879. 40, 238, 288; BuU.
Soc. Chim. 1877, 27, 81; 1879, 32, 493; Mon. Sci. 1876, 18, 1218; Ber. 1872,

5, 485: 1876, 9, 650, 949; Chem. Centr. 1876, 47, 564; Chem. Tech. Rep.

1872, 11, II, 46; Jahr. Chem. 1872, 25, 771; 1876, 29, 837, 838, 1147; 1879,
32, 845; Wag. Jahr. 1876, 22, 717; Bayer. Bierbrauer, 1876, 91. Rep. Anal.
Chem. 1884, 11, Chem. News, 1883, 48, 244. J. C. S. 1884, 43, 1; abst.
Ber. 1884, 17, R, 88; Chem. Tech. Rep. 1884, 23, I, 249; Jahr. Chem. 1884,

37, 1635. C. O'Sullivan, Proc. Chem. Soc. 1904, 20, 65; J. C. S. 1904, 85,
616; abst. J. S. C. I. 1904, 23, 449; Jahr. Chem. 1904, 57, 1153; Bull. Soc.
Chim. 1904, 32, 1175.

5. Compt. rend. 1878, 86, 1459; abst. Chem. News, 1878, 38, 33, 115;
J. C. S. 1878, 34, 778; Bull. Soc. Chim. 1878, 30, 54; J. pharm. chim. 1878,
28, 308; Ber. 1879, 12, 287; Chem. Tech. Rep. 1878. 17, II, 137; Jahr. Chem.
1878 31* 924.

*6. Compt rend. 1875, 81, 972, 1212; abst. Chem. News, 1875, 32,
281; 33, 18; J. C. S. 1876, 29, 365; Bull. Soc. Chim. 1876, 25, 2; J. pharm.
chim. 1876. 23, 34; Ber. 1876, 9, 61, 69; Jahr. Chem. 1875, 78, 789.

7. Ber. 1882, 15. 3100; 1883, 16, 2509; J. prakt. Chem. 1882, 133,
348; 134, 324; 1883, 136, 82, 122; abst. J. C. S. 1884, 46, 36; J. S. C. I. 1882,
1, 329; Bull. Soc. Chim. 1884, 42, 292; J. pharm chim. 1885, 11, 535; Jahr.
Chem. 1882, 35, 1124; 1883, 36. 1366; 1884, 37, 1408; 1885, 38, 1756.

8. Chem. Centr. 1877, 48, 732; Leipziger Naturforsch. Gess. Ber. 1877,
30; abst. Chem. News, 1879, 39,264; Chem. Tech. Rep. 1878, 17, 1, 297; Jahr.
Chem. 1877, 30, 898; Jahr. rein Chem. 1877, 5, 175; Zts. Chem. Grossgewerbe,
1877, 2, 588.

9. J. prakt. chem. 1883, 136, 311; abst. Chem. News, 1884. 49, 70;
J. C. S. 1884, 46, 284; Bull. Soc. Chim. 1884, 42, 292; Ber. 1883, 16, 1364;
Chem. Tech. Rep. 1883,22,11, 133; Chem. Ztg. 1883, 7, 1552; Jahr. Chem.
1883. 36, 1366; Wag. Jahr. 1883, 29, 671; Zts. deut. Spiritu§fabr. 1883, 1022.

10. Gaz. chim. ital. 1885, 15, 376; abst. J. C. S. 1886, 50, 221; 1888,
54, 126; J. pharm. chim. 1886, 13, 130; Ber. 1885, 19, 103; Jahr. Chem. 1885,

38, 1756.

STARCH 479

dach,^ Naegeli,^ H. Johnson,' G. Rolfe, G. Defren, W. Faxon and
H. Geromanos,* C. Sovereign and A. Lenders,* W. Squire,' G.
Defren,^ C. Duryea^ and A. Fembadi and M. Schoen,' it may
be stated that dextrose is the final hydrolylic product, but that
the action of acids continues on the dextrose, yielding compounds
as yet imperfectly investigated. The immediate substances dex-
trin and maltose are first produced, the rapidity of the change
being dependent upon the strength of the acid, the temperature
and the pressure. The maximum production of dextrose takes
place when pressure and 1.5%-2.0% of acid is used, and the pro-
portion of dry starch to acid solution does not exceed 1 to 3.

The colloidal body, gallisin, found in commercial glucose, ^°
is identical with the isomaltose of E. Fischer^^ obtained by the

1. U. S. P. 337448. E. P. 8000, 1885. F. P. 166905, 1885. D. R. P.
37236, 39573; abst. J. C. S. 1887, M, 792; J. S. C. I. 1886, 5, 453; 1887, 6,
46; Ber. 1886, 19, R, 863; 1887, 20, R, 409; Chem. Centr. 1887, 58, 376;
Chem. Tech. Rep, 1886, 25, 1, 112; 1887, 26, II, 195; 1888, 27, II, 171; Jahr.
Chem. 1886, 39, 2129; 1887, 40, 2632, 2661; Tech. Chem. Jahr. 1885-1886,
8, 295; Wag. Jahr. 1887, 33, 874; Zts. Chem. Ind. 1887, 1, 348. N. Zts.
Riibenzuckerind. 1885, 17, 186; Industbl. 1886, 70; Zts. Spiritusind. 1885,
107; La Sucrerie indigene et coloniale, 1885, 26, 507; Chem. Ztg. Rep.
1888, 12, 51 ; Zts. Ver. Rubenzuckerind. im ZoUverein, 1888, 84.

2. Starkegnippe, Leipzig, 1874, 33, 99.

3. Proc. Chem. Soc. 1898, 106; abst. J. S. C. I. 1898, 17, 477; J. C. S.
1898, 73, 490; Bull. Soc. Chim. 1899, 22, 184; Chem. Centr. 1898, 69, I,
1292; II, 279; Jahr. Chem. 1898, SI, 1352.

4. J. A. C. S. 1896, 18, 869; 1897, 19, 6981; 903, 25, 1003, 1015; abst.
J. S. C. I. 1897, 16, 167, 1048; 1903, 22. 1252; J. C. S. 1904, 86, i, 17; Ber.
1896, 29, R, 1156; Chem. Centr. 1897, 68, II, 918; 1903, 74, II, 1318; Jahr.
Chem. 1897, 50, 1514; 1903, 56, 995, 1006.

5. U. S. P. 948485, 1910; 1183408, 1916; abst. J. S. C. I. 1910, 29, 367;
1916, 35, 750; C. A. 1910,4, 1113; 1916, 10, 1943; Chem. Ztg. Rep. 1910, 34,
127. See also Soc. Franc, des Distilleries de I'lndo-Chine. F. P. 449155,
1911; 459634, 459815, 1912; abst. J. S. C. I. 1913, 32, 502, 1166; Mon. Sci.
1914, 81, 42; C. A. 1914, 8, 3215; Chem. Ztg. Rep. 1914, 38, 392, 393.

6. J. S. C. I. 1884, 3, 543; abst. Chem. Ind. 1884, 7, 290; Jahr. Chem.
1884, 37, 1802.

7. Orign. Comm. Eighth Inter. Cong. Appl. Chem. 1912, 13, HI;
abst. J. S. C. I. 1912, 31, 892; J. C. S. 1913, 104, i, 832, C. A. 1912, 6, 3034,
3155.

8. Abst. J. vS. C. I. 1911, 30, 789; J. C. S. 1911, 100, i, 711; C. A. 1911,
5» 3353; Rep. Chim. 1911, 11, 461; Chem. Zentr. 1911, 82, II, 749.

9. Bull. Soc. Chim. 1912, 11, 303; abst. J. S. C. I. 1912, 31, 402; C. A.
1912, 6, 1552; Chem. Zentr. 1912, 83, I, 1617; Meyer Jahr. Chem. 1912, 22,
430.

10. C. Schmitt and A. Cobenzl, Ber. 1884, 17, 1000; abst. J. C. S. 1884,
46, 981; J. S. C. I. 1884, 3, 453; Bull. Soc. Chim. 1885, 44, 155; Jahr. Chem.
1884, 37, 1406. C. Schmitt and J. Rosenhek, Ber. 1884, 17, 2456; abst. J. C.
S. 1885, 48, 134; Bull. Soc. Chim. 1886, 45, 24; Jahr. Chem. 1884, 37, 1406.

11. Ber. 1890, 23, 3687; abst. J. C. S. 1891, 60, 412; J. S. C. I. 1891,
10, 377; Chem. Centr. 1891, 62, I, 539; Jahr. Chem. 1890, 43, 2141.

480 TECHNOLOGY OF CELLULOSE ESTERS

action of concentrated HCl on dextrose.^ Starch may also be
inverted by platinum black.*

Further details on the action of acids upon starch is to be
found in the work of Societe d' Exploitation des Processes H.
Boulard,^ C. Rheinfels/ S. Lillie,^ F. Jewson,^ F. Grueters,^ H.
Gayon and E. Dubourg,^ G. Flourens,^ L. Aubert and V. Giraud,^®
E. Donath/i W. Hiepe,i2 p Roehmann,i' Roehr,i* H. Ost,»^ M.
Stumpf,^* J. Ducreux," H. Wulkan and H. Straetz^® and Societe des

1. C. Scheibler and H. Mittelmeier, Ber. 1891, 24, 301; abst. J. C. S.
1891, 60, 536; J. S. C. I. 1891, 10, 378; Bull. Soc. Chim. 1891, 6, 678; Chem.
Centr. 1891, 62, 1, 632; Jahr. Chem. 1891, 44, 2175.

2. C. Neilson, Am. J. Physiol. 1906, 15, 412; J. C. S. 1906, 90, i, 235;
Chem. Centr. 1906, 75, I, 1152; Jahr. Chem. 1905-1908, II, 943.

3. F. P. 464601, 1913; 475792, 477927, 1914; abst. J. S. C. I. 1916,
35, 11, 64, 1170; C. A. 1915, 9, 1223; 1916, 10, 1716. E. P. 25406, 1913.

4. Woch. f. Brau. 1906, 23, 510; abst. J. S. C. I. 1906, 25, 998.

5. U. S. P. 959237, Re. 13592, 1910; 1038397, 1023257, 1014311,
1014237, 1912; abst. J. S. C. I. 1910, 29, 834; 1912, 31, 197, 505, 945; Chem.
Ztg. Rep. 1910, 34, 303; 1912, 36, 296, 483; C. A. 1912, 6, 693, 1690. 3539;
Mon. Sci. 1193, 79, 111.

6. E. P. 12291, 1906; abst. J. S. C. I. 1907, 26, 704.

7. Zts. ang. Chem. 1904, 17, 1169; abst. J. S. C. I. 1904, 23, 875; J. C.
S. 1904,86,1,852; Chem. Centr. 1904, 75, II, 825; Jahr. Chem. 1904. 57,
1153; Tech. Chem. Jahr. 1904, 27, 262; Wag. Jahr. 1904, 50, II, 224.

8. Compt. rend. 1886, 103, 885; abst. J. S. C. I. 1887, 6, 144; abst.
J. C. S. 1887, 52, 171; Chem. News, 1886, 54, 273; Bull. Soc. Chim. 1887,
47, 649; Ber. 1887, 20, R, 13; Chem. Tech. Rep. 1887, 26, II, 95; Jahr. Chem.
1888 41« 2499.

'9. Compt. rend. 1890, 110, 12(M; abst. J. C. S. 1890, 56, 1089; J. S.
C. I. 1890, 19, 815; Bull. Soc. Chim. 1891, 5, 716; Ber. 1890, 23, 461; Jahr.
Chem. 1890, 43, 2152.

10. D. R. P. 32388, 1884; abst. J. C. S. 1885, 48. 1274; Ber. 1885, 18,
674; Chem. Ind. 1885, 8, 292; Chem. Tech. Rep. 1885,24,11, 143; Jahr. Chem.
1885, 38, 2146; Tech. Chem. Jahr. 1885-1886, 8, 291; Wag. Jahr. 1885. 31,
764. Dingl. Poly. 1885, 257, 298.

11. Chem. Ztg. 1891, 15, 597; abst. J. S. C. I. 1891, 10, 843; Jahr.
'Chem. 1891, 44, 2735. J. prakt. Chem. 1894, 49, 546; abst. T. C. S. 1894,
66, i, 436; J. S. C. I. 1894, 13, 823; Bull. Soc. Chim. 1894, 12, 1463; Ber.
1894, 27, R, 574; Jalir. Chem. 1894, 49, 546.

12. The Country Brewers Gaz. 1893, No. 431; 1894, No. 433, 434, 435;
abst. J. S. C. I. 1894, 13, 264; Woch. f. Brau. 11, 28; Chem. Centr. 1894,
65, I, 417; Jahr. Chem. 1894, 47, 1116.

13. Biochem. Zts. 1917, 84. 399; abst. J. C. S. 1918, 114, i, 138; C. A.
1918, 12, 1300; J. S. C. I. 1918, 37, 162-A.

14. Bied. Centr. 1880, 9, 547; abst. J. C. S. 1880, 38, 932; Chem. Tech.
Rep. 1880, 19, I, 108.

15. Chem. Ztg. 1895, 19, 1501 ; abst. J. S. C. I. 1895, 14, 877, 895. Ber.
1913, 46, 2995; abst. J. C. S. 1913, 104, i, 1148. H. Ost. F. WesthoflF and L.
Gessner, Ann. 1911, 382, 340; abst. J. S. C. I. 1911, 30, 1024.

16. Oest. Ver. Zuckerind. 1878, 25. Zts. Spiritusind. 1878, 259. Bied.
Centr. 1880, 9, 457; abst. J. C. S. 1880, 38, 834.

17. Addn. dated Jan. 30, 1912 to F. P. 425714, 1911; abst. J. S. C. I
1911,30,974; 1912,31,742.

18. K. P. 13659, 1900; abst. J. S. C. I. 1901, 20, 824. Aust. P. 5792,

STARCH 481

Produits Amylaces,* as well as numerous other investigators.

F. Soxhlet first showed in 1881 that starch subjected to the
action of water under high pressure was converted into sugar '
when a temperature of 149® was reached.*

The action of concentrated nitric and sulfuric acids upon
starch results in the formation of starch nitrates, explosive esters
which are described in detail in a succeeding chapter of this
volume.

Amylose, or amylocellulose, separates when starch solution
or starch paste is allowed to stand for some time. It is partially
soluble in boiling water and completely so in water at 150°. The
solutions are devoid of gelatinizing power, but give with iodine a
blue coloration, and are quantitatively converted by diastase
into maltose. Amyloid exists in a liquid form by heating under
pressiwe to 150°, and upon cooling the solution the material sep-
arates out in a granular form.

T. Chrzaszcz and K. Terlikowski' have studied the power

1901. H. Wulkan, U. S. P. 696156, 1912; abst. J. S. C. I. 1902, 21, 630.
D. R. P. 223301, 1908; abst. J. S. C. I. 1910, 29, 1264. H. Wulkan and Dex-
trin Automat Ges. U. S. P. 1139620, 1915; abst J. S. C. I. 1916, 34, 727.

1. E. P. 3930, 1902; abst. J. S. C. I. 1903, 22, 152. Addn. dated
March 11, 1902 to F. P. 316582, 1901; abst. J. S. C. I. 1902, 21, 1546.

2. F. Soxhlet, Bied. Centr. 1881, 10, 654; abst. J. C. S. 1882, 42, 30.
Zts. f. ges. Br. 1881. 177. Zts. Spiritusind. 1884. 195. Zts. anal. Chem.
1885, 24, 618. T. van Korvin Sakovicz, E. P. 718, 1883; abst. J. S. C. I.
1883, 2, 483. Wahl-Henius Research Laboratory and R. Wahl, E. P. 101406,
1916; abst. J. S. C. I. 1917, 36, 936.

3. Woch. Brauw. 1912, 2B, 590. 607, 623, 636; abst. J. S. C. I. 1912, 31,
1089. T. Chrzakzcz, Zts. Spiritusind. 1909, 32, 620, 535, 639, 544, 566, 667,
569, 571, 578; 1911, 34, 546; abst. C. A. 1912. 6, 1050; J. C. S. 1910, 38, ii,
994; 1912, 102, i, 402; J. S. C. I. 1910, 29, 103; 1911, 30, 1401; Chem. Zentr.
1910, 81, I, 288; Jahr. Chem. 1910, 83, 1640; Meyer Jahr. Chem. 1909, 1$,
414. 426. T. Chrzakzcz and S. Pierozek, Zts. Spiritusind. 1910, 33, 66, 81.
98, 132, 145; abst. C. A. 1910, 4, 2540; 1911, 5, 756; J. S. C. I. 1910, 29, 683;
Chem. Zentr. 1910, 81, I, 1635; Wochenschr. f. Brauerei, 27, 69, 89, 98, 120,
134, 151, 163, 175, 186, 199. See also H. Brown and J. Heron, J. C. S. 1879,
35, 696; abst. Chem. News, 1879, 39, 284; T. C. S. 1880. 41, 22; 42, 62; 1881,
43, 154; Ann. 1879, 199, 166; Ber. 1879, J2, 1477; Chem. Tech. Rep. 1879.
8, II, 163; Jahr. rein Chem. 1879, 7, 607; Jahr. Chem. 1879, 32, 838; Zts.
Chem. Grossgewerbe, 1879, 6, 153, 254, 269; Zts. ges. Brauw. 14, 442. See
A. Herzfeld, Ber. 1879, 12, 2120; abst. Jahr. rein Chem. 1879, 7, 608;-Zts.
ges. Brauw. 14, 449; Zts. Chem. Grossgewerbe. 1879. 6, 153. H. Brown and
G. Morris, J. C. S. 1885, 47, 627; abst. Chem. News. 1886, 51, 308; J. S. C.
I. 1885, 4, 682; Bull. Soc. Chim. 1888, (2), 50, 390; Ber. 1886. 18, 615; Ann.
1885, m, 72; Jahr. Chem. 1885. 38, 1757, 1768. H. Brown and G. Morris,
Proc. Chem. Soc. 1896, (148), 36; J. C. S. 1896, 67, 309, 709; abst. J. S. C. I.
1895, 14, 288; Bull. Soc. Chim. 1897,(3), 18, 871, 936, 937; Ber. 1896. 28,
642; 1896,29, 1135; Chem. Tech. Rep. 1896, 34, II, 112; Chem. Ztg. 1899,
13, 1366. In this connection, see also Chem. News. 1886, 53, 37; 1888, 57,

482 TECHNOUXJY OF CBI*I*UW)SB ESTERS

of amylase to liquefy starch grains. In experiments made by
A. Fembach' on the action of small amounts of amylase on an
excess of starch, it was found that the action was most rapid
under conditions of neutrality to helianthin, in contradistinction
to the results of L. Maquenne and E. Roux, who found an alkaline
reaction most favorable.^

F. Botazzi and C. Victoroff* have been able to corroborate
the work of Fouard* along the lines that the amylose of starch
forms a colloidal solution with water which is perfectly clear and
transparent, but is non-dialyzable, but can be filtered through

196; 1889, 59, 295; 1895, 72, 45. A. HiU, Proc. Chem. Soc. 1898. 156; J. C.
S. 1898, 73, 634; abst. Chem. News, 1897. 7S, 19; J. S. C. I. 1898. 17, 684;
Bull. Soc. Chim. 1899. (3), 22, 669; Chem. Centr. 1898, 69, II, 632; Jahr.
Chem. 1898, 51, 222; Meyer Jahr. Chem. 1898, 8, 149, 257; Zts. physik.
Chem. 1899, 29, 171. Proc. Chem. Soc. 1901, 17, 184; abst. Chem. News,
1901, 83, 138; J. S. C. I. 1901, 20, 491, 736; Rept. Chem. 1901, 1, 544; Chem.
Centr. 1901, 72, I, 823; II, 437; Jahr. Chem. 1901, 54, 876; Meyer Jahr.
Chem. 1901, U, 349; Zts. ang. Chem. 1901, H, 344; Rev. phys. Chim. 1901,
5, 517; Zts. ges. Brauw. 24, 627. Ber. 1901, 34, 600, 1380; abst. Chem.
News. 1901, 84, 23; J. C. S. 1901, 80, 452; Jahr. Chem. 1901, 54, 1780. J.
Physiol. 28, XXVI; abst. J. C. S. 1902, 82, ii, 515. Proc. Chem. Soc. 1903,
19, 99; J. C. S. 1903, 83, 578; abst. Chem. News, 1903, 87, 198; J. S. C. I.
1903, 22, 505; Bull. Soc. Chim. 1903, (3), 30, 298; Chem. Centr. 1903, 74,

I, 1115; II, 1334; Jahr. Chem. 1903, 56, 240; Zts. physik. Chem. 1904. 48,
249. A. Ling and B. Davis, J. Fed. Inst. Brewing, (4), 8, 475; abst. Zts.
Brauw. 1902, 556; J. C. S. 1902, 82, i, 732; J. S. C. I. 1902, 21, 1088; Chem.
Centr. 1902. 73, II, 1223; Jahr. Chem. 1902, 55, 1991; Wag. Jahr. 1902, 48,

II, 414. C. Lintner and E. Kroeber, Ber. 1895, 28, 984, 1034, 1050; abst.
Zts. ges. Brauw. 1895, 153; J. C. S. 1895, 08, i, 429; J. S. C. I. 1895, H, 690;
Bull. Soc. Chim. 1896, (3), IS, 647; Chem. Centr. 1895, 00, II, 66, 163; Chem.
Tech. Rep. 1895. 34, 1, 275; Chem. Ztg. Rep. 1895, 19, 142; Jahr. Chem.
1895, 48, 3012; Meyer Jahr. Chem. 1895. 5, 189, 241; Wag. Tahr. 1895, 41,
859, 861. J. Wolff and A. Fernbach, Compt. rend. 1903, 137, 718; abst.
J. S. C. I. 190;3, 22, 1302; Bull. Soc. Chim. 1904, (3), 31, 766; Chem. Centr.
1903, 74, II. 1451; Jahr. Chem. 1903. 50, 1912.

1. Compt. rend. 1906, M2, 285; abst. J. C. S. 1906, 90, i, 327; J. S-
C. I. 1906, 25, 192; Rep. Chim. 1906, 0, 187; Chem. Ztg. Rep. 1906, 25,
385; Chem. Zts. 1907, 0, 40, 266; Jahr. Chem. 1905-1908, II, 4670; Wag.
Jahr. 1906, 52, II, 339, 350; Ann. de la Brass. 1906, No. 5, 12; Woch. f.
Brauer. 1906, 23, 159. 160; Zts. Bierbr. 1906, 349.

2. Compt. rend. 1906, 112, 124; abst. J. C. S. 1906, 90, i, 327; J. S.
C. I. 1906, 25, 192; Rep. Chim. 1906, 0, 174; Chem. Zts. 1907, 0, 266; Jahr.
Chem. 1905-1908, II, 4670; Wag. Jahr. 1906. 52, II, 225.

3. Atti. R. Accad. Lincei, 1910, (5), 19, 7; abst. J. C. S. 1910, 98, i,
655; C. A. 1911, 5, 1406; J. S. C. I. 1910, 29, 1323; Bull. Soc. Chim. 1911, (4),
10, 88.3; Rep. Chim. 1911, U, 10; Chem. Zentr. 1910, O, II, 969; Jahr. Chem.
1910, 03, II, 408; Woch. f. Brauer. 1910, 27, 575.

4. Compt. rend. 1908. 147, 813; abst. J. C. S. 1908, 94, i, 953; Bull.
vSoc. Chim. 1908, (4), 3, 1170; Chem. Zentr. 1908, 79. II, 2000; Jahr. Chem.
1905-1908, II, 940. Sec also Compt. rend. 1908, 117, 931; 1909, HO, 502;
abst. J. S. C. I. 1908. 27, 1215; Jahr. Chem. 1905-1908. II, 940; Wag. Jahr.
1909, 55, II, 226; Chem. Ztg. 1908, 32, 247, 520, 597, 771. 1178, 1215.

STARCH 483

hardened gelatin under pressure (ultra filtration). When an elec-
tric current is passed through it, no migration. The amylopectin
of starch forms with water a suspension in which the granules
are ultramicroscopically visible.

The investigations of L. Maquenne^ and L. Maquenne and
E. Roux,* show that starch deposited in a granular form resembling
nattu'al starch grains from E. Fouard's starch solution' is identical
with the amylose described by Maquenne.* Its resemblance to
natural starch has led to the conclusion that starch consists of a
perfect solution of amylose thickened by amylopectin. The opales-
cence and precipitation observed by Fouard in the phenomenon call-
ed **retrogradaf ion** by Maquenne and Roux, who suggested that it
is due to either pseudo-crystallization or to a polymerization sim-
ilar to those undergone by certain sugars, dihydroxyacetone.

C. Tanret* found starches from many sources to contain

1. Compt. rend. 1908, 146, 317, 542; abst. C. A. 1908, 2, 1522, 1631,
1647; J. C. S. 1908, »4, i, 249; J. S. C. I. 1908, 27, 291; Bull. Soc. Chim.
1908, (4), 3, 403; Rep. Chim. 1908, 8, 230; Chem. Zentr. 1908, 79, I, 1264;
II, 1534; Jahr. Chem. 1905^1908, II, 944; Wag. Jahr. 1908, 54, II, 193.

2. Compt. rend. 1906, 142, 124; abst. J. C. S. 1906, 90, i, 327; J. S.
C. I. 1906, 25, 192; Rep. Chim. 190e, 6, 174; Chem. Zts. 1907, 6, 266; Jahr.
Chem. 1905-1908, II, 4670; Wag. Jahr. 1906, 52, II, 225; Ann. Chim. Phys.
1906, (8), 9, 179. L. Maquenne, Compt. rend. 1903, 137, 88, 658, 797, 1266;
abst. J. C. S. 1903, 84, i, 679; 1904, 88, i, 17, 18; BuU. Soc. Chim. 1903, (3),
29, 1218; Rep. Chim. 1904, 4, 57, 102, 130, 177; Chem. Centr. 1903, 74, II,
757; 1904, 75, I, 16, 361, 467; Chem. Zts. 1903-1904, 3, 642; Jahr. Chem.
1903, 56, 1005; Wag. Jahr. 1904, 50, II, 224. Ann. Chim. Phys. 1904, (8),
2, 124; abst. J. C. S. 1904, 86, i, 800; Rep. Chim. 1904, 4, 318; Chem. Centr.
1903, 74, II, 557; 1904, 75, 1, 16, 1576; Jahr. Chem. 1904, 57, 1151. Compt.
rend. 1904, 138, 213; abst. J. C. S. 1904, 86, i, 294; J. S. C. I. 1904, 23, 197;
Rep. Chim. 1904, 4, 202; Chem. Centr. 1904, 75, I, 682; Jahr. Chem. 1904,
57, 1151; Wag. Jahr. 1904, 50, II, 224. Compt. rend. 1904, 138, 375; abst.
J. C. S. 1904, 86, i, 294; J. S. C. I. 1904, 23, 261; Rep. Chim. 1904, 4, 250;
Chem. Centr. 1904, 75, I, 819; Jahr. Chem. 1904, 57, 1151, 2150. See also
Chem. News, 1903, 87, 90; 88, 269, 305; 1904, 89, 59, 101.

3. Compt. rend. 1908, 146, 285, 978; abst. C. A. 1908, 2, 197, 1380,
2330; J. C. S. 1908. 94, i, 138, 503; J. S. C. I. 1908, 27, 238, 635; BuU. Soc.
Chim. 1908, (4), 3, 836, 1170, 1182; Rep. Chim. 1908, 8, 204, 404; Chem.
Zentr. 1908,7, 1, 1264; II, 1098; Jahr. Chem. 1905-1908, II, 937, 939; Wag.
Jahr. 1908, 54, II, 193. Bull. Assoc. Sucr. dist. 24, 1207; 25, 165; abst.
C. A. 1907. 1, 1781; 1908, 2, 197; Compt. rend. 1907, 144, 1368; Rep. Chim.

1908, 8, 33. Se? also J. C. S. 1907, 92, i, 391, 677; Bull. Soc. Chim. 1908,
(4), 3, 402, 757, 836, 1110; C. A. 1908, 2, 1522, 1631, 1647.

4. Compt. rend. 1905, 140, 1303; abst. Chem. News, 1905, 91, 279;
J. C. S. 1905, 88, i, 511; J. S. C. I. 1905, 24, 630; Bull. Soc. Chim. 1905, (3),
33, 723; Rep. Chim. 1905, 5, 318; Chem. Centr. 1905, 76, II. 121, 314; Chem.
Zts. 1906, 5, 10; Meyer Jahr. Chem. 1910, 15, 410; Biochem. Centr. 1905-
1906, 4, 138, 380; Tech. Chem. Jahr. 1905, 28, 274.

6. Compt. rend. 1909, 146, 1775; abst. C. A. 1909, 3, 2676; J. C. S.

1909, 96, i, 556; J. S. C. I. 1909, 28, 847; Bull. Soc. Chim. 1909, (4), 5, 310,

484 TECHNOLOGY OP CELLULOSE ESTERS

amylopectin and amylosey the amylopectin content ranging from
67% in chestnut starch to 79.5% in banana. The amylose from
different starches appears to possess varying solubilities in water.
Z. Gatin-Gruzewska^ claims to have separated amylopectin and
states that it forms the envelope of the starch granule, consisting
of a plurality of sacs fitting one into the other, these being insolu-
ble in cold water, but swelling in hot water to a gelatinous paste.

With alkali, amylopectin gives opalescent solutions which
are dextro-rotatory. Amylose dried to a fine powder partially
dissolves in cold water, and entirely so in hot water, and coloring
iodine blue. It rapidly dissolves in the presence of minute amounts
of alkali, and the alkaline solutions are dextro-rotatory.

Additional recent data on the nature of solutions of starch
in formalin,* the modifying of starch,' preparation of stable solu-
tions of starch and oxalic acid,* autolysis of starch,* sizing with
starch,® starch adhesives,^ diastatic properties of formaldehyde,*
artificial ageing of starch,® substitutes^®, and the enzymatic hy-
drolysis of starch, ^^ indicate the latest tendencies in research.

823; Rep. Chim. 1910, 10, 66; Chem. Ztg. 1909, 33, 837; Jahr. Chem. 1910,
62, II, 374; Wag. Jahr. 1909, 55, II, 226. Compt. rend. 1914, 158,
1353; 159, 530; abst. C. A. 1914, 8, 2964; 1915, 9, 1912, 2323; J. C. S. 1914,
108, i, 665, 1167; J. S. C. I, 1914, 33, 607. 1068; Bufl. Soc. Chim. 1914, (4),
15, 702; 1915, (4), 17, 83.

1. Compt. rend. 1908, 146, 540; abst. C. A. 1908, 2, 1631; J. C.
S. 1908, 94, i, 320; J. S. C. I. 1908, 27, 415; Bull. Soc. Chim. 1908, (4),
3, 1007; Rep. Chim. 1908. 8, 276; Chem. Zentr. 1908, 79, I, 1534; Jahr.
Chem. 1905-1908, II, 931; Wag. Jahr. 1908. 54, II, 193. See also Compt.
rend. Soc. Biol. 1908, 64, 178.

2. M. Jacoby, Ber. 1919, 52, B, 558; abst. C. A. 1919, 13, 2528. W.
V. Kaufmann and A. Lewite, Ber. 1919, 52, B, 616; abst. C. A. 1919, 13,
2528. See W. Kaufmann, Ber. 1917, 50, 198; abst. J. C. S. 1917, 112, i,
251; C. A. 1917, 11, 2792. G. Woker, Ber. 1917, 50, 679; abst. J. C. S. 1917.
ii^ J 447' c A^ 1917 U, 3259.

' 3. R. Stutzke. U. S. P. 1320719, 1919; abst. J. S. C. I. 1920, 38, 37-A.;
C. A. 1920, 14, 231.

4. A. Junk, Chem. Ztg. 1919, 43, 258; abst. C. A. 1920, 14, 36.

5. W. Biedermann, Fermentforschung, 1916, 1, 474; 1919, 2, 458;
abst. Chem. Zentr. 1919, 90, III, 635; J. S. C. I. 1917, 36, 230; 1919, 38,
958-A; J. C. S. 1917, 112, i, 62.

6. J. Whittaker, E. P. 130204, 1918; abst. C. A. 1920, 13, 105.

7. J. Paiton, U. S. P. 13181061919; abst. C. A. 1920, 14, 105.

8. H. Sallinger, Ber. 1919, 52, B, 651; abst. C. A. 1919, 13, 2529.

9. Ibid., KoUoid. Zts. 1919, 25, HI; abst. J. S. C. I. 1920, 39, 76-A.

10. A. Winter, Farber Ztg. 1919, 30, 104; abst. C. A. 1919, 13, 2605.

11. H. Sherman and F. Walker, J. A. C. S. 1919, 41, 1866; abst. J. S.
C. I. 1920, 39, 37-A. H. Sherman. F. Walker and M. Caldwell, J. A. C. S.
1919, 41, 1123; abst. J. S. C. I. 1919, 13, 651-A. G. Johnston, Austral.
P. 5593, 1917.

CHAPTER III.

COTTON.

The official definition for cotton in the United States^ is '*the
hairs of the seed from one or more of the cultivated varieties of
Gossypium herbaceum I^inne. (Fam. Malvaceae), freed from adher-
ing impurities and linters and deprived of fatty matter." This
refers to the mechanically ptuified filament. In Great Britain
purified cotton is designated as* "the hairs of the seed of Gossypium
barbadense Linne., and of other species of Gossypium, freed from
fatty matter."

History of Cotton. As a textile cotton appears to have been
used from the earliest times, the first reference to the use of cotton
going back to 800 B.C.' Herodotus (Book 3), when writing of
India, mentions "trees bearing a sort of wool instead of fruit,
which was better and finer than that of sheep." He refers to the
use of cotton clothes by the Indians. In 500 B.C., India employed
cotton to a large extent for textile piuposes, and early records
show that hand spinning, weaviftg and dyeing were extensively
developed. Spain seems to have been the first European country
to produce cotton goods, the, industry flourishing in that country
from about the middle of the 13th centiuy. Ages earlier, how-
ever, India, Eg3rpt, and China had made use of the fiber.

In Pliny's History (ig, 5), there is described a "kind of cloth,
xylina, made from wool, growing on a shrub, called by some
Xylon and by some Gossypium." There is no doubt but what
this referred to cotton. Cotton was probably introduced into
Europe by the Saracens and first manufacttu-ed in Spain in the
early part of the 13th century. It was introduced into England
by the Dutch, and the first mention made of it in trade appears
in I^. Roberts, "Treasury and Traffic," pubUshed in 1641, which
says: "They buy cotton wool in England that comes from

1. United States Pharmacopea, IX, 208.

2. British Pharmacopea.

3. Asvalayana Sranta Seitra.

486 TECHNOLOGY OF CELLULOSE ESTERS

Cyprus and Smjrma, and at home work the same and perfect it
into velveteens, fustians, dimities, and such stufiFs, where it is
returned and sold in London."

It is interesting to note that cotton wool was used about
1250 in England for candle-wicks, though the extent of the in-
dustry is not recorded.* In the Western Hemisphere, the first
voyage of Columbus to the West Indies in 1492 found cotton
cultivated, and woven fabrics made from it being worn by the
inhabitants. Cortes, in 1519, was presented with cotton gar-
ments by the natives of the Yacatan.* At the beginning of the
16th century the Mexicans used cotton garments to a large ex-
tent. In Peru, about the time of Pizarro's conquest in 1523,
many of the inhabitants were clothed in cotton garments. This
may be accounted for from the fact that cotton is indigenous to
Peru. According to the historian Bancroft, the first attempt at
cotton cultivation in the American Colonies was at Virginia in
1621.

It has been stated that the cotton plant was not actually
grown as a fiber crop until the beginning of the 17th centiuy,'
and that until towards the close of the 18th centiuy the methods
employed in cultivation, treatment, etc., were empirical. The
ginning process was carried out by primitive means and the daily
output per man was less than 5 pounds of cotton. The simplest
form of ginning machine was known as a Churka. It consisted
essentially of two wooden rollers fixed in a rough frame, the top
roller being usually stationary and the lower roller rotated by a
handle. On passing the fibers of the seed cotton between the
rollers the lint is drawn through, while the seed does not pass
the rollers but falls to the ground. The fiber is uninjtu-ed by this
simple type of machine.

The modem development of the cotton industry dates from
1792, when the saw-gin was patented by Eli Whitney, this inven-
tion considerably simplifying the ginning process. This epoch-
making improvement in the early treatment of the cotton fiber

1. Encyclopedia Britannica, 11th Ed. 7, 281. For details of the fiber
from diflFerent pickings of Egyptian cotton, see T. Kearney, Bur. Plant Ind.,
Circ. 110, 37; abst C. A. 1914, 8, 1211.

2. Encyclopedia Britannica, Uth Ed. 7, 265.

3. "Cotton and the Vegetable Fibers/' E. Goulding and W. Dunstan,
49.

COTTON 487

was as important from many considerations as the inventions of
Arkwright and others with regard to textile manufacture. In
1787 at Beverly, Mass., the first mill for the production of cotton
goods is stated to have been erected. In 1788 there were 143
water mills in the United Kingdom engaged in the cotton indus-
try; of these mills, 41 were in Lancashire. About this period
much attention was given to the question of cotton production.
We find, for example, the East India Company making efforts to
improve the growing of cotton in India. Unsuccessful endeavors
were made to acclimatize exotic cottons,^ best results being ob-
tained by improving indigenous cotton plants. In 1790, one and
one-half million pounds of cptton were produced in the United
States; by 1800 the number of pounds had risen to 35 millions.
In 1850 the figure was 1021 millions, while in 1918 it reached
7,950 millions.

Botany of Cottonr Long unicellular hairs envelop the cap-
sule seeds in various species of the plants of the genus Gossypium
belonging to the Mallow (Malvaceae) order, and, when freed from
wax, fat, and other non-cellulose products, these hairs constitute
the extremely important fiber known as cotton. The seed itself
is usually covered with a coarse yellow or brownish hairy growth,
whereas the cotton hair or down-like substance is many times
longer and is also nearly colorless.

Cotton plants are usually perennial, but crops in other than
the first or second year are generally poor, so that from an econ-
omic aspect the plants are considered as annuals. Yearly plants
are also easier to cultivate, and insect and fungoid pests more
readily combated.

With the opening of the flower buds,* white or yellow petals

1. Encyclopedia Britannica, 11th Ed. 7, 266.

2. Monie ("The Cotton Fiber") gives the following description of the
cultivation of the cotton plant: "The plant, although indigenous to almost
all warm climates, is nevertheless only cultivated within a very limited area
for commercial purposes, the principal centers of cotton agriculture being
in Egypt, the southern portions of the United States, India, Brazil, the west
and southern coasts of Africa, and the West India Islands.^ A large amount
of white cotton is raised in China, but this is almost entirely used in the
home manufactures. The time when sowing is begun in the several dis-
tricts varies considerably, being largely dependent upon the climatic influ-
ences. The seasons, however, are generally as follows: American. — From
the middle of March to the middle of April. Egyptian. — From the begin-
ning of March to the end of April. Peruvian and Brazilian. — From the
end of December to the end of April. Indian or Surat. — From May to the

488 TECHNOI.OGY Olf CEI.I.UI.OSB ESTERS

generally appear and these darken in color for 3 to 4 days and
then deciduate. The color of the flower varies generally with the
different species. Upland American plants show a white or whit-
ish yellow flower, from which are gradations in color to the pur-
plish red of the cotton trees of India. When the petals and sta-
mens separate, the young fruit calyx gradually increases and is
known as a pod or boll.

This pod at first has a green color but on ripening turns
brown. The surface of the boll gradually hardens and ridges are

beginning of August. In the various American plantations the sowing time
begins and ends almost simultaneously, while in other countries, especially
where the atmosphere and climate are subject to much variation, the period
of planting fluctuates. The plants in some parts being several inches above
the ground, while in other parts of the same country the fields may be only
under preparation. When the sowing is finished and before, and some time
after the crop makes its appearance, keeping the ground free from weeds is
the main object to be looked to, otherwise the soil would become much
impoverished, and the product would be an inferior quality. In from eight
days to a fortnight after sowing, the young shoots first appear above the
ground in the form of a hook, but in a few hours afterwards the seed end
of the stalk or stem is raised out of the ground, disclosing two leaves folded
over and closed together. The leaves and stems of these young plants are
very smooth and oily and of a fleshy color and appearance, and, as before
stated, extremely tender. In examining the cotton plant from time to time
during its growth, some interesting and instructive objects will be observed.
Firstly, in regard to the formation of the leaves, it will be found that they
will vary in form in different parts of the stem, thus, for instance, on a Gallini
Egyptian (G. barbadense) plant, the lower leaves were entire, the center or
middle 3-lobed, while the upper leaves were 6-lobed. In the G. hirsutum
species, the lower leaves have 5 and some 3 lobes, with the small branched
petioles of a hairy nature, while the upper leaves are entire and undivided.
In the Peruvian cotton plant, the lower leaves are entire and of an oval
shape, while the upper leaves have 5 acuminated lobes. Another interesting
point observable in the growth of the cotton plant is the presence of a small
cavity situated at the lower end of the main vein of each leaf. Through
this opening, on warm days, the plant discharges any excess of resinous
matter which circulates through its branches. Before the plant attains its
full height it begins to throw off flower-stalks which are generally (when
perfectly formed) small in diameter and of considerable length; on the ex-
tremity of these stalks, the blossom pod after a time appears, encased in three
leaf-sheaths or calyxes, with the fringes of various lengths. Gradually this
pod expands until it attains to about the size of a bean, when it bursts and
displays the blossom. This blossom only exists in full development for about
twenty-four hours, when it begins to revolve imperceptibly on its axis and in
about a day's time twists itself completely off. When the blossom has fallen,
a smaU 3-, and in some cases, 5-celled triangular capsule or pod of a dark-
green color is disclosed, which increases in size until it reaches that of a large
Albert. Meanwhile the seeds and filaments have been in course of formation
inside the pod, and when growth is completed the expansion of the fiber
causes it to burst into sections, each cell of which, and adhering firmly to
the seeds, is a tuft of the downy material." See also "Varieties of American
Upland Cotton," F. Tyler, Bull. 163, U. S. Bureau Plant Industry, 1910,
pp. 127, pi. 8, fig. 67.

COTTON

489

formed on it, down the center of one of the ridges being a groove.
As the white boll opens along this groove, the contents of the
capsule spreads out, forming a white downy mass. The cotton
fiber requires plenty of air and light for complete maturing. The
mixed cotton and seeds are easily picked as soon as the boll is
dry.i

Long staple cotton fiber has a length of IV4 to 2 inches or
more. In this class is Sea-Island and improved Upland American
cotton. A medium staple such as Peruvian and Brazilian ranges
from ^/g-l in., and a shorter staple '/g-'A in., representatives of
this latter class being the cottons from India. In general, the
whiter, cleaner, longer and more silky the individual fiber, or the
smaller the diameter, the higher in commercial value as a textile
does the cotton become. The longest staple and most highly
prized variety is the "Sea-Island" cotton known as "long Georgia."

Cotton even of a definite species is influenced by many con-
ditions and the length of fiber is not a constant. The following
table gives lengths and diameters of various cotton fibers :

Place of
Growth

Description of
Cotton

United States' New Orleans.
Sea Islands . . | Long Stapled .

S. America . . . ; Brazilian

Egypt ! Egyptian

Indigenous or

Indian.

Native
American Seed
Sea Island or

Egyptian.. .

Length of

Staple
(In Inches)

Min.

0.88
1.41
1.03
1.30

0.77
0.96

1.36

Max.

1.16
1.80
1.31
1.62

1.02
1.21

1.65 .

Diameter of Fiber
(Inches)

Min.

0.00058
0.00046
0.00062
Q. 00059

0.000649
0.000654

0.000596

Max.

0.00097
0.00082
0.00096
0.00072

0.001040
0.000996

0.000864

Frac-
tion
(Mean)

V
V
V
V

1190
16CS

ites

1816

Vii«

^211

V.

'/

13 N

The isolated cotton fiber is a single elongated cell, broken
roughly at the base from being torn from the seed, and terminating
at the end in an elongated solid point. Upon magnification the
fiber appears as a granular striped band, twisted spirally, thicker
at the edges and containing a central canal without liquid, the

1. "Cotton and Other Vegetable Fibers," E. Goulding and W. Dun-
stan, p. 12. For details of Caravonica cotton, see T. Hanausek, Chem,
Ztg. Rep. 1910, 34, 455; abst. J. Soc. Dyers Col 1910, 26, 251.

490 technouk;y op cBi«i«uu>se esters

enveloping sheath being so far collapsed that the inner walls
appear in contact. This becomes more noticeable upon moisten-
ing the fiber — a characteristic of cotton.^

Externally the fiber is enveloped in a thin skin called the
cuticle, which substance differs chemically from cellulose, and has
been regarded as a conversion product of the latter induced by
moisture and air.*

According to F. Bowman' a typical cotton fiber when exam-

1. A. Flatters has published a work (1906), "The Cotton Plant," on
the microscopical development of the cotton liber, accompanied by excellent
photomicrographs of the various species of cotton, and different periods of
the developing fiber. As the result of his investigations the following con-
clusions are arrived at: "1. That the cotton fiber is a cuticular outgrowth
of the ovule. 2. That the fibers are not all developed at the same time, on
the same ovule. 3. That the deposit of cellulose on the cell-wall of the
fiber is not uniform and regular. 4. That the spiral twisting of the fiber
is dependent upon the uniform deposit of cellulose, and subsequent evapora-
tion of moisture and cuticular contraction. 5. That an average long-
stapled fiber and an average short-stapled one have practically the same
cavity-area for the deposit of cellulose. 6. That all fibers lacking spiral
twisting are not necessarily unripe fibers, but fibers which may have attained
solidity by continued deposit. 7. That the cotton fiber is made up of three
primary elements — (a) the cuticular envelope ; (6) the secondary deposit of
cellulose; (c) the endochromic coloring matter. 8. That these primary
elements are demonstrable by microscopic and chemical analysis."

2. This spiral formation has been attributed to the fact that upon
ripening, the juices in the fiber are drawn back into the plant or dry up,
and in doing so cause the fiber to become twisted from the unequal contrac-
tion and collapse of the cell wall. It has been noticed that when fibers which
have had a stunted or immattu-e growth, usually either have no inner canal,
or the canal has been stopped up. This is a decidedly inferior cotton. The
fiber is weak, brittle, of reduced strength and durability. This inferiority
is readily apparent in attempting to spin or to nitrate or acetate the fiber;
the internal diameter being so much greater, and the absence of Uie inner
canal, causes slower and more unequal penetration of acids, and more diffi-
culty in washing the finished product free from contained acid. Such cotton
is known in the trade as "dead."

It has been stated by Humboldt, that the most suitable section for
the cultivation of the Gossypium barbadense, G. arboreutn, and G. hirsutum
is between the equator and the 34th degree of latitude, a mean yearly tem-
perature of 68 "-86" F. being required. G. herbaceum thrives hist in those
zones where the winter temperature does not fall below 50** F., nor rise
above 77 ° F. in summer. In the United States the cotton plant is cultivated
up to 38° latitude north, but the most desirable fiber is obtained along the
eastern coast and in proximity to the ocean, between 25" and 33" north
latitude.

3. In the unripe fiber, the canal is filled with protoplasmic matter,
but in the ripening of the plant this liquid dries up, and the walls of the
tube collapse and flatten out. As the ripening process increases, the adhe-
sion of the fiber to the seed decreases much in the same manner as the ripen-
ing of fruits, so that the ripe cotton is easily separated in the ginning process.
In some species, this separation of hair from the seed is so perfect that after
ginning the seed shows a polished black appearance, and is locally called

COTTON 491

ined microscopically, shows (a) an outer cuticle or integument
forming the skin of the fiber; (b) an inner tube attached to the
outer cuticle consisting of cellulose and protoplasm, which forms
the substance of the fiber; (c) an inner layer of a firmer deposit;
and (d) a pith-like deposit containing coloring matter which may
be present and existing in detached pieces or filling the central
lumen.^

The plants of the Mallow order — ^to which the cotton belongs
— and which include both herbs, shrubs and small trees, are from
3-20 feet high and have been cultivated for ages over a wide area.
They are indigenous mainly to maritime tropical regions.* Under
cultivation their range has been extended to approximately 40^
either side of the equator (or to the isothermal line 60^ F.).'

The botanical classification of cotton plants is difficult on

"black seed" cotton in distinction from the upland or "green seed" cotton.
The length of the liber, which varies considerably even among the same var-
iety, wiU range from 2 inches (5 cm.) iil the Egyptian to '/< inch (18 mm.)
in the inferior grades. (Structm-e of the Cotton Fiber, 19) gives the diam-
eter of the fiber as 0.0004-0.0016 inch.

The central cavity known as the lumen is generally small in compari-
son with the diameter of the cell walls, the thickness of the latter being of
considerable importance in the speed of acid penetration in nitrating proc-
esses. Sometimes the lumen is several times as broad as the cell wall.
Such a cotton will both nitrate readily, wash easily, and sustain considerable
mechanical loss in the several processes of treatment.

1. Whereas cellulose is readily soluble in ammoniacal cupric oxid^
solution, and also in concentrated sulfuric acid, cuticle is difficultly so. In
treating cotton fiber with either of these reagents, a peculiar phenomenon
is observed. The cotton swells up, but the cuticle is>not visibly affected.
As the bast fibers contain no cuticle, they do not exhibit this reaction, which
therefore is a method of differentiation between the two classes of fibers.

In commerce there are 8 different degrees of fineness in cotton recog-
nized, varying in diameter from 0.0O4r-0.008 inch. The oil extracted from
raw cotton appears to be very similar to, if not identical with, cottonseed oil,
and has been supposed to have been carried up the fiber from the seed itself.

2. The "count" of cotton is a term applied to the number of hanks
of 840 yards each contained in 1 pound. Size 60's, for instance, means that
60 hanks, each 840 yards in length, will weigh 1 pound. The English sys-
tem of numbering, used mostly in England, United States, India, Switzerland,
Germany, includes designation of twisted as well as single yams. For in-
stance, if 2 single threads of count 60 are twisted together, this would be
designated at 2-60's. The Belgium system is to use the number 840-yard
hanks in 500 grams; that of the French is based on the decimal system,
the count being the number of 1000-meter length hanks required to weigh
500 grams. In Austria, the method is to count the number of hanks of 950
cells each in 600 grams. According to the number of the twisted threads,
there is a decrease in length of 2%-6% in twisting with an increase in
diameter.

3. The following description of the typical cotton plant is abstracted
from Bulletin 33, U. S. Department of Agriculture. "The cotton plant be-
longs to the Malvaceae, or mallow family, and is known under the generic

492 TECHNOI.OGY OF CBLI.UI.OSE ESTERS

account of several considerations. The plants of this genus re-
spond readily and are influenced by intensive cultivation and
selection, and with variations in environment, dimate and soil,
and easily undergo hybridization. The large interchange of seeds
between diflFerent coimtries has natturally greatly altered the dis-
tinctive characteristics of the individual species.

Of the large number of species of the Gossypium genus*

name Gossypium. It is indigenous principally to the islands and maritime
regions of the tropics, but tmder cultivation its range has been extended
to 40° or more either side of the equator, or to the isothermal line of 60° P.

In the U. S., latitude 37° N. about represents the limit of economic
growth. The Gossypium plant is herbaceous, shrubby, or arborescent, peren-
nial, but in cultivation herabceous annual or biennial, often hairy, with long,
simple, or slightly branched hairs, or soft and tomentose, or hirsute, or all
the pubescence short and stellate, rarely smooth throughout; stem, branches,
petiolate; peduncles, leaves, involucre; corolla, ovary, style, capsule, and
sometimes the cotyledons more or less covered with small black spots or
glands. Roots, tap-rooted, branching, long, and penetrating the soil deeply.
Stems erect, terete, with dark-colored ash-red or red bark and white wood,
branching or spreading widely. Br^ches terete or somewhat angled, erect
or spreading, or in cultivation sometimes very short. Leaves alternate,
petioled, cordate, or subcordate, 3- to 7-, or rarely, 9-lobed, occasionally
some of the lower and upper ones entire, 3- to 7-veined. Veins branching
and netted; the mid vein and sometimes adjacent ones bear a gland one-
third or less the distance from their bases, or glands may be wholly absent.
Stipules in pairs, linear-lanceolate, acuminate, often ceduous. Flowers ped-
unculate. Peduncles subangular or angular, often thickened towards the
ends, short or very short, erect or spreading; the fruit is sometimes pendulous,
sometimes gladular, bearing a leafy involucre. Involucre 3-leaved or in
cultivation sometimes 4-; bracteoles often large, cordate, erect, appressed,
or spreading at summit, sometimes coalescent at base or adnate to calyx,
dentate, or lancinate, sometimes entire or nearly so, rarely linear; calyx short,
cup-shaped, truncate, shortly 6-dentate or more or less 6-parted. Corolla
hypogynous. Petals 5, often coalescent at base and by their daws adnate
to the lower part of stamen tube, obovate, more or less unequally trans-
versely dilated at summit, convulute in bud. Stamintd column dilated at
base, arched, surrounding the ovary, naked below, above narrowed, and
bearing the anthers. Filaments ntmierous, filiform, simple or branched,
conspicuous. Anthers reniform, 1-celled, dehiscent by a semicircular open-
ing into two halves. Ovary sessile, simple, 3- to 5-celled. Ovules few
or many, in two series. Style clavate, 3- to 5-parted; divisions sometimes
erect, sometimes twisted and adhering together, channeled, and bearing the
stigmas. Capsule more or less thickened, lethery, oval, ovate-acuminate,
subglobose, mucronate, loculicidally dehiscent by 1 to 6 valves. Seed num-
erous, subglobose, ovate of subovate, oblong or angular, densely covered
with cotton or rarely glabrous. Fiber sometimes of two kinds, one short and
closely adherent to the seed, the other longer, more or less silky, of single,
simple, flattened cells, more or less spirally twisted, more readily separable
from the seed. Albumen thin, membranous or none. Cotyledons pilcate,
auricula te at base, enveloping the straight radical."

1. A. Henckel (Bull. Bur. Plant Ind. (U. S.) 1909, No. 139. pp. 40)
has presented an unusually good illustrated description of Gossypium species.
See H. Rusby, Pharm. Era, 1909, 42, 634. F. Tyler, Bull. No. 163, Bur.
Plant Ind. (U. S.) 1910, pp. 127. For interesting description of the methods
used in the maintenance of the quality of Egyptian cotton, see G. Dudgeon,
Bull. Imper. Inst. June 1918, 160-170.

COTTON 493

known, only about 20 are cultivated. Their principal habitats
are North America and India, although the species is more or
less indigenous to all sub-tropical countries. A. Todaro records
52 distinct species. The Index Kewensis gives 42 species and 88
synonyms. However, only about twenty species are cultivated.
A much smaller ntunber than this (4 or 5), however, are of exten-
sive economic importance, among which may be mentioned the
following:

Gossypium herbaceunt (I^inn.) or Gossypium hirsutum (Linn.).
The distinction between these two species is indefinite. The first
is considered to be indigenous to Asiatic Turkey (Smjrma cotton)
— also known as G. indicum. In localities where other varieties of
cotton cannot be grown with profit, this variety is cultivated in
America, Egjrpt and China and produces a short, relatively coarse
fiber often called Siwat or Indian cotton. The staple, however,
is very strong.

G. hirsutum is regarded as indicative of the extremely im-
portant upland cottons of the United States of America, ^and the
cotton of Texas and New Orleans. According to Watt, the
upland cottons are to be more properly regarded as made up of
various hybrid forms between G. hirsutum and G. mexicanum,
the plants of these species being very hardy and attaining a height
of 7-8 feet.

Gossypium barbadense (Linn). This species includes the
highly prized, silky haired. Sea Island cotton, although again ac-
cording to some authorities, this variety is more properly con-
sidered a hybrid, and allied to G, vitifolium. It has a yellow
flower and small, black, smooth seeds. This most valuable cotton,
which is native to West Indies, produces the * 'finest staple" ccft-
ton and is only obtained by cultivation. This species yields not
only the very strong, long fiber, but yields a lower percentage of
lint and inferior fibers than any other variety of cotton. The
individual fibers are very fine, with numerous uniform twists and
it has a lustrous creamy color. In consequence, its net value in
spinning and thread manufacture is correspondingly enhanced,
while it produces an extremely fine yam,^ being largely used for

1. •Monie, "Structure of the Cotton Fiber," p. 40. For earlier anal-
yses of the composition of crude cotton, see C. vSchmidt and Hecker, J. prakt.
chem. 1847, 40, 267; Poly. Centr. 1847, 13, 36; Jahr. Chem. 1847-1848, 1,
1130.

494 TECHNOLOGY OF CHLLUI.OSE ESTERS

the finer numbers of thread and yams. Its cultivation to greatest
perfection is in regions where there is a hot moist atmosphere
combined with a heavy rainfall. Consequently it is found at
its best near the sea in tropical countries, such as off the coast
of Georgia, South Carolina and Florida, although that grown in
Jamaica and in some of the West Indies — due to adverse climatic
conditions — is of a rather inferior grade. It is grown also in
Eg3T>t, where it has been claimed this species to be of African
origin.* Watt considers some Eg3rptian cottons to be hybrids of
G, peruvianum (Engler).

Gossypium brasiliense (Macf.) and G. peruvianum (Engler)
are related tropical species native of South America, being cul-
tivated mainly in Brazil and Peru. The plants are 10-15 feet
in height and bear a yellow flower. The pods, which usually
contain 8-10 black seeds, each 3aeld a long staple of great tensile
strength, although a somewhat coarse fiber, which is perhaps next
in value to Sea Island cotton. Most of the fibers are only partly
twisted.. This cotton usually has a light creamy color. The
hair is readily separated from the seeds but the latter are grouped
together, adhering in clusters. The fiber is known by the term
"kidney cotton." Usually the commercial cottons contain much
immatiwely developed and short fiber product as well as a large
amount of foreign matter such as broken leaf, sand, seeds, etc.

Gossypium arboreum (Linn.) represents a species from which
Indian cottons are derived. G, neglectum, G. herbaceum (Linn.),
G. obtustfolium, G. wightianum and other species are also con-
sidered to represent some Indian cottons. G, arboreum is really
a large shrub or a small tree rising to a height of 15-20 feet. It
produces only a relatively small proportion of fiber, and is not very
extensively cultivated.

Gossypium religiosum {G, Chinese (Fisch) and (Otto)) repre-
sents a type of cotton plant from China and Siam. It 3aelds the
so-called yellow "nankin" cotton. It is not, however, of especial
commercial significance, and is probably related to the G. arboreum,

F. Parlatore^ also includes G, tahitense, which flourishes in
the Pacific Islands, and G, sanwichense which occurs in the
Hawaiian, among the commercial cottons. These last two species

1. Masters, J. Linn. Soc. 19, 213.

2. See F. Parlatore, **Le specie dei cotoni," 1866.

COTTON 495

may, with propriety, be included under G, barbadense and G.
hirsuium.

Commercial cottons may also be classified into two groups
(1) and (2) with various sub-sections, as follows:

(1) Seeds covered with long hairs only, flowers yellow, turning
to red.

(A) Seeds separate, as G, barnadense (Linn.).

(B) Seeds of each loculus united, as G, brasiliense (Macf.).

(2) Seeds covered with short hairs.

(A) Flowers yellow or white, turning red.^

(a) Leaves 3 to 5 lobed, often large, flowers yellow, &s

G. hirsutum (Linn.).

(b) Leaves 3 to 5, seldom 7, lobed, small, flowers yel-

low, as G, herbaceum (Linn.).

(B) Flowers purple or red, leaves 3 to 5 lobed, as G. ar-
boreum (Linn.).

Bombax cotton is a species of fiber quite similar to that of
the cotton plant, having been collected for centuries from various

1. A. Perkin, J. C. S. 1916, 109, 145; abst. C. A. 1916. 10, 1326. He
has made an attempt to ascertain if there is any chemical distinction not only
between the Egyptian and ordinary Indian yellow cotton flower, Gossypium
herbaceum, but also between these and the red, pink, and colorless petals
of other varieties; also whether the red coloring matter in the red and yel-
low flowers is due to the red oxidation products of either gossypetin or gossy-
pitrin. Red cotton flowers, G. arboreum, Linn.: The red alcoholic extract
of 1600 gm. flowers was concentrated, diluted with hot water, and the alco-
hol evaporated ofT. After extraction with ether the liquid was boiled with
lead acetate solution and the greenish brown precipitate decomposed with
HtS. Filtration of the maroon liquid and evaporation in vacuo for several
days gave a red, semi-gelatinous product from which was isolated isoquer-
cetin. Other flavone glucosides could not be detected, thus showing a marked
difference from the yellow Egyptian flowers. The red, viscous mass obtained
by concentrating in vclcuo the filtrate from the isoquercitrin did not yield
the typical color reactions of gossypitone after hydrolysis with boiling 1%
HtSO^ and removal of quercetin by dissolving in pyridine and precipitating
with ether, repeating the process, indicating that the color may be due rather
to a true anthocyanin. Yellow flowers, G. neglectum: the concentrated
alcoholic extract, on long keeping, gradually gave a precipitate which, dis-
solved in hot water, treated with lead acetate solution, decomposed with
HsS, and concentrated in vacuo, gave a semi-gelatinous mass, which, re-
crystallized flrst from dilute alcohol, then from boiling water, yielded gossy-
pitrin m. 240^-242°, whereas the (^4) isolated from the Egyptian flowers
{loc. cit.) m. 200*'-202*'. It was found that by boiling the higher m. variety
with acetone, finer needles with 1H«0 were formed, and that these m. 200®-
202® whether anhydrous or not. This form is converted into the higher
m. variety by boiling with water. The mother liquors from the crude (A),
on further evaporation in vacuo, gave a small amount of a soluble glucoside
which yielded quercetin on hydrolysis, while the final mother liquors con-
tained a readily soluble quercetin glucoside, from which, by the methods

496 TECHNOLOGY OP CElrLULOSE ESTERS

fruit capsules of the Bombax family which are closely allied to the
Malvaceae (cotton family), and has found commercial uses. This
form of cotton is variously known as "vegetable down," and "veg-
etable edredon."

Bombax cotton comprises soft fibers possessing considerable
luster, and white to yellow in color. Like cotton, they are seed
hairs, and therefore are morphologically similar. There is an
entire absence of spiral twist, the fibers being shorter and the
cell walls decreased in thickness, all of which tends to the pro-
duction of diminished tensile strength. This form of cotton
fhids its principal uses in wadding for upholstery work, being
too weak for spinning. When nitrated this cotton forms a nitro-
cellulose of ready solubility and fluidity.

Of the cotton grown in the United States, the Sea Island
variety is the longest and finest cotton produced in the world,
being soft and silky and possessing an excellent luster. This
cotton is cultivated chiefly in the Sea Islands off South Carolina,
and in the interior of Georgia and Florida, and is also extensively
cultivated in the West Indies. In order to maintain the quality
of Sea Island cotton, it is necessary that careful seed selection
be practiced, or the strain will deteriorate in quality.

Inasmuch as the plant is more delicate than other varieties,
it requires special treatment during growth, and especial attention
is placed on the question of fertilization. It thrives best in a
rather sandy soil and highly humid atmosphere. Inasmuch as
Georgia and Florida also grow considerable quantities of Up-
described for the red flowers, was finally separated a small amount of a red
powder very similar to that isolated from the G. arboreum. The filtrate from
the lead precipitate, treated with basic lead acetate, gave a precipitate which
yielded isoquercitrin when decomposed as tisual. The ordinary yellow Indian
cotton flower, G. herbaceum, gave the same results as the G. neglectum, the
surprising feature being ihe absence of quercitnerilrin, an important constituent
of the Egyptian yellow flowers. The white and pink Indian flowers yielded
no definite results. Like gossypetin, (A) and 0:CeH4:0 in alcohol when
gently warmed, yielded maroon needles of gossypitrone, CsiHigOis, gradually
decomposed above 200°, m. about 255*'-259°, dyes Al-mordanted cotton
green. Like the red cotton petals, it gives a greenish brown precipitate
with lead acetate. The ease with which it is reduced to (A ) by SO2 indicates
that it is the quinone of (A). On wool the shades were identical with those
produced by (}l), thus showing the reverse properties of those of gossypetin
and its quinone. Heated to boiling with 7% HtSOi it is both hydrolyzed
and reduced, the main product being apparently gossypetin; this is an im-
portant difference from the behavior of the red product obtained above
from the red petals, indicating that the two are not identical.

COTTON 497

land cotton, great care must be exercised to guard against deteri-
oration of the Sea Island cottons by means of hybridization in-
duced by insect cross fertilization. It has been found expedient
to frequently obtain new seed from the coast districts. Sea
Island cotton is seldom if ever used for nitration, being employed
in commerce for spinning only the finest and best yams.

The American Upland cottons are grown to a much larger
extent than the other varieties, being used in the manufacture of
yams of medium quality. Of this cotton, the United States an-
nually produces something like three million tons — approximately
two-thirds of the world's production of this commodity. The
seeds are usually covered with fuzz or down, differing in this
re;3pect from the seeds of the Sea Island variety, which are smooth
and black. This down is used extensively for nitration in the
manufacture of smokeless powder, p)rroxylin lacquers, artificial
leather and bronzing fluids.

Microscopy of Cotton. The individual cotton filament is a
flattened, hollow, unicellular cell of ribbon-like form, or a col-
lapsible tube twisted a number of times, closed at the apex to
form a point, and without transverse partitions. The central
canal is comparatively large and runs nearly to the apex of the
fiber, the seed walls being membraneous. As the hair ripens, it
loses its cylindrical form and becomes more or less flattened, and
then appears as a narrow, somewhat opaque ribbon or band with
slightly thickened rounded edges. The cotton fiber, like all seed
hairs, naturally has but one end closed, the other being broken
off at the point of attachment. * The outer wall is covered with

1. The tmst in cotton fiber is not present in the early stages, but only
becomes developed after the boll has opened and the cotton has been exposed
to both light and air. These twists do not represent complete revolutions of
the fiber on its central axis, some being right-handed, and others in the oppo-
site direction. They occur at irregular distances from one another, and vary
greatly in the degree of convolution. There is great variation in the number
of twists in a given length of fiber, being increased by the care exercised in
cultivation. The number of twists vary directly with the fineness of the
fiber, and hence are most numerous per given length in Sea Island cotton.
It is a peculiarity that the presence of the twist imparts a roughness to the
fibers which apparently enables them to exert a certain amount of grip on
one another, thus facilitating their spinning. Unripe cotton is comprised
of thin, immature, transparent filaments, possessing little or no twist, and
are technically known as dead fibers. They acetate and nitrate with diffi-
culty, and yield cellulose esters which are not readily stabilized. For this
and other' reasons, the presence of much immature cotton reduces the com-
mercial value of the product.

498 TeCHNOI^OGY OP CEl,I^UIX)SE ESTERS

a waxy substance, — cutin (cuticular cellulose) — ^while dried-up
residues of protoplasm and cholesterin coat the wall of the central
canal. The peculiar swelling of the cellulose and bursting, coupled
with the partial breaking away of the cuticle under the action of
cuprammonium has been described by Wiesner. The protoplas-
mic inner wall, like the cuticle, also resists the solvent action of
this reagent. R. Haller^ has observed that both the cuticle and
protoplasmic layer resists the severe alkaline treatments of the
industrial bleaching processes, at all events in a great majority
of the fibers. The canal and protoplasmic layers readily absorb
basic dyestuffs such as safranine, and retain the color when
washed with boiling alcohol, whereas the cellulose remains un-
changed. The retention of dyestuff under these conditions is
considerable in the case of raw cotton, but decreases in propor-
tion as the waxy material is removed; in all cases, however, the
cellulose itself remains substantially colorless. The cutin of the
cuticular celluloses is completely removed by treatment for half
an hour with a caustic soda solution of mercerizing strength.
When a mercerized fiber is dyed with a substantive or direct
dyeing dyestuff, the cellulose itself is deeply colored, and on
treatment with cuprammonium it then swells uniformly and ul-
timately dissolves, leaving the protoplasmic wall of the central
canal as a translucent colored line. The unmercerized fiber, when
similarly dyed and treated with cuprammonium, exhibits a strongly
colored cuticle and lumen and only a slightly colored cellulose.
It would appear from the investigations of Haller that the cuticle
and protoplasmic wall of the lumen, besides possessing a mor-
danting property towards basic dyestuffs, constitute layers which
also exercise a strong affinity for substantive dyestuffs, and which,
being penetrated by these dyestuffs, only with diflSculty hinder
the access of the color to the cellulose between them. In this
manner the author endeavors to explain the darker shades ob-
tained with substantive dyestuffs on mercerized fibers deprived
of their cutin, whereas unmercerized cotton fiber when treated
with cuprammonium and then washed, and dyed with a sub-

1. Zts. Farben Ind. 1907, 6, 125; abst. J. S. C. I. 1907, 26, 523; Chem.
Zentr. 1907, 78, II, 953; 1908. 79, II. 1139; Jahr. Chem. 1905-1908. II,
3185; Wag. Jahr. 1908, 54, II, 376; Zts. ang. Chem. 1907. 20, 2085; 1908,
21, 267. See also R. Haller, Text. u. Farben Ztg. 14, 221; abst. C. A. 1907,
1, 2495; Chem. Zt^. 1908. 52, 838; abst. Meyer Jahr. Chem. 1908' IS, 505.

COTTON 499

stantive dyestuff, it is found that those portions from which the
cuticle has broken away are intensely colored, while those parts
which are still protected by the cuticular layer are only slightly
stained. Cuprammonium swells and dissolves the cellulose and
leaves the cuticular cellulose unchanged in the form of flax,
whereas strong alkaline solutions dissolve not only the cutin from
the cuticular cellulose, leaving the cellulose portion of the cuticle
as part of the normal cellulose of the fiber.

The microscopic characteristics of the cotton filament are so
pronotmced as to readily differentiate it from all other naturally
occurring fibers. As stated, it exhibits the appearance of a flat,
ribbon-like band, more or less twisted on its longitudinal axis, the
edges of the fiber, however, being somewhat thicker and usually
presenting irregular corrugations. At times, however, the fila-
ment presents the appearance of a smooth, flat band, with little
or no thickening at the periphery. It is a peculiar fact that the
twisted fiber does not appear to be continuous in any one direc-
tion, it having been observed that the fiber may be not only
twisted axially to the right, naturally then exhibiting a flattened
portion without any twist at all, but may also show an axial
twist to the left. It would appear that the twist of the cotton
fiber is a phenomenon coincident through cultivation, and is not
possessed, — at least in so noticeable a degree, — ^by wild cotton.

According to Monie,* the rotary motion begins with the proc-
ess of vacuation in the fiber, and this, in turn, is caused by the
withdrawal of some of the fluid in the fiber when the seed begins
to ripen, and as this is effected slowly and progressively, com-
mencing at the extremity farthest from the seed, i. e., the apex,
gradually receding toward the base, the free end or opened apex,
twists on its own axis several times, thus producing the convolute
form shown under the microscope.

According to Hanausek,^ with the increase in the number of
fiber twists in a given length of fiber, the greater is the regularity
of these twists, and correspondingly is the commercial value of
the cotton enhanced.

Herbig* takes exception to this statement. In general, how-
ever, for about three-quarters of its length, the fiber maintains

1. "The Cotton Fibre," page 25.

2. "Microscopy of Technical Products," page 61.

3. Zts. ges. Text. Ind. 1900, 17.

500 TECHNOU)GY OI^ CEl<I<ULOSB ESTERS

a comparatively uniform twist, then gradually tapers to a point,
which point is not only perfectly cylindrical but usually solid.
In some instances, portions of the fiber may exhibit cylindrical and
apparently solid spaces, which doubtless are caused by irregu-
larities in the growth of the cell. At such places the strength of ^
the fiber is materially weakened and will not absorb solutions
with the same avidity or to the same degree as the balance of the
filament. The cell wall is comparatively thin, the lumen occupy-
ing about two-thirds of the entire breadth. Between its thick-
ened edges the fiber tmder the microscope appears finely granular
and occasionally the siuiace is reticulated. Fibers of dead cot-
ton, or those which are immattu'e, are seldom twisted spirally and
do not have a lumen, but appear as thin transparent or translucent
bands. Unripe cotton or immattu'e cotton, therefore, has a de-
creased value for ptu'poses of manufacttu'e, as it contracts and
curls up in the warm atmosphere and high humidity of the mill,
and consequently, yam containing much imripe fibers depreciates
considerably.

J. Matthews^ has divided cotton fibers, from a microscopical
viewpoint, into the foiu* following classes:

(a) Those fibers which exhibit a smooth, straight, flat ap-
pearance with no suggestion of internal structure. These include
immature cotton fibers and also filaments which have been over-
ripe. The external wall, in general, of such fibers, is very thin.

(b) Filaments exhibiting a normal appearance through some
portions of their length and in other parts a structm-eless appear-
ance as in "a" above. These are termed *'kempy" fibers; the
solid tubular portion of which is particularly resistant to the
absorption of liquids and dyestuifs and consequently remain tm-
colored or are imperfectly colored, while the rest of the fiber is
dyed.

(c) Straight, tubular fibers, exhibiting a well-defined in-
ternal structure and a transparent cell wall of varying thickness.
Fibers of this character, under the microscope, have some of the
morphological appearance of linen, especially where the cell wall
is thick. The fibers of Gossypium conglomeratum are especially
liable to show this form.

(d) Normal structure of twisted band-like form. In cross-
1. "The Textile Fibres/' page 248.

COTTON 501

section, the immature fibers exhibit only a single line with little
or no structure and but slight indication of an internal opening.

The matme fiber is thicker in cross-section and usually ex-
hibits a central opening. The main charcteristic of the micro-
chemical reactions for cotton is that with cuprammonium solu-
tion previouly mentioned, cotton which has been bleached often
indicates the external cuticle to be absent, and hence such a fiber
may show but little or no distinction.

With iodine and sulfuric acid the cotton fiber becomes blue
in color, although the cuticle usually remains colorless. Tincture
of madder, gamboge, and dragon's blood, give an orange color;
magenta produces a red color, distroyed upon the application of
ammonia. The latter test serves as a chemical distinction be-
tween cotton ^and linen, provided the linen is unbleached, as flax
does not show this latter reaction to an appreciable extent. With
cotton filaments, anhydrous stannic chloride gives a black color.

E. Stanford and E. Viehoever^ have recently minutely de-
scribed the location and structure of the various glands of Upland
cotton {Gossypiufn hirstUum),^

Anatomical Structure of the Cotton Fiber. The individual
cotton filament appears to consist structurally of four distinct
parts as observed from its behavior with a solution of ammoniacal
copper oxide, and under the microscope is observed to swell with-
out uniformity, there appearing at regular intervals annular sec-
tions upon which the cuprammonium appears to act only super-
ficially, the result being that such fibers assume the form of a
distended tube constructed at irregular intervals somewhat after
the manner of string of sausages.

Hohnel believes these ligatmes are merely portions of the
cuticle, and explains their formation upon the assumption that
the fiber swells so considerably as to rupture the undisturbed
cuticle which, in places, adheres to the fiber in the form of irregu-

1. J. Agric. Research, 1918, 13, 419; abst. J. S. C. I. 1918, 37, 460-A.
See also A. Viehoever, L. Chemoff and C. Johns, J. Agric. Res. 1918, 13,
346; abst. J. S. C. I. 1918, 37, 485-A; C. A. 1918, 12, 1662.

2. The glands exposed to light were found to be surrounded by an
anthocyan-bearing envelope of flattened cells and to contain quercetin,
"probably partly or wholly in the form of its glucosides querdmeritrinor
isoquercitrin," together with ethereal oil, resins, and perhaps tannins while
the glands not exposed to the light were found to contain gossypol but no
anthocyans. A table is given showing the microchemical reactions of the
secretions of the internal glands and substances isolated from them.

502 TKCHNOUXJY OI^ CBLLXn^SB ESTERS

lar patches visible under the microscope only with difSculty by
reflected light, but readily so upon the interposition of a nicol
prism. Occasionally the rupture is observed to occur obliquely
in respect to the length of the fiber, in which instance the cuticle
becomes drawn together in annular bands surrounding the per-
iphery, while between these rings the greatly distended cellular
portions protrude in the form of globules. With bleached cotton
the cuticle may be almost entirely obliterated, and such fibers
will, therefore, not exhibit the characteristic appearance above out-
lined. When the fiber has become greatly swollen by the action
of the reagent it soon begins to pass into solution, whereupon
the walls of the central canal appear quite prominently. The
dissolving action proceeds with great rapidity; however, there is
a cuticular tissue siuroimding the fiber which resists the action
of the solvent for a much longer period than the inner paren-
chymetous portion. The four structiu*al parts thus made, ob-
served by the treatment with the reagents are:

(a) The main protoplasmic cell wall consisting primarily of
piu*e cellulose and rapidly and readily completely soluble in the
cuprammonium reagent;

(b) An external cuticula, perhaps slight sclerenchymetous,
of a inodified cellulose, much more resistant to the action of the
reagent;

(c) The central canal wall containing fatty, waxy and cho-
lesterol-hke bodies which resist the reagent of the solvent much
more energetically than the cuticula;

(d) The annular ligattu'es which sturound the fiber at ir-
regular intervals and which persist even after the canal walls have
been obliterated by solution.

Butterworth has examined cotton fiber after treatment with
cuprammonium solution under high magnification (from 1200 to
IGOO diameters), and has observed spiral threads which appar-
ently cross and tightly bind around the fiber at irregular distances,
as well as spiral threads which pass from one structiwe to another,
the core of the fiber exhibiting a spiral form which, in cross-
section, appears to be made up of concentric rings.

Upon immature or unripe fibers, cuprammonium solution
has a greater solvent action, such fibers exhibiting no structiu'al
differences. The tubular-shaped fibers, in general, swell greatly

COTTON 503

and finally dissolve without any appreciable structural modifica-
tions except that the usual inner core is left. Examination with
a mega-microscope, tmder the highest magnification, has not
resulted in indicating any cellular structure pertaining to cellu-
losic contents of the cellular fiber. M. Fort* has dealt with the
details of the destructive breakdown of cotton tmder the process
of beetling, and C. Cross and E. Bevan^ have examined a sam-
ple of powdered cellulose thus produced. The sample was found
non-reactive towards polarized light in comparison with the
original cotton fibers; the hygroscopic moisture 5%-6%; formula
of the dry product CftHioOs; and treatment with 17.5% NaOH
solution gave indications of a decided modification, yielding
40%-56% of the soluble forms of cellulose (a- and 7-celluloses),
a large proportion of which was precipitable on acidification.
The product showed many analogies with the starches in behavior.'

Dimensions of Individual Cotton Fibers. According to the
United States Department of Agricultiu'e BuUetm No. 33, the
following table compiled by them from numerous measurements

1. J. Soc. Dyers Col. 1918, 34, 9; abst C. A. 1918, 12, 2694; J. S. C. I.
1918, 37, 121-A; Ann. Rept. Soc. Chem. Ind. 1918, 3, 161.

2. J. Soc Dyers Col. 1918, 34, 215; abst. C. A. 1919, 13, 910; J. S. C.

I. 1919, 3S, 7-A. C. Cross, J. Soc. Dyers, 1919, 35, 271, found in this treat-
ment considerable heat was developed up to a maximum temperature of 200**.
The following results were obtained on examination of the fiber under the
action of sodium hydroxide solution of 17.5% concentration. Original cotton:
a-cellulose, 99.7%; /3-cellulose, 0.8%. Half -tendered portion: a-cellulose,
92.3%; /3-cellulose, 4.9%; hygroscopic moisture, 3.6%. Fully tendered por-
tion: a-cellidose, 78.0%; /^-cellulose, 16.2%; hygroscopic mixture, 3.3%. The
results show that the destroyed fiber was not identical with the fine powder
previously described.

3. R. Haller (Chem. Ztg. 1908, 32, 838; abst. C. A. 1909, 3, 489; J. S.
C. I. 1908, 27, 976; Bull. Soc. Chim. 1909, 6, 479; Chem. Zentr. 1908, 73,

II, 1138; Meyer Jahr. Chem. 1908, IS, 505; Wag. Jahr. 1908, 54, II, 376;
Zts. ang. Chem. 1908, 21, 2556. See also Zts. Parben Ind. 1907, S, 125,
127. J. Soc. Dyers Col. 1907, 23, 167) has recorded observations made on
ripe and tmripe fibers obtained from Gossypium arboreum. He describes
the "dead cotton" as ribbon-shaped with many indentations, distinct stripes
and granular appearance. The interior appears full of a deposit. Am-
moniacal cuprous oxide causes only a swelling and the indentations dis-
appear. Considerable time is required to dissolve the fibers and the very
young fibers seem to be totally unaffected by this reagent. The change of
color from yellow to dark blue which is observed when ZnCls-I solution is
applied takes place more quickly with the ripe than with the dead cotton.
A solution of I in KI colors dead cotton a pale yellow; ripe cotton, yellow to
brown. Under the microscope it is seen that only the contents (protoplasm)
of the dead fibers is colored. An 18% solution of NaOH mercerizes ripe cotton
as usual while dead cotton retains its shape and becomes more transparent.
The lumen and contents almost disappear. Examined in a ray of polarized
light the dead fibers appear non-luminous in a dark field (i. e., no double

504

TECHNOLOGY OF CELLUtOSE ESTERS

taken, coveringa period of years, shows the maxiniiitn, tnitiimiitn and
and average length of some of the more important varieties of cotton :

Variety

•

Length in Inches

Diameter
Inches

Maximum

Minimum

Average

Sea-island .................

1.80
1.16
1.12
1.06
1.52
1.31

1.02
1.21
1.65

1.41
0.88
0.87
0.81
1.30
1.03

0.97
0.95
1.36

1.61
1.02
1.00
0.93
1.41
1.17

0.89
1.08
1.50

0.000640
0.000775
0.000763
0.000763
0.000655
0.000790

0.000844
0.000825
0.000730

New Orleans

Texas

Upland

Hfi^yptian

Brazilian

Indian varieties:
Native

American seed

Sea-island seed

The varieties and qualities of cotton met with in commerce
and all suitable for nitration, according to Hannan, are as follows:^

refraction), the ripe fibers under the same conditions show up brightly.
The small affinity of dead cotton for dye-stuffs may be confirmed by dyeing
in an indigo vat. However, in the case of the substantive dyes the dead
cotton seems to have a much greater affinity than the ripe cotton. If dead
cotton be mordanted with tannin and tartar emetic and then dyed in methyl-
ene blue only the cell contents will be colored. By treating such fibers with
Schweizer's solution the difference in color of the contents and cell wall is
more noticeable. The peculiar properties of dead cotton seem to point to
an abnormal composition of the cell membrane.

M. Adam, Can. P. 170435, 1916. R. Adler, D. R. P. 314311, 1914;
abst. J. S. C. I. 1920, 39, 60-A. J. Aktschourin, Norw. P. 22900; abst.
Chem. Ztg. 1913, 37, 244. C. Ahny, U. S. P. 1191142. M. Althaussc, U. S.
P. 679203, 679204, 1901; E. P. 19039, 1900; P. P. 304723; D. R. P. 123121.
K. Asker, Pap. Fabrikant, 16, 133; abst. Chem. Zentr. 1918, 89, II, 161;
C. A. 1920, 14, 345. F. Barrett, J. S. C. I. 1920, 39, 81-T. E. Berl, F. P.
454753, 1913; D. R. P. Anm. B-67713; abst. Chem. Ztg. 1913, 37, 142. E.
Becker, Pap. Fabrikant, 1919, 17, 1325; abst. C. A. 1920, 14, 837. R. Bloch-
mann, D. R. P. Anm. 68060; abst. Chem. Ztg. 1913, 37, 245. C. Braun,
E. P. 137831, 1920. D. Brauns, Proc. Roy. Acad. Amsterdam, Sec. Sci. 1908,
10, (2), 563; abst. C. A. 1909, 3, 318. S. Bom and J. Nelson, J. A. C. S.
1915, 37, 1763; abst. J. S. C. I. 1915, 34, 845; C. A. 1915, 9, 2249. See C. A.
1914, 8, 1435. A. Bomer, E. P. 16262, 1904. B. Bull, J. C. S. 1897, 71,
1090; abst. Chem. News, 1897, 78, 249; Chem. Centr. 1897, 88, II. 733;
Jahr. Chem. 1897, 50, 1507; Meyer Jahr. Chem. 1897, 7, 151, Burgess
Sulphite Fiber Co., Can. P. 161395, 162161, 162163, 1915. C. Clerc, E. P.
Appl. 1965, 1918. L. Collardon, Can. P. 161932, 1915. Compagnie Francaise
des Applications de la Cellulose, Swiss P. 57951, 1911. J. Cottin and J. Four,
Belg. P. 251556; abst. Chem. Ztg. 1913, 37, 245. C. Cross, J. S. C. I, 1920.
39, 124-R. C. Cross and E. Bevan, J. C. S. 1918, 113, 182; abst. C. A. 1918.
12, 1380. J. DeCew, Can. P. 170723, 1916. P. and C. Depoully, and la
Societe C. Garnier and F. Voland, E. P. 8642, 1884. V. Drewsen, U. S. P.
1283113, 1918; 1298479, 1298480, 1298481, 1919.

1. This table is taken, with the kind permission of the author. Dr.
J. Merritt Matthews, from "The Textile Fibres."

COTTON

505

Types

Sea-Uland.

Bgyptian...

Peruvian . . .

Brazilian .

American .

Variety

L'gth
Ins.

Diam-
eter,
Inches

Hdisto

2.20

.00063

Ploridai

1.85

.00063

Fiji

1.75

.00063

Tahiti

1.80

.00063

Brown

1.50

.00070

GaUini

1.60

.00066

Menouffieh....

1.50

.00066

Mitafifl

.1.25

.00066

White

1.00

.00078

Rough

1.25

.00078

Smooth

1.00

.00078

Red

1.25

1.50
1.15
1.15

.00078

.00079
.00079
.00079

Pemambuco.
Maranham....
Ceara

Paraiba

1.20

.00079

Rio Grande . .

1.15

.00079

Maceio

1.20

.00084

Santos

1.30

.00084

Bahia

Orleans

1.1

.00077

Texas

1.05

.00077

Allansced

1.20

.00077

Mobile

1.00

.00076

NorfoUcs

1.00

.00076

St. Louis. . . .

0.90

.00076

Roanokes ....

0.90

.00076

Boweds

Benders

1.10

.00077

Memphis. . . .

1.00

00077

Peelers

1.25

.00077

Uplands

1.00

.00077

Alabama

0.90

.00077

Counts

Use

300-400

Warp
or weft

150-300

do.

100-250

do.

100-250

do.

120-down

do.

250-down

Warp

200-down

Weft

100
70

Warp

or weft

do.

50-70

Warp

50-70

Weft

40-50

Warp

50-70

50-60

60

Warp

do.

Weft

50-60
40-50

Warp

or weft

Weft

40-60
50-60

Warp

or weft

Weft

40-50
34-46

Warp

or weft

do.

32-40

do.

50-60

Warp

40-50
40-50

Warp

or weft

Weft

30-32

Warp

30-34

do.

36
60

Weft
Warp

40-50

do.

60-80

Weft

3O40

do.

26-30

Warp
or weft

Properties

Ixmg, fine silky, and
of uniform diam-
eter

Shorter, but similar
to above

Less uniform in
length, but silky
and cohesive

Good, fine, and glossy
staple

Long, strong, highly
endochromatic

High-class staple of
good strength

Of good staple and
luster

Fairly good staple

Pearly white, good

long staple
Strong, woolly, and

harsh staple
Less woolly and

scoter staple
Color weaker and

harsher than brown

Egyptian
Strong and wiry
Harsh and wiry
Goodj white, and co-
hesive staple
Fairly strong, harsh,
of gbod color
Soft, white, and harsh

staple
Soft, pliable, and

good for hosiery
Exotic from American

seed, white and

silky staple
Fairly strong, but

harsh and wiry
Medium length,

pearly, white
Similar to above.

rather harsher and

more glossy
Good, white, long;

blends with brown

Egyptian
Even-running staple,

soft and cohesive
Used for Oldham

counts of 50's
Staple irregular,

glossy, but short
A white and strong

staple
Similar to Uplands
Strong, creamy or

white, for Turkey-
red dyes
Bluish white, for ex-
tra hard twists
Long, silkv, fine sta-
ple ; adapted for

velvets, etc.
Glossy when clean.

apt to be dull,

sandy, and leafy,
Short staple of less

strength, varying

color

506

TBCHNOUXJY OP CBLLULOSS BSTBRS

Diam-

Types

Variety

L'gth
Ins.

eter
Inches

Counts

Use

Properties

American . . .

Linters

8-10

Weft

Short-stapled gin
waste

Tennessee....'

0.00

.00077

28

Warp
or weft

Of varying length
and color

Greek

Smyrna

1.25

35-40

Warp

Harsh and strong,
adapted for double
yams

African

Lagos

0.80

20-26

Weft

Dull and oil-stained,
irregular in length
and strength

Carthagena . .

1.50

26

Warp

Prom exotic seeds;

West Indian.

fairiy strong

La Guayran..

1.20

40

Warp

or weft

but silky staple

China

China

1.00

30

Weft

Harsh, short, and
white

Australian....

Queensland . .

1.76

.00066

120-200

W«rp
or weft

Long, white, silky,
fine diameter

East Indian.

Oomrawuttee

1.00

.00083

26-32

Warp

Short, strong, and
white

Hingunghat. .

1.00

.00083

2»-36

Weft

Best white Indian

staple
Generally dull and

Comptah. . . .

1.05

Warp

or weft

charged with leaf
Like Hingunghat.

Broach

0.90

• ••■«■•

2»-36

Weft

gives g(x>d white

weft

Dharwar

1.00

28

Warp

Bzotic from American
seeds

Assam

0.50

15-20

Warp

White, but harsh, to
blend with other
cottons

Bengals

0.80

20-30

Warp
or weft

Dull and generally
charged with leaf

Bilatu

0.60

10-20

do.

Weak, brittle, and
coarse

DhoUerah

0.70

15-20

do.

Strong, dull, and co-
hesive

Surat

0.60

10-15

do.

Dull and leafy, often
stained

Scinde

0.50

to 10

do.

Very strong, dull,
short, and poor
staple

Tinnevclly. . .

0.80

24-30

do.

Lustrous, white, soft,
and adapted for
hosiery

Bhownuggar.

1.00

28-30

Warp

White when clean :
often leafy and
dirty

Kast Indian.

Cocoanada. . .

0.70

• •«•■!«

10-14

Brown
weft

Brown and dull; use
as quasi- Egyptian

Bourbon

1.00

30

Weft

Exotic; of good sta-
ple; scarce

Khandeish . . .

0.80

.00083

20-26

Warp

Similar in class to

Madras or

or weft

Bengal

Western ....

0.70

15-20

do.

Used for low yams in
coarse toweling, etc.

Rangoon

0.60

to 10

Warp
or weft

Weak. dull, often
stained and leafy

Kurrachee. . .

0.90

28

do.

Pairiy strong, dull
and leafy

Italian

Calabria

0.90

26-28

do.

Pairiy strong, irregu-
lar and dull, leafy

Turkey

Levant

1.25

.00077

36-40

Warp

Harsh, strong, and
white

The extreme variation in the length and diameter of diflfer-
ent kinds of cotton, according to Bowman/ is as follows:
1. "Structure of the Cotton Fiber."

COTTON

507

Cotton

American (Orleans)

Sea-Island

Brazilian

Eg3rptian

Indian (Surat)

Variation in
length

0.28 in.
0.39 in.
0.28 in.
0.22 in.
0.25 in.

Variation in
Diameter

0.000390 in.
0.000360 in.
0.000340 in.
0.000130 in.
0.000391 in.

Bowman has found that Egyptian cotton is the most regular
both in length and in diameter of filament, while Sea-Island
cotton, although possessing the greatest length and fineness of
staple, also exhibits the maximum in variation. He has also ob-
served that the variation in diameter is proportionately much
larger than the variation in length. He has computed that if
a single filament of American cotton be magnified until its diam-
eter reaches one inch, the length will be slightly over one hundred
feet, while a similar fiber of Sea-Island cotton of identical diameter
would extend about one hundred twenty feet. It requires from
14,000 to 20,000 individual fibers of American cotton to weigh
one grain, this being Equivalent to about 140,000,000 per avoirdu-
pois pound, the individual fiber having an average weight of only
about one six hundred thousandth of a grain. If the separate
fibers contained in one pound of such a cotton were placed end to
end in a straight line they would extend some 2,200 miles.

The length of staple of the more readily occurring varieties
of cotton, according to Hohnel, is as follows:

Gossypium barbadense (Sea-Island) 4 . 05 cm.

Gossypium barbadense (Brazilian) 4 . 00 cm.

Gossypium barbadense (Egyptian) 3 .89 cm.

Gossypium vitifolium (Pemambuco) 3 . 59 cm.

Gossypium conglomercUum (Martinique) 3 . 51 cm.

Gossypium acuminatum (Indian) 2 . 84 cm.

Gossypium arboreum (Indian) 2 . 50 cm.

Gossypium herbaceum (Macedonian) .... 1 .82 cm.

Gossypium herbaceum (Bengal) 1 . 03 cm.

The length and diameter of individual cotton filaments, as
shown by mean determinations of Deschamps, Leigh, Alcan,
Kuhn, Monie and Bowman, as arranged by C. Mitchell and R.
Prideaux, are given in the following two tables:

508

TECHNOIXXJY OF CEU.UU)SE ESTERS

TABLE XXXVIII.— DIAMETER OF FIBERS
In Micromilliiiieters (n) and Fractions of an Inch (1 ^ « 0.000039 inch)

D^schamps

Alcan

Monic

(Micro-
milli-
meters)

In.

M

In.

l>

Mean
In.

Sea-Island

Fiji

16.5
17.2
10.4

0.00064
0.00067
0.00076

6.6-13.3

0.00025-0.00052

3.5
16.3
17.3

0.000635
0.000637
0.000675

Egyptian

Algerian

ia-25
10-22.2

0.00039-0.00007
0.00039-0.00057

U. S. A

U. S. A.:

Bourbon ....

Orleans

21.0
22.2

0.00062
0.00087

19.3
19.7

20.1
20.1
20.0

21.3
21.7
21.3
21.7
22.1
21.3

0.000757
0.000769

0.000787
0.000787
0.000781

0.000833
0.000847
0.000833
0.000847
0.000869
0.000833

West Indian.. .

Brazilian:
Pemambuco
Maranham. .

28.0

0.00100

Peruvian

Indian:

Hinffunfthat .

21.5

0.00084

13.3-20

0.00025-0.00078
0.00039-0.00129

DhoUerah.. .

10-33.3

Broach

Comptah... .

22.5

0.00088

0.00055-0.00118

14.2-30.3

Bengal

W. Madras. .
N. Madras..
Scinde

25.3
22.5
20.0

0.00098
0.00088
0.00078

11.1-16.6

11.1-16.6

13.3-25

0.00043-0.00065
0.00043-0.00065
0.00025-0.00097

21.0
19.7

o.ooosio

0.000769

African

Smyrna

Chinese

26.2

0.00122

25-27

0.00097-0.00105

Moisture in Cotton. The normal hygroscopicity of cotton
is less than either that of wool or silk. Under favorable condi-
tions it varies between 5% and 8%, although in an unusually
moist atmosphere this amount may be materially increased.

According to Kuhn^ a portion of this moisture must be re-
garded as a constituent of the cotton filament, that is ** water of
constitution." He states the amount is usually about 2% which
can be expelled at 105° C. and above, when the fiber then becomes
harsh and brittle and loses substantially all its elasticity. The
observations of Kuhn, however, have not been corroborated by
other investigators.

According to F. Beltzer,^ Indian cottons tmder preferable

1. Die Baumwolle page 131. According to J. Huebner and W.
Pope (J. S. C. I. 1904, 23, 404; abst. Zts. Farben. u. Textil. Chem. 2, 315.
Chem. Centr. 1904, 75, I, 1625; Chem. Zts. 1903-1904, 3, 77; Jahr. Chem.
1904, 57, 1813; Zts. ang. Chem. 1904, 17, 777, the article being illustrated
with microphotographs), treatment in boiling water appears to increase the
affinity of cotton for substantive dyestuffs, and to decrease it for basic dye-
stuffs.

2. Les Matieres Cellulosiques.

COTTOK

509

0

•••

a

>

r

s

Lagos

Smvma

African :
Natal

s-

?

^

s

s

Peruvian

Indian:

Hingungha
DhoUerah .
Cotnbtah . .

Brazilian :
Pemambuc
Maranham
Paraiba

5

U. S. A. (U

Georgia. . . ,

(Orleans) Mis

Louisiana. . . .

1

3

w

3

e.

5

Sea-Island, E
Fiii

Descriptioc
Cotton

f*

0

• 2. "0

■ 0.

s •—

►••

o

IS : s
2: Q-

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td'

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?^ioSS

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10-

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. H«00

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•J

tOCn
CnO

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cn

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bo-

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ooo

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510

TECHNOLOGY OI? CEI<I<ULOSB ESTERS

atmospheric conditions, absorb about 1.5% more moisture than
American cottons, although this difference is manifested only
within well-defined limits as to the sattu'ation of the air with
aqueous vapor. When the relative humidity is 40%-60% the
diflFerence in the amount of moistitfe absorbed is only one per cent.
Egyptian cotton is claimed to occupy a position intermediate be-
tween the Indian and American cottons in this respect. Beltzer
has not corroborated these assertions by experimental proof.
The hygroscopicity of cotton as well as other vegetable fibers is
of extreme moment in its proper conditioning during the variQUS
processes of spinning, carding and finishing to which it is neces-
sarily subjected in the textile arts. This also has an influence on
the commercial valuation of the raw material, as the hygroscopical
moisture varies proportionately with increase of water vapor in
the atmosphere and it, therefore, is necessary to establish a normal
standard of reference. The amount of "regain" allowed in the
condition of cotton on the European continent is 8.5%. Harts-
home has computed the following table as to the regain of cotton
for various temperatures and humidities:

TABLE XL.— REGAIN FOR COTTON AT VARIOUS TEMPERATURES

AND PERCENTAGES OP HUMIDITY,

Degrees Fahrenheit

Percentage
Humidity

50

60

70

80

90

100

40

5.90

5.79

5.65

5.47

5.25

5.05

50

. 6.89

6.78

6.63-

6.45

6.18

5.86

60

8.00

7.87

7.69

7.44

7.13

6.80

70

9.14

9.00

8.79

8.58

8.32

8.05

80

10.58

10.42

10.23

9.95

9.70

9.60

90

12.28

12.10

11.85

11.56

11.43

11.85

100

14.12

14.00

13.80

13.65

13.70

14.50

In determining the influence of moisture on the strength of
cotton and cotton fabrics, the Societe Industrielle de Mulhouse^

1. A. Scheurer, Bull. Soc. Ind. Midhouse, 1902, 73, 34; abst. J. S. C. I.
1902, 21, 701 ; Wag. Jahr. 1902, 48, 11, 562. The absorption property of filter
paper appears to be due, not so much to the absorption by the capillary
tubes of the filaments themselves, as to the capillary interstices formed by
the arrangement of the fibers in proximity or juxtaposition to each other
(Papierfabr. 1906, 4, 1834).

COTTON 511

have established the following as the normal standards:

Normal strength of cloth 100

Saturated with moisture 104

Dried on hot cylinder 86

Again dampened 103

It would appear from these results therefore, that the alter-
nate moistening and hot drying of cotton induces little or no
deterioration. Combination of cotton with water may occur in
two distinct forms:

1. As hygroscopic moisture, and

2. As water of hydration.

The hygroscopic moisture is considered as that absorbed from
normally moist air and varies in quantity from 8% to 12% de-
pending upon the temperature and vapor tension of the air. This
water is completely eliminated by heating the cotton to 105°,
the latter then being termed in the trade "desiccated." The water
of hydration or water of constitution is separable only at a
higher temperature — ^from 150° to 170° has been required. At
these temperatures an additional loss of weight of from 1% to
3% results. The water of hydration may also be estimated by
first desiccating the cellulose at 105°, then boiling in toluene and
distilling as first pointed out by C. Schwalbe.^ Cotton contain-
ing water of hydration has been called cellulose hydrate or hydro-
cellulose (see p. 127). The limit of the hydration in cotton msly
be considered as corresponding to mercerized cotton (see Cellulose
Hydrate, p. 213).

It should be noted, however, that the above statements re-
quire experimental verification in many instances before final
acceptation. Schwalbe determines the hygroscopic water in
cotton or other cellulosic fiber as follows: Approximately 3 grams
of the material is boiled in 300-500 cc. of pure toluene, which has
a boiling point of about 110°. The water is collected by distilla-
tion in a graduated tube and from a determination of its volume
the percentage of moistiu-e may be calculated, the distillate con-
sisting of two layers of which the water forms the lower. This
method is applicable not only to the determination of moicture
in normal cellulose but in mercerized cotton and hydrated cellu-

1. Zts. ang. Chem. 1908, 21, 401, 1321; abst. J. S. C. I. 1908, 27, 295;
Chem. Zentr. 1908, 73, 1, 1336; 11. 447; J. C. S. 1908, 94, ii, 627; C. A. 1908,
2, 1885, 2448,

512 TECHNOIX)GY OI^ CELLUW)SE ESTERS

lose as well. The following results indicate the amount of mois-
ture as determined by Schwalbe in this manner with varying
materials:

Paper made from cotton 6,5%

Mercerized cotton 9 .25%

Mercerized wood pulp 10.25%

Viscose 11 .25%

Vegetable silk 6.7 %

Cotton which has been deprived of its hygroscopic moisttu'e by
drying in an oven at 100° to 105** by the usual method, rapidly
recovers its original amotmt of moisture after exposure to the
atmosphere at room temperature for 10 to 12 hoiu*s. When mois-
ture has been removed, however, by means of boiling toluene, the re-
covery in percentage of water is much less. When the drying opera-
tion is conducted at an abnormally high temperature the recovery
of moisture is considerably less, so that the normal recovery may
be taken as the exact measure of the hygroscopic moisttu'e after
the elimination of the water of hydration.

A. Sclmeizer' contends that the estimation of the percentage
of moisture in cotton gives only relative figures since the drying
is not carried out in an absolutely anhydrous atmosphere but in
a more or less moist atmosphere at 105° to 110°. Cotton dried
to constant weight at 110° still loses water when dried at 150°,
which is taken up again if the temperature is dropped to 110°.
If a sample of cotton is conditioned on a damp day and again on
a dry day, appreciable different results are obtained, which, in
the purchase of large quantities may lead to litigation. Proper
significance has not hitherto been attached to these conditions.
This author appears in his deductions to have left out of considera-
tion an important factor, viz., the element of time.

Schulz has shown that certain carbohydrates when heated even
to 100° become permanently changed, and the same holds good
for the cotton fiber if the heating be sufficiently prolonged. Fur-
thermore, J. Lester, contradictory to Schweizer, has shown that
when cotton is dried at 110° it never regains the whole of the
amount of moisture lost in drying. Lester* has found that by

1. Leipz. Monatsch f. Text. Ind. 1908, 139; abst. J. Soc. Dyers Col.
1908, 24, 268; Chem. Ztg. Rep. 1908, 32, 436.

2. J. S. C. I. 1902, 21, 388; 1905, 24, 171; abst. J. Soc. Dyers Col.
1902, IS, 187; Jahr. Chem. 1902, 55, 1051; Meyer Jahr. Chem. 1905, IS,
511; Zts. ang. Chem. 1905, IS, 1988; Chem. Ccntr. 1905, 78, II, 83; Wollen
und Uincnind, 1905, 25, 640.

COTTON 513

extracting pure cotton with boiling distilled water, there was
frequently obtained as much as 2% of soluble matter and never
less than 1.5%. The nature of this ''water extract" is very com-
plicated and has, as j^et, not been determined, but it is, however,
exceedingly hygroscopic, absorbing as much as 28% of moisture.
The power of cotton for the absorption of moisttu-e from the at-
mosphere appears to depend largely upon the presence of this
substance. It is apparent that the author's statements evidently
refer to raw cotton.

Will* has determined the hygroscopicity of a large number of
celluloses, by drying the material to constant weight at 40° and
exposing it subsequently to an atmosphere satiu'ated with aqueous
vapor. His figures for hygroscopicity give the increase of mois-
ture content compared with by the material at 40° in the drying
oven to that at 25° in water vapor saturated air.

(A) Natural Cottons:

Texas wool 7.3%

Sea-Island 7.3%

Superfine machine ginned Seinde 7.4%

Mid fair Georgia 7.9%

Fine Churka Belati 7.3%

East Indian wool, not further designated 8.0%

(B) Other Celluloses:

Cotton from spinning waste 7 . 5%

Cleaned cotton rags 6 . 4%

Swedish woodpulp 7.0%

Woodpulp from Waldhof 6.7%

Hemp 7.7%

Jute 10.87o

The determinations by the same author concerning the in-
fluence of purifying the cellulose on the hygroscopicity are as
follows:

1. Mitteilungen, 4, 12. Anon., Pap. Fabr. 1919, 17, 1919; abst. C. A.
1920, 14L 469. A. Berglind. Can. P. 192666, 1919; abst. C. A. 1919, 13,
2762. E. Cadoret and A. Jost, E. P. 8558, 1894. E. Carstensen de Segundo,
E. P. 114435, 114450. 1918. N. Fleming and A. Thaysen, Biochem. J.
1920, 14, 25; abst. J. S. C. I. 1920, 39, 263-A. C. Henry, E. P. 20092, 1899.
M. Mayer, D. R. P. 312178, 1918; abst. J. S. C. i. 1919, 38, 756-A. T.
Moreul, Bull. sd. Pharmacolog. 20, 101. T. Ogle, U. S. P. 1312348, 1919;
E. P. 116214, 1917; abst. J. S. C. I. 1918, 37, 461-A; 1919. 38, 678-A. R.
Kadish and T. Buscher, U. S. P. 1327394, 1920; abst. C. A. 1920, 14, 849.
O. Kress, Paper, 1920, 25, 964, 1009; abst. J. S. C. I. 1920. 39, 858-A. See
also J. S. C. I. 1919, 38, 263-A. F. Stockton, U. S. P. 1295078. 1919; E. P.
132422, 1918; abst. J. S. C. I. 1919. 38, 319-A. 814-A. A. Streiff, Swiss P.
62103. 1913; abst. C. A. 1914. 8, 2262. A. Deiss and C. Fournier. D. R. P.
Anm. D-22139, 1909; F. P. 403518, 1909.

514

TECHNOLOGY OF CKLLUlrOSE ESTERS

Manner of Treatment

Initial material

Pulped

Extracted with ether

Treated cold with 2% HCl. .

Treated with 5% HjS04

Boiled with NaOH 10%

Bleached with CaOClj 10%. .
Boiled with H2O for 50 hours

Dried at 70°

Dried at 100 *»

Dried at 170°

Dried at 200°

Hygroscopicity of Cottons

Texas

Dynamite Sea- Georgia

Wool

Cotton Island

7.3

' 7.5 7.3 7.9

9.8

8.4 9.4 9.3

9.7

8.5 9.4 11.2

5.5

5.4 6.6 5.9

6.5

6.5 6.6 6.3

6.6

6.6

6.3

7.5

7.8 •

6.3

7.0

7.5

6.8

7.2

6.7

7.2

6.1

5.04

C. Beadle and O. Dahl^ have determined the gain in weight
and also the rise in temperature when the following anhydrous
celluloses are exposed to the air: (1) Cotton wool. (2) Cot-
ton wool mechanically pulverized so as to reduce the fibers to
about one-twentieth of their former length. (3) Coarsely ground
viscoid (an amorphous cellulose). (4) Finely ground viscoid.

(1) and (2) take about 60 minutes to come to constant weight.
(1) gains considerably less than (2). The two viscoid samples
took nearly four hours to come to a constant weight, but the
finely powdered gained considerably less than the coarse. The
curves given for the increase in weight show that there is increased
regularity with the increased subdivision of the cellulose. The
results also show that this holds good whether the cellulose is in
the fibrous or amorphous condition.

The temperature curves in which the temperattu-e of the air
is reduced to a straight line, show that cotton reaches a maximum
of about 4.5° F. in 10 minutes. The temperature gradually falls,
and reaches the atmospheric temperature in about 60 minutes.
Disintegrated cotton reaches a maximum of 7° F. in 20 minutes,
and takes much longer to fall. The curve is also much more
regular than that of cotton wool. Both kinds of viscoid fall sud-

1. Chem. News, 1896, 73, 180; abst. J. S. C. I. 1896. 15, 362; Bull.
Soc. Chim. 1896,16, 1851; Chem. Centr. 1896, 67, I, 1227; Jahr. Chem.
1896, 49, 1029.

COTTON 515

denly below the atmospheric temperature during the first min-
ute. They reach the atmospheric temperature again in about
two minutes. They reach a maximum of 7° F., and fall slowly
but somewhat irregularly. It appears that each cellulose has a
characteristic temperattwe curve. In each case the degree of
fineness affects the regularity of the curves.

It would appear from^the investigation of Sindall^ that the
hygroscopic moisttu-e content of completely pulped cellulose is
greater than that of ordinary fibrous cellulose, also ground in the
pulper. Air-dry sheets of paper gave the following values:

Duration of Pulping Hygroscopicity

4 hours 5.8%

10 hours

5.9%

17 hours

6.9%

25 hours

6.8%

33 hours

7.0%

After complete drying and exposure

to the

: air for 3

4 hours

5.18%

10 hours

6.55%

17 hours

6.02%

25 hours

6.00%

33 hours

6.11%

After complete sattu-ation with moisture:

4 hours

11.2%

10 hours

11.7%

17 hours

12.9%

25 hours

12.5%

33 hours

14.0%

0. Masson^ has investigated the wetting of cotton by water
and by water vapor, and has found that when dried cotton is
immersed in water, its temperature rises for some time, and after-
wards slowly falls. The same phenomenon occurs when the
cotton-wool is exposed to air saturated with aqueous vapor; and
in both cases the courses of the curve representing the rise and
fall are similar, and are similarly affected by previous moisture
and other conditions. In the latter case the effect is due to the
condensation on the cotton of vapor which it absorbs, for both
absorption and heat-production occur for many hours, and the
amount of heat is approximately that calculated from the quantity
of vapor absorbed. In the former case, though absorption cannot
be directly observed, it must occur, and the air adhering to the

1. Mon. papet. franc. 1909, 45, 31.

2. Proc. Roy. Soc. 1904, 74, 230; abst. J. S. C. I. 1904. 23, 1143;
Chem. Centr. 1905, 76, I, 27.

516 TECHNOU)GY OF CELLULOSE ESTERS

fiber maintains the separation necessary for distillation to occur.
Medical or "absorbent" cotton-wool, though it behaves like
ordinary cotton-wool in saturated air, does not show the same
rise of temperatm^e in water. The water condensed on the cot-
ton certainly does not combine chemically with it; and it is not
simply condensed as a film on the surface, for the quantity is
too great for the recognized maximum thickness of such film.
It probably undergoes osmotic diffusion into the fiber and forms
a sort of solid solution of cellulose and water, having a vapor
pressure always lower than that of water. Cotton in air satur-
ated with alcohol vapor, or guncotton or glass wool in air satur-
ated with water vapor, showed similar behavior, though to a
slighter extent, and no effect was produced when cotton was
inlmersed in absolute alcohol or glass wool in water, so that the
air-insulation is necessary to produce the effect. This thermal
effect is much greater than, and probably quite different from
that investigated by Parks, occurring when finely divided solids
are mixed with water; but the effects long ago observed by Pouillet
when finely divided solids were placed in water were probably
in part at least, due to distillation.

0. Masson and £. Richards^ have also determined the amount
of moisttu'e which is absorbed by cotton when exposed to an at-
mosphere of known humidity. "Absorbent" cotton was em-
ployed, which, after being washed with distilled water and dried,
was wotmd around the bulb of a thermometer and brought to a
constant weight by exposing it for 24 hotu^ in a desiccator con-
taining phosphorus pentoxide. It was then transferred to a
porous pot suspended in sulfuric acid of known strength (and
hence of known vapor pressure), by which means the interior of
the pot was kept constant as to humidity by evaporation from its
walls. It is not sufficient to expose the dry cotton to the atmo-
sphere of a given humidity until an apparently constant weight
results, because the rate of absorption — ^which rapidly dimin-
ishes— becomes almost inappreciable before absorption is com-
plete. The amount of hygroscopic moisture required by a given
weight of cotton to put it in true equilibrium with an atmosphere

1. Proc. Roy. Soc. 1906, 78, A, 412; abst. J. vS. C. I. 1907, », 89; Chem.
Zentr. 1907, 78, 1, 594; Meyer Jahr. Chem. 1906, IS, 28. He considers that
the liquids are absorbed by the solids, passing into the solid state them-
selves. See Martine, Phil. Mag. 47. 329; 50, 618.

COTTON

517

of given humidity, below the saturation value, is therefore ascer-
tained by taking the mean of the apparent equilibrium values
reached by absorption (cotton initially dry) and evaporation
(cotton initially over-moist). The progress of either change may
be followed by observing the characteristic temperattu-e curve
given by the thermometer.

The results obtained are expressed in the following table,
which shows the amount of moisture absorbed by 0.948 gm. (W)
of pure cotton over sulfuric acid solution at 20°; "p" is the actual
pressure of water vapor in the atmosphere employed; "P" is the
saturation pressure of water vapor at the same temperature; **Ma"
is the weight of water absorbed by the sample of dry cotton of
weight W, after exposure in the apparatus imtil fiulher absorp-
tion appears negligible. "Me" is the weight of water retained
by the same sample after it has been supersaturated by expostu'e
over water and then allowed to evaporate in the apparatus imtil
fiulher loss appears negligible, -^nd "M" is the arithmetic mean
of Ma and Me, and is taken as indicating the amount of
absorbed moisture which is required to establish true equilibrium.

Add Employed

Ma

Me

M

M/W

'

Sp. gr.

HtS04

p/p

20** C.

%

1.6516

73.8

0.060

0.0120

0.0145

0.0132

0.0139

1.5724

67.0

0.100

0.0175

0.0198

0.0186

0.0196

1.4850

50.0

0.198

0.0264

0.0311

0.0288

0.0304

1.4167

52.6

0.294

0.0356

0.0406

0.0381

0.0402

1.3672

47.2

0.408

0.0441

0.0497

0.0469

0.0495

1.3282

43.1

0.500

0.0509

0.0593

0.0551

0.0581

1.3028

40.5

0.556

0.0630

0.0655

0.0592

0.0624

1.2887

38.8

0.598

0.0699

0.0690

0.0644

0.0679

1.2368

32.3

0.710

0.0716

0.0840

0.0778

0.0821

1 . 1930

26.8

0.794

0.0860

0.1002

0.0931

0.0982

1.1616

23.2

0.844

0.0989

0.1107

0.1048

0.1106

1 . 1398

20.3

0.874

0.1045

0.1250

0.1148

0.1210

1.1226

18.1

0.894

0.1114

0.1300

0.1207

0.1274

1.0686

10.3

0.952

0.1378

0.1606

0.1492

0.1574

1.0378

6.2

0.972

0.1563

0.1792

0.1678

0.1770

By multiplying the last columns by 100, the percentage absorption is
shown.

Cotton containing a definite proportion of moisture resem-

518 TECHNOlrOGY OF CELLULOSE ESTERS

bles an aqueous solution in that it exercises a vapor tension which
is, at different temperatures, a constant fraction of that of pure
water. Different weights of the same cotton have the same vapor
tension when they contain the same percentage weights of hygro-
scopic moisture, and the results are not influenced by tight or
loose packing. Filter paper gives results very similar to those
obtained with cotton-wool. It is also shown that, by observing
the rate of rise of temperature of dry cotton when first exposed
to moist air, the pressure of aqueous vapor in the atmosphere may
be determined, thus providing a new method of hygrometry.

L- Vignon^ has determined the specific gravity of cellulose
when wetted with benzine, selecting this fluid because it wets the
fiber well, and also permits the elimination of adhering air and
other gases by vacuum exhaustion. Using an ordinary hydro-
static balance, at 18**, and cotton of normal atmospheric mois-
ture, he found absorbent cotton to have a sp. gr. 1.50 and ordinary
cotton yam, 1.51. In measuring the absorptive power of cotton
for water at ordinary temperatures, Vignon' obtained independ-
ently from the weight of the fiber, an absorption of 495, calcu-
lated on 100 gm. According to C. Beadle' cotton takes up 100%
in the cold, and 63% when warm, the moisture being taken up
through the cell-wall.

Cellulose undergoes peculiar changes through freezing and
the subsequent expansion by the solidification of the intersticial
water. The aqueous crystals forming in the intercellular lumen
cause a loosening and breaking of the fiber or fiber btmdles. It
is the opinion of Erfurt* that the freezing of half-finished paper
pulp materially changes the paper-forming qualities of the stock.
Such frozen pulp is especially suitable for the manufacture of
filter paper, and in fact, the so-called Swedish filter paper, gen-

1. Compt. rend. 1892, 114, 424; abst. J. S. C. I. 1892, U, 1002; Chem.
Centr. 1892, €3, I, (>16; Jahr. Chem. 1892, 45, 2906; Chem. Tech. Rep. 1892,
n, I, 103; Ber. 1892, 25, 268; BuU. Soc. Chim. 1892, 7, 247; Mon. Sci.
1892, 39, 309; Rev. g^n. sci. 1892, 3, 170; Deut. Chem. Ztg. 1892, 92.

2. Compt. rend. 1898, 127, 73; abst. J. S. C. I. 1898, 17, 841; Bull.
Soc. Chim. 1898, 19, 919; Mon. Sci. 1898, £L, 607; Chem. Centr. 1898, 09,
II, 455; Jahr. Chem. 1898, 51, 834.

3. Chem. News, 1897, 75, 74; 1902, 86, 88; Chem. Centr. 1897. €8,
I, 571, 573; Jahr. Chem. 1897, 50, 485, 1506. D. R. P. 70999; abst. Mon.
Sci. 1893, 42, 304; 1897, 50, 128; 1905, 03, 325; Ber. 1893, 20, 999; Chem.
Centr. 1894, 05, I, 365; Wae. Jahr. 1893, 39, 1001.

4. Papierfabr. 1907, 1, 1687.

COTTON 519

erally conceded as one of the best, owes its desirable qualities to
such a treatment.

It is the judgment of C. Rothwell^ that the individual cellu-
lose filaments do not lose in strength through repeated freezing
and thawing. Boiling water has but little effect upon cotton
cellulose. H. Tauss* found that Swedish filter paper on being
boiled with water for three hours under ordinary pressure with
distilled water, gave off traces of an extract, which reduced Feh-
ling*s solution. Boiling water also induces a small but evident
plasticity in cellulose, which, however, is permanent. Boiling in
water, however, does not appreciably affect the hygroscopicity.

In printing, changes in cellulose have been observed when
the fiber has been treated with steam. It is possible to thus fix
diamine and other substantive colors on cotton fiber by wet
steaming, especially when glycerol is present.' J. Mueller* con-
siders this process a transformation of the fiber in the state of gel,
i. e., indicating the colloidal properties of the fiber.

Cellulose is partly dissolved by boiling with water imder pres-
sure. H. Tauss found the following results for Swedish filter
paper: 20 gm. cellulose in 1 liter water heated for 3 hom^ imder
a pressure of 5 atmospheres:

Drying Residue of the Aqueous

Extracts: 1

For 20 gm. 0.148

For 100 gm. 0 . 740

The boiling was repeated successively for three times with the
same material. The decrease of the soluble matter in each boil-
ing becomes very apparent. The liquids were evaporated, dried
carefully at 100** for 3 hours and weighed. A blue to bluish violet
sugar-like substance was determined with Fehling*s solution and
calculated as dextrose:

Sugars Found: 12 3 Total

For 20 gm. 0.021 0.0025 0.0012 0,0247 gm.

For 100 gm. 0 . 105 0 . 0125 0 . 0060 0 . 1235 gm.

h Faerb. Ztg. 1892-1893, 75; J. S. C. I. 1892, 11, 320; abst. Chem.
Ztg. 1892, IB, 191; Jahr. Chem. 1892, 45, 2906; Wag. Jahr. 1892, 3S, II, 962.

2. Dingl. Poly. 1889, 273, 276; Chem. News, 1890, 61, 169; J. S. C. I.
1889, 8, 913; Mon. Sci. 1890, 35, 164; Ber. 1889, 22, R, 769; Chem. Centr.

1889. 60, II, 444; Chem. Ind. 1889, 12, 514; Chem. Tech. Rep. 1890, 39,
II, 105; Jahr. Chem. 1889, 42, 2a38; Wag. Jahr. 1889, 35, 1; Apotheker Ztg.

1890, 232; Chem. Ztg. 1890, 14. 232.

3. Zts. Farb. Ind. 1904, 3, 390; Faerb. Ztg. 1905, IB, 138.

4. Bull. soc. ind. Rouen, 1904, 390.

2

3

Total

0.088

0.049

0.277 gm.

0.400

0.245

1 .385 gm.

520 TECHNOLOGY OF CELLULOSE ESTERS

According to the statement of Mulder,^ a little glucose re-
sults when cellulose is boiled with water at 200**. F. Hoppe-
Seyler* observed that when filter paper is heated for 4-5 hours in
sealed tubes at 200**, carbon dioxide is given off, while formic,
acetic and protocatechuic acids and pjrrocatechol are formed.
However, when the experiments were conducted in a neutral
(platinum) receptacle,' no protocatechuic acid or pyrocatechol
is formed, thus proving that alkali is required for its formation
from cellulose. C. Williams* found furfurol in the liquid from
heating cellulose with water under pressure.

Nitrogen in Cotton. R. Haller^ has shown that cotton at
any stage of its manufacture is dyed slightly by an acidulated
solution of safranine, the shades obtained being fast to washing.
He ascribed this property to the cutinized outer cuticle and to
the presence of nitrogenous substances in the inner cuticle and in
the dried-up residue of the cell contents. Bleached cotton is less
deeply tinted than unbleached. A. Schindler* confirms Haller's
view by a determination of the nitrogen contents of Egyptian
cotton in the raw and partially bleached states. The cotton
used was in the form of silver and the nitrogen was estimated by
Kjeldahl's process. Two determinations on the raw material gave
0.256% and t).250% of nitrogen. Two determinations on material
which had been boiled for eight hours in caustic soda of 1.01 sp. gr.
showed 0.066% and 0.064% nitrogen respectively. Another sam-
ple, boiled for eight hours with caustic soda of 0.05 sp. gr. con-
tained only 0.028% of nitrogen. It was found that on boiling in

1. J. prakt. Chem. 1844, 32, 336; abst. Scheik Onderzoek, 2, 76; Ann.
1841, 39, 150.

2. Ber. 1871, 4, 15; abst. Chem. News, 1871, 23, 131; J. C. S. 1871,
24, 226; Bull. Soc. Chim. 1871, 15, 98; J. pharm. chim. 1872, (4), V, 414;
Jahr. Chem. 1871, 24, 476.

3. Zts. physiol. Chem. 1889. 13, 66-121; abst. J. S. C. I. 1889, 8, 404.
See also C. Eggertz, Bied. Centr. 1889. 18, 75; abst. J. S. C. I. 1889, 8, 293.

4. Chem. News, 1872, 26, 231, 293; abst. J. C. S. 1873, 26, 162; Bull.
Soc. Chim. 1873, 19, 162; Jahr. Chem. 1872, 25, 760; Amer. Chem. 1872, 3,
308, 353.

5. Zts. Farben. Ind. 1907, 6, 125, 127; abst. J. S. C. I. 1907, 26, 523;
Chem. Zentr. 1907, 78, II, 953; 1908, 79, II, 113; Chem. Ztg. Rep. 1907, 31,
257; Jahr. Chem. 1905-1908, II, 3185; Wag. Jahr. 1908, 54, II. 376; Zts. anc.
Chem. 1907, 20, 20a5; 1903. 21, 267. See also Textile u, Farben. Ztg. 14,
221; abst. C. A. 1907,1,2495; Chem. Ztg. 1908,32,838; abst. Meyer Jahr.
Chem 1908 18 505

6. J. W. Dyers Col. 1908, 24, 106; abst. J. S. C. I. 1908, 27, 497;
Meyer Jahr. Chem. 1908. 18, 504. Compare Chem. Ztg. Rep. 1908, 32, 314.

COTTON 521

strong caustic soda of 77° Tw., ammonia was evolved correspond-
ing to 0.06% of nitrogen in the cotton taken, and two determina-
tions of thenitrogen remaining in the cotton under this treatment
gave 0.019% and 0.016%; thus it appears tkat upon boiling with
caustic soda, the bulk of the nitrogenous matter present in the
cotton, goes into solution in the caustic liquor.

E. Knecht and W. HalP have made systematic extractions of
2-ply, 60*s American and Egyptian yams. Both the alcoholic
and aqueous extracts were extremely rich in mineral matter, a
considerable portion of which consisted of potassium salts. On
dialysis of the aqueous extract, it was separated into a diffusible
portion extremely hygroscopic, and a residue, which on evapora-
tion yielded a non-hygroscopic, brittle, resinous substance. Nitro-
gen determinations carried out on the yam after each treatment,
gave results showing that benzene, water and alcohol extracted
only 14.1%-16.7% of the total nitrogenous matter. Experiments
on the removal of the nitrogenous matter from raw cotton in a
single treatment showed that boiling at atmospheric pressure for
6 hours with 2% caustic soda solution removed 78%-80% of the
total nitrogen; boiling with lime for 12 hours removed 37.5%,
but this amotmt was increased by subsequent souring to 53.1%;
hot soaping removed only 17.5%.

Further experiments in imitation of the industrial process,
boiling imder 35 lbs. pressure per sq. in. showed with a yam con-
taining originally 0.248% nitrogen, the following results repre-
senting the proportion of N remaining in the yam after each
stage (original = 100): After lime boil, 54%; sour, 40.5%; after
caustic boil, 27.1%; after sour, 26.8%; after bleach liquor, 6.7%;
after sour, 5.8%.

A preliminary examination made of the various extracts,
yielded the following results: The lime extract gave a gelatinous
precipitate with alcohol, free from N and corresponding with
pectic acid. The alcohol-soluble portion gave two brown resin-
ous substances of different solubilities, containing 9.1% and 9.6%
of nitrogen respectively. A small quantity of fatty acid was also
isolated. The total substances extracted from the cotton by the
lime boil was 2.1%, which included the major portion of the

1. J. Soc. Dyers Col. 1908, 34, 220; abst. C. A, 1919, 13, 909; J. S. C.
I. 1919, 38, 7- A.

522 TECHNOLOGY OI? CELLUlrOSH ESTERS

mineral constituents of the cotton. The first HCl extract (Ume
sour) comprised mainly a fatty acid apparently corresponding
with stearic acid, together with a dark colored wax, m. pt. 77°-
80°; there was also a small quantity of a brown resinous substance
similar to that present in the lime extract. The portion extracted
by caustic soda yielded a brown residue fairly rich in nitrogen
and phosphoric acid.

The solid residue yielded a further quantity of alcohol-sol-
uble coloring matter; the alcohol-insoluble portion giving the
general reactions of protein. On acidification of the soda extract
a dark-colored protein containing 18.75% nitrogen was isolated.
From this extract was also obtained a black, brittle shining mass,
soluble in ammonia and assaying 9.6% N, together with a mix-
ture of pectic acid and coloring matter. The total amounts of
substances extracted from cotton by the three main treatments
outlined above was 4%. The hygroscopic moisture of the raw
cotton was 7.36%, and that of the scoured and bleached cotton,
6.14%, thus confirming that the moisture content of unbleached
yam is not wholly dependent on the cellulose present, but partly
on the normal accompanying hygroscopic substances.

According to S. Higgins^ it is quite certain that the proteins
of cotton fiber are similar to the protein of the seed intelf. It
has been shown by other investigators that a boil with strong
sodium hydroxide removed a high per cent, of nitrogen from
cotton. During extractions with weak alkalis the proteins are
probably little changed, and if the alkali is not too strong this
can be used as a method of separating proteins. In the present
study the method of T. Osborne, C. Leavenworth and C. Braut-
lecht* was used consisting in distilling 1 gram air-dried protein
with 300 cc. of tenth-normal sodium hydroxide, titrating the
first 200 cc. distillate with N/IO sulfuric acid, making up
the residual solution to 300 cc. with A^/10 sodium hydrox-
ide and again distilling, etc. In the experiments, 30 grams of
air-dried material were used. Warp threads were used as these
represented foreign matter in addition to actual fiber introduced

1. J. Soc. Dyers Col. 1019, 35, 165; abst. C. A. 1919, 13, 2604.

2. Amer. J. Physiol. 1908, 23, 179; abst. C. A. 1910, 4, 2153;
J. C. S. 1909, 96, 1, 72; Chem. Zentr. 1909, 80, I, 385; Tahr. Chem. 1909,
62, 1479.

COTTON 523

during the manufacturing process. The amount of sodium hy-
droxide used was equivalent to a 4% boil based on the weight of
the material.

The results are recorded in four tables : (1) With American
yam, Egyptian yam, and linen yam. (2) Results of 1 calcu-
lated to nitrogen and compared with nitrogen in two tj^ical pro-
teins from wheat and peas. Using the customary method of
multiplying nitrogen by 6.25 for proteins we have Egyptian
0.275 nitrogen or 1.72% protein, which is not the case. The
inference is that not all the nitrogen in the sample was present as
protein, and it can be said that the elimination of proteins from
cotton during bleaching cannot be measured by simple nitrogen
determinations as indicated by C. Cross. ^ (3) Shows compar-
ative results of original American yarn, with yam in various
stages of treatment with sodium carbonate, sodium hydroxide,
calcium hydroxide, calcium hypochlorite, etc. (4) Same as for
linen. It is a noteworthy fact that sodium hydroxide removes
the proteins more effectively from linen than from cotton,
which is also the case with lime boil, sour or soda ash boil. In
the case of soda ash, however, the effect is not the same as with
cotton as the proteins are only partly removed from linen.

It is shown that cotton or linen when scoured with sodium
hydroxide or treated with lime sour soda ash, is incapable of
forming chloramines on treatment with bleaching powder solu-
tions because it no longer contains appreciable quantities of pro-
teins, and it may be concluded that the formation of chloramines
is of no interest to bleachers of cotton and linen. -With linen an
eight-hour boil with soda ash did not remove all protein and com-
merically boiled yams contain a large amount of residual i^ptein.
When these boiled yams are brought into contact with bleaching
powder solution to produce what is commonly called commercial
"cream" yams one has the only possibility of the existence of
chloramines in the bleachers experience. Cotton piece goods
contain warp threads sized with flour, and therefore the nitrogen
content of the goods is higher than linen piece goods which are
not sized with materials having a high nitrogen content. This
fact and the results given in this paper are difficult to reconcile

1. J. Soc. Dyers Col. 1918, 34, 76.

524 TECHNOLOGY OF CELLULOSE ESTERS

with the statement of C, Cross, E. Bevan and J. Briggs^ that
cotton cellulose is permanently stained by the taking up of prod-
ucts (containing nitrogen) of the action of the alkali upon flax
constituents. Moreover their statement that the nitrogenous
constituents of fiber are extremely resistant and only gradually
broken down by alkali wash is not borne out by his experience.

Mineral Constituents of Cotton. The average ash content
of raw cotton as recorded by different investigations vary within
comparatively wide limits and may be set down as from 1% to
2%. Whether or not the ash constituents participate materially
in the structm^al formation of the fiber, whether the base is potas-
sium, sodium, calcium, iron and aluminium found in the ash are
boimd to the organic molecule in some manner, and whether this
is or is not the same in the case of silicic acid, are questions which
have not as yet been definitely determined. Regarding the latter,
the earlier investigations of A. Ladenburg* and W. Lange* have
shown that silicic acid does not play any important part in the
building up of the shafts of straw. W. Tottingham investigated
the organic silicon compotmds in Graminae.^ It is quite probable
that the mineral matters are merely impiuities retained by the
colloidal cellulose, a view which is partly confirmed, if it is con-
sidered that the so-called ashless filters contain only 0.003%-
0.05% of ash.*

For incandescent mantle manufacture, cotton and ramie
cellulose have been produced which contain but 0.015% ash.
and absorbent cotton with less than 0.3%.* The above named
bases are frequently bound to chlorine and sulfuric and phosphoric

1. J. S. C. I. 1908, 27, 260; abst. C. A. 1909, 3, 1213; J. C. S. 1908,
34, i. 374; Chem. Zentr. 1908, 79, II, 639; Jahr. Chem. 1905-1908, II, 4505;
Meyer Jahr. Chem. 1908, IS, 505; Wag. Jahr. 1908, 54, II. 473 ; Zts. ang. Chem.
1908 2^. 2509.

'2. Ber. 1872, 5, 568; abst. Jahr. Chem. 1872, 25, 795; Bull. Soc. Chim.
1872, IS, 271; Chem. News, 1872, 26, 36; J. C. S. 1872, 25, 910.

3. Ber. 1878, U, 822; abst. J. C. S. 1878, 34, 682; Chem. Centr. 1878.
43, 458; Jahr. Chem. 1878, 31, 948; Jahr. rein Chem. 1878, 6, 48.

4. Trans. Amer. Chem. Soc. Jmie 6 and July 7, 1908; abst. Science, 28,
188; abst. Zts. ang. Chem. 1908, n, 2419.

5. G. Bumcke and R. Wolffenstein, Ber. 1899, 32, 2495; abst. J. S. C.
I. 1899, IS, 940; Jahr. Chem. 1899, 52, 1290; J. C. S. 1899, 76, i, 852; Chem.
Centr. 1899, 70, II, 752; Bull. Soc. Chim. 1900, 24, 620; Meyer Jahr. Chem.
1899, 3, 300.

6. C. Bohm, Prom. 1908, 13, 14. See also Chem. Ztg. 33, 447; C. A.
1909, 3, 2218; Chem. Zentr. 1909, SO, I, 1732; Meyer Jahr. Chem. 1909, 13,
329, 330; Zts. ang. Chem. 1909, 22, 1280; J. Gasbel. 52, 855; Bayer. Ind.
1909, 255; Wag. Jahr. 1909, 55, I, 102.

COTTON

525

acids. Fluorine is but rarely found, but frequently overlooked
on accoimt of its volatility. Zinc is also occasionally met with.
With the latter, however, it is claimed that it is a regular con-
stituent of the ash from plants. The United States Department
of Agriculture in Bulletin No. 23 gives the average composition
of the American cotton plant and its parts as follows: Roots,
8.8%; stems, 3.15%; leaves, 20.25%; bolls, 14.21%; seed, 23.5%;
lint, 10.56%.

The mineral constituents in a crop of cotton yielding one
hundred poimds of lint per acre, expressed in pounds per acre —
the weight of the entire crop being 947 pounds — are given as
follows:

Part of
Plant

Lbs.

Nitrogen

Phosphoric
Acid

Potash

Lime

Magnesia

Roots

Stem

Leaves

Bolls

Seed

Lint

83
219
192
135
218
100

0.76
3.20
6.16
3.43
6.82
0.34

0.43
1.29
2.28
1.30
2.77
0.10

1.06
3.09
3.46
2.44
2.56
0.46

0.53
2.12
8.52
0.69
0.55
0.19

0.34
0.92
1.67
0.54
1.20
0.08

Total

•

947

20.71

8.17

13.06

12.60

4.75

The following table indicates the amount of ash contained
in different varieties of cotton lint according to Matthews and
Monie:

Matthews

Monie

Dharwar

4.16
6.02
1.25
1.68
1.15
3.98
3.14
2.52
1.73
1.19
1.60

1.52

• • • •

4.10
1.10
1.80
1.25
5.30
2.58
2.93
1.60
1.75
1.98

( Texas 2 . 1
(Orleans 1.6

Dhollerah

Sea-Island

Peruvian soft

Peruvian rouch

Beneal

Broach

Oomrawuttde

EfiTVDt brown

Est ypt white

Pemambuco

American

526 TECHNOLOGY OF CELLULOSE ESTERS

J. Barnes^ has reported upon the analyses of five samples
of American cotton which gave f^^om 1.18% to 1.92% of ash; two
samples of Egyptian cotton gave 1.37%-1.50% respectively;
twelve samples of Indian cotton averaged 2.48% ash, the extremes
being 1.34% and 3.99%. The amoimt.of silica and chlorine in
the ash support the figures for total ash. There was no apparent
relation observable between the moisttu-e content of the lint and
the amotmt of ash. The mineral substances which appear in the
ash are in the fiber end on the outside. Analysis of the ash of a
Bombay sample of lint gave:

Silicon dioxide 15.66%

Aluminum oxide 10.80%

Ferric oxide 5.80%

Calcium oxide 9 . 75%

Magnesium oxide 1 .87%

Potassium oxide 27.32%

Sodium oxide 4 . 51%

Sulfur dioxide 1 .96%

Phosphorus pentoxide 3 .26%

Chlorine 6.55%

Carbon dioxide 12. 19%

Undetermined 0.34%

A Punjab sample of cotton ash gave:

Silicon dioxide 14 ..40%

Aluminum oxide 12 . 87%

Ferric oxide 12.92%

Calcium oxide 10.65%

Magnesium oxide 4 .36%

Potassium oxide 26.03%

Sodium oxide 8.40%

Sulfur dioxide 2.52%

Phosphorus pentoxide 4 .46%

Chlorine 3.84%

Carbon dioxide 8.03%

Undetermined 2.52%

Analyses have indicated that cotton grown on saline soil does
not contain more mineral matter than cotton grown on other
soils. There is little doubt but that the high mineral content of
cotton affects the action of the fiber to dyes.

Matthews, ''Textile Fibers," page 212 gives the following:

1. J. S. C. I. 1916, 35, 1191; abst. C. A. 1917, 11, 890; Ghem. Zentr.
1917, 88, 1, 832; Ann. Rep. Soc. Chem. Ind. 1917, 2, 126, 161.

COTTON

527

MINERAL CONSTITUENTS OF TRUE COTTON FIBER.

Ure

%

Davis, Dreyfuss and
Holland.*

%

Potassium carbonate

44.8
9.9
9.3

• • • •

9.0

10.6

8.4

• • • ■

3.0
5.0

33.22

10.21

13.02

3.35

20.26
8,73
7.81
3.40

Potassium chloride

Potassium sulfate

Sodium carbonate

Calcium phosphate

Calcium carbonate

Magnesium phosphate.

Magnesium carbonate

Ferric oxide

Aluminum oxide and loss

* Mean % 12 different varieties.

Tensile Strength of Cotton. Cotton stands midway be-
tween silk and wool in tensile strength, whereas in elasticity and
resiliency it is considerably below either of the other two named
fibers. The breaking strain of cotton usually varies from 2.5 to
10 grams, depending on the fineness of the staple; the finer the
staple, of course, the less will be its breaking strain. The follow-
ing table indicates the results of experiments on the tensile strength
of different varieties of cotton :

Cotton

Sea-island (Edisto)

Queensland

Egyptian

Maranham

Bengal

Pemambuco

New Orleans

Upland

Surat (DhoUerah) .
Surat (Comptah) . .

Mean Breaking Strain

Grains

Grams

83.9

5.45

147.6

9.69

127.2

7.26

107.1

6.96

100.6

6.53

140.2

9.11

147.7

9.61

104.5

6.79

141.9

9.22

163.7

10.64

Herzfeld^ has prepared the following table as showing the
strength in grams of single cotton yams, of different counts, the
numbering of the yams being according to the metric system:

1. "Yarns and Textile Fabrics," page 95.

528

TECHNOLOGY OP CELLULOSE EStERS

Very

Very

No.

4

Weak

Medium

Strong

Strong

No.

Weak

Medium

Strong

Strong

880

1000

1250

32

125

170

200

250

6

670

920

1080

1340

34

120

160

190

220

8

500

690

810

1000

36

110

150

180

210

10

400

550

650

800

38

105

140

170

200

12

330

' 460

540

660

40

100

135

160

190

14

285

390

460

570

50

110

130

140

16

250

340

400

500

60

90

110

125

18

220

300

360

440

70

80

90

105

20

200

280

320

400

80

70

80

95

22

180

250

295

360

90

60

70

85

24

170

230

270

330

100

55

65

80

26

150

210

250

310

110

50

60

70

28

140

200

230

290

120

45

55

60

30

130

180

215

260

■ ■ • ■

A. Scheurer^ has studied the influence of various operations
upon the tenacity of cotton tissues, the numbers given below
representing the average result obtained in 20 experiments, the
breaking strain of the warp threads of the tissue employed (75 X

26 Alsation coimts) being determined:

Relative
Tenacity

1. Bleached tissue (standard) 100

2. Hung for a month in an ageing room 98

3. Hung for a month in a drying chamber 96

4. Hung for a month in a drying chamber for woolen tis-

sues 96

5. Exposed for a month to air and rain 98

6. Passed 20 times through a bleach-house washing ma-

chine 96

7. Soaped for six hours at 212*" C. (2 gm. of soap per liter) 101

8. Soaped for 12 hours at 212** C. (2 gm. of soap per liter) 99

9. Passed 10 times round a calendering roller (=20

crushes) 80

10. Treated as 9, followed by a washing 78

11. Damped and dried on a drying cylinder 20 times in

succession 97

12. Boiled for 30 minutes in a solution of sodium car-

bonate (10 gm. per liter) 100

13. Treated with a 5% solution of hypochlorite of lime

at "7® B6.," dried on a drying cylinder, and then
treated as 12 100

14. Treated as 13 twice 98

Two experiments were made with sateen tissue which was
passed twenty times through a continuous washing machine with

1. Bull. Soc. Ind. Mulhouse, 1902, 72, 33; abst. J. S. C. I. 1902, 21,
702; J. Soc. Dyers Col. 1902, IS, 188; Wag. Jahr. 1902, 48, II. 562.

COTTON 529

tension. On testing it the tenacity was found to have dimin-
ished in one experiment by 88 (warp threads) and 82 (weft threads) ,
and in the other experiments to 86 and 96 respectively, the orig-
inal tenacity of the tissue being taken as 100.

Absorption of Gases by Cotton. Cotton has an enormous
capacity for the absorption of gases, and it is to this property
that the greater effect of chlorine upon cotton than upon other
bleached fibers, such as flax, is attributable. In the anhydrous
condition, cotton fibers are said to be capable of absorbing more
than one hundred times their volume of ammonia gas.

Effect of Reagents on Cotton Fiber. It ha§ generally been
stated that in mercerized and well-bleached cotton the cuticula
is absent^ but the observations of W. Minajeff ^ do not support
this contention. The cuticula contains as incrustants, fat, wax,
coloring matter, and a substance called cutin which is insoluble
in sulftuic acid, so that processes in which alkaline agents are
used such as boiling and mercerizing, as well as bleaching, will
aflFect it, only so far as these waxy and fatty bodies are concerned.
In most cases it is difficult to distinguish cuticula under the micro-
scope, the different mechanical and chemical treatments through
which the cotton undergoes from the raw state, preparatory to
its acceptability for nitrating increasing the difficulties of dis-
tinction.

The author has studied the action of reagents on the cotton
fiber under the microscope and arrived at the following conclu-
sions: The cuticula of the raw cotton fiber resists treatment with
concentrated cuprammonium solution, fairly strong sulfuric acid
(but not the concentrated acid) and concentrated alkaline liquors
both dtuing boiling and during mercerizing; the cuticula of the
bleached fiber have the same properties as those of the unbleached
filament although not so strongly marked; the fiber walls are sub-'
stantially completely soluble in concentrated cuprammonium solu-
tion and swell strongly when treated with more dilute solutions
They are dissolved by concentrated sulfuric acid, being changed
to a substance of the nature of amyloid, and swell in weaker

1. Zts. Farben. Ind. 1905. 4, 81; 1907, €, 234, 252, 309, 345; 1908, 7,
1, 17; 1909, 8, 313; abst. J. S. C. I. 1907, 26, 1236; Chem. Centr. 1905, 7€,
I, 906; 1908, 79, I, 308, 1652; Chem. Ztg. Rep. 1908, 32, 220; Jahr. Chem.
1905-1908, II, 3175; Wag. Jahr. 1908, 54, II, 458; Zts. ang. Chem. 1908,
21, 1252, 1255. . -

530 TECHNOU>GY O? CHLLUU>SB ESTERS

solutions but show no change under the microscope when left for
a long time in a 10% solution of the acid. They are changed
during mercerizing in a manner well known. The fiber walls
suffer important changes during the process of oxidation (produc-
tion of oxycellulose) ; they become weakened and brittle in this
state but are not dissolved by cuprammonium solution. The
inner protoplasmic covering of the fiber behaves somewhat sim-
ilar to the cuticula.^ ''

Composition of Cotton. Raw cotton contains the following
constituents: (a) cellulose; (b) moisture; (c) oily matter, iden-
tical with cotton seed oil, and also other fatty substances; (d) a
small proportion of a solid wax, resembling ceresin, which is
present as a thin protective layer on the outer walls of the cotton
fiber; (e) nitrogenous (proteid and amido) bodies consisting mainly
of the protoplasmic residue in the lumen with other related prod-
ucts, which substances coat the walls of the central canal; (f)
pectins and other gum-like bodies; (g) cutin (cuticular celluloses)
and tmchanged cell-contents; (h) small quantities of other organic
substances as tannic acid, coloring matter, etc., the latter being
present only in traces. They are of a resinous non-crystalline
nature, and contains 6%-9% of nitrogen;* and (i) mineral matter
(containing potassium, calcium, sodium, magnesium, aluminium,
and iron with carbonates, chlorides, phosphates and sulfates).

According to the U. S. Department of Agriculture' the fol-
lowing represents the composition of the cotton fiber: cellulose
83.71; water 6.74; nitrogen-free extract 5.79; ash 1.65; protein
1.50 and fat 0.61. A more detailed analysis is also given of sub-
stances (called "fertilizing constituents") present in the cotton
fiber ; the analyses having been made from representative specimens

1. H. Lange, Farber. Ztg. 1898, 9, 197. 234; abst. J. S. C. I. 1898. 17,
839, 917. In this connection see J. Huebner and W. Pope. J. S. C. I. 1904.
23, 404; Zts. Farben. u, Textil Chem. 2, 314; Rep. Chim. 1904. 4, 446; Rev.
g^n. sci. 1904, 15, 470; Chem. Centr. 1904, 75, I, 1625; Chem. Zts. 1903-
1904, 3, 77; Jahr. Chem. 1904, 57, 1813; Zts. ang. Chem. 1904, 17, 777.

2. See E. Schunck, Mem. Manchester Lit. Phil. See. 1868, (3), 4, 95.
Refer to topic "Wax in Cotton."

3. Bulletin 33. As the result of a large number of tests, the U. S.
Dept. Agriculture gives the following, as representing the average composi-
tion of a large number of cotton fiber analyses: water, 6.74%; ash. 1.65%;
protein, l.SO^ri cellulose, 83.71%; nitrogen-free extract. 5.70%; fat, 0.6lCf.

COTTON

531

selected so as to insure an average composition from a wide area:

Per Cent.

Water 6.07

Ash 1.37

Nitrogen 0.34

Phosphoric acid 0 . 10

Potash 0.46

Soda 0.09

Lime 0. 19

Magnesium 0.08

Ferric oxide 0.02

Sulfuric acid 0.60

Chlorine 0.07

Insoluble matter 0.05

According to Mitchell and Prideaux,^ there is considerable
difiference in the ash and phosphoric acid content of various cot-
tons. Indian cotton (Bengal) they find to contain 0.15% phos-
phoric acids and as high a figure as 0.37% in Pemambuco cotton.
F. Calyert* obtains 0.027% of soluble phosphoric acid in Surat
cotton and 0.055% in Egyptian.

The above figures can only be accepted as representative of
a particular cotton, as the proportion of the various constituents
present in cotton depends to some extent on the nature of the
cotton, the conditions under which it grew, the climate, the soil,
the extent of ripeness when collected, cultivation and harvesting.
F. Bowman' gives the following figures as the average composi-
tion of various types of cotton fiber selected during three seasons:

Surat

American

Egyptian

Cellulose

91.35
0.40
0.53
0.22
7.50

91.00
0.35
0.53
0.12
8.00

90.80
0.42
0.68
0.25
7.85

Wax, oil, and fat

Protoplaism and derivatives (pectoses)
Mineral matter

Water

The cotton as received for nitration often contains impurities
introduced during the treatments which the raw material has

1. "Fibers Used in Textile Industries," p. 96.

2. J. Chem. Soc. 1867, 20, 303; Compt. rend. 1867, 65, 1150; J. prakt.
Chem. 1867, IM, 441 ; 1869, 107, 122; Chem. News, 1869, 20, 121 ; Jahr Chem.
1869, 22, 800; 1870, 23, 1150; Chem. Centr. 1867, 12, 831; Bull. Soc. Chim.
1868, 10, 174; Zts. Chem. 1867, 539. His figures are: Maceo cotton, 0.05%
phosphoric acid; Carthegena, 0.035%; Bengal, 0.055%; Cyprus, 0.05%;
Egyptian, 0.055%; New Orleans, 0.049%. Analysis of the cotton seeds gave
in phosphates, results as follows: Magnesium phosphate, 0.652; iron phos-
phate, 0.053%; alkali phosphates, 0.387%; other salts, 2.428%; total ash,
3.152%.

3. "Structure of the Cotton Fiber," p. 147.

53?

TBCHNOLOGY OF CHl^LULOSE ESTERS

undergone. Thus cotton waste may contain a considerable
amount of foreign material and dirt as well as oil and starch. The
oil is, in part, a different kind to that found in raw cotton and
may be traced to the machinery in which the cotton fiber has
been spun. Starch may often be traced to the previous use of
sizing agents.

According to Lefevre/ the following represent typical analyses
of mercerized Egyptian cotton :

Kind of Cotton

Per Cent.
Ash

Per Cent.

Iron Oxide

in Ash

Color of Ash

Natural Eevutian

0.624
0.137
0.403
0.088

1.50
8.02
2.31
5.45

White
Greenish
Yellowish gray
Greenish

Mercerized KirvDtian

Grey mercerized Egyptian

Bleached mercerized Egyptian . .

A. Viehoever* is authority for the statement that Upland
cotton, Gossypium hirsutum, contains quercimeritrin and isoquer-
citrin, which have been previously isolated from other types of
cotton plant, but does not contain gossypitrin and gossypetin.
The ethereal oil isolated from Upland cotton differs from that
found in the root back of G. herbaceum. The greater part distils
between 200° and 300°, the lower fractions of the distillate being
yellow to greenish yellow, and the higher fractions light bluish
green to dark blue. The oil is said to attract the boll weevil.

Tissue Paper. It is generally conceded that the finest qual-
ities of pyroxylin lacquers, bronzing fluids and transparent color-
less pyroxylin plastics can only be obtained by the nitration of
fine tissue paper, and it is a fact, that at the present time in the
United States at least, substantially all of the celluloids are
manufactured from tissue paper rather than linters or other forms
of cotton cellulose. It is also a fact that best results up to the

1. Rev. g6n. mat. color. 1909, 13, 281; abst. C. A. 1910, 4, 251;
Rep. Chim. 1910, 10, 30; Zts. ang. Chem. 1910, 23, 79. For the presence of
iron in mercerized cotton see L. Lefevre and £. Blondel, Rev. gdn. mat.
color. 1909,13,^13; abst. J. S. C. I. 1909, 28, 1192; C. A. 1910, 4, 386; Rep.
Chim. 1910, 10, 130; Zts. ang. Chem. 1910, 23, 235.

2. A. Viehoever, L. ChemoflF and C. Jones, J. Agric. Res. 1918, 13,
345; abst. J. S. C. I. 1918, 37, 485-A; C. A. 1918, 12, 1562; T. C. S. 1918,
114, i, 367. In this connection see Perkins, J. C. S. 1909, 95, 1856. 2181;
1916, 109, 145.

COTTON 533

present time have been obtained from cellulose acetates esterified
from tissue paper as the source of cellulose. The main advan-
tages observed are ease and completeness of esterification, facility
of clarification of the esterified cellulose by paper or plate filtra-
tion, water white solutions being invariably produced. The
statement has also been made, that in the formation of nitrocellu-
lose plastics typified by celluloid, less of the plastifying agent is
required for coUoiding purposes, where tissue paper is nitrated
rather than cotton.

The color of nitrated paper is influenced greatly by the purity
of the water used in the several processes of paper purification
preliminary to esterification. - Where the water used is unusually
free from organic matter obtained from leaf mold, and from filtra-
tion through decaying vegetable matter or ferruginous strata, the
final nitrated or acetated paper gives correspondingly clearer and
lighter colored solutions when dissolved in the usual solvents and
solvent conbinations.

Paper pyroxyUn is considered essential to the celluloid manu-
facture in the preparation of transparent celluloid sheets, and for
high class cinematographic and other continuous photographic
films, where freedom from specks is absolutely necessary on ac-
count of the high magnification to which the film is necessarily
subjected to when thrown upon the screen. Another point of
importance is, that the extreme thinness of tissue paper renders
nitration apparently more uniform, and in the case of acetation,
tissue paper more readily disintegrates in the acetylating bath
and hence esterifies more uniformly and quickly. The paper, of
course, must consist of pure cellulose without loading, and should
not be calendared. So-called "grass bleached" paper is preferred
for nitration for the celluloid industry, and also for the manufac-
ture of cellulose acetate.

0. Kress and S. Wells ^ have pointed out the value of cotton
linters and shavings as paper making materials, and report the
varying conditions of manufacture as influencing the quality of
the finished paper.*

1. Paper, 1919, 24, 569; abst. C. A. 1919, 13, 1927.

2. They state that (1) with shavings, 12 lbs. of caustic soda are re-
quired for cooking 100 lbs. of dry shavings at 100 lbs. pressure for 4 hours.
The yield is 70% and the bleach not over 4%, calculated, as bleaching powder
with 35% available chlorine. On account of the loss of fine fiber in wash-

534 TECHNOI<OGY OF CELlyUI<OSB ESTERS

The nitrating processes of J. Hyatt/ M. Delpy,^ Darapsky,'
G. Mowbray/ V. Pallotti/ S. Emmens/ E. LiesegangJ Selwig
and Lange/ and J. Swan,' were all designed for tissue paper and
are described in detail elsewhere in this work. The processes of
G. Melland^° and J. Clouet/^ may also be mentioned.

Cotts^n Wax. The substance known as cotton wax was first
isolated by,E. Schunk from East Indian and Middling Orleans
cotton.^* His method of extracting the wax consisted in boiling
a large quantity of carefully spun cotton yam in amounts varying
from 450 to 2400 lbs., in a kier with soda ash for TVs hours, acidu-
lating the dark brown kier liquor with sulfuric acid filtering and
washing the resulting light brown flocculent precipitate, from which
he extracted the wax by boiling alcohol. He described the product
as a wax-like substance, melting at 86° and closely resembling

ing, the yield of paper from shavings Was 55% based on bone-dry weights.
(2) With cotton linters, 9 lbs. of caustic soda are required to cook 100 lbs.
of bone-dry materials at 100 lbs. for 4 hours. The yield is 90% of bone-dry
pulp, which can be satisfactorily bleached with not over 2% bleach. Bleach-
ing and washing losses will reduce the yield of finished paper to 70%. (3)
Hull fiber can be successfully pulped with 18 lbs. of caustic soda or a total
of 15 lbs. of caustic soda and sodium sulfide per 100 lbs. of material by boil-
ing at 90 lbs. for 3-4 hours. A pulp yield of 66%-76% is obtained and the
pulp can be satisfactorily bleached with 5%-8% bleaching powder. Wash-
ing and bleaching losses reduce the final yield of paper to 47%-51%, all yields
being calculated to the bone-dry weight basis. Photomicrographs and tabu-
lated data are presented.

1. U. S. P. 210611. 1878. D. R. P. 3392, 1878; abst. Tech. Rep. 1878,
29; Dingl. Poly. 1879, 232, 620.

2. F. P. 458558, 1913; abst. J. S. C. 1. 1913, 32, 1063. D. R. P. 256788,
1912; abst. C. A. 1913, 7, 2116; Chem. Zentr. 1913, 85, I, 1080; Chem. Ztg.
Rep. 1913, 37, 144; Wag. Jahr. 1913, 59, I, 438; Zts. Schiess. Spreng. 1913.
8, 138.

3. Dingl. Poly. 1865, 175, 357, 451 ; abst. Jahr. Chem. 1865, 18, 784.

4. U. S. P. 350497, 350498, 1886; abst. J. A. C. S. 1886, 8, 239.

5. Ital. P. 34559, 1913.

6. E. P. 3852, 1890; abst. J. S. C. I. 1891, 10, 484.

7. "The CoUege Courant," February 26, 1870.

8. F. P. 409220, 1909; abst. J. S. C. I. 1910, 29, 751; Mon. vSd. 1910.
73, 295.

9. E. P. 21729, 1894; abst. J. S. C. I. 1895, 14, 1062.

10. Mechanic's Mag. April 13, 1866; abst. Jahr. Chem. 1866, 19, 859;
Dmgl. Poly. 1866, 181, 150; D. Ind. Ztg. 1866, 175; Chem. Tech. Rep. 1866,
5, I, 101; Eisner Mitth. 1866-1867, 249; Cosmos, 1866, (2), 101.

11. Dingl. Poly. 1877, 226, 646; abst. Jahr. Chem. 1877, 90» 1223; BuU.
Soc. Rouen, 1877, 36; Pap. Ztg. 1877, 462; Chem. Tech. Rep. 1877, IB, I.
288; Zts. fur Chem. Grossgewerbe, 1877, 2, 778.

12. Mem. Man. Lit. and Phil. vSoc. 1868, (3), 4, 95; Chem. News, 1868,
17, 118; 1874, 29, 5; Bull. Soc. Chim. 1868, 10, 70; Chem. Centr. 1868, SS,
113; 1869, 40, 112; Jahr. Chem. 1868, 21, 980; Wag. Jahr. 1868, 14, 614;
Poly. Centr. 1868, 34, 1006; Dingl. Poly. 1868, 188, 496; Schwiez. poly. Zts.
1868, 121; J. de Pharm. (4), 8, 232; Deut. Ind. Ztg. 1868, 262.

COTTON 535

the wax extracted by Avequin from the leaves of sugar cane and
camauba wax extracted from the leaves of the Camauba Palm.
By saponification he was able to obtain from it a small quantity
of cerosic acid. Schunck obtained in this manner from the cot-
ton only 0.004% of wax which was insoluble in water, but solu-
ble in alcohol and ether. He succeeded in isolating from the alco-
holic extract a small quantity of a fatty acid which he identified
as margaric acid, and which fused at 53°.

E. Elnecht and J. Allan, ^ by extraction of raw cotton in a
Soxhlet by means of benzol, have obtained 0.38% of crude cot-
ton wax from Bengal cotton, 0.47% from Egyptian and 0.05%
from American cotton. They were able to separate the crude wax
into two fractions, designated by them cotton wax **A" and cot-
ton wax "B." The former extracted by petroleum, boiling be-
tween 55®-65** was odorless, of a dull, yellow color closely resem-
bling beeswax in texture and structure, though somewhat softer
and much more sticky when softened by heat. The following
constants were obtained:

Melting point, 66^-67° C.

Acid No. 44.1; equals 22.2% calculated as oleic acid.
Saponification value, 84.3; equals 664.2 saponification equivalent.
Iodine value, 28.35.

On repeated treatment with boiling 96% alcohol, 18.82% of
the wax remained insoluble.

Cotton wax B: Dark green, almost black, granular plastic
mass of complex nature, giving the following constituents:

Melting point 68°.

Acid No. 4.05; equals 2.03% calculated as oleic acid.

Saponification value 83.3, equals 671.5 saponification equivalent.

E. Knecht* exhaustively extracted raw Egyptian cotton-sliver
with benzene yielding 0.47% crude cotton wax, having the appear-
ance and consistence of beeswax. The Egyptian cotton deprived
of wax yielded on extraction with alcohol 0.68% of solid extract,
amorphous, very hygroscopic and of a dark brown color. Aque-
ous extraction which followed gave 1.46% of a brown, hygro-
scopic substance similar to the alcohoUc extract.

Texas cotton yielded 0.55% of crude wax soluble in benzene.

1. J. Soc. Dyers Col. 1911, 27, 142; abst. C. A. 1911, 5, 3911; J. C. S.
1911, 100, ii, 645; J. S. C. I. 1911, 30, 813; Meyer Jahr. Chem. 1911, 21,
448, 514; Wag. Jahr. 1911, 57, II, 428; Zts. ang. Chem. 1911, 24, 2183.

2. Text. Inst. 1911, 2, 22; abst. C. A. 1912, 0, 935; J. S. C. I. 1911,
1007; J. Soc. Dyers Col 19U, 27, 254.

536 TECHNOUKJY OF CELLULOSE ESTERS

The alcoholic extract amounted to 0.90% and contained 1.07%
of nitrogen; reduced Fehling's solution strongly; while the aqueous
extract was 1.61%; the ammoniacal extract 0.39% and the formic
acid extract 0.72%. When the exhausted Texas cotton was
digested with cold dilute HCl it yielded a fiurther 0.43% of ex-
extract. Bengal cotton yielded but 0.38% crude wax. Innum-
erable samples of raw cotton cloth have been examined by M.
Freiberger' for fat content, the results varying within wide limits,
according to the quality of the cotton. In the preliminary desiz-
ing generally practiced by the bleacheries with soap, the fats are
largely split. In the bowking liquors from several bleacheries,
considerable diflference in the quantitative and qualitative char-
acter of the fatty acids were observed. Chemicking and souring
were found to change the remaining fatty substance by the
oxidization action of the chlorine.

C. Piest^ has subjected raw American cotton (linters) to
extraction with the following solvents in a Soxhlet apparatus:
benzene, petroleum ether, ethyl ether and absolute alcohol. The
following table gives the results obtained:

Petroleum Alcohol Extract

Ether Benzene Ether

Extract Extract Extract Saponification Iodine

% % % % Number Value

0.74 0.87 0.50 1.27 159 22.1

The iodine value of the cotton wax obtained (22.1) is close to
that found by Knecht and Allan (28.5) for the cotton wax which
they obtained by extracting raw Egyptian cotton with petroleum
ether. The quantity of so-called wood gum (probably xylan)
present in the raw cotton, was found to be 1.32% and was obtained
by extraction with cold 5% caustic soda solution. The copper
number as determined by Schwalbe's method was 3.57.

Cotton was also examined after it had passed through the
normal purification process used in preparing it for nitration.

1. Farber. Ztg. 1915. 26, 295; abst. C. A. 1916, 10, 2304; Chem. Zentr.

1916, 87, I, 446. In this connection see M. Freiberger, Zts. anal. Chem.

1917, 56, 229; abst. J. S. C. I. 1917, 36, 923; Ann. Rep. See, Chem. Ind. 1917.
2, 127.

2. Zts. ang. Chem. 1912, 25, 396; abst. Chem. Zentr. 1912, 83, 1, 1643;
C. A. 1912, 6, 1688; Chem. Ztg. 1913, 37, 753; abst. J. S. C. I. 1913, 32, 694;
C. A. 1913, 7, 3545; Chem. Zentr. 1913, 84, II, 550. See also Zts. ang. Chem.
1912, 25, 2518; abst. Chem. Zentr. 19 J3, 84, 1, 1145; J. C. S. 1908, 34, i, 138;
C. A. 1913, 7, 895.

COTTON ^ 537

The process consisted first in the mechanical purification; second
in heating with dilute caustic soda solution under pressure; and,
finally, washing with dilute normal hydrochloric acid solution : Nine
samples of such prepared cotton were investigated in duplicate.
The ether extracts ranged from 0.09% to 0.36%; carbon tetra-
chloride extracts from 0.12% to 0.31%; the alcohol extract from
0.23% to 0.52%. The lowest "wood gum" or xylan content found
was 0.33% and the highest 0.89%. The copper numbers were
found to be roughly proportional to the xylan content. In another
series of experiments a sample of the prepared cotton was taken
and extracted with the three solvents in succession, the results of
the t3rpical experiments being tabulated below.

ETHER EXTRACT

% Saponification Value Iodine Value

0.12 180.0 10.37

0.13

TETRACHLORIDE EXTRACT AFTER THE ETHER

EXTRACTION

% Saponification Value Iodine Value

0.09 231.7 6.60

0.14

ALCOHOL EXTRACT AFTER THE TETRACHLORIDE

EXTRACTION

% Saponification Value Iodine Value

0.23 149.5 7.40

0.29

The experiments indicate that the copper number is increased
by the presence of cotton wax.

Absorbent Cotton, is cotton which generally is suitable for
nitrdtion, irrespective of preliminary processes of purification to
which it may have been subjected. Absorbent cotton is merely,
of course, purified cotton in which the ether extract (fat) is seldom
more than four- tenths of one per cent., which cotton will almost
immediately sink when immersed in water.

According to A. Chaplet,* in the absorbent cotton industry
in France, the cotton is first given a 12 to 48 hour bath in 1%
caustic soda under slight pressure, then chemicked for 20 min-

1. Rev. chim. Ind. 1914, 25, 117; abst. C. A. 1914, 8, 2951. L.
Warneke (Phot. Mitth. No. 177, 239; Chem. Ztg. 1879, 3, 198; Chem. Tech.
Rept. 1879, 8, I, 288) has described a method of producing absorbent cotton
especially suitable for the manufacture of cellulo^ esters. The J. Pierce
tnethod of producing absorbent cotton is described in U. S. P. 239398, I88j,

538 TECHNOLOGY OF CELLULOSE ESTERS

utes, washed, soured and washed again. It is then submitted to
a weak sodium hydrate bath, washed, soured, and well washed,
squeezed and quickly dried. Sometimes an antichlor is used, but
tmless great attention is given to its application, the white color
is apt to take on a yellowish tinge after standing.

The French tests for suitable absorbent cotton are that it
should be neutral to all indicators, should sink at once in cold
water and leave less then 0.2% ash, and should show less than
0.5% of combined ethereal-ethyl alcoholic extract.

In the judgment of F. Kilmer,^ absorbent cotton should pre-
ferably be made from the type of cotton known as Texas Strict
Middlings, as other grades are apt to give inferior results. An
imbleached absorbent cotton, largely used on the Continent, is
made by similar extraction of the fiber mass by the aid of solvents.
The best bleached product, according to Kilmer, is made as fol-
lows: washing in water, slight alkaline hydrolysis consisting of a
boil with 1% caustic soda for 12 to 48 hoiu^ imder low pressure;
washing; then oxidation with hypochlorite of lime or soda, the
latter being the better, the action is prolonged, the solution con-
taining about 0.1% of chlorine, this treatment being continued
tmtil the cellulose is sufficiently oxidized to show the oxycellulose
reaction. Then follows hydro-extraction, acid treatment in a 2%
solution of sulfuric acid, washing and hydro-extraction followed
by a second alkaline hydrolysis, this time consisting of a short
boil with 0.25 caustic soda, washed, hydro-extracted, treated with
antichlor or a solution of soap, followed by final washing. Of
coiu^se sterilizing by steam or rendering antiseptic by means of
treatment with formaldehyde gas is never resorted to in the l5rep-
aration of cotton intended for nitrating purposes-.

According to J. Garcon,* Sea Island and Egyptian grades of
cotton, with their fine and long fibers are not suitable for the pre-
paration of absorbent cotton as it is very difficult to make them
absorbent. Brazilian cotton is too woolly and when colored,

1. J. S. C. I. 1904, 23, 967; abst. J. Soc. Dyers Col. 1905, 21, 19; Chem.
Centr. 1904, 75, II, 1752; Chem. Ztg. 1904, 28, 363. C. Dodge, Sci. Amef.
Suppl. 1910, 69, 358.

2. Textile Mfg. 31, 387; abst. J. vSoc. Dyers Col. 1906, 22, 103. In
the Amer. Druggist, 1907, 50, 136, are reported the analyses of 15 samples
Of absorbent cotton, the fatty matter therein ranging from 0.32%-0.98%.
vSee J. Gilmour, Year Book Pharm. (Lon.) 1907, 446. K. Helfritz. Pharm.
Zentralh. 1910, 51, 101; abst. Chem. Zentr. 1910, 81, I, 1163.

COtTON 539

«

difficult to bleach.' Indian cotton is little used because of its
tender and dirty fiber. The best grades are those of New Orleans,
Texas, Allen Seed, Mobile and Benders of Middling Grades.
Unripe fibers, dead cotton, and those to which the seed is attached
must be removed because they do not possess the cellular canal
and are therefore not absorbent. They become brittle when
treated chemically. Cotton card wa^te is suitable for use but
usually does not yield a high class article. On the Continent, ab-
sorbent cotton is obtained by removing all trace of fatty matters
by means of volatile solvents.

Garcon shows that the operations necessary in the prepara-
tion of absorbent cotton can be divided into the mechanical opera-
tion, such as sampling, sorting, cleaning, picking and carding;
chemical operations, such as boiling, washing, treatment with
alkaline solutions,- bleaching and drying, acidifying and drying,
a second treatment with alkali, acidifying, neutralizing and finally
drying. The mechanical operations embrace cleaning and dry-
ing at 105®, carding and winding on spools. Care should be taken
in the use of absorbent cotton for nitration that it has not been
overbleached, as often the chemical treatment to which it is sub-
jected is unnecessarily harsh.

In bleaching with sodium h5rpochlorite or with calcium hypo-
chlorite, the process is usually carried much further than is the
case with ordinary chemicking and this is the reason why absorb-
ent cotton has increased affinity for basic dyes, which affinity can
be used as a test of the absorbing power of cotton. The removal
of acids is one of the most important features of the process and
is difficult unless great attention be paid to seemingly unimportant
details.

V. Vaughan is authority for the statement that approx-
imately 25,000 short tons per annum of absorbent cotton was
recoverable from the hospital and medical tmits on the allies'
front, provided such material is suitable for the production of
nitrocellulose or the cellulose esters and provided also that it
would be delivered and purified at a cost not greater than that of
the present market price for cotton linters and hull fibers. Of
course, in connection with this suggestion is the possibility of
traces of mercuric chloride remaining in the used cotton from the
an tiseptics employed, traces of mercuric chloride, as it is well

540 TECHNOLOGY OF CELLULOSE ESTERS

known, have a tendency to mask the stability tests of the finished
nitrocellulose.

In the Ninth Revision of the United States Pharmacopeia,
absorbent cotton is olB&cially described as follows:

"Purified cotton occurs in white, soft, fine filaments, appear-
ing under the microscope as hollow, flattened and twisted bands,
spirally striate, and slightly thickened at the edges; inodorous and
almost tasteless; insoluble in ordinary solvents, but soluble in an
anmionia solution of cupric oxide.

When purified cotton, previously compressed in the hand, is
thrown on the surface of cold water, it readily absorbs the latter
and sinks.

Incinerate 5 gm. of purified cotton; not more than 0.2% of
ash remains.

Thoroughly saturate about 10 gm. of purified cotton with 100
mils of distilled water, then with the aid of a glass rod press out
two portions of the water, 25 mils each, into white porcelain
dishes. Add to one portion 3 drops of phenolphthalein T. S. ^and
to the other portion 1 drop of methyl orange R. S. ; no pink color
develops in either portion (alkali or acid).

Extract 5 gm. of purified cotton, tightly packed in a narrow
percolator, with ether, until the percolate measures 20 mils, and
evaporate this to dryness; the residue does not exceed 0.6 per
cent, (fatty matter).

Extract 10 gm. of purified cotton, in a narrow percolator,
with alcohol, until the percolate measures 100 mils. When ob-
served downward through a column 20 cm. in depth, the perco-
late may show a yellowish color, but no blue or green tint (dyes) ;
and, on evaporating this percolate to drjrness, the weight of the
residue does not exceed 0.5 per cent, (resins and soap)."

F. Kilmer has recorded in detail the methods of preparation
of cotton fiber for surgical purposes, in which condition it is es-
pecially suitable for either nitration or acetation, when deprived
of substantially all of its atmospheric moisture. In the prelim-
inary treatment of cellulose for technical purposes, E. BerP advo-

1. Zts. Schiess vSprengst. 1909, 4, 81; abst. J. S. C. I. 1909, 28, 380;
C. A. 1909, 3, 1926; Chem. Zentr. 1909, 80, I, 1275; Jahr. Chcm. 1909, 82,
384; Chem. Tech. Rep. 1909, 33, 194; Wag. Jahr. 1909, 5S, I, 431. For in-
formation concerning errors in appraisement of absorbent cotton, refer to
Morenl, Bol. chim. farm. 51, 151; abst. C. A. 1912, 6, 2817.

COTTON 541

cates the reduction in the viscosity of the esteris^d cellulose,
either by a depolymerization of the cellulose, mercerization, or
regulated hydrolysis before esterification.

Methods of Cotton Analysis.^ 1. Specifications: The
usual smokeless powder specifications require the use of bleached
cellulose containing not more than 0.4% of extractive matter;
not more than 0.8% of ash; and state that it should not contain
more than "traces" of lime, chlorides and sulfates. For some
•commercial grades of nitrocellulose, unbleached ^cotton is used,
but the methods of analysis are the same as for bleached cotton.
The routine analysis of cotton includes the determination of
moisture, ether extract, ash, solubility in 95% sulfuric acid and
solubility in 10% caustic potash. The furfural value is also
figured in the determination and on crude fiber the amount of
**dust" is determined by a sieving test as described.

2. Sampling: In sampling fiber in bales, a section extend-
ing from one side to approximately the center is taken from each
bale sampled, the samples being taken from not less than one-
tenth of the number of bales in the lot. In sampling crude fiber,
special note should be made and samples taken of any bale show-
ing large proportions of mouldy fiber or of very oily fiber as indi-
cated by a pronounced yellow color. The samples for moisture
are quickly and thoroughly blended by hand and a sample of
about 20 gm. placed in a previously weighed glass or in a vessel
with tightly fitting cover. The, remainder of the sample is opened
up by hand or in a mill or picker if available, and after being
thoroughly blended is reduced to proper size by quartering and
dried at 105® C. All determinations except moisture and dust
are made on the dry sample.

3. Moisture: About 20 gm. of a sample prepared for
moisture determinations are weighed under conditions to avoid
changes in moisture content, dried at 105*^ for three hours, or,
if the moisture is high, as may happen with samples taken from
^ales that have lain out in the rain, heating is continued until
constant weight is reached. The loss in weight is calculated to
the per cent, of the sample as received.

4. Ash: At least 5 gm. of dry material, prepared as above,

1. This is supplementary to the general topic in Chap. I, and es-
pecially applicable to cotton cellulose.

542 TECHNOLOGY OF CELLULOSE ESTERS

is placed in a platinum or silica dish of 80 to 100 cc. capacity,
moistened with a small amount of pure nitric acid, covered, and
heated on the water bath imtil active decomposition ceases. In-
cineration is then completed kt a low red heat, care being taken
to avoid loss of ash and to keep the incineration below the vapor-
izing point of the alkali chlorides. The dish is then cooled, the
ash moistened with a few cubic centimeters of distilled water, and
after evaporating the water on the steam bath or hot plate, the
ash is again heated to a low red heat. This procedure causes the
ash to deposit on the dish in a small layer which is not affected
by air currents through handling. Under these conditions the
ash is largely in the form of carbonate. The dish and con-
tents are finally cooled in a desiccator and weighed and the result
calculated to the per cent, of dry weight of the cotton. The
powder specifications usually call for the digestion of a 1.5 gm.
sample with a little pure nitric acid, and incineration at a red
heat. The use of a smaller sample of cotton and a higher tem-
perature of incineration are likely to give too low results.^

5. Ether Extract:^ About 5 gm. of dry material are thor-
oughly extracted with pure ethyl ether in a suitable extraction
apparatus (preferably that of Knorr's) for about eight hours or
until further extraction removes no additional substances soluble

1. E. Justin-Mueller has pointed out (I'lnd. chim. 1918, 5, 218; abst.
C. A. 1919, 13, 74) that of the non-cellulosic matters particularly the cuticle
or epidermis, is not dissolved but is carbonized and remains with the in-
soluble mineral compounds which are determined as "ash." These consist
largely of calcium phosphate and carbonate, and an error may enter into
this determination through the action of the sulfuric acid converting them
into sulfates. These compounds, which amotmt to 25% of the weight of
insolubles in a cotton of good quality, are increased to 32.59% by the treat-
ment with sulfuric acid. Mueller details the method of calculation to be
followed to avoid this error. The tests determined were as follows: (1)
The percentage of waste; (2) the tensile strength of the yam; (3) tiie bleach-
ing properties of the yam and cloth; (4) the moisture content; and (5) other
manufacturing properties of the cotton. The sources of the samples, method
of sampling, methods and conditions of the various tests employed to deter-
mine the 5 factors above mentioned, are described in detail and the results
assembled in 10 tables and 11 charts. The tests show that after making
allowance for the losses due to the cleaning process there is comparatively
little difference between the grades above and those below Middling in the
price paid by the manufacturer for each pound of nisable cotton obtained from
bales of different grades, but that there is a difference in the intrinsic value
per pound of the manufactured product.

2. G. MacNider (Proc. Assoc. Off. Agrl. Chem. 1910. 155; Bull. 137,
U. S. Dept. Agr.) has presented a comparison of petroleum ether and ethyl
ether for determining fat in cotton products.

COTTON 543

in ether. The extractive matter is weighed after drying at 100*
to constant weight and the result (after deducting the weight of
the residue in the ether in a control experiment) is calculated to
the per cent, of dry weight of material. Care must be taken to
have the extractive matter free from even particles of fiber which
may be present there mechanically. After extraction with ether
the sample may be dried and used for the determination of non-
cellulose, as below.

6. Solubility in Sulfuric Acid. — Determination of Non-cellu-
lose: The sidfuric acid used must be within 0.1% of 95% abso-
lute acid. The determmation is made by treating five grams of
dry cotton at about 20° with 50 cc. acid at the same temperature.
In the case of crude fibers it is important to remove the oils by
extraction with ether before making this determination. The
fiber is stirred vigorously in the acid for five minutes, then slowly
poured in ten liters of cold distilled water. The aqueous soluticm
is heated on a hot plate for at least four hours, with frequent
stirring, keeping the temperature as near as possible to 100°.
The insoluble matter is filtered out on a Gooch crucible with a
carefully prepared asbestos mat. The contents of the Gooch are
thoroughly washed with boiling distilled water to remove the last
traces of sulfuric acid and then dried for three hoturs at 100°,
cooled and weighed, and the result calculated to the per cent, on
the dry weight taken. It is important to use asbestos for the
Gooch that does not lose weight when treated with dilute sulfiuic
acid. It is also important that the fiber is well opened up and
free from Itmips, for if lumps are present a higher result may be
obtained.

7. Approximate Cellulose: The approximate cellulose in the
fiber is found by adding together the percentage of ash, ether
extract, and non-cellulose, and subtracting the total from 100%.

8. Solubility in Caustic Potash: Cellulose is insoluble in
alkalis, so that in the crude fiber, solubiUty in caustic potash is
a measure of the non-cellulose present. In the purified fiber it
is a measure of the severity of the bleaching and indicates the
amount of hydrocellulose and oxycellulose present. A solution
of pure potassium hydroxide of a concentration within 0.1% of
10% is prepared by dissolving the proper weight of the purest

544 TECHNOLOGY OF CBLLUU)SE ESTERS

obtainable potassium hydroxide in distilled water. The strength
of the solution is to be carefully checked by titrating and it must
be carefully protected from carbon dioxide.

Approximately two grams of the sample are dried in a wide
mouthed weighing bottle to constant weight at 102**-105°, the
contents of the bottle transferred to a 250 cc. Jena glass beaker,
covered with 100 cc. of 10% potassium hydroxide solution, the
beaker covered with a watch glass and the contents heated to
100** for three hours. Heating on the steam bath is unsatisfactory
for this purpose as it does not give a sufficiently high temperature.
Care must be taken to avoid concentration of the solution or
undue oxidation of the fiber due to exposure of the alkali-soaked
fiber to the air. It is also necessary that the temperature be
kept as close to 100° as possible, since variations in temperature
materially affect the resultant material. After the heating is
completed, the contents of the beaker are poured into a flask
containing one liter of distilled water and any residue in the small
beaker is washed into the other. The alkali is then neutralized
with a decided excess of acetic acid, this excess of acid being neces-
sary in order to break up the combination of alkah and cellulose.
The undissolved cotton is then filtered into a weighed Gooch
crucible having an asbestos mat, is thoroughly washed succes-
sively with hot water, then alcohol, and finally ether. It is then
rapidly dried to constant weight at 102**-105°. The loss of
weight of material is calculated to per cent.

In making this determination on crude fiber the amount sol-
uble in hot water alone is deducted from the total and expressed
separately and a further correction must be made for the oils
extracted by ether and the per cent, of ash which goes into solu-
tion in the acetic acid, though these corrections are not necessary
on the bleached fiber. In order to determine the amount of ash
which goes into solution, the ash determination must be made on
the fiber after treatment.

9. Furfural Value (Pentosans). —Preparation of Reagents:
The purity of the phloroglucinol is tested by dissolving a small
quantity in a few drops of acetic anhydride heating almost to
boiling and adding a few drops of concentrated sulfuric acid. A
violet color indicates the presence of diresorcinol. If the phloro-
glucinol gives more than a faint coloration it should be purified

COTTON 545

by the following method:

. Heat in a beaker about 300 cc. of hydrochloric acid (sp. gr.
1.06) and 11 gm. of commercial phloroglucinol added in small
quantities at a time, stirring constantly until it has almost en-
tirely dissolved. Some impurities may resist solution but it is
unnecessary to dissolve them. Pour the hot solution into a suffi-
cient quantity of the same hydrochloric acid (cold) to make the
volume 1500 cc. Allow it to stand at least over night, better
several days, to allow the diresorcinol to crystallize out and filter
immediately before using. The solution may turn yellow but
this does not interfere with usefulness. In using it, add the vol-
ume containing the required amount to the distillate.

Determination: Place a quantity of the material, chosen so
that the weight of the phloroglucinol obtained shall not exceed
0.300 gm. in a flask together with 100 cc. of 12% hydrochloric
acid (sp. gr. 1.06) and several pieces of recently heated pumice
stone. Place the flask on a wire gauze, connect with a condenser,
and heat rather gently at first and so regulate as to distill over
30 cc. in about 10 minutes, the distillate passing through a small
filter paper. Replace the 30 cc. driven over by a like quantity
of the dilute acid added by means of a separatory funnel in such
a manner as to wash down the particles adhering to the sides of
the flask and continue the process until the distillate amounts to
360 cc. To the completed distillate gradually add a quantity of
phloroglucinol (purified if necessary) distilled in 12% hydrochloric
acid and thoroughly stir the resulting mixture. The amount of
phloroglucinol used should be about that of the furfural expected.
The solution first turns yellow, then green and very soon an amor-
phous greenish precipitate appears, which grows rapidly darker,
till it finally becomes almost black. Make the solution up to
400 cc. with 12% hydrochloric acid, and allow to stand over night.

Filter the amorphous black precipitate into a tared Gooch
crucible through an asbestos felt, wash carefully with 150 cc. of
water in such a way that the water is not entirely removed from
the crucible until the very last, then dry for four hours at the
temperature of boiling water, cool and weigh, in a weighing bottle,
the increase in weight being reckoned as phloroglucinol, using the
following formulas given by Kroeber :

546 TECHNOLOGY OF CELLULOSE ESTERS

(a) for weight of phloroglucinol "w'' under 0.030 gm., furfural equals
(w 4- 0.0052) times 0.5170.

(b) for weight of phloroglucinol "w" over 0.300 gm., furfural equals
(w -^ 0.0052) times 0.5180.

For weight of phloroglucinol *V*' from 0.030 gm. use the
following formula :

Furfural equals (W -5- 0.0052) times 5185.

10. Determination of Copper Value: In order to insure that
the cotton has not been over-bleached and is reasonably free from
oxycellulose and other reducing substances, the "copper value"
may be determined. The results obtained by this depends to a
large extent upon the exact procedure in carrying out the test,
but a standard method has been worked out by Schwalbe as fol-
lows: 3 grams of air-dry cotton are cut into small pieces and
mixed with 200 cc. water and 100 cc. Fehling's solution. This
blue liquid is actively boiled for fifteen minutes under a reflux
condenser by means of a water-glyccrol bath^ with frequent agita-
tion, the time being reckoned from the moment when full ebulli-
tion commences. The liquid is filtered with the aid of a suction
pump through a Gooch crucible with asbestos mat and the residue
containing cuprous oxide is washed with boiling water until the
filtrate is colorless. The copper oxide is then dissolved in nitric
acid and the amount of copper determined, preferably, electro-
lytically. The "copper value" is the percentage of metallic cop-
per, calculated on the dry cotton sample.

Or, after the heating the liquid is filtered, and the precipitate
after washing first with water, then with Rochelle salt solution,
and finally with water, is dried and ignited. The sish is dissolved
in a few drops of nitric acid, the solution warmed and then diluted,
made sliglitly alkaline with sodium bicarbonate, and then just
brought back to neutrality with acetic acid.

Excess of KI is added and the liberated iodine titrated back
with N/\Q sodium thiosulfate, the copper equivalent of the iodine
found being calculated as cuprous oxide.

The following results are given by Schwalbe as obtained from
various materials:*

1. The composition of water and glycerol in this bath is so adjusted
as to give a boiling temperature of 105°, which is usually equivalent to 100°
inside the flask.

2. According to E. Hagglund (Papierfabr. 1919, 17, 301; abst. Chem.
Zentr. 1919, 90, II. 296; J. S. C. I. 1919, 38, 894-A), Schwalbe's method for

COTTON 547

11. Dyeing Test: The presence of oxycellulose, as has pre-
viously been pointed out, is also indicated by the depth of color
which certain basic dyestufiFs, as fuchsine, impart to the cellulose
fiber. This may be determined by immersing one gram of the
sample to be tested in 100 cc. of a 0.2% fuchsine solution, the
mixture being then gently boiled for 30 minutes. The cotton is
then removed and washed, first with cold and then with hot
water, until no further amount of color is extracted. The depth
of color is an indication of the oxycellulose present.

12. Viscosity Valtie, H. Ost^ has called attention to the

the estimation of the copper value may be simplified by using Bertrand's
volumetric method for the titration of the reduced cuprous oxide. Four
gm. of the finely disintegrated cellulose is stirred with 200 cc. of water, which
is then heated to boiling, and 100 cc. of boiling Fehling's solution added.
The mixture is boiled for 15 minutes and then filtered in a Neubauer platinum
crucible or else on a double filter paper with the assistance of kieselguhr
paste. The cellulose containing the cuprous oxide is washed with hot water
and then treated with 100 cc. of boiling ferric sulfate solution containing
50 gm. of ferric sulfate and 200 gm. of sulfuric acid per liter. The iron solu-
tion should previously be tested for inertness towards permanganate. The
cuprous oxide is thereby dissolved, and the cellulose is washed several times
with boiling water. The filtrate is then titrated with N/10 permanganate,
and shows a sharp end-point from green to pink. With regard to tests for
the quality of unbleached Mitscherlich sulfite pulp, the author has deter-
mined the copper sulfate absorption values, but finds no connection between
these and the bleaching capacity of the ptdps. The bleaching quality, how-
ever, shows a more consistent relationship with the lignin value as determined
by Klason's method. None of the usual chemical tests, such as copper
value, hydrolysis value, etc., showed any satisfactory concordance with the
strength and mechanical qualities of the cellulose. Only in certain very
pronounced cases can any definite relation be found between the tensile
strength and the degree of digestion of the pulp. It may frequently happen
that a fully digested pulp is as strong as or stronger than an tmder-digested
material.

Surgical cotton wool 1 .64 to 1 .8

Mercerized bleached Egyptian cotton 1.9 to 1 . 6

Glanzstoff artificial silk 1.1

Hydrocellulose 5.2 to 5.8

Parchment paper 4.2

Bleached sulfite wood pulp 3.9

1. Zts. ang. Chem. 1911, 24, 1892; abst. Wag. Jahr. 1911, 57, II, 428;
abst. J. S. C. I. 1911, 30, 1247; C. A. 1912, 6, 684; Chem. Zentr. 1911, 82,
II, 1518; J. C. S. 1911, 100, i, 838; W. Dean and F. Taylor (U. S. Dept. Agr.,
Bull. 501, 27 pp. (1917) have described in detail the manufacttuing tests
of the official cotton standards for grade, spinning tests being conducted for
the purpose of determining the relative intrinsic values of cotton of the
grades of Middling Fair, Good Middling, Middling, Low Middling, and Good
Ordinary. M. Lahache (Union pharm. Mar. 15, 1915; Repert. pharm. 1916,
28, 4; C. A. 1916, 10, 950) has detailed simple tests for the principal con-
stituents of medicated cotton and gauzes as well as physical qualifications
for absorbent cotton and gauzes. For the testing of cotton by steaming,
consult M. Freiburger, Farber Ztg. 1917, 28, 221, 235, 249; abst. Zts. ang.

548 TECHNOUXJY OF CEI.LULOSE ESTERS

determination of the viscosity of solutions in cellulose in copper
ammonia of definite composition as a means of distinguishing
cotton and allowing conclusions to be drawn regarding its prelim-
inary treatment.

13. Viscosity Value (Woolwich Method) : The viscosity of
cellulose is determined in cuprammonium solution, and it is of
the utmost importance in order to obtain reliable results to use
a cuprammonium solution prepared according to the standard'
method, and to avoid the action of light and air on the cellulose
solution.

Preparation of the Cuprammonium Solution: 60 gm. of cop-
per sulfate are dissolved in 1 liter of hot water in a wide necked
bottle, a few drops of sulfuric acid being added. The solution is
allowed to cool to 50^ and ammonia (sp. gr. 0.880) added until
the precipitation of basic copper sulfate is complete, any excess
of ammonia being neutralized with a few drops of sulfuric acid.
The precipitated bs^^ic sulfate is allowed to settle and the super-
natant liquid decanted. The precipitate is washed by decanta-
tion with water at 80°, until the wash water is free from sulfate.
200 cc. of 20% caustic soda are then added and the whole well
shaken at ordinary temperature. The precipitate is converted to
blue cupric hydroxide which is then allowed to settle, the super-
natant liquid decanted and the precipitate washed by decantation
with cold water till the wash waters are free from alkali. The

Chem. 1918. 31, 146; J. S. C. I. 1918. S7, 408-A. L. Dewey and M. Goodloe
(Bur. Plant Ind. Circ. 128-B. 17-21) have described a machine for testing
the breaking strain of cotton fibers. B. Rogalski (Russ. j. Tagric. experi-
mentale, 1916, 17, 13; abst C. A. 1915. 10, 3165) has reported analyses of
cotton taken during the general stages of its evolution. Samples of cotton
{Gossypium hirsutum L.) were taken diuring 4 stages of its growth: at the
commencement of budding, at the commencement of flowering, at the time
of harvest, and after frost. It was found that the amount of nitrogenous
substances and the relative amount of nitrogenous non-albuminous sub-
stances decreased with the age of the plant. The same took place in the
case of non-nitrogenous substances soluble in water, and in the case of the
ashes. The latter are composed of chlorides and sulfates. The part solu-
soluble in acids consists largely of compounds of potassium. Parallel to
the growth of the cotton, an accumulation of lignin and pentosans takes
place in the cell walls. It is believed that pure lignin and hemi-cellulose
are present at the same time in the fiber, and that complete hydrolysis of
the hemi-cellulose is not obtained. This latter is evidently staUe after boil-
ing with 2% hydrochloric acid for three hours. A high amount of crude
fat characterizes the green parts of the plant and the seeds, and their qtuin-
tity generally depends on the % for the entire plant. The iodine number for
the crude fat of parts of the pod other than the seed and fresh leaves leads
to the belief that these capsules have not attained maturity.

COTTON 549

precipitate is then transferred to a Biichner funnel and washed
with distilled water and sucked dry. It is then dried on a porous
plate in an air oven at 40**.

The dried cupric hydroxide is transferred to an aspirator
bottle and 800 gm. of ammonia per liter are added. The whole
is well shaken and the excess of cupric hydroxide allowed to set-
tle. The supernatant liquid is run off through a glass wool filter
and the volume measured. The copper in the solution is deter-
mined volumetrically and the theoretical quantity of ammonia,
containing 200 gm. of ammonia per liter, is added to reduce the
concentration of copper to 10 gm. per liter. The finbhed solu-
tion should be kept in a tightly stoppered aspirator bottle, and
its copper content should occasionally be determined by titration.

Determination of Viscosity by Falling Sphere Method: The
general arrangements are the same as for the determination of
the viscosity of nitrocellulose solutions, but owing to the deep
blue color of the solution it is necessary to use a tube of 1 cc.
diameter.

In Pig. 1 is shown an apparatus for conducting this test, and
consisting of a tube 1 cc. in diameter, about 30 cc. long with 5
graduations at 5 cc. intervals.

The water baths should be covered with brown paper with
two vertical slits at opposite sides, and the head of the observer
should be screened so that all light reaching him should pass
through the blue solution.

Preparation of the Cellulose Solution: 2.1 gm. of air dried
cotton cut up finely and degreased if necessary are weighed out,
an allowance of 5% being made for moisture in all cases.

100 cc. of standard cuprammonium solution together with 8
or 9 glass beads are placed in a stout bottle of about 150 cc.
capacity and the weighed quantity of cotton added. The bot-
tle is then at once closed with an india-rubber stopper, through
which a short capillary tube passes one end being flush with the
bottom of the stopper, the other end being connected to a short
length of india-rubber pressure tubing closed with a screw clip.

The pressure tubing is connected to a water pump and by
opening the screw clip, the air in the bottle is displaced by am-
monia evaporating from the solution. As soon as the bubbles
reach the cork the screw clip must be at once closed and the

550 TECHNOUKJY OF CEl.I<ULOSE ESTERS

bubbles axe broken by a sharp tap given at frequent intervals.

This operation is repeated four times to enstu'e complete re-
moval of the air from the bottle. The bottle is immediately
shaken vigorously for five minutes and then at frequent intervals
till solution is complete.

It is advizable to keep the bottle immersed in a covered bath
of water at 20^ C. as a protection for air and light.

Filling the Viscotneter Tube: When solution is complete, the
cork is removed from the bottle without disturbing the liquid and
is replaced by a cord carrying a short inlet tube reaching to 1
cm. from the bottom and an outlet flush with the cord and about
50 cc. long.

The bore of the tubes is about 5 mm.

The viscometer tube is slipped over the long outlet tube and
the bottle is then inverted carefully without shaking the liquid.
The solution then flows down into the viscometer tube. When
the tube is full, the outlet tube must be raised from the bottom
of the viscometer tube, and care must be taken ^to avoid air bub-
bles forming in withdrawing it. It should not be raised above
the surface of the Hquid in the tube and the filling then proceeds
further.

When the tube is filled to within 3 cc. of the top, the bottle
is removed.

Determination of Viscosity: The tube is fitted with an india-
rubber cork carrying a releasing tube. Care must be taken to place
this centrally in the tube. It is then placed in position in the
water bath and the viscosity determination carried out at 20** C.

In time of fall of a Vw i^^ch steel ball through 15 cc. is deter-
mined in the usual way.

Standardization of Viscometer Tube: The tube is standardized
by taking the time of fall for castor oil of known viscosity.

Statement of Results: The time of fall through 15 cc. in a 1
cc. tube should be quoted. In addition the absolute viscosity
should be calculated and quoted, as this allows for all corrections
due to irregularities in the tubes which become important in tubes
of 1 cc. diameter.

The absolute viscosity is given by the equation :

n T(s — sM
ni Ti(s — s»)

COTTON

661

Ml

I

^mm .Mtmo/afia.

Releasing TUife
Small Hole

level of //qu/'cf
Graafuafion Mark

Gnaduo fion Mark

Graduation Mark

Graduation Mark

Graefuatfon Mark

^—^kitemol da. /cmto-OSem,
K^y^Bufhahout/S'Z'Ocm d/o.

13

Stout I.HTuifing F/^OM BoTTLB

Screw C/ip

Air Met Tutfe l_Ji

IhHfe^
OhssTuife SoluHon

lR.Stof>per

2HoMJ.RCon
BOTTLS FOff
PRePARiNO SOLUr/ON

STOUT GLASS

Class Tubtrtg ahout 4min6ore

w.

-Il

M

12cm.

y/scomehr Tubt

f

1

Fig. I. — Sl^ERK ViSCOSIMBTBR FOR CSLLtJLOSK SOLUTIONS

(Woolwich Method)

552 raCHNOW)GY OI^ CELLULOSE ESTERS

Tests of Cotton for Nitration purposes. Irrespective v^hether
the cotton is in the form of waste, cop bottoms, linters or other
short or long fiber, it should be as free as possible from foreign
matter as string, pieces or metal or seed particles. The moisture
should not exceed 7% or 8%. The oily matter is determined
in the usual manner by extraction in a Soxhlet or similar appa-
ratus with anhydrous ether, and whereas formerly as high as one
per cent, ether extract was considered allowable, that permissible
amount of fat is generally restricted to about 0.4% or less. To
determine whether cotton has been over-bleached and reasonably
free from oxycellulose and other reducing substances, it is sub-
jected to a determination of the "copper value." A determina-
tion of the ''alkali-caustic copper" will indicate as to whether
the cotton has or has not been mercerized. The loss on boihng
with caustic alkali under specified conditions should also be ascer-
tained or the "wood gum" may be determined, but the insistence
on low results by these tests has an incentive to the supplier to
submit the cotton to prescribed treatment with alkalis whereby
the cotton may readily be damaged.

An indication of the amotmt of oxycellulose is also deter-
mined by ascertaining the power of cotton to combine with basic
dyestuffs such as magenta or methylene blue. Either the cotton
may be treated with a dilute solution of a dye and well washed
and the depth of color compared with that taken by a standard
sample under comparable conditions, or the actual quantity of
dye removed from the solution may be ascertained, the latter
procedure being the more difficult.

G. Lunge and J. Bebie^ soaked 0.5 gm. of cotton in 150
cc. of a 0.5% solution of methylene blue for one hour in a covered
beaker on a boiling water bath. When cold, 100 cc. are poiu-ed
off and the color compared with that of the original solution by
means of a Lovebond tintometer or other colorimeter. In a
typical experiment recorded, one gram of pure cellulose took up
0.0012 gm. of dyestuff.

Inspection of Cotton for Nitration Purposes. Professor
Charles E. Munroe^ has called attention to the fact that when

1. Zts. ang. Chem. 1901, U, 510; abst. Chem. Centr. 1901. 72, II.
34; J. C. S. 1901, 80, i, 508; J. A. C. S. 1901, 23, 527; Jahr. Chem. 1901. 54,
893; Meyer Jahr. Chem. 1901, U, 316; Wag. Jahr. 1901, 47, I, 495.

2. J. A. C. S. 1895, 17, 783; abst. Jahr. Chem. 1895, 48, 1359; J. S. C.

COTTON 553

converting cotton into nitrocellulose by immersion in mixed acid,
it is essential that the cotton should rapidly absorb the acid, for
if the portion that is taken for immersion be but slightly absorbent,
it is quite likely that when but partly saturated, it will rise to
the surface of the acid and on exposure tmdergo the rapid decom-
position technically known as "firing," or "fuming off." To
secure the desired result, therefore, the cotton should be free from
oil, grease, or any protecting body. Their presence not only di-
minishes the absorptive power of the cotton but in common with
the knots, tangles, cops, hulls, seeds, or similar formed bodies
promote decomposition, decrease the speed of nitration, and re-
sult in the production of a body of deficient stability. Therefore
in the determination of the relative value of various samples of
cotton offered for purchase, the amount of the grease, foreign
bodies and waste to be removed and of knots and tangles present,
together with the general cleanliness of the sample given, are
prime points for consideration. A method of inspection, there-
fore, should embrace the following:

1. Optical inspection for color, cleanliness, presence of cops,
knots, tangles and foreign bodies and for relative length, appear-
ance and strength of the fiber.

2. Odor and the presence of fungi and mold on the cotton
filaments.

3. Moisture, as determined by drying a portion at 100° to
105° C. to constant weight.

4. Ether extraction as given in detail elsewhere herein.

5. Extraction with alkali.

6. Determination of ash.

7. Rate of absorption of water.

In making this latter test a sample of the material is thrown
or dropped lightly on the siuiace of cold distilled water and the
time noted between when it touches the surface and when (through
absorption of the water by capillarity) it sinks to the bottom.
One of the requisites for cotton suitable for the manufacture of

I. 1896, 15, 214; Bull. Soc. Chim. 1896, 16, 646; Chem. Centr. 1895, €S, II,
1182. For use of cotton in the manufacture of explosives, see Nature, 1915,
95, 481. For "Cotton as a High Explosive," consult B. Blount, Nature,
1915. 95, 591. For the preparation of cotton for nitration, refer to H.
Barthelemy, Le Caout. Guttap. 191.*^, 10, 7353; abst. Kunst. I9l4, 4, 13;
C, A. 1913, 7, 4067.

554 TECHNOWXJY OF CELI<UW)SE ESTERS

nitrocellulose and smokeless powder is that it shall sink in two
minutes.

In the samples examined by Mtmroe, the moisture varied
from 3.38% to 8.40%; the ether extract from 0.0% to 7.10%;
the caustic soda extract from 3.53% to 5.38%, and the ash from
0.05% to 1.79%. A sample of cotton seed lint gave moisture
6.16%; ether extract 2.35%; soda lye extract 28.54%; ash, 4.83%;
A sample of waste cotton gauze gave moisture 7.37%; ether ex-
tract 0.50%; soda lye extract 3.89%; ash, 0.95%; rate of absorp-
tion, 7 seconds.

U. S. Ordnance Requirements for Cotton. The require-
ments of the Ordnance Department of the United States Army,
as revised April 18, 1908, prescribe that the cellulose prepared
for nitration, must be bleached cellulose which will be obtained
by purifying unspun cotton waste and thoroughly washing to
remove purifying materials or salts; containing not more than
0.7% extractive matter; not more than 1.25% of ash; of uniform
character, and clean and free from such lumps as will prevent
tmiform nitration. The "extractive matter** is determined by
extracting about 1.5 gm. of cotton in a Wiley extractor with
ethyl ether, and weighing the extracted matter after drying at
100**. The percentage is calculated on dry cotton. Ash is deter-
mined by digesting about one gram of cotton with a little pure
nitric acid and incinerating at red heat, being residue and calcu-
lated percentages on dry cotton. Moisture is determined by dry-
ing about three grams of cotton at 105** to constant weight.^

Eng^sh Requirements for Nitrating Cotton. The specifi-
cations for cotton waste for the manufacture of guncotton
(74/6/3623) are as follows: To be bleached cotton cellulose,
specially suitable for the manufacture of guncotton.

To consist largely of fibers of long staple, preferably twisted ;
and to contain as little as possible of felted unspun short fiber
cotton, or dust, technically known as "fly.** The short lint ob-
tained from the cotton seed after removal of the long staple
cotton must not be used, however treated for purification. Sptm

1. Where large amounts of cotton are nitrated it is customary to send
one bale in each 20 or 25 to the bale breakers, from which a representative
sample is obtained. This is kept in a glass-stoppered bottle. Where a large
number of bales are examined at one time, the individual samples are united
by careful blending into one composite sample, and from this portions are
withdrawn for analysis.

COTTON 555

material such as cops or cop bottoms may be used. Weaving mill
waste may not be used.

The waste must not show more than the following figures
calculated as percentages on the dry material:

Moisture 7.0%

Oily matter 0.6%

Soluble on boUing 1 hour in 3% NaOH 5.0%

Reduction of Fehling solution (1 vol. to 2 vols,

water on heating 15 minutes at 100 ** C. (CuiO) 1.0%

Mineral matter 0 . 5%

Starch 0.2%

Except as regards the above figures, it must be entirely free
from organic matter other than pure resistant normal cellulose
and, on dyeing with a basic dye such as Fuchsine (rosaniline
acetate), the fixation of color must be slight and uniform and must
show no deeply dyed particles or fibers.

(1) Oil: 5 gm. of the dry cotton to be extracted for four
hours with 100 cc. ether in a Soxhlet extracting apparatus, and
the ethereal solution evaporated. The residue must not exceed
0.8%.

(2) Moisture: 5 gm. dried in air bath at 100 C. must
'not lose more than 8%.

Specifications of Cotton for Nitration in Germany. Accord-
ing to Hertzog,^ the military authorities specify a cotton suitable
for nitration shall be one which, when thrown into water, sinks
within two minutes; when nitrated, does not disintegrate; when
treated with ether yields not more than 0.9% of fat, and contain-
ing only small traces of chlorine, calcium oxide, magnesium oxide,
nitric oxide, sulfuric acid, and phosphoric acids.

The wastes from the spinning machine and lumps are ptuified
by first boiling with caustic soda, tmder pressure, washing, bleach-
ing with chlorine, washing, treating with sulfuric acid or hydro-
chloric acid, washing, centrifugalizing and then drying. When the
cotton is very greasy it is first boiled with lime water. The loss
in these several treatments varies considerably. For example,
moisture 3 to 15 per cent., packing and in transit 2 to 5 per cent.,
boiling and washing 5%, and bleaching 1.5 to 2 per cent.

Cellulose used for Nitration. It has been stated, and prob-
ably correctly, that at least 95% of the cellulose nitrated consists

1. Centr. f. Text. Ind. 1890, 21, 975; abst. J. S. C. I. 1891, 10, 161;
Chem. Tech. Rep. 1890, 29, II, 143; Chem. Ztg. Rep. 1890, 14, 355.

556 TECHNOLOGY OF CELLULOSE ESTERS

of some form of cotton. In general the purer the cellulose used,
the less difficulty in nitration and subsequent elimination of the
acid, the higher the yield, and the more stable the nitrate formed.
There is an economic limit, however, to the cost of the cotton
which can be used, due to keen competition. The higher grades
of Sea Island and Egyptian long-fiber cottons are never used,
mainly on accoimt of the cost of the raw material. Tissue paper
which finds extensive use with the celluloid manufacturers and
producers of fine pjrroxylin lacquers has previously been men-
tioned. The skeins of long stapled yam used by von Lenk were
undoubtedly of high purity and unusually free from waxy mat-
ters and inorganic constituents. At the same time, however, the
fact that the skein condition was maintained throughout the
entire nitration and purification process made it much more
difficult and tedious to free the nitrocotton from the subsidiary
products of the nitration process. The reduction of the cotton
fibers to extremely short lengths in the pulping treatment re-
moves in a great measure this difficulty.

Ordinary cotton waste is the principal form of cellulose used
in the United States at the present time to produce the cellulose *
nitrates of industrial importance as distinguished from the higher
nitrates used for explosives and as propulsive agents. This waste
as obtained from the mills is in a very impure state, but so great
has the consumption of this form of cotton become, that a sep-
arate industry has sprung up for the purpose of converting this
mill waste into a form and purity suitable for nitration. The
processes to which it is subjected are: degreasing by means of ex-
traction with solvents, usually benzine or carbon tetrachloride;
scouring, bleaching, and washing.

The effect of these treatments, when properly carried out, is
to produce a fairly pure and resistant short-fiber cellulose, and
these processes have now reached such a high state of perfection
that it is not unusual to procure cottons of an ether-extract of
not over 0.2%, and practically free from hydro- and oxy-cellu-
lose. Cellulose nitrates of as high degree of purity as regards
application of the heat test are not required for the production
of photographic films and lacquers,, and a mixed cotton waste
can be used. The chief disadvantage of containing bits of wood,
rubber, and other foreign bodies, is being overcome by improved

COTTON 557

methods of mechanical separation of these impurities* the pres-
ence of which, no doubt, are important sources of decreased
stability.

The fact that cotton waste is plentiful, easily procured and
reasonably cheap, can be depended upon to produce a nitrate
satisfactory as regards nitrogen content, and solubility, gives it
preference over other sources of cellulose. Some have claimed
that cotton produced in a cold, wet season, in which the growth
has been slow, as indicated by the thickened cellular wall and
smaller canal, does not nitrate or neutralize as readily as a cotton
grown in a favorable locality as regards humidity and high tem-
perature, where the microscopic examination shows a thin-walled
tube with a larger lumen. However, in practice no variation in
the nitrating process is made as the result of the microscopical
structure of the individual cotton fiber. Cotton waste has been
used since the early days of guncotton manufacture.

In regard to the structure of the cellulose fiber as influencing
ease of nitration, F. Nettlefold* says "it will be readily tmder-
stood that the thin side- wall tubes of the cotton fibers are readily
penetrated by the mixed acid, as compared with flax or other
hard-walled fibers. In the latter, the walls are comparatively
thick, and the central canal small," and the fact noted that flax
is more difficult of nitration and subsequent neutralization is un-

1. So-called weaving-mill waste is a material composed entirely of
woven cotton fabric, often pieces of miderwear and stockings, partly broken
down by mechanical means. It differs materially in character, and as ob-
tained contains starched and unstarched pieces. It is also apt to be over-
bleached and contain an undue amount of altered cellulose. In its best
form it is a pure cotton cellulose and makes excellent pyroxylin, especially
as regards yield, the large pieces retaining perfectly their shape during the
nitrating process. It is at present difficultly procurable, and its cost is
higher than the normal price of cotton waste. The short fiber from the
cotton seed or the "combings" from cotton thread spinning and twisting,
would no doubt make excellent material, if it could readily be obtained free
from dust and particles of the seed husk. As it appears difficult to entirely
remove the husk by mechanical means without subjecting to drastic chem-
ical treatment, it is not used to any considerable extent.

2. Chem. News, 1887, 55, 306; abst. Proc. U. S. Naval Inst. 1888,
14, 162; J. C. S. 1887, 52, 792; Tech. Chem. Jahr. 1887-1888, 10, 187; Ber.
1887, 20, R, 676; Chem. Tech. Rep. 1887, 26, I, 227; Jahr. Chem. 1887, 40,
2273; Wag. Jahr. 1887, S3, 569. G. Wolfram (Dingl. Poly. 1878, 230, 45;
abst. Chem. Centr. 1878, 49, I, 403; Wag. Jahr. 1878, 24, 449; Jahr. rein
Chem. 1878, 6, 478; Zts. Chem. Grossgew. 1878, 3, 860) finds that concen-
trated acids give with cellulose from various sources the same final product,
but with dilute acids, nitrating under the same conditions, cotton is the most
readily attacked, then hemp, paper, straw and linen.

558

TECHNOLOGY OF CELLULOSE ESTERS

doubtedly due to the variation in microscopical structure. New
Zealand flax gives the most perfectly fluid nitrates of any of the
flaxes, it is claimed. It is therefore evident, that a given fiber
requires an adaptation of the nitrating method to accord with
the structure of its filaments, and in the most compact cells, as in
certain evergreen trees, the ligneous fibers are very difficult of
penetration.

G. Lunge, ^ who has examined the subject experimentally,
**procured from the leading cotton mills in Switzerland authentic
samples of the most varying grades of cotton, which were care-
fully cleaned mechanically and washed in the same way as in
the manufacture of guncotton and nitrated with the same acid
mixture (63.84 sulfiu-ic, 16.96 nitric acid, 19.20 water), keeping
all the conditions of the experiments exactly alike. Together he
nitrated a sample of "chemically pure cotton wool," with the
following results:

No.

Commercial Designation

Nitrogen

%

SolubUity
in Ether-
Alcohol %

Yield

%

1

2
3
4
5

Chemically pure surgical cotton

wool

American cotton "middling fair".

American cotton "Florida"

Egyptian cotton, white, "Abassi"
Egyptian cotton, natural yellow. .

11.76
11.56
11.67
11.69
11.61

100
100
100
100
100

159
157
153
155
154

**This shows that there is no essential difference in the quality
of the colloidal cotton obtained from these extremely differing
grades of cotton. They are all completely soluble; the nitrogen
differs only by 0.13% among all the commercial cottons, and only
by 0.20 in maxima against the pure surgical cotton. The latter
is easily explained by the difference in purity, the surgical cot-
tons containing only 0.05% ash, the commercial cottons averag-
ing 0.5% ash.

Notwithstanding the above, it is the practical experience of
manufacturers covering a number of years, and in which several
hundred pounds of collodion nitrocotton was daily produced, that
there is a great difference in the facility with which various kinds

1. J. A. C. S. 1901, 23, 678; abst. J. S. C. I. 1901. 20, 1021; Chem.
Centr. 1901, 72, II, 34, 92, 764. See also Chem. Centr. 1899. 7i, I. 1272.

COTTON 559

of cotton can be nitrated, and the ease with which the acid may
be removed after nitration. The tendency to "bum" or fume
in the nitrating bath, and toughness of cotton after nitration, are
properties apparently sufl5ciently inherent in the cotton itself to
differentiate one grade of cotton from another.

In the judgment of E. Piest,^ for the manufacture of highly
nitrated nitrocellulose, the material most largely employed is a
mixture of spinning waste and American "linter- waste." The
threads are first torn up and the lint passed through a cleaning
machine to remove all mechanical impurities. Oil, natural wax,
proteins, etc., are then removed by digesting with about 1%
caustic soda solution under 3 atmos. pressure. The material must
be tightly packed in the boilers and good circulation ensured;
high piurity of the soda and the exclusion of air during boiling
and washing are advantageous. Bleaching must be very care-
fully controlled to preserve the chemical integrity of the cellulose;
a little acetic acid may be added. The "copper value" (Schwalbe's
test) must not exceed 1.0; fat and waxy matters, extracted by
absolute alcohol, 0.5%; wood-gum, 2%. Tissue paper, from sul-
fite wood-pulp, may also be used for nitrating but is dearer than
cotton-waste and yields an inferior product. For celluloid, great
mechanical purity is required to avoid specks in the product; a
low "copper value," not above 1.0 is specified. For collodion
cotton, long, fine fibers and freedom from metallic impurities are
required. For nitro-artificial silk, resin and oil are most objec-
tionable impurities; as highly concentrated solutions of low vis-
cosity are employed, the degree of bleaching, as indicated by the
"copper value," may be higher. Wood celluloses give a softer
but weaker silk; they should be purified by boiling under pres-
sure with dilute sodium carbonate solution with the addition of
a little caustic soda or sodium sulfide. For leather-substitutes
the requirements are the same as for celluloid, but a higher de-
gree of bleaching may be permitted. For cellulose acetate, free-
dom from knots is an additional requirement. For cuprammon-
ium silk also, the cotton must be free from knots and the "copper
value" must hot exceed 1.0. According to one process, the cot-
ton is bleached, then mercerized, washed, centrifuged and dissolved

1. Papierfabr. 1914, 12, 860; abst. C. A. 1914, 8, 3362; J. S. C. I. 1914,
33, 856; Zts. ang. Chem. 1914. 27, II, 663.

560 TECHNOLOGY OF CELLULOSE ESTERS

without drying. For viscose, only wood cellulose is employed,
generally purified by steeping in 2% hydrofluoric acid and then
boiling out with 1% caustic soda; the "copper value** should not
exceed 4.0.

According to R. S. Schwarz/ for use in the manufacture of
nitrocellulose the waste from textile factories and cotton and linen
rags are purified by boiling with dilute alkali under pressure, fol-
lowed by mechanical treatment to remove knots, impurities, etc.
bleaching with calcium hypochlorite, and disintegration in two
machines. The loss in these operations varies according to the
kind of rags from about 20% to 40%. To prevent loss in the
form of dust attempts have been made to cut the rags into frag-
ments before bleaching, but this caused irregular nitration. The
following specifications have been issued: Maximum ash in nitra-
tion cotton wool, 0.6% (or 1.2% in the torn partially purified rag
material); fat, 0.4% (or 1.0% in the impure material) ; and water,
6%. A white color, freedom from chlorine, acidity, and dust, and
the absence of vegetable impurities are also specified. Too high ash
results in waste of the nitrating acids, and causes difficulty in
gelatinizing the nitrocellulose powder, while fat in excess of the
specified amotmt increases the difficulty of nitration and leads t(P
overheating of the mixture. Short fiber fragments are unsuit-
able for nitration, since some of the nitrocellulose then remains
dissolved in the waste nitrating acid, and causes explosions when
this is redistilled.

Preparation of Cotton for Nitration. As has previously
been mentioned, the celluloses of commerce in their natural state
are not in a favorable condition for the manufacture of cellulose
nitrates, being usually mixtures composed partly of cellulose of
varying degrees of purity and freedom from incrusting matter
and partly of various kinds of conglomerates closely adhering
thereto. The chemical purity of cellulose to be nitrated is of the
utmost importance in the manufacture of a pure cellulose nitrate,
the uniformity of the action of the nitrating agents (nitric and
sulftmc adds) and the thoroughness of the washing by which
these acids are subsequently removed from the nitrated product
depends in a great measure upon the uniformity or completeness

1. Oesterr. Chem. Ztg. 1919, 22, 50. 57; abst. J. S. C. I. 1919, St,
602- A.

COTTON 561

of the mechanical condition or division of the cellulose employed
for esterification. Many attempts which have been made to
bring the cellulose of commerce into the condition in which it is
free from the defects above mentioned have failed, partly because
the material manufactured was not perfectly free from incrust-
ing bodies, and also to the fact that the fat and other extraneous
matter had not been completely removed from the cotton filament.

In the later and well known process of J. Lewin* the cotton
by successive treatment with alkali and acids is freed from the
usually occurring impurities, then reduced to a fine powder by
means of a reducing cylinder, after which it is submitted to the
action of steam at high pressure until reaction takes place, the
operation being arrested when a gelatinous mass is obtained which
can be preserved indefinitely from change by storage under water.
Cellulose prepared in this manner is especially applicable for nitra-
tion purposes where a cellulose nitrate is to be combined with
nitroglycerol, for the gelatinous mass, even if incompletely
nitrated, appears to go into a homogenous plastic mass when
incorporated with nitroglycerol.

J. Daniel and F. Benoist* first boil the cellulose in an auto-
clave with circulation device andtmder one to four atmos. pressure
with a mixture of 2% caustic soda, 1% sodium carbonate, 1%
sodium sulfate, and 1% of ethylene trichloride. After this com-
bined saponification and extraction has been carried on for 4 to
12 hours, the cotton is rinsed with ordinary water, washed with
soap, bleached with hypochlorite and then dried. It is claimed
cotton prepared in this way is especially suitable for nitration of
the finer grades of nitrocellulose, specifically those intended for
the manufacture of continuous photographic film, and thermo-
plastic nitrocelluloses.

J. Foltzer' first boils 100 kilos of cotton in 1000 liters of a
solution containing 30 kilos of sodium carbonate and 50 kilos of
sodium hydroxide. The solution is placed in a hermetically sealed
reservoir, heated to 110°-120° under a pressure of Va atmosphere
continuously during a four-hour period.

In order to remove the fat, wax and resinous matter from

1. E. P. 4943. 1880: abst. Chem. Ind. 1882, 4, 65, 180.

2. F. P. 46M71, 1913; abst. J. S. C. I. 1914, 33, 588; 1916, 35, 597;
Mon. Sci. 1916, 83, 12; Chem. Ztg. Rep. 1914, 38, 582.

3. F. P. 345687, 1904; abst. J. S. C. I. 1905, 24, 85; Zts. ang. Chem.
1905, 18, 434; Mon. Sci. 1906, «5, 36; 1907, 67, 603.

562 TECHNOLOGY OF CELLULOSE ESTERS

cotton and similar fibers, P. Girard' treats with solvents as
methyl, ethyl or amyl alcohols, acetone, carbon tetrachloride,
tridiloroethane, or the chlorine derivatives of ethylene and ethane,
either alone or in mixture to which may be added from 5% to
10% of a solution of aqueous commercial formaldehyde. The
cost of the solvents renders this method unduly expensive.

In the process carried out by J. France,* cotton or other
fiber, preferably in its natural state, but also in the state of rov-
ing or loose twisting, is ground or cut into short lengths so as to
form virtually a powder, in which condition it is subject to the
action of the nitrating acids, applied in the usual proportions for
producing either the soluble or insoluble kinds of cellulose, and
after being well washed with water so as to remove these residues
is ready to use in the form of a pulp or may be dried and utilized
in the condition of a powder. This process, which was designed
to increase the stability of the resulting nitrocellulose, failed in
that the yields obtained were too low due to the large amount of
cotton being obtained in the nitrating acids in suspension and
in solution.

In the, process of O. Rohn,* the treatment of raw cotton
with boiling alkalis preparatory to bleaching is omitted and the
material is softened by steeping in 0.1% aqueous solution of pan-
creatin at 20°-40° for some hours and then bleached with the
usual agents. Other enzymes such as papayotin, or ridnus
enzymes may be used or fresh organs or preparations instead of
the commercial enzyme. It will be observed that the essence of
this invention consists in the attempt to emulsify fatty materials
by means of an amylolytic enzyme.

E. Berl* proposes to depolymerize the cellulose molecule by
heating the cotton in an inert gas, claiming that nitrocellulose
prepared from cellulose depolymerized in this manner is better
in that it gives more fluid solutions and a higher stability and

1. F. P. 443897, 1912; abst. Kunst. 1912, 2, 456; J. S. C. I. 1912. SI,
1120; J. Soc. Dyers, 1912, 28, 310.

2. U. S. P. 420445, 1890. E. P. 5364, 1890; abst. J. S. C. 1. 1890, 3, 821.

3. E. P. 100224, 1916; abst. J. S. C. I. 1916, 35, 1057; J. S. C. I. Ann.
Rep. 1917, 2, 127. D. R. P. 297324, 1915; abst. J. S. C. I. 1917, 36, 869;
Chem. Zentr. 1917, 88, I, 983; Chem. Ztg. Rep. 1917, 41, 148.

4. D. R. P. 199885, 1907; abst. Mon. Sci. 1911, (5), 74, 93; Zts. ang.
Chem. 1908, 21, 2233; Chem. Zentr. 1908. 79, II, 466. Chem. Ztg. Rcpcrt.
1908, 32, 382; Chem. Ind. 1908, 31, 454; J. S. C. I. 1908, 27, 937; Wag. Jahr.
1908, 54, II, 355. Aust. P, 37030, 1908.

COTTON 563

capacity for gelatinization than nitrocellulose made from ordinary
cotton.

I. Kitsee^ has described a method for obtaining cotton "fly"
or linters in a manner so that it is especially adaptable for sub-
sequent nitration. H. de Chardonnet^ prefers to heat during 6
to 8 hoiurs continuously at a constant temperature, from 150° to
170° the cellulose material in a stove having shelves, which are
gratings of tubes for circulation of steam at a pressure of 8 to 10
atmospheres. Suitable valves serve to regidate the air circula-
tion so as to determine the desired temperatiure. The cellulose
when the operation is ended, is immersed still warm in the nitrat-
ing bath. Nitrocellulose prepared from cotton treated in the
above described manner gives a very low viscosity and thin solu-
tions which are especially applicable to the formation of nitro-
cellulose artificial filaments and aeroplane lacquers.

C. Waite and J. Hedin' have described a process whereby a
raw material containing cellulose is digested with caustic soda
which has been treated with a small quantity of sulfur so that
the amount of sodium sulfide present is less than 0.5%. This
small quantity of sulfide, according to the patentees, is sufficient
to neutralize the effect of the formed oxygen present, and thus
prevent or at least retard the formation of oxycellulose, while on
the other hand it is insufficient to exert an appreciable digesting
action.

In the C. Kellner process,* cellulose which is to be purified
is treated with water or preferably with milk of lime or a very
weak solution of an alkaline carbonate or hydroxide and after
the excess of liquid has been removed by means of a hydro-ex-
tractor or otherwise, as, for example, by pressing, the cellulose
under treatment is subjected to the action of chlorine gas derived

1. U. S. P. 789978, 1905; abst. J. S. C. I. 1905. 24^686. D. R. P.
188077; abst. Wagjahr. 1907, II, 498; Chem. Zentr. 1907, 78, II, 1879; Zts.
ang. Chem. 1908, 21, 269.

2. E. P. 19560, 1891; abst. J. S. C. I. 1892, U, 939; J. Soc. Dyers,
1802, 8, 19. D. R. P. 64031, 1891; abst. Mon. Sci. 1893, 42, 15, 16; Ber.
1892, 25, 892; Chem. Centr. 1892, 63, II, 1088; Wag. Jahr. 1892, 38, 376;
Zts. ang. Chem. 1892, S, 499.

3. U. S. P. 1212158, 1917; abst. J. S. C. I. 1917, 36, 288; C. A. 1917,
11, 705.

4. E. P. 24542, 1902. Fr. P. 326313, 1902; abst. J. S. C. I. 1903, 817,
1145; Mon. Sci. 1904, 61, 46; Cheni. Ztg. 1903, 27, 902. See also C. Kellner,
R. P. 6420, 1890; abst. J. S. C. I. 1891, 10, 62.

504 TECHNOLOGY OF CELWJLOSE ESTERS

from the electrolysis of a metallic chloride.

0. Schmidt^ prefers to reduce the cellulose to a firm granular
condition which is accomplished by treatment, for instance, by
means of chum-shaped pounding mills (in order to effect the
separation of any cells which may adhere mechanically) and there-
upon it is passed in the wet state through a grinding process,
for instance, in edge runner mills. The moist plastic mass
obtained is then granulated by passing through sieves and the
grains rounded off, for instance, by the aid of polishing casks,
whereupon they are dried, the resulting granulated material being
firm and horn-like. The cellulose thus reduced to the granulated
condition is then changed into nitrocellulose in the usual manner.

In the method as devized by C. Budde and the Hendon Paper
Works Co.,^ cellulose is satiu'ated with free chlorine or bromine
prior to nitration, the process being alleged as particularly applic-
able to wood, esparto or straw cellulose, or impture or degenerated
cotton. Cellulose when made by the method devised by H.
Arledter* is treated in an apparatus* in the presence of alum-
inium sulfate or of alums or of sulfate or sulfite of zinc or of com-
pounds known to have a parchmentizing effect and are either
subjected to an alternative vacuation and admission of air which
may be ozonized, or a peroxide of hydrogen or other oxidizing
agents. This treatment results in the hydrolysis of the cellulose
and the formation of a more or less jelly-like material which can
be used as a base for the manufacture of nitrocellulose explosive.
H. Landell* purifies cotton waste for making cellulose by treating
waste successively with boiling 5% caustic soda solution for 10
hours, washing, treating with a 4° Tw. calcium hypochlorite solu-
tion, again washing, shredding and finally drying. The process
of E. Nowicki® is similar. According to A. Hertzog,' the prepar-

1. E. P. 116, 1904; abst. J. S. C. I. 1904, 23, 385; Chem. Ztg. 1905,
29, 514.

2. E. P. 10292, 1915; abst. C. A. 1917, U, 100; J. S. C. I. 1916, SS,
656;Kunst. 1917,7, 114.

3. E. P. 16085, 1912; 684, 1913; abst J. S. C. I. 1913, 32, 865; C. A.
1914 8 247.

'4.' Similar to that described in E. P. 2018, 1910; abst. C. A, 1910, 5,
2947; J. S. C. I. 1911, 30, 205. F. P. 418584; abst. J. S. C. I. 1911, 30, 80.

5. U. S. P. 1222422, 1917; abst. C. A. 1917. U, 1904; J. S. C. L 1917
36, 544.

6. F. P. 402197, 1909; abst. J. S. C. I. 1909, 2S, 1274.

7. Centr. f. d. Textil Indus. 1890, 21, 975; abst. J. S. C. I. 1891. It,
161; Chem. Tech. Rep. 1890. 29, II, 143; Chem. Ztg. Rep. 1890, 14, 365.

COTTON 565

ation of cotton waste for the manufacture of smokeless powder
has been brought to a high state of perfection in England, due to
the fact that a large amount of cotton waste is the natural result
of the spinning and weaving processes used there.

In Germany, according to M. Gladbach,* in order to meet the
requirements of the military authorities for purified cotton suitable
for smokeless powder manufacture, the cotton must sink in water,
within two minutes, when nitrated must not become brown
must yield not over 0.9% material soluble in ether and the cotton
must be free from chlorine, lime, magnesium, iron or sulfiuic or
phosphoric acid compounds. Cotton wool or waste to fulfill the
above requirements may be purified in the following manner:
first, boiling the cotton in caustic soda solution tmder pressure,
washing, then bleaching, washing again, treating with sulfuric or
hydrochloric acids, washing again, then centrifugalizing and fin-
ally drying. Waste cotton containing fat may be preferably
treated in the following manner. First boil in lime water under
pressure, then wash, after which the product is boiled in a caustic
soda solution under' pressure, then wash, bleached with chlorine,
washed again, acidified and finally centrifugalized and dried. In
very impure waste the boiling process in lime water requires a
longer period of time but the caustic soda boil should not be pro-
longed. The boiling process may more preferably be carried out
in an autoclave of the system supplied by Schenrei-Roth. For
the drying, M. Gladbach recommends the employment of a Zit-
taeur machine, claiming the washing may more preferably be done
by means of a Mather-Platt bleaching apparatus. When piuify*
ing cotton waste by the above process the following are the losses
on a commercial scale:

Transportation and packing 2 to 5%

Boiling first and washing 5 to 40%

Bleaching with chlorine 15 to 20%

In the process as practiced in Austria, the purification of raw
cotton from seed and other matters foreign to cellulose consti-
tutes a most important preliminary operation for the formation
of cellulose for military and peaceful purposes. The cotton waste
now used in making gtmcotton it is stated, has undergone so thor-
ough a purification of the various manufacturing processes through
which it has passed that while no further preliminary purification

1. Chem. Ztg. Rep. 1890, 14, 354.

566 TECHNOI.OGY OF CSLLUIX)SE ESTERS

is required, the finished guncotton as obtained from it is prac-
tically pure nitrocellulose of high stability.

J. Hall^ has patented a process for artificially mattuing cot-
ton» the fibers of which have greater tensile strength and a greater
percentage of cellulose than the fibers of naturally matured cot-
ton, and this is obtained by artificially maturing cotton bolls,
after dusting them with a mixture containing starch 50 and tal-
cum 25 parts.

The process for preparing artificial cotton as elaborated by J.
Boturbon and P. Gassier^ consists in pouring the viscose preparation
of cellulose into a rotating centrifugal of the same type as it used
for obtaining sugar in the form of fine threads ("sucre fils").
This apparatus throws the cellulose out of the cage into the sur-
rounding vessel where it collects in the form of a very fine loose
cotton, which can be spun in the ordinary way or used for nitrat-
ing by merely drying.

In the preparation of fleece from wood pulp suitable for nitra-
tion, the dry fibrous material is projected by air blast against
beating arms which open and clean the fibers, whence it is then
driven upwards by an air blast through the beating chamber
against moving sieve surfaces. It is then conveyed by suction
in the usual manner to form a firm fleece.'

A. de Salas^ prepares flock cotton for the manufacture of
nitrocellulose by soaking rags in a solution of soap and an alkali,
washing and drying, and then mechanically comminuting the cot-
ton to a flocculent condition. H. Nishida' has compared loose
cotton of various kinds, mercerized cotton yam, and tissue papers
prepared from other cellulosic materials as raw material for the
manufacture of celluloid. Prom the results obtained the various
raw materials are classified as follows as to their suitability: (1)
Unbleached mercerized cotton; tissue paper from white rags and
cotton fishing nets. (2) Itleached mercerized cotton; tissue

1. U. S. P. 1201288, 1916; abst. C. A. 1916, 10, 3167; Kunst. 1917,
7,83.

2. F. P. 429679, 1911; abst. J. S. C. I. 1911, M, 1297; Kunst. 1911.
1, 456; J. Soc. Dyers, 1911. 27, 224.

3. D. R. P. 294079, 1915; abst. C. A. 1918, 12, 868; Chem. Ztg. Rep.
1916 40 400.

'4. ' U. S. P. 1249726; abst. C. A. 1918, 12, 428.

5. Jour. Ind. Eng. Chem. 1916. 8. 1096; abst. J. S. C. I. 1917, 26, 27.
Paper, IS, No. 17, p. 13; C. A. 1917, 11, 209; Ann. Rep. Soc. Chem. Ind.
1917, 2, 137.

• COTTON 567

from colored rags; tissue from linen fibers. (3) Papers from
bast fibers; weavers waste cotton yam, scoured and bleached.
(4) Bamboo tissues as free from adulteration as possible, and
wet beaten. (5) Chemical wood fiber and straw, as free from
knots as possible. (6) Mechanical wood fiber mixed with a
little cotton.

In the method of T. Nordenfelt and V. Meurling,^ vegetable
fiber is treated with hydrochloric acid, either in the liqtiid or
gaseous form, and dried, when it is then in a condition, according
to the patentees, for easy nitration. The process of Liedbeck*
is somewhat similar and results in the formation of very finely
divided cellulose. Readily soluble derivatives upon esterifica-
tion, may, according to O. Glum & Co.,' by treating the cotton
with glycerol at temperatures above 100° C. Drjdng the cellu-
lose in an oihbath at 140° C. for 4 hours, and then proceeding
with the nitration in the usual manner. By the preliminary
treatment of the cotton in this manner, the patentees claim to
be able to produce cellulose esters which require much less sol-
vent for solution, and of lower viscosity, without at the same
time interfering in any way with the desirable qualities of the
ester.

The "cellulose substitute" of O. Mueller* is prepared by boil-
ing cotton-seed hulls in 3% NaOH solution, washed with water,
treated with 0.1% potassium permanganate solution, heated to
40° in a solution containing 0.6% HCl and sodium acid sulfite,
and bleached with chlorine.* The method of preparing cotton

1 E. P. 6515 1884.

2. D. R- P. 96109, 1897; abst. Chem. Centr. 1898. W, I, 1222; Mon.
Sci. 1898. S2, 178; Jahr. Chem. 1898. SI, 1382; Wag. Jahr. 1898. 44, 372;
Zts. ang. Chem. 1898. U, 167.

3. Belg. P. 211385. 1908. D. R. P. 217316. 1910; abst. J. S. C. I.
1910, 29, 417; Wag. Jahr. 1910, 5€, II. 433; Zts. ang. Chem. 1910. 23, 526;
Chem. Centr. 1910, 0, 1,490; Chem. Ztg.Rep. 1910.34,47; Chem. Ind. 1910,
33, 59; Chem. Zts. 1910. 3, No. 1670. E. Berl (D. R. P. 199885. 1907; abst.
Chem. Zentr. 1908. 73, II. 466; J. S. C. I. 1908, 27, 937; Mon. Sci. 1911, 74,
93; 1916, 83, 80; Chem. Ind. 1908, 31, 454; Chem. Ztg. Rep. 1908, 32, 382;
Wag. Jahr. 1908, S4, II, 355; Zts. ang. Chem. 1908. n, 2233) first removes
the water from cellulose, then is heated at a temperature above 100*^ C.
in the presence of inert gases (Ns, COs, water gas, coal fire ga^. or super-
heated steam, thus apparently inducing polymerization of the cellulose.

4. U. S. P. 930874, 1909; abst. C. A. 1909. 3, 2627; J. S. C. I. 1909,
28, 1001. E. P. 3211, 1906; abst. J. S. C. I. 1906, 25, 865. See O. Mueller,
U. S. P. 931634, 1909. Mon. Sci. 1910, 73, 94.

5. Neutralization of the sodium hydroxide extract yields a precipitate
said to be useftil as a varnish gum or lac substitute.

568 TECHNOUXJY OF CELLULOSE ESTERS

for nitrating as patented by the Zellstoff-Fabrik Waldhof * is sim-
ilar to those already described.

A recent invention has been published^ which describes the
treatment of cellulose with free chlorine or bromine before nitVa-
tion, to enhance its value.

The Dynamit A. G. NobeP hafve described a method of treat-
ment of cellulose before nitration with sulfuric acid or zinc chlor-
ide, in order to impart desirable properties to the cellulose. They
first treat cotton with 5% H2SO4 at 100°, wash until neutral, and
then dry, after which the usual nitration process is carried on.
After the sulfuric acid trea;tment, the cellulose may readily be
reduced to a structureless powder.

The Utilization of Short Fibers. In the earlier formative

1. D. R. P. 64878; Mon Sci. 1893, 42, 208; Ber. 1893, 26, 78; Wag.
Jahr. 1892, 38, 371; Zts. ang. Chem. 1892, 5, 706. C. Budde and Hendon
Paper Works, E. P. 10292, 1915; abst. C. A. 1917, U, 100; J. S. C. I. 1916,
35, 656; Kunst. 1917, 7, 114. The main advantages claimed for this process
are that secondary reactions during nitration do not occur to anything like
the same extent as in the case when the treatment with free chlorine or
bromine is omitted, this fact being most strikingly observed when the nitra-
tion takes place tmder partial .vacuum, in which case esparto cellulose de-
velops a continual current of gases. If the same cellulose has been pre-
viously treated with chlorine or bromine, hardly any gas is said to occur.
It is also alleged that the tendency toward rise in temperature during nitra-
tion is materially diminished, and the final nitrated product instead of being
yellow or brown, is of a pure white color. The stability of the nitrat^
product is also said to be increased.

2. D. R. P. 4410, 1878; abst. Chem. Centr. 1879, 50, 720. See also;
E. Fremy and V. Urbain, D. R. P. 22370, 1882; abst. J. S. C. I. 1883, 2,
276; Dingl. Poly. J. 1883, 248, 472; Wag. Jahr. 1883, 29, 1036; Chem. Ind.
1883, 6, 135; Mon. Sci. 1884, 2S, 27. G. Bentley, E. P. 2262, 1874. C.
Chevalier and A. Lejeune, Bull, assoc. instit. Meurice, 1, 250; abst. Bull.
Soc. Chim. Belg. 27, 99; C. A. 1913, 7, 2312. H. Dutschke, F. P. 467670,
1914. E. P. 2164, 1914; abst. J. S. C. I. 1914, 33, 860; C. A. 1915, 3,
1997. M. Henry, E. P. 1454, 1860. R. HoUins and T. Taylor, K. P. 23192,
1908; abst. J. S. C. I. 1909, 28, 1270; C. A. 1910, 4, 1544; J. Soc. Dyers.

1910, 28, 13. J. Ketcheson, F. P. 407616, 1909; abst. J. S. C. I. 1910, 29,
559. E. P. 22111, 1909; abst. J. S. C. I. 1910, 29, 875; Chem. Ztg. Rep.

1911, 35, 112; Kunst. 1911, 1, 34; U. S. P. 987629, 1911; abst. C. A. 1911,
5, 2003. G. MacDonald, Arms and Explosives, 1909, 17, 23; abst. C. A.
1909, 3, 1459. J. Mewbum, E. P. 7187, 1885; abst. J. S. C. I. 1886, 5, 322;
J. Soc. Dyers, 1886, 2, 110. A. Miintzing, F. P. 376894, 1907. U. S. P.
882790, 1908; abst. J. S. C. I. 1907, 28, 1027; 1908, 27, 418; C. A. 1908, 2,
2300. C. Piest, Der Papier Fabrikant, 1914, 78; abst. Kunst. 1914, 4,
293. O, Silberrad, E. P. 28193, 1910. F. P. 434709, 1910; abst. J. S. C. I.

1912, 31, 67; C. A. 1912, 8, 1534; J. Soc. Dyers, 1912, 28, 85; Mon. Set
1912, 77, 569; 1913, 79, 181; Chem. Ztg. Rep. 1912, 38, 273.

3. D. R. P. 4410, 1878; abst. Chem. Tech. Mitth. 1878-1879, 28,
295; Zts. Chem. Grossgew. 1879, 4, 287; Dingl. Poly. 1879, 232, 188; Deutsche
Ind. Ztg. 1879, 170; Ber. 1879. 12, 712; Chem. Ztg. 1879, 3, 197; Wag. Jahr.
1879, 25, 419; Chem. Ind. 1879, 2, 171; Chem. Tech. Rep. 1879, I, 287;
J. A. C. S. 1879, 1, 303.

COTTON 569

days of the cellulose nitrate art, it was the common practice, in
order to maintain a high yield, to employ the higher priced long-
staple cotton in nitrating processes, but with the development, re-
finement and ramifications of the art, competition became so keen
as to necessitate the employment of the cheaper short staple va-
rieties of cotton for this purpose; for instance, W. Crum,Mnhis
investigations upon the nitrogen content of nitrocellulose em-
ployed fine Sea Island cotton, carded, bleached, purified by boil-
ing with caustic soda and a final treatment with dilute nitric acid.
The cotton so employed lost 5.5% of its weight containing but
0.09% ash.

A Grand jean^ developed a new product termed by him "snow
paper" or "snow pulp," and produced by disintegrating paper con-
taining no size, which was afterwards rolled and made iAto sheets
and either in the loose or compressed form employed for nitrating
purposes, specifically for the manufacture of collodion and cellu-
loid. The artificial cotton wool patented by A. Bloch' is prepared
by first washing cellulose with alkali to free it from fatty matters,
then bleached in a solution composed of 10 kilos of calcium hypo-
chlorite, 6 kilos of aluminium sulfate, 2 to 3 kilos of magnesium
sulfate and 200 kilos of water. After washing and drying in a
centrifugal extractor, cellulose is purified by solution in Schwei-
zer's reagent, the solution filtered and then precipitated. To pre^
vent the precipitated fibers from becoming agglomerated mechan-
ical arrangements are specified.*

The Verein f. Chemische Industrie in Mainz* prefer to treat

1. Phi!. Mag. 1847, (3), 30, 426; abst. J. prakt. Cheni. 1847, 41, 201;
J. Pharm. 1847, (3), 12. 296; Jahr. Chem. 1847-1&48. 1, 1130; Glasgow Phi!.
Soc. Proc. 1844-1848, i, 163; Ann. I»i7. S2, 233.

2. K. P. 22566, 1894; abst. J. S. C. I. 1896, 15, 132. See W. Ragsdale,
E. P. 10182, 1906. Also E. P. 8591, 1891; 15164, 1893; 10183, 1906.

3. F. P. 447068, 1911; abst. J. S. C. I. 1913, 32, 283; Kunst. 1913,
3, 74. I. Kitsee (U. S. P. 789977, 1905; abst. J. S. C. I. 1905, 24 686) prefers
to nitrate the cotton seed with its adherent fit)er, the nitrated product t>eing
then treated with a solvent which dissolves the nitrocellulose. The solution
is then separated from the residue of the seed. The author, in trying this
method, found "fume oflfs" very liable to occur. The Rheinische Kunstse-
idefab. (D. R. P. 208675, 1909; abst. Chem. Zentr. 1909, 80, I, 1444; Chem.
Ztg. Rep. 1909. 33, 216; Wag. Jahr. 1909, 55, II, 508; Zts. ang. Chem. 1909,
22, 942) purify linters by boiling with aUcali or alkaline permanganate, fol-
lowed by a light bleaching with chlorine.

4. Bloch, Belg. P. Appl. Aug. 18. 1911.

5. 1). R. P. 290131, 1913; abst. I. S. C. I. 1910, 35, 533; C. A. 1916.
10, 2803. See also Poly. Centr. 1866, 32, 75; Chem. Zentr. 1916, 87, I, 352;
Chem. Ztg. Rep. 1916, 40, 96; Zts. ang. Chem. 1916, 29, 144.

570 TECHNOLOGY OP CELLULOSE ESTERS

cotton with a small quantity of acid or acid salts, e. g., 0.01-0.02
sulfiuic acid, subsequently drying at a low temperature. By this
treatment the patentees claim the strength of the cotton is in-
creased by 10% to 30% and not more than traces of oxy- or
hydro-cellulose are formed. The cotton so treated is claimed to
behave like mercerized cotton in giving viscose solution of im-
proved solubility and to be especially applicable for the nitration
of cotton where solutions of great fluidity are desired.

In the use of short staple cotton, specifically linters, G.
Mowbray* apparently was the first to recognize the commer-
cial advantages accruing from the use of short fiber cotton
as linters. In the process as disclosed in the application of T.
Newsome,* the short cotton fibers which remain attached to the
seed hulls after the fibers fit for spinning have been taken away,
are, as the patentee has pointed out, difficult of utilization due
to the tenacity with which the brown fragments of hull adhere
to the cotton filaments. The carded cotton fiber containing waxy
constituents of an unusually resistant nature and insoluble in
water are extracted by means of volatile hydrocarbons, such as
petroleum naphthas to remove these waxes as well as other in-
crustated matters of the hull without injiuy to the fiber.

To attain this end the inventor treats the seed hulls and the
attached fibers with the vapors of boiling naphtha, the vapors
entering at the top of the extraction vessel, condensing and flow-
ing down through the mass, the solvent containing the dissolved
matters being passed back into the evaporator. After the solu-
ble matters have all been extracted in this manner, the naphtha

1. E. P. 20978, 1890; abst. J. S. C. I. 1891, 10, 271. D. R. P. 60595;
abst. Wag. Jahr. 1891, 37, 431; Ber. 1892, 2S, 352; Mon. Sd. 1892, 40, 172;
1893 42 861.

'2. 'u. S. P. 683785, 1901; abst. J. S. C. I. 1902, 21, 63; Papier Ztg.

1901, 24, 3321; Mon. Sci. 1902, 58, 16. E. P. 19585, 1901; abst. J. S. C. I.

1902, 21, 788. R. Fabre (E. P. 10260, 1912; abst. C. A. 1913, 7, 3546; J. S.
C. I. 1913, 32, 284) employs carbon tetrachloride and trichloroethylene for
the same purpose. For the cotton waste cleansing apparatus of A. Poulson
and W. Mate, see E. P. 110691, 1917; abst. J. S. C. I. 1918, 37, 5-A. O.
Guttmann described the use of cotton waste for nitrocellulose manufacture
in 1883 (Dingl. Poly. 1883, 249, 509). In the F. Stockton method of purifi-
cation (U. S. P. 1295078, 1919; abst. J. S. C. I. 1919, 38, 319-A. E. P. 13242i2
1919; abst. J. S. C. I. 1919, 38, 745-A) cottonseed hull fiber is softened by
boiling in a 4% solution of caustic soda for about 5 hours. The boiled fiber
is placed between rollers in order to disintegrate the associated hull par-
ticles, and then subjected to a cleaning operation to separate the fine, dis-
integrated hull particles from the fibers.

COTTON 571

adhering to the mass is driven off by hot water and the contents
of the extraction vessel removed and boiled with alkali, prefer-
ably with a 2% solution of caustic soda, under a pressure of 50
lbs. per square inch, for four hours. By this treatment the resi-
dues of seed hulls are dissolved by the alkali and the fibers are
then, after washing, in suitable condition for nitration. The
method of F. and A. Van den Bosch and O. Miiller^ is similar.

The treatment of cotton seed hulls, as elaborated by C.

1. E. P. 3211, 1906; abst. C. A. 1907, 1, 658; J. S. C, I. 1906, 2S, 865-
U. S. P. 930874; abst. J. S. C. I. 1909, 28, 1001; C. A. 1909, 3, 2627; Mon.
Sci. 1910, 73, 94. They boil the cotton seed husks including the non-fibrous
portion, with caustic soda solution of 3^-10*^ B^., according to the origin
of the cotton seed and the composition of the material operated upon, either
at atmospheric or increased pressure. The material after being washed free
from alkali is next oxidized in a 0.1% potassium permanganate bath for .30
minutes at about 20° with stirring. From this bath, the mass without
being washed is brought into a bath of sulfurous acid, the action being as-
sisted by warming. When the cellulose has been transformed into a "trans-
parent grissly mass," it is finally washed to neutrality and dried.

M. Wertz (E. P. 12422, 1910; abst. 1. vS. C. I. 1911, 30, 798; J. Soc.
Dyers Col. 1911, 27, 214; Kunst. 1911, 1, 295; Chem. Ztg. 1911. 35, 520)
uses for the preparation of artificial filaments and for nitrocellulose manu-
facture, fibers from the so-called "silk cotton family," obtaining best re-
sults from kapok (the fiber covering the sides of the tropical tree, Eriodendron
anfractuosum), as well as the fiber obtained from the cotton free, Bombax
malabaricum. The fiber from either of the above mentioned sources is first
treated with alkali to remove fat and oleaginous matter, then bleached, when
it may be directly dissolved, as in cuprammonia or zinc chloride. The
patentee has fotmd that by the use of the above fibers, artificial filaments
can be manufactured of comparatively high counts.

P. Minck and Bremer Baumwollewerke (E. P. 12718. 1906) have devised
an apparatus for separating in a purely mechanical manner and by means of a
dry method, waste products containing fiber, especially cottonseed hulls
eiUier alone, or when mixed with cotton, linen or hemp waste. The loosening
or opening processes to which they are subjected when n^orking according to
the directions laid down in the patent specification, are ^uch that the fibrous
constituents are obtained undamaged and not reduced in length more than
is proper considering their intended industrial utilization for piui)oses of
nitration.

G. Atkins (E. P. 7058, 1903; abst. J. S. C. I. 1904. 23, 386; Chem. Ztg.
1904, 28, 732; Mon. Sci. 1905, G2, 68) has received patent protection for an
invention which relates to the manufacture of nitrated cellulose from any
suitable organic material of cellular origin, but more especially from the
waste from cottonseed remaining after the oil has been expressed from the
seed and the material suitable for making oilcake has been sifted out. This
waste, which ordinarily consists of the husk of the seed with tufts of cotton
still adhering thereto, is considered very suitable for nitrocellulose manu-
facture when submitted to the following treatment : The waste is first treated
with an alkali, washed and then bleached in the usual manner. The patentee
claims that a specially novel feature of his process is the bleaching with
"chloride and oxychloride of soda," for "when nitrated material is to be
used for the manufacture of celluloid it materially improves its color and
consequently the market value of the product."

572 TECHNOLOGY OF CELLULOSE ESTERS

Cross, ^ involves the treatment of the hulls with an alkaline solu-
tion, preferably caustic soda, so as to obtain a dark colored liquor
and a fibrous residue, the cellulose component portion being ob-
tained in a pure form by boiling and washing and finally sub-
mitting to the action of chlorine gas in a suitable chamber until
such constituents as will combine with the chlorine are saturated.
• The chlorinated product is then washed to remove acid constituents,
next digested with boiling water or with an alkaline solution,
preferably a mixture of sodium carbonate and sodium sulfite,
in which the chlorinated products are soluble and is finally
washed.

J. Cochran^ has assigned to F. Taylor an invention consisting
in the utilization of the fuzz of cotton seed hulls to produce a
cellulose useful for the manufacture of gimcotton and other ex-
plosives in which the cotton seed, after being divested of all staple
fiber, such as cotton and lint, there still remains on the hull a
long staple not of the order of fuzz which, by means of the pat-
entee's process, is made commercially useful. In order to attain
his object, the divested hull is subjected to attrition whereby the
fuzz is disconnected from the hull proper and by an air blast
or other means the fuzz is separated from the hull and collected
by itself. In this manner the use of solvents is eliminated.

The method of L. Guiguet' is really an immaterial improve-
ment upon the previously described process of P. Girard.*

M. Marsden* recovers fibers from waste portions of cotton
plants by comminuting and mechanically separating the light and
heavy portions by a blower or cyclone separator, treating with
water and steam under pressure to extract the sugar, tannin, col-
oring matters, etc., and then treating with an alkaline solution,

1. E. P. a545, 1904; abst. J. S. C. I. 1905, 24, 288. See also U. S. P.
807250, 1<X)5; abst. Mon. Sci. 1907, €6, 15: 1910, 73, 160; J. S. C. I. 1906,
25, 34; Chem. Zts. 1906, 5, 63. E. P. 8544; abst. J. S. C. I. 1905, 24, 340.

2. U. S. P. 822430, 1906. Chem. Ztg. Rep. 1907, 31, 91; Chem. Zts.
1906, S, 376; Zts. Schiess. Spreng. 1906, 1, 364. E. P. 12920, 1906; abst.
J. S. C. I. 1907, 2S, 775; C. A. 1907, 1, 2512.

3. F. P. 464028, 1913; abst. J. S. C. I. 1914, 33, 376; C. A. 1914, 8,
3122; Mon. Sci. 1916. 83, 67; Chem. Ztg. Rep. 1914, 38, 363.

4. F. P. 438131, 1911; abst. Kunst. 1912, 2, 437; J. Soc. Dyers Col.
1912, 28, 200; Mon. Sci. 1913. 79, 14.

5. U. vS. P. 1143587, 1915; abst. C. A. 1915, 9, 2311. The J. Cochran
method of obtaining the fuzz from cotton-seed hulls for use as cellulose in
the manufacture of guncotton is described in E. P. 12920, 1906; C. A. 1907,
1, 2512; J. S. C. 1. 1907, 26, 775.

COTTON 573

also under priessure. to remove incrustating substances.

E. de Segundo has devized a machine applicable for this pur-
pose.^

A process for separating the short cotton fibers from cotton
seed after the bulk of the cotton has been removed, and now said
to be employed on the continent, has been described by E. Drab-
ble* in which the cotton is first of all mechanically removed from
the seeds and is then "winnowed" and collected. After this it is
subjected to chemical treatment to remove the impurities, and
short fiber cotton thus prepared is said to have been used with
great success not only in the manufacture of blotting paper, owing
to its high absorptive value, but especially for the preparation of
guncotton and other forms of nitrocellulose.

In the employment of linters and other short fiber cottons,
the loss in the various mechanical treatments to which it is neces-
sarily subjected as a preliminary to use for nitrating purposes is
considerable. The following figures, based on the actual factory
runs, are representative of these various losses:

Shipper's weight, gross . . * 36,294 lbs.

Tare 556 lbs.

Net weight paid for 35.738 lbs.

The tare comprised wire bale 143 lbs., paper and string, 413
lbs., total, 556 lbs. The moisture in the cotton 5-19%, giving a
net weight of dry cotton of 33,880 lbs. The waste of cotton at the
picking house was 86 lbs., at the drying house 91 lbs., in the
weighing room 50 lbs., a total of 227 lbs. 1173 wringers were
dipped, none of which fired, employing 148,920 lbs. of forti-
fying acid, equivalent to 72,345 lbs. of 100% nitric acid.
The nitrogen in the nitrocellulose produced averaged 12.66%;
the estimated weight of pyrocoUodion powder obtained was
49,655 lbs., and 49,484 were actually found. The yield there-:
fore of pjrrocoUodion per pound of dry cotton is 1.35 and of
powder per potmd of dry cotton 1.46; therefore each pound of
powder required 0.684 lb. of dry cotton; 0.722 lb. of cotton as
received; 1.46 lbs. of 100% HNO3; and 3.01 lbs. of fortifying acid.

According to T. Moreul,* the cellulose most suitable for the

1. E. P. 24336. 1913; abst. C. A. 1915, 3, 1251.

2. Quart. J. Liverpool Univ. Inst, of Commercial Research in the
Tropics. 1907, 2, 32; abst. J. Soc. Dyers Col. 1907, 23, 192; J. S. C. I. 1907,
2S, 605.

3. Bull. Sci. Pharmacolog. 20, 101.

574 TECHNOLOGY 0I^ CELLULOSE ESTERS

manufacture of the French smokeless powder, is short cotton
fibers stripped from the seeds from the crushing plants, the dead
and immatiure fibers having been removed during the crushing
process.

It has been claimed that cotton grown in a cold, wet season,
where the growth has been slow — as indicated by the thickened
cellular wall and smaller inner filamentous canal — does not as
readily esterif y as a cotton grown in a locality more favorable as
^ egards humidity and high temperature, and these differences are
a^so reflected in the shorter fiber.

In the method as described by I. Kitsee,' the cottonseed is
first subjected to a treatment whereby the hull is broken and
the kernel separated. The hulls and the adherent fibers are then
nitrated, the nitrated product treated with a nitrocellulose sol-
vent, and the solution is separated from the hulls and other undis-
solved portion by filtration. There is a question as to the stability
of such a product.

0. Kress and S. Wells' are authority for the statement that
cottonseed as delivered to the oil mills, contains about 200 lbs.
of adherent fiber per ton. From this a first cut of 75 lbs. of lint-
ers is taken, having sufficient length for use as a stufiSng material.
Afterwards, a second cut of linters of 75-100 lbs. per ton may
be removed by means of carbonmdum wheels or plates, and this
lint, being almost free from hull particles, is easily purified for
paper-making purposes. The seed is then decorticated, and the
residual hull fibers are shaved or cut off by treatment in steel
attrition mills; this material is very specky. The average length
of the linters fiber is 4.62 mm. (max. 25.44; min. 0.80 mm.), and
the average length of the hull shavings fiber 2.41 mm. (max. 8.00;
min. 0.51 mm.). According to another process, after the removal
of the 75 lbs. of lint with the ordinary linting machine, the sec-
ond cut with carbonmdum wheels is omitted, and the seeds are
directly decorticated, about 75 lbs. of hull fiber being then re-
moved by the steel grinding or attrition plates. This hull fiber
resembles the shavings in length of fiber and contamination with
shell particles. A number of samples of these various products
have been treated for the manufacture of paper pulp. This class

1. U. S. p. 789978, 1905; abst. J. S. C. I. 1905, 24, 686.

2. Pulp and Paper Mag. 1919, 17, 697, 726; abst. J. S. C. I. 1919, SS,
858-A.

COTTON 575

of material is best treated in a rotary type of digester, and it is
extremely important to allow sufficient digester space to permit
of efficient circulation of the liquor. Not more than 11 lbs. of
dry weight of material should be packed per cu. ft. of digester
space, and at least 52 galls, of liquor per 100 lbs. of material
should be used. For the elimination of specks, high tempera-
tures of digestion are necessary, with pressures of 80-100 lbs.
per. sq. in., the time of digestion being 4 hours. The quantity
of caustic soda required varies according to the degree of con-
tamination with shell particles. Cotton linters requires about
9% NaOH on the dry weight of the material; the yield is 90%
of boiled pulp, but is reduced dturing washing and bleaching,
owing to loss of short fibers, to about 70% of bleached paper
calculated on the basis of dry weights. Cotton shavings require
about 12% NaOH and yield 70% of boiled pulp, which is reduced
to about 55% in the finished paper. Hull fiber requires 18%
NaOH and yields 65%-75% of pulp, or 47%-51% of finished
paper, which is suitable for nitration purposes.

In a comprehensive article, J. Wallace,^ has pointed out,
how, in the United States, cellulose for nitration is manufacttured
from a mixtiure of 75% of cotton linters and 25% of cottonseed
hull fibers. The materials are blended in the "devil duster"
machines, into which the cotton is fed from the bale-opening
machines. From the dusters it is blown over into storage bins
each capable of holding a charge of 6500 lbs., sufficient for one
digester of 1200 cu. ft. capacity. For this quantity of cotton,
1360 lbs. of caustic soda is employed, equivalent to 21% of the
weight of the cotton, the caustic soda solution being mixed with
some of the "black liquor" from a previous charge. The total
amount of digestion liquor is about 825 cu. ft. and this is heated
to the boiling point before passing to the digester. The digester
has a perforated false bottom and the circulation of the liquor
is effected by a centrifugal pump through ah external heater.
The liquor is circulated through the cotton and the heater until
it reaches 160° C. corresponding to a steam pressure of 72 lbs.
per sq. in.; thus no live steam is admitted to the digester and the
concentration of the liquor is not reduced. When the temper-

1. Paper, 1919, 23, 34; abst. J. I. E. C. 1919, 11, 391; C. A. 1919,
13, 1016; J. S. C. I. 1919, 3S, 569-A.

576 TECHNOLcxjy of cellulose esters

ature of the charge has reached the desired point, the circulation
is stopped and the charge is allowed to stand under pressure for
a given time. Afterwards, live steam is admitted to the digester,
the pressure is raised to 100-110 lbs., and the whole charge is
blown over into a difTuser. The time of heating up is about
1*72 hours and the time under pressure about 2 hours. In the
diffusers the black liquor is drained off and the cotton is washed
by downward displacement, first with weak washings from a
previous charge and then with hot water. The washed fiber is
discharged from the diffusers into a stuff-chest below, where it
is stirred and suspended in water. Thence it is pumped to a
washing engine where it is further washed and the excess of water
is removed. The thickened charge is then transferred to a bleach-
* ing engine holding about 7000 lbs. of dry fiber, and bleached
with about 2.5% of bleaching powder at a temperature of 36^ C.
for about one hour. Finally the pulp is acidified with about 30
lbs. of sulfuric acid and washed in drainers with warm water.
The washed fiber is stirred with water in a stuff -chest and pumped
over on to a "wet-end" or rinsing machine at a concentration of
about 1% of fiber. The water is squeezed out and the fiber,
after going through a picking machine, is delivered on an apron,
8 feet wide and 90 feet long, on which it is dried by hot air from
steam coils. Each dryer has a capacity of 800 lbs. of cotton per
hour with steam at 75 lbs. pressure. The **white water" is used
again for diluting the stuff and any excess is discharged through
*'save-alls.** The recovery of soda from the black liquor is per-
formed in the usual way, the use of black liquor in the digester
charge facilitating the recovery process by maintaining the
strength of the solution.

According to E. deSegundo,* in the treatment of cotton seed
in the United States, the textile or "staple" fiber is first removed
by the process of "ginning," either by pulling the fibers off the
seeds by means of rollers between which the seeds cannot pass,
or in the case of the "saw gin" by tearing them off by means of
a toothed rotary disc. The seed then retains after ginning about
10% to 12% of its weight of residual fiber consisting partly of

1. J. S. C. T. 1918, 37, 118-T, 172-T; abst. C. A. 1918. 12, 1601; Ann.
Rep. Soc. Chem. Ind. 1918, 3, 117; J. Roy. Soc. Arts, 1919, 184; abst. J. S.
C. I. 1919, 3S, 185-A,

COTTON 577

second quality textile cotton but mostly of quite short non-textile
fiber.

This seed is next treated by a saw linting machine which
produces '*linters.'' The quantity of linters extracted may be
varied partly voluptarily, by adjusting the saws closer together
or further apart, and partly involimtarily, by the wearing down
of the cutting edges. If the latter are sharpened at very fre-
quent intervals, the percentage of linters removed may be main-
tabied at a maximum. So long as linters were employed solely
for second grade textile purposes, the commercial yield from the
seed was not increased by increasing the quantity of the linters
extracted, since the value depended only on the quantity of
longer fibers and the short fibers counted only as a diluent of qual-
ity. Moreover, in setting the saws to remove large proportions
of linters, the saw linting machine is working at an economical
disadvantage and further, the shells of the seed are damaged,
thereby introducing dirty particles into the product. However,
since linters have been largely or entirely used for the manu-
facture of nitrocellulose, the tendency has been to strip the seeds
closer and closer in order to increase the yield pf this grade of
material and the manufacturer is only restrained by the limits
imposed upon him by the necessities of the subsequent oil-extract-
ing purposes. E. de Segimdo quotes the following figures showing
the quantities of linters stripped from the American seeds in
recent years:

Year 1898/99 1908/09 1913/14 1916/17

Linters. . . 24 lbs. 45 lbs. 68 lbs. 148 lbs.

all calculated per American ton (2000 lbs.) of seed.

The effect of the war on the above figures is remarkable,
and at one period the U. S. Government made an order that at
least 145 lbs. of linters must be extracted per ton in order to main-
tain the supply for explosives. It is noted, however, that even
before the war the tendency was rapidly upwards, owing to the
demand for nitrocellulose materials for peaceful purposes.

E. de Segtmdo contends that the saw linting machine is not
mechanically designed for the extraction of such large propor-
tions of linters and that its legitimate function is its original one,
namely, to recover the second grade textile fibers which have
escaped the action of the gins. He has designed a machine^ which

1. E. P. 114435, 114450; Ann. Rep. Soc. Chem. Ind. 1918, 3, 117.

578 TECHNOW)GY OF CELLULOSE ESTERS

detaches the shorter fibers far more eflFectively in any proportion
which may be desired and produces a far more tmiform product
than the latter-day linters, while avoiding injury to the husks
of the seeds.

In the American system of seed crushing for the extraction
of the oil, it is not practicable to strip the short fibers entirely.
A certain proportion must be left on the seeds for the subsequent
operations, but on the other hand, the removal of some of the
wool is essential for good crushing, as an excess of seed lint tends
to absorb the oil. The de-linted seeds are first decorticated, that
is, the shell is split and the kernel liberated. The mixture is
shaken on screens and the fibers attached to the shells make them
felt together to from a mat which will not pass through the screens.
The clean kernels pass through and are pressed, yielding a pale-
colored oil and a clean cake, provided the separation of the dark
colored shells has been effectively complete. The effect of re-
moving too much fiber in the delinting process is to diminish
the matting effect so that some of the husks fall through and
contaminate both oil and cake. This defect has been much in
evidence in recent years. The separated shells still retain a por-
tion of the short seed-fibers and these are removed by a special
treatment depending on friction, the products being cleanly sep-
arated into "cotton hull-fibers" on the one hand and perfectly
bare shells or "hulls" on the other.

Segtmdo makes a proposition for a more rational revision of
the linter question as it stands at the present day, in order to con-
serve the maximum values of the products. Taking the seed as
it leaves the gins with approximately 11% of the total fiber, he
would restore to the saw linting machine its original function and
remove only 2% of linters of textile quality. The textile indus-
try can pay higher prices for useful fiber than any of the chemical
cellulose industries, and these selected linters, being free from
chips of shell, would command a good market. Next, in order
to facilitate the crushing process he would remove 3% of "seed
lint" by means of his seed defibrating machine, which operating
on the whole seeds would yield a cellulose raw material of a purity
most nearly approaching that of the raw cotton. Finally 6%
of fiber would be left on the seeds for decortication and would be
recovered as "hull fiber" after the separation of the kernels. The

COTTON 579

seed defibrator is capable of stripping the seeds perfectly bare if
so desired and it is to be noted that Egyptian and Indian seeds
do not carry sufficient short lint to enable them to be crushed
by the American decortication process to form a mat. Such seeds
have to be crushed whole and the husks are mixed with the cakes.
Nevertheless, the Indian seed does contain about 2% of short
fiber and the removal of this by the seed defibrator before crush-
ing would yield important additional supplies of "seed-lint" and
would be of considerable advantage to the oil industry.

Cotton Hull Fibers; Until about the year 1905, the cotton
seed hull refuse, separated on the screens as described above, was
practically a waste product of no commercial value, consisting
of a matted mass of seed hulls and incidental dirt (86%-88%)
and adherent fibers (12%-14%). In some varieties, e. g., Brazil-
ian, and by some methods of delinting, the percentage of fiber
ranged as high as 25% of the material, while the minimum which
can be expected from improved working may be taken at about
10% of fiber. From this hull refuse, drastic chemical treatments
failed to separate even an approximately clean cellulose capable
of industrial utilization. The introduction of machines which
detached the fiber from the shells by a rubbing action and sep-
arated the -two components in a imiform condition placed the
problem in an entirely diflferent aspect. An accotmt of these
products was given in an article by C. Beadle and H. Stevens,^
from which the following information is extracted.

The machines in question were the invention of P. Minck
and £. de Segundo,^ working at first in collaboration and later
independently. One form of the Minck mill consists of a fixed
vertical cylinder with a fluted lining, provided in the center with
a vertical shaft from which project a number of arms or beaters.
The agitation produced by these arms as the material is fed into
the top effects a complete separation of the cotton from the husk
without reducing the size of the husk particles. The husk being
heavy and deprived of its woolly coating, passes to the bottom
and is discharged through a grating; the cotton is winnowed up-
wards into a *'cyclone" or other form of condenser, from which

1. J. S. C. I. 1909, 28, 1015; abst. C. A. 1910, 4, 482; Bull. Soc. Chim.
1910, 8, 523; Rep. Chim. 1910, 10, 112, 130; Chem. Zentr. 1910, 81, I, 779;
Zts. ang. Chem. 1910, 23, 852.

2. E. P. 12718, 1906.

580 TECHNOW)GY OF CELLUlrOSE ESTERS

it is discharged to a baling machine. The other ingredients of
the seed, if present (i. e., meal, etc.), can be collected at conven-
ient stages by settlement from the air current. A constant sup-
ply of cotton seed hulls is kept up by mechanical feed to each mill
and the separated ingredients are automatically removed. The
various factors of rate of rotation, diameter of the mill, number
and forms of beaters and speed, arrived at, after careful study,
not only effect the output of the mill, consumption of power
and thoroughness of the separation, but also determine the
physical character of the fiber produced. Statistics gathered at
the time the article was written indicated that from cotton seed
hulls yielding at least 10% of the fiber, the American production
should amount to about 100,000 tons of this grade of cotton per
annum.

Impurities in Cotton. It has previously been stated that
raw cotton fiber consists of approximately 90% cellulose and
6% to 7% water, with smaller quantities of oils, waxes, gums,'
nitrogenous materials, cuticular products, mineral matter and
traces of other substances. Weaving mill waste which is in part
made up from the sweepings of the cotton mills, is largely used
for the preparation of nitrocellulose. This material, unless care-
fully collected, may contain appreciable amounts of wood-chips,
pieces of metal, especially iron, starchy rags, string, colored
thread, cardboard, fine stones, seed particles, etc. It may also
contain a considerable amount of fly and dust-like cotton.

The substances other than cellulose in the raw cotton, may
be removed by the usual chemical methods. In their complete
removal there is always the risk, especially if drastic reagents
are employed, of slightly attacking the cellulose and forming
oxycellulose. Ordinary bleached cotton gives from 0.2%-0.6% of
furfural on boiling with hydrochloric acid and this may be taken
as an indication of the presence of a small amount of oxycellu-
lose in the cellulose. Some types of cotton waste contain an undue
proportion of altered cellulose (from over-bleaching) and thus are
unsuitable for nitration. If the oil and substances other than normal
resistant cellulose are present in large amounts in the cotton, a
more drastic purification is necessary to obtain a pure cotton.

1. For the determination of wood gum in incompletely purified cot-
ton, see M. Freiberger. Zts. anal. Chem. 1917, 56, 299; abst. J. S. C. I. 1917,
3€, 923; C. A. 1917, 11, 3445; Ann. Rep. Soc. Chem. Ind. 1917, 2, 127.

COTTON 581

Thus, in the case of Imters, a vigorous treatment is necessary to
remove resin and seed-husk. With short fiber from the cotton
seed, it is difficult to remove the seed husk completely by mechan-
ical means. Even drastic chemical treatment with the imavoid-
able production of an appreciable amount of oxycellulose and
reducing substances still leaves some husk particles. With in-
creased oxycellulose content, there is more difficulty in obtaining
a stable product on nitration. In comparative nitrations, a
cotton containing appreciable quantities of oxycellulose, gives a
lower nitrogen nitrocellulose, with a higher percentage soluble in
ether-alcohol, than that obtained from normal cotton.

The experiments of C. Piest^ show that a nitrocellulose from
cotton which has received drastic purification (either excess
bleaching or alkali treatment) tends to produce imstable nitro-
celluloses as judged by the Bergmann and Junk stability, test.
To obviate the risk of obtaining oxycellulose a pure form of cot-
ton, such as cop-bottoms or sliver, might be employed. These,
owing to the small amount of matter requiring removal, give a
very pure material free from oxycellulose. They are, however,
too expensive for general use.

The source and nature of the cotton has an important bear-
ing when the material is needed for spinning and for textile
purposes generally. When required for nitrocellulose, these dif-
ferent types of cotton containing the normal cellulose, do not
show much variation on nitration as far as yield and stability are
concerned, although viscosities of the nitrated product may vary.
G. Lunge and J. Bebie* found practically no difference (when
allowance was made for ash) in the yields of nitrocellulose from
the following materials with the same mixed acid (H2SO4, 63.84%;
HNO3, 16.96%; H2O, 19.2%): (a) cotton wool, chemically pure,
(b) American cotton (middling fair), (c) American cotton (Florida),

1. Zts. ang. Chexn. 1908, ZL, 2497; 1909. 22, 1215; 1910, 23, 1009;
abst. C. A. 1909, 3, 485, 2227; 1910, 4, 2570; J. C. S. 1910, 98, i, 464; J. S.
C. I. 1909, 28, 746; 1910, 29, 841; Bull. Soc. Chim. 1909, 6, 232, 1165; 1910,
8, 1563; Chem. Zentr. 1909, 80, 1, 474; II, IO9O; 1910, 81, II, 508; Jahr. Chem.
1905-1908, II, 973; 1909, 82, II, 388; 1910, 83, II, 423; Meyer Jahr. Chem.
1909, 18, 309; 1909, 19. 335; 1910, 20, 327; Wag. Jahr. 1908, S4, II, 368;
1909, SS, I, 431; 1910, 58, 1, 493.

2. Zts. ang. Chem. 1901, 14, 541; abst. J. A. C. S. 1901, 23, 527; J. C.
S. 1901, 80, 1, 508; Chem. Centr. 1901, 72, II, 34; Jahr. Chem. 1901, S4, 893;
Meyer Jahr. Chem. 1901, 11, 316; Wag. Jahr. 1901, 47, I, 495. In this con-
nection see Lunge and Weintraub, Zts. ang. Chem. 1899, 12, 441; abst. Chem.
Centr. 1899, 70, 1, 1272.

582 TKCHNOWGY OF CKLI^ULOSK ESTERS

(d) Egyptian cotton, white (Abassi), (e) Egyptian cotton, natural
yellow quality. The resulting nitrocelluloses contained approx-
imately 11.6% N, and then were all soluble in ether-alcohol. C.
Hake and M. Bell, however, find that the physical condition of
the cotton greatly affects the course of the nitration.^

During the nitration and subsequent ptuification of nitro-
cellulose the majority of the impturities will be removed. The
influence of those which remain on the stability of the nitric ester
does not appear to have been specially investigated. The fly and
fine sand, etc., in the cotton waste will be eliminated during the
mechanical piuification (see these topics). The larger pieces of
foreign material, as wood-chips, etc., are removed by thorough
hand-picking before nitration. Some of the foreign matter which
passes through the nitration stage may be collected on blankets
over which the nitrocellulose is passed during the purification.
Metallic iron may be removed from the nitrocellulose by magnets
(see Guncotton Purification).

Cop Bottoms. For the manufactture of the lower nitraLted
celluloses — the collodion cottons used for blasting gelatin, and
less often for photographic films and fine p)rroxylin lacquers — cop
bottoms are often used. This is spun thread in a tangled condi-
tion, and is the last portion remaining on the spindle. It is a
comparatively long fiber cotton, and makes an excellent nitro-
cotton. It is usually considered as too expensive for use in nitro-
cellulose intended for artificial leather, bronzing liquids and
smokeless powder.

1. J. S. C. I. 1909, 28, 460; abst. C. A. 1909, 3, 1687; J. C. S. 1909.
96, i, 457; Bull. Soc. Chim. 1909, 8, 61; Rep. Chim. 1909, 9, 398; Chem. Ccntr,
1909, 80, II, 903; Jahr. Chem. 1909, 82, I, 387; Meyer Jahr. Chem. 1909,
19, 334; Wag. Jahr. 1909, SS, I, 434; Zts. ang. Chem. 1909, 22, 1772. For
polemic on above see J. S. C. I. 1909, 28, 823; abst. C. A. 1909, 3, 2503; Jahr.
Chem. 1909, 82, II, 388. In this connection see C. Hake and J. Lewis»

. S. C. I. 1905, 24, 374; abst. J. C. S. 1905, 88, i, 512; Chem. Centr. 1905,

6, I, 1702; Meyer Jahr. Chem. 1905, 15, 357.

I

CHAPTER IV.

PREPARATION OF COTTON FOR ESTERIFICATION.

The various processes and treatments to which cotton cel-
lulose is ordinarily subjected preparatory to esterification — either
nitration or acetation — is, in its completeness indicated by the
following distinct steps:

1. Raw cotton storage.

2. Bale breaking operation.

3. Pressure boil-off with .alkali, followed by washing.

4. Bleaching the cotton, followed by washing and drying.

5. Weighing the cotton batches, and storage until needed
for nitration.

A flow sheet of these various steps as exemplifying the pre-
ferred practice in the United States is shown in Fig. 2, as carried
out at the Government explosives plant at Nitro, West Virginia.
The practice in Great Britain is indicated in Fig. 3, showing the
method of procedure at H. M. Explosives Plant, Gretna, Scotland.

Weight of Cotton Bales. An American bale weighs from
400-500 lbs. and occupies 32-33 cu. ft. A ton of cotton therefore
requires approximately a storage capacity of 4' X 3' X 10'. The
American bales are said to be badly packed, the covering being
made of inferior material often inadequate to protect the fiber.
The density of the American bale is approximately 18-22 lbs.,
per cu. ft., the Egyptian 37 lbs., and the average Indian 45 lbs.,
while some special Indian and Chinese bales show 55-60 lbs.
density.^ Two and a half times as much Indian bale cotton as
Axnerican may therefore be stored, given equal storage capacity.
There is seemingly no apparent reason why a considerably higher
density bale should not be general with American cotton. This
improvement may be achieved by replacing the existing steam
operated machines by more powerful hydraulic presses. With
the Cummins **Medium Rapid" horizontal bale presses,* a density
of 56 lbs. per cubic foot may be obtained — a 500 lb. bale measuring
9.5 cu. ft. The saving on inland and ocean transportation would
be considerable if such high baling were generally employed.*

1 . "Cotton and Other Vegetable Fibers." E. Goulding and W. Dunstan.

2. Textile Recorder, Apr. 15, 1918. Textile World Jour. Mar. 16, 1918.

3. The Engineer, Nov. 23, 1917.

584

TECHNOUKiY OF CELLUWSE ESTERS

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586 TECHNOlrOGY OF CELLULOSE ESTERS

The bales of other countries diflfer considerably from the American
standard bale. The Egyptian bale is 700 lbs., the Indian and
West African 400 lbs., the Brazilian 200-260 lbs., and the Peruvian
170-200 lbs. The Indian and Egyptian bales are usually well
made.^

D. Bridge & Co., Manchester, Eng., are manufacturers of
the E. Cummins cotton press (Fig. 4) in which the end-way
system has been adopted, with one very long filling box, having
doors throughout its entire length, and large enough to accom-
modate the cotton thrown into it. At one end of the box is pro-
vided a condensing chamber, at the end of which is attached a
powerful hydraulic cylinder working a double-acting ram. By
means of multiple rope gearing attached to the ram the required
preliminary pressure to pull loose cotton into the chamber is
provided on the return stroke. This is accomplished by the use
of a follower inside the filling box.

Opening the Bale. Many types of suitable machinery for
opening the cotton bale are on the market. The piuTX)se of the
machine is to open the bale and mix the cotton waste with other
cottons such as card-sliver waste, etc. The waste is drawn di-
rectly into the waste hopper and torn up by the action of the
spiked apron and combs in the machine. Before being placed
on the hopper, spinners' "stick waste*' is first run through a thread-
extractor and "roving waste" is passed through a machine specially
constructed for the economical handling of this substance. The
waste hopper may also be used to mix in lower grade or shorter
staple bales which may be necessary for distribution among a
number of bales.

The hopper breaker, as made by Piatt Bros., Oldham, Eng-
land, is so arranged that it delivers the cotton direct to the lat-
tice of the hopper feeding machine, and dispenses with mixing
bins. It substitutes a combing action instead of a roller tearing
action and therefore does not damage the fibers. The material
is taken from the bale in large pieces and placed in the hopper,
the horizontal lattice carrying the cotton forward and pressing
it against the spikes of an inclined elevating lattice, where it is
subjected to a combing action. It is next carried upwards to a
spiked roller which fiuther combs the cotton, and throws back

1. W. Taylor, Textile Recorder, Sep. 16, 1917.

Fig. 4.— Cummins Hvdkauuic Cotton Balini

588 TECHNOLOGY OF CELLULOSE ESTERS

into the hopper any large or unopened pieces. The spiked roller
is stripped and kept clear by a stripping roller, the surplus cotton
falling back into the hopper. The cotton, after passing the
spiked roller, is stripped from the inclined lattice by a beater
and falls on a grid in the delivery sheet. Fans and hoods with
reversible grids are supplied to prevent rise of dust and dirt.
An improved machine for the blowing room is made by Taylor
Lang & Co., of Stalybridge, England. For the opening and
cleaning of the cotton they employ a special single-cylinder (Buck-
ley type) opener, without beater (see Fig. 7). The machinery
is especially adapted to the treatment of fine material such as
Sea Island and Egyptian cotton. Although the machine very
efficiently removes dirt, leaf, nep, and other impurities, it does
not injure the staple. There is no risk of ^'stringing" or "nepping,"
as may occur when the **Exhaust" or "Creighton" type of opener
is used. The cotton is combed from the feed roller by blades of
the cylinder which are so deposited as to cover the whole length
of the feed roller in one revolution of the cylinder. The cotton
is thrown by the centrifugal action of the cylinder, revolving at
a high speed, against the bars, and the impurities are ejected by
a suitable disposition of the bars.

When the cotton waste contains appreciable amounts of
dirt, it is advizable to use a machine which combines opening,
cleaning, and willowing processes.

In order to obtain a representative sample upon which to
perform the usual specification tests, 10% of the bales are usually
opened as soon as they are received at the factory. "Grab"
portions are taken at different points. After the tests have been
concluded and the supplies accepted the cotton is drawn upon
according to the demands of the nitration house.

Boil-off. Irrespective of the nature or source, raw cotton
always contains an appreciable but variable amount of oily and
fatty matter, cholestrin and similar bodies which are insoluble
in water and only removable by a saponification, solvent or
emulsification treatment. These normally occurring constitu-
ents of cotton prevent the latter from rapidly absorbing water,
so that such cotton will float on the surface of water for an in-
definite period without becoming wetted. That is, raw cotton
is not absorbent. It becomes necessarv, therefore, to remove

Fic. 5.— Mbcranical HANDLma of Cotton Balbs (Gretna, Scotland)

590 TeCHNOI^OGY OP CELLULOSE ESTERS

these oily and fatty constituents. Several methods have been
proposed for accomplishing this purpose, as by solvent extraction,
saponification with dilute alkali, or emulsification with dilute
acid. In solvent extraction — ^which is not resorted to ordinarily
and only in those instances where either alkaline or acid treat-
ment might be injurious to the cellulose, or the fatty and waxy
matter is imduly high-;— a light petroleum ether, straw colored
benzol, or an uninflammable solvent as carbon tetrachloride or
acetylene tet^-achloride (tetrachlorethane) is usually employed.

If the cotton is treated by "souring" before bleaching, the
impurities are emulsified by boiling under pressure with dilute
acid — ^usually hydrochloric, the cellulose being washed with cold
water after the treatment until the wash waters are substantially
neutral. In the B. Leech method,^ pectic and other matters are
removed by treatment with HCl at or near the boiling temper-
atiu'e, the amount of acid to be used being such as will completely re-
move all extraneous matters, but insufficient to detrimentally afTect
the fiber, the amount to be used being predetermined by prelim-
inary tests. A slight alkaline wash is recommended in this process as
assisting in the removal of organic impurities and soluble chlorides,^

Where the fiber is submitted to an alkaline instead of acid
treatment, the operation is known as ''scouring," and chemically
is a saponification with sodium hydroxide or carbonate, some-
times aided by the addition of smaller amounts of sodium silicate
(water glass). All cotton before nitration must be submitted to
a process for the removal of fatty and waxy products, i. e., it
must be rendered absorbent. In general, tmless immense quan-
tities of cotton are esterified at one place, it is most economical
and satisfactory for the scouring to be done by those who make
a practice of this branch on a large scale.^ The process of scour-

1. U. S. p. 1263685, 1918; abst. C. A. 1918, 12, 1703; J. S. C. I. 1918,
37, 332-A; Mon. Sci. 1918, 8S, 77. E. P. 104202, 1916; abst. C. A. 1917,
U, 1911; J. S. C. I. 1917, 36, 45; Ann. Rep. Soc. Chem. Ind. 1917, 2, 165.

2. J. Garcon, Textile World Record, 1914, 4S, 76.

3. On the surface of the individual fiber there is a protecting layer
of wax and oily matter, while in the central canal is the dried remains of
the protoplasmic material. The object of the boiling out and scouring
processes, is, of course, the removal of these materials. When purified from
adhering fatty and waxy materials the cotton becomes very absorbent,
which quality is explained on the supposition that the ripe cotton fiber is
made up of a series of tissues of cellulose, separated by intercellular material,
in this way forming a series of capillary surfaces capable of inducing con-
siderable capillary attraction upon any liquid in which the fiber may be
immersed.

592 TECHNOLOGY OP CBLlrULOSE ESTERS

ing-'-of course — has for its object to render the cellulose more
susceptible to reaction with nitrating agents, and to produce a
more uniform and stable cellulose ester.

The scouring operation is best carried out by heating cotton
in any physical form, under pressure with dilute sodium hydroxide
or carbonate solution, either one or both, for several hours in
iron, or better zinc-lined kiers with clamped down covers, at a
pressure of from three to five atmospheres pressure for from 5
to 10 hours. After the kier has been loaded with cotton, weights
are placed on the top to guard against undue expansion, and in
the best practice, the kier is never filled more than four-fifths
full for the same reason. Sodium hydroxide has an excellent
saponifying power, and sodium carbonate desirable detergent and
emulsifying properties.^

In the process as elaborated by R. MuUer,^ the material is
first treated with an aqueous solution of combined alkaline hy-
droxide and carbonate. In following out the patented descrip-
tion of R. Roberts' the cellulose is **de-gummed" by subjecting
to a boiling solution of caustic potash, borax and sal soda, and
containing in addition a small amount of saponifiable oil. H.
Landell^ advocates circulating boiling NaOH through the closely
packed cotton, the material afterwards being washed and given
a dilute acid treatment. The washed material is subsequently
agitated and shredded in the upper portion of a body of water
so as to allow the foreign impurities to settle out in the quiescent
portion of the water, the sediment being drawn off from time
to time from the bottom.

J. Daniel and F. Benoist^ obtain the best results by digest-
ing the raw cotton under a pressure of 1-4 atmospheres with a
liquid containing 2% of sodium hydroxide, 1% sodium carbonate,

1. The author's experience is that sodium hydroxide (caustic soda)
should never be used, on account of its energetic action on cellulose. (See
Viscose.) Crystallized sodium carbonate (10 HtO) is often employed on
account of its supposedly milder action. See J. Parcon, Textile Mfr. 31, 387.

2. E. P. 9369, 1910; abst. C. A. 1911, 5, 3136; J. S. C. I. 1911, 30,
82. D. R. P. 240037, 1911; abst. Zts. ang. Chem. 1911, 24, 2335; J. Soc.
Dyers Col. 1912, 28, 75; C. A. 1912, 6, 2177; Chem. Zentr. 1911. 82, II.
1563; Chem. Ztg. Rep. 1911, 35, 576; Wag. Jahr. 1911, 57, II, 443; Chem.
Zts. 1912, U, No. 2667.

3. Can. P. 121639, 1909.

4. U. S. P. 1222422, 1917; abst. J. S. C. I. 1917, 36, 544.

5. F. P. 465571, 1913; abst. J. S. C. I. 1914. 33, 588; C. A. 1914, 8,
3502.

594 TECHNOLOGY OP CBI*I*UW)SB ESTERS

1% soditun sulfite and 0.1% ethylene trichloride, for 4-12 hours.
In the C. Waite patent/ the cellulose is digested with caustic
soda which has been treated with a small quantity of sulfur so
that the amount of sodium sulfide present is less than 0.5%.
This small amount of sulfide is said to be sufficient to neutralize
the possible effect of the free oxygen present in the formation of
oxycellulose, but insufficient to exert an appreciable digesting
action.

J. Fair prefers to first' treat with a small amount of nascent
chlorine generated by the. action of HCl on a chlorate, and sub-
sequently boiling in dilute alkaline solution.* The fat is removed
in the W. Zimmermann process' by treating the fiber in a stirring
vessel with a mixture of fullers earth, a potash soap, soda, salt
and a small amount of ammonia.

In the process of W. Roehrig and designed especially for
cleaning cotton for nitration,* an emulsion of excess of free fatty
acid (or a mixture of fatty acids) with soap is employed as an
addition to the de-fatting -lye. The treatment of the cotton
with lye should commence with a low temperature, preferably
below 70°, the mixture consisting of 18.5 k. resin added to a
solution of 4.5 k. NaOH in 80 1. of water, the mixture being
finally heated to nearly the boiling temperature of water. About
48 1. of technical oleic acid are then added in small amounts at
a time, together with about 2.5 k. tallow. After thorough ad-
mixture of the several constituents, the emulsion is added to the
de-fatting lye. From 2%-4% of the emulsion is sufficient as an
addition to a lye which contains 3 %-6% NaOH of 12.5'' B^., cal-
culated on the weight of the cotton.

According to J. Foltzer,*^ cotton is preferably boiled imder
pressure with a solution of sodium carbonate and sodium hydrox-
ide. The product, which, to be pioperly acted upon by the
mixture, should contain at least 12%-15% of moisture. After

1. C. Waite and J. Hedin, U. S. P. 1212158, 1917; abst. J. S. C. I.
1917, 36, 288; Mon. Sci. 1918, 8S, 4.

2. U. S. P. 1053125, 1913; abst. C. A. 1913, 7, 1287; Mon. Sci. 1913.
73, 151.

3. F. P. 466806, 1913; abst. C. A. 1915, S, 1376; Chem. Ztg. Rep.
1914, 38, 582; Mon. Sd. 1916, 83, 71.

4. D. R. P. 289155, 1914; abst. C. A. 1914, 8, 2526; Chem. Zentr.
1916, 87, I, 240; Chem. Ztg. Rep. 1916, 40, 23. Wag. tahr. 1916, 82, I. 255.

5. P. P. 345687, 1904; abst. J. S. C. I. 1905, 24, 85; Zts. ang. Chem.
1905, 18, 434. Mon. Sci. 1916, 65, 36.

596 TECHNOLOGY OF CSLLULOSB ESTERS

12-24 hours' treatment, the fiber may, according to the patentee,
be washed free from all fatty and mcnisting substances.

Notwithstanding the various modifications and alleged re-
finements as described above, the general arrangement and
method of rendering cotton absorbent as a preliminary to ester-
ification, is generally carried on in accordance with the following
general or type method: Alter packing the cotton in the kier,
which usually consists of a circular or egg-shaped, upright iron
vessel containing a perforated false bottom, and built strong
enough to withstand 10 atmospheres pressure, steam is turned
on, and the contents of the kier heated to 90°-95°. Where the
kier is of cylindrical shape, the capacity ranges from one to three
tons of cotton at a charge. An iron pipe is affixed to the false
bottom, and rises about three-quarters up the interior of the kier.

Pig. S. — Tna E. Lbhhahn Hakd Wastb Opensr por Cotton and au.

VaCBTABU FiBBKS

A cowl is placed on the top of the pipe so as to deflect the water
in a downward and outward direction, liquid being introduced
by an injection apparatus and a centrifugal pump. The liquid
is caused to continuously or intermittently (vomiting kiers) cir-
culate through the cotton, usually by means of a steam injector.
High pressure steam, for convenience, is used in the heating.

A_cominonly employed type of kier is shown in Fig. 10, the
boiling in this kier being done through hollow trunnions, steam
being admitted at one side, and liquid at the other. The appa-
ratus is so constructed that it nlay be loaded while boiling, and
arrangement is provided so that water may at any time be ad-
mitted through the trunnions. The liquid passes down to the

COTTON 597

bottom of the kier and then gradually wotIcs up through the mass
of cellulose, coming out by a pipe (shown at each side in the
illustration), for this purpose. The bleaching tank may be placed
in front and below the kier so that when the apparatus is tipped
over at an angle of about 45°, the cotton may be dumped out
into the bleach tank. The length of time of heating, and the
concentration of alkali is determined and regulated by control

Fig. 10.— Tipping Prbssurb KiSR

WITH ENTtRB TOP TO OPEN

tests. This apparatus, constructed by the Textile Finishing
Machinery Co., Providence, R. I., is extensively used in the
United States.'

When the operation is completed as shown by the laboratory
I. In the cotton treatment process of T. Taylor, E. P. 112969, 1917;
abst. J. S. C. I. 1918, 37, 203-A, the rollowing arrangement is described. In
the steam ejector employed, additional steam is admitted into the delivery
nozzle to heat the induced fluid, giving simultaneous circulation and heating
of the bleaching or other hquor. See also E. P. 2869, 188:1; 15174. 1893;
5744, 1915.

598 TBCHNOI.OGY OP CELI.UIX)SE BSTBRS

tests» the contents of the apparatus is cooled, and the cover raised.
The stock is next washed for three or four hours with water, the
washing being continued until the runnings are colorless, or at
most only pale yellow. The resulting dark colored cotton is then
ready for the bleaching process. A usual control test is to remove
a sample from the kier, wash and dry and determine the extractive
in a Soxhlet apparatus with ether. The ether-extract when evap-
orated to dryness should not exceed 1% of the weight of the
sample taken. ^

It must be remembered that thorough but not too harsh
alkaline boiling is the foundation of successful bleaching, and is
of paramount importance where nitrated cottons of high stability
are subsequently to be prepared from cellulose. Unless the
natural oil and wax are substantially completely saponified and
removed by the washing process, a uniform esterification is ex-
tremely difficult if not well-nigh impossible. Adventitious grease
and tmsaponified oil are directly antagonistic to the entrance of
nitric acid into the cellulose aggregate, and these bodies mater-
ially increase the proneness of the batch to **fume oflF" in the
nitrator. Badly boiled or incompletely "bottomed" cotton, in the
earlier days of the nitrocellulose art, were imdoubtedly sources
of much instability in the nitrated ester produced. It should
also be remembered that the incomplete removal of nitrogenous
compounds contained in the cotton undoubtedly can cause a
similar trouble owing to the power which proteids possess in the
absorption of chlorine in the bleaching process, giving rise to
chloroamines. Tannic acid if not completely removed may cause
slight stains when the cotton is placed in the nitrator, but this
is drawing the point rather fine. The pectins, which dissolve in
the alkali and are washed out, are intimately associated mth the
coloring matters of the cotton.

In a series of experiments made by S. Trotman and S. Pen-
tecost* it was clearly shown that in a given length of time, less
than that necessary for complete action by soda, potassium

1. According to A. Hertzog (Centr. f. Text. Ind. 1890, 21, 975) the Gennan
military authorities require a cotton which when treated with ether yields not
over 0.9% fat; when nitrated does not disintegrate; and containing only
traces of chlorine, lime, magnesia, iron and sulfuric and phosphoric acids.
See also "Inspection of Cotton Waste for Manufacture of Guncotton," C. E.
Munroe, J. A. C. S. 1895, 17, 783.

2. J. S. C. I. 1910, 29, 4; C. A. 1911, 5, 2726; Jahr. Chem. 1910, 1145.

600 TECHNOLOGY OF CELI^ULOSE ESTERS

hydroxide will always remove about 20% more than soda, when
used in equimolecular solutions. They contend the conditions
necessary to secure a satisfactory soda boil are: (1) The water
used should be soft (softened water is -not as good); (2) The
cotton should be regularly and closely packed in the kier so that
spaces where steam or air can collect will not be formed, and
circulation must be good and uniform throughout the mass. It
is recommended to saturate the fiber with the solution before
packing to ensure uniform wetting; (3) Good circulation. The
degree of saponification varies directly with the cube of the rate
of circulation. Dilute boiling NaOH readily attacks cellulose in
the presence of oxygen. Of the various types of circulatory
apparatus available, the centrifugal pump is probably the best.
(4) Absence of oxygen and air. (5) The presence of sufficient
soda. No old lye should be used without a determination of
the percentage of hydroxide and carbonate present. (6) Rapid
removal of the caustic soda after boiling, to avoid the possibility
of producing oxy cellulose or mercerization due to concentration.
(7) Absence of direct contact with steam pipes. (8) Purity of
reagents used. In the boiling off process, it is advizable to use
a combination of alkaline hydroxide and carbonate, with borax
as emulsifiers, with sodium silicate on account of its scouring
properties.

The physical changes induced in the cotton as the result of
the boilmg-off process are stated as: (l) Average loss in weight,
about 4.5%-5%. (2) Alteration in the count. The alteration
gradually increases with the count, a point not of interest in this
connection. (3) Loss in length of fiber is less than 5 %. (4)
Increase in tensile strength. Any weakening which might result
from the removal of waxy matters is probably more than counter-
balanced by the thickening and felting of the fibers. (5) Altera-
tion in twist. In addition to the alteration in the natural twist
of the cotton fiber, there is an increase of about 15% in the num-
ber of the turns per inch in a yam.

C. Schwalbe* has shown that only cellulose which has already

1. Chem. Ztg. 1910, 34, 551 ; abst. J. S. C. I. 1910, 29, 750. In a sub-
sequent investigation of hydro- and oxycelluloses from wood cellulose (see
C. Schwalbc and E. Becker, Zts. ang. Chem. 1919, 32, 265; abst. J. Soc. Dyers
Col. 1920, 36, 27; J. S. C. I. 1919, 38, 858-A) it has been found that these
substances in common with naturally occurring degradtion products of celiu-

602 TECHNOLOGY OP CELLUIX)SE ESTERS

been chemically effected by excessive bleaching, etc., imdergoes
hydrolysis when heated with water at high temperatures. He,
together with M. Robinoflf,^ has recorded some oirious observa-
tions as regards the effect upon cotton when boiled with caustic
soda solutions of various strengths and at diiBFerent temperatures.
They tried the effect upon pure cotton cellulose which had been
prepared by the method of Tamin,^ the cotton cellulose having
been prepared by boiling piu-e unbleached Egyptian cotton with
alkaline rosin soap solution, washing with hot water and very
carefully bleaching. The resulting product had a corrected cop-
per value of only 0.04. It was found that in bleaching the'cellu-
lose with hypochlorite solution, followed by "souring" with
hydrochloric (or acetic) acid, the formation of oxycellulose was
promoted by the use of lower strengths of acids. In addition
to determinations of the solubility of the cellulose in dilute lyes,
the results of which confirmed those previously obtained (loc. cit.)
the * 'mucilage values" (i. e., the weight of the flocculent matter
precipitated by alcohol after neutralization of th^ alkaline ex-
tracts) were also ascertained. Above 150° C, much larger
mucilage values were obtained, and hence for this value, too,
150° C. appears to be "critical temperature" in the case of cotton

lose, such as cellulose, dextrin, and the hemicelluloses, are converted into
mucilage by mechanical means, and particularly by pressure. This mucilage
is converted into an irreversible colloid on drying, which has lost Uie property
of swelling in an atmosphere .sattu-ated with water vapor. The substances
named, by prolonged boiling with water or steaming, are rendered partially
water soluble, and lose their property of forming a mucilage. Similar mucil-
age was prepared by purely mechanical treatment in presence of water and
air at 30^-40®. These hydro- and oxycelluloses possess a considerable
affinity for mordant bases such as aluminium hydrate. This affinity is so
great in the case of the mucilage that the base can be removed entirety from
a solution of aliuninitmi sulphate, leaving the free acid in the liquor, by
addition of wood cellulose mucilage. Such absorptions are not affected by
the base (lime) content of the fibre. Neutral salts such as magnesium chloride
are similarly affected. The relation between the moisture content bf the
atmosphere and the temperature plays an important part in this action,
complete saturation of the air with water vapor appears to be unfavorable.
In cotton dyeing and in calico printing with basic colors the formation of
small quantities of hydro- and oxycellulose is possible £lnd may influence
favorably the fixation of mordant and dyestuff. Mucilage formation in
mechanical processes during dyeing and printing in the jigger or padding
machines seems possible. The sticky lumps formed from the mucilage
diminish t^ie permeability. Treatment of the fibre with mucilage for fixing
mordants and dyes dnd for preparing waterproof surfaces may be advanta-
geous.

1. Zts. ang. Chem. 1911, 24, 256; abst. J. S. C. I. 1911, 30, 277.

2. Rev. Mat. Col. 1908, 313.

604 TECHNOU)GY OF CELLUW>SE ESTERS

cellulose. A determination of the cotton values of cotton cellu-
lose treated with hot lyes, showed that a concentration of 4%
o^ alkali was (as in the case of cold lyes) the most destructive.
Tiie products of hydrolysis formed by the action of 1 and 2 per
cent, sodium hydroxide solution appeared to undergo decompo-
sition above 100° C, since there was a decrease in the copper
values. In the case of products formed by lyes of 3% strength
(or over), this decrease (decomposition) did not begin below
135° C. The decrease in the hydrolysis effected by lyes of 5%
strength and over is probably due to the beginning of merceriza-
tion (hydration). There appears to be a diflference in these
respects between different kinds of cotton, American cotton, for
instance, giving much higher copper values than Egyptian cotton.

Bleaching the Cotton. After the alkali from the boil-off
treatment has been substantially eliminated by thorough wash-
ing, the coloring matter remaining in the fiber may be removed
by bleaching. Unless the bleaching process be very carefully
conducted so as to avoid the possible formation of oxycellulose,
it is better to nitrate the cellulose directly after it has been made
absorbent, and without any attempt to remove the coloring
matter. With linters and other short fibers it is quite customary
to forego the bleaching treatment, and to nitrate directly the
boiled-off fiber after opening up and drying. With smokeless
powder, absence of color in the cellulose is not of great moment,
while on the other hand, where the cellulose is to be nitrated or
acetated and dissolved for lacquers and the protection of woody,
metallic or fabric surfaces, especially those lacquers which are
used to protect silver and nickel plated surfaces, it is essential
that a thorough bleaching of the cellulose be performed before
esterification. These so-called "water- white" lacquers are often
made by the nitration or acetation of paper. Where a fairly
clear and colorless pyroxylin lacquer is demanded, a partial
bleaching only of the fiber is resorted to, the process being known
as "half-bleach."i

Bleaching is usually accomplished by means of a hypo-

. 1. C. Piest (Zts. ang. Chem. 1908, 21, 2497), found that bleaching
appears to have a greater effect on the formation of reducing substances
than does treatment with alkali, as determined by the reducing action of
Fehling's solution on cotton (Schwalbe, C. A. 1907, 1, 1696, 2179), the oxy-
celluloses giving lower nitration products than cellulose under similar con-
ditions!

606 TOCHNOIXKJY O^ CSttUW>SE ESTERS

chlorite solution, that of sodium, or more often calcium (chlor-
ide of lime?) being used. Where calcium hypochlorite is em-
ployed, a stock solution is prepared in which the ordinary com-
mercial bleaching powder, averaging 34% to 35% available chlo-
rine, is dissolved in water and the solution clarified by allowing
the insoluble material to subside. From this solution an amount
equivalent to about 0.5% available chlorine calculated on the
weight of the cellulose is used for bleaching. The fiber is placed
in vats or tubs, made either of stoneware slabs, concrete or wooden
containers tile-lined, and the bleaching solution pumped over
the fiber by means of a centrifugal pump for a period of three to
four hours. After this the cotton is washed, still in the same
containers, until the wash water gives but a faint test for chlorine
with starch iodide paper, when a dilute solution of sulfuric add
or preferably hydrochloric acid is pumped over the material for
a period of two to four hours, the cotton being then carefully
washed until free from acid.^

In the process for treating cellulose as devised by A. de
Vains and J. Peterson,^ a mass is charged through an opening
in a cylinder, of preferably reinforced concrete, through which
the chlorine is introduced by a separate opening. The mass is
then agitated by means of a pump until it is found that the
chlorine is well absorbed, whereupon the chlorinated cellulose is
transferred to a washing apparatus. This apparatus comprizes
a reinforced concrete cylinder having a false bottom of copper
or antimony-lead alloy having a siphon and a cock together with
a suitable pump and connections. As soon as the cellulose has
attained the proper degree of whiteness, it is flushed away
to a bleaching engine where it is treated with calcium hypo-
chlorite.

J. Matthews' has recently discussed the bleaching of cotton,
including permanganates, peroxides, and perborates, giving com-
parative costs of various methods together with comparative costs
of bleaching, and the proportions of the bleaching materials re-

1. Where bleaching powder has been used, it is exceedingly difficult
to wash out all traces of chlorine, a minute trace of which may cause the
nitrated cotton to turn slightly acid after drying.

2. E. P. 19099, 1913; abst. J. S. C. I. 1914, 33, 746. Wirth, E. P.
2619, 1878.

3. Color Trade J. 1918, 2, 53; abst. C. A. 1918, 12, 2251. See A.
Bouret and F. Verbiese, E. P. 24768, 1898.

608 TECHNOLOGY OF CELLUU)SE ESTERS

quired. R. Sansone^ has emphasized the fact that cotton is best
bleached when it is as nearly pure cellulose as possible. This con-
dition according to Sansone, is found after removing the natural
fat, wax, and other impurities. The construction and operation of
suction and of pressure vats for the rapid bleaching and rinsing
are described by him with illustrations and methods of out-door
bleaching, and bleaching by ferments. His summary shows that
bleaching before spinning is attained with less breaking of the
fiber, greater economy in spinning especially for fine, numbered
yams, the production of a pure white cotton and a better control
in the purchase of unspun cotton.* In the bleaching and purifjring
process of E. Favier' carbon tetrachloride is used as an adjunct
to the alkali boil-off and bleaching operation. G. Atkins* has
described a method for the treatment of cotton with hypochlor-
ite,'' the claim being made that the silica is also removed by
this treatment.®

Electroljrtic bleaching solutions have also been used in order
to hasten the period of bleaching. To hypochlorite and other
solutions, A. Lehmaiin^ suggests the use of malt or malt prepara-
tions, this being added directly to the bleaching bath of hypo-
chlorite. According to him, the successive addition of malt in-
creases the activity of the chlorine so that the bleaching process
is rendered twice as rapid and only approximately half the amount
of calcium hypochlorite is required. The process requires 2 hours
time, after which the material is rinsed, acidified, and the acid re-
moved by washing.

R. Mueller,^ treats cotton by bleaching with alkali solution
with or without the addition of small quantities of metallic com-

1. Leip. Farber. Ztg. 1914, 63, 85, 97; abst. C. A. 1915, 9, 863. W.
MitscherUng, Kunst. 1912, 2, 261, 285, 308; abst. C. A. 1912, 5, 3185.

2. S. Higgins, J. S. C. I. 1914, 33, 902; abst. C. A. 1915, 9, 246. G.
Atkins, E. P. 7058, 1903; abst. Mon. Sci. 1905, (4), €2, 68; J. S. C. I. 1904.
23, 385. E. P. 5596. 1901, abst. J. S. C. I. 1901. 20, 518.

3. F. P. 368036. 1906.

4. E. P. 7058, 1903; abst. J. S. C. I. 1904, 23, 385; Chem. Ztg. 1904,
21, 732; Mon. Sci. 1905. 63, 68.

5. Prepared according to E. P. 5596, 1901 ; abst. J. S. C. 1. 1901, 20, 518.

6. Removal of silica by digestion with hydrofluoric acid is never
resorted to commercially.

7. D. R. P. 279993, 1913; abst. C. A. 1915, 9, 1396; J. S. C. I. 1916,
34, 657; Chem. Zentr. 1915, 86, I, 227; Chem. Ztg. Rep. 1914, 38, 674; Wag.
Jahr. 1914, 60, II, 365.

8. E. P. 9369, 1910; abst. C. A. 1911, 5, 3136; J. S. C. I. 1911. 30, 82,
1727, 1911; abst. J. S. C. I. 1911, 30, 680; J. Soc. Dyers Col. 1911, 27, 73.

610 thchnoux;y of cellulose esters

pounds and with simultaneous exposiu'e to a current of air or
oxygen. The introduction of this current being arranged so that
direct contact between the gas and the material to be bleached
is avoided as far as possible. In an example as cited by him,
cotton is boiled for some time imder two atmospheres pressiu-e
in a solution of sodium carbonate and manganese sulfate in a
pressure vat, the material being prevented from floating at the
stuiace, air is then forced into the liquor from above at 3V2
atmospheres pressvu-e. The darker liquor then becomes lighter
and the treating is continued until the liquor becomes practically
a light yellow. The bleaching material is then washed, treated
with dilute sodium bisulfite solution, washed free from acid and
dried. In the method of bleaching as devized by W. Matger,^

1. K. P. 8960, 1905; abst. J. Soc. Dyers Col. 1907. 23, 47; J. S. C. I.

1906, 25, 864. R. Haller, Zts. Farben-Ind. 1907, 6, 125; abst. J. S. C. I.

1907, 26, 523; has studied the structure of cotton as affected by bleach-
ing, mercerization, and dyeing and has found that the fiber, b^ing a seed-
hair, has only. one end naturally closed, the other being broken off at the
point of attachment. The outer wall is covered with a waxy substance,
cutin (cuticular cellulose), while dried-up residues of protoplasm coat the
wall of the central canal. The peculiar swelling of the cellulose and the
bursting and partial breaking away of the cuticle under the action of cupram-
monium has been described by Wiesner; the protoplasmic inner wall, like
the cuticle, also resists the solvent action of the reagent.

The author has observed that both the cuticle and the protoplasmic
layer resist the severe alkaline treatments of the industrial bleaching process,
at all events in the great majority of the fibers. The cuticular and proto-
plasmic layers absorb basic dyestuffs, such as Safranine, and retain the
color when washed with boiling alcohol, whereas the cellulose remains un-
stained. The retention of dyestuff under these conditions is considerable in
the case of raw cotton, but decreases in proportion as the fiber is piuified;
in all cases, however, the cellulose itself remains colorless. The cutin of
the cuticular cellulose is completely removed by treatment for half an hour
with caustic soda lye of mercerizing strength. When the mercerized fiber
is dyed with a substantive dyestuff, the cellulose itself is deeply colored,
and on treatment with cupr ammonium it sweUs uniformly and ultimately
dissolves, leaving the protoplasmic wall of the central canal as a colored line.
The unmercerized fiber, when similarly dyed and treated with cuprammonium,
shows a strongly colored cuticle and lumen, and only slightly colored cellulose.
It would appear that the cuticle and the protoplasmic wall of the lumen,
besides possessing a mordanting property towards basic dyestuffs, constitute
layers which also have a strong affinity for substantive dyestuffs, and which,
being penetrated by these dyestuffs only with difficulty, hinder the access
of the color to the cellulose between them. In this way the author is inclined
to explain the darker shades obtained with substantive dyestuffs on mer-
cerized fibers deprived of their cutin. If an unmercerized cotton fiber be
treated with cuprammonium, and then washed, and dyed with a substantive
dyestuff, those places from which the cuticle has broken away are intensely
colored, while those parts which arc still protected by the cuticle are only
slightly stained. Cuprammonium swells and dissolves the cellulose, leaving
the cuticular cellulose imchanged in the form of flakes, whereas strong soda
lye dissolves the cutin from the cuticular cellulose, leaving the cellulose
portion of the cuticle as part of the normal cellulose of the fiber.

COTTON 611

the cotton is treated by confining it in a chamber or cell between
sieves or diaphragms, where it is treated successively with boil-
ing alkali, -with water, and with chlorine gas mixed with air,
which are caused to successively circulate through the chamber.
The bleaching of cellulose obtained from asparagus by treating
with alkaline sulfite lyes has also been suggested.^ In the process
of bleaching as elaborated by R. Buggenhoudt^ the fibers are
delivered in a lap or sUver to an endless apron and subjected to
successive sprays of a bleaching solution, e. g., sodium hypo-
chlorite. Between the aprons the fibers are conducted through
squeezing rollers, the operation of spray and squeezer being re-
peated imtil a tmiform and complete saturation of the fibers is
obtained. These are then automatically dehvered from the apron
into superposed layers into a tank, where they are steeped until
the bleaching operation is complete. Water at ordinary tempera-
ture is then run into a tank from the bottom and passed upward
through all the layers until thoroughly washed. After the wash-
ing is completed, the water is drawn off from the tank and the
lap or sliver taken to a hydro-extractor, and is then dried.

The ordinary bleaching process may be carried out in wooden
or stoneware vessels.' The vessel is fitted, for preference so that
the cleansing liquid may circulate through the cotton. The
strength of the bleaching solution varies from V2-l° Tw.* If
stronger solutions are employed some oxycellulose may be formed.

1. O. Reinke, D. R, P. 273389, 1912; abst. C. A. 1914, 8, 2806; Chem.
Zentr. 1914, 8S, I, 1796; Chem. Ztg. Rep. 1914, 38, 301; Wag. Jahr. 1914,
€0, II, 408.

2. U. S. P. 872097, 1907; abst. Chem. Ztg. Rep. 1908, 32, 137; J. Soc.
Dyers Col. 1908, 24, 141. In this connection, refer to E. Mann and J. Heess,

E. P. 24938, 1913; F. P. 464483, 1913; abst. J. S. C. I. 1914, 33, 478, 859.

F. Dobson, D. R. P. 260306; abst. Kunst. 1913, 3, 220. Barlow, E. P. 916,
1915; abst. J. S. C. I. 1915, 34, 10. A. Chaplet, Rev. gen. Chim. Pure et
appl. 11, 314; abst. Chem. Zentr. 1908, 79, II, 1391.

3. S. Trotman and E. Thorp, "The Principles of Bleaching and Finish-
ing of Cotton," 193.

4. To make a solution of bleaching powder, take bleaching powder
and stir it up with cold water to a thin uniform paste. Allow to settle a
sufficiently long time to have the upper layer a clear yellowish green color.
Run this clear liquid oflF and dilute it with water to a density (by hydrometer)
of 1.05. To each 1000 lbs. of cotton rags add 350 gal. bleaching solution and
60 pounds commercial HCl (assuming the HCl is 38% strength). Mix this
solution, immerse the neutralized textile in it and let stand all night, next
morning take out and wash in cold water until neutral and no chlorine can
be detected. If the bleaching powder is not 33% available chlorine and the
acidifying acid of strength assumed, errors proportionate to variations in
strength of above two will be introduced.

612 TECHNOLOGY OP CELLULOSE ESTERS

The bleaching solution remains in contact with the cotton for
about Vs"! hour, the liquid meanwhile being kept in constant
circulation. At the end of this period, the solution is drawn off
and water circulated through the cotton. In the same con-
tainer, or more preferably, in another similar vat, the cotton
receives a treatment with very dilute acid (V2 to 1%) preferably
with hydrochloric acid. With sulfuric acid there is a tendency
to obtain some calcium sulfate in the fiber. The stock is finally
washed free from acid, and then passed to the centrifugal wringer
for preliminary drying. The bleaching process may also be
carried out in a closed rotary vessel,* aild air, chlorine' or other
suitable gas added under pressure. To facilitate the entrance of
the solution into the fiber, E. Cadvert and A. Jost' first evacuate
the vessel containing the cotton and then introduce liquor or gas
under pressure. By this means the fiber is more readily impreg-
nated. In steaming cotton or flax, C. Cross and Parkes* use,
in addition to the special hydrolyzing agent, an alkali and a
mixture of soap with mineral or other oils. The presence of
these latter, it is claimed, effectually aids in the removal of the
by-products.

E. Simonsen* has investigated the action of bleaching pow-
der on cellulose materials generally. His conclusions were de-
rived from experiments on easy-bleaching Scandinavian sulfite
pulp, (a) The action of the bleaching solution is somewhat more
rapid in the early stages if the stock is kept agitated, but the
ultimate bleach consumption is the same whether the stock is
shaken or kept at rest, (b) At fixed concentration the higher
the temperature the more rapid is the bleaching, but the bleach
consumption also increases, (c) At fixed temperature increased
concentration of bleach solution results in increased consumption.
The most favorable bleaching conditions are at 20° with a solu-
tion containing 0.3% CI. (d) Nothing is gained in point of time
or efficiency by use of excess bleach over that required for re-

1. F. Dobson, E. P. 3801, 1913; al?st. J. S. C. I. 1914, 33, 196; C. A.
1914, 8, 2482. Addn. to E. P. 3181, 1911; abst. J. S. C. I. 1912, 31, 225;
C. A. 1912, 6, 1989.

2. Swiss P. 77516, 1918; abst. C. A. 1918, 12, 2439.

3. E. P. 8558, 1894; abst. J. S. C. I. 1895, 14, 569; J. Soc. Dyers Col.
1894. 10, 127.

4. E. P. 25076, 1899; abst. J. Soc. Dyers Col. 1900, IS, 41; 1901. 17,
30 39.

'5. Pap. Ztg. 38, 3523; abst. C. A. 1914, 8, 1202.

COTTON 613

moval of non-cellulose, (e) Bleached cellulose is very consider-
ably attacked by bleach solutions, especially in the concentrated
form, (f) Loss of weight of pulp in bleaching increases with
increased temperature, provided total amount of chlorme in the
solution is the same; the concentration of the solution has no influ-
ence within the limits studied, (g) No advantage is derived from
use of acetic add during bleaching (Lunge's process). The
use of adds, especially sulfuric acid, very slightly accelerates
the bleaching action but results in increased bleach consumption.
The fact that cellulose is partly altered to oxycellulose was
noticed in 1883 by G. WiW^ E. Berl and Klaye,^ and E.
Berl and W. Smith® have also studied the influence of the pre-
vious treatment of cellulose, espedally bleaching, upon the prop-
erties of the resulting nitrates in the laboratory, and C. Piest*
has subjected cotton to the following treatments: (1) Bleaching
for forty-eight hours in bleaching powder solution of 3°-5® B^. ; (2)
and (3), bleaching for eight days in solutions prepared by mixing
2-5 k. and 5 k. respectively of bleaching powder with 5 1. of
water; (4) mercerization by treatment with 18.5% caustic soda
lye for twenty minutes; (5) heating for ten hours at 150° in a
current of carbon dioxide. *° The results obtained showed that
with a given nitrating acid and temperature of nitration the
nitrocellulose prepared from strongly bleached cotton has a some-
what lower nitrogen content and a considerably higher solubility
in ether-alcohol than that prepared from ordinary cotton. The
solubility of the nitro-compound in absolute alcohol increases as
the cotton is more strongly bleached. Nitrocellulose from strongly
bleached cotton is more difficult to stabilize than that from or-
dinary cotton. The stabilized nitrocellulose is more soluble in

1. Bull. soc. ind. Rouen, 1883, 10, 416; U, 169.

2. H. Schmidt, Dingl. Poly. 1883, 2S0, 271.

3. Franchimont, Rec. trav. Chim. 1883, 241.

4. Noelting and Rosenstiehl, BuU. soc. ind. Rouen, 18&3, 170, 239.

5. Nastjukow, BuU. Soc. Mulhouse, 1892, 493.

6. J. CoUie, J. C. S. 1894, €5, 262.

7. J. S.C. I. 1907, 26, 1167.

8. Zts. Schiess. Spreng. 1909, 4, 81; abst. J. S. C. I. 1909, 28, 380;
Wag. Jahr. 1909, 55, 1, 431.

9. Zts. ang. Chem. 1909, 22, 1215.

10. D. R. P. 199885, 1908; abst. J. S. C. I. 1908, 27, 937; Zts. ang.
Chem. 1908, 21, 2233; Chem. Zentr. 1908, 7S, II, 466; Chem. Ztg, Rep,
1908, 32, 382; Wag. Jahr. 1908, 54, II, 355; Mon. Sci. 1911, 75, 93; 1916, U,
180.

614 TECHNOLOGY OI? CELLULOSE ESTERS

ether-alcohol than the non-stabilized product. Nitrocellulose
from mercerized cotton has a slightly lower nitrogen content, a
much higher solubility in ether-alcohol, about the same solubility
in absolute alcohol, and is more difficult to stabilize than that
from ordinary cotton. Nitrocellulose prepared from cotton which
has been heated in a current of carbon dioxide has a shghtly
higher nitrogen content, about the same solubility in absolute
alcohol and in ether-alcohol, and is more difficult to stabilize than
than that from ordinary cotton. O. Guttmann,^ has made ex-
periments during a period of two years with samples of cotton
from English and Gennan sources, the history of which is known,
from their obtainment from the cotton-spinning works to the
finished, and in some cases, stored nitrocellulose. Some of the
samples of cotton were unbleached, others had been strongly
bleached with bleaching powder, and some were highly contami-
nated with dust, etc. The results obtained confirm those of
Piest, namely, that the stronger the degree of bleaching of the
cotton, that is, the higher the content of oxycellulose, the more
difficult it is to stabilize the nitrocellulose obtained therefrom,
and the more soluble is the nitro-derivative in ether-alcohol, and
in addition the solution has a lower viscosity. The view formerly
held that in the bleaching process some cellulose is chlorinated'
is not supported by C. Schwalbe.^*^

The ideal bleaching process is one which would completely
remove by oxidation or otherwise, the impurities in the cotton,
leaving the cellulose completely unchanged. Although cellulose
is resistant to chemical action to a great extent, nevertheless
during the purification and bleaching process it is slightly attacked.
In order not to subsequently produce an imstable nitrocellulose,
it is necessary to limit the action of the bleachers on the cellulose
within small limits. With the attack of bleaching agents on the
cellulose, oxycellulose is formed. The presence of this latter is
shown by its properties of absorbing basic dyes more readily
than normal cellulose. H. Wrede has worked out a process
employing basic dye-products to determine the extent of the

1. Zts. ang. Chem. 1909, 22, 1717.

2. C. Cross and E. Bevan, J. S. C. I. 1890, Id, 450.

3. Zts. ang. Chem. 1908, 21, 302; abst. J. C. S. 1908, 94, i, 138.

4. Chem. Ztg. 1907, 31, 940; abst. J. S. C. I. 1907, 2€, 1107. Zts. ang.
Chem. 1908, 21, 302.

COTTON 615

bleaching treatment.^ According to J. Korselt,* the risk of forma-
tion of oxycellulose in the bleaching process may be reduced by
a fractional bleaching of the fiber. Hypochlorite solution is used
and the concentration is steadily increased with the progress of
the bleaching process. Even when no apparent change is notice-
able in cotton which has been bleached without careful control,
the material may be altered sufliciently to effect the resulting
nitrocellulose.^ R. Namias^ has examined samples of cotton which
had received excessive bleaching treatment. He found that
although the samples showed no weakness of fiber, contained but
traces of fatty matter and showed no apparent difference in appear-
ance from good cotton even when examined by the microscope, yet
when nitrated for varying periods from 2 to 24 hoiu^, the nitrogen
contents of the resulting nitro-products varied considerably. They
were incompletely soluble in ether-alcohol in every case because, it is
claimed, that they contained unnitrated cotton. Modifications in
the compositions of the nitrating bath did not correct this defect.
With properly bleached cottons, the results obtained showed that
in 2 hours the nitration was complete. The difference between the
two types of cotton is attributed to the presence of oxycellulose
in the overbleached cotton.

C. Piest^ employs five methods for the determination of the
degree of bleaching of cotton, (a) **Cotton wax method."^ (b)
**Cu numbers (Schwalbe's method'*)'"^® (c) '*Acid number

1. Chem. Ztg. 1909, 33, 970; abst. J. S. C. I. 1909, 28, 811.

2. D. R. P. 287240, 1913; abst. C. A. 1916, 10, 2048; J. S. C. f. 1916,
35, 174; Zts. ang. Chem. 1915, 28, II, 568; Chem. Zentr. 1915, 86, II, 768;
Chem. Ztg. 1915, 39, 407; Wag. Jahr. 1915, 81, II, 270.

3. E. Berl, Zts. Schiess. Spreng. 1909, 4, 81; abst. J. S. C. I. 1909, 28,
380; Wag. Jahr. 1909, 55, 1, 431.

4. Mon. Sci. 1918, 85, 5; abst. C. A. 1918, 12, 996; J. S. C. I. 1918, 37,
167-A.

5. Zts. ang. Chem. 1912. 25, 2518; abst. C. A. 1913, 7, 895.

6. C. Piest, Zts. ang. Chem. 1909, 22, 1215; abst. J. S. C. I. 1909,28,
746; C. A. 1909, 3, 2227. See also C. Piest, Zts. ang. Chem. 1908, 21,2497;
abst. C. A. 1909, 3, 485.

7. According to C. Schwalbe (Faerber Ztg. 1908. 19, 33; abst. J. S:
C. I. 1908, 27, 156) overbleached cotton reduces Fehling's solution, whereas
with pure cotton cellulose no such action takes place. By estimating the
amount of copper produced by the reduction of Fehling's solution, the degree
of bleaching of the cotton can be ascertained. A weighed quantity of cotton
is boUed with a measured quantity of Fehling's solution, the liquor being
well stirred during the reduction. The copper separated is filtered ofF,
washed with hot water, dissolved in nitric acid and estimated by electrolytic
deposition; the electrolysis is carried out in a platinum bowl with the aid
of a revolving anode. In this way the "copper value" for the sample of

616 TECHNOLOGY OF CELLULOSE ESTERS

(Vieweg's method.") (d) '*Ost*s viscosity method** (employing

cotton is obtained. Different varieties of cotton give different figures, those
for mercerized cotton being higher than those for ordinary cotton. The
"copper value" is referred to dry cotton. The moisture in the sample of
cotton is determined by using a toluol drying stove. The estimation is
recommended for application in the artificial silk industry.

8. C. Schwalbe, (Zts. ang. Chem. 1917, 30, 121; abst. J. S. C. I. 1917,
37, 707; C. A. 1917, 1, 3430) contends that in order to obtain trustworthy
results in the determination of Schwalbe's copper value for cellulose certain
precautions are essential. The alkaline tartrate solution should be freshly
prepared, since traces of sodium silicate dissolved from the glass will mater-
ally increase the copper value. For preparing the solution pure sodium
hydroxide made from metallic sodium should be used. It is dissolved in a
polished iron vessel which has previously been freed from fat by treatment
with alcohol and ether, and the potassium sodium tartrate is added to the
cold solution. Old copper sulfate solutions give too high results, and this
solution should also be freshly prepared. To avoid solution of silica the
distilled water should be kept in a stoneware instead of a glass vessel, and
rubber stoppers, which yield particles to the liquid, should not be used. The
method of boiling the Fehling's solution in Gnehm's apparatus has an influ-
ence on the results. The sides of the flask should be protected against over-
heating, by means of an asbestos screen, and the liquid should always show
numerous steam bubbles. After removal of the burner the supernatant
liquid is at once poured into a beaker, and the fibers in .the flask are rapidly
washed several times by decantation with water at about 80° C, and allowed
to stand covered with warm water while the Fehling's solution and washings
are being filtered. In this way the further deposition of copper which takes
place when dilute Fehling's solution is heated is prevented. Finally the
fiber residue is repeatedly washed and removed from the flask. Filtration
through paper (No. 595 Schleicher and Schtill) gives more uniform results
than filtration through asbestos in a Gooch crucible. The copper is dissolved
in nitric acid, and the solution allowed to stand for 1 to 2 days, and filtered
shortly before electrolysis. A blank determination should also be made,
and the amount of copper obtained should be deducted from the copper
value, but only a slight quantity of copper should separate in the blank test.

9. He (Zts. ang. Chem. 1914, 33, 567; abst. J. S. C. I. 1915, 34, 23;
C. A. 1915, 9, 23) finds in the determination of the cupric-reducing value of
cellulose (J. S. C. I. 1910, 29, 689), the limits of variation between duplicate
tests should not exceed 0.2 in the "copper value," but abnormal results, e. f^.,
values ranging from 0.6 to 1.3, may be obtained through the presence of cupric-
reducing impurities in the rochelle salt or the water employed. Commer-
cial specimens of rochelle salt frequently contain small proportions of oxalate,
which reduces the Fehling's solution on boiling and discolors the cellulose
at the conclusion of the test. Cupric reducing impurities have also been
found when condensed steam contaminated with volatile oily matters was
used for making up the reagents. The solutions used should always be con-
trolled by a blank test, by adding the hot mixture of 50 cc. of each of the
ingredients of Fehling's solution to 400 cc. of water and boiling for 15 mins.
under a reflux condenser. The liquid should neither turn greenish in color
nor deposit a precipitate of cuprous oxide on standing. If pure normal
cotton has been boiled with the mixture, it should show no brownish dis-
coloration. In performing the determinations, the heating arrangements
must be adjusted to avoid over-heating of the walls of the flask, as drops of
the liquid thrown against the heated glass by the stirrer may be decomposed,
forming products which affect t^e results.

10. Zts. ang. Chem. 1909, 22, 197; abst. C. A. 1909, 3, 1143; J. S. C. I.
1909, 28, 216; Bull. Soc. Chim. 1909, €, 552; Rep. Chim. 1909, 9, 490; Chem.
Zentr. 1909, 80, I, 840; Chem. Ztg. Rep. 1909, 33, 120; Jahr. Chem. 1909.
82, II, 385; Wag. Jahr. 1909, 55, II, 514.

COTTON 617

solution of cellulose in ammoniacal copper sulfate), and (e) '*The
copper sulfate method.**

B. Johnsen,^ in the case of wood-cellulose, measures the de-
gree of bleaching by the action of nitrous acid solution followed
by dilute alkali treatment. In the early stages of the bleaching
treatment a brown color is produced on a test sample by this
treatment; when the bleaching process is complete, however,
these reagents give no color with the cellulose material.

The process of bleaching after the cotton is nitrated,*^ has
never passed beyond the stage of patent protection.'

After the bleaching treatment the cotton is washed with
dilute acid (souring) to remove traces of the hypochlorite bleach.
This operation is followed by thoroughly washing with water.
Some matting of the fiber usually occurs and the cotton may
require an opening out (see Teasing).

S. Higgins^ has observed the rate at which oxygen is evolved
from bleaching powder solutions, and from sodium peroxide
solutions when in contact with cupric oxide, the oxygen being
measured at definite intervals of time. He found that although
oxygen was evolved more rapidly from the peroxide solutions,
when the results were plotted, the curves were very similar in
nature, thus pointing to the similarity of the chemical actions
taking place to cause oxygen evolution. The addition of lime to
the bleaching solution caused a retardation of O evolution, whereas
the addition of small amounts of hydrochloric acid had an oppo-
site effect.

While it is known that the addition of these chemicals to
bleaching powder solutions has a similar effect on the bleaching
properties of the latter, also the addition of alkali increases the
stability of hypochlorites in air, and the addition of acids has a
contrary effect. Higgins concludes that during the decompo-
sition in the air, in contact with cupric oxide, or in the bleaching
vat, hypochlorites undergo the same decomposition, the oxidiz-
able matter in the bleaching vat merely using up the nascent

1. Papicrfabr. 1913, 11, 979; abst. J. S. C. I. 1913, 22, 863.

2. G. Mowbray, U. S. P. 349658, 1886, the pyroxylin being decolor-
ized by a hydrochloric acid acidified solution of oxalic acid.

3. For structure of cotton fiber as affected by bleaching, see G. Witz,
Bull. soc. ind. Rouen, 1883, 10, 416. Nastjukow, Bull. Mulhouse, 1892, 493.
R. Haller, Zts. Farb. Ind. 1907, 6, 126.

4. Text. Col. 1919, 41, 277; abst. C. A. 1919, 13, 3017.

618 TECHNOLOGY OP CHLLULOSH BSTBRS

oxygen which in other cases would ordinarily be evolved.

R. Taylor maintains^ that with linen, chlorine or hypo-
chlorous acid will not bleach linen, and that a hypochlorite must
be present. He alleges that cotton and linen contain two color-
ing matters of the same general characteristics, a statement
brought into question by S. Higgins.*

In endeavoring to find a rapid method of bleaching without
chlorine or other oxidants, and to avoid the deposition in the
cotton fiber which requires careful machine washing, R. Weiss'
has experimented with the hydroxides of calcium, strontium and
barium as saponifying agents, and has been able to show that
for molecular equivalents of the three bases, barium hydroxide
was less active than the other two, which were about equal to
each other. As bleaching agents, the calcium and barium com-
pounds were about equal, but strontium hydroxide was about
three times as rapid and more complete than calcium hydroxide.
E. GilUeron is of the opinion that the use of strontitun hydrox-
ide is impractical on account of cost, and that under certain con-
ditions strontium compounds exercise a destructive action upon
the .fiber.

E. Cadoret* has described an improved process for bleaching
depending upon the principle that a liquid or gas injected into
the pores of any substance penetrates more completely if it meets
no elastic medium in its course, and consequently if the air with
which the cotton is impregnated be removed, the bleaching com-
position will readily take the place of the latter. The A. de
Vains process* is similar. E. Watremez* bleaches cotton fiber
by means of a metallic salt whose oxide is soluble in an excess of
alkali.

In the patented method of I. Bronn^ a partial vacuum is
employed, the air being withdrawn imtil the material boils vig-

1. J. Soc. Dyers Col. 1914, 30. 85; abst. C. A. 1915, 9, 1120.

2. J. Soc. Dyers Col. 1914, 30, 326, 1257; abst. C. A. 1914, 8, 255.
3369; 1915, 9, 1120. J. C. S. 1913, 103, 1816.

3. BuU. Soc. Mulhouse, 1914, 84, 499; abst C. A. 1919, 13, 76.

4. E. P. 8558, 1894; abst. J. Soc. Dyers Col. 1894, 10, 127.

5. U. S. P. 1106994, 1914; abst. J. S. C. I. 1914, 33, 916; C. A. 1914,
8, 3363; Chem. Ztg. Rep. 1915, 39, 328; Mon. Sci. 1914, 81, 191. F. P.
449497, 1912; abst. J. S. C. I. 1913, 32, 482. A. de Vains and J. Peterson,
Belg. P. 260042, 1913.

6. Belg. P. 253529, 1913.

7. E. P. 12319, 1901; abst. J. S. C. I. 1902, 21, 857; J. Soc. Dyers CoL
1901, 17, 210; 1902, 18, 198.

COTTON

619

orously at 40**. In this manner, it is sought to more rapidly
exhaust the air from the interior of the cotton filament, and cause
a more ready and complete penetration of the bleaching solu-
tion without injury to the desirable qualities of the fiber. ^ The
opposite effect is produced in the J. Vanlohe method,* who first
compresses the cotton and then subjects to the action of bleach-
ing liquids. F. Ferrand' adds formaldehyde to the bath to pro-
tect against the possible formation of hydro- and oxy-cellulose.
In a study of the chemistry of bleaching made by J. Hebden,*
samples of cloth taken from goods being regularly bleached after
the caustic boiling process were examined at different stages with
the following results:

PERCENTAGES OF ORIGINAL SUBSTANCES REMOVED AT THE

END OF EACH OPERATION

Steep

First
Boil

Second
Boil

Chemick

Sour

Ash

%
70.6

• • • •

6.6
60.0

%
87.3

91.5

20.4
100.0

%
95.4

91.7
64.0

• • « •

%

93.0
92.2

67.8

• ■ • ■

%

95.0
92.7

60.6

• • • •

Proteins (N X 6.25) . . .
Fats and waxes (ether
extract)

Bhosphoric acid

The samples were also submitted to wetting-out and steam-
ing tests, and it is concluded that the yellowing produced by
steaming is due to the proteins rather than to fats and waxes.
It is suggested that the bleaching process be controlled by ulti-
mate analyses of the cotton, checked by determinations of ash,
and of ether and alcohol extracts.

Preliminary Drying. After kier, bleaching and souring
treatments, the cotton may yet receive a ** wet-picking." It then

1. Bleachers Assoc, and Higgins, E. P. 131798; abst. J. S. C. I. 1919,
3S, 700-A.

2. U. S. P. 297319, 1884; abst. J. A. C. S. 1884, G, 205.

3. E. P. 12086, 1914; abst. J. S. C. I. 1915, 34, 830. The foUowing
reports on the bleaching of wood and other forms of celluloses previous to
nitration have been issued by the "Poudrerie Nationale D'angouleme," Compt.
rend. No. 1, April 6, 1917. No. 39856-6, Sept. 20. 1915. 21521-B6, June
11, 1916; 12156-F6, April 1, 1916; 38008-6, Sept. 8, 1915; 8473-F6, March
6, 1916; 4360-B6, January 30, 1917; 1224-B6, January 10, 1917; 4106-B6,
Jan. 29, 1917; 4796, December 27, 1916.

4. J. Ind. Eng. Chem. 1914, 6, 714; abst. C. A. 1914, 8, 3632; J. S. C.
I. 1914, 33, 969.

620 TECHNOLOGY OP CELLULOSE ESTERS

remains to dry the cotton before nitration. The drying process
is usually carried out in two stages. As much water as possible
is removed mechanically by rinsing or hydro-extraction. This
operation constitutes the preliminary drying. The final drying
is carried out by methods depending upon the evaporation of
the remaining moisture. (See topic Final Drying.) An efficient
type of rinser is made by the C. G. Sargent's Sons, Graniteville,
Mass. (see Fig. 17). The machine is fed by an automatic feed
into the hopper and from there is gradually and evenly delivered
to the rinser. Extending the entire length of the bowl and form-
ing a partition thereby is a perforated brass false bottom, 13
inches from the top of the bowl and below which no cotton passes.
Operating above this false bottom and suspended from overhead
is the rake or harrow with solid brass teeth which by its action
continually passes the cotton, while fully immersed in'the washing
bath, from the feed end toward the delivery end of the machine.

Fici, 17— Sabcbnt Drying Cotton Rinsbr

At the forward end of the bowl is an independent rake or carrier
which operates at a faster speed than the rake and which further
passes the submerged cotton in a thin sheet into the press rolls.
The press-rolls are 12 inches in diameter and are made of solid
metal. The top roll is wound with some form of resilient material
in order to obtain the best results from squeezing. The press-
rolls exert a pressure of from 8 to 10 tons and leave the cotton
ready for the removal of the residual moisture by the usual
evaporation methods. The cotton may receive an intermediate
picking between the rinser and the drier.

Tea^ng. As obtained from the factory, cotton waste eon-
tains colored threads which must be removed by hand, and often
a considerable amount of foreign matter — wood, iron, rubber and

l\

622 TECHNOtXXJY OF CELLULOSE

strings — as well as knots and hard lumps. These are removed by
a carding machine, where, by means of a series of iron-teeth
rollers, the fiber is pulled out and separated, and the lumps opened
up. The apparatus of J. France' is useful for this purpose.

The form of teasing machine, as used at Waltham Abbey,
London,* consisted of a combination of rollers armed with iron
teeth y/hich separate the fibers of the cotton and opened out
knots and lumps. The cotton, as it leaves the teasing machine,
is delivered on to an endless band which carries it to the drying
machine. The stock, especially if it contains a large amount of
foreign material, is again hand-picked in its passage to the drying

Fig. 19. — Coooswell Mn.L

apparatus. The old procedure, as used in conjunction with the
Abel process, was to cut the teased cotton in a type of guillotine
into three-inch lengths. This operation is not commonly carried
out now, as it was found that the cotton, along the cut edges,
was felted together to such an extent as to resist the action of
the mixed acids in nitration.

Where short or long-fiber cotton is used as the source of
cellulose rather than cotton waste, two methods of separating
and picking are used in the United States, depending on the
length of the cotton fiber. For that length corresponding to
"linters" and longer, the Davis & Furber "Mixing Picker" with

1. E. P. 2(m4. 1880; 5364. !890,

2. F. Nathan, J. S. C. I. 1909, 28, 180.

§3
3 I

? i

624 technoixx;y of cbllulosb esters

pin-feed roll and shell (see Fig. 18) is the type of machine giving
most satisfactory results.* In recent years, however, the appli-
cation of cotton has been greatly extended by the gradual use of
fibers of shorter length, and for picking such cottons the "Coggs-
well Mill" (see Fig. 19) has been the type widely used, it con-
sisting of two-ribbed disks revolving at high speed in opposite
directions.* By means of connection with a Sturtevant or other
suction blower and pipe connection to the dry house, which is
usually located near the picking house; the cotton, after passing
through the picking machine, is automatically carried over to the
dry house, where by means of shut-offs located in tlie carrying
pipes in the several drying chambers, the cotton may be bloMm
into any dry-room desired.

The time of beating, during the purification of nitrocellulose,
is reduced when the cotton has previously been teased by the
methods already given, i. e., material is passed through a Davis
& Furber **Mixed Picker,** and then automatically by pipes
through a Coggswell mill. The Cellulose Manufacturing Co.,
Waldhof finds that, for the preparation of cellulose hexanitrate,
it is advizable to have the cotton not only pure, but as uniformly
distributed as possible. After freeing from incrusting matter
and all soluble impurities, the cotton is thoroughly dried and

1. The machine is heavily constructed, consisting of a main cylinder
fitted with special teeth, together with a feed apron and roll. The cotton
is received by the feed apron, carried to the feed roll, the latter holding the
stock while the revolving teeth in the cylinder tear it apart. The cylinder
revolving at high speed carries the disintegrated cotton around and throws
it out at the back of the machine, or into a suction pipe, where it is carried
over into the dry house. These machines, which are of large capacity, open
up the cotton in such a manner as to make it fluffy and feathery in appearance.

2. Manufactured by the A. & F. Brown Co., New York City. The
mill is run with two belts, one cross and one straight, which drive the grind-
ing disks in opposite directions at a speed of about 2,000 revolutions per
minute. All that is needed for the successful operation of the mill is a well
built, well balanced counter-shaft for high speed, with a friction-clutch pul-
ley for starting the mill up slowly, and a heavy immovable foundation, so
there will be little or no vibration. When properly set up, the mill requires
no skilled labor to operate. The only adjustment needed is in the turning
of the tail pin one way or the other as the material may be wanted, coarser
and finer. After the mill has been running a few months it is good practice
to reverse the belts, thus giving a fresh wear to the grinding surfaces. The
plates are about the only parts which may require renewing, and under favor-
able conditions may last upwards of two years.

3. E. P. 336, 1891; abst. J. S. C. I. 1892, U, 180; Mon. Sci. 1892.
49, 166. In this connection see the disintegration method of treatment of
cotton mentioned elsewhere in this work by the Dynamit Akt. Ges., D. R.
P. 4410, 1878; abst. Ber. 1879. 12, K, 712; J. A. C. S. 1878, 1, 303.

TBCHNOWHJV OF ceU.Ul.OS8 8STBRS

corroK 627

then disintegrated in a specially constructed disintegrator. The
stock is passed through the apparatus several times until treat-
ment of a sample of the material with the usual mixed acids gives
a product which passes definite specification tests.

Where cotton waste is used composed of card room and
spinning room sweepings, roller laps and similar materials, which
are composed of "soft" waste mixed with a fair proportion of
threads, a * 'thread extractor** as shown in Fig. 22 is useful. The
machine shown in the illustration is made by W. Tatham, Ltd.,
Rochdale, England, and takes the place of the former slow and
tedious process of hand picking. The material to be treated is
placed on the tray attached to the cover Of the machine, and is
then passed through a ftmnel at the right-hand side and fixed
directly over one of three spiked rollers which are caused to re-
volve at high speed in order to thoroughly loosen the material
so that the "soft** may be separated from the thread waste. The
thread portion is retained by the spiked rollers around which they
are wrapped, and from which they are periodically removed by
a special form of knife drawn by an attendant along a groove in
each roller.

In the picking or teasing process, it may be desirable to first
break the knots and hard lumps of waste before it is fed into a
waste opening machine. By so doing, the waste is rendered soft
so that it can be much more evenly fed on the feeder bed or
plate. The Gamett Preparer or Knot Breaker shown in Fig, 23,
is useful for this purpose. Attention is drawn to the advizability
of a thorough opening out of the cotton stock as an aid to uniform
and ready nitration.

Willowing. The process of separating or blowing out the
fly, dust, etc., and disintegrating the cotton is known as willow-
ing. This operation may be carried out after the bale is opened
or after the cotton is dried, depending to a large extent on the
t3rpe of the cotton waste. A usual form of willower consists of
a machine fitted with a revolving drum composed of three cast
iron rings keyed on to a steel shaft. To these rings are attached
wooden lags each fitted with cast iron teeth. The cylinder re-
volves at about 350 revolutions per minute and strikes the material
down from the feed rollers. Below the lower shaft of the cylin-
der is fitted a grid constructed of flat steel bars set at a suitable

TBcHNoux;y or crixulosb sstbrs

COTTON 629

distance apart and through the space thus formed dust and for-
eign matter fall. Fly and fine material is removed by means of
a fan and piping to a large cyclone chamber. The heavier matter
which collects beneath the chamber is collected at intervals.
Along the cylinder and carried by the sides of the cover are
usually two slowly revolving toothed rollers which in conjunction
with the cylinder serve to loosen the material previous to delivery.

The willowing machine shown in Fig. 24 is made by J. Hether-
ington & Sons of Manchester, Eng. It is used mainly with soft
wastes (such as lump yam strippings, roller waste, scutcher drop-
pings, etc.). The machine is fitted with feed and delivery lat-
tices which travel at a uniform speed. The motion of the feed
is intermittent, and may be adjusted so as to allow the charge of
cotton to remain in the machine for any necessary period, in
order to obtain the required cleanliness. The apparatus is fitted
with special "willow teeth" by the use of which the cotton is
distributed laterally over the periphery of the cylinder, and is
disintegrated and cleaned from dirt very effectually. When the
bale is opened and the cotton cleaned and willowed, it still may
contain cop-cottons and other hard wastes. The material in
this condition is not suflRciently uniform for nitration. It is
necessary to open these lumps by teasing or picking machinery.
The fly and other cotton material which collects in the cyclones
is*drawn from the machines by the suction of the fan attached to
the former. A cyclone is an inverted conical vessel usually about 8
feet in diameter at the widest point and 9 feet in height. The current
of air which draws in the fly and fine cotton enters tangentially
at the top and gradually falls until at the apex, the fly enters the
cupboards from which it may be taken at intervals for retreat-
ment. A chimney to carry away the excess of air passes from the
top of the cyclone through the roof.

The fly and other material which gather under the various
machines and in the cyclones contain much good cotton and in
order to extract this it is retreated in automatic willowing machines.
The latter may be similar to the willowers already described, but
is fitted, in addition, with a time gearing which operates the feed-
ing lattice at definite intervals and also governs the period of
willowing. From this machine three products are obtained. (1)
Good long fiber cotton which is blended with current unteased

TBCHNOLOGY OF CBLLULOSB ESTBRS

632 TECHNOUXJY Olf CELLULOSE ESTERS

waste. (2) Rejected material containing much grit and sand
(Scroll). (3) Fine cotton dust which is abstracted by a fan and
deposited in a separate cyclone. The second or scroll portion is
again retreated three times in order to save as much good cotton
as possible, and an overall recovery, varying from 30% to 50%
on the original weight of fly is obtained. In a machine with
a 4' 6' feeding lattice and a 14' delivery belt, 0.5 ton of fly may
be retreated per day with ease.

Conveying. It is necessary at various periods during the
purification treatment to convey the cotton from one machine to
another. When these machines are close together, there is not
much difiiculty in transferring the stock, but in some cases, as
when the cotton is sent long distances, there is need for special
conveyers in order to save unnecessary handling and labor. Con-
veyers may be used between each stage in the purification of
cotton. They are particularly useful, however, at certain points.
After the opening of the cotton bale, the cotton may be sent by
a conveyor to the picker. An opener, equipped with such a con-
veyer, ismadebyP. Gamett, Cleckheaton. The conveyer at this
stage not only saves labor, but prevents the formation of dust
in the atmosphere. The cotton is also thoroughly circulated
through the fan and in the tubes and exhaust box; in consequence,
the blending is much improved.

After the cotton has passed the washers, it requires trans-
ferring to the bleachers or steeping boxes. At this stage, convey-
ers are also useful. Again, after teasing, the cotton will require
conveying to the dryers.

An endless band or chain connected together by cross-rods
is a type of conveyer often employed. The cotton may also be
forced through a pipe by means of a blower from the picker to
the dryer.

Another method of conveying is to feed the material itito
enclosed or open pipes or troughs through which liquid flows
carrying with it the cotton material.^ The pipes or troughs may
be mounted on pivots so as to be capable of inclination in either
direction and may be provided with outlets or gates for discharge

1. T. Taylor, N. Beswick, E. Jenkins, E. P. 104214, 104524. 1916;
abst. C. A. 1917, 11, 2048; J. S. C. I. 1917, 36, 451.

634 TECHNOUKJY OP CEtI.UU>SE RSTORS

at any desired point^ in the conveying apparatus or machine.

Final Drying. As the cotton leaves the teasing or picking
machines, it invariably contains 6%-10% moistm'e, and 85%-90%
of this moisture should be removed before the nitration stage.
If the cellulose is to be acetated, a higher percentage of moisture
is permissable. If the cotton is not dried to this extent, it be-
comes difficult to obtain uniform nitrations, and the fiber is prone
to '*fume off" during nitration. Furthermore, there is added
dilution with water of the waste nitrating acids, and their per-
petual rejuvenation, therefore, becomes increasingly difficult and
expensive, necessitating the use of nearly absolute nitric acid and
ol6um. Another point is, that in the nitration of cellulose con-
taining relatively large amounts of moisture, often an undue
amount of cellulose passes into solution or suspension in the
nitrating acids, rendering special clarification imperative if the
acid is to be continually fortified for use again.

It must be remembered that although a cellulose containing
but 3 or 4% of moisture may cause but a small alteration in the
composition of the mixed esterifying acid as a whole, yet in the
immediate vicinity of the fibers the dilution of the acid may be
appreciable. With this lack of uniformity it becomes increasingly
difficult to control the nitration process so as to obtain depend-
able esters from the viewpoint of uniformity and stability. Cotton
containing much moisture usually gives decreased yields, and
such a pyroxylin, when dissolved in such solvents as acetone and
amyl acetate, produce lacquers with a decreased adhesiveness to
wooden and metallic surfaces. For this and othe^ reasons, it is
of paramount importance that for nitration the cellulose should
not contain over 1% moisture when immersed into the esterifying
bath, and for acetation, the moisture should not exceed 4%,
although cotton can be acetated containing a higher percentage
of moistiu-e than can tissue paper, other factors remaining the
same. However, the question of moisture in the acetation of
cellulose is exceedingly important, due to the action of the cat-
alysts and dehydrating agents employed in the normal ester-
izing bath.

In one method of cellulose drying, the cotton is placed in

1. In this connection, see E. P. 13626, 1889; 5560, 1891; 11929, 1899;
abst. J. S. C. I. 1890, 9, 856; 1900, 19, 689.

636 TECHNOI/X^Y OP CHUAJU>SH BSTHRS

large steam jacketed iron cylinders, the circulation of steam in
the swTounding jacket being so adjusted that a temperature of
70^-90^ is maintained in the interior. It is not customary to dry
cellulose for esterification at temperatures above 95°, and pre-
ferably between 80° and 90°. This applies particularly to cellu-
lose intended for soluble nitrocellulose (the lower nitrated deriv-
atives). When the latter is to be manufactured, it is inadvisable
to use cotton which has been wetted after drying, and then re-
dried. It has been found that the cotton after the second drying
is slightly more brittle, especiaDy the outer layers of the indi-
vidual filament. The difference between a once-dried and a
twice-dried cotton can also be detected in the ease and com-
pleteness of solution of the nitrocellulose in a given solvent or
solvent combination.^

Circulation of air during drying is maintained by means of
a compressed air reservoir, and may enter the cylinder at either
the top or bottom. The hot air preferably enters at the top so
that the first heat is blown directly on to the cotton most com-
pletely dried, and then the heating is gradually extended across
the length of the chamber to the cotton containing the greater
proportion of moisture. At the end of five or six hours, the
moisture content has been reduced to the minimum of 0.6%.

An alternative method of drying consists in placing cellulose
in a large room on wire screens heated from below by means of
a series of steam pipes, a slow current of air being aspirated under
the shelves and through the cotton mass. As soon as the drying
p/ ocess has been completed, the heat is sometimes continued until
the cotton is to be used, or, more usual, the cotton is removed,
weighed out into batches and placed in air-tight containers as tin
milk cans, where it is stored until ready for use. Cotton is always
allowed to cool before nitration, although several methods have
been proposed whereby the cellulose is immersed into the ester-
izing bath at a temperature equal to or greater than that of the
acid bath. Less equipment is required to dry a given weight of

1. H. Hofmann, Papier Ztg. 1906, 32, 433, has called attention to the
chemical change which sulfite cellulose and paper undergoes when being
dried, which begins at a temperature of about 90°, and is dependent upon
the temperature and time of heating. This change renders the cellulose
more susceptible to attack by acids, but the sugar obtained by hydrolysis
is the same (xylose). Straw, wood and rye are said not to be affected by
drying at 100°.

638 TECHNOLOGY OF CELLULOSE ESTERS

cotton per unit length of time, where the cotton is taken out of
the dry box as soon as dried and stored into air-tight receptacles
until ready for use.

The drying process as carried out at Waltham Abbey, Lon-
don, is as follows:^ The cotton as it leaves the Ceasing machine
is delivered on to an endless band which carries it t(^the drying
machines. The cotton slowly passes through the machine, and
issues at the end after about 45 minutes, with 0.5% moisttu'e
contained therein. The dry, hot cotton is then quickly weighed out
into charges suitable for nitration, placed in sheet-iron boxes or other
suitable receptacles with tight lids, and allowed to cool for about
eight hours. Dining the cooling the moisture content of the
cotton rises to about 1%, which is the amount of water con-
tained in it, when it is plunged into the nitrating bath. Dtuing
the passage, of the fiber through the drying compartment, it is
heated by a blast of hot air supplied by a fan or centrifugal
blower, and warmed by a steam heater.

In some factories after .the cotton has been dried, carbon
dioxide gas from a cylinder is blown into the dry cotton until
it is used. This practice is advantageous when the cotton drying
units are situated close to the nitrating house, and the air may
contain an appreciable amount of nitrous fumes.*

The A. Solod cotton dryer' comprises a rotary cylinder
mounted on roils in an inclined position, carriers at either end to
feed and discharge the material into and out of the cylinder, and
a perforated pipe in one side of the cylinder, through which heated
air is forced from a hot air chamber.

In the B. Sturtevant method, the cotton is first passed
through an opening machine or picker, then through an arrange-
ment called by them the Empire Duplex Gin Company's C. O. B.
machine. This process reduces the moisture content of ordinary
staple cotton to about 2%. A small supplemental blower with

1. F. Nathan, J. S. C. I. 1909, 28, 180.

2. Whereas a normal bone-dry cotton will average 0.4% nitrogen
content when prepared for nitration, it has been found that when in dose
proximity to the nitrating house for some length of time, the nitrogen per-
centage will gradually rise to 0.8%-0.9%, and in heavy, foggy and rainy
weather to as high as one per cent. It is claimed that cotton which hiu
previously been charged with carbon dioxide nitrates more evenly and uni-
formly. This method of protecting dry cellulose has been used mainly in
those factories producing nitrocellulose for artificial silk formation.

3. U. S. P. 1238589, 1917; abst. J. S. C. I. 1917, 36, 1126.

640 TECHNOLOGY OP CBLLULOSE ESTERS

heater finishes the drying process after the fiber has been placed
in small bins. Thence it is handled as soon as dry by another
blower which carries it to the nitrating plant.

The Proctor and Schwartz, Inc., of Philadelphia, Penna.,
have devized an automatic continuous system of drying. The
apparatus is made of fire-proof material, is extensively used for
this purpose, and is shown in detail in Figs. 26 to 31.

The apparatus is made of steel. The roofs of the dryers,
as shown in illustrations, are insulated with asbestos and auto-
matic fire-extinguishers located within the machine. Steam is
used for heating, the coils being located in compartments at one
side of each dryer, and the machinery parts may be either motor
or engine driven. A mechanical conveyer system takes the
moist cotton to the hoppers of the automatic feeds, located at
the end of the dryers nearest to the teasers. Spiked feed aprons
deposit the cotton in a uniform layer of the proper thickness on
slowly moving conveyer screens. These carry it through the
drying machines in about 30 minutes. Dtu*ing this time it is
continuously subjected to the drying action of large volumes of
moderately heated air in rapid circulation. Upon reaching the
end of the machine in a uniformly dry condition the cotton either
falls directly on the floor, into containers, or into a second hopper
from which it is conveyed to any desired point.

In the 'Troctor'* automatic dryer system, the cotton is
thrown into the hopper of an automatic feeder at the feed end of
the machine. The feed automatically distributes the cotton on
an endless conveyer which carries it through successive chambers
graded from a moderately high heat at the feed end to a low tem-
perature at the exit. Heated air is recirculated alternately
through the material and the heating coils. In passing through
the apparatus, the cotton is subjected to the opening action of
rapidly revolving "kickers'* or beaters. To this feature most of
the efiiciency of the machine, it is claimed, is due. Not only is
uniform drying obtained, but the air-blast material assists in
cleaning the cotton of dirt and grit which have resisted the earlier,
cleaning processes. The dirt falls to the floor and is removed
through doors placed in the side of the dryer.

In their single conveyor type (Fig. 26), the dryer consists
essentially of metal housings built up in sections on a structural

COTTON 641

steel framework. Pans for recirculating the warm air, steam
coils for heating the air, exhaust for moist air and intake of dry
air, and either one or three wire screen conveyors for carrying
the cotton through the machine, are all located inside the hous-
ing. An automatic feeder is provided to evenly distribute the
cotton in a thin uniform layer on the dryer conveyor.

The metal housing is made in sections so that it may be
easily removed, or units added to increase the capacity. The
dryer is divided into two compartments from end to end by a
metal partition, one containing the steam coils and the other the
conveyors. The fans are moimted on horizontal shafts and are
located in the partition between the coil and conveyor chambers.
The bearings of the fan shafts are all outside the enclosure, apart
from the heat, and yet low enough to be reached from the floor.
Fig. 28 shows the single conveyor dryer viewed from the delivery
end.

The Proctor three-conveyor cotton dryer (Figs. 29, 30) is stated
to be capable of handling two and one-half times as much cotton
as a single conveyor dryer of the same length of main body, ex-
clusive of the self-feed, and therefore is only recommended where
large production is required. As the height of the three-conveyor
dryer is considerably more than that of the single conveyor tjrpe,
the height of room available will often be the determining factor.

The single and three-conveyor dryers operate on the same
general principle, except that in the latter, the cotton is carried
through the machine three times, and is dropped from one con-
veyor to another, twice. In the single conveyor type, the cotton
passes through the housing but once. The imits of both are made
up in three widths, i. e., four, six, and nine feet. The length
depends upon the number of units necessary to insure the capacity
desired.

In Fig. 31 is shown in detail the interlocking sectional con-
veyor of the roJler chain type used only in this form of cotton
dryer, the individual sections of wire screen being 12 inches wide,
and are bent over on the edges as shown. The sections interlock
over a pipe which acts on the principle of a door hinge, the ends
of the pipe fitting over studs on the roller chain on each side,
while the ends of the screen are covered top and bottom by

642 TECHNOWK>Y OF CELLULOSE ESTERS

flanges on the chain. The figure shows a side view of the chain
with two wire screen sections attached.

The manufacturers claim for this type of dryer — ^which has
been used extensively in the United States for drying not only
cotton, but a wide variety of products as well — the following
points of superiority:

1. Economy in operation both in boiler house power, owing
to the recircidation of air, and motive horse power owing to the
large diameter of fans moving at comparatively slow speeds, and
yet circulating the maximum amoimt of air.

2. The roller chain type conveyor, which rolls, not drags,
through the dryer.

3. The pre-heating device on the delivery end of the dryers
tends to cool the material coming from the conveyor, and at the
same time warms the dry, fresh air which is being taken into the
dryer.

4. The machine being substantially fire proof, and the abso-
lutely uniform drying of the material on the conveyor from one
side to the other, is of especial importance.

The method of Rosenberg^ for drying in enclosed chambers
consists of mechanical devices for regulating the entrance and
exit of air, and was designed primarily for the drying of varnishes
and resins.

Saco-Lowell Method of Cotton Preparation. The follow-
ing description and illustrations (Figs. 32-36) indicate the gen-
eral method of preparatory cotton treatment as devized and per-
fected by the Saco-Lowell Shops of Boston, Mass.

For cleaning the cotton or waste, a vertical opener with
bale breaking feeder attached is employed, as indicated in Pig.
32, comprizing a heavy framework, each of the four sides and top
being cast in one piece. Large clean-out doors are provided, also
small doors at the bottom of sides for cleaning. The production
is 6000-10000 poimds per 10 hours. The stock is run through
this machine which delivers it into a pipe and can be conveyed
by air to any desired location. At the end of this pipe is a con-
denser (Fig. 34) consisting of a screen with air passages from

1. E. Rosenberg, E. P. 12070, 1913; abst. C. A. 1014, 8, 3636; J. S.
C. I. 1913, 32, 1147. For the Norton apparatus for drying cotton previous
to nitration, see Dingl. Poly. 1861, 160, 428. The Semper method is described
in Dingl. Poly. 1866. ISO, 344.

644 TECHNOLOGY OF CBLLUU)SB ESTERS

each end, these passages being connected to a fan, as above de-
scribed.

This fan draws the cotton from the vertical opener through
a pipe to a screen on the condenser, the air, and dust, going
through the condenser and fan blower into the separator. By
this method the stock drops from the condenser screen into a
bin, truck or machine, as desired. . To provide additional clean-
ing, the stock is taken from bins and run through a breaker
picker, as illustrated in Pig. 35, and from there to a finisher lapper
(Pig. 36). The stock may be taken off in card form if desired,
and then is in condition for boil-off and bleaching, preliminary
to drying before nitration.

Treatment of Cotton for Esterification in Great Britain.^ In

the manufacture of nitrocotton, purified waste cotton from the
spinning mills is mostly used, this material having been adopted
by the Government many years ago. As the demand for the
material increased, a special industry for its collection and treat-
ment came into being in the cotton spinning districts. The raw
waste is in a more or less dirty condition, the series of treatments
to which it is subjected consists in freeing it from the various
impurities picked up in the spinning mills, in order to leave, as
far as possible, only normal resistant cellulose.

Formerly there was little connection between the cotton
waste bleachers and the explosive manufacttu'ers, the treatment
of the waste being carried out by various firms each with a process
of its own. The practice at this time was to buy to specification,
but not to interfere with methods. The waste manufacturers
had, of course, no knowledge of the effect of their processes on
the resulting nitrocotton, and on the other hand, the explosive
manufacturers were imf amiliar with the details of the treatment
to which the waste was subjected.

With a colloidal body like cellulose, which cannot be purified
by crystallization, it has come to be recognized that conformity
to certain tests is not always indicative of purity or suitability
for certain uses, it being desirable that the history of the material
should also be known. An important step in the direction of

1. For data contained in this topic, and elsewhere in this work, the
author is indebted to Nobel's Explosives Company, their technical staff,
and to Mr. F. W. Jones.

646 TECHNOU>GY OF CELLULOSE ESTERS

closer connection and greater chemical control was taken when
Nobel's Explosives Company, some years ago, took over a tnill
and started waste manufacture on their own accoimt. Various
improvements and refinements were introduced by them — ^notably
the omission of bleaching with chlorine, which had hitherto been
considered an essential part of the treatment, but which is now
recognized may produce harmful effects — ^were introduced, and
have since found general application.

A further progessive step towards standardization of processes
became possible during the recent war when Government control
of all munitions became necessary, and the Waste Mills were
taken over by the Ministry of Munitions. Considerable
work was carried out by the Department in conjimction with
the explosives manufacturers in the direction of arriving at the
most suitable and expeditious purification treatment.

Although cotton waste comprizes a wide range of materials,
this waste material as used in Great Britain may be divided into
the following three classes:

(1) Waste from the ginning operations usually carried out
on the plantations. This includes short fiber material like linters
and wadding, and also a very low grade material known as hull
fiber, which remains attached to the seeds after the removal of
the linters.

(2) Waste from the spinning mills, including mill sweepings,
and also a certain proportion of refuse from the preliminary clean-
ing operations known as flocks, scutchings, etc.

(3) Waste from the weaving mills.

As above mentioned, the materials generally employed are
spinning mill sweepings, wadding known as old China wadding,
the latter being used to a minor extent, and imported from China,
where it is employed for padding and quilting dothing, chiefly
in Manchuria and the colder regions. The length of individual
fiber of this material is quite satisfactory.

Linters, although largely used in the United States and
Europe, have not been used to any great extent in England.
Hull fiber contains a very large proportion of husks and woody
matter, and is, therefore, unsuitable unless submitted to improved

648 TECHNOU>GY OF CBLirUI^OS^ ESTERS

methods of purification. In the F. Stockton process^ the fiber
separated from cottonseed hulls is purified by boiling in a 4%
aqueous solution of a caustic alkali for about 5 hours to soften
the hull particles, mashing and disintegrating the latter by pass-
ing the material between rolls, and then subjecting the mashed
mixture to a cleaning operation to separate the fiber from the
disintegrated htdl material.*

Weaving mill waste, although otherwise excellent material
consisting of high grade cotton, is liable to contain starch which
is used in the mills to strengthen the fiber during weaving, and
as nitrostarch with its diminished stability may be formed in
nitration, the use of this material is not permitted by the British
Government, whose standard of stabSity is of an exacting nature.
Dyed material has also been found unsuitable.

Spinning mill sweepings consist of good unspun cotton of
long staple and almost husk-free, being only discarded in the mill
as inevitable waste, and not on account of defects in the fiber.
It contains a variable amount of spun cotton, as well as consider-
able (15%-25%) lubricating oil from the machinery, other im-
purities consisting of pieces of wood, metal, string, paper, and
sandy matter picked up from the mill floor.

China wadding is tmspun material, felted and somewhat dis-
colored, but usually dean materials It contains no oil, and de-
oiling treatment is, therefore, not required.

The general treatment consists in removing the mechanical
impurities by hand picking and treatment in dusting machines,
the solvent extraction of the oil, boiling under pressure with dilute
sodium hydroxide solution, washing, centrifugalizing to remove
water, drying, and further treatment in teasing and willowing to
open out the material and remove foreign matter. The fiinished
waste is then weighed and press packed into bales for transit to
the Explosives Factories.

For hand picking wire gauze tables are used to allow the
fine refuse to fall out, the material being then passed through a

1. U. S. P. 1296078, 1919; abst. C. A, 1919. IS, 1166; J. S. C. I. 1919,
38, 319-A. E P. 132422.

2. Ordinarily, second cut linters has a maximum length of about 26
mm., a Tnitiitniim of 0.8 mm., and an average of about 4.0 mm. Hull shav-
ings will average about 2.4 mm. with a maximum of 8 mm., depending on
how much linters have been removed from the seeds, and a minimum of 0.6
mm.

650 tbcknolOgy op cbllulosb esters

long revolving sieve in which detritus is further removed, and is
then loaded into large spherical revolving kiers in which the de-
oiling takes place. Formerly benzine was used for this purpose,
but has now been replaced by trichloroethylene (Westrosol), which
being non-inflammable, is much safer. When the oil has been
extracted by successive extractions with solvent, the residual
solvent is expelled by means of steam and recovered. The mass
at this stage has considerably contracted, and material which
requires no de-oiling is now added, and treatment with alkaline
solution given. The strength of the solution, the pressure and
time of treatment are- carefully coordinated, depending on the
type of cotton required. Special care is taken not to expose the

Fig. 34.— Saco-Lowhlu Conobmser

material to the air while it is in contact with alkali to avoid
oxidation.

The cotton having been discharged from the kier, is washed
in a paddle washing machine in which it is kept in constant
motion, fresh water being continuously admitted and removed
by means of a gauze drum. The cotton is then removed from
the washer by means of an endless belt conveyor, and wnmg in
centrifugal machines until the moisture content is reduced to
about 45%, after which it is passed through an opening machine
consisting essentially of revolving spiked rollers, preparatory to
the final drying.

For this purpose a Petrie drying machine of large size is gen-
erally used, the machine consisting of a chamber filled with

652 TECHNOLOGY OF CELLULOSE ESTERS

moving shelves, arranged one above the other, over which a cur-
rent of hot air from a fan and tubular heater is passed. The
cotton is fed into the top of the machine by means of a belt con-
veyor, and by a special motion, slowly passes along each shelf
until it is delivered at the bottom in a sulficiently dried condition.
The time taken for the cotton to pass through the machine is
about one hour, and the moisture content has then been reduced
to about 7% — the amount usually present in air dry cotton.

The cotton is now passed through the willowing machine in
which a rotating drum fitted with blunt spikes beats it against a
grating, small pieces of wood, sand, and other mechanical impur-
ities being in this way removed. From the willowing machine
the cotton passes to a teasing machine, consisting essentially of
ah arrangement of spiked rollers, which uniformly opens out the
stock. It is then again hand picked (see Fig. 37), and is finally
weighed off and press packed into bales for despatch. /

The cotton was formerly subjected to bleaching with chlorine
and souring with weak acid, but these treatments are now omitted,
as they are considered unnecessary^ and may in addition lead
to the formation of oxycellulose and hydrocellulose.

In the manufacture of those explosives and products of lower
nitration in which a solvent is required, it is of importance from
the economic standpoint that the minimum of solvent be used,
and the nitrocotton, therefore, should have a low viscosity.
Much attention, therefore, has been given to lowering the vis-
cosity of the cotton, as this is intimately related to the viscosity
of the nitric ester for^ied therefrom, and a somewhat drastic
treatment is given.

For nitrocotton for blasting gelatin and other blasting ex-
plosives on the other hand, a high viscosity is desired, and the
treatment indicated in this case, therefore, is much less drastic.
It has been proposed to purify the cotton by means of alcoholic
sodium hydroxide solution, but this is unduly expensive. The
nitration of squirted dissolved cotton has also been proposed,^
but has not been adopted in manufacture.

Due to the rapid deterioration owing to the action of bac-
teria, cotton should not be stored in a damp condition. Wet
1. Ball's "Nature." 1915. 7, 15.

654 TECHNOU)GY OF CELLULOSE ESTERS

purified cotton containing 15%-20% of moisture has been found
to develop a temperature of 60°, when stored under conditions
which prevented free access of air (see p. 338). The number of
bacteria rapidly multiplies when the moisture content exceeds 9%,
and it is a difl&cult matter to destroy them — an exposure for one
to two hours at a temperature of 150°-!^*' being required.

The examination of the finished cotton waste includes the
estimation of moistiu-e, which should not exceed 7%, ether extract
(oil), 0.6%; solution in 3% NaOH solution (1 vol. to 2 vols,
water), after 15 minutes heating at 100°, 1%; calcium oxide and
other mineral matter, 1.25%.

Application of a basic dyestuff as fuchsine should not show
deeply dyed particles or fibers, and the viscosity of the solution
in Schweizer's reagent should also be determined.

In the preparation of the cotton for nitration, as the stock
arrives at the Explosives Factories in bale form, it is necessary
to open it out before nitration in order to insure uniform penetra-
tion of the cotton by the nitrating mixtiu-e. The moisture con-
tent is also reduced as far as possible to obviate the weakening of the
acid, and make the nitrating process better controllable. While
it is advantageous that all cleaning treatment, so far as possible,
be carried out at the waste mills, but as a fiuther precaution the
explosives manufacturers usually give an additional treatment
with the object of removing mechanical impurities, such as sand
and small pieces of woody matter -still present in the cotton.

The general line of treatment consists in opening up the
bale of cotton, teasing, drying, willowing, or dusting to eliminate
foreign matter, and weighing off for nitration. The cdtton was
at one time also hand picked^ but improved treatment at the
waste mills has made this sqperfiuous. For this purpo^ wire
gauze tables were used, which allowed sand and other extraneous •
particles to fall out, as shown in Fig. 38.

After passing through the teasing machine similar to that
described under the prehminary purification, and then through
a drying machine (see Fig. 39), in which the moisture is reduced
to about 1%, the cotton is passed through a willower, or in a
dusting machine consisting of a revolving sieve in which foreign
matter is removed, and is finally weighed off into sheet iron

TECHNOLOGY OP CELLULOSE ESTERS

COTTON 657

boxes with tightly fitting lids, where it is allowed to cool for
several hours before nitration.

The machines are arranged in series and are fitted with
draught hoods connected to an exhaust fan for the removal of
fluff and dust. The exhaust from the fan is led into a dust col-
lector known as a "cyclone," consisting of an inverted cone,
round which the air circulates (see Fig. 40). The friction of the
air on the sides causes the fluff to be deposited and to fall to the
bottom, where it drops into a suitable receptacle, while the air
escapes at the top.

In preparing cotton for nitration, it is essential that it should
be well opened to ensure imiform and complete acid penetration,
as defective opening lowers the nitrogen content, and raises the
solubility of the resulting nitrocotton.^ This is an important

1. A. Classen, U. S. P. 647805, 654518, 1900; Re. 12069, 1902; 695795,
1902; 825808, 1906. C. Cross, U. S. P. 807250, 1905. M. Ewen and G.
Tomlinson, U. S. P. 763472, 1904; India Appl. 470, 1909. P. Ekstrom.
Swed. P. 33546; Hung. Anm. E-1796; abst. Chem. Ztg. 1913, 37, 11, 163,
R. Eisentraut, E. P. 1443, 1887. Elektro-Osmose, D. R. P. 296053, 305118,
1917; abst. J. S. C. I. 1917, 36, 593; 1920, 39, 60-A. S. Eraly, A. ChrisUan-
sen, The Farringdon Works, Ltd., and H. Pontifex & Sons, E. P. 3602, 1911;
F. P. 429934; abst. C. A. 1912, 6, 2022; J. S. C. I. 1911, 30,
1301; 1912, 31, 218. A. Fest, Can. P. 173954, 1916. E. Fischer, Ber. 1916,
40, 584; abst. C. A. 1916, 10. 1532. E. Fischer and H. Noth, Ber. 1918.
51, 321; abst. C. A. 1918. 11, 2558; J. C. S. 1918, 114, i, 225. See
C. A. 1917, 10, 1040. F. Fischer and W. Schneider, Ges. Abhandl. Kenntn.
Kohle, 1919, 3, 287; abst. Chem. Zentr. 1919, 90, III, 287; abst. J. S. C. I.
1920. 39, 225-A. F. Fischer and M. Kleinstiick, Ges. Abhandl. Kenntn.
Kohle, 1919, 3, 301; Chem. Zentr. 1919, 90, IV, 940. J. Flack, Can. P.
ia3164, 1918. Gewerkschaft Pionier, F. P. 415566, 1910. Glanzfaden
Actiengesellschaft, D. R. P. Anm. F-26697; abst. Chem. Ztg. 1913, 37, 387.
W. Glover, U. S. P. 828472, 1906. W. Glover and L. Wilson, U. S. P. 1279329,

1918. M. Gostling, Proc. Chem. Soc. 1902, 250. H. Grothe, Dingl. Poly.
1870, 196, 553; abst;. Poly. Centr. 1870, 36, 641. E. Hagglund, Ark. Kemi.
Min. och Geol. 1918, 7, 1; abst. Chem. Zentr. 1919, 90, III, 186; J. S. C. I.

1919. 38, 895-A. T. Hanausek, Chem. Ztg. 1894, 18, 441. Holzstoffwerke
Brixem-Pfeffersberg Otto Kurz A. G., Aust. P. Anm. 10723, 1911; abst. Chem.
Ztg. 1913, 37, 254. C. Hoepfner, U. S. P. 663759, 1900. M. Honig and J.
Spitzer, Monatsh. Chem. 1918, 39, 1; abst. J. C. S. 1918, 114, i, 375; J. S.

C. I. 1918, 37. 502-A. C. Hudson, J. A. C. S. 1915, 37, 1591; J. Ind. Eng.
Chem. 1916, 8, 380; C. A. 1915, 9, 2092; 1916. 10, 1501. C. Hudson and

D. Brauns, J. A. C. S. 1915, 37, 1283; J. C. S. 1915, 108, i. 320, 502; C. A.
1915, 9, 1771. C. Hudson and J. Dale, J. A. C. S. 1915, 37, 1280; 1918,
40, 992, 997; C. A. 1915, 9, 1771; 1918, 12, 1778; J. C. S. 1915, 108, i, 502.
C. Hudson and J. Johnson, J. A. C. S. 1915, 37, 1270, 1276; abst. C. A.
1915 9, 1770; J. C. S. 1915, 108, i, 502, 503. C. Hudson and H. Parker,
J. A. C. S. 1915, 37, 1598; abst. C. A. 1915, 9, 2092. International CeUulose
Co., Can. P. 176178, 1917. G. Jenssen, Can. P. 180612, 1917. A. Jern-
berg, Can. P. 181513, 1918. F. Jaeger, Proc. Acad. Sci. Amsterdam, 1917,
20, 280; abst. C. A. 1918, 11, 1047. C. Kellner, U. S. P. 773941, 1904; E. P.
6420. 1890. I. Kitsee, U. S. P. 703136, 1902; 767822, 1904. J. Konig and

E. Becker, Pap. Fabr. 1919, 17, 982, 1014, 1171; abst. C. A. 1920, 14, 626.

TBCHNOUXiY OP CELLULOSB BSTBRS

Fio. 40. — Cyclonb Dust Collbctob (Nobhl's Explosivbs Co,)

660 TECHNOLOGY OF CELLULOSE ESTERS

point which has not been given the consideration that it should.

W. Koenigs and E. Knorr, Ber. 1901, 34, 4343; abst. J. S. C. I. 1902, 21,
196. H. Kunz-Krause and R. Richt^r, Arch. Pharm. 1917, 255, 507; abst.
J. C. S. 1919, 116, ii, 436; C. A. 1920, U, 796. H. Lange, Farber Ztg. 7,
441. W. Lawrence, Can. Chem. J. 1919, 3, 329; abst. C. A. 1920, 14, 127.
J. Leonard, U. S. P. 237440, 1881. A. Lietzenmayer, Swiss P. 58688; abst.
Chem. Ztg. 1913, 37, 284. J. London and H. Bailey, E. P. 12711, 1895.
E. Masera, Ital. P. 385/141/125268; abst. Chem. Ztg. 1913, 37, 272. W.
Mather, J. Hiibner and W. Pope, U. S. P. 824255, 1906. T. McFarland.
U. S. P. 858411, 1907. R. McKee, U. S. P. 1284739, 1284740, 1918; abst.
J. S. C. I. 1919, 38, 71-A; C. A. 1918, 13, 186, 187. P. Menaul and C. Dowell,
J. Ind. Eng. Chem. 1919, U, 1024; abst. C. A. 1920, 14, 258. W. Mensing,

D. R. P. 304349; abst. J. S. C. I. 1920, 39, 274-A. P. Minck, U. S. P. 1317306,
1919; abst. J. S. C. I. 1920, 39, 103-A. J. Minor, Paper. 1919, 25, 700;
abst. C. A. 1920, 14, 344. M. Moore, Can. P. 153445, 1914. H. Morrow,

E. P. 9319, 1885. M. Murai, D. R. P. 257609; abst. Chem. Ztg. 1913. 37,
245. H. NastukofF, Ber. 1900, 33, 2237; abst. J. S. C. I. 1900, 19, 733. A.
Neilson, Can. P. 197280, 1920. A. Nodon, Can. P. 154820, 1914; Belg.
P. 253427, Chem. Ztg. 1913, 37, 397. Z. Ostenberg, U. S. P. 1315393, 1919;
abst. J. S. C. I. 1919, 38, 897-A. A. Pellerin, Can. P. 148405. 1913. L.
Peufaillit, Can. P. 150817, 1913. M. Petzold, Aust. 57989; abst. Chem.
Ztg. 1913, 37, 262. M. Pomeranz, Chem. Ztg. 1918, 42, 177; Chem. Zentr.

1918, 89, II, 227; C. A. 1920. 14, 353. HaUer, Chem. Ztg. 1917, 41, 852.
D. Porter, E. P. 8184, 1909. H. Pringsheim and H. Magnus, Zts. ang. Chem.
1920, 33, 56; abst. J. S. C. I. 1920. 39, 266-A. M. Platsch, Hung. Anm.
P-3702. 1912; abst. Chem. Zte. 1913, 37, 272. W. Quist, Pap. Fabr. 1919,
17, 818; abst. C. A. 1920, 14, 344. H. Riesenfeld and F. Taurke, Proc.
Amer. Pharm. Assoc. 1906. 54, 909; Chem. News, 1905, 201; Ber. 1905, 3ft,
12. E. Rinman, E. P. 8175, 1909; 6652, 1912; Can. P. 168362, 180925, 1917.
D. Rosenblum. L. Brech and E. Tyborowski, D. R. P. 252321, 257544;
Hung. Anm. 3134; abst. Chem. Ztg. 1913, 37, 245, 272. L. Brech, Can. P.
145860, 1913. E. Savery, Dingl. Poly. 1879, 2n, 558; abst. Jahr. Chem.
1879, 32, 1152. W. Schach, D. R. P. 306366, 1918; abst. J. S. C. I. 1920,
39, 60-A. E. Schauffelberger, U. S. P. 1282835, 1918; Can. P. 187949, 1918.

F. Schreyer, Can. P. 141089; Aust. P. 58102; abst. Chem. Ztg. 1913, 37,
272. C. Schwalbe, F. P. 410460, 1910; Can. P. 141034, 1912. Zts. ang.
Chem. 1919, 32, 355; abst. J. S. C. I. 1920, 39, 58-A. See also J. S. C. I.

1919, 38, 858-A. C. Schwalbe and E. Becker, Zts. ang. Chem. 1919, 32, I.
265; abst. C. A. 1920, 14, 837. E. Simonsen, U. S. P. 607091, 1898. Soc.
anon. La Soie Artificielle, F. P. 477655, 1915; Ital. P. 385/185 125107; abst.
Chem. Ztg. 1913. 37, 284. A. Pictet, Can. P. 195897, 1920. S. Lagermarck,
Can. P. 162481, 1915. I. Soraas. Can. P. 196329, 1920. Peter Spence and
Sons, Ltd., Belg. P. 250441; abst. Kunst. 1913, 3, 235. O. Stafford, Can.
P. 182877, 1918. O. Stage, U. S. P. 1279604, 1918; Can. P. 187316, 1918.
R. Sthamer, U. S. P. 692497, 1902; D. R. P. 123121; abst. Chem. Zentr. 1901,
72, II, 567. H. Stockbridge, Paper, 22, No. 11; C. A. 1913, 7, 2305; 1917,
U, 1299. R. Strehlenert, Can. P. 151445, 1913. F. Taylor, E. P. 10864,
1884. C. Thome, Can. P. 153694, 1914. G. Tomlinson, Can. P. 182387,
1918. C. Vanderkleed and J. Brewer, U. S. P. 1269340, 1918. T. Wagner,
U. S. P. 1261328, 1918; Can. P. 186713, 1918. E. Wallin, Swed. P. 43761,
1918; abst. C. A. 1919, 13, 251. R. v. Walther, D. R. Anm. 38809; abst.
Chem. Ztg. 1913, 37, 379. A. Westad and E. Hagg, Can. P. 195943, 1920.
H. Wichelhaus, Ber. 1919, 52, 2054; abst. J. S. C. I. 1920, 39, 59-A. See also
J. S. C. I. 1916, 35, 1151; 1918, 37, 120-A. A. Wilbaux. E. P. 17268, 1890.
J. Williams, E. P. 1358, 1898. E. Winterstein, Zts. Physiol. Chem. 17,
391; J. C. S. 1893, 64, i, 127. Zellstoff-fabrik Waldhof, E. P. 132815. 1917;
abst. J. S. C. I. 1920, 39, 14-A; C. A. 1920, 14, 346. D. R. P. 304214, 1916.
Norw. P. 29748, 29763, 1919; abst. C. A. 1920, 14, 1219; J. S. C. I. 1920,

662 TBCHNOLOtv OI^ CBLLUIX>SE ESTERS

K. Hess^ has recently contributed an important paper on
the consitution of cellulose in which it is suggested tha^ the
molecule of hydrocellulose, for which the name celluxose is now
suggested, consists of a dextrose or a cellobiose molecule in which
the hydroxyl groups are etherified by dextrose or cellobiose resi-
dues. Of the various possibilities, the formula

CH. (OX) .CH.(OX) .CH. (OX) .CH.CH(OX) .CH,OX,
I o 1

in which X represents the residue

-CH.CH(OH).CH(OH).CH.CH(OH).CH20H,
I o^ 1

is in closest agreement with the proportions of cellobiose acetate
(6.2 gm.) and pentacetyldextrose (12 gm.) obtained from cellu-
lose (10 gm.) by acetolysis. The dextrins, which are present in
the form of acetates when the maximum proportion of cellobiose
acetate is not reached, are looked on as mixed partial degrada-
tion products of the cellulose molecule, resulting from the re-
moval by hydrolysis in a variety of ways of one or more dextrose
or cellobiose residues. Experiments on the acetolysis imder very
mild conditions of ethylcellulose uniformly confirmed the deduc-
tion from the above formula that when degradation has proceeded
sufficiently far, the ethoxy number of the ethyldextrin acetates
produced should be less than that of the ethyldextrose; this
result is not explained by the older formulas. The marked dif-
ference between cellulose and its derivatives, e. g., nitrate, acetate,
and the products obtained by the action of acids, alkalis, or
zinc or copper ammonium compounds is accounted for by con-

39, 60-A. G. Zemplen and E. Laszlo, Ber. 1915, 4S, 915; abst. Chem. Zentr.
1915, 86, II, 123.

P. Bettinger, Btill. assoc. chim. sucr. dist. 1919, 37, 126; abst. C. A.
1920, U, 1235. A. Claessen, U. S. P. 602697, 1898. J. David, U. S. P.
769061. 1904. J. Kantorowicz, U. S. P. 785216, 1905. H. Pomeranz. Drog.
Ztg. 1919, 236; Pharm. Zentralhall. 1918, 60, 510; C. A. 1919, 13, 521. 915;
1920, U, 1235. G. Raynaud, U. S. P. 761642, 1904. J. BoUing, U. S. P.
1305518, 1919; abst. C. A. 1919, 13, 1961. R. Kadish and T. Buschcr, U.
S. P. 1327394, 1920; abst. J. S. C. I. 1920, 39, 228-A. I. Meunier, Rev. Sci.
1919, 57, 135; abst. C. A. 1919, 13, 1255. E. Rasser, Papfabr. 1918, 16,
274; abst. C. A. 1919, 13, 2595. R. Weiss, Bull. Soc. Ind. Mulh. 1914, 84,
499; (Sealed communications deposited May 28 and June 23, 1902.) A.
Ber^lind, U. S. P. 1329824, 1920. J. Bland and E. Gelligan, U. S. P. 739751.
1903. J. Cochran, U. S. P. 822430, 822883, 1906. R. Van Buggenboudt.
U. S. P. 872097, 1907. D. "Winn, U. S. P. 739246, 1903.

1. Zts. Elektrochem. 1920, 26, 232; abst. J. S. C. I. 1920, 39, 232.
See also H. Ost, Zts. ang. Chem. 1906, 19, 993; abst. J. S. C. I. 1906, 2S, 606.

COTTON 663

sidering such derivatives to be derived from the above formula,
while cellulose consists of a ntmiber of such molecules, imited
through residual afi^ities of hydroxyl groups.- The disintegra-
ting effect of the agents named is due to their competition for these
residual valencies. It . is also suggested that the physical char-
acteristic of cellulose as a hollow fiber is reproduced in the arrange-
ment of the ceUuxose molecules in the cellulose complex, and that
this complex may be broken down by mechanical means.

In continuing his researches on lignin, P. Klason^ has come
to the conclusion that a hypothetical conif eryl aldehyde and con-
iferyl alcohol are the most important and sole chemically active
constituents of coniferous lignin. E. Knecht and F. Femandes*
have recorded tables showing the percentage of matter extracted
from Egyptian and American cotton by different solvents, the
effect of heat on the extracts, and their nitrogen content.

The heat of combustion of absorbent cotton has recently'
been determined as 4020 cal. per gm. W. Qvist* has determined
the alkalinity of various samples of cellulose, using an ether solu-
tion of iodeosine as indicator, hydrocellulose and oxycellulose
showing an acidic reaction which became alkaline on washing,
while cellulose and especially oxycellulose, could absorb both
acids and alkalis from solutions. C. Schwalbe and E. Becker^
have* found a variety of cellulose which is practically without
reducing power, and is obtained by the action of boiling milk of
lime on all sulfite celluloses, hydro- and oxy-celluloses. The gas
mantle of the Deutsche Gasgliihlicht A.-G.® is composed of hydro-
cellulose.

1. Ber. 1920, 53, B, 706; abst. J. C. S. 1920, 118, i, 474.

2. J. Soc. Dyers Col. 1920, 36, 43; abst. J. S. C. I. 1920, 39. 481- A.
Cf. E. Knecht, Text. Inst. J. 1911, 2, 22; abst. J. S. C. I. 1911, 30, 1007.
E. Knecht and W. HaU, J. Soc. Dyers Col. 1918, 34, 220; abst. J. S. C. I.
1919 38 7-A.

3. ' T. Richards and H. Davis, J. A. C. S. 1920, 42, 1608.

4. Pulp and Paper Mag. 1920, 18, 261, 286; abst. J. S. C. I. 1920, 39,
443-A.

5. J. prakt. Chem. 1919, (2), 100, 19; abst. J. C. S. 1920, 118, i, 474;
C. A. 1920, 14, 2081. See also Zts. ang. Chem. 1920, 33, 57, 58; abst. J. S.
C. I. 1920, 39, 330-A. C. Schwalbe, Zts. ang. Chem. 1919, 32, I, 355; abst.
C. A. 1920, 14, 1437. Further contributions to the chemistry of cellulose
have been made by F. Fischer and W. Schneider, Ges. Abhandl. Kenntn.
Kohle, 1919, 3, 287; abst. C. A. 1920, 14, 2081. F. Barret, J. S. C. I. 1920,
39, 81-T; abst. C. A. 1920, 14, 1757. E. Heusef, Chem. Ztg. 1915, 39, 89,
141, 170.

6. D. R. P. 312577, 1918; abst. J. S. C. I. 1920, 39, 441-A.