Inorganic chemical preparations

INORGANIC CHEMICAL
PREPARATIONS

INORGANIC CHEMICAL

PREPARATIONS

BY

FELIX LENGFELD

ASSISTANT PROFESSOR OF INORGANIC CHEMISTRY IN THE
UNIVERSITY OF CHICAGO

jfotfe
THE MACMILLAN COMPANY

LONDON : MACMILLAN & CO., LTD.
1905

All rights reserved

COPYRIGHT, 1899,
BY THE MACMILLAN COMPANY.

Set up and electrotyped. Published August, 1899. Reprinted
December, 1905.

Xortoooti

J. S. Cashing k Co. — Berwick & Smith Co.
Norwood, Mass., U.S.A.

PREFACE

THIS manual was written for the classes
in Inorganic Preparations at the University
of Chicago. The course is intended to
familiarize advanced students with the
methods and processes used in making
inorganic compounds, and serves at the
same time as a review in General Chemis-
try. It is supposed that the student who
has finished the course is able without fur-
ther assistance from an instructor to make
any inorganic preparation. An attempt
has been made to introduce all processes
generally used, and at the same time to
avoid repetition. The student should study
each preparation in detail, work out other
methods of making the same substance,

VI PREFACE

understand and criticise every step he
takes and read some original articles.
Therefore references to the literature have
been given. No attempt has been made
to make the list of references complete, as
the student should learn to use dictiona-
ries of chemistry, such as Dammer, Graham-
Otto, etc.

The instructor must remember that the
Manual is merely a laboratory guide, and
that unless the work is carefully supervised
it may become purely mechanical and the
course lose half its value.

The preparations have not been arranged
alphabetically or according to composition,
but rather in the order of increasing dif-
ficulty. The methods have all been tried
and have been found to give good results
in the hands of careful students. A table
of solubilities is appended.

TABLE OF CONTENTS

GENERAL DIRECTIONS . xi

PREPARATIONS :

Sodium Chloride I

Potassium Chlorate 2

Bicarbonate of Soda 3

Sodium Nitrite 4

Basic Lead Nitrite . . ... . 5

Cuprous Chloride 6

Lead Dioxide 7

Mercuric Oxide . 8

Boric Acid 9

Boron ......... 10

Sodium Thiosulphate 1 1

Barium Dithionate 12

Ammonium Nitrate 13

Sodium Ammonium Phosphate . . . 13

Zinc free from Arsenic 14

Arsenic Acid 15

Chrome Alum 15

viii TABLE OF CONTENTS

PACK

PREPARATIONS :

Chromic Anhydride ...... 16

Chromous Acetate 17

Hydrobromic Acid 18

Hydriodic Acid 19

Tin Tetrachloride 21

Sulphuryl Chloride 22

Phosphorus Trichloride 23

Fluorsilicic Acid 25

Antimony Trichloride 25

Antimony Oxychloride ...... 27

Silver Nitrate 27

Silver Hyponitrite 29

Strontium Chloride 30

Strontium Hydroxide 30

Manganous Chloride 31

Manganese 31

Iodine Trichloride 33

lodic Acid 34

Potassium Fluortitanate 34

Titanic Oxide 35

Sulphur Monobromide 35

Nitrogen Iodide 36

Nitrogen Tetroxide 36

Nitric Anhydride 37

TABLE OF CONTENTS ix

PAGE

PREPARATIONS :

Sulphuric Anhydride 39

Aluminium Chloride 40

Potassium Permanganate 41

Crystallized Silicon . . . . . . .42

Silicochloroform 43

Hydrogen Persulphide 45

Barium Oxide 46

Hydrated Barium Peroxide 47

Hydrogen Dioxide 48

Hydroxylamine Sulphate 49

Phosphonium Iodide 51

TABLE OF SOLUBILITIES 54

INDEX 57

GENERAL DIRECTIONS

A GAS should always be washed unless
there is specific reason for not doing so.
If the gas is very soluble in water, and
washing would involve too much loss, it
may frequently be purified by passing it
into a litre bottle before using so that some
of the impurities settle. If a dry gas is
needed, the drying agent used depends upon
the nature of the gas. Sulphuric acid,
calcium chloride, calcium oxide, potassium
hydroxide, etc., are commonly used, and the
gas finally dried if necessary by phosphoric
anhydride mixed with beads or by sodium.
As the sodium must present a large surface,
it may be used as wire or as the powder

xii GENERAL DIRECTIONS

obtained when it is melted under toluene and
shaken violently (care). In generating a
gas a safety tube should always be used
when possible. When a gas is being
absorbed by a liquid precautions should
always be taken to prevent the liquid run-
ning back into the generating flask. For
this purpose the delivery tube may dip
under mercury, the wash-bottle may be pro-
vided with a valve, etc. An excellent device
is to place between the wash-bottle and the
absorption flask an empty reversed wash-
bottle large enough to hold all the absorb-
ing liquid. The long tube of the wash-
bottle is next to the absorption flask, so
that if liquid runs back it remains in the
safety bottle as long as all the gas is
absorbed, and any gas not absorbed forces
it back into the absorption flask.

If a solid is formed by the action of a
gas on a liquid, the delivery tube should

GENERAL DIRECTIONS xiii

have a wide exit, and should dip just below
the surface. A funnel tube is well adapted
to this purpose.

Always absorb excess of chlorine, ammo-
nia, sulphur dioxide, etc.

The gases generally used in the labora-
tory are hydrogen, oxygen, nitrogen, carbon
dioxide, hydrochloric acid, chlorine, sulphur
dioxide, and ammonia.

Hydrogen and carbon dioxide generators
must always be on hand. Oxygen and
nitrogen are most conveniently used from
gasometers. Nitrogen may be made by
heating gently a solution of 60 grammes
each sodium nitrite, ammonium chloride,
and potassium bichromate in 2 litres water.
It is purified by passing over hot copper.

The most convenient source of gaseous
hydrochloric acid is the concentrated solu-
tion. Some of this is placed in a flask with
about one-sixth its weight of common salt

xiv GENERAL DIRECTIONS

and concentrated sulphuric acid slowly added
from a drop funnel. In a short time the gas
is evolved, and may be controlled by regulat-
ing the flow of sulphuric acid. The drop
funnel must have a long stem, and this must
be full of sulphuric acid so as to overcome
the pressure of the liquid in the wash-bottles.

A steady stream of chlorine may be
obtained by heating in a water-bath one
part pyrolusite and four parts crude hydro-
chloric acid contained in a flask or stone
jug. The spent liquid should not be thrown
away but worked for manganous chloride.

Sulphur dioxide is easily obtained by
heating on asbestos board copper turnings
with two or three times their weight of
concentrated sulphuric acid. The addition
of a few small pieces of charcoal is advis-
able. Unless entirely used up the acid
should be separated from the powder that
settles to the bottom and kept for future

GENERAL DIRECTIONS XV

use. The powder dissolved in water yields
crystals of copper sulphate.

Gaseous ammonia is evolved when ammo-
nia water is gently heated. It should be
dried with lime and potassium or sodium
hydroxide.

Liquids are usually purified by redistilla-
tion collecting the fraction or fractions with
constant boiling-point. It may at times be
necessary to distil under diminished press-
ure. For that purpose the apparatus of
Brlihl will be found convenient. Never put
the distilling flask above the level of the
eyes, and when distilling under diminished
pressure always use goggles.

In distilling always leave an opening for
the escape of any gas formed and of the air
in the apparatus. The opening may be
protected from the air and moisture by a
mercury valve, a drying tube, etc. When
a liquid cannot be distilled without decom-

xvi GENERAL DIRECTIONS

position it may be identified by its color,
density, index of refraction, etc.

Solids may usually be purified by recrys-
tallization. If the substance is much less
soluble in the cold than in the hot solvent, a
hot saturated solution is first made and then
cooled rapidly with constant stirring. After
one or more repetitions the product is pure,
and large crystals may now be obtained by
dissolving in little cold solvent and allowing
to evaporate slowly. Water is the usual
inorganic solvent, but sometimes it is neces-
sary to extract with alcohol, ether, etc.
Occasionally the impure product is dissolved
and the impurity or the substance desired
thrown out by adding another liquid, in
which it is insoluble.

Solids are sometimes purified by sublima-
tion, though for obvious reasons this is less
convenient and less used than the distilla-
tion of liquids.

GENERAL DIRECTIONS xvil

Organic matter is frequently objection-
able, and as corks and rubber are almost
indispensable, they may be protected by
wrapping thin asbestos paper around the
stoppers or around the ends of the glass
tubes connected by the rubber.

It is not usually necessary to use chemi-
cally pure reagents in making preparations.
Common sense must here be the guide.

Complete notes should be kept. It is
particularly important to record yield and
purity of products.

xviii GENERAL DIRECTIONS

ABBREVIATIONS OF REFERENCES

A. Liebig's Annalen.

A. ch. Annales de Chimie.

A. ch. p. Annales de Chimie et de Physique.

Am. J. Sc. American Journal of Science and Arts.

A. Min. Annales des Mines.

B. Berichte der deutschen chemischen Gesell-

schaft.

Bl. Bulletin de la Societ£ chimique de Paris.

Ch. C. Chemisches Centralblatt

Ch. N. Chemical News.

C. r. Comptes-rendus des Stances de l'Acad£mie

des Sciences.

D. Dingler's Polytechnisches Journal.

J. Jahresbericht liber die Fortschritte der

Chemie.

J. pr. Journal fur praktische Chemie.

P. A. Poggendorf's Annalen.

Ph. C. Pharmaceutische Centralhalle.

Rec. Recueil des Travaux chimiques des Pays-Bas.

Scher. Scherer's Journal der Chemie.

Soc. Journal of the Chemical Society of London.

Z. Zeitschrift fur Chemie und Pharmacie.

Z. Anorg. Zeitschrift ftir anorganische Chemie.

Z. phys. Zeitschrift fur physikalische Chemie.

INORGANIC CHEMICAL
PREPARATIONS

SODIUM CHLORIDE

Wittstein, Buchner's Repertorium 65, 361.

Dissolve 150 grammes common salt in
500 c.c. water; filter, and to the hot solution
add milk of lime containing 2*/£ grammes
calcium hydroxide, then a slight excess of
barium chloride. Allow to stand, filter, and
add a solution of 5 grammes sodium car-
bonate; heat to boiling, filter, neutralize
with dilute hydrochloric acid, and evaporate
to 150 c.c. as rapidly as possible. Collect
the sodium chloride on a platinum cone,
wash with little hot water, and dry by

2 INORGANIC CHEMICAL PREPARATIONS

heating gently in a platinum or porcelain
dish.

POTASSIUM CHLORATE

Liebig, A. 41, 307.

Slake 75 grammes quicklime, mix it
with 30 grammes potassium chloride, and
add sufficient water to make a thin paste.
Heat almost to boiling, and pass in chlorine
(using wide delivery tube) until no more is
absorbed and all the lime has passed into
solution. When necessary add water to
keep the volume constant. Boil for one
hour, passing carbon dioxide the last ten
minutes, and filter hot. Evaporate to
100 c.c., and set aside to crystallize. Evapo-
rate the mother liquor further, and again
set aside. Purify the potassium chlorate
by recrystallization until it is free from
chloride.

BICARBONATE OF SODA 3

BICARBONATE OF SODA

Schlosing & Reliant, A. ch. p. (4) 14, 5.
Mond, Ch. C. 1886, 189.

Dissolve 100 grammes salt in 300 c.c.
water, and saturate the solution with
ammonia, keeping it cold with ice water.
Filter if necessary, and put into a tall,
narrow cylinder. Cork the cylinder, and
have a wide glass tube pass through the
cork, and dip about 20 centimetres below
the surface of the liquid. Connect with a
carbon dioxide generator (Kipp's), uncork
the cylinder, and allow carbon dioxide to
pass through. When all the air is expelled
from the cylinder cork tightly, and allow
carbon dioxide to pass in as rapidly and as
long as it will, removing the cork from
time to time. Filter from the bicarbonate,
wash it with cold water, and spread it out
to dry, covering it with filter paper. After

4 INORGANIC CHEMICAL PREPARATIONS

two or three days again wash with ice
water, and dry at 40°.

SODIUM NITRITE

Hampe, A. 125, 336.

Melt 85 grammes sodium nitrate in a
small, flat, iron dish (sand-bath), and add
slowly 206 grammes granulated lead. Stir
until the lead is completely oxidized (30-50
minutes), and pour the molten mass upon
an iron or slate slab. Powder and wash
thoroughly with boiling water. Cool the
filtrate, pass in carbon dioxide for a few
minutes, heat to boiling, and filter hot.
Evaporate until crystals separate on cooling.
Unless the evaporation has been carried
too far, the crystals are almost pure sodium
nitrate. Pour off 'the solution, again evapo-
rate and cool, and repeat until the solid
shows a decided test for nitrite. Then

BASIC LEAD NITRITE 5

evaporate the mother liquor to dryness, and
extract repeatedly with boiling absolute
alcohol. Evaporate the alcohol and recrys-
tallize from water. To determine the
strength of the nitrite, dissolve a weighed
portion in considerable water, add the quan-
tity of potassium permanganate it would
require if pure, acidify with sulphuric acid,
and titrate the excess of permanganate.

BASIC LEAD NITRITE

Chevreul, A. ch. 83, 72.

Pdigot, A. ch. p. (3) 2, 87.

v. Lorenz, Wien. Akad. Ber. (2) 84, 1133.

Dissolve 25 grammes lead nitrate in 2
litres water, add gradually 50 grammes
finely granulated lead, and heat on the
water-bath for several days. Cool in ice
water, pass in carbon dioxide fifteen min-
utes, boil two or three minutes, filter hot,
and evaporate to crystallization.

6 INORGANIC CHEMICAL PREPARATIONS

CUPROUS CHLORIDE

Proust, Scher. 8, 49.
A. ch. 28, 218 ; 32, 48.

Dissolve 20 grammes cupric oxide in
200 c.c. commercial hydrochloric acid and
heat with 25 grammes copper turnings until
the green color disappears. Pour the liquid
into a tall cylinder containing at least i litre
distilled water. Allow the white precipitate
to settle, and wash it with very dilute hydro-
chloric acid until the washings are colorless,
decanting or siphoning off the liquid. Then
bring the precipitate upon a filter, and, using
a filter-pump, wash as rapidly as possible,
first with very dilute hydrochloric acid, then
with alcohol, and finally with ether. Until
all the water is washed out, the precipitate
should be kept covered with liquid so as to
protect it from the air. If the precipitate
is white after washing, bring it into a vacuum

LEAD DIOXIDE 7

desiccator over paraffine and sulphuric acid,
and when dry keep in a tightly stoppered
bottle. If the product is reddish or green,
dissolve it in concentrated hydrochloric acid,
pour into water, and wash as before.

LEAD DIOXIDE
Dry Method

Kassner, D. 274, 136, 183, 226, 270.
Archiv der Pharmacie, 228, 109.

Mix intimately 50 grammes each lead
oxide and calcium carbonate, put into a clay
roasting dish, and heat for thirty minutes to
redness, stirring with a pipe-stem so as to
expose the hot mass to the action of the air.
Cool, powder, and again heat for thirty
minutes, repeating the operation until the
color no longer changes on heating. Add
the powder gradually to 500 c.c. dilute
nitric acid, decant, wash two or three times

8 INORGANIC CHEMICAL PREPARATIONS

with 200 c.c. dilute nitric acid, then with hot
water, and dry at 125°.

Wet Method

Wdhler, A. 90, 383.

Rivot, Bendant and Daguin, A. Min. (5) 4, 221.

Bottger, J. pr. 76, 235.

Dissolve 50 grammes lead acetate in
200 c.c. water, add 200 c.c. sodium hydroxide
solution (20%), and pass in chlorine as long
as any action is observed. Decant, wash
with water, boil with 300 c.c. dilute nitric
acid, again wash with water, and dry at
125°.

MERCURIC OXIDE
Red Mercuric Oxide, Dry Method

Heat cautiously 10 grammes mercuric
nitrate in a porcelain crucible until red
fumes cease to come off, and mercury con-
denses on a cold crucible cover held above
the heated mass.

BORIC ACID 9

Red Mercuric Oxide, Wet Method

Bosetti, Pharmaceut. Zeitung 35, 471.

To a boiling solution of 30 grammes
mercuric chloride in 100 grammes water
add a hot solution of barium hydroxide I : 4,
at first rapidly, then drop by drop, until the
dark brown precipitate changes to deep red.
Then pour into 4 litres hot water, wash,
and dry.

Yellow Mercuric Oxide

Siewert, A. 125, 226.
Oswald, Z. phys. 18, 159.
Bosetti, loc. cit.

Dissolve 30 grammes mercuric chloride
in 300 c.c. water, and pour the solution into
250 c.c. potassium hydroxide solution (10%).
Wash and dry.

BORIC ACID

Dissolve 50 grammes borax in 200 c.c.
boiling water, and add 30 c.c. concentrated

10 INORGANIC CHEMICAL PREPARATIONS

hydrochloric acid. Allow to stand 24 hours,
and collect the boric acid on a filter. Wash
it with little cold water, and heat to 150°
for one hour ; dissolve in little boiling water
and allow to crystallize.

BORON

Jones, Soc. 35, 4 1-
Gattermann, EL 22, 195.
Winkler, B. 23, 772.
Moissan, C. r. 114, 392.

Melt 250 grammes borax in a Hessian
crucible, and when it reaches a state of
quiet fusion pour upon a slab. Powder
while hot, and mix at once 25 grammes with
12 grammes powdered magnesium. Put
the mixture into the same crucible, pack
tightly, and add a layer of the fused and
powdered borax. Close the crucible with
a well-fitting cover. (Work as rapidly as
possible.) Heat for fifteen to twenty min-

SODIUM THIOSULPHATE II

utes to redness. When the crucible is cold
break it and remove the contents, discard-
ing carefully adhering pieces of crucible.
Powder and boil successively with water,
concentrated hydrochloric acid and water.
The residue is impure boron. To purify,
mix with 20 grammes fused borax in a
Hessian crucible, add a layer of borax, cover
the crucible, and put it in a bed of titanium
oxide and charcoal in a larger crucible,
surrounding it completely with the mixture.
Heat and wash as before, repeating if
necessary.

SODIUM THIOSULPHATE

Walchner, A. 46, 235.

Divide into two equal portions a hot
saturated aqueous solution of 200 grammes
sodium carbonate. Keep one portion warm
on the water-bath, pass through sulphur

12 INORGANIC CHEMICAL PREPARATIONS

dioxide as long as it is absorbed, and add
at once the other portion. Boil the solution
of sodium sulphite with flowers of sulphur
until no more dissolves. Filter, evaporate
to a small bulk, and allow to crystallize.
Purify by recrystallization.

BARIUM DITHIONATE

Gay-Lussac & Welter, A. ch. p. 10, 313.
Spring & Bourgeois, Bl. (2) 46, 151.

Suspend 50 grammes precipitated man-
ganese dioxide in water, put the flask in ice
water, and lead in sulphur dioxide as long
as anything goes into solution. Filter, heat
to boiling, cool, and add barium hydroxide
solution until ammonium sulphide added to
a small portion no longer gives a flesh-
colored precipitate. Filter, wash the pre-
cipitate with boiling water, add the washings
to the main filtrate, heat to boiling, and
pass in carbon dioxide until the liquid is

SODIUM AMMONIUM PHOSPHATE 13

neutral to litmus. Filter hot, evaporate, and
allow to crystallize.

AMMONIUM NITRATE

To 250 c.c. nitric acid kept cold by a
freezing mixture, add slowly and with con-
stant stirring concentrated ammonia water
in slight excess. Allow to stand over night,
and separate by decantation and filtration
from any brown sediment. Should crystals
separate, redissolve in little cold water and
add to the main liquid. Evaporate on the
water-bath until the density of the hot liquid
is 1.25. Allow to crystallize, separate the
crystals, dry them between filter paper, and
work the mother liquor further.

SODIUM AMMONIUM PHOSPHATE

Mitscherlich, A. ch. p. 19, 399.

Dissolve 375 grammes crystallized sodium
phosphate in 125 c.c. water, and to the hot

14 INORGANIC CHEMICAL PREPARATIONS

solution add slowly 65 grammes ammonium
chloride. When all is dissolved boil for
a moment and filter, using hot water funnel.
Cool rapidly with constant stirring and
drain the crystals. Redissolve in 75 c.c.
boiling water and recrystallize adding a little
ammonia. Repeat until free from sodium
chloride. Dry at 30° and keep in well-
closed bottle.

ZINC — FREE FROM ARSENIC

L'Hote, C. r. 98, 1491.

Melt 500 grammes zinc in a Hessian
crucible, and by means of a thick iron wire
hold 6 to 8 grammes magnesium chloride
below the surface of the molten mass, stirring
gently. When all the magnesium chloride
has disappeared, heat almost to the boiling-
point of zinc 15 minutes, then allow the zinc
to cool somewhat and granulate by pouring
into water.

CHROME ALUM 1 5

ARSENIC ACID

Kopp, C. r. 42, 1060.

In a retort heat 100 grammes arsenious
oxide in small pieces (why not in powder ?)
with 100 c.c. fuming nitric acid. When
fumes are no longer evolved, pour off the
liquid and evaporate to dryness. Test for
arsenious acid, and if any is present add
aqua regia and again evaporate to dryness.
Again test for arsenious acid and repeat
evaporation with aqua regia until free from
arsenious acid. Then dissolve in boiling
water and evaporate to a thin syrup. Heat
on the water-bath until crystals form on
cooling.

CHROME ALUM

Bottger, J. pr. 36, 318.
Traube, A. 66, 169.

Dissolve 100 grammes potassium bichro-
mate in 400 c.c. warm water, add 140

1 6 INORGANIC CHEMICAL PREPARATIONS

grammes sulphuric acid and cool to 30°.
Add slowly alcohol until there is no further
action, taking care to keep the temperature
below 50°. Cool to zero and decant from
the crystals. Evaporate the liquid to icoc.c.,
keeping the temperature below 50° ; again
cool to zero and decant from the crystals.
Combine the two crops and purify by re-
crystallization, keeping the temperature of
the solution below 50°.

CHROMIC ANHYDRIDE

Bolley, A. 56, 113.
Traube, A. 66, 169.

Dissolve 300 grammes potassium bichro-
mate in 500 c.c. water, add 420 c.c. sulphuric
acid, and allow to stand over night. Filter
through glass wool and wash the acid potas-
sium sulphate with not over 10 c.c. cold
water. To the filtrate add 20 c.c. sulphuric

CHROMOUS ACETATE l?

acid and evaporate until chromic acid begins
to separate. Allow to stand over night and
collect on a platinum cone. Wash with
50 c.c. nitric acid and dry in desiccator
over potassium hydroxide.

CHROMOUS ACETATE

Moissan, A. ch. p. (5) 25, 416.

Heat 50 grammes chromic anhydride with
500 c.c. fuming hydrochloric acid until no
more chlorine is evolved. Evaporate to
200 c.c., pour the liquid upon 250 grammes
granulated zinc in a large flask, and add
125 c.c. hydrochloric acid. When the first
violent action is over, place in the neck of
the flask a rubber stopper carrying two
tubes, one terminating just below the stop-
per, the other going to the bottom of the
flask. Connect the longer with a bent tube
reaching below the surface of a solution of
400 grammes crystallized sodium acetate

1 8 INORGANIC CHEMICAL PREPARATIONS

in \\ litres water. When the liquid is a
pure blue, close the shorter tube and the
hydrogen evolved will force the liquid into
the sodium acetate solution. If necessary
filter the chromous chloride solution by
inserting a bulb tube with glass wool. Wash
the red precipitate of chromous acetate
repeatedly with boiled water through which
carbon dioxide has been passed, and keep
as a paste. Keep the flask containing the
chromous acetate full of carbon dioxide
while washing, and siphon off the water used
for washing.

HYDROBROMIC ACID

Linnemann, A. 161, 198.

Mix 10 grammes red phosphorus with
80 grammes sand, put into a small flask and
moisten with 20 grammes water. Close the
flask with a stopper carrying a glass tube

HYDRIOTIC ACID 19

and a drop funnel, and by means of the
latter gradually drop in 60 grammes bromine.
Pass the gaseous hydrobromic acid through
a U-tube containing moist red phosphorus
mixed with plenty of beads or pieces of
glass and then into 60 grammes water. To
prevent water running back, pass the delivery
tube into the tubular of a small retort whose
neck dips into the 60 grammes water con-
tained in a beaker. Loss of bromine may
be avoided and a steady flow obtained by
closing the drop funnel with a cork through
which a glass tube drawn to a capillary is
passed. Determine the strength of the
aqueous acid obtained.

HYDRIODIC ACID

Naumann, A. 151, 145.
Berthelot, C. r. 76, 741.

Powder 50 grammes iodine, suspend it
in 250 c.c. water in a 500 c.c. flask and pass

in hydrogen sulphide. Provide the flask
containing the iodine and water with a
stopper through which the delivery tube
passes, and as soon as all the air is displaced,
close the flask and leave it connected with
the hydrogen sulphide generator over night.
If the iodine has not all disappeared, lift
the stopper every hour for a minute or two
and shake vigorously from time to time. As
soon as the iodine has disappeared, heat
gently on water-bath passing hydrogen
through to drive out excess of hydrogen
sulphide. Filter from sulphur, and distil
in a current of hydrogen, collecting the por-
tion between 125° and 130°. Sometimes
the iodine gets coated with sulphur and is
not further acted upon. It must then be
removed and powdered. If large quantities
of hydriodic acid are to be made, it is advisa-
ble to dissolve the iodine instead of suspend-
ing it.

TIN TETRACHLORIDE 21

Fifty to sixty grammes hydriodic acid
may be made as above and without first
concentrating used to dissolve the iodine.

TIN TETRACHLORIDE

Lorenz, Z. Anorg. 10, 44.

Seal one end of a glass tube 2 or 3 centi-
metres in diameter and 40 centimetres long
and fit into it a double bored rubber stopper.
Through one of the holes pass an inverted
condenser, and through the other a long
glass tube that may be raised or lowered.
Fill the larger tube with granulated tin,
have the delivery tube reach to the bottom
and pass in dry chlorine. Liquid tin tetra-
chloride soon forms. Move the delivery
tube so that it just dips into the liquid, and
pass the chlorine until action ceases. Pour
from the little tin usually left, purify by

22 INORGANIC CHEMICAL PREPARATIONS

redistillation and keep in sealed tubes. Tin
tetrachloride boils at 114°.

SULPHURYL CHLORIDE

Schulze, J. pr. (2) 24, 168.

Put 30 grammes camphor into an absorp-
tion flask, place in ice water and lead in
sulphur dioxide as long as it is absorbed.
Then lead in chlorine until it passes through
unabsorbed, then sulphur dioxide and chlo-
rine in rotation until the liquid no longer
increases in bulk. Put into a retort and
collect the portion coming over below 100°.
If required, the portion boiling above 100°
may be treated in the same way as the
camphor, i.e. sulphur dioxide and chlorine
led in alternately, and thus a large quantity
of low boiling liquid obtained from little
camphor. The low boiling liquid is sub-

PHOSPHORUS TRICHLORIDE 23

jected to fractional distillation, the sulphuryl
chloride coming over between 68° and 71°.

PHOSPHORUS TRICHLORIDE

Michaelis, Graham-Otto's Lehrbuch II. 324.

Cover the bottom of a tubulated retort
with dry sand and connect with a double-
necked receiver, protecting the corks with
asbestos paper. In the second neck of the
receiver put a drying tube and absorb the
gas which passes this in sodium hydroxide
solution, using a safety bottle or mercury
valve. (If no double-necked receiver is at
hand, an ordinary flask and double-bored
cork may be used.) Fill the apparatus with
carbon dioxide, throw in 100 grammes yellow
phosphorus dried between filter paper, and
then dipped successively into alcohol and
ether, again pass carbon dioxide for fifteen
minutes, put the retort into a pail of warm

24 INORGANIC CHEMICAL PREPARATIONS

water and pass in a current of chlorine.
The chlorine delivery tube must move easily
in the stopper so that it may be raised or
lowered. If the end of the tube is too
near the phosphorus, the latter gets hot and
distils, forming a red crust. If the tube
is too far away, the action is slow, the excess
of chlorine acts and phosphorus pentachlo-
ride is formed. The position must be such
that the retort remains uncoated. As soon
as action begins, as indicated by a tongue
of flame from the tube to the phosphorus,
the retort may be removed from the hot
water, but water should always be kept
under the retort to catch the phosphorus
in case of accident. Toward the end, the
voluminous phosphorus remaining may be
cautiously heated. Purify the trichloride
by redistillation, excluding water. Be care-
ful not to inhale any. Boiling-point 74°.

ANTIMONY TRICHLORIDE 25

FLUORSILICIC ACID

Berzelius, J. 1825, 89; P. A. I, 169.
Stolba, D. 197, 336.

Mix 50 grammes each fluor-spar and sand,
and heat in an old flask with 150 c.c. sul-
phuric acid. Lead the gas evolved through
an empty flask, and then into 200 c.c. water,
using a mercury valve or a thistle tube.
When the action is over press the liquid
from the separated silicic acid, wash with
little water, and filter. Determine strength
of acid by titration.

ANTIMONY TRICHLORIDE

In a 500 c.c. flask heat 50 grammes gray
antimony ore with 250 c.c. concentrated
hydrochloric acid, adding gradually a few
grammes potassium chlorate. As soon as
all the ore is acted upon filter through

26 INORGANIC CHEMICAL PREPARATIONS

glass wool and evaporate to 100 c.c. Pour
into 2000 c.c. water, wash the precipitate
with cold water, and dissolve it in 75 c.c.
concentrated hydrochloric acid, leading in
gaseous hydrochloric acid until no more is
absorbed. Pour the solution into a tubu-
lated retort containing some bits of glass to
prevent bumping, and distil. As soon as a
drop of the distillate gives a white precipi-
tate with water change the receiver, and do
this again when the distillate begins to
solidify on. a glass rod. The last portion
is antimony trichloride, a white crystalline
substance. If colored by iron it must be
redissolved in concentrated hydrochloric
acid and redistilled. The portion of the
distillate that gives a white precipitate with
water is a solution of antimony trichloride
in hydrochloric acid, and may be used for
the next preparation.

SILVER NITRATE 2/

ANTIMONY OXYCHLORIDE

Johnston, J. pr. 6, 55.
Malaguti, A. ch. p. 59, 220.
Pdigot, A. ch. p. (3) 20, 288.

Powder of Algaroth

Pour the acid solution of antimony tri-
chloride obtained in the previous experiment
into 400-500 c.c. water, wash the precipitate
carefully, dry and preserve.

SILVER NITRATE

Place a porcelain crucible in a Hessian
crucible with a layer of sand between them.
Cover the sand with fused borax, and heat
to redness. Gradually bring into the hot
porcelain crucible a mixture of 100 grammes
silver chloride, 100 grammes dry sodium
carbonate, and i^ grammes potassium
nitrate. Add slowly, or it may foam over.

28 INORGANIC CHEMICAL PREPARATIONS

When the mass is in quiet fusion stir with a
pipe-stem, allow to settle, cool slightly, and
pour the contents of the porcelain crucible
into water. The coating of borax should
keep sand from dropping in. Brush the
silver clean, and boil for a few minutes with
dilute sulphuric acid. -Wash, dissolve in
nitric acid, evaporate to dryness, and recrys-
tallize from water.

From the silver residues of the laboratory
(chloride, bromide, cyanide, etc.), the chlo-
ride may be obtained as follows : Dissolve
the residues in 10% potassium cyanide solu-
tion, and digest on the water-bath with zinc
dust until all silver is precipitated. Wash
with water, boil with hydrochloric acid,
again wash thoroughly with water, dissolve
in nitric acid, and precipitate with hydro-
chloric acid. If necessary, redissolve in
ammonia, and precipitate with hydrochloric
acid.

SILVER HYPONITRITE 29

SILVER HYPONITRITE

Divers, Ch. N. 23, 206.
Divers & Haga, Soc. 45, 78.
Van der Plaats, B. 10, 1507.
Miihlhauser, Z. 1864, 720.

Dissolve 10 grammes sodium nitrite in
30 grammes water, cool in ice water, and add
slowly 250 grammes 3% sodium amalgam.
When action ceases pour from the mercury,
neutralize with acetic acid, and precipitate
with silver nitrate. To get rid of any silver
acetate in the precipitate expose to diffused
sunlight for a few hours, dissolve in very
dilute sulphuric acid, and precipitate with
ammonia, carefully avoiding an excess.
Wash with a little ice water, and dry in
desiccator. Keep all solutions ice cold, and
avoid direct sunlight.

To prepare sodium amalgam, heat sodium
to 90° under low melting paraffine, and pour

30 INORGANIC CHEMICAL PREPARATIONS

in the mercury in a fine stream, stirring con-
stantly. The operation is harmless, but
should be carried on in the hood. When
working with molten sodium use care, and
protect the eyes with goggles.

STRONTIUM CHLORIDE

Berthier, A. ch. p. 22, 231.

In a Hessian crucible heat to bright red-
ness for two hours a mixture of 200 grammes
celestine and 75 grammes charcoal. When
cool powder, and add to 2 litres dilute hydro-
chloric acid 5 %. Heat to boiling, filter hot,
and evaporate to dryness. Redissolve in
water, remove iron, etc. by ammonium sul-
phide, and barium by digesting with stron-
tium sulphate, and recrystallize.

STRONTIUM HYDROXIDE

Dissolve 75 grammes strontium chloride
in boiling water, add 75 grammes sodium

MANGANESE 31

hydroxide solution (30 %), cool, collect on a
platinum cone, and wash with cold water.

MANGANOUS CHLORIDE

Everitt, Phil. Mag. 6, 193.
Kolbe, J. pr. (2) 5, 445.

Evaporate to dryness i litre of the liquid
obtained in making chlorine from manga-
nese dioxide and hydrochloric acid. Heat
the residue for several hours, cool, wash
with boiling water, and filter. To ^ of the
filtrate add sodium carbonate, wash the pre-
cipitate, and digest it on the water-bath with
the main portion until ammonium sulphide
gives a fresh-colored precipitate entirely sol-
uble in dilute acetic acid. Filter and recrys-
tallize.

MANGANESE

Glatzel, B. 22, 2857.

Heat 150 grammes manganous chloride
until anhydrous, and mix 75 grammes of the

32 INORGANIC CHEMICAL PREPARATIONS

anhydrous salt with 100 grammes dry potas-
sium chloride and 50 grammes anhydrous
calcium chloride. Pack the mixture in a
Hessian crucible, and heat to quiet fusion.
Then add 18 grammes magnesium in pieces
of 3 to 4 grammes. As each piece is
thrown in cover the crucible, and wait until
the action is over before adding another.
If the mass is too hot it will foam over.
Therefore, have it as cold as is consistent
with complete fusion while adding the mag-
nesium, but as soon as all the magnesium
is in bring to a white heat as rapidly as
possible. Keep at white heat 20-30 min-
utes. Allow to cool, break the crucible,
and wash the regulus of manganese. If the
mass was brought to a white heat imme-
diately on adding the magnesium, the man-
ganese will be in one or two pieces at or
near the bottom. Otherwise it will be found
as small, fairly stable pellets, or as an

IODINE TRICHLORIDE 33

unstable powder distributed through the
mass.

IODINE TRICHLORIDE
Brenken, B. 8, 487.

Connect a large-necked flask or double-
necked receiver with both a chlorine genera-
tor and a small retort holding 15 grammes
iodine, taking care to leave an outlet for the
air. Fill the receiver with dry chlorine, and
slowly distil the iodine, generating chlorine
in the meanwhile as fast as it is used up so
as to always have an excess of chlorine in
the receiver. When all the iodine has been
used up, drive out the excess of chlorine by
passing air through the apparatus. Remove
the crystals from the walls, and keep in
sealed tube. The portion which cannot be
loosened may be dissolved in water and the
solution kept.

34 INORGANIC CHEMICAL PREPARATIONS

IODIC ACID

Kammerer, J. pr. 79, 94.

Heat gently in a hard glass flask 15
grammes iodine and 80 grammes fuming
nitric acid, passing a current of air through
the liquid. If the iodine does not all dis-
solve, add more fuming nitric acid from time
to time until it does. Evaporate to a small
bulk, and recrystallize from rather dilute hot
nitric acid until the product is white.

POTASSIUM FLUORTITANATE

Wohler, A. ch. p. (3) 29, 185.

Heat to redness 25 grammes rutile, and
throw into cold water. Dry, reduce to a
fine powder, mix with 50 grammes potas-
sium carbonate and fuse in a platinum
crucible placed inside of a Hessian crucible.
Cool, powder, and dissolve in hot dilute

SULPHUR MONOBROMIDE 35

hydrofluoric acid, avoiding much excess of
the latter. Evaporate to small bulk and
allow to cool. Decant, wash the potassium
fluortitanate with ice-cold water, and purify
by recYystallization.

TITANIC OXIDE

Wohler, A. ch. p. (3) 29, 186.

To the cold mother liquor obtained in pre-
paring potassium fluortitanate add ammonia
in slight excess, and filter at once from the
brown precipitate. Heat to boiling, collect
and dry the white precipitate.

SULPHUR MONOBROMIDE

Muir, Soc. 28, 845.

Wash and dry carefully 20 grammes
flowers of sulphur, and add it gradually to
50 grammes bromine, shaking thoroughly
after each addition. Distil carefully, heat-
ing to 225°-23o°. Purify by redistillation.

36 INORGANIC CHEMICAL PREPARATIONS

NITROGEN IODIDE

Mallet, Ch. N. 39, 257.

Dissolve 2 grammes iodine in 20 grammes
warm alcohol, and pour into 200 c.c. cold
water. Wash the powder carefully with
water, put it into a beaker, pour upon it
50 c.c. strong ammonia water at zero, and
decant. Repeat twice, using no rod or
other solid to stir. Wash with alcohol two
or three times, then with absolute alcohol,
and finally with ether. Divide into small
portions before the final washing. Care ! ! !
The nitrogen iodide cannot be kept.

NITROGEN TETROXIDE

Gay-Lussac, A. ch. p. I, 405.

Powder and dry 100 grammes lead nitrate.
Heat it in a hard glass tube or retort to dull
redness, passing the fumes into an empty

NITRIC ANHYDRIDE 37

wash bottle kept at 30°, then into a U-tube
containing fused calcium nitrate, and finally
into a dry U-tube kept in ice water and pro-
tected from the moisture of the air by a
calcium nitrate tube. Pass dry air or oxy-
gen into the liquid thus obtained until it is
straw colored. Keep in sealed tubes. Care
must be taken to protect the nitrous fumes
from organic matter; therefore corks must
be wrapped in asbestos paper. Where glass
tubes are connected by rubber, wrap the
glass in asbestos paper and put the rubber
over it, tying with string if necessary.

NITRIC ANHYDRIDE

Weber, J. pr. (2) 6, 342.
Berthelot, Bl. (2) 21, 53.

To 200 c.c. concentrated colorless nitric
acid add slowly 100 c.c. sulphuric acid, keep-
ing cold. Distil gently until 1 50 c.c. passes

38 INORGANIC CHEMICAL PREPARATIONS

over. To the distillate add 100 c.c. sul-
phuric acid, and again distil, collecting
100 c.c., to which add 75 c.c. sulphuric acid,
and again distil, collecting 50 c.c., which
must be carefully protected from moisture
and organic matter. Put the distillate into
a tubulated retort, and add 30 grammes
phosphoric anhydride mixed with beads,
keeping below zero. When the whole is
thoroughly mixed keep at zero for a few
minutes, then allow it to come gradually to
the temperature of the room, and finally
heat in a water-bath until nitric anhydride
comes over. Collect in a small flask kept in
ice, and use at once. If the distillation is
carried too far a liquid collects on the
crystals of nitric anhydride. It should be
poured off. It is not as a rule necessary
to make connection between the retort and
receiver tight to exclude moisture. Organic
matter must be rigidly excluded and a vent

SULPHURIC ANHYDRIDE 39

provided for the escape of gas. Usually
nitric anhydride comes over when the tem-
perature of the water-bath reaches 60°. It
must not get above 70°, and should be kept
as near 60° as is consistent with the distilla-
tion of nitrogen pentoxide.

SULPHURIC ANHYDRIDE

Osann, D. 151, 158.
Weber, P. A. 159, 315.

Into a retort about one-third full of fum-
ing sulphuric acid put a platinum spiral long
enough to project above the surface of the
liquid and distil, collecting the first fourth.
Redistil and keep the product in sealed
tubes. While distilling protect from mois-
ture and organic matter. Leave a vent for
the escape of gas. As a precaution put a
porcelain jar under the retort.

40 INORGANIC CHEMICAL PREPARATIONS

ALUMINIUM CHLORIDE

Escales, B. 30, 1314.

Fit a tubulated bell-jar with a glass plate,
and cover the glass plate within the jar
with asbestos paper. Put upon the asbestos
paper an evaporating dish containing 30
grammes aluminium filings. Pass in hydro-
chloric acid, and as soon as all the air is
expelled heat a little aluminium to redness,
and lifting the stopper drop it upon the
aluminium in the dish. The action con-
tinues without further heating if a lively
current of hydrochloric acid is passed in.
Should the action stop, pass in hydrochloric
acid until all the hydrogen is out, and drop
in more aluminium heated to redness.
When all the aluminium is used up re-
move the aluminium chloride from the sides
and bottom, and keep in tightly closed
bottles.

POTASSIUM PERMANGANATE 41

POTASSIUM PERMANGANATE

Aschoff, J. pr. 81, 29.
Bottger, J. pr. 90, 157.
Graeger, J. pr. 96, 169.

In an iron dish fuse 20 grammes potas-
sium hydroxide, 5 grammes potassium chlo-
rate, and 5-6 c.c. water. Remove the flame,
and slowly add 20 grammes powdered man-
ganese dioxide, stirring constantly. Heat to
dull redness until the mass is hard and dry.
Repeat three or four times with new por-
tions, unite, and powder. Boil the powder
with 2 litres water, leading carbon dioxide
and air into the boiling solution until a drop
leaves a red mark on paper. Filter through
glass wool or a Pasteur-Chamberland filter,
wash the residue thoroughly, and evaporate
until crystals form on cooling. Allow to
stand twenty-four hours, pour from the crys-
tals, concentrate the mother liquor, and

42 INORGANIC CHEMICAL PREPARATIONS

again allow to crystallize, repeating until
the crystals are plainly not permanganate.
Redissolve all the crystals in boiling water,
filter through a Pasteur-Chamberland filter,
and recrystallize, excluding all organic mat-
ter. Or redissolve all the crystals in cold
water, let stand a week, decant carefully
from the mud, filter through glass wool,
and evaporate to crystallization, excluding
organic matter.

CRYSTALLIZED SILICON

Caron, A. ch. p. (3) 63, 26.

Deville & Caron, A. ch. p. (3) 67, 437.

Vigouroux, A. ch. p. (7) 12, 50.

Mix 75 grammes potassium fluorsilicate,
100 grammes granulated zinc, and 20
grammes sodium in small pieces. Throw
the mixture into a red-hot crucible, and
cover immediately. Unless the contents of

SILICOCHLOROFORM 43

the crucible become liquid at once, heat to
fusion and stir with a pipe-stem for a minute
or two. Cool slowly, separate the lump of
zinc, wash it carefully, and treat with com-
mercial hydrochloric acid. Wash the resi-
due, heat with concentrated nitric acid for a
few minutes, wash thoroughly, heat with
hydrofluoric acid, wash and dry.

SILICOCHLOROFORM

Friedel & Ladenburg, A. 143, 118.
Gattermann, B. 22, 186, 190.
Gattermann & Weinlig, B. 27, 1943.
Vigouroux, A. ch. p. (7) 12, 31.

Dry 25 grammes magnesium in the air-
bath at 150°, and while still warm (60° to
70°) mix with 40 grammes warm sand pre-
viously heated to redness, and then placed in
a desiccator. Put the mixture into a small,
flat, iron dish (sand-bath), pour upon it a

44 INORGANIC CHEMICAL PREPARATIONS

coating of dry magnesium oxide, and cover
with an iron plate or asbestos board. Heat
to redness in one place with a Bunsen
burner. As soon as action begins the part
heated glows, and the burner may be re-
moved as the action continues throughout
the whole mass. When cold throw into
cold water, and add hydrochloric acid care-
fully (Hood). Decant, add concentrated
hydrochloric acid, and boil for half an hour.
Cool, decant, and wash with hot water until
free from magnesia and hydrochloric acid.
Put the impure silicon into a combustion
tube, and heat to redness in a current of
hydrogen. Cool to dull redness, connect
one end with a receiver (U-tube or spiral)
and the other with a generator of gaseous
hydrochloric acid. Put the receiver into
ice and brine. To its free end attach a
drying tube, and to this a delivery tube
dipping into water. Pass a steady stream of

HYDROGEN- PERSULPHIDE 45

the carefully dried hydrochloric acid, keep-
ing the combustion tube at or just below
dull red heat. The water is soon covered
with flaky silico-formic anhydride, and unless
the delivery tube is dry and wide it soon
gets stopped up. A mixture of chlorides of
silicon collects in the receiver. If the /tem-
perature within the combustion tube was
not too high, two-thirds of this is silico-
chloroform. It may be obtained pure by
redistillation. The distilling flask must not
be heated with the naked flame, but placed
in a water-bath kept at 4O°-5O°. Boiling
point of silicochloroform, 37°-38°.

HYDROGEN PERSULPHIDE

Sabatier, Bl. (2) 44, 169.
Rebs, A. 246, 356.

Dissolve 40 grammes potassium hydrate
in 125 c.c. water, saturate with hydrogen

46 INORGANIC CHEMICAL PREPARATIONS

sulphide, and boil in a flask with sulphur as
long as any dissolves. Allow to stand until
clear, and pour the clear solution slowly
into an ice-cold mixture of 60 c.c. each
hydrochloric acid (S. G. 1.18) and water.
Allow to stand in a separating funnel sur-
rounded by ice until the oil settles. Collect
the oil, wash it with ice water, and dry with
filter paper. Distil carefully at a pressure
of 40 to 80 mm. Boiling-point below 80°.

BARIUM OXIDE

Fourcroy & Vauquelin, A. ch. 21, 277.
Berthier, A. ch. p. 22, 231.

Put 2 kilos heavyspar and 500 grammes
charcoal, carefully mixed, into a Hessian
crucible, cover with a layer of powdered
charcoal, and heat to bright redness for two
hours. When cool throw into cold water
and add slowly dilute nitric acid, avoiding

HYDRATED BARIUM PEROXIDE 47

much excess of acid (Hood). When all
is in, heat to boiling, filter while hot, and
evaporate to small bulk. Purify the barium
nitrate by crystallization, and bring it little
by little into a hot porcelain or graphite
crucible coated with barium sulphate. Heat
to quiet fusion, put the crucible into a tight
iron box to cool, separate the core from
the outer layer, break it up and keep in
tightly stoppered bottles.

HYDRATED BARIUM PEROXIDE

Th6nard, A. ch. p. 8, 306.
Boussingault, C. r. 32, 261.
Thomsen, B. 7, 73.

Heat barium oxide in a combustion tube
to dull redness, and pass in a rapid current
of moderately dry oxygen, free from carbon
dioxide, as long as any is absorbed. Cool
and dissolve in the calculated quantity of

48 INORGANIC CHEMICAL PREPARATIONS

ice-cold, dilute hydrochloric acid. Add solu-
tion of barium hydroxide little by little
until the precipitate formed is perfectly
white. Then filter, and to the filtrate add
baryta water to complete precipitation,
avoiding, however, any excess of barium
hydroxide. Wash the precipitate with ice
water, and dry on clay plates.

HYDROGEN DIOXIDE

Thomsen, B. 7, 73.
Wolfenstein, B. 27, 3307.
Spring, Z. Anorg. 8, 424.
Brtihl, B. 28, 2853.

Cool a mixture of 50 c.c. sulphuric acid
and 500 c.c. water with ice and salt, and
add slowly hydrated barium peroxide until
almost neutral. Filter and add more perox-
ide until barium chloride no longer gives a
precipitate. Test for barium salts with sul-

HYDROXYLAMINE SULPHATE 49

phuric acid, and if present add sulphuric
acid. By thus alternating if necessary a
solution may be obtained giving no test for
either barium or sulphuric acid. Allow to
stand in the refrigerator for a day, filter and
evaporate on the water-bath in a smooth
platinum or porcelain dish until the liquid
begins to decompose, then cool rapidly, and
concentrate further by distillation in vacuo.

HYDROXYLAMINE SULPHATE

Divers, Soc. 69, 1665.

Dissolve 75 grammes commercial sodium
nitrite and 140 grammes crystallized sodium
carbonate in as little ice water as possible,
and lead in sulphur dioxide until just acid,
agitating thoroughly, and keeping the tem-
perature 2°-3° below zero by immersing in
brine and ice. Add a few drops of sulphuric
acid, and heat very slowly to between 90°

50 INORGANIC CHEMICAL PREPARATIONS

and 95°. Keep at 9O°-95° for about two
days, or until all the sodium oxamido-sul-
phonate has been hydrolyzed. (To deter-
mine this add to some of the solution an
excess of barium chloride, filter, add to the
filtrate some potassium chlorate, and boil
for a few minutes; if no precipitate forms
the action is over.) When the hydrolysis is
completed neutralize with sodium carbonate,
using methyl orange as indicator ; evaporate
until the solution weighs 800-825 grammes,
and cool to 5°-8° below zero. Separate
from the sodium sulphate, and evaporate
until the solution yields at the ordinary tem-
perature abundant crystals of hydroxylamine
sulphate. Powder the crystals of sodium sul-
phate which first separated, wash with little ice
water, and add washings to the mother liquor
from the hydroxylamine sulphate. Work
this up carefully. Purify the crude hydroxyl-
amine sulphate by recrystallization. Devise

PHOSPHONIUM IODIDE 51

a method for getting hydroxylamine chloride
from the sulphate, and try it.

PHOSPHONIUM IODIDE

Baeyer, A. 155, 269.

Dry carefully 100 grammes phosphorus in
a 500 c.c. tubulated retort, add sufficient
carbon disulphide to dissolve it, and then
slowly and carefully 170 grammes dry
iodine, keeping the whole cold, and the
apparatus filled with carbon dioxide. Distil
the carbon disulphide very slowly in a water-
bath until it is entirely driven off. Allow to
cool, and by means of a long, thin-walled
glass tube connect the retort with a receiver
protected by a drying tube, which communi-
cates with the outer air or a good draught.
Bring a drop funnel into the tubular, and
drop in very slowly 60 grammes water.
Heat until no more phosphonium iodide

$2 INORGANIC CHEMICAL PREPARATIONS

comes over, or until it no longer comes over
white. Transfer the phosphonium iodide,
most of which will be found in the glass
tube, as quickly as possible to tightly stop-
pered bottles. The apparatus must be con-
stantly full of carbon dioxide.

EXERCISES 53

Make three or four of the following
substances, consulting the original articles
for methods of preparation: —

Allotropic Forms of Silver. M. Carey
Lea, Am. J. Sc. (3) 37, 476.

Ammonium Peroxide. Melikoff and Pis-
sarjewsky, B. 30, 3144; Z. Anorg. 18, 89.

Calcium. Moissan, C. r. 126, 1753.

Chromium. Moissan, C. r. IIQ, 185.

Ferrotitanium. Goldschmidt, A. 301, 19.

Hydrazoic Acid. W. Wislicenus, B.
25, 2085.

Hydroxylamine. Lobrey de Bruijn, Rec.
II, 18.

Nickel Carbonyl. Mond, Langer &
Quincke, Soc. 57, 750.

Potassium Persulphate. Marshall, Soc.
59, 772.

Uranium. Moissan, A. ch. p. (7) 9, 268.

54 INORGANIC CHEMICAL PREPARATIONS

TABLE OF SOLUBILITIES

When the aqueous solution is saturated at the temperature
indicated it contains for every 100 grammes water (X)
grammes salt (calculated in every case as anhydrous salt).

TEMPERATURES INDICATED.

Zero.

15°.

100°.

Ammonium Carbonate ....
Ammonium Chloride ....
Ammonium Hydrogen Carbonate
Ammonium Nitrate
Ammonium Sulphate ....
Barium Chloride ......

29
12

97
7i
31

10

1.6

5°
0.17
0.19

15

36.5

55
5
5

100

35
18
161

75
34-5

20

3-1
3-3
66
0.16

O.2

8 to 9

20

75

almost

insol.

very sol.
48
67
sol.

65

7

10

77

97-5
59
9°
So
3i
155
0.08
0.17

73

127
123

53
54

100

Barium Dithionate
Barium Hydrate

Calcium Chloride

Manganous Chloride ....
Manganous Dithionate ....
Manganous Sulphate ....
Mercuric Chloride
Potassium Bichromate ....

TABLE OF SOLUBILITIES

55

TEMPERATURES INDICATED.

Zero.

iS°.

100°.

Potassium Carbonate ....

90

no

156

Potassium Chlorate

3.7

6

c6

Potassium Chloride

28

33

56

Potassium Fluortitanate . . .

0.5

i

—

Potassium Hydrogen Sulphate .

36

46

121

Potassium Nitrate

13

26

247

Potassium Nitrite

Potassium Permanganate . . .

—

6

—

Potassium Sulphate

8 c

IO.3

26

Silver Hyponitrite

almost
insol.

Silver Nitrate

1 20

2OO

IOOO

7

16.5

4$.?

Sodium Chloride

7C 6

T?.8

•jo 8

Sodium Hydrogen Carbonate . .

7

9

Sodium Hydrogen Phosphate

2.5

6

99

T\

85

1 80

very sol.

c

19

A2

Id.

2O

Sodium Tetraborate

I.C

4

CC

Sodium Thiosulphate ....

47

65

Strontium Chloride

44

Si

102

0.4

0.66

21.8

The figures given have been largely taken from Comey's
Dictionary of Chemical Solubilities. In most cases fractions
have been omitted. Where two or more observers give
different data, an average has generally been struck.

INDEX

Aluminium Chloride, 40.
Ammonium Nitrate, 13.
Ammonium Sodium Phosphate,

13-

Antimony Oxychloride, 27.
Antimony Trichloride, 25.
Arsenic Acid, 15.

Barium Dithionate, 12.

Barium Oxide, 46.

Barium Peroxide, hydrated, 47.

Boric Acid, 9.

Boron, 10.

Chromic Anhydride, 16.
Chromium Potassium Sulphate,

'5-

Chromous Acetate, 17.
Cuprous Chloride, 6.

Fluorsilicic Acid, 25.

Hydriodic Acid, 19.
Hydrobromic Acid, 1 8.
Hydrogen Dioxide, 48.
Hydrogen Persulphide, 45.
Hydroxylamine Sulphate, 49.

lodic Acid, 34.
Iodine Trichloride, 33.

Lead Dioxide, 7.
Lead Nitrite, basic, 5.

Manganese, 31.
Manganous Chloride, 31.
Mercuric Oxide, 8.

Nitric Anhydride, 37.
Nitrogen Iodide, 36.
Nitrogen Tetroxide, 36.

Phosphonium Iodide, 51.
Phosphorus Trichloride, 23.
Potassium Chlorate, 2.
Potassium Fluortitanate, 34.
Potassium Permanganate, 41.

Silicochloroform, 43.

Silicon, 42.

Silver Hyponitrite, 29.

Silver Nitrate, 27.

Sodium Ammonium Phosphate;

13-

Sodium Chloride, I.
Sodium Hydrogen Carbonate, 3.
Sodium Nitrite, 4.
Sodium Thiosulphate, n.
Strontium Chloride, 30.
Strontium Hydroxide, 30.
Sulphur Monobromide, 35.
Sulphuric Anhydride, 39.
Sulphuryl Chloride, 22.

Tin Tetrachloride, 21.
Titanic Oxide, 35.

Zinc free from Arsenic, 14.

57

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ORGANIC CHEMISTRY

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