%^
*s » it. rri
W
THE MEDICAL STUDENT'S
MANUAL
OF
CHEMISTRY
•^
R. A. WITTHAUS, A.M., M.D.,
Professor of Chemistry and Physics in the University of the City of New York j Professor of Chem-
istry and Toxicology in the University of Vermont ; Member of the Chemical Societies of
Paris and Berlin ; Member of the American -Chemical Society ; Fellow of the Amer-
ican Academy of Medicine ; of the N. Y. Academy of Medicine ; of the
American Association for the Advancement of Science, etc.
ffourtb E&ition.
NEW YORK
WILLIAM WOOD & COMPANY
1893
COPYRIGHTED, 1893
WILLIAM WOOD & COMPANY
PREFACE TO THE PRESENT EDITION.
THE arrangement and classification followed in previous edi-
tions have been retained.
The rules of orthography adopted by the Chemical Section of
the American Association for the Advancement of Science, and
by the National Bureau of Education (see Appendix A), have
been followed.
That portion of the work treating of the chemistry of the
carbon compounds has been much extended and in great part
rewritten. The organic substances have been, as in previous
•editions, classified according to their constitution so far as
known, and those alkaloids whose molecular structure has been
completely or partially determined have been removed from the
miscellaneous position among "alkaloids" to their proper places
in the classification. The prominence given to this branch of
the subject the author believes to be justified, notwithstanding
Its intricacy and the consequent difficulty of teaching it satisfac-
torily to medical students, by reason of the intimate connection
of organic chemistry Avith physiology and with modern phar-
macy, and the rapidly increasing use of complex organic pro-
ducts, natural and synthetic, as medicines.
R. A. W.
YORK, September 21st, 1893.
PREFACE TO THE FIRST EDITION.
IN venturing to add another to the already long list of chemi-
cal text-books, the author trusts that he may find some apology
in this, that the work is intended solely for the use of a class of
students whose needs in the study of this science are peculiar.
While the main foundations of chemical science, the philosophy
of chemistry, must be taught to and studied by all classes of stu-
dents alike, the subsequent development of the study in its de-
tails must be moulded to suit the purposes to which the student
will subsequently put his knowledge. And particularly in the
case of medical students, in our present defective methods of
medical teaching, should the subject be confined as closely as
may be to the general truths of chemistry and its applications
to medical science.
In the preparation of this Manual the author has striven to
produce a work which should contain as much as possible of
those portions of special chemistry which are of direct interest
to the medical practitioner, and at the same time to exclude so
far as possible, without detriment to a proper understanding of
the subject, those portions which are of purely technological in-
terest. The descriptions of processes of manufacture are there-
fore made very brief, while chemical physiology and the chemis-
try of hygiene, therapeutics, and toxicology have been dwelt upon.
The work has been divided into three parts. In the first part
the principles of chemical science are treated of, as well as so much
of chemical physics as is absolutely requisite to a proper under-
standing of that which follows. A more extended study of phy-
sics is purposely avoided, that subject being, in the opinion of the
author, rather within the domain of physiology than of chemistry.
The second part treats of special chemistry, and in this certain
departures from the methods usually followed in chemical text-
PKEFACE TO THE FIRST EDITION. V
books are to be noted. The elements are classed, not in metals
and metalloids, a classification as arbitrary as unscientific, but
into classes and groups according to their chemical characters.
In the text the formula of a substance is used in most instances
in place of its name, after it has been described, with a view to
giving the student that familiarity with the notation which can
only be obtained by continued use.
In the third part those operations and manipulations which
will be of utility to the student and physician are briefly described ;
not with the expectation that these directions can take the place
of actual experience in the laboratory, but merely as an outline
sketch in aid thereto.
Although the Manual puts forth no claim as a work upon an-
alytical chemistry, we have endeavored to bring that branch of
the subject rather into the foreground so far as it is applicable
to medical chemistry. The qualitative characters of each element
are given under the appropriate heading, and in the third part,
a systematic scheme for the examination of urinary calculi is
given. Quantitative methods of interest to the physician are also
described in their appropriate places. In this connection the au-
thor would not be understood as saying that the methods rec-
ommended are in all instances the best known, but simply
that they are the best adapted to the limited facilities of the
physician.
The author would have preferred to omit all mention of Troy
and Apothecaries' weight, but in deference to the opinions of
those venerable practitioners who have survived their student
days by a half-century, those weights have been introduced in
brackets after the metric, as the value of degrees Fahrenheit have
been made to follow those Centigrade.
R. A. W.
BUFFALO, N. Y., September 16th, 1883.
TABLE OF CONTENTS.
PAGE
PART I.— INTRODUCTION 1
GENERAL PROPERTIES OF MATTER 2
Indestructibility 2
Impenetrability 2
Weight 2
Specific gravity 3
States of matter 9
Divisibility 10
PHYSICAL CHARACTERS OF CHEMICAL INTEREST 10
Crystallization 10
Allotropy 15
Solution 15
Diffusion of liquids 17
Change of state 18
Specific heat 19
Thermometers 20
Spectroscopy 21
Polarimetry 25
Chemical effects of light 26
Galvanic electricity 27
CHEMICAL COMBINATION 30
Elements 30
Combination of elements 30
Atomic theory 32
Atomic and molecular weights 34
Valence or atomicity 38
Symbols, formulae, equations 39
Acids, bases and salts 41
Stoichiometry 44
Nomenclature 46
Radicals 49
Composition and constitution 50
Classification of elements 52
Vlll TABLE OF CONTENTS.
"A.OK
PART II.— SPECIAL CHEMISTRY 55
TYPICAL ELEMENTS 55
Hydrogen 55
Oxygen 59
Ozone 62
Water 64
Hydrogen dioxid 77
ACIDULOUS ELEMENTS 79
CHLORIN GROUP 79
1'luorin 79
Hydrogen fluorid 79
Chlorin 80
Hydrogen chlorid 8S
Compounds of chlorin and oxygen 85
Bromin 86
Hydrogen bromid 87
Oxacids of bromin 87
lodin 88
Hydrogen iodid 89
Chlorids of iodin 90
Oxacids of iodin 90
SULFUR GROUP 90
Sulfur 91
Hydrogen sulfid 92
Sulfur dioxid 95
Sulfur trioxid 96
Hyposulfurous acid 97
Sulfurous acid 97
Sulfuric acid 98
Thiosulfuric acid 100
Pyrosulf uric acid 100
Selenium and Tellurium 101
NITROGEN GROUP 101
Nitrogen 101
Atmospheric air 102
Ammonia ... 104
Hytirazin , 105
Hydrazoic acid 105
Hydroxylamin 105
Nitrogen monoxid 106
Nitrogen dioxid 106
Nitrogen trioxid 107
Nitrogen tetroxid 107
Nitrogen pentoxid 108
Nitrogen acids 108
Hyponitrous acid 108
TABLE OP CONTENTS. ix
PAGE
Nitrous acid 108
Nitric acid 109
Compounds of nitrogen with the halogens Ill
Phosphorus 112
Hydrogen phosphids 117
Oxids of phosphorus 118
Phosphorus acids 118
Compounds of phosphorus with the halogens 120
Arsenic 121
Hydrogen arsenids 122
Oxids of arsenic 123
Arsenic acids 125
Sulfids of arsenic 127
Haloid compounds of arsenic 127
Arsenical poisoning 128
Analytical 131
Antimony 137
Hydrogen antimonid 138
Oxids of antimony 138
Antimony acids 139
Chlorids of antimony 139
Sulfids of antimony 140
Antimonial poisoning • 141
Analytical 141
BORON GROUP • — . 142
Boron 142
CARBON GROUP 143
Carbon 143
Silicon 145
VANADIUM GROUP 146
MOLYBDENUM GROUP 146
AMPHOTERIC ELEMENTS 148
GOLD GROUP 148
IRON GROUP 148
Chromium 149
Manganese 150
Iron 152
Compounds of iron 153
Salts of iron 155
ALUMINIUM GROUP 158
Glucinium 158
Aluminium 150
Scandium 162
Gallium 162
Indium ... • 163
URANIUM GROUP 163.
TABLE OF CONTENTS.
PAGE
LEAD GROUP 163
BISMUTH GROUP 168
TIN GROUP 171
PLATINUM GROUP 173
BASYLOUS ELEMENTS 176
SODIUM GROUP 176
Lithium 176
Sodium 177
Potassium 184
Silver 192
Ammonium 194
THALLIUM GROUP .- 197
CALCIUM GROUP 197
Calcium 197
Strontium 203
Barium 203
MAGNESIUM GROUP 204
Magnesium 204
Zinc 207
Cadmium 209
NICKEL GROUP 209
COPPER GROUP 210
Copper 210
Mercury 215
COMPOUNDS OP CARBON '. 222
Homologous series 224
Isomerism 225
Classification of organic substances 226
ACYCLIC HYDROCARBONS . 229
First Series of Hydrocarbons — Paraffins 229
Haloid derivatives-. 232
Monoatouiic alcohols 237
Simple ethers 251
Monobasic acids 254
Anhydrids, chlorids, etc 262
Compound ethers 2(52
Aldehydes 266
Acetals 271
Ketones or acetones 271
Nitroparaffins 273
Monamins or amidoparaffins 274
Monamids 278
Amido acids 280
Betalns 290
Amid-ins, acetonamins, aldehydins, hydrazins 290
TABLE OF CONTENTS. xi
PAGE
Azoparaffins— Cyanogen compounds 291
Hydroxylamin derivatives 296
Sulfur derivatives 297
Compounds with other elements 299
Allylic series ; 301
Acrylic acids and aldehydes 304
Second Series of Hydrocarbons — Oleflns ; 308
Diatomic alcohols 310
Acids derived from the glycols 311
Diatomic, monobasic acids 313
Oxids and sulfids of carbon 316
Diatomic, dibasic acids 327
TJnsaturated acids 330
Compound ethers 331
Aldehydes and anhydrids 332
Diamins and triamins 332
Diamids, imids, and carbonic acids 335
Compound ureas 346
Carbonic acids 354
Triatomic alcohols 355
Acids 357
Ethers 358
Fats and oils 360
Lecithins— Nerve-tissue 368
Diamids of the tartronic series 370
Third Series of Hydrocarbons 370
Tetratomic alcohols 371
Acids 372
Hexatomic alcohols 374
Carbohydrates 374
Glucoses 375
Saccharoses 382
Amyloses 886
CYCLIC HYDROCARBONS 393
Monobenzenic Hydrocarbons. 395
Hyaloid derivatives 401
Phenols 402
Substituted phenols 406
Diatomic phenols 408
Triatomic phenols 409
Phenol dyes 410
Aromatic alcohols 411
Alphenols 411
Aldehydes 412
Ketones 413
xii TABLE OF CONTENTS.
PAGE
Acids 413
Sulfonic acids 416
Nitro derivatives of benzene 417
Ainido derivatives of benzene 418
Derivatives of anilin 419
Hydrazins • 421
Azo- and diazo- derivatives 421
Py rid in bases 422
Products of substitution of pyridin 423
Homologues of pyridin 424
Carbopyridic acids 425
Piperidin and related alkaloids 425
Compounds of other substituted benzenes 429
Compounds with Pentagonal Nuclei 430
Incomplete Benzenic Hydrocarbons 432
Alcohols 433
Bi- and Polybenzoic Hydrocarbons 434
Hydrocarbons with Indirectly United Benzene Nuclei 434
Derivatives of the phenylmethanes 435
Hydrocarbons with Directly United Benzene Nuclei. . 436
Alkaloids containing dipyridyl or phenanthrene
nuclei 438
Opium alkaloids 439
Substitution derivatives of naphthalene 445
Quinolin bases 447
INDIGO GROUP 450
ANTHRACENE GROUP 452
Derivatives of anthracene 452
Terebenthic Series 453
COMPOUNDS OP UNKNOWN CONSTITUTION 460
Glucosids 460
Alkaloids 463
Volatile alkaloids 466
Fixed alkaloids 466
Albuminoid Substances 472
Animal Cryptolytes 490
Animal Coloring Matters 491
PART III.— CHEMICAL TECHNICS 493
General rules 493
Reagents 494
Glass tubing 495
Collection of gases 496
Solution 497
Precipitation, decantation, etc 498
TABLE OF CONTENTS. Xlll
PAGE
Evaporation, drying, etc 500
Weighing 503
Measuring 504
Scheme for Analysis of Calculi 507
APPENDIX A. — Orthography and pronunciation 511
APPENDIX B.— Tables 516
INDEX.. . 523
THE MEDICAL STUDENT'S
MANUAL OF CHEMISTRY.
PART I.
INTRODUCTION.
THE simplest definition of chemistry is a modification of that
given by Webster : That branch of science which treats of the
composition of substances, their changes in composition, and the
laws governing- such changes.
If a bar of soft iron be heated sufficiently it becomes luminous ;
if caused to vibrate it emits sound ; if introduced within a coil of
wire through which a galvanic current is passing, it becomes
magnetic and attracts other iron brought near it. Under all
these circumstances the iron is still iron, and so soon as the heat,
vibration, or galvanic current ceases, it will be found with its
original characters unchanged ; it has suffered no change in
composition. If now the iron be heated in an atmosphere of
oxygen gas, it burns, and is converted into a substance which,
although it contains iron, has neither the appearance nor the
properties of that metal. The iron and a part of the oxygen
have disappeared, and have been converted into a new sub-
stance, differing from either ; there has been change in composi-
tion, there has been chemical action. Changes wrought in mat-
ter by physical forces, such as light, heat, and electricity, are
temporary, and last only so long as the force is active ; except in
the case of changes in the state of aggregation, as when a sub-
stance is pulverized or fashioned into given shape. Changes in
chemical composition are permanent, lasting until some other
change is brought about by another manifestation of chemical
action.
However distinct chemical may thus be from physical forces, it
is none the less united with them in that grand correlation whose
1
MANUAL OF CHEMISTRY.
existence was first announced by Grove, in 1842. As, from chem-
ical action, manifestations of every variety of physical force may
be obtained : light, heat, and mechanical force from the oxida-
tion of carbon ; and electrical force from the action of zinc upon
sulfuric acid — so does chemical action have its origin, in many
instances, in the physical forces. Luminous rays bring about
the chemical decomposition of the salts of silver, and the chem-
ical union of chlorin and hydrogen ; by electrical action a decom-
position of many compounds into their constituents is instituted,
while instances are abundant of reactions, combinations, and de-
compositions which require a certain elevation of temperature
for their production. While, therefore, chemistry in the strictest
sense of the term, deals only with those actions which are
attended by a change of composition in the material acted upon,
yet chemical actions are so frequently, nay universally, affected
by existing physical conditions, that the chemist is obliged to
give his attention to the science of physics, in so far, at least, as
it has a bearing upon chemical reactions, to chemical physics — a
branch of the subject which has afforded very important evidence
in support of theoretical views originating from purely chemical
reactions.
General Properties of Matter.
Indestructibility. — The result of chemical action is change in
the composition of the substance acted upon, a change accom-
panied by corresponding alterations in its properties. Although
we may cause matter to assume a variety of different forms, and
render it, for the time being, invisible, yet in none of these
changes is there the smallest particle of matter destroyed. When
carbon is burned in an atmosphere of oxygen, it disappears, and,
so far as we can learn by the senses of sight or touch, is lost ; but
the result of the burning is an invisible gas, whose weight is equal
to that of the carbon which has disappeared, plus the weight of
the oxygen required to burn it.
Impenetrability. — Although one mass of matter may penetrate
another, as when a nail is driven into wood, or when salt is dis-
solved in water ; the ultimate particles of which matter is com-
posed cannot penetrate each other, and, in cases like those above
cited, the particles of the softer substance are forced aside, or the
particles of one substance occupy spaces between the particles of
the other. Such spaces exist between the ultimate particles of
even the densest substances.
Weight. — All bodies attract each other with a force which is
in direct proportion to the amount of matter which they contain.
The force of this attraction, exerted upon surrounding bodies by
GENERAL PROPERTIES OF MATTER. S
the earth, becomes sensible as weight, when the motion of the
attracted body toward the centre of gravity of the earth is
prevented.
In chemical operations we have to deal with three kinds of
weight : absolute, apparent, and specific.
The Absolute Weight of a body is its weight in vacuo. It is
determined by placing the entire weighing apparatus under the
receiver of an air-pump.
The Apparent Weight, or Relative Weight, of a body is that
which we usually determine with our balances, and is, if the
volume of the body weighed be greater than that of the counter-
poising weights, less than its true weight. Every substance in a
liquid or gaseous medium suffers a loss of apparent weight equal
to that of the volume of the medium so displaced. For this
reason the apparent weight of some substances may be a minus
quantity. Thus, if the air contained in a vessel suspended from
one arm of a poised balance be replaced by hydrogen, that arm
of the balance to which the vessel is attached will rise, indicating
a diminution in weight. (See Weighing ; Part III.)
The Specific Weight, or Specific Gravity, of a substance is the
weight of a given volume of that substance, as compared with
the weight of an equal bulk of some substance, accepted as a
standard of comparison, under like conditions of temperature
and pressure. The sp. gr. of solids and liquids are referred to
water ; those of gases to air or to hydrogen.* Thus the sp. gr.
of sulfuric acid being 1.8, it is, volume for volume, one and
eight-tenth times as heavy as water. As, by reason of their
different rates of expansion by heat, solids and liquids do not
have the same sp. gr. at all temperatures, that at which the
observation is made should always be noted, or some standard
temperature adopted. The standard temperature adopted by
some continental writers and in the U. S. P. is 15° (59° P.). Other
standard temperatures are 4° (39°. 2 P.), the point of greatest
density of water, used by most continental writers, and 15°. 6
{60° P.), used in Great Britain and to some extent in this country.
The determination of the specific weight of a substance is
frequently of great service. Sometimes it affords a rapid means
of distinguishing between two substances similar in appearance ;
sometimes in determining the quantity of an ingredient in a
mixture of two liquids, as alcohol and water ; and frequently in
determining approximately the quantity of solid matter in
solution in a liquid. It is the last object which we have in view
in determining the sp. gr. of the urine.
* As the sp. gr. of pure air (hydrogen = l'i is 14.42, the sp. gr. in terms of air X
14.4;! = sp. gr. in terms of hydrogen. Thus, the sp. gr. of hydrochloric acid gas
.(A = 1) is 1.259. Its sp. gr. (H = 1) is therefore 1.259 x 14.42 = 36.31.
4 MANUAL OF CHEMISTRY.
An aqueous solution of a solid heavier than water has a higher
sp. gr. than pure water, the variation in sp. gr. following a
regular but different rate with each solid. In a simple solution —
one of common salt in water, for instance — the proportion of
solid in solution can be determined from the sp. gr. In complex
solutions, such as the urine, the sp. gr. does not indicate the
proportion of solid in solution with accuracy. In the absence of
sugar and albumen, a determination of the sp. gr. of urine affords
an indication of the amount of solids sufficiently accurate for
usual clinical purposes. Moreover, as urea is much in excess over
other urinary solids, the oscillations in the sp. gr. of the urine, if
the quantity passed in twenty-four hours be
considered, and in the absence of albumen
and sugar, indicate the variations in the elim-
ination of urea, and consequently the activity
of disassimilation of nitrogenous material.
To determine the sp. gr. of substances, dif-
ferent methods are adopted, according as the
substance is in the solid, liquid, or gaseous
state ; is in mass or in powder ; or is soluble
or insoluble in water.
SOLIDS. — The substance is heavier than
water, insoluble in that liquid, and not in
powder. — It is attached by a fine silk fibre or
platinum wire to a hook arranged on one arm
of the balance, and weighed. A beaker full of
pure water is then so placed that the body is immersed in it (Fig.
1), and a second weighing made. By dividing the weight in air
by the loss in water, the sp. gr. (water = 1.00) is obtained. Ex-
ample :
A piece of lead weighs in air 82.0
A piece of lead weighs in water 74.9
Loss in water. 7.1
82.0
-~~* = 11.55 = sp. gr. of lead.
FIG. 1.
The substance is in powder, insoluble in water. — The specific
gravity bottle (Fig. 3), filled with water, and the powder, pre-
viously weighed and in a separate vessel, are weighed together.
The water is poured out of the bottle, into which the powder is
introduced, with enough water to fill the bottle completely. The
weight of the bottle and its contents is now determined. The
weight of the powder alone, divided by the loss between the first
and second weighings, is tbe specific gravity. Example :
GENERAL PROPERTIES OF MATTER. 5
Weight of iron filings used 6.562
Weight of iron filings and sp. gr. bottle filled with water 148.327
Weight of sp. gr. bottle containing iron filings and filled
with water 147.470
Water displaced by iron 0.857
6.562
O g57 = 7.65 = sp. gr. of iron.
The substance is lighter than water.— A sufficient bulk of some
heavy substance, whose sp. gr. is known, is attached to it and
the same method followed, the loss of weight of the heavy sub-
stance being subtracted from the total loss. Example :
A fragment of wood weighs 4.3946
A fragment of lead weighs 10.6193
Wood with lead attached weighs in air 15.0139
Wood with lead attached weighs in water 5.9295
Loss of weight of combination ....... . .............. 9.0844
L6ss of weight of lead in water (determined as above) 0. 7903
Loss of weight of wood ........................... 8.2941
6 = 0.529 = sp. gr. of wood.
The substance is soluble in or decomposable by water. — Its spe-
cific gravity, referred to some liquid not capable of acting on it,
is determined, using that liquid as water is used in the case of
insoluble substances. The sp. gr. so obtained, multiplied by that
of the liquid used, is the sp. gr. sought. Example :
A piece of potassium weighs ....................... 2.576
A sp. gr. bottle full of naphtha, sp. gr. 0. 758, weighs 22. 784
25.360
The bottle with potassium and naphtha weighs ... 23. 103
Loss 2.257
2'576 = 1.141 X 0.758 = 0.865 = sp. gr. of potassium.
2.257
LIQUIDS. — The sp. gr. of liquids is determined by the specific
gravity balance, by the specific gravity bottle, sometimes called
picnometer, or by the spindle or hydrometer.
By the balance. — The liquid, previously brought to the proper
temperature, is placed in the cylinder a (Fig. 2), and the plunger
immersed in it, and attached to the arm of the balance. The
weights are now adjusted, beginning with the largest, until the
balance is in equilibrium. The sp. gr. indicated by the balance
in Fig. 2 is 1.98.
6
MANUAL OF CHEMISTRY.
By the bottle. — An ordinary analytical balance is used. A bottle
of thin glass (Fig. 3) is so made as to contain a given volume of
water, say 100 c.c., at 15° C., and its weight is determined once-
for all. To use the picnorneter, it is filled with the liquid to be
examined and weighed. The weight obtained, minus that of the
bottle, is the sp. gr. sought, if the bottle contain 1000 c.c.; 1-10 if
100 c.c., etc. Example : Having a bottle whose weight is 35.35,
and which contains 100 c.c.; filled with urine it weighs 137.91, the
sp. gr. of the urine is 137.91-35.35 = 102.56 X 10 = 1025.6—
Water = 1000.
FIG. 2.
By the spindle.— The method by the hydrometer is based upon
the fact that a solid will sink in a liquid, whose sp. gr. is greater
than its own, until it has displaced a volume of the liquid whose
weight is equal to its own ; and all forms of hydrometers are
simply contrivances to measure the volume of liquid which they
displace when immersed. The hydrometer most used by physi-
cians is the urinometer (Fig. 4). It should not be chosen too
small, as the larger the bulb, and the thinner and longer the
stem, the more accurate are its indications. It should be tested
by immersion in liquids of known sp. gr., and the error at differ-
ent points of the scale should be noted on the box. The most
convenient method of using the instrument is as follows : The
cylinder, which should have a foot and rim, but no pouring lip,
(iKXERAL PROPERTIES OF MATTER. 7
is filled to within an inch of the top ; the spindle is then floated
and the cylinder completely filled with the liquid under exami-
nation (Fig. 4). The reading is then taken at the highest point a,
where the surface of -the liquid comes in contact with the
spindle.*
In all determinations of sp. gr. the liquid examined should
have the temperature for which the instrument is graduated, as
all liquids expand with heat and contract when cooled, and con-
FIG. 3.
FIG. 4.
sequently the result obtained will be too low if the urine or
other liquid be at a temperature above that at which the instru-
ment is intended to be used, and too high if below that tempera-
ture. An accurate correction may be made for temperature in
simple solutions. In a complex fluid like the urine, however,
this can only be done roughly by allowing 1 ° of sp. gr. for each
3° C. (5°. 4 Fahr.) of variation in temperature.
* The advantages of the method described over that iisually followed are : Greater
facility in reading, less liability to error, the possibility of taking the readiug in
opaque liquids, and the fact that readings are made upward, not downward.
8 MANUAL OF CHEMISTEY.
GASES AXB VAPORS. — The specific gravities of gases and va-
pors are of1 great importance in theoretical chemistry, as from
them we can determine molecular weights, in obedience to the
law of Avogadro (p. 33).
Bases. — The specific gravities of gases are obtained as follows :
A glass flask of about 300 c.e. capacity, having a neck 20 centi-
metres long and 6 millimetres in diameter, and fitted with a glass
stopcock, is filled with mercury; reversed over mercury ; and filled
with the gas to just below the stopcock. The stopcock is now
closed; the temperature, t; the barometric pressure, H ; and the
height of the mercurial column in the neck above that in the
trough, h, are determined, and the flask weighed. Let P be
the weight found, and V the capacity of the flask, determined
once for all, then
-= V0= the volume of
--60 (i+O 00366 £)
The flask is then brought under the receiver of an air pump,
the glass stopcock being open, and the air alternately exhausted
and allowed to enter until the gas in the flask is replaced by
air. The temperature t', the barometric pressure H', and the
weight of the flask filled with air P', are now determined. From
these results the weight, K, of the gas occupying the volume V0
is obtained by the formula :
The sp. gr. referred to air is found by the formula :
K
VoXO.001293
and that referred to hydrogen by the formula :
_ K _
VoX 0.001293X0. 06927
Vapors. — The specific gravity of vapors is best determined by
Meyer's method, as follows : A small, light glass vessel (Fig. 5) is
filled completely with the solid or liquid whose vapor density is
to be determined and weighed ; from this weight that of the ves-
tsel is subtracted ; the difference being the weight of the
substance P. The small vessel and contents are now in-
troduced into the large branch of the apparatus (Fig. 6),
whose weight is then determined. The apparatus is now
filled with mercury, the capillary opening at the top of
the larger branch is closed by the blow-pipe, and the
whole again weighed. The apparatus is suspended by a
*• 5- metallic wire near the bottom of a long tube closed at the
bottom, and containing about 50 c.c. of some liquid whose boil-
ing-point is constant and higher than that of the substance
experimented on. When the liquid has been heated to active
GENERAL PROPERTIES OF MATTER. 9
boiling, and the mercury ceases to escape from the small tube,
the barometric pressure and the temperature of the air are
observed. After the apparatus is cooled, the tube (Fig. 6), with
its contents is weighed,- and the difference in the level of mercury
which existed in the two branches during the heating determined
by breaking the capillary point, tilting the apparatus until the
smaller branch is completely filled, marking the level of mercury
in the larger branch, and afterward measuring the distance from
that point to the opening.
By the above process the following factors are determined :
P=weight of substance ;
T=boiling-point of external liquid ;
Z=temperature of air ;
H=barometric pressure reduced to 0" ;
h = difference in level of mercury in two branches of tube ;
./V=tension of vapor of mercury at T ;
a = weight of mercury used ;
<?=weight of mercury required to fill the tube Fig. 5 ;
r=weight of mercury remaining in the apparatus after
heating.
From these the specific gravity, air = 1, is obtained by the
•equation :
B_ P 760 (1+0.00367 T) 13.59
~ (H+h+h') 0.0012932 \(a+q) •{ 1+0.0000303 (T— t) }- —r •{ 1+
0.00018 (T— t) H [1+0.00018 t]
The sp. gr. in terms of air=l may be reduced to sp. gr. referred
to hydrogen =2, by dividing by 0.06927.
States of Matter. — Matter exists in one of three states ; solid,
liquid, and gaseous. In the solid form, the particles of matter
are comparatively close together, and are separated with more
difficulty than are those of liquid or gaseous matter ; or in other
words the cohesion of solid matter is greater than that of the
other two forms. In the liquid, the particles are less firmly
bound together, and are capable of freer motion about one an-
other. In the gas, the mutual attraction of the particles disap-
pears entirely, and their distance from each other depends upon
the pressure to which the gas is subjected.
The term fluid applies to both liquids and gases, the former
beiiiy; designated as incompressible, from the very slight degree
to which their volume can be reduced by pressure. The gases
are designated as compressible fluids, from the fact that their
volume can be reduced by pressure, to an extent limited only by
their passage into the liquid form.
It 's highly probable that all substances, which are not decom-
posed when heated, are capable of existing in the three forms of
solid, liquid, and gas. There are, however, some substances
which are only known in two forms — as alcohol ; or in a single
10
MANUAL OF CHEMISTRY.
form — as carbon ; probably because we are as yet unable to pro-
duce artificially a temperature sufficiently low to solidify the one,
or sufficiently high to liquefy or volatilize the other.
A vapor is an aeriform fluid into which a substance, solid or
liquid at the ordinary temperature, is converted by elevation
of temperature, or by diminution of pressure.
Since the liquefaction of the so-called permanent
gases, the distinction between gases and vapors is
only one of degree and of convenience. A liquid is
said to be volatile when, like ether, it is readily
converted into vapor. It is said to be fixed if,
like olive oil, it does not yield a vapor when
heated. Certain solids are directly volatile, like
camphor, passing from the condition of solid to
that of vapor without liquefaction.
Divisibility. — All substances are capable of be-
ing separated, with greater or less facility, by
mechanical means into minute particles. With
suitable apparatus, gold may be divided into
fragments, visible by the aid of the microscope,
whose weight would be TnjTjTrawffTnrTra °f a grain ;
and it is probable that when a solid is dissolved in.
a liquid a still greater subdivision is attained.
Although we have no direct experimental evi-
dence of the existence of a limit to this divisibility,
we are warranted in believing that matter is not
infinitely divisible. A strong argument in favor
of this view being that, after physical subdivision has reached
the limit of its power with regard to compound substances,
these may be further divided into dissimilar bodies by chemical
means.
The limit of mechanical subdivision is the molecule of the physi-
cist, the smallest quantity of matter with which he has to deal,
the smallest quantity that is capable of free existence.
Physical Characters of Chemical Interest.
Crystallization. — Solid substances exist in two forms, amor-
phous and crystalline. In the former they assume no definite
shape ; they conduct heat equally well in all directions ; they
break irregularly ; and, if transparent, allow light to pass through
them equally well in all directions. A solid in the crystalline
form has a definite geometrical shape ; conducts heat more read-
ily in some directions than in others ; when broken, separates in
certain directions, called planes of cleavage, more readily than in
others ; and modifies the course of luminous rays passing through
PHYSICAL CHARACTERS OF CHEMICAL INTEREST. 11
it differently when they pass in certain directions than when tl ey
pass in others.
Crystals are formed in one of four ways : 1.) An amorphous
substance, by slow and gradual modification, may assume the
crystalline form ; as vitreous arsenic trioxid (q. v.) passes to the
crystalline variety. 2.) A fused solid, on cooling, crystallizes;
as bismuth. 3.) When a solid is sublimed it is usually condensed
FIG. 7.
in the form of crystals. Such is the case with arsenic trioxid. 4.>
The usual method of obtaining crystals is by the evaporation of
a solution of the substance. If the evaporation be slow and the
solution at rest, the crystals are large and well-defined. If the
crystals separate by the sudden cooling of a hot solution, espe-
cially if it be agitated during the cooling, they are small.
Most crystals may be divided by imaginary planes into equal,
9 B
FIG. 8.
symmetrical halves. Such planes are called planes of symmetry.
Thus in the crystals in Fig. 7 the planes ab ab, ac ac, and be be
are planes of symmetry.
When a plane of symmetry contains two or more equivalent
linear directions passing through the centre, it is called the prin-
cipal plane of symmetry ; as in Fig. 8 the plane ab ab, containing:
the equal linear directions aa and bb.
MANUAL OF CHEMISTRY.
Any normal erected upon a plane of symmetry, and prolonged
in both directions until it meets opposite parts of the exterior of
the crystal, at equal distances from the plane, is called an axis
of symmetry.
The axis normal to the principal plane is the principal axis.
Thus in Fig. 8, aa, &&, and cc are axes of symmetry, and cc is the
principal axis.
Upon the relations of these imaginary planes and axes a classi-
fication of all crystalline forms into six systems has been based.
I. The Cubic, Regular, or Monometric System. — The crystals
of this system have three equal axes, aa, &&, cc, Fig. 7, crossing
•each other at right angles. The simple forms are the cube ; and
FIG. 9.
its derivatives, the octahedron, tetrahedron, and rhombic dode-
cahedron. The crystals of this system expand equally in all
directions when heated, and are not doubly refracting.
II. The Bight Square Prismatic, Pyramidal, Quadratic, Tetrag-
onal, or Dimetric System contains those crystals having three
axes placed at ri^ht angles to each other — two as aa and &&, Fig.
8, being equal to each other and the third, cc, either longer or
shorter. The simple forms are the right square prism and the
right square based octahedron. The crystals of this system ex <
pand equally only in two directions when heated. They refract
light doubly in all directions except through one axis of single
refraction.
III. The Rhombohedral or Hexagonal System includes crys-
tals having four axes, three of which «a, aa, aa, Fig. 9, are of
PHYSICAL CHARACTERS OF CHEMICAL INTEREST.
equal length and cross each other at 60° in the same plane ; to-
which plane the fourth axis, cc, longer or shorter than the others,
is at right angles. The. simple forms are the regular six-sided
prism, the regular dodecahedron, the rhombohedron, and the
scalenohedron. These crystals expand equally in two directions
when heated, and refract light singly through the principal axis,
but in other directions refract it doubly.
IV. The Rhombic, Right Prismatic, or Trimetric System. —
The axes of crystals of this system are three in number, all at
right angles to each other, and all of unequal length. Fig. 8
represents crystals of this system, supposing aa, &&, and cc to be
unequal to each other. The simple forms are the right rhombic
octahedron, the right rhombic prism, the right rectangular octa-
hedron, and the right rectangular prism. The crystals of this
FIG. 10.
system, like those of the two following, have no true principal
plane or axis.
V. The Oblique, Monosymmetric, or Monoclinic System. — The
crystals of this system have three axes, two of which, aa, and cc.
Fig. 10, are at right angles ; the third, bb, is perpendicular to one
and oblique to the other. They may be equal or all unequal in
length. The simple forms are the oblique rectangular and
oblique rhombic prism and octahedron.
VI. The Doubly Oblique, Asymmetric, Triclinic, or Anorthic
System contains crystals having three axes of unequal length,
crossing each other at angles not right angles ; Fig. 10, aa, bb,
and cc being unequal and the angles between them other than 90°.
The crystals of the fourth, fifth, and sixth systems, when
heated, expand equally in the directions of their three axes.
They refract light doubly except in two axes.
Secondary Forms. — The crystals occurring in nature or pro-
duced artificially have some one of the forms mentioned above,
or some modification of those forms. These modifications, or
14
MAXUAL OF CHEMISTRY.
secondary forms, may be produced by symmetrically removing
the angles or edges, or both angles and edges, of the primary
forms. Thus, by progressively removing the angles of the cube,
the secondary forms shown in Fig. 11 are produced.
It sometimes happens in the formation of a derivative form
that alternate faces are excessively developed, producing at
length entire obliteration of the others, as shown in Fig. 12.
Such crystals are said to be hemihedral. They can be developed
only in a system having a principal axis.
FIG. 11.
Isomorphism. — In many instances two or more substances
crystallize in forms identical with each other, and, in most cases,
such substances resemble each other in their chemical constitu-
tion. They are said to be isomorphous. This identity of crystal-
line form does not depend so much upon the nature of the ele-
ments themselves, as upon the structure of the molecule. The
protoxid and peroxid of iron do not crystallize in the same form,
nor can they be substituted for each other in reactions without
radically altering the properties of the resultant compound. On
the other hand, all that class of salts known as alums are isomor-
phous. Not only are their crystals identical in shape, but a crys-
tal of one alum, placed in a saturated solution of another, grows
TIG. 12.
by regular deposition of the second upon its surface. Other
alums may be subsequently added to the crystal, a section of
which will then exhibit the various salts, layer upon layer.
Dimorphism. — Although most substances crystallize, if at all,
in one simple form, or in some of its modifications, a few bodies
are capable of assuming two crystalline forms, belonging to
different systems. Such are said to be dimorphous. Thus, sul-
fur, as obtained by the evaporation of its solution in carbon
disulfid, forms octahedra, belonging to the fourth system.
When obtained by cooling melted sulfur the crystals are
PHYSICAL CHARACTERS OF CHEMICAL INTEREST. 15
oblique prisms belonging to the fifth system. Occasional in-
stances of trimorphism, of the formation of crystals belonging to
three different systems- by the same substance, are also known.
Many substances, on assuming the crystalline form, combine
with a certain amount of water which exists in the crystal in a
solid combination. Thus nearly half of the weight of crystallized
alum is water. This water is called water of crystallization, and
is necessary to the maintenance of the crystalline form, and
frequently to the color. If blue vitriol be heated, it loses its
water of crystallization, and is converted into an amorphous,
white powder. Some crystals lose their water of crystallization
on mere exposure to the air. They are then said to effloresce.
Usually, however, they only lose their water of crystallization
wrhen heated. (See p. 66.)
AUotropy. — Dimorphism apart, a few substances are known to
exist in more than one solid form. These varieties of the same
substance exhibit different physical properties, while their chem-
ical qualities are the same in kind. Such modifications are said
to be allotropic. One or more allotropic modifications of a sub-
stance are usually crystalline, the other or others amorphous or
vitreous. Sulfur, for example, exists not only in two dimor-
phous varieties of crystals, but also in a third, allotropic form, in
•which it is flexible, amorphous, and transparent. Carbon exists
in three allotropic forms : two crystalline, the diamond and
graphite ; the third amorphous.
In passing from one allotropic modification to another, a sub-
stance absorbs or gives out heat.
Solution. — A solid, liquid, or gas is said to dissolve, or form a
solution with a liquid when the two substances unite to form a
homogeneous liquid. Solution may be a purely physical process
or a chemical combination.
In simple or physical solution there is no modification of the
properties of the solvent and dissolved substance, beyond the
liquefaction. The latter can be regenerated, in its primitive
form, by simple evaporation of the former ; and the act of solu-
tion is usually attended by a diminution of temperature.
In chemical solution the properties of both solvent and dis-
solved are more or less modified. The dissolved substance cannot
be obtained from the solution by simple evaporation of the sol-
vent, unless the compound formed be decomposable, with forma-
tion of the original substance, at the temperature of the evapora-
tion. The act of chemical solution is usually attended by an
elevation of temperature.
The amount of solid, liquid, or gas which a liquid is capable of
dissolving by simple solution depends upon the following condi-
tions :
16 MANUAL OF CHEMISTRY.
1. The nature of the solvent and substance to be dissolved. — No
rule can be given, which will apply in a general waj to the
solvent power of liquids, or to the solubility of substances.
Water is of all liquids the best solvent of most substances. In it
some substances are so readily soluble that they absorb a suffi-
ciency from the atmosphere to form a solution ; as calcium
ehlorid. Such substances are said to deliquesce. Other sub-
stances are insoluble in water in any proportion ; as barium
sulfate. Elementary substances (with the exception of chlorin)
are insoluble, or sparingly soluble, in water. Substances rich in
carbon are insoluble in water, but soluble in organic liquids.
2. The temperature usually has a marked influence on the
solubility of a substance. As a rule, water dissolves a greater
quantity of a solid substance as the temperature is increased.
This increase in solubility is different in the case of different
soluble substances. Thus the increase in solubility of thechlorids
of barium and of potassium is directly in proportion to the
increase of temperature. The solubility of sodium ehlorid is
almost imperceptibly increased by elevation of temperature. The
solubility of sodium sulfate increases rapidly up to 83° (91°. 4 F.),
above which temperature it again diminishes.
The solubility of gases, except hydrogen, in water is the greater
the lower the temperature, and the greater the pressure.
The amount of a substance that a given quantity of solvent is
capable of dissolving at a given temperature is fixed. A solution
containing as much of the dissolved substance as it is capable of
dissolving is said to be saturated. If made at high temperatures
it is said to be a hot saturated, and if at ordinary temperatures a
cold saturated solution.
If a hot saturated solution of a salt be cooled, the solid is in
most instances separated by crystallization. If, in the case of
certain substances, such as sodium sulfate, however, the solution
be allowed to cool while undisturbed, no crystallization occurs,
and the solution at the lower ^temperature contains a greater
quantity of the solid than it could dissolve at that temperature.
Such a solution is said to be supersaturated. The contact of
particles of solid material with the surface of a supersaturated
solution induces immediate crystallization, attended with eleva-
tion of temperature.
3. The presence of other substances already dissolved. — If to a
saturated solution of potassium nitrate, sodium ehlorid be added,
a further quantity of potassium nitrate may be dissolved. In
this case there is double decomposition between the two salts,
and the solution contains, besides them, potassium ehlorid and
sodium nitrate.
4. The presence of a second solvent. — If two solvents, a and b,
PHYSICAL CHARACTERS OF CHEMICAL INTEREST. 17
incapable of mixing with each other, be brought in contact with
a substance which both are capable of dissolving ; neither a nor
b takes up the whole of the substance to the exclusion of the
other, however greatly the solvent power or bulk of the one may
exceed that of the other. The relative quantities taken up by
each solvent is in a constant ratio.
Diffusion of Liquids — Dialysis.— If a liquid be carefully floated
upon the surface of a second liquid, of greater density, with
which it is capable of mixing, two distinct layers will at first be
formed. Even at perfect rest, mixture will begin immediately,
and progress slowly until the two liquids have diffused into each
other to form a single liquid whose density is the same throughout.
Substances differ from each other in the rapidity with which
FIG. 13.
they diffuse. Substances capable of crystallization, crystalloids,
are much more diffusible than those which are incapable of
crystallization — colloids.
If, in place of bringing two solutions in contact with each
other, they be separated by a solid or semi-solid, moist, colloid
layer, diffusion takes place in the same way through the inter-
posed layer. Advantage is taken of this fact to separate
crystalloids from colloids by the process of dialysis. The mixed
solutions of crystalloid and colloid are brought into the inner
vessel of a dialyser, Fig. 13, whose bottom consists of a layer of
moist parchment paper, while the outer vessel is filled with pure
water. Water passes into the inner vessel, and the crystalloid
passes into the water in the outer vessel. By frequently chang-
ing the water in the outer vessel, solutions of the albuminoids or
of ferric hydrate, etc., almost entirely free from crystalloids, may
be obtained.
2
18 MANUAL OF CHEMISTRY.
Change of State— Latent Heat. — The passage of a substance
from one form to another is always attended by the absorption
or liberation of a definite amount of heat. In passing from the
solid to the gaseous form, a body absorbs a definite amount of
heat with each change of form. If a given quantity of ice at a
temperature below the freezing-point of water be heated, its
temperature gradually rises until the thermometer marks 0°
(32° F.), at which point it remains stationary until the last parti-
cle of ice has disappeared. At that time another rise of the
thermometer begins, and continues until 100° (212° F.) is reached
(at 760 mm. of barometric pressure), when the water boils, and
the thermometer remains stationary until the last particle of
water has been converted into steam ; after which, if the applica-
tion of heat be continued, the thermometer again rises. During
these two periods of stationary thermometer, heat is taken up by
the substance, but is not indicated by the thermometer or by
the sense. Not being sensible, it is said to be latent, a term
Avhich is liable to mislead, as conveying the idea that heat is
stored up in the substance as heat ; such is not the case. During
the periods of stationary thermometer the heat is not sensible as
heat, for the reason that it is being used up in the work required
to effect that separation of the particles of matter which consti-
tutes its passage from solid to liquid or from liquid to gas.
The amount of heat required to bring about the passage of a
given weight of a given substance from the denser to the rarer
form is always the same, and the temperature indicated by the
thermometer during this passage is always the same for that sub-
stance, unless in either case a modification be caused by a varia-
tion in pressure.
When a solid is liquefied it is said to fuse, or to melt.
The degree of temperature indicated by the thermometer while
a substance is passing from the solid to the liquid state is called
its fusing-point ; that indicated during its passage from the
liquid to the solid form, its freezing-point ; and that indicated dur-
ing its passage from the liquid to the gaseous form, its boiling-
point.
The absorption of heat by a volatilizing liquid is utilized in the
arts and in medicine for the production of cold (which is simply
the absence of heat), in the manufacture of artificial ice, and
in the production of local anaesthesia by the ether-spray. The
removal of heat from the body in this way, by the evaporation of
perspiration from the surface, is an important factor in the main-
tenance of the body temperature at a point consistent with life.
When a substance passes from a rarer to a denser form it gives
out — liberates — an amount of heat equal to that which it absorbed
in its passage in the opposite direction. It is for this reason that,
PHYSICAL CHAKACTEKS OF CHEMICAL INTEREST. 19
Awhile we apply heat to convert a liquid into a vapor, we apply
«old (or abstract heat) to reduce a gas to a liquid. As a rule, the
Ihermometrical indication is the same in whichever direction the
<;hange of form occurs. Some substances, however, solidify at a
"temperature slightly different from that at which they fuse.
Usually a solid, when sufficiently heated, passes suddenly into
"the liquid form, and the fusing-point is sharply denned, and
•easily determined. Some solids, however, like iron and the fats,
when heated to the proper degree, are gradually liquefied, first
becoming pasty. Such substances have no true fusing-point, as
the thermometer passes through several degrees during their
liquefaction.
Most solids, when heated, are first converted into liquids, and
"these into gases. There are, however, some exceptions to this
rule. Most vapors, when condensed, pass into the liquid form,
and this in turn into the solid. Some substances, however, are
•condensed from the form of vapor directly to that of solid, in
which case they are said to sublime.
Law of Raoult. — When a substance is dissolved in a liquid the
freezing point of the latter is lowered and the amount by which
it is lowered varies with the nature and quantity of the dissolved
substance. Raoult found that the product obtained by mul-
tiplying the amount by which the freezing point of a solution
•containing a fixed quantity of the dissolved substance (1 gram in
100 c.c.), is lowered by the molecular weight of that substance
is nearly constant at 18°. 5 C. or at 87° C. (See molecular weight,
p. 38.) The following are some of the results of Raoult. D. =de-
pression of freezing point in one per cent, solution ; M.W.=molec-
ular weight ; M.D. = molecular depression.
M. W.
D.
M.D.
Hydrogen sulfid
34
0 560
19 2
Sulfurous acid
82
0 232
19 1
Nitrous acid
47
0 404
19 0
Hydrocyanic acid
27
0 718
19 4
Acetic acid
60
0 317
19 0
Ammonia
17
1 117
16 9
Methyl alcohol
32
0 541
17 3
Glvcerin
92
0 186
17 1
•Cane sugar .
342
0 054
18 5
Chloral hvdrate
165 5
0 114
18 9
Hydrochloric acid
36 5
1 006
36 7
Nitric acid
63
0 568
35 8
Sulfuric acid
98
0 389
38 2
Phosphoric acid
98
0 438
42 9
Sodium hydroxid
40
0 905
36 2
Potassium hvdroxid . .
56
0.630
35.2
Specific Heat. — Equal volumes of different substances at the
same temperature contain different amounts of heat. If two
20
MANUAL OF CHEMISTRY.
— til.
— 100
—80
equal volumes of the same liquid, of different temperatures, be-
mixed together, the resulting mixture has a temperature which
is the mean between the temperatures of the original volumes.
If one litre of water at 4° (39°. 2 F.) be mixed with a litre at 38°
(100°. 4 F.), the resulting two litres will have a temperature of 21°
(69°. 8 F.). Mixtures of equal volumes of different substances, at
different temperatures, do not have a temperature which is the
mean of the original temperatures
of its constituents. A litre of water
at 4° (39°. 2 F.), mixed with a litre of
mercury at 38° (100°. 4 F.), forms a
mixture whose temperature is 27"
(80°. 6 F.). Mercury and water,
therefore, differ from each other in
their capacity for heat. The same
difference exists in a more marked
degree between equal weights of
dissimilar bodies. If a pound of
mercury at 4° (39°. 2 F.) be agitated
with a pound of water at 70°
(158° F.), both liquids will have a,
temperature of 67° (152°. 6 F.).
The amount of heat required to
raise a kilo of water from 0° C. ta
1° C. is the unit of heat, and is
known as a calorie. The specific
heat of any substance is the
amount of heat required to raise
one kilo of that substance 1° in
temperature, expressed in calories.
Thermometers. — Temperatures-
below and slightly above the boil-
ing point of mercury are measured
by thermometers. The thermometer is usually a glass tube,
having a bulb blown at one extremity and closed at the other.
The bulb and part of the tube are filled with mercury, or with
alcohol, whose contraction or expansion indicates a fall or rise
of temperature. The alcoholic thermometer is used for measur-
ing temperatures below the freezing point of mercury (—40°), and
the mercurial for temperatures between that point and the boil-
ing point of mercury, 360°(680° F.). Mercurial thermometers are
also constructed to read still higher temperatures, the boiling
point of the mercury being raised by filling the upper part of the
tube with nitrogen under pressure.
In every thermometer there are two fixed points, determined
by experiment. The freezing point is fixed by immersing the in-
R.
PlIlSiOAL CHARACTERS OF CHEMICAL INTEREST. 21
strument in melting ice, and marking the level of the mercury
in the tube upon the stem. The boiling point is similarly fixed
by suspending the instrument in the steam from boiling water.
The instrument is graduated according to one of three scales ;
the Celsius or Centigrade, the Fahrenheit, and the Reaumur.
The freezing point is marked 0° in the Centigrade and Reaumur
.scales, and 32° in the Fahrenheit. The boiling point is marked
100° in the Centigrade, 212° in the Fahrenheit, and 80° in the
Reaumur (Fig. 14). The space between the fixed points is di-
vided into 100 equal degrees in the Centigrade scale, into 180 in
the Fahrenheit, and into 80 in the Reaumur. Five degrees Centi-
grade are therefore equal to nine degrees Fahrenheit.
To convert a thermometric reading in one scale into its equiva-
lent in another the following formulae are used :
Centigrade into Fahrenheit,
Fahrenheit into Centigrade,
CX9
+32=F.
(F-32)X5
9
The Reaumur scale is not used in this country. The Fahren-
heit scale is used for unscientific, medical and meteorological
purposes, in England and America. The Centigrade scale is used
FIG. 15.
among all nations for all scientific purposes other than those
mentioned, and for all uses on the continent of Europe, except
in Germany.
Spectroscopy. — A beam of white light, in passing through a
prism, is not only refracted, or bent into a different course, but
is also dispersed, or divided into the different colors which con-
stitute the spectrum (Fig. 15). The red rays, being the least de-
MANUAL OF CHEMISTRY.
Red. Orange. Yellow. Green. Blue. Indigo. Violet^
15.
FIG. 1G.
PHYSICAL CHARACTERS OF CHEMICAL INTEREST. 23
fleeted are the least refrangible, the violet rays, being the most
deflected are the most refrangible.
A spectrum is of one of three kinds : 1.) Continuous, consisting
of a continuous band of colors : red, orange, yellow, green, blue,
cyan-blue, and violet. Such spectra are produced by light from
white-hot solids and liquids, from gas-light,candle-light, lime-light,
and electric light. 2.) Bright-line spectra, composed of bright
lines upon a dark ground, are produced by glowing vapors and
gases. 3.) Absorption spectra consist of continuous spectra,
crossed by dark lines or bands, and are produced by light pass-
ing through a solid, liquid, or gas, capable of absorbing certain
rays. Examples of bright-line and absorption spectra are shown
in Fig. 16.
The spectrum of sun-light belongs to the third class. It is not
FIG. 17.
continuous, but is crossed by a great number of dark lines,
known as Fraunhofer's lines, the most distinct of which are
designated by letters (No. 1, Fig. 16).
The spectroscope consists of four essential parts : 1st, the slit,
a, Fig. 17 ; a linear opening between two accurately straight and
parallel knife-edges. 3d, the colimating lens, b ; a biconvex lens
in whose principal focus the slit is placed, and whose object it is
to render the rays from the slit parallel before they enter the
prism. 3d, the prism, or prisms, c, of dense glass, usually of 60°,
and so placed that its refracting edge is parallel to the slit. 4th,
an observing telescope, d. so arranged as to receive the rays as
24
MANUAL OF CHEMISTKY.
they emerge from the prisms. Besides these parts spectroscopes
are usually fitted with some arbitrary graduation, which serves
to fix the location of lines or bands observed. (
In direct vision spectroscopes a compound prism is used, so
made up of prisms of different kinds of glass that the emerging
ray is nearly in the same straight line as the entering ray.
The micro-spectroscope (Fig. 18) is a direct vision spectroscope
used as the eye-piece of a microscope. With it the spectra of
very small bodies may be observed.
As the spectra produced by different substances are character-
ized by the positions of the lines or bands, some means of fixing
FIG. 18.
their location is required. The usual method consists in
determining their relation to the principal Fraurihofer lines. As,
however, the relative positions of these lines vary with the
nature of the substance of which the prism is made, although
their position with regard to the colors of the spectrum is fixed,
no two of the arbitrary scales used will give the same reading.
The most satisfactory method of stating the positions of lines
and bands is in wave-lengths. The lengths of the waves of rays
of different degrees of refrangibility have been carefully deter-
PHYSICAL CHARACTERS OF CHEMICAL INTEREST. 25
mined, the unit of measurement being the tenth-metre, of which
10" make a metre. The wave-lengths, — \ of the principal
Fraunhofer lines, are : .
A....
... 7604.00
D.
5892 12
G
430725
a. . . .
... 7185.00
E
... 5269.13
Hi
3968 01
B....
. . . 6867.00
b
. 5172 00
H3
3933 00
C .
. 6562.01
F..
. 4860.72
The scale of wave-lengths can easily be used with any
spectroscope having an arbitrary scale, with the aid of a curve
constructed by interpolation. To construct such a curve, paper
is used which is ruled into square inches and tenths. The
ordinates are marked with a scale of wave-lengths, and the
abscisses with the arbitrary scale of the instrument. The posi-
tion of each principal Fraunhofer line is then carefully determined
in terms of the arbitrary scale, and marked upon the paper with
-a X at the point where the line of its wave-length and that of its
position in the arbitrary scale cross each other. Through these
X a curve is then drawn as regularly as possible. In noting the
position of an absorption-band, the position of its centre in the
arbitrary scale is observed, and its value in wave-lengths obtained
from the curve, which, of course, can only be used with the scale
and prism for which it has been made.
Polarimetry. — A ray of light passing from one medium into
another of different density, at an angle other than 90° to the
plane of separation of the two media, is deflected from its course,
or refracted. Certain substances have the power, not only of
deflecting a ray falling upon them in certain directions, but also
of dividing it into two rays, which are peculiarly modified. The
splitting of the ray is termed double refraction, and the altered
rays are said to be polarized. When a ray of such polarized light
meets a mirror held at a certain angle, or a crystal of Iceland
spar peculiarly cut (a NicoFs prism), also at a certain angle, it is
extinguished. The crystal which produces the polarization is
called the polarizer, and that which produces the extinction the
analyzer.
If, when the polarizer and analyzer are so adjusted as to extin-
guish a ray passing through the former, certain substances are
brought between them, light again passes through the analyzer ;
and in order again to produce extinction, the analyzer must be
rotated upon the axis of the ray to the right or to the left. Sub-
stances capable of thus influencing polarized light are said to be
optically active. If, to produce extinction, the analyzer is
turned in the direction of the hands of a watch, the substance is
said to be dextrogyrous ; if in the opposite direction, loevogyrous.
The distance through which the analyzer must be turned de-
26 MANUAL OF CHEMISTRY.
pends upon the peculiar power of the optically active substance,,
the length of the column interposed, the concentration, if in solu-
tion, and the wave-length of the original ray of light. The
specific rotary power of a substance is the rotation produced, in
degrees and tenths, by one gram of the substance, dissolved in
one cubic centimetre of a non-active solvent, and examined in a
column one decimetre long. The specific rotary power is deter-
mined by dissolving a known weight of the substance in a given,
volume of solvent, and observing the angle of rotation produced
by a column of given length. Then let p = weight in grams of
the substance contained in 1 c.c. of solution ; I the length of the
column in decimetres ; a the angle of rotation observed ; and [oj
the specific rotary power sought, we have
r n a
[a] = — j.
pi
In most instruments monochromatic light, corresponding to the-
D line of the solar spectrum, is used, and the specific rotary
power for that ray is expressed by the sign [a]o. The fact that
the rotation is right-handed is expressed by the sign +, and that
it is left-handed by the sign — .
It will be seen from the above formula that, knowing the value
of [«]D for any given substance, we can determine the weight of
that substance in a solution by the formula
The polarimeter or saccharometer is simply a peculiarly con-
structed polariscope, used to determine the value of a.
Chemical effects of light. — Many chemical combinations and
decompositions are much modified by the intensity, and the kind
of light to which the reacting substances are exposed. Hydrogen
and chlorin gases do not combine, at the ordinary temperature,
in the absence of light ; in diffused daylight or gaslight, they
unite slowly and quietly ; in direct sunlight, or in the electric
light, they unite suddenly and explosively. The salts of silver,
used in photography, are not decomposed in the dark, but are
rapidly decomposed in the presence of organic matter, when ex-
posed to sunlight.
The chemical activity of the different colored rays of which
the solar spectrum is composed is not the same. Those which
are the most refrangible possess the greatest chemical ac-
tivity— the greatest actinic power. The visible solar spectrum
represents only about one-third of the rays actually emitted
from the sun. Two-thirds of the spectrum are invisible as light,
PHYSICAL CHARACTERS OF CHEMICAL INTEREST. 27
and are only recognizable by their heating effects, or by chemical
decompositions which they provoke.
Galvanic Electricity. — If two plates, one of pure zinc, the other
of pure copper, be immersed in pure, dilute hydrochloric acid, in
such a way that the metals are not in contact with each other,
there is no action. But if the two metals be connected, outside
of the liquid, by a copper wire, the zinc immediately begins to
dissolve, and bubbles of hydrogen gas are collected on, and escape
from, the surface of the copper, the action continuing so long as
the wire connection is maintained, and ceasing so soon as it is in-
terrupted. If a magnetic compass be approached near to the
wire, while it is connected with the two plates, the needle will
assume a position at right angles to the wire whether the latter
be in an east and west position or not. But if the wire be discon-
nected from either plate, the needle returns to its normal, north
and south, position. While the two plates are connected by the
wire, an electrical current is produced by the chemical action be-
tween the zinc and hydrochloric acid, and passes through the
liquid and through the wire. A similar electrical current is pro-
duced whenever two plates, of different substances, which are
conductors of electricity, are connected with each other by aeon-
ducting wire, and the free ends dipped into a liquid which has a
more intense chemical action upon one plate than upon the other.
The plate upon which the greater chemical action is exerted is
known as the negative plate, or negative pole, or anode, and, in
most batteries consists of zinc. The other plate is called the col-
lecting plate, the positive pole, or the cathode, and usually is
made of platinum, carbon or copper. The wires attached to the
two plates, as well as any plate, knob or other apparatus in which
they terminate are known as the positive and negative electrodes.
The current is said to pass from the negative to the positive
plate in the battery, and from the positive to the negative in the
connecting wire, or apparatus outside the battery. The exciting
liquid, the two plates, and the connecting wire, with any con-
ducting apparatus that may be interposed in the course of the
wire, is called the circuit. The circuit is said to be closed when
the conducting circle is complete. It is open, or broken, when it
is interrupted at one or more points.
Electrolysis. — When a galvanic current of sufficient power
passes through a compound liquid, or through a solution of a
compound, capable of conducting the current, the compound is
decomposed. The decomposition of a compound by this means
is called electrolysis, and the substance so decomposed is known
as the electrolyte.
When compounds are subjected to electrolysis the constituent
elements are not discharged throughout the mass, although the
28 MANUAL OF CHEMISTRY.
decomposition occurs at all points between the electrodes. In
compounds made up of two elements only, one element is given
off at each of the poles, entirely unmixed with the other, and
always from the same pole. Thus, if hydrochloric acid be sub-
jected to electrolysis, pure hydrogen is given off at the negative
pole and pure chlorin at the positive pole.
In the case of compounds containing more than two elements,
a similar decomposition occurs ; one element being liberated at
one pole and the remaining group of elements separating at the
other. This primary decomposition is frequently modified, as to
its final products, by intercurrent chemical reactions. Indeed,
the group of elements liberated at one pole is rarely capable of
.separate existence. When, for instance, a solution of potassium
sulfate is subjected to electrolysis, the liquid surrounding the
positive electrode becomes acid in reaction, and gives off oxygen.
At the same time the liquid on the negative side becomes alka-
line, and gives off a volume of hydrogen double that of the
oxygen liberated. In the first place the potassium sulfate,
which consists of potassium, sulfur, and oxygen, is decomposed
into potassium, which separates at the negative pole ; and sul-
fur and oxygen, combined together, which go to the positive
pole. The potassium liberated at the negative pole immediately
decomposes the surrounding water, forming potash, and liberat-
ing hydrogen. The sulfur and oxygen group at the positive
pole immediately reacts with water to form sulfuric acid and lib-
erate oxygen.
In the electrolysis of chemical compounds the different elements
and groups of elements, such as the sulfur and oxygen group in
the example given above, known as residues or radicals, seem to
be possessed of definite electrical characters, and are given off at
one or the other pole in preference. Those which are given off
at the positive or platinum pole are supposed to be negatively
electrified, and are therefore known as electro-negative or acidu-
lous elements or residues. Those given- off at the negative pole,
being positively electrified, are known as electro-positive or basy-
lous elements or residues. The following are the electrical char-
acters of the principal elements and residues :
ELECTRO-NEGATIVE OB ACIDULOUS.
Oxygen,
Molybdenum,
Arsenic, Silicon,
Sulfur,
Tungsten,
Chromium, Osmium.
Nitrogen,
Boron,
•Chlorin,
lodin,
Fluorin,
Carbon,
Antimony,
Tellurium,
Residues of acids remaining
after the removal of a number
Phosphorus,
Niobium,
of hydrogen atoms equal to the
iSelenium,
Titanium,
basicity of the acid.
PHYSICAL CHARACTERS OF CHEMICAL INTEREST. 29
ELECTRO-POSITIVE OR BASYLOUS.
Hydrogen,
Potassium,
Sodium,
Lithium,
Barium,
Strontium,
Calcium,
Magnesium,
Nickel,
Cobalt,
Cerium, '
Lead,
Tin,
Bismuth,
Uranium,
Copper,
Glucinium, Silver,
Yttrium, Mercury,
Aluminium, Palladium,
Zirconium, Platinum,
Manganese, Rhodium,
Zinc, Iridium,
Cadmium, Gold,
Iron, Alcoholic radicals.
30 MANUAL OF CHEMISTRY.
CHEMICAL COMBINATION.
Elements. — The great majority of the substances existing in
and upon the earth may be so decomposed as to yield two or
more other substances, distinct in their properties from the sub-
stance from whose decomposition they resulted, and from each
other. If, for example, sugar be treated with sulfuric acid, it
blackens, and a mass of charcoal separates. Upon further exam-
ination we find that water has also been produced. From this
water we may obtain two gases, differing from each other widely
in their properties. Sugar is therefore made up of carbon and
the two gases, hydrogen and oxygen ; but it has the properties of
sugar, and not those of either of its constituent parts. There is
no method known by which carbon, hydrogen, and oxygen can
be split up, as sugar is, into other dissimilar substances.
An element is a substance which cannot by any known means
be split up into other dissimilar bodies.
Elements are also called elementary substances or simple sub-
stances.
The number of well-characterized elements at present known
is sixty-nine. Of these, either free, or united with each other in
varied proportion, and in different ways, all matter is composed.
Laws governing the combination of elements. — The alchemists,
Arabian and European, contented themselves in accumulating a
store of knowledge of isolated phenomena, without, as far as we
know, attempting, in any serious way, to group them in such a
manner as to learn the laws governing their occurrence. It was
not until the latter part of the last century, 1777, that Wenzol,
of Dresden, implied, if he did not distinctly enunciate, what is
known as the law of reciprocal proportions. A few years later,
Richter, of Berlin, confirming the work of Wenzel, added to it the
law of definite proportions, usually called Dalton's first law.
Finally, as the result of his investigations from 1804 to 1808, Dai-
ton added the law of multiple proportions, and, reviewing the
work of his predecessors, enunciated the results clearly and dis-
tinctly.
Considering these laws, not in the order of their discovery, but
in that of their natural sequence, we have :
THE LAW OP DEFINITE PROPORTIONS. — The relative weights
of elementary substances in a compound are definite and invari-
able. If, for example, we analyze water, we find that it is com-
posed of eight parts by weight of oxygen for each part by weight
of hydrogen, and that this proportion exists in every instance,
whatever the source of the water. If, instead of decomposing, or
CHEMICAL COMBINATION. 31
analyzing water, we start from its elements, and by synthesis,
cause them to unite to form water, we find that, if the mixture
be made in the proportion of eight oxygen to one hydrogen by
weight, the entire quantity of each gas will be consumed in the
formation of water. But if an excess of either have been added
to the mixture, that excess will remain after the combination.
Compounds are substances made up of two or more elements
united with each other in definite proportions. Compounds
exhibit properties of their own, which differ from those of the
•constituent elements to such a degree that the properties of a com-
pound can never be deduced from a knowledge of those of the
constituent elements. Common salt, for instance, is composed
of 39.32 per cent, of the light, bluish- white metal, sodium, and
60.68 per cent, of the greenish-yellow, suffocating gas, chlorin.
Compounds made up of two elements only are called binary
compounds ; those consisting of three elements, ternary com-
pounds ; those containing four elements, quaternary compounds,
etc.
A mixture is composed of two or more substances, elements
or compounds, mingled in any proportion. The characters of a
mixture may be predicated from a knowledge of the properties
of its constituents. Thus sugar and water may be mixed in any
proportion, and the mixture will have the sweetness of the sugar,
and will be liquid or solid, according as the liquid or solid ingre-
dient predominates in quantity.
THE LAW OF MULTIPLE PROPORTIONS. — When two elements
unite with each other to form more than one compound, the re-
sulting compounds contain simple multiple proportions of one
element as compared with a constant quantity of the other.
Oxygen and nitrogen, for example, unite with each other to
form no less than five compounds. Upon analysis we find that
in these the two elements bear to each other the following rela-
tions by weight :
In the first, 14 parts of nitrogen to 8 of oxygen.
In the second, 14 parts of nitrogen to 8x2=16 of oxygen.
In the third, 14 parts of nitrogen to 8X3=24 of oxygen.
In the fourth, 14 parts of nitrogen to 8x4=32 of oxygen.
In the fifth, 14 parts of nitrogen to 8X5=40 of oxygen.
THE LAW OF RECIPROCAL PROPORTIONS. — The ponderable
quantities in which substances unite with the same substance
express the relation, or a simple multiple thereof, in which they
unite with each other. Or, as Wenzel stated it, "the weights
6, &', b" of several bases which neutralize the same weight a of an
acid are the same which will neutralize a constant weight a of
another acid; and the weights a, a', a" of different acids which
32 MANUAL OF CHEMISTRY.
neutralize the same weight 6 of a base are the same which will
neutralize a constant weight of another base &'." For example :
71 parts of chlorin combine with 40 parts of calcium, and 16 parts,
of oxygen also combine with 40 parts of .calcium, therefore 71
parts of chlorin combine with 16 parts of oxygen, or the two ele-
ments combine in the proportion of some simple multiples of 71
and 16.
The Atomic Theory. — The laws of Wenzel, Richter, and Dai-
ton, given above, are simply generalized statements of certain
groups of facts, and, as such, not only admit of no doubt, but
are the foundations upon which chemistry as an exact science is
based. Dalton, seeking an explanation of the reason of being of
these facts, was led to adopt the view held by the Greek philoso-
pher, Democritus, that matter was not infinitely divisible. He
retained the name atom (aro/zof = indivisible), given by Democri-
tus to the ultimate particles, of which matter was supposed by
him to be composed ; but rendered the idea more precise by
ascribing to these atoms real magnitude, and a definite weight,
and by considering elementary substances as made up of atoms
of the same kind, and compounds as consisting of atoms of differ-
ent kinds.
This hypothesis, the first step toward the atomic theory as en-
tertained to-day, afforded a clear explanation of the numerical
results stated in the three laws. If hydrogen and oxygen always
unite together in the proportion of one of the former to eight of
the latter, it is because, said Dalton, the compound consists of an
atom of hydrogen, weighing 1, and an atom of oxygen, weighing
8. If, again, in the compounds of nitrogen and oxygen, we have
the two elements uniting in the proportion 14 : 8 14 : 8X2
14 : 8x3 14 : 8x4 14 : 8x5, it is because they are sev-
erally composed of an atom of nitrogen weighing 14, united to
1, 2, 3, 4, or 5 atoms of oxygen, each weighing 8. Further, that
compounds do not exist in which any fraction of 8 oxygen enters,
because 8 is the weight of the indivisible atom of oxygen.
Dalton's hypothesis of the existence of atoms as definite quan-
tities did not, however, meet with general acceptance. Davy,
Wollaston, and others considered the quantities in which Dalton
had found the elements to unite with each other, as mere propor-
tional numbers or equivalents, as they expressed it, nor is it
probable that Dalton's views would have received any further
recognition until such time as they might have been exhumed
from some musty tome, had their publication not been closely
followed by that of the results of the labors of Humboldt and of
Gay Lussac, concerning the volumes in which gases unite with
each other.
CHEMICAL COMBINATION. 33
In the form of what are known as Gay Lussac's laws, these
results are :
First. — There exists a simple relation between the volumes oi
gases which combine with each other.
Second. — There exists a simple relation between the sum of
the volumes of the constituent gases, and the volume of the gas
formed by their union. For example : .
1 TO ume chlorin unites with 1 volume hydrogen to form 2 volumes hydrochloric acid.
1 vo ume oxygen unites with 2 volumes hydrogen to f onn 2 volumes vapor of water.
1 vo ume nitrogen unites with 3 volumes hydrogen to form 2 volumes ammonia.
1 vo ume oxygen unites with 1 volume nitrogen to form 2 volumes nitric oxid.
1 vo ume oxygen unites with 2 volumes nitrogen to form 2 volumes nitrous oxid.
Berzelius, basing his views upon these results of Gay Lussacr
modified the hypothesis of Dalton and established a distinction
between the equivalents and atoms. The composition of water
he expressed, in the notation which he was then introducing, a&
being HaO, and not HO as Dalton's hypothesis called for. As,
however, Berzelius still considered the atom of oxygen as weigh-
ing 8, he was obliged also to consider the atoms of hydrogen and
of certain other elements as double atoms — a fatal defect in his
system, which led to its overthrow, and to the re-establishment
of the formula HO for water.
It was reserved to Gerhardt to clearly establish the distinction
between atom and molecule ; to observe the bearing of the dis-
coveries of Avogadro and Ampere upon chemical philosophy ;
and thus to establish the atomic theory as entertained at present.
As a result of his investigations in the domain of organic
chemistry, Gerhardt found that, if Dalton's equivalents be ad-
hered to, whenever carbon dioxid or water is liberated by the
decomposition of an organic substance, it is invariably in double
equivalents, never in single ones. Always 2COa or 2HO, or some
multiple thereof, never CO2 or HO. He further found that if the
equivalents C=6, H=l, andO=8 be retained, the formulae became
such that the equivalents of carbon are always divisible by two.
In fact, he found the same objections to apply to the notation
then in use that had been urged against that of Berzelius.
In 1811, Avogadro, from purely physical researches, had been
enabled to state the law which is now known by his name, to the
effect that equal volumes of all gases, under like conditions of
temperature and pressure, contain equal numbers of molecules.
This law is also known as the law of Ampere, the French
physicist having enunciated it about the same time as, and in-
dependently of, his Italian colaborer.
In the hands of Gerhardt this law, in connection with those of
Gay Lussac, became the foundation of what is sometimes called
the " new chemistry.'' Bearing in mind Avogadro's law, we may
3
34 MANUAL OF CHEMISTRY.
translate the first three combinations given in the table on p. 33
into the following :
1 molecule chlorin unites with 1 molecule hydrogen, to form 2 molecules hydrochloric acid.
1 molecule oxygen unites with 2 molecules hydrogen, to form 2 molecules vapor of water.
1 molecule nitrogen unites with 3 molecules hydrogen, to form 2 molecules ammonia.
But the ponderable quantities in which these combinations
take place are :
35.5 chlorin to 1 hydrogen.
16 oxygen to 2 hydrogen.
14 nitrogen to 3 hydrogen.
And as single molecules of hydrogen, oxygen, and nitrogen are in
these combinations subdivided to form 2 molecules of hydro-
chloric acid, water, and ammonia, it follows that these molecules
must each contain two equal quantities of hydrogen, oxygen, and
nitrogen, less in size than the molecules themselves. Arid, further,
as in these instances each molecule contains two of these smaller
quantities, or atoms, the relation between the weights of the
molecules must be also the relation between the weights of the
atoms, and we may therefore express the combinations thus :
1 atom chlorin weighing 35.5 unites with 1 atom hydrogen weighing 1 ;
1 atom oxygen weighing 16 unites with 2 atoms hydrogen weighing 2 ;
1 atom nitrogen weighing 14 unites with 3 atoms hydrogen weighing 3 ;
and consequently, if the atom of hydrogen weighs 1, that of
chlorin weighs 35.5, that of oxygen 16, and that of nitrogen 14.
Atomic Weight. — The distinction between molecules and
atoms may be expressed by the following definitions :
A molecule is the smallest quantity of any substance that
can exist in the free state.
An atom is the smallest quantity of an elementary substance
that can enter into a chemical reaction.
The molecule is always made up of atoms, upon whose nature,
number, and arrangement with regard to each other, the proper-
ties of the substance depend. In an elementary substance the
.atoms composing the molecules are the same in kind, and usu-
ally two in number. In compound substances they are dissimi-
lar, and vary in quantity from two in a simple compound, like
hydrochloric acid, to hundreds or thousands in more complex
substances.
The word atom, can only be used in speaking of an elementary
body, and that only while it is passing through a reaction. The
term molecule applies indifferently to elements and compounds.
The atoms have definite relative weights ; and upon an exact
determination of these weights depends the entire science of
quantitative analytical chemistry. (See stoichiometry, p. 44.)
CHEMICAL COMBINATION.
35
They have been determined by repeated and careful analyses of
perfectly pure compounds of the elements, and express the
^weight of one atom of .the element as compared "with the weight
•of one atom of hydrogen, that being the lightest element known.
It is also the weight of a volume of the element, in the form of
gas, which would occupy the same volume, under like pressure
.and temperature, as an amount of hydrogen weighing one. What
the absolute weight of an atom of any element may be we do
not know, nor would the knowledge be of any service did we pos-
sess it.
The following table contains a list of the elements at present
known, with their atomic weights :
ELEMENTS.
NAME.
A.
Symbol.
B.
Atomic
Weight.
NAME.
A.
Symbol.
B.
Atomic
Weight.
Aluminium . . .
Al.
27.02
Mercury
Hg.
199.7
Antimony
Arsenic
Sb.
As.
120
74 9
Molybdenum..
Nickel
Mo.
Ni.
95.5
58
Barium
Ba.
136.8
Nitrogen
N.
14 044
Bismuth
Bi.
206.5
Osmium
Os.
198 5
Boron
Bo.
11
Oxygen..
o
16
Broniin
Br.
79 952
Palladium ....
Pd
105 7
Cadmium
Cesium
Cd.
Cs.
111.8
132.6
Phosphorus . . .
Platinum..
P.
Pt
31
194 4
Calcium
Ca
40
Potassium
K
39 137
Carbon
c
11 974
Rhodium . . .
Rh
104 1
Cerium
Ce.
141
Rubidium. . .
Rb.
85 3
Chlorin
Cl.
35.457
Ruthenium. ...
Ru.
104 2
Chromium. . . .
Cobalt
Cr.
Co.
52.4
58.9
Samarium
Scandium. . . .
Sm.
Sc.
150
44
Columbium .
Cb
94
Selenium ....
Se
78 8
Copper
Cu.
63 2
Silicon
Si
28
Davyium
Da
154
Silver
As.
107 675
Didymium. . . .
D.
144.78
Sodium
Na.
22.998
Erbium
E.
165.9
Strontium
Sr.
87.4
Fluorin
F
19
Sulfur .'.. .
S
31 984
Gallium.
Ga.
68 8
Tantalum
Ta.
182
Germanium. . .
Glucinuni. . . .
Gold ...
Gr.
GI.
Au
72.32
9
196 2
Tellurium
Thallium
Thorium
Te.
Tl.
Th.
128
203.7
233
Hvdrogen
H
1
Tin
Sn.
117 7
Indium
In.
113.4
Titanium
Ti.
49.85
lodin
I
126 85
Tungsten . . .
W.
183.6
Iridium
Ir.
192.7
Uranium
U,
238.5
Iron
Fe.
55.9
Vanadium ....
V.
51.3
Lanthanium . .
Lead
La.
Pb.
188. 5
206.92
Ytterbium
Yttrium
Yb.
Y.
172.7
89.8
Lithium.
Li.
7
Zinc
Zn.
64.9
Magnesium... .
Manganese ....
Mg.
Mn.
24
54
'Zirconium
Zr.
89.6
36 MANUAL OF CHEMISTRY.
In some cases the results of analyses are such as would agree
with two values as the atomic weight of au element equally well.
In this case we can decide which is the correct value by the law
of Dulong and Petit. These observers found that while the
atomic weights of the elements vary greatly from each other, the
specific heats (see p. 19) differ from each other in an opposite
manner, and to such an extent that the product obtained by
multiplying the two together does not vary much from 6.4. This
product is known as the atomic heat. When it is not possible
to determine by analysis which of two numbers is the cor-
rect atomic weight of an element, that one is selected which,
when multiplied by the specific heat, gives a result most nearly
approaching 6.4.
The atomic heats of boron, carbon, silicon, sulfur, and phos-
phorus are subject to great variations, as is shown in the follow-
ing table :
Specific Atomic
^ Heat. Heat.
BORON.
Crystallized at- 39.6° 0.1915 2.11
Crystallized at 4- 76.7° .....0.2737 3.01
Crystallized at + 233.2° 0.3663 3.99
Amorphous 0.255 2.81
CARBON.
Diamond at - 50.5° 0.0635 0.76
Diamond at + 140° 0.2218 2.66
Diamond at + 985° 0.4589 5.51
Graphite at- 50.3° 0.1138 1.37
Graphite at + 138.5° 0.2542 3.05
Graphite at + 977.9° 0.4670 9.60
Wood charcoal 0.2415 2.90
SILICON.
Crystallized at — 39.8° 0.1360 3.81
Crystallized at + 128.7° 0.1964 5.50
Crystallized at + 232.4° 0.2029 5.68
Fused at + 100° 0.175 4.90
SULFUR.
Orthorhombic at + 45° 0.163 5.22
Orthorhombic at + 99° 0.1776 5.68
Liquid at + 150° 0.234 7.49
Recently fused at + 98° 0.20259 6.48
CHEMICAL COMBINATION. 37
Specific Atomic
_. Heat. Heat.
PHOSPHORUS.
Yellow at --78° 0.174 5.39
Yellow at + 36° 0.202 6.26
Liquid at + 100° 0.212 6.57
Amorphous at + 98° 0.170 5.27
It will be observed that, as the temperature of the solid element
is increased, the atomic heat more nearly approaches 6.4. It will
further be noticed that those elements with which the perturba-
tions occur are those which are capable of existing in two or more
allotropic forms (see p. 15). As in the passage of an element from
one allotropic condition to another, absorption or liberation of
heat always takes place, as the result of "interior work ;" it is
probable that these p'erturbations are due to a constant ten-
dency of the element to pass from one allotropic condition to an-
other.
The atomic heats of those elementary gases which have only
been liquefied by enormous cold and pressure are tolerably con-
stant at about 2.4.
Molecular Weight. — The molecular weight of a substance is the
^weight of its molecule as compared with the weight of an atom,
of hydrogen. It is also, obviously, the sum of the weights of all
the atoms making up the molecule.
A very ready means of determining the molecular weight of a
gaseous substance or of one which may be converted into vapor,
is based upon Avogadro's law. The sp. gr. of a gas is the weight
of a given volume as compared with that of an equal volume of
hydrogen. But these equal volumes contain equal numbers of
molecules (p. 33), and therefore, in determining the sp. gr. of a
gas, we obtain the weight of its molecule as compared with that
of a molecule of hydrogen ; and, as the molecule contains two
atoms of hydrogen, while one atom of hydrogen is the unit of
comparison, it follows that the specific gravity of a gas compared
•with hydrogen, multiplied by two, is its molecular weight.
For example, the gas acetylene and the liquid benzene each
contain 92.31 per cent, of carbon, and 7.69 per cent, of hydrogen ;
which is equivalent to 24 parts, or two atoms of carbon ; and 2
parts, or two atoms of hydrogen. The sp. gr. of acetylene, re-
ferred to hydrogen =2, is 13 ; its molecular weight is, therefore,
26, and its molecule contains two atoms of carbon and two atoms
of hydrogen. The sp. gr. of vapor of benzene is 39 ; its molecular
weight is, therefore, 78, and its molecule contains six atoms of
•carbon and six atoms of hydrogen.
When a substance is not capable of being volatilized, its mo-
lecular weight may be obtained by determining its percentage
38 MANUAL OF CHEMISTRY.
composition by analysis, and selecting that value which is near-
est in obedience to the law of Raoult (see p. 19).
The vapor densities of comparatively few elements are known :
Vapor" Atomic Molecular
Density. Weight. Weight.
Hydrogen 112
Oxygen 16 16 32
Sulfur 32 32 64
Selenium 82 79 164
Tellurium 130 128 260
Chlorin 35.5 35.5 71
Bromin 80 80 160
lodin 127 127 254
Phosphorus 63 31 124
Arsenic 150 75 300
Nitrogen 14 14 28
Potassium 39- 39 78
Cadmium 56 112 112
Mercury 100 200 200
The atomic weight being, in most of the above instances, equal
to the vapor density, and to half the molecular weight, it may be
inferred that the molecules of these elements consist of two atoms.
Noticeable discrepancies exist in the case of four elements. The
molecular weights of phosphorus and arsenic, as obtained from,
their vapor densities, are not double, but four times as great
as their atomic weights. The molecules of phosphorus and
arsenic are, therefore, supposed to contain four atoms. Those of
cadmium and mercury contain but one atom.
Valence or Atomicity. — It is known that the atoms of different
elements possess different powers of combining with and of re-
placing atoms of hydrogen. Thus :
One atom of chlorin combines with one atom of hydrogen.
One atom of oxygen combines with two atoms of hydrogen.
One atom of nitrogen combines with three atoms of hydrogen.
One atom of carbon combines with four atoms of hydrogen.
The valence, atomicity, or equivalence of an element is the sat-
urating power of one of its atoms as compared with that of one
atom of hydrogen.
Elements may be classified according to their valence into —
Univalent elements, or monads Cl'
Bivalent elements, or dyads O"
Trivalent elements, or triads B'"
Quadrivalent elements, or tetrads Ciy
Quinquivalent elements, or pentads Pv
Sexvalent elements, or hexads Wvi
Elements of even valence, i. e., those which are bivalent, quad-
rivalent, or sexvalent, are sometimes called artiads ; those of un-
even valence being designated as perissads.
CHEMICAL COMBINATION. 39
In notation the valence is indicated, as above, by signs placed
to the right and above the symbol of the element.
But the valence of the elements is not fixed and invariable.
Thus, while chlorin and iodin each combine with hydrogen, atom
for atom, and in those compounds are consequently univalent,
they unite with each other to form two compounds — one contain-
ing one atom of iodin and one of chlorin, the other containing
one atom of iodin and three of chlorin. Chlorin being univalent,
iodin is obviously trivalent in the second of these compounds.
Again, phosphorus forms two chlorids, one containing three, the
other five atoms of chlorin to one of phosphorus.
In view of these facts, we must consider, either : 1, that the
valence of an element is that which it exhibits in its most satu-
rated compounds, as phosphorus in the pentachlorid, and that
the lower compounds are non-saturated, and have free valences ;
or 2, that the valence is variable. The first supposition depends
too much upon the chances of discovery of compounds in which
the element has a higher valence than that which might be con-
sidered the maximum to-day. The second supposition — notwith-
standing the fact that, if we admit the possibility of two dis-
tinct valences, we must also admit the possibility of others — is
certainly the more tenable and the more natural. In speaking,
therefore, of the valence of an element, we must not consider it as
an absolute quality of its atoms, but simply as their combining
power in the particular class of compounds under consideration.
Indeed, compounds are known in whose molecules the atoms of
one element exhibit two distinct valences. Thus, ammonium
cyanate contains two atoms of nitrogen : one in the ammonium
group is quinquivalent, one in the acid radical is trivalent.
When an element exhibits different valences, these differ from
each other by two. Thus, phosphorus is trivalent or quinqui-
valent : platinum is bivalent or quadrivalent.
Symbols — Formulae — Equations. — Symbols are conventional ab-
breviations of the names of the elements, whose purpose it is to
introduce simplicity and exactness into descriptions of chemical
actions. They consist of the initial letter of the Latin name of
the element, to which is usually added one of the other letters.
If there be more than two elements whose names begin with the
same letter, the single-letter symbol is reserved for the commonest
element. Thus, we have nine elements whose names begin with
C •, of these the commonest is Carbon, whose symbol is C ; tho
others have double-letter symbols, as Chlorin, Cl ; Cobalt, Co ;
Copper, Cu (Cuprum), etc.
These symbols do not indicate simply an indeterminate quan-
tity, but represent one atom, of the corresponding1 element.
40 MANUAL OF CHEMISTRY.
When more than one atom is spoken of, the number of atoms
which it is desired to indicate is written either before the symbol
or, in small figures, after and below it. Thus, H indicates one
atom of hydrogen ; 2C1, two atoms of chlorin ; C4, four atoms of
carbon, etc.
What the symbol is to the element, the formula is to the com-
pound. By it the number and kind of atoms of which the mole-
cule of a substance is made up are indicated. The simplest kind
of formulae are what are known as empirical formulse, which
indicate only the kind and number of atoms which form the
compound. Thus, HC1 indicates a molecule composed of one
atom of hydrogen united with one atom of chlorin ; 5H2O, five
molecules, each composed of two atoms of hydrogen and one
atom of oxygen, the number of molecules being indicated by the
proper numeral placed before the formula, in which place it
applies to all the symbols following it. Sometimes it is desired
that a numeral shall apply to a part of the symbols only, in
which case they are enclosed in parentheses ; thus, Al» (80.1)3
means twice Al and three times SO4.
For other varieties of formulae, see pp. 50-52.
Equations are combinations of formulse and algebraic signs so
arranged as to indicate a chemical reaction and its results. The
signs used are the plus and equality signs ; the former being
equivalent to "and," and the second meaning "have reacted
upon each other and have produced." The substances entering
into the reaction are placed before the equality sign, and the
products of the reaction after it ; thus, the equation
means, when translated into ordinary language : two molecules
of potash, each composed of one atom of potassium, one atom
of hydrogen, and one atom of oxygen, and one molecule of sul-
furic acid, composed of one atom of sulfur, four atoms of
oxygen, and two atoms of hydrogen, have reacted upon eacJi
other and have produced one molecule of potassium sulfate,
composed of one atom of sulfur, four atoms of oxygen, and
two atoms of potassium, and two molecules of water, each com-
posed of two atoms of hydrogen and one atom of oxygen.
As no material is ever lost or created in a reaction, the number
of each kind of atom occurring before the equality sign in an
equation must always be the same as that occurring after it. In
writing equations they should always be proved by examining
whether the half of the equation before the equality sign con-
tains the same number of each kind of atom as that after the
equality sign. If it do not the equation is incorrect.
CHEMICAL COMBINATION. 41
Acids, Bases, and Salts. — All ternary and quaternary mineral
substances have one of three functions.
The function of a substance is its chemical character and rela-
tionship, and indicates certain general properties, reactions and
decompositions which all substances possessing the same function
possess or undergo alike. Thus, in mineral chemistry we have
acids, bases, and salts ; in organic chemistry alcohols, aldehydes,
ketones, ethers, etc.
An acid is a compound of an electro-negative element or resi-
due with hydrogen ; which hydrogen it can part with in exchange
for an electro-positive element without formation of a base. An
acid may also be defined as a compound body which evolves water
by its action upon pure caustic potash or soda.
No substance which does not contain hydrogen can, therefore,
be called an acid.
The basicity of an acid is the number of replaceable hydrogen
atoms contained in its molecule.
A monobasic acid is one containing a single replaceable atom
of hydrogen, as nitric acid, HNO3; a dibasic acid is one contain-
ing two such replaceable atoms, as sulfuric acid, HaSCh ; a tri-
Tjasic acid is one containing three replaceable hydrogen atoms, as
phosphoric acid, H3PC>4. Polybasic acids are such as contain
more than one atom of replaceable hydrogen.
Hydracids are acids containing no oxygen ; oxacids or oxyacids
•contain both hydrogen and oxygen.
The term base is regarded by many authors as applicable to
any compound body capable of neutralizing an acid. It is, how-
ever, more consistent with modern views to limit the application
of the name to such compound substances as are capable of en-
tering into double decomposition with acids to form salts and
water. They may be considered as one or more molecules of
water in which one-half of the hydrogen has been replaced by an
electro-positive element or radical ; or as compounds of such
elements or radicals with one or more groups, OH. Being thus
considered as derivable from water, they are also known as hy-
droxids. They have the general formula, MTO (OH)w. They are
monatomic, diatomic, triatomic. etc., according as they contain
one, two, three, etc., groups oxhydryl (OH).
A double decomposition is a reaction in which both of the re-
acting compounds are decomposed to form two new compounds.
Sulfobases, or hydrosulfids, are compounds in all respects re-
sembling the bases, except that in them the oxygen of the base
is replaced by sulfur.
Salts are substances formed by the substitution of basylous
radicals or elements for a part or all of the replaceable hydrogen
of an acid. They are always formed, therefore, when bases and
42 MANUAL OF CHEMISTRY.
acids enter into double decomposition. They are not, as was
formerly supposed, formed by the union of a metallic with a non-
metallic oxid, but, as stated above, by the substitution of one or
more atoms of an element or radical for the hydrogen of the acid.
Thus, the compound formed by the action of sulfuric acid upon
quicklime is not SO3CaO, but CaSO4, formed by the interchange
of atoms :
8
"}a
H, > — _0
and not
S
(H'<
(o
/Ca
VO
it is, therefore, calcium sulfate, and not sulfate of lime.
The term salt, as used at present, applies to the compounds
formed by the substitution of a basylous element for the hydro-
gen of any acid ; and indeed, as used by some authors, to the-
acids themselves, which are considered as salts of hydrogen. It
is probable, however, that eventually the name will be limited to-
such compounds as correspond to acids whose molecules contain
more than two elements. Indeed, from the earliest times of
modern chemistry a distinction has been observed between the
haloid salts, i.e, those the molecules of whose corresponding acids
consist of hydrogen, united with one other element, on the one
hand ; and the oxysalts, the salts of the oxacids, i.e., those into-
whose composition oxygen enters, on the other hand. This dis-
tinction, however, has gradually fallen into the background, for
the reason that the methods and conditions of formation of the
two kinds of salts are usually the same when the basylous ele-
ment belongs to that class usually designated as metallic.
There are, however, important differences between the two
classes of compounds. There exist compounds of all of the ele-
ments corresponding to the hydracids, binary compounds of
chlorin, bromin, iodin, and sulfur. There is, on the other
hand, a large class of elements the members of which are incapa-
ble of forming salts corresponding to the oxacids. No salt of an
oxacid with any one of the elements usually classed as metalloids
(excepting hydrogen) has been obtained.
Haloid salts may be formed by direct union of their constituent
elements ; oxysalts are never so produced.
Action of Acids and Bases on Salts, and of Salts on each other.
— If an acid be added to a solution of a salt whose acid it nearly
equals in chemical activity, the salts of both acids and the free
CHEMICAL COMBINATION. 43
acids themselves will probably exist in the solution, provided
both acids and salts are soluble. Thus :
2HaSO4 + 3KNO3 = K2SO4 + KNO3 + H.SO, -f 2HNO,
Sulfuric Potassium Potassium Potassium Sulfuric Nitric
acid. nitrate. sulfate. nitrate. acid. acid.
If an acid be added to a solution of a salt whose acid it greatly
exceeds in activity, the salt is decomposed, with formation of the
salt of the stronger acid and liberation of the weaker acid ; both
acids and salts being soluble :
H,S04 + 2CaH3OaNa = NaaSO4 + 2CaH3O,H
Sulfuric acid. Sodium acetate. Sodium sulfate. Acetic acid.
If to a solution of a salt whose acid is insoluble in the solvent
used, an acid be added capable of forming a soluble salt with the
basylous element, such soluble salt is formed and the acid is de-
posited :
HaSO4 -f- 2C,8H35OaNa = NaaSO4 + 2Cl8H35OaH
Sulfuric acid. Sodium stearate. Sodium sulfate. Stearic acid.
If to a salt whose acid is volatile at the existing temperature,.
an acid capable of forming with the basylous element a salt fixed
at the same temperature be added, the fixed salt is formed and
the volatile acid expelled. Thus, with the application of heat :
HaS04 + 2NaNO, = NaaSO4 + 2HNO,
Sulfuric acid. Sodium nitrate. Sodium sulfate. Nitric acid.
If to a solution of a salt an acid be added which is capable of
forming an insoluble salt with the base, such insoluble salt is
formed and precipitated :
HSSO4 + Ba(NO3)a = BaSO, + 2HNO3
Sulfuric acid. Barium nitrate. Barium sulfate. Nitric acid.
If to a solution of a salt whose basylous element is insoluble a
soluble base is added, capable of forming a soluble salt with the
acid, such soluble salt is formed, with precipitation of the insol-
uble base :
CuSO4 + 2KHO = KaSO4 + CuH2Oa
Cupric sulfate. Potassium hydroxid. Potassium sulfate. Cupric hydroxid.
If a base be added to a solution of a salt with whose acid it is
capable of forming an insoluble salt, such insoluble salt is formed
and precipitated, and the base of the original salt, if insoluble,
is also precipitated :
BaHaOa
Barium hydroxid.
BaHaOa -f
Barium hydroxid.
f KaSO,
Potassium sulfate.
AgaS04
Silver fulfate.
BaSO4 + 2KHO
Barium sulfate. Potassium hydroxid.
BaSO, -f 2AgHO
Barium sulfate. Silver hydroxid.
44 MANUAL OF CHEMISTRY.
When solutions of two salts, the acids of both of which form
soluble salts with both bases, are mixed, the resultant liquid con-
tains the four salts :
3KaSO4 + 3NaNO3 = 2K2SO4 + Na.,SO4 -fr 2KNO3 + NaNO,
Potassium Sodium Potassium Sodium Potassium Sodium
sulfate. nitrate. sulfate. sulfate. nitrate. nitrate.
or in some other proportion.
If solutions of two salts, the acid of one of -which is capable of
uniting with the base of the other to form an insoluble salt, are
mixed, such insoluble salt is precipitated :
Ba(NOs).. + Na2SO4 = BaSO4 + 2NaNOs
Barium nitrate. Sodium sulfate. Barium sulfate. Sodium nitrate.
Stoichiometry (GTOIXEIOV = an element; jutrpov = a measure) — in its
strict sense refers to the law of definite proportions, and to its
-applications. In a wider sense, the term applies to the mathe-
matics of chemistry, to those mathematical calculations by
which the quantitative relations of substances acting upon each
other, and of the products of such reactions are determined.
A chemical reaction can always be expressed by an equation,
Avhich, as it represents not only the nature of the materials in-
volved, but also the number of molecules of each, is a quantita-
tive as well as a qualitative statement.
Let it be desired to determine how much sulfuric acid will be
required to completely decompose 100 parts of sodium nitrate,
a,nd what will be the nature and quantities of the products of
the decomposition. First the equation representing the reaction
is constructed r
HaSO4 + 2NaNO3 = NaaSO4 -f 2HNOi
Sulfuric acid. Sodium nitrate. Disodic sulfate. Nitric acid.
which shows that one molecule of sulfuric acid decomposes two
molecules of sodium nitrate, with the formation of one molecule
of sodium sulfate and two of nitric acid. The quantities of the
different substances are, therefore, represented by their molecular
weights, or some multiple thereof, which are in turn obtained by
adding together the atomic weights of the constituent atoms :
H2SO4 + 2NaNO3 = NaaSO4 + 2HNO3
1X2= 2 23X1=23 23x2=46 1x1= 1
32X1=32 14X1=14 32x1=32 14X1=14
16X4=64 16X3=48 16x4=64 16X3=48
98 85X2=170 142 63x2=126
CHEMICAL COMBINATION. 45
Consequently, 98 parts H3SO4 decompose 170 parts NaNO3, and
produce 142 parts Na2SO4 and 126 parts HNO3. To find the
result as referred to 100 parts NaNO3, we apply the simple pro-
portion :
170
170
170
100
100
100
142
126
57.64— 57. 64= parts H2SO4 required.
83.53—83.53= " Na2SO4 produced.
74.11—74.11= " HNO3
As in writing equations (see p. 40), the work should always be
proved by adding together the quantities on each side of the
equality sign, which should equal each other : 98+170=268=
142+126=268 or 57.64+100=157.64=83.53+74.11=157.64.
In determining quantities as above, regard must be had to the
purity of the reagents used, and, if they be crystallized, to the
amount of water of crystallization (see p. 15) they contain.
Let it be desired to determine how much crystallized cupric:
sulfate can be obtained from 100 parts of sulfuric acid of 92%
strength. As cupric sulfate crystallizes with five molecules of
water of crystallization the reaction occurs according to the;
equation :
H2SO4 + CuO + 4H-.O = CuSO45Aq.
Sulfuric acid. Cupric oxid. Water. Cupric sulfate.
63 1X2= 2 63X1=63
1X2= 2 16 16X1=16 32X1=32
32X1=32 16X4=64
16X4=64 18X5=90
98 79 18X4=72 249
98 + 79+72 = 249.
98 parts of 100$ HaSO4 will produce, therefore, 249 parts of crys-
tallized cupric sulfate. But as the acid liquid used contains only
92 parts of true H2SO4 in 100; 100 parts of such acid will yield
233.75 parts of crystallized sulfate, for 98 : 92 : : 249 : 233.75.
In gravimetric quantitative analysis the substance whose quan-
tity is to be determined is converted into an insoluble compound,
which is then purified, dried, and weighed (see Part III.), and
from this weight the desired result is calculated.
Let the problem be to determine what percentage of silver is
contained in a silver coin. Advantage is taken of the formation
of the insoluble silver chlorid. A piece of the coin is then
chipped off and weighed : Weight of coin used = 2.5643 grams.
The chip is then dissolved in nitric acid, forming a solution of
silver nitrate. From this solution the silver is precipitated a&
chlorid, by the addition of hydrochloric acid, according to the
equation :
46 MANUAL OF CHEMISTRY.
AgNO-3 + HC1 AgCl + HNC-3
Silver nitrate. Hydrochloric acid. Silver chlorid. Nitric acid.
108X1 = 108 1 108 1X1= 1
14X1= 14 35.5 35.5 14X1=14
16X3=^8 16X3=48
170 136.5 143.5 63
170 + 36.5 = 206.5 = 143.5 + 63.
The silver chlorid is collected, dried, and weighed :
Weight of coin used 2.5643 grams.
Weight of AgCl obtained 3.0665 "
c.z 143.5 grams AgCl contain 108 grams Ag— 143.5 : 108 :: 3. 0665 :
2.3078—2.5643 grams of the coin contain 2.3078 grams of silver,
or 90^—2.5643 : 100 : : 2.3078 : 8.
Nomenclature. — The names * of the elements are mostly of
Oreek derivation, and have their origin in some prominent prop-
erty of the substance. Thus, phosphorus, 0wf, light, and fyepeiv,
to bear. Some are of Latin origin, as silicon, from silex, flint ;
some of Gothic origin, as iron, from iarn ; and others are de-
rived from modern languages, as potassium from pot-ash. Very
little system has been followed in naming the elements, beyond
applying the termination ium to the metals, and in or on to the
metalloids ; and even to this rule we find such exceptions as a
metal called manganese and a metalloid called sulfur.
The names of compound substances were formerly chosen upon
the same system, or rather lack of system, as those of the ele-
ments. So long as the number of compounds with which the
chemist had to deal remained small, the use of these fanciful
appellations, conveying no more to the mind than perhaps some
unimportant quality of the substances to which they applied,
gave rise to comparatively little inconvenience. In these later
days, however, when the number of compounds known to exist,
or whose existence is shown by approved theory to be possible,
is practically infinite, some systematic method of nomenclature
has become absolutely necessary.
The principle of the system of nomenclature at present used
is that the name shall convey the composition and character of
the substance.
Compounds consisting of two elements, or of an element and a
radical only, binary compounds, are designated by compound
names made up of the name of the more electro-positive, followed
by that- of the more electro-negative, in which the termination
id has been substituted for the termination, in, on, ogen, ygen,
*For rules governing orthography and pronunciation of chemical terms see
Appendix A.
CHEMICAL COMBINATION. 47
orus, ium, and ur. For example : the compound of potassium
and chlorin is called potassium chloric?, that of potassium and
oxygen, potassium oxid, that of potassium and phosphorus, po-
tassium phosplu'd.
In a few instances the older name of a compound is used in
preference to the one which it should have under the above rule,
for the reason that the substance is one which is typical of a
number of other substances, and therefore deserving of ex-
ceptional prominence. Such are ammonia, NH3 ; water, HaO.
When, as frequently happens, two elements unite with each
•other to form more than one compound, these are usually dis-
tinguished from each other by prefixing to the name of the ele-
ment varying in amount the Greek numeral corresponding to
the number of atoms of that element, as compared with a fixed
number of atoms of the other element.
Thus, in the series of compounds of nitrogen and oxygen, most
of which contain two atoms of nitrogen, Na is the standard of
comparison, and consequently the names are as follows :
N2O = Nitrogen monoxid.
NO (=N2O2)=Nitrogen dioxid.
NaO3 — Nitrogen trioxid.
NOa (=NaO4) = Nitrogen tetroxid.
NnOs = Nitrogen pentoxid.
Another method of distinguishing two compounds of the same
two elements consists in terminating the first word in ous, in that
compound which contains the less proportionate quantity of the
more electro-negative element, and in ic in that containing the
greater proportion ; thus :
SOa=Sulfurows oxid.
SO3=Sulfur«c oxid.
HgaCla (2Hg : 2Cl)=Mercurows chlorid.
HgCla (2Hg : 4C1)= Mercuric chlorid.
This method, although used to a certain extent in speaking of
compounds composed of two elements of Class II. (see p. 54), is
used chiefly in speaking of binary compounds of elements of
different classes.
In naming the oxacids the word acid is used, preceded by the
name of the electro-negative element other than oxygen, to which
a prefix or suffix is added to indicate the degree of oxidation. If
there be only two, the least oxidized is designated by the suffix
ous, and the more oxidized by the suffix ic, thus :
HNO2 = Nitrous acid.
HNO3 = Nitr/c acid.
48 MANUAL OF CHEMISTRY.
If there be more than two acids, formed in regular series, the
least oxidized is designated by the prefix hypo&nd the suffix ous ;
the next by the suffix ous ; the next by the suffix ic ; and the
most highly oxidized by the prefix per and the suffix ic ; thus :
HC1O = Hypoctilorous acid.
HC1O2 = Chlorows acid.
HC1C-3 = Chloric acid.x
HC1O4 = Perchloric acid.
Certain elements, such as sulfur and phosphorus, exist in
acids which are derived from those formed in the regular way,
and which are specially designated.
The names of the oxysalts are derived from those of the acids
by dropping the word acid, changing the termination of the other
•word from ous into ite, or from ic into ate, and prefixing the name
of the electro-positive element or radical ; thus :
KNO,
Potassium nitrite.
HNC-3 KNO-3
Nitric acid. Potassium nitrate.
HC1O KC1O
Hypochlorous acid. Potassium hypochlorite.
Acids whose molecules contain more than one atom of replace-
able hydrogen are capable of forming more than one salt with
electro-positive elements, or radicals, whose valence is less than the
basicity of the acid. Ordinary phosphoric acid, for instance, con-
tains in each molecule three atoms of basic hydrogen, and conse-
quently is capable of forming three salts by the replacement of
one, two, or three of its hydrogen atoms, by one, two, or three
atoms of a univalent metal. To distinguish these the Greek pre-
fixes mono, di, and tri are used, the termination ium of the name
of the metal being changed to ic, thus :
= Monopot&ssic phosphate.
HK2PO4 = Dipotsissic phosphate.
K3PO4 = Tripotassic phosphate.
The first is also called dihydropot&ssic phosphate, and the second,
hydrodipot&ssic phosphate.
In the older works, salts in which the hydrogen has not been
entirely displaced are sometimes called bisalts (bicarbonates), or
acid salts ; those in which the hydrogen has been entirely dis-
placed being designated as neutral salts.
Some elements, such as mercury, copper, and iron, form two
distinct series of salts. These are distinguished, in the same way
as the acids, by the use of the suffix ous in the names of those
CHEMICAL COMBINATION. 49
containing the less proportion of the electro-negative group,
the suffix ic in those containing the greater proportion, e.g. :
(Cu2)2SO4 .............. (1SO4 : 4Cu) = Cuprows sulfate.
CuaSO4 .................. (2SO4 : 4Cu) = Cupnc sulfate.
FeSO4 ................... (2SO4 : 2Fe) = Ferrous sulfate.
(Fea)(S04)3 ............... (3S04 : 2Fe) = Ferric sulfate.
The names, basic salts, subsalts, and oxysalts have been ap-
plied indifferently to salts, such as the lead subacetates, which
are compounds containing the normal acetate and the hydrate
or oxid of lead ; and to salts such as the so-called bismuth subni-
trate, which is a nitrate, not of bismuth, but of the univalent
radical (Bi "O")r.
By double salts are meant such as are formed by the substitu-
tion of different elements or radicals for two or more atoms of
replaceable hydrogen of the acid, such as aiuinonio-inagriesian
phosphate, PO4Mg" (NH4)'.
Radicals. — Many compounds contain groups of atoms which
pass from one compound to another, and, in many reactions, be-
have like elementary atoms. Such groups are called radicals, or
compound radicals.
Marsh gas has the composition CH4. By acting upon it in
suitable ways we can cause the atom of carbon, accompanied by
three of the hydrogen atoms, to pass into a variety of other com-
pounds, such as : (CH3)C1 ; (CH3)OH ; (CH3)2O ; C2H3O2 (CH,).
Marsh gas, therefore, consists of the radical (CH3) combined with
an atom of hydrogen : (CH3) H.
It is especially among the compounds of carbon that the exist-
ence of radicals comes into prominent notice. They, however,
occur in inorganic substances also. Thus the nitric acid mole-
cule consists of the radical NO2, combined with the group OH.
Like the elements, the radicals possess different valences, de-
pending upon the number of unsatisfied valences which they
contain. Thus the radical (CH3) is univalent, because three of
the four valences of the carbon atom are satisfied by atoms of
hydrogen, leaving one free valence. The radical (PO) of phos-
phoric acid is trivalent, because two of the five valences of the
phosphorus atom are satisfied by the two valences of the biva-
lent oxygen atom, leaving three free valences.
In notation the radicals are usually enclosed in brackets, as
above, to indicate their nature. The names of radicals termi-
nate in yl or in gen; thus : (CH3) = methyl ; (CN) = cyanogen.
The terms radical and residue, although sometimes used as
synonyms, are not such in speaking of electrical decompositions
(see p. 27). Thus the radical of sulfuric acid is SO2 ; but when
4:
60 MANUAL OF CHEMISTRY.
sulfuric acid is electrolyzed it is decomposed into hydrogen and
the residue SO4.
Composition and Constitution. — The characters of a compound
depend not only upon the kind and number of its atoms, but
also upon the manner in which they are1 attached to each other.
There are, for instance, two substances, each having the empirical
formula C2H4Oa, one of which is a strong acid, the other a neu-
tral ether. As the molecule of each contains the same number
a,nd kind of atoms, the differences in their properties must be due
to differences in the manner in which the atoms are linked to-
gether.
The composition of a compound is the number and kind of
atoms contained in its molecule ; and is shown by its empirical
formula.
The constitution of a compound is the number and kind of
atoms and their relations to each other, within its molecule ; and
is shown by its typical or graphic formula.
In the system of typical formulae all substances are considered
as being so constituted that their rational formulae may be re-
ferred to one of three classes or types, or to a combination of two
of these types. These three classes, being named after the most
common substance occurring in each, are expressed thus :
The hydrogen The water The ammonia
type. type. type.
H) II } TJ
L *•* (. r\ **
Hj H I U H
a 2 f) 2
Ha J Ha f U2 Ha
etc., etc., Ha
etc.,
it being considered that the formula of any substance of known
constitution can be indicated by substituting the proper ele-
ment, or radical, for one or more of the atoms of the type, thus :
CU (CaH5'H0 (C9H.)') CM (SO,)" in (c°)"
H )' H ) u H !• N.' Oft I H* ) Ha
H) Ha
Hydrochloric Alcohol. Ethylamin. Calcium Sulfuric Urea.
acid. chlorirt. acid.
Typical formulae are of great service in the classification of
compound substances, as well as to indicate, to a certain degree,
their nature and the method of the reactions into which they
enter. Thus in the case of the two substances mentioned above,
as both having the composition C2H4Oa, we find on examination
that one contains the group (CH3)', while the other contains the
CHEMICAL COMBINATION. 51
group (CaHsO)'. The difference in their constitution at once
becomes apparent in their typical formulae, /rjjj y r O and
//-i TT /-\y j
3 H \ ^' indicating differences in their properties, which we
find upon experiment to exist. The first substance is neutral in
reaction and possesses no acid properties ; it closely resembles a
salt of an acid having the formula ^ Vr [ O. The second sub-
stance, on the otner hand, has a strongly acid reaction, and
markedly acid properties, as indicated by the oxidized radical
and the extra-radical hydrogen. It is capable of forming salts
by the substitution of an atom of a univalent, basylous element
//~1 TT pvy J
for its single replaceable atom of hydrogen : v *-*r' 5- O.
Although typical formulae have been and still are of great ser-
vice, many cases arise, especially in treating of the more complex
organic substances, in which they do not sufficiently indicate the
relations between the atoms which constitute the molecule, and
thus fail to convey a proper idea of the nature of the substance.
Considering, for example, the ordinary lactic acid, we find its
composition to be CsHeOa, which, expressed typically, would be
(C3 O) [ O2, a constitution supported by the fact that the
radical (C3H4O)" may be obtained in other compounds, as
//-I TT f)\" )
4 Q] > . This constitution, however, cannot be the true one,
because in the first place, lactic acid is not dibasic, but monoba-
sic ; and in the second place, there is another acid, called para-
lactic acid, having an identical composition, yet differing in
its products of decomposition. These differences in the proper-
ties of the two acids must be due to a different arrangement of
atoms in their molecules, a view which is supported by the sources
from which they are obtained and the nature of their products
of decomposition.
To express the constitution of such bodies graphic formulae
are used, in which the position of each atom in relation to the
others is set forth. The constitution of the two lactic acids would
te expressed by graphic formulae in this way :
/H /H
C— H C— H
\H I \0-H
/H and ' /H
\0-H
J-,/0
*->^ r»
\O— H ^\O— H
52 MANUAL OF CHEMISTRY.
or, CH3 CH2OH
CH.OH and CH2
CO.OH CO.OH
Ordinary Paralactic
lactic acid. acid.
It must be understood that these graphic formulae are simply
intended to show the relative attachments of the atoms, and are
in nowise intended to convey the idea that the molecule is-
spread out upon a flat surface, with the atoms arranged as in-
dicated in the diagram.
Great care and much labor are required in the construction of
these graphic formulae, the positions of the atoms being deter-
mined by a close study of the methods of formation, and of the
products of decomposition of the substance under consideration.
Naturally, in a matter of this nature, there is always room for
differences of opinion — indeed, the entire atomic theory is open
to question, as is the theory of gravitation itself. But whatever
may be advanced, two facts cannot be denied : first, that chem-
istry owes its advancement within the past half-century to the
atomic theory, which to-day is more in consonance with observed
facts than any substitute which can be offered ; second, that
without the use of graphic formulae it is impossible to offer any
adequate explanation of the reactions which we observe in deal-
ing with the more complex organic substances.
In chemistry, as in other sciences, a sharp distinction must
always be made between facts and theories : the former, once ob-
served, are immutable additions to our knowledge ; the latter
are of their nature subject to change with our increasing knowl-
edge of facts. We have every reason for believing, however, that
the supports upon which the atomic theory rests are such that,
although it may be modified in its details, its essential features
will remain unaltered.
Classification of the Elements. — Berzelius was the first to di-
vide all the elements into two great classes, to which he gave the
names metals and metalloids. The metals, being such substances
as are opaque, possess what is known as metallic lustre, are good
conductors of heat and electricity, and are electro-positive ; the
metalloids, on the other hand, such as are gaseous, or, if solid,
do not possess metallic lustre, have a comparatively low power
of conducting heat and electricity, and are electro-negative.
This division, based upon purely physical properties, which, in.
many cases, are ill-defined, has become insufficient. Several ele-
ments formerly classed under the above rules with the metals,,
CHEMICAL COMBINATION. 53
resemble the metalloids in their chemical characters much more
•closely than they do any of the metals. Indeed, by the charac-
ters mentioned above, it is impossible to draw any line of deinar-
-cation which shall separate the elements distinctly into two
groups.
The classification of the elements should be such that each
group shall contain elements whose chemical properties are simi-
lar— the physical properties being considered only in so far as
they are intimately connected with the chemical. The arrange-
ment of elements into groups is not equally easy in all cases.
.Some groups, as the chlorin group, are sharply defined, while the
members of others differ from each other more widely in their
properties. The positions of most of the more recently discovered
•elements are still uncertain, owing to the imperfect state of our
knowledge of their properties.
The method of classification which we will adopt, and which
we believe to be more natural than any hitherto suggested, is
based upon the chemical properties of the oxids and upon the
valence of the elements. AVe abandon the division into metals
•and metalloids, and substitute for it a division into four great
classes, according to the nature of the oxids and the existence or
non-existence of oxysalts. In the first of these classes hydrogen
and oxygen are placed together, for the reason that, although
they differ from each other in many of their properties, they to-
gether form the basis of our classification, and may, for this and
other reasons, be regarded as typical elements. They both play
important parts in the formation of acids, and neither would find
& suitable place in either of the other classes. Our primary divi-
sion would then be as follows :
Class I. — Typical elements.
Class IL— Elements whose oxids unite with water to form
acids, never to form bases. Which do not form, oxysalts.
This class contains all the so-called metalloids except hydro-
gen and oxygen.
Class III. — Elements whose oxids unite with water, some to
form, bases, others to form acids. Which form oxysalts.
Class IV. — Elements whose oxids unite with, water to form
bases ; never to form acids. Which form oxysalts.
In this class are included the more strongly electro-positive
metals.
Within the classes a further subdivision is made into groups,
each group containing those elements within the class which have
equal valences, which form corresponding compounds, and whose
chemical characters are otherwise similar.
For the sake of convenience the term metal is retained to apply
54 MANUAL OF CHEMISTKY.
to the members of Classes III. and IV. ; the term non-metal being
used for those belonging to Class II.
GROUP I. — Hydrogen.
GROUP II.— Oxygen.
Class I.
Class II.
GROUP I. — Fluorin, chlorin, bromin, iodin.
GROUP II. — Sulfur, selenium, tellurium.
GROUP III. — Nitrogen, phosphorus, arsenic, antimony.
GROUP IV. — Boron.
GROUP V. — Carbon, silicon.
GROUP VI. — Vanadium, columbium, tantalium.
GROUP VII. — Molybdenum, tungsten, osmium (?).
Class III.
GROUP I.— Gold.
GROUP II. — Cromium, manganese, iron.
GROUP III. — Glucinium, aluminium, scandium, gallium, in-
dium.
GROUP IV.— Uranium.
GROUP V. — Lead.
GROUP VI. — Bismuth.
GROUP VII. — Titanium, zirconium, tin.
GROUP VIII. — Palladium, platinum.
GROUP IX. — Rhodium, ruthenium, iridium.
Class IV.
GROUP I. — Lithium, sodium, potassium, rubidium, cesium,
silver.
GROUP II. — Thallium.
GROUP III. — Calcium, strontium, barium.
GROUP IV. — Magnesium, zinc, cadmium.
GROUP V. — Nickel, cobalt.
GROUP VI. — Copper, mercury.
GROUP VII. — Yttrium, cerium, ytterbium, lanthanium, didy-
miurn, erbium.
GROUP VIII.— Thorium.
PART II.
SPECIAL CHEMISTRY.
CLASS L
TYPICAL ELEMENTS.
• HYDROGEN — OXYGEN.
ALTHOUGH, in a strict sense, hydrogen is regarded by most
chemists as the one and only type-element — that whose atom is
the unit of atomic and molecular weights — the important part
which oxygen plays in the formation of those compounds whose
nature forms the basis of our classification, its acid-forming
power in organic compounds, and the differences existing between
its properties and those of the elements of the sulfur group, with
which it is usually classed, warrant us in separating it from the
other elements and elevating it to the position it here occupies.
HYDROGEN.
Symbol=H — Univalent— Atomic weight = 1 — Molecular weight
= 2—Sp. gr.= 0.06926 A*— Owe litre weighs 0.0896 gram}— 100
cubic inches weigh 2.1496 grains^ — 1 gram measures 11.16 litres\ —
1 grain measures 46.73 cubic inches^ — Name derived from vfiup =
water, and jewdu — I produce — Discovered by Cavendish in 1766.
O«currence. — Occurs free in volcanic gases, in fire-damp, oc-
cluded in meteorites, in the gases exhaled from the lungs, and in
those of the stomach and intestine. In combination in water,
hydrogen sulfid, amuioniacal compounds, and in many organic
substances.
Preparation. — (1.) By electrolysis of water, H is given off at
the negative pole. Utilized when pure H is required.
*Air = 1. When the sp. gr. is referred to H = 1, A is replaced by H.
tAt 0° C. and 760 mm. barometric pressure.
£At 60° F. and 30 inches bar. pressure.
56
MANUAL OF CHEMISTRY.
(2.) By the disassociation of water at very high temperatures.
(3.) By the decomposition of water by certain metals. The
alkali metals decompose water at the ordinary temperature :
Na, -f 2H2O = 2NaHO -f Ha
Sodium. AYater. Sodium hydroxid. Hydrogen.
Some other metals, such as iron and copper, effect the decom-
position only at high temperatures :
3Fea + 8HaO = 2FesO< + 8H3
Iron. Water. Triferric tetroxid. Hydrogen.
(4.) By decomposition of water, passed over red-hot coke :
C + 2H.O = CO, + 2Ha
Carbon. Water. Carbon dioxid. Hydrogen.
or at a higher temperature :
20
Carbon.
2H2O
Water.
= 200 '+ 2H2
Carbon monoxid. Hydrogen.
(5.) By decomposition of mineral acids, in the presence of water,
by zinc and certain other metals :
Zn + H2SO4 + xH,O = ZnSO4 + Ha -f a?H2O
Zinc. Sulfuric acid. Water. Zinc sulfate. Hydrogen. Water.
The water serves to dissolve the zinc sulfate. Chemically
FIG. 19.
pure zinc, or zinc whose surface has been covered with an alloy
of zinc and mercury, does not decompose the acid unless it forms
part of a galvanic battery whose circuit is closed. The zincs of
galvanic batteries are therefore covered with the alloy mentioned
— are amalgamated — to prevent waste of zinc and acid.
HYDROGEN.
57
This is the method usually resorted to for obtaining H. The
gas so obtained is, however, contaminated with small quantities
of other gases, hydrogen phosphid, sulfid, and arsenid.
FIG. 20.
Hydrogen, carbon dioxid, hydrogen sulfid, and other gases
produced by the action of a liquid upon a solid at ordinary tem-
peratures, are best prepared in one of the forms of apparatus
shown in Figs. 19, 20, and 21.
The solid material is placed in
the larger bottle (Fig. 19), or, over
a layer of broken glass about five
centimetres thick, in the bottle A
(Fig. 20). The liquid reagent is
from time to time introduced by
the funnel tube, Fig. 19 ; or the
bottle B, Fig. 2u, is filled with it.
The wash-bottles are partially
filled with water to arrest any
liquid or solid impurity. The ap-
paratus, Figs. 20 and 21, have the
advantage of being always ready
• for use. When the stopcock is
open the gas escapes. When it is
closed the internal pressure de-
presses the level of the liquid in
A into the layer of broken glass,
and the action is arrested. Kipp's
apparatus, Fig. 21, is another con-
venient form of constant appara-
tus. The solid reagent is placed
in the central bulb.
(8.) By heating together a mix-
ture of zinc dust and dry slacked lime :
FIG. 21.
Zn
Zinc.
CaHaO,
Calcium hydroxid.
ZnO
Zinc oxid.
Calcic monoxid.
H2
Hydrogen.
Properties. — Physical. — Hydrogen is a colorless, odorless, taste-
less gas ; 14.47 times lighter than air, being the lightest substance
58 MANUAL OF CHEMISTEY.
known. The weight of a litre, 0.0896 gram, is called a crith.
(Kpidti = barleycorn). It is almost insoluble in water and alcohol.
It conducts heat arid electricity better than any other gas. In
obedience to the law: The diffusibility of two gases varies in-
versely as the square roots of their densities, it is the most rap-
idly diffusible of gases. The rapidity with which this diffusion
takes place renders the use of hydrogen, which has been kept
for even a short time in gas-bags or gasometers, dangerous. At
—140° (—229° P.), under a pressure of 650 atmospheres, it forms a
steel-blue liquid.
Certain metals have the power of absorbing large quantities of
hydrogen, which is then said to be occluded. Palladium absorbs
376 volumes at the ordinary temperature ; 932 vols. at 90° (194° P.)
and 526 vols. at 245° (473° P.). The occluded gas is driven off by
the application of heat, and possesses great chemical activity,
similar to that which it has when in the nascent state. This
latter quality, and the fact that heat is liberated during the oc-
clusion, would seem to indicate that the gas is contained in the
inetal, not in a mere physical state of condensation, but in chem-
ical combination.
Chemical. — Hydrogen exhibits no great tendency to combine
with other elements at ordinary temperatures. It combines ex-
plosively, however, with chlorin under the influence of sunlight,
and with fluorin even in the dark. It does not support com-
bustion, but, when ignited, burns with a pale blue and very hot
flame ; the result of the combination being water. Mixtures of
hydrogen and oxygen explode violently on the approach of flame,
or by the passage of the electric spark, the explosion being
caused by the sudden expansion of the vapor of water formed,
under the influence of the heat of the reaction. Hydrogen also
unites with oxygen when brought in contact with spongy
platinum. Many compounds containing oxygen give up that
element when heated in an atmosphere of hydrogen :
CuO + H, = Cu + H2O
Cupric oxid. Hydrogen. Copper. Water.
The removal of oxygen from a compound is called a reduction
or deoxidation.
At the instant that H is liberated from its compounds it has a
deoxidizing power similar to that which ordinary H possesses
only at elevated temperatures, and its tendency to combine with
other elements is greater than under other conditions. The
greater energy of H, and of other elements as well, in this
nascent state, may be thus explained. Free H exists in the form
of molecules, each one of which is composed of two atoms, but
at the instant of its liberation from a compound, it is in the form
OXYGEN. 59-
of individual atoms, and that portion of force required to split
up the molecule into atoms, necessary when free H enters into-
reaction, is not required when the gas is in the nascent state.
In its physical and chemical properties, this element more
closely resembles those usually ranked as metals than it does
those forming the class of metalloids, among which it is usually
placed. Its conducting power, its appearance in the liquid form,
as well as its relation to the acids, which may be considered as
salts of H, tend to separate it from the metalloids.
Analytical Characters. — (1.) Burns with a faintly blue
flame, which deposits water on a cold surface brought in contact
with it ; (2.) Mixed with oxygen, explodes on contact with flame,,
producing water.
OXYGEN.
Symbol = 0— Bivalent — Atomic weight = 16 ; molecular weight
= 32— Sp. gr.= 1.10563 A (calculated = 1.1088) ; 15.95 H ; sp. gr. of
liquid = 0.9787 — One litre weighs 1.4300 grams — 16 criths — 100
cubic inches weigh 34.27 grains — Name derived from o^vg = acid,
and -yewdu — I produce — Discovered by Mayow in 1674 ; re-discov-
ered by Priestley in 1774.
Occurrence. — Oxygen is the most abundant of the elements. It
exists free in atmospheric air ; in combination in a great number-
of substances, mineral, vegetable, and animal.
Preparation. — (1.) By heating certain oxids:
2HgO 2Hg 4 Oa
Mercuric oxid. Mercury. Oxygen.
This was the method used by Priestley. 100 grams of mercuric
oxid produce 5.16 litres of oxygen :
3MnO, Mn3O4 + O,
Manganese dioxid. Trimanganic tetroxid. Oxygen.
The black oxid of manganese is heated to redness in an iron or
clay retort (Scheele, 1775) ; and 100 grams yield 8.51 litres of
oxygen.
(2.) By the electrolysis of water, acidulated with sulfuric acid,
O is given off at the positive pole.
(3.) By the action of sulfuric acid upon certain compounds
rich in O : manganese dioxid. potassium dichromate, and plumbic
peroxid:
2MnO2 + 2H2SO4 = 2MnSO4 + 2H2O + Oa
Manganese dioxid. Sulfuric acid. Manganous sulfate. Water. Oxygen.
100 grams of manganese dioxid produce 12.82 litres of O.
(4.) By decomposing H^SO* at a red heat, 2HaSOt = 2SOa-ir
2HaO+O3.
60 MANUAL OF CHEMISTRY.
(5.) By the decomposition by heat of certain salts rich in O :
alkaline permanganates, nitrates, and chlorates.
The best method, and that usually adopted, is by heating a
mixture of potassium chlorate arid manganese dioxid in equal
parts, moderately at first and more strongly toward the end of
the reaction. The chlorate gives up all its O (27.33 litres from 100
grams of the salt), according to the equation :
2KC1O3 = 2KC1 + 3Oa
Potassium chlorate. Potassium chlorid. Oxygen.
At the end of the operation the manganese dioxid remains,
apparently unchanged. The most probable explanation of its
action is that potassium permanganate and free chlorin are first
produced, while a part of the oxygen is liberated :
4KC1O3 + 2MnOa = K2Mn2O8 + 2KC1 + Cl« + 4Oa
Potassium Manganese Potassium Potassium Chlorin. Oxygen,
chlorate. dioxid. permanganate. chlorid.
that the permanganate so formed is decomposed at a compara-
tively low temperature, according to the equation :
K2MnaO8 = K2MnO4 + MnO» + O,
Potassium Potassium Manganese Oxygen,
permanganate. mangauate. dioxid.
and, finally, that the manganate so formed is decomposed by the
chlorin produced in the first reaction, according to the equation :
K,MnO4 + 01, = 2KC1 + MnO. + O2
Potassium Chlorin. Potassium Manganese Oxygen,
manganate. chlorid. dioxid.
A small quantity of free chlorin usually exists in the gas pro-
duced by this reaction. If the oxygen is to be used for inhala-
tion, the chlorin should be removed by allowing the gas to stand
over water for 24 hours.
When heat is required for the generation o'f gases the opera-
tion is conducted in retorts of glass or metal, or in the apparatus
shown in Fig. 22. If the gas be collected over water the disen-
gagement tube must be withdrawn from the water, before the
source of heat is removed. Nejrlect of this precaution will cause
an explosion, by the entrance of water into the hot flask, by the
contraction of the gas contained in it, on partial cooling.
(6.) By the mutual decomposition of potassium permanganate
and hydrogen peroxid, in the presence of sulfuric acid:
H2Oa + K2MnaO8 + 3H2SO4 = K2SO4 +
Hydrogen Potassium Sulfuric Potassium
peroxid. permanganate. acid. sulfate.
+ 2MnSO4 + 4H2O + 3O,
Manganous Water. Oxygen.,
sulfate.
OXYGEN.
61
One kilo H2Oa (3%) and 500 cc. dilute H2SO4 (1:5) are placed in
the generating flask and 56 grams K2Mn2O8, dissolved in H3O, are
gradually added. With -these quantities 20 litres O are obtained.
(7.) By the action of dilute hydrochloric acid upon a mix-
ture of 2 parts barium peroxid, 1 part manganese dioxid, and
1 part plaster of Paris, compressed into cubes about H cent,
square.
Methods 6 and 7 have the advantage that heat is not required,
and the forms of apparatus, Figs. 19, 20, and 21, may be used.
Properties. — Physical. — Oxygen is a colorless, odorless, tasteless
gas, soluble in water in the proportion of 7.08 cc. in 1 litre of
water at 14°. 8 (58°. 6 F.), somewhat more soluble in absolute alco-
FIG. 22.
hoi. It liquefies at -140° (—229° F.) under a pressure of 300 at-
mospheres. Liquid oxygen boils at — 187°.4 (— 294°.5 F.) at the
ordinary pressure.
Chemical. — Oxygen is characterized, chemically, by the strong
tendency which it exhibits to enter into combination with other
elements. It forms binary compounds with all elements except
fluorin and bromin. With most elements it unites directly,
especially at elevated temperatures. In many instances this
union is attended by the appearance of light, and always by the
extrication of heat. The luminous union of O with another ele-
ment constitutes the familiar phenomenon of combustion, and is
the principal source from which we obtain so-called artificial heat
and light. A body is said to be combustible when it is capable of
so energetically combining with the oxygen of the air as to liber-
'62 MANUAL OF CHEMISTRY.
ate light as well as heat. Gases are said to be supporters of com-
bustion, when combustible substances will unite with them, or
with some of their constituents, the union being attended with
the appearance of heat and light. The distinction between
combustible substances and supporters of combustion is, how-
ever, one of mere convenience. The action (taking place between
the two substances, one is as much a party to it as the other. A
jet of air burns in an atmosphere of coal-gas as readily as a jet
of coal-gas burns in air.
The compounds of oxygen — the oxids — are divisible into three
groups :
1. Anhydrids — oxids capable of combining with water to form
acids. Thus sulfuric arihydrid, SO3, unites with water to form
sulfuric acid, H2SC>4.
The term anhydrid is not limited in application to binary com-
pounds, but applies to any substance capable of combining with
water to form an acid. Thus the compound C4H6O3 is known as
acetic anhydrid, because it combines with water to form acetic
acid: C4H6O3 + H2O = SCaELOa. (See compounds of arsenic and
sulfur.)
2. Basic Oxids are such as combine with water to form bases.
Thus, calcium oxid, CaO, unites with water to form calcium
Jiydroxid, CaH2O2.
3. Saline, neutral, or indifferent oxids are such as are neither
acid nor basic in character. In some instances they are essentially
neutral, as in the case of the protoxid of hydrogen, or water. In
other cases they are formed by the union of two other oxids, one
basic, the other acid in quality, such as the red oxid of lead,
Pb3O4, formed by the union of a molecule of the acidulous per-
oxid, PbOa, with two of the basic protoxid, PbO. It is to oxids
of this character that the term "saline" properly applies.
The process of respiration is very similar to combustion, and
as oxygen gas is the best supporter of combustion, so, in the
diluted form in which it exists in atmospheric air, it is not only
the best, but the only supporter of animal respiration. (See
<iarbon dioxid.)
Analytical Characters. — 1.) A glowing match-stick bursts into
flame in free oxygen. 2.) Free O, when mixed with nitrogen
dioxid, produces a brown gas.
Ozone. — Allotropic oxygen. — Air through which discharges of
static electricity have been passed, and oxygen obtained by the
decomposition of water (if electrodes of gold or platinum be
used), have a peculiar odor, somewhat resembling that of sulr
fur, which is due to the conversion of a part of the oxygen into
ozone.
Ozone is produced : 1.; By the decomposition of water by the
OXYGEN. 63
Tmttery. 2.) By the slow oxidation of phosphorus in damp air.
3.) By the action of concentrated sulfuric acid upon barium
dioxid. 4.) By the passage of silent electric discharges through
air or oxygen.
In the preparation of ozonized oxygen the best results are ob-
tained by passing a slow current of oxygen through an apparatus
made entirely of glass and platinum, cooled by a current of cold
water, and traversed by the invisible discharge of an induction
coil.
Pure, liquid ozone has been obtained by subjecting ozonized
oxygen to the temperature of liquid oxygen at the atmospheric
pressure. It is a dark blue liquid, almost opaque in layers
2 mm. thick, which is not decomposed at the ordinary tempera-
ture, but converted into a blueish gas.
When oxygen is ozonized it contracts slightly in volume, and
when the ozone is removed from ozonized oxygen by mercury or
potassium iodid the volume of the gas is not diminished. These
facts, and the great chemical activity of ozone, have led chemists
to regard it as condensed oxygen ; the molecule of ozone being
represented thus (OOO), while that of ordinary oxygen is (OO).
Ozone is very sparingly soluble in water, insoluble in solutions
of acids and alkalies. In the presence of moisture it is slowly
converted into oxygen at 100° (212° F.), a change which takes
place rapidly and completely at 237° (459° F.). It is a powerful
oxidant ; it decomposes solutions of potassium iodid with for-
mation of potassium hydroxid, and liberation of iodin; it oxidizes
all metals except gold and platinum, in the presence of moisture;
it decolorizes indigo and other organic pigments, and acts rapidly
upon rubber, cork, and other organic substances.
Analytical Characters. — 1.) Neutral litmus paper, impregnated
with solution of potassium iodid, is turned blue when exposed to
air containing ozone. The same litmus paper without iodid is
not affected. 2.) Manganous sulfate solution is turned brown
by ozone. 3.) Solutions of thallous salts are colored yellow or
brown by ozone. 4.) Paper impregnated with fresh tincture of
natural (unpurified) guaiacum is colored blue by ozone. 5.)
Paper impregnated with solution of manganous sulfate, or lead
hydroxid, or palladium chlorid is colored dark brown or black by
ozone. 6.) Metallic silver is blackened by ozone.
When inhaled, air containing 0.07 gram of ozone per litre
•causes intense coryza and haemoptysis. It is probable that ozone
is by no means as constant a constituent of the atmosphere as
was formerly supposed. (See Hydrogen dioxid.)
64 MANUAL OF CHEMISTRY.
Compounds of Hydrogen and Oxygen.
Two are known — hydrogen oxid or water, H2O ; hydrogen per-
oxid or oxygenated water, H2O2.
Water.
H2O — Molecular weight— \^> — Sp. gr. = l — Vapor density— 0.6218
A; caleulated=Q.6234 — Composition discovered by Priestley in
1780.
Occurrence. — In unorganized nature H2O exists in the gaseous
form in atmospheric air and in volcanic gases ; in the liquid form
very abundantly ; and as a solid in snow, ice, and hail.
As water of crystallization it exists in definite proportion in
certain crystals, to the maintenance of whose shape it is neces-
sary.
In the organized world H2O forms a constituent part of every
tissue and fluid.
Formation. — Water is formed : 1. By union, brought about by
elevation of temperature, of one vol. O with two vols. H.
2. By burning H, or substances containing it, in air or in O.
3. By heating organic substances containing H to redness with
cupric oxid, or with other substances capable of yielding O. This-
method of formation is utilized to determine the amount of H
contained in organic substances.
4. When an acid and a hydroxid react upon each other to form
a salt:
HuSOi + 2KHO = K2SO4 + 2H2O
Sulfuric acid. Potassium hydroxid. Potassium sulfate. Water.
5. When a metallic oxid is reduced by hydrogen :
CuO + H2 = Cu + H2O
Cupric oxid. Hydrogen. Copper. Water.
C. In the reduction and oxidation of many organic substances.
Pure H2O is not found in nature. When required pure it is.
separated from suspended matters by filtration, and from dis-
solved substances by distillation.
Properties. — Physical. — With a barometric pressure of 760 in in.
H2O is solid below 0° (32° F.) ; liquid between 0° (32° F.) and 100°
(212° F.) ; and gaseous above 100° (212° F.). When H2O is enclosed
in capillary tubes, or is at complete rest, it may be cooled to
— 15° (5° F.) without solidifying. If, while at this temperature,
it be agitated, it solidifies instantly, and the temperature sud-
denly rises to 0° (32° F.). The melting-point of ice is lowered
0.0075° (0.0135° F.) for each 'additional atmosphere of pressure.
The boiling-point is subject to greater variations than the
freezing-point. It is the lower as the pressure is diminished, and-
WATER. 65
the higher as it is increased. Advantage is taken of the reduced
boiling-point of solutions in vacuo for the separation of sub-
stances, such as cane sugar, which are injured at the temperature
of boiling H2O. On the other hand, the increased temperature
that may be imparted to liquid H2O under pressure is utilized in
many processes, in the laboratory and in the arts, for effecting
solutions and chemical actions which do not take place at lower
temperatures. The boiling-point of H2O holding solid matter in
solution is higher than that of pure H2O, the degree of increase
depending upon the amount and nature of the substance dissolved.
On the other hand, mixtures of H2O with liquids of lower boiling-
point boil at temperatures less than 100° (212° F.). Although the
conversion of water into water-gas takes place most actively at
100" (212° F.), water and ice evaporate at all temperatures.
Water is the best solvent we have, and acts in some instances
as a simple solvent, in others as a chemical solvent.
Vapor of water is colorless, transparent, and invisible. Sp. gr,
0.6234 A or 9 H. A litre of vapor of water weighs 0.8064. The
latent heat of vaporization of water is 536.5 ; that is, as much
heat is required to vaporize 1 kilo, of water at 100° as would
suffice to raise 536.5 kilos, of water 1° in temperature. In passing
from the liquid to the gaseous state, water expands 1,696 times
in volume.
Chemical. — Water may be shown to consist of 1 vol. O and 2
vols. H, or 8 by weight of O and 1 by weight of H, either by
analysis or synthesis.
Analysis is the reducing of a compound to its constituent
elements.
Synthesis is the formation of a compound from its elements.
A partial synthesis is one in which a complex compound is pro-
duced from a simpler one, but not from the elements.
Water may be resolved into its constituent gases : 1st. By
electrolysis of acidulated water ; H being given off at the nega-
tive and O at the positive pole. 2d. By passing vapor of H2O
through a platinum tube heated to whiteness, or through a
porcelain tube heated to about 1,100°. 3d. By the action of the
alkali metals. Hydrogen is given off, and the metallic hydroxid
remains in solution in an excess of H2O. 4th. By passing vapor
of H2O over red-hot iron. Oxid of iron remains and H is given
off.
Water combines with oxids to form new compounds, some of
which are acids and others bases, known as hydroxids.
A hydroxid is a compound formed by the replacement of half of
the hydrogen of water by a metal.
A hydrate is a compound containing' chemically combined
water.
66 MANUAL OF CHEMISTEY.
The hydrates of the electro-negative. elements and radicals are
acids ; most of those of the electro-positive elements and radicals
are basic hydroxids.
Certain substances, in assuming the crystalline form, combine
with a definite proportion of water, which is known as water of
crystallization, and whose presence, although necessary to the
maintenance of certain physical characters, such as color and
crystalline form, does not modify their chemical reactions. In
many instances a portion of the water of crystallization may be
driven off at a comparatively low temperature, while a much
higher temperature is required to expel the remainder. This
latter is known as water of constitution.
The symbol Aq (Latin, aqua) is frequently used to designate
the water of crystallization, the water of constitution being indi-
cated by H2O. Thus MgSO4,H2O+6 Aq represents magnesium
sulfate with one molecule of water of constitution and six mole-
cules of water of crystallization. We consider it preferable,
however, as the distinction between water of crystallization and
water of constitution in many salts is only one of degree and not
of kind, to use the symbol Aq to designate the sum of the two;
thus, MgSO4+7 Aq.
Water decomposes the chlorids of the second class of elements
(those of carbon only at high temperatures and under pressure);
while the chlorids of the elements of the third and fourth classes
are either insoluble, or soluble without decomposition.
Natural Waters.— Water, as it occurs in nature, always con-
tains solid and gaseous matter in solution and frequently solids
in suspension.
Natural waters may be classified, according to the nature and
quantity of foreign matters which they contain, into potable and
unpotable waters. To the first class belong rain-water, snow-
.and ice-water, spring-water (fresh), river-water, lake-water, and
well-water. To the second class belong stagnant waters, sea-
water, and the waters of mineral springs.
Rain-water is usually the purest of natural waters, so far as
dissolved solids are concerned, containing very small quantities
of the chlorids, sulfates, and nitrates of sodium and ammo-
nium. Owing to the large surface exposed during condensa-
tion, rain-water contains relatively large quantities of dissolved
.gases— oxygen, nitrogen, and carbon dioxid ; and sometimes
hydrogen sulfid and sulfur dioxid. The absence of carbon-
ates and the presence of nitrates and oxygen render rain-water
particularly prone to dissolve lead, when in contact with that
metal. In summer, rain-water is liable to become charged with
vegetable organic matter suspended in the atmosphere.
Ice-water contains very small quantities of dissolved solids or
WATER. 61
gases, which, during freezing, remain in great part in the un-
frozen water. Suspended impurities are imprisoned in the ice
and liberated when this is melted.
Melted snow contains about the same proportion of fixed solid
matter as rain-water, but a less proportion of ammoniacal salts
And of gases.
Spring-water is rain-water which, having percolated through a
portion of the earth's crust (in which it may also have been sub-
jected to pressure), has become charged with solid and gaseous
matter ; varying in kind and quantity according to the nature of
the strata through which it has percolated, the duration of con-
tact, and the pressure to which it was subject during such con-
tact.
Spring-waters from igneous rocks and from the older sedi-
mentary formations are fresh and sweet, and any spring-water
may be considered such whose temperature is less than 20°
(68° F.), and which does not contain more than 40 parts in 100,000
of solid matter ; provided that a large proportion of the solid
matter does not consist of salts having a medicinal action, and
that sulfurous gases and sulfids are absent.
Artesian wells are artificial springs, produced by boring in a
low-lying district, until a pervious layer, between two imper-
vious strata, is reached ; the outcrop of the system being in an
-adjacent elevated region.
River-water is a mixture of rain-water, spring-water, and the
drainage water of the district through which the river flows, to
which snow-water, ice-water, or sea-water is sometimes added.
The water of a river flowing rapidly through a granitic region is,
unless polluted by manT bright, fresh, and highly aerated. That
of a stream flowing sluggishly through rich alluvial land is un-
aerated, and rich in dissolved and suspended solids.
The amount of dissolved solids in river-water increases with
the distance from its source.
The chief sources of pollution of river-water are by the dis-
charge into them, of the sewage of towns and cities, or of the
waste products of factories.
Lake-water is an accumulation of river- and rain- water. As the
waters of lakes are kept in constant agitation both by the wind
and by the current, they become to a certain extent purified
from organic contamination.
Well-water may be very good or very bad. If the well be
simply a reservoir dug over a spring, and removed from sources of
contamination, it has all the characters of fresh spring-water.
If, on the other hand, it be simply a hole dug in the earth, the
water which it contains is the surface water which has percolated
through the thin layer of earth corresponding to the depth of the
68 MANUAL OF CHEMISTKY.
well, and is consequently warm, unaerated and charged with:
organic impurity. Such water is sometimes called " ground
water."
Wells dug near dwellings are very liable to become charged
with the worst of contaminations, animal excreta, by their nitra-
tion through the soil, either by reason of the fracture of the
house-drain or otherwise.
Impurities in Potable Waters. — A water to be fit for drinking
purposes should be cool, limpid, and odorless. It should have an
agreeable taste, neither flat, salty, nor sweetish, and it should
dissolve soap readily, without formation of any flocculent precip-
itate.
Although it is safe to condemn a water which does not possess
the above characters, it is by no means safe to regard all waters
which do possess them as beyond suspicion. To determine
whether a water is potable it must be more carefully examined
as to the following constituents :
Total Solids. — The amount of solid material dissolved in pota-
ble waters varies from 5 to 40 in 100,000 ; and a water containing
more than the. latter quantity is to be condemned on that account
alone.
To determine the quantity of total solids 500 c.c. of the filtered
water are evaporated to dryness in a previously weighed plati-
num dish, over the water-bath. The dish with the contained
dry residue is cooled in a desiccator and again weighed. The in-
crease in weight, multiplied by 200, gives the total solids in parts-
per 100,000.
Hardness. — The greater part of the solid matter dissolved in
natural fresh waters consists of the salts of calcium, accompanied
by less quantities of the salts of magnesium. The calcium salt is
usually the bicarbonate or the sulfate ; sometimes the chlorid,
phosphate, or nitrate.
A water containing an excess of calcareous salt is said to be
hard, and one not so charged is said to be soft. If the hardness
be due to the presence of the carbonate it is temporary, if due to
the sulfate it is permanent. Calcium carbonate is almost insol-
uble in pure water, but in the presence of free carbonic acid the
more soluble bicarbonate is dissolved. But, on the water being
boiled, it is decomposed, with precipitation of the carbonate, if
the quantity exceed 50 in 100,000. As calcium sulfate is held in
solution by virtue of its own, albeit sparing, solubility, it is not
deposited when the water is boiled.
An accurate determination of the quantity of calcium and
magnesium salts in water is rarely required. It is, however,,
frequently desirable to determine their quantity approximately,
the result being the degree of hardness.
WATEE. 69
For this purpose a solution of soap of known strength is re<
<juired. This is made by dissolving 10 grams of air-dried, white
Castile soap, cut into thin shavings, in a litre of dilute alcohol
(sp. gr. 0.949). To determine whether this solution contains the
proper amount of soap, 10 c.c. of a solution, made by dissolving
1.11 grams of pure, recently fused calcium chlorid in a litre of
water, are diluted with 60 c.c. of water and the soap solution
.added until a persistent lather is produced on agitation. If 11
c.c. of soap solution have been used it has the proper strength ;
if a greater or less quantity have been added it must be concen-
trated or diluted in proportion to the excess or deficiency. The
soap solution must not be filtered, but, if turbid, must be shaken
before using.
To determine the hardness, 70 c.c. of the water to be tested are
placed in a glass-stoppered bottle of 250 c.c. capacity, and the
soap solution gradually added from a burette. After each addi-
tion of soap solution the bottle is shaken, and allowed to lie upon
its side five minutes. This is continued until at the end of five
minutes a lather remains upon the surface of the liquid in the
bottle. At this time the hardness is indicated by the number of
c.c. of soap solution added, minus one. If more than 16 c.c. of
.soap solution are added the liquid in the bottle must be diluted
with 70 c.c. of distilled water.
A good drinking-water should not have a hardness of more than
fifteen.
Chlorids. — The presence of the chlorids of the alkaline metals,
in quantities riot sufficient to be detectable by the taste, is of no
importance per se ; but in connection with the presence of or-
ganic impurity, a determination of the amount of chlorin affords
a ready method of indicating the probable source of the organic
contamination. As vegetable organic matter brings with it but
.small quantities of chlorids, while animal contaminations are rich
in those compounds, the presence of a large amount of chlorin
serves to indicate that organic impurity is of animal origin. In-
deed, when time presses, as during an epidemic, it is best to rely
upon determinations of chlorin, and condemn all waters contain-
ing more than 1.5 in 100,000 of that element.
For the determination of chlorin two solutions are required : a
solution of silver nitrate containing 4. 79 grams per litre ; a strong
solution of potassium chrouiate. One hundred c.c. of the water
are placed in a beaker with enough of the chromate solution to
communicate a distinct yellow color. If the reaction be acid it
is rendered neutral or faintly alkaline by the addition of sodium
carbonate solution. The silver solution is now allowed to flow in
from a burette, drop by drop, during constant agitation, until a
faint reddish tinge persists. At this time the burette reading is
taken ; each c.c. of silver solution added represents 0.01 of chlorin
per litre.
Organic Matter. — The most serious of the probable contamina-
tions of drinking-water is that by organic matters containing
nitrogen. "When these are present in even moderate quantity,
and when, at the same time, the proportion of chlorin is greater
70 MANUAL OF CHEMISTRY.
than usual, the water has been contaminated by animal excreta
and contains, under suitable conditions, the causes of disease, be
they germs or poisons.
Of the methods suggested for the determination of the amount
of organic matter in natural waters there is, unfortunately, none
which is easy of application and at the same time reliable. That
which yields the best results is Wanklyn's process :
The following solutions are required : a. Made by dissolving 200
grams of potassium hydroxid and b grams of potassium permanga-
nate in a litre of water. The solution is boiled down to about
725 c.c., cooled, and brought to its original bulk by the addition of
boiled distilled water, b. Nessler's reagent. 35 grains of potassium
iodid and 13 grams of mercuric chlorid are dissolved in 800 c.c. of
water by the aid of heat and agitation. A cold, saturated solution
of mercuric chlorid is then added, drop by drop, until the red pre-
cipitate which is formed is no longer redissolved on agitation : 160
grams of potassium hydroxid are then dissolved in the liquid, to
and the bulk of the whole made up to a litre with water. The
solution is allowed to stand, decanted, and preserved in com-
pletely filled, well-stoppered bottles, c. Standard solutions of
ammonia. The stronger of these is made by dissolving 3. 15 grams
of ammonium chlorid in a litre of water. The weaker, by mixing
one volume of the stronger with 99 volumes of water. The latter
contains 0.00001 gram of ammonia in each c.c., and is the one
used in the determinations, the stronger solution serving only
for its convenient preparation, d. A saturated solution of sodium
carbonate, e. Distilled water. The middle third of the distillate,
100 c.c. of which must not be perceptibly colored in ten minutes
by the addition of 2 c.c. of Nessler's reagent.
The testing of a water is conducted as follows : Half a litre of
the water to be tested (before taking the sample the demijohn or
other vessel containing the water must be thoroughly shaken) is
introduced, by a funnel, into a tubulated retort capable of hold-
ing one litre. If the water be acid, 10 c.c. of the solution of
sodium carbonate d are added. Having connected the retort
with a Liebig's condenser, the joint being made tight by a.
packing of moistened filter-paper, the water is made to boil as
soon as possible by applying the flame of a Bunsen burner brought
close to the bottom of the naked retort. The first 50 c.c. of dis-
tillate are collected in «, cylindrical vessel of clear glass, about an
inch in diameter. The following 150 c.c. are collected and thrown
away, after which the fire is withdrawn. While these are passing
over, the first 50 c.c. are Nesslerized (vide infra), and the result,
plus one-third as much again, is the amount of free ammonia
contained in the half-litre of water.
When 200 c.c. have distilled over, all the free ammonia has
been removed, and it now remains to decompose the organic
material, and determine the amount of ammonia formed. To
effect this, 50 c.c. of the permanganate solution a are added
through the funnel to the contents of the retort, which is shaken,,
stoppered, and again heated. The distillate is now collected in
separate portions of 50 c.c. each, in glass cylinders, until 3 such
portions have been collected. These are then separately Ness-
lerized as follows : 2 c.c. of the Nessler reagent are added to the
WATER. 71
sample of 50 c.c. of distillate ; if ammonia be present, a yellow or
brown color will be produced, dark in proportion to the quantity
of ammonia present. Into another cylinder a given quantity of
the standard solution of ammonia c is allowed to flow from a
burette ; enough water is added to make the bulk up to 50 c.c.,
and then 2 c.c. of Nessler reagent. This cylinder, and that con-
taining the 50 c.c. of Nesslerized distillate, are then placed side by
side on a sheet of white paper and their color examined. If the
shade of color in the two cylinders be exactly the same, the 50 c.c.
of distillate contain the same amount of ammonia as the quantity
of standard solution of ammonia used. If the colors be different
in intensity, another comparison-cylinder must be arranged,
using more or less of the standard solution, as the first compari-
son-cylinder was lighter or darker than the distillate. When the
proper similarity of shades has been attained, the number of
cubic centimetres of the standard solution used is determined by
the reading on the burette. This process, which, with a little
practice, is neither difficult nor tedious, is to be repeated with the
first 50 c.c. of distillate and with the three portions of 50 c.c.
each, distilled after the addition of the permanganate solution.
If, for example, it required 1 c.c. of standard solution in Nessler-
izing the first 50 c.c., and for the others 3.5 c.c., 1.5 c.c., and 0.2
c.c., the following is the result and the usual method of recording
it:
Free ammonia 01
Correction 003
.013
Free ammonia per litre 026 milligr.
Albuminoid ammonia 035
.015
.002
.052
Albuminoid ammonia per litre 104 milligr.
If a water yield no albuminoid ammonia it is organically pure,
even if it contains much free ammonia and chlorids. If it contain
from .02 to .05 milligrams per litre, it is still quite pure. When
the albuminoid ammonia reaches 0.1 milligr. per litre the water
is to be looked upon with suspicion ; and it is to be condemned
when the proportion reaches 0.15. When free ammonia is also
present in considerable quantity, a water yielding 0.05 of albumi-
noid ammonia is to be looked upon with suspicion.
Nitrates and Nitrites — Are present in rain-water in quantities
less than 2 parts in 100,000, calculated as N2O6. When the amount
exceeds this, these salts are considered as indicating previous
contamination by organic matter which has been oxidized and
whose nitrogen has been to some extent converted into nitrites
and nitrates.
To determine the amount of nitrous acid the following solutions
are used : 1.) Dilute sulfuric acid 1 : 3 ; 2.) A solution containing
5 grams of metaphenylendiamin and sufficient sulfuric acid to
72 MANUAL OF CHEMISTRY.
form an acid reaction in 1 litre of H2O ; 3.) A solution made by
dissolving 0.406 gram pure, dry silver nitrite in hot water, adding
pure sodium chlorid so long as a precipitate is formed, diluting
with H2O to 1 litre, after cooling and without nitration. 100 c.c.
of the clear liquid are then diluted to 1 litre. 1 c.c. of this solution
contains 0.01 mgr. N2O3.
To make the determination 100 c.c. of the water are placed in a
glass cylinder and 1 c.c. each of solutions 1 and 2 added. Three
other cylinders are at the same time prepared, by diluting from
0.3 to 2.5 c.c. of solution 3 to 100 c.c. with pure H2O, and adding to
each 1 c.c. each of solutions 1 and 2. The shade of color of the
water-cylinder is then compared with that of the others, as
described above in Nesslerizing. The amount of N2O3 in the
water is equal to that in the comparison-cylinder having the
same shade.
Poisonous Metals. — Those most liable to occur in drinking-
waters are iron, copper, and lead, and of these the last is the
most important.
The power possessed by a water of dissolving lead varies
materially with the nature of the substances which it holds in
solution. Lead is not dissolved by water as lead, but only after
conversion into an oxid ; therefore any condition favoring the
oxidation of the metal favors its solution. The presence of
nitrates is favorable to the solution of lead, an influence which
is, however, much diminished by the simultaneous presence of
other salts. A water highly charged with oxygen dissolves lead
readily, especially if the metallic surface be so exposed to the
action of the water as to be alternately acted upon by it and by
the air. On the other hand, waters containing carbonates or free
carbonic acid may be left in contact with lead with comparative
impunity, owing to the formation of a protective coating of the
insoluble carbonate of lead on the surface of the metal. This
does not apply, however, to water charged with a large excess of
carbon dioxid under pressure. Of all natural waters, that most
liable to contamination with lead is rain-water. It contains
ammonium nitrate with very small quantities of other salts ; and
it is highly aerated, but contains no carbonates, and compara-
tively small quantities of carbon dioxid. Obviously, therefore,
rain-water should neither be collected from a leaden roof, nor
stored in leaden tanks, nor drank after having been long in
contact with lead pipes. As a rule, the purer the water the more
liable it is to dissolve lead when brought in contact with that
metal, especially if the contact occur when the water is at a high
temperature, or when it lasts for a long period.
To determine the power of water for dissolving lead, take two
tumblers of the water to be tested ; in one place a piece of lead,
whose surface has been scraped bright, and allow them to stand
twenty-four hours. At the end of that time, remove the lead and
WATER. 73
pass hydrogen sulfld through the water in both tumblers. If
the one which contained the metal become perceptibly darker
than the other, the water has a power of dissolving lead, such as
to render its contact with surfaces of that metal dangerous if
prolonged beyond a short time.
To test for the presence of poisonous metals, solution of am-
monium sulfhydrate is added to the water, contained in a porce-
lain capsule. If a dark color be produced, which is not discharged
on addition of hydrochloric acid, the water is contaminated with
lead or copper.
For quantitative determinations, solutions containing known
quantities of the poisonous metals are used : for iron 4.96 grams
of ferrous sulfate in a litre of water ; for copper 3.93 grams of
cupric sulfate to the litre; and for lead 1.66 gram of lead ace-
tate to the litre. One c.c. of each solution contains 0.001 gram
of the metal. To use the solutions 100 c.c. of the water to be
tested and 100 c.c. of pure water are placed in two porcelain cap-
sules, to each of which some ammonium sulfhydrate is then
added. The appropriate standard solution is then allowed to
flow into the capsule containing the pure water, until the shade
of color produced is the same as that of the liquid in the other
capsule. The burette reading at this time gives the number of
centigrams of the metal in a litre of water.
Suspended Solids. — Most natural waters deposit, on standing,
more or less solid, insoluble material. These substances have
been either suspended mechanically in the water, which deposits
them when it remains at rest, or they have been in solution, and
are deposited by becoming insoluble as the water is deprived of
carbon dioxid by exposure to air and by relief from pressure.
The suspended particles should be collected by subsidence in a
conical glass, and should be examined microscopically for. low
forms of animal and vegetable life. The quantity of suspended
solids is determined by passing a litre of the turbid water through
a dried and weighed filter, which, with the collected deposit, is
again dried and weighed. The difference between the two
weights is the weight of suspended matter in a litre of the water.
Bacteriological Examination of Water. — In recent years much
attention has been given to the examination of natural waters by
bacteriological methods, plate cultures on gelatin, cultures in
blood serum and on potatoes, and experiments on animals.
Although in some instances pathogenic bacteria have been found
in water, and although in the future valuable results will proba-
bly be attained by these methods, the chief reliance in deter-
mining the quality of a drinking-water is still to be placed upon
the older chemical processes.
Purification ofWater. — The artificial means of rendering a more
or less contaminated water fit for use are of five kinds : 1. Distil-
74 MANUAL OF CHEMISTRY.
lation ; 2. Subsidence ; 3. Filtration ; 4. Precipitation ; 5. Boil-
ing.
The method of distillation is used in the laboratory when a
very pure water is desired, and also at sea. Distilled water is,
however, too pure for continued use, being hard of digestion, and
flat to the taste from the absence of gases and of solid matter in
solution. When circumstances oblige the use of such water, it
should be agitated with air, and should be charged with inorganic
matter to the extent of about 0.03 gram each of calcic bicarbonate
and sodium chlorid to the litre.
Purification by subsidence is adopted only as an adjunct to
precipitation and filtration, and for the separation of the heavier
particles of suspended matter.
The ideal process of filtration consists in the separation of all
particles of suspended matter, without any alteration of such
substances as are held in solution. In the filtration of potable
waters on a large scale, however, the more minute particles of
suspended matters are only partially separated, while, on the
other hand, an important change in the dissolved materials takes
place, at least in certain kinds of filters, in the oxidation of or-
ganic matters, whether in solution or in suspension. In the filtra-
tion of large quantities of water it is passed through sand or
charcoal, or through both substances arranged in alternate layers.
Filtration through charcoal is much more effective than that
through sand, owing to the much greater activity of the oxida-
tion of nitrogenized organic matter in the former case.
Precipitation processes are only adapted to hard waters, and
are designed to separate the excess of calcium salt, and at the
same time a considerable quantity of organic matter, which is
mechanically carried down with the precipitate. The method
usually followed consists in the addition of lime (in the form of
lime-water), in just sufficient quantity to neutralize the excess of
carbon dioxid present in the water. The added lime, together
with the calcium salt naturally present in the water, is then pre-
cipitated, except that small portion of calcium carbonate which
the water, freed from carbon dioxid, is capable of dissolving. To
determine when sufficient lime-water has been added, take a
sample from time to time during the addition, and test it with
solution of silver nitrate until a brown precipitate is formed. At
this point cease the addition of lime-water and mix the limed
water with further portions of the hard water, until a sample,
treated with silver-nitrate solution, gives a yellowish in place of
a brown color. Alum is also used as a precipitant, particularly in
combination with filtration.
The purification of water by boiling1 can only be carried on
upon a small scale. It is, however, of great value for the soften-
ing of temporarily hard waters, and for the destruction of organ-
WATER. 75
ized impurities, for which latter purpose it should never be neg-
lected during outbreaks of cholera and typhoid.
Natural Purification of Water. — The water of brooks, rivers, and
lakes which have been contaminated by sewage and other
organic impurity becomes gradually purified by natural proc-
esses. Suspended particles are deposited upon the bottom and
sides of the stream, more or less rapidly, according to their grav-
ity and the rapidity of the current. The bicarbonates of cal-
cium, magnesium, and iron gradually lose carbon dioxid, and are
precipitated as carbonates, which mechanically carry down dis-
solved as well as suspended impurities. The fermentations, oxi-
dations, and reductions to which organic matters are subject
bring about their gradual mineralization and the conversion of
ammonia into nitrates. The processes of nutrition of aquatic
plant life absorb dissolved organic impurity, as well as the prod-
ucts of decomposition of nitrogenized substances. This natural
purification proceeds the more rapidly the more contact with air
is favored.
Mineral Waters. — Under this head are classed all waters which
are of therapeutic or industrial value, by reason of the quantity
or nature of the dissolved solids which they contain ; or which
have a temperature greater than 20° (68° F.).
The composition of mineral waters varies greatly, according to
the nature of the strata or veins through which the water passes,
and to the conditions of pressure and previous composition under
which it is in contact with these deposits.
The substances almost universally present in mineral waters
are : oxygen, nitrogen, carbon dioxid ; sodium carbonate, bicar-
bonate, sulfate and chlorid ; and calcium bicarbonate. Of sub-
stances occasionally present the most important are : sulfhydric
acid ; sulfids of sodium, iron, and magnesium ; bromids and
iodids of sodium and magnesium ; calcium and magnesium chlo-
rids ; carbonate, bicarbonate, sulfate, peroxid, and crenate of
iron ; silicates of sodium, calcium, magnesium, and iron ; alu-
minium salts ; salts of lithium, cesium, and rubidium ; free
sulfuric, silicic, arsenic, and boric acids ; and ammoniacal
salts.
Although a sharply defined classification of mineral waters is
not possible, one which is useful, if not accurate, may be made,
based upon the predominance of some constituent, or constit-
uents, which impart to the water^ a well-defined therapeutic
value. A classification which has been generally adopted includes
five classes :
I. Acidulous waters ; whose value depends upon dissolved car-
bonic acid. They contain but small quantities of solids, princi-
pally the bicarbonates of sodium and calcium and sodium chlorid.
76 MANUAL OF CHEMISTRY.
II. Alkaline waters; which contain notable quantities of the
carbonates or bicarbonates of sodium, potassium, lithium, and
calcium, sufficient to communicate to them an alkaline reaction,
and frequently a soapy taste ; either naturally, or after expulsion
of carbon dioxid by boiling.
III. Chalybeate waters ; which contain salts of iron in greater
proportion than 4 parts in 100,000. They contain ferrous bicar-
bonate, sulfate, crenate, and apocrenate, calcium carbonate,
sulfates of potassium, sodium, calcium, magnesium, and alu-
minium, notable quantities of sodium chlorid, and frequently
small amounts of arsenic. They have the taste of iron and are
usually clear as they emerge from the earth. Those containing
ferrous bicarbonate deposit a sediment on standing, by loss of
carbon dioxid, and formation of ferrous carbonate.
IV. Saline waters ; which contain neutral salts in considerable
quantity. The nature of the salts which they contain is so
•diverse that the group may well be subdivided :
a. Chlorin waters ; which contain large quantities of sodium
chlorid, accompanied by less amounts of the chlorids of potas-
sium, calcium, and magnesium. Some are so rich in sodium
chlorid that they are not of service as therapeutic agents, but
are evaporated to yield a more or less pure salt. Any natural
water containing more than 300 parts in 100, 000 of sodium chlorid
belongs to this class, provided it do not contain substances more
active in their medicinal action in such proportion as to warrant
its classification elsewhere. Waters containing more than 1,500
parts in 100,000 are too concentrated for internal administration.
/3. Sulfate waters are actively purgative from the presence of
considerable proportions of the sulfates of sodium, calcium, and
magnesium. Some contain large quantities of sodium sulfate,
with mere traces of the calcium and magnesium salts, while in
others the proportion of the sulfates of magnesium arid calcium
is as high as 3,000 parts in 100,000 to 2,000 parts in 100,000 of so-
dium sulfate. They vary much in concentration ; from 500 to
nearly 6,000 parts of total solids in 100,000. They have a salty,
bitter taste, and vary much in temperature.
>'. Sromin and iodin waters are such as contain the bromids or
iodids of potassium, sodium, or magnesium in sufficient quantity
io communicate to them the medicinal properties of those salts.
V. Sulfurous waters ; which hold hydrogen sulfid or metallic
sulfids in solution. They have a disagreeable odor and are
usually warm. They contain 20 to 400 parts in 100,000 of total
solids.
Physiological. — Water is taken into the body both as a liquid
and as a constituent of every article of food ; the amount ingested
by a healthy adult being 2.25 to 2.75 litres (2$ to 3 quarts) per
HYDKOGEN DIOXID. < <
diem. The greater the elimination and the drier the nature of
the food the greater is the amount of H2O taken in the liquid form.
Water is a constituent of every tissue and fluid of the body,
varying from 0.2 per cent, in the enamel of the teeth to 99.5 per-
cent, in the perspiration and saliva. It constitutes about 60 per
cent, of the weight of the body.
The consistency of the various parts does not depend entirely
upon the relative proportion of solids and H2O, but is influenced
by the nature of the solids. The blood, although liquid in the
ordinary sense of the term, contains a less proportional amount
of H2O than does the tissue of the kidneys, and about the same
proportion as the tissue of the heart. Although the bile and
mucus are not as fluid as the blood, they contain a larger propor-
tion of H2O to solids than does that liquid.
Water is discharged by the kidneys, intestine, skin, and pul-
monary surfaces. The quantity discharged is greater than that
ingested ; the excess being formed in the body by the oxidation
of the H of its organic constituents.
Hydrogen Dioxid.
Hydrogen peroxid — Oxygenated water.
H2O2— Molecular weight — 34— Sp. gr. = 1.455— Discovered by-
Thenard in 1818.
Exists naturally in very minute quantity in rain-water, in air;
and in the saliva.
This substance may be obtained in a state of purity by accu-
rately following the process of Thenard. It may also be obtained,
mixed with a large quantity of H2O, by the action of carbon di-
oxid on barium perhydroxid : BaO3H2 + CO2 = BaCO3 + H2O2 or
of dilute sulfuric acid on barium peroxid : BaO2 + H2SO4 =
BaSO4 + H202. It is also formed in small quantity during the
slow oxidation of many elements and compounds, such as P, Pb,
Zn, Cd, Al, alcohol, ether, and the essences.
It is prepared industrially of 10-12 volume strength by gradu-
ally adding barium peroxid to dilute hj drofluoric acid solution,
the mixture being maintained at a low temperature and con-
stantly agitated.
The pure substance is a colorless, syrupy liquid, which, when
poured into H2O, sinks under it before mixing. It has a disagree-
able, metallic taste, somewhat resembling that of tartar emetic.
When taken into the mouth it produces a tingling sensation, in-
creases the flow of saliva, and bleaches the tissues with which it
comes in contact. It is still liquid at —30° ( —22° F.). It is very
unstable, and, even in darkness and at ordinary temperature, is
gradually decomposed. At 20° (68° F.) the decomposition takes
78 MANUAL OF CHEMISTRY.
place more quickly, and at 100° (212° F.) rapidly and with effer-
vescence. The dilute substance, however, is comparatively stable,
and may be boiled and even distilled without suffering decompo-
sition. Yet it is liable to explosive decomposition when exposed
to summer temperature in closed vessels.
Hydrogen peroxid acts both as a reducing and an oxidizing
agent. Arsenic, sulfids, and sulfur dioxid are oxidized by it
at the expense of half its oxygen. When it is brought in contact
with silver oxid both substances are violently decomposed, water
and elementary silver remaining. By certain substances, such
as gold, platinum, and charcoal in a state of fine division, fibrin,
or manganese dioxid, it is decomposed with evolution of oxygen ;
the decomposing agent remaining unchanged.
The pure substance, when decomposed, yields 475 times its vol-
ume of oxygen ; the dilute 15 to 20 volumes.
In dilute solution it is used as a bleaching agent and in the
renovation of old oil-paintings. It is an energetic disinfectant
•and antiseptic, and is extensively used in surgery.
Analytical Characters. — 1. To a solution of starch a few drops
of cadmium iodid solution are added, then a small quantity of
the fluid to be tested, and, finally, a drop of a solution of ferrous
sulfate. A blue color is produced in the presence of hydrogen
peroxid, even if the solution contain only 0.05 milligram per litre.
2. Add freshly prepared tincture of guaiacuin and a few drops
of a cold infusion of malt. A blue color — 1 in 2,000,000.
3. Add to the liquid a few drops of potassium dichromate and
a little dilute sulfuric acid, and agitate with ether. The ether
assumes a brilliant blue-violet color.
4. Add to 6 c.c. of the liquid sulfuric acid, iodid of zinc, starch-
paste, two drops of a two per cent, solution of cupric sulfate,
and a little one-half per cent, solution of ferrous sulfate, in the
order named. A blue color.
5. Add a trace of acetic acid, some a naphthylamin and solid
sodium chlorid. After a short time a blue or blue-violet color
and, after some hours, a flocculent ppt. of the same color.
Atmospheric Hydrogen Dioxid. — It has been claimed that
atmospheric air, rain-water, snow, and hoar-frost constantly
contain small quantities of hydrogen peroxid ; the amount in
rain-water varying from 0.0008 to 0.05 part in 100,000. The most
recent experiments bearing upon the supposed presence of ozone
and hydrogen peroxid in atmospheric air seem, however, to
justify the belief that those substances, if present in air at all,
are not met with in the amounts and with the constancy that
have been claimed. According to this later view, the appear-
ances from which the presence of ozone and hydrogen peroxid
has been inferred are not caused by those substances, but by
nitrous acid and the oxids of nitrogen.
FLUORIN. 70
CLASS IL— ACIDULOUS ELEMENTS.
Elements all of whose Hydrates are Acids, and which do not form
Salts with the Oxacids.
I. CHLORIN GROUP.
FLUORIN. CHLORIN. BROMIN. IODIN.
The elements of this group are univalent. With hydrogen they
form acid compounds, composed of one volume of the element in
the gaseous state wit^h one volume of hydrogen. Their hydrates
are monobasic acids when they exist (fluorin forms no hydrate).
The first two are gases, the third liquid, the fourth solid at ordi-
nary temperatures. They are known as the halogens. The
relations of their compounds to each other are shown in the fol-
lowing table :
u -p .
J.-L-L
HC1 C130 CU03 C1SO4 HC10 HC1O, HC1O3 HC1O4
HBr HBrO HBrO3 HBrO4
HI I2O4 HIO HIO3 HIOs HIO4
Hydro-ic Monoxid. Trioxid. Tetroxid. Hypo- -ous acid, -ic acid. Per-ic
acid. ous acid. acid.
FLUORIN.
/Symbol = F — Atomic weight = 19 — Sp. gr. 1.265 A (calculated =
1.316)— Discovered by Sir H. Davy in 1812.
Fluorin has been isolated by the electrolysis of HF at —23°
(-9°.4 F.).
It is a gas, colorless in thin layers, greenish-yellow in layers 50
cent, thick.
It decomposes H2O, with formation of HF and ozone. In it Si,
Bo, As, Sb, S, and I fire spontaneously. With H it detonates
violently, even in the dark. It attacks organic substances vio-
lently. The apparatus in which it is liberated must be made of
platinum and fluor-spar. It forms compounds with all other
elements except oxygen.
Hydrogen Fluorid — Hydrofluoric acid = HF — Molecular weight
= 20. Hydrofluoric acid is obtained by the action of an excess of
sulfuric acid upon fluor-spar or upon barium fluorid, with the
aid of gentle heat : CaF2+ H2SO4 = CaSO4 + 2 HF. If a solution
be desired, the operation is conducted in a platinum or lead re-
tort, whose beak is connected with a U-shaped receiver of the
same metal, which is cooled and contains a small quantity of
water.
The aqueous acid is a colorless liquid, highly acid and corro-
80 MANUAL OF CHEMISTRY.
sive, and having a penetrating odor. Great care must be exer-
cised that neither the solution nor the gas come in contact with
the skin, as they produce painful ulcers which heal with diffi-
culty, and also constitutional symptoms which may last for days.
The inhalation of air containing very small quantities of HF has
caused permanent loss of voice and, in two cases, death. When
the acid has accidentally come in contact with the skin the part
should be washed with dilute solution of potash, and the vesicle
which forms should be opened.
Both1 the gaseous acid and its solution remove the silica from
glass, a property utilized in etching upon that substance, the
parts upon which no action is desired being protected by a coat-
ing of wax.
The presence of fluorin in a compound is detected by reducing
the substance to powder, moistening it with sulfuric acid in a
platinum crucible, over which is placed a slip of glass prepared
as above ; at the end of half an hour the wax is removed from the
glass, which will be found to be etched if the substance examined
contained a fluorid.
CHLOBIN.
Symbol = Cl — Atomic weig?it=35.5 — Molecular weight = 71 — Sp.
gr. = 2.4502 A — One litre weighs 3.17 grains — 100 cubic inches-
weigh 76.3 grains— Name derived from x^P^ — yellowish-green —
Discovered by Scheele in 1774.
Occurrence. — Only in combination, most abundantly in sodium
chlorid.
Preparation. — (1.) By heating together manganese dioxid and
hydrochloric acid (Scheele). The reaction takes place in two
stages. Manganic chlorid is first formed according to the equa-
tion: MnO2 + 4HC1 = MnCh + 2H2O ; and is subsequently de-
composed into manganous chlorid arid chlorin : MnCl4 = MriCl2
This and similar operations are usually conducted in an appa-
ratus such as that shown in Fig. 23. The earthenware vessel A
(which on a small scale may be replaced by a glass flask) is two-
thirds filled with lumps of manganese dioxid of the size of hazel-
nuts, and adjusted in the water-bath ; hydrochloric acid is
poured in through the safety-tube and the bath heated. The
disengaged gas is caused to bubble through the small quantity
of water in B, is then dried by passage over the fragments of
calcium chlorid in C, and is finally collected by displacement of
air in the vessel D.
When the vessel A has become half filled with liquid it is best
to decant the solution of manganous chlorid, wash the remaining
oxid with water and begin anew. A kilo, of oxid yields 257.5
litres of Cl.
CHLORIN.
81
(2.) By the action of manganese dioxid upon hydrochloric acid
in the presence of sulfuric acid, manganous sulfate being also
formed: MnOa + 2HC1 + H2SO4 = MnSO4 + 2H2O + CU. The
same quantity of chlorin is obtained as in (1), with the use of
half the amount of hydrochloric acid.
(3.) By heating a mixture of one part each of manganese dioxid
and sodium chlorid, with three parts of sulfuric acid. Hydro-
chloric acid and sodium sulfate are first formed: H2SO4 -f-
2NaCl = Na2SO4 + 2HC1; and the acid is immediately decom-
posed by either of the reactions indicated in (1) and (2), according
as sulfuric acid is or is not present in excess.
(4.) By the action of potassium dichromate upon hydrochloric
FIG. 23.
acid ; potassium and chromic chlorids being also formed :
K2CrsO7 + 14HC1 = 2KC1 + Cr2Cl« -f 7H2O + 8CU. Two parts of
powdered dichromate are heated with 17 parts of acid of sp. gr.
1.16 ; 100 grams of the salt yielding 22.5 litres of Cl.
(5.) A convenient method of obtaining chlorin on a laboratory
scale is by the use of "chlorin cubes." These are made by press-
ing together 1 part of plaster of Paris and 4 parts of chlorid of
lime (q. v.), cutting into small cubes and drying. The cubes are
used in one of the forms of constant apparatus (Figs. 19, 20, 21),
with dilute hydrochloric acid, Cl being evolved at the ordinary
temperature.
When a slow evolution of Cl, extending over a considerable
82 MANUAL OF CHEMISTRY.
period of time, is desired, as for ordinary disinfection, moistened
chlorid of lime is exposed to the air, the calcium hypochlorite
being decomposed by the atmospheric carbon dioxid. If a more
rapid evolution of gas be desired, the chlorid of lime is moist-
ened with dilute hydrochloric acid in place of with water.
(6.) By the action of potassium chlorate upon hydrochloric
acid Cl is liberated, slowly at the ordinary temperature, more
rapidly at the temperature of the water-bath :
2KC1C-3 + 4HC1 = Ch + C12O4 + 2KC1 + 2H2O.
Potassium Hydrochloric Chlorin. Chlorin Potassium Water,
chlorate. acid. tetroxid. chlorid.
Properties. — Physical. — A greenish-yellow gas, at the ordinary
temperature and pressure ; it has a penetrating odor, and is, even
when highly diluted, very irritating to the respiratory passages.
Being soluble in H2O to the extent of one volume to three vol-
umes of the solvent, it must be collected by displacement of air,
as shown in Fig. 23. A saturated aqueous solution of Cl is known
to chemists as chlorin water, and in pharmacy as aqua chlori
(U. $.), Liquor chlori (Br.). It should bleach, but not redden,
litmus paper. Under a pressure of 6 atmospheres at 0° (32° F.),
or 8£ atmospheres at 12° (53°. 6 F.), Cl becomes an oily, yellow
liquid, of sp. gr. 1.33 ; and boiling at -33.6° (— 28°.5 F.).
Chemical. — Chlorin exhibits a great tendency to combine with
other elements, with all of which, except F, O, IN", and C, it unites
directly, frequently with evolution of light as well as heat, and
sometimes with an explosion. With H it combines slowly, to form
hydrochloric acid, under the influence of diffuse daylight, and
violently in direct sunlight, or in highly actinic artificial lights.
A candle burns in Cl with a faint flame and thick smoke, its H
combining with the Cl, while carbon becomes free.
At a red fheat Cl decomposes H2O rapidly, with formation of
hydrochloric, chloric, and probably hypochlorous acids. The
same change takes place slowly under the influence of sunlight,
hence chlorin water should be kept in the dark or in bottles of
yellow glass.
In the presence of H2O, chlorin is an active bleaching and dis-
infecting agent. It acts as an indirect oxidant, decomposing H2O,
the nascent O from which then attacks the coloring or odorous
principle.
Chlorin is readily fixed by many organic substances, either by
addition or substitution. In the first .instance, as when Cl and
olefiant gas unite to form ethylene chlorid, the organic substance
simply takes up one or more atoms of chlorin : C2H4 -f- C12 =
C2H4C12. In the second instance, as when Cl acts upon marsh
gas to produce methyl chlorid : CH4 + pit = CH3C1 + HC1, each
CHLOEIN. 83
•substituted atom of Cl displaces an atom of H, which combines
with another Cl atom to form hydrochloric acid.
Hydrate of chlorin, Cl 5H2O, is a yellowish-green, crystalline
substance, formed when Cl is passed through chlorin water,
«ooled to 0° (32° F.). It is decomposed at 10° (50° P.).
Hydrogen Chlorid— Hydrochloric Acid — Muriatic Acid —
Acidum Hydrochloricum (U. S.; Br.)— HC1 — Molecular weight =
36.5— Sp. yr. 1.259 A— A litre weighs 1.6293 gram.
Occurrence. — In volcanic gases and in the gastric juice of the
mammalia.
Preparation. — (1.) By the direct union of its constituent ele-
ments.
(2.) By the action of sulfuric acid upon a chlorid, a sulfate
being at the same time formed: H2SO4 + 2NaCl = NasSO* +
2HC1.
This is the reaction by which the HC1 used in the arts is pro-
duced.
(3.) Hydrochloric acid is also formed in a great number of reac-
tions, as when Cl is substituted in an organic compound.
Properties. — Physical. — A. colorless gas, acid in reaction and
taste, having a sharp, penetrating odor, and producing great
irritation when inhaled. It becomes li'quid under a pressure of
40 atmospheres at 4° (29° F.). It is very soluble in H2O, one vol-
ume of which dissolves 480 volumes of the gas at 0° (32° F.).
Chemical. — Hydrochloric acid is neither combustible nor a sup-
porter of combustion, although certain elements, such as K and
IN"a, burn in it. It forms white clouds on contact with moist air.
Solution of Hydrochloric Acid. — It is in the form of aqueous
solution that this acid is usually employed in the arts and in
pharmacy. It is, when pure, a colorless liquid (yellow when im-
pure), acid in taste and reaction, whose sp. gr. and boiling-point
vary with the degree of concentration. "When heated, it evolves
HC1, if it contain more than 20 per cent, of that gas, and H2O if
it contain less. A solution containing 20 per cent, boils at 111°
(232° F.), is of sp. gr. 1.099, has the composition HC1 + 8H2O, and
distils unchanged.
Commercial muriatic acid is a yellow liquid ; sp. gr. about
1.16; contains 32 per cent. HC1 ; and contains ferric chlorid,
sodium chlorid, and arsenical compounds.
Acidum hydrochloricum is a colorless liquid, containing small
quantities of impurities. It contains 31.9 per cent. HC1 and its
«p. gr. is 1.16 (U. S. ; Br.). The dilute acid is the above diluted
with water. Sp. gr. 1.049 — 10 per cent. HC1 (U. S.); sp. gr. 1.052
= 10.5 per cent. HC1 (Br.).
84 MANUAL OF CHEMISTRY.
C. P. (chemically pure) acid is usually the same as the strong:
pharmaceutical acid and far from pure (see below).
Hydrochloric acid is classed, along with nitric and sulfuric
acids, as one of the three strong mineral acids. It is decom-
posed by many elements, with formation of a chlorid and libera-
tion of hydrogen: 2HC1 + Zn = ZnCU + Hs. With oxids and
hydroxids of the metals it enters into double decomposition,,
forming H2O and a chlorid: CaO + 2HC1 = CaCl2 + H2O or
CaH2O2 + 2HC1 = CaCU + 2H2O.
Oxidizing agents decompose HC1 with liberation of Cl. A mix-
ture of hydrochloric and nitric acids in the proportion of three-
molecules of the former to one of the latter, is the acidum nitro-
hydrochloricum (U. IS.; Br.), or aqua regia. The latter name
alludes to its power of dissolving gold, by combination of the
nascent Cl, which it liberates, with that metal, to form the solu-
ble auric chlorid.
Impurities. — A chemically pure solution of this acid is exceed-
ingly rare. The impurities usually present are : Sulfurous
acid — hydrogen sulfid is given off when the acid is poured
upon zinc; Sulfuric acid — a white precipitate is formed with
barium chlorid; Chlorin colors the acid yellow; Lead gives a.
black color when the acid is treated with hydrogen sulfid;
Iron — the acid gives a red color with ammonium sulfocyanate;
Arsenic — the method of testing by hydrogen sulfid is not suffi-
cient. If the acid is to be used for toxicological analysis, a litre,,
diluted with half as much H2O, and to which a small quantity
of potassium chlorate has been added, is evaporated over the
water-bath to 400 c.c. ; 25 c.c. of sulfuric acid are then added,
and the evaporation continued until the liquid measures about
100 c.c. This is introduced into a Marsh apparatus and must
produce no mirror during an hour.
Chlorids. — A few of the chlorids are liquid, SnCh, SbCl5 ; the
remainder are solid, crystalline and more or less volatile. The
metallic chlorids are soluble in water, except AgCl, Hg2Cl2, Avhich
are insoluble, and PbCla, which is sparingly soluble. The chlorids.
of the non-metals are decomposed by H2O.
The chlorids are formed : 1.) By the direct union of the ele-
ments: P -f- C15 = PC16; 2.) By the action of chlorin upon a
heated mixture of oxid and carbon : A12O3 + 30 + 3Cla = A12C16
+ 3CO; 3.) By solution of the metal, oxid, hydroxid, or carbonate
inHCl: Zn-f- 2HC1 = ZnCU + H2; 4.) By double decomposition
between a solution of a chlorid and that of another salt whose
metal forms an insoluble chlorid : AgNO3 + NaCl = AgCl -+-
NaNO,.
Analytical Characters. — 1.) "With AgNO3 a white, flocculent ppt.,
insoluble in HNO3, soluble in NH4HO. 2.) With Hg2(NO3)2, a
White ppt., which turns black with NH4HO.
CHLORIN. 85
Toxicology. — Poisons and corrosives. — A poison is any sub-
stance which, being in solution in the blood, produces death or
.serious bodily harm.
A corrosive is a substance capable of producing death by its
chemical action upon a tissue with which it comes in direct
contact.
The corrosives act much more energetically when concentrated
than when dilute ; and when the dilution is great they have no
-deleterious action. The degree of concentration in which the
true poisons are taken is of little influence upon their action if the
•dose taken remain the same.
Under the above definitions the strong mineral acids act as
corrosives rather than as poisons. They produce their injurious
results by destroying the tissues with which they come in contact,
-and will cause death as surely by destroying a large surface of
skin, as when they are taken into the stomach.
The symptoms of corrosion by the mineral acids begin immedi-
ately, during the act of swallowing. The chemical action of the
acid upon every part with which it comes in contact causes acute
burning pain, extending from the mouth to the stomach and
intestine, referred chiefly to the epigastrium. Violent arid dis-
tressing vomiting of dark, tarry, or "coffee-ground," highly acid
material 'is a prominent symptom. Eschars, at first white or
gray, later brown or black, are formed where the acid has come
in contact with the skin or mucous membrane. Respiration is
labored and painful, partly by pressure of the abdominal
muscles, but also, in the case of hydrochloric acid, from entrance
of the irritating, acid gas into the respiratory passages. Death
may occur within 24 hours, from collapse ; more suddenly from
perforation of large blood-vessels, or from peritonitis ; or after
several weeks, secondarily, from starvation, due to closure of the
pylorus by inflammatory thickening, and destruction of the
gastric glands.
The object of the treatment in corrosion by the mineral acids
is to neutralize the acid and convert it into a harmless salt. For
this purpose the best agent is magnesia (magnesia usta), sus-
pended in a small quantity of water, or if this be not at hand, a
strong solution of soap. Chalk and the carbonates and bicar-
bonates of sodium and potassium should not be given, as they
generate large volumes of gas. The scrapings of a plastered wall,
or oil, are entirely useless. The stomach-pump, or any attempt
at the introduction of a tube into the oesophagus, is not to be
thought of.
Compounds of Chlorin and Oxygen. — Three compounds of chlorin
and oxygen have been isolated, two being anhydrids. They are
86 MANUAL OF CHEMISTRY .
all very unstable, and prone to sudden and violent decomposi-
tion.
Chlorin Monoxid. — C12O — 87 — Hypochlorous anhydrid or oxidt
is formed by the action, below 20° (68° P.), of dry Cl upon pre-
cipitated mercuric oxid : HgO -f- 2C12 = HgCl2 + CUO.
On contact with H2O it forms hypochlorous acid, HC1O, which,
owing to its instability, is not used industrially, although th&
hypochlorites of Ca, K, and Na are.
Chlorin Trioxid — Chlorous anhydrid or oxid, C1203 — 119 — is a yel-
lowish-green gas formed by the action of dilute nitric acid upon
potassium chlorate in the presence of arsenic trioxid. At 50°
(122° F.) it explodes. It is a strong bleaching agent ; is very irri-
tating when inhaled and readily soluble in H2O, the solution
probably containing chlorous acid, HC1O2.
Chlorin Tetroxid — Chlorin peroxid, C12O4 — 135 — is a violently
explosive body, produced by the action of sulfuric acid upon
potassium chlorate. Below — 20° (— 4° F.) it is an orange-col-
ored liquid; above that temperature a yellow gas. It explodes-
violently when heated to a temperature below 100° (212° F.).
There is no corresponding hydrate known, and if it be brought
in contact with an alkaline hydroxid, a mixture of chlorate and
chlorite is formed.
Besides the above, two oxacids of Cl are known, the anhydrids
corresponding to which have not been isolated.
Chloric Acid — HC1O3 — 84.5 — obtained, in aqueous solution, as
a strongly acid, yellowish, syrupy liquid, by decomposing its ba-
rium salt by the proper quantity of sulfuric acid.
Perchloric Acid— HC1O4 — 100.5 — is the most stable of the
series. It is obtained by boiling potassium chlorate with hydro-
fluosilicic acid, decanting the cold fluid, evaporating until white
fumes appear, decanting from time to time, and finally distilling.
It is a colorless, oily liquid ; sp. gr. 1.782 ; which explodes on
contact with organic substances or charcoal.
BROMIN.
Bromum, U.S., Br. — Symbol = Br — Atomic weight = 80 — Molec-
ular weight — 160 — Sp. gr. of liquid = 3.18H2 at 0° ; of vapor —
5.52 A — Freezing-point =— 24° .5 (—12°.! F.) — Boiling-point —
63° (145°. 4 F.) — Name derived from j3pufj.o^ = a stench — Discovered-
by Balard in 1826.
Occurrence. — Only in combination, most abundantly with Na,
and Mg in sea-water and the waters of mineral springs.
Preparation. — It is obtained from the mother liquors, left by
the evaporation of sea-water, and' of that of certain mineral
springs, and from sea-weed. These are mixed with sulfuria
BKOMIX. 87
acid and manganese dioxid and heated, when the bromids are
decomposed by the Cl produced, and Br distils.
Properties. — Physical. — A dark reddish-brown liquid, volatile
at all temperatures above — 24°. 5 (—12°. 1 F.); giving off brown-
red vapors which produce great irritation when inhaled. Solu-
ble in water to the extent of 3.2 parts per 100 at 15° (59° F.) ;
more soluble in alcohol, carbon disulfid, chloroform, and ether.
Chemical. — The chemical characters of Br are similar to those
of Cl, but less active. With H2O it forms a crystalline hydrate
at 0° (32° F.) : Br 5H2O. Its aqueous solution is decomposed by
exposure to light, with formation of hydrobromic acid.
It is highly poisonous.
Hydrogen Brornid— Hydrobromic acid — Acidum hydrobromi-
cum dil. (U. S.) = HBr— Molecular weight = 81— Sp. gr. = 2.71
A — A litre weighs 3.63 grams — Liquefies at — 69° (—92°. 2 F.) —
Solidifies at — 73° (- 99°.4 F.).
Preparation. — This substance cannot be obtained from a bromid
as HC1 is obtained from a chlorid. It is produced, along with
phosphorous acid, by the action of H2O upon phosphorus tri-
bromid : PBr3 + 3H2O - H3PO3 + 3HBr ; or by the action of
Br upon paraffin.
Properties. — A colorless gas ; produces white fumes with moist
air ; acid in taste and reaction, and readily soluble in H2O, with
which it forms a hydrate, HBr 2H2O. Its chemical properties are
similar to those of HC1.
Bromids closely resemble the chlorids and are formed under sim-
ilar conditions. They are decomposed by chlorin, with formation
of a chlorid and liberation of Br : 2KBr + Cl2 = 2KC1 + Br2. The
metallic bromids are soluble in H2O, except AgBr and Hg2Br2,
which are insoluble, and PbBr2, which is sparingly soluble. The
bromids of Mg, Al, Ca are decomposed into oxid and HBr on
evaporation of their aqueous solutions.
Analytical Characters. — (1.) With AgNO3, a yellowish-white
ppt., insoluble in HNO3, sparingly soluble inNH4HO. (2.) With
chlorin water a yellow solution which communicates the same
color to chloroform and to starch-paste. (3.) With palladic
nitrate a black ppt. in the absence of chlorids.
Oxacids of Bromin. — No oxids of bromin are known, although
three oxacids exist, either in the free state or as salts :
Hypobromous Acid — HBrO — 97 — is obtained, in aqueous solu-
tion, by the action of Br upon mercuric oxid, silver oxid, or silver
nitrate. When Br is added to concentrated solution of potassium
hydroxid no hypobromite is formed, but a mixture of broniate
and bromid, having no decolorizing action. With sodium hy-
88 MANUAL OF CHEMISTRY.
droxid, however, sodium hypobromite is formed in solution ; and
such a solution, freshly prepared, is used in Knop's process for
determining urea (q. v.).
Bromic Acid— HBrO3— 129 — has only been obtained in aqueous
solution, or in combination. It is formed by decomposing
barium bromate with an equivalent quantity of sulfuric acid:
Ba (BrO3)a+ H2SO4=2HBrO3+BaSO4. In combination it is pro-
duced, along with the bromid, by the action of Br on caustic
potassa : 3Br2 -f 6KHO = KBrO3 -f 5KBr + 3H2O.
Perbromic Acid — HBrO4 — 145 — is obtained on a comparatively
stable, oily liquid, by the decomposition of perchloric acid by
Br, and concentrating over the water-bath.
It is noticeable in this connection that, while HC1 and the
chlorids are more stable than the corresponding Br compounds,
the oxygen compounds of Br are more permanent than those
of 01.
IODIN.
lodum (U. S. ; Br.) — Symbol = I — Atomic weight = 127 — Molec-
ular weight — 254 — Sp. gr. of solid = 4.948 ; of vapor = 8.716 A
—Fuses at 113°. 6 (236°.5 F.)— Soils at 175° (347° F.}—Name derived
from iudris — violet — Discovered by Courtois in 1811.
Occurrence. — In combination with Na, K, Ca, and Mg, in sea-
water, the waters of mineral springs, marine plants and animals.
Cod-liver oil contains about 37 parts in 100,000.
Preparation.— It is obtained from the ashes of sea- weed, called
kelp or varech. These are extracted with H2O, and the solution
evaporated to small bulk. The mother liquor, separated from
the other salts which crystallize out, contains the iodids, which
are decomposed by 01, aided by heat, and the liberated iodin
condensed.
Properties. — Physical. — Blue-gray, crystalline scales, having a
metallic lustre. Volatile at all temperatures, the vapor having a
violet color, and a peculiar odor. It is sparingly soluble in H2O,
which, however, dissolves larger quantities on standing over an
excess of iodin, by reason of the formation of hydriodic acid.
The presence of certain salts, notably potassium iodid. increases
the solvent power of H2O for iodin. The Liq. lodi Comp. (U. S.),
Liq. lodi, Br. is solution of potassium iodid containing free iodin.
Very soluble in alcohol ; Tinct. iodi (U. S.; Sr.); in ether, chloro-
form, benzol, and carbon disulfld. With the three last-named
•solvents it forms violet solutions, with the others brown solutions.
Chemical. — In its chemical characters I resembles 01 and Br,
•"but is less active. It decomposes H2O slowly, and is a weak
bleaching and oxidizing agent. It decomposes hydrogen sulfid
IODIN. 89
-with formation of hydriodic acid, and liberation of sulfur. It
-does not combine directly with oxygen, but does with ozone.
Potassium hydroxid solution dissolves it, with formation of po-
tassium iodid, and some hypoiodite. Nitric acid oxidizes it to
iodic acid. With ammonium hydroxid solution it forms the ex-
plosive nitrogen iodid.
Impurities. — Non-volatile substances remain when the I is
heated. Water separates as a distinct layer when I is dissolved
in carbon disulfid. Cyanogen iodid appears in white, acicular
crystals among the crystals of sublimed I, when half an ounce of
the substance is heated over the water-bath for twenty minutes,
in a porcelain capsule, covered with a flat-bottomed flask filled
with cold water. The last named is the most serious impurity as
it is actively poisonous.
Toxicology. — Taken internally, iodin acts both as a local irri-
tant and as a true poison. It is discharged as an alkaline iodid
by the urine and perspiration, and when taken in large quantity
it appears in the faeces.
The poison should be removed as rapidly as possible by the use
of the stomach-pump and of emetics. Farinaceous substances
may also be given.
Hydrogen Iodid — Hydriodic acid — HI — Molecular weight—
128— Sp. gr. 4.443 A.
Preparation. — By the decomposition of phosphorus triiodid by
water : PI3 -(- 3H2O = H3PO3 + 3HI. Or, in Solution by passing
hydrogen sulfid through water holding iodin in suspension :
Properties. — A colorless gas, forming white fumes on contact
with air, and of strongly acid reaction. Under the influence of
cold and pressure it forms a yellow liquid, which solidifies at
— 55"(— 67° F.). Water dissolves it to the extent of 425 volumes
for each volume of the solvent at 10° (50° F.).
It is partly decomposed into its elements by heat. Mixed with
O it is decomposed, even in the dark, with formation of H2O aiid
liberation of I. Under the influence of sunlight the gas is slowly
decomposed, although its solutions are not so affected, if they be
free from air. Chlorin and bromin decompose it, with liberation
of iodin. With many metals it forms iodids. It yields up its H
readily and is used in organic chemistry as a source of that ele-
ment in the nascent state.
Iodids — are formed under the same conditions as the chlorids
and bromids, which they resemble in their properties. The
metallic iodids are soluble in water except Agl, Hgala, which are
insoluble, and PbI2, which is very slightly soluble. The iodids of
ihe earth metals are decomposed into oxid and HI on evapora-
90 MANUAL OF CHEMISTRY.
tion of their aqueous solutions. Chlorin decomposes the iodide
as it does the broinids.
Analytical Characters. — (1.) With AgNO3, a yellow ppt., insol-
uble in HNO3, and in NH4HO. (2.) With fuming HNO3 or with
chlorin water, a yellow liquid, which colors starch-paste black or
purple, and chloroform violet. (3.) With palladic nitrate, a black
ppt., insoluble in cold HNO3 and in solutions of alkaline chloridsr
but forming a dark brown solution with alkaline iodids.
Chloricls of lodin. — Chlorin and iodin combine with each other
in two proportions : Iodin monochlorid, or protochlorid — IC1 is a
red-brown, oily, pungent liquid, formed by the action of dry CI
upon I, and distilling at 100° (212° F.). Iodin trichlorid or per-
chlorid — IC13 is a yellow, crystalline solid, having an astringent,
acid taste, and a penetrating odor ; very volatile ; its vapor irri-
tating ; easily soluble in water. It is formed by saturating H2O
holding I in suspension with Cl, and adding concentrated sul-
furic acid. IC13 has been used as an antiseptic.
Oxacids of Iodin. — The best known of these are the highest two-
of the series — iodic and periodic acids.
lodic Acid — HIO3 — 176 — is formed as an iodate, whenever I is
dissolved in a solution of an alkaline hydroxid : I« -f 6KHO =
KIOs + 5KI + 3H2O. As the free acid, by the action of strong-
oxidizing agents, such as nitric acid, or chloric acid, upon I ; or by
passing Cl for some time through H2O holding I in suspension.
Iodic acid appears in white crystals, decomposable at 170°
(338° F.), and quite* soluble in H2O, the solution having an acid
reaction, and a bitter, astringent taste.
It is an energetic oxidizing agent, yielding up its O readily, with
separation of elementary I or of HI. It is used as a test for the
presence of morphin (q. V.).
Periodic Acid— HIOj — 192— is formed by the action of Cl upon
an alkaline solution of sodium iodate. The sodium salt thus ob-
tained is dissolved in nitric acid, treated with silver nitrate, and
the resulting silver periodate decomposed with H2O. From the
solution the acid is obtained in colorless crystals, fusible at 130°
(266° F.), very soluble in water, and readily decomposable by
heat.
II. SULFUR GEOUP.
SULFUR— SELENIUM — TELLURIUM.
The elements of this group are bivalent. With hydrogen they
form compounds composed of one volume of the element, in the
form of vapor, with two volumes of hydrogen — the combination
being attended with a condensation in volume of one-third.
SULFUR. 91
Their hydrates are dibasic acids. They are all solid at ordinary
temperatures. The relation of their compounds to each other
is shown in the following table :
HS8 SO, SO, HaSO, HaSOs H2SO4
H2Se SeO, SeO3 HaSeO3 H2SeO4
H2Te TeO, TeO3 H,TeO, H2TeO«
Hydro-ic acid. Dioxid. Trioxid. Etypo-ous acid, -ous acid. -ic acid.
SULFUR.
Symbol = S — Atomic weight = 32 — Molecular weight = 64 — Sp~
gr. of vapor = 2.22 A— Fuses at 114° (237.2° P.)— Boils at 447.3° (837°
P.).
Occurrence. — Free in crystalline powder, large crystals, or
amorphous, in volcanic regions. In combination in sulfids and
sulfates, and in albuminoid substances.
Preparation. — By purification of the native sulfur, or decom-
position of pyrites, natural sulfids of iron.
Crude sulfur is the product of a first distillation. A second
distillation, in more perfectly constructed apparatus, yields re-
fined sulfur. During the first part of the distillation, while the
air of the condensing chamber is still cool, the vapor of S is sud-
denly condensed into a fine, crystalline powder, which is flowers
of sulfur, sulfur sublimatum (U. S.). Later, when the tempera-
ture of the condensing chamber is above 114°, the liquid S col-
lects at the bottom, whence it is drawn off and cast into sticks of
roll sulfur.
Properties. — Physical. — Sulfur is usually yellow in color. At
low temperatures, and in minute subdivision, as in the precipi-
tated milk of sulfur, sulfur prsecipitatum (U. S.), it is almost or
quite colorless. Its taste and odor are faint but characteristic.
At 114° (237°. 2 F.) it fuses to a thin yellow liquid, which at 150°-
160° (302°-320° F.) becomes thick and brown ; at 330°-340° (626°-
642°. 2 F.) it again becomes thin and light in color ; finally it boils,
giving off brownish-yellow vapor at a temperature variously-
stated between 440° (824° F.) and 448° (838°.4 F.). If heated to-
about 400° (752° F.) and suddenly cooled, it is converted into plas-
tic sulfur, which may be moulded into any desired form. It is
insoluble in water, sparingly soluble in anilin, phenol, benzene,
benzin, and chloroform ; readily soluble in protochlorid of sul-
fur and carbon disulfid. It dissolves in hot alcohol, and crys-
tallizes from the solution, on cooling, in white prismatic crystals.
It is dimorphous. When fused sulfur crystallizes it does so in
oblique rhombic prisms. Its solution in carbon disulfid de-
posits it on evaporation in rhombic octahedra. The prismatie
MANUAL OF CHEMISTRY.
-variety is of sp. gr. 1.95 and fuses at 120° (248° F.) ; the sp. gr. of
the octahedral is 2.05, and its fusing point 1 14°. 5 (238° F.). The
prismatic crystals, by exposure to air, become opaque, by reason
of a gradual conversion into octahedra.
Chemical. — Sulfur unites readily with other elements, espe-
cially at high temperatures. Heated in air or O, it burns with a
blue flame to sulfur dioxid, SOa. In H it burns with formation
of hydrogen sulfid, H2S. The compounds of S are similar in
constitution, and to some extent in chemical properties, to those
of O. In many organic substances 8 may replace O, as in sul-
focyanic acid, CNSH, corresponding to cyanic acid, CNOH.
Sulfur is used principally in the manufacture of gunpowder ;
also to some extent in making sulfuric acid, sulfur dioxid,
and matches, and for the prevention of fungoid and parasitic
•growths.
Hydrogen Monosulfid — Sulf hydric acid — Hydrosulfuric acid —
Sulfuretted hydrogen — HaS — Molecular weight — 34 — Sp. gr. =
1.19 A.
Occurrence.— In volcanic gases ; as a product of the decomposi-
tion of organic substances containing S ; in solution, in the waters
of some mineral springs ; and, oc-
casionally, in small quantity, in
the gases of the intestine.
Preparation. — (1.) By direct
union of the elements ; either by
burning S in H, or by passing H
through molten S.
(2.) By the action of nascent H
upon sulfuric acid, if the mixture
become heated. (See Marsh test
for arsenic.)
(3.) By the action of HC1 upon
antimony trisulfid : SbaS3 + 6HCl
= 2SbCl3 + 3HaS.
(4.) By the action of dilute sul-
furic acid upon ferrous sulfid :
FeS+HaSO4=FeSO4+H2S. This
is the method generally used. The
gas should be purified by passage
— :s^"5^=- over dry calcium chlorid, then
FIG 24. through a tube, 20 cent, long,
loosely filled with solid iodin and,
finally, through a solution of potassium sulfid.
(5.) By the action of HC1 upon calcium sulfid : CaS + 2HC1 =
SULFUR. 93
The gas is usually obtained in the laboratory by reaction (4),
either in an apparatus such as that shown in Fig. 20 (p. 43) or in
one of the forms of apparatus shown in Figs. 24, 25. The sulfid
is put into the bulb 6, Fig. 24, through the opening e, or into the
bottle &, Fig. 25. The dilute acid, with which the uppermost and
lowest bulbs, Fig. 24, are filled, comes in contact with the sulfid
FIG. 25.
when the stopcock is opened, or in the apparatus, Fig. 25, is-
poured through the funnel tube c. a is a wash-bottle partly
filled with water.
As ferrous sulfid is liable to contain arsenic, and as hydrogen-
sulfid generated from it may be contaminated with hydrogen
arsenid, the gas, when required for toxicological analysis should
always be obtained by reaction (5) in the apparatus, Fig. 24, or
should be purified as above directed.
Properties. — Physical. — A colorless gas, having the odor of rot-
ten eggs and a disgusting taste ; soluble in H2O to the extent of
3.23 parts to 1 at 15° (59° F.) ; soluble in alcohol. Under 17 atmos-
pheres pressure, or at —74° (—101°. 2 F.) at the ordinary press-
ure, it liquefies; at —85.5° (—122° F.) it forms white crystals.
Chemical. — Burns in air with formation of sulfur dioxid and
water : 2H2S + 3Oa = 2SOS -f- 2H»O. If the supply of oxygen be
deficient, HaO is formed, and sulfur liberated : 2H2S -f- O» =
2H2O + Sa. Mixtures of H2S and air or O explode on contact
with flame. Solutions of the gas when exposed to air become
oxidized with deposition of S. Such solutions should be made
with boiled H2O, and kept in bottles which are completely filled,
and well corked. Oxidizing agents, Cl, Br, and I remove its H
•94
MANUAL OP CHEMISTRY.
•with deposition of S. Hydrogen sulfid and sulfur dioxid mutu-
ally decompose each other into water, pentathionic acid and sul-
fur: 4SO3 + 3H8S = 2H»O -f HSSSO8 + S,.
When the gas is passed through a solution of an alkaline hy-
droxid its S displaces the O of thehydroxid to form a sulf hydrate:
H2S + KHO = H2O + KHS. With solutions of metallic salts
H2S usually relinquishes its 8 to the metal: CuSO4 -f H2S = CuS
-f H3SO4, a property which renders it of great value in analyti-
cal chemistry.
Physiological. — Hydrogen sulfld is produced in the intestine
by the decomposition of albuminous substances or of taurochloric
acid; it also occurs sometimes in abscesses, and in the urine in
tuberculosis, variola, and cancer of the bladder. It may also
reach the bladder by diffusion from the rectum.
Toxicology. — An animal dies almost immediately in an atmos-
phere of pure H2S, and the diluted gas is still rapidly fatal. An
.atmosphere containing one per cent, may be fatal to man,
although individuals habituated to its presence can exist in an
atmosphere containing three per cent. Even when highly diluted
it produces a condition of low fever, and care is to be taken that
the air of laboratories in which it is used shall not become con-
taminated with it. Its toxic powers are due primarily, if not
entirely, to its power of reducing and combining with the blood-
coloring matter.
The form in which hydrogen sulfid generally produces dele-
terious effects is as a constituent of the gases emanating from
sewers, privies, burial vaults, etc. These give rise to either slow
poisoning, as when sewer gases are admitted to sleeping and
other apartments by defective plumbing, or to sudden poisoning,
as when a person enters a vault or other locality containing the
noxious atmosphere.
The treatment should consist in promoting the inhalation of
pure air, artificial respiration, cold affusions, and the administra-
tion of stimulants.
After death the blood is found to be dark in color, and gives
the spectrum shown in Fig. 26, due to sulfhaemoglobin.
Sulfids and Hydrosulfids. — These compounds bear the same
SULFUR DIOXID. 95
Telation to sulfur that the oxids and hydroxids do to oxygen.
The two sulflds of arsenic, AS2S3 arid AS2S5, correspond to the
two oxids, ASaOs and ASsSs, and the hydrosulfid of potassium,
KHS, corresponds to the hydroxid, KHO.
Many metallic sulflds occur in nature and are important ores
of the metals, as the sulflds of zinc, mercury, cobalt, nickel, and
iron. They are formed artificially, either by direct union of the
elements at elevated temperatures, as in the case of iron: Fe + S
= FeS; or by reduction of the corresponding sulfate, as in the
case of calcium: CaSO4 + 20 = CaS + 2COa.
The sulfids are insoluble in H2O, except those of the alkali
metals. Many of the sulfids are soluble in alkaline liquids,
and behave as sulfanhydrids, forming sulfo- or thio-salts, cor-
responding to the oxysalts. Thus potassium arsenate, K»AsO4
and thioarsenate, K3AsS4; antimonate, K3SbO4, and thioantimo-
nate, K3SbS4.
The metallic sulfids are decomposed when heated in air, usually
with the formation of sulfur dioxid and the metallic oxid; some-
times with the formation of the sulfate; and sometimes with
the liberation of the metal, and the formation of sulfur dioxid.
The strong mineral acids decompose the sulfids with formation
of hydrogen monosulfid.
Analytical Characters. — Hydrogen Sulfid. — (1.) Blackens pa-
per moistened with lead acetate solution. (2.) Has an odor of
rotten eggs.
Sulflds. — (1.) Heated in the oxidizing flame of the blowpipe,
give a blue flame and odor of SO2. (2.) With a mineral acid give
off H2S (except sulflds of Hg, Au, and Pt).
Sulfur Dioxid— Sulfurous oxid, or anhydrid — Acidum sulfuro-
sum (TJ. S.; Br.)— SO3— Molecular weight = 64 — Sp. gr. of gas —
2.213; of liquid — 1.45— Soils at— 10° (14° F.); solidifies at— 75°
<-103° F.).
Occurrence. — In volcanic gases and in solution in some mineral
waters.
Preparation. — (1.) By burning S in air or O.
(2.) By roasting iron pyrites in a current of air.
(3.) During the combustion of coal or coal-gas containing S or
its compounds.
(4.) By heating sulf uric acid with copper: 2HaSO4+Cu=CuSO4
+2HaO+SOa.
(5.) By heating sulf uric acid with charcoal: 2HaSO4+C = 2SOa
+ COa+2HaO.
(6.) By decomposing calcium sulflte, made into cubes with
plaster of Paris, by HC1, at the ordinary temperature.
When the gas is to be used as a disinfectant it is usually ob-
96 MANUAL OF CHEMISTRY.
tained by reaction (1); in sulfuric acid factories (2) is used; (3) in-
dicates the method in which atmospheric SO2 is chiefly produced ;
in the laboratory (4) and (6) are used; (5) is the process directed
by the U. S. and Br. Pharmacopoeias.
Properties. — Physical. — A colorless, suffocating gas, having a
disagreeable and persistent taste. Very soluble in HaO, which
at 15° (59° F.) dissolves about 40 times its volume (see below); also
soluble in alcohol. At —10° (14° F.) it forms a colorless, mobile,
transparent liquid, by whose rapid evaporation a cold of —65°
(—85° F.) is obtained.
Chemical. — Sulfur dioxid is neither combustible nor a supporter
of combustion. Heated with H it is decomposed: SOa+2H» = &
+ 2H2O. With nascent hydrogen, H2S is formed : SO» + 3Ha —
BUS + 2H2O.
Water not only dissolves the gas, but combines with it to form
the true sulfurous acid, H2SO3. With solutions of metallic hy-
drates it forms metallic sulfltes : SO2 + KHO = KHSOS; or SO*
+ 2KHO = KaSOsi + HaO. A hydrate having the composition
HaSOs, 8H2O has been obtained as a crystalline solid, fusible at
+4° (39°. 2 F.).
Sulfur dioxid and sulfurous acid solution are powerful reducing
agents, being themselves oxidized to sulfuric acid: SOa + HaO +
O = H2SO4; or H2SO3 + O = HSSO4. It reduces nitric acid with
formation of sulfuric acid and nitrogen tetroxid: SOa + 2HNOt
= HaSO4 + 2NOa. It decolorizes organic pigments, without,
however, destroying the pigment, whose color may be restored
by an alkali or a stronger acid. It destroys H2S, acting in thi&
instance, not as a reducing, but as an oxidizing agent: 4SOa +
3HaS = 2HaO + HaS6O6 + Sa. With Cl it combines directly
under the influence of sunlight to form sulfuryl chlorid (SO3)"
Cla.
Analytical Characters. — (1.) Odor of burning sulfur.
(2.) Paper moistened with starch-paste and iodic acid solution
turns blue in air containing 1 in 3,000 of SOa.
Sulfur Trioxid — Sulfuric oxid or anhydrid — SO3 — Molecular
weight = 80— Sp. gr. 1.95.
Preparation.— (1.) By union of SO, and O at 250°-300° (482°-
572° F.) or in presence of spongy platinum.
(2.) By heating sulfuric acid in presence of phosphoric anhy-
drid: HaSO4 + PaO5 = SO3 + 2HPO3.
(3.) By heating dry sodium pyrosulfate : Na2S2O7 = Na2SO*
+ S03.
(4.) By heating pyrosulfuric acid below 100° (212° F.), in a retort
fitted with a receiver, cooled by ice and salt : H2S2O7 = H2SO4 +
SO3.
OXACIDS OF SULFUR. 97
Properties. — White, silky, odorless crystals which give off white
fumes in damp air. It unites with H2O with a hissing sound,
and elevation of temperature, to form sulfuric acid. When dry
it does not redden litmus.
Sulfur trioxid exists in two isomeric (see isomerism) modifica-
tions, being one of the few instances of isomerism among mineral
substances. The a modification, liquid at summer temperature,
solidifies in colorless prisms at 16° (60°.8 F.) and boils at 46° (114°.8
F.). The ft isomere is a white, crystalline solid which gradually
fuses and passes into the a form at about 50° (122° F.).
Oxacids of Sulfur.
HjSOa Hyposulfurous acid.
HaSUs ISulturous acid.
H2SO4 Sulfuric acid.
Thiosulfuric acid.
H»S2O7 Pyrosulfuric acid.
HaSnOe Dithionic acid.
HjSsO* Trithionic acid.
HaS4O8 Tetrathionic acid.
H2S5O8 Pentathionic acid.
Hyposulfurous Acid — H2SO2 — 66. — HydrosulfuroiLS acid— Is an
unstable body only known in solution, obtained by the action of
zinc upon solution of sulfurous acid. It is a powerful bleaching
and deoxidizing agent.
Sulfurous Acid— H ,SO3 — 82. — Although sulfurous acid has not
been isolated, it, in all probability, exists in the acid solution,
formed when sulfur dioxid is dissolved in water: SO2 + H2O =
SOsHj. Its salts, the sulfites, are well defined. From the exist-
ence of certain organic derivatives (see sulfonic acids) it would
seem that two isomeric modifications of the acid may exist. They
are distinguished as the symmetrical, in which the S atom is
quadrivalent,
-
\OH'
and the unsymmetrical, in which the S atom is hexavalent,
Xo/
O/b\OH'
Sulfites. — The sulfites are decomposed by the stronger acids,
with evolution of sulfur dioxid. Nitric acid oxidizes them to
sulfates. The sulfites of the alkali metals are soluble, and are
active reducing agents.
The analytical characters of the sulfites are: (1.) With HC1
they give off SO2. (2.) With zinc and HC1 they give off HaS. (3.)
With AgNO3 they form a white ppt., soluble in excess of sulfite,
and depositing metallic Ag when the mixture is boiled. (4.) With
Ba (NO8)2they form a white ppt., soluble in HC1. If chlorin water
98 MANUAL OF CHEMISTRY.
be added to the solution so formed a white ppt., insoluble in
acids, is produced.
Sulfuric Acid — Oil of Vitriol— Acidum sulfuricum (TJ. S.; Br.)
— H2SO4— 98.
Preparation. — (1.) Bv the union of sulfur trioxid and water :
S03 + H,O = HaS04. "
(2.) By the oxidation of SO2 or of S in the presence of water :
2SO2 + 2H2O + O2 = 2H2SO4 ; or S2 + 2H2O + 3O2 = 2H2SO4.
The manufacture of H2SO4 may be said to be the basis of all
chemical industry, as there are but few processes in chemical
technology into some part of which it does not enter. The
method followed at present, the result of gradual improvement,
may be divided into two stages : 1st, the formation of a dilute
acid ; 2d, the concentration of this product.
The first part is carried on in immense chambers of timber,
lined with lead, and furnishes an acid having a sp. gr. of 1.55,
and containing 65 per cent, of true sulfuric acid, H2SC>4. Into
these chambers SO2, obtained by burning sulfur, or by roast-
ing pyrites, is driven, along with a larg-e excess of air. In the
chambers it comes in contact with nitric acid, at the expense of
which it is oxidized to H2SO4, while nitrogen tetroxid (red fumes)
is formed : SO2 + 2HNO3 = H2SO4 + 2NO2. Were this the only
reaction, the disposal of the red fumes would present a serious
•difficulty and the amount of nitric acid consumed would be very
great. A second reaction occurs between the red fumes and
H2O, which is injected in the form of steam, by which nitric
acid and nitrogen dioxid are produced : 3NO2 + H2O = 2HNO3
+ NO. The nitrogen dioxid in turn combines with O to produce
the tetroxid, which then regenerates a further quantity of nitric
acid, and so on. This series of reactions is made to go on contin-
uously, the nitric acid being constantly regenerated, and acting
merely as a carrier of O from the air to the SO2, in such manner
that the sum of the reactions may be represented by the equa-
tion : 2SO2 + 2H2O + O2 = 2H2SO4.
The acid is allowed to collect in the chambers until it has the
sp. gr. 1.55, when it is drawn off. This chamber acid, although
used in a few industrial processes, is not yet strong enough for
most purposes. It is concentrated, first by evaporation in shal-
low leaden pans, until its sp. gr. reaches 1.746. At this point it
begins to act upon the lead, and is transferred to platinum stills,
where the concentration is completed.
Varieties. — Sulfuric acid is met with in several conditions of
concentration and purity:
(1.) The commercial oil of vitriol, largely used in manufactur-
ing processes, is a more or less deeply colored, oily liquid, vary-
OXACIDS OF SULFUR. 99
ing in sp. gr. from 1.833 to 1.842, and in concentration from 93
per cent, to 99| per cent, of true H2SO4.
(2.) C. P. acid = Acidum sulfuricum (U. S. ; Br.), of sp. gr. 1.84,
•colorless and comparatively pure (see below).
(3.) Glacial sulfuric acid is a hydrate of the composition
H2SO4,H2O, sometimes called bihydrated sulfuric acid, which
crystallizes in rhombic prisms, fusible at +8°. 5 (47°. 3 F.) when an
ticid of sp. gr. 1.788 is cooled to that temperature.
(4.) Ac. sulf. dil. (U. 8.; 2?r.)is a dilute acid of sp. gr. 1.069
and containing between i» and 10 per cent. ±i2SO4 (U. S.), or of
sp. gr. 1.094, containing between 12 and 13 per cent. HaSO4 (Br.).
Properties.— Physical. — A colorless, heavy, oily liquid ; sp. gr.
1.842 at 12° (53°. 6 F.) ; crystallizes at 10°.5 (50°.9 F.); boils at 338°
(640°. 4 F.). It is odorless, intensely acid in taste and reaction,
«,nd highly corrosive. It is non- volatile at ordinary temperatures.
Mixtures of the acid with H2O have a lower boiling-point, and
lower sp. gr. as the proportion of EUO increases.
Chemical. — At a red heat vapor of H3SO4 is partly dissociated
into SO3 and H2O ; or, in the presence of platinum, into SO2, H2O
.and O. When heated with S, C, P, Hg, Cu, or Ag, it is reduced,
with formation of SO2.
Sulfuric acid has a great tendency to absorb H2O, the union
being attended with elevation of temperature, increase of bulk,
and diminution of sp. gr. of the acid, and contraction of volume
of the mixture. Three parts, by weight, of acid of sp. gr. 1.842,
when mixed with one part of H2O produce an elevation of tem-
perature to 130° (266° F.), and the resulting mixture occupies a
volume 1-6 less than the sum of the volumes of the constituents.
Strong H2SO4 is a good desiccator of air or gases. It should not
be left exposed in uncovered vessels lest, by increase of volume,
it overflow. When it is to be diluted with H2O, the acid should
Tae added to the H2O in a vessel of thin glass, to avoid the pro-
jection of particles or the rupture of the vessel. It is by virtue
of its affinity for H2O that H2SO4 chars or dehydrates organic
substances. Sulfuric acid is a powerful dibasic acid.
Impurities. — The commercial acid is so impure that it is only
fit for manufacturing and the coarsest chemical uses. The so-
called C. P. acid may further contain : Lead ; -becomes cloudy
when mixed with ten times its volume of HSO, if the quantity of
Pb be sufficient. The dilute acid gives a black color with H2S.
Salts ; leave a fixed residue when the acid is evaporated. Sul-
fur dioxid ; gives off H2S when the acid, diluted with an equal
volume of H2O, comes in contact with Zn. Carbon,' communi-
cates a brown color to the acid. Arsenic ; is very frequently
present. When the acid is to be used for toxicological analysis, the
test by H3S is not sufficient. The acid, diluted with an equal
100 MANUAL OF CHEMISTRY.
volume of HaO, is to be introduced into a Marsh apparatus, In-
which no visible stain should be produced during an hour. Oxids-
of jiitrogen are almost invariably present ; they communicate a
pink or red color to pure brucin.
Sulfates. — Sulfuric acid being dibasic, there exist two sul-
fates of the univalent metals : HKSCh and KaSO4, and but one
sulfate of each bivalent metal : CaSO«. The sulfates of Ba,
Ca, Sr, and Pb are insoluble, or very sparingly soluble, in H»O.
Other sulfates are soluble in HaO, but all are insoluble in al-
cohol.
Analytical Characters.— (1.) Barium chlorid (or nitrate) ; a
white ppt., insoluble in acids. The ppt., dried and heated
with charcoal, forms BaS, which, with HC1, gives off HSS.
(2.) Plumbic acetate forms a white ppt., insoluble in dilute acids.
(3.) Calcium chlorid forms a white ppt., either immediately
or on dilution with two volumes of alcohol ; insoluble in dilute
HC1 or HNO3.
Toxicology.— Sulfuric acid is an active corrosive, and maybe,
if taken in sufficient quantity in a highly diluted state, a true
poison. The concentrated acid causes death, either within a few
hours, by corrosion and perforation of the walls of the stomach
and O3sophagus, or, after many weeks, by starvation, due to de-
struction of the gastric mucous membrane and closure of the py-
loric orifice of the stomach.
The treatment is the same as that for corrosion by HC1. (See
p. 85.)
Thiosulfuric Acid. — Hyposulfurous acid — H2Sa03 — 114— may-
be considered as sulfuric acid, H2SO4, in which one atom of
oxygen has been replaced by one of sulfur. The acid itself has
not been isolated, being decomposed, on liberation from the thio-
sulfates, into sulfur, water and sulfur dioxid ; H8SaOs=S-|-
SOa + H,0.
Pyrosulfuric Acid— Fuming sulfuric acid — Nordhausen oil of
vitriol — Disulfuric hydrate— H2S2O7— - Molecular weight = 178 —
Sp. gr. = 1.9— Soils at 52°.2 (126° F.).
Preparation. — By distilling dry ferrous sulfate ; and purifica-
tion of the product by repeated crystallizations and fusions, until
a substance fusing at 35° (95° F.) is obtained.
Properties. — The commercial Nordhausen acid, which is a mix-
ture of H2S2r>7 with excess of SO3, or of H2SO4, is a brown, oily
liquid, which boils below 100° (212° F.) giving off SOs ; and is solid
or liquid according to the temperature. It is used chiefly as a
solvent for indigo, and in the anilin industry.
NITROGEN. 101
SELENIUM AND TELLURIUM.
Se— 79.5. Te— 128.
These are rare elements which form compounds similar to those
-of sulfur. Elementary selenium is used in some forms of elec-
trical apparatus.
III. NITROGEN GROUP.
NITROGEN — PHOSPHORUS— ARSENIC — ANTIMONY.
The elements of this group are trivalent or quinquivalent, oo-
•casionally univalent. With hydrogen they form non-acid com-
pounds, composed of one volume of the element in the gaseous
.state with three volumes of hydrogen, the union being attended
with a condensation of volume of one-half. Their hydrates are
acids containing one, two, three, or four atoms of replaceable hy-
drogen.
Bismuth, frequently classed in this group, is excluded, owing
to the existence of the nitrate Bi(NO3)3. The relations existing
between the compounds of the elements of this group are shown
in the following table :
NH3,
N,0,
NO,
N203,
NO,,
N205,
—
PH3,
—
—
PaO3,
—
P2O5,
H3PO,,
AsH3,
—
—
As3O3,
—
AS!lO5,
—
SbH3,
—
—
Sb2O3,
—
SbaO5,
—
Hyd-
Mon-
Di-
Tri-
Tetr-
Pent-
Hypo-ous
nd.
oxid.
oxid.
oxid.
oxid.
oxid.
acid.
—
—
—
HNO3
H3P03,
H3P04,
H4P2O7,
HPO3
H3AsO3,
H3AsO«,
H4As;iO7,
HAsOs
—
H3SbO4,
H4Sb,O7,
HSbO3
-ous
-ic
Pyro-ic
Meta-ic
acid.
acid.
acid.
acid.
NITROGEN.
Azote — /Symbol=N — Atomic weight=14: — Molecular weight=28
— Sp. gr. =0.9701 — One litre weighs 1.254 grains — Name from
viTpov=nitre, jeveaiq =source ; or from a, privative £u>r/=life — Dis-
covered by Mayow in 1669.
Occurrence. — Free in atmospheric air and in volcanic gases. In
•combination in the nitrates, in ammoniacal compounds and in a
great number of animal and vegetable substances.
Preparation. — (1.) By removal of O from atmospheric air; by
102 MANUAL OF CHEMISTRY.
burning P in air, or by passing air slowly over red-hot copper-
It is contaminated with CO2, HaO, etc.
(2.) By passing Cl through excess of ammonium hydroxid solu-
tion. If ammonia be not maintained in excess, the Cl reacts with
the ammonium chlorid formed, to produce the explosive nitrogen
chlorid.
(3.) By heating ammonium nitrite, (NH4) NO2: or a mixture of
ammonium chlorid and potassium nitrite.
Properties. — A colorless, odorless, tasteless, non-combustible
gas; not a supporter of combustion; very sparingly soluble in
water.
It is very slow to enter into combination, and most of its com-
pounds are very prone to decomposition, which may occur ex-
plosively or slowly. Nitrogen combines directly with O under
the influence of electric discharges ; and with H under like condi-
tions, and, indirectly, during the decomposition of nitrogenized
organic substances. It combines directly with magnesium, boron,
vanadium and titanium.
Nitrogen is not poisonous, but is incapable of supporting respi-
ration.
Atmospheric Air. — The alchemists considered air as an element,
until Mayow, in 1669, demonstrated its complex nature. It was
not, however, until 1770 that Priestley repeated the work of
Mayow ; and that the compound nature of air, and the characters
of its constituents were made generally known by the labors (1770-
1781) of Priestley, Rutherford, Lavoisier, and Cavendish. The
older chemists used the terms gas and air as synonymous.
Composition. — Air is not a chemical compound, but a mechani-
cal mixture of O and N, with smaller quantities of other gases.
Leaving out of consideration about 0.4 to 0.5 per cent, of other
gases, air consists of 20.93 O and 79.07 N, by volume; or 23 O and
77 N, by weight ; proportions which vary but very slightly at dif-
ferent times and places ; the extremes of the proportion of O found
having been 20.908 and 20.999.
That air is not a compound is shown by the fact that the pro-
portion of its constituents does not represent a relation between
their atomic weights, or between any multiples thereof ; as well
as by the solubility of air in water. "Were it a compound it would
have a definite degree of solubility of its own, and the dissolved
gas would have the same composition as when free. But each of
its constituents dissolves in H2O according to its own solubility,
and air dissolved in H2O at 14°. 1 (57.4 F.) consists of N and O, not
in the proportion given above, but in the proportion 66.76 to-
33.24.
Besides these two main constituents, air contains about 4-5
NITROGEN. 103
thousandths of its bulk of other substances : vapor of water, car-
bon dioxid, aminoniacal compounds, hydrocarbons, ozone, oxids
of nitrogen, and solid particles held in suspension.
Vapor of Water. — Atmospheric moisture is either visible, as in
fogs and clouds, when it is in the form of a finely divided liquid ;
or invisible, as vapor of water. The amount of H2O which a
given volume of air can hold, without precipitation, varies ac-
cording to the temperature and the pressure. It happens rarely
that air is as highly charged with moisture as it is capable of
being for the existing temperature. The difference between the
amount of water which the air is capable of holding at the exist-
ing temperature, and that which it actually does hold is its frac-
tion of saturation, or hygrometric state, or relative humidity.
Ordinarily air contains from 66 to 70 per cent, of its possible
amount of moisture. If the quantity be less than this, the air is
too dry, and causes a parched sensation, and the sense of " stuffi-
ness " so common in furnace-heated houses. If it be greater, evap-
oration from the skin is impeded, and the air is oppressive if
warm.
The actual amount of moisture in air is determined by passing
a known volume through tubes filled with calcium chlorid ; whose
increase in weight represents the amount of HaO in the volume
of air used. The fraction of saturation is determined by instru-
ments called hygrometers, hygroscopes or psychrometers.
Carbon dioxid. — The quantity of carbon dioxid in free air varies
from 3 to 6 parts in 10,000 by volume. (See Carbon dioxid.)
Ammoniacal compounds. — Carbonate, nitrate, and nitrite of
ammonium occur in small quantity (0.1 to 6.0 parts per million
of NHS) in air, as products of the decomposition of nitrogenized
organic substances. They are absorbed and assimilated by plants.
Nitric and nitrous acids, usually in combination with ammo-
nium, are produced either by the oxidation of combustible sub-
stances containing N, or by direct union of X and H2O during
discharges of atmospheric electricity. Rain-water, falling during
thunder-showers, has been found to contain as much as 3. 71 per
million of HNO3. (See Hydrogen peroxid, p. 77.)
Sulfuric and sulfurous acids occur, in combination with
NH4, in the ah* over cities, and manufacturing districts, where
they are produced by the oxidation of S, existing in coal and
coal-gas.
Hydrocarbons have been detected in the air of cities, and of
swampy places, in small quantities.
Solid particles of the most diverse nature are always present in
air and become visible in a beam of sunlight. Sodium chlorid is
almost always present, always in the neighborhood of salt water.
Air contains myriads of germs of vegetable organisms, mould,
104: MANUAL OF CHEMISTRY.
etc., which are propagated by the transportation of these germs
by air-currents. It seems probable, also, that the germs or poi-
sons by which certain diseases are propagated float in the air.
The continued inhalation of air containing large quantities of
solid particles in suspension may cause severe pulmonary disor-
der, by mere mechanical irritation, and apart from any poisonous
quality in the substance; such is the case with the air of carpeted
ball-rooms, and of the workshops of certain trades, furniture-
polishers, metal-filers, etc.
Compounds of Nitrogen and Hydrogen. — Three are known :
Ammonia, NH3 ; Hydrazin, N2H4, and Hydrazoic acid, NSH; as
well as salts corresponding to two hydroxids.
Ammonia. Hydrogen nitrid — Volatile alkali — NH3 — Molec-
ular weight=17 — Sp. gr. =0.589 A — Liquefies at — 40° (— 40° F.) —
Boils at —33°. 7 (— 28°.7 F.}— Solidifies at -75° (-103° F.)—A litre
weighs 0.7655 gram.
Preparation. — (1.) By union of nascent H with N.
(2.) By decomposition of organic matter containing N, either
spontaneously or by destructive distillation.
(4.) By heating solution of ammonium hydroxid : NIhHO =
NH3 + H2O.
Properties.— Physical. — A colorless gas, having a pungent odor,
and an acrid taste. It is very soluble in H2O, 1 volume of which
at 0° (32° F.) dissolves 1050 vols. NH3, and at 15° (59° F.), 727 vols.
NH3. Alcohol and ether also dissolve it readily. Liquid ammo-
nia is a colorless, mobile fluid, used in ice machines for producing
artificial cold, the liquid absorbing a great amount of heat in
volatilizing.
Chemical. — At a red heat ammonia is decomposed into a mix-
ture of N and H, occupying double the volume of the original gas.
It is similarly decomposed by the prolonged passage through it
of discharges of electricity. It is not readily combustible, yet it
burns in an atmosphere of O with a yellowish flame. Mixtures of
NH3 with O, nitrogen monoxid, or nitrogen dioxid, explode on
contact with flame.
The solution of ammonia in H2O constitutes a strongly alkaline
liquid, known as aqua ammoniee, which is possessed of strongly
basic properties. It is neutralized by acids with the formation of
crystalline salts, which are also formed, without liberation of hy-
drogen, by direct union of gaseous NH3, with acid vapors. The
ammoniacal salts and the alkaline base in aqua ammonise are
compounds of a radical, ammonium, NH4, which forms compounds
corresponding to those of potassium or sodium. The compound
NITROGEN. 105
formed by the union of ammonia and water is ammonium hy-
droxid, NH4HO: NH3 + H2O = NH4HO ; and that formed by
the union of hydrochloric acid and ammonia is ammonium
chlorid, NH4C1 : NH3 -f HC1 = NH4C1.
Hydrazin — Diamid— H2N.NH2— is known in the form of its
hydroxid, corresponding to ammonium hydroxid,in the form of
its salts and in numerous organic derivatives. The sulfate is
produced by the action of H2SO4 upon triazoacetic acid, and the
hydroxid by decomposition of the sulfate by caustic soda. The
hydroxid is an oily liquid, intensely corrosive, capable of attack-
ing glass. It combines with acids to form •well-defined salts, and
precipitates many metals from solutions of their salts.
Hydrazoic acid — Azoimid — N3H — is a substance recently ob-
tained from benzoyl-diazoimid, which, although containing the
-same elements as ammonia, is distinctly acid in character. It is
•a colorless liquid, boiling at 37°, having a very pungent and un-
pleasant odor. It is extremely unstable and explodes with great
violence. It reacts with metals, oxids, and hydroxids, as does
hydrochloric acid, to form nitrids, which like the free acid are
very explosive.
Hydroxylamin — NH2HO — 33. — The amins and amids (q.v.)
are compounds derived from ammonia by the substitution of
radicals for a part or all of its hydrogen. This substance, which
is intermediate in composition between ammonia and ammo-
nium hydroxid, may be considered as ammonia, one of whose hy-
drogen, atoms has been replaced by the radical hydroxyl, HO.
It is obtained in aqueous solution by the union of nascent hydro-
gen with nitrogen dioxid : NO-fH3=NH2HO ; or by the action of
nascent hydrogen upon nitric acid : HNO3+3H2=2H2O+NHa
HO. Hydroxylamin is only known in solution and in combina-
tion. Its aqueous solution, which probably contains the corre-
sponding hydrate, NH3O, HO, is strongly alkaline and behaves
with regard to acids as does ammonium hydroxid solution, form-
ing salts corresponding to those of ammonium. Thus hydroxyl-
ammonium chlorid, NH4OC1, crystallizes in prisms or tables, fusi-
ble at 100° (212° F.), and decomposed into HC1, H2O and NH4C1
at a slightly higher temperature.
Hydroxylammonium chlorid has been used in the treatment
of cutaneous disorders. It is an actively toxic agent, converting
oxyhaemoglobin into methsernoglobin.
Oxids of Nitrogen. — Five are known, forming a regular series:
N2O, NO, N2O3, NOa, N2O6. Of these two, the trioxid, N2O3, and
pentoxid, N2O5, are anhydrids.
106 MANUAL OF CHEMISTRY.
Nitrogen Monoxid. Nitrous oxid — Laughing gas — Nitrogen.
protoxid — N2O — Molecular weight=4A — Sp. gr. = 1.527 A — Fuses at
—100° (—148° F.)— Boils at —87° (-134° F.)— Discovered in 1776 by
Priestley.
Preparation. — By heating ammonium nitrate: (NH4)NO3 =
N2O -f- 2H2O. To obtain a pure product there should be no am-
monium chlorid present (as an impurity of the nitrate), and the
heat should be applied gradually, and not allowed to exceed 250°
(482° F.), and the gas formed should be passed through wash-bot-
tles containing sodium hydroxid and ferrous sulfate.
Properties. — Physical. — A colorless, odorless gas, having a-
sweetish taste ; soluble in H2O ; more so in alcohol. Under a
pressure of 30 atmospheres, at 0° (32° F.), it forms a colorless,
mobile liquid which, wnen dissolved in carbon disulfid and
evaporated in vacuo, produces a cold of —140° (— 220° F.).
Chemical. — It is decomposed by a red heat and by the contin-
uous passage of electric sparks. It is not combustible, but is,
after oxygen, the best supporter of combustion known.
Physiological. — Although, owing to the readiness with which
N2O is decomposed into its constituent elements, and the nature
and relative proportions of these elements, it is capable of main-
taining respiration longer than any gas except oxygen or air ; an
animal will live for a short time only in an atmosphere of pure
nitrous oxid. When inhaled, diluted with air, it produces the
effects first observed by Davy in 1799: first an exhilaration of
spirits, frequently accompanied by laughter, and a tendency to
muscular activity, the patient sometimes becoming aggressive;
afterward there is complete anaesthesia, and loss of consciousness.
It has been much used, by dentists especially, as an anaesthetic
in operations of short duration, and in one or two instances an-
aesthesia has been maintained by its use for nearly an hour.
A solution in water under pressure, containing five volumes of
the gas, is sometimes used for internal administration.
Nitrogen Dioxid. Nitric oxid — NO — Molecular weight—
Sp. 0r.=1.039J. — Discovered ~by Hales in 1772.
Preparation. — By the action of copper on moderately diluted
nitric acid in the cold : 3Cu + 8HNO3 = 3Cu(NO3)2 + 4HaO + 2NO ;
the gas being collected after displacement of air from the ap-
paratus.
Properties. — A colorless gas, whose odor and taste are unknown ;
very sparingly soluble in HaO; more soluble in alcohol.
It combines with O, when mixed with that gas or with air, to
form the reddish-brown nitrogen tetroxid. It is absorbed by
solution of ferrous sulfate, to which it communicates a dark
NITROGEN. 107
brown or black color. It is neither combustible nor a good sup-
porter of combustion, although ignited C and P continue to burn
in it, and the alkaline metals, when heated in it, combine with its.
O with incandescence.'
Nitrogen Trioxid. Nitrous anhydrid — N3O3 — 76 — Is prepared
by the direct union of nitrogen dioxid and oxygen at low temper-
atures, or by decomposing liquefied nitrogen tetroxid with a small
quantity of H2O at a low temperature : 4NO2 -f- H2O = 2HNO3 +
N2O3. It is a dark indigo-blue liquid, which, boiling at about 0°
(32° F.), is partly decomposed. It solidifies at - 82° (- 115°.6 F.).
Nitrogen Tetroxid. Nitrogen peroxid — Hyponitric acid — Ni-
trous fumes — NOa — Molecular weight=46 — Sp. gr.=1.58A (at 154°
C.)— Soils at 22° (71°.6 F.)— Solidifies at 9° (15°.8 F.).
Preparation. — (1.) By mixing one volume O with two volumes-
NO ; both dry and ice-cold.
(2.) By heating perfectly dry lead nitrate, O being also pro-
duced : 2Pb(NO3)a = 2PbO + 4NO2 -f O2.
(3.) By dropping strong nitric acid upon a red -hot platinum
surface.
Properties. — When pure and dry, it is an orange-yellow liquid
at the ordinary temperature ; the color being darker the higher
the temperature. The red fumes, which are produced when ni-
tric acid is decomposed by starch or by a metal, consist of NO2,
mixed with N2O3. It dissolves in nitric acid, forming a dark yel-
low liquid, which is blue or green if N2O3 be also present. With
SOa it combines to form a solid, crystalline compound, which is-
sometimes produced in the manufacture of H2SO4. This sub-
stance, which forms the lead chamber crystals, is a substituted sul-
furous acid, nitrosulfonic acid, NO2SO2OH (see sulfonic acids).
A small quantity of H2O decomposes NOa into HNO3 and N2O3,
which latter colors it green or blue. A larger quantity of H2O
decomposes it into HNO3 and NO. By bases it is transformed
into a mixture of nitrite and nitrate : 2NO2 -f- 2KHO = KNO2 -(-
It is an energetic oxydant, for which it is largely used. With
certain organic substances it does not behave as an oxydant, but
becomes substituted as an univalent radical ; thus with benzene-
it forms nitro-benzene : CeHs (NO2).
Toxicology. — The brown fumes given off during many processes,
in which nitric acid is decomposed, are dangerous to life. AIL
such operations, when carried on on a small scale, as in the labor-
atory, should be conducted under a hood or some other arrange-
ment, by which the fumes are carried into the open air. When
108 MANUAL OF CHEMISTRY.
in industrial processes, the volume of gas formed becomes such
,as to be a nuisance when discharged into the air, it should be
utilized in the manufacture of H2SO4 or absorbed by HaO or an
alkaline solution.
An atmosphere contaminated with brown fumes is more dan-
gerous than one containing Cl, as the presence of the latter is
more immediately annoying. At first there is only coughing, and
it is only two to four hours later that a difficulty in breathing is
felt, death occurring in ten to fifteen hours. At the autopsy the
lungs are found to be extensively disorganized and filled with
black fluid.
Even air containing small quantities of brown fumes, if breathed
for a long time, produces chronic disease of the respiratory organs.
To prevent such accidents, thorough ventilation in locations
where brown fumes are liable to be formed is imperative. In
-cases of spilling nitric acid, safety is to be sought in retreat from
the apartment until the fumes have been replaced by pure air
from without.
Nitrogen Pentoxid. Nitric anhydrid — NaO5 — Molecular
weight— \Q^— Fuses at 30° (86° F.)— Boils at 47° (116°.6 F.).
Preparation. — (1.) By decomposing dry silver nitrate with dry
Ol in an apparatus entirely of glass: 4AgNO3+2Cl2 — 4AgCl-[-
3N2O6+O2.
(2. ) By removing water from fuming nitric acid with phosphorus
pentoxid : 6HNO3+P2O5=2HsPO4-t-3N!1O5.
Properties. — Prismatic crystals at temperatures above 30° (86°
P.). It is very unstable, being decomposed by a heat of 50° (122°
P.); on contact with H2O, with which it forms nitric acid; and
«ven spontaneously. Most substances which combine readily
with O, remove that element from N2OB.
Nitrogen Acids.— Three are known, either free or in combina-
tion, corresponding to the three oxids containing uneven num-
bers of O atoms :
N2O -f- H2O = H2N2O2 — Hyponitrous acid.
N2OS + H.O = 2HNOa— Nitrous acid.
N2O5 + HSO = 2HNO3— Nitric acid.
Hyponitrous acid — H2N2O2 — 31 — Known only in combination.
'Silver hyponitrite is formed by reduction of sodium nitrate by
nascent H and decomposition with silver nitrate.
Nitrous acid — HNO, — 47— has not been isolated, although its
•salts, the nitrites, are well-defined compounds : M'NO2 or M"(NOj)2.
The nitrites occur in nature, in small quantity, in natural
waters, where they result from the decomposition of nitrogenous
NITROGEIST.
organic substances ; also in saliva. They are produced by heat-
ing the corresponding nitrate, either alone or in the presence of
a readily oxidizable metal, such as lead. Solutions of the nitrites
are readily decomposed by the mineral acids, with evolution of
brown fumes. They take up oxygen readily and are hence used as
reducing agents. Solutions of potassium permanganate are in-
stantly decolorized by nitrites. A mixture of thin starch paste
and zinc iodid solution is colored blue by nitrites, which decom-
pose the iodid, liberating the iodiri. A solution of inetaphenylen-
diamin, in the presence of free acid, is colored brown by very
minute traces of a nitrite, the color being due to the formation
of triamido-azobenzene (Bismark brown).
Nitric Acid. Aquafortis — Hydrogen nitrate— Acidum nitri-
cum— U.S. ; Br.— HNO3— 68.
Preparation. — (1.) By the direct union of its constituent ele-
ments under the influence of electric discharges.
(2.) By the decomposition of an alkaline nitrate by strong
H2SO4. With moderate heat a portion of the acid is liberated.'
2NaNO3+H2SO4=NaHSO4+Na]SrO3-f-HNO3, and at ahigher tem-
perature the remainder is given off : NaNO3+NaHSO4=Na2SO4-i-
HNO3. This is the reaction used in the manufacture of HNO3.
Varieties. — Commercial — a yellowish liquid, impure, and of two
degrees of concentration: single aquafortis; sp. gr. about 1.25 =
39$ HNO3 ; and double aquafortis ; sp. gr. about 1.4=64$ HNO3.
Fuming — a reddish-yellow liquid, more or less free from impuri-
ties; charged with oxids of nitrogen. Sp. gr. about 1.5. Used as
an oxidizing agent. C. P. — a colorless liquid, sp. gr. 1.522, which
should respond favorably to the tests given below. Acidum ni-
tricum, IT. S.; Br. — a colorless acid, of sp. gr. 1.42=70$ HNO3.
Acidum nitricum dilutum, IT. S.; Br. — the last mentioned, diluted
with H2O to sp. gr. 1.059=10$ HNO3 (U. &), or to sp. gr. 1.101
=17.44$ HNOS (Br.).
Properties. — Physical. — The pure acid is a colorless liquid ; sp.
gr. 1.522; boils at 86° (186°.8 P.); solidifies at -40° (-40° P.); gives
off white fumes in damp air ; and has a strong acid taste and reac-
tion. The sp. gr. and boiling-point of dilute acids vary with the
concentration. If a strong acid be distilled, the boiling-point
gradually rises from 86° (186°.8 F.) until it reaches 123° (253°.4 P.),
when it remains constant, the sp. gr. of distilled and distillate
being 1.42=70$ HNO3. If a weak acid be taken originally the
boiling-point rises until it becomes stationary at the same point.
Chemical. — When exposed to air and light, or when strongly
heated, IfNOs is decomposed into NO2 ; H2O and O. Nitric acid
is a valuable oxydant; it converts I, P, S, C, B, and Si or their
110 MANUAL OF CHEMISTRY.
lower oxids into their highest oxids ; it oxidizes and destroys most
organic substances, although with some it forms products of sub-
stitution. Most of the metals dissolve in HNOs as nitrates, a
portion of the acid being at the same time decomposed into NO
and H2O : 4HNO3+ 3Ag=3AgNO3+NCH-2H2O. The chemical ac-
tivity of HNO3 is much reduced, or even almost arrested, when
the intervention of nitrous acid is prevented by the presence of
carbamid. The so-called " noble metals," gold and platinum, are
not dissolved by either HNO3 or HC1, but dissolve as chlorids in
a mixture of the two acids, called aqua regia. In this mixture
the two acids mutally decompose each other according to the
equations: HNO3+3HC1=2H2O+NOC1+C12 and 2HNO3+6HC1
=4H2O+2NOCl2-}-Cl2 with formation of nitrosyl eWorld, NOC1
and bichlorid, NOC12, and nascent Cl; the last named combin-
ing with the metal. Iron dissolves easily in dilute HNO3, but if
dipped into the concentrated acid, it is rendered passive, and
•does not dissolve when subsequently brought in contact with the
dilute acid. This passive condition is destroyed by a temper-
ature of 40° (104° F.) or by contact with Pt, Ag or Cu. "When
HNO3 is decomposed by zinc or iron, or in the porous cup of a
Grove battery, N2O3 and NO2 are formed, and dissolve in the
acid, which is colored dark yellow, blue or green. An acid so
charged is known as nitroso-nitric acid. Nitric acid is monobasic.
Impurities. — Oxids of Nitrogen render the acid yellow, and de-
colorize potassium permanganate when added to the dilute acid.
JSulfuric acid produces cloudiness when BaCla is added to the
acii, diluted with two volumes of H2O. Chlorin, iodin cause a
white ppt. with AgNOs. Iron gives a red color when the diluted
acid is treated with ammonium sulfocyanate. Salts leave a
fixed residue when the acid is evaporated to dryness on platinum.
Nitrates. — The nitrates of K and Na occur in nature. Nitrates
are formed by the action of HNO3 on the metals, or on their oxids
or carbonates. They have the composition M'NOs, M (NO3)a or
M'" (NO3)3, except certain basic salts, such as the sesquibasic
lead nitrate, Pb (NO3)2, 2PbO. With the exception of a few basic
salts, the nitrates are all soluble in water. When heated, they
fuse and act as powerful oxidants. They are decomposed by
H2SO4 with liberation of HNO8.
Analytical Characters. — (1.) Add an equal volume of concen-
trated H2SO4, cool, and float on the surface of the mixture a solu-
tion of FeSO4. The lower layer becomes gradually colored
brown, black or purple, beginning at the top.
(2.) Boil in a test-tube a small quantity of HC1, containing
•enough sulfindigotic acid to communicate a blue color, add the
suspected solution and boil again ; the color is discharged.
(3.) If acid, neutralize with KHO, evaporate to dryness, add to
NITROGEN. Ill
the residue a few drops of HaSO4 and a crystal of brucin (or some
sulfanilic acid) ; a red color is produced.
(4.) Add H2SO4 and Cu to the suspected liquid and boil, brown
fumes appear (best visible by looking into the mouth of the test-
tube).
(5.) A solution of diphenylamLn in concentrated H3SO4 (.01 grm.
in 100 c.c.) is colored blue by nitric acid A similar color is pro-
duced by other reducing agents.
(6.) To 0.5 c.c. nitrate solution add 1 drop aqueous solution of
resorcin (10#), and 1 drop HC1 (15#), and float on the surface of 2 c.c.
•concentrated H2SO4 ; a purple-red band.
Toxicology. — Although most of the nitrates are poisonous when
taken internally in sufficiently large doses, their action seems to
be due rather to the metal than to the acid radical. Nitric acid
itself is one of the most powerful of corrosives.
Any animal tissue with which the concentrated acid comes in
-contact is immediately disintegrated. A yellow stain, afterward
turning to dirty brownish, or, if the action be prolonged, an
-eschar, is formed. When taken internally, its action is the same
-as upon the skin, but, owing to the more immediately important
function of the parts, is followed by more serious results (unless a
large cutaneous surface be destroyed).
The symptoms following its ingestion are the same as those
produced by the other mineral acids, except that all parts with
which the acid has come in contact, including vomited shreds of
mucous membrane, are colored yellow. The treatment is the
same as that indicated when H2SO4 or HC1 have been taken; i.e.
neutralization of the corrosive by magnesia or soap.
Compounds of Nitrogen with the Halogens. — Nitrogen chlorid —
NC13 — 120.5 — is formed by the action of excess of Cl upon NH3 or
an ammoniacal compound. It is an oily, light yellow liquid; sp.
gr. 1.053; has been distilled at 71° (159°. 8 F.). When heated to 96°
(204\8 F.), when subjected to concussion, or when brought in con-
tact with phosphorus, alkalies or greasy matters it is decomposed,
with a violent explosion, into one volume N and three volumes Cl.
Nitrogen bromid — NBr3 — 254 — has been obtained, as a reddish-
brown, syrupy liquid, very volatile, and resembling the chlorid
in its properties, by the action of potassium bromid upon nitro-
gen chlorid.
Nitrogen iodid — NI3 — 395 — When iodin is brought in contact
•with ammonium hydroxid solution, a dark brown or black pow-
der, highly explosive when dried, is formed. This substance va-
ries in composition according to the conditions under which the
action occurs ; sometimes the iodid alone is formed ; under other
•circumstances it is mixed with compounds containing N, I andH.
MANUAL OF CHEMISTRY.
PHOSPHORUS.
Symbol=f — Atomic weight=Sl — Molecular weight=l24: — Sp.
gr. o/mpor=4.2904 A — Name from $<Jx;=light, <t>epu=Ibear — Din-
covered by Brandt in 1669 — Phosphorus (U. S.; Br.).
Occurrence. — Only in combination ; in the mineral and vegeta-
ble worlds as phosphates of Ca, Mg, Al, Pb, K, Na. In the ani-
mal kingdom as phosphates of Ca, Mg, K and Na, and in organic
combination.
Preparation. — From bone-ash, in which it occurs as tricalcic
phosphate. Three parts of bone-ash are digested with 2 parts of
strong HaSO4, diluted with 20 volumes H2O, when insoluble calcic
sulfate and the soluble monocalcic phosphate, or "superphos-
phate," are formed: Ca3(PO4)2+2H2SO4=H4Ca(PO4)2+2CaSO4.
The solution of superphosphate is filtered off and evaporated,
the residue is mixed with about one-fourth its weight of powdered
charcoal and sand, and the mixture heated, first to redness, finally
to a white heat, in earthenware retorts, whose beaks dip under
water in suitable receivers. During the first part of the heating
the monocalcic phosphate is converted into metaphosphate :
CaH4(POi)2=Ca(PO3)2+2H2O; which is in turn reduced by the
charcoal, with formation of carbon monoxid and liberation of
phosphorus, while the calcium is combined as silicate : 2Ca(PO3)2
+2SiO2+5C2 =2CaSiO3+10CO-fP4.
Another process consists in dissolving bone-ash or mineral phos-
phate in HNO3. K2SO4 is then added to the solution, and the
greater part of the Ca removed by filtration as CaSO4. Mercurous
phosphate is then formed by addition of mercurous nitrate to the
solution. The dried Hg salt is finally mixed with carbon, and
decomposed by heat, when Hg and P distil over.
The crude product is purified by fusion, first under a solution
of bleaching powder, next under ammoniacal H2O, and finally
underwater containing a small quantity of H2SO4 and potassium
dichromate. It is then strained through leather and cast into
sticks under warm H2O.
Properties. — Physical. — Phosphorus is capable of existing in
four allotropic forms :
(1.) Ordinary, or yellow variety, in which it usually occurs in
commerce. This is a yellowish, translucid stolid of the consistency
of wax. Below 0° (32° F.) it is brittle; it fuses at 44°.3 (111°.7 F.) ;
and boils at 290° (554° F.) in an atmosphere not capable of acting
upon it chemically. Its vapor is colorless; sp. gr.=4.5A — 65 H at
1040° (1940° F.). It volatilizes below its boiling-point, and H2O
boiled upon it gives off steam charged with its vapor. Exposed to
PHOSPHORUS. 113
air, it gives off white fumes, and produces ozone. It is luminous in
the dark. It is insoluble in H2O ; sparingly soluble in alcohol and
ethr^r ; soluble in carbon disulfid, and in the fixed and volatile
oils. It crystallizes on evaporation of its solutions in octahedrae
or dodecahedrse. Sp. gr. 1.83 at 10° (50° F.).
(2. ) White phosphorus is formed as a white, opaque pellicle upon
the surface of the ordinary variety, when this is exposed to light
under ae'rated H2O. Sp. gr. 1.515 at 15° (59° F.). When fused it
reproduces ordinary phosphorus without loss of weight.
(3.) Black 'variety is formed when ordinary phosphorus is heated
to 70° (158° F.) and suddenly cooled.
(4.) Red variety is produced from the ordinary by maintaining
it at from 240° (464° F.) to 280° (536° F.) for two or three days, in
an atmosphere of carbon dioxid ; and, after cooling, washing out
the unaltered yellow phosphorus with carbon disulfid. It is
also formed upon the surface of the yellow variety, when it is ex-
posed to direct sunlight.
It is a reddish, odorless, tasteless solid, which does not fume in
air, nor dissolve in the solvents of the yellow variety. Sp. gr. 2.1.
Heated to 500° (932° F.) with lead, in4:he absence of air, it dissolves
in the molten metal, from which it separates on cooling in violet-
black, rhombohedral crystals, of sp. gr. 2.34. If prepared at 250°
(482° F.) it fuses below that temperature, and at 260° (500° F.) is
transformed into the yellow variety, which distils. The crystal-
line product does not fuse. It is not luminous at ordinary tem-
peratures.
Chemical. — The most prominent property of P is the readiness
with which it combines with O. The yellow variety ignites and
burns with a bright flame if heated in air to 60° (140° F.), or if
exposed in a finely divided state to air at the ordinary tempera-
ture; with formation of P2O3; PaOB; H3PO3, or H3PO4, according
as O is present in excess or not, and according as the air is dry or
moist. The temperature of ignition of yellow P is so low that it
must be preserved under boiled water. By directing a current
of O upon it, P may be burned under H2O, heated above 45° (113°
F.). The red variety combines with O much less readily, and may
be kept in contact with air without danger.
The luminous appearance of yellow P is said to be due to the
formation of ozone. It does not occur in pure O at the ordinary
temperature, nor in air under pressure, nor in the absence of
moisture, nor in the presence of minute quantities of carbon
disulfid, oil of turpentine, alcohol, ether, naphtha, and many
gases.
Yellow phosphorus burns in Cl with formation of PC13 or PC15,
according as P or Cl is present in excess. Both yellow and red
varieties combine directly with Cl, Br, and I.
114 MANUAL OF CHEMISTRY.
Phosphorus is not acted on by HC1 or cold HSSO4, Hot H3SO4
oxidizes it with formation of phosphorous acid and sulfur dioxid :
P4+6HaSO4=4H3PO3+6SO2. Nitric acid oxidizes it violently to
phosphoric acid and nitrogen di- and tetr-oxids : 12HNO3+P4=
4H,PO«+8NO,+4NO.
Phosphorus is a reducing agent. When immersed in cupric
sulfate solution, it becomes covered with a coating of metallic
copper. In silver nitrate solution it produces a black deposit of
silver phosphid.
Toxicology. — The red variety differs from the other allotropic
forms of phosphorus in not being poisonous, probably owing to
its insolubility, and in being little liable to cause injury by burn-
ing.
The burns produced by yellow phosphorus are more serious
than a like destruction of cutaneous surface by other substances.
A burning fragment of P adheres tenaciously to the skin, into
which it burrows. One of the products of the combustion is
metaphosphoric acid (q. v.) which, being absorbed, gives rise to
true poisoning. Burns by P should be washed immediately with
dilute javelle water, liq. sod*e chlorinatse, or solution of chlorid
of lime. Yellow P should never be allowed to come in contact
with the skin, except it be under cold water.
Yellow P is one of the most insidious of poisons. It is taken or
administered usually as " ratsbane " or match-heads. The former
is frequently starch paste, charged with phosphorus ; the latter,
in the ordinary sulfur match, a mixture of potassium chlorate,
very fine sand, phosphorus, and a coloring matter. The symp-
toms in acute phosphorus-poisoning appear with greater or less
rapidity, according to the dose, and the presence or absence in the
stomach of substances which favor its absorption. Their appear-
ance may be delayed for days, but as a rule they appear within a
few hours. A disagreeable garlicky taste in the mouth, and heat
in the stomach are first observed, the latter gradually developing
into a burning pain, accompanied by vomiting of dark-colored
matter, which, when shaken in the dark, is phosphorescent ; low
temperature and dilatation of the pupils. In some cases, death
follows at this point suddenly, without the appearance of any
further marked symptoms. Usually, however, the patient rallies,
seems to be doing well, until, suddenly, jaundice makes its ap-
pearance, accompanied by retention of urine, and frequently de-
lirium, followed by coma and death.
There is no known chemical antidote to phosphorus. The
treatment is, therefore, limited to the removal of the unabsorbed
portions of the poison by the action of an emetic, zinc or copper
sulfate, or apomorphin, as expeditiously as possible, and the
administration of French oil of turpentine — the older the oil the
PHOSPHORUS.
115
better — as a physiological antidote. The use of fixed oils or fats
is to be avoided, as they favor the absorption of the poison, by
their solvent action. The prognosis is very unfavorable.
As commercial phosphorus is usually contaminated with arsenic,
the effects of the latter substance may also appear in poisoning
by the former.
Analysis. — When, after a death supposed to be caused by phos-
phorus, chemical evidence of the existence of the poison in the
body, etc., is desired, the investigation must be made as soon after
FIG. 28.
death as possible, for the reason that the element is rapidly oxi-
dized, and the detection of the higher stages of oxidation of phos-
phorus is of no value as evidence of the administration of the
element, because they are normal constituents of the body and of
the food.
The detection of elementary phosphorus in a systematic toxico-
logical analysis is connected with that of prussic acid, alcohol,
ether, chloroform, and other volatile poisons. The substances
under examination are diluted with H2O, acidulated with HoSCh,
and heated over a sand-bath in the flask a (Fig. 28). This flask
is connected with a CO2 generator, 5, whose stopcock is closed,
MANUAL OF CHEMISTKY.
and with a Liebig's condenser, c, which is in darkness (the opera-
tion is best conducted in a dark room), and so placed as to de-
liver the distillate into the flask d. The odor of the distillate is-
noted. In the presence of P it is usually alliaceous. The con-
denser is also observed. If, at the point of greatest condensation,
a faint, luminous ring be observed (in the absence of all reflec-
tions), it is proof positive of the presence of unoxidized phos-
phorus. The absence, however, of that poison is not to be in-
ferred from the absence of the luminous ring (see above). If this
fail to appear, when one-third the fluid contents of the flask a
have distilled over, the condenser is disconnected at e, and in its
place the absorbing apparatus, Fig. 29, partly filled with a neu-
FIG. 29.
FIG. 30.
tral solution of silver nitrate, is adjusted by a rubber tube at-
tached at g, and a slow and constant stream of CO2 is caused to
traverse the apparatus from &, Fig. 28. If, during continuation
of the distillation, no black deposit is formed in the silver solu-
tion, the absence of P may be inferred. If a black deposit be
formed, it must be further examined to determine if it be silver
phosphid. For this purpose the apparatus shown in Fig. 30 is
used. In the bottle a hydrogen is generated from pure Zri and
H2SO4, the gas passing through the drying-tube b, filled with
fragments of CaCl2, and out through the platinum tip at c ; d
and e are pinch-cocks. When the apparatus is filled with H, d is
closed until the funnel-tube / is three-quarters filled with the
liquid from a; then e is closed and d opened, and the black silver
deposit, which has been collected on a filter and washed, is
PHOSPHOKUS. 117
thrown into// e is then slightly opened and the escaping gas
ignited at c, the size of the flame being regulated by e. If the
deposit contain P, the flame will have a green color ; and, when
•examined with the spectroscope, will give the spectrum of bright
bands shown in Fig. 31.
Chronic phosphorus poisoning, or Lucifer disease, occurs
.among operatives engaged in the dipping, drying, and packing of
phosphorus matches. Those engaged in the manufacture of
phosphorus itself are not so affected. Sickly women and children
are most subject to it. The cause of the disease has been ascribed
to the presence of arsenic, and to the formation of oxids of phos-
phorus, and of ozone. The progress of the disorder is slow, and
its culminating manifestation is the destruction of one or both
maxillae by necrosis.
The frequency of the disease may be in some degree diminished
by thorough ventilation of the shops, by frequent washing of the
face and mouth with a weak solution of sodium carbonate, and
FIG. 31.
by exposing oil of turpentine in saucers in the workshops. None
of these methods, however, effect a perfect prevention, which
can only be attained by the substitution of the red variety of
phosphorus for the yellow in this industry.
Hydrogen Phosphids. — Gaseous hydrogen phosphid— Phosphin
— Phosphonia, Phosphamin, PH3— 34 — A colorless gas, having a
strong alliaceous odor, which is obtained pure by decomposing
phosphonium iodid, PH4I, with H2O. Mixed with H and vapor
of PaH4, it is produced, as a spontaneously inflammable gas, by the
action of hot, concentrated solution of potassium hydroxid on P,
or by decomposition of calcium phosphid by H2O. It is highly
poisonous. After death, the blood is found to be of a dark violet
«olor, and to have, in a great measure, lost its power of absorbing
oxygen.
Liquid hydrogen phosphid — P2H4 — 66 — is the substance whose
vapor communicates to PH3 its property of igniting on contact
with air. It is separated by passing the spontaneously inflam-
mable PH3 through a bulb tube, surrounded by a freezing mix-
ture.
118 MANUAL OF CHEMISTRY.
It is a colorless, heavy liquid, which is decomposed by exposure
to sunlight, or to a temperature of 30° (86° F.).
Solid hydrogen phosphid — P4H2 — 126 — is a yellow solid, formed
when P2H4 is decomposed by sunlight. It is not phosphorescent
and only ignites at 160° (320° P.).
Oxids of Phosphorus. — Two are known: P2O3 and P2O6.
Phosphorus trioxid — Phosphorous arihydrid, Phosphorous oxid
— P2O3 — 110 — is formed when P is burned in a very limited supply
of perfectly dry air, or O. It is a white, flocculent solid, which,
on exposure to air, ignites by the heat developed by its union
with HuO to form phosphorous acid.
Phosphorus pentoxid — Phosphoric anhydrid, Phosphoric oxid-
— P2O5 — 142 — is formed when P is burned in an excess of dry O.
It is a white, flocculent solid, which has almost as great a ten-
dency to combine with H2O as has P2O3. It absorbs moisture
rapidly, deliquescing to a highly acid liquid, containing, not
phosphoric, but metaphosphoric acid. It is used as a drying
agent.
Phosphorous acids. — Five oxyacids of phosphorus are known :
/O— H
Hypophosphorous acid : O=P — H
\H
/O— H
Phosphorous acid : O=P — O — H
\H
/O— H
Phosphoric acid : O=P— O— H
\0— H
/O— H
O=P— O— H
Pyrophosphoric acid : ^O
O=P— O— H
\O— H
/O— H
Metaphosphoric acid : O=P=O
Only those H atoms which are connected with the P atoms:
through O atoms are basic. Hence H3PO2 is monobasic; H3POa
is dibasic; H3PO4 is tribasic; H4P2C>7 is tetrabasic, and HPO3 is
monobasic.
Hypophosphorous acid — H3POi, — G6 — is a crystalline solid, or,
PHOSPHORUS. 119
more usually, a strongly acid, colorless syrup. It is oxidized by
air to a mixture of H3PO3 and H3PO4.
The hypophosphites as well as the free acid, are powerful re-
ducing agents.
Phosphorous acid — H3PO3 — 82 — is formed by decomposition of
phosphorous trichlorid by water: PC13+3H2O=H3PO3+3HC1. It
is a highly acid syrup, is decomposed by heat, and is a strong re-
ducing agent.
Phosphoric acid — Orthophosphoric acid — Common, or tribasic,
phosphoric acid — Acidum phosphoricuxn, U. S.; Br.— H3PO4 — 98 —
does not occur free in nature, but is widely disseminated in com-
bination, in the phosphates, in the three kingdoms of nature.
It is prepared : (1) By converting bone phosphate, Ca3(PO4)2,
into the corresponding lead or barium salt, Pb3(PO4)2 or Ba3(PO4):i,
and decomposing the former by H2S, or the latter by H2SO4. (2)
By oxidizing P by dilute HNO3, aided by heat. The operation
should be conducted with caution, and heat gradually applied by
the sand-bath. It is best to use red phosphorus. This is the
process directed by the U. S. and Br. Pharm.
The concentrated acid is a colorless, transparent, syrupy liquid ;
still containing HaO, which it gives off on exposure over H2SO4,
leaving the pure acid, in transparent, deliquescent, prismatic
crystals. It is decomposed by heat to form, first, pyrophosphoric
acid, then uietaphosphoric acid. It is tribasic.
If made from arsenical phosphorus, and commercial phosphorus
is usually arsenical, it is contaminated with arsenic acid, whose
presence may be recognized by Marsh's test (q. v.). The acid
should not respond to the indigo and ferrous sulfate tests for
HN03.
Phosphates. — Phosphoric acid being tribasic the phosphates
have the composition MH2PO4 ; M'2HPO4; M'3PO4; M^H^PO^;
M',(HPO4)a; H"3(PO4),; M"M'PO4 ; and M"TO4. The monometallic
salts are all soluble and are strongly acid. Of the dimetallic salts,
those of the alkali metals only are soluble and their solutions
are faintly alkaline ; the others are unstable, and exhibit a marked
tendency to transformation into monometallic or trimetallic salts.
The normal phosphates of the alkali metals are the only soluble
trimetallic phosphates. Their solutions are strongly akaline, and
they are decomposed even by weak acids :
NasPO4 + COaH, = HNaaPO4 + HNaCO3
Trisodic Carbonic Disodic Monosodic
phosphate. acid. phosphate. carbonate.
All the monometallic phosphates, except those of the alkali
metals, are decomposed by ammonium hydroxid, with precipita-
tion of the corresponding trimetallic salt.
120 MANUAL OF CHEMISTRY.
Analytical Characters. — (1) With ammoniacal solution of silver
nitrate, a yellow precipitate. (2) With solution of ammonium
molybdate in HNO3, a yellow precipitate. (3) With magnesia
mixture,* a white, crystalline precipitate, soluble in acids, insolu-
ble in ammonium hydroxid.
Pyrophosphoric acid— H4P2O7 — 178. — When phosphoric acid
(or hydro-disodic phosphate) is maintained at 213° (415°. 4 F.),
two of its molecules unite, with the loss of the elements of a
molecule of water: 2H3PO4 = H4P2O7+H2O, to form pyrophos-
phoric acid.
Metaphosphoric acid — Glacial phosphoric acid — HPO3 — 80 — is
formed by heating H3PO4 or H4P2O7 to near redness: H3PO4=
HPO3-fH2O; or H4P2C>7=2HPO3-}-H2O. It is usually obtained
from bone phosphate; this is first converted into ammonium
phosphate, which is then subjected to a red heat.
It is a white, glassy, transparent solid, odorless, and acid in
taste and reaction. Slowly deliquescent in air, it is very soluble
in H2O, although the solution takes place slowly, and is accom-
panied by a peculiar crackling sound. In constitution and basic-
ity it resembles HNO3.
The metaphosphates are capable of existing in five polymeric
modifications (see polymerism) : Mono- di- tri- tetra- and hexmeta-
phosphates : M'PO3 ; M'2(PO3)2 and M"(PO3)2 ; M'3(PO3)3 ; M'4(PO3)4
and M"2(PO3)4 ; and M'6(PO3)6.
Action of the Phosphates on the Economy. — The salts of phos-
phoric acid are important constituents of animal tissues, and
give rise, when taken internally, in reasonable doses, to no un-
toward symptoms. The acid itself may act deleteriously, by vir-
tue of its acid reaction. Meta- and pyro-phosphoric acids, even
when taken in the form of neutral salts, have a distinct action
(the pyro being the more active) upon the motor ganglia of the
heart, producing diminution of the blood-pressure, and, in com-
paratively small doses, death from cessation of the heart's action.
Compounds of Phosphorus with the Halogens. — Phosphorus tri-
chlorid — PC13 — 137.5 — is obtained by heating P in a limited supply
of Cl. It is a colorless liquid; sp. gr. 1.61 ; has an irritating odor;
fumes in air; boils at 76° (169° F.). Water decomposes it with
formation of H3PO3 and HC1.
Phosphorus pentachlorid — PC1B — 208.5 — is formed when P is
burnt in excess of Cl. It is a light yellow, crystalline solid : gives
off irritating fumes; and is decomposed by H2O.
Phosphorus oxychlorid — POC13 — 153.5 — is formed by the ac-
* Made by dissolving 11 pts. crystallized magnesium chlorid and 28 pts. ammo-
nium chlorid in 130 pts. water, adding 70 pts. dilute ammonium hydroxid and filter-
ing after two days.
ARSENIC. 121
iion of a limited quantity of H2O on the pentachlorid : PC15+
H2O=POC13+2HC1. It is a colorless liquid; sp. gr. 1.7; boils at
110' (230: F.); and solidifies at -10° (+14° F.).
With bromin P forms compounds similar in composition and
properties to the chlorin compounds. With iodin it forms two
compounds, P2I4 and PI3. With fluorin it forms two compounds,
PF3 and PF5) the former liquid, the second gaseous.
ARSENIC.
Symbol=Aa — Atomic weight=75 — Molecular weight=3QQ — Sp.
gr. of solid=5.75 ; of vapor=10.6A at 860° (1580° F.}— Name from
Occurrence. — Free in small quantity ; in combination as ar-
.senids of Fe, Co, and Ni, but most abundantly in the sulfids,
orpiment and realgar, and in arsenical iron pyrites or mispickel.
Preparation. — (1.) By heating mispickel in clay cylinders, which
communicate with sheet iron condensing tubes.
(2.) By heating a mixture of arsenic trioxid and charcoal; and
purifying the product by resublimation.
Properties. — Physical. — A brittle, crystalline, steel gray solid,
having a metallic lustre, or a dull, black, amorphous powder. At
the ordinary pressure, and without contact of air, it volatilizes
without fusion at ISO3 (356° F.); under strong pressure it fuses at
a dull red heat. Its vapor is yellowish, and has the odor of gar-
lic. It is insoluble in H2O and in other liquids unless chemically
altered.
Chemical. — Heated in air it is converted into the trioxid and
ignites somewhat below a red heat. In O it burns with a bril-
liant, bluish-white light. In dry air it is not altered, but in the
presence of moisture its surface becomes tarnished by oxidation.
In H2O it is slowly oxidized, a portion of the oxid dissolving in
the water. It combines readily with Cl. Br, I, and S, and with
most of the metals. With H it only combines when that element
is in the nascent state. Warm, concentrated H2SO4 is decom-
posed by As, with formation of SO2, As2O3, and H2O. Nitric acid
is readily decomposed, giving up its O to the formation of arsenic
acid. With hot HC1, arsenic trichlorid is formed. When fused
ivith potassium hydroxid, arsenic is oxidized, H is given off, and
a mixture of potassium arsenite and arsenid remains, which by
greater heat is converted into arsenic, which volatilizes, and po-
tassium arsenate. which remains.
Elementary arsenic enters into the composition of fly poison
and of shot, and is used in the manufacture of certain pigments
and fire-works.
122 MANUAL OF CHEMISTRY.
Compounds of Arsenic and Hydrogen. — Two are known : the
solid As2H (?), and the gaseous, AsHa.
Hydrogen arsenid — Arsin—Arseniuretted or arsenetted hydro-
gen=Arsenia — Arsenamin — AsHs— Molecular weight=r!8 — Sp.gr.
=2.695 A— Liquefies at -40° ( -40° F.).
Formation.— (1.) By the action of H2O upon an alloy, obtained
by fusing together native sulfid of antimony, 2 pts.; cream of
tartar, 2 pts. ; arid arsenic trioxid, 1 pt.
(2.) By the action of dilute HC1 or H2SO4 upon the arsenids of
Zn and Sn.
(3.) Whenever a reducible compound of arsenic is in presence-
of nascent hydrogen. (See Marsh test.)
(4.) By the action of H2O upon the arsenids of the alkali
metals.
(5.) By the combined action of air, moisture and organic mat-
.ter upon arsenical pigments.
(6.) By the action of hot solution of potassium hydroxid upon
reducible compounds of As in the presence of zinc.
Properties. — Physical. — A colorless gas; having a strong allia-
ceous odor; soluble in 5 vols. of H2O, free from air.
Chemical. — It is neutral in reaction. In contact with air and
moisture its H is slowly removed by oxidation, and elementary
As deposited. It is also decomposed into its elements by the pas-
sage through it of luminous electric discharges ; and when sub-
jected to a red heat. It is acted on by dry O at ordinary temper-
atures with the formation of a black deposit which is at first
solid hydrogen arsenid, later elementary As. A mixture of AsH3
and O, containing 3 vols. O and 2 vols. AsH3, explodes when
heated, forming As2O3 and HaO. If the proportion of O be less, ele-
mentary As is deposited.
The gas burns with a greenish flame, from which a white cloud
of arsenic trioxid arises. A cold surface, held above the flame,
becomes coated with a white, crystalline deposit of the oxid. If
the flame be cooled, by the introduction of a cold surface into it,
the H alone is oxidized, and elementary As is deposited. Chloriii
decomposes the gas explosively, with formation of HC1 and ar-
senic trioxid. Bromin and iodin behave similarly, but with less
violence.
All oxidizing agents decompose it readily ; H3O and arsenic tri-
oxid being formed by the less active oxidants, and H2O and ar-
senic acid by the more active. Solid potassium hydroxid decom-
poses the gas partially, and becomes coated with a dark deposit,
which seems to be elementary arsenic. Solution of the alkaline
hydroxids absorb and decompose it; H is given off and an alkaline
AKSENIC.
arsenite remains in the solution. Many metals, when heated in
H3As, decompose it with formation of a metallic arsenid and lib-
eration of hydrogen. Solution of silver nitrate is reduced by it;
elementary silver is deposited, and the solution contains silver
arsenite.
Although H2S and H3As decompose each other to a great ex-
tent, with formation of arsenic trisulfld, in the presence of air,
the two gases do not act upon each other at the ordinary temper-
ature, even in the direct sunlight, either dry or in the presence of
HaO, when air is absent. Hence in making HaS for use in toxico-
logical analysis, materials free from As must be used; or the HaS
must be purified as described on p. 92.
Compounds of Arsenic and Oxygen. — Two are known : AsaO»
and AsuOs.
Probably the gray substance formed by the action of moist air
on elementary arsenic is a lower oxid.
Arsenic trioxid — Arsenious anhydrid — Arsenious oxid — White
arsenic — Arsenic — Arsenious acid — Acidum arseniosum, TJ. S. ;
Br.— As3O3— 198.
Preparation. — (1.) By roasting the native sulfids of arsenic in a
current of air.
(2.) By burning arsenic in air or oxygen.
Properties.— Physical.— It occurs in two distinct forms: crys-
tallized or "powdered," and vitreous or porcelainous. When,
freshly fused, it appears in colorless or faintly yellow, trans-
lucent, vitreous masses, having no visible crystalline structure.
Shortly, however, these masses become opaque upon the surface,
and present the appearance of porcelain. This change, which is.
due to the substance assuming the crystalline form, slowly pro-
gresses toward the centre of the mass, which, however, remains-
vitreous for a long time. The change is attended by the slow
liberation of heat, and, if it be made to take place more rapidly,
a faint light is visible in obscurity. When arsenic trioxid is sub-
limed, if the vapors be condensed upon a cool surface, it is de-
posited in the form of brilliant octahedral crystals, which are
larger and more perfect the nearer the temperature of the con-
densing surface is to 180° (356° F.). The crystalline variety may
be converted into the vitreous, by keeping it for some time at a
temperature near its point of volatilization.
The taste of arsenic trioxid in solution is at first faintly sweet,,
afterward very slightly metallic. The solid is almost tasteless.
It is odorless. In aqueous solution (see below) it has a faintly
acid reaction. The sp. gr. of the vitreous variety is 3.785; that
of the crystalline, 3.689.
124
MANUAL OF CHEMISTRY.
Its solubility in water varies with the temperature, the method
of making the solution, the presence of foreign substances and
the nature of the oxid :
Transparent
Form.
Opaque Form.
Fresh Crystal-
line Oxid.
1,000 parts of cold distilled
water, after standing 24
hours dissolved
1 74 parts
1,000 parts of boilingwater
poured on the oxid, and
allowed to stand for 24
hours, dissolved
10.12 parts.
5 4 parts
15.0 parts.
1.000 parts of water boiled
for one hour, the quan-
tity being kept uniform
by the addition of boil-
ing water from time to
time, and filtered imme-
diately, dissolved
64.5 parts.
76 5 parts
87.0 parts.
The vitreous variety is more soluble than the crystalline, but,
by prolonged boiling, the crystalline is converted into the vitre-
ous, or, at all events, the solubility of the two forms becomes the
same. The solution of the crystallized oxid in cold H2O is always
very slow (the vitreous oxid dissolves more rapidly), and contin-
ues for a long time. If white arsenic be thrown upon cold H2O,
only a portion of it sinks, the remainder floating upon the sur-
face, notwithstanding its high specific gravity. This is due to
a repulsion of the H2O from the surfaces of the crystals, which
also accounts, to some extent at least, for its slow solution. Even
after several days, cold H2O does not dissolve all the oxid with
which it is in contact. If one part of oxid be digested with 80
parts of H2O, at ordinary temperatures for several days, the re-
sulting solution contains^; with 160 parts H2O, T^7; with 240
parts, TJ^; with 1,000 parts H2O, y^ff! and even, when 16,000 or
100,000 parts of H2O are used, a portion of the oxid remains un-
dissolved. Arsenious oxid, which had remained in contact with
cold H2O in closed vessels for eighteen years, dissolved to the ex-
tent of 1 part in 54 of H2O, or 18.5 parts in 1,000, which may be
given as the maximum solubility of the crystallized oxid in cold
water. The power of H2O of holding the acid in solution, once
it is dissolved, is not the same as its power of dissolving it. If a
•concentrated solution be made, by boiling HaO upon the oxid,
and filtering hot, the filtrate may be evaporated to one-half its
original bulk, without depositing any of the acid, of which this
concentrated fluid now contains as much as one part in six of
ARSENIC. 125
H2O, or 166.6 parts per 1,000. If a hot solution of the acid be al-
lowed to cool, the solution will contain 62.5 parts per 1,000 at 16°
(60°.8 F.), and 50 parts per 1,000 at 7° (44°. 6 R).
The solubility of the o"xid in alcohol varies with the strength of
the spirit, and the nature of the oxid, the vitreous variety being
more soluble in strong than in weak alcohol, while the contrary
is the case with the crystalline, as is shown in the following table :
. .. , Alcohol Alcohol Alcohol Absolute
1,000 parts dissolve at 56*. at 79*. at 86*. alcohol.
n f IT ^ • •, (At 15° (59° F.) 16.80 14.30 7.15 0.25
oxm] At the boiling-point 48.95 45.51 31.97 34.02
Vitreous oxid at 15° (59° F.) 5.04 5.40 10.60
The presence of the mineral acids and alkalies, ammonia and
ammoniacal salts, alkaline carbonates, tartaric acid, and the tar-
trates, increases the solubility of arsenic trioxid in water. It is
less soluble in fluids containing fats, or extractive or other or-
ganic matters (the various liquid articles of food), than it is in
pure water.
In chemico-legal cases, in which the question of the solubility
of arsenic is likely to arise, it must not be forgotten that the
quantity of AsaOs which a person may unconsciously take in a
given quantity of fluid is not limited, under certain circumstances,
to that which the fluid is capable of dissolving. A much greater
quantity than this may be taken, while in suspension in the
liquid, especially if it be mucilaginous.
CHEMICAL. — Its solutions are acid in reaction, and probably
contain the true arsenious acid, H3AsO3. They are neutralized
by bases, with formation of arsenites. Solutions of sodium or
potassium hydroxid dissolve it, with formation of the correspond-
ing arsenite. It is readily reduced, with separation of As, when
lieated with hydrogen, carbon, or potassium cyanid, and at lower
temperatures by more active reducing agents. Oxidizing agents,
such as HNOs, the hydrates of chlorin, chromic acid, convert it
into arsenic pentoxid or arsenic acid. Its solution, acidulated
with HC1 and boiled in presence of copper, deposits on the metal
a gray film, composed of an alloy of Cu and As.
Arsenic pentoxid — Arsenic anhydrid — Arsenic oxid — As:0. —
230 — is obtained by heating arsenic acid to redness. It is a white,
amorphous solid, which, when exposed to the air, slowly absorbs
moisture. It is fusible at a dull red heat, and at a slightly higher
temperature decomposes to As2O3 and O. It dissolves slowly in
H2O, forming arsenic acid, H3AsO4.
Arsenic Acids. — The oxyacids of arsenic form a series, corre-
sponding to that of the oxyacids of phosphorus, except that the
hypoarsenious acid is unknown
126 MANUAL OF CHEMISTRY.
/O— H
/O— H O=As— O— H
Arseniousacid: O=As — O — H Pyroarsenic acid : ^O
XH 0=As— O— H
/O-H X°-H
Arsenic acid : O=As — O — H /O jj
^0 H Metarsenic acid : O=As=O
Arsenious Acid — H3AsO3 — 126 — exists in aqueous solutions of the
trioxid, although it has not been separated. Corresponding to
it are important salts, called arsenites, which have the general
formulae HM'2AsO3, HM"AsO3, H4M"(AsO3)2.
Arsenic Acid — Orthoarsenic acid — H3AsO4 — 142 — is obtained
by oxidizing As2O3 with HNO3 in the presence of H2O : As2O3-f-
2H2O-f2HN03=2H3AsO4+N2O3. A similar oxidation is also ef-
fected by Cl, aqua regia, and other oxidants.
A syrupy, colorless, strongly acid solution is thus obtained,
which, at 15° (59° P.) becomes semi-solid, from the formation of
transparent crystals, containing 1 Aq. These crystals, which are
very soluble and deliquescent, lose their Aq. at 100° (212° P.), and
form a white, pasty mass composed of minute white, anhydrous
needles. At higher temperatures it is converted into H4As2O7,
HAsOs, and As2O5. In presence of nascent H it is decomposed
into H2O and AsH3. It is reducible to H3AsO3 by SO2.
The action of H2S upon acid solutions of arsenic acid, or of the
arsenates, varies with the rapidity of the action, and the temper-
ature at which it occurs. With a slow current of H2S, at a low
temperature, no precipitate is formed, and the solution remains
colorless, under these conditions sulfoxyarsenic acid, H3AsO3S is
formed : H3AsO4 + H2S = H3 AsSO3 + H2O. By a further action
of H2S, arsenic pentasulfid is formed : 2H3AsO3S + 3H2S = As2S5
+ 6HSO. If the current of H2S be very slow, the sulfoxyarsenic
acid produced is decomposed according to the equation: 2H3AsO3S
=As2O3+3H2O+S2 and the precipitate then produced consists of
a mixture of As2S3, As2S6 and S.
Like phosphoric acid, arsenic acid is tribasic ; and the arsenates
resemble the phosphates in composition, and in many of their
chemical and physical properties.
Pyroarsenic acid— H4As2O7— 260.— Arsenic acid, when heated
to 160° (320° P.), is converted into compact masses of pyroarsenic
acid: 2H3AsO4=H4As2O7-fH2O. It is very prone to revert to ar-
senic acid, by taking up water.
Metarsenic acid— HAsO3— 124.— At 200°-206° (392°-403° P.) H4
As2O7 gradually loses HSO to form metarsenic acid: H4As2O7=
2HAsO3-f H2O. It forms white, pearly crystals, which dissolve
readily in H2O, with regeneration of H3AsO4. It is monobasic.
ARSENIC. 127
Compounds of Arsenic and Sulfur. — Arsenic disulfid — Red sul-
Jid of arsenic — Realgar — Red orpiment — Ruby sulfur — Sandarach
— AsiS- — 214 — occurs in nature, in translucent, ruby-red crystals.
It is also prepared by heating a mixture of As2O3 and S. As so
obtained it appears in brick-red masses.
It is fusible, insoluble in H»O, but soluble in solutions of the
alkaline sulfids, and in boiling solution of potassium hydroxid.
Arsenic trisulfid — Orpiment — Auripigmentum — Yellow sulfld
of arsenic — King's yellow — As.S — 246 — occurs in nature in bril-
liant golden yellow flakes. Obtained by passing H2S through an
acid solution of As-jOs; or by heating a mixture of As and S, or
•of As2O3 and S in equivalent proportions.
When formed by precipitation, it is a lemon-yellow powder, or
in orange-yellow, crystalline masses, when prepared by sublima-
tion. Almost insoluble in cold H2O, but sufficiently soluble in
hot H2O to communicate to it a distinct yellow color. By con-
tinued boiling with H2O it is decomposed into H2S and As2O3.
Insoluble in dilute HC1; but readily soluble in solutions of the
alkaline hydroxids, carbonates, and sulfids. It volatilizes when
heated.
Nitric acid oxidizes it, forming H3AsO4 and H2SC>4. A mixture
of HC1 and potassium chlorate has the, same effect. It corre-
sponds in constitution to As2O3, and, like it, may be regarded as
an anhydrid, for, although sulfarsenious acid, H3AsS3, has not
been separated, the sulfarsenites, pyro- and meta-sulfarsenites
are well-characterized compounds.
Arsenic pentasulfid — As2S5 — 310 — is formed by fusing a mixture
of As2S3 and S in proper proportions, and, by the prolonged
action of H2S, at low temperatures, upon solutions of the arsen-
ates.
It is a yellow, fusible solid, capable of sublimation in absence
of air. There exist well-defined sulfarsenates, pyro- and meta-
sulfarsenates.
Compounds of Arsenic with the Halogens. — Arsenic trifluorid —
AsF3— 132.— A colorless, fuming liquid, boiling at 63° (145° F.), ob-
tained by distilling a mixture of As2O3, H2SO4 and fluorspar. It
attacks glass.
Arsenic trichlorid— AsCl3— 181.5.— Obtained by distilling a mix-
ture of AsaOs, H2SO4 and NaCl, using a well-cooled receiver.
It is a colorless liquid, boils at 134° (273° P.), fumes when ex-
posed to the fair, and volatilizes readily at temperatures below its
boiling-point. Its formation must be avoided in processes for
the chemico-legal detection of arsenic, lest it be volatilized and
lost. It is formed by the action of HC1, even when compara-
tively dilute, upon As2O3at the temperature of the water-bath;
128 MANUAL OF CHEMISTRY.
but, if potassium chlorate be added, the trioxid is oxidized to-
arsenic acid, and the formation of the chlorid thus prevented.
Arsenic trioxid, when fused with sodium nitrate, is converted into
sodium arsenate, which is not volatile. If, however, small quan-
tities of chlorids be present, AsCl3 is formed. It is highly poi-
sonous.
Arsenic tribromid— AsBr3 — 315. — Obtained by adding pow-
dered As to Br, and distilling the product at 220° (428° F.). A
solid, colorless, crystalline body, fuses at 20°-2r>° (68°-77° F.), boils
at 220° (428° F.), and is decomposed by HaO.
Arsenic triiodid— Arsenii iodidum, TJ. S.— AsI3— 456. — Formed
by adding As to a solution of I in carbon disulfid; or by fusing
together As and I in proper proportions. A brick-red solid, fusi-
ble and volatile. Soluble in a large quantity of H2O. Decom-
posed by a small quantity of H3O into HI, As2Os, H2O and a resi-
due of AsI3.
Action of Arsenical Compounds upon the Animal Economy.
The poisonous nature of many of the arsenical compounds has
been known from remote antiquity, and it is probable that more
murders have been corurnitted by their use than by that of all
other toxic substances combined. Even at the present time —
notwithstanding the fact that, suspicion once aroused, the detec-
tion of arsenic in the dead body is certain and comparatively
easy — criminal arsenical poisoning is still quite common, espe-
cially in rural districts.
The poison is usually taken by the mouth, but it has also been
introduced by other channels; the skin, either uninjured or
abraded; the rectum, vagina and male urethra. The forms in
which it has been taken are : (1.) Elementary arsenic, which is not
poisonous so long as it remains such. In contact with water, or
with the saliva, however, it is converted into an oxid, which is
then dissolved, and, being capable of absorption, produces the
characteristic effects of the arsenical compounds. Certain fly-
papers and fly-poisons contain As, a portion of which has been
oxidized by the action of air and moisture. (2.) Hydrogen ar-
senid, the most actively poisonous of the inorganic compounds of
arsenic, has been the cause of several accidental deaths, among
others, that of the chemist Gehlen, who died in consequence of
having inhaled the gas while experimenting with it. In other
cases death has followed the inhalation of hydrogen, made from
zinc and sulfuric acid contaminated with arsenic. (3.) Arsenic
trioxid is the compound most frequently used by criminals. It
lias been given by every channel of entrance to the circulation;
in some instances concealed with great art, in others merely held
ARSENIC. 129
in suspension by stirring in a transparent fluid, given to an in-
toxicated person. If the poison have been in quantity, and un-
dissolved, it may be found in the stomach after death, in the form
of eight-sided crystals,. more or less worn by the action of the sol-
vents with which it has come in contact.
The lethal dose is variable, death having occurred from two and
one-half grains, and recovery having followed the taking of a
dose of two ounces. It is more active when taken fasting than
when taken on a full stomach, in which latter case all, or nearly
all, the poison is frequently expelled by vomiting, before there
has been tune for the absorption of more than a small quantity.
(4.) Potassium arsenite, the active substance in " Fowler's solu-
tion," although largely used by the laity in malarial districts as
an ague-cure, has, so far as the records show, produced but few
cases of fatal poisoning. (5.) Sodium arsenite is sometimes used
to clean metal vessels, a practice whose natural results are exem-
plified in the death of an individual who drank beer from a pew-
ter mug so cleaned ; and in the serious illness of 340 children in
an English institution, in which this material had been used for
cleaning the water-boiler. (6.) Arsenic acid and arsenates. — Tne
acid itself has, so far as we know, been directly fatal to no one.
The cases of death and illness, however, which have been put to
the account of the red anilin dyes, are not due to them directly,
but to arsenical residues remaining in them as the result of de-
fective processes of manufacture. (7.) Sulfids of arsenic. — Poison-
ing by these is generally due to the use of orpiment, introduced
into articles of food as a coloring matter, by a combination of
fraud and stupidity, in mistake for turmeric. (8.) The arsenical
greens. — Scheele's green, or cupric arsenite, and Schweinfurth
green, or cupric aceto-metarsenite (the latter commonly known
in the United States as Paris green, a name applied in Europe to
one of the anilin pigments). These substances, although rarely
administered with murderous intent, have been the cause of death
in a great number of cases. Among suicides in the lower orders
of the population in large cities, Paris green has been the favorite.
The arsenical pigments may also produce disastrous results by
" accident ; " by being incorporated in ornamental pieces of con-
fectionery; by being used in the dyeing of textile fabrics, from
which they may be easily rubbed off ; from their use for the de-
struction of insects, and by being used in the manufacture of
wall-paper. Many instances of chronic or subacute arsenical poi-
soning have resulted from inhabiting rooms hung with paper
whose whites, reds, or greens were produced by arsenical pig-
ments. From such paper the poison is disseminated in the at-
mosphere of the room in two ways : either as an impalpable pow-
der, mechanically detached from the paper and floating in the
130 MANUAL OF CHEMISTRY.
air, or by their decomposition, and the consequent diffusion of
volatile arsenical compounds in the air.
The treatment in acute arsenical poisoning is the same, whatever
may be the form in which the poison has been taken, if it have
been taken by the mouth. The first indication is the removal of
any unabsorbed poison from the alimentary canal. If vomiting
have not occurred from the effects of the toxic, it should be in
duced by the administration of zinc sulfate, or by mechanical
means. The stomach-pump should not be used unless the case i»
seen soon after the taking of the poison. When the stomach has
been emptied, the chemical antidote is to be administered, with
a view to the transformation, in the stomach, of any remaining
arsenical compound into the insoluble, and therefore innocuous,
ferrous arsenate. To prepare the antidote, a solution of ferric
sulfate, Liq. ferri tersulphatis (U. S.)=Liq. ferri persulphatis
(Br.) is diluted with three volumes of water, and treated with
aqua aminonise in slight excess. The precipitate formed is col-
lected upon a muslin filter, and washed with water until the
washings are nearly tasteless. The contents of the filter — Ferri
oxidum hydratum (U. S.), Ferri peroxidum humidum (Br.) are to
be given moist, in repeated doses of one to two teaspoonfuls,
until an amount of the hydrate equal to 20 times the weight of
white arsenic taken has been administered. Dialyzed iron may
be given while the hydrate is in preparation, or when the mate-
rials for its preparation are not obtainable.
Precautions to be taken by the Physician in cases of suspected
Poisoning.
It will rarely happen that in a case of suspected homicidal poi-
soning by arsenic, or by other poisons, the physician in charge
will be willing or competent to conduct the chemical analysis,
upon which, probably, the conviction or acquittal of the accused
will mainly depend. Upon his knowledge and care, however,
the success or futility of the chemist's labors depends in a great
measure.
It is, as a rule, the physician who first suspects foul play; and,
while it is undoubtedly his duty to avoid any public manifesta-
tion of his suspicion, it is as certainly his duty toward his patient
and toward the community, to satisfy himself as to the truth or
falsity of his suspicion by the application of a simple test to the
excreta of the patient during life, the result of which may enable
him to prevent a crime, or, failing that, take the first step toward
the punishment of the criminal.
In a case in which, from the symptoms, the physician suspects
poisoning by any substance, he should himself test the urine or
AESE1STIC. 131
faeces, or both, and govern his treatment and his actions toward
the patient, and those surrounding the patient, by the results of
his examination. Should the case terminate fatally, he should at
once communicate his suspicions to the prosecuting officer, and
require a post-mortem investigation, which should, if at all pos-
sible, be conducted in the presence of the chemist who is to con-
duct the analysis. For, be the physician as skilled as he may,
there are odors and appearances, observable in many cases at the
opening of the body, full of meaning to the toxicological chemist,
which are ephemeral, and whose bearing upon the case is not
readily recognized by those not thoroughly experienced.
Cases frequently arise in which it is impossible to bring the
chemist upon the ground in time for the autopsy. In such cases
the physician should remember that that portion of the poison
remaining in the alimentary tract (we are speaking of true poi-
sons) is but the residue of the dose in excess of that which has
been necessary to produce death ; and, if the processes of elimina-
tion have been active, there may remain no trace of the poison
in the alimentary canal, while it still may be detectable in deeper-
seated organs. The poison may also have been administered by
another channel than the mouth, in which event it may not
reach the stomach.
For these reasons it is not sufficient to send the stomach alone
for analysis. The chemist should also receive the entire intestinal
canal, at least one-half the liver, the spleen, one or both kidneys,
a piece of muscular tissue from the leg, the brain, and any urine
that may remain in the bladder. The intestinal canal should be
removed and sent to the chemist without having been opened, and
with ligatures, enclosing the contents, at the two ends of the
stomach, and at the lower end of the intestine. The brain and
alimentary canal are to be placed in separate jars, and the other
viscera in another jar together; the urine in a vial by itself. All
of these vessels are to be new and clean, and are to be closed by
newr corks, or by glass stoppers, or covers (not zinc screw-caps),
which are then coated with paraffin (not sealing-wax), and so
fastened with strings and seals, that it is impossible to open the
vessels without cutting the strings, or breaking the seals. Any
vomited matters are to be preserved. If the physician fail to ob-
serve these precautions, he has probably made the breach in the
evidence through which the criminal will escape, and has at the
outset defeated the aim of the analysis.
Analytical Characters of the Arsenical Compounds. — Arsenious
Compounds. — (1.) H2S, a yellow color in neutral or alkaline liquids ;
a yellow ppt. in acid liquids. The ppt. dissolves in solutions of
the alkaline hydroxids, carbonates, and sulfhydrates ; but is
scarcely affected by HC1. Hot HNOs decomposes it.
132 MANUAL OF CHEMISTRY.
(2.) AgNO3, in the presence of a little NH4HO, gives a yellow
ppt. This test is best applied by placing the neutral arsenical
solution in a porcelain capsule, adding neutral solution of AgNO3,
and blowing upon it over the stopper of the NH4HO bottle, moist-
ened with that reagent.
(3.) CuSO4 under the same conditions as in (2) gives a yellowish-
green ppt.
(4.) A small quantity of solid As2O3 is placed in the point a of
the tube, Fig. 32; above it, at 6, a splinter of recently ignited
charcoal ; 6 is first heated to redness, then a ; the vapor of As2O3,
passing over the hot charcoal, is reduced, and elementary As is
deposited at c in a metallic ring. The tube is then cut between.
6 and c, the larger piece held with d uppermost and heated at c;:
FIG. 32.
the deposit is volatilized, the odor of garlic is observed, and bright,,
octahedral crystals (Fig. 34), appear in the cool part of the tube.
(5.) Beinsch. test. — The suspected liquid is acidulated with one-
sixth its bulk of HC1. Strips of electrotype copper are immersed
in the liquid, which is boiled. In the presence of an arsenious
compound, a gray or bluish deposit is formed upon the Cu. A
similar deposit is produced by other substances (Bi, Sb, Hg). To
complete the test the Cu is removed, washed, and dried between
folds of filter-paper, without removing the deposit. The copper,
with its adherent film, is rolled into a cylinder, and introduced
into a dry piece of Bohemian tubing, about \ inch in diameter
and six inches long, which is held at the angle shown in Fig. 33
and heated at the point containing the copper. If the deposit
consist of arsenic, a white deposit is formed at a, which contains
brilliant specks, and, when examined with a magnifier, is found
to consist of minute octahedral crystals, Fig. 34.
The advantages of this test are : it may be applied in the pres-
ence of organic matter, to the urine for instance ; it is easily con-
ARSENIC.
•ducted; and its positive results are not misleading, if the test be
carried to completion. These advantages render it the most suit-
able method for the physician to use, during the life of the pa-
tient. It should not be used after death by the physician, as by
FIG. 33.
FIG. 34.
It copper is introduced into the substances under examination,
which may subsequently interfere seriously with the analysis.
The purity of the Cu and HC1 must be proved by a blank testing
before use. Reinsch's test is not as delicate as Marsh's, and it
only reacts slowly and imperfectly when the arsenic is in the
higher stage of oxidation, or in presence of oxidizing agents.
(6.) Marsh's test is based upon the formation of AsH3 when a
.reducible compound of arsenic is in presence of nascent H ; and
FIG. 35.
the subsequent decomposition of the arsenical gas by heat, with
.separation of elementary arsenic.
The apparatus used (Fig. 35) consists of a glass generating ves-
sel a, of about 150 c.c. capacity (5 fl f ), into whose upper opening
134 MANUAL OF CHEMISTRY.
a funnel tube c is either ground, or fitted by a section of rubber
tube. The lateral outlet is connected with a tube d, filled with
fragments of calcium chlorid ; which in turn connects with the
Bohemian glass tube gg, which should be about 0.5 cent, in diam-
eter, and about 80 cent. long.. This tube is protected by a tube
of wire gauze, within which it is adjusted in the furnace as shown
in the figure. The other end of gg is bent downward, and dips
into a solution of silver nitrate in the test-tube/.
The vessel a is first charged with about 25 grams (6| 3 ) of pure
granulated zinc, which has been in contact with a diluted solu-
tion of platinic chlorid for half an hour, and then washed. The
apparatus is then connected in such a manner that all joints are
gas-tight, and the funnel-tube c about half filled with H2SO4,
diluted with an equal bulk of H2O, and cooled. By opening the
stopcock, the acid is brought in contact with the zinc in small
quantities, in such a manner that during the entire testing bub-
bles of gas pass through/, at the rate of 60-80 per minute. After
fifteen minutes the burner is lighted, and the heating continued,
during evolution of gas from zinc and BUSO^ for an hour. At
the end of that time, if no stain have formed in g beyond e, then
zinc arid acid may be considered pure and the suspected solution,
prepared as described on page 137, introduced slowly through the
funnel-tube.
If arsenic be present in the substance examined, a hair-brown
or gray deposit is formed in the cool part of g beyond e. At the
same time the contents of / are darkened if the amount of As.
present is so great that all the AsH3 produced is not decomposed
in the heated portion of gg.
To distinguish the stains produced by arsenical compounds
from the similar ones produced by antimony the following differ-
ences are noted :
The Arsenical Stain. The Antimonial Stain.
First. — Is farther removed First. — Is quite near the
from the heated portion of the heated portion of the tube,
tube, and, if small in quantity,
is double — the first hair-brown,
the second steel-gray.
Second. — Volatilizes readily Second. — Requires a much
when heated in an atmosphere higher temperature for its vola •
of hydrogen, being deposited tilization; fuses before volatil-
farther along in the tube. The izing. Escaping gas has no al-
escaping gas has the odor of liaceous odor,
garlic.
Third. — When cautiously Third. — No crystals formed
heated in a current of oxygen, by heating in oxygen,
brilliant, white, octahedral crys-
tals of arsenic trioxid are depos-
ited farther along in the tube.
ARSENIC.
135
The Arsenical Stain.
Fourth. — Instantly soluble in
solution of sodium hypochlor-
ite.
Fifth.— Slowly dissolved by
solution of ammonium sulfhy-
drate; more rapidly when
warmed.
Sixth. — The solution ob-
tained in 5 leaves, on evapora-
tion over the water-bath, a
bright yellow residue.
Seventh. — The residue ob-
tained in 6 is soluble in aqua
ammonite, but insoluble in hy-
drochloric acid.
Eighth. — Is soluble in warm
nitric acid; the solution on
evaporation yields a white resi-
due, which turns brick-red
when moistened with silver ni-
trate solution.
Ninth. — Is not dissolved by a
solution of stannous chlorid.
The Antimonial Stain.
Fourth. — Insoluble in solu-
tion of sodium hypochlorite.
Fifth. — Dissolves quickly in
solution of ammonium sulfhy-
drate.
Sixth. — The solution ob-
tained in 5 leaves, on evapo-
ration over the water-bath, an
orange-red residue.
Seventh. — The residue ob-
tained in 6 is insoluble in aqua
ammonise, but soluble in hy-
drochloric acid.
Eighth. — Is soluble in warm
nitric acid; the solution on
evaporation yields a white resi-
due, which is not colored when
moistened with silver nitrate
solution.
Ninth. — Dissolves slowly in
solution of stannous chlorid.
If. however, the process described on p. 136 have been followed,
there can be no antimony in the liquid which would contain ar-
senic, if present. The silver solution in /is tested for arsenious
acid, by floating upon its surface a layer of diluted NH4HO solu-
tion, which, in the presence of arsenic, produces a yellow (not
brown) band, at the point of junction of the two liquids.
In place of bending the tube gg' downward, it may be bent up-
ward and drawn out to a fine opening. If the escaping gas be
then ignited, the heating of the tube being discontinued, a white
deposit of As2O3 may be collected on a glass surface held above the
flame ; or a brown deposit of elementary As upon a cold (porcelain)
surface held in the flame.
In place of generating nascent hydrogen by the action of Zn on
H2SO4, it may be produced by the decomposition of acidulated
H3O by the battery, in a Marsh apparatus especially modified for
that purpose.
In another modification of the Marsh test the AsH3 is decom-
posed, not by passage through a red-hot tube, but by passing
through a tube traversed by the spark from an induction coil.
(7.) Fresenius' and von Babo's test. — The sulfid, obtained in
(1), is dried, and mixed with 12 parts of a dry mixture of 3 pts.
sodium carbonate and 1 pt. potassium cyanid, and the mixture
brought into a tube, drawn out to a fine opening, through which
a slow current of CO2 is allowed to pass. The tube is then
heated to redness at the point containing the mixture, when, if
136 MANUAL OF CHEMISTRY.
arsenic be present, a gray deposit is formed at the constricted
portion of the tube; which has the characters of the arsenical
stain indicated on pp. 134, 135.
(8.) Place a small crystal of sodium sulfite in a solution of
0.3-0.4 gram of stannous chlorid in pure HC1, sp. gr. 1.13. Float
the liquid to be tested on the surface of this mixture. If As be
present a yellow band is formed at the junction of the two liquids,
and gradually increases upward.
ARSENIC COMPOUNDS— (1.) H2S does not form a ppt. in neu-
tral or alkaline solutions. In acid solutions a yellow ppt., con-
sisting either of As2S3 or As2S6, or a mixture of the sulfids with
free S, is formed only after prolonged passage of H2S at the or-
dinary temperature, more rapidly at about 70° (158° F.).
(2.) AgNO3, under the same conditions as with the arsenious com-
pounds, produces a brick-red ppt. of silver arsenate.
(3.) CuSO4 under like circumstances produces a bluish-green ppt.
Arsenic compounds behave like arsenious compounds with the
tests 4, 6 and 7 for the latter.
Method of Analysis for Mineral Poisons. — In cases of suspected
poisoning a systematic course of analysis is to be followed by
which the presence or absence of all the more usual poisons can
be determined.
In the search for mineral poisons (see alkaloids), the first step
is the destruction of organic matter. To this end the material
to be examined, if liquid, is concentrated, and, if solid, is divided
into small pieces and suspended in H2O. About TV the volume of
concentrated HC1, and a small quantity of potassium chlorate
are added, and the mixture allowed to stand 24 hours at the ordi-
nary temperature, in a porcelain capsule covered by a glass plate.
The contents of the capsule are then heated over the water-bath,
while potassium chlorate, in small quantities, and, if necessary,
HC1, are added from time to time, and the mixture is occasionally
stirred, and lumps of solid matter crushed with a flattened glass
rod, until the mass has a uniform light-yellow color. If the
liquid smell strongly of Cl, CO2 is passed through it. When the
odor of Cl has disappeared, the liquid is filtered, and the residue
v^ashed with hot water. If a deposit form on cooling, the liquid
is again filtered. The clear filtrate and washings, if strongly
acid, are partially neutralized with sodium carbonate, and treated
with H2S; the gas being passed slowly through the liquid for
about half an hour at a time, at intervals of 4-6 hours, during
3 days ; the vessel being well corked during the intervals. The
precipitate formed, which may contain Sn, As, Sb, Hg, Pb, Bi or
Cu, is collected on a filter, and washed with H2O, containing a
small quantity of H2S, until the washings fail to give the faititest
cloudiness when boiled, acidulated with HNO3 and treated with
silver nitrate.
Solution of ammonium sulfhydrate is added to the precipitate
on the filter, which is then washed with water. The solution
passing through may contain As, Sb, Sn and Cu ; the residue on
ANTIMONY. 137
the filter (A) may contain Hg, Pb, Bi and Cu. The solution is
evaporated over the water-bath to dryness, and the residue moist-
ened with fuming HNO3, dried, moistened with H2O, and dried
several times, and then, after neutralization with caustic soda,
fused with a mixture qf sodium carbonate and nitrate, until it is
colorless, or contains only a black, granular deposit, the heat
being slowly increased. The cooled residue of fusion is dissolved
in a small quantity of warm H2O, and CO2 is passed through the
solution, whether it be clear or cloudy. The solution, if not per-
fectly clear, is filtered. Any deposit retained by the filter (B) may
contain Sn, Sb or Cu. The filtrate is strongly acidulated with
H3SO4, and slowly evaporated and heated, with addition of more
H2SO4, if necessary, until abundant white fumes are given off.
The cooled residue, which may contain As, is dissolved in H2O,
and introduced into the Marsh apparatus when cold.
The residue B, if black, is dissolved in hot HNO3) and the solu-
tion tested for Cu. If it be white, it is ignited, with the filter,
in a porcelain crucible ; fused with potassium cyanid ; and washed
with H2O. The residue is extracted with warm HC1, and the
solution tested for Sn. If any residue remain, it is extracted with
HC1, to which a few drops of HNO3 have been added, and the
solution tested for Sb.
The residue A, after washing, is boiled with HNO3, diluted with
H2O and filtered. The filtrate is tested for Cu, Bi and Pb. The
residue, if any, is tested for Hg and Pb.
ANTIMONY.
Syml>ol=&b (Latin, stibium) — Atoyiic weight— 120 — Molecular
weight=d)—Sp. gr. =6.175— Fuses at 450° (842° F.}.
• Occurrence. — Free in small quantity ; principally in the trisul-
fld, Sb2S3.
Preparation. — The native sulfid (black, or crude antimony) is
roasted, and then reduced, by heating with charcoal. The com-
mercial antimony so obtained may be purified by fusing a mix-
ture of antimony, 16 pts. ; native sulfid of antimony, 1 pt. ; and
dry sodium carbonate, 2 pts. After cooling, the button is pow-
dered, and fused with 1| pts. sodium carbonate and \% ferrous
sulfid. The antimony is again separated, powdered, and fused
with sodium carbonate and a small quantity of sodium nitrate.
Each fusion is maintained for an hour.
Properties. — Physical. — A bluish-gray, brittle solid, having a
metallic lustre; readily crystallizable ; tasteless and odorless;
volatilizes at a red heat, and may be distilled in an atmosphere
of H.
Chemical. — Is not altered by dry or moist air at ordinary tem-
peratures. When sufficiently heated in air, it burns, with forma-
tion of SbaOs, as a white, crystalline solid. It also combines
directly with Cl, Br, I, S, and many metallic elements. It com-
bines with H under the same circumstances as does As. Cold,
138 MANUAL OF CHEMISTRY.
dilute H2SO4 does not affect it ; the hot, concentrated acid forms
with it antimonyl sulfate, (SbO)2SO4 and SO2. Hot HC1 dis-
solves it, when finely divided, with evolution of H. It is readily
oxidized by HNO3, with formation of H3SbO4 or Sb2O4. Aqua
regia dissolves it as SbCl3, or SbCU. Solutions of the alkaline
hydroxids do not act on it.
The element itself does not form salts with the oxyacids. There
are, however, compounds, formed by the substitution of the
group antimonyl (SbO), for the basic hydrogen of those acids.
(See tartar emetic.)
It enters into the composition of type metal, antifriction metals,
and britannia metal.
Hydrogen Antixnonid — Stibin — Antimoniuretled hydrogen —
Stibamin—Stibonia — SbH3— 123. — It has not been obtained in a
condition of purity, but is produced, mixed with H, when a reduci-
ble compound of Sb is in presence of nascent H. It is obtained in
larger amount, by decomposing an alloy of 400 parts of a 2% so-
dium amalgam, and 8 parts of freshly reduced, and dried Sb, by
H2O, in a current of CO2.
It is a colorless, odorless, combustible gas, subject to the same
decompositions as AsH3 ; from which it differs in being by no
means as poisonous, and in its action upon silver nitrate solu-
tion. The arsenical gas acts upon the silver salt according to the
equation : 6AgNO3+2AsH3+H!1=Ag!1+2AgiHAsO3+6HNO2, and
the precipitate formed is elementary silver, while Ag2HAsO3 re-
mains in the solution. In the case of SbH3 the reaction is 3AgNO3
-f SbH3=3HNO3+SbAg3, all of the Sb being precipitated in the
black silver antimonid.
Compounds of Antimony and Oxygen. — Three are known, Sb2O3r
SbaCX and Sb2O5.
Antimony trioxid — Antimonous arihydrid — Oxid of antimony
— Antimonii oxidum (TJ. S.; Br.) — Sb2O3 — 288 — occurs in nature;
and is prepared artificially by decomposing the oxychlorid ; or by
heating Sb in air.
It is an amorphous, insoluble, tasteless, odorless powder ; white
at ordinary temperatures, but yellow' when heated. It fuses
readily, and may be distilled in absence of oxygen. Heated in
air, it burns like tinder, and is converted into SbsO4.
It is reduced, with separation of Sb, when heated with char-
coal, or in H. It is also readily oxidized by HNO3, or potassium
permanganate. It dissolves in HC1 as SbCls ; in Nordhausen sul-
furic acid, from which solution brilliant crystalline plates of
antimonyl pyrosulfate, (SbO)2S2O7, separate ; and in solutions
of tartaric acid, and of hydropotassic tartrate (see tartar emetic)..
ANTIMONY. 139
Boiling solutions of alkaline hydroxids convert it into antimonic
acid.
Antimony pentoxid — Antimonic anhydrid — Sb2OB — 320 — is ob-
tained by heating metantiruonic acid to dull redness. It is an
amorphous, tasteless^ odorless, pale lemon-yellow colored solid;
very sparingly soluble in water and in acids. At a red heat it is
decomposed into SbaCh and O.
Antimony antimoniate — Intermediate oxid — Diantimonic te-
troxid — Sb2O4 — 304 — occurs in nature, and is formed when the
oxids or hydrates of Sb are strongly heated, or when the lower
stages of oxidation or the sulfids are oxidized by HNO3, or by
fusion with sodium nitrate. It is insoluble in HaO ; but is decom-
posed by HC1, hydropotassic tartrate, and potash.
Antimony Acids. — The normal antimonous acid, H3SbO3, cor-
responding to H3PO3, is unknown; but the series of antimonic
acids: ortho — H3SbO4, pyro — H4SbaO7, and meta — HSbO3, is com-
plete, either in the form of salts, or in that of the free acids.
There also exists, in its sodium salt, a derivative of the lacking
antimonous acid : metantimonous acid, HSbO2.
The compound sometimes used in medicine under the name
washed diaphoretic antimony is potassium metantimoriate, uni-
ted with an excess of the pentoxid : 2KSbO3, Sb2O5. The hydro-
potassic pyroantimonate, KaH2Sb2O7,6Aq is a valuable reagent
for the sodium compounds. It is obtained by calcining a mixture
of one part of antimony with four parts of potassium nitrate, and
fusing the product with its own weight of potassium carbonate.
Chlorids of Antimony. — Antimony trichlorid — Protochlorid or
butter of antimony — SbCl3— 226.5 — is obtained by passing dry Cl
over an excess of SbaS3; by dissolving SbaS3 in HC1; or by distil-
ling mixtures, either of SbaS3 and mercuric chlorid, or of Sb
and mercuric chlorid, or of antimonyl pyrosulfate and sodium,
chlorid.
At low temperatures it is a solid, crystalline body ; at the ordi-
nary temperature a yellow, semi-solid mass, resembling butter;
at 73°. 2 (164° F.) it fuses to a yellow, oily liquid, which boils at
223° (433°. 4 F.). Obtained by solution of Sb2S3 in HC1 of the-
usual strength, it forms a dark yellow solution, which, when con-
centrated to sp. gr. 1.47, constitutes the Liq. Antimonii chloridi
(Br.).
It absorbs moisture from air, and is soluble in a small quantity
of HaO ; with a larger quantity it is decomposed, with precipita-
tion of a white powder, powder of Algaroth, whose composition is
SbOCl if cold HaO be used, and Sb4O6Cla if the HaO be boiling.
In HaO containing 15 per cent, or more HC1, SbCl3 is soluble with-
out decomposition.
140 MANUAL OF CHEMISTRY.
Antimony pentachlorid — SbCl5 — 297.5— is formed by the action
of Cl, in excess, upon Sb or SbCl3, and purified by distillation, in
a current of Cl.
It is a fuming, colorless liquid, which solidifies at —20° (—4° F.),
the solid fusing at —6° (21°. 2 F.). It absorbs moisture from air.
"With a small quantity of H2O, and by evaporation over H2SO4,
it forms a hydrate, SbCl64H2O, which appears in transparent,
deliquescent crystals. With more H2O, a crystalline oxychlorid,
SbOCla, is formed; and with a still greater quantity, a white pre-
cipitate of orthoantimonic acid, H3SbO4.
Sulfids of Antimony. — Antimony trisulfid — Sesquisulfld of
antimony — Slack antimony — Antimonii sulfidum (U. S.) — Anti-
monium nigrum (Br.) — Sb_S;, — 336 — is the chief ore of antimony ;
and is formed when H2S is passed through a solution of tartar
emetic.
The native sulfid is a steel-gray, crystalline solid ; the artificial
product, an orange-red, or brownish-red, amorphous powder.
The crude antimony of commerce is in conical loaves, prepared
by simple fusion of the native sulfid. It is soft, fusible, readily
pulverized, and has a bright metallic lustre.
Heated in air, it is decomposed into SO2 and a brown, vitreous,
more or less transparent mass, composed of varying proportions
of oxid and oxysulfids, known as crocus, or liver, or glass of
antimony. Sb2S3 is an anhydrid, corresponding to which are
salts known as sulfantimonites, having the general formula
M'2HSbS3. If an excess of Sb2S3 be boiled with a solution of pot-
ash or soda, a liquid is obtained, which contains an alkaline sulf-
antimonite, and an excess of Sb2S3. If this solution be filtered,
^nd decomposed by an acid while still hot, an orange-colored,
amorphous precipitate is produced, which is the antimonium sul-
furatum (U. S. ; Br.), and consists of a mixture, in varying pro-
portions, of Sb2S3 and Sb2O3. If, however, the solution be al-
lowed to cool, a brown, voluminous, amorphous precipitate
separates, which consists of antimony trisulfid and trioxid,
potassium or sodium sulfid, and alkaline sulfantimonite in vary-
ing proportions ; and is known as Kermes mineral. If now the
solution from which the Kermes has been separated, be decom-
posed with H2SO4, a reddish-yellow substance separates, which
is the golden sulfuret of antimony, and consists of a mixture of
TSb2S3 and Sb2S&. The precipitate obtained when H2S acts upon
^a solution of an antimonial compound is, according to circum-
stances, Sb2S3 or Sb2SB, mixed with free S. By the action of
HC1 on Sb^Ss, H2S is produced.
Antimony pentasulfid— Sb2Ss— 400 — is obtained by decompos-
ing an alkaline sulfantimonate by an acid. It is a dark orange-
ANTIMONY. 141
red, amorphous powder, readily soluble in solutions of the alka-
lies, and alkaline sulfids, with which it forms sulfantimonates.
An oxysulfid, SbeSoOa, is obtained by the action of a solution
of sodium hyposulfite upon SbCl3 or tartar emetic. It is a fine
red powder, used as a pigment, and called antimony cinnabar or
antimony vermilion.
Action of Antimony Compounds on the Economy. — The com-
pounds of antimony are poisonous, and act with greater or less
energy as they are more or less soluble. The compound which
is most frequently the cause of antimonial poisoning is tartar
emetic (q. v.), which has caused death in a dose of half a grain,
although recovery has followed the ingestion of half an ounce in
several instances. Indeed, the chances of recovery seem to be
better with large, than with small doses, probably owing to the
more rapid and complete removal of the poison by vomiting with
large doses. Antimonials have been sometimes criminally admin-
istered in small and repeated doses, the victim dying of exhaus-
tion. In such a case an examination of the urine will reveal the
cause of the trouble.
If vomiting have not occurred in cases of acute antimonial poi-
soning it should be provoked by warm water, or the stomach
should be evacuated by the pump. Tannin in some form (decoc-
tion of oak bark, cinchona, nutgalls, tea) should then be given,,
with a view to rendering any remaining poison insoluble.
Medicinal antimonials are very liable to contamination with
arsenic.
Analytical characters of Antimonial Compounds. — (1.) With
HaS in acid solution, an orange-red ppt., soluble in NH4HS and
in hot HC1.
(2.) A strip of bright copper, suspended in a boiling solution of
an Sb compound, acidulated with HC1, is coated with a blue-gray
deposit. This deposit when dried (on the copper), and heated in
a tube, open at both ends yields a white, amorphous sublimate-
(see No. 5, p. 132).
(3.) Antimonial compounds yield a deposit by Marsh's test, sim-
ilar to that obtained with arsenical compounds, but differing in
the particulars given above (see No. 6, p. 134).
If, in cases of suspected poisoning, the examination have been
conducted as directed on p. 136. any Sb present is separated dur-
ing the fusion with sodium nitrate and carbonate, and the subse-
quent solution and nitration, so completely that As and Sb can-
not be mistaken for one another.
142 MANUAL OF CHEMISTRY.
IV.— BORON GROUP.
BORON.
Symbol="B — Atomic weight—^ — Molecular weight=22 (?)=
•lated by Davy in 1807.
Boron constitutes a group by itself; it is trivalent in all of its
compounds; it forms but one oxid, which is the anhydrid of a
tribasic acid ; and it forms no compound with H.
It is separable in two allotropic modifications. Amorphous
boron is prepared by decomposition of the oxid, by heating with
metallic potassium or sodium. It is a greenish-brown powder;
sparingly soluble in H2O; infusible, and capable of direct union
with Cl, Br, O, S, and N.
Crystallized boron is produced when the oxid, chlorid or fluorid
is reduced by Al. It crystallizes in quadratic prisms ; more or
less transparent, and varying in color from a faint yellow to deep
garnet-red ; very hard ; sp. gr. 2. 68. It burns when strongly heated
in O, and readily in Cl ; it also combines with N, which it is ca-
pable of removing from NH3 at a high temperature.
Boron trioxid — Boric or boracic anhydrid — B2O3 — 70 — is ob-
tained by heating boric acid to redness in a platinum vessel. It is a
transparent, glass-like mass, used in blowpipe analysis under the
name vitreous boric acid.
Boric Acids. — Boric acid — Boracic acid — Acidum boricum (TJ.
S.) — H3BO3 — 62 — occurs in nature; and is prepared by slowly de-
composing a boiling, concentrated solution of borax, with an ex-
cess of H2SO4, and allowing the acid to crystallize.
It forms brilliant crystalline plates, unctuous to the touch;
odorless; slightly bitter ; soluble in 25 parts H2O at 10° (50° F.);
soluble in alcohol. Its solution reddens litmus, but turns tur-
meric paper brown. When its aqueous solution is distilled, a
portion of the acid passes over.
Boric acid readily forms ethers with the alcohols. When heated
with ethylic alcohol, ethyl borate is formed, which burns with
a green flame. Heated with glycerin a soluble, neutral ether is
formed, known as boroglycerid, and used as an antiseptic.
If H3BO3 be heated for some time at 80° (176° F.), it loses H3O
and is converted into metaboric acid, HBO3. If maintained at
100° (212° F.) for several days, it loses a further quantity of H2O,
and is converted into tetraboric or pyroboric acid, H2B4OT, whose
sodium salt is borax.
CARBOX. 143
V.— CARBON GROUP.
' CARBON — SILICON.
The elements of this group are bivalent or quadrivalent. The
saturated oxid of each is the anhydrid of a dibasic acid. They
are both combustible, and each occurs in three allotropic forms.
CARBON.
Symbol=C — Atomic weight=l2 — Molecular weight— ^A (?).
Occurrence. — Free in its three allotropic forms : The diamond in
octahedral crystals; in alluvial sand, clay, sandstone and con-
glomerate; graphite, in amorphous or imperfectly crystalline
forms ; amorphous, in the different varieties of anthracite and bi-
tuminous coal, jet, etc. In combination, it is very widely distrib-
uted in the so-called organic substances.
Properties.— Diamond. — The crystals of diamond, which is al-
most pure carbon, are usually colorless or yellowish, but may be
blue, green, pink, brown or black. It is the hardest substance
known, and the one which refracts light the most strongly. Its
index of refraction is 2.47 to 2.75. It is very brittle ; a bad con-
ductor of heat and of electricity; sp. gr. 3.50 to 3.55. When very
strongly heated in vacuo, it swells up, and is converted into a
black mass, resembling coke.
Graphite is a form of carbon almost as pure as the diamond,
capable of crystallizing in hexagonal plates; sp. gr. 2.2; dark
gray in color ; opaque ; soft enough to be scratched by the nail ;
and a good conductor of electricity. It is also known as black
lead or plumbago. It has been obtained artificially, by allowing
molten cast-iron, containing an excess of carbon, to cool slowly,
and dissolving the iron in HC1.
Amorphous carbon is met with in a great variety of forms, nat-
ural and artificial, in all of which it is black; sp. gr. 1.6-2.0; more
or less porous ; and a conductor of electricity.
Anthracite coal is hard and dense ; it does not flame when burn-
ing; is difficult to kindle, but gives great heat with a suitable
draught. It contains 80-90 per cent, of carbon. Bituminous coal
differs from anthracite in that, when burning, it gives off gases,
which produce a flame. Some varieties are quite soft, while
others, such as jet, are hard enough to assume a high polish. It
is usually compact in texture, and, very frequently, contains im-
pressions of leaves, and other parts of plants. It contains about
75 per cent, of carbon.
Charcoal, carbo ligni, TJ. S., is obtained by burning woody fibre,
144 MANUAL OF CHEMISTKY.
with an insufficient supply of air. It is brittle and sonorous ; has
the form of the wood from which it was obtained, and retains all
the mineral matter present in the woody tissue Its sp. gr. is
about 1.57. It has the power of condensing within its pores odor-
ous substances, and large quantities of gases ; 90 volumes of am-
monia, 55 of hydrogen sulfid, 9.25 of oxygen. This property is
taken advantage of in a variety of ways. Its power of absorbing
odorous bodies renders it valuable as a disinfecting, and filtering-
agent, and in the prevention of putrefaction and fermentation
of certain liquids. The efficacy of charcoal as a filtering material
is due also, in a great measure, to the oxidizing action of the
oxygen condensed in its pores ; indeed, if charcoal be boiled with
dilute HC1, dried, and heated to redness, the oxidizing action of
the oxygen, which it thus condenses, is very energetic.
Lamp-black is obtained by incomplete combustion of some res-
inous or tarry substance, or natural gas, the smoke or soot from
which is directed into suitable condensing-chambers. It is a light,
amorphous powder, and contains a notable quantity of oily and
tarry material, from which it may be freed by heating in a cov-
ered vessel. It is used in the manufacture of printer's ink.
Coke is the substance remaining in gas-retorts, after the distil-
lation of bituminous coal, in the manufacture of illuminating gas.
It is a hard, grayish substance, usually very porous, dense, and
sonorous. When iron retorts are used, a portion of the gaseous
products are decomposed by contact with the hot iron surface,
upon which there is then deposited a layer of very hard, compact,
grayish carbon, which is a good conductor of electricity, and fur-
nishes the best material for making the carbons of galvanic bat-
teries and the points for the electric light. It does not form when
gas is made in clay retorts.
Animal charcoal is obtained by calcining animal matters in
closed vessels. If prepared from bones it is known as bone-black,
carbo animalis, TJ. S.; if from ivory, ivory black. The latter is
used as a pigment, the former as a decolorizing agent. Bones
yield about GO per cent, of bone-black, which contains, besides
carbon, nitrogen and the phosphates and other mineral sub-
tances of the bones. It possesses in a remarkable degree the
power of absorbing coloring matters. "When its decolorizing
power is lost by saturation with pigmentary bodies, it may be
restored, although not completely, by calcination. For certain
purposes purified animal charcoal, i.e., freed from mineral mat-
ter, carbo animalis purificatus, TJ. S., is required, and is obtained
by extracting the commercial article with HC1, and washing it
thoroughly. Its decolorizing power is diminished by this treat-
ment. Animal charcoal has the power of removing from a solu-
tion certain crystalline substances, notably the alkaloids, arid a
SILICON. 145
method has been suggested for separating these bodies from,
organic mixtures by its use.
All forms of carbon are insoluble in any known liquid.
Chemical. — All forms of C combine with O at high temperatures,
with light and heat. The product of the union is carbon dioxid
if the supply of air or O be sufficient ; but if O be present in lim-
ited quantity, carbon monoxid is formed. The affinity of C for
O renders it a valuable reducing agent. Many metallic oxids are
reduced, when heated with C, and steam is decomposed when
passed over red-hot C: H2O+C=CO-fH2. At elevated tempera-
tures C also combines directly with S, to form carbon disulfid.
With H, carbon also combines directly, under the influence of
the voltaic arc.
FOR COMPOUNDS OF CARBON SEE PAGE 222.
SILICON.
Symbol=8i — Atomic weight=28 — Molecular weight=56 (?)— Dis-
covered by Davy 1807 — Name from silex=flint.
Also known as silicium ; occurs in three allotropic forms : Amor-
phous silicon, formed when silicon chlorid is passed over heated
K or Na, is a dark brown powder, heavier than water. When
heated in air, it burns with a bright flame to the dioxid. It dis-
solves in potash and in hydrofluoric acid, but is not attacked by
other acids. Graphitoid silicon is obtained by fusing potassium
fluosilicate with aluminium. It forms hexagonal plates, of sp.
gr. 2.49, which do not burn when heated to whiteness in O, but
may be oxidized at that temperature, by a mixture of potassium
chlorate and nitrate. It dissolves slowly in alkaline solutions,
but not in acids. Crystallized silicon, corresponding to the dia-
mond, forms crystalline needles, which are only attacked by a
mixture of nitric and hydrofluoric acids.
Silicon, although closely related to C, exists in nature in com-
paratively few compounds. It has been caused to form artificial
combinations, however, which indicate its possible capacity to
exist in substances, corresponding to those C compounds com-
monly known as organic, e.g., silicichlorofonn and silicibromo-
form, SiHCl3 and SiHBr,.
Hydrogen silicid — SiH« — 32 — is obtained as a colorless, insolu-
ble, spontaneously inflammable gas, by passing the current of a
galvanic battery of twelve cells through a solution of common
salt, using a plate of aluminium, alloyed with silicon, as the posi-
tive electrode.
Silicon chlorid — SiCl4 — 170 — a colorless, volatile liquid, having
10
146 MANUAL OF CHEMISTRY.
an irritating odor; sp. gr. 1.52; boils at 59° (138°. 2 P.); formed
when Si is heated to redness in Cl.
Silicic oxid — Silicic anhydrid — Silex — SiO» — 60 — is the most im-
portant of the compounds of silicon. It exists in nature in the
different varieties of quartz, and in the rocks and sands contain-
ing that mineral, in agate, carnelian, flint, etc. Its purest native
form is rock crystal. Its hydrates occur in the opal, and in solu-
tion in natural waters. When crystallized, it is fusible with diffi-
culty. When heated to redness with the alkaline carbonates it
forms silicates, which solidify to glass-like masses, on cooling.
It unites with H2O to form a number of acid hydrates. The nor-
mal hydrate, H4SiO«, has not been isolated, although it probably
exists in the solution, obtained by adding an excess of HC1 to a
solution of sodium silicate. A gelatinous hydrate, soluble in
water and in acids and alkalies, is obtained by adding a small
quantity of HC1 to a concentrated solution of sodium silicate.
Hydrofluosilicic acid — H2SiF6— 144 — is obtained in solution by
passing the gas, disengaged by gently heating a mixture of equal
parts of fluorspar and pounded glass, and 6 pts. HaSCh, through
water ; the disengagement tube being protected from moisture by
a layer of mercury. It is used in analysis as a test for K and Na.
VI. VANADIUM GROUP.
VANADIUM— COLUMBIUM— TANTALUM.
The elements of this group resemble those of the N group, but
are usually quadrivalent.
Vanadium— V— 51.3— a brilliant, crystalline metal; sp. gr.=5.5;
which forms a series of oxids similar to those of N. No salts of
V are known, but salts of vanadyl (VO) are numerous, and are
used in the manufacture of anilin black.
Columbium — Nb — 94— a bright, steel-gray metal ; sp. gr. 7.06;
which burns in air to NbaO6 and in Cl to NbCU ; not attacked by
acids.
Tantalum — Ta — 182— closely resembles Nb in its chemical char-
acters.
VII. MOLYBDENUM GROUP.
MOLYBDENUM — TUNGSTEN — OSMIUM.
The position of this group is doubtful ; and it is probable that
the lower oxids will be found to be basic in character: in which
case the group should be transferred to the third class.
Molybdenum — Mo — 95.5 — a brittle white metal. The oxid MoO3,
molybdic anhydrid, combines with HSO to form a number of
acids; the ammonium salt of one of which is used as a reagent
for H3PO4 ; with which it forms a conjugate acid, phosphomolyb-
dic acid, used as a reagent for the alkaloids.
Tungsten— Wolfram — W— 183.6— a hard, brittle metal; sp. gr.
TUNGSTEN, OSMIUM. 147
17.4. The oxid, WO3, tunpstic anhydrid, is a yellow powder,
forming with H2O several acid hydrates; one of which, meta-
tungstic acid, is used as a test for the alkaloids, as are also the
conjugate silicotungstiu and phosphotungstic acids. Tissues im-
pregnated with sodium tungstate are rendered uninflammable.
Osmium — Os— 198.5--occurs in combination with Ir in Pt ores;
combustible and readily oxidized to OsO4. This oxid, known as
osmic acid, forms colorless crystals, soluble in H^O, which give
off intensely irritating vapors. It is used as a staining agent by
histologists, and also in dental practice.
148 MANUAL OF CHEMISTRY.
CLASS III.— AMPHOTERIC ELEMENTS.
Elements whose Oxids Unite with Water, Some to Form Bases,
Others to Form Acids. Which Form Oxysalts.
I. GOLD GROUP.
GOLD.
Symbol = Au (ATJRTJM) —Atomic weight = 196.2 — Molecu-
lar weight = 392.4 (?)— Sp. gr. = 19.258-19.367— Fuses at 1200°
(2192° P.).
This, the only member of the group, forms two series of coin-
pounds ; in one, AuCl, it is univalent ; in the other, AuCls, tri-
valent. Its hydroxid, auric acid, Au(OH)3, corresponds to the
oxid AuaOa. Its oxysalts are unstable.
It is yellow or red by reflected light, green by transmitted
light, reddish-purple when finely divided ; not very tenacious ;
softer than silver ; very malleable and ductile. It is not acted
on by H2O or air, at any temperature, nor by any single acid. It
combines directly with Cl, Br, I, P, Sb, As, and Hg. It dissolves
in nitromuriatic acid as auric chlorid. It is oxidized by alkalies
in fusion on contact with air.
Auric chlorid — (fold trichlorid — AuCl3 — 302.7 — obtained by dis-
solving Au in aqua regia, evaporating at 100° (212° P.), and puri-
fying by crystallization from H3O. Deliquescent, yellow prisms,
very soluble in H2O, alcohol and ether ; readily decomposed,
with separation of Au, by contact with P, or with reducing
agents. Its solution, treated with the chlorids of tin, deposits a.
purple double stannate of Sn and Au, called " purple of cas-
sius." With alkaline chlorids it forms double chlorids, chlorau-
rates (auri et sodii chloridum, U. S.).
Analytical Characters. — (1.) With HUS, from neutral or acid
solution, a blackish-brown ppt. in the cold ; insoluble in HNO3
and HC1 ; soluble in aqua regia, and in yellow NH4HS. (2.)
With stannous chlorid and a little chlorin water, a purple-red
ppt., insoluble in HC1. (3.) With ferrous sulfate a brown de-
posit, which assumes the lustre of gold when dried and bur-
nished.
II. IRON GROUP.
CHROMIUM — MANGANESK — IRON.
The elements of this group form two series of compounds. In
one they are bivalent, as in Fe"Cla or Mn"SO4, while in the other
CHROMIUM. 149
they are quadrivalent ; but when quadrivalent, the atoms do
not enter into combination singly, but grouped, two together, to
form a hexavalent unit I | , as in (Fe2)viCl6, (Cra)viO3. They
form several oxids ; of which the oxid MO3 is an anhydrid, cor-
responding to which are acids and salts. Most of the other
oxids are basic.
CHROMIUM.
Symbol = Cr — Atomic weight = 52.06 — Molecular weight = 104.12
•(?) — Sp. gr. = 6.8 — Discovered by Vauquelin, 1797 — Name from
= color.
Occurs in nature principally as chrome ironstone, a double
oxid of Cr and Fe. The element is separated with difficulty by
reduction of its oxid by charcoal, or of its chlorid by sodium. It
is a hard, crystalline, almost infusible metal. Combines with O
only at a red heat. It is not attacked by acids, except HC1 ; is
readily attacked by alkalies.
Chromic Oxid — Sesquioxid, or green oxid of chromium — Cr2O3
— 152.8 — obtained, amorphous, by calcining a mixture of potas-
sium dichromate and starch, or, crystallized, by heating neutral
potassium chromate to redness in 01.
It is green ; insoluble in H»O, acids, and alkalies ; fusible with
difficulty, and not decomposed by heat; not reduced by H. At a
red heat in air, it combines with alkaline hydroxids, and nitrates,
to form chromates. It forms two series of salts, the terms of one
of which are green, those of the other violet. The alkaline hy-
droxids separate a bluish-green hydrate from solutions of the green
salts, and a bluish-violet hydrate from those of the violet salts.
Chromium, green, or emerald green, [s a green hydrate, formed
by decomposing a double borate of chromium and potassium by
H2O. It is used in the arts as a substitute for the arsenical greens,
^,nd is non-poisonous.
Chromic Anhydnd— Acidum chromicum (U. S.)—CrO3— 100.4 — is
formed by decomposing a solution of potassium dichromate by
excess of H3SO4, and crystallizing.
It crystallizes in deliquescent crimson prisms, very soluble in
H2O, and in dilute alcohol. It is a powerful oxidant, capable of
igniting strong alcohol.
The true chromic acid has not been isolated, but salts are known
which correspond to three acid hydrates : H3CrO« = chromic
acid ; H»Cr2O7 = dichromic acid ; and H^CrsOio = trichromic acid.
Chlorids. — Two chlorids and one oxychlorid of chromium are
known. Chromous chlorid, CrClj, is a white solid, soluble, with.
150 MANUAL OF CHEMISTRY.
a blue color, in HaO. Chromic chlorid, (Cra)Cl«, forms large, red
crystals, insoluble in H2O when pure.
Sulfates. — A violet sulf&te crystallizes in octahedra, (Cr)a(SO4)a-h
15 Aq, and is very soluble in HaO. At 100° it is converted into a
green salt, (Cr)a(SO4)3 + 5 Aq, soluble in alcohol; which, at higher
temperatures, is converted into the red, insoluble, anhydrous salt.
Chromic sulfate forms double sulfates, containing 24 Aq, with
the alkaline sulfates. (See Alums.)
Analytical Characters. — CHROMOUS SALTS. — (1.) Potash, a.
brown ppt. (2.) Ammonium hydroxid, greenish-white ppt. (3.)
Alkaline sulflds, black ppt. (4.) Sodium phosphate, blue ppt.
CHROMIC SALTS.— (1.) Potash, green ppt.; an excess of precip-
itant forms a green solution, from which Cr2O3 separates on boil-
ing. (2.) Ammonium hydroxid, greenish-gray ppt. (3.) Ammo-
nium sulfhydrate, greenish ppt.
CHROMATES. — (1.) H2S in acid solution, brownish color, chang-
ing to green. (2.) Ammonium sulfhydrate, greenish ppt. (3.)
Barium chlorid, yellowish ppt. (4.) Silver nitrate, brownish-red
ppt., soluble in HNO3 or NH4HO. (5.) Lead acetate, yellow ppt.,
soluble in potash, insoluble in acetic acid.
Action on the Economy. — Chromic anhydrid oxidizes organic
substances, and is used as a caustic.
The chromates, especially potassium dichromate (q. t>.), are
irritants, and have a distinctly poisonous action as well. Work-
men handling the dichromate are liable to a form of chronic
poisoning.
In acute chromium-poisoning, emetics, and subsequently mag-
nesium carbonate in milk, are to be given.
MANGANESE.
Symbol = Mn — Atomic weight = 54 — Molecular weight = 108 (?)
— Sp. gr. =7.138-7.206.
Occurs chiefly in pyrolusite, MnO2, hausmanite, Mn3O4, brau-
nite, Mn2O3, and manganite, Mn2O3, HaO. A hard, grayish,
brittle metal ; fusible with difficulty ; obtained by reduction of
its oxids by C at a white heat. It is riot readily oxidized by cold,
dry air ; but is superficially oxidized when heated. It decom-
poses H2O, liberating H ; and dissolves in dilute acids.
Oxids. — Manganese forms six oxids or compounds representing
them: Manganous oxid, MnO; manganoso-manganic oxid, Mn3O4;
manganic oxid, Mri2O3 ; permanganic oxid, MnO2, and perman-
ganic anhydrid, Mn2O7, are known free. Manganic anhydrid,
MnO3, has not been isolated. MnO and MnaO3 are basic ; Mn3O4
MANGANESE. 151
and MnOa are indifferent oxids ; and MnO3 and MnaO7 are anhy-
drids, corresponding to the manganates and permanganates.
Permanganic Oxid — Manganese dioxid, or black oxid — Man-
gani oxidum nigrum (17. S.) — Manganesii ox. nig. (Br.) — MnO: —
86 — exists in nature as pyrolusite, the principal ore of manganese,
in steel gray, or brownish-black, imperfectly crystalline masses.
At a red heat it loses 12 per cent, of O : 3MnOa = Mn3O4+Oa ;
and, at a white heat, a further quantity of O is given off :
2Mn3O4 = 6MnO+Os. Heated with HaSO4, it gives off O, and
forms manganous sulfate : 2MnOa+2HaSO4 = 2MnSO4+2HjO4-
Oa. With HC1 it yields manganous chlorid, HaO and Cl : MnOa+
4HC1 = MnCla+2HaO+Cla. It is not acted on by HNO3.
Chlorids. — Two chlorids of Mn are known : manganous chlorid,
MnCla, a pink, deliquescent, soluble salt, occurring, mixed with
ferric chlorid, in the waste liquid of the preparation of Cl ; and
manganic chlorid, MnaCl«.
Salts of Manganese. — Manganese forms two series of salts :
Manganous salts, containing Mn" ; and manganic salts, contain-
ing (Mna)vi ; the former are colorless or pink, and soluble in
water ; the latter are unstable.
Manganous Sulfate — Mangani sulfas (U. S.) — MnSO4 4- ?i Aq —
150 + 7il8— is formed by the action of HaSO4 on MnOa. Below
6° (42°.8 F.) it crystallizes with 7 Aq, and is isomorphous with
ferrous sulfate; between 7°-20° (44°. 6-68° F.) it forms crystals
with 5 Aq, and is isomorphous with cupric sulfate ; between
20°-30° (68°-86° F.), it crystallizes with 4 Aq. It is rose-colored,
darker as the proportion of Aq increases, soluble in HaO, insolu-
ble in alcohol. With the alkaline sulfates it forms double salts,
with 6 Aq.
Analytical Characters. — MANGANOUS.— (1.) Potash, white ppt.,
turning brown. (2.) Alkaline carbonates, white ppts. (3.) Am-
monium sulf hydrate, flesh-colored ppt.. soluble in acids, spar-
ingly soluble in excess of precipitant. (4.) Potassium ferrocyanid,
faintly reddish-white ppt., in neutral solution ; soluble in HC1.
(5.) Potassium cyanid, rose-colored ppt., forming brown solution
with excess.
MANGANIC.— (1.) HaS, ppt. of sulfur. (2.) Ammonium sulf hy-
drate, flesh-colored ppt. (3.) Potassium ferrocyanid, greenish
ppt. (4.) Potassium ferricyanid, brown ppt, (5.) Potassium
cyanid, light brown ppt.
MANGANATES — are green salts, whose solutions are only stable
in presence of excess of alkali, and turn brown when diluted and
acidulated.
PERMANGANATES — form red solutions, which are decolorized
by SOa, other reducing agents, and many organic substances.
152 MANUAL OF CHEMISTRY.
IRON.
Symbol = Fe (FERRTJM)— Atomic weight = 55.9— Moleculat
weight = 111.8 (t}—Sp. gr. = 7. 25-7. 9 -Fuses at 1600° (2912° F.)—
Name from the Saxon, iren.
Occurrence. — Free, in small quantity only, in platinum ores and
meteorites. As Fe2O3 in red hcematite and specular iron; as
hydrates of Fe2O3 in brown haematite and oolitic iron; as Fe3O4
in magnetic iron; as FeCO3 in spathic iron, clay ironstone and
bog ore ; and as FeS2 in pyrites. It is also a constituent of most
soils and clays, exists in inany mineral waters, and in the red
blood pigment of animals.
Preparation. — In working the ores, reduction is first effected in
a blast-furnace, into which alternate layers of ore, coal and
limestone are fed from the top, while air is forced in from below.
In the lower part of the furnace COa is produced, at the expense
of the coal ; higher up it is reduced by the incandescent fuel to
CO, which, at a still higher point, reduces the ore. The fused
metal, so liberated, collects at the lowest point, under a layer of
slag ; and is drawn off to be cast as pig iron. This product is
then purified, by burning out impurities, in the process known
as puddling.
Pure iron is prepared by reduction of ferrous chlorid, or of
ferric oxid, by H at a temperature approaching redness.
Varieties. — Cast iron is a brittle, white or gray, crystalline
metal, consisting of Fe 89-90$ ; C 1-4.5$ ; and Si, P, S, and Mn.
As pig iron, it is the product of the blast-furnace.
Wrought, or bar iron, is a fibrous, tough metal, freed in part
from the impurities of cast iron, by refining and puddling.
Steel is Fe combined with a quantity of C, less than that exist-
ing in cast iron, and greater than that in bar iron. It is prepared
by cementation ; which consists in causing bar iron to combine
with C ; or by the Bessemer method ; which, as now used, consists
in burning the C out of molten cast iron, to which the proper
proportion of C is then added in the shape of spiegel eisen, an
iron rich in Mn and C.
The purest forms of commercial iron are those used in piano-
strings, the teeth of carding machines, and electro-magnets;
known as soft iron.
Reduced iron-Ferru.no. reductum (U. S.) — Fer. redactum (Br.) —
is Fe, more or less mixed with FeaO3 and Fe3O4, obtained by
heating Fe2O3 in H.
Properties. — Physical. — Pure iron is silver-white ; quite soft ;
crystallizes in cubes or octahedra. Wrought iron is gray, hard,
very tenacious, fibrous, quite malleable and ductile, capable of
IRON. 153
"being welded, highly magnetic, but only temporarily so. Steel
is gray, very hard and brittle if tempered, soft and tenacious if
not, permanently magnetic.
Chemical. — Iron is not altered by dry air at the ordinary tem-
perature. At a red heat it is oxidized. In damp air it is converted
into a hydrate, iron rust. Tinplate is sheet iron, coated with
tin ; galvanized iron is coated with zinc, to preserve it from the
action of damp air.
Iron unites directly with Cl, Br, I, S, N, P, As, and Sb. It
dissolves in HC1 as ferrous chlorid, while H is liberated. Heated
with strong H2SO4, it gives off SO2 ; with dilute H2SO4, H is given
off and ferrous sulfate formed. Dilute HNO3 dissolves Fe, but
the concentrated acid renders it passive, when it is not dissolved
by either concentrated or dilute HNO3, until the passive condi-
tion is destroyed by contact with Pt, Ag or Cu, or by heating to
40° (104° F.).
Compounds of Iron. — Oxids. — Three oxids of iron exist free :
FeO ; Fe2O3 ; Fe3O4.
Ferrous Oxid — Protoxid of iron — FeO— 71.9— is formed by
heating Fe2O3 in CO or CO».
Ferric Oxid — Sesquioxid or peroxid of iron — Colcothar — Jewel-
ler's rouge — Venetian red — Fe2O3 — 159.8 — occurs in nature (see
above ; and is formed when ferrous sulfate is strongly heated,
as in the manufacture of pyrosulfuric acid. It is a reddish,
amorphous solid, is a weak base, and is decomposed at a white
heat into O and Fe3O4.
Magnetic Oxid — Slack oxid — Ferri oxidum magneticum (Br.)
— Fe3O4 — 231.7 — is the natural loadstone, and is formed by the
action of air, or steam, upon iron at high temperatures. It is
probably a compound of ferrous and ferric oxids (FeO, FeaO3), as
acids produce with it mixtures of ferrous and ferric salts.
Hydrates. — Ferrous. — When a solution of a ferrous salt is de-
composed by an alkaline hydroxid, a greenish-white hydroxid,
FeHaOs, is deposited; which rapidly absorbs O from the air, with
formation of ferric hydroxid.
Ferric.— When an alkali is added to a solution of a ferric salt,
a brown, gelatinous precipitate is formed, which is the normal
ferric hydroxid, (Fe^HeOe — Ferri peroxidum hydratum (TJ. S.);
Fer. perox. humidum (Br.). It is not formed in the presence of
fixed organic acids, or of sugar in sufficient quantity. If pre-
served under H2O, it is partly oxidized, forming an oxyhydrate
which is incapa,ble of forming ferrous arsenate with AsaO3.
If the hydroxid, (Fe2)H6O6, be dried at 100° (212° F.), it loses
2H2O, and is converted into (Fea)Oa, HaOz, which is the Ferri
peroxidum hydratum (Br.}.
154: MANUAL OP CHEMISTRY.
If the normal hydroxid be dried in vacuo, it is converted into
(Fe2)aH6O8, and this, when boiled for some hours with H2O, is
converted into the colloid or modified hydrate (Fe2)H2C>4 (?),
which is brick-red in color, almost insoluble in HNO3 and HC1,
gives no Prussian blue reaction, and forms a turbid solution with
acetic acid. If recently precipitated ferric hydroxid be dissolved
in solution of ferric chlorid or acetate, and subjected to dialysis,
almost all the acid passes out, leaving in the dialyzer a dark red
solution, which probably contains this colloid hydrate, and which
is instantly coagulated by a trace of H2SO4, by alkalies, nianjr
salts, and by heat ; dialyzed iron.
Ferric Acid.— H2Fe2O4. — Neither the free acid nor the oxid,.
FeO3, are known in the free state ; the ferrates, however, of Na,.
K, Ba, Sr, and Ca are known.
Sulfids. — Ferrous Sulfid — Protosulfid of iron— FeS — 87.9— is
formed :
(1) By heating a mixture of finely divided Fe and S to redness ;
(2) by pressing roll-sulfur on white-hot iron ; (3) in a hydrated
condition, FeS,H3O, by treating a solution of a ferrous salt with
an alkaline sulfhydrate.
The dry sulfid is a brownish, brittle, magnetic solid, insoluble
in H2O, soluble in acids with evolution of H2S. The hydrate is a,
black powder, which absorbs O from the air, turning yellow, by
formation of Fe2O3, and liberation of S. It occurs in the faeces of
persons taking chalybeate waters or preparations of iron.
Ferric Sulfid — Sesquisulfid — Fe2S3 — 207.8 — occurs in nature in.
copper pyrites, and is formed when the disulfid is heated to
redness.
Ferric Disulfid — FeS2 — 119.9 — occurs in the white and yellow-
Martial pyrites, used in the manufacture of H2SO4. When
heated in air, it is decomposed into SO2 and magnetic pyrites :
3FeS2 + 2O2 =FesS4 +2SO2.
Chlorids.— Ferrous Chlorid — Protochlorid—'FeCl-t— 129.9— is pro-
duced : (1) by passing dry HC1 over red-hot Fe ; (2) by heating
ferric chlorid in H ; (3), as a hydrate, FeCl2, 4H2O, by dissolving
Fe in HC1.
The anhydrous compound is a yellow, crystalline, volatile, and
very soluble solid. The hydrated is in greenish, oblique rhombic
prisms, deliquescent and very soluble in H2O and alcohol.
When heated in air it is converted into ferric chlorid, and an;
oxychlorid.
Ferric Chlorid — Sesquichlorid — Perchlorid — Ferri chloridum
(U. S.) — Fe2Cl6 — 324.8 — is produced, in the anhydrous form, by
heating Fe in Cl. As a hydrate, Fe2Cl6,4H2O, or Fe2Cl6,6H2O, it
is formed : (1) by solution of the anhydrous compound ; (2) b^
dissolving Fe in aqua regia ; (3) by dissolving ferric hydroxid in.
155
HCl ; (4) by the action of Cl or of HNO3 on solution of ferrous
chlorid. It is by the last method that the pharmaceutical prod-
uct is obtained.
The anhydrous compound forms reddish-violet, crystalline
plates, very deliquescent. The hydrates form yellow, nodular,
imperfectly crystalline masses, or rhombic plates, very soluble in
H2O, soluble in alcohol and ether. In solution, it is converted
into FeCla by reducing agents. The Liq. ferri chloridi (IT. S.) =
Liq. fer. perchloridi (Br.) is an aqueous solution of this com-
pound, containing excess of acid. The Tinct. fer. chlor. (U. S.)
and Tinct. fer. perchl. (Br.) are the solution, diluted with alcohol;
and contain ethyl chlorid and ferrous chlorid.
Bromids. — Ferrous Bromid — FeBr., — 215.9— is formed by the
action of Br on excess of Fe, in presence of HaO.
Ferric Bromid — Fe3Br6 — 591.8 — is prepared by the action of
excess of Br on Fe.
lodids.— Ferrous lodid— Ferri iodidum (U. S.; Br.)—FeI3— 309.9
— is obtained, with 4HaO, by the action of 1 upon excess of Fe in
the presence of warm H2O. When anhydrous, it is a white
powder ; hydrated, it is in green crystals. In air it is rapidly
decomposed, more slowly in the presence of sugar.
Ferric lodid — Fe2I6 — 873.8 — is formed by the action of excess of
I on Fe.
Salts of Iron.— Sulfates.— Ferrous Sulfate— Prot osulfate— Green,
vitriol — Copperas— Ferri sulfas (U. S.; Br.)— FeS04 + 7 Aq— 151.9
+ 126 — is formed: (1) by oxidation of the sulfid, Fe3S4, formed
in the manufacture of H2SO4; (2) by dissolving Fe in dilute
H2SO4.
It forms green, efflorescent, oblique rhombic prisms, quite solu-
ble in H2O, insoluble in alcohol. It loses 6 Aq at 100° (212° F.)
(Ferr. sulf. exsiccatus, TJ. S.); and the last Aq at about 300°
(572° F.). At a red heat it is decomposed into Fe2O3; SO2 and
SO3. By exposure to air it is gradually converted into a basic
ferric sulfate, (Fea)(SO4)3,5Fe2O3.
Ferric Sulfates are quite numerous, and are formed by oxida-
tions of ferrous sulfate under different conditions. The normal
sulfate, (Fe2)(SO4)3, is formed by treating solution of FeSO* with
H.XO3, and evaporating, after addition of one molecule of H2SO4
for each two molecules of FeSO4. The Liq. fer. tersulfatis (U.S.)
contains this salt. It is a yellowish-white, amorphous solid.
Of the many basic ferric sulfates, the only one of medical in-
terest is Monsel's salt, 5(Fea)(SO4)3-f-4Fe2O3, which exists in the
Liq. ferri subsulfatis (U. S.) and Liq. fer. persulfatis (Br.). Its
solution is decolorized, and forms a white deposit with excess of
H2SO4.
156 MANUAL OF CHEMISTRY.
Nitrates. — Ferrous Nitrate — Fe(NO3)2 — 179.9 — a greenish, un-
stable salt, formed by double decomposition between barium,
nitrate and ferrous sulfate; or by the action of HNOt on FeS.
Ferric Nitrates — The normal nitrate— (Fev)(NO3)e—483.S — is ob-
tained in solution by dissolving Fe in HNO3 of sp. gr. 1.115 ; or
by dissolving ferric hydroxid in HNO3. It therefore exists in the
Liq. ferri nitratis (U. S.). It crystallizes in rhombic prisms with
18 Aq, or in cubes with 12 Aq.
Several basic nitrates are known, all of which are uncrystal-
lizable, and by their presence (as when Fe is dissolved in HNO3
to saturation) prevent the crystallization of the normal salt.
Phosphates. — Triferrous Phosphate— Fe3(PO4)2 — 357. 7. — A white
precipitate, formed by adding disodic phosphate to a solution of
a ferrous salt, in presence of sodium acetate. By exposure to
air it turns blue ; a part being converted into ferric phosphate.
The ferri phosphas (Br.) is such a mixture of the two salts. It
is insoluble in H2O ; sparingly soluble in H2O containing car-
bonic or acetic acid.
It is probably this phosphate, capable of turning blue, which
sometimes occurs in the lungs in phthisis, in blue pus, and in
long-buried bones.
Ferric Phosphate — (Fe2)(PO4)ii — 301.8 — is produced by the action
of an alkaline phosphate on ferric chlorid. It is soluble in HC1,
HNO3, citric and tartaric acids, insoluble in phosphoric acid and
in solution of hydrosodic phosphate. The ferri phosphas (U. S.)
is a compound, or mixture of this salt with disodic citrate, which
is soluble in water.
There exist quite a number of basic ferric phosphates.
Ferric Pyrophosphate — (Fe2)2(P2O7)3 — 745.6 — is precipitated by
•decomposition of a solution of a ferric compound by sodium py-
rophosphate ; an excess of the Na salt dissolves the precipitate
when warmed, and, on evaporation, leaves scales of a double
salt, (Fea)a(PaO7)3, Na8(P2O,)2 + 20 Aq.
The ferri pyrophosphas (TJ. S.) is a mixture of ferric pyrophos-
phate, trisodic citrate, and ferric citrate.
Acetates. — Ferrous Acetate — Fe(C2H3O2)2— 173.9 — is formed by
decomposition of ferrous sulfate by calcium acetate, in soluble,
silky needles.
Ferric Acetates. — The normal salt, (FeaXCsHsOOe, is obtained
by adding slight excess of ferric sulfate to lead acetate, and de-
canting after twenty-four hours. It is dark red, uncrystallizable,
very soluble in alcohol, and in H2O. If its solution be heated it
•darkens suddenly, gives off acetic acid, and contains a basic
acetate. When boiled, it loses all its acetic acid, and deposits
ferric hydrate. When heated in closed vessels to 100° (212° F.),
and treated with a trace of mineral acid, it deposits the modified
ferric hydrate.
IRON. 1ST
Ferrous Carbonate — FeCO3 — 115.9 — occurs as an ore of iron, and
is obtained, in a hydrated form, by adding an alkaline carbonate-
to a ferrous salt. It is a greenish, amorphous powder, which on
exposure to air, turns red by formation of ferric hydrate ; a
change which is retarded by the presence of sugar, hence the
addition of that substance in the ferri carbonas saccharatus
(U. S.; Br.). It is insoluble in pure H2O, but soluble in H2O
containing carbonic acid, probably as ferrous bicarbonate,.
H2Fe(CO3)a, in which form it occurs in chalybeate waters.
Ferrous Lactate— Ferri lactas (U. S.)— Fe(C3HsO3)2+3Aq— 233.9+
54 — is formed when iron filings are dissolved in lactic acid. It
crystallizes in greenish-yellow needles ; soluble in H2O ; insol-
uble in alcohol ; permanent in air when dry.
Ferrous Oxalate— Ferri oxalas (U. S.) FeC2O4+Aq— 143.9+36 — is
a yellow, crystalline powder ; sparingly soluble in HaO ; formed
by dissolving iron filings in solution of oxalic acid.
Tartrates — Ferrous Tartrate — FeC4H4O6+2Aq— 203.9+36.— A.
white, crystalline powder ; formed by dissolving Fe in hot concen-
trated solution of tartaric acid.
Ferric Tartrate — Fe2(C4H4O6)3+3Aq — 555.8+54 — A dirty yel-
low, amorphous mass, obtained by dissolving recently precipi-
tated ferric hydroxid in tartaric acid solution, and evaporating
below 59° (122° F.).
A number of double tartrates, containing the proup (FesOj)"
are also known. Such are : Ferrico-ammonic tartrate = ferri
et ammonii tartras (TJ. S.), (C4H4Oe)2{Fe2O2), (NH)4+4Aq, and
Ferrico-potassic tartrate = ferri et potassii tartras (TJ. S.),
(C4H4O«)2(Fe2O2)K2. They are prepared by dissolving recently
precipitated ferric hydroxid in hot solutions of the hydro-alkaline
tartrate. They only react with ferrocyanids and sulfocyanates
after addition of a mineral acid.
Citrates.— Ferric Citrate — Ferri citras (TJ. S.)— (Fe2)(C6H5O7)2 -j-
6Aq — 489.8-fl08 — is in garnet-colored scales, obtained by dissolv-
ing ferric hydrate in solution of citric acid, and evaporating the
solution at about 60° (140° F.). It loses 3 Aq at 120° (248° F.), and
the remainder at 150° (302° F.). If a small quantity of ammo-
nium hydroxid be added, before the evaporation, the product
consists of the modified citrate — ferri et ammonii citras (U. S.),
which only reacts with potassium ferrocyanid after addition of
HC1.
The various citrates of iron and alkaloids are not definite
compounds.
Ferric Ferrocyanid — Prussian blue — (Fea)2(FeCeN6)3 + 18Aq —
859.3+324— is a dark blue precipitate, formed when potassium
ferrocyanid is added to a ferric salt. It is insoluble in H2O,
alcohol and dilute acids ; soluble in oxalic acid solution (blue
ink). Alkalies turn it brown.
158 MANUAL OF CHEMISTRY.
Ferrous Ferricyanid — Turnbull's blue— Fe3(Fe2CiaNi2)+riAq —
591.5-t-ril8 — is a dark blue substance produced by the action of
potassium ferricyanid on ferrous salts. Heated in air it is con-
verted into Prussian blue and ferric oxid.
Analytical Characters. — FERROUS — Are acid ; colorless when
anhydrous ; pale green when hydrated ; oxidized by air to basic
ferric compounds. (1.) Potash : greenish-white ppt. ; insoluble in
excess ; changing to green or brown in air. (2.) Ammonium hy-
droxid : greenish ppt.; soluble in excess; not formed in presence
of ammoniacal salts. (3.) Ammonium sulf hydrate : black ppt. ;
insoluble in excess ; soluble in acids. (4.) Potassium ferrocyanid
(in absence of ferric salts) : white ppt. ; turning blue in air. (5.)
Potassium ferricyanid : blue ppt. ; soluble in KHO ; insoluble in
HC1.
FERRIC — Are acid, and yellow or brown. (1.) Potash, or am-
monium hydroxid: voluminous, red-brown ppt.; insoluble in ex-
cess. (2.) Hydrogen sulfid: in acid solution; milky ppt. of sulfur;
ferric reduced to ferrous compound. (3.) Ammonium sulfhydrate:
black ppt. ; insoluble in excess; soluble in acids. (4.) Potassium
ferrocyanid: dark blue ppt. ; insoluble in HC1; soluble in KHO.
<5.) Potassium sulfocyariate : dark-red color ; prevented by tar-
taric or citric acid; discharged by mercuric chlorid. (6.) Tannin:
blue-black color.
III. ALUMINIUM GROUP.
GLUCINIUM — ALUMINIUM— SCANDIUM — GALLIUM — INDIUM.
This group is placed in the third class by virtue of the exist-
ence of the aluminates, and of the relations between the com-
pounds of these elements and some of those of the previous
group. They form one series of compounds, corresponding to
the ferric, containing the group (M2)vi, but no compounds corre-
sponding to the ferrous M" are known. Indeed, certain organic
compounds, such as aluminium acetylacetonate, A1(C6H7O2)3,
seem to contain single, trivalent atoms of the metal. No acids or
salts of the members of the group, other than aluminium, are
known ; yet their resemblances in other points are such as to for-
bid their separation.
GLUCINIUM.
Symbol — Gl or Be (Beryllium) — Atomic weight = 9 — Sp. gr. —
2.1.
A rare element occurring in the emerald and beryl. The metal
resembles aluminium and its compounds resemble those of Al,
ALUMINIUM. 159
and, in some respects, those of Mg. Its soluble salts are sweet in
taste (yfowvf = sweet).
ALUMINIUM.
Symbol =. Al — Atomic weight = 27 — Molecular weight = 55 (?) —
Sp. gr. = 2.56-2.67— Fuses at about 700° (1292° F.)— Name from
alunien=aZwm — Discovered by Wohler, 1827.
Occurrence. — Exceedingly abundant in the clays as silicate.
Preparation. — (1.) By decomposing vapor of aluminium chlorid
by Na or K(W6hler). (2.) Aluminium hydroxid, mixed with sodium
•chlorid and charcoal, is heated in CI, by which a double chlorid
•of Na and Al (2NaCl, A12C18) is formed. This is then heated with
.Na, when Al and NaCl are produced. (The industrial process.)
Properties. — Physical. — A bluish-white metal ; hard ; quite
malleable, and ductile, when annealed from time to time ; slightly
magnetic ; a good conductor of electricity ; non-volatile ; very
light, and exceedingly sonorous.
Chemical. — It is not affected by air or O, except at very high
temperatures, and then only superficially. If, however, it con-
tain Si, it burns readily in air, forming aluminium silicate. It
does not decompose HaO at a red heat ; but in contact with Cu,
Pt, or I, it does so at 100° (212° F.). It combines directly with B,
Si, Cl, Br, and I. It is attacked by HC1, gaseous or in solution,
with evolution of H, and formation of AluClg. It dissolves in
alkaline solutions, with formation of aluminates, and liberation
of H. It alloys with Cu to form a golden yellow metal (alumin-
ium bronze).
Aluminium Oxid — Alumina — A1203 — 102 — occurs in nature,
nearly pure, as corundum, emery, ruby, sapphire and topaz; and
is formed artificially, by calcining the hydrate, or ammonia alum,
at a red heat.
It is a light, white, odorless, tasteless powder ; fuses with diffi-
culty ; and, on cooling, solidifies in very hard crystals. Unless it
have been heated to bright redness, it combines with H2O, with
elevation of temperature. It is almost insoluble in acids and
alkalies. H^SCX, diluted with an equal bulk of H3O, dissolves it
slowly as (ALXSO^s. Fused potash and soda combine with it to
form aluminates. It is not reduced by charcoal.
Aluminium Hydroxid — Aluminium hydrate — Aluminii hydras
(U. S.) — ALHeOs — 156 — is formed when a solution of an aluminium
salt is decomposed by an alkali, or alkaline carbonate. It con-
stitutes a gelatinous mass, which, when dried, leaves an amor-
phous, translucid mass ; and, when pulverized, a white, tasteless,
amorphous powder. When the liquid in which it is formed con-
tains coloring matters, these are carried down with it, and the
dried deposits are used as pigments, called lakes.
160 MANUAL OF CHEMISTKY.
When freshly precipitated, it is insoluble in H20 ; soluble in
acids, and in solutions of the fixed alkalies. When dried at a-
temperature above 50° (122° P.), or after 24 hours1 contact with the
mother liquor, its solubility is greatly diminished. With acids it
forms salts of aluminium ; and with alkalies, aluminates of the
alkaline metal. Heated to near redness, it is decomposed into
A12O3 and H2O. A soluble modification is obtained by dialyzing
a solution of Al2HeO6 in A12C16, or by heating a dilute solution of
aluminium acetate for 24 hours.
Aluminates are for the most part crystalline, soluble com-
pounds, obtained by the action of metallic oxids or hydroxids
upon alumina. Potassium aluminate, K2Al2O4-|-3Aq, is formed
by dissolving recently precipitated aluminium hydroxid in pot-
ash solution. It forms white crystals ; very soluble in H2O, in-
soluble in alcohol ; caustic and alkaline. By a large quantity of
H2O it is decomposed into aluminium hydroxid, and a more alka-
line salt, KeAUOo.
Sodium Aluminate. — The aluminate NasAlaO4 is not known.
That having the composition Na8Al4O9 is prepared by heating to
redness a mixture of 1 pt. sodium carbonate and 2 pts. of a native
ferruginous aluminium hydrate (beauxite). It is insoluble in
H2O, and is decomposed by carbonic acid, with precipitation of
aluminium hydroxid.
Aluminium Chlorid — ALCL — 267 — is prepared by passing Cl
over a mixture of A12O3 and C, heated to redness ; or by heating
clay in a mixture of gaseous HC1 and vapor of CSa.
It crystallizes in colorless, hexagonal prisms ; fusible ; volatile ;
deliquescent ; very soluble in H2O and in alcohol. From a hot,
concentrated solution, it separates in prisms with 12 Aq.
The disinfectant called chloralum is a solution of impure A12C16.
Aluminium Sulfate— Aluminii sulfas (U.S.)— (A12)(SO4)3 + 18
Aq— 342 -|- 324— is obtained by dissolving A12H6O8 in H2SO4 ; or
(industrially) by heating clay with H2SO4.
It crystallizes, with difficulty, in thin, flexible plates ; soluble
in H2O ; very sparingly soluble in alcohol. Heated, it fuses in its
Aq, which it gradually loses up to 200° (392° P.), when a white,
amorphous powder, (A12)(SO4)3, remains; this is decomposed at a,
red heat, leaving a residue of pure alumina.
Alums— are double sulfates of the alkaline metals, and the
higher sulfates of this, or the preceding group. When crystal-
lized, they have the general formula : (M2)vl (SO4)3, R'2SO4 + 24
Aq, in which (M) may be (Fe2), (Mri2), (Cr2), (A12), or (Ga2) ; and
R2 may be K2, Nas, Rb2, Cs2, T12, or (NH4)a. They are isomor-
phous with each other.
Alumen (U. S.)— A13(SO4)3,K,SO4 + 24 Aq— 516 + 432— is manu-
factured from "alum shale," and is formed when solutions of the
sulfates of Al and K are mixed in suitable proportion.
ALUMINIUM. 161
It crystallizes in large, transparent, regular octahedra ; has a
sweetish, astringent taste, and is readily soluble in HaO. Heated,
it fuses in its Aq at 92° (197°. 6 F.) ; and gradually loses 45.5 per
cent, of its weight of H3O, as the temperature rises to near red-
ness. The product, known as burnt alum = alumen exsiccatum
(U. S.), is (Al)a(SO4)3, K2SO4, and is slowly, but completely solu-
ble in 20-30 pts. H2O. At a bright red heat, SO2 and O are given
off, and AUOs and potassium sulfate remain ; at a higher tem-
perature, potassium aluininate is formed. Its solutions are acid
in reaction ; dissolve Zn and Fe with evolution of H ; and deposit
AUHeOe when treated with ammonium hydroxid.
Alumen (Br.)— Al^SO^CNH^SO* + 24 Aq— 474 + 432— is the
compound now usually met with as alum, both in this country
and in England. It differs from potash alum in being more solu-
ble in HjO, between 20°-dO' (68°-86° F.), and less soluble at other
temperatures; and in the action of heat upon it. At 92°(197°.6F.)
it fuses in its Aq ; at 205° (401° F.) it loses its ammonium-sulfate,
leaving a white, hygroscopic substance, very slowly and incom-
pletely soluble in HaO. More strongly heated, it leaves alumina.
Silicates — are very abundant in the different varieties of clay,
feldspar, albite, labradorite, mica, etc. The clays are hydrated
aluminium silicates, more or less contaminated with alkaline and
earthy salts and iron, to which last certain clays owe their color.
The purest is kaolin, or porcelain clay, a white or grayish pow-
der. They are largely used in the manufacture of the different
varieties of bricks, terra cotta, pottery, and porcelain. Porcelain
is made from the purer clays, mixed with sand and feldspar ; the
former to prevent shrinkage, the latter to bring the mixture into
partial fusion, and to render the product translucent. The fash-
ioned articles are subjected to a first baking. The porous, baked
clay is then coated with a glaze, usually composed of oxid of lead,
sand, and salt. During a second baking, the glaze fuses, and coats
the article with a hard, impermeable layer. The coarser articles
of pottery are glazed by throwing sodium chlorid into the fire ; the
salt is volatilized, and, on contact with the hot aluminium sili-
cate, deposits a coating of the fusible sodium silicate, which
hardens on cooling.
Analytical Characters. — (1.) Potash, or soda ; white ppt. ; solu-
ble in excess. (2.) Ammonium hydroxid; white ppt. ; almost in-
soluble in excess, especially in presence of ammoniacal salts. (3.)
Sodium phosphate ; white ppt. ; readily soluble in KHO and
NaHO, but not in NH4HO ; soluble in mineral acids, but not in
acetic acid. (4.) Blowpipe — on charcoal does not fuse, and moist-
ened with cobalt nitrate solution turns dark sky-blue.
11
162
MANUAL OF CHEMISTEY.
SCANDIUM.
Symbol — Sc — Atomic weight = 44.9 — Discovered byNilson (1879)
— Name from Scandia.
Occurs in minute traces in gadolinite and euxenite. It forms
an oxid, Sc2O3 ; a light, white, infusible powder ; sp. gr. 3.8 ; re-
sembling alumina.
GALLIUM.
Symbol = Oa — Atomic weight — 68.8 — Sp. gr. — 5.9 — Fuses at 36°
(86° F.)— Name from Gallia — Discovered by Lecoq de Soisbaudran
(1876).
Occurs in very small quantity in certain zinc blendes. It is a
hard, white metal; soluble in hot HNO3, in HC1, and in KHO
solution. In chemical characters it closely resembles Al ; forms
an oxid, Ga2O3, and a series of alums.
The discovery of Sc and Ga affords most flattering verifications
of predictions based upon purely theoretical considerations.
It has been observed that there exist numerical relations be-
tween the atomic weights of the elements, which, in groups
of allied elements, differ from each other by (approximately)
some multiple of eight. Upon this variation Mendelejeff has
based what is known as the Periodic Law, to the effect that :
" The properties of elements, the constitution of their compounds,
and the properties of the latter, are periodic functions of the
atomic weights of the elements."
In accordance with this law the elements may be thus arranged :
Series.
Group
Group
II.
Group
III.
Group
IV.
Group
V.
Group
VI.
Group
VII.
Group.
VIII.
1
RH4
RO2
RH3
R805
RH2
RO3
RH
R20,
(R2H)
(R04)
RaO
H-l
RO
Ra03
2
Li=7
Be=9
B=ll
C=12
N=14
O=16
F=19
3
Na=23
K=39
Mg=24
Ca=40
Al=27
Sc-44
Si=28
Ti=48
P=31
V=51
8=32;
O=52
Cl=35
Mn=55
Cu=63
Fe=56
Co=59
Ni=59
4
5
(Cu=63)
Rb=85
Zn=65
Sr=87
Ga=69
Yt=88
Ge=72
Zr=90
As=75
Nb=94
Se=78
Mo=96
Br=80
?=100
Ru=104
Rh=104
Pd^l06
Ag=108
6
1
(Ag=108)
Cs=133
Cd=112
Ba=137
In=113
La=139
Sn=118
Ce=142
Sb=120
Di=145
Te=125
Sm=i50
1=127
Da=154
8
9
E-166
Os=195
Ir=193
Pt=195
Au=197
10
Yb-173
Ta=182
W=184
?=190
J5
(Au=196)
Hg=200
Tl=204
Pb=207
Th-231
Bi=208
12
U-238
INDIUM, TTKAIMUM, LEAD. 163
The atomic weights and chemical characters, which were an-
nounced by Mendelejeff in 1870 as those of the undiscovered ele-
ments which would occupy the positions 4 and 5 in group III.
have been since found to be those of Sc and Ga. Still later, the
vacant positions 10, III., 5, IV., 8, VI., and 8, VII., have been
filled by the discovery of Yb, Ge, Sm, and Da.
INDIUM.
Symbol = In — Atomic weight = 113.4 — Sp. gr.= 7.42 — Fuses at
176° (348°. 8 F.)— Discovered by Reich and Richter in 1863.
A soft, silver-white, ductile metal, which occurs in small quan-
tity in certain zinc blendes. It is characterized spectroscopically
by two principal lines — /. = 4511 and 4101.
IV. URANIUM GROUP.
URANIUM.
Symbol = Ur — Atomic weight = 238.5 — Sp. gr.= 18.4 — Discovered
by Klaproth (1789).
This element is usually classed with Fe and Or, or with Ni and
Co. It does not, however, form compounds resembling the
ferric ; it forms a series of well-defined uranates, and a series of
compounds of the radical uranyl (UO)'. Standard solutions of
its acetate or nitrate are used for the quantitative determina-
tion of H3PO4.
V. LEAD GROUP.
LEAD.
Symbol = Pb (PLUMBUM)— Atomic weight = 206.9— Molecular
weight = 413.8 (l)—8p. gr.= 11.445— Fuses at 325° (617° F.)— Name
from Iced = heavy (Saxon).
Lead is usually classed with Cd, Bi, or Cu and Hg. It differs,
however, from Bi in being bivalent or quadrivalent, but not
trivalent, and in forming no compounds, resembling those of
bismuthyl (BiO) ; from Cd, in the nature of its O compounds ;
and from Cu and Hg in forming no compounds similar to the
mercurous and cuprous salts. Indeed, the nature of the Pb
compounds is such that the element is best classed in a group by
itself, which finds a place in this class by virtue of the existence
of potassium plumbate.
164 MANUAL OF CHEMISTRY.
Occurrence. — Its most abundant ore is galena, PbS. It also
occurs in white lead ore, PbCOs, in anglesite, PbSO4, and in-
horn lead, PbCl2.
Preparation. — Galena is first roasted with a little lime. The
mixture of PbO, PbS, arid PbSO4, so obtained, is strongly heated
in a reverberatory furnace, when SO2 is driven off. The impure
work lead, so formed, is purified by fusion in air, and removal of
the film of oxids of Sn and Sb. If the ore be rich in Ag, that
metal is extracted, by taking advantage of the greater fusibility
of an alloy of Pb and Ag, than of Pb alone ; and subsequent
oxidation of the remaining Pb.
Properties. — Physical. — It is a bluish-white metal ; brilliant
upon freshly cut surfaces ; very soft and pliable ; not very malle-
able or ductile ; crystallizes in octahedra ; a poor conductor of
electricity ; a better conductor of heat. When expanded by
heat, it does not, on cooling, return to its original volume.
Chemical. — When exposed to air it is oxidized, more readily
and completely at high temperatures. The action of H2O on Pb
varies with the conditions. Pure unaerated H2O has no action
upon it. By the combined action of air and moisture Pb is oxi-
dized, and the oxid dissolved in the H2O, leaving a metallic sur-
face for the continuance of the action. The solvent action of
HSO upon Pb is increased, owing to the formation of basic salts,
by the presence of nitrogenized organic substances, nitrates,
nitrites, and chlorids. On the other hand, carbonates, sulfa,tesv
and phosphates, by their tendency to form insoluble coatings,
diminish the corroding action of H2O. Carbonic acid in small
quantity, especially in presence of carbonates, tends to preserve
Pb from solution, while H2O highly charged with it (soda water)
dissolves the metal readily. Lead is dissolved, as a nitrate, by
HNOa. H2SO4 when cold and moderately concentrated, does not
affect it ; but, when heated, dissolves it the more readily as the
acid is more concentrated. It is attacked by HC1 of sp. gr. 1.12,
especially if heated. Acetic acid dissolves it as acetate, or, in the
presence of CO2, converts it into white lead.
Oxids. — Lead Monoxid — Protoxid — Massicot — Litharge — Plum-
bi oxidum (U. S.; Br.)— PbO— 222.9— is prepared by heating Pb, or
its carbonate, or nitrate, in air. If the product have been fused,
it is litharge ; if not, massicot. It forms copper-colored, mica-like
plates, or a yellow powder ; or crystallizes, from its solution in
soda or potash, in white, rhombic dodecahedra, or in rose-colored
cubes. It fuses near a red heat, and volatilizes at a white heat ;
sp. gr. 9.277-9.5. It is sparingly soluble in H2O, forming an alka-
line solution.
Heated in air to 300° (572° F.) it is oxidized to minium. It is
LEAD. 165
readily reduced by H or C. With Cl it forms PbCl-, and O. It is
•a strong base ; decomposes alkaline salts, with liberation of the
alkali. It dissolves in HNO3, and in hot acetic acid, as nitrate or
acetate. When ground up with oils it saponifies the glycerin
ethers, the Pb combining with the fatty acids to form Pb soaps,
one of which, lead oleate, is the emplastrum plumbi, TJ. S.; Br.
It also combines with the alkalies and earths to form plumbites.
Calcium plumbite, CaPb2O3, is a crystalline salt, formed by heat-
ing PbO with milk of lime, and used in solution as a hair-dye.
Plumboso-plumbic Oxid — Red oxid — Minium — Red lead — Pb3
•O4 — 684.7 — is prepared by heating massicot to 300° (572" F.) in air.
It ordinarily has the composition Pb3O4, and has been considered
-as composed of PbO», 2PbO ; or as a basic lead, salt of plumbic
.acid, PbO3Pb, PbO. An orange-colored variety is formed when
lead carbonate is heated to 300° (572° P.).
It is a bright red powder, sp. gr. 8.62. It is converted into PbO
when strongly heated, or by the action of reducing agents. HNO3
changes its color to brown, dissolving PbO and leaving PbOa.
It is decomposed by HC1, with formation of PbCls, H3O and Cl.
Lead Dioxid — Peroxid, or puce oxid, or brown oxid, or binoxid
of lead— Plumbic anhydrid — PbO2 — 238.9— is prepared, either by
dissolving the PbO out of red lead by dilute HNOa. or by passing
a current of Cl through HaO, holding lead carbonate in suspen-
sion.
It is a dark, reddish-brown, amorphous powder; sp. gr. 8.903-
9.190; insoluble in H3O. Heated, it loses half its O, and is con-
verted into PbO. It is a valuable oxidant. It absorbs SO2
to form PbSO4. It combines with alkalies to form plumbates,
Plumbic Acid— PbOsHa— 256.9— forms crystalline plates, at the
+ electrode, when alkaline solutions of the Pb salts are decom-
posed by a weak current.
Lead Sulfid— Galena— PbS— 238.9— exists in nature. It is also
formed by direct union of Pb and S ; by heating PbO with S, or
vapor of CSa; or by decomposing a solution of a Pb salt by H2S
•or an alkaline sulfid.
The native sulfid is a bluish-gray, and has a metallic lustre ;
sp. gr. 7.58 ; that formed by precipitation is a black powder ; sp.
gr. 6.924. It fuses at a red heat and is partly sublimed, partly
converted into a subsulfate. Heated in air it is converted into
PbSO4, PbO and SO,. Heated in H it is reduced. Hot HNO3
oxidizes it to PbSO4. Hot HC1 con verts it into PbCla. Boiling
H»SO4 converts it into PbSO4 and SO-,.
LeadChlorid — PbCl2 — 277.9 — is formed by the action of Clupon
Pb at a red heat ; by the action of boiling HC1 upon Pb ; and by
•double decomposition between a lead-salt and a chlorid.
166 MANUAL OF CHEMISTKY.
It crystallizes in plates, or hexagonal needles ; sparingly solu-
ble in cold H8O, less soluble in H2O containing HC1 ; more solu-
ble in hot H2O, and in concentrated HC1.
Several oxychlorids are known. Cassel, Paris, Verona, or
Turner's yellow is PbCl2, 7PbO.
Lead lodid— Plumbi iodidum (TJ. S.; Br.)— PbI2— 460.9— is de-
posited, as a bright yellow powder, when a solution of potassium
iodid is added to a solution of a Pb salt. Fused in air, it is con-
verted into an oxyiodid. Light and moisture decompose it, with
liberation of I. It is almost insoluble in H2O, soluble in solu-
tions of ammonium chlorid, sodium hyposulfite, alkaline iodids,
and potash.
Nitrates. — Lead Nitrate — Plumbi nitras — (TJ. S. ; Br.) —
Pb(NO3)2 — 330.9 — is formed by solution of Pb, or of its oxids, in.
excess of HNO3. It forms anhydrous crystals ; soluble in H2O.
Heated, it is decomposed into PbO, O and NO2.
Besides the neutral nitrate, basic lead nitrates are known,
which seem to indicate the existence of nitrogen acids similar to
those of phosphorus ; PbsCNCMa — orthonitrate ; and Pb2NsO7—
pyronitrate.
Lead Sulfate— PbS04— 302.9— is formed by the action of hot,
concentrated H2SO4 on Pb ; or by double decomposition between
a sulfate and a Pb salt in solution. It is a white powder,
almost insoluble in H2O, soluble in concentrated H2SO4, from
which it is deposited by dilution.
Lead Chromate— Chrome yellow— PbCrO4 — 323.3 — is formed by
decomposing Pb(NO3)2 with potassium chromate. It is a yellow,
amorphous poAvder, insoluble in H2O, soluble in alkalies.
Acetates. — Neutral Lead Acetate — Salt of Saturn — Sugar of
Lead— Plumbi acetas (U.S.; Br.)—Pb(C2H3O2)2+3Aq— 324.9+54— is
formed by dissolving PbO in acetic acid ; or by exposing Pb in
contact with acetic acid to air.
It crystallizes in large, oblique rhombic prisms, sweetish, with
a metallic after-taste ; soluble in H2O and alcohol ; its solutions,
being acid. In air it effloresces, and is superficially converted
into carbonate. It fuses at 75°. 5 (167°. 9 F.) ; loses Aq, and a part
of its acid at 100° (212° P.), forming the sesquibasic acetate ; at
280° (536° F.) it enters into true fusion, and, at a slightly higher
temperature, is decomposed into CO2 ; Pb, and acetone. It*
aqueous solution dissolves PbO, with formation of basic acetates.
Sexbasic Lead Acetate— Pb(C2H3Os)OH, 2PbO— 728. 7— is the
main constituent of Goulard's extract = Liq. plumbi subacetatis
(TJ. S. ; Br.), and is formed by boiling a solution of the neutral
acetate with PbO in fine powder. The solution becomes milky
on addition of ordinary H2O, from formation of the sulfate and.
carbonate.
LEAD. 167
Lead Carbonate — PbC03 — 266.9 — occurs in nature as cerusite ;
and is formed, as a white, insoluble powder, when a solution of a
Pb compound is decomposed by an alkaline carbonate, or by
passing CO2 through a solution containing Pb.
The plumbi carbonas (U. S. ; Br.), or white lead or ceruse, is a
basic carbonate (PbCO3);i, PbH2O2— 774.7 — mixed with varying
proportions of other basic carbonates. It is usually prepared by
the action of CO2 on a solution of the subacetate, prepared by the
action of acetic acid on Pb and PbO. It is a heavy, white powder;
insoluble in H2O, except in the presence of CO2 ; soluble in acids
with effervescence ; and decomposed by heat into CO2 and PbO.
Analytical Characters. — (1.) Hydrogen sulfid, in acid solu-
tion: a black ppt. ; insoluble in alkaline sulfids, and in cold,
dilute acids. (2.) Ammonium sulf hydrate: black ppt.; insolu-
ble in excess. (3.) Hydrochloric acid : white ppt. ; in not too
dilute solution ; soluble in boiling H2O. (4.) Ammonium hy-
droxid: white ppt. ; insoluble in excess. (5.) Potash: white ppt. ;
soluble in excess, especially when heated. (6.) Sulfuric acid:
white ppt. ; insoluble in weak acids, soluble in solution of am-
monium tartrate. (7.) Potassium iodid : yellow ppt. ; sparingly
soluble in boiling H2O ; soluble in large excess. (8.) Potassium
chromate : yellow ppt. ; soluble in KHO solution. (9,) Iron or
zinc separate the element from solution of its salts.
Action on the Economy. — All the soluble compounds of Pb, and
those which, although not soluble, are readily convertible into
soluble compounds by H2O, air, or the digestive fluids, are ac-
tively poisonous. Some are also injurious by their local action
upon tissues with which they come in contact ; such are the
acetate, and, in less degree, the nitrate.
The chronic form of lead intoxication, painter's colic, etc., is
purely poisonous, and is produced by the continued absorption
of minute quantities of Pb, either by the skin, lungs, or stomach.
The acute form presents symptoms referable to the local, as well
as to the poisonous, action of the Pb salt, and is usually caused
by the ingestion of a single dose of the acetate or carbonate.
Metallic Pb, although probably not poisonous of itself, causes
chronic lead-poisoning by the readiness with which it is convertible
into compounds capable of absorption. The principal sources of
poisoning by metallic Pb are : the contamination of drinking
water which has been in contact with the metal (see p. 72) ; the
use of articles of food, or of chewing tobacco, which has been
packed in tin-foil, containing an excess of Pb ; the drinking of
beer or other beverages which have been in contact with pewter ;
or the handling of the metal and its alloys.
168 MANUAL OF CHEMISTRY.
Almost all the compounds of Pb may produce painter's colic.
The carbonate, in painters, artists, manufacturers of white lead,
and in persons sleeping in newly painted rooms ; the oxids, in
the manufactures of glass, pottery, sealing-wax, and litharge, and
by the use of lead-glazed pottery ; by other compounds, by the
inhalation of the dust of cloth factories, and by the use of lead
hair-dyes.
Acute lead-poisoning is of by no means as common occurrence
as the chronic form, and usually terminates in recovery. It is
caused by the ingestion of a single large dose of the acetate, sub-
acetate, carbonate, or of red lead. In such cases the administra-
tion of magnesium sulfate is indicated ; it enters into double
decomposition with the Pb salt to form the insoluble PbSO4.
Lead, once absorbed, is eliminated very slowly, it becoming
fixed by combination with the albuminoids, a form of combina-
tion which is rendered soluble by potassium iodid. The channels
of elimination are by the perspiration, urine and bile.
In the analysis for mineral poisons (see p. 136), the major part
of the Pb is precipitated as PbS in the treatment by HSS. The
PbS remains upon the filter after extraction with ammonium
sulfhydrate. It is treated with warm HC1, which decolorizes it
by transforming the sulfid into chlorid. The PbCla thus formed
is dissolved in hot HaO, from which it crystallizes on cooling.
The solution still contains PbCla in sufficient quantity to respond
to the tests for the metaL
Although Pb is not a normal constituent of the body, the
every-day methods by which it may be introduced into the econ-
omy, and the slowness of its elimination, are such as to render
the greatest caution necessary in drawing conclusions from the
detection of Pb in the body after death.
VI. BISMUTH GROUP.
BISMUTH.
Symbol = Bi — Atomic weight = 207.5 — Molecular weight = 420
(1)—Sp. gr. = 9.677-9.935— Fuses at 268° (514°.4 F.).
This element is usually classed with Sb ; by some writers among
the metals, by others in the phosphorus group. We are led to
class Bi in our third class, and in a group alone, because : (1)
while the so-called salts of Sb are not salts of the element, but of
the radical (SbO)', antimonyl, Bi enters into saline combination,
not only in the radical bismuthyl (BiO)', but also as an element ;
(2) while the compounds of the elements of the N group in which
those elements are quinquivalent are, as a rule, more stable than
those in which they are trivalent, Bi is trivalent in all its known
BISMUTH. 169
•compounds except one, which is very unstable, in which it is
•quinquivalent ; (3) the hydrates of the N group are strongly acid,
and their corresponding salts are stable and well denned ; but
those hydrates of Bi which are acid are but feebly so, and the
bisniuthates are unstable ; (4) no compound of Bi and H is
known.
Occurrence. — Occurs principally free, also as Bi^Os and Bi2S2.
Properties. — Crystallizes in brilliant, metallic rhornbohedra ;
hard and brittle.
It is only superficially oxidized in cold air. Heated to redness
in air, it becomes coated with a yellow film of oxid. In HaO, con-
taining CO2, it forms a crystalline subcarbonate. It combines
directly with Cl, Br, and I. It dissolves in hot HaSCX as sulfate,
and in HNO3 as nitrate.
It is usually contaminated with As, from which it is best puri-
fied by heating to redness a mixture of powdered bismuth, po-
tassium carbonate, soap and charcoal, under a layer of charcoal.
After an hour the mass is cooled ; the button is separated and
fused until its surface begins to be coated with a yellowish-brown
oxid.
Oxids. — Pour oxids are known : Bi2Oi; Bi3Os ; Bi-jO* ; and
Bi2O5.
Bismuth. Trioxid — Bismuthous oxid — Protoxid — Bi203 — 468 — is
formed by heating Bi, or its nitrate, carbonate, or hydrate. It
is a pale yellow, insoluble powder ; sp. gr. 8. 2 ; fuses at a red heat ;
soluble in HC1, HNO3 and HaSO4 and in fused potash.
Hydrates. — Bismuth forms at least four hydrates.
Bismuthous Hydroxid— BiH3O3— 261 — is formed, as a white pre-
cipitate, when potash or ammonium hydroxid is added to a cold
solution of a Bi salt. When dried, it loses H2O, and is converted
into bismuthyl hydroxid (BiO)HO.
Bismuthic Acid — (BiO2)HO — 259 — is deposited, as a red powder,
when Cl is passed through a boiling solution of potash, holding
bismuthous hydroxid in suspension. When heated it is converted
into the pentoxid, Bi2O6.
Pyrobismuthic Acid— H4Bi2O7— 536 — is a dark brown powder,
precipitated from solution of bismuth nitrate by potassium
<jyanid. . '
Bismuth Trichlorid— Bismuthous chlorid — BiCl3 — 316.5 — is
formed by heating Bi in Cl ; by distilling a mixture of Bi and
mercuric chlorid ; or by distilling a solution of Bi in aqua regia.
It is a fusible, volatile, deliquescent solid ; soluble in dilute HC1.
On contact with H3O it is decomposed with formation of bis-
muthyl chlorid (BiO)Cl, or pearl white.
170 MANUAL OF CHEMISTKY.
Bismuth Nitrate — Bi(NO3)3+5 Aq — 396+90 — obtained by dis-
solving Bi in HNO3. It crystallizes in large, colorless prisms ; at
150° (302° F.), or by contact with H2O, it is converted into bis-
uiuthyl nitrate ; at 260° (500° F.) into Bi4O3.
Bismuthyl Nitrate — Trisnitrate or subnitrate of bismuth —
Flake white— Bismuthi subnitras (U. S. ; Br.)— (BiO)NO3H20—
306— is formed by decomposing a solution of Bi(NO3)3 with a large
quantity of H2O. It is a white, heavy, faintly acid powder ; sol-
uble to a slight extent in H2O when freshly precipitated, the solu-
tion depositing it again on standing. It is decomposed by pure
HaO, but not by H2O containing ^5 ammonium nitrate. It
usually contains 1 Aq, which it loses at 100° (212° F.).
Bismuth subnitrate, as well as the subcarbonate, is liable to
contamination with arsenic, which accompanies bismuth in its
ores. The method for separating this dangerous impurity,
directed by the British Pharmacopoeia, is more perfect than that
usually followed in this country. The metal is first purified by
fusion with potassium nitrate, which dissolves any arsenic present
in the form of sodium arsenite, and the purified metal is then
converted into nitrate by solution in HNO3, and this in turn into
subnitrate by decomposition with a large volume of H2O.
The maximum amount of arsenic which has been found in
commercial bismuth subnitrate is one-tenth of one per cent.
To detect the presence of arsenic, the subnitrate (or subcarbon-
ate) is boiled for half an hour with an equal weight of pure
sodium carbonate, dissolved in ten times its weight of H2O. The
solution is filtered ; the filtrate evaporated to dryness ; the resi-
due strongly heated ; and, after cooling, cautiously decomposed
with strong H2SO4. The mass is then gradually heated, during
stirring, until dense white fumes are given off. The cooled resi-
due is finally treated with water and the liquid introduced into'
a Marsh apparatus. (See page 133.)
Bismuthyl Subcarbonate — Bismuthi subcarbonas (TJ. S.) — Bis-
muthi carbonas (Br.) — (BiO)2CO3H2O — 530 — is a white or yellowish,
amorphous powder, formed when a solution of an alkaline car-
bonate is added to a solution of Bi(NO3)3. It is odorless and taste-
less, and insoluble in H2O and in alcohol.
When heated to 100° (212° F.), it loses H2O, and is converted
into (BiO)2CO3. At a higher temperature it is further decom-
posed into Bi2O3 and CO2.
Analytical Characters. — (1.) Water : white ppt., even in pres-
ence of tartaric acid, but not of HNO3, HC1, or H2SO4. (2.)
Hydrogen sulfid: black ppt.; insoluble in dilute acids and in
alkaline sulfids. (3.) Ammonium sulfhydrate : black ppt.; in-
soluble in excess. (4.) Potash, soda, or ammonia : white ppt., in-
TITANIUM, ZIRCONIUM. 171
soluble in excess, and in tartaric acid ; turns yellow when the
liquid is boiled. (5.) Potassium ferrocyanid : yellowish ppt. ; in-
soluble in HC1. (6.) Potassium ferricyanid : yellowish ppt.; solu-
ble in HC1. (7.) Infusion of galls : orange ppt. (8.) Potassium
iodid : brown ppt. ; soluble in excess. (9.) Reacts with Reinsch's
test (q. •».), but gives no sublimate in the glass tube.
Action on the Economy. — Although the medicinal compounds
of bismuth are probably poisonous, if taken in sufficient quantity,
the ill effects ascribed to them are in most, if not all cases, refer-
able to contamination with arsenic. Symptoms of arsenical
poisoning have been frequently observed when the subnitrate
has been taken internally, and also when it has been used as a
cosmetic.
When preparations of bismuth are administered, the alvine
discharges contain bismuth sulfid, as a dark brown powder.
VII. TIN GROUP.
TITANIUM. ZIRCONIUM. TIN.
Ti and Sn are bivalent in one series of compounds, SnCl2, and
quadrivalent in another, SnCl4. Zr, so far as known, is always
quadrivalent. Each of these elements forms an acid (or salts
corresponding to one) of the composition H3MO3, and a series of
oxysalts of the composition Mlv(NO3)4.
TITANIUM.
Symbol = Ti — Atomic weight — 48 — Sp. gr. — 5.3.
Occurs in clays and iron ores, and as TiO2 in several minerals.
Titanic anhydrid, TiO2, is a white, insoluble, infusible powder,
used in the manufacture of artificial teeth ; dissolves in fused
KHO, as potassium titanate. Titanium combines readily with
N, which it absorbs from air when heated. When NH3 is passed
over red-hot TiO2, it is decomposed with formation of the violet
nitrid, TiNa. Another compound of Ti and N forms hard, cop-
per-colored, cubical crystals.
ZIRCONIUM.
Symbol — Zr — Atomic weight = 89.6 — Sp. gr. = 4.15.
Occurs in zircon and hyacinth. Its pxid, zirconia, ZrO2, is a.
white powder, insoluble in KHO. Being infusible, and not altered
by exposure to air, it is used in pencils to replace lime in the
calcium light.
172 MANUAL OF CHEMISTRY.
TIN.
Symbol = Sn (ST ANNUM)— Atomic weight = 117. 7— Molecular
weight = 235.4 (?)— £p. gr. = 1.285-7.293— Fuses at 228° (442°.4 P.).
Occurrence. — As tinstone (SnO2) or cassiterite, and in stream tin.
Preparation. — The commercial metal is prepared by roasting
the ore, extracting with H2O, reducing the residue by heating
with charcoal, and refining.
Pure tin is obtained by dissolving the metal in HC1 ; filtering ;
evaporating ; dissolving the residue in H3O ; decomposing with
ammonium carbonate ; arid reducing the oxid with charcoal.
Properties. — A soft, malleable, bluish-white metal ; but slightly
tenacious ; emits a peculiar sound, the tin-cry, when bent. A
good conductor of heat and electricity. Air affects it but little,
except when it is heated ; more rapidly if Sn be alloyed with Pb.
It oxidizes slowly in H2O, more rapidly in the presence of sodium
chlorid. Its presence with Pb accelerates the action of H2O upon
the latter. It dissolves in HC1 as SnCl2. In presence of a small
quantity of H2O, HNO3 converts it into metastannic acid. Alka-
line solutions dissolve it as metastannates. It combines directly
with Cl, Br, I, S, P, and As.
Tin plates are thin sheets of Fe, coated with Sn. Tin foil con-
sists of thin laminae of Sn, frequently alloyed with Pb. Copper
and iron vessels are tinned after brightening, by contact with
molten Sn. Pewter, bronze, bell metal, gun metal, britannia
metal, speculum metal, type metal, solder, and fusible metal
contain Sn.
Oxids.— Stannous Oxid — Protoxid — SnO — 133.7— obtained by
heating the hydroxid or oxalate without contact of air. It is a
white, amorphous powder, soluble in acids, and in hot concen-
trated solution of potash. It absorbs O readily.
Stannic Oxid. — Binoxid of tin — SnO2 — 149.7 — occurs native as
tinstone or cassiterite, and is formed when Sn or SnO is heated in
air. It is used as a polishing material, under the name of putty
powder.
Hydrates. — Stannous Hydroxid — SnHjOa — 151.7 — is a white pre-
cipitate, formed by alkaline hydroxids and carbonates in solu-
tions of SnCl2.
Stannic Acid. — H2SnO3 — 167.7 — is formed by the action of alka-
line hydroxids on solutions of SnCh. It dissolves in solutions of
the alkaline hydroxids, forming stannates.
Metastannic Acid. — H2Sn5On — 766.5 — is a white, insoluble pow-
<ler, formed by acting on Sn with HNO3.
Chlorids.— Stannous Chlorid — Protochlorid — Tin crystals— Sn
Cla + 2 Aq— 188.7 + 36— is obtained by dissolving Sn in HC1. It
PLATINUM. 173-
ery stall izes in colorless prisms ; soluble in a small quantity of
HaO ; decomposed by a large quantity, unless in the presence of
free HC1, with formation of an oxychlorid. Loses its Aq at 100°
(212° F.). In air it is transformed into stannic chlorid and oxy-
chlorid. Oxidizing and chlorinating agents convert it into SnCh.
It is a strong reducing agent.
Stannic Chlorid— Bichlorid — Liquid of Libamus—Sndt — 259.7
— is formed by acting on Sn or SnCl2 with Cl, or by heating Sn
in aqua regia. It is a fuming yellowish liquid ; sp. gr. 2.28 ; boils
at 120' (248° F.).
Analytical Characters. — STAXXOUS. — (1.) Potash or soda : white
ppt. ; soluble in excess ; the solution deposits Sn when boiled.
(2.) Ammonium hydroxid: white ppt.; insoluble in excess; turns
olive-brown when the liquid is boiled. (3.) Hydrogen sulfid :
dark brown ppt. ; soluble in KHO, alkaline sulfids, and hot H2O.
(4.) Mercuric chlorid: white ppt.; turning gray and black. (5.)
Auric chlorid: purple or brown ppt., in presence of small quan-
tity of HNO3. (6.) Zinc : deposit of Sn.
STANNIC. — (1.) Potash or ammonia : white ppt. ; soluble in
excess. (2.) Hydrogen sulfid : yellow ppt. ; soluble in alkalies,
alkaline sulfids, and hot HCL. (3.) Sodium hyposulfite : yellow
ppt. when heated.
VIII. PLATINUM GROUP.
PALLADIUM. PLATINUM.
IX. RHODIUM GROUP.
RHODIUM. RUTHENIUM. IBIDIUM.
The elements of these two groups, together with osmium, are
usually classed as "metals of the platinum ores." They all form
hydrates (or salts representing them) having acid properties.
Osmium has been removed, because the relations existing be-
tween its compounds, and those of molybdenum and tungsten,
are much closer than those which they exhibit to the compounds
of these groups. The separation of the remaining platinum
metals into two groups is based upon resemblances in the coin-
position of their compounds, as shown in the following table :
PdCl, PtCl,
PdCL. PtCL.
Chlorid*,
RhCU. . .RuCU. ?
- RuCl4... IrCh
l9 Ru3Cl8 Ir-jCl
174 MANUAL OF CHEMISTRY.
PdO PtO
PdO2 PtO,
Oxids.
RhO RuO IrO
Rh2O3 Ru2O3 lr2O3
RhO2 RuO2 Ir02
RhO3 RuO3 IrO3
RuO4
PLATINUM.
Symbol = "Pi— Atomic weight = 194.4— Molecular weight = 388.8
•(1)— Sp.gr. =21.1-21.5.
Occurrence. — Free and alloyed with Os, Ir, Pd, Rh, Ru, Fe, Pb,
Au, Ag, and Cu.
Properties. — The compact metal has a silvery lustre ; softens
at a white heat ; may be welded ; fuses with difficulty ; highly
malleable, ductile and tenacious. Spongy platinum, is a grayish,
porous mass, formed by heating the double chlorid of Pt and
NH4. Platinum black is a black powder, formed by dissolving
PtCla in solution of potash, and heating with alcohol. Both
platinum black and platinum sponge are capable of condensing
large quantities of gas, and act as indirect oxidants.
Platinum is not oxidized by air op O ; it combines directly with
Cl, P, As, Si, S, and C ; is not attacked by acids, except aqua
regia, in which it dissolves as PtCl4. It forms fusible alloys when
heated with metals or reducible metallic oxids. It is attacked
by mixtures liberating Cl, and by contact with heated phos-
phates, silicates, hydroxids, nitrates, or carbonates of the alka-
line metals.
Platinic chlorid — Tetrachlorid or perchlorid of platinum —
PtCl4 — 336.4 — is obtained by dissolving Pt in aqua regia, and
evaporating. It crystallizes in very soluble, deliquescent, yel-
low needles. Its solution is used as a test for compounds
K.
PALLADIUM.
Symbol ='Pd — Atomic weight = 105.7 — Molecular weight = 211.4
f!)—Sp. gr. =11.5.
Awhile metal, resembling Pt in appearance; but usually exhib-
Hing a reddish reflection. It is harder, much lighter, and more
readily fusible than Pt. It dissolves in HNOs, as Pd(NO3)2. It
possesses the property of occluding1 gases, notably hydrogen, in
a much more marked degree than any other metal. One volume
of palladium condenses 640 volumes of hydrogen at 100° (212° F.).
RHODIUM, EUTHEJSTIUM, IEIDIUM. 175
RHODIUM.
Symbol = Bh — Atomic weight = 104.1 — Molecular weight =
208.2 (?)— £p. gr. = 11.4.'
A hard, malleable, white metal, insoluble in aqua regia. Its
compounds are mostly red, whence its name, from p66ov, a rose.
RUTHENIUM:.
Symbol = Bu — Atomic weight = 104.2 — Sp. gr. = 11.4.
A hard, brittle, very difficultly fusible metal, not dissolved by
aqua regia, occurring in small quantity in platinum ores.
IBIDIUM.
Symbol = Ir— Atomic weight = 192.7 — Sp. gr. = 22.3.
A hard, brittle metal which occurs in nature in platinum ores,
and alloyed with osmium. It is not attacked by aqua regia. It
is used to make an alloy with platinum, which is less fusible,
more rigid, harder, denser, and less readily attacked chemically
than pure platinum.
176 MANUAL OF CHEMISTRY.
CLASS IV.— BASYLOUS ELEMENTS.
Elements whose Oxids Unite with Water to form Bases ; never to
form Acids. Which form Oxysalts.
I. SODIUM GROUP.
Alkali Metals.
LITHIUM — SODIUM — POTASSIUM— RUBIDIUM — CAESIUM — SILVER^
Each of the elements of this group forms a single chlorid, M'Cl,
and one or more oxids, the most stable of which has the compo-
sition M'aO ; they are, therefore, univalent. Their hydroxids,
M'HO, are more or less alkaline and have markedly basic charac-
ters. Silver resembles the other members of the group in chemi-
cal properties, although it does not in physical characters.
LITHIUM.
Symbol = Li — Atomic weight = 7 — Molecular weight = 14 (?) —
8p. gr. = 0.589— Fuses at 180° (356° F.)— Discovered by Arfoedson
in 1817 — Name from Mdeiog = stony.
Occurrence. — Widely distributed in small quantity ; in many
minerals and mineral waters ; in the ash of tobacco and other
plants ; in the milk and blood.
Properties. — A silver-white, ductile, volatile metal ; the lightest
of the solid elements ; burns in air with a crimson flame ; decom-
poses H-iO at ordinary temperatures, without igniting.
Lithium Oxid — LiaO — 30 — is a white solid, formed by burning Li
in dry O. It dissolves slowly in H2O to form lithium hydroxid —
LiHO.
Lithium Chlorid— LiCl— 43.5— crystallizes in deliquescent, reg-
ular octahedra; very soluble in H2O and in alcohol.
Lithium Bromid— Lithii bromidum (U.S.)— LiBr— 87— is formed
by decomposing lithium sulfate with potassium bromid; or by
saturating a solution of HBr with lithium carbonate. It crystal-
lizes in very deliquescent, soluble needles.
Lithium Carbonate — Lithii carbonas (U. S.; Br.) — Li.CO — 74 — is
a white, sparingly soluble, alkaline, amorphous powder. With
uric acid it forms lithium urate (q. v.).
Analytical Characters. — (1.) Ammonium carbonate : white ppt.
in concentrated solutions ; not in dilute solutions, or in presence
of ammoniacal salts. (2.) Sodium phosphate : white ppt. in neu-
tral or alkaline solution ; soluble in acids and in solutions of
ammoniacal salts. (3.) It colors the Bunsen flame red ; and ex-
hibits a spectrum of two lines — /t = 6705 and 6102 (Fig. 16, No. 4).
SODIUM. 177
SODIUM.
Symbol = Na (NATRIUM) — Atomic weight = 23— Molecular
weight = 46 (?)— Sp. gr. — 0.973— Fuses at 95°. 6 (204°. 1 F.)— Boils
at 742° (1368° F.)— Discovered by Davy, 1807.
Occurrence. — As chlorid, very abundantly and widely distrib-
uted ; also as carbonate, nitrate, sulfate, borate, etc.
Preparation. — By heating a mixture of dry sodium carbonate,
chalk, and charcoal to whiteness in iron retorts, connected with
suitable condensers, in which the distilled metal collects, under a
layer of coal naphtha.
Properties. — A silver-white metal, rapidly tarnished, and coated
with a yellow film in air. Waxy at ordinary temperatures ; vola-
tile at a white heat, forming a colorless vapor, which burns in
air with a yellow flame.
In air it is gradually oxidized from the surface, but may be
kept in closed vessels, without the protection of a layer of
naphtha. It decomposes H2O, sometimes explosively. Burns
with a yellow flame. Combines directly with Cl, Br, I, S, P, As,
Pb, and Sn.
Oxids. — Two oxids are known : Sodium monoxid — NaaO — a
grayish-white mass ; formed when Na is burnt in dry air, or by
the action of Na on NaHO. Sodium dioxid — Na2O2 — a white
solid, formed when Na is heated in dry air to 200° (392° F.).
Sodium Hydroxid— Sodium-hydrate— Caustic Soda — Soda (U. S.)
—Soda caustica (Br.)— NaHO— 40— is formed : (1) when H2O is
decomposed by Na; (2) by decomposing sodic carbonate by cal-
cium hydroxid: Na2CO3 + CaH2O2 = CO3Ca-}- 2NaHO (soda by
lime); (3) in the same manner as in (2), using barium hydroxid in
place of lime (soda by baryta). It frequently contains considera-
ble quantities of As.
It is an opaque, white, fibrous, brittle solid ; fusible below red-
ness ; sp. gr. 2.00 ; very soluble in H2O, forming strongly alkaline
and caustic solutions (soda lye and liq. sodse). When exposed to
air, solid or in solution, it absorbs H-iO and COs, and is converted
into carbonate. Its solutions attack glass.
Sodium chlorid— Common salt— Sea salt — Table salt — Sodii
chloridum (U. S., Br.) — NaCl — 58.5 — occurs very abundantly in
nature, deposited in the solid form as rock salt; in solution in all
natural waters, especially in sea and mineral spring waters ; in
suspension in the atmosphere ; and as a constituent of almost all
animal and vegetable tissues and fluids. It is formed in an infi-
nite variety of chemical reactions. It is obtained from rock salt,
or from the waters of the sea or of saline springs ; and is the
12
178 MANUAL OF CHEMISTRY.
source from which all the Na compounds are usually obtained,
directly or indirectly.
It crystallizes in anhydrous, white cubes, or octahedra ; sp. gr.
2.078 ; fuses at a red heat, and crystallizes on cooling ; sensibly
volatile at a white heat ; quite soluble in H»O, the solubility
varying but slightly with the variations of temperature. Dilute
solutions yield almost pure ice on freezing. It is precipitated
from concentrated solutions by HC1. It is insoluble in absolute
alcohol ; sparingly soluble in dilute spirit. It is decomposed by
H2SO4 with formation of HC1 and sodium sulfate : 2NaCl -f-
H2S04 = 2HC1 + Na,S04.
PHYSIOLOGICAL. — Sodium chlorid exists in every animal tissue
and fluid, and is present in the latter, especially the blood, in
tolerably constant proportion. It is introduced with the food,
either as a constituent of the alimentary substances, or as a con-
diment. In the body it serves to aid the phenomena of osmosis,
and to maintain the solution of the albuminoids. It is probable,
al&o, that it is decomposed in the gastric mucous membrane with
formation of free hydrochloric acid.
It is discharged from the economy by all the channels of elimi-
nation, notably by the urine, when the supply by the food is
maintained. If, however, the food contain no salt, it disappears
from the urine before it is exhausted from the blood.
The amount of Cl (mainly in the form of NaCl) voided by a
normal male adult in 24 hours is about 10 grams (154 grains), cor-
responding to 16.5 grams (255 grains) of NaCl. When normal or
excessive doses are taken, the amount eliminated by the urine is
less than that taken in ; when small quantities are taken, the
elimination is at first in excess of the supply. The hourly elimi-
nation increases up to the seventh hour, when it again diminishes.
The amount of NaCl passed in the urine is less than the normal
in acute, febrile diseases ; in intermittent fever it is dimin-
ished during the paroxysms, but not during the intervals. In
diabetes it is much increased, sometimes to 29 grams (448 grains)
per diem.
Quantitative determination of chlorids in urine. — The process
is based upon the formation of the insoluble silver chlorid, and
upon the formation of the brown silver chroiiiate in neutral
liquids, in the absence of soluble chlorids. The solutions required
are : (1) A solution of silver nitrate of known strength, made by
dissolving 29.075 grams of pure, fused silver nitrate (see p. 193) in
a litre of water ; (2) a solution of neutral potassium vhromate.
To conduct the determination, 5-10 c.c. of the urine are placed
in a platinum basin, 2 grams of sodium nitrate (free from chlorid)
are added ; the whole is evaporated to dryness over the water-
bath, and the residue heated gradually until a colorless, fused
SODIUM. 179
mass remains. This, on cooling, is dissolved in H2O, the solution
placed in a small beaker, treated with pure, dilute HNOS to
faintly acid reaction, and neutralized with calcium carbonate.
Two or three drops of the chromate solution are added, and then
the silver solution from a burette, during constant stirring of the
liquid in the beaker, until a faint reddish tinge remains perma-
nent. Each c.c. of the silver solution used represents 10 milli-
grams NaCl (or 6.065 milligrams Cl) in the amount of urine used.
Example. — 5 c.c. urine used ; 6 c.c. silver solution added ; 1,200
c.c. urine passed in 24 hours : • '•——* — — Xl, 200=14.4 grams NaCl
in 24 hours.
If the urine contain iodids or bromids, they must be removed,
by acidulating the solution or the residue of incineration with
HaSO4, removing the iodin or bromiii by shaking with carbon
disulfld, neutralizing the aqueous solution with calcium car-
bonate and proceeding as above.
Sodium Bromid — Sodii bromidum (U. S.)— NaBr— 103— is formed
by dissolving Br in solution of NaHO to saturation ; evaporating ;
calcining at dull redness ; redissolving ; filtering ; and crystal-
lizing. It crystallizes in anhydrous cubes ; quite soluble in H2O,
soluble in alcohol.
Sodium lodid— Sodii iodidum (17. S.) — Nal — 150— is prepared
by heating together H2O, Fe, and I in fine powder ; filtering ;
.adding an equivalent quantity of sodium sulfate, and some
slacked lime; boiling; decanting and evaporating. Crystallizes
in anhydrous cubes ; very soluble in BUO ; soluble in alcohol.
Sodium Nitrate — Cubic or Chili saltpetre — Sodii nitras (TJ. S.)
— Sodse nitras (Br.) — NaNO3 — 85 — occurs in natural deposits in
Chili and Peru. It crystallizes in anhydrous, deliquescent rhom-
bohedra; cooling and somewhat bitter in taste; fuses at 310°
(590° F.); very soluble in H2O. Heated with H2SO,, it is decom-
posed, yielding HNO3 and hydrosodic sulfate: H3SO4 + NaNO3
= HNaSO4-fHNO3. This reaction is that used for obtaining
HNO3.
Sulfates. — Monosodic sulfate — Hydrosodic sulfate— Acid sodium
sulfate— Bisulfate-H.Na.SOi— 120— crystallizes in long, four-sided
prisms; is unstable and decomposed by air, H2O or alcohol, into
H2SO4 and Na2SO4. Heated to dull redness it is converted into
sodium pyrosulfate, NaaSsOT, corresponding to Nordhausen sul-
furic acid.
Disodic Sulfate — Sodic sulfate — Neutral sodium sulfate— Glau-
ber's salt— Sodii sulfas (TJ. S.)— Sodae sulfas (Br.)— Na3SO4 + n Aq
— 142 -f- n 18 — occurs in nature in solid deposits, and in solu-
tion in natural waters. It is obtained as a secondary product
in the manufacture of HC1, by the action of HuSO* on NaCl,
180 MANUAL OF CHEMISTRY.
the decomposition occurring according to the equation : 2 NaCl
+ H2SO4 = Na2SO4 + 2 HC1, if the temperature be raised suffi-
ciently. At lower temperatures, the monosodic salt is produced,
with only half the yield of HC1 : NaCl + H2SO4 = NaHSO4 + HC1.
It crystallizes with 7 Aq, from saturated or supersaturated,
solutions at 5° (41° F.) ; or, more usually, with 10 Aq. As usually
met with it is in large, colorless, oblique rhombic prisms with 10'
Aq ; which effloresce in air, and gradually lose all their Aq. It
fuses at 33° (91°. 4 F.) in its Aq, which it gradually loses. If fused
at 33° (91°. 4 F.), and allowed to cool, it remains liquid in super-
saturated solution, from which it is deposited, the entire mass
becoming solid, on contact with a small particle of solid matter.
It dissolves in HC1 with considerable diminution of temperature..
PHYSIOLOGICAL. — The neutral sulfates of Na and K seem to-
exist in small quantity in all animal tissues and fluids, with the
exception of milk, bile, and gastric juice ; certainly in the blood
and urine. They are partially introduced with the food, and
partly formed as a result of the metamorphosis of those constit-
uents of the tissues which contain S in organic combination.
The principal elimination of the sulfates is by the urine. All
the sulfuric acid in the urine is not in simple combination with
the alkali metals. A considerable amount exists in the form,
of the alkaline salts of conjugate, monobasic, ether acids, which,
on decomposition, yield an aromatic organic compound. The
amount of H2SO4 discharged by the urine in 24 hours, in the
form of alkaline sulfates, is from 2.5 to 3.5 grams (38.5-54 grains).
That eliminated in the salts of conjugate acids. 0.617 to 0.094
gram (9.5-1.5 grains).
Sodium Sulflte— Sodii sulfls (U. S.)— Na2SO3 -f 7 Aq— 126 + 126—
is formed by passing SO2 over crystallized Na2CO3. It crystal-
lizes in efflorescent, oblique prisms; quite soluble in H2O, forming
an alkaline solution. It acts as a reducing agent.
Sodium Thiosulfate — Sodium hyposulfite — Sodii hyposulfis
(TJ. S.) — Na2S2O3 + 5 Aq — 158 + 90— is obtained by dissolving S in
hot concentrated solution of Na2SO3, and crystallizing.
It forms large, colorless, efflorescent prisms; fuses at 45° (113°
F.); very soluble in H2O; insoluble in alcohol. Its solutions pre-
cipitate alumina from solutions of Al salts, without precipitating
Fe or Mn; they dissolve many compounds insoluble in H2O; cu-
prous hydroxid, iodids of Pb, Ag and Hg, sulfids of Ca and Pb.
It acts as a disinfectant and antiseptic. H2SO4 and most other
acids decompose Na2S2O3 according to the equation: Na2S2O3 +
H2SO4 = Na2SO4+SO2+S + H2O. Oxalic, and a few other acids,
decompose the thiosulfate with formation of H2S as well as SO2
and S.
Silicates. — Quite a number of silicates of !Na are known. If
SODIUM. 181
silica and xSaaCOs be fused together, the residue extracted with
HaO, and the solution evaporated, a transparent, glass-like mass,
soluble in warm water, remains ; this is soluble glass or water
glass. Exposed to air in contact with stone, it becomes insoluble,
-and forms an impermeable coating.
Phosphates. — Trisodic Phosphate — Basic sodium phosphate —
Ha3PO4 + 12 Aq— 164 + 216— is obtained by adding NaHO to diso-
•dic phosphate solution, and crystallizing. It forms six-sided
prisms ; quite soluble in H2O. Its solution is alkaline, and, on
exposure to air, absorbs COa, with formation of HNaaPO4 and
XasCOi. 4
Disodic Phosphate — Hydro-disodic phosphate — Neutral sodium,
pliosphate — Phosphate of soda — Sodii phosphas (TJ. S.) — Sodae
phosphas (Br.)— HNasPO4 + 12 Aq— 142 + 216— is obtained by con-
verting tricalcic phosphate into monocalcic phosphate, and de-
composing that salt with sodium carbonate : Ca(PO4Ha)a 4-
2Na2CO3 = CaCO3 + HaO + CO, + 2HNa2PO4.
Below 30° (863 F.) it crystallizes in oblique rhombic prisms, with
12 Aq ; at 33° (91 A F.) it crystallizes with 7 Aq. The salt with
12 Aq effloresces in air, and parts with 5 Aq ; and is very soluble
in H2O. The salt with 7 Aq is not efflorescent, and less soluble
in HsO. Its solutions are faintly alkaline.
Monosodic Phosphate — Acid sodium phosphate — H2NaPO4+Aq
— 120+18 — crystallizes in rhombic prisms; forming acid solu-
tions. At 100° (212° F.) it loses Aq ; at 200° (392° F.) it is converted
into acid pyrophosphate, Na2H2PaO7 ; and at 204° (399°. 2 F.) into
the metaphosphate, _NaPOs.
PHYSIOLOGICAL. — All the sodium phosphates exist, accom-
panied by the corresponding K salts, in the animal economy.
The disodic and dipotassic phosphates are the most abundant,
and of these two the former. They exist in every tissue and
fluid of the body, and are more abundant in the fluids of the car-
nivora than in those of the herbivora. In the blood, in which
the Xa salt predominates in the plasma, and the K salt in the
corpuscles, they serve to maintain an alkaline reaction. With
strictly vegetable diet the proportion of phosphates in the blood
diminishes, and that of the carbonates (the predominating salts
in the blood of the herbivora) increases.
The monosodic and monopotassic phosphates exist in the urine,
the former predominating, and to their presence the acid reac-
tion of that fluid is largely due. They are produced by decom-
position of the neutral salts by uric acid. The urine of the her-
bivora, whose blood is poor in phosphates, is alkaline in reaction.
The greater part of the phosphates in the body are introduced
with the food. A portion is formed in the economy by the oxida-
tion of phosphorized organic substances, the lecithins.
182 MANUAL OF CHEMISTRY.
Disodic Tetraborate — Sodium pyroborate — Borate of sodium—
Borax — Tincal — Sodii boras (TJ. S.)— Borax (Br.)— Na2B4O7 + 10:
Aq— 202+180 — is prepared by boiling boric acid \vith Na2COa and
crystallizing. It crystallizes in hexagonal prisms with 10 Aq ;
permanent in moist air, but efflorescent in dry air ; or in regular
octahedra with 5 Aq, permanent in dry air. Either form, when
heated, fuses in its Aq, swells considerably ; at a red heat be-
comes anhydrous ; and, on cooling, leaves a transparent, glass-
like mass. When fused, it is capable of dissolving many metallic
oxids, forming variously colored masses, hence its use as a flux
and in blow-pipe analysis.
Sodium Hypochlorite — NaCIO — 74.5 — only known in solution —
Liq. sodae chloratae (IT. S. ; Br.) or Labarraque's solution — ob-
tained by decomposing a solution of chlorid of lime by Na2CO3.
It is a valuable source of 01, and is used as a bleaching and dis-
infecting agent.
Sodium Manganate— Na2Mn04 + 10 Aq— 164+180 — faintly col-
ored crystals, forming a green solution with H2O — Condy's green
disinfectant.
Sodium. Permanganate — NasM^Os — 282 — prepared in the same
way as the K salt (q. «.), which it resembles in its properties. It
enters into the composition of Condy's fluid, and of "chloro-
zone," which contains Na2Mn2O8 and NaClO.
Sodium Acetate — Sodii acetas (U. S.)— Sodee acetas (Br.) —
NaC2H3O2+3Aq — 82+54 — crystallizes in large, colorless prisms ;
acid and bitter in taste ; quite soluble in H2O ; soluble in alco-
hol ; loses its Aq in dry air, and absorbs it again from moist air.
Heated with soda lime, it yields marsh gas. The anhydrous salt,
heated with H2SO4, yields glacial acetic acid.
Carbonates. — Three are known : Na2CO3 ; HNaCO3, and H2Nai
(C03)3.
Disodic Carbonate — Neutral carbonate — Soda — Sal soda —
Washing soda — Soda crystals — Sodii carbonas (17. S.)— Sodse
carbonas (Br.) — Na2CO3 + 10Aq — 106+180 — industrially the most
important of the Na compounds, is manufactured by Leblanc's-
or Solvay's processes ; or from cryolite, a native fluorid of Na.
and Al.
Leblanc's process, in its present form, consists of three dis-
tinct processes: (1.) The conversion of NaCl into the sulfate, by
decomposition by H2SO4. (2.) The conversion of the sulfate into
carbonate, by heating a mixture of the sulfate with calcium car-
bonate and charcoal. The product of this reaction, known as.
black ball soda, is a mixture of sodium carbonate, with charcoal
and calcium sulfid and oxid. (3.) The purification of the product
obtained in (2). The ball black is broken up, disintegrated by
steam, and lixiviated. The solution on evaporation yields the
soda salt or soda of commerce.
SODIUM. 183
Of late years Leblanc's process lias been in great part replaced
by Solvay's method, or the ammonia process, which is more eco-
nomical, and yields a purer product. In this process sodium
chlorid and ammonium bicarbonate react upon each other, with
production of the sparingly soluble sodium bicarbonate, and the
very soluble ammonium chlorid. The sodium bicarbonate is
then simply collected, dried, and heated, when it is decomposed
into Na2CO3, H2O, and CO2.
The anhydrous carbonate, Sodii carbonas exsiccatus (U. $.),
Na2CO3, is formed, as a white powder, by calcining the crystals.
It fuses at dull redness, and gives off a little CO2. It combines
with and dissolves in H2O with elevation of temperature.
The crystalline sodium carbonate, Na2CO3+10 Aq, forms large
rhombic crystals, which effloresce rapidly in dry air ; fuse in
their Aq at 34° (93°. 2 F.) ; are soluble in H2O, most abundantly
at 38° (100°. 4 F.). The solutions are alkaline in reaction.
Monosodic Carbonate — Hydrosodic carbonate — Bicarbonate of
soda — Acid carbonate of soda — Vichy salt — Sodii bicarbonas
(U. S.) — Sodae bicarbonas (Br.) — NaHCOs — 84— -exists in solution in
many mineral waters. It is obtained by the action of CO2 upon
the disodic salt in the presence of H2O ; or, as above described,
by the Solvay method.
It crystallizes in rectangular prisms, anhydrous and permanent
in dry air. In damp air it gives off CO2, and is converted into
the sesquicarbonate, ^Xa4H2(CO3)3. When heated, it gives off
CO2 and H2O. arid leaves the disodic carbonate. Quite soluble in
water • above 70° (158° F.) the solution gives off CO2. The solu-
tions are alkaline.
PHYSIOLOGICAL. — The fact that the carbonates of Is a and K
are almost invariably found in the ash of animal tissues and
fluids, is no evidence of their existence there in life, as the car-
bonates are produced by the incineration of the Na and K salts
of organic acids. There is, however, excellent indirect proof of
the existence of the alkaline carbonates in the blood, especially
of the herbivora, in the urine of the herbivora at all times, and
in that of the carnivora and omnivora, when food rich in -the
salts of the organic acids, with alkali metals, is taken. The car-
bonates in the blood are both the mono- and disodic, and potas-
sic ; and the carbonic acid in the plasma is held partially in
simple solution, and partly in combination in the monometallic
carbonates.
Analytical Characters. — (1.) Hydrofluosilicic acid : gelatinous
ppt., if not too dilute. (2.) Potassium pyroantimonate : in
neutral solution and in absence of metals, other than K and Li :
a white flocculent ppt. ; becoming crystalline on standing. (3.)
184 MANUAL OF CHEMISTRY.
Periodic acid in excess : white ppt., in not too dilute solutions.
(4.) Colors the Bunsen flame yellow, and shows a brilliant double
line at a = 5895 and 5889 (Fig. 16, No. 2).
POTASSIUM.
Symbol = K (KALITJM) — Atomic weight = 39 — Molecular
weight = 78 (1)—Sp. gr. = 0.865— Fuses at 62°. 5 (144°. 5 F.)— Boils at
667° (1233° F.) — Discovered by Davy, 1807 — Names from pot ash,
and Kali = ashes (Arabic).
It is prepared by a process similar to that followed in obtaining
Na ; is a silver-white metal ; brittle at 0° (32° F.) ; waxy at 15° (59°
F.) ; fuses at 62°. 5 (144°. 5 F.) ; distils in green vapors at a red heat,
condensing in cubic crystals.
It is the only metal which oxidizes at low temperatures in dry
air, in which it is rapidly coated with a white layer of oxid or hy-
droxid, and frequently ignites, burning with a violet flame. It
must, therefore, be kept under naphtha. It decomposes H2O, or
ice, with great energy, the heat of the reaction igniting the liber-
ated H. It combines with Cl with incandescence, and also unites
directly with S, P, As, Sb, and Sn. Heated in CO2 it is oxidized,
and liberates C.
Oxids. — Three are known : K2O ; K2O2 ; and K2O4.
Potassium hydroxid — Potassium hydrate — Potash — Potassa —
Common caustic — Potassa (U. S.)— Potassa caustica (Br.)— KHO —
56 — is obtained by a process similar to that used in manufactur-
ing NaHO. It is purified by solution in alcohol, evaporation and
fusion in a silver basin, and casting in silver moulds — potash by
alcohol ; it fs then free from KC1 and K2SO4, but contains small
quantities of K2COS, and frequently As.
It is usually met with in cylindrical sticks, hard, white, opaque,
and brittle. The KHO by alcohol has a bluish tinge, and a
smoother surface than the common ; sp. gr. 2.1 ; fuses at dull red-
ness ; is freely soluble in H2O, forming a strongly alkaline and
caustic liquid ; less soluble in alcohol. In air, solid or in solution,
it absorbs H2O and CO2, and is converted into K2CO3. Its solu-
tions dissolve Cl, Br, I, S, and P. It decomposes the ammoniacal
salts, with liberation of NH3 ; and the salts of many of the
metals, with formation of a K salt, and a metallic hydroxid. It
dissolves the albuminoids, and, when heated, decomposes them
with formation of leucin, tyrosin, etc. It oxidizes the carbohy-
drates with formation of potassium oxalate and carbonate. It
decomposes the fats with formation of soft soaps.
Sulfids.— Five are known : K2S, K2S2, K2S3, K2S4, and K2S6 ;
also a sulf hydrate : KHS.
POTASSIUM. 185
Potassium Monosulfid— K2S— 110 — is formed by the action of
KHO on KHS. Potassium Disulfid— K2S2— 142— is an orange-
colored solid, formed by exposing an alcoholic solution of KHS
to the air. Potassium Trisulfid— K2S3— 174— a brownish-yellow
mass, obtained by fusing together K2CO3 and S in the propor-
tion : 4K2COH-10S=SO4KH-3K2S3+4CO2. Potassium Pentasul-
fid— K2S5— 238— is formed, as a brown mass, when K2CO3 and S
are fused together in the proportion : 4K2CO3 + 16S = 4CO2
+3K2S5-fK2SO4. Liver of Sulfur— hepar swZ/wrt.9— potassii sul-
furatum (TJ. S. ; Br.) — is a mixture of K2S3 and K2S5.
Potassium Sulfhydrate— KHS — 72— is formed by saturating a
solution of KHO with H,S.
Potassium Chlorid. — Sal digestivum Sylvii — KC1 — 74.5 — exists
in nature, either pure or mixed with other chlorids ; principally as
carnallite, KC1, MgCl2 + 6 Aq. It crystallizes in anhydrous, per-
manent cubes, soluble in H2O.
Potassium Bromid — Potassii bromidum (U. S. ; Br.) — KBr — 119
— is formed, either by decomposing ferrous broniid by K2CO3, or
by dissolving Br in solution of KHO. In the latter case the
bromate formed is converted into KBr, by calcining the product.
It crystallizes in anhydrous cubes or tables ; has a sharp, salty
taste ; very soluble in H2O, sparingly so in alcohol. It is decom-
posed by Cl with liberation of Br.
Potassium lodid — Potassii iodidum (U. S. ; Br.) — KI — 166 — is
obtained by saturating KHO solution with I, evaporating, and
calcining the resulting mixture of iodid and iodate with charcoal.
It frequently contains iodate and carbonate. It crystallizes in
cubes, transparent if pure ; permanent in air ; anhydrous ; sol-
uble in H2O, and in alcohol. It is decomposed by Cl, HNO3 and
HNO2, with liberation of I. It combines with other iodids to
form double iodids. Its solutions dissolve iodin and many me-
tallic iodids.
Potassium. Nitrate — Nitre — Saltpetre— Potassii nitras (TJ. S.) —
Potassas nitras (Br.) — KNO. — 101 — occurs in nature, and is pro-
duced artificially, as a result of the decomposition of nitrogenized
organic substances. It is usually obtained by decomposing native
NaNOs by boiling solution of K2CO3 or KC1.
It crystallizes in six-sided, rhombic prisms, grooved upon the
surface ; soluble in H2O, with depression of temperature ; more
soluble in H2O containing NaCl ; very sparingly soluble in alcohol;
fuses at 350° (662° F.) without decomposition ; gives off O, and is
converted into nitrite below redness ; more strongly heated, it is
decomposed into N, O, and a mixture of K oxids. It is a valuable
oxidant at high temperatures ; heated with charcoal it deflag-
rates.
186 MANUAL OF CHEMISTRY.
Gunpowder is an intimate mixture of KNO3 with S and C, in
such proportion that the KNO3 yields all the O required for the
combustion of the 8 and C.
Potassium Chlorate— Potassii chloras (U. S.) — Potassae chloras
(Br.) — KClOs — 122.5 — is prepared : (1) by passing Cl through a
solution of KHO ; (2) by passing Cl over a mixture of milk of
lime and KC1, heated to 60° (140° R). It crystallizes in trans-
parent, anhydrous plates ; soluble in H2O ; sparingly soluble in
weak alcohol.
It fuses at 400° (752° F.). If further heated, it is decomposed
into KC1 and perchlorate, and at a still higher temperature the
perchlorate is decomposed into KC1 and O : 2KC1O3 = KC1O4 +
KC1 + O2 and KC1O4 = KC1 + 2O2. It is a valuable source of O,
and a more active oxidant than KNO3. When mixed with readily
oxidizible substances, C, S, P, sugar, tannin, resins, etc., the
mixtures explode when subjected to shock. With strong HsSCh
it gives off C12O4, an explosive yellow gas. It is decomposed by
HNO3 with formation of KNOs, KC1O4, and liberation of Cl and
O. Heated with HC1 it gives off a mixture of Cl and C12O4, the
latter acting as an energetic oxidarit in solutions in which it i&
generated.
Potassium Hypochlorite — KC1O — 90.5 — is formed in solution by
imperfect saturation of a cooled solution of KHO with hypo-
chlorous acid. An impure solution is used in bleaching : Javelle
•water.
Sulfates. — Dipotassic sulfate — Potassium sulfate — Potassii sul-
fas (U. S.) — Potassee sulfas (Br.) — K,SO, — 174 — occurs native ; in
the ash of many plants ; and in solution in mineral waters. It
crystallizes in right rhombic prisms ; hard ; permanent in air ;
salt and bitter in taste ; soluble in H2O.
Monopotassic Sulf&te—Hydropotassic sulfate— Acid sulfate —
KHSd — 136 — is formed as a by-product in the manufacture of
HNO3. When heated it loses H2O, and is converted into the
pyrosulfate, K2S2O7, which, at a higher temperature, is decom-
posed into K2SO4 and SO3.
Dipotassic Sulfite — Potassic sulfite — Potassii Sulfls (U. S.) —
K2SO3 — 158 — is formed by saturating solution of K2CO3 with SO2,
and evaporating over H2SO4. It crystallizes in oblique rhombo-
hedra ; soluble in H2O. Its solution absorbs O from air, with
formation of K2SO4.
Potassium Bichromate — Bichromate of potash — Potassii bi-
chromas (U. S.) — Potassae bichromas (Br.) — K2Cr2O7 — 294.8 — is
formed by heating a mixture of chrome iron ore with KNO3, or
K-jCO3 in air ; extracting with H2O ; neutralizing with dilute
H2SO4 ; and evaporating. It forms large, reddish-orange colored
prismatic crystals ; soluble in H2O ; fuses below redness, and at
POTASSIUM. 187
•
a higher temperature is decomposed into O, potassium chromate,
and sesquioxid of chromium. Heated with HC1, it gives off Cl.
Potassium Permanganate — Potassii permanganas (U. S.) — Po-
tassae permanganas (Br,) — KjMn.,0. — 314 — is obtained by fusing
a mixture of manganese dioxid, KHO, and KC1O3, and evapora-
ting the solution to crystallization ; K2MnO4 and KC1 are first
formed ; on boiling with H2O, the inanganate is decomposed into
KaMn^Os, KHO, and MriOa.
It crystallizes in dark prisms, almost black, with greenish re-
flections, which yield a red powder when broken. Soluble in
H2O, communicating to it a red color, even in very dilute solu-
tion. It is a most valuable oxidizing agent. With organic mat-
ter its solution is turned to green, by the formation of the man-
ganate, or deposits the brown sesquioxid of manganese, accord-
ing to the nature of the organic substance. In some instances
the reaction takes place best in the cold, in others under the in-
fluence of heat ; in some better in acid solutions, in others in alka-
line solutions. Mineral reducing agents act more rapidly. It*
oxidizing powers render its solutions valuable as disinfectants.
Potassium. Acetate — Potassii acetas (TT. S.) — Potassae acetas(Br.>
— KCoH3O2 — 110 — exists in the sap of plants ; and it is by its cal-
cination that the major part of the carbonate of wood ashes is
formed. It is prepared by neutralizing acetic acid with K2COs
or KHC03.
It forms crystalline needles, deliquescent, and very soluble in
H»O ; less soluble in alcohol. Its solutions are faintly alkaline.
Carbonates. — Dipotassic Carbonate — Potassic Carbonate — Salt
of tartar — Pearl ash — Potassii Carbonas (U. S.) — Potasses car-
bonas (Br.) — K2CO3— 138— exists in mineral waters, and in the
animal economy. It is prepared industrially, in an impure form,
known as potash, or pearlash, from wood ashes, from the molasses
of beet-sugar, and from the native Stassfurth chlorid. It is ob-
tained pure by decomposing the monopotassic salt, purified by
several recrystallizations, by heat ; or by calcining a potassium
salt of an organic acid. Thus cream of tartar, mixed with nitre
and heated to redness, yields a black mixture of C and K2CO3,
called black flux ; on extracting which with H2O, a pure carbon-
ate, known as salt of tartar, is dissolved.
Anhydrous, it is a white, granular, deliquescent, very soluble
powder. At low temperatures it crystallizes with 2 Aq. Its
solution is alkaline.
Monopotassic Carbonate — Hydropotassic carbonate — Bicarbon-
ate— Potassii bicarbonas — (TJ. S.) — Potasses bicarbonas (Br.) —
HKCO3— 100 — is obtained by dissolving K2CO3 in H2O, and sat-
urating the solution with CO2. It crystallizes in oblique rhom-
bic prisms, much less soluble than the carbonate. In solution, it
188 MANUAL OF CHEMISTEY.
is gradually converted into the dipotassic salt when heated, when
brought into a vacuum, or when treated with an inert gas.
The solutions are alkaline in reaction and in taste, but are not
caustic.
The substance used in baking, under the name salaeratus, is
this or the corresponding Na salt, usually the latter. Its exten-
.sive use in some parts of the country is undoubtedly in great
measure the cause of the prevalence of dyspepsia. When used
alone in baking, it "raises" the bread by decomposition into
carbon dioxid and dipotassic (or disodic) carbonate, the latter
producing disturbances of digestion by its strong alkaline reac-
tion.
Monopotassic oxalate — Hydropotassic oxalate — Binoxalate of
potash— HKC2O4 — 128 — forms transparent, soluble, acid needles.
It occurs along with the quadroxalate HKC2O4,H2C2O4+2 Aq,
in salt of lemon or salt of sorrel, used in straw bleaching, and for
the removal of ink-stains, etc. It closely resembles Epsom salt
in appearance, and has been fatally mistaken for it.
Tartrates. — Dipotassic tartrate — Potassia tartrate — Soluble tar-
tar— Neutral tartrate of potash — Potassii tartras (U. S.) — Potassse
tartras (Br.) — K,C,H,Ot — 226 — is prepared by neutralizing the
hydropotassic salt with potassium carbonate. It forms a white,
crystalline powder, very soluble in H2O, the solution being dex-
trogyrous, [a]D = +28°. 48 ; soluble in alcohol. Acids, even acetic,
decompose its solution^ with precipitation of the monopotassic
•salt.
Monopotassic tartrate — Hydropotassic tartrate — Cream of tartar
— Potassii bitartras (U. S.) — Potassse bitartras (Br.) — HKCiH ,0,,
— 188. — During the fermentation of grape juice, as the porportion
of alcohol increases, crystalline crusts collect in the cask. These
constitute the crude tartar, or argol, of commerce, which is com-
posed, in great part, of monopotassic tartrate. The crude prod-
uct is purified by repeated crystallization from boiling H»O ;
digesting the purified tartar with HOI at 20° (68° P.) ; washing
with cold H2O, and crystallizing from hot H2O.
It crystallizes in hard, opaque (translucent when pure), rhom-
bic prisms, which have an acidulous taste, and are very sparingly
soluble in H2O, still less soluble in alcohol. Its solution is acid,
and dissolves many metallic oxids with formation of double tar-
trates. When boiled with antimony trioxid, it forms tartar
emetic.
It is used in the household, combined with monosodic carbon-
ate, in baking, the two substances reacting upon each other to
form Rochelle salt, with liberation of carbon dioxid.
Baking Powders are now largely used as substitutes for yeast
in the manufacture of bread. Their action is based upon the de-
POTASSIUM.
189
composition of HNaC03 by some salt having an acid reaction,
or by a weak acid. In addition to the bicarbonate and flour, or
corn-starch (added to render the bulk convenient to handle and
to diminish the rapidity of the reaction), they contain cream of
tartar, tartaric acid, alum, or acid phosphates. Sometimes am-
monium sesquicarbonate is used, in whole or in part, in place of
sodium carbonate.
The reactions by which the CO2 is liberated are :
1. HKC4H4O8 + NaHCO3 = NaKC4H«O8 + H2O + CO2
Monopotassic Monosodic Sodium potassium Water. Carbon
tartrate. carbonate. tartrate. dioxid.
Tartaric acid.
Monosodic
carbonate.
= Na2C4H4O8 + 2H2O
Disodic tartrate. Water.
2COa
Carbon,
dioxid.
8. Al2(S04)3,KaS04
Aluminium
potassium alum.
6NaHCO3 = K2SO4 + 3Na2SO4 +-
Monosodic
carbonate.
AlaH8O.
Aluminium
hydroxid.
Dipotassic
sulfate.
6COS
Carbon
dioxid.
Disodic
sulfate.
4. Al,(SO4)t,(NH«),S(V+6NaHCOi = (NH4)2SO4 + 3Na2SO4
Aluminium Monosodic Diammonic Disodic
ammonium alum. carbonate. sulfate. sulfate.
A12H608
Aluminium
hydroxid.
6CO2
Carbon
dioxid.
5. AU(SO4)3
Aluminium
sulfate.
Monosodic
phosphate.
6NaHCO3 =
Monosodic
carbonate.
NaHCO3
Monosodic
carbonate.
3Na2SO4
Disodic
sulfate.
A12H6O«
Aluminium
hydroxid.
6CO,
Carbon
dioxid.
CO,
Disodic
phosphate.
H20 +
Water. Carbon
dioxid.
Sodium Potassium Tartrate — Rochelle salt — Sel de seignette —
Potassii et sodii tartras (U. S.) — Soda tartarata (Br.) — NaKC4H4
O« + 4 Aq — 210 + 72 — is prepared by saturating monopotassic
tartrate with disodic carbonate. It crystallizes in large, trans-
parent prisms, which effloresce superficially in dry air, and attract
moisture in damp air. It fuses at 70°-80° (158°-176° P.), and loses 3
Aq at 100° (212° P.). It is soluble in H»O, the solutions being
dextrogyrous, [«]D= + 29°. 67.
Potassium Antimony! Tartrate — Tartarated antimony — Tartar
emetic — Antimonii et potassii tartras (IT. S.) — Antimonium tar-
taratum (Br.)— (SbO)KC4H4O8— 323— is prepared by boiling a
mixture of 3 pts. SbaO3 and 4 pts. HKCiH4O8 in H2O for an hour,
190 MANUAL OF CHEMISTRY.
^filtering, and allowing to crystallize. When required pure, it
must be made from pure materials.
It crystallizes in transparent, soluble, right rhombic octahedra,
which turn white in air. Its solutions are acid in reaction, have
a nauseating, metallic taste, are laevogyrous, [a]D= —156°. 2, and
are precipitated by alcohol. The crystals contain | Aq, which
they lose entirely at 100° (212° F.), and, partially, by exposure to
air. It is decomposed by the alkalies, alkaline earths, and alka-
line carbonates, with precipitation of SbaOs. The precipitate
is redissolved by excess of soda or potash, or by tartaric acid.
HC1, H2SO4 and HNO3 precipitate corresponding aritimonyl com-
pounds from solutions of tartar emetic. It converts mercuric
into mercurous chlorid. It forms double tartrates with the tar-
trates of the alkaloids.
Potassium Cyanid — Potassii cyanidum (IT. S.) — KCN — 65 — is
obtained by heating a mixture of potassium ferrocyanid and dry
K2CO3, as long as effervescence continues ; decanting and crystal-
lizing.
It is usually met with in dull, white, amorphous masses. Odor-
less when dry, it has the odor of hydrocyanic acid when moist.
It is deliquescent, and very soluble in H8O ; almost insoluble in
alcohol. Its solution is acrid and bitter in taste, with an after-
taste of hydrocyanic acid. It is very readily oxidized to the
cyanate, a property which renders it valuable as a reducing agent.
Solutions of KCN dissolve I, AgCl, the cyanids of Ag and Au, and
many metallic oxids.
It is actively poisonous, and produces its effects by decomposi-
tion and liberation of hydrocyanic acid (q. v.).
Potassium Ferrocyanid — Yellow prussiate of potash — Potassii
ferrocyanidum (U.S.) — Potassae prussias flava (Br.) — K4[Fe(CN)6]
+ 3 Aq — 367.9 + 54. — This salt, the source of the other cyanogen
compounds, is manufactured by adding organic matter (blood,
bones, hoofs, leather, etc.) and iron to K2CO3 in fusion ; or by
other processes in which the N is obtained from the residues of
the purification of coal-gas, from atmospheric air, or from am-
moniacal compounds.
It forms soft, flexible, lemon-yellow crystals, permanent in air
at ordinary temperatures. They begin to lose Aq at 60° (140° F.),
and become anhydrous at 100° (212° F.). Soluble in H2O ; in-
soluble in alcohol, which precipitates it from its aqueous solution.
When calcined with KHO or K2CO3, potassium cyanid and cya-
nate are formed, and Fe is precipitated. Heated with dilute
H2SO4, it yields an insoluble white or blue salt, potassium sul-
fate, and hydrocyanic acid. Its solutions form with those of
many of the metallic salts insoluble ferrocyanids ; those of Zn, Pb,
•and Ag are white, cupric ferrocyanid is mahogany-colored, fer-
POTASSIUM. 191
rous ferrocyanid is bluish-white, ferric ferrocyanid, Prussian blue,
is dark blue. Blue ink is a solution of Prussian blue in a so-
lution of oxalic acid. .
Potassium Ferricyanid — Bed prussiate of potash — K8Fe2(CN)ia
— 657.8 — is prepared by acting upon the ferrocyanid with chlorin ;
or, better, by heating the white residue of the action of HaSO*
upon potassium ferrocyanid, in the preparation of hydrocyanic
acid, with a mixture of 1 vol. HNO3 and 20 vols. H2O ; the blue
product is digested with HaO, and potassium ferrocyanid, the
solution filtered and evaporated. It forms red, oblique, rhombic
prisms, almost insoluble in alcohol. With solutions of ferrous
salts it gives a dark blue precipitate, Turnbull's blue.
Analytical Characters. — (1.) Platinic chlorid, in presence of
HC1 : yellow ppt. ; crystalline if slowly formed ; sparingly sol-
uble in HaO, much less so in alcohol. (2.) Tartaric acid, in not
too dilute solution : white ppt. ; soluble in alkalies and in con-
centrated acids. (3.) Hydrofluosilicic acid : translucent, gelatin-
ous ppt. ; forms slowly ; soluble in strong alkalies, (4.) Perchloric
acid : white ppt. ; sparingly soluble in H2O ; insoluble in alcohol.
<5.) Phosphomolybdic acid : white ppt. ; forms slowly. (6.) Colors
the Bunsen flame violet (the color is only observable through
blue glass in presence of Na), and exhibits a spectrum of two
bright lines : ?- = 7860 and 4045 (Pig. 16, No. 3).
Action of the Sodium and Potassium Compounds on the Econ-
omy.— Thehydroxids of Na and of K, and in a less degree the car-
bonates, disintegrate animal tissues, dead or living, with which
they come in contact, and, by virtue of this action, act as powerful
caustics upon a living tissue. Upon the skin, they produce a
soapy feeling, and in the mouth a soapy taste. Like the acids,
they cause death, either immediately, by corrosion or perforation
of the stomach ; or secondarily, after weeks or months, by closure
of one or both openings of the stomach, due to thickening, conse-
quent upon inflammation.
The treatment consists in the neutralization of the alkali by an
acid, dilute vinegar. Neutral oils and milk are of service, more
by reason of their emollient action than for any power they have
to neutralize the alkali, by the formation of a soap, at the temper-
ature of the body.
The other compounds of Na, if the acid be not poisonous, are
"without deleterious action, unless taken in excessive quantity.
Common salt has produced paralysis and death in a dose of half
a pound. The neutral salts of K, on the contrary, are by no
means without true poisonous action when taken internally, or
injected subcutaneously, in sufficient quantities ; causing dysp-
192 MANUAL OF CHEMISTRY.
ncea, convulsions, arrest of the heart's action, and death. In
the adult human subject, death has followed the ingestion of
doses of 1 ss.- 1 i. of the nitrate, in several instances ; doses of
3 ij.- 5 ij. of the sulfate have also proved fatal.
Cesium— Symbol = Cs— Atomic weight = 132.6 ; and Rubidium
—Symbol='Kb — Atomic weight=85.3—are two rare elements, dis-
covered in 1860 by Kirchoff and Bunsen while examining spectro-
scopically the ash of a spring water. They exist in very small
quantity in lepidolite. They combine with O and decompose-
H3O even more energetically than does K, forming strongly alka-
line hydroxids.
SILVER.
Symbol = Ag (ARGENTUM)— Atomic weight = 107.9— Molecular
weight = 216 (T)—Sp. yr. = 10.4-10.54- Fuses at 1,000° (1,832° R).
Although silver is usually classed with the " noble metals," it
differs from Au and Pt widely in its chemical characters, in which
it more closely resembles the alkaline metals.
When pure Ag is required, coin silver is dissolved in HNO3 and
the diluted solution precipitated with HC1. The silver chlorid
is washed, until the washings no longer precipitate with silver
nitrate ; and reduced, either (1) by suspending it in dilute H2SO«
in a platinum basin, with a bar of pure Zn, and washing thor-
oughly, after complete reduction ; or (2) by mixing it with chalk
and charcoal (AgCl, 100 parts ; C, 5 parts ; CaCO3, 70 parts), and
gradually introducing the mixture into a red-hot crucible.
Silver is a white metal ; very malleable and ductile ; the best
known conductor of heat and electricity. It is not acted on by
pure air, but is blackened in air containing a trace of H3S. It
combines directly with Cl, Br, I, S, P, and As. Hot H2SO4 dis-
solves it as sulfate, and HNO3 as nitrate. The caustic alkalies
do not affect it. It alloys readily with many metals ; its alloy
with Cu is harder than the pure metal.
Silver seems to exist in a number of allotropic modifications,
besides that in which it is ordinarily met with. In one of these
it is brilliant, metallic, bluish-green in color, and dissolves in
H2O, forming a deep red solution ; in another it has the color of
burnished gold, when dry ; and in still another it has also a
bluish-green color, but is insoluble in water. Very dilute min-
eral acids immediately convert these modifications into normal
gray silver, without evolution of any gas.
Oxids. — Three oxids of silver are known : Ag4O, Ag2O, and
Ag2O2.
Silver Monoxid — Protoxid— Argenti oxidum— (IT. S.; Br.)— Ag2O
— 231.8 — formed by precipitating a solution of silver nitrate with
SILVER. 193
potash. It is a brownish powder ; faintly alkaline and very
slightly soluble in H2O ; strongly basic. It readily gives up its
oxygen. On contact with ammonium hydroxid it forms a fulmi-
nating powder.
Chlorid— AgCl — 143.4 — formed when HC1 or a chlorid is added
to a solution containing silver. It is white ; turns violet and
black in sunlight; volatilizes at 260° (500° F.); sparingly soluble
in HC1 ; soluble in solutions of the alkaline chlorids, hyposul-
fids, and cyanids, and in ammonium hydroxid. It crystallizes
in octahedra on exposure of its ainmoniacal solution.
Bromid — AgBr ; and lodid — Agl — are yellowish precipitates,
formed by decomposing silver nitrate with potassium bromid and
iodid. The former is very sparingly soluble in ammonium hy-
droxid, the latter is insoluble.
Argentic Nitrate— Argenti Ultras (U. S. ; Br.) — AgN03 — 169.9 —
is prepared by dissolving Ag in HNO3, evaporating, fusing, and
recrystallizing. It crystallizes in anhydrous, right rhombic
plates ; soluble in HaO. The solutions are colorless and neutral.
In the presence of organic matter it turns black in sunlight.
The salt, fused and cast into cylindrical moulds, constitutes
lunar caustic, lapis infernalis ; argenti nitras fusa (TJ. S.). If,
during fusion, the temperature be raised too high, it is converted
into nitrite, O, and Ag ; and if sufficiently heated, leaves pure Ag.
Dry Cl and I decompose it, with liberation of anhydrous HNO3.
It absorbs NH3, to form a white solid, AgNO3, 3NH3, which gives
up its NH3 when heated. Its solution is decomposed very slowly
by H, with deposition of Ag.
Argentic Cyanid— Argenti Cyanidum (TJ. S.)— AgCN— 133.9— is
prepared by passing HCN through a solution of AgNO3. It is a
white, tasteless powder ; gradually turns brown in daylight ; in-
soluble in dilute acids ; soluble in ammonium hydroxid, and in
solutions of ammoniacal salts, cyanids, or hyposulfites. The
strong mineral acids decompose it with liberation of HCN.
Analytical Characters. — (1.) Hydrochloric acid : white, floccu-
lent ppt. ; soluble in NH4HO ; insoluble in HNO3. (2.) Potash or
soda : brown ppt. ; insoluble in excess ; soluble in NH4HO. (3.)
Ammonium hydroxid, from neutral solutions : brown ppt. ; sol-
uble in excess. (4.) Hydrogen sulfid or ammonium sulfhydrate ;
black ppt.; insoluble in NH4HS. (5.) Potassium bromid : yellow-
ish-white ppt. ; insoluble in acids, if not in great excess ; soluble
in NH4HjO. (6.) Potassium iodid : same as KBr, but the ppt. is
less soluble in NH4HO.
Action on the Economy. — Silver nitrate acts both locally as a
corrosive^ and systemically as a true poison. Its local action is
due to its decomposition, by contact with organic substances, re-
sulting in the separation of elementary Ag, whose deposition
194 MANUAL OF CHEMISTRY.;
causes a black stain, and liberation of free HNO3, which acts as
a caustic. When absorbed, it causes nervous symptoms, refera-
ble to its poisonous action. The blue coloration of the skin,
observed in those to whom it is administered for some time, is
due to the reduction of the metal, under the combined influence
of light and organic matter ; especially of the latter, as the dark-
ening is observed, although it is less intense, in internal organs.
In acute poisoning by silver nitrate, sodium chlorid or white of
egg should be given ; and, if the case be seen before the symptoms
of corrosion are far advanced, emetics.
AMMONIUM COMPOUNDS.
The ammonium theory. — Although the radical ammonium,
NH4, has probably never been isolated, its existence in the
ammoniacal compounds is almost universally admitted. The
ammonium hypothesis is based chiefly upon the following facts :
(1) the close resemblance of the ammoniacal salts to those of K
and Na ; (2) when ammonia gas and an acid gas come together,
they unite, without liberation of hydrogen, to form an ammoni-
acal salt ; (3) the diatomic anhydrids unite directly with dry am-
monia with formation of the ammonium salt of an amido acid :
8O3 + 2NH3 = S03(NH2)(NH4)
Sulfur trioxid. Ammonia. Ammonium sulfamate.
(4) when solutions of the ammoniacal salts are subjected to elec-
trolysis, a mixture, having the composition NH3 + H is given off
at the negative pole ; (5) amalgam of sodium, in contact with a
concentrated solution of ammonium chlorid, increases much in
volume, and is converted into a light, soft mass, having the lustre
of mercury. This ammonium amalgam is decomposed gradually,
giving off ammonia and hydrogen in the proportion NH3 + H ; (6)
if the gases NH3+H, given off by decomposition of the amalgam,
exist there in simple solution, the liberated H would have the
ordinary properties of that element. If, on the other hand, they
exist in combination, the H would exhibit the more energetic
affinities of an element in the nascent state. The hydrogen so
liberated is in the nascent state.
Ammonium Hydroxid— Caustic ammonia— NH4HO— 35— has
never been isolated, probably owing to its tendency to decompo-
sition ; NH4HO=NH3 + H2O. It is considered as existing in the
so-called aqueous solutions of ammonia. These are colorless
liquids ; of less sp. gr. than H2O ; strongly alkaline ; and having
the taste and odor of ammonia, which gas they give off on ex-
posure to air, and more rapidly when heated. They are neutral-
ized by acids, with elevation of temperature and formation of
AMMONIUM COMPOUNDS. 195
^ammoniacal salts. The Aqua ammoniae (TJ. S.) and Idq. am-
monias (Br.) are such solutions.
Sulfids.— Four are. known: (NH4)2S ; (NH4)2S2 ; (NH4)2S4 ; and
<NH4)2S6; as Avell as a sulfhydrate (NH4)HS.
Ammonium Sulfhydrate — NH4HS — 51 — is formed, in solution,
by saturating a solution of NH4HO with H2S ; or, anhydrous, by
mixing equal volumes of dry NH3 and dry H2S.
The anhydrous compound is a colorless, transparent, volatile
and soluble solid; capable of sublimation with decomposition.
The solution, when freshly prepared, is colorless, but soon be-
comes yellow from oxidation, and formation of ammonium disul-
fid and hyposulfite, and finally deposits sulfur.
The sulfids and hydrosulfid of ammonium are also formed
•during the decomposition of albuminoids, and exist in the gases
formed in burial vaults, sewers, etc.
Ammonium Chlorid— Sal ammoniac— Ammonii chloridum (U.S. ;
Ur.) — NH;C1 — 53.5 — is obtained from the ammoniacal water of
gas-works. It is a translucid, fibrous, elastic solid ; salty in taste,
neutral in reaction ; volatile without fusion or decomposition ;
soluble in HSO. Its solution is neutral, but loses NH3 and be-
comes acid when boiled.
Ammonium chlorid exists in small quantity in the gastric juice
of the sheep and dog ; also in the perspiration, urine, saliva, and
tears.
Ammonium Bromid — Ammonii bromidum (TJ. S.) — (NH4)Br — 98
— is formed either by combining NH3 and HBr ; by decomposing
ferrous bromid with NH4HO ; or by double decomposition be-
tween KBr and (NH4)2SO4. It is a white, granular powder, or
crystallizes in large prisms, which turn yellow on exposure to air ;
quite soluble in H2O ; volatile without decomposition.
Ammonium lodid — Ammonii iodidum (TJ. S.) — NH4I — 145 — is
formed by union of equal volumes of NH3 and HI ; or by double
decomposition of KI and (NH4)2SO4. It crystallizes in deliques-
cent, very soluble cubes.
Ammonium Nitrate — Ammonii nitras (TJ. S.) — (N"H4)N03 — 80 — is
prepared by neutralizing HNO3 with ammonium hydroxid or car-
bonate. It crystallizes in flexible, anhydrous, six-sided prisms ;
very soluble in H2O, with considerable diminution of tempera-
ture; fuses at 150° (30?° F.), and decomposes at 210° (410° F.), with
formation of nitrous oxid: (NH4)NO3 = NaO+2EUO. If the heat
be suddenly applied, or allowed to surpass 250° (482° F.), NH3,
NO, and N2O are formed. When fused it is an active oxidant.
Sulfates. — Diammonic Sulfate — Ammonic sulfate — Ammonii
sulfas (TJ. S.)— (NH4)2SO4— 133— is obtained by collecting the
distillate from a mixture of ammoniacal gas liquor and lime
in HaSOi. It forms anhydrous, soluble, rhombic crystals; fuses
196 MANUAL OF CHEMISTRY.
at 140° (284° F.), and is decomposed at 200° (392° F.) into NH3 and
H(NH4)SO4.
Monoammonic Sulfate — Hydroammonic sulfate — Bisulfate of
ammonia— H(NH4)SO4 — 115— is formed by the action of H2SO/
on (NH4)2SO4. It crystallizes in right rhombic prisms, soluble in
H3O and in alcohol.
Ammonium Acetate — (NH4)C2H3O2 — 77 — is formed by saturating
acetic acid with NHS, or with ammonium carbonate. It is a
white, odorless, very soluble solid ; fuses at 86° (186°. 8 F.), and
gives off NH3 ; then acetic acid, and finally acetamid. Liq. am-
monii acetatis= Spirit of Mindererus is an aqueous solution of
this salt.
Carbonates. — Diammonic Carbonate — Ammonic carbonate —
Neutral ammonium carbonate — (NH4)2CO3+Aq — 96+18 — has been
obtained as a white crystalline solid. In air it is rapidly decom-
posed into NH3 arid H(NH4)CO8.
Monoammonic Carbonate — Hydroammonic carbonate — Acid
carbonate of ammonia — H(NH4)CO3 — 79 — is prepared by saturat-
ing a solution of NH4HO or ammonium sesquicarbonate with
CO2. It crystallizes in large, rhombic prisms ; quite soluble in
HaO. At 60° (140° F.) it is decomposed into NH3 and CO2.
Ammonium Sesquicarbonate — Sal volatile— Preston salts — Am-
monii carbonas (U. S.) — Ammoniee carbonas (Br.) — (NH4)4Ha(CO3)3
—254 — is prepared by heating a mixture of NH4Cland chalk, and
condensing the product. It crystallizes in rhombic prisms ; ha&
an ammoniacal odor and an alkaline reaction ; soluble in HaO.
By exposure to air or by heating its solution, it is decomposed
into HaO, NH3, and H(NH4)CO3.
Analytical Characters. — (1.) Entirely volatile at high tempera-
tures. (2.) Heated with KHO, the ammoniacal compounds give
off NH3, recognizable : (a) by changing moist red litmus to blue ;
(&) by its odor ; (c) by forming a white cloud on contact with a
glass rod moistened with HC1. (3.) With platinic chlorid : a yel-
low, crystalline ppt. (4.) With hydrosodic tartrate, in moder-
ately concentrated and neutral solution : a white crystalline ppt.
Action on the Economy. — Solutions of the hydroxid and carbon-
ate act upon animal tissues in the same way as the correspond-
ing Na and K compounds. They, moreover, disengage NH3r
•which causes intense dyspnoea, irritation of the air-passages, and
suffocation.
The treatment indicated is the neutralization of the alkali by
a dilute acid. Usually the vapor of acetic acid or of dilute HC1
must be administered by inhalation.
THALLIUM, CALCIUM. 197
II. THALLIUM GROUP.
THALLIUM.
Symbol=T\.— Atomic weight=2Q3.rt—Sp. 0r. =11.8-11.9— Fuses at
294° (561° F.)— Discovered by Crookes (1861).
A rare element, first obtained from the deposits in flues of sul-
furic acid factories, in which pyrites from the Hartz were used,
It resembles Pb in appearance and in physical properties, but
differs entirely from that element in its chemical characters. It
resembles Au in being univalent and trivalent, but differs from
it, and resembles the alkali metals in being readily oxidized, in
forming alums, and in forming no acid hydrate. It differs from
the alkali metals in the thallic compounds, which contain Tl". It
is characterized spectroscopically by a bright green line — /'.=5349.
III. CALCIUM GROUP.
Metals of the Alkaline Earths.
CALCIUM — STRONTIUM — BARIUM.
The members of this group are bivalent in all their compounds;
each forms two oxids : MO and MO2 ; each forms a hydroxid, hav-
ing well marked basic characters.
CALCIUM.
8ymbol=Ga. — Atomic weight=40 — Molecular weight =80 (?) — Sp.
gr. =1.984 — Discovered by Davy in 1808 — Name from calx=h'me.
Occurs only in combination, as limestone, marble, chalk (CaCO3) ;
/gypsum, selenite, alabaster (CaSO4), and many other minerals.
In bones, egg-shells, oyster-shells, etc., as Ca3(PO.i):i and CaCO3,
and in many vegetable structures.
The element is a hard, yellow, very ductile, and malleable
metal ; fusible at a red heat ; not sensibly volatile. In dry air it
is not altered, but is converted into CaHaOa in damp air; decom-
poses H2O ; burns when heated in air.
Calcium Monoxid — Q,uick lime — Lime — Calx (U. S.; Br.) — CaO —
56 — is prepared by heating a native carbonate (limestone); or,
when required pure, by heating a carbonate, prepared by precip-
itation.
It occurs in white or grayish, amorphous masses; odorless;
-alkaline; caustic; almost infusible ; sp. gr. 2.3. With H2O it gives
off great heat and is converted into the hydroxid (slacking). In
air it becomes air-slacked, falling into a white powder, having
the composition
198 MANUAL OF CHEMISTRY.
Calcium Hydroxid — Slacked lime— Calcis hydras (Br.) — CaH.CX
— 74 — is formed by the action of H2O on CaO. If the quantity of
H2O used be one-third that of the oxid, the hydroxid remains as a
dry, white, odorless powder; alkaline in taste and reaction; more
soluble in cold than in hot H2O. If the quantity of H2O be
greater, a creamy, or milky liquid remains, cream or milk of
lime; a solution holding an excess in suspension. With a suffi-
cient quantity of H2O the hydroxid is dissolved to a clear solution,
which is lime water — Liquor calcis (TJ. S. ; Br.). The solubility
of CaH2O2 is diminished by the presence of alkalies, and is in-
creased by sugar or mannite : Liq. calc. saccharatus (Br.). Solu-
tions of CaH2O2 absorb CO2 with formation of a white deposit of
CaCO3.
Calcium Chlorid— Calcii chloridum (U. S. ; Br.)— CaCl2 — 111— is.
obtained by dissolving marble in HC1: CaCO»-|-2HCl=CaClH-
H2O+CO2. It is bitter; deliquescent; very soluble in H2O ; crys-
tallizes with 6 Aq, which it loses when fused, leaving a white,,
amorphous mass ; used as a drying agent.
Chloride of Lime — Bleaching powder — Calx chlorata (U.S.; Br.)
— is a white or yellowish, hygroscopic powder, prepared by pass-
ing Cl over CaH2O2, maintained in excess. It is bitter and acrid
in taste; soluble in cold H2O; decomposed by boiling H2O, and
by the weakest acids, with liberation of Cl. It is decomposed by
CO2, with formation of CaCO3, and liberation of hypochlorous-
acid, if it be moist ; or of Cl, if it be dry. A valuable disinfectant.
Bleaching powder was formerly considered as a mixture of cal-
cium chlorid and hypochlorite, formed by the reaction: 2CaO-|-
2Cl2=CaCl2-|-Ca(ClO)2, but it is more probable that it is a definite
compound having the formula CaCl(OCl), which is decomposed
by H2O into a mixture of CaCl2 and Ca(ClO)2 ; and by dilute
HNO3 or H2SO4 with formation of HC1O.
Calcium Sulfate— CaSO4— 136— occurs in nature as anhydrite;
and with 2 Aq in gypsum, alabaster, selenite; and in solution in
natural waters. Terra alba is ground gypsum. It crystallizes,
with 2 Aq in right rhombic prisms ; sparingly soluble in H2O,,
more soluble in H2O containing free acids or chlorids. When the--
hydrated salt (gypsum) is heated to 80° (176° F.), or, more rapidly,
between 120°-130° (248°-266° F.), it loses its Aq and is converted
into a white, opaque mass; which, when ground, is plaster-of-
Paris.
The setting of plaster when mixed with H2O, is due to the con-
version of the anhydrous into the crystalline, hydrated salt. The
ordinary plastering should never be used in hospitals, as, by rea-
son of its irregularities and porosity, it soon becomes saturated
with the transferrers of septic disease, be they germs or poisons,
and cannot be thoroughly purified by disinfectants. Plaster sur-
CALCIUM. 199
faces may, however, be rendered dense, and be highly polished,
so as to be smooth and impermeable, by adding glue and alum,
or an alkaline silicate to the water used in mixing.
Phosphates.— Three are known: Ca3(PO4)a; Ca^HPChK and
Ca(H2PO4)2.
Tricalcic Phosphate — Tribasic or neutral phosphate — Bone
phosphate — Calcii phosphas prsecipitatus (U. S.) — Calcis phosphas
(Br.) — Ca3(PO4)2 — 310 — occurs in nature, in soils, guano, coprolites,
phosphorite, in all plants, and in every animal tissue and fluid.
It is obtained by dissolving bone-ash in HC1, filtering, and pre-
cipitating with NH4HO; or by double decomposition between
CaCl2 and an alkaline phosphate. When freshly precipitated it is
gelatinous; when dry, alight, white, amorphous powder ; almost
insoluble in pure H2O ; soluble to a slight extent in H2O contain-
ing ammoniacal salts, or NaCl or NaNOs ; readily soluble in dilute
acids, even in H2O charged with carbonic acid. It is decomposed
by H2SO4 into CaSO4 and Ca(H2PO4)2. Bone-ash is an impure
form of Ca3(PO4)2, obtained by calcining bones, and used in the
manufacture of P and of superphosphate.
Dicalcic Phosphate — Ca2(HPO4)2-f2Aq— 272+36 — is a crystal-
,line, insoluble salt; formed by double decomposition between
CaCl2 and HNa2PO4 in acid solution.
Monocalcic Phosphate — Acid calcium phosphate — Superphos-
phate of lime — Ca(H2PO4)2 — 234 — exists in brain tissue, and in
those animal liquids whose reaction is acid It is also formed
when Ca3(PO4)2 is dissolved in an acid, and is manufactured, for
use as a manure, by decomposing bone-ash with H2SO4. It crys-
tallizes in pearly plates ; very soluble in H2O. Its solutions are
acid.
Physiological. — All three calicum phosphates, accompanied by
the corresponding Mg salts, exist in the animal economy. The
tricalcic salt occurs in all the solids of the body, and in all fluids
not having an acid reaction, being held in solution in the latter
by the presence of chlorids. In the fluids it is present in very
small quantity, except in the milk, in which it is comparatively
abundant; 2.5 to 3.95 parts per 1,000 in human milk, and 1.8 to
3.87 parts per 1,000 in cow's milk; constituting about 70 per cent,
of the ash. The bones contain about 35 parts of organic matter,
combined Avith 65 parts of mineral material. The average of
human bone-ash is : Cas(PO4)2— 83.89; CaCO3— 13.03; Ca, combined
with G1,F, and organic acids— 0.35; F— 0.23; Cl— 0.18. The aver-
age quantity of Ca3(PO4):z in male adult bones is 57 per cent. ; that
of CaCO3, 10 per cent. ; and that of Mg3(PO4)2, 1.3 per cent. In
pathological conditions the composition of bone is modified as
shown in the following table :
200
MANUAL OF CHEMISTRY.
ANALYSES OP BONES.
of «
oSO
.s~S
«r»
3
1
L
_2 i
I-
it
SI
* s*
If
S
«s
:• >
In 100 parts.
J?«
O uf 3
S * h
o oT 3
o-
i'
.ZjZj
<S
""-fl *
.s
's &>§
Q c8 M
III
111
•"3 b
1
3 4>
'§
« « S
yWS
E
H
O
O
O
(S
M
O
O
*
Collagen
48.83
29 18
32.54
4 15
75.22
6 12
72.20
7 20
J-81.12J
35.69
3 00
41.42
8.36
19.58
1 22
Fats
Tricalcic phosphate
Calcium nuorid
56.9
17.56
53.25
12.56
14.78
1 00
15.60
j-51.53
44.05
72.63
Calcium carbonate
10.2
3.04
7.49
3.20
3 00
2.66
5.44
3 45
4.03
Trimagnesic phosphate.
1.3
0.23
1.22
0.92
0.80
*
3.43
1.02
1.93
Other salts
0 37
1 35
1 98
1 02
0 62
0 91
1 70
0 61
Organic matter. . .
35 8
78 01
36 69
81 34
79 40
81 12
38 09
49.78
20.80
Ash
64 2
21 20
63 31
19 66
20 60
18 88
61 31
50 22
79 20
J
i
•d
•o
t
•J
t
* Included in tricalcic
phosphate.
1
1
&
3
n
o3
1
fi
|||
N|
f>
3
a
.
S
>
s
»
I
« ^
a
>
The teeth, consist largely of Ca3(PO4)ii; the dentin of human
molars containing 66.72 per cent., and the enamel 89.82 per cent.
From the urine, tricalcic phosphate is frequently deposited,
either in the form of an amorphous, granular sediment, or as
calculi. The dicalcic salt occurs occasionally in urinary sedi-
ments, in the form of needle-shaped crystals, arranged in rosettes,
and also in urinary calculi. The monocalcic salt is always pres-
ent in acid urine, constituting, with the corresponding mag-
nesium salt, the earthy phosphates. The total elimination of
H3PC>4 by the urine is about 2.75 grams (42.5 grains) in 24 hours;
of which two-thirds are in combination with Na and K ; and one-
third with Ca and Mg. The hourly elimination follows about the
same variation as that of the chlorids. The total elimination is
greater with animal than with vegetable food ; is diminished dur-
ing pregnancy ; and is above the normal during excessive mental
work. The elimination of *earthy phosphates is greatly increased
in osteomalacia, often so far that they are in excess of the alkaline
phosphates.
So long as the urine is acid, it contains the soluble acid phos-
phates. When the reaction becomes alkaline, or even on loss of
CO2 by exposure to air, the acid phosphate is converted into the
insoluble Ca3(PO4)2. Alkaline urines are, for this reason, almost
always turbid, and become clear on the addition of acid. It 'is in
such urine that phosphatic calculi are invariably formed, usually
about a nucleus of uric acid, or of a foreign body. If the alka-
linity be due to the formation of ammonia, the trimagnesic phos-
phate is not formed, but ammonio-magnesian phosphate (q.v.).
Quantitative determination of phosphates in urine. — A process
CALCIUM. 201
for determining the quantity of phosphates in urine is based upon
the formation of the insoluble uranium phosphate, and upon the
production of a brown color when a solution of a uranium salt is
brought in contact with a solution of potassium ferrocyanid.
Pour solutions are required : (1) a standard solution of disodic
jyhosphate, made by dissolving 10.085 grams of crystallized, non-
effloresced HNa2PO4 in H2O, and diluting to a litre; (2) an acid
solution of sodium acetate, made by dissolving 100 grams sodium
acetate in H2O, adding 100 c.c. glacial acetic acid, and diluting
with H2O to a litre; (3) a strong solution of potassium ferrocy-
anid; (4) a standard solution of uranium acetate, made by dis-
solving 20.3 grams of yellow uranic oxid in glacial acetic acid, and
diluting with H2O to nearly a litre. Solution 1 serves to deter-
mine the true strength of this solution, as follows : 50 c.c. of Solu-
tion 1 are placed in a beaker, 5 c.c. of Solution 2 are added, the
mixture heated on a water-bath, and the uranium solution grad-
ually added, from a burette, until a drop from the beaker pro-
duces a brown color when brought in contact with a drop of the
ferrocyanid solution. At this point the reading of the burette,
which indicates the number of c.c. of the uranium solution, cor-
responding to 0.1 — P2O5, is taken. A quantity of H2O, determined
by calculation from the result thus obtained, is then added to the
remaining uranium solution, such as to render each c.c. equiva-
lent to 0.005 gram P,O6.
To determine the total phosphates in a urine: 50 c.c. are placed
in a beaker, 5 c.c. sodium acetate solution are added; the mix-
ture is heated on the water-bath, and the uranium solution de-
livered from a burette, until a drop, removed from the beaker
and brought in contact with a drop of ferrocyanid solution, pro-
duces a brown tinge. The burette reading, multiplied by 0.005,
gives the amount of PaO5 in 50 c.c. urine; and this, multiplied by
•g^ the amount of urine passed in 24 hours, gives the daily elimi-
nation.
To determine the earthy phosphates, a sample of 100 c.c. urine
is rendered alkaline with NH4HO, and set aside for 12 hours. The
precipitate is then collected upon a filter, washed with aminoni-
acal water, brought into a beaker, dissolved in a small quantity
of acetic acid ; the solution diluted to 50 c.c. with H2O, treated
with 5 c.c. sodium acetate solution, and the amount of PaO5 de-
termined as above.
Calcium Carbonate — CaCO3 — 100 — the most abundant of the nat-
ural compounds of Ca, exists as limestone, calcspar, chalk, mar-
ble, Iceland spar, and arragonite ; and forms the basis of corals,
shells of Crustacea and of molluscs, etc.
The precipitated chalk — Calcii carbonas prsecipitata (TJ. S. ; Br.)
— is prepared by precipitating a solution of CaCU with one of
202 MANUAL OF CHEMISTRY.
Prepared chalk — Creta preeparata (U. S.; Br.) — is native-
chalk, purified by grinding with H2O, diluting, allowing the
coarser particles to subside, decanting the still turbid liquid, col-
lecting, and drying the finer particles. A process known as
elutriation.
It is a white powder, almost insoluble in pure HSO ; much more
soluble in H2O containing carbonic acid, the solution being re-
garded as containing monocalcic carbonate H2Ca(CO3)2. At a
red heat it yields CO2 and CaO. It is decomposed by acids with
liberation of COa.
PHYSIOLOGICAL. — Calcium carbonate is much more abundant in
the lower than in the higher forms of animal life. It occurs in
the egg-shells of birds, in the bones and teeth of all animals ; in
solution in the saliva and urine of the herbivora, and deposited
in the crystalline form, as otoliths, in the internal ear of man.
It is deposited pathologically in calcifications, in parotid calculi,
and occasionally in human urinary calculi and sediments.
Calcium Oxalate — Oxalate of lime—GaG^O^ — 128 — exists in the
sap of many plants, and is formed as a white, crystalline precipi-
tate, by double decomposition, between a Ca salt and an alkaline
oxalate. It is insoluble in H2O, acetic acid, or NH4HO; soluble
in the mineral acids and in solution of HsNaPC>4.
PHYSIOLOGICAL. — Calcium oxalate is taken into the body in
vegetable food, and is formed in the economy, where its produc-
tion is intimately connected with that of uric acid.
It occurs in the urine, in which it is increased in quantity when
large amounts of vegetable food are taken; when sparkling wines
or beers are indulged in ; and when the carbonates of the alkalies,
lime- water and lemon- juice, are administered. It is deposited as
a urinary sediment in the form of small, brilliant octahedra, hav-
ing the appearance of the backs of square letter-envelopes ; or in
dumb-bells. It is usually deposited from acid urine, and accom-
panied by crystals of uric acid. Sometimes, however, it occurs in
urines undergoing alkaline fermentation, in which case it is ac-
companied by crystals of ammonio-magnesian phosphate.
The renal or vesical calculi of calcium oxalate, known as mul-
berry calculi, are dark brown or gray, very hard, occasionally
smooth, generally tuberculated, soluble in HC1 without efferves-
cence ; and when ignited, they blacken, turn white, and leave an
alkaline residue. <See oxalic acid.)
Analytical Characters. — (1.) Ammonium sulf hydrate : nothing,
unless the Ca salt be the phosphate, oxalate or fluorid, when it
forms a white ppt. (2.) Alkaline carbonates: white ppt. ; not
prevented by the presence of ammoniacal salts. (3.) Ammonium
oxalate : white ppt. ; insoluble in acetic acid ; soluble in HC1, or
STRONTIUM, BARIUM. 20$
HNO3. (4.) Sulfuric acid : white ppt., either immediately or
on dilution with three volumes of alcohol; very sparingly soluble
in H2O; insoluble in alcohol; soluble in sodium, hyposulflte solu-
tion. (5.) Sodium tungstate : dense white ppt., even from dilute-
solutions. (6.) Colors the flame of the Bunsen burner reddish-
yellow, and exhibits a spectrum of a number of bright bands, the-
most prominent of which are : A=6265, 6202, 6181, 6044, 5982, 5933,.
5543, and 5517.
STRONTIUM.
Symbol=Sr — Atomic weight=87A — Sp. fir. =2.54.
An element, not as abundant as Ba, occurring principally in the-
minerals strontianite (SrCO3) and celestine (SrSCh). Its com-
pounds resemble those of Ca and Ba. Its nitrate is used in mak-
ing red fire.
Analytical Characters. — (1.) Behaves like Ba with alkaline
carbonates and Na2HPO4. (2.) Calcium siilfate : a white ppt.
which forms slowly ; accelerated by addition of alcohol. (3.) The-
Sr compounds color the Bunsen flame red, or, as observed through,
blue glass, purple or rose color. The Sr flame gives a spectrum
of many bands, of which the most prominent are: ^=6694, 6664,
6059, 6031, 4607.
BARIUM.
Symbol— Ba — Atomic weight=lSQ.8 — Molecular weight=2f!3.Q (?)
— Sp. gr.—A.Q — Discovered by Davy, 1808 — Name from /3a/wf=
heavy.
Occurs only in combination, principally as heavy spar (BaSO4)
and witherite (BaCO3). It is a pale yellow, malleable metal,
quickly oxidized in air, and decomposing H2O at ordinary tem-
peratures.
Oxids. — Barium Monoxid — Baryta — BaO— 152.8 — is prepared by
calcining the nitrate. It is a grayish-white or white, amorphous,
caustic solid. In air it absorbs moisture and CO2, and combines
with HaO as does CaO.
Barium Dioxid— Barium peroxid— BaO2 — 168.8 — is prepared by
heating the monoxid in O. It is a grayish-white, amorphous solid.
Heated in air it is decomposed: BaO2=BaO-f O. Aqueous acids
dissolve it with formation of a barytic salt and H2O2.
Barium Monohydroxid — Ba2HO2 — 170.8 — is prepared by the
action of H2O on BaO. It is a white, amorphous solid, soluble in
H2O. Its aqueous solution, baryta water, is alkaline, and absorbs.
CO2, with formation of a white deposit of BaCO3.
Barium Chlorid — BaCl2-f-2Aq — 207. 8+36 — is obtained by treating
BaS or BaCO3 with HC1. It crystallizes in prismatic plates, per-
manent in air, soluble in H2O.
204 MANUAL OF CHEMISTKY.
Barium Nitrate— Ba(NO3)a— 260.8— is prepared by neutralizing
HNOs with BaCQ3. It forms octahedral crystals, soluble in H2O.
Barium Sulfate— BaSO4 — 232.8 — occurs in nature as heavy spar,
And is formed as an amorphous, white powder, insoluble in acids,
by double decomposition between a Ba salt and a sulfite in
solution. It is insoluble in H2O and in acids. It is used as a pig-
ment, permanent white.
Barium Carbonate — BaCO3 — 196.8— occurs in nature as witherite,
-and is formed by double decomposition between a Ba salt and a
-carbonate in alkaline solution. It is a heavy, amorphous, white
powder, insoluble in H2O, soluble with effervescence in acids.
Analytical Characters. — (1.) Alkaline carbonates : white ppt., in
alkaline solution. (2.) Sulfuric acid, or calcium sulfate : white
ppt.; insoluble in acids. (3.) Sodium phosphate: white ppt.;
soluble in HNO3. (4.) Colors the Bunsen flame greenish-yellow,
-and exhibits a spectrum of several lines, the most prominent of
which are: A=6108, 6044, 5881, 5536.
Action on the Economy. — The oxids and hydroxid act as cor-
rosives, by virtue of their alkalinity, and also as tri>.> poisons.
All soluble compounds of Ba, and those which are readily con-
Averted into soluble compounds in the stomach, are actively
poisonous. Soluble sulfids, followed by emetics, are indicated as
^antidotes. The sulfate, notwithstanding its insolubility in water,
is poisonous to some animals.
IV. MAGNESIUM GKOTJP.
MAGNESIUM— ZINC— CADMIUM.
Each of these elements forms a single oxid — a corresponding
ijasic hydroxid, and a series of salts in which its atoms are bivalent.
MAGNESIUM.
8ymbol='SILg — Atomic weight— 24 — Molecular weight— 4S (?) —
ISp. gr. =1.75— Fuses at 1000° (1832° F.)— Discovered by Davy, 1808.
Occurs as carbonate in dolomite or magnesian limestone, and
«,s silicate in mica, asbestos, soapstone, meerschaum, talc, and in
other minerals. It also accompanies Ca in the forms in which it
Is found in the animal and vegetable worlds.
It is prepared by heating its chlorid with Na. It is a hard,
light, malleable, ductile, white metal. It burns with great bril-
liancy when heated in air (magnesium light), but may be distilled
in H. The flash light used by photographers is a mixture of
powdered Mg with an oxidizing agent, KC1O3 or KNO3. It de-
MAGNESIUM. 205
composes vapor of H2O when heated ; reduces CO» with the aid of
heat, and combines directly with 01, S, P, As, and N. It dissolves
in dilute acids, but is not affected by alkaline solutions.
Magnesium Oxid — Calcined magnesia — Magnesia (TJ. S. ; Br.) —
MgO — 40 — is obtained by calcining the carbonate, hydroxid, or
nitrate. It is a light, bulky, tasteless, odorless, amorphous, white
powder; alkaline in reaction; almost insoluble in HaO; readily
soluble without effervescence in acids.
Magnesium Hydroxid— MgH2O2— 58— occurs in nature, and is
formed when a solution of a Mg salt is precipitated with excess
of NaHO, in absence of ammoniacal salts. It is a heavy, white
powder, insoluble in HaO; absorbs CO2.
Magnesium Chlorid — MgClQ — 95— is formed when MgO or MgCOs
is dissolved in HC1. It is an exceedingly deliquescent, soluble
substance, which is decomposed into HC1 and MgO when its
aqueous solutions are evaporated to dryness. Like all the solu-
ble Mg compounds it is bitter in taste, and accompanies the
sulfate and bicarbonate in the bitter waters.
Magnesium Sulfate — Epsom salt — Sedlitz salt — Magnesii sul-
fas (U. S.)— Magnesise sulfas (Br.)— MgSO4 + 7 Aq— 120 -f 126 —
exists in solution in sea-water and in the waters of many mineral
springs, especially those known as bitter waters. It is formed by
the action of H2SO4 on MgCO3. It crystallizes in right rhombic
prisms; bitter; slightly effervescent, and quite soluble in H2O.
Heated, it fuses and gradually loses 6 Aq up to 132° (269°. 6 F.);
the last Aq it loses at 210° (410° F.).
Phosphates. — Resemble those of Ca in their constitution and
properties, and accompany them in the situations in which they
occur in the animal body, but in much smaller quantity.
Magnesium also forms double phosphates, constituted by the
substitution of one atom of the bivalent metal for two of the
atoms of basic hydrogen, of a molecule of phosphoric acid, and
of an atom of an alkaline metal, or of an ammonium group, for
the remaining basic hydrogen.
Ammonio-Magnesiaii Phosphate — Triple phosphate — Mg(NH4}
PO4+6 Aq — 137-|-108 — is produced when an alkaline phosphate
and NH 4HO are added to a solution containing Mg. When heated
it is converted into magnesium pyrophosphate Mg2P2O7, in which
form H3PO4 and Mg are usually weighed in quantitative analysis.
In the urine, alkaline phosphates and magnesium salts are al-
ways present, and consequently when, by decomposition of urea,
the urine becomes alkaline, the conditions for the formation of
this compound are fulfilled. Being practically insoluble, espe-
cially in the presence of excess of phosphates and of ammonia, it
is deposited in crystals, usually tabular, sometimes feathery and
stellate in form. When it is formed in the bladder, in the pres-
206 MANUAL OF CHEMISTRY.
-ence of some body to serve as a nucleus, the crystallization takes
place upon the nucleus, and a fusible calculus is produced.
Carbonates. — Magnesium Carbonate — Neutral carbonate — Mg
CO3 — 84 — exists native in magnesite, and, combined with CaCO3,
in dolomite. It cannot be formed, like other carbonates, by de-
composing a Mg salt with an alkaline carbonate, but may be ob-
tained by passing COa through H2O holding tetramagnesic tricar-
l^onate in suspension.
Trimagnesic Bicarbonate — (MgCO3)2MgH2O2-|-2Aq — 226+36— is
formed, in small crystals, when a solution of MgSO4 is precipi-
tated with excess of Na2CO3, and the mixture boiled.
Tetramagnesic Tricarbonate — Magnesia alba — Magnesii car-
"bonas (U. S.) — Magnesias carbonas (Br.) — 3(MgCO3)MgH2O2+3Aq
— 310-J-54 — occurs in commerce in light, white cubes, composed of
•a powder which is amorphous, or partly crystalline. It is pre-
pared by precipitating a solution of MgSO4 with one of Na2CO3.
If the precipitation occur in cold, dilute solutions (Magnesias
carbonas loevis, Br.), very little CO2 is given off; a";ight, bulky
precipitate falls, and the solution contains magnesium, probably
in the form of the bicarbonate Mg(HCO3)2. This solution, on
standing, deposits crystals of the carbonate, MgCO3-|-3Aq. If
.hot concentrated solutions be used, and the liquid be then boiled
upon the precipitate, CO2 is given off, and a denser, heavier pre-
cipitate is formed, which varies in composition, according to the
length of time during which the boiling is continued, and to the
presence or absence of excess of sodium carbonate. The pharma-
ceutical product frequently contains 4(MgCO3),MgH2O2-(-4H2O,
or even 2(MgCO3),MgH2O2-f-2H2O. All of these compounds are
very sparingly soluble in H2O, but much more soluble in H3O
•containing ammoniacal salts.
Analytical Characters. — (1.) Ammonium hydroxid: voluminous,
Avhite ppt. from neutral solutions. (2.) Potash or soda : volumi-
nous, white ppt. from warm solutions ; prevented by the presence
of NH4 salts, and of certain organic substances. (3.) Ammonium
-carbonate : slight ppt. from hot solutions ; prevented by the pres-
ence of NH4 salts. (4.) Sodium or potassium carbonate: white
ppt., best from hot solution; prevented by the presence of NH4
compounds. (5.) Disodic phosphate: white ppt. in hot, not too
olilute solutions. (6.) Oxalic acid: nothing alone, but in presence
of NH4HO, a white ppt. ; not formed in presence of salts of NH4.
ZINC. 207
ZINC.
Symbol— Zn — Atomic weight=Q4:.Q — Molecular
JSp. gr. =6.862-7.215— Fuses at 415° (779° F.)— Distils at 1040° (1904°
F.).
Occurs principally in calamine (ZnCO3); and blende (ZnS); also
as oxid and silicate ; never free. It is separated from its ores by
calcining, roasting, and distillation.
It is a bluish- white metal; crystalline, granular, or fibrous;
quite malleable and ductile when pure. The commercial metal is
usually brittle. At 130°- 150° (26G°-302° F.) it is pliable, and be-
comes brittle again above 200°-210° (392°-410° F.).
At 500° (932° F.) it burns in air, with a greenish- white flame,
and gives off snowy white flakes of the oxid (lana philosophica ;
nil album ; pompholix). In moist air it becomes coated with a
film of hydrocarbonate. It decomposes steam when heated.
Pure H2SO4 and pure Zn do not react together in the cold. If
the acid be diluted, however, it dissolves the Zn, with evolution
of H, and formation of ZnSO«, in the presence of a trace of Pt or
Cu. The commercial metal dissolves readily in dilute H2SO4,
with evolution of H, and formation of ZnSO4, the action being
accelerated in presence of Pt, Cu, or As. Zinc surfaces, thor-
oughly coated with a layer of an amalgam of Hg and Zn, are only
attacked by H2SO4 if they form part of closed galvanic circuit ;
hence the zincs of galvanic batteries are protected by amalgama-
tion. Zinc also decomposes HNO3, HC1, and acetic acid.
When required for toxicological analysis, zinc must be perfectly
free from As, and sometimes from P. It is better to test samples
until a pure one is found, than to attempt the purification of a
•contaminated metal.
Zinc surfaces are readily attacked by weak organic acids. Ves-
sels of galvanized iron or sheet zinc should therefore never be
used to contain articles of food or medicines.
Zinc Oxid — Zinci oxidum (TT. S. ; Br.) — ZnO — 80.9 — is prepared
either by calcining the precipitated carbonate, or by burning Zn
in a current of ah*. An impure oxid, known as tutty, is deposited
in the flues of zinc furnaces, and in those in which brass is fused.
When obtained by calcination of the carbonate, it forms a soft,
white, tasteless, and odorless powder. When produced by burn-
ing the metal, it occurs in light, voluminous, white masses. It is
neither fusible, volatile, nor decomposable by heat, and is com-
pletely insoluble in neutral solvents. It dissolves in dilute acids,
with formation of the corresponding salts.
It is used in the arts as a white pigment in place of lead carbon-
ate, and is not darkened by H2S.
208 MANUAL OF CHEMISTRY.
Zinc Hydroxid— ZnHuOa — 98.9— is not formed by union of ZnO
and H2O ; but is produced when a solution of a Zn salt is treated"
with KHO. Freshly prepared, it is very soluble in alkalies, and
in solutions of NH4 salts.
Zinc Chlorid — Butter of zinc — Zinci chloridum (TJ. S.; Br.) — ZnCl?
-|-Aq — 135.9+18 — is obtained by dissolving Zn in HC1; or by heat-
ing Zn in Cl. It is a soft, white, very deliquescent, fusible, vola-
tile mass; very soluble in H2O, somewhat less so in alcohol. Its-
solution has a burning metallic taste ; destroys vegetable tissues ;
dissolves silk ; and exerts a strong dehydrating action upon or-
ganic substances in general.
' In dilute solution it is used as a disinfectant and antiseptic
(Burnett's fluid), as a preservative of wood and as an embalming-
injection.
Zinc Sulfate— White vitriol— Zinci sulfas (U. S.; Br.)— ZnSO,
-fwAq— 160.9-fwl8— is formed when Zn, ZnO, ZnS, or ZnCO3 is.
dissolved in diluted H2SO4. It crystallizes below 30° (86° F.) with
7 Aq; at 30° (86° F.) with 6 Aq; between 40°-50° (104°-122" -F.) with
5 Aq; at 0° (32° F.) from concentrated acid solution with 4 Aq.
From a boiling solution it is precipitated by concentrated H-iSC^
with 2Aq; from a saturated solution at 100° (212° F.) with 1 Aq;
and anhydrous, when the salt with 1 Aq is heated to 238° (460° F.).
The salt usually met with is that with 7 Aq, which is in large,
colorless, four-sided prisms; efflorescent; very soluble in H2O;
sparingly soluble in weak alcohol. Its solutions have a strong,
styptic taste ; coagulate albumin when added in moderate quan-
tity, the coagulum dissolving in an excess; and form insoluble
precipitates with the tannins.
Carbonates. — Zinc Carbonate — ZnCO3 — 124.9 — occurs in nature as
calamine. If an alkaline carbonate be added to a solution of a.
Zn salt, the neutral carbonate, as in the case of Mg, is not formed,
but an oxycarbonate, nZnCO3, wZnHQO2 [Zinci carbonas (U. S. ;
Br.)], whose composition varies with the conditions under which
it is formed.
Analytical Characters. — (1.) K, Na or NH4 hydroxid : white
ppt., soluble in excess. (2.) Carbonate of K or Na: white ppt.,
in absence of NH4 salts. (3.) Hydrogen sulfld, in neutral solu-
tion: white ppt. In presence of an excess of a mineral acid, the
formation of this ppt. is prevented, unless sodium acetate be
also present. (4.) Ammonium sulf hydrate: white ppt., insoluble
in excess, in KHO, NH4HO, or acetic acid; soluble in dilute min-
eral acids. (5.) Ammonium carbonate : white ppt., soluble in ex-
cess. (6.) Disodic phosphate, in absence of NH4 salts : white ppt.,
soluble in acids or alkalies. (7.) Potassium ferrocyanid: white
ppt., insoluble in HC1.
Action on the Economy. — All the compounds of Zn which are
CADMIUM, NICKEL. 209
soluble in the digestive fluids behave as true poisons ; and solu-
tions of the chlorid (in common use by tinsmiths, and in disin-
fecting fluids) have also well-marked corrosive properties. When
Zn compounds are taken, it is almost invariably by mistake for
other substances : the sulfate for Epsom salt, and solutions of
the chlorid for various liquids, gin, fluid magnesia, vinegar, etc.
Metallic zinc is dissolved by solutions containing Nad, or or-
ganic acids, for which reason articles of food kept in vessels of
galvanized iron become contaminated with zinc compounds, and,
if eaten, produce more or less intense symptoms of intoxication.
For the same reason materials intended for analysis, in cases of
supposed poisoning, should never be packed in jars closed by zinc
caps.
CADMIUM.
8ymbol=Gd — Atomic weight=lll.S — Molecular weight— -111.8 —
A'p. #7-. =8. 604— Fuses at 227°. S (442° F.)— Soils at 860° (1580° P.).
A white metal, malleable and ductile at low temperature, brit-
tle when heated ; which accompanies Zn in certain of its ores. It
resembles zinc in its physical as well as its chemical characters.
It is used in certain fusible alloys, and its iodid is used in pho-
tography.
Analytical Characters. — Hydrogen sulfld : bright yellow ppt. ;
insoluble in NH4HS, and in dilute acids and alkalies, soluble in
boiling HNO3 or HC1.
V. NICKEL GROUP.
NICKEL — COBALT.
These two elements bear some resemblance chemically to those
of the Fe group ; from which they differ in forming, so far as
known, no compounds similar to the ferrates, chromates, and
manganates, unless the barium cobaltite, recently described by
Rousseau, be such. They form compounds corresponding to
FeaOs, but those corresponding to the ferric series are either want-
ing or exceedingly unstable.
MTCKEL.
8ymbol=TS\ — Atomic weight=58 — Sp. gr.=8.631.
Occurs in combination with S, and with S and As.
It is a white metal, hard, slightly magnetic, not tarnished in
air. German silver is an alloy of Ni, Cu, and Zn. Nickel is now
extensively used for plating upon other metals, and for the rnan-
14
210 MANUAL OF CHEMISTRY.
ufacture of dishes, etc., for use in the laboratory. Its salts are
green.
Analytical Characters.— (1.) Ammonium sulf hydrate : black
ppt.; insoluble in excess. (2.) Potash or soda: apple-green ppt.,
in absence of tartaric acid; insoluble in excess. (3.) Ammonium
hydroxid : apple-green ppt. ; soluble in exoess ; forming a violet
solution, which deposits the apple-green hydrate, when heated
with KHO.
COBALT.
Symbol=Co — Atomic weight=58.9 — 8p. gr. =8.5-8.7.
Occurs in combination with As and S. Its salts are red when
hydrated, and usually blue when anhydrous. Its phosphate is
used as a blue pigment.
Analytical Characters. — (1.) Ammonium sulf hydrate: black
ppt.; insoluble in excess. (2.) Potash: blue ppt.; turns red,
slowly in the cold, quickly when heated; not formed in the cold
in the presence of NH4 salts. (3.) Ammonium hydroxid : blue
ppt. ; turns red in absence of air, green in its presence.
| VI. COPPER GROUP.
COPPER — MERCURT.
Each of these elements forms two series of compounds. One
contains compounds of the bivalent group
which are designated by the termination ous; the other contains
compounds of single, bivalent atoms Cu" or Hg", which are des-
ignated by the termination ic.
COPPER.
Symbol = Cu (CUPRUM)— Atomic weight = 63.1 — Molecular
weight=127 (?)— Sp. ^r.= 8. 914-8. 952— Fuses at 1091° (1996° F.).
Occurrence. — It is found free, in crystals or amorphous masses,
sometimes of great size; also a sulfid, copper pyrites ; oxid, ruby
ore and black oxid ; and basic carbonate, malachite.
Properties. — Physical. — A yellowish-red metal; dark brown
when finely divided; very malleable, ductile, and tenacious; a
good conductor of heat and electricity ; has a peculiar, metallic
taste and a characteristic odor.
Chemical. — It is unaltered in dry air at the ordinary tempera-
ture ; but, when heated to redness, is oxidized to CuO. In damp
COPPER. 211
air it becomes coated with a brownish film of oxid ; a green film
of basic carbonate ; or, in salt air, a green film of basic chlorid.
Hot H2SO4 dissolves it with formation of CuSO4 and SO2. It is
dissolved by HNO3 with formation of Cu(NO3)a and NO; and by
HC1 with liberation of H. Weak acids form with it soluble salts,
in presence of air and moisture. It is dissolved by XH4HO, in
presence of air, with formation of a blue solution. It combines
directly with Cl, frequently with light.
Oxids. — Cuprous Oxid — Suboxid or red oxid of copper — (Cu2)O —
142.4 — is formed by calcining a mixture of (Cu2)Cl2 and Na2CO3;
or a mixture of CuO and Cu. It is a red or yellow powder ; per-
manent in air; sp. gr. 5. 749-6. 093; fuses at a red heat; easily
reduced by C or H. Heated in air it is converted into CuO.
Cupric Oxid — Binoxid or black oxid of copper — CuO — 79.2 — is
prepared by heating Cu to dull redness in air ; or by calcining
Cu(NOs)2 ; or by prolonged boiling of the liquid over a precipitate,
produced by heating a solution of a cupric salt, in presence of
glucose, with KHO. By the last method it is sometimes produced
in Trommer's test for glucose, when an excessive quantity of
CuSO4 has been used.
It is a black, or dark reddish-brown, amorphous solid ; readily
reduced by C, H, Na, or K at comparatively low temperatures.
When heated with organic substances, it gives up its O, convert-
ing the C into CO., and the H into H2O: C2H»O+6CuO=6Cu+
2CO2+3H2O; a property which renders it valuable in organic
-analysis, as by heating a known weight of organic substance with
CuO, and weighing the amount of CO2 and H2O produced, the
percentage of C and H may be obtained. It dissolves in acids
Avith formation of salts.
Hydroxids.— Cuprous Hydroxid — (Cu)2Ha02(?) — 160.4 (?) — is
formed as a yellow or red powder when mixed solutions of CuSO4
and KHO are heated in presence of glucose. By boiling the
solution it is rapidly dehydrated with formation of (Cua)O.
Cupric Hydroxid— ChiHaOa — 97.2 — is formed by the action of
KHO upon solution of CuSO4, in absence of reducing agents and
in the cold. It is a bluish, amorphous powder; very unstable,
and readily dehydrated, with formation of CuO.
Sulfids.— Cuprous Sulfld — Subsulfid or protosulfid of copper —
CuaS — 158.4 — occurs in nature as copper glance or chalcosine, and
in many double sulfids, pyrites.
Cupric Sulfid— CuS— 95.2 — is formed by the action of HaS, or
of NH4HS, on solutions of cupric salts. It is almost black when
moist, greenish-brown when dry. Hot HXOs oxidizes it to Cu
SO4 ; hot HC1 converts it into CuCl2, with separation of S, and
formation of H2S. It is sparingly soluble in NH4HS, its solubil-
ity being increased by the presence of organic matter.
212 MANUAL OF CHEMISTRY.
Chlorids. — Cuprous Chlorid — SubcJilorid or protochlorid — (Cu2>
C12 — 197.4 — is prepared by heating Cu with one of the chlorids of
Hg; by dissolving (Cu2)O in HC1, without contact of air; or by
the action of reducing agents on solutions of CuCl2. It is a heavy,
white powder; turns violet and blue by exposure to light; solu-
ble in HC1; insoluble in H2O. It forms a crystallizable com-
pound with CO; and its solution in HC1 is used in analysis to
absorb that gas.
Cupric Chlorid — Chlorid or deutochlorid — CuCl2 — 134.2 — is-
formed by dissolving Cu in aqua regia. If the Cu be in excess,
it reduces CuCl2 to (Cu2)Cl2. It crystallizes in bluish-green, rhom-
bic prisms with 2 Aq; deliquescent; very soluble in H2O and in
alcohol.
Cupric Nitrate — Cu(NO3)2 — 187.2 — is formed by dissolving Cur.
CuO, or CuCOa in HNO3. It crystallizes at 20°-25° (68°-77° F.)
with 3 Aq ; below 20° (68° F.) with 6 Aq, forming blue, deliques-
cent needles. Strongly heated, it is converted into CuO.
Cupric Sulfate — Blue vitriol— Blue stone — Cupri sulfas (TT.
S. ; Br.) — CuSO4-|-5Aq — 159.2-f90 — is prepared: (1) by roasting Cu
S; (2) from the water of copper mines; (3) by exposing Cu, moist-
ened with dilute H2SO4, to air; (4) by heating Cu with H2SO4.
As ordinarily crystallized, it is in fine, blue, oblique prisms ; solu-
ble in H2O; insoluble in alcohol; efflorescent in dry air at 15° (59°
F.), losing 2 Aq. At 100° (212° F.) it still retains 1 Aq, which it
loses at 230° (446° F.), leaving a white, amorphous powder of the
anhydrous saltf, which, on taking up H2O, resumes its blue color.
Its solutions are blue, acid, styptic, and metallic in taste.
When NH4HO is added to a solution of CuSO4, a bluish-white
precipitate falls, which redissolves in excess of the alkali, to form
a deep blue solution. Strong alcohol floated over the surface of
this solution separates long, right rhombic prisms, having the
composition CuSO4,4NH3-f-H2O, which are very soluble in H2O.
This solution constitutes ammonio-sulfate of copper or aqua
sapphirina.
Arsenite — Scheele's green — Mineral green — is a mixture of cu-
pric arsenite and hydrate ; prepared by adding potassium arsenite
to solution of CuS04. It is a grass-green powder, insoluble in
H2O ; soluble in NH4HO, or in acids. Exceedingly poisonous.
Schweinfurt Green — Mitis green or Paris green — is the most fre-
quently used, and the most dangerous of the cupro-arsenical pig-
ments. It is prepared by adding a thin paste of neutral cupric
acetate with H2O to a boiling solution of arsenious acid, and con-
tinuing the boiling during a further addition of acetic acid. It is
an insoluble, green, crystalline powder, having the composition
(C2H3O2)2Cu-(-3(As2O4Cu). It is decomposed by prolonged boiling
in H2O, by aqueous solutions of the alkalies, and by the mineral
acids.
COPPER. 213
Carbonates. — The existence of cuprous carbonate is doubtful.
'Cupric carbonate — CuC03 — exists in nature, but has not been ob-
tained artificially. Dicupric carbonate— CuCO3,CuH2O2 — exists in
nature as malachite. When a solution of a cupric salt is decom-
posed by an alkaline carbonate, a bluish precipitate, having the
composition CuCO3,CuHoO2+H2O, is formed, which, on drying,
loses H2O, and becomes green ; it is used as a pigment under the
name mineral green. Tricupric carbonate — Sesqtiicarbonate of
•copper — 2(CuCO3),CuH202 — exists in nature as a blue mineral,
called azurite or mountain blue, and is prepared by a secret proc-
ess for use as a pigment known as blue ash.
Acetates. — Cupric Acetate — Diacetate — Crystals of Venus — Cupri
acetas (U. S.)— Cu(C2H3O2)2-f Aq— 181.2+18— is formed when CuO
or verdigris is dissolved in acetic acid ; or by decomposition of a
solution of CuSO4 by Pb(C2H3O2)2. It crystallizes in large, bluish-
green prisms, which lose their Aq at 140° (284° F.). At 240°-260°
<464°-500° F. ) they are decomposed with liberation of glacial acetic
acid.
Basic Acetates. — Verdigris — is a substance prepared by ex-
posing to air piles composed of alternate layers of grape-skins and
plates of copper, and removing the bluish-green coating from the
copper. It is a mixture, in varying proportions, of three differ-
ent substances: (C2H3O2)2CuH2b;,-f5Aq; [(C2H3O2)2Cu]2,CuH2O2
+5Aq; and (CaH3O2)2Cu,2(CuH2O!1).
•
Analytical Characters. — CUPROUS — are very unstable and read-
ily converted into cupric compounds. (1.) Potash: white ppt.;
turning brownish. (2.) Ammonium hydroxid, in absence of air:
a colorless liquid; turns blue in air.
CUPRIC — are white when anhydrous; when soluble in H2O they
form blue or green, acid solutions. (1.) Hydrogen sulfid: black
ppt.; insoluble in KHS or NaHS; sparingly soluble in NH4HS;
soluble in hot concentrated HNO3 and in KCN. (2.) Alkaline
sulfhydrates: same as H2S. (3.) Potash or soda: pale blue ppt.;
insoluble in excess. If the solution be heated over the ppt., the
latter contracts and turns black. (4.) Ammonium hydroxid, in
small quantity : pale blue ppt. ; in larger quantity, deep blue
solution. (5.) Potassium or sodium carbonate: greenish-blue ppt. ;
insoluble in excess; turning black when the liquid is boiled. (6.)
Ammonium carbonate : pale blue ppt. ; soluble with deep blue
color in excess. (7.) Potassium cyanid : greenish-yellow ppt. ; sol-
uble in excess. (8.) Potassium ferrocyanid : chestnut-brown ppt. ;
insoluble in weak acids; decolorized by KHO. (9.) Iron is coated
with metallic Cu.
Action on the Economy. — The opinion, until recently universal
214 MANUAL OF CHEMISTRY.
among toxicologists, that all the compounds of copper are poi-
sonous, has been much modified by recent researches. Certain,
of the copper compounds, such as the sulfate, having a tendency
to combine with albuminoid and other animal substances, pro-
duce symptoms of irritation by their direct local action, when
brought in contact with the gastric or intestinal mucous mem-
brane. One of the characteristic symptoms of such irritation is
the vomiting of a greenish matter, which develops a blue color
upon the addition of NH4HO.
Cases are not wanting in which severe illness, and even death,
has followed the use of food which has been in contact with im-
perfectly tinned copper vessels. Cases in which nervous and other
symptoms referable to a truly poisonous action have occurred.
As, however, it has also been shown that non-irritant, pure cop-
per compounds may be taken in considerable doses with impu-
nity, it appears at least probable that the poisonous action attrib-
uted to copper is due to other substances. The tin and solder
used in the manufacture of copper utensils contain lead, and in
some cases of so-called copper-poisoning, the symptoms have been
such as are as consistent with lead-poisoning as with copper-
poisoning. Copper is also notoriously liable to contamination
with arsenic, and it is by no means improbable that compounds
of that element are the active poisonous agents in some cases of
supposed copper-intoxication. Nor is it improbable that articles
of food allowed to remain exposed to air in copper vessels should
undergo those peculiar changes which result in the formation of
poisonous substances, such as the sausage- or cheese-poisons, or-
the ptomains.
The treatment, when irritant copper compounds have been
taken, should consist in the administration of white of egg or of
milk, with whose albuminoids an inert compound is formed by
the copper salt. If vomiting do not occur spontaneously, it
should be induced by the usual methods.
The detection of copper in the viscera after death is not with-
out interest, especially if arsenic have been found, in which case
its discovery or non-discovery enables us to differentiate between
poisoning by the arsenical greens, and that by other arsenical
compounds. The detection of mere traces of copper is of no sig-
nificance, because, although copper is not a physiological constit-
uent of the body, it is almost invariably present, having been
taken with the food.
Pickles and canned vegetables are sometimes intentionally
greened by the addition of copper; this fraud is readily detected
by inserting a large needle into the pickle or other vegetable ; if
copper be present the steel will be found to be coated with copper
after half an hour's contact.
MERCURY. 215
MERCURY.
Symbol='H.g (HYDRARGYRUM)— Atomic weight=19Q. 7— Mo-
lecular weight— 199.7 — Sp. gr. of liqiiid=13.5SQ; of vapor=G.97 —
Fuses at -38°.8 (-37°.9 F.)— Soils at 350° (662° F.).
Occurrence. — Chiefly as cinnabar (HgS) ; also in small quantity
free and as chlorid.
Preparation. — The commercial product is usually obtained by
simple distillation in a current of air : HgS-|-O2 = Hg-|-SO2. If re-
quired pure, it must be freed from other metals by distillation,
and agitation of . the redistilled product with mercurous nitrate
solution, solution of FesCl8, or dilute HXO3.
Properties. — Physical. — A bright metallic liquid ; volatile at all
temperatures. Crystallizes in octahedra of sp. gr. 14.0. When
pure, it rolls over a smooth surface in round drops. The forma-
tion of tear-shaped drops indicates the presence of impurities.
Chemical. — If pure, it is not altered by air at the ordinary tem-
perature, but, if contaminated with foreign metals, its surface
becomes dimmed. Heated in air, it is oxidized superficially to
HgO. It does not decompose H2O. It combines directly with Cl,
Br, I and S. It alloys readily with most metals to form amal-
gams. It amalgamates with Fe and Pt only with difficulty. Hot,
concentrated H2SO4 dissolves it, with evolution of SO2, and for-
mation of HgSO4. It dissolves in cold HXO3, with formation of
a nitrate.
Elementary mercury is insoluble in H2O, and probably in the
digestive liquids. It enters, however, into the formation of three
medicinal agents : hydrargyrum cum creta (U.S. ; Br.) ; massa hy-
drargyri (U. S.)=pilula hydrargyri (Br.) ; and unguentum hydrar-
gyri (U. S. ; Br.), all of which owe their efficacy, not to the metal
itself, but to a certain proportion of oxid, produced during their
manufacture. The fact that blue mass is more active than mer-
cury with chalk is due to the greater proportion of oxid contained
in the former. It is also probable that absorption of vapor of Hg
by cutaneous surfaces is attended by its conversion into HgCl2.
Oxids. — Mercurous Oxid — Protoxid or black oxid of mercury —
(Hg2)O — 415.4 — is obtained by adding a solution of (Hg2)(NO3)2 to
an excess of solution of KHO. It is a brownish-black, tasteless
powder ; very prone to decomposition into HgO and Hg. It is
converted into (Hg2)Cl2 by HC1 ; and by other acids into the cor-
responding mercurous salts.
It is formed by the action of CaH2O2 on mercurous compounds,
and exists in black wash.
216 MAJSTUAL OF CHEMISTRY.
Mercuric Oxid— Red, or binoxid of mercury— Hydrargyri ox-
idum flavum (U. S.; Br.) — Hydrargyri oxidum rubrum (U. S.; Br.)
— HgO— 215.7 — is prepared by two methods: (t) by calcining Hg
(NO3)2, as long as brown fumes are given off (Hydr. oxid. rubr.);
or, (2) by precipitating a solution of a mercuric salt by excess of
KHO (Hydr. oxid. flavum). The products obtained, although
the same in composition, differ in physical characters and in the
activity of their chemical actions. That obtained by (1) is red
and crystalline ; that obtained by (2) is yellow and amorphous.
The latter is much the more active in its chemical and medicinal
actions.
It is very sparingly soluble in H2O, the solution having an alka-
line reaction, and a metallic taste. It exists both in solution and
in suspension in yellow wash, prepared by the action of CaH2O2
on a mercuric compound.
Exposed to light and air, it turns black, more rapidly in pres-
ence of organic matter, giving off O, and liberating Hg: HgO=
Hg-)-O. It decomposes the chlorids of many metallic elements in
solution, with formation of a metallic oxid and mercuric oxy-
chlorids. It combines with alkaline chlorids to form soluble
double chlorids, called chloromercurates or chlorhydrargyrates ;
and forms similar compounds with alkaline iodids and bromids.
Sulfids. — Mercurous Sulfld — (Hg2)S — 431.4 — a very unstable
compound, formed by the action of H2S on mercurous salts.
Mercuric Sulfid— Red sulfld of mercury — Cinnabar — Vermilion
— Hydrargyri sulndum rubrum (TJ. S.) — HgS — 231.7 — exists in
nature in amorphous red masses, or in red crystals, and is the
chief ore of Hg. If Hg and S be ground up together in the cold,
or if a solution of a mercuric salt be completely decomposed by
HaS, a black sulfid is obtained, which is the JEthiops mineralis
of the older pharmacists.
A red sulfld is obtained for use as a pigment (vermilion), by
agitating for some hours at 60° (140° F.) a mixture of Hg, S, KHO,
and H2O. It is a fine, red powder, which turns brown, and finally
bla'ck, when heated. Heated in air, it burns to SO2 and Hg. It
is decomposed by strong H2SO4, but not by HNO3 or HC1.
Chlorids. — Mercurous Chlorid — Protochlorid or mild chlorid of
mercury — Calomel — Hydrargyri chloridum mite (U. S.) — Hydrar-
gyri subchloridum (Br.) — (Hg2)Cl2— 470.4 — is now principally ob-
tained by mutual decomposition of NaCl and (Hg2)SO4. Mer-
curic sulfate is first obtained by heating together 2 pts. Hg and
3 pts. H2SO4; the product is then caused to combine with a quan-
tity of Hg equal to that first used, to form (Hg2)SO4 ; which is
then mixed with dry NaCl, and the mixture heated in glass ves-
sels, connected with condensing chambers; 2NaCl+(Hgs)SO4=
Na2SO4-f(Hg2)Cla.
MERCURY. 217
In practice, varyirig quantities of HgCl2 are also formed, and
must be removed from the product by washing with boiled, dis-
tilled HaO, until the washings no longer precipitate with NH4HO.
The presence of HgCl2 in calomel may be detected by the forma-
tion of a black stain upon a bright copper surface, immersed in
the calomel, moistened with alcohol ; or by the production of a
black color by H2S in H2O which has been in contact with and
filtered from calomel so contaminated.
Calomel is also formed in a number of other reactions: (1) by
the action of Cl upon excess of Hg; (2) by the action of Hg upon
Fe2Cle ; (3) by the action of HC1, or of a chlorid, upon (Hga)O, or
upon a mercurous salt ; (4) by the action of reducing agents, in-
cluding Hg, upon HgClj.
Calomel crystallizes in nature, and when sublimed, in quadratic
prisms. When precipitated it is deposited as a heavy, amorphous,
white powder, faintly yellowish, and producing a yellowish mark
when rubbed upon a dark surface. It sublimes, without fusing,
between 420° and 500° (?88°-932° P.), is insoluble in cold H2O and
in alcohol ; soluble in boiling H2O to the extent of 1 part in 12,000.
When boiled with H2O for some time, it suffers partial decomposi-
tion, Hg is deposited and HgCl2 dissolves.
Although HgaCln is insoluble in H2O, in dilute HC1, and in pep-
sin solution, it is dissolved at the body temperature in an aqueous
solution of pepsin acidulated with HC1.
When exposed to light, calomel becomes yellow, then gray,
owing to partial decomposition, with liberation of Hg and forma-
tion of HgCl2 : (Hg2)Cl2 = Hg+HgCl2. It is converted into HgCl,
by Cl or aqua regia: (Hg2)Cl-H-Cl2=2HgCl2. In the presence of
H2O, I converts it into a mixture of HgCl2 and HgI2 : (Hg2)Cla-|-
I2=HgCl2+HgI2. It is also converted into HgCl2 by HC1 and by
alkaline chlorids: (Hg2)Cl2=HgCl2+Hg. This change occurs in
the stomach when calomel is taken internally, and that to such
an extent when large quantities of NaCl is taken with the food,
that calomel cannot be used in naval practice as it may be with
patients who do not subsist upon salt provisions. It is converted
by KI into (Hg2)Ia: (Hg2)Cl2+2KI=2KCl+(Hg2)I2; which is then
decomposed by excess of KI into Hg and HgI2, the latter dissolv-
ing: (Hg)Ja = Hg + HgI2. Solutions of the sulfates of Na, K,
and NH4 dissolve notable quantities of (Hg2)Cl2. The hydroxids
and carbonates of K and Na decompose it with formation of
(Hg2)O : (Hg2)Cl2+Na2CO3=(Hg2)O-f CO2-f2ISraCl; and the (Hg2)O
so formed is decomposed into HgO and Hg. If alkaline chlorids
be also present, they react upon the HgO so produced, with for-
mation of HgCU.
Mercuric Chlorid — Perchlorid or bichlorid of mercury — Corro-
sive sublimate — Hydrargyri chloridum corrosivum (TJ. S.) — Hy-
218 MANUAL OF CHEMISTKY.
drargyri perchloridum (Br.)—HgCl2— 270.7— is prepared by heat-
ing a mixture of 5 pts. dry HgSO4 with 5 pts. dry NaCl, and 1 pt.
HnO2 in a glass vessel communicating with a condensing chamber.
It crystallizes by sublimation in octahedra, and by evaporation
of its solutions in flattened, right rhombic prisms ; fuses at 265°
(509° F.), and boils at about 295° (563° F.); soluble in H2O and in
alcohol; very soluble in hot HC1, the solution gelatinizing on
cooling. Its solutions have a disagreeable, acid, styptic taste,
and are highly poisonous.
It is easily reduced to (Hg2)Cl2 and Hg, and its aqueous solu-
tions are so decomposed when exposed to light ; a change which
is retarded by the presence of NaCl. Heated with Hg, it is con-
verted into (Hg2)Cl2. When dry HgCl2, or its solution, is heated
with Zn, Cd, M, Fe, Pb, Cu, or Bi, those elements remove part or
all of its Cl, with separation of (Hg2)Cl2 or Hg. Its solution,., is
decomposed by H2S, with separation of a yellow sulfochlorid,
which, with an excess of the gas, is converted into black HgS. It
is soluble without decomposition in HaSO4, HNO3, and HC1. It is
decomposed by KHO or NaHO, with separation of a brown oxy-
chlorid if the alkaline hydroxid be in limited quantity; or of the
orange-colored HgO if it be in excess. A similar decomposition is
effected by CaH2O2 and MgH2O2 ; which does not, however, take
place in presence of an alkaline chlorid, or of certain organic mat-
ters, such as sugar and gum. Many organic substances decom-
pose it into (Hg2)Cl2 and Hg, especially under the influence of
sunlight. Albumen forms with it a white precipitate, which is
insoluble in H2O, but soluble in an exces of fluid albumen and in
solutions of alkaline chlorids. It readily combines with metallic
chlorids, to form soluble double chlorids, called chloromercurates
or chlorhydrargyrates. One of these, obtained in flattened, rhom-
bic prisms, by the cooling of a boiling solution of HgCl2 and NH4
Cl, has the composition HgCl2, 2(NH4Cl)-|-Aq, and was formerly
known as sal alembroth or sal sapiential.
Mercurammonium Chlorid — Mercury chloramidid — Infusible
white precipitate — Ammoniated mercury — Hydrargyrum amino-
niatum (TJ. S. ; Br.)— NHoHgCl — 251.1 — is prepared by adding a
slight excess of NH4HO to a solution of HgCl2. It is a white pow-
der, insoluble in alcohol, ether, and cold H2O; decomposed by
hot H2O, with separation of a heavy, yellow powder. It is en-
tirely volatile, without fusion. The fusible white precipitate
is formed in small crystals when a solution containing equal parts
of HgCl2 and NH4C1 is decomposed by Na2CO3. It is mercurdi-
ammoniuni chlorid, NH2HgCl,NH4Cl.
lodids.— Mercurous lodid — Protoiodid or yellow iodid — Hydrar-
gyri iodidum viride (U. S. ; Br.)—Hg2I2— 653.4— is prepared by
grinding together 200 pts. Hg and 127 pts. I with a little alcohol,.
MERCURY. 219-
until a green paste is formed. It is a greenish- yellow, amorphous
powder, insoluble in H2O and in alcohol. When heated, it turns
brown, and volatilizes completely. When exposed to light, or
even after a tune in the dark, it is decomposed into Hgla and Hg.
The same decomposition is brought about instantly by KI; more
slowly by solutions of alkaline chlorids, and by HC1 when heated.
NH4HO dissolves it with separation of a gray precipitate.
Mercuric lodid — Biniodid or red iodid — Hydrargyri iodidum
rubrum (U. S. ; Br.)— HgI2 — 453.7 — is obtained by double decom-
position between HgCla and KI, care being had to avoid too great
an excess of the alkaline iodid, that the soluble potassium iodhy-
drargyrate may not be formed.
It is sparingly soluble in H2O; but forms colorless solutions-
with alcohol. It dissolves readily in many dilute acids, and in
solutions of ammoniacal salts, alkaline chlorids, and mercuric
salts ; and in solutions of alkaline iodids. Iron and copper con-
vert it into (Hg2)I2, then into Hg. The hvdroxids of K and Na
decompose it into oxid or oxyiodid, and combine with another
portion to form iodhydrargyrates, which dissolve. NH4HO sepa-
rates from its solution a brown powder, and forms a yellow solu-
tion, which deposits white flocks.
Cyanids. — Mercuric Cyanid — Hydrargyri cyanidum (U. S.) —
Hg(CN)2— 251.7— is best prepared by heating together, for a quar-
ter of an hour, potassium ferrocyanid, 1 pt. ; HgSO.i, 2 pts. ; and
H2O, 8 pts. It crystallizes in quadrangular prisms ; soluble in &
pts. of cold H2O, much less soluble in alcohol ; highly poisonous.
When heated dry it blackens, and is decomposed into (CN)a and
Hg; if heated in presence of H2O it yields HCN, Hg, CO2, and
^H3. Hot concentrated H2SO4, and HC1, HBr, HI, and H2S in
the cold decompose it, with liberation of HCN. It is not de-
composed by alkalies.
Nitrates. — There exist, besides the normal nitrates :
and Hg(NO3)2, three basic mercurous nitrates, three basic mercu-
ric nitrates, and a mercuroso-mercuric nitrate.
Mercurous Nitrate— (Hg2)(NO3)2+2 Aq— 523.4+36— is formed
when excess of Hg is digested with HNO3, diluted with \ vol.
H2O; until short, prismatic crystals separate.
It effloresces in air; fuses at 70° (158° F.); dissolves in a small
quantity of hot H2O, but with a larger quantity is decomposed
with separation of the yellow, basic trimercuric nitrate Hg(NO3)2»
2HgO+Aq.
Dimercurous Nitrate — (Hg2)(NO3)2, Hg.O+Aq — 938.8+18 — is
formed by acting upon the preceding salt with cold H2O until it
turns lemon-yellow ; or by extracting with cold H2O the residue
of evaporation of the product obtained by acting upon excess of
Hg with concentrated HNOj.
220 MANUAL OF CHEMISTRY.
Trimercurous Nitrate— (Hg2)2(NO3)4, Hg2O-f3 Aq— 1462.2+54—
is obtained in large, rhombic prisms, when excess of Hg is boiled
with H]NTO3, diluted with 5 pts. H2O, for 5-6 hours, the loss by
evaporation being made up from time to time.
Mercuric Nitrate— Hg(NO3)2"-323. 7— is formed when Hg or HgO
is dissolved in excess of HNO3, and the solution evaporated at a
gentle heat. A syrupy liquid is obtained, which, over quick-
lime, deposits large, deliquescent crystals, having the composition
2[Hg(NO3)2]+Aq, while there remains an uncrystallizable liquid,
Hg(N03)2+2 Aq.
This salt is soluble in H20, and exists in the Liq. hydrargyri
nitratis (U. S.), Liq. hydrargyri nitratis acidus (Br.) ; in the volu-
metric standard solution used in LieMg^s process for urea; arid
probably in citrine ointment=TJng. hydrar. nitratis (U. S. ; Br.V,
Dimercuric Nitrate— Hg(NO3)2, HgO+Aq— 539.4— is formed
when HgO is dissolved to saturation in hot HNO3, diluted with 1
vol. H2O; and crystallizes on cooling. It is decomposed by HaO
into trimercuric nitrate, Hg(NO3)a, 2HgO, and Hg(NO3)2.
Hexamercuric Nitrate— Hg(NO3)2, 5 HgO — 1402.2— is formed as
a red powder, by the action of H2O on trimercuric nitrate.
Sulfates. — Mercurous Sulfate — (Hg.2)SO4 — 495.4 — is a white, crys-
talline powder, formed by gently heating together 2 pts. Hg
-and 3 pts. H2SO4, and causing the product to combine with 2 pts.
Hg. Heated with NaCl it forms (Hg2)Cl2.
Mercuric Sulfate— Hydrargyri sulfas (Br.) — HgSO4— 295.7— is
obtained by heating together Hg and H2SO, or Hg, H2SO4, and
HNO3. It is a white, crystalline, anhydrous powder, which, on
contact with H2O, is decomposed with formation of trimercuric
sulfate, HgSO4, 2HgO ; a yellow, insoluble powder, known as
turpeth mineral = Hydrargyri subsulfas flavus (U. S.).
Analytical Characters.— MEHCUROUS. — (1.) Hydrochloric acid:
white ppt. ; insoluble in H2O and in acids; turns black withNH4
HO; when boiled with HC1, deposits Hg, while HgCl2 dissolves.
(2.) Hydrogen sulfid: black ppt.; insoluble in alkaline sulfhy-
drates, in dilute acids, and in KCN; partly soluble in boiling
HNO3. (3.) Potash: black ppt. ; insoluble in excess. (4.) Potas-
sium iodid: greenish ppt.; converted by excess into Hg, which is
deposited, and HgI2, which dissolves.
MERCURIC.— (1.) Hydrogen sulfld: black ppt. If the reagent
be slowly added, the ppt. is first white, then orange, finally black.
<2.) Ammonium sulfhydrate: black ppt.; insoluble in excess, ex-
cept in the presence of organic matter. (3.) Potash or soda: yel-
low ppt.; insoluble in excess. (4.) Ammonium hydroxid: white
ppt.; soluble in great excess and in solutions of NH4 salts. (5.)
Potassium carbonate: red ppt. (6.) Potassium iodid: yellow ppt.,
MERCURY. 221
rapidly turning to salmon color, then to red; easily soluble in
excess of KI, or in great excess of mercuric salt. (7.) Stannous
chlorid : in small quantity white ppt. ; in larger quantity gray
ppt. ; and when boiled, deposit of globules of Hg.
Action on the Economy. — Mercury, in the metallic form, is with-
out action upon the animal economy so long as it remains such.
On contact, however, with alkaline chlorids it is converted into a
soluble double chlorid, and this the more readily the greater the
degree of subdivision of the metal. The mercurials insoluble in
dilute HC1 are also inert until they are converted into soluble
compounds.
Mercuric chlorid, a substance into which many other compounds
of Hg are converted when taken into the stomach or applied to
the skin, not only has a distinctly corrosive action, by virtue of
its tendency to unite with albuminoids, but, when absorbed, it
produces well-marked poisonous effects, somewhat similar to those
of arsenical poisoning. Indeed, owing to its corrosive action, and
to its greater solubility, and more rapid absorption, it is a more
dangerous poison than As2O3. In poisoning by HgCl2, the symp-
toms begin sooner after the ingestion of the poison than in arsen-
ical poisoning, and those phenomena referable to the local action
of the toxic are more intense.
The treatment should consist in the administration of white of
egg, not in too great quantity, and the removal of the compound
formed, by emesis, before it has had time to redissolve in the alka-
line chlorids contained in the stomach.
Absorbed Hg tends to remain in the system in combination
with albuminoids, from which it may be set free, or, more prop-
erly, brought into soluble combination, at a period quite removed
from the date of last administration, by the exhibition of alkaline
iodids.
Mercury is eliminated principally by the saliva and urine, in
which it may be readily detected. The fluid is faintly acidulated
with HC1, and in it is immersed a short bar of Zn, around which
a spiral of dentist's gold-foil is wound in such a way as to expose
alternate surfaces of Zn and Au. After 24 hours, if the saliva or
urine contain Hg, the Au will be whitened by amalgamation ; and,
if dried and heated in the closed end of a small glass tube, will
give off Hg, which condenses in globules, visible with the aid of
a magnifier, in the cold part of the tube.
222 MANUAL OF CHEMISTBY.
COMPOUNDS OF CARBON.
Organic Substances.
In the seventeenth and eighteenth centuries, chemists had
observed that there might be extracted from animal and vegeta-
ble bodies substances which differed much in their properties
from those which could be obtained from the mineral world ;
substances which burned without leaving a residue, and many
of which were subject to the peculiar changes wrought by the
processes of fermentation and putrefaction. It was not until the
beginning of the present century, 'however, that chemistry was
divided into the two sections of inorganic and organic.
In the latter class were included all such substances as existed
only in the organized bodies of animals and vegetables, and
which seemed to be of a different essence from that of mineral
bodies, as chemists had been unable to produce any of these
organic substances by artificial means. Later in the history of
the science it was found that these bodies were all made up of
a very few elements, and that they all contained carbon.
Gmelin at this time proposed to consider as organic substances
all such as contained more than one atom of C, his object in thus
limiting the minimum number of atoms of C being that sub-
stances containing one atom of C, such as carbon dioxid and
marsh-gas, were formed in the mineral kingdom, and conse-
quently, according to then existing views, could not be consid-
ered as organic. Such a distinction, still adhered to in text-
books of very recent date, of necessity leads to most incongru-
ous results. Under it the first terms of the homologous series
(see p. 224) of saturated hydrocarbons, CH4, alcohols, CH4O,
acids, CH2Oa, and all of their derivatives are classed among
mineral substances, while all the higher terms of the same series
are organic. Under it urea, COH4NS, the chief product of ex-
cretion of the animal body, is a mineral substance, but ethene,
C2H4, obtained from the distillation of coal, is organic.
The idea of organic chemistry conveyed by the definition :
" that branch of the science of chemistry which treats of the car-
bon compounds containing hydrogen," adopted in a text-book of
medical chemistry printed during the present year (1890), is still
more fantastic. Under it hydrocyanic acid, CNH, is "organic,"
but the cyanids, CNK, are "mineral." Oxalic acid, CaCXHa, is
"organic," and potassium hydroxid, KHO, unquestionably "min-
eral." If these two act upon each other in the proportion of 90
parts of the former to 56 of the latter, the " organic " monopo-
COMPOUNDS OF CARBON. 223
tassic oxalate, C»OiHK, is formed, but if the proportion of KHO
be doubled, other conditions remaining the same, the " mineral11
dipotassic oxalate, CsOiKs, is produced. Similarly one of the
sodium carbonates/Na-zCOs, is "mineral;'' the other, NaHCOs,
is " organic."
The notion that organic substances could only be formed by
some mysterious agency, manifested only in organized beings,
was finally exploded by the labors of Wohler and Kolbe. The
former obtained urea from ammonium cyanate ; while the latter,
at a subsequent period, formed acetic acid, using in its prepara-
tion only such unmistakably mineral suosuuiees as coal, sulfur,
aqua regia, and water.
During the half-century following Wohler's first synthesis,
chemists have succeeded not only in making from mineral mate-
rials many of the substances previously only formed in the
laboratory of nature, but have also produced a vast number of
carbon compounds which were previously unknown, and which,
so far as we know, have no existence in nature.
At the present time, therefore, we must consider as an organic
substance any compound containing carbon, whatever may be its
origin and whatever its properties. Indeed, the name organic is
retained merely as a matter of convenience, and not in any way
as indicating the origin of these compounds. Although, owing
to the great number of the carbon compounds, it is still con-
venient to treat of them as forming a section by themselves, their
relations with the compounds of other elements are frequently
very close. Indeed, within the past few years, compounds of
silicon have been obtained, which indicate the possibility that
that element is capable of forming series of compounds as inter-
esting in numbers and variety as those of carbon.
Nevertheless, there are certain peculiarities exhibited by C in
its compounds, which are not possessed to a like extent by any
other element, and which render the study of organic substances
peculiarly interesting and profitable.
In the study of the compounds of the other elements, we have
to deal with a small number of substances, relatively speaking,
formed by the union with each other of a large number of ele-
ments. With the organic substances the reverse is the case.
Although compounds have been formed which contain C along
•with each of the other elements, the great majority of the organic
substances are made up of C. combined with a very few other
elements ; H, O and N occurring in them most frequently.
It is chiefly in the study of the carbon compounds that we have
to deal with radicals (see p. 49). Among mineral substances there
are many whose molecules consist simply of a combination of two
atoms. Among organic substances there is none which does not
224 MANUAL OF CHEMISTKY.
contain a radical : indeed, organic chemistry has been denned as
"the chemistry of compound radicals."
The atoms of carbon possess in a higher degree than those of
any other element the power of uniting with each other, and in
so doing of interchanging valences. Were it not for this property
of the C atoms, we could have but one saturated compound of
carbon and hydrogen, CH4, or, expressed graphically :
H
H— C— H
H
There exist, however, a great number of such compounds, which
differ from each other by one atom of C and two atoms of H. In
these substances the atoms of C may be considered as linked
together in a continuous chain, their free valences being satisfied
by H atoms ; thus :
H H H H H H H
H— C— H H— C— C— H H— C-C— C— C— H
H H H H H H H
If now one H atom be removed from either of these combinations,
we have a group possessing one free valence, and consequently
univalent. The decompositions of these substances show that
they contain such radicals, and that their typical formulae are :
CH3 ) C2H5 ) C4H9 )
H f > H f ' H f '
Homologous Series. — It will be observed that these formulae
differ from each other by CH2, or some multiple of CH2, more or
less. In examining numbers of organic substances, which are
closely related to each other in their properties, we find that we
can arrange the great majority of them in series, each term of
which differs from the one below it by CH2 ; such a series is
called an homologous series. It will be readily understood that
such an arrangement in series vastly facilitates the remembering
of the composition of organic bodies. In the following table, for
example, are given the saturated hydrocarbons, and their more
immediate derivatives. At the head of each vertical column is
an algebraic formula, which is the general formula of the entire
series below it ; n being equal to the numerical position in the
series.
COMPOUNDS OF CARBON.
HOMOLOGOUS SERIES.
225
Saturated hy-
drocarbons,
CHHan + j.
Alcohols,
OiH.,;. + .,O.
Aldehydes,
CttH,,nO.
Acids,
CnHonOj.
Ketones,
C/iHj«O.
CH4
CH4O
COjH2
C,H«
CoHaO
C2H4O
C/sHs
C4Hio
CsHu
C3H80
C4H10O
C6H130
G«Hi*O
C3H6O
C4H80
C6H10O
CgHnO
CaOsHe
C4OaH8
CeOiHio
C3H80
C4H80
CsH.oO
C,H,«
CiHi«O
C,H,4O
c'c^R12
CSH,*O
CSH,BO
/-,7Q2TT14
CTT
nV/H1"
C "H
G" H° O
c" d H-8
C H
r/'jj24
C O H
C H
G H
But the arrangement in homologous series does more for us
than this. The properties of substances in the same series are
similar, or vary in regular gradation according to their position
in the series. Thus, in the series of monoatomic alcohols (see above)
each member yields on oxidation, first an aldehyde, then an acid.
Each yields a series of compound ethers by the action of acids
upon it. The boiling-points of the first six are, 66°. 5, 78°. 4, 96°. 7,
111°. 7, 132°. 2, 153°. 9 ; from which it will be seen that the boiling-
point of any one of them can be determined, with a maximum error
of 3°, by taking the mean of those of its neighbors above and be-
low. In this way we may prophesy, to some extent, the proper-
ties of a wanting member in a series before its discovery.
The terms of any homologous series must all have the same
constitution, «.e., their constituent atoms must be similarly
arranged within the molecule.
Isomerism — Metamerism— Polymerism. — Two substances are
said to be isomeric, or to be isomeres of each other, when they
have the same centesimal composition. If, for instance, we
analyze acetic acid and methyl formiate, we find that each body
consists of C, O and H, in the following proportions :
Carbon 40 24 = 12x2
Oxygen 53.33 32 = 16X2
Hydrogen 6.67 4 = 1X4
15
100.00
60
226 MANUAL OF CHEMISTRY.
This similarity of centesimal composition may occur in two
ways. The two substances may each contain in a molecule the
same numbers of each kind of atom ; or one maty contain in each
molecule the same kind of atoms as the other, but in a higher
multiple. In the above instance, for example, each substance
may have the composition C2H4O2; or one may have that formula
and the other, CeHiaOe, or C2H4O!iX3. In the former case the
substances are said to be metameric, in the latter polymeric.
Whether two substances are metameric or polymeric can only be
determined by ascertaining the weights of their molecules, which
is usually accomplished by determining the sp. gr. of their vapors
(see p. 37).
The sp. gr. of the vapor of acetic acid is the same as that of
methyl formiate, and, consequently, each substance is made up
of molecules, each containing C2H4O2. But the two substances
differ from each other greatly in their properties, and their dif-
ferences are at once indicated by their typical or graphic for-
mulae :
or graphically :
0
H ) U (CH
CH3 H
iand
OOH COOCHa.
y j 0 .
,)' j U '
Classification of Organic Substances. — The practically unlimited
number of carbon compounds which are known to exist, or whose
existence is possible according to accepted theories, imposes the
necessity of a rational classification, that they may be satisfac-
torily studied and that their reactions and decompositions may
be understood. Such a classification has been constructed, em-
bracing not only known compounds, but capable of extension, to
include in a systematic whole, any compounds which may be
•discovered in the future. The rules governing the naming of
organic substances constitute a part of the system ; and the names
used, cumbrous and barbarous as they may seem to the uniniti-
ated, indicate to the educated not only the constitution of the
substance, but also its position in the classification, its relation-
ship to other bodies, and the reactions and decompositions of
which it is capable or incapable.
The simplest of the carbon compounds, the hydrocarbons, or
substances consisting of carbon and hydrogen only, form the
framework of the classification, and are divided into families and
groups, according to the relations of the carbon and hydrogen
atoms in the structure of the molecule :
COMPOUNDS OF CARBON. 227
Tamily L — Arborescent, acyclic, or open chain hydrocarbons. —
In the hydrocarbons of this family the number of hydrogen
Atoms, or this number, plus the number of univalent atoms that
can be introduced into the molecule by addition (i.e., by the
introduction of other atoms without the removal of any already
contained in the molecule) is equal to twice the number of car-
bon atoms plus two. Or, if n — the number of carbon atoms, and
X — the number of univalent atoms which the molecule can re-
ceive by addition, these hydrocarbons will have the algebraic
formula : CnH.(in + *-x).
Group A — Paraffin, or Methane Series. — These are the most
highly saturated hydrocarbons possible. Their algebraic formula
is CnHan + a. The graphic formulae of the first, second and fourth
are given on p. 224.
Group B — Olefin. Ethene, or Ethylene Series — contain two
atoms of hydrogen less than the corresponding paraffins and
have the algebraic formula CnH-m. No compound of this series
containing a single C atom can exist. The first term is HSC =
CH2.
Group C — Acetylene, or Ethine Series —contain two atoms of
hydrogen less than the corresponding olefins. Their algebraic
formula is CnH2n - a. The first term is HC = CH.
Family H. — Cyclic or Closed Chain Hydrocarbons. — The com-
pounds of this family all contain a "nucleus" or "ring," in which
•every carbon atom is linked to at least two other carbon atoms,
thus forming a " cycle," or closed chain. The number of possible
groups in this series is very large. Representatives of the follow-
ing are known :
Group A — Paraffene Series — have the algebraic formula
OnHan. This is the simplest form of cyclic hydrocarbon, each
carbon atom exchanging a valence with its neighbor on each
side. Some representatives of the group exist in petroleum and
have been formed synthetically. They are isomeric with the
terms of Group B, Family I.
Group B — Terebenthic Series — have the algebraic formula
CnHun - 4. The lower terms of the series are not well known.
Among the higher terms are a great number of isomeres existing
in nature among the essential oils.
Group C — Benzenic Series. — This series includes the most im-
portant of the closed chain hydrocarbons, and their derivatives.
They have the algebraic formula CnH3re- e, and all contain the
benzene nucleus C8H8, or some product of substitution thereof.
The number of derivatives obtainable by substitution, by graft-
ing together of two or more benzene nuclei, or by grafting of
open-chain hydrocarbons, or of their derivatives, upon a benzene
228 MANUAL OF CHEMISTRY.
nucleus is apparently unlimited. They are all very stable sub-
stances.
The other carbon compounds may be regarded as derived from
the hydrocarbons by the substitution or addition of an atom or
group of atoms in or upon the hydrocarbon, the character, or
function of the substance so produced depending upon the char-
acter and position of the substituted or added atom or group.
This will be developed as we proceed.
ACYCLIC HYDROCARBONS.
229
ACYCLIC HYDROCARBONS AND THEIR DERIVATIVES.
FIRST SERIES OF HYDROCARBONS.
SERIES CnHan + a.
The hydrocarbons of this series at present known are the fol-
lowing :
Name.
Formula.
Specific
Gravity oi Liquid.
Boiling-point.
Centigrade.
Methyl hydrid. .
CH3H
Ethyl hydrid
Propyl hydrid
C3H7H
Butyl hydrid
0.600 at 0°
0°
Amyl hydrid
0 628 at 18°
30°
Hexyl hydrid
0.669 at 18°
68°
Heptyl hydrid
0.690 at 18°
92°-94°
Octyl hydrid
0.726 at 18°
116°-118°
J^onyl hydrid . . .
0 741 at 18°
136°-188°
Decyl hydrid
0.757 at 18°
158°-162°
Undecyl hydrid
0.766 at 18°
180°-182°
Dodecyl hydrid
0.778 at 18°
198°-200°
Tridecyl hydrid
0.796 at 18°
218°-220°
Tetradecyl hydrid
Pentadecyl hydrid
Hexadecyl hydrid
C^HasH
CisHsiH
0.809 at 18°
0.825 at 18°
236°-240°
258°-262°
about 280°
They form an homologous series whose general formula is
•CnHan + s, and are known as paraffins from their stability
{parum = little, affinis = affinity). The radicals CnHan+i, of
which they are the hydrids, are sometimes designated as the rad-
icals of the nionoatomic alcohols, or monoatoniic alcoholic rad-
icals.
Corresponding to the higher terms of the series (those above
the third) there are one or more isomeres, which may be arranged
in four classes. (1.) The normal paraffins, or regularly formed
series, in which each C atom is linked to two other C atoms. (2.)
The isoparaffins, those in which one C atom is linked to three
others. (3.) The neoparaffins, those in which two C atoms are
each linked to three others. (4.) The mesoparaffins, those in
which one C atom is linked to four others. The constitution of
these series is explained by the graphic formula? -,
230 MANUAL OF CHEMISTRY.
(1.) (2.) (3.) (4.)
OH3 Oxl3 Oils OHs
OH;) H — C — CH3 H — C — CH3 H3C — C — CJHs
III I
CHa OHa H — C> — OH3 OHj
OHa OHj Cy.H3 OH3
CH, CH3
CH3
The number of possible isorueres increases rapidly with an in-
creasing number of carbon atoms. It has been calculated that
the number of possible isomeres with increasing values of n are
as follows :
72, = 1 n = 2 n = o n — 4: n = 5 n = 6
1 1 1 2,3 5
n = 7 n = S n = 9 n = 10 n = 11 n = 12
9 18 35 75 159 357
Many of these hydrocarbons exist in nature, in petroleum, and
in the gases accompanying it. They may be produced by the
following general reactions :
1.) By the action of zinc, either alone, at elevated temperatures^
or in the presence of H2O, upon the corresponding iodids :
2C2H6I+Zn!1+2H!1O =ZnH2O2 + ZnI., +20,11,,
or
2C2HJ+Zn = ZnIa+C4H10.
2.) By electrolysis of the corresponding fatty acid :
3.) By the action of the organo-zincic derivative upon the iodid
of the alcoholic radical, upon the corresponding olefin iodid, or
upon the allylic iodid.
4.) By the action of highly concentrated hydriodic acid at
275°-300° (527°-572° F.) upon hydrocarbons of the ethene and
ethine series, upon alcohols, amins, etc. This is a method of
hydrogenation applicable in many other cases.
5.) By the destructive distillation of many organic substances.
General properties. — They are gaseous, liquid, or solid, and
have sp. gr. and boiling points increasing with the number of C
atoms (see table, p. 229). They are lighter than H2O, neutral,
insoluble in H2O, soluble in alcohol, ether, and in liquid hydro-
carbons. Their odor is faint and not unpleasant.
ACYCLIC HYDROCARBONS. 231
They are very stable and incapable of modification by addi-
tion. Chlorin and broinin decompose them, with formation of
products of substitution. They are inflammable and burn with
a luminous flame. Nitric acid forms nitro-derivatives with the
higher terms.
Methyl hydrid— Methane— Marsh-gas— Light carburetted hy-
drogen— Fire-damp— CH4— 16— is given off in swamps as a product
of decomposition of vegetable matter, in coal mines, and in the
gases issuing from the earth in the vicinity of petroleum deposits.
Coal-gas contains it in the proportion of 36-50 per cent. It may
be prepared by strongly heating a mixture of sodium acetate
with sodium hydroxid and quicklime.
It is a colorless, odorless, tasteless gas; very sparingly soluble
in H2O; sp. gr. 0.559A. At high temperature it is decomposed
into C and H. It burns in air with a pale yellow flame. Mixed
with air or O it explodes violently on contact with flame, pro-
ducing water and carbon dioxid ; the latter constituting the
after-damp of miners. It is not affected by Cl in the dark, but,
under the influence of diffuse daylight, one or more of the H
atoms are displaced by an equivalent quantity of Cl. In direct
sunlight the substitution is accompanied by an explosion.
Petroleum. — Crude petroleum differs in composition and in
physical properties in the products of different wells, even in the
same section of country. It varies in color from a faintly yel-
lowish tinge to a dark brown, nearly black, with greenish reflec-
tions. The lighter-colored varieties are limpid, and the more
highly colored of the consistency of thin syrup. The sp. gr.
varies from 0.74 to 0.92. Crude petroleums contain all the hydro-
carbons mentioned in the list on p. 229 (the lowest terms of the
seriss being found in the gases accompanying petroleum and
held in solution by the oil under the pressure it supports in
natural pockets), besides hydrocarbons of the olefin. paraffene,
and benzene series. They also contain varying quantities of sul-
fur compounds, which communicate a disgusting odor to some
oils.
The crude oil is highly inflammable, usually highly colored,
and is prepared for its multitudinous uses in the arts by the proc-
esses of distillation and refining. The products of lowest boiling
point are usually consumed, but are sometimes condensed.
The principal products of petroleum are: Petroleum ether L,
or Cymogene, boils at 0" (32° F.), used in ice machines ; -Petroleum
ether II., or Rhigolene, a highly inflammable liquid, sp. gr.
about 0.60, boils at about 20° (68° F.), used to produce cold by its
rapid evaporation, and as a solvent. Its use in the vicinity of
flame is attended with danger. Gasolene boils from 45° (113° F.)
MANUAL OF CHEMISTRY.
to 76° (168°. 8 F.) ; used as a fuel and for the manufacture of " air
gas." Naphtha, divided into three grades, C, B, and A, boils
from 82°.2 (180° F.) to 148°.8 (300° F.) ; used as a solvent for fats,
etc., and in the manufacture of "water gas." Sometimes called
"safety oil." Benzine, or benzolene, boils from 148° (298° F.) to
160° (320° F); used as a solvent in making paints and varnishes.
The most important product of petroleum is that portion which
distils between 176° (349° F.) and 218° (424° F.) and which consti-
tutes kerosene and other oils used for burning in lamps. An oil
to be safely used for burning in lamps should not "flash," or
give off inflammable vapor, below 37°. 4 (100° F.), and should not
burn at temperatures below 149° (300° F.).
From the residue remaining after the separation of the kero-
sene, many other products are obtained. Lubricating oils,
of too high boiling-point for use in lamps. Paraffin, a white,
crystalline solid, fusible at 45°-65° (113°-149° F.), which is used
in the arts for a variety of purposes formerly served by wax, such
as the manufacture of candles. In the laboratory it is very use-
ful for coating the glass stoppers of bottles, and for other pur-
poses, as it is not affected by acids or by alkalies. It is odorless,
tasteless, insoluble in H2O and in cold alcohol ; soluble in boiling
alcohol and in ether, fatty and volatile oils, and mineral oils. It
is also obtained by the distillation of certain varieties of coal, and
is found in nature in fossil wax or ozocerite.
The products known as vaseline, petrolatum (U. S.), cosmoline,
etc., which are now so largely used in pharmacy and perfumery,
are mixtures of paraffin and the heavier petroleum oils. Like
petroleum itself, its various commercial derivatives are not defi-
nite compounds, but mixtures of the hydrocarbons of this series.
HALOID DERIVATIVES OF THE PARAFFINS.
By the action of Cl or Br upon the paraffins, or by the action
of HC1, HBr or HI upon the corresponding hydrates, com-
pounds are obtained in which one of the H atoms of the hydro-
carbon has been replaced by an atom of Cl, Br or I : CaHe+Bra =
CaH6Br+HBr, or C2H5OH+HC1 = C2H5C1 + H2O. These com-
pounds may be considered as the chlorids, bromids or iodids of
the alcoholic radicals ; and are known as haloid ethers.
When Cl is allowed to act upon CH4, it replaces a further
number of H atoms until finally carbon tetrachlorid, CC14, is pro-
duced. Considering marsh gas as methyl hydrid, CH3,H, the
first product of substitution is methyl chlorid, CH3,C1 ; the
second monochlormethyl chlorid, CH2C1,C1 ; the third dichlor-
methyl chlorid, or chloroform, CHClaCl ; and the fourth carbon
tetrachlorid, CCU.
HALOID DERIVATIVES OF THE PARAFFINS 233
Similar derivatives are formed with Br and I and with the
wther hydrocarbons of the series.
Methyl chlorid — CHaCl — 50.5 — is a colorless gas, slightly soluble
in H2O, and having a sweetish taste and odor. It is obtained by
distilling together H2SO4, sodium chlorid and methyl alcohol.
It may be condensed to a liquid which boils at —22° (—7°. 6 F.). It
burns with a greenish flame. Heated with potassium hydroxid it
is converted into methyl alcohol.
Monochlormethyl chlorid — Methf.ne chlorid — Dichloromethane
— Nethylene chlorid — Chloromethyl — CH2C1,C1 — 85 — is obtained by
the action of Cl upon CH3C1 ; or by shaking an alcoholic solution
of chloroform with powdered zinc and a little ammonium hy-
droxid. In either case the product must be purified.
It is a colorless, oily liquid, boils at 40°-42° (104°-107°.6 F.) ; sp.
gr. 1.36 ; its odor is similar to that of chloroform ; it is very
slightly soluble in H2O ; and is not inflammable. Like most of
the chlorinated derivatives of this series, it is possessed of anaes-
thetic powers. Its use as an anaesthetic is attended with the
same (if not greater) danger as that of chloroform.
Dichlormethyl chlorid — Methenyl chlorid — Formyl chlorid —
Trichloromethane — Chloroform — Chlorofonnum (U. S., Br.) —
CHCl-i.Cl — 120.5 — is obtained by heating in a capacious still, 35-40
litres (9-11 gall.) of H2O, adding 5 kilos (11 lbs.)of recently slacked
lime and 10 kilos (22 Ibs.) of chlorid of lime; 2.5 kilos (4 qts.) of
alcohol are then added and the temperature quickly raised until
the product begins to distil, when the fire is withdrawn, heat
being again applied toward the end of the reaction. The crude
chloroform so obtained is purified, first by agitation with HaSO4
then by mixing with alcohol and recently ignited potassium car-
bonate, and distilling the mixture.
Chloroform is now extensively manufactured by the action
of bleaching powder upon acetone, the reaction being expressed
by the equation : 2CO(CH3)3+6CaCl(OCl) = 2CHCl3+2Ca(HO),+
<CH3,COO)2Ca+3CaCl.,.
It is a colorless, volatile liquid, having a strong, agreeable,
ethereal odor, and a sweet taste ; sp. gr. 1.497; very sparingly sol-
uble in H2O ; miscible with alcohol and ether in all proportions ;
boils at 60D.8 (141°. 4 F.). It is a good solvent for many substances
insoluble in H2O, such as phosphorus, iodin, fats, resins, caout-
chouc, gutta-percha and the alkaloids.
It ignites with difficulty, but burns from a wick with a smoky,
red flame, bordered with green. It is not acted on by HaSCX,
except after long contact, when HC1 is given off. In direct sun-
light Cl converts it into CC14 and HC1. The alkalies in aqueous
solution do not act upon it, but, when heated with them in
alcoholic solution, it is decomposed with formation of chlorid and
234 MANUAL OF CHEMISTRY.
forrniate of the alkaline metal. When perfectly pure it is not
altered by exposure to light ; but if it contain compounds of Nr
even in very minute quantity, it is gradually decomposed by
solar action into HC1, Cl and other substances.
Impurities. — Alcohol, if present in large amount, lowers the sp.
gr. of the chloroform, and causes it to fall through H3O in opaque,,
pearly drops. If present in small amount it produces a green
color with ferrous dinitrosulfid (obtained by acting on ferrous-
chlorid with a mixture of potassium nitrate and ammonium
hydrosulfid). Aldehyde produces a brown color when CHCls
containing it is heated with liquor potassse. Hydrochloric acid
reddens blue litmus, and causes a white precipitate in an aqueous-
solution of silver nitrate shaken with chloroform. Methyl and
empyreumatic compounds are the most dangerous of the impuri-
ties of chloroform. Their absence is recognized by the following-
characters : (1.) When the chloroform is shaken with an equal
volume of colorless H2SO4, and allowed to stand 24 hours ; the
upper (chloroform) layer should be perfectly colorless, and the
lower (acid) layer colorless or faintly yellow. (2.) When a small
quantity is allowed to evaporate spontaneously, the last portions,
should have no pungent odor, and the remaining film of moisture?
should have no taste or odor other than those of chloroform.
Analytical Characters. — (1.) Add a little alcoholic solution of
potash and 2-3 drops of anilin and warm ; a disagreeable odorv
resembling that of witch-hazel, is produced. (2.) Vapor of CHCl3v
when passed through a red-hot tube, is decomposed with forma-
tion of HC1 and Cl, the former of which is recognized by the pro
duction of a white ppt., soluble in ammonium hydroxid, in an
acid solution of silver nitrate. This test does not afford reliable
results when the substance tested contains a free acid and chlorid s.
(3.) Dissolve about 0.01 gin. of ft naphthol in a small quantity of
KHO solution, warm, and add the suspected liquid ; a blue color
is produced. (4.) Add about 0.3 grni. resorcin in solution, and 3-
gtts. NaHO solution and boil strongly. In the presence of CHCU
or of chloral a yellowish-red color is produced, and the liquid ex-
hibits a beautiful yellow-green fluorescence.
Toxicology. — The action of chloroform varies as it is taken by
the stomach or by inhalation. In the former case, owing to its
insolubility, but little is absorbed, and the principal action is the
local irritation of the mucous surfaces. Recovery has followed a
dose of four ounces, arid death has been caused by one drachm,
taken into the stomach. Chloroform vapor acts much more
energetically, and seems to owe its potency for evil to its paralyz-
ing influence upon the respiratory nerve centres, and upon the
cardiac ganglia. While persons suffering from heart disease are
particularly susceptible to the paralyzing effect of chloroform
HALOID DERIVATIVES OF THE PARAFFINS. 235
vapor, there are many cases recorded of death from the inhalation
of small quantities, properly diluted, in which no heart lesion
was found upon a post-mortem examination. Chloroform is
apparently not altered in the system, and is eliminated with the
expired air. ,
No chemical antidote to chloroform is known. When it has
been swallowed, the stomach-pump and emetics are indicated ;
when taken by inhalation, a free circulation of air should be
established about the face ; artificial respiration and the appli-
cation of the induced current to the sides of the neck should be
resorted to.
The nature of the poison is usually revealed at the autopsy by
its peculiar odor, which is most noticeable on opening the cranial
and thoracic cavities. In a toxicological analysis, chloroform is
to be sought for especially in the lungs and blood. These are
placed in a flask ; if acid, neutralized with sodium carbonate ; and
subjected to distillation at the temperature of the water-bath.
The vapors are passed through a tube of difficultly fusible glass ;
at first the tube is heated to redness for about an inch of its
length, and test No. 2 applied to the issuing gas. The tube is
then allowed to cool, and the distillate collected in a pointed
tube, from the point of which any CHC13 is removed by a pipette
and tested according to Nos. 1, 3, and 4 above.
Carbon tetrachlorid — Chlorocarbon — CC14 — 154 — is formed by
the prolonged action, in sunlight, of Cl upon CH3C1 or CHC13 ;
or more rapidly, by passing Cl, charged with vapor of carbon
disulfid, through a red-hot tube, and purifying the product.
It is a colorless, oily liquid, insoluble in H2O ; soluble in alcohol
and in ether ; sp. gr. 1.56 ; boils at 78° (172°. 4 F.). Its vapor is
decomposed at a red heat into a mixture of the dichlorid, CuCl4,
trichlorid, C2Cle. and free Cl.
Methyl bromid — CH3Br — 95. — A colorless liquid; sp. gr. 1.664;:
boils at 13° (55°. 4 F.) ; formed by the combined action of P and
Br on methyl hydrate.
Dibromomethyl bromid — Methenyl bromid — Formyl bromid —
Bromoform — CHBr.,,Br — 253— is prepared by gradually adding
Br to a cold solution of potassium hydroxid in methyl alcohol
until the liquid begins to be colored ; and rectifying over calcium
chlorid.
A colorless, aromatic, sweet liquid; sp. gr. 2.13; boils at 150°-
152° (302°-306° F.) ; solidifies at -9° (15°.8 F.) ; sparingly soluble in
H2O ; soluble in alcohol and ether. Boiled with alcoholic potash
it is decomposed in the same way as is CHC13.
Its physiological action is similar to that of CHC13. It occurs
as an impurity of commercial Br, accompanied by carbon tetra-
bromid, CBr4.
236 MANUAL OF CHEMISTEY.
Methyl iodid— CH3I— 142— a colorless liquid, sp. gr. 2.237 ; boils
at 45° (113° F.) ; burns with difficulty, producing violet vapor of
iodin. It is prepared by a process similar to that for obtaining
the bromid ; and is used in the anilin industry.
Diiodomethyl iodid— Methenyl iodid — Eormyl iodid— lodoform
— lodoformum, TJ. S.—CHI2I— 394.— Formed, like chloroform and
bromoform, by the combined action of potash and the halogen
upon alcohol ; it is also produced by the action of I upon a great
number of organic substances, and is usually prepared by heating
a mixture of alkaline carbonate, H2O, I and ethylic alcohol, and
purifying the product by recrystallization from alcohol. It is
also produced from acetone by making a solution containing
50 gm. KI, 6gm. acetone, and 2 gm. NaHO in 2L. HSO and gradu-
ally adding a dilute solution of KC1O3.
lodoform is a solid, crystallizing in yellow, hexagonal plates,
which melt at 115°-120° (239°-248° P.). It may be sublimed, a
portion being decomposed. It is insoluble in water, acids, and
alkaline solutions: soluble in alcohol, ether, carbon disulfid,
and the fatty and essential oils: the solutions, when exposed to
the light, undergo decomposition and assume a violet-red color.
It has a sweet taste and a peculiar, penetrating odor, resembling,
when the vapor is largely diluted with air, that of saffron. When
heated with potash, a portion is decomposed into formiate and
iodid, while another portion is carried off unaltered with the
aqueous vapor. It contains 96.7% of its weight of iodin.
Ethyl chlorid — Hydrochloric or muriatic ether — C2HBC1 — 64.5. —
A colorless, white, ethereal liquid ; boils at 11° (51°. 8 F.) ; obtained
by passing gaseous HC1 through ethylic alcohol to saturation,
and distilling over the water-bath.
By the continued action of Cl in the sunshine upon ethyl
chlorid, oruponethene chlorid, CsH^Cls, a white, crystalline solid,
Hexachlorethane or carbon trichlorid, C2C16, is produced. It is
insoluble in H2O, soluble in alcohol and in ether, has an aromatic
odor, fuses at 160° (320° F.), and boils at 182° (359°. 6 F.).
Ethyl bromid — Hydrdbromic ether — C2HBBr — 109. — A colorless,
ethereal liquid; boils at 40°. 7 (105°. 3 F.) ; obtained by the com-
bined action of P and Br on ethylic alcohol.
Ethyl iodid — Hydriodic ether — CaHBI — 156 — is prepared by plac-
ing absolute alcohol and P in a vessel surrounded by a freezing
mixture and gradually adding I ; when the action has ceased,
the liquid is decanted, distilled over the water-bath, and the
-distillate washed and rectified.
It is a colorless liquid ; boils at 72°. 2 (162° F.) ; has a powerful,
ethereal odor ; burns with difficulty. It is largely used in the
.anilin industry.
MONOATOMIC ALCOHOLS. 237
MONOATOMIC ALCOHOLS.
The name alcohol, formerly applied only to the substance now
popularly so called, has gradually come to be used to designate
a large class of important bodies, of which vinic alcohol is the
representative. These substances are mainly characterized by
their power of entering into double decomposition with acids, to
form neutral compounds, called compound ethers, water being at
the same tune formed, at the expense of both alcohol and acid.
They are the hydroxids of hydrocarbon radicals, and as such.
resemble the metallic hydroxids, while the compound ethers are
the counterparts of the metallic salts :
(CaH5) ) 0 , (C.H.O) ) o _(C,H,0) I 0 , H
H fu H fu (C2H6HU~TH
Ethyl hydroxid. Acetic acid. Ethyl acetate. Water.
Potassium Acetic acid. Potassium Water.
hydroxid. acetate.
As the metallic hydroxids may be considered as formed by the
union of one atom of the metallic element with a number of
groups OH', corresponding to its valence, so the alcohols are
formed by union of an unoxidized radical with a number of
groups OH', equal to or less than the number of free valences of
the radical. When the alcohol contains one OH, it is designated
as monoatomic ; when two, diatomic ; when three, triatomic, etc.
The simplest alcohols are those of this series derivable from
the saturated hydrocarbons, and having the general formula
C«H3n + !iO, or CnHan + iOH. They may be formed synthetically :
(1.) By acting upon the corresponding iodid with potassium
hydroxid: C2HJ+KHO = KI+C2H5OH. (2.) From the alcohol
next below it in the series, bv direct addition of CH2, only, how-
ever, by a succession of five reactions. (3.) By the action of
H2SO4 and HaO upon the corresponding hydrocarbon of the
series CnH2n.
The saturated monoatomic alcohols are, however, not limited
to one corresponding to each alcoholic radical. There exist^
corresponding to the higher alcohols — a number of substances
having the same centesimal composition and the same alcoholic
properties, but differing in their physical characters and in their
products of decomposition and oxidation. These isomeres have
been the subject of much careful study of late years. It has been
found that the molecules of methyl, ethyl, and other higher alco-
238 MANUAL OF CHEMISTRY.
hols are made up of the group (CHaOH)' united to H or to
CnHan + i, thus :
CHaOH CHaOH CHaOH
H CH3 CaH,
Methyl alcohol. Ethyl alcohol. Propyl alcohol.
and all monoatomic alcohols containing this group, CH2OH, have
been designated as primary alcohols. Isomeric with these are
other bodies, which, in place of the group (CHaOH)', contain the
group (CHOH)", and are distinguished as secondary alcohols.
Thus we have :
(CHaOH)' CH3
CHa (CHOH)"
I j
CH3 CH3
C3H8O C3H8O
Primary Secondary
propyl alcohol. propyl alcohol.
And further, other isomeric substances are known which contain
the group (COH)'", and which are called tertiary alcohols, thus :
(CHaOH)' C2HB CH3
C4H9 (CHOH)" (CaH6)— (COH)'"
I I
CXI OTT
aria L/±13
CTJ r\ a tr f\ /~i tr o
ailiaw \jtHiv\J Vj5n.i2V^
Primary amylic Secondary amylic Tertiary amylic
alcohol. alcohol. alcohol.
The alcohols of these three classes are distinguished from each
other principally by their products of oxidation. The primary
alcohols yield by oxidation, first an aldehyde and then an acid,
each containing the same number of C atoms as the alcohol, and
formed, the aldehyde by the removal of, H2 from the group
<CH2OH), and the acid by the substitution of O for Ha in the
same group, thus :
CH2OH COH COOH
CH3 CH3 OH3
Ethyl alcohol. Ethyl aldehyde. Acetic acid,
In the case of the secondary alcohols, the first product of oxida-
tion is a ketone, containing the same number of C atoms as the
alcohol, and formed by the substitution of O for HOH in the
distinguishing group :
MONOATOMIC ALCOHOLS. 239
CH, CH8
CHOH CO
CH3 CH3
Secondary propyl Propyl ketone
. alcohol. or acetone.
The tertiary alcohols yield by oxidation ketones or acids, whose
molecules contain a less number of C atoms than the alcohol
from which they are derived.
But the complication does not end here : isomeres exist corre-
sponding to the higher alcohols, which are themselves primary
alcohols, and contain the group (CHaOH)'. Thus there exist no
less than seven distinct substances, all having the centesimal com-
position of amyl alcohol, C6Hi2O, and the properties of alcohols ;
-and theoretical considerations point to the probable existence of
-another. Of these eight substances, four are primary, three
secondary alcohols, and the remaining one a tertiary alcohol. As
•each of these bodies contains the group of atoms characteristic
of the class of alcohol to which it belongs, it is obvious that the
differences observed in their properties are due to differences in
the arrangement of the other atoms of the molecule. Experi-
mental evidence, which it would require too much space to
discuss in this place, has led chemists to ascribe the following
formulae of constitution to these isomeres :
Primary amylic alcohols :
CHs — GHa — CHa — CHa — OH a, OH
Normal amylic alcohol. .
fitr ,CH — CHa — CHa, OH
Amylic alcohol o? fermentation.
CH3— CHa/CH~CH''OH
Methylethylethylic alcohol.
CH3\
CH3— C— CH2,OH
CH,/
Unknown.
Secondary amylic alcohols :
CH3 — CHa\/-iTj /"\TT
CH3— CHa/0±1'UJ
Diethyl carbinol.
OlTsN^f-iTT PVTT
CH3— CHa— CH3/U±1'UJ
Methyl-propyl carbinol.
240 MANUAL OF CHEMISTRY.
CH3/
Methyl-isopropyl carbinol.
Tertiary amylic alcohol :
CH3\
CH3— C,OH
CH8— CHa/
Methyl hydroxid— Carbinol— Pyroxylic spirit — Methylic alco-
hol—Wood spirit— H,CH2OH— 32— may be formed from marsh-gas,
CH3H, by first converting it into the iodid, and acting upon this
with potassium hydroxid: CH8I+KHO=KI-fCH3HO. It is usu-
ally obtained by the destructive distillation of wood. The crude
wood vinegar so produced is a mixture of acetic acid and methyl
alcohol with a variety of other products. The crude vinegar,
separated from tarry products, is redistilled; the first tenth of
the distillate is treated with quicklime and again distilled ; the
distillate treated with dilute HaSO4 ; decanted and again distilled.
The product, still quite impure, is the wood alcohol, wood naphtha,
or pyroxylic spirit of commerce. The pure hydroxid can only
be obtained by decomposing a crystalline compound, such as
methyl oxalate, and rectifying the product until the boiling-point
is constant at 66°. 5 (151°.7 F.).
Pure methyl alcohol is a colorless liquid, having an ethereal and
alcoholic odor, and a sharp, burning taste ; sp. gr. 0.814 at 0° ; boils
at 66°. 5 (151°. 7 P.); burns with a pale flame, giving less heat than
that of ethylic alcohol; mixes with water, alcohol, and ether in
all proportions ; is a good solvent of resinous substances, and also-
dissolves sulfur, phosphorus, potash, and soda.
Methyl hydroxid is not affected by exposure to air under ordi-
nary circumstances, but in the presence of platinum-black it is-
oxidized, with formation of the corresponding aldehyde and acid,
formic acid. Hot HNO3 decomposes it with formation of nitrous-
fumes, formic acid and methyl nitrate. It is acted upon by
H2SO4 in the same way as ethyl alcohol. The organic acids form
methyl ethers with it. With HC1 under the influence of a gal-
vanic current, it forms an oily substance having the composition
C2H3C1O.
Methylated spirit is ethyl alcohol containing sufficient wood
spirit to render it unfit for the manufacture of ardent spirits, by-
reason of the disgusting odor and taste which crude wood alcohol
owes to certain empyreumatic products which it contains. Spirits-
so treated are not subject to the heavy duties imposed tipon ordi-
nary alcohol, and are, therefore, largely used in the arts and for
the preservation of anatomical preparations. It contains one-
ninth of its bulk of wood naphtha.
MONOATOMIC ALCOHOLS. 2-il
Ethyl hydroxid — Ethylic alcohol — Methyl Carbinol — Vinic al-
cohol— Alcohol — Spirits of wine — C2H5HO — 46.
Preparation, — Industrially alcohol and alcoholic liquids are ob-
tained from substances rich in starch or glucose.
The manufacture of alcohol consists of three distinct processes:
1st, the conversion of starch into sugar ; 2d, the fermentation of
the saccharine liquid; 3d, the separation, by distillation, of the
alcohol formed by fermentation.
The raw materials for the first process are malt and some sub-
stance (grain, potatoes, rice, corn, etc.) containing starch. Malt
is barley which has been allowed to germinate, and, at the proper
stage of germination, roasted. During this growth there is de-
veloped in the barley a peculiar nitrogenous principle called dias-
tase. The starchy material is mixed with a suitable quantity of
malt and water, and the mass maintained at a temperature of 65°-
70° (149°-158° F.) for two to three hours, during which the diastase
rapidly converts the starch into dextrin, and this in turn into'
glucose.
The saccharine fluid, or wort, obtained in the first process, is
drawn off, cooled, and yeast is added. As a result of the growth
of the yeast-plant, a complicated series of chemical changes take
place, the principal one of which is the splitting up of the glucose
into carbon dioxid and alcohol: C«H1!1O6=2C!1Hi,OH-f 2CO2. There
are formed at the same time small quantities of glycerin, succinic
acid, and propyl, butyl, and amyl alcohols.
An aqueous fluid is thus obtained which contains 3-15 per cent,
of alcohol. This is then separated by the third process, that of
distillation and rectification. The apparatus used for this pur-
pose has been so far perfected that by a single distillation an
alcohol of 90-95 per cent, can be obtained.
In some cases alcohol is prepared from fluids rich in glucose,
such as grape-juice, molasses, syrup, etc. In such cases the first
process becomes unnecessary.
Commercial alcohol always contains H8O, and when pure or
absolute alcohol is required, the commercial product must be
mixed with some hygroscopic solid substance, such as quicklime,
from which it is distilled after having remained in contact twenty-
four hours.
Fermentation. — This term (derived from fervere—to boil) was
originally applied to alcoholic fermentation, by reason of the bub-
bling of the saccharine liquid caused by the escape of COa ; sub-
sequently it came to be applied to all decompositions similarly
attended by the escape of gas.
At present it is used by many authors to apply to a number of
heterogeneous processes; and some writers distinguish between
" true " and " false " fermentation. It is best, we believe, to limit
16
242 MANUAL OF CHEMISTRY.
the application of the term to those decompositions designated
as true fermentations.
Fermentation is a decomposition of an organic substance, pro-
duced by the processes of nutrition of a low form of animal or
vegetable life.
The true ferments are therefore all organized beings, such as
torula ceremsioe, producing alcoholic fermentation ; penicillium
glaucum, producing lactic acid fermentation; and mycoderma
aceti, producing acetic acid fermentation.
The false fermentations are not produced by an organized
body, but by a soluble, unorganized, nitrogenous substance, whose
method of action is as yet imperfectly understood. They may
be, therefore, designated by the term cryptolysis. Diastase, pep-
sin and trypsin are cryptolytes.
Properties. — Alcohol is a thin, colorless, transparent liquid,
having a spirituous odor, and a sharp, burning taste; sp. gr.
0.8095 atO°, 0.7939 at 15° (59° F.); it boils at 78°.5 (173°.3 P.), and has
not been solidified. At temperatures below —90° (—130° P.) it is
viscous. It mixes with water in all proportions, the union being
attended by elevation in temperature and contraction in volume
(after cooling to the original temperature). It also attracts moist-
ure from the air to such a degree that absolute alcohol only re-
mains such for a very short time after its preparation. It is to
this power of attracting H2O that alcohol owes its preservative
power for animal substances. It is a very useful solvent, dissolv-
ing a number of gases, most of the mineral and organic acids and
alkalies, most of the chlorids and carbonates, some of the nitrates,
all the sulfates, essences, and resins. Alcoholic solutions of fixed
medicinal substances are called tinctures ; those of volatile prin-
ciples, spirits.
The action of oxygen upon alcohol varies according to the
conditions. Under the influence of energetic oxidants, such as
chromic acid, or, when alcohol is burned in the air, the oxidation
is rapid and complete, and is attended by the extrication of much
heat, and the formation of carbon dioxid and water: CaHeCH-SOa
=2CO2-)-3H2O. Mixtures of air and vapor of alcohol explode
upon contact with flame. If a less active oxidant be used, such as
platinum-black, or by the action of atmospheric oxygen at low tem-
peratures, a simple oxidation of the alcoholic radical takes place,
with formation of acetic acid C^6 j- O+O2= °2H3g I O+H-.O,
a reaction which is utilized in the manufacture of acetic acid
and vinegar. If the oxidation be still further limited, aldehyde
is formed: 2C2H6O+Oa=2C2H4O+2H2O. If vapor of alcohol be
passed through a tube filled with platinum sponge and heated
to redness, or if a coil of heated platinum wire be introduced into
MONOATOMIC ALCOHOLS. 248
an atmosphere of alcohol vapor, the products of oxidation are
quite numerous : among them are water, ethylene, aldehyde, ace-
tylene, carbon monoxid, and acetal. Heated platinum wire in-
troduced into vapor of alcohol continues to glow by the heat re-
sulting from the oxidation, a fact which has been utilized in the
thermocautery.
Chlorin and bromin act energetically '::pon alcohol, producing
^i number of chlorinated and brominated derivatives, the final
products being chloral and bromal (q. v.}. If the action of Cl be
moderated, aldehyde and HC1 are first produced. lodin acts
quite slowly in the cold, but old solutions of I in alcohol (tr. iodin)
are found to contain HI, ethyl iodid, and other imperfectly
-studied products. In the presence of an alkali, I acts upon al-
cohol to produce iodoform. Potassium arid sodium dissolve in
alcohol with evolution of H ; upon cooling, a white solid crystal-
lizes, which is the double oxid of ethyl and the alkali metal, and
is known as potassium or sodium ethylate. Nitric acid, aided by
.a gentle heat, acts violently upon alcohol, producing nitrous
ether, brown fumes, and products of oxidation. (For the action
of other acids upon alcohol see the corresponding ethers.) The
hydroxids of the alkali metals dissolve in alcohol, but react upon
it slowly; the solution turns brown and contains an acetate. If
alcohol be gently heated with HNO3 and nitrate of silver or of
mercury, a gray precipitate falls, which is silver or mercury ful-
minate.
Varieties. — It occurs in different degrees of concentration : ab-
solute alcohol is pure alcohol, C2H6O. It is not purchasable, and
must be made as required. The so-called absolute alcohol of the
shops is rarely stronger than 98 per cent. Alcohol (U. S.), sp. gr.
0.820, contains 94 per cent, by volume, and spiritus rectificatus
(Br.), sp. gr. 0.838, contains 84 per cent. This is the ordinary rec-
tified spirit used in the arts. Alcohol dilutum (U. S.)— Spiritus
tenuior (Br.), sp. gr. 0.920, used in the preparation of tinctures,
contains 53 per cent. It is of about the same strength as the proof
spirit of commerce.
Analytical Characters. — (1.) Heated with a small quantity of
solution of potassium dichromate and H2SO4, the liquid assumes
an emerald-green color, and, if the quantity of C2H6O be not very
small, the peculiar fruity odor of aldehyde is developed. (2.)
Warmed and treated with a few drops of potash solution and a
small quantity of iodin, an alcoholic liquid deposits a yellow,
crystalline ppt. of iodoform, either immediately or after a time.
(3.) If HNO3 be added to a liquid containing C2H6O, nitrous ether,
recognizable by its odor, is given off. If a solution of mercurous
nitrate with excess of HNO3 be then added, and the mixture
heated, a further evolution of nitrous ether occurs, and a yellow-
244 MANUAL OF CHEMISTRY.
gray deposit of fulminating mercury is formed, which may be
collected, washed, dried and exploded. (4.) If an alcoholic liquid
be heated for a few moments with H2SO4 diluted with H2O and
distilled, the distillate, on treatment with H2SO4 and potassium
permanganate, and afterward with sodium hyposulfite, yields-
aldehyde, which may be recognized by the production of a violet
color with a dilute solution of f uchsin.
None of the above reactions, taken singly, is characteristic of
alcohol.
Action on the Economy. — In a concentrated form alcohol exerts
a dehydrating action upon animal tissues with which it comes
in contact ; causing coagulation of the albuminoid constituents.
When diluted, ethylic alcohol may be a food, a medicine, or a
poison, according to the dose and the condition of the person
taking it. When taken in excessive doses, or in large doses for
a long time, it produces symptoms and lesions characteristic of
pure alcoholism, acute or chronic, modified or aggravated by
those produced by other substances, such as amyl alcohol, which
accompany it in the alcoholic fluids used as beverages. Taken
in moderate quantities, with food, it aids digestion and produces
a sense of comfort and exhilaration. As a medicine it is a valua-
ble stimulant.
Much has been written concerning the value of alcohol as a
food. If it have any value as such, it is as a. producer of heat
and force by its oxidation in the body. Experiments have failed
to show that more than a small percentage (16 per cent, in 24
hrs.) of medium doses of alcohol ingested are eliminated by all
channels; the remainder, therefore, disappears in the body, as
the idea that it can there " accumulate " is entirely untenable.
That some part should be eliminated unchanged is to be expected
from the rapid diffusion and the high volatility of alcohol.
On the other hand, if alcohol be oxidized in the body, we should
expect, in the absence of violent muscular exercise, an increase in
temperature, and the appearance in the excreta of some product
of oxidation of alcohol: aldehyde, acetic acid, carbon dioxid, or
water, while the elimination of nitrogenous excreta, urea, etc.,
would remain unaltered or be diminished. While there is no
doubt that excessive doses of alcohol produce a diminution of
body temperature, the experimental evidence concerning the
action in this direction of moderate doses is conflicting and in-
complete. Of the products of oxidation, aldehyde has not been
detected in the excreta, and acetic acid only in the intestinal
canal. The elimination of carbonic acid, as such, does not seem
to be increased, although positive information upon this point is
wanting. If acetic acid be produced, this would form an acetate,
which in turn would be oxidized to a carbonate, and eliminated
MOISTOATOMIC ALCOHOLS. 245
as such by the urine. The elimination of water under the influ-
ence of large doses of alcohol is greater than at other times : but
whether this water is produced by the oxidation of the hydrogen
of the alcohol, or is removed from the tissues by its dehydrating
-action, is an open question.
While physiological experiment yields only uncertain evidence,
the experience of arctic travellers and others shows that the use
of alcohol tends to diminish rather than increase the capacity to
withstand cold. The experience of athletes and of military com-
manders is that intense and prolonged muscular exertion can be
best performed without the use of alcohol. The experience of
most literary men is that long-continued mental activity is more
difficult with than without alcohol.
In cases of acute poisoning by alcohol, the stomach-pump and
•catheter should be used as early as possible. A plentiful supply
of air, the cold douche, and strong coffee are indicated.
Alcoholic Beverages. — The variety of beverages in whose prepa-
ration alcoholic fermentation plays an important part is very
great, and the products differ from each other materially in their
composition and in their physiological action. They may be
divided into four classes, the classification being based upon the
sources from which they are obtained and upon the method of
their preparation.
I. — Those prepared by the fermentation of malted grain — beers,
ales, and porters.
II. — Those prepared by the fermentation of grape juice — wines
III. — Those prepared by the fermentation of the juices of fruits
other than the grape — cider, fruit-wines.
IV. — Those prepared by the distillation of some fermented sac-
charine liquid — ardent spirits.
Beer, ale, and porter are aqueous infusions or decoctions of
malted grain, fermented and flavored with hops. They contain,
therefore, the soluble constituents of the grain employed ; dextrin
«,nd glucose, produced during the malting; alcohol and carbon
dioxid, produced during the fermentation; and the soluble con-
stituents of the flavoring material. The alcoholic strength of
malt liquors varies from 1.5 to 9 per cent. Weiss beer contains
1.5-1.9 per cent. ; lager, 4.1-4.5 per cent. ; bock beer, 3.88-5.23 per
cent. ; London porter, 5.4-6.9 per cent. ; Burton ale, 5.9 per cent. ;
Scotch ale, 8.5-9 per cent. Malt liquors all contain a considerable
quantity of nitrogenous material (0.4-1 per cent. X), and succinic,
lactic, and acetic acids. The amount of inorganic material, in
which the phosphates of potassium, sodium, and magnesium pre-
dominate largely, varies from. 0.2 to 0.3 per cent. The sp. gr. is
from 1.014 to 1.033.
The adulterations of malt liquors are numerous and varied.
246 MANUAL OF CHEMISTKY.
Sodium carbonate is added with the double purpose of neutral-
izing an excess of acetic acid and increasing the foam. The most
serious adulteration consists in the introduction of bitter princi-
ples other than hops, and notably of strychnin, cocculus indicus.
(picrotoxin), and picric acid.
Wines are produced by the fermentation of grape-juice. In
the case of red wines the marc, or mass of skins, seed and stems,
is allowed to remain in contact with the must, or fermenting
juice, until, by production of alcohol, the liquid dissolves a por-
tion of the coloring matter of the skins. A certain proportion of
tannin is also dissolved, whose presence is necessary to prevent
stringiness. Sweet wines are produced from must rich in glu-
cose, and by arresting the fermentation before that sugar has-
been completely decomposed. Dry wines are obtained by more
complete fermentation of must less rich in glucose. Tartaric acid
is the predominating acid in grape-juice, and as the proportion
of alcohol increases during fermentation the acid potassium tar-
trate is deposited.
Most wines of good quality improve in flavor with age, and this-
improvement is greatly hastened by the process of pasteuring,
which consists in warming the wine to a temperature of 60° C..
(140° F.), without contact of air.
Light wines are those whose percentage of alcohol is less than
12 per cent. In this class are included the clarets, Sauternes,
Rhine, and Moselle wines ; champagnes, Burgundies, the Ameri-
can wines (except some varieties of California wine), Australian,.
Greek, Hungarian, and Italian wines.
The champagnes and some Moselle wines are sparkling, a qual-
ity which is communicated to them by bottling them before the
fermentation is completed, thus retaining the carbon dioxidr
which is dissolved by virtue of the pressure which it exerts.
When properly prepared they are agreeable to the palate, and
assist the digestion ; when new, however, they are liable to com-
municate their fermentation to the contents of the stomach and
thus seriously disturb digestion.
Of the still wines, the most widely used are the cZarefe,Vinum
rubrum (T7. S.), or red Bordeaux wines, and the hocks, Vinum album.
(IT. S.), or white Rhine, Moselle and American wines. The former
are of low alcoholic strength, mildly astringent, and contain but
a small quantity of nitrogenous material, qualities which render
them particularly adapted to table use and as mild stimulants.
The Rhine wines are thinner and more acid, and generally of
lower alcoholic strength than the clarets. The Burgundy and
Rhone wines are celebrated for their high flavor and body ; they
are not strongly alcoholic, but contain a large quantity of nitro-
genous material, to which they are indebted for their notoriety
MONOATOMIC ALCOHOLS. 247
as developers of gout. Our native American wines, particularly
those of the Ohio Valley and of California, are yearly improving
in flavor and quality ; they more closely resemble the Rhine wines
and Sauternes than other European wines.
Heavy wines are those whose alcoholic strength is greater than
12 per cent., usually 14 to 17 per cent. ; they include the sherries,
ports, Madeiras, Marsala, and some California wines, and are all
the products of warm climates. Sherry is an amber-colored wine,
grown in the south of Spain, Vinum Xericum (Br.). Marsala
closely resembles sherry in appearance, and is frequently substi-
tuted for it. Port is a rich, dark red wine, grown in Portugal.
The adulteration of wine by the addition of foreign substances
is confined almost entirely to their artificial coloration, which is
produced by the most various substances, indigo, logwood, fuch-
sin, etc. The addition of natural constituents of wines, obtained
from other sources, and the mixing of different grades of wine are,
however, extensively practised. "Water and alcohol are the chief
substances so added ; an excess of the former may be detected by
the taste, and the low sp. gr. after expulsion of the alcohol. Most
wines intended for export are fortified by the addition of alcohol.
When the alcoholic spirit used is free from amyl alcohol, and is
added in moderate quantities, there can be no serious objection
to the practice, especially when applied to certain wines which,
without such treatment, do not bear transportation. The mix-
ing of fine grades of wine with those of a poorer quality is exten-
sively practised, particularly with sherries, champagnes, clarets,
and Burgundies, and is perfectly legitimate. The same cannot
be said, however, of the manufacture of factitious wine, either
entirely from materials not produced from the grape, or by con-
verting white into red wines, or by mixing wines with coloring
matters, alcohol, etc., to produce imitations of wines of a differ-
ent class, an industry which flourishes extensively in Normandy,
at Bingen on the Rhine, and at Hamburg. The wines so pro-
duced are usually heavy wines, port and sherry so called.
Cider is the fermented juice of the apple, prepared very much
in the same way as wine is from grape-juice, and containing 3.5
to 7.5 per cent, of alcohol. It is very prone to acetous fermenta-
tion, which renders it sour and not only unpalatable, but liab'.j
to produce colic and diarrhtea with those not hardened to its use.
Spirits are alcoholic beverages, prepared by fermentation and
distillation. They differ from beers and wines in containing a
greater proportion of alcohol, and in not containing any of the
non-volatile constituents of the grains or fruits from which they
are prepared. Besides alcohol and water they contain acetic,
butyric, valerianic, and cenanthic ethers, to which they owe their
flavor; sometimes tannin and coloring matter derived from the
248 MANUAL OF CHEMISTRY.
cask ; amylic alcohol remaining after imperfect purification ; sugar
intentionally added ; and caramel. It is to the last-named sub-
stance that all dark spirits owe their color: although, after long
keeping in wood a naturally colorless spirit assumes a straw color.
The varieties of spirituous beverages in common use are:
Brandy, spiritus vini gallici (U. S., Br.), obtained by the distilla-
tion of wine, and manufactured in France and in California and
Ohio. It is of sp. gr. 0.929 to 0.934, is dark or light in color, ac-
cording to the quantity of burnt sugar added, and contains about
1.2 per cent, of solid matter. American whiskey, spiritus fru-
menti (TJ. S.), prepared from wheat, rye, barley, or Indian corn;
has a sp. gr. of 0.922 to 0.937 and contains 0.1 to 0.3 per cent, of
solids. Scotch and Irish whiskies, colorless spirits distilled from
fermented grains; sp. gr. 0.915 to 0.920, having a peculiar smoky
flavor produced by drying the malted grain by a peat fire. Gin,
also distilled from malted grain, sp. gr. 0.930 to 0.944, flavored with
juniper, and sometimes fraudulently with turpentine. Rum, a
spirit distilled from molasses, and varying in color and flavor from
the dark Jamaica rum to the colorless St. Croix rum. The former
is of sp. gr. 0.914 to 0.926, and contains one per cent, of solid
matter.
Liqueurs or cordials are spirits sweetened and flavored with veg-
etable aromatics, and frequently colored ; anisette is flavored with
aniseed ; absinthe, with wormwood ; curacoa, with orange-peel ;
kirschwasser, with cherries, the stones being cracked and the
spirits distilled from the bruised fermented fruit ; kilmmel, with
cummin and caraway seeds ; maraschino, with cherries ; noyeau,
with peach and apricot kernels.
Propyl hydroxid — Ethyl carbinol — Primary propyl alcohol —
CH3.CH2,CH2OH — 60— is produced, along with ethylicalcohol,dur-
ing fermentation, and obtained by fractional distillation of marc
brandy, from cognac oil, huile de marc (not to be confounded
with oil of wine), an oily matter, possessing the flavor of inferior
brandy, which separates from marc brandy, distilled at high tem-
peratures ; and from the residues of manufacture of alcohol from
beet-root, grain, molasses, etc. It is a colorless liquid, has a hot
alcoholic taste, and a fruity odor; boils at 96°. 7 (206°. 1 F.); and is
miscible with water. It has not been put to any use in the arts.
Its intoxicating and poisonous actions are greater than those of
ethyl alcohol. It exists in small quantity in cider.
Butyl alcohols— C4H9OH— 74.— The four butyl alcohols theoret-
ically possible are known to exist :
Propyl carbinol — Primary normal butyl alcohol — Butyl alcohol
of fermentation — CH3 — CH2— CH2— CH2OH — is formed in small
quantities during alcoholic fermentation, and may be obtained
by repeated fractional distillation from the oily liquid left in the
MONOATOMIC ALCOHOLS. 249
Tectiflcation of vinic alcohol. It is a colorless liquid; boils at
114°. 7 (238°. 5 F.). It is more actively poisonous than ethyl or
methyl alcohol.
CTT \
Isopropyl carbinol— Isobutyl alcohol — Xjj /CH — CH2OH — oc-
curs in the fusel oil obtained in the products of fermentation and
distillation of beet-root molasses. It is a colorless liquid, sp.
gr. 0.8032; boils at 110° (230° F.).
Ethyl-methyl carbinol; secondary butyl alcohol —
°H3~CH3/CHOH~a li(luid which boils at 99° (210°.2 F.).
CH3\
Trimethyl carbinol ; tertiary butyl alcohol, CH3 — COH — a crys-
CH3/
talline solid, which fuses at 20°-25° (68°-77° F.), and boils at 82°
<179°.6 F.).
Amylic alcohols— CsHnOH— 88. — Of the eight amyl alcohols
theoretically possible (see p. 239) seven have been obtained. The
-substance usually known as amylic alcohol, potato spirit, fusel
rtTT \.
•oil, alcohol amylicum (Br.), is the primary alcohol rjjj3 /CH — CHa
— CHaOH — with lesser quantities of other alcohols, differing in na-
ture and amount with the grain used, and the conditions of the
fermentation and distillation. Each kind of " spirit " furnishing
and containing a peculiar fusel.
In the process of manufacture of ardent spirits the fusel oil ac-
cumulates in great part in the still, but much of it distils over,
and is more or less completely removed from the product by the
process of defuselation.
Spirits properly freed of fusel oil give off no irritating or foul
fumes, when hot. They are not colored red when mixed with
three parts C2H6O and one part strong H2SO4. They are not col-
ored red or black by ammoniacal silver nitrate solution. When
150 parts of the spirit, mixed with 1 part potash, dissolved in a
little H2O, are evaporated down to 15 parts, and mixed with an
equal volume of dilute H2SO4, no offensive odor should be given
off.
While young spirits owe their rough taste and, in great measure,
their intoxicating qualities to the presence of fusel oil, it is a pop-
ular error that a spirit would be improved by complete removal
of all products except ethyl alcohol. The improvement of a spirit
by age is due to chemical changes in the small amount of fusel
retained in a properly manufactured product, and, were this ab-
sent, the spirit would deteriorate rather than improve by age.
The individual amylic alcohols have the following characters :
Butyl carbinol ; normal amylic alcohol, CH3— CH2— CH2 — CH2—
CH.OH — is a colorless liquid, boils at 135° (275° F.). Obtained
250 MANUAL OF CHEMISTKY.
from normal butyl alcohol. It yields normal valerianic acid on
oxidation.
PITT v
Isobutyl carbinol— Amyl alcohol— gg3 ^CH— CH2— CH2OH— is
the principal constituent of the fusel oil from grain and potatoes.
It is obtained from the last milky products of rectification of
alcoholic liquids. These are shaken with H2O to remove ethyl
alcohol, the supernatant oily fluid is decanted, dried by contact
with fused calcium chlorid, and distilled; that portion which
passes over between 128° and 132° (262°. 4-269°. 6 F.) being collected.
It is a colorless, oily liquid, has an acrid taste and a peculiar
odor, at first not unpleasant, afterward nauseating and provoca-
tive of severe headache. It boils at 132° (269°. 6 F.) and crystal-
lizes at -20° (4° F.); sp. gr. 0.8184 at 15° (5° F.). It mixes with al-
cohol and ether, but not with water. It burns difficultly with a.
pale blue flame.
When exposed to air it oxidizes very slowly ; quite rapidly, how-
ever, in contact with platinum-black, forming valerianic acid.
The same acid, along with other substances, is produced by the
action of the more powerful oxidants upon amyl alcohol. Chlorin
attacks it energetically, forming amyl chlorid, HC1, and other
chlorinated derivatives. SuJfuric acid dissolves in amyl alcohol,
with formation of ainyl-sulfuric acid, SO4(C6HU)H, correspond-
ing to ethyl-sulfuric acid. It also forms similar acids with phos-
phoric, oxalic, citric, and tartaric acids. Its ethers, when dis-
solved in ethyl alcohol, have the taste and odor of various fruits,
and are used in the preparation of artificial fruit-essences. Amyl
alcohol is also used in analysis as a solvent, particularly for cer-
tain alkaloids, and in pharmacy for the artificial production of
valerianic acid and the valerianates.
rjJT _ CH \
Diethyl carbinol — ' _ 2 CHOH — is produced by the action
of a mixture of zinc and ethyl iodid on ethyl formiate, with the
subsequent addition of H2O. It is a liquid which boils at 116°. 5-
(241°.7 F.).
CH \
Methyl-propyl-carbinol — QJJ _ QJJ _ QJJ" /CHOH — a liquid,
boiling at 118°. 5 (245°. 3 F.), obtained by the hydrogenation of
methylpropylic acetone.
Methyl-isopropyl-carbinol — Amylene hydrate —
(CH3)3— CH^\CHOH_obta.ned by the hydrogenation of methyl-
isopropylic acetone; or by the action of hydriodic acid upon arny-
lene, and the action of moist silver oxid upon the product so ob-
tained. It is a colorless liquid, sp. gr. 0.829 atO° (32° F.), having a
pungent, ethereal odor; boils at 108° (226°. 4 F.); soluble in H2O
and in alcohol. Has been used as a hypnotic.
SIMPLE ETHEES. 251
Ethyl-dimethyl-carbinol — Tertiary amylic alcohol —
CH2\
CH3— CH3— COH— is a liquid which solidifies at -12° (10°.4 F.)and
CHS/
boils at 102°.5 (216°.5 F.); formed by the action of zinc methyl
upon propionyl chlorid, or by decomposition of tertiary sulfamy-
lic acid by boiling H2O. It is a colorless liquid; sp. gr. 0.828 at 0°
(32° F.), crystallizes at —30° (-22° F.), boils at about 100° (212° F.).
The nitrite of this alcohol has been used as a substitute for aniyl
nitrite.
Cetyl hydrate— Cetylic alcohol— Ethal— C16H33OH— 242— is ob-
tained by the saponification of spermaceti (its palmitic ether). It
is a white, crystalline solid; fusible at 49° (120°. 2 F.); insoluble in
HSO ; soluble in alcohol and ether ; tasteless and odorless.
Ceryl hydrate — C^HsoOH— 396 — and Myricyl hydrate — C3oH8t
OH — 438 — are obtained as white, crystalline solids: the former
from China wax ; the latter from beeswax, by saponification.
SIMPLE ETHERS.
OXIDS OF ALCOHOLIC RADICALS OF THE SERIES CnHm+i.
The term ether was originally applied to any volatile liquid
obtained by the action of an acid upon an alcohol.
The simple ethers are the oxids of the alcoholic radicals. They
bear the same relation to the alcohols that the oxids of the basyl-
ous elements bear to their hydroxids:
CjH.
Ca
Ethyl oxid Potassium oxid. Ethyl hydroxid Potassium hydroxid.
(ethylic ether). (alcohol).
H5 ) ft K ^ ft CnHB ) ft K )
H5fu K}U HfU Hf
When the two alcoholic radicals are the same, as in the above
instance, the ether is designated as simple ; when the radicals are
/-ITT ^
different, as in methyl-ethyl oxid, ^ TJ - O> they are called mixed
v^2.n& )
ethers.
CH i
Methyl oxid — X-rr3 \ O — 46 — isomeric with ethyl alcohol, is ob-
l>JCLs )
tained by the action of H2SO4 and boric acid upon methyl al-
cohol, or by the action of silver oxid on methyl iodid. It is a
colorless gas; has an ethereal odor; burns with a pale flame;
liquefies at —36° (-32°. 8 F.); and boils at -21° (-5°. 8 F.); is solu-
ble in H2O, HsSCK and ethyl alcohol.
Ethyl oxid — Ethylic ether — Ether— Sulfuric ether — .SJther
fortior (TJ. S.)— JEther purus (Br.)— f!2?5 [ O— 74.
U»Af )
Preparation. — A mixture is made of 5 pts. of alcohol, 90#, and 9
252 MANUAL OF CHEMISTEY.
pts. of concentrated H2SO4, in a vessel surrounded by cold H2O.
This mixture is introduced into a retort, over which is a vessel
from which a slow stream of alcohol is made to enter the retort.
Heat is applied, and the addition of alcohol and the heat are so
regulated that the temperature does not rise above 140° (284° F.).
The retort is connected with a well-cooled condenser, and the
process continued until the temperature in the retort rises above
the point indicated. It is important that the tube by which the
alcohol is introduced be drawn out to a small opening, and dip
well down below the surface of the liquid. The distillate thus
obtained contains ether, alcohol, water, and gases resulting from
the decomposition of the alcohol and H2SO4, notably SOS. It is
subjected to a first purification bv shaking with H2O containing
potash or lime, decanting the supernatant ether and redistilling.
The product of this process is "washed ether," or sether (17. S.).
It is still contaminated with water and alcohol, and when desired
pure, as for producing anaesthesia and for processes of analysis, it
is subjected to a second purification. It is again shaken with
H2O, decanted after separation, shaken with recently fused cal-
•cium chlorid and newly burnt lime, with which it is left in con-
tact 24 hours, and from which it is then distilled.
It was known at an early day that a small quantity of HaSO* is
capable of converting a large quantity of alcohol into ether, and
that at the end of the process the H2SO4 remains in the retort
unaltered, except by secondary reactions. A metaphysical ex-
planation of the process was found in the assertion that the acid
acted by its mere presence, by catalysis, as it was said. In other
words, it acts because it acts, a very ready but a very feminine
method of explaining what is not understood, which is still in-
voked by some authors as a covering for our ignorance of the
rationale of certain chemico-physiological phenomena. It was
only in 1850 that Alex. Williamson, by a series of ingenious expe-
riments, determined the true nature of the process. In the con-
version of alcohol into ether, an intermediate substance, sulfo-
vinic acid, is alternately formed at the expense of the alcohol,
and destroyed with formation of ether and regeneration of H2SO4.
At first H2SO4 and alcohol act upon each other, molecule for
molecule, to form H2O and sulfovinic acid : C^ I O+S^2 I Ot
H ) S°2 I
— TJ r O4- CaH6 > O2. The new acid as soon as formed reacts with
H)
a second molecule of alcohol, with regeneration of H2SO4 and for-
mation of ether: C*nl [ O,+C9^| | O=Sj^3 1 O*+c2H° } °'
Theoretically, therefore, a given quantity of H2SO4 could con-
SIMPLE ETHERS. 253
vert an unlimited amount of alcohol into ether. Such would also
be the case in practice, were it not that the acid gradually be-
comes too dilute, by admixture with the H2O formed during the
reaction, and at the same tune is decomposed by secondary reac-
tions, into which it enters with impurities in the alcohol; causes
which in practice limit the amount of ether produced to about
four to five times the bulk of acid used.
Ether is a colorless, limpid, mobile, highly refracting liquid ; it
has a sharp, burning taste, and a peculiar, tenacious odor, char-
acterized as ethereal. Sp. gr. 0.723 at 12°. 5 (54°. 5 F.); it boils at
34°.5 (94°.l F.), and crystallizes at -31° (-23°.8 F.). Its tension of
vapor is very great, especially at high temperatures ; it should,
therefore, be stored in strong bottles, and should be kept in situ-
ations protected from elevations of temperature. It is exceedingly
volatile, and, when allowed to evaporate freely, absorbs a great
amount of heat, of which property advantage is taken to produce
local anaesthesia, the part being benumbed by the cold produced
by the rapid evaporation of ether sprayed upon the surface.
Water dissolves one-ninth its weight of ether. Ethylic and me-
thylic alcohols are miscible with it in all proportions. Ether is
an excellent solvent of many substances not soluble in water and
alcohol, while, on the other hand, it does not dissolve many sub-
stances soluble in those fluids The resins and fats are readily
soluble in ether; the salts of the alkaloids and many vegetable
coloring matters are soluble in alcohol and water, but insoluble
in ether, while the free alkaloids are for the most part soluble in
ether, but insoluble, or very sparingly soluble, in water.
Ether, whether in the form of vapor or of liquid, is highly in-
flammable; and burns with a luminous flame. The vapor forms
with air a violently explosive mixture. It is denser than air,
through which it falls and diffuses itself to a great distance ; great
caution is therefore required in handling ether in a locality in
which there is a light or fire, especially if the fire be near the
floor.
Pure ether is neutral in reaction, but, on exposure to air or O,
especially in the light, it becomes acid from the formation of a
small quantity of acetic acid. H2SO4 mixes with ether, with
elevation of temperature, and formation of sulfovinic acid.
Sulfuric anhydrid forms ethyl sulfate. HNO3, aided by heat,
oxidizes ether to carbon dioxid and acetic and oxalic acids. Ether,
saturated with HC1 and distilled, yields ethyl chlorid. Cl, in the
presence of H2O, oxidizes ether, with formation of aldehyde, acetic
acid, and chloral. In the absence of H2O, however, a series or
products of substitution are produced, in which 2, 4 and 10 atoms
of H are replaced by a corresponding number of atoms of Cl.
These substances in turn, by substitution of alcoholic radicals, or-
254 MANUAL OF CHEMISTRY.
of atoms of elements, for atoms of Cl, give rise to other deriva-
tives.
Action on the Economy. — Ether is largely used in medicine for
producing anaesthesia, either locally by diminution of tempera-
ture due to its rapid evaporation, or generally by inhalation.
When taken in overdose it causes death, although it is by no
means as liable to give rise to fatal accidents as is chloroform. Pa-
tients suffering from an overdose may, in the vast majority of
cases, be resuscitated by artificial respiration and the induced
current, one pole to be applied to the nape of the neck, and the
other carried across the body just below the anterior attachments
of the diaphragm.
In cases of death from ether the odor is generally well marked
in the clothing and surroundings, and especially on opening the
thoracic cavity. In the analysis it is sought for in the blood and
lungs at the same time as chloroform (q.v.).
MONOBASIC ACIDS.
SERIES CnH2"O8.
As the higher terms of this series are obtained from the fats,
and the lower terms are volatile liquids, these acids are some-
times designated as the volatile fatty acids.
Although formed in a variety of ways, these acids may be con-
sidered as being derived from the primary inonoatomic alcohols,
by the substitution of O for H2 in the group CH2OH :
CHs — GHz — CH2 — CHs — CH2,OH
Normal ainylic alcohol.
CH3— CH2— CH2— CH2— CO, OH
Normal valerianic acid.
Considered typically, the substitution of O for H2 occurs in the
radical : C ^ ' ' j- O— C eH 9^ j- O, and communicates to the radical
electro-negative or acid qualities.
Formic acid — HCO,OH — 46 — occurs in the acid secretion of red
ants, in the stinging hairs of certain insects, in the blood, urine,
bile, perspiration, and muscular fluid of man, in the stinging-
nettle, and in the leaves of trees of the pine family. It is pro-
duced in a number of reactions ; by the oxidation of many or-
ganic substances : sugar, starch, fibrin, gelatin, albumin, etc. ; by
the action of potash upon chloroform arid kindred bodies; by
the action of mineral acids in hydrocyanic acid ; during the fer-
mentation of diabetic urine ; by the direct union of carbon mon-
MONOBASIC ACIDS. 255
oxid and water ; by the decomposition of oxalic acid under the
influence of glycerin at about 100° (212° F.).
It is a colorless liquid, having an acid taste and a penetrating
odor; it acts as a vesicant; it boils at 100° (212° F.), and, when
pure, crystallizes at Oa (32° F.). It is uiiscible with HaO in all
proportions.
The mineral acids decompose it into H2O and carbon monoxid.
Oxidizing agents convert it into HaO and carbon dioxid. Alka-
line hydroxids decompose it with formation of a carbonate and
liberation of H. It acts as a reducing agent with the salts of the
noble metals.
Acetic acid — Acetyl hydrate — Hydrogen acetate — Pyroligneous
acid— Acidum aceticum (U. S. ; Br.)— CH3,COOH— 60.
It is formed— (1.) By the oxidation of alcohol :
CH,, CHaOH+02 =CHS, COOH+HaO.
(2.) By the dry distillation of wood.
(3.) By the decomposition of natural acetates by mineral acids.
(4.) By the action of potash in fusion on sugar, starch, oxalic,
tartaric, citric acids, etc.
(5.) By the decomposition of gelatin, fibrin, casein, etc., by
H2SO4 and manganese dioxid.
(6.) By the action of carbon dioxid upon sodium methyl:
COa-(-XaCH3=C2H3O3^a; and decomposition of the sodium ace-
tate so produced.
The acetic acid used in the arts and in pharmacy is prepared
"by the destructive distillation of wood. The products of the dis-
tillation, which vary with the nature of the wood used, are
numerous. Charcoal remains in the retort, while the distilled
product consists of an acid, watery liquid ; a tarry material ; and
gaseous products. The gases are carbon dioxid, carbon monoxid,
and hydrocarbons. The tar is a mixture of empyreumatic oils,
hydrocarbons, phenol, oxyphenol, acetic acid, ammonium ace-
tate, etc.
The acid water is very complex, and contains, besides acetic
acid, formic, propionic, butyric, valerianic, and oxyphenic acids,
acetone, naphthalene, benzene, toluene, cumene, creasote, methyl
alcohol, and methyl acetate, etc. Partially freed from tar by de-
cantation, it still contains about 20 per cent, of tarry and oily
material, and about 4 per cent, of acetic acid ; this is the crude
pyroligneous acid of commerce.
The crude product is subjected to a first purification by distil-
lation ; the first portions are collected separately and yield methyl
alcohol (q.v.); the remainder of the distillate is the distilled
pyroligneous acid, used to a limited extent as an antiseptic, but
principally for the manufacture of acetic acid and the acetates.
256 MANUAL OF CHEMISTEY.
It can only be freed from the impurities which it still contains by
chemical means. To this end slacked lime and chalk are added,
at a gentle heat, to neutralization ; the liquid is boiled and allowed
to settle twenty-four hours ; the clear liquid, which is a solution
of calcium acetate, is decanted and evaporated ; the calcium salt
is converted into sodium acetate, which is then purified by cal-
cination at a temperature below 330° (626° F.), dissolved, filtered,
and recrystallized ; the salt is then decomposed by a proper quan-
tity of H2SO4, and the liberated acetic'acid separated by distilla-
tion.
The product so obtained is a solution of acetic acid in water,,
containing 36 per cent, of true acetic acid, and being of sp. gr.
1.047, U. S. (the acid of the Br. Ph. is weaker — 33 per cent. C2H4O2r
and sp. gr. 1.044).
Pure acetic acid, known as glacial acetic acid, acidum aceticum.
glaciale (U. S.), is obtained by decomposition of a pure dry ace-
tate by heat.
Acetic acid is a colorless liquid. Below 17° (62°. 6 F.), when
pure, it is a crystalline solid. It boils at 119° (246°. 2 F.); sp. gr.
1.0801 at 0° (32° F.); its odor is penetrating and acid; in contact
with the skin it destroys the epidermis and causes vesication; it
mixes with H2O in all proportions, the mixtures being less in vol-
ume than the sum of the volumes of the constituents. The sp.
gr. of the mixtures gradually increase up to that containing 23
per cent, of H2O, after which they again diminish, arid all the
mixtures containing more than 43 per cent, of acid are of higher
sp. gr. than the acid itself.
Vapor of acetic acid burns with a pale blue flame ; and is de-
composed at a red heat. It only decomposes calcic carbonate in
the presence of H2O. Hot H2SO4 decomposes and blackens it,
SO2 and CO2 being given off. Under ordinary circumstances Cl
acts upon it slowly, more actively under the influence of sunlight,
to produce monochloracetic acid, CH2C1CO,OH ; dichloracetic acidr
CHC12CO,OH; and trichloracetic acid, CC13CO,OH. The last
named is an odorless, acid, strongly vesicant, crystalline solid ;
fuses at 46° (114°.8 F.) and boils at 195°-200° (383°-392° F.).
Analytical Characters. — (1.) Warmed with H2SO4 it blackens.
(2.) With silver nitrate a white crystalline ppt., partly dissolved
by heat; no reduction of Ag on boiling. (3.) Heated with H2SO4
and C2H6O, acetic ether, recognizable by its odor, is given off.
(4.) When an acetate is calcined with a small quantity of As2O3
the foul odor of cacodyl oxid is developed. (5.) Neutral solution
of ferric chlorid produces in neutral solutions of acetates a deep
red color, which turns yellow on addition of free acid.
Vinegar is an acid liquid owing its acidity to acetic acid, and
holding certain fixed and volatile substances in solution. It is.
MONOBASIC ACIDS. 257
obtained from some liquid containing 10 per cent, or less of al-
cohol, which is converted into acetic acid by the transferring of
atmospheric oxygen to the alcohol during the process of nutri-
tion of a peculiar vegetable ferment, known as mycoderma aceti,
or, popularly, as mother of vinegar. Vinegar is now manufac-
tured principally by one of two processes — the German method,
and that of Pasteur. In the former, the alcoholic fluid, which
must also contain albuminous matter, is allowed to trickle slowly
through barrels containing beech-wood shavings, supported by a
perforated false bottom. By a suitable arrangement of holes and
tubes, an ascending current of air is made to pass through the
barrel. The acetic ferment clings to the shavings, and under its
influence acetification takes place rapidly, owing to the large sur-
face exposed to the air. In Pasteur's process, the ferment is sown
upon the surface of the alcoholic liquid, contained in large, shal-
low, covered vats, from which the vinegar is drawn off after acet-
ification has been completed; the mother is collected, washed,
and used in a subsequent operation.
The liquids from which vinegar is made are wine, cider, and
beer, to which dilute alcohol is frequently added ; the most es-
teemed being that obtained from white wine. Wine vinegar has
a pleasant, acid taste and odor ; it consists of water, acetic acid
(about 5 per cent.), potassium bitartrate, alcohol, acetic ether,
glucose, malic acid, mineral salts present in wine, a fermentesci-
ble, nitrogenized substance, coloring matter, etc. Sp. gr. 1.020 to
1.025. When evaporated, it yields from 1.7 to 2.4 per cent, of
solid residue.
Vinegars made from alcoholic liquids other than wine contain
no potassium bitartrate, contain less acetic acid, and have not
the aromatic odor of wine vinegar. Cider vinegar is of sp. gr.
1.020; is yellowish, has an odor of apples, and yields 1.5 per cent,
of extract on evaporation. Beer vinegar is of sp. gr. 1.032; has a
bitterish flavor, and an odor of sour beer ; it leaves 6 per cent,
of extract on evaporation.
The principal adulterations of vinegar are : Sulfuric acid,
which produces a black or brown color when a few drops of the
vinegar and some fragments of cane-sugar are evaporated over
the water-bath to dryness. Water, an excess of which is indicated
by a low power of saturation of the vinegar, in the absence of
mineral acids. Two parts of good wine vinegar neutralize 10
parts of sodium carbonate ; the same quantity of cider vinegar,
3.5 parts; and of beer vinegar, 2.5 parts of carbonate. Pyrolig-
neous acid may be detected by the creasote-like odor and taste.
Pepper, capsicum, and other acrid substances, are often added
to communicate fictitious strength. In vinegar so adulterated
an acrid odor is perceptible after neutralization of the acid with
17
258 MANUAL OF CHEMISTRY.
sodium carbonate. Copper, zinc, lead, and tin f req uently occur
in vinegar which has been in contact with those elements, either
during the process of manufacture or subsequently.
Distilled vinegar is prepared by distilling vinegar in glass ves-
sels; it contains none of the fixed ingredients of vinegar, but its
volatile constituents (acetic acid, water, alcohol, acetic ether, odor-
ous principles, etc.), and a small quantity of aldehyde.
When dry acetate of copper is distilled, a blue, strongly acid
liquid passes over; this, upon rectification, yields a colorless,
mobile liquid, which boils at 56° (132°. 8 F.), has a peculiar odor,
and is a mixture of acetic acid, water, and acetone, known as
radical vinegar.
Toxicology. — "When taken internally, acetic acid and vinegar
(the latter in doses of 4-5 fl. § ) act as irritants and corrosives,
causing in some instances perforation of the stomach, and death
in 6-15 hours. Milk of magnesia should be given as an antidote,
with the view to neutralizing the acid.
Propionic acid — CH3,CH2 — COOH — is formed by the action of
caustic potassa upon sugar, starch, gum, and ethyl cyanid ; dur-
ing fermentation, vinous or acetic ; in the distillation of wood ;
during the putrefaction of peas, beans, etc. ; by the oxidation of
normal propylic alcohol, etc. It is best prepared by heating ethyl
cyanid with potash until the odor of the ether has disappeared ;
the acid is then liberated from its potassium compound by H2SO4
and purified.
It is a colorless liquid, sp. gr. 0.996. does not solidify at —21°
{—5°. 8 P.), boils at 140° (284° F.), mixes with water and alcohol in
all proportions, resembles acetic acid in odor and taste. Its salts
are soluble and crystallizable.
, Butyric acid— Propyl-formic acid — CH3 — CH2 — CH2 — COOH— has
been found in the milk, perspiration, muscular fluid, the juices of
the spleen and of other glands, the urine, contents of the stomach
and large intestine, faeces, and guano; in certain fruits, in yeast,
in the products of decomposition of many vegetable substances ;
and in natural waters ; in fresh butter in small quantity, more
abundantly in that which is rancid.
It is formed by the action of H2SO4 and manganese dioxid,
aided by heat, upon cheese, starch, gelatin, etc. ; during the com-
bustion of tobacco (as ammonium butyrate) ; by the action of
HNO3 upon oleic acid ; during the putrefaction of fibrin and other
albuminoids; during a peculiar fermentation of glucose and
starchy material in the presence of casein or gluten. This fer-
mentation, known as the butyric, takes place in two stages ; at
first the glucose is converted into lactic acid : CeH^Oe^^sHeOa) ;
and this in turn is decomposed into butyric acid, carbon dioxid,
and hydrogen: 2C3H6O3=04HdO2+2CO2+2H2.
MONOBASIC ACIDS. 259
Butyric acid is obtained from the animal charcoal which has
been used in the purification of glycerol, in which it exists as cal-
cium butyrate. It is also formed by subjecting to fermentation
,a mixture composed of glucose, water, chalk, and cheese or gluten.
The calcium butyrate is decomposed by H2SO4, and the butyric
^cid separated by distillation.
Butyric acid is a colorless, mobile liquid, having a disagreeable,
persistent odor of rancid butter, and a sharp, acid taste ; soluble
in water, alcohol, ether, and methyl alcohol; boils at 164° (327'J.2
F.), distilling unchanged; solidifies in a mixture of solid carbon
dioxid and ether; sp. gr. 0.974 at 15° (59° F.); a good solvent of
fats.
It is not acted upon by H2SO4 in the cold, and only slightly
under the influence of heat. Nitric acid dissolves it unaltered in
the cold, but on the application of heat, oxidizes it to succinic
acid. Dry Cl under the influence of sunlight, and Br under the
influence of heat and pressure, form products of substitution
with butyric acid. It readily forms ethers and salts.
Butyric acid is formed in the intestine, by the process of fermen-
tation mentioned above, at the expense of those portions of the
carbohydrate elements of food which escape absorption, and is
discharged with the faeces as ammonium butyrate.
CH \
Isobutyric acid— Isopropyl-formic acid— QH3 ^CH— COOH — boils
at 152° (305°. 6 F.), has been found in human faeces. It corresponds
to isobutyl alcohol, from which it is produced by oxidation.
Valerianic acids — C4HUCO,OH — 102. — Corresponding to the four
primary amylic alcohols, there are four possible amylic or valeri-
anic acids, of which three, I., II., and IV., are known.
I. CH3— CH2— CH2— CH-,— CO,OH.
II. ;53^CH— CH2— CO,OH.
Uxis/
III. CHa~£53S)CH— CO,OH. IV. CH33— C— CO,OH.
Ha/ CH3/
I. Normal valerianic acid — Butylformic acid — Propylacetic acid
— is obtained by the oxidation of normal amylic alcohol. It is an
oily liquid, boils at 185° (365° F.), and has an odor resembling that
of butyric acid.
II. Ordinary valerianic acid — Delphinic acid — Phocenic acid —
Isovaleric &ci&—Isopropyl acetic acid — Isobutylformic acid —
Acidum valerianicum (Br.). — This acid exists in the oil of the por-
poise, and in valerian root and in angelica root. It is formed
during putrid fermentation or oxidation of albuminoid sub-
stances. It occurs in the urine and faeces in typhus, variola, and
260 MANUAL OF CHEMISTRY.
acute atrophy of the liver. It is also formed in a variety of chem-
ical reactions, and notably by the oxidation of amylic alcohol.
It is prepared either by distilling water from valerian root, orr
more economically, by mixing rectified amylic alcohol with H2SO4,
adding when cold, a solution of potassium dichromate, and dis-
tilling after the reaction has become moderated : the distillate is
neutralized with sodium carbonate ; and the acid is obtained from
the sodium valerianate so produced, by decomposition by H2SOt
and rectification.
The ordinary valerianic acid is an oily, colorless liquid, having-
a penetrating odor, and a sharp, acrid taste. It solidifies at — 16°
(3°.2 F.); boils at 173°-175° (343°.4-347° F.); sp. gr. 0.9343-0.9465 at
20° (68° F.); burns with a white, smoky flame. It dissolves in 30'
parts of water, and in alcohol and ether in all proportions. It
dissolves phosphorus, camphor, and certain resins.
IV. Trimethyl acetic acid — Pwalic acid — is a crystalline solid,,
which fuses at 35°. 5 (96° F.) and boils at 163°. 7 (326°. 7 F.); spar-
ingly soluble in H2O ; obtained by the action of cyanid of mer-
cury upon tertiary butyl iodid.
Caproic acids — Hexylic acids — CBHn,COOH — 116. — There proba-
bly exist quite a number of isomeres having the composition in-
dicated above, some of which have been prepared from butter,
cocoa-oil, and cheese, and by decomposition of amyl cyanid, or
of hexyl alcohol.
The acid obtained from butter, in which it exists as a glyceric
ether, is a colorless, oily liquid, boils at 205° (401° F.); sp. gr. 0.931
at 15° (59° F.) ; has an odor of perspiration and a sharp, acid taste;
is very sparingly soluble in water, but soluble in alcohol.
(Enanthylic acid — Heptylic acid — C6Hj3,COOH — 130 — exists in
spirits distilled from rice and maize, and is formed by the action
of HNO3 on fatty substances, especially castor-oil. It is a color-
less oil; sp. gr. 0.9167; boils at 212° (413°. 6 F.).
Caprylic acid — Octylic acid— C7Hi6,COOH — 144 — accompanies
caproic acid in butter, cocoa-oil, etc. It is a solid; fuses at 15° (59°
F.); boils at 236° (457° F.); almost insoluble in HaO.
Pelargonic acid — Nonylic acid — C8Hi7,COOH — 158. — A colorless
oil, solid below 10° (50° F.); boils at 260° (500° F.); exists in oil of
geranium, and is formed by the action of HNO3 on oil of rue.
Capric acid — Decylic acid— C9Hi9,COOH— 172 — exists in butter,
cocoa-oil, etc., associated with caproic and caprylic acids in their
glyceric ethers, and in the residues of distillation of Scotch
whiskey, as amyl caprate. It is a white, crystalline solid ; melts
at 27°.5 (81°.5 F.); boils at 273° (523°.4 F.).
Laurie acid — Laurostearic acid — CiiH23,COOH — 200 — is a solid,
fusible at 43°. 5 (110°. 3 F.), obtained from laurel berries, cocoa-but-
ter, and other vegetable fats.
MOXOBASIC ACIDS. 261
Myristic acid — Ci3Ho7,COOH— 228. — A crystalline solid, fusible
.•at 54° (129'. 2 P.); existing in many vegetable oils, cow's butter,
.and spermaceti.
Palmitic acid — Ethalic acid — Ci5H31,COOH — 256 — exists in palm-
oil, in combination when the oil is fresh, and free when the oil is
old ; it also enters into the composition of nearly all animal and
vegetable fats. It is obtained from the fats, palm-oil, etc., by
.saponification with caustic potassa and subsequent decomposition
of the soap by a strong acid. It is also formed by the action of
caustic potash in fusion upon cetyl alcohol (ethal), and by the
.action of the same reagent upon oleic acid.
Palmitic acid is a white, crystalline solid; odorless, tasteless;
lighter than H2O, in which it is insoluble ; quite soluble in alcohol
and in ether; fuses at 62° (143°. 6 F.) ; distils unchanged with vapor
of water.
Margaric acid— Ci 6H33,COOH — 270 — formerly supposed to exist as
a glycerid in all fats, solid and liquid. "What had been taken for
inargaric acid was a mixture of 90 per cent, of palmitic and 10 per
•cent, of stearic acid. It is obtained by the action of potassium
hydroxid upon cetyl cyanid, as a white, crystalline body; fusible
.at 59°. 9 (140° F.).
Stearic acid— CnH35,COOH — 284 — exists as a glycerid in all solid
fats, and in many oils, and also free to a limited extent.
To obtain it pure, the fat is saponified with an alkali, and the
;soap decomposed by HC1; the mixture of fatty acids is dissolved
in a large quantity of alcohol, and the boiling solution partly
precipitated by the addition of a concentrated solution of barium
.acetate. The precipitate is collected, washed, and decomposed by
HC1 ; the stearic acid which separates is washed and recrystallized
from alcohol. The process is repeated until the product fuses at
70° (1583 F.). Stearic acid is formed from oleic acid (q.v.) by the
action of iodin under pressure at 270°-2805 (518°-536° P.).
Pure stearic acid is a colorless, odorless, tasteless solid ; fusible
at 70° (158° F.); unctuous to the touch; insoluble in H2O; very
soluble in alcohol and in ether. The alkaline stearates are solu-
ble in H2O ; those of Ca, Ba, and Pb are insoluble.
Stearic and palmitic acids exist free in the intestine during the
digestion of fats, a portion of which is decomposed by the action
of the pancreatic secretion into fatty acids and glycerol. The
same decomposition also occurs in the presence of putrefying
albuminoid substances.
Arachic acid— Ci9H39lCOOH— 312 — exists as a glycerid in peanut-
oil (now largely used as a substitute for olive-oil), in oil of ben,
and in small quantity in butter. It is a crystalline solid, which
.melts at 75° (167° P.).
262 MANUAL OF CHEMISTRY.
ANHYDRIDS, CHLORIDS, ETC., CORRESPONDING TO
THE MONOBASIC ACIDS.
The anhydrids of the acid radicals bear the same relation to
the acids themselves that the simple ethers bear to the alcohols :
CH3-COOH CH3-CH2OH
Acetic acid. Ethylic alcohol.
CH3-CO\n CH3CH2\n
CH3-CO/U CH3CH2/U
Acetic anhydrid. Ethylic ether.
Acetic anhydrid— (CH 3 CO) 2O— is produced by the action of car-
bon disulfld upon lead acetate :
= 2 0 + CO, + 2 PbS.
The acid radicals also unite with the halogens to form com-
pounds corresponding to the chlorids, bromids, and iodids of the
alcoholic radicals.
Acetyl chlorid — CH3COC1— 78.5— obtained by the action of phos-
phorus trichlorid upon glacial acetic acid, is used in synthetic
investigations for the introduction of the group CH3CO into
other molecules.
Acetyl-acetic acid — CH3— CO — CH3— COOH is produced as
the ethylic ether of a sodium derivative by the action of metallic
Na upon ethyl acetate. The acid itself may be obtained as a Arery
unstable, acid liquid, soluble in water in all proportions. It is
the type of a great number of similarly constituted acids, contain-
ing other radicals and their derivatives, and is extensively used
in the preparation of synthetic products of great variety, as, for
instance, in the manufacture of antipyrin (q. v.).
COMPOUND ETHERS.
As the alcohols resemble the mineral bases, and the organic acids
resemble those of mineral origin, so the compound ethers are
similar in constitution to the salts, being formed by the double
decomposition of an alcohol with an acid, mineral or organic, a»
a salt is formed by double decom position of an acid and a mineral
base, the radical playing the part of an a,tom of corresponding;
valence :
Potassium hydroxid. Nitric acid. Water. Potassium nitrate.
(NO,) ) H > (NO,)
H >
H H f H \
Ethyl hydroxid Nitric acid. Water. Ethyl nitrate
(alcohol). (nitric ether;.
COMPOUND ETHERS. 263
Therefore the compound ethers are acids whose hydrogen has
been partially or completely displaced by a hydrocarbon radical
or radicals.
Some of the compouod ethers still contain a portion of the acid
hydrogen which, being replaceable by another radical or by a
metal, communicates acid qualities to the substance, which is at
the same time a compound ether and a true acid.
The compound ethers are produced :
1.) By the action of the acid upon the alcohol :
H,SO4 + CaH5,OH = 03H.,HSO4 + H2O
Sulfuric Ethyl Ethylsulfuric Water,
acid. hydroxid. acid.
HaSO4 + 2C2H5,OH = (C2H5),,S04 + 2HaO
Sulfuric acid. Ethyl hydroxid. Ethyl sulf ate. Water.
2.) By the action of the corresponding haloid ethers upon the
silver salt of the acid :
AgNO3 + C2HJ = Agl + C2H5,NO3
Silver nitrate. Ethyl iodid. Silver iodid. Ethyl nitrate.
3.) By the action of the chlorids of the acid radicals upon the
sodium derivatives of the alcohols, and in some instances upon
the alcohols themselves :
C2H3O2C1 + C2H6Na = NaCl + (C^H^CsHsO,,.
Acetyl chlorid. Sodium ethylate. Sodium chlorid. Ethyl acetate.
All compound ethers are decomposed into acid and alcohol by
the action of water at high temperatures, or of caustic potash or
soda:
(CiHs)NOi + KHO = KNO, + C,H.HO
Ethyl Potassium Potassium Ethyl
nitrate. hydroxid. nitrate. hydroxid.
As this decomposition is analogous to that utilized in the man-
ufacture of soap (q. v.), it is known as saponiflcation, and when-
ever an ether is so decomposed it is said to be saponified.
Ethyl nitrate— Nitric ether — nja t^ — 91- — A colorless liquid;
has a sweet taste and bitter after-taste; sp. gr. 1.112 at 17°
(62°. 6 F.) ; boils at 85° (185° F.); gives off explosive vapors. Pre-
pared by distilling a mixture of HNO3 and C2H6O in the pres-
ence of urea.
Ethyl nitrite — Nitrous ether — Q jj [ O— 75— is best prepared by
directing the nitrous fumes, produced by the action of starch on
HNO3 under the influence of heat, into alcohol, contained in a
retort connected with a well-cooled receiver.
It is a yellowish liquid ; has an apple-like odor, and a sharp,
sweetish taste; sp. gr. 0.947; boils at 183 (64°. 4 F.); gives off in-
264 MANUAL OP CHEMISTRY.
flammable vapor; very sparingly soluble in H2O; readily soluble
in alcohol and ether.
It is decomposed by warm H20, by alkalies, by H2SO4, H2S, and
the alkaline sulflds, and is liable to spontaneous decomposition
especially in the presence of H2O. Its vapor produces anaesthe-
sia, and it exists in alcoholic solution in Spiritus aetheris nitrosi
(U. S., Br.), which also contains aldehyde, which latter substance
by its oxidation frequently renders the spirit acid and unfit for
use. (See Nitro-paraffins.)
Ethyl sulfates.— These are two in number: (C2H5)HSO4 =
Ethyl-sulfuric or sulfovinic acid and (C2H5)2SO4 — Ethyl sul-
fate — Sulfuric ether.
S02)
Ethyl-sulfuric acid— (C2H5) f 02— 126— is formed as an inter-
H i
mediate product in the manufacture of ethylic ether (q. v.). It is
a colorless, syrupy, highly acid liquid; sp. gr. 1.316; soluble in
water and alcohol in all proportions, insoluble in ether.
It decomposes slowly at ordinary temperatures, more rapidly
when heated. When heated alone or with alcohol, it yields ether
and H2SO4. When heated with H2O, it yields alcohol and H2SO4.
It forms crystalline salts, known as sulfovinates, one of which,
sodium sulfovinate (C2H5)NaSO4, has been used in medicine.
It is a white, deliquescent solid; soluble in H2O.
Ethyl sulfate— (C2H5)2SO4— 154— the true sulfuric ether, is ob-
tained by passing vapor of SO3 into pure ethylic ether, thoroughly
cooled.
It is a colorless, oily liquid ; has a sharp, burning taste, and the
odor of peppermint; sp. gr. 1.120; it cannot be distilled without
decomposition; in contact with H2O it is decomposed with for-
mation of sulfovinic acid.
By the action of an excess of H2SO4 upon alcohol; by the dry
distillation of the sulfovinates ; and in the last stages of manufac-
ture of ether, a yellowish, oily liquid, having a penetrating odor,
and a sharp, bitter taste, is formed. This is sweet or heavy oil
of wine, and its ethereal solution is Oleum eethereum (U. S.). It
seems to be a mixture of ethyl sulfate with hydrocarbons of the
series CnH2n. On contact with H2O or an alkaline solution, it is
decomposed, sulfovinic acid is formed, and there separates a col-
orless oil, of sp. gr. 0.917, boiling at 280° (536° P.), which is light
oil of wine. This oil is polymeric with ethylene, and is probably
cetine, Ci6H32. It is sometimes called etherin or etherol.
Sulfurous and Hyposulfurous Ethers. — These compounds have
recently assumed medical interest from their relationship to
mercaptan, sulfonal and a number of aromatic derivatives used as
medicines.
There exist two isomeric sulfurous acids (see p. 97), both of
COMPOUND ETHERS. 265
which yield neutral ethers, but only one of which, tbe unsym-
metrical, Q^ S /QH, forms acid ethers. These acid ethers are
known as sulfonic acids. (See Aromatic swlfonic acids, mercap-
tan, sulfones, sulfonal.)
Diethyl sulfite— (C2H6)2SO3— is produced* by the action of thionyl
chlorid on absolute alcohol : SOC12 + 2CaH5HO = SO3 (C2H6) +
2HC1. It is a colorless liquid, having a powerful odor: sp. gr.
1.085, boils at 161° (321°.8 F.). H2O decomposes it into alcohol
a,nd sulfurous acid.
Ethyl sulfonic acid— SO2/Q^5— is formed by the action of
«thyl iodid on potassium sulfite: C2H6I+SO3K2=:C2H5, SO2OK
+KI. It forms salts and ethers.
Sulfinic acids — are the acid ethers of hyposulfurous acid
x Tl
SO^Qjj, and are analogous to the sulfonic acids.
C TT O)
Ethyl acetate— Acetic ether — JEther aceticus (TJ. S.) — Q pT [• O —
€8 — is obtained by distilling a mixture of sodium acetate, alco-
hol and H2SO4 ; or by passing carbon dioxid through an alcoholic
solution of potassium acetate.
It is a colorless liquid, has an agreeable, ethereal odor ; boils
at 74° (165°.2 F.) ; sp. gr. 0.89 at 15° (59° F.) ; soluble in 6 pts. wa-
ter, and in all proportions in methyl and ethyl alcohols and in
ether ; a good solvent of essences, resins, cantharidin, morphin,
gun-cotton, and in general, of substances soluble in ether ; burns
with a yellowish- white flame. Chlorin acts energetically upon
it, producing products of substitution, varying according to the
intensity of the light from C4H6Cl2Oa to C4CleOa.
Amyl nitrate — ^ jj i O — 133 — obtained by distilling a mix-
ture of HNO3 and amylic alcohol in the presence of a small
quantity of urea. It is a colorless, oily liquid ; sp. gr. 0.994 at 10°
{50° F.) ; boils at 148° (298°. 4 F.) with partial decomposition.
Amyl nitrite — Amyl nitris (IT. S.) — ^ — 117 — prepared
by directing the nitrous fumes, evolved by the action of HNOs
upon starch, into amyl alcohol contained in a retort heated over
a water-bath ; purifying the distillate by washing with an alka-
line solution and rectifying.
It is a slightly yellowish liquid; sp. gr. 0.877; boils at 95°
(203° F.); its vapor explodes when heated to 260° (500° F.) ; insolu-
ble in water ; soluble in alcohol in all proportions ; vapor orange-
colored. Alcoholic solution of potash decomposes it slowly, with
formation of potassium nitrite and oxids of ethyl and amyl.
When dropped upon fused potash, it ignites and yields potas-
sium valerianate.
266 MANUAL OP CHEMISTRY.
Amyl nitrite is frequently impure ; its boiling-point should not
vary more than two or three degrees from that given above.
Cetyl palmitate — Cetin— Ck6^°[o— 480— is the chief con-
stituent of spermaceti =cetaceum(U. S., Br.), which, besides cetin,
contains ethers of palmitic, stearic, myristic, and laurostearic
acids; and of the alcohols: lethal, Ci2H20O ; methal, Ci4H3oO;
ethal, C,, H., 4O ; and stethal, C, H -O.
Q TT Q V
Melissyl palmitate— Melissin — rf^r [ O— 676. — Beeswax con-
OaoJtloi )
sists mainly of two substances ; cerotic acid, C27H53O,OH, which
is soluble in boiling alcohol, and melissyl palmitate, insoluble in
that liquid, united with minute quantities of substances which
communicate to the wax its color and odor. Yellow wax melts
at 62°-63° (143°.6-145°.4 F.) ; after bleaching, which is brought
about by exposure to light, air, and moisture, it does not fuse
below 66° (150°. 8 F.). China wax, a white substance resembling
spermaceti, is a vegetable product, consisting chiefly of ceryl
cerotate, CaiHssOaCCaiHss).
ALDEHYDES.
SERIES CnH2nO.
It will be remembered that the monobasic acias are obtained
from the alcohols by oxidation of the radical :
(C2H5) ) n (C2HsO)' ) 0
Hf° HfU
Ethyl alcohol. Acetic acid.
These oxidized radicals are capable of forming compounds similar
in constitution to those of the non-oxidized radicals. There are
chlorids, broniids, and iodids ; their hydrates are the acids,
' 2 3VjK O = acetic acid ; their oxids are known as anhydrids,
(C HO) \'®~ acetic anhydrid; and their hydrids are the aldehydes
3 IT [ = acetic aldehyde. The name aldehyde is a corruption
of alcohol dehydrogenatum, from the method of their formation,
by the removal of hydrogen from alcohol.
The aldehydes all contain the group of atoms (COH)', and theii
constitution may be thus graphically indicated :
COH
COH |
I CHa
CH3 I
CH3
Acetic aldehyde. Propionic aldehyde.
ALDEHYDES, 267
They are capable, by fixing H2, of regenerating the alcohol ^
and, by fixing O, of forming the corresponding acid :
COH CH2OH CO,OH
CH, CH3 CH3
Acetic aldehyde. Ethylic alcohol. Acetic acid.
The aldehydes combine with the acid sulfites of the alkali met-
als to form crystalline compounds. They com bine with ammonia
to form aldehyde-ammonias: CH3CHO+NH3 = CH3C
They are converted by Cl and Bf into the chlorids or bromids of
the acid radicals.
The aldehydes are formed -:
1.) By the limited oxidation of the corresponding alcohol :
CH3CH2OH+O = CH3COH+H2O.
2.) By the action of nascent H upon the chlorids or anhydrids
of the corresponding acids : CH3COCl+Ha = CH3,COH+HC1 or
(CH3CO)2O+2H2 = 2CH3COH+H3O.
3.) By the distillation of a mixture of calcium formiate and the
Ca salt of the corresponding acid : (HCOO)2Ca+(CH3COO)2Ca =
2CO3Ca+2CH3,COH.
Formaldehyde — Formyl hydrid — H,COH — 30 — is formed when
air charged with vapor of methylic alcohol is passed over an in-
candescent platinum wire. It is also produced by the dry distil-
lation of calcium formiate : (HCOO)2Ca = CaCO3+HCOH. It has
not been obtained pure, but is known in solution in methyl al-
cohol.
Corresponding to this aldehyde is a product of condensation.
Paraformaldehyde, or Trioxymethane (H,COH)3, which is ob-
tained, as a crystalline substance, fusing at 152° (305°. 6 F.), in-
soluble in H2O, alcohol and ether, by distilling glycollic acid with
H2SO4, or by the action of silver oxalate or oxid on methene iodid :
3CH J,+3COOAga = (HCOH)3+6AgI+3CO.
Acetaldehyde— Acetic aldehyde— Acetyl hydrid— CH3COH — 44
— is formed in all reactions in which alcohol is deprived of H
without introduction of O. It is prepared by distilling from a
capacious retort, connected with a well-cooled condenser, a mix-
ture of H2SO4, 6 pts. ; H2O, 4 pts. ; alcohol, 4 pts. ; and powdered
manganese dioxid, 6 pts. The product is redistilled from calcium
chlorid below 50° (122° F.). The second distillate is mixed with
two volumes of ether, cooled by a freezing mixture, and saturated
with dry NH3 ; there separate crystals of ammonium acetylid,
C2H3O, NH4, which are washed with ether, dried, and decom-
posed in a distilling apparatus, over the water-bath, with the
proper quantity of dilute H2SO4 ; the distillate is finally dried
over calcium chlorid and rectified below 35° (95° F.).
268 MANUAL OF CHEMISTRY.
Aldehyde is a colorless, mobile liquid ; has a strong, suffocating
odor; sp. gr. 0.790 at 18° (64°.4 F.) ; boils at 21° (69°. 8 F.) ; soluble
in all proportions in water, alcohol and ether. If perfectly pure,
it may be kept unchanged ; but if an excess of acid have been
used in its preparation, it gradually decomposes. When heated
to 100° (212° F.), it is decomposed into water and crotonic alde-
hyde.
In the presence of nascent H, aldehyde takes up H2 and re-
generates alcohol. Cl converts it into acetyl chlorid, CaEUO, Cl,
and other products. Oxidizing agents quickly convert it into
acetic acid. At the ordinary temperature HaSCh ; HC1 ; and SOa
convert it into a solid substance called paraldehyde, C,H; ,0: (?),
which fuses at 10°. 5 (50°. 9 F.) ; boils at 124° (255°. 2 F.), and is more
soluble in cold than in warm water. When heated with potas-
sium hydroxid, aldehyde becomes brown, a brown resin separates,
and the solution contains potassium formiate and acetate. If a
watery solution of aldehyde be treated, first with NHS and then
with H2S, a solid, crystalline base, thialdin, CeHiaNSa, separates.
It also forms crystalline compounds with the alkaline bisulfites.
It decomposes solutions of silver nitrate, separating the silver in
the metallic form, and under conditions which cause it to adhere
strongly to glass.
Vapor of aldehyde, when inhaled in a concentrated form, pro-
duces asphyxia, even in comparatively small quantity ; when
diluted with air it is said to act as an anaesthetic. When taken
internally it causes sudden and deep intoxication, and it is to its
presence that the first products of the distillation of spirits of
inferior quality owe in a great measure their rapid, deleterious
action.
Trichloraldehyde — Trichloraeetyl hydrid— Chloral— CCLCOH
— 147.5 — is one of the final products of the action of Cl upon
alcohol, and is obtained by passing dry Cl through absolute
-alcohol to saturation ; applying heat toward the end of the re-
action, which requires several hours for its completion. The
liquid separates into two layers ; the lower is removed and shaken
with an equal volume of concentrated H2SO4 and again allowed
to separate into two layers ; the upper is decanted ; again mixed
with HaSO-i, from which it is distilled ; the distillate is treated
with quicklime, from which it is again distilled, that portion
which passes over between 94° and 99° (201°. 2-210°. 2 F.) being col-
lected. It sometimes happens that chloral in contact with HaSCK
is converted into a modification, insoluble in H2O, known as
metachloral ; when this occurs it is washed with H2O, dried and
heated to 180° (356° F.), when it is converted into the soluble
variety, which distils over.
Chloral is a colorless liquid, unctuous to the touch ; has a pene-
ALDEHYDES. 2691
trating odor and an acrid, caustic taste ; sp. gr. 1.502 at 18° (64°. 4
F.); boils at 94°. 4 (201°. 9 F.) ; very soluble in water, alcohol, and
ether ; dissolves Cl, Br, I, S and P. Its vapor is highly irritat-
ing. It distils without alteration.
Although chloral has not been obtained by the direct substitu-
tion of Cl for H in aldehyde, its reactions show it to be an alde-
hyde. It forms crystalline compounds with the bisultites; it
reduces solutions of silver nitrate in the presence of NH3 ; NH3
and H2S form with it a compound similar to thialdin; with
nascent H it regenerates aldehyde ; oxidizing agents convert it
into trichloracetic acid. Alkaline solutions decompose it with
formation of chloroform and a formiate.
With a small quantity of H2O chloral forms a solid, crystalline
hydrate, heat being at the same time liberated. This hydrate
has the composition CaHClsC^HaO, and its constitution, as well
as that of chloral itself, is indicated by the formulae :
CH3 CC1, CC1,
CHO CHO CHCOH),
Aldehyde. Trichloraldehyde Chloral hydrate,
(chloral).
Chloral hydrate — Chloral (U. S.) — is a white, crystalline solid ;
fuses at 57° (134°. 6 F.) ; boils at 98° (208°.4 F.), at which tempera-
ture it suffers partial decomposition into chloral and H2O ; vola-
tilizes slowly at ordinary temperatures ; is very soluble in H2O ;
neutral in reaction ; has an ethereal odor, and a sharp, pungent
taste. Concentrated H2SO4 decomposes it with formation of
chloral and chloralid. HNO3 converts it into trichloracetic acid.
When pure it gives no precipitate with silver nitrate solution,
and is not browned by contact with concentrated HaSCh. Under
the influence of sunlight it is violently decomposed by potassium
chlorate. Chlorin, phosgene gas, carbon dioxid, and chloroform
are given off, and after a time, crystals of potassium trichlor-
acetate separate from the cooled mixture.
Chloral also combines with alcohol, with elevation of tem-
perature, to form a solid, crystalline body — chloral alcoholate :
CCls~CH\0-C2H5.
Action of Chloral Hydrate upon the Economy. — Although it
was the ready decomposition of chloral into a formiate and
chloroform which first suggested its use as a hypnotic to Lie-
breich, and although this decomposition was at one time believed
to occur in the body under the influence of the alkaline reaction
of the blood, more recent investigations have shown that the-
formation of chloroform from chloral in the blood is, to say the
least, highly improbable, and the chloral has, in common with
:270 MANUAL OF CHEMISTEY.
many other chlorinated derivatives of this series, the property of
acting directly upon the nerve-centres.
Neither the urine nor the expired air contains chloroform when
chloral is taken internally ; when taken in large doses, chloral
appears in the urine. The fact that the action of chloral is pro-
longed for a longer period than that of the other chlorinated
derivatives of the fatty series is probably due, in a great measure,
to its less volatility and less rapid elimination.
When taken in overdose, chloral acts as a poison, and its use
as such is rapidly increasing as acquaintance with its powers
becomes more widely disseminated.
No chemical antidote is known. The treatment should be
directed to the removal of any chloral remaining in the stomach
by the stomach-pump, and to the maintenance or restoration of
respiration.
In fatal cases of poisoning by chloral that substance may be
-detected in the blood, urine, and contents of the stomach by the
following method : the liquid is rendered strongly alkaline with
potassium hydroxid ; placed in a flask, which is warmed to 50°-
60° (122°-140° F.), and through which a slow current of air, heated
to the same temperature, is made to pass ; the air, after bubbling
through the liquid, is tested for chloroform by the methods
described on p. 234. If affirmative results are obtained in this
testing, it remains to determine whether the chloroform detected
existed in the fluid tested in its own form, or resulted from the
decomposition of chloral ; to this end a fresh portion of the sus-
pected liquid is rendered acid and tested as before. A negative
result is obtained in the second testing when chloral is present.
Bromal — CBrs,COH — 281. — A colorless, oily, pungent liquid ; sp.
gr. 3.34 ; boils at 172° (341°.6 F.) ; neutral ; soluble in H2O, alcohol,
and ether. It combines with H2O to form bromal hydrate,
CBr3,CH(OH)2 ; large transparent crystals ; soluble in HaO ; de-
composed by alkalies into bromoforni and a formiate. Produces
anaesthesia without sleep ; very poisonous.
Thioaldehydes. — By the action of H2S on aldehyde in the pres-
ence of HC1 two products are obtained, having the composition
(CH3CSH)3, known as a and /3 Trithioaldehyde. The former is in
large prismatic crystals, fusible at 101° (213°.8 F.), the latter in
long needles, fusible at 125°-126° (257°-258°.8 F.).
Propaldehyde — Propionic aldehyde — CH3,CH2,COH — 58 — ob-
tained by the general reaction from propylic alcohol, is a colorless
liquid, resembling acetic aldehyde ; boils at 40° (120°. 2 F.).
Normal Butaldehyde— Butyric aldehyde— CH3,CH2,CH2,COH—
72 — is an oily liquid, boiling at 73° (163\4 F.). Its trichlorinat-
ed derivative, Trichlorhutaldehyde, or Butyric chloral, CC1S,
CHj,COH — is the substance whose hydrate is used as a medicine
ACETALS, KETONES OK ACETONES. 271
under the name croton chloral hydrate. It is a colorless liquid,
boiling at 160" (320° P.), obtained by the action of Cl on acet-
aldehyde.
ACETALS.
These substances may be considered as derived from the alde-
hydes by the substitution of two groups OR (R = an alcoholic
radical CnH3n + i) for the O of an aldehyde.
/ OC!!
Methylal— Formal— CH— 76— is formed by distilling a
mixture of MnO2, methyl alcohol, H2SO4 and H2O. It is a color-
less liquid ; sp. gr. 0.8551 at 17° (62°.6 P.), boiling at 42° (107°.6 F.) ;
soluble in H2O, alcohol, and oils. It has a burning, aromatic
taste and an odor resembling those of chloroform and acetic acid.
It has been used as a hypnotic.
Acetal— CHs/0)0,^— 104— a colorless liquid, boils at 104°
(219°. 2 P.), sp. gr. 0.8314 ; sparingly soluble in H2O, readily in al-
cohol ; obtained by heating a mixture of aldehyde, alcohol and
glacial acetic acid, or in the same manner as formal, using ethylic
in place of methylic alcohol.
KETONES OB ACETONES.
SERIES CnH2nO.
These substances all contain the group of atoms (CO)", and
their constitution may be represented graphically thus :
CH3
CHS |
CO
CO
CH,
CH,
CH3
Dimethyl ketone Methyl-ethyl ketone.
(acetone).
the first being a symmetrical ketone and the latter an unsym-
metrical. The ketories are isomeric with the aldehydes, from
which they are distinguished : 1st, by the action of H, which
produces a primary alcohol with an aldehyde, and a secondary
alcohol with a ketone :
COH CHaOH
OHj -f- Ha = OHa
CH3 CH3
Propionic aldehyde. Propyl alcohol.
272 MANUAL OF CHEMISTEY.
CH3 CH3
CO + H, CH,OH
CH3 CH,
Acetone. Isopropyl alcohol.
2d, by the action of O, which unites directly with an aldehyde to»
produce the corresponding acid, while it causes the disruption of
the molecule of the ketone, with formation of two acids :
COH CO,OH
CH, + O CH2
Propionic aldehyde. Propionic acid.
CH3
CO,OH
X> + 03 = I +
CH
CO,OH CO,OH
Cf
!•
H
H3
:one. Formic acid. Acetic acid.
Dimethyl ketone — Acetone — Acetylmethylid — Pyroacetic ether
/CH
or spirit — CO' — 58 — is formed as one of the products of the
dry distillation of the acetates ; by the decomposition of the
vapor of acetic acid at a red heat ; by the dry distillation of
sugar, tartaric acid, etc. ; and in a number of other reactions. It
is obtained by distilling dry calcium acetate in an earthenware
retort at a dull red heat ; the distillate, collected in a well-cooled
receiver, is freed from H2O by digestion with fused calcium chlo-
rid, and rectified ; those portions being collected which pass over
at 60° (140° F.). It is also formed in large quantity in the prepa-
ration of anilin.
It is a limpid, colorless liquid; sp. gr. 0.7921 at 18° (64°. 4 F.) ;
boils at 56° (132°.8 F.) ; soluble in H2O, alcohol, and ether ; has a
peculiar, ethereal odor, and a burning taste ; is a good solvent
of resins, fats, camphor, gun-cotton ; readily inflammable. It
forms crystalline compounds with the alkaline bisulfites. Cl and
Br, in the presence of alkalies, convert it into chloroform or
bromoform ; Cl alone produces with acetone a number of chlo-
rinated products of substitution. Certain oxidizing agents
transform it into a mixture of formic and acetic acids ; others
into oxalic acid.
Acetone has been found to exist in the blood and urine in cer-
tain pathological conditions, and notably in diabetes ; the pecu-
liar odor exhaled by diabetics is produced by this substance,
NITROPAKAFFINS. 273
•which has also been considered as being the cause of the respira-
tory derangements and coma which frequently occur in the last
stages of the disease.
That acetone exists in the blood in such cases is certain ; it is
not certain, however, -that its presence produces the condition
designated as acetoneemia. It can hardly be doubted that the
acetone thus existing in the blood is indirectly formed from dia-
betic sugar, and it is probable also that a complex acid, known
as ethyldiacetic, C6H9O3H, is formed as an intermediate product.
See aromatic ketones.
NITBOPABAFFINS.
There exist two distinct isomeric series having the composition-
CnHan + iNOii. One contains the true nitrous ethers (see com-
pound ethers), formed by the substitution of the hydrocarbon
radical for the hydrogen of nitrous acid, and having the consti-
tution O = N — O, CH3 = methyl nitrite. The other contains
substances in which the hydrocarbon radical is directly attached
to the N atom, which may be considered as paraffins in which
the group (NO2) has taken the place of an atom of hydrogen, and
°\
have the constitution | ,N — CH3 = nitromethane.
0/
These bodies are formed by the action of the inonoiodie deriva-
tives of the paraffins upon silver nitrite :
CHJ + AgNO2 = Agl + O2NCHS
Methyl iodid. Nitromethane.
They are converted by nascent hydrogen into amidoparaffins
or monamins :
O,NCH3 + 3H2 = HsNCHa + 2H2O
Nitromethane. Methylamin.
They are decomposed by H2SO4 or HC1 into hydroxylammo-
nium salts, and acids CnHanOa, containing all the C :
0,NC2H5 + HaO CH8,COO(NH«0)
Nitroethane. flydroxylammonium acetate.
Nitrous acid converts the primary nitroparaffins into powerful
acids, called nitrolic acids, having the general formula : CnHsn + i
But the same agent converts the secondary ni-
troparaffins into pseudonitrols, having the general formula :
18
274 MANUAL OF CHEMISTRY.
MONAMINS— AMIDOPAEAFFINS.
The monamins are substances which may be considered as be-
ing derived from one molecule of NH3 by the substitution of one,
two, or three alcoholic radicals for one, two, or three H atoms.
They are designated as primary, secondary, and tertiary, accord-
ing as they contain one, two, or three alcoholic radicals :
H H H CHa— CH3
N— H N— CHa— CH3 N— CHa— CH3 N— CH,— CH3
HTJ OTJ f~<TJ r^TJ/^HT
OXla — OJ13 V_>xla — L/U3
NH3 (CaHe)HaN (CaH6)aHN (CSH6)3N
Ammonia. Ethylamin Diethylainin Triethylamin
(primary). (secondary). (tertiary).
They are also known as compound ammonias, and resemble
ammonia in their chemical properties ; uniting with acids, with-
out elimination of H2O, to form salts resembling those of ammo-
nium. They also combine with HaO to form quaternary ammo-
nium hydroxids, similar in constitution to ammonium hydroxid.
The alkalinity and solubility in H2O of the primary monamins
are greater than those of the secondary, and those of the secon-
dary greater than those of the tertiary. Their chlorids form
sparingly soluble compounds with platinic chlorid. ,
The primary monamins are formed by the action of potassium
hydroxid upon the corresponding cyanic ether:
CNOCaH5 + 2KHO = NH2CaH» + CO3Ka
Ethyl cyanate. Potash. Ethylamin. Potassium
carbonate.
or by heating together an alcoholic solution of ammonia and an
ether :
C2H5I + NH3 = HI + NH3CaHB
Ethyl Ammonia. Hydriodic Ethylamin.
iodid. acid.
or by the action of nascent H upon the cyanids of the alcoholic
radicals :
/"^"VTT^TT i OHJ "MTT C* T-T
i^JM Uxls + <i±la 1> Jiav^riB
Methyl cyanid. Hydrogen. Ethylamin.
The secondary monamins are formed by the action of the iodids
or bromids of the alcoholic radicals upon the primary monamins :
TSJTJ t~i U i Pi TT T "WTJ/T^ 11 \ j^ T-TT
li-naV^ario -p OarlsL — .li Jn^v^a-ri aja
Ethylamin. Ethyl iodid. Diethylamin.
The tertiary monamins are produced by the distillation of the
MOXAMINS — AMIDOPARAFFINS. 275
liydroxids or iodids of the quaternary ammoniums, or by the
action of the iodids of the alcoholic radicals upon the secondary
inonamins.
It is obvious from the above-described properties of these sub-
stances that they are true alkaloids, among which also belong the
•diamins and triamins.
CH )
Methylamin — Methylia — ^|3 - N — 31 — is a colorless gas ; has a
fishy, arumoniacal odor; inflammable ; is the most soluble gas
known, one volume of HaO dissolving 1,154 volumes of methylia
at 12°.5 (54°.5 F.).
The aqueous solution possesses the odor of the gas, and is
liighly caustic and alkaline. It neutralizes the acids with forma-
tion of rnethylairmioniuin salts (e.g., CH3H3NNO3 = niethylam-
monium nitrate), which are for the most part crystallizable and
very soluble in H2O. Its chloraurate crystallizes in beautiful
golden-yellow needles, soluble in water, alcohol, and ether. Its
•chloroplatinate crystallizes in golden-yellow scales, soluble in
water, insoluble in alcohol.
See trimethylamin, below.
Dimethylamin — Dimeihylia — ^ Y| '- N — 45 — is a liquid below
S? (46°. 4 F.) ; has an ammoniacal odor, and is quite soluble in H2O.
It constitutes about 50 per cent, of the commercial trimethyl-
amin, which also contains 5 to 10 per cent, of trimethylamin,
the remainder being a mixture of monomethylamin, isobutyl-
ninin. and propylarnin. Its chloroplatinate forms long needles.
See trimethylamin, below.
Trimethylamin — Trimethylia — (CHs^N— 59 — is formed by the
action of methyl iodid upon !NH3, and as a product of decompo-
sition of many organic substances, it being one of the products
of the action of potash on many vegetable substances, alkaloids,
«tc. It also occurs naturally in cod liver oil, ergot, chenopo-
diuru, yeast, guano, human urine, the blood of the calf, and
many flowers.
It is an oily liquid, having a disagreeable odor of fish; boils at
8° (48°. 2 F.) ; alkaline ; soluble in H2O, alcohol, and ether ; in-
flammable. It combines with acids to form salts of trimethyl-
amuionium, which are crystallizable.
Trimethylamin has long been known to exist in the pickle in
which hei'rings have been preserved. More recently it has been
found to be an important product of putrefactive changes in fish,
starch-paste, brain-tissue, muscular tissue, and other albuminoid
substances, being accompanied by lesser quantities of mono-
methylamin, dimethylaiuin, ethylamin, and diethylainin, as well
as by other peculiar alkaloidal bodies. It has also been observed
accompanying more active alkaloids in blood-serum, etc., which
276 MANUAL OF CHEMISTRY.
have served for the culture of various bacilli. See cholin and.
neuriri, below, and ptomains.
Its chloroplatinate crystallizes in octahedra, insoluble in alco-
hol.
The commercial trimethylamin, obtained by the dry distilla-
tion of distillery- waste, contains but T% per cent, of the substance
whose name it bears. (See dimethylamin, above.) It has fre-
quently been mistaken by writers upon niateria inedica for its
(C* T~T ^ )
isomere propylamin, ^ 3 u f N, which differs from it in odor, and
in boiling at 50° (122° F.). Its chlorid, under the names chlorid
of propylamia, of secalia, of secalin, has been used in the treat-
ment of gout and of rheumatism.
Tetramethyl Ammonium Hydroxid — (CHs^NOH — 91. — This
substance, whose constitution is similar to that of ammonium
hydroxid, is obtained by decomposing the corresponding iodid
(CHs^NI, formed by the action of methyl iodid upon trimethyl-
amin. It is a crystalline solid ; deliquescent ; very soluble in
H2O ; caustic ; not volatile without decomposition. It attracts-
carbon dioxid from the air, and combines with acids to form crys-
tallizable salts.
The iodid is said to exert an action upon the economy similar
to that of curare.
Cholin — Trimethyloxeihylammoniurrv hydrate —
(G~B. } )
CH CH —OH) -NjO^^CsH^NOa — 121— is a quaternary monam-
monium hydroxid, containing three methyl groups and one ethy-
lene hydroxid (oxethyl) group. It occurs in hops, in fungi, in
certain seeds, in the human placenta, in bile and in the yolks of
eggs. It is a constituent of an important class of substances, the
lecithins (q. v.).
It is produced during the first twenty-four to forty-eight hours
of putrefaction of animal tissues, from the decomposition of the
lecithins, and diminishes from the third day, when other ptomains
(neuridin, putrescin, cadaverin) increase in amount. It has been
obtained synthetically by the action of trimethylamin upon ethy-
lene oxid, or upon ethylene chlorhydrin. When heated, it splits
up into glycol and trimethylamin. Nitric acid converts it into
muscarin.
It appears as a thick syrup, soluble in H2O and in alcohol, and
strongly alkaline in reaction. Even in dilute aqueous solution it
prevents the coagulation of albumin and redissolves coagulated
albumin and fibrin. It is a. strong base ; attracts carbon dioxid
from the air ; forms with HC1 a salt, soluble in alcohol, which
crystallizes in plates and needles, very much resembling in ap-
pearance those of cholesterin. Its chloroplatinate is purified with
difficulty ; its chloraurate readily. Solutions of its chlorid differ
MONAMINS — AMIDOPARAFFINS. 27T
in their behavior with alkaloidal reagents from those of neurin
in forming no precipitate withtannic acid, and in forming a volu-
minous white precipitate with phosphomolybdic acid, which
becomes crystalline on -standing.
It is poisonous only in large doses, in which respect it differs
from neurin (see below).
Amanitin — Trimethyloxethylideneammonium hydroxid —
(CHa— CHOH) | N'OH - CJJjsNOs— 121— is an isomere of cholin
existing along with muscarin (see below) in Agaricus muscarin^.
JBy oxidation with HNO3 it yields muscarin.
Muscarin— (S^k . j N,OH = C.H..JJO,— is a substituted tetra-
(u3rt5U2; \
methylammonium hydroxid related to cholin. neurin and amani-
tin, from which it may be obtained by oxidation.
It occurs in nature in Agaricus muscarius, and is produced
during putrefactive decomposition of albuminoid substances.
The free alkaloid occurs in very deliquescent, irregular crystals,
or, if not perfectly dry, a colorless, odorless, and tasteless, but
strongly alkaline syrup; readily soluble in all proportions in
water and in alcohol; very sparingly soluble in chloroform; in-
soluble in ether. It is a more powerful base than ammonium
hydroxid, forming an alkaline carbonate and neutral salts with
other acids. When decomposed it yields trimethylamin. Its
chloroplatinate crystallizes in octahedra. Its chlorid forms color-
less, brilliant, deliquescent needles.
When administered to animals, muscarin causes increased se-
cretion of saliva and tears ; vomiting ; evacuation of faeces, at
first solid, later liquid ; contraction of the pupils, almost to the
extent of closure ; diminution of the rapidity of the pulse ; inter-
ference with respiration and locomotion ; gradual sinking of the
Tieart's action and respiration ; and death. Atropin prevents the
action of muscarin, and diminishes its intensity when already
established.
CH ^ )
Neurin— Trimethylmnylammonium hydroxid— -\Q ^;? > NOH=
CsHiaNO — is a substance nearly related to cholin, and long con-
founded with it, supposed by Liebreich to exist in the brain.
The same body is one of the alkaloids produced by the putrefac-
tion of muscular tissues, and is endowed with poisonous quali-
ties, resembling, but less intense than, those of muscarin.
Another cadaveric alkaloid, related to neurin and produced un-
der similar conditions, is a diamin : neuridin, C3HnN2 (see p. 333).
278 MANUAL OF CHEMISTRY.
MONAMIDS.
These bodies differ from the amins in containing oxygenated, or
acid radicals, in place of alcoholic radicals. Like the amins, they
are divisible into primary, secondary, and tertiary. They are
the nitrids of the acid radicals, as the amins are the nitrids of the
alcoholic radicals.
The monamids may also be regarded as the acids in which the
OH of the group COOH has been replaced by (NH2) :
CH3 CH,
COOH CONH,
Acetic acid. Acetamid.
The primary monamids, containing radicals of the acids of the
acetic series, are formed : (1.) By the action of heat upon an am-
moniacal salt :
(C2H3oy ) 0 _ H ) 0 + (c,H,oy
Ammonium acetate. Water. Acetamid.
(2.) By the action of a compound ether upon ammonia :
(C,H,O)' '
+H t N =(C'H'0)' I N +C,H5 >
jj j Jtia ) ±i \
Ethyl acetate. Ammonia. Acetamid. Alcohol.
(3.) By the action of the chlorid of an acid radical upon dry
Acetyl chlorid. Ammonia. Ammonium Acetamid.
chlorid.
The secondary monamids of the same class are obtained : (l.>
By the action of the chlorids of acid radicals upon the primary
ainids :
(CsHaO)' ) w (C.HsO)' ) ._ (C,HsO)2 ) N H )
H2 f ^ Cl f ' H f •" ^ 01 f
Acetamid. Acetyl chlorid. Diacetamid. Hydrochloric
acid.
(2.) By the action of HC1 upon the primary monamids at high
temperatures :
(C,H,0)' I N\ H ) ._ (C2H30)2 I N NH4
-H.f ^J + Clf ' Hf ^ +C1
Acetamid. Hydrochloric Diacetamid. Ammonium
acid. chlorid.
The tertiary monamids of this series of radicals have been but
MONAMIDS. 279
imperfectly studied ; some of them have been obtained by the
action of the chlorids of acid radicals upon metallic derivatives
of the secondary amids.
The primary monamids containing radicals of the fatty acids
are solid, crystallizable, neutral in reaction, volatile without de-
composition, mostly soluble in alcohol and ether, and mostly
capable of uniting with acids to form compounds similar in con-
stitution to the ammoniacal salts. They are capable of uniting
with H2O to form the ammoniacal salt of the corresponding acid,
and with the alkaline hydroxids to form the metallic salt of the
corresponding acid and ammonia. The secondary monamids.
containing two radicals of the fatty series, are acid in reaction,
and their remaining atom of extra-radical H may be replaced by
an electro-positive atom.
Formamid— CHO.HjiN— 45 — is a colorless liquid, soluble in HaO
and in alcohol, boils at 192°-195° (377°. 6— 385° F.), suffering partial
decomposition, obtained by heating ethyl formiate with an
alcoholic solution of ammonia, or by the dry distillation of am-
monium formiate. It is decomposed by dehydrating agents, with
formation of hydrocyanic acid. Mercury formamid is obtained
in solution by gently heating freshly precipitated mercuric oxid
with HaO and formamid.
Under the name chloralamid a compound, formed by the
union of chloral and formamid, and having the constitution,
/OH
CC13CH ' NHCHO' ^as been recently used as a hypnotic. It
forms colorless, odorless, faintly bitter crystals, fusible at 115°
(239° F.), sparingly soluble in water. It is decomposed by alka-
lies, chloroform and ammonia being among the products of the
decomposition. It is not affected by acids.
Chloralimid— CCl3,C^jj — is another related derivative,
formed by the action of ammonium acetate upon chloral hydrate,
or by the action of heat upon chloral ammonia. It is a crystal-
line solid, sparingly soluble in water, readily soluble in ether and
in alcohol. When heated to 180° (356° F.) it is decomposed into
chloroform and formamid.
(C H OV )
Acetamid — v a 3iv -N — 59 — is obtained bv heating, under
•Ha )
pressure, a mixture of ethyl acetate and aqua ammonise, and
purifying by distillation. It is a solid, crystalline substance,
very soluble in H3O, alcohol, and ether ; fuses at 78° (172°. 4 F.) ;
boils at 221° (429°. 8 F.) ; has a sweetish, cooling taste, and an odor
of mice. Boiling potassium hydroxid solution decomposes it
into potassium acetate and ammonia. Phosphoric anhydrid de-
prives it of H2O, and forms with it acetonitril or methyl cyanid.
280 MANUAL OF CHEMISTKY.
AMLDO-ACIDS OF THE FATTY SERIES.
These compounds, also known as glycocols, are of mixed func-
tion, acid and basic, obtained by the substitution of the univa-
lent group (NH9)' for an atom of radical H of an acid :
CH3 CH2(NHa)
COOH COOH
Acetic acid. Amido-acetic acid (glycocol).
Some of them, and many of their derivatives, exist in animal
bodies. Corresponding to them are many isomeres belonging to
other series.
Amido-acetic acid — Glycocol — Sugar of gelatin — Glycolamic
acid — Gflycin — | — 75 — was first obtained by the action of
COOH
HaSCN upon gelatin. It is best prepared by acting upon glue
with caustic potassa, NH3 being liberated ; H2SO4 is then added,
and the crystals of potassium sulfate separated; the liquid is
evaporated, the residue dissolved in alcohol, from which solution
the glycocol is allowed to crystallize.
It may also be obtained synthetically by a method which indi-
cates its constitution — by the action of ammonia upon chloracetic
acid :
CH2C1 H\ CH2NHa TT
I + H-N =| + £,
COOH H/ COOH
Chloracetic Ammonia. Amido-acetic Hydrochloric
acid. acid. acid.
It may be obtained from ox-bile, in which it exists as the salt
of a conjugate acid ; from uric acid by the action of hydriodic
acid ; and by the union of formic aldehyde, hydrocyanic acid
/~i TT r\ T_T f^ (~\ \
and water. It is isomeric with glycolamid— H ( ^'
It has been found to exist free in animal nature only in the
muscle of the scallop, and, when taken internally, its constituents
are eliminated as urea. In combination it exists in the gelati-
noids, and with cholic acid as sodium glycocholate (g. v.) in the
bile. It is one of the products of decomposition of glycocholic
acid, hyoglycocholic acid, and hippuric acid by dilute acids and
by alkalies, and of the decomposition of tissues containing gelati-
noids.
It appears as large, colorless, transparent crystals ; has a sweet
taste ; melts at 170° (338° F.) ; decomposes at higher temperatures ;
sparingly soluble in cold H2O ; much more soluble in warm H2O ;
insoluble in absolute alcohol and in ether ; acid in reaction.
AMIDO-ACIDS OF THE FATTY SERIES. 281
It combines with acids to form crystalline compounds, which
are decomposed at the temperature of boiling, water ; hot HSS04
carbonizes it ; HNO3 converts it into glycolic acid (q. v.) ; with
HC1 it forms a chlorid ; heated under pressure with benzoic acid
it forms hippuric acid. Its acid function is more marked ; it
expels carbonic and acetic acids from calcium carbonate and
plumbic acetate. The presence of a small quantity of glycocol
prevents the precipitation of cupric hydroxid from cupric sulfate
solution by potassium hydroxid; the solution becomes dark blue,
does not yield cuprous hydroxid on boiling, and precipitates
crystalline needles of copper glycolamate on the addition of
alcohol to the cold solution. With ferric chlorid it gives an
intense red solution, whose color is discharged by acids, and re-
appears on neutralization. With phenol and sodium hypochlorite
it gives a blue color, as does ammonia. By oxidation with potas-
sium permanganate in alkaline solution it yields carbon dioxid,
oxalic, carbonic, and oxaniic acids, and water. It also forms
crystalline compounds with many salts and ethers. Methyl
amido-acetate is isomeric with sarcosin.
CH3NHa CHSNH, CH2NH(CH3)
COOH COOCHs COOH
Glycocol Methyl Sarcosin
(amido-acetic acid). amido-acetate. (methyl-glycocol).
CH2[NH(CH3)]
Methyl-glycocol — Sarcosin— | — 89— isomeric with
COOH
alanin and with lactaruid (q. v.), does not exist as such in animal
nature, but has been obtained from creatin (q. v.) by the action
of barium hydroxid:
C<H9N3Oa + HS0 = C3H7NOa + CON,H4
Creatin. Water. Sarcosin. Urea.
urea being formed at the same time, and decomposed by the
further action of the barium hydroxid into NH3 and barium car-
bonate.
Its constitution is indicated by its synthetic formation from
chloracetic acid and methylamin :
CHifCl CH3\ CHa[NH(CH,)]
I + H-N =| + PI
COOH H/ COOH
Ciiloracetic Methylamin. Sarcosin. Hydrochloric
acid. acid.
It crystallizes in colorless, transparent prisms ; very soluble in
water ; sparingly soluble in alcohol and ether. Its aqueous solu-
tion is not acid, and has a sweetish taste ; it unites with acids to
282 MANUAL OP CHEMISTRY.
form crystalline salts, but does not form metallic salts. It is ca-
pable of combining with cyanamid to form creatin.
Amido-propionic acids — Alanins — CaH7N02 — 89. — Two are
known, isomericwith sarcosin and with lactamid. One, « Alanin,
CH3— CH (NH2)— COOH, is formed by the reduction of a nitroso-
propionic acid by Sn-(-HC]. The other, (3 Alanin, CH2NH2— CH4
— COOH, whose constitution is similar to that of glycocol, is formed
either by the reduction of /? nitrosopropionic acid, or by the action
of p iodopropionic acid on ammonia. Neither exists, so far as
known at present, in nature.
Both are crystalline solids, sparingly soluble in alcohol, insolu-
ble in ether, and very soluble in water, forming neutral, sweet
solutions. They differ in the solubility of their Cu compounds,
and in that on treatment with CHaI the a compound yields tri-
niethylalanin, while the fi compound forms trirnethylamin.
The a compound acts as a cerebro-spinal depressant in frogs,
and causes spinal paralysis, diminution of temperature, and death
in pigeons in doses of one gram.
Amidobutyric acids — Butalanins — C4HaN02— and Amidovale-
rianic acids — C5HnNO2 — are only of theoretic interest at present.
The latter has been found in the tissue of the pancreas and
among the products of the action of pancreatic juice upon albu-
min. They are among the products of the decomposition of al-
bumin by caustic baryta.
CH2~C3H6-CH2(NH2)
Amidocaproic Acid — Leucin — | =C6H13NO2
COOH
— 131 — has been obtained from the normal spleen, pancreas, sali-
vary, lymphatic, thymus, and thyroid glands, lungs, and liver.
Pathologically, its quantity in the liver is much increased in
diseases of that organ, and in typhus and variola ; in the bile in
typhus ; in the blood in leucocythaemia, and in yellow atrophy
of the liver ; in the urine in yellow atrophy of the liver, in ty-
phus, and in variola ; in choleraic discharges from the intestine ;.
in pus ; in the fluids of dropsy ; and of atheromatous cysts. In
these situations it is usually accompanied by tyrosin (q. ID.).
It is formed along with tyrosin by the decomposition of nitro-
genized animal and vegetable substances, by heating with strong
alkalies or dilute acids ; and is one of the products of putrefaction.
It is best obtained by the action of hot dilute H2SO4 on bone
shavings. It has also been formed synthetically by the action of
NH3 upon bromocaproic acid, in the same way that alanin is
formed from iodopropionic acid (see above).
Leucin crystallines from alcohol in soft, pearly plates, lighter
than H2Q, and somewhat resembling cholesterin ; sometimes in
round masses composed of closely grouped needles radiating from
a centre. It is sparingly soluble in cold H2O; readily in warm:
AMIDO- ACIDS OF THE FATTY SERIES. 285
H5O ; almost insoluble in cold alcohol and ether ; soluble in boil-
ing alcohol ; it is odorless and tasteless, and its solutions are neu-
tral. It sublimes at 170° (338° F.) without decomposition ; if
suddenly heated above 180° (356° F.), it is decomposed into ainyl-
ainin and carbon dioxid.
When heated to 140° (284° F.), with hydriodic acid under press-
ure, it is decomposed into caproic acid and ammonia. Nitrous
acid converts it into leucic acid, C, H; ,0: . H2O and N. It unites
with acids to form soluble, crystalline salts. It also dissolves
readily in solutions of alkaline hydroxids, forming crystalline
compounds with the metallic elements.
The formation of leucin in the body is one of the steps of the
transformation of at least some part of the albuminoids into urea.
When leucin and tyrosin appear in the urine," that fluid is poor
in urea and usually contains biliary coloring matters ; the sub-
stitution of leucin for urea may be so extensive that the urine
contains no urea, and contains leuein in such quantity that it
crystallizes out spontaneously.
The presence of leucin and tyrosin in the urine may be detected
as follows : the freshly collected urine is treated with basic lead
acetate, filtered, the filtrate treated with HiS, filtered from the
precipitated lead sulfid, and the filtrate evaporated over the
water-bath; leucin and tyrosin crystallize; they may be separated
by extraction of the residue with "hot alcohol, which dissolves the
leucin and leaves the tyrosin. The leucin left by evaporation of
the alcoholic solution may be recognized by its crystalline form
and by the following characters : (1) a small portion is moistened
on platinum foil with HNO3, which is then cautiously evaporated;
a colorless residue remains, which, when warmed with caustic
soda solution, turns yellow or brown, and by further concentra-
tion is converted into oily drops, which do not adhere to the plat-
inum (Scherer's test) ; (2) a portion of the residue is heated in a
dry test-tube ; it melts into oily drops, and the odor of amylamin
(odor of ammonia combined with that of fusel oil) is observed ;
(3) if a boiling mixture of leucin and solution of neutral lead ace-
tate be carefully neutralized with ammonia, brilliant crystals of
a compound of leucin and lead oxid separate ; (4) leucin carefully
heated in a glass tube, open at both ends, to 170° (338° F.), sub-
limes without fusing, and condenses in flocculent shreds. If
heated beyond 180° (35(5° F.), the decomposition mentioned in (2)
occurs.
Tyrosin — CBHnNO3 — 145 — is an amido-acid belonging among
the aromatic compounds. Its constitution is represented by the
formula C8H4(gH(j))_cH(NH2)_cooH (see pp. 397_399)) but
as it always accompanies leucin in nature, it is best considered
here.
The methods of its formation are given under leucin. It
crystallizes from its watery and ammoniacal solutions in silky
284: MANUAL OF CHEMISTRY.
needles, arranged in stellate bundles ; very sparingly soluble in
cold H2O ; almost insoluble in alcohol ; more soluble in hot H2O.
When heated, it turns brown and yields an oily matter having
the odor of phenol ; when heated in small quantities to 270° (518°
F.), it is decomposed into carbon dioxid and a white solid, having
the composition C8HuNO, which sublimes. It combines with
both acids and bases.
When taken into the stomach it is not altered in the economy,
but is eliminated in the urine and faeces.
When moistened with HNO3 and carefully evaporated, a deep
yellow residue remains, which turns darker with NaHO. With
concentrated H2SO4 and slightly warmed, it dissolves with a
transient red color — the solution, filtered and neutralized with
CaCO3, gives a violet color with Fe2Cl6 solution.
Biliary Acids. — The bile of most animals contains the sodium
salts of two amido-acids of complex constitution. These acids
may be decomposed into a non-nitrogenized acid (cholic acid), and
either an amido-acid (glycocol), or an amido-sulfurous acid (tau-
rin). The following biliary acids have been described:
Glycocholic acid — Cse^aNOe — 465 — exists as its sodium salt in
the bile of the herbivora, and in much smaller proportion in that
of the carnivora ; it exists in small quantity in human blood and
urine in icterus.
It is best obtained from fresh ox-bile; this is mixed with ether
and 5 volume per cent of the bile of concentrated HC1 added.
The liquid becomes turbid and soon forms a crystalline mass
upon which floats colored ether. The ether, which contains col-
oring matters, cholesterin and fats, is decanted off. The solid
mass is agitated with H2O and washed so long as the washings re-
main green. The residue, dissolved in boiling water, yields pure
glycocholic acid. The green-wash waters contain taurocholic
•acid and other biliary principles.
Glycocholic acid forms brilliant, colorless, transparent needles,
which are sparingly soluble in cold H2O, readily soluble in warm
H2O and in alcohol, almost insoluble in ether. The watery solu-
tion is acid in reaction, and tastes at first sweet, afterward
intensely bitter. Its alcoholic solution exerts a right-handed
polarization [a]D= +29°.
When heated with potash, baryta, or dilute H8SC>4 or HC1, it
is decomposed into cholic acid and glycocol :
C28H43NO6 + H2O = C24H4oO5 + C2H6NO,.
Glycocholic acid. Water. Cholic acid. Glycocol.
Glycocholic acid dissolves unchanged in cold concentrated
HsSCh, and is precipitated on dilution of the solution with H2O.
If the mixture be warmed the bile acid is decomposed, and there
AMIDO- ACIDS OF THE FATTY SERIES. 285-
separate oily drops of cholonic acid, C^MnNOb. differing from
glycocholic acid by — H2O. When allowed to remain long in con-
tact with concentrated HaSO4, glycocholic acid is converted into-
a colorless, resinous mass, which slowly forms a saffron-yellow
solution with the mineral acid, which turns flame-red when
warmed, and which, on dilution, deposits a flocculent material
which is colorless, greenish, or brownish, according to the tem-
perature at which it is formed. Glycocholic acid, altered by
contact with concentrated H2SO4, absorbs O when exposed to the
air, and turns red, then blue, and finally brown after a few days.
Sodium Glycocholate, CJ; H i;NO,-Na, exists in the bile ; it crys-
tallizes in stellate needles, very soluble in HaO, less so in abso-
lute alcohol, and insoluble in ether ; its alcoholic solution exerts
right-handed polarization [a]D = +25°. 7.
Lead Glycocholate, (C26H42N'Oe)i Pb(?), is formed as a white,
flocculent precipitate, when solution of lead subacetate is added
to a solution of a glycocholate or of glycocholic acid ; with the
neutral acetate the precipitation does not occur in the presence
of an excess of acetic acid. It is soluble in alcohol, and in an ex-
cess of lead acetate solution.
The glycocholates of the alkaline earths are soluble in HaO.
Glycocholic acid and the glycocholates react with Pettenkofer's
test (see below).
Glycocholic acid forms compounds with the alkaloids, some of
which are crystalline, others amorphous ; they are for the most
part very sparingly soluble in H2O, but readily soluble in solu-
tions of the biliary salts and in bile.
Taur6cholic acid— C2eH45N07S— 515— exists as its sodium salt in
the bile of man and of the carnivora, and in much less abun-
dance in that of the herbivora. In the bile of the dog it seems to
be unaccompanied by any other biliary acid. It may be obtained
from dog's bile by evaporating with animal charcoal, extraction
with absolute alcohol and precipitation with ether. The precip-
itated taurocholate is then dissolved in H2O and precipitated
with slightly ainmoniacal (C2H3O2)2 Pb solution. The lead salt is
dissolved in boiling absolute alcohol and decomposed by H2S.
Finally the filtered alcoholic solution of free taurocholic acid is
precipitated with ether in slight excess.
It forms silky, crystalline needles, which, when exposed to the
air, deliquesce rapidly, and which, even under absolute ether,
are gradually converted into a transparent, amorphous, resinous .
mass. It is soluble in H2O and alcohol ; insoluble in ether ; its
aqueous solution is very bitter ; in alcoholic solution it deviates
the plane of polarization to the left, [a]o = —34°. 5; its solutions,
are acid in reaction.
Taurocholic acid is decomposed by heating with barium hy-
drate, with dilute acids, and even by evaporation of its solution,.
286 MANUAL OF CHEMISTRY.
into cholic acid and taurin :
C28H45NO,S + H2O = C24H40O8 + CaH7NO3S
Taurocholicacid. Water. Cholic acid. Taurin.
The same decomposition occurs in the presence of putrefying
material, and in the intestine. Taurocholic acid has not been
found to accompany glycocholic in the urine of icteric patients.
The taurocholates are neutral in reaction ; those of the alka-
line metals are soluble in alcohol and in water ; and by long
•contact with ether they assume the crystalline form. They may
be separated from the glycocholates in watery solution, either :
<1) by dilute H2SO4 in the presence of a small quantity of ether,
which precipitates glycocholic acid alone ; or (2) by adding neu-
tral lead acetate to the solution of the mixed salts (which must
be neutral in reaction) lead glycocholate is precipitated and
separated by filtration. To the mother liquor basic lead acetate
and ammonia are added, when lead taurocholate is precipitated.
The acids are obtained from the hot alcoholic solutions of the
Pb salts by decomposition with JI2S, filtration, concentration,
arid precipitation by ether.
Solutions of the taurocholates, like those of the glycocholates,
have the power of dissolving cholesterin and of emulsifying the
fats. They also form with the salts of the alkaloids compounds
which are insoluble in H-iO, but soluble in an excess of the biliary
salt. The taurocholate of morphin is crystallizable. They react
with Pettenkofer's test.
Hyoglycocholic acid, C27H43NO5, and Hyotaurocholic acid,
C2H46NO6S (?), are conjugate acids of hyocholic acid, C2SH40O4,
and glycocol and taurin, which exist in the bile of the pig.
Chenotaurocholic acid, a conjugate acid of taurin and chenocholic
acid, C27H44O4, is obtained from the bile of the goose.
Cholic acid — C24H4006 — 408 — is a product of decomposition of
glyco- and taurocholic acids, obtained as indicated above. It also
occurs, as the result of a similar decomposition, in the intestines
and faeces of both herbivora and carnivora. It forms large, clear,
deliquescent crystals ; sparingly soluble in H3O, readily soluble
in alcohol and ether ; intensely bitter in taste, with a sweetish
after-taste. In alcoholic solution it is dextrogyrous [a]D = +35°.
The alkaline cholates are crystallizable and readily soluble in
HaO, the others difficultly soluble. Cholic acid and the cholates
respond to Pettenkofer's test.
By boiling with acids or by continued heating to 200° (392° F.),
cholic acid loses the elements of H2O, and is transformed into
dyslysin, C24H36O3, a neutral, resinous material, insoluble in H2O
and alcohol, sparingly soluble in ether.
AMIDO-ACIDS OF THE FATTY SERIES. 287
Dehydrocholic acid — C2;H:6Oo — is produced from cholic acid by
careful oxidation with chromic and glacial acetic acids. It forms
crystalline needles sparingly soluble in water, readily soluble in
hot alcohol. It is monobasic, dextrogyrous, and bitter. It does
not respond to the Pettenkofer reaction. Further oxidation con-
verts it into
Bilianic acid— C^-Ms&OaC!) — which is also produced, along with
isobilianic acid, by the action of chromic and sulfuric acids upon
cholic acid. It is a crystalline solid, sparingly soluble in cold H2O,
readily soluble in hot H3O and in alcohol. It is dextrogyrous,
not bitter, and does not respond to the Pettenkofer reaction.
Deoxycholic acid — C:1H4, 0; — has been obtained from bile which
had become putrid and from which cholic acid had completely
-disappeared. It is a monobasic acid, produced by the reduction
of cholic acid.
Choleic acid — C^H^CX — is formed, along with cholic acid, by
the saponification of ox-bile by alkalies. On oxidation it yields
dehydrocholeic acid — GyJ3L3tlO4 — and cholanic acid — Co5H3eO7, the
Jorrner monobasic, the latter tri basic, as well as isocholanlc acid.
Fellic acid— CS3H.ioO4 — is said to exist in and to be peculiar to
human bile.
The Pettenkofer Reaction. — Glycocholic, taurocholic, cholic and
choleic acids and their salts have the property of forming a yellow
solution with concentrated HaSCh, the color of which rapidly in-
creases in intensity, and which exhibits a green fluorescence.
Their watery solutions also, when treated with a small quantity
of cane-sugar and with concentrated H-jSO4, so added that the
mixture acquires a temperature of 70° (158° F.) but does not be-
come heated much beyond thai point, develop a beautiful cherry-
red color, which gradually changes to dark reddish-purple. Al-
though this reaction is observed in the presence of very small
quantities of the biliary acids, it loses its value, unless applied as
directed below, from the fact that many other substances give the
same reaction, either with H3SO4 alone, or in the presence of
oane-sugar. Among these substances are many which exist nat-
urally in animal fluids, or which may be introduced with the
food or as medicines ; such are cholesterin, the albuminoids, leci-
thin, oleic acid, cerebrin, phenol, turpentine, tannicacid, salicylic
acid, morphin, codein, many oils and fats, cod-liver oil, etc.
288 MANUAL OF CHEMISTRY.
The following method of applying Pettenkofer's test to the
urine and other fluids removes, we believe, every source of error.
The urine, etc., is first evaporated to dryness at the temperature
of the water-bath, a small quantity of coarse animal charcoal
having been added ; the residue is extracted with absolute alco-
hol, the alcoholic liquid filtered, partially evaporated, and treated
with ten times its bulk of absolute ether ; after standing an hour
or two, any precipitate which. may have formed is collected upon
a small filter, washed with ether, and dissolved in a small quan-
tity of HaO ; this aqueous solution is placed in a test-tube, a drop
or two of a strong aqueous solution of cane-sugar (sugar, 1 ;
water, 4), and then pure concentrated H2SO4 are added ; the ad-
dition of the acid being so regulated, and the test-tube dipped
from time to time in cold water, that the temperature shall be
from 60°-75° (140°-167° P.). In the presence of biliary acids the
mixture usually becomes turbid at first, and then turns cherry-
red and finally purple, the intensity of the color varying with the
amount of biliary acid present.
Physiological Chemistry of the Biliary Acids. —These sub-
stances are formed in the liver, and they are not reabsorbed from
the intestine unchanged. Solutions of the biliary salts, injected
into the circulation in small quantity, cause a diminution in the
frequency of the pulse and of the respiratory movements, a
lowering of the temperature and arterial tension, and disintegra-
tion of the blood-corpuscles. In large doses (2-4 grams [30-60
grains] for a dog) they produce the same effects to a more marked
degree ; epileptiform convulsions, black and bloody urine, and
death more or less rapidly. These effects do not follow the injec-
tion of the products of decomposition of the biliary acids, except
cholic acid, and in that case the symptoms are much less marked.
Nor are the biliary acids discharged unaltered with the faeces ;
they are decomposed in the intestine. The extract, suitably
purified, of the contents of the upper part of the small intestine,
gives a well-marked reaction with Pettenkofer's test ; while simi-
lar extracts of the contents of the lower part of the large intes-
tine, or of the faeces, fail to give the reaction, and consequently are
free from glyco- or taurocholic, cholic acid, or dyslysin ; the feeces,
moreover, do not contain either taurin or glycocol. During the
processes which take place in the intestine, the bile-acids are de-
composed into cholic acid and taurin or glycocol, which are
subsequently reabsorbed, either as such, or after having been
subjected to further decomposition ; and as a consequence of
their decomposition they probably have some influence upon in-
testinal digestion.
Taurocholic acid added to a solution of peptone causes a slight
precipitate which has been shown to consist entirely of the acid
itself; but albumen and syntonin are precipitated in coarse flocks
from their solutions by and along with taurocholic acid, and that
so completely that the filtered liquid fails to react with the most
AMIDOACIDS OF THE FATTY SERIES.
289
delicate tests for albumen. This acid is therefore an excellent re-
agent for the quantitative separation of the albuminoids from
the peptones.
A saturated aqueous solution of glycocholic acid is not precip-
itated either by peptone or propeptone ; but if a peptone followed
by an acid is added to a concentrated solution of sodium gly-
cocholate, a precipitate of glycocholic acid, without peptone, is
formed. A mixture of the human biliary acids acts in the same
manner as taurocholic acid.
Taurocholic acid when present in the proportion of 0.2 to 0.5 per
cent prevents the putrefaction of a mixture of muscular tissue and
pancreas, as well as lactic and alcoholic fermentations. Glyco-
cholic acid is much less active. This antiseptic power is possessed
only by the free acids, not by their salts, hence bile putrefies
readily, if neutral or alkaline. But the acidity of the chyme in
the intestine, which persists for quite a distance from the pylorus,
by liberating the acids, permits of their exerting their antiseptic
action and thus retarding pancreatic putrefaction.
The proportion of biliary salts in human bile varies considera-
bly, as shown by the following analyses :
Mucin
I.
II.
in.
IV.
V.
VI.
VII.
VIII.
IX.
2.66
0.16
0.32
7.22
2.98
0.26?
0.92 f
9.14
2.91
4.73
10.79
1.45
3.09
5.65
( 6.25
}0.04
] 4.48
0.64
3.86
2.48
0.25
0.05
0.75
2.09
0.82
0.46?
90.88
1.29
0.34
0.36
1.93
0.44
1.63
1.46V
91.08
'1.57
4.90
1.46
1.29
0.35
0.73
0.87
3.03
1.39
Cholesterin . . .
Fats
Biliary salts. ..
Soaps
Mineral salts. .
Water
0.65
86.00
14.00
0.77
85.92
14.08
1.08
82.27
17.73
0.63
89.81
10,19
Total solids . .
9.12
8.92
I. Frerichs : Bile from man, set. 18. killed by a fall. II. Fre-
richs : Male, set. 22, died of a wound. III. Gorup-Besanez : Male,
set. 49, decapitated. IV. Gorup-Besanez : Female, set. 29, decap-
itated. V. Jacobsen : Male, biliary fistula. VI., VII. Trifanow-
ski : Males. VIII. Socolof : Mean of six analyses of human bile.
IX. Hoppe-Seyler : Mean of five analyses of bile from subjects
with healthy livers.
Pathologically, the biliary acids may be detected in the blood
and urine in icterus and acute atrophy of the liver ; although by
no means as frequently as the biliary coloring matters.
290 MANUAL OF CHEMISTRY.
BETAINS.
R--CO
The Betains are the anhydrids : | | corresponding to sub-
EEN-0,
stances of mixed function, partly acid and derived from the ami-
R"— COOH
do-acids, and partly quaternary ammonium : | in
=N-OH,
-which R" may be either methylene, ethylene, etc., or a bivalent,
closed chain residue such as C6H4 ; and the remaining =N valences
satisfied either by three univalent radicals, such as CH3, or by a
single trivalent radical, such as (C6H5)'", as in pyridin-betaln ; or
the trivalent radical may take the place of R as in nicotic-methyl
C6H4— CO
betarn :
CHs-N - O.
Betam — Trimethyl-acetic betaln — Oxyneurin—Oxycholin —
CH.,— CO
| = CoHuNOa — 117 — was first obtained from the
(CH3)3N — O
juice of the sugar-beet ; afterward it was obtained by oxidation
of neurin ; and is also produced synthetically, either by acting
upon trimethylamin with monochloracetic acid, as gycocol is
obtained by the action of the same acid upon ordinary ammonia ;
or by acting upon glycocol itself with methyl iodid.
Betain crystallizes in large, brilliant crystals, containing one
molecule of water of crystallization. At the ordinary tempera-
ture they are deliquescent, but effloresce at 100° (212° F.). It is
very soluble in water and in alcohol. It is decomposed by heat,
with evolution of trimethylamin. It forms crystalline salts. Its
chloraurate is crystalline, and very sparingly soluble in cold water.
AMIDINS— ACETONAMINS— ALDEHYDINS— HYDRA-
ZINS.
The amidins are basic substances formed by the substitution
of (NH)" for the oxygen of the aniids. They therefore have the
general formulaR— Cjj , derived from that of the monamids:
R— C in which R represents a hydrocarbon radical. They
form mono-, di- and trisubstituted derivatives by the replacement
of the H in the groups NH and NH2 by atoms or radicals.
The acetonamins are basic substances formed by the action of
ammonia or of the monamins upon acetone.
The aldehydins are substances produced by the action of am-
monia or of the monamins upon aldehyde. The most important
of the class belong to the aromatic series. By the action of al-
cohol on butyric aldehyde, dibutyraldin, C8HJ7NO is produced;
AZOPARAFFINS — CYANOGEN COMPOUNDS. 291
•which, by dehydration, is converted into paraconiin, C.H, N,
& base which is isomeric with conicein, a derivative of coniin, but
not with the latter alkaloid, which is a pyridin base (see p. 425).
The hydrazins are derivable from the group H.,N — NHQ (see p.
105) by the substitution of radicals for one or more of the hydro-
gen atoms. Although the most important of the class, belong-
ing among the aromatic compounds (see p. 421), some are deriva-
tives of the fatty series, such as ethylhydrazin : C2H5, HN— NH2.
AZOPARAFFINS— NITRILS— CYANOGEN COMPOUNDS.
These substances may be considered either as compounds of
the univalent radical cyanogen, (Civ N'")' ; or as paraffins,
CnH2n + 2, in which three atoms of hydrogen have been replaced
by a trivalent N'" atom, hence azoparaffins ; or as nitrils, com-
pounds of N with the trivalent radicals CnHa»-i.
Dicyanogen — (CN)2 — 52 — is prepared by heating mercuric
cyanid. It is a colorless gas ; has a pronounced odor of bitter
almonds ; sp. gr. 1.8064 A.; burns in air with a purple flame, giv-
ing off N and CO2. It is quite soluble in H2O, the solution turn-
ing brown in air.
It has a very deleterious action upon both animal and vegeta-
ble life, even when largely diluted with air.
Hydrogen cyanid — Cyanogen hydrid — Hydrocyanic acid — Prus-
sia acid — ^jj |- — 27 — exists ready formed in the juice of cassava,
and is formed by the action of H3O upon bitter almonds, cherry-
laurel leaves, etc. It is also formed in a great number of reactions :
by the passage of the electric discharge through a mixture of
acetylene and N ; by the action of chloroform on NH3 ; by the
distillation of, or the action of HNO3 upon many organic sub-
stances ; by the decomposition of cyanids.
It is always prepared by the decomposition of a cyanid or
a ferrocyanid. Usually by acting upon potassium ferrocyanid
with dilute sulfuric acid, and distilling. Its preparation in the
pure form is an operation attended with the most serious danger,
and should only be attempted by those well trained in chemical
manipulation. For medical uses a very dilute acid is required ;
the acid hydrocyanicum dil. (TJ. S., Br.) contains, if freshly and
properly prepared, two per cent, of anhydrous acid. That of
the French Codex is much stronger — ten per cent.
The pure acid is a colorless, mobile liquid, has a penetrating
and characteristic odor ; sp. gr. 9.7058 at 7° (44°. 6 F.) ; crystallizes
at —15° (5" F.); boils at 26°. 5 (79°. 7 F.); is rapidly decomposed by
exposure to light. The dilute acid of the U. S. P. is a colorless
liquid, having the odor of the acid ; faintly acid, the reddened
292 MANUAL OF CHEMISTRY.
litmus returning to blue on exposure to air; sp. gr. 0.997; 10s
grams of the acid should be accurately neutralized by 1.27 gram,
of silver nitrate. The dilute acid deteriorates on exposure ta
light, although more slowly than the concentrated ; a trace of
phosphoric acid added to the solution retards the decomposition.
Most strong acids decompose HCN. The alkalies enter into-
double decomposition with it to form cyanids. It is decomposed
by Cl and Br, with formation of cyanogen chlorid or bromid..
Nascent H converts it into methylainin.
Analytical Characters. — (1.) With silver nitrate a dense, white
ppt. ; which is not dissolved on addition of HNO3 to the liquid,
but dissolves when separated and heated with concentrated.
HNO3 ; soluble in solutions of alkaline cyanids or hyposul-
fites. (2.) Treated with NH4HS, evaporated to dryness, and
ferric chlorid added to the residue; a blood-red color. (3.) "With
potash and then a mixture of ferrous and ferric sulfates; a
greenish ppt., which is partly dissolved with a deep blue color
by HC1. (4.) Heated with a dilute solution of picric acid and
then cooled ; a deep red color. (5.) Moisten a piece of filter paper
with a freshly prepared alcoholic solution of guaiac ; dip the
paper into a very dilute solution of CuSO4, and, after drying, in-
to the liquid to be tested. In the presence of HCN it assumes a.
deep blue color.
Toxicology. — Hydrocyanic acid is a violent poison, whether it
be inhaled as vapor, or swallowed, either in the form of dilute
acid, of soluble cyanid, or of the pharmaceutical preparations
containing it, such as oil of bitter almonds and cherry -laurel
water ; its action being more rapid when taken by inhalation or
in aqueous solution than in other forms. When the medicinal
acid is taken in poisonous dose, its lethal effect may seem to
be produced instantaneously ; nevertheless, several respiratory
efforts usually are made after the victim seems to be dead, and
instances are not wanting in which there was time for consider-
able voluntary motion between the time of the ingestion of the
poison and unconsciousness. In the great majority of cases the
patient is either dead or fully under the influence of the poison
on the arrival of the physician, who should, however, not neg-
lect to apply the proper remedies if the faintest spark of life re-
main. Chemical antidotes are, owing to the rapidity of action
of the poison, of no avail, although possibly chlorin, recom-
mended as an antidote by many, may have a chemical action on
that portion of the acid already absorbed. The treatment indi-
cated is directed to the maintenance of respiration ; cold douche,
galvanism, artificial respiration, until elimination has removed
the poison. If the patient survive an hour after taking the
poison, the prognosis becomes very favorable ; in the first stages
AZOPARAFFINS — CYANOGEN COMPOUNDS. 293
it is exceedingly unfavorable, unless the quantity taken has been
"very small.
In cases of death from hydrocyanic acid a marked odor of the
poison is alinost always observed in the apartment and upon
•opening the body, even several days after death. In cases of
suicide or accident, the vessel from "which the poison has been
taken will usually be found in close proximity to the body, al-
though the absence of such vessel is not proof that the case is
necessarily one of homicide.
Notwithstanding the volatility and instability of the poison,
its presence has been detected two months after death, although
the chances of separating it are certainly the better the sooner
after death the analysis is made. The search for hydrocyanic
acid is combined with that for phosphorus ; the part of the dis-
tillate containing the more volatile products is examined by the
tests given above. It is best, when the presence of free hydrocy-
anic acid is suspected, to distil at first without acidulating. In
cases of suspected homicide by hydrocyanic acid the stomach
.should never be opened until immediately before the analysis.
Cyanids. — The most important of the metallic cyanids are those
of K and Ag (see pp. 190, 193).
The hydrocyanic ethers of the univalent alcoholic radicals are
called nitrils, and are frequently the starting-points from which
other organic products are obtained.
They are produced :
1.) By distilling a mixture of potassium cyanid and the potas-
sium salt of the corresponding monosulfate of the alcoholic
radical :
KCN + s3j£|-O, = CaH5,CN + K2SO4
.Potassium cyanid. Potassium ethylsulfate. Ethyl cyanid. Dipotassic sulfate.
2.) By complete dehydration, by the action of P2OB, of the arn-
;moniacal salt of the corresponding acid, or of its amid :
CH3,COO(NH4) CH3,CN + 2HSO
Ammonium acetate. Methyl cyanid.
d^CCXNH, CH3,CN 4- H2O
Acetamid. Acetonitril.
3.) By the action of the chloridsof the acid radicals upon silver
cyanate :
CNOAg + CH3COC1 = AgCl + CH3CN + CO*
Silver cyanate. Acetyl chlorid. Methyl cyanid.
The nitrils combine with nascent hydrogen to form the corre-
sponding arums :
294 MANUAL OF CHEMISTRY.
CHS,CN + 2Ha CaH.,H,N
Acetonitril. Ethylamin.
Hydrating agents convert the nitrils into ammonia and the
corresponding acid :
CaH6,CN + 2H2O = NH3 + Ca
Propionitril. Propionic acid.
Sulfuric acid, or sulfur trioxid, converts the nitrils into sulfo-
acids and monoarumonic sulfate :
CaH5,CN + HaO + 2HaSO4 = NH4H(SO4) + SO3,C2H6,COOH
Ethylcyanid. Sulfopropionic acid.
Isomeric with the nitrils are substances known as isocyanids^
carbylamins or carbamins, which are formed :
1.) By the action of a primary monainin on chloroform in the
presence of caustic potash :
CH3,HaN + CHC13 = 3HC1 + CN,CH,
Methylamin. Methyl isocyanid.
2.) By the action of the iodoparaffins on silver cyanid :
CH3I 4- AgCN = Agl + CN,CH,
Methyl iodid. Methyl carbylamin.
The difference in the constitution of the two classes of bodies is
due to the N being trivalent in the nitril, and quinquivalent in
the carbylamin :
N^C— CH3 C=N— CH3
Methyl cyanid. Methyl isocyanid.
The isocyanids do not yield ammonia and an acid by the action
of hydrating agents, but are converted into formic acid and a.
primary amin :
NC,CaHB + 2HaO = NH,,C,H. + H,COOH
Ethyl isocyanid. Ethylamin. Formic acid.
The nitrils and carbamins combine with the hydracids to form
crystalline salts, decomposable by water. The latter much more
energetically than the former. They are all volatile liquids ; the
nitrils having ethereal odors when pure, the isocyanids odors.
which are very powerful and disagreeable.
Cyanogen chlorids. — Two polymeric chlorids are known.
Gaseous cyanogen chlorid — CNC1 — is formed by the action of Cl
upon anhydrous hydrocyanic acid or upon mercuric cyanid in the
dark. It is a colorless gas, intensely irritating and poisonous.
Solid cyanogen chlorid — CaN3Cl3 — is formed, as a crystalline
solid, when anhydrous hydrocyanic acid is acted upon by Cl in
AZOPARAFFINS — CYANOGEN COMPOUNDS. 295
sunlight. It fuses at 140° C. (284° P.).
Cyanic acid — Cyanogen hydrate — TT /O — ^ — does not exist in
nature. It is obtained by calcining the cyanids in presence of an
oxidizing agent ; or by the action of dicyanogen upon solutions of
the alkalies or alkaline carbonates ; or by the distillation of cya-
nuric acid.
It is a colorless liquid ; has a strong odor, resembling that of
formic acid ; its vapor is irritating to the eyes, and it produces
vesication when applied to the skin. It is soluble in water.
When free it is readily changed by exposure to air into an iso-
mere, cyamelid.
The acid forms salts and ethers which constitute two isonieric
series, indicating the existence of two acids, the normal, having
the constitution N=C — OH, and the iso, having the constitu-
tion O = C = N— H.
Ammonium isocyanate O = C = N — NH4 is converted into
urea by heat.
Cyanuric acid — C3N3H3O3 — is a polymere of cyanic acid, formed
by the action of heat or of Cl upon urea. It forms colorless
crystals, sparingly soluble in HaO, the solutions odorless, almost
tasteless, and feebly acid. It is a tribasic acid. It is very stable
and may be dissolved in strong HaSO4 or HNO3 without suffering
decomposition.
Fulminic acid — C.NjH.Oj — is a bibasic acid whose Ag and Hg
salts are formed by the action of nitrous acid upon alcohol in the
presence of the salts of Ag and Hg. These are the fulminating
powders used in the manufacture of percussion caps.
Fulminuric acid— CsNsHsOa — metameric with cyanuric acid, is
a bibasic acid, formed by the action of a metallic chlorid upon a
solution of mercuric fulminate.
Thiocyanic acid — Sulfocyanic acid — Cyanogen sulfhydrate —
TJ /S — 59— bears the same relation to cyanic acid that CS2 does
to COa. It is obtained by the decomposition of its salts, which
are obtained by boiling a solution of the cyanid with S ; by the
action of dicyanogen upon the metallic sulfid; and in several
other ways.
The free acid is a colorless liquid ; crystallizes at —12°. 5 (9°.5 F.) ;
boils at 102°. 5 (216°. 5 F.) ; acid in reaction. The prominent re-
action of the acid and of its salts is the production of a deep red
color with the ferric salts ; the color being discharged by solution
of mercuric chlorid, but not by HC1.
Sulfocyanic acid exists in human saliva in combination, prob-
ably with sodium. The free acid is actively poisonous and its
salts were formerly supposed to be so also, It is probable,
296 MANUAL OF CHEMISTRY.
however, that much of the deleterious action of the potassium
salt — that usually experimented with — is due as much to the
metal as to the acid.
Cyanamid — CN,NH2 — is produced by the action of gaseous
cyanogen chlorid upon ammonia: CNC1+-2NH3 = NH4C1+
CN.NHj. It forms colorless crystals, soluble in water, alcohol or
ether. Corresponding to it are substituted cyanaruids, which
may be formed by substituting a primary amin for ammonia in
the above-mentioned method of preparation : CNCl+2NHaCH3 =
NH3,CH3,C1+CN,NHCH3.
Metallocyanids.— The radical cyanogen, besides combining
with metallic elements to form true cyanids, in which the radical
(ON) enters as a univalent atom, is capable of combining with
certain metals (notably those of the iron and platinum groups)
to form complex radicals. These combining with H, form acids,
and with basic elements form salts in which the analytical re-
actions of the metallic element entering into the radical are com-
pletely masked. Of these metallocyanids the best known are
those in which iron enters into the radical. As iron is capable of
forming two series of compounds, in one of which the single atom
Fe" enters in its bivalent capacity, and in the other of which the
hexavalent double atom (Fea)^ is contained ; so uniting with
cyanogen, iron forms two ferrocyanogen radicals : [(CN)'«Fe"]lv,
ferrocyanogen, and [(CN)'ia(Fea)vi]vl ferricyanogen ; each of which
unites with hydrogen to form an acid, corresponding to which
are numerous salts : (C«N8Fe)H4, hydroferrocyanic acid, tetra-
basic ; and (daNiaFea)He, hydroferricyanic acid, hexabasic (see
potassium and iron salts).
HYDBOXYLAMIN DERIVATIVES.
Hydroxylamin, itself an amin (see p. 105), still contains three
atoms of hydrogen which may be replaced by radicals to form
primary, secondary, and tertiary derivatives (see p. 274) whose
relations to the corresponding ammonia derivatives are indicated,
by the following formula :
H\ CH3\ C,H5O\ C7H5O\
H-N H -N H-N C,H5O-N
H/ H / H/ C,H6O/
Ammonia. Methylamin. Benzamid. Tribenzamid.
H\ CH3\ C,H6O\ C,H6O\
H-N H -N H-N C,H50-N
HO/ HO / HO/ C,H6O-O/
Hydroxylamin. Methyl- Benzhydrox- Tribenzhydrox-
hydroxylamin. amic acid. ylamin.
Hydroxylamin also enters into reaction directly with aldehydes,
acetones and nitrils to form compounds called oxims.
SULFUR DERIVATIVES OF PARAFFINS. 297
The derivatives of the aldehydes are called aldoxims, whose
/ FT
general formula is R—CN , and those of the acetones are
known as acetoxims, . whose general formula is R — (
which R is a hydrocarbon radical. They are both formed by the
action of the hydroxylamin chlorid upon the corresponding al-
dehyde or acetone.
The amidoxims are formed by direct union of the nitrils with
hydroxylamin, and have the general formula R— C/^ Q^. The
first of the series, Isuretin, or Carbamidoxim, H — C<. i^ QTT, isiso-
meric with urea, and is produced by direct union of hydroxyl-
amin and hydrocyanic acid.
SULFUR DERIVATIVES OF THE PARAFFINS.
Sulfur and oxygen, being equal in valence, may replace each
other in organic compounds as, for instance, in sulfocyanic acid
CNSH, corresponding to cyanic CNOH.
There exist many derivatives of the paraffins in which S thus
takes the place of O. Thus :
CHaOH C2H5\
/"I TT / \J V^Xls"'^'
f~1TT V^S-tla/
Ethylic alcohol. Ethylic ether, Acetal.
or ethyl oxid.
CH2SH C2HS\
CH C2H5/k
Thioalcohol Ethyl sulfid. Mercaptal.
or mercaptan.
Methyl Sulfids.— Three are known. The monosulfid, (CH3)2S,
is a colorless liquid, boils at 41° (105°. 8 F.), has a very disagree-
able odor, as have all the alcoholic sulfids and sulfhydrates. It is
formed by the action of gaseous methyl chlorid on potassium
monosulfid. The bisulfid, (CH3)2S2, is similarly formed from po-
tassium bisulfid, and is a colorless liquid, boiling at 116°-118I>
.(240°. 8-244°. 4 F.). The trisulfid, (CH3)2SS, is formed in the same
way from potassium pentasulfid, and boils at 200° (392° F.).
Ethyl sulfids are formed in the same manner as the methyl
compounds, and have the same constitution.
Methyl hydrosulfid— Methyl mercaptan— H,CH2SH — is a very
offensive liquid formed by distilling together calcium methyl-
sulfate and potassium hydrosulfid.
298 MANUAL OF CHEMISTRY.
Ethyl sulfhydrate— Thioalcohol— Mercaptan— CHg,CH2SH— is-
best prepared by treating alcohol with H2SO4, as in the prepara-
tion of sulfovinic acid (q.v.); mixing the crude product with ex-
cess of potash ; separating from the crystals of potassium sulfate ;
saturating with H2S; and distilling.
It is a mobile, colorless liquid ; sp. gr. 0.8325; has an intensely
disagreeable odor, combined of those of garlic and H2S ; boils at
86°. 2 (97°. 2 R); ignites readily and burns with a blue flame ; may
be readily frozen by the cold produced by its own evaporation ;
neutral in reaction ; sparingly soluble in H2O, soluble in all pro-
portions in alcohol and ether ; dissolves I, S and P.
Potassium and sodium act with mercaptan as with alcohol, re-
placing the extra-radical hydrogen. In its behavior toward the
oxids it more closely resembles the acids than the alcohols, being
capable even of entering into double decomposition to form salts,
called sulfethylates or mercaptids. Its action with mercuric
oxid is characteristic, forming a white, crystalline sulfid of ethyl
and mercury :
Ethyl sulfhydrate. Mercuric oxid. Ethyl-mercuric sulfid. Water.
When a mixture of one molecule of a mercaptan with two
molecules of an aldehyde is treated with dry HC1, a stable com-
pound is produced which is called a mercaptal, being an acetal
whose O is replaced by 8.
If the reaction take place with an acetone, in place of with an
aldehyde, a mercaptol is produced, which differs from the mer-
captal in that an alcoholic radical is substituted for the remain-
ing H atom of the methane :
H \n/OC2H5 H \r/SC2H5 CH3\P/SC2H5
CH3/U\OC2H6 CH./^NSCaH. CH3/°\SC2H6
Acetal. Mercaptal. Mercaptol.
Ethyl mercaptol — (CH3)a = C = (SCaB^g-is formed as one of the
steps in the manufacture of sulfonal. It is produced by the
action of dry HC1 upon a mixture of acetone and ethylmer-
captan, or upon a mixture of sodium ethylthiosulfate, C2H6,
SO,ONa, and acetone. It is a mobile liquid, whose odor is not
disagreeable. When heated it begins to boil at a.bout 80° (176°
R) and the temperature rises rather regularly to 192° (377°. 6 R).
Oxidizing agents act readily upon the mercaptals and mercap-
tols to produce compounds called sulfones, whose constitution
is represented by one of the three following formulae, in which R.
is a univalent alcoholic radical :
COMPOUNDS OF THE ALCOHOLIC RADICALS. 299'
H\n/SO2R R\n/SO2R R
Methylendisulfone. Methenyldisulfone. Ketondisulfone.
Sulfonal — Diethylsulfondimethylmethane — (
— is obtained by the oxidation of ethyl-mercaptol, prepared as
above described, by potassium permanganate. It crystallizes in
thick, colorless prisms, difficultly soluble in cold water or alcohol,
readily soluble in hot water or alcohol, and in ether, benzene and
chloroform. It fuses at 130n-131° (266°-267°.8 F.), and boils at
300° (572° F.), suffering partial decomposition. It dissolves in
concentrated H2SO4, and is decomposed by the acid when heated,
but may be precipitated from the cold solution unchanged bjr
dilution with H2O. Nitric acid does not affect it, even when
heated. It is not attacked by Br, by caustic alkalies or by nas-
cent H.
Ichthyol — is the Na salt of a complex sulfonic acid, having the
empirical formula C2t,H36S3Na2Oe, obtained by the distillation
and purification of an ozocerite-like mineral deposit. It is a dark
brown, pitch-like mass having a disagreeable odor.
COMPOUNDS OF THE ALCOHOLIC RADICALS WITH
OTHER ELEMENTS.
Phosphins, arsins, and stibins, are compounds resembling the
amins in constitution, in which the N is replaced by P, As, or Sb.
Like the amins, they may be primary, secondary, or tertiary :
CTJ ^ r* ~u \ r* ~u \ r* ~H \
a-tifi I v^aJls t V-'aXls j v^2Xi5 J
HVN HVP C2HsVAs C2HBVSb
Ethylamin Ethylphospin Diethyl-arsin Trietkyl-stibin
(primary). (primary). (secondary). (tertiary).
There also exist compounds containing P, As, or Sb, which are
similar in constitution to the hydroxids and salts of ammonium,
and of the compound ammoniums :
NHJ N(CH3)4I As(CH3)4I
Ammonium Tetramethyl ammonium Tetramethyl arsenium
iodid. iodid. iodid.
Most of these compounds, which are very numerous, are as yet
only of theoretic interest. One of them, however, is deserving of
notice here :
CH3 )
Dimethyl Arsin, CH3 [• As — 106 — which may be considered as
being the hydrid of the radical [As(CH3)2], does not exist as such.
There is, however, a liquid known as the fuming liquor of Cadet,
300 MANUAL OF CHEMISTRY.
or alkarsin, which is obtained by distilling a mixture of potas-
sium acetate and arsenic trioxid. This liquid contains the oxid
of the above radical, and a substance which ignites on contact
with air, and which consists of the same radical united to itself,
•2[As(CH3)2]. This radical, called cacodyle (/ca/c6c = evil), is capa-
ble of entering into a great number of other combinations. Ca-
codyle and its compounds are all exceedingly poisonous, espe-
cially the cyanid, an ethereal liquid, very volatile, the presence
of whose vapor in inspired air, even in minute traces, produces
symptoms referable both to arsenic and to hydrocyanic acid.
It is probable that during the putrefaction of cadavers injected
with arsenical embalming liquids one or more arsins may be
formed.
Organo-metallic substances are compounds of the alcoholic
radicals with metals. They are very numerous, usually obtained
by the action of the iodid of the alcoholic radical upon the me-
tallic element, in an atmosphere of H. They are substances
which, although they have been put to no uses in the arts or in
medicine, have been of great service in chemical research. As
typical of this class of substances we may mention :
Zinc-ethyl — £j^ j-Zn— 123— obtained by heating at 130° (266°
F.) in a sealed tube a mixture of perfectly dry zinc amalgam with
ethyl iodid ; the contents of the tube are then distilled in an
-atmosphere of coal-gas, or H, and the distillate collected in a
receiver, in which it can be sealed by fusion of the glass without
contact with air.
It is a colorless, transparent, highly refracting liquid ; sp. gr.
1.182 ; boils at 118° (244°. 4 F.). On contact with air it ignites and
burns with a luminous flame, bordered with green, and gives off
dense clouds of zinc oxid, a property which renders it very dan-
gerous to handle. On contact with HSO it is immediately
decomposed into zinc hydrate and ethyl hydrid. It is chiefly use-
ful as an agent by which the radical ethyl can be introduced into
organic molecules.
ALLYLIC SERIES.
301
ALLYING SERIES.
The compounds heretofore considered may be derived more or
less directly from the saturated hydrocarbons ; in the deriva-
tives, as in the hydrocarbons, the valences of the C atoms are
all satisfied, and that in the simplest and most complete man-
ner, two neighboring C atoms always exchanging a single
valence. There exist, however, other compounds containing less
H in proportion to C than those already considered, and yet
resembling them in being monoatomic. These compounds have
usually been considered as non-saturated, because all the possible
valences are not satisfied, and the substances are therefore capa-
ble of forming products of addition, while the saturated com-
pounds can only form products of substitution.
In this sense the substances composing this series are non-
saturated, but they are not so in the sense that they contain C
or other atoms whose valences are not satisfied. The following-
formulae indicate the constitution of the substances of this series,
and their relation to those of the previous one. It will be
observed that in the allyl compounds, two neighboring C atoms
exchange two valences :
CH3
CH,
CH,H
CH3
CH,
CH,
OH
or
CH,
CH,
COH
or
CH,
CH,
COOH
fCH,
CH,
CH.
1 1
(C.HTy j (c,H,y ) n (C3H50)' ) (C.H.oy ? n
H f H fu Hf Hfu
Propyl hydrid Propyl hydroxid
(hyurocarbon). (alcohol).
Propionyl hydrid
(aldehyde).
Propionyl hydroxid • Propyl
(acid). (radical). .
f /~<TT ~1 r^TT
V^Xl, V^Jtl,
CH,
CH, fCH,
2
SH
f
SH
CH
CH
CH,
CH,OH
COH
COOH
CH,
I 1 J
or or
or
or
C3H6
(c.H.y \ 0 (c,H,oy )
Hfu H \
0
Diallyl Allyl hydroxid Acrolein
(hydrocarbon). (alcohol). (aldehyde).
Acrylic acid
(acid).
Allyl
(radical).
Diallyl — Q3 jj5 r — 82 — formerly known as allyl, is obtained by
the action of sodium upon allyl iodid, and is not, as its empirical
302 MANUAL OF CHEMISTRY.
formula would seem to indicate, a superior homologue of acety-
lene and allylene (q.v.).
It is a colorless liquid, having a peculiar odor, somewhat re-
sembling that of horseradish ; boils at 59° (138°. 2 P.) ; sp. gr. 0.684
•at 14° (57°. 2 F.).
C H )
Vinyl hydrate — Vinyl alcohol — 2 jj j- O — is produced by dis-
tilling vinyl suli'uric acid, (C2H3)H,SO4, formed by the action
of H2SO4 on acetylene, with HaO. It is an unstable liquid, having
a very pungent odor.
C H )
Allyl hydrate — Allylic alcohol — 3 jj |- O — 58 — may be obtained
by the action of sodium upon dichlorhydrin in ethereal solution ;
or by heating four parts of glycerol with one part of crystallized
oxalic acid.
Allylic alcohol is a colorless, mobile liquid ; solidifies at —54°
(-65°.2 P.) ; boils at 97° (206°.6 F.) ; sp. gr. 0.8507 at 25° (77° F.) ;
soluble in H2O ; has an odor resembling the combined odors of
alcohol and essence of mustard ; burns with a luminous flame.
Allyl alcohol is isomeric with propylic aldehyde and with ace-
tone. Being an unsaturated compound, it is capable of forming
products of addition with Cl, Br and I, etc., which are isomeric
or identical with products of substitution obtained by the action
of the same elements upon glycerol. Oxidizing agents convert it
first into acrolein, acrylic aldehyde, C3H4O, and finally into
acrylic acid. It does not combine readily with H, but in the
presence of nascent H combination takes place slowly, with
formation of propylic alcohol.
C H )
Allyl oxid — Allylic ether — f,3-,, ' - O — 98 — exists in small quan-
tities in crude essence of garlic. It is obtained as a colorless
liquid, having an alliaceous odor ; insoluble in H2O ; boiling at
82° (179°. 6 F.), by a number of reactions, but best by the action
of allyl iodid upon sodium-allyl oxid.
C H )
Allyl sulfid— Essence of garlic— X3jj f S— 114— is obtained by
the action of an alcoholic solution of potassium sulfid upon
allyl iodid ; also as a constituent of the volatile oil of garlic, by
macerating garlic, or other related vegetables, in water, and dis-
tilling. Crude essence of garlic is thus obtained as a heavy, fetid,
brown oil ; this is purified by redistillation below 140" (284° F.) ;
contact with potassium, and subsequent redistillation from
calcium chlorid.
It is a colorless, transparent oil ; lighter than HaO, sparingly
soluble in H2O, very soluble in alcohol and ether ; boils at 140"
(280° F.) ; has an intense odor of garlic. It does not exist natu-
rally in the plant, but is formed during the process of extraction
ALLYLIC SERIES. 303
l>y the action of HUG. probably in a manner similar to that in
which essence of mustard is formed under similar circumstances.
It is to the formation of allyl sulfid, which is highly volatile,
that garlic owes the odor which it emits.
Allyl chlorid — C3fioCl— a colorless liquid, boils at 46° (114°.8
F.). has an irritating odor ; formed by slowly adding PC13 to
allyl alcohol.
Allyl bromid— C8H6Br— a liquid boiling at 71° (159".8 F.), ob-
tained in the same manner as the chlorid, using PBr3.
Allyl iodid — C3H§I — a colorless liquid having a peculiar odor ;
boils at 101°. 5 (214°. 7F.) ; insoluble in HaO ; obtained by carefully
mixing allyl alcohol, red P, and I, and distilling after 24 hours.
Allyl tribromid- (C3H5Br)3 — a colorless liquid, very soluble in
ether, boiling at 217D (422° F.), solidifying at -10° (14° F.) ; ob-
tained by acting upon allyl iodid with 2£ times its weight of Br.
Has been recommended as a nervous sedative.
Allyl sulfocyanate — Essential oil of mustard — Oleum sinapis
volatile (U. S.)— ~G£ \ S— 99.— If the seeds of white or black
Os-Hs }
mustard be strongly expressed, a bland, neutral oil is obtained,
which resembles rape-seed and colza oils in its physical proper-
ties, and in being composed of the glycerids of stearic, oleic, and
erucic acids. The cake remaining after the expression of this
oil from black mustard, or the black- mustard seeds themselves,
pulverized and moistened with H2O, gives off a strong, pungent
odor. If the H2O be now distilled, a volatile oil passes over with
it, which is the crude essential oil of mustard.
In practice the powdered cake of black-mustard seeds, from
which the fixed oil has been expressed, is digested with H2O for
24 hours, after which the H2O is distilled as long as any oily
matter passes over; the oil is collected, dried by contact with
calcium chlorid, and redistilled. Essence of mustard may also
be obtained synthetically by the action of allyl bromid or iodid
upon potassium sulfocyanate, or by the action of allyl iodid upon
.silver sulfocyanate.
This essence does not exist preformed in the mustard, but re-
sults from the decomposition of a peculiar constituent of the
seeds, potassium myronate, determined by cryptolytic action set
up by another constituent, myrosin, in the presence of H2O.
Potassium myronate exists only in appreciable quantity in the
black variety of mustard, from which it may be obtained in the
shape of short prismatic crystals, transparent, odorless, bitter ;
very soluble in H2O, sparingly so in alcohol.
Myrosin is a nitrogenized cryptolite, existing in the white as
well as in the black mustard, and in other seeds. It may be ob-
tained from white mustard seeds, in an impure form, by extrac-
304 MANUAL OF CHEMISTRY.
tion with cold H2O, filtering and evaporating the solution at a,
temperature below 40° (104° P.) ; the syrupy fluid so obtained is
precipitated with alcohol, the precipitate washed with alcohol,
redissolved in HSO, and the solution evaporated below 40°
(104° F.) to dry ness.
At temperatures above 40° (104° F.) my rosin becomes coagu-
lated and incapable of decomposing potassium myronate, a.
change which is also produced by contact with acetic acid. As-
the rubefacient and vesicant actions of mustard when moistened
with HaO, are due to the production of allyl sulfocyanate, neither
vinegar, acetic acid, nor heat greater than 40° (104° F.) should be
used in the preparation of mustard cataplasms.
Pure allyl sulfocyanate is a transparent, colorless oil; sp. gr.
1.015 at 20° (68° F.) ; boils at 143° (289°.4 F.) ; has a penetrating,
pungent odor, sparingly soluble in H2O, very soluble in alcohol
and ether. When exposed to the light it gradually turns brown-
ish-yellow and deposits a resinoid material. When applied to
the skin it produces rubefaction, quickly followed by vesication.
ACIDS AND ALDEHYDES OF THE ACRYLIC SERIES.
These substances bear the same relation to the alcohols of the
allyl series that the volatile fatty acids and the corresponding-
aldehydes bear to the ethylic series of alcohols.
The acids of this series differ from those containing the same
number of C atoms in the formic series, by containing two atoms
of H less ; they are readily converted into acids of the formic
series by the action of potassium hydroxid in fusion.
C H! O )
Acrylic acid — ^ j- 0 — 72 — is obtained by oxidation of acro-
lein by silver oxid, and is formed in a number of other reactions.
It is a colorless, highly acid liquid ; has a penetrating odor ;
solidifies at 7° (44°.6 F.) ; boils at 140° (284° F.). Nascent H unites
with it to form propionic acid. It forms crystalline salts and
ethers.
C H O )
Acrylic aldehyde — Ally lie aldehyde — Acrolein — 3 ij j- — 56. —
When the fats and fixed oils are decomposed by heat, a disagree-
able, irritating odor is produced, which is due to the formation
of acrolein by the dehydration of the glycerol contained in the
fatty material. Acrolein may be obtained by heating glycerol
with strong H2SO4, or with hydropotassic sulfate. Glycerol is
the alcohol (hydroxid) of a radical having the same composition
as allyl, but so differing from it in constitution as to be trivalent
in place of univalent.
ACIDS AND ALDEHYDES, ACRYLIC SERIES. 305
(CSH6)"'(OH)3 = 2H,O + (C3H3O)'H
Glycerol. Water. Acrolein.
Acrolein is a colorless, limpid liquid ; lighter than HaO ; boils
at 52°. 4 (126°.3 F.) ; sparingly soluble in HaO, more soluble in
alcohol ; very volatile ; its vapor is very pungent and irritating.
When freshly prepared it is neutral in reaction, but on contact
with air it rapidly becomes acid by oxidation. For the same
reason it does not keep well, even in closed vessels ; on standing
it deposits a flocculent material, which has been called disocryl,
while at the same time formic, acetic, and acrylic acids are
formed. Oxidizing agents convert it into acrylic acid, or, if
they be energetic, into a mixture of formic and acetic acids.
The caustic alkalies produce from it resinoid substances similar
to those formed from acetic aldehyde. With NH3 it forms a.
crystalline, odorless compound, which behaves as a base.
Aerolein is formed whenever glycerin, or any substance con-
taining it or its compounds with the fatty acids, is heated to a
temperature sufficient to effect its decomposition ; for this reason;
and because of the irritating action of the acrolein, the heavy
petroleum-oils are preferable to those of vegetable or animal ori-
gin for the lubricating of machinery operated in enclosed places.
Crotonic acid — 4 W - O — 86 — was first obtained from croton-oil,
oleum tiglii (U. $.), oleum crotonis(Br.\ in which it exists in com-
bination with glycerin, and accompanied by the glycerin ethers
of several other fatty acids ; it is, however, neither the vesicant
nor the purgative principle of the oil. It may be obtained by
saponification of croton-oil, or, better, by the action of potassium
hydroxid upon allyl cyanid.
It is an oily liquid ; solidifies at —5° (23° F.) ; acrid in taste ;
gives off highly irritating vapors at temperatures slightly above
0° (32° F.). When taken internally it acts as an irritant poison.
An acid obtained by oxidation of crotonic aldehyde is probably
an isomere, as it is in the form of crystals at ordinary tempera-
tures, and only fuses at 73° (163°.4 F.).
Crotonic aldehyde— CjH^ I —70.— If aldehyde, H2O, and HC1 be
mixed together at a low temperature, and the mixture exposed to
diffused daylight for some days, an oily liquid is formed, which,
after purification, has the composition C4H8Oii. This substance,
known as aldol. when exposed to heat, is decomposed into water
and crotonic aldehyde : C4H6Oii = HaO+C^eO.
Crotonic aldehyde is a colorless liquid ; boils at 105° (221° F.) ;
gives off highly irritating vapors. It bears the same relation to
croton chloral that aldehyde does to chloral.
306 MANUAL OF CHEMISTRY.
C H O )
Angelic acid — 5 Vj > O — 100 — exists in angelica root, in the
flowers of chamomile, Anthemis (U. S.), and in croton-oil.
It crystallizes in colorless prisms, which fuse at 45°. 5 (113°. 9 F.) ;
boils at 185° (365° F.) ; has an aromatic odor and an acid, pungent
taste ; sparingly soluble in cold HaO ; readily soluble in hot HaO,
alcohol, and ether. By the action of heat it is converted into its
C U iCH ^O )
isomere, inethylcrotonic acid, 3'j| - O.
Oleic acid— Acidum oleicum (U. S.)— 18 3^ I O— 246 — exists as
its glyceric ether, olein, in most, if not in all the fats and in all
fixed oils. It is obtained in an impure form on a large scale as a
by-product in the manufacture of candles. This product is, how-
ever, very impure. To purify it, it is first cooled to 0° (32° F.),
the liquid portion collected ; cooled to —10° (14° F.), expressed,
and the solid portion collected ; this is melted and treated with
half its weight of massicot ; the lead oleate so obtained is dis-
solved out by ether ; the decanted ethereal solution is shaken with
HC1, the ethereal layer decanted and evaporated, when it leaves
oleic acid, contaminated with a small quantity of oxyoleic acid,
from which it can be purified only by a tedious process.
Pure oleic acid is a white, pearly, crystalline solid, which fuses
to a colorless liquid at 14° (57°. 2 F.) ; it is odorless and tasteless ;
soluble in alcohol, ether, and cold H2SO4 ; insoluble in HaO »
sp. gr. 0.808 at 19° (66°. 2 F.). Neutral in reaction. It can be dis-
tilled in vacuo without decomposition, but when heated in con-
tact with air, it is decomposed with formation of hydrocarbons,
volatile fatty acids, and sebacic acid. It dissolves the fatty acids
readily, forming mixtures whose consistency varies with the pro-
portions of liquid and solid acid which they contain. The solid
acid is but little altered by exposure to air, but when liquid it
absorbs O rapidly, becomes yellow, rancid, acid in reaction, and
incapable of solidifying when cooled ; these changes take place
the more rapidly the higher the temperature.
When heated with a small amount of chlorin, bromin or iodin
Tinder pressure to 270°-280° (518°-536° F.) for several hours, oleic
acid is converted into a mixture of solid fatty acids containing 70
per cent, of stearic acid.
Cl and Br under ordinary pressure attack oleic acid with for-
mation of products of substitution. If oleic acid be heated with
an excess of caustic potassa to 200° (392° F.), it is decomposed
into palmitic and acetic acids : deB^On + 2KHO = Ci6H3iOaK +
CaHsOaK + Ha ; a reaction which is utilized industrially to obtain
hard soaps, palmitates, from olein, which itself only forms soft
soaps. Cold HaSCh dissolves oleic acid, and deposits it unaltered
ACIDS AND ALDEHYDES, ACRYLIC SERIES. 307
on the addition of H2O, but if the acid solution be heated it turns
brown and gives off SOa. Nitric acid oxidizes it energetically,
with formation of a number of volatile fatty acids and acids of
another series — suberic, adipic, etc. The oleates of the alkali
metals are soft, soluble soaps ; those of the earthy metals are in-
soluble in H2O, but soluble in alcohol and in ether.
Elaidic acid is an isomere of oleic acid, produced by the action
upon it of nitrous acid in the preparation of Unguentum Tiydrar-
gyri nitratis (U. S.; Br.). The nitrous fumes formed convert the
oleic acid, contained in the oil and lard used, into elaidic acid,
which exists in the ointment in combination with mercury.
SOS MANUAL OF CHEMISTRY.
SECOND SERIES OF HYDROCARBONS— OLEFINS.
SERIES CnH3n.
The terms of this series contain two H atoms less than the cor-
responding terms of the first series. They differ in constitution
in this, that, while in the first series a single valence is exchanged
between each two neighboring C atoms, in the second series two
valences are exchanged between two of the C atoms :
C=H2 C— H
I II
C=H3 C=H,
Propane. Prepylene.
They are designated as olefins ; or, to distinguish them from
the terms of the first series, by the terminations ylene or ene, thus
the second is called ethylene or etliene. They behave as bivalent
radicals.
Ethene — Ethylene — Olefiant gas — Elayl — Heavy carburetted
CH3
hydrogen — 1 1 — 28 — is formed by the dry distillation of fats,
CH2
resins, wood, and coal, arid is one of the most important constit-
uents of illuminating gas. It is also obtained by the dehydration
of alcohol or ether.
It has been obtained synthetically : (1) by passing a mixture of
H2S and carbon monoxid over iron or copper heated to redness ;
(2) by heating acetylene in the presence of H, or by the action of
nascent H upon copper acetylid ; (3) by the action of H upon the
chlorid CaCU, obtained by the action of Cl upon carbon disulfid.
It is prepared in the laboratory by the dehydration of alcohol : a.
mixture of 4 pts. H2SO4 and 1 pt. alcohol is placed in a flask con-
taining enough sand to form a thin paste, and gradually heated
to about 170° (338° F.); the gas, which is given off in abundance,
is purified by causing it to pass through wash-bottles containing
HaO, an alkaline solution, and concentrated H2SO4.
Pure ethylene is a colorless gas ; tasteless ; has a faint odor re-
sembling that of salt water, or an ethereal odor when impure ;
irrespirable ; sparingly soluble in H-iO, more soluble in alcohol.
It burns with a luminous, white flame, and forms explosive mix-
tures with air and oxygen.
When heated for some time at a dull red heat it is converted
into acetylene, ethyl and methyl hydrids, a tarry product, and
carbon.
Ethylene readily enters into combination. It unites wibh H to
form ethyl hydrid, C2H6. With O it unites explosively on the
approach of a flame, with formation of carbon dioxid and H2O.
SECOND SERIES OF HYDROCARBONS — OLEFINS. 309
Oxidizing agents, such as 'potassium permanganate in alkaline
.solution, convert it into oxalic acid and H2O. A mixture of Cl
and ethene, in the proportion of two volumes of the former to
one of the latter, unite with an explosion on contact with flame,
the union being attended with a copious deposition of C and the
formation of HC1. Chlorin and ethene, mixed in equal volumes
and exposed to diffused daylight, unite slowly, with formation of
an oily liquid; ethene chlorid, C3H4Cl2= Dutch liquid, to whose
formation ethene owes the name oleflant gas. By suitable means
ethene may also be made to yield chlorinated products of substi-
tution, the highest of which is carbon dichlorid, C2Ca.4. Br and I
.also form products of addition and of substitution with ethene.
By union with (OH)2 it forms glycol (Q.V.). It slowly dissolves
in ordinary H2SO4, with formation of sulfovinic acid. With
fuming H2SO4 it combines with elevation of temperature and for-
mation of ethionic anhydrid.
When inhaled, diluted with air, ethene produces effects some-
what similar to those of nitrous oxid.
The name ethylidene is given to a grouping of C2H4 which
"would be isorneric with ethene were it capable of free existence.
It has not been isolated, but exists in a series of compounds whose
relations to the etheue derivatives is shown in the following for-
mulae:
CH2 CH2C1 CH2OH
CH2 CH2C1 CH3OH
Ethene. Ethene chlorid. Ethene glycoL
CIl3 CHa Cxia
CH CHCla CH(OH).,
II
Ethylidene. Ethylidene chlorid. Ethylidene glycol.
Two of the isomeric lactic acids (see p. 314) are derived from
ethene and ethylidene by addition of COsHj.
CHsCl
Ethene chlorid — Bichlorid of ethylene — Dutch liquid— |
CH2C1
99 — is obtained by passing a current of ethene through a retort in
which Cl is being generated, and connected with a cooled receiver.
The distillate is washed with a solution of caustic potassa, after-
ward with H2O, and is finally rectified.
It is a colorless, oily liquid, which boils at 82°.5 (180°. 5 F.) ; has
a sweetish taste and an ethereal odor. It is isomeric with the
CaH«Cl
chlorid of monochlorinated ethyl, | , which boils at 64 "(147°. 2
Cl
P.). It is capable of fixing,other atoms of Cl by substitution for
H, and thus forming a series of chlorinated derivatives, the high-
est of which is CaCl«.
310 MANUAL OF CHEMISTRY.
Pentene— Amylene or valerene— C6H10— 70— a colorless, mobile
liquid, boiling at 39° (102°. 2 P.) ; obtained by heating alcohol with
a concentrated solution of zinc chlorid.
Its use as an anaesthetic has been suggested.
DIATOMIC ALCOHOLS.
SERIES CnHan+aOa.
These substances are designated as glycols. They are the
hydroxids of the hydrocarbons of the series C«H3n, and consist
of those hydrocarbons, playing the part of bivalent radicals,
united with two groups OH ; their general typical formula is then.
(CnHa,0 j. Q2 We have geen (p 238) that the primary monoatomie
alcohols contain the group of atoms (CHaOH), united with
n(CnHa» + i); the primary glycols are similarly constructed, and
consist of twice the group (CHaOH), united in the higher terms
to n(CHa). The constitution of the glycols and their relations to-
the monoatomic alcohols are indicated by the following formulae :
CHaOH CHaOH
! I
CHj CHj
CHS CHaOH
Primary propyl alcohol. Primary propyl glycol.
As the monoatomic alcohols are such by containing in their
molecules a group (OH), closely attached to an electro-positive
group, and capable of removal and replacement by an electro-
negative group or atom, so the glycols are diatomic by the fact
that they contain two such groups (OH). As the monoatomic alco-
hols are therefore only capable of forming a single ether with a,
monobasic acid, the glycols are capable of forming two such ethers :
CHa(CaH3Oa)' CHa(CaH3Oa)' CHa(CaH3Oa)'
H3 CHaOH CHa(CaH3O3)'
Ethyl acetate. Monoacetic glycol. Diacetic glycol.
C
/OTT
Methene glycol, which would have the composition HaC' X1
is not known. Its haloid ethers are, however, known. A con-
densation product corresponding to it exists as methene dime-
/OCH
thylate, ^&(, also called methylal and formal, as a thin
liquid, boiling at 42° (107°. 6 F.), soluble in alcohol, ether, and water,.
sp. gr. 0.855; formed by oxidizing methyl alcohol with H3SO4 and
MnOa. It has been used as a medicine.
Ethene glycol — Ethylene glycol or Alcohol or Hydroxid —
DIATOMIC ALCOHOLS. 311
CHaOH
—62. —This, the best known of the glycols, is prepared by
CHaOH
the action of dry silver acetate upon ethylene bromid. The
ether so obtained is purified by redistillation, and decomposed
by heating for some time with barium hydroxid.
It is a colorless, slightly viscous liquid ; odorless ; faintly sweet ;
sp. gr. 1.125 at 0° (32° F.); boils at 197° (386°. 6 F.); sparingly solu-
ble in ether ; very soluble in water and in alcohol.
It is not oxidized by simple exposure to air, but on contact with
platinum-black it is oxidized to glycolic acid ; more energetic oxi-
dants transform it into oxalic acid. Chlorin acts slowly upon
glycol in the cold ; more rapidly under the influence of heat, pro-
ducing chlorinated and other derivatives. By the action of dry
HC1 upon cooled glycol, a product is formed, intermediate between
it and ethylene chlorid, a neutral compound — ethene chlorhydrin,
CH2OH
, which boils at 130° (266° F.).
CHaCl
Ethene oxid— Ethylene oxid — (C2H4)"O — 44.— This substance,
isomeric with aldehyde, is obtained by the action of potassium
hydroxid upon ethene chlorhydrate.
It is a transparent, volatile liquid; boils at 13°. 5 (54°. 3 F.) ; gives
off inflammable vapors; mixes with H2O in all proportions. It is
capable of uniting directly with H2O to form glycol; and with
HC1 gas to regenerate ethene chlorhydrin.
Taurin— SO3C2H,N— 125 — is isomeric with a derivative of glycol,
isethionamid. It is obtained from ox-bile by boiling with dilute
HC1 ; decanting and concentrating the liquid ; separating from the
sodium chlorid which crystallizes ; evaporating further, and pre-
cipitating with alcohol. The deposit is purified by recrystalliza-
tion from alcohol.
It crystallizes in large, transparent, oblique, rhombic prisms,
permanent in air, soluble in H2O, almost insoluble in absolute
alcohol and ether.
Taurin has acid properties and forms salts ; it is not attacked
by H2SO4, HNO3, or nitromuriatic acid, but is oxidized by nitrous
acid, with formation of H2O, N, and isethionic acid.
It exists in the animal economy, in the bile in taurocholic acid
(q.v.); and has also been detected in the intestine and faeces,
muscle, blood, liver, kidneys, and lungs. The pneumic acid, de-
scribed as existing in the lung, is taurin. When taken internally,
it is eliminated by the urine, not in its own form, but as taurocar-
bamic or isethionuric acid, C; H.N-.SO.-.
ACIDS DERIVED FROM THE GLYCOLS.
As the acids of the acetic series are obtained from the primary
monoatomic alcohols by the substitution of O for Ha in the char-
312 MANUAL OF CHEMISTRY.
acterizing group CHaOH :
CH3 CH3
CEU,OH CO,OH
Ethyl alcohol. Acetic acid.
so the diatomic alcohols may, by oxidation, be made to yield acids,
formed by the same substitution of O for H2. But the glycols
differ from the inonoatomic alcohols in containing two groups
CH2OH, and they consequently yield two acids, as the substitu-
tion occurs in one or both of the alcoholic groups :
CH,,OH CH2,OH CO,OH
CH2,OH CO,OH CO,OH
Ethene glycol. Glycolic acid. Oxalic acid.
A study of these two acids shows them to be possessed of pecu-
liar differences of function. Each of them contains two groups
(OH), whose hydrogen is capable of replacement by an acid or
alcoholic radical :
CUa,OOari5
COOH
Ethylglycolic
acid.
CHa,OH
CO,OC8H5
Ethyl gly-
colate.
CH3OC.,H6
CO,OC2H6
Ethyl ethyl-
glycolate.
CO,OH
CO,O'CaHs
Ethyloxalic
acid.
CO,OCaH»
CO,OCaH»
Ethyl oxa-
late.
They are, therefore, both said to be diatomic. The ability, how-
ever, of the two acids to form salts is not the same, for while-
oxalic acid is capable of forming two salts of univalent metals,
and a salt of a bivalent metal with a single molecule of the acid;
glycolic acid only forms a single salt of an univalent metal, and
two of its molecules are required to form a salt of a bi valent metal ;
in other words, glycolic acid is monobasic, while oxalic acid is di-
basic. It is only that H atom which is contained in the electro-
negative group COOH which is replaceable as acid hydrogen,
while that of the electro-positive group CH2OH is only replacea-
ble, as is the corresponding hydrogen of an alcohol.
In general terms, therefore, the atomicity of an organic acid
may be greater than its basicity, the former representing the
number of H atoms contained in its molecule which are capable
of being displaced by alcoholic radicals, while the latter repre-
sents the number of H atoms replaceable by electro-positive ele-
ments or radicals, with formation of salts or of ethers.
There may, therefore, be obtained from the glycols, by more
or less complete oxidation, two series of acids; those of the first
are diatomic and monobasic ; those of the second diatomic and
dibasic.
DIATOMIC AND MONOBASIC ACIDS. 313
DIATOMIC AND MONOBASIC ACIDS.
SERIES CnH2nO3.
The acids of this series at present known are :
•(Carbonic acid) CO3H., Oxyvaleric acid CsO3Hi0
Olycolic acid C<jO3H4 Leucic acid CgOsHu
Ethyleno-lactic acid — C3O3H« (?) CEnanthic acid C^OsHna
Butylactic acid C4O3H8
The first-named of these acids, although not capable, so far as
yet known, of existing in the free state, is widely represented in
nature in the shape of its salts, the carbonates. Its position in
this series is an anomaly, and at first sight a contradiction, as it
is certainly not a monobasic, but a distinctly dibasic acid, or,
more properly speaking, would be such were it obtained in a
.state of purity. It is, however, in this position, as the inferior
homologue of glycolic acid, that carbonic acid is most naturally
placed, and the dibasic nature of the latter acid does not present
any valid objection to such a position, for, if we consider one term
of a series as derivable from its superior homologue by the sub-
traction of CH2, and if we bear in mind that the basic nature of
the hydrogen atom in a group OH depends upon its close union
with the group CO (or with some other electro-negative group),
it will become evident that the inferior homologue of glycolic
acid must contain two groups OH united to one CO, and must,
therefore, be dibasic :
CH3OH OH
— CH3 = | or
CO, OH CO, OH
Glycolic acid. Carbonic acid
The other acids of the series are formed : (1.) By the partial
oxidation of the corresponding glycol :
CH.OH CHaOH Wx
+ oa = i + ;>o
CH2OH CO,OH
Glycol. Glycolic acid. Water.
(2.) By the combined action of water and silver oxid upon the
monochloracid of the acetic series, or by heating the alkaline salt
of such an acid with water or potassium hydroxid :
•CH2C1 CH3OH
+ }> ml + KC1
+ H>° = I
COOK CO,
OH
Potassium Water. Glycolic acid. Potassium
monochloracetate. chlorid.
(3.) By reducing the corresponding acid of the oxalic series by
nascent hydrogen :
314: MANUAL OF CHEMISTRY.
COOH CHaOH
I + 2H, = | + £^0
COOH COOH
Oxalic acid. Glycolic acid. Water.
/OH
Carbonic acid — CO:f QJX — 62. — Although this acid has not been
isolated, it probably exists in aqueous solutions of CO2, which
have an acid reaction, while dry CO2 is neutral. Its salts, the-
carbonates, are well characterized.
Ethers are also known corresponding to orthocarbonic acid,
C(OH)4 although the acid itself is unknown.
CH2OH
Glycollic acid— | — 76 — is formed by the oxidation of gly-
COOH
col, by the action of nitrous acid on glycocol, and by the action
of potash on monochloracetic acid.
It forms deliquescent, acicular crystals; very soluble in water;.
soluble in alcohol and ether; has a strongly acid taste and reac-
tion; fuses at 78° (172°.4 R); is decomposed at 150° (302° P.); at an
intermediate temperature it loses H3O, forming glycollid, or gly-
collic anhydrid, CjH,(X
Lactic acids — C3H6O3 — 90. — There are probably three, certainly
two, acids having this composition. Two of these would seem,
from their products of decomposition, to be of similar constitu-
tion, while the molecular composition of the third is distinct.
The two of similar constitution are sometimes designated as-
ethylidene lactic acids, because of their containing the group of
atoms CH3, while the third is designated as ethyleno-lactic acid,
as it contains the group CHS. Their constitution is expressed by
the formulae :
CH, CHaOH
CH,OH CHa
C
OOH COOH
Ethylidene lactic acid. Ethyleno-lactic acid.
Obviously it is the ethylene acid which is the superior homologue
of glycollic acid.
Ethyleno-lactic Acid. — Muscular tissue contains a mixture of
this and optically active ethylidene lactic acid, which has been
known as sarcolactic acid.
Ethyleno-lactic acid may be obtained from muscular tissue or
from Liebig's extract of meat. It is optically inactive, as are also-
solutions of its salts ; its zinc salt contains 2 Aq, and is very solu-
ble in water and quite soluble in alcohol. When oxidized by
chromic acid it yields malonic acid.
DIATOMIC AND MONOBASIC ACIDS. 315
Of the two eth.ylid.ene lactic acids, that which is optically active
is the one accompanying ethylene lactic acid, and predominating
over it in amount, in dead muscle. It is to this acid that the
name paralactic acid, is most properly applied. It may be ob-
tained from Liebig's meat extract.
Paralactic acid differs from its two isomeres in that its solutions
are dextrogyrous, and the solutions of its salts are laevogyrous.
The specific rotary power of the acid is [a]D=+3°.5 ; that of the
zinc salt [a]D= — 7". 6 ; and of the calcium salt [OS]D= — 3°.8. Its prod-
ucts of decomposition are the same as those of ordinary lactic acid.
Ordinary Lactic Acid — Lactic acid of fermentation — Optically
inactive ethylidene lactic acid — Acidum lacticum (U. S.) — exists
in nature, widely distributed in the vegetable kingdom, and as
the product of a fermentation which is designated as the lactic,
in milk, sour-krout, fermented beet-juice, and rice, and in the
liquid refuse of starch factories and tanneries.
Lactic acid is obtained as a product of the fermentation of cer-
tain sugars, milk-sugar and grape-sugar; as a result of the proc-
esses of nutrition of a minute vegetable, the lactic ferment, in
which the sugar is converted into its inferior polymere : CeHnOe^
2C3HeO3. It is usually produced by allowing a mixture of cane-
sugar, tartaric acid, water, rotten cheese, skim milk and chalk
to ferment for 10 days at 35° (95° P.). The calcium lactate pro-
duced is separated, purified and decomposed with an equivalent
quantity of H2SO4.
It has also been obtained synthetically by oxidation of the
propylglycol of Wurtz, which is a secondary glycol, a synthesis
which indicates its constitution :
+ H,0
Water.
It is a colorless, syrupy liquid; sp. gr. 1.215 at 20° (68° F.); does
not solidify at —24° (—11°. 2 F.); soluble in water, alcohol, and
ether ; is not capable of distillation without decomposition ; when
heated to 130° (266° F.) it loses water and is converted into dilac-
tic acid, C6H1005, and, when heated to 250° (432° F.), into lactid,
C3H402. It is a good solvent of tricalcic phosphate.
Oxidizing agents convert this acid into formic and acetic acids,
without the formation of any malonic acid.
The three lactic acids occur in animal nature, either free or in
combination. Free lactic acid of fermentation occurs in the con-
tents of the small intestine, and, when vegetable food has been
taken, in the stomach. It is not, however, the acid to which the
CH,
CHOH
CH,OH
Propylglycol.
+ 0, =
Oxygen.
CH3
CHOH
COOH
Lactic acid.
316 MANUAL OF CHEMISTRY.
normal, unmixed gastric juice owes its acidity. Its salts have
been found to exist in the contents of the stomach and those of
"the intestines, chyle, bile, parenchymatous fluid of spleen, liver,
thymus, thyroid, pancreas, lungs, and brain ; urine. Pathologi-
cally in the blood in leucocythaemia, pyaemia, puerperal fever,
and after excessive muscular effort ; in the fluids of ovarian cysts
and transudations. In the urine it is abundant in phosphorus-
poisoning, in acute atrophy of the liver, and in rachitis and osteo-
malachia.
Muscular tissue, after death or continued contractions, contains
the mixture of acids known as sarcolactic acid. Normal, quies-
cent muscle is neutral in reaction; but, when rigor mortis ap-
pears, or if the muscle be tetanized, its reaction becomes acid
from the liberation of sarcolactic acid. Whether these acids are
formed de novo during the contraction of the muscle, or whether
they are produced by the decomposition of lactates existing in the
quiescent muscle, is still undetermined; certain it is, however,
that a given quantity of muscle has when separated from the cir-
culation, a fixed maximum of acid-producing capacity, which is
greater in a muscle that has been tetanized during the interval
between its removal and the establishment of rigor, than in one
which has been at rest.
There exist no grounds upon which to base the supposition
that, in rheumatic fever, lactic acid is present in the blood.
OXIDS AND SULFIDS OF CARBON.
As the saturated compound of carbon and oxygen is the anhy-
•drid of carbonic acid, the first of the series of acids just considered,
it and its congeners may be appropriately treated of in this place.
Carbon monoxid — Carbonous oxid — Carbonic oxid — CO — 28 — is
formed: (1.) By burning C with a limited supply of air. (2.) By
passing dry carbon dioxid over red-hot charcoal. (3.) By heating
oxalic acid with H2SO4 : CaO4H2 = HaO-|-CO-|-COa; and passing
the gas through sodium hydroxid to separate COa. (4.) By heat-
ing potassium ferrocyanid with HaSCh.
It is a colorless, tasteless gas; sp. gr. 0.9678 A; very sparingly
soluble in HaO and in alcohol.
It burns in air with a blue flame and formation of carbon
dioxid ; it forms explosive mixtures with air and oxygen ; it is oxi-
dized to carbon dioxid by cold chromic acid. It is a valuable re-
ducing agent, and is used for the reduction of metallic oxids at a
red heat. Ammoniacal solutions of the cuprous salts absorb it
readily. Being non-saturated, it unites readily with O to form
COa, and with Cl to form COC12, the latter a colorless, suffocating
gas, known as phosgene, or carbonyl chlorid.
OXIDS AND SULFIDS OF CARBON. 31 T
Toxicology. -^Carbon monoxid is an exceedingly poisonous gas,
and is the chief toxic constituent of the gases given off from blast-
furnaces, from defective flues, and open coal or charcoal fires,
and of illuminating gas. An atmosphere containing but a small
proportion of this gas' produces asphyxia and death, even if the
quantity of oxygen present be equal to or even greater than that
normally existing in the atmosphere; 0.5 per cent, of CO in air is
sufficient to kill a small bird in a few moments, and one per cent,
proves fatal to small mammals.
Poisoning by CO may occur in several ways. By inhalation of
the gases discharged from blast-furnaces and from copper-fur-
naces, the former containing 25 to 32 per cent. , and the latter 13 to
19 per cent, of CO. By the fumes given off from charcoal burned
in a confined space, which consist of a mixture of the two oxids-
of carbon, the dioxid predominating largely, especially when the
combustion is most active. The following is the composition of
an atmosphere produced by burning charcoal in a confined space,
and which proved rapidly fatal to a dog: oxygen, 19.19; nitrogen,.
76.62; carbon dioxid, 4.61; carbon monoxid, 0.54; marsh-gas, 0.04.
Obviously the deleterious effects of charcoal-fumes are more rap-
idly fatal in proportion as the combustion is imperfect and the
room small and ill- ventilated.
A fruitful source of CO poisoning, sometimes fatal, but more
frequently producing languor, headache, and debility, is to be
found in the stoves, furnaces, etc., used in heating our dwellings
and other buildings, especially when the fuel is anthracite coal.
This fuel produces in its combustion, when the air-supply is not
abundant, considerable quantities of CO, to which a further ad-
dition may be made by a reduction of the dioxid, also formed, in
passing over red-hot iron.
Of late years cases of fatal poisoning by illuminating gas are of
very frequent occurrence, caused either by accidental inhalation,
by inexperienced persons blowing out the gas, or by suicides-
The most actively poisonous ingredient of illuminating gas is CO,
which exists in the ordinary coal-gas in the proportion of 4 to 7.5
per cent., and in water-gas, made by decomposing superheated
steam by passage over red-hot coke, and subsequent charging
with vapor of hydrocarbons, in the large proportion of 30-35 per
cent.
The method in which CO produces its fatal effects is by form-
ing with the blood-coloring matter a compound which is more
stable than oxyhaemoglobin, and thus causing asphyxia by de-
stroying the power of the blood-corpuscles of carrying O from
the air to the tissues. This compound of CO and haemoglobin is-
quite stable, and hence the symptoms of this form of poisoning
are very persistent, lasting until the place of the coloring-matter
318
MANUAL OF CHEMISTRY.
thus rendered useless is supplied by new formation. The prog-
nosis is very unfavorable when the amount of the gas inhaled has
been at all considerable. The treatment usually followed, i.e.,
artificial respiration, and inhalation of O, failing to restore the
altered coloring-matter. There would seem to be no form of
poisoning in which transfusion of blood is more directly indicated
than in that by CO.
Detection after death. — The blood of those asphyxiated by CO
is persistently bright red in color. When suitably diluted and
examined with the spectroscope, it presents an absorption spec-
trum (Fig. 36) of two bands similar to that of oxyhsemoglobin
{Fig. 16, No. 11), but in which the two bands are more equal and
somewhat nearer the violet end of the spectrum. Owing to the
greater stability of the CO compound, its spectrum may be read-
ily distinguished from that of the O compound by the addition of
a reducing agent (an ammoniacal solution of ferrous tartrate),
which changes the spectrum of oxyhsemoglobin to the single-
band spectrum of haemoglobin (Fig. 16, No. 12), while that of the
CO compound remains unaltered, or only fades partially.
Fia. 36.
If a solution of caustic soda of sp. gr. 1.3 be added to normal
blood a black, slimy mass is formed, which, when spread upon a
white plate, has a greenish-brown color. The same reagent added
to blood altered by CO forms a firmly clotted mass, which in thin
layers upon a white surface is bright red in color.
A piece of gun-cotton upon which platinum-black has been
dusted fires in air containing 2.5 in 1,000 of CO.
For the method of determining CO in gaseous mixtures, see
p. 325.
Carbon dioxid — Carbonic anhydrid — Carbonic acid gas — COa — 44
— is obtained: (1.) By burning C in air or O. (2.) By decom-
posing a carbonate (marble=CaCO3) by a mineral acid (HC1 di-
luted with an equal volume of H2O).
At ordinary temperatures and pressures it is a colorless, suffo-
cating gas; has an acidulous taste; sp. gr. 1.529 A; soluble in an
equal volume of H2O at the ordinary pressure ; much more solu-
ble as the pressure increases. Soda water is a solution of carbonic
acid in H2O under increased pressure. When compressed to the
OXIDS AND SULFIDS OF CARBON.
319
extent of 38 atmospheres at 0° (32° F.); 50 atm. at 15° (59° F.); or
73 atm. at 30° (86° F.) it forms a transparent, mobile liquid, by
whose evaporation, when the pressure is relieved, sufficient cold
is produced to solidify a portion into a snow-like mass, which, by
spontaneous evaporation in air, produces a temperature of —90°
<-130°F.).
Carbon dioxid neither burns nor does it support combustion.
When heated to 1,300° (2,370° F.), it is decomposed into CO and O.
A similar decomposition is brought about by the passage through
it of electric sparks. When heated with H it yields CO and H2O.
When K, Na or Mg is heated in an atmosphere of CO2, the gas is
decomposed with formation of a carbonate and separation of
carbon. When caused to pass through solutions of the hydroxids
•of Na, K, Ca, or Ba, it is absorbed, with formation of the carbon-
ates of those elements, which, in the case of the last two, are de-
posited as white precipitates. Solution of potash is frequently
used in analysis to absorb CO2, and lime and baryta water as
tests for its presence. The hydroxids mentioned also absorb CO»
from moist air.
Atmospheric Carbon Dioxid. — Carbon dioxid is a constant con-
stituent of atmospheric air in small and varying quantities; the
mean amount in free country air being about 4 in 10,000. The
variation in amount under different conditions is shown in the
following table :
AMOUNT OF CABBOX DIOXID ix AIR.
Collected at
Parts in 10,000.
Determined by
Paris . ....
3 190
Boussingault and Lewy.
Andilly — twenty miles from Paris
2.989
Boussingault and Lewy.
Paris — Day
3.9
Boussingault.
Night
4.2
Boussingault.
Ocean — Day
5.42
Lewy.
Night
3346
Lewy.
4.68
Saussure.
Meadow— three-fourths mile from Geneva
Dry months
4 79 to 5 18
Saussure.
After long rains
3.57 to 4.56
Saussure.
December, damp and cloudy
3.85 to 4.25
Saussure.
January, frost .*
457
Saussure.
January, thaw
4.27
Saussure.
Lake Geneva
4.39
Saussure.
Arctic regions
4.83 to 6.41
Moss.
Gosport Barracks
6.45
Chaumont.
Anglesey Barracks
14.04
Chaumont.
Hilsey Hospital
4.72
Chaumont.
Portsmouth Hospital
9.78
Chaumont.
Cell in Pentonville Prison
9.89
Chaumont.
Cell in Chatham Prison . .
16.91
Chaumont.
Boys' school— 69 cubic feet per head
Boom — 51 cubic feet per head
31.0
52.8
Boscoe.
Weaver.
Girls' school — 150 cubic feet per head
Greenhouse — Jardin des Plantes
72.3
1.0
Pettenkofer.
Theatre — Parquet
23.0
Near ceiling
43.0
Lead mine — Lamps burn
80.0
F. Leblanc.
Lamps extinguished
390.0
F. Leblanc.
Grotto del Cane ".
7,360.0
F. Leblanc.
320 MANUAL OF CHEMISTRY.
It "will be observed that on land the amount is greater by night
than by day, while the reverse is the case at sea ; on land the
green parts of plants absorb CO2 during the hours of sunlight,
but not during those of darkness. The increase in the amount
in air over large bodies of water during the daytime is due to the
less solubility of CO2 in the surface-water when heated by the
sun's rays. The absence of vegetation accounts for the large
quantity of CO2 in the air of the polar regions, and the same
cause, aided by an increased production, for its excess in the air
of cities over that of the country.
The sources of atmospheric CO2 are :
(1.) The respiration of animals. — The air expired from the
lungs of animals contains a quantity of CO2, varying with the
age, sex, food, and muscular development and activity, while, at
the same time, a much smaller quantity is discharged by the skin
and in solution in the urine.
The expired air under ordinary conditions contains about 4.&
per cent, by volume of CO2, the proportion being greater the
slower the respiration.
(2.) Combustion. — The greater part of the atmospheric CO2 is a
product of the oxidation of C in some form as a source of light
and heat, In the table on p. 321 are given the amounts of CO2
produced, and of air consumed, by different kinds of fuel and
illuminating materials. In equal times, an ordinary gas-burner
produces nearly six times as much CO2, and consumes nearly ten
times as much air as a man. The amount of air consumed by
fuel is, for practical purposes, greater than that given in the
table, as the oxidation is never complete, the air in the chimney
frequently containing ten per cent, of oxygen by volume.
(3.) Fermentation. — Most fermentations, including putrefactive
changes, are attended by the liberation of CO2. Thus, alcoholic
fermentation takes place according to the equation :
C6H12O9 = 2C2H6O + 2CO2
180 92 88
and consequently discharges into the air 88 parts by weight of
CO2 for every 92 parts of alcohol formed, or 384 litres, of gas for
every litre of absolute alcohol obtained.
(4.) Tellural sources. — Volcanoes in activity discharge enormous
quantities of CO2, and, in volcanic countries, the same gas is
thrown out abundantly through fissures in the earth. All waters,
sweet and mineral, hold this gas in solution, and those which
have become charged with it under pressure in the earth's crust,
upon being relieved of the pressure when they reach the surface,,
discharge the excess into the air.
OXIDS AND SULFIDS OF CARBON.
321
(5.) Manufacturing processes. — Large quantities of CO2 are
added to the air in the vicinity of lime- and brick-kilns, ceinenfr-
works, etc.
(6.) In mines, after explosions of " fire-damp." These explosions
are caused by the sudden union of the C and H of CH4, with the
O of the air, and are consequently attended by the formation of
large volumes of CO2, known to miners as after-damp.
ij
w
f
s
$E|
O
fc
o
—
B
m
M
o
O
'001 saiP
-treo prepays m ;q3n
| ::::::: :*2*S :::::: : |
•sr>ran TB8H
lllllll^lll : 111 ill
Air deoxidized by
In one hour.
fll
^
•
§? .^JT^g S
>-< -oooo o
•s-t.u-nu oiq
-no ui on^l 8nQ
ooSoi3^soSfe25sN SSSo!o?l3 :
tDO'fl'OWOJi-iW'Ni-iaOOO iOOC-^OCOSOO
**
•fwuinjOA
» -g-ogS^1
o» - .5,0=3*-
Carbon dioxid pro-
duced by
o
1
a
4
^ V.rwo o
" -01
sl
• - 2S^°° fe
o -oooo o
sjj'Bd ni '^M.
jCq i-recl auQ
:S :fees&gi:a«S SSS£8§
•TO --(NTO^mTOHOJH rH«,«CC93-
•saiuniOA
. . . O
• • -OOO3D
• • -.-"-I5JO
Average per-
centage of
— «*
8 : - :88oooo*8o 8 :«. :«3
O • • • Jffi -t & TO CC TO 'ff O •>* •'-i '5J»
" ' '
•uoqJBQ
•ooSo^coo«S™ 2oooo«
:8838S33teegg Sg^feSS
• anoq auo ui panjnq
:::::: is ^ t- ^ t" .:::::
'
:::••.:: ~ :::: ::::::
• •: '53 •••§•••• *• —
• ,-^0 o ' . ® ' . . « 5§
;88§j 1; 2; ^§ * fl
§2SS§ •«» §-• ^S « §
f«a a c ^a § ag o'o 5c3 §-3 S
|lll|l|l§|ll llllll 1
BOOOSSOOM?»O ^^PnO-UO <1
Constancy of the amount of atmospheric carbon dioxid. — It has
been roughly estimated by Poggendorff that 2,500,000,000,000 cubic
metres of CO2 are annually discharged into our atmosphere, and
322 MANUAL OP CHEMISTRY.
that this quantity represents one-eighty-sixth of the total amount
at present existing therein. This being the case, with the present
production, the percentage of atmospheric CO2 would be doubled
in eighty-six years. No such increase has, however, been observed,
and the average percentage found by Angus Smith, in 1872, is
about the same as that observed by Boussingault in 1840, i.e.,
four parts in ten thousand. The CO2 discharged into the air is,
therefore, removed from it about as fast as it is produced. This
removal is effected in two ways : (1) by the formation of deposits
of earthy carbonates by animal organisms, corals, mollusks, etc. ;
(2) principally by the process of nutrition of vegetables, which
absorb CO2 both by their roots and leaves, and in the latter,
under the influence of the sun's rays, decompose it, retaining the
C, which passes into more complex molecules ; and discharging a
volume of O about equal to that of the CO2 absorbed.
Air contaminated with excess of carbon dioxid, and its effects
•upon the organism. — "When, from any of the above sources, the
air of a given locality has received sufficient CO3 to raise the pro-
portion above 7 in 10,000 by volume, it is to be considered as con-
taminated ; the seriousness of the contamination depending not
only upon the amount of the increase, but also upon the source
of the CO2. If the gas be derived from fermentation, or from
tellural or manufacturing sources, it is simply added to the other-
wise unaltered air, and the absolute amount of oxygen present
remains the same. When, however, it is produced in a confined
space by the processes of combustion and respiration, the com-
position of the air is much more seriously modified, as not only
is there addition of a deleterious gas, but a simultaneous removal
of an equal volume of O ; hence the importance of providing, by
suitable ventilation, for the supply of new air from without to
habitations and other places where human beings are collected
within doors, especially where the illumination is artificial.
Although an adult man deoxidizes a little over 100 litres of air
in an hour, a calculatior* of the quantity which he would require
in a given time cannot be based exclusively upon that quantity,
as the deoxidation cannot be carried to completeness; indeed,
when the proportion of CO2 in air exceeds five percent., it be-
<comes incapable of supporting life, while a much smaller quan-
tity, one per cent., is provocative of severe discomfort, to say the
least.
In calculating the quantity of air which should be supplied to
a given enclosed space, most authors have agreed to adopt as a
basis that the percentage of CO2 should not be allowed to exceed
0.6 volume per 1,000; of which 0.4 is normally present in air, and
0.2 the product of respiration or combustion. Taking the amount
of COs eliminated by an adult at 19 litres (=0.7 cubic foot) per
OXIDS AND SULFIDS OF CARBON.
323
tour, a man will have brought the air of an air-tight space of 100
•cubic metres (=3,500 cubic feet) up to the permissible maximum
of impurity in an hour.
Practically, owing to the imperfect closing of doors and win-
dows, and to ventilation by chimneys, inhabited spaces are never
hermetically closed, and a less quantity of air-supply than would
be required in an air-tight space will suffice.
A sleeping-room occupied by a single person should have a
cubic space of 30 to 50 cubic metres (=1,050 to 1,800 cubic feet),
conditions which are fulfilled in rooms measuring 10x13x8 feet,
and 13x15.6X9 feet.
In calculating the space of dormitories to be occupied by sev-
eral healthy people, the smallest air-space that should, under any
circumstances, be allowed, is 12 cubic metres (=420 cubic feet) for
«ach person. To determine the number of individuals that may
sleep in a room, multiply its length, width, and height together,
and divide the product by 420 if the measurement be in feet, or
l»y 12 if it be in metres. Thus, a dormitory 40 feet long, 20 feet
wide, and 10 feet high, is fitted for the accommodation of 19 per-
sons at most; for 40x20x10=8,000 and ^j°-=19.0o.
As a rule, in places where many persons are congregated, it is
necessary to resort to some scheme of ventilation by which a
sufficient supply of fresh air shall be introduced and the vitiated
air removed, the quantity to be supplied varying according to
circumstances. Experiment has shown that, in order to keep the
air pure to the senses, the quantity of air which must be supplied
per head and per hour in temperate climates is as shown in the
table :
Situation.
Cubic
metres .
Cubic
feet.
Situation.
Cubic
metres.
Cubic
feet.
Barracks (day-time)
.Barracks (night-time)
"Workshops (mechanical) .
School-rooms
35
70
70
35
1,236
2,472
2,472
1 236
Hospital wards (surgical).
Contagious and lying-in. .
Mines, metalif erous
170
170
150
170
6,004
6,004
5,297
6 004
Hospital wards
85
3,002
The amounts given are the smallest permissible, and should be
exceeded wherever practicable.
Lights. — Each cubic foot of illuminating-gas consumes in its
combustion a quantity of O equal to that contained in 7.14 cubic
feet of air, and produces 0.8 cubic feet of CO», besides a large
quantity of watery vapor, and less amounts of HjSCh, SO2, and
sometimes CO ; and an ordinary gas-burner consumes about three
feet per hour. It is obvious, therefore, that a much larger quan-
tity of pure ah* must be furnished to maintain the atmosphere of
an apartment at the standard of 0.6 per 1,000 of CO2, when the
vitiation is produced by the combustion of gas, than when it is
324 MANUAL OF CHEMISTRY.
the result of the respiration of a human being, and that to such
an extent that a single three-foot burner requires a supply of air
which would be sufficient for six human beings.
In theatres the contamination of the air by the burning of gas
should be entirely eliminated by placing the burners either under
the dome ventilator, or in boxes which open to the air of the
house only below the level of the burner, arid which are in com-
munication with a ventilating-shaft.
When artificial illumination is obtained from lamps or candles,
or from gas in small quantity and for a short time, the contami-
nation of the air is sufficiently compensated by the ventilation
through imperfect closing of the windows. A room without a.
window should never be used for human habitation.
One important advantage of the electric light is that it con-
sumes no O and produces no CO2.
Although, by the combustion of fuel, O is consumed and COZ
produced, heating arrangements only become a source of vitiation
of air when they are improperly constucted. Indeed, in the ma-
jority of cases, if properly arranged, they are the means of venti-
lation, either by aspirating the vitiated uir of the apartment, or
by the introduction of air from without.
Action on the economy. — An animal introduced into an atmos-
phere of pure CO2 dies almost instantly, and without entrance of
the gas into the lungs, death resulting from spasm of the glottis,,
and consequent apnoea.
When diluted with air, the action of COa varies according to its
proportion, and according to the proportion of O present.
When the proportion of O is not diminished, the poisonous action
of CO2 is not as manifest, in equal quantities, as when the air is
poorer in oxygen. An animal will die rapidly in an atmosphere
composed of 21 per cent. O, 59 per cent. N, and 20 per cent. CO2
by volume; but will live for several hours in an atmosphere
whose composition is 40 per cent. O, 37 per cent. N, 23 per cent.
CO2. If CO2 be added to normal air, of course the relative quan-
tity of O is slightly diminished, while its absolute quantity re-
mains the same. This is the condition of affairs existing in nature
when the gas is discharged into the air; under these circum-
stances an addition of 10-15 per cent, of COa renders an air rap-
idly poisonous, and one of 5-8 per cent, will cause the death of
small animals more slowly. Even a less proportion than this may-
become fatal to an individual not habituated.
In the higher states of dilution, CO2 produces immediate loss
of muscular power, and death without a struggle; when more
dilute, a sense of irritation of the larynx, drowsiness, pain in the-
head, giddiness, gradual loss of muscular power, and death in.
coma.
OXIDS AND SULFIDS OF CARBON. 325
If the COs present in air be produced by respiration, or com-
bustion, the proportion of O is at the same time diminished, and
much smaller absolute and relative amounts of the poisonous gas
•will produce the effects mentioned above. Thus, an atmosphere
containing in volumes 19.75 per cent. O, 74.25 per cent. N, 6 per
<;ent. CO2, is much more rapidly fatal than one composed of 21
per cent. O, 59 per cent. N, 20 per cent. CO2. With a correspond-
ing reduction of O, 5 per cent, of CO2 renders an air sufficiently
poisonous to destroy life; 2 per cent, produces severe suffering;
1 per cent, causes great discomfort, while 0.1 per cent., or even
less, is recognized by a sense of closeness.
The treatment in all cases of poisoning by CO2 consists in the
inhalation of pure air (to which an excess of O may be added),
aided, if necessary, by artificial respiration, the cold douche, gal-
vanism, and friction.
Detection of carbon dioxid and analysis of confined air. — Carbon
dioxid, or air containing it, causes a white precipitate when
caused to bubble through lime or baryta water. Normal air con-
tains enough of the gas to form a scum upon the surface of these
.solutions when exposed to it.
It was at one time supposed that air in which a candle contin-
ued to burn was also capable of maintaining respiration. This
is, however, by no means necessarily true. A candle introduced
into an atmosphere in which the normal proportion of O is con-
tained, burns readily in the presence of 8 per cent, of CO2 ; is per-
ceptibly dulled by 10 per cent. ; is usually extinguished with 13
per cent. ; always extinguished with 16 per cent. Its extinction
is caused by a less proportion of CO2, 4 per cent., if the quantity
of O be at the same time diminished. Moreover, a contaminated
atmosphere may not contain enough CO2 to extinguish, or per-
ceptibly dim the flame of a candle, and at the same time contain
enough of the monoxid to render it fatally poisonous if inhaled.
The presence of CO2 in a gaseous mixture is determined by its
absorption by a solution of potash ; its quantity either by measur-
ing the diminution in bulk of the gas, or by noting the increase
in weight of an alkaline solution.
To determine the proportions of the various gases present in
^iir the apparatus shown in Fig. 37 is used. A is an aspirator of
known capacity, filled with water at the beginning of the opera-
tion. It connects by a flexible tube from its upper part with an
absorbing appai-atus consisting of a, a U-shaped tube containing
fragments of pumice-stone, moistened with H2SO4 ; by the in-
crease in weight of this tube the weight of watery vapor in the
^volume of air drawn through by the aspirator is determined ; &, a
Xiiebig's bulb filled with a solution of potash; c, a U-tube filled
•with fragments of pumice moistened with H2Sp< ; b and c are
"weighed together and their increase in weight is the weight of
320
MANUAL OF CHEMISTRY.
CO2 in the volume of air operated on. Every gram of increase in
weight represents 0.50607 litre, or 31. (50856 cubic inches; d is a tube
of difficultly fusible glass, filled with black oxid of copper and
heated to redness ; e is a U-tube filled with pumice moistened with
H3SO4 ; its increase in weight represents H2O obtained from de-
composition of CH4. Every gram of increase in weight of e rep-
resents 0.444 gram, or 0.621 litre, or 38.781 cubic inches of marsh-
gas ; / and g are similar to & and c, and their increase in weight
represents CO2 formed by oxidation of CO and CH< in d. From
this the amount of CO is thus calculated: First, 2.75 grams are
deducted from the increase of weight of / and g for each gram of
CH4 formed by e ; of the remainder, every gram represents 0.6364
gram, or 0.5085 litre, or 31.755 cubic inches of CO. The air is
drawn through the apparatus by opening the stopcock of A to-
such an extent that about 30 bubbles a minute pass through b.
FIG. 37.
Carbon disulfid — Bisulfid of carbon — Carbonei bisulfidum
(U. S.)— CS2— 76— is formed by passing vapor of S over C heated
to redness, and is partly purified by rectification.
It is a colorless liquid; when pure it has a peculiar, but not
disagreeable odor, the nauseating odor of the commercial product
being due to the presence of another sulfurated body ; boils at
47° (116° 6 F )• sp. gr. 1.293; very volatile; its rapid evaporation
in vacuo produces a cold of -60° (-76° F.); it does not mix with
H2O ; it refracts light strongly.
It is highly inflammable, and burns with a bluish flame, giving-
off CO, and S03 ; its vapor forms highly explosive mixtures with
air, which detonate on contact with a glass rod heated to -50
(482° F.). Its vapor forms a mixture with nitrogen dioxid, which,
when ignited, burns with a brilliant flame, rich in actinic rays.
DIATOMIC AND DIBASIC ACIDS. 32T
There also exists a substance intermediate in composition be-
tween CO2 and CS2, known as carbon oxysulfid, CSO, which is
an inflammable, colorless gas, obtained by decomposing potas-
sium sulfocyanate with dilute H2SO4.
Toxicology. — Cases of acute poisoning by CSa have hitherto
only been observed in animals; its action is very similar to that
of chloroform.
Workmen enga.ged in the manufacture of CS2 and in the vul-
canization of rubber, as well as others exposed to the vapor of
the disulfid, are subject to a form of chronic poisoning which
may be divided into two stages. The first, or stage of excitation,
is marked by headache, vertigo, a disagreeable taste, cramps in
the legs; the patient talks, laughs, sings, and weeps immoder-
ately, and sometimes becomes violently delirious. In the second
stage the patient becomes sad and sleepy, sensibility diminishes,
sometimes to the extent of complete anaesthesia, especially of the
lower extremities, the headache becomes more intense, the ap-
petite is greatly impaired, and there is general weakness of the
limbs, which terminates in paralysis.
The only remedy which has been suggested is thorough venti-
lation of the workshops, and abandonment of the trade at the
first appearance of the symptoms.
DIATOMIC AND DIBASIC ACIDS.
SERIES CHs»_B)iO«.
Oxalic acid CaCXHj Pimelic acid C7O4Hi2
Malonic acid C3O4H4 Suberic acid C8O4Hi*
Succinic acid C4O4H8 Azelaic acid CgCKHis
Deoxyglutanic acid . . . .C6O4H8 Sebacic acid CioO4Hi&
Adipic acid C6O4Hi0 Roccellic acid. . CnO4H32
They are derived from the primary glycols by complete oxida-
tion ; they are diatomic and dibasic, and contain two groups, CO,
OH. They form two series of salts with the univalent metals,
and two series of ethers, one of which contains neutral, and the
other acid ethers. They may be obtained from the correspond-
ing glycols, or from acids of the preceding series, by oxidation.
COOH
Oxalic acid — | — 90 — C3O4H2,2Aq— 126 — does not occur free
COOH
in nature, but in the oxalates of K, Na, Ca, Mg, and Fe in the
juices of many plants: sorrel, rhubarb, cinchona, oak, etc. ; as a
native ferrous oxalate ; and in small quantity in human urine. It
is prepared artificially by oxidizing sugar or starch by HNO3, or
by the action of an alkaline hydroxid in fusion upon sawdust. The
soluble alkaline oxalate obtained by the latter method is con-
328 MANUAL OF CHEMISTRY.
verted into the insoluble Ca or Pb salt, which is washed and de-
composed by an equivalent quantity of H2SO4 or H2S ; and the
liberated acid purified by recrystallization.
Oxalic acid is also formed by the oxidation of many organic
substances — alcohol, glycol, sugar, etc. ; by the action of potassa
in fusion upon the alkaline formates ; and by the action of K or
Na upon CO2.
It crystallizes in transparent prisms, containing 2Aq, which
effloresce on exposure to air, and lose their Aq slowly but com-
pletely at 100° (212° F.), or in a dry vacuum. It fuses at 98° (208°. 4
F.) in its Aq; at 110°-132° (230°-269°.6 F.) it sublimes in the anhy-
drous form, while a portion is decomposed; above 160° (320° F.)
the decomposition is more extensive; H2O, CO2, CO, and formic
acid are produced, while a portion of the acid is sublimed un-
changed. It dissolves in I1}. 5 parts of water at 10° (50° F.); the
presence of HNO3 increases its solubility. It is quite soluble in
alcohol. It has a sharp taste and an acid reaction in solution.
Oxalic acid is readily oxidized; in watery solution it is con-
verted into CO2 and H2O, slowly by simple exposure to air, more
rapidly in the presence of platinum-black or of the salts of plati-
num arid gold ; under the influence of sunlight ; or when heated
with HNO3, manganese dioxid, chromic acid, Br, Cl, or hypo-
chlorous acid. Its oxidation, when it is triturated dry with lead
dioxid, is sufficiently active to heat the mass to redness. H2SO4,
H3PO4, and other dehydrating agents decompose it into H2O, CO,
and CO2.
Analytical Characters. — (1.) In neutral or alkaline solution a
white ppt. with a solution of a Ca salt. (2.) Silver nitrate, a white
ppt., soluble in HNO3 and in NH4HO. The ppt. does not darken
when the fluid is boiled, but, when dried and heated on platinum
foil, it explodes. (3.) Lead acetate, in solutions not too dilute, a
white ppt., soluble in HNO3, insoluble in acetic acid.
Toxicology. — Although certain oxalates are constant constitu-
ents of vegetable food and of the human body, the acid itself, as
well as hydropotassic oxalate, is a violent poison when taken in-
ternally, acting both locally as a corrosive upon the tissues with
which it comes in contact, and as a true poison, the predominance
of either action depending upon the concentration of the solution.
Dilute solutions may produce death without pain or vomiting,
and after symptoms resembling those of narcotic poisoning.
Death has followed a dose of 3 i. of the solid acid, and recovery
a dose of § i. in solution. When death occurs, it may be almost
instantaneously, usually within half an hour; sometimes after
weeks or months, from secondary causes.
The treatment, which must be as expeditious as possible, con-
sists in the administration, first, of lime or magnesia, or a soluble
DIATOMIC AND DIBASIC ACIDS. 329
salt of Ca or Mg suspended or dissolved in a small quantity of
HaO or mucilaginous fluid ; afterward, if vomiting have not oc-
curred spontaneously, and if the symptoms of corrosion have not
been severe, an emetic may be given. In the treatment of this
form of poisoning several points of negative caution are to be ob-
served. As in all cases in which a corrosive has been taken in-
ternally, the use of the stomach-pump is to be avoided. The
alkaline carbonates are of no value in cases of oxalic-acid poison-
ing, as the oxalates which they form are soluble, and almost as
poisonous as the acid itself. The ingestion of water, or the ad-
ministration of warm water as an emetic, is contraindicated when
the poison has been taken in the solid form (or where doubt
exists as to what form it was taken in), as they dissolve, and thus
favor the absorption of the poison.
Analysis. — In fatal cases of poisoning by oxalic acid the con-
tents of the stomach are sometimes strongly acid in reaction;
more usually, owing to the administration of antidotes, neutral,
or even alkaline. In a systematic analysis the poison is to be
sought for in the residue of the portion examined for prussic acid
and phosphorus ; or, if the examination for those substances be
omitted, in the residue or final alkaline fluid of the process for
alkaloids. If oxalic acid alone is to be sought for, the contents
of the stomach, or other substances if acid, are extracted with
water, the liquid filtered, the filtrate evaporated, the residue ex-
tracted with alcohol, the alcoholic fluid evaporated, the residue
redissolved in water (solution No. 1). The portion undissolved
by alcohol is extracted with alcohol acidulated with hydrochloric
.acid, the solution evaporated after filtration, the residue dissolved
in water (solution No. 2). Solution No. 1 contains any oxalic acid
which may have existed free in the substances examined ; No. 2
that which existed in the form of soluble oxalates. If lime or
magnesia have been administered as an antidote, the substances
must be boiled for an hour or two with potassium carbonate (not
the hydroxid), filtered, and the filtrate treated as above. In the
solutions so obtained, oxalic acid is characterized by the tests
given above. The urine is also to be examined microscopically
for crystals of calicuin oxalate. The stomach may contain small
quantities of oxalates as normal constituents of certain foods.
/COOH
Malonic acid — CH2\cOOH~is a Pro(iuct of the oxidation of
malic acid, or of normal propyl glycol. It forms large prismatic
•crystals, soluble in water, alcohol and ether; fusible at 132° (269°. 6
P.), and decomposed at about 150° (302° F.) into acetic acid and
carbon dioxid.
CH2— COOH
Succinic acid— | — 118 — exists in amber, coal, fossil
CH2— COOH
330 MANUAL OF CHEMISTRY.
wood, and in small quantity in animal and vegetable tissues. Its
presence has been detected in the normal urine after the use of
fruits and of asparagus, in the parenchymatous fluids of the
spleen, thyroid, and thymus, and in the fluids of hydrocele and
of hydatid cysts. It is also formed in small quantity during al-
coholic fermentation ; as a product of oxidation of many fats and
fatty acids ; and by synthesis from ethylene cyanid.
It may be obtained by dry distillation of amber, or, preferably,
by the fermentation of malic acid.
It crystallizes in large prisms or hexagonal plates, which are
colorless, odorless, permanent in air, acid in taste, soluble in
water, sparingly so in ether and in cold alcohol. It fuses at ISO0'
(356° F.), and distils with partial decomposition at 235° (455° F.).
It withstands the action of oxidizing agents; reducing agents
convert it into the corresponding acid of the fatty series, butyric
acid; with Br it forms products of substitution; HsSCX is with-
out action upon it ; phosphoric anhydrid removes H2O and con-
verts it into succinic anhydrid, C4H4O3.
/GOOH
Isosuccinic acid — CH3— CH^ QQOH~ *s f°rme(l by the action of
hydrating agents upon cyanopropionic acid. It forms prismatic
crystals, fusible at 130° (266° F.), and is decomposed at higher
temperatures into propionic acid and carbon dioxid.
TJNSATT7RATED ACIDS
These acids contain two atoms of H less than the correspond-
ing acids of the oxalic series, like which, they are dibasic. In
the higher terms there are many instances of isomerism, as shown
in the formulae of the derivatives of aconitic acid given below.
They are obtainable by the action of KI upon the dibromin-
ated derivatives of the acids of the oxalic series.
Fumaric and Maleic Acids— C4H4O4— are produced together by
the dry distillation of malic acid, by loss of the elements of a
molecule of water. The difference in their molecular structure^
is shown by the formulae :
HC,COOH CHa
l| /COOH
HC,COOH , ^\COOH
Fumaric acid. Maleic acid.
Fumaric acid exists in many plants, is a solid, crystalline body,,
sparingly soluble in cold, readily soluble in hot water. Nascent
H converts it into succinic acid.
COMPOUND ETHERS. 331
Mesaconic, Citraconic, Itaconic and Paraconic Acids— C6HSO4 —
may be considered as being the homologues, the first two of fu-
maric acid, the last two of inaleic acid :
HC— COOH
CH
1
HC— COOH
II
C— COOH
1
CHa
C— COOH
H2C,COOH
CH3
H2C— COOH
Mesaconic acid.
Citraconic acid.
Itaconic acid.
CHa
H
C
Paraconic acid.
Citraconic and itaconic acids are produced by the action of
heat upon citric acid. Mesaconic and paraconic by the action
of heat upon citrachloropyrotartaric and itachloropyrotartaric
acids respectively.
COMPOUND ETHERS OF THE ACIDS OF THE SERIES
CnHanOs AND CnH2n— nO4.
The members of both of these series contain two atoms of H
replaceable by alcoholic radicals. In those of the series CnHjmOs
(with the exception of carbonic acid), being monobasic, although
diatomatic, it is not immaterial which H is so replaced. If it be
that of the group CHaOH, the resulting compound is a mono-
basic acid, in which the H of the group COOH may be replaced
by another alcoholic radical to form a neutral ether of the new
acid. If, on the other hand, the H of the group COOH be first
replaced, a neutral compound ether is formed. In the members-
of the series CnH2n— 2Oi, which are dibasic, the substitution of an
alcoholic radical for the H of either group COOH produces a
monobasic acid, in which the H of the other COOH may be
replaced by another radical to form a neutral ether. The follow-
ing formulae indicate the differences in the nature of these com-
pounds :
CH»OH CHaOC,Hs CH2OH CH2OCaHs
COOH COOH COOC2H6 COOC2H6
Glycolic acid. Ethylglycolic acid. Ethyl glycolate. Ethyl ethylglycolate.
COOH COOC2HS COOC,HS
COOH COOH COOCsHs
Oxalic acid. Ethyloxalic acid- Ethyl oxalate.
332 MANUAL OF CHEMISTRY.
ALDEHYDES AND ANHYDRIDS OF THE SERIES
CnHjmOs AND CnHan— aO4.
In treating of the monoatomic compounds, it was stated that
substances existed corresponding to the fatty acids, known as
aldehydes and anhydrids, the former differing from the acids in
that they contained the group COH instead of COOH ; the latter
being the oxids of the acid radicals. Similar compounds exist
corresponding to the acids of these two series.
The aldehydes corresponding to the series C?iH2nO3 contain the
group COH in place of the group COOH, and as they also con-
tain the group CH2OH, they are possessed of the double function
of primary alcohol and aldehyde. Those of the series CnH-m-vOt
form two series ; in one of which only one of the groups COOH is
deoxidized to COH ; in the other, both. Those of the first series,
still containing a group COOH, are monobasic acids as well as
Aldehydes :
CH3OH CHaOH COOH COOH COH
COOH COH COOH COH COH
Glycolic acid. Glycolic aldehyde. Oxalic acid. Glyoxalic acid. Glyoxol.
While the anhydrids of the fatty series may be considered as
derived from the acids by the subtraction of H2O from two mole-
cules of the acid ; those of both the series of acids under consider,
ation are derived from a single molecule of the acid by the sub-
traction of H2O :
CH3 CH2OH CH2— COOH
COOH COOH CH2— COOH
Acetic acid. Glycolic acid. Succinic acid.
CH3-COX CH2. CH2-COV
>0 I/O I /°
CH.-CO7 CO / CHa-CO7
Acetic anhydrid. Glycolic anhydrid. Succinic anhydrid.
DIAMINS AND TBIAMINS.
The diamins are derived from a double molecule of NH3, or of
ammonium hydroxid, by the substitution of the diatomic radicals
of the glycols (hydrocarbons of the series CnH2n) for an equivalent
number of H atoms.
When it is considered that in the formation of these substances
any number of groups CnH2n of different constitution may be in-
troduced between two NH2 groups, thus :
H
H
CH,
D-NH2
H,N-C-NH,
HaN-C-NH,
H
CH,
CH,
idiamin.
Ethylendiamin.
Propylendianain.
DIAMINS AND TRIAMINS. 33$
H H
I I
-C-C-
I I
H H
that the remaining hydrogen atoms may be replaced by univa-
lent or bivalent radicals ; that the H atoms may be replaced by
OH, etc. ; and finally that similar compounds of P, As and Sb ex-
ist, it is not astonishing that the study of the great number of
substances, the possibility of whose existence is thus indicated, is
still in its infancy.
Among the diamins are included several of the alkaloidal prod-
ucts of putrefaction known as ptomains (see pp. 276; 334).
Trimethylendiamin — H2N— (CH2)3— NH2— is said to have been
obtained from the cultures of the comma bacillus.
Putrescin — Tetramethylendiamin? — H3N — (CH2)4 — NH2 — is
produced along with cadaverin during the putrefaction of mus-
cular tissue, internal organs of man and animals, and of fish, and
in the culture media of the comma bacillus from three days to
four months. The free base is a colorless liquid, having a semi-
nal odor, which absorbs CO2 from the air and unites with acids-
to form crystalline salts. It is not actively poisonous.
Cadaverin — Pentamethylendiamin — H2N— (CH2)6 — NH2 — is iso-
meric with neuridin and is produced during the later stages of
putrefaction of many animal tissues, the cholin disappearing as
this and the other diamins are formed. The free base is a clear
syrupy liquid, having a strong, disagreeable odor, resembling
that of coniin, boils at 175% and fumes in air. It absorbs CO2
rapidly with formation of a crystalline carbonate. Its salts are
crystalline. The chlorid on dry distillation is decomposed into
ammonium chlorid and piperidin (q. v.).
Neuridin — C5H14N2 — a diamin of undetermined constitution,
is produced, along with cholin (q. -p.), during the earlier stages of
putrefaction, particularly of gelatinoid substances, and increases
in quantity as putrefaction advances, while the quantity of
cholin diminishes. The free base is a gelatinous substance,
having a very marked seminal odor, readily soluble in water,
insoluble in alcohol and in ether. Its chlorid is crystalline
and very soluble in water. It seems to be non-poisonous when
pure.
Saprin — CsHieNs — another diamin of undetermined constitu-
tion, has been obtained from putrid spleens and_livers after three
weeks' putrefaction.
CSee Ptomains, pp. 276, 334, 424, 470.)
334 MANUAL OF CHEMISTRY.
Among the diamins are included the amidins, having the con-
stitution R — ^\NH ' in wh*cl1 R is a hydrocarbon radical ; and
these, on oxidation, yield a class of substances known as amid-
oxims, having the constitution R — Cv STT .
\1> xla
The guanidins are triamins, more or less modified by substitu-
tion. The type of the group is
Guanidin— Carbotriamin— CH5N3— first obtained by oxidation
of guanin (see p. 352). Its synthesis has been accomplished by
heating together ethyl orthocarbonate, C(OC2H5)4, and NH3. It
is a crystalline substance, which absorbs CO2 and H2O from the
air and forms crystalline salts. Some of its derivatives are im-
portant physiologically.
Methyl-guanidin — Methyluramin — HN - C(NH3)NH(CH3) —
was first obtained by the oxidation of creatin and of creatinin
(see below). It has also been obtained as a product of putrefac-
tion of muscular tissue at a low temperature in closed vessels,
when it probably results from the decomposition of creatin. It
is a colorless, crystalline, deliquescent, strongly alkaline sub-
stance, and is highly poisonous.
The relations of guanidin and methyl-guanidin to each other
and to creatin and creatinin is shown by the following formulae :
j^jj CO
'\NH3
Guanidin. Creatinin.
HN=
\N(CH3).CHa.COOH
Methyl-guanidin. Creatin.
Creatin — C4H9N302 + Aq — is, as is shown by the above graphic
formula, a complex amido-acid. It is a normal constituent of
the juices of muscular tissue, brain, blood, and amniotic fluid.
It is best obtained from the flesh of the fowl, which contains
0.32 per cent., or from beef-heart, which contains 0.14 percent.
It is soluble in boiling H2O and in alcohol, insoluble in ether ;
crystallizes in brilliant, oblique, rhombic prisms ; neutral, taste-
less, loses aq at 100° (212° P.) ; fuses and decomposes at higher
temperatures. When long heated with H2O or treated with con-
centrated acids, it loses HaO, and is converted into creatinin.
Baryta water decomposes it into sarcosin and urea. It is not
precipitated by silver nitrate, exeept when it is in excess and in
presence of a small quantity of potassium hydroxid. The white
precipitate so obtained is soluble in excess of potash, from which
a jelly separates, which turns black, slowly at ordinary tempera-
tures, rapidly at 100° (212° F.). A white precipitate, which turns
DIAMINS AND TRIAMINS. 335
"black when heated, is also formed when a solution of creatin. is
similarly treated with mercuric chlorid and potash.
Creatinin — C4H,N3O — 113 — a product of the dehydration of crea-
tin, is a normal and constant constituent of the urine and amni-
•otic fluid, and also exists in the blood and muscular tissue.
It crystallizes in oblique, rhombic prisms, soluble in H»0 and
in hot alcohol , insoluble in ether. It is a strong base, has an
alkaline taste and reaction ; expels JsH3 from the ammoniacal
salts, and forms well denned salts, among which is the double
chlorid of zinc and creatinin, (C^TNaO^ZnCls, obtained in very
sparingly soluble, oblique prismatic crystals, when alcoholic
solutions of creatinin and zinc chlorid are mixed.
The quantity of creatinin eliminated is slightly greater than
that of uric acid, 0.6-1.3 gram (9.25-20 grains) in 24 hours. It
is not increased by muscular exercise, but is diminished in pro-
gressive muscular atrophy. It is obtained from the urine by
precipitation with zinc chlorid.
Cruso-creatinin — CoHsN^O — is an orange-yellow, crystalline
solid, alkaline in reaction; Xantho-creatinin — C5Hi0N4O — is in
yellow crystalline plates ; Amphi-creatinin — C9Hi9N7O4 — forms
yellowish- white prismatic crystals. These are basic substances,
forming crystalline chlorids and belonging to the class of leuco-
mains, which include alkaloidal substances produced by physio-
logical processes. (See p. 470.) They are obtained from the juices
of muscular tissue, and from Liebig's meat extract, in which they
accompany creatin and creatinin.
DIAMLDS— IMIDS— AND CABBAMIC ACIDS.
Among these substances, derivable from the acids of the series
CnHanOa and CnH2n— 2O4, are several of great medical interest.
The diamids correspond to the diamins (see p. 332), from which
they differ in that the substituted groups are oxidized in place of
hydrocarbon. The imids differ from the secondary monamids
(see p. 278) in that the group NH is attached to a bivalent group
in place of to two univalent groups. The -amic acids are dibasic
acids of the series mentioned above in which an OH is replaced
by NH2.
The constitution and relations of these bodies are shown by
the_f olio wing graphic formulae of those derived from carbonic acid :
H3N-C-NH., O = C=NH n_p/OH
O
Carbamid. Carbimid. Carbamic
Primary diamid. Imid=Secondary monamid. acid.
336 MANUAL OF CHEMISTRY.
Carbimid— CONH— is identical with cyanic acid (p. 295).
Carbamid— TJrea— H2N— CO— NH2 — 60 — does not occur in the
vegetable world. It exists principally in the urine of the mam-
malia ; also in smaller quantity in the excrements of birds, fishes,
and some reptiles ; in the mammalian blood, chyle, lymph, liver,
spleen, lungs, brain, vitreous and aqueous humors, saliva, perspi-
ration, bile, milk, amniotic and allantoic fluids, muscular tissue,
and in serous fluids (see below).
It is formed — (1.) As a product of the decomposition of urie
acid, usually by oxidation :
CBH4N4O3 + H,O + O = CON3H4 + C4HaN3O4
Uric acid. Water. Oxygen. Urea. Alloxan.
(2.) By the oxidation of oxamid.
(3.) By the action of caustic potassa upon creatin :
C4H9N3O3 + H3O = CON3H4 + C3H7NO3
Creatin. Water. Urea. Sarcosin.
4.) By the limited oxidation of albuminoid substances, by
potassium permanganate, and during the processes of nutrition.
(5.) By the action of carbon oxychlorid on dry ammonia.
(6.) By the action of ammonium hydroxid on ethyl carbonate
at 180° (356° P.).
(7.) By heating ammonium carbonate in sealed tubes to 130°
(266° P.).
(8.) By the slow evaporation of an aqueous solution of hydro-
cyanic acid.
(9.) By the molecular transformation of its isomerid, ammonium
isocyanate:
CN (CO) )
I = H,SN,
O (NH4) H3 )
Ammonium cyanate. Urea.
It is obtained :
(1.) From the urine. — Fresh urine is evaporated to the consist-
ency of a syrup over the water-bath ; the residue is cooled and
mixed with an equal volume of colorless HNO3 of sp. gr. 1.42 ; the
crystals are washed with a small quantity of cold H3O, and dis-
solved in hot H3O ; the solution is decolorized, so far as possible,
without boiling, with animal charcoal, filtered, and neutralized
with potassium carbonate ; the liquid is then concentrated over
the water-bath, and decanted from the crystals of potassium
nitrate which separate ; then evaporated to dry ness over the
water-bath, and the residue extracted with strong, hot alcohol ;
the alcoholic solution, on evaporation, leaves the urea more or
less colored by urinary pigment.
(2.) By synthesis. — Urea is more readily obtained in a state of
DIAMIDS. 337
purity from potassium isocyanate. This is dissolved in cold H2O,
and dry ammonium sulfate is added to the solution. Potassium
sulfate crystallizes out, and is separated by decanting the liquid,
which is then evaporated over the water-bath, fresh quantities of
potassium sulfate crystallizing and being separated during the
first part of the evaporation ; the dry residue is extracted with
strong, hot alcohol ; this, on evaporation, leaves the urea, which,
by a second crystallization from alcohol, is obtained pure.
Urea crystallizes from its aqueous solution in long, flattened
prisms, and by spontaneous evaporation of its alcoholic solution
in quadratic prisms with octahedral ends. It is colorless and
odorless ; has a cooling, bitterish taste, resembling that of salt-
petre ; is neutral in reaction ; soluble in one part of H2O at 15°
(59° F.), the solution being attended with diminution of tempera-
ture : soluble in five parts of cold alcohol (sp. gr. 0.816) and in
one part of boiling alcohol ; very sparingly soluble in ether.
When its powder is mixed with that of certain salts, such as
sodium sulfate, the Aq of the salt separates, and the mass be-
comes soft or even liquid. When pure it is not deliquescent, but
is slightly hygrometric. Fuses at 130° (266° F.).
Heated a few degrees above 180° (266° F.) urea boils, giving off
ammonia and ammonium carbonate, and leaves a residue of am-
melid, C6H9N9O3. When heated to 150°-170° (302°-338° F.), it is
decomposed, leaving a mixture of ammelid, cyanuric acid, and
biuret :
4 = 2CO, + CeH9N9O3 + 7NH3 + H2O
Urea. Carbon dioxid. Ammelid. Ammonia. Water.
4 = CaOsNsH, + 3NH3
Urea. Cyanuric acid. Ammonia.
2CON,H4 C2H5N3O2 + NH3
Urea. Biuret. Ammonia.
If urea is maintained at 150°-170° (302°-338° F.) for some time,
a dry, grayish mass remains, which consists principally of cya-
nuric acid. In this reaction, the volatile products contain urea,
not that that substance is volatile, but because a portion of the
cyanuric acid and ammonia unite to regenerate urea by the re-
verse action to that given above.
Dilute aqueous solutions of urea are not decomposed by boil-
ing ; but if the solution be concentrated, or the boiling prolonged
for a long time, the urea is partially decomposed into CO2 and
NH3. The same decomposition takes place more rapidly and
completely when a solution of urea is heated under pressure to
140° (284° F.). A pure aqueous solution of urea is not altered by
exposure to filtered air. If urine be allowed to stand, putre-
838 MANUAL OF CHEMISTKY.
f active changes take place under the influence of a peculiar, or-
ganized ferment, or of a diastase-like body which is a constituent
of normal urine.
Chlorin decomposes urea with production of COa, IS", and HC1.
Solutions of the alkaline hypochlorites and hypobromites effect
a similar decomposition in the presence of an excess of alkali,
according to the equation :
CON2H4 + SNaCIO = CO2 4- 2H2O + N2 + SNaCl
Urea. Sodium Carbon Water. Nitrogen. Sodium
hypochlorite. dioxid. chlorid.
Upon this decomposition are based the quantitative processes
of Knop, Hufner, Yvon, Davy, Leconte, etc.
Nitrous acid, or HNO3 charged with nitrous vapors, decomposes
urea according to the equation :
CON2H4 + N2O3 = COa + N4 + 2H2O (1)
Urea. Nitrogen Carbon Nitrogen. Water,
trioxid. dioxid.
or the equation :
2CON2H4 + N2O3 = CO3(NH4)2 + N4 + CO, (2)
Urea. Nitrogen Ammonium Nitrogen. Carbon
trioxid. carbonate. dioxid.
If the mixture be made in the cold, of one molecule of nitrogen
trioxid to two molecules of urea, the decomposition is that in-
dicated by Equation 2. If, on the other hand, the trioxid be
gradually added to the previously warmed urea solution in the
same proportion, half the urea is decomposed while the remain-
der is left unaltered, and, upon the addition of a further and
sufficient quantity of the trioxid, all the urea is decomposed
according to Equation 1. Upo'n this reaction are based the proc-
esses of Gr6hant, Boymond, Draper, etc.
When heated with mineral acids or alkalies, urea is decom-
posed with formation of CO2 and NH3 ; if the decomposing agent
be an acid, CO2 is given off, and an ammoniacal salt remains ; if
an alkali, a carbonate of the alkaline metal remains, and NH3 is
given off. Upon this decomposition are based the processes of
Heintz and Ragsky, Bunsen, etc.
Urea forms definite compounds, not only with acids, but also
with certain oxids and salts. Of the compounds which it forms
with acids, the most important are those with nitric and oxalic
acids.
Urea nitrate — CON2H4,HNO3 — is formed as a white, crystalline
mass when a concentrated solution of urea is treated, in the cold,
with HNO3. It is much less soluble in H2O than is urea, espe-
cially in the presence of an excess of HNO3. It decomposes the
carbonates with liberation of urea. If a solution of urea nitrate
DIAMIDS. 339
t>e evaporated over the water-bath, it is decomposed, bubbles of
gas being given off beyond a certain degree of concentration, and
large crystals of urea, covered with smaller ones of urea nitrate,
separate.
Urea oxalate — 2CONaH4,H:iCaO4 — separates as a fine, crystalline
powder from mixed aqueous solutions of urea and oxalic acid of
sufficient concentration. It is acid in taste and reaction, less
soluble in cold HaO than the nitrate, and less soluble in the pres-
ence of an excess of oxalic acid than in pure H2O. Its solution
may be evaporated at the temperature of the water-bath without
suffering decomposition.
Of the compounds of urea with oxids, the most interesting are
those with mercuric oxid, three in number :
a. CON2H4,2HgO is formed by gradually adding mercuric oxid
to a solution of urea, heated to near its boiling-point ; the fil-
tered liquid, on standing twenty-four hours, deposits crystalline
•crusts of the above composition.
/?. CON2H4,3HgO is formed as a gelatinous precipitate when
mercuric chlorid solution is added to a solution of urea containing
potassium hydroxid.
y. CON!»H4,4HgO is formed as a white, amorphous precipitate
when a dilute solution of mercuric nitrate is gradually added to a
•dilute alkaline solution of urea, and the excess of acid neutralized
from time to time. A yellow tinge in the precipitate indicates
the formation of mercuric subnitrate after the urea has been
all precipitated (Liebig's process).
Of the compounds of urea with salts, that with sodium chlorid
is the only one of importance :
CONaH4,NaCl,H3O. — It is obtained in prismatic crystals when
solutions of equal molecules of urea and sodium chlorid are
evaporated together. It is deliquescent and very soluble in
water. Its solution, when mixed with solution of oxalic acid,
only forms urea oxalate after long standing, or on evaporation.
Urea is a constant constituent of normal mammalian blood and
urine, and is the chief product of the oxidation of albuminoid
substances which occur in the body ; the bulk of the N assimi-
lated from the food ultimately making its exit from the body in
the form of urea in the urine .
The determinations of the amount of urea in the blood and
fluids other than the urine are, owing to imperfections in the
processes of analysis, not as accurate as could be desired, the
error being generally a minus one.
The average proportion of urea in parts per 1000 in animal fluids
other than urine is : In blood of dog, normal, 0.24-0.53 ; same three
hours after nephrectomy, 0.45-0.93; same twenty-seven hours
later, 2.06-2.76; human blood, normal, 0.14-0.4; human placental
340
MANUAL OF CHEMISTRY.
blood, 0.28-0.62; human foetal blood, 0.27; human blood in chol-
era, 2.4-3.6; human blood in Bright's, 15.0; lymph and chyle
(cow), 0.19; milk, 0.13; saliva, 0.35; bile, 0.3; fluid of ascites, 0.15;.
perspiration, 0.38-0.88.
Under normal conditions, the quantity of urea voided in.
twenty-four hours is subject to considerable variations, as is
shown in the subjoined table :
AMOUNT OF UREA IN HUMAN URINE — NORMAL.
Parts per
1,000.
Urine of sp. gr. 1009.2 9.88
Urine of sp. gr. 1011.6 11.39
Urine of sp. gr. 1019.0 18.58
Urine of sp. gr. 1026.0. 25.80
Urine of sp. gr. 1027.7 29.70
Urine of sp. gr. 1028.0 27.08
Urine of sp. gr. 1029.0 31.77
Urine of adult male (average) 30.0
Urine of adult male (average)
Urine of adult male (average) 25-32
Urine of adult male (average)
Urine of adult male (average) 23.3
Urine of adult male, animal food
Urine of adult male, mixed food
Urineof adult male, vegetable food ....
Urine of adult male, non-iiitrogen-
ized food
Urine of old men, 84-86 years.
Urine of adult female (average)
Urine of pregnant female
Urine of female 24 hours after de-
livery
Urine of infant, first day
Urine of infant, fifth day
Urine of infant, eighth day
Urine of infant, fifteenth day
Urine of child four years old
Urine of child eight years old
Urine of boy eighteen months old . . .
Urine of girl eighteen months old . . .
Grams in total urine
of 24 hours.
Millon.
Millon.
Boymond.
Millon.
Millon.
. . Boymond.
Millon.
Berzelius.
28.052 Lecanu.
22-35 Neubauer..
32^3 Kerner.
35 Vogel.
51-92 Franque.
36-38 Franque.
24-28 Franqne.
16 Franque.
8.11 Lecanu.
19.116 Lecanu.
30-38 Quinquand.
20-22
0.03-0.04
0.12-0.15
0.2 -0.28
0.3 -0.04
4.505
13.471
8-12
6-9
Quinquand.
Quinquand.
Quinquand.
Quinquand.
Quinquand.
Lecanu.
Lecanu.
Harley.
Harley.
The variations are produced by :
(1.) Age. — In new-born children the elimination of urea is insig-
nificant. By growing children the amount voided is absolutely
less than that discharged by adults, but, relatively to their
weight, considerably greater ; thus, Harley gives the following
amounts of urea in grams for each pound of body-weight in
twenty-four hours : Boy, eighteen months, 0.4 ; girl, eighteen
months, 0.35; man, twenty-seven years, 0.25; woman, twenty-
seven years, 0.20. During adult life the mean elimination of urea
remains stationary, unless modified by other causes than age.
DIAMIDS.
341
In old age the amount sinks to below the absolute quantity dis-
charged by growing children.
(2.) Sex. — At all periods of life females eliminate less urea than
males. The proportion given by Beigel differs slightly from that
of Harley, viz.: one kilo of male, 0.35 gram urea in twenty-four
hours ; one kilo of female, 0.25 gram. During pregnancy
females discharge more urea than males ; very shortly after de-
livery the amount sinks to the normal, below which it passes
during lactation.
(3.) Food. — The quantity of urea eliminated is in direct propor-
tion to the amount of N contained in the food. The ingestion of
large quantities of watery drinks increases the amount, and a
•contrary effect is produced by tea, coffee, and alcohol. With in-
sufficient food the excretion of urea is diminished, although not
•arrested, even in extreme starvation.
(4.) Exercise. — The question whether the elimination of urea is
increased during violent muscular exercise is one which has been
the subject of many observations and of much discussion. An
examination of the various results shows that, while the ex-
cretion of urea is slightly greater during violent exercise than
during periods of rest, the increase is so insignificant in com-
parison to the work done, and, in some instances, to the loss of
body- weight, as to render the assumption that muscular force is
the result of the oxidation of the nitrogenized constituents of
muscle improbable. (See Gamgee, ''Physiological Chemistry,"
I., pp. 385-401, for a full review of the subject.)
The percentage of urea in the urine of the same individual is
not the same at different times of the day. The minimum hourly
elimination is in the morning hours ; an increase begins immedi-
ately after the principal meal, and reaches its height in about
six hours, when a diminution sets in and progresses to the time
of the next meal. Gorup-Besanez gives a curve representing the
hourly variations in the elimination of urea, which, reduced to
figures, gives the following :
Hour.
Urea in
Grams.
Hour.
Urea in
Grams-
Hour.
Urea in
Grams.
8-9 A. M
1.5
4- 5 P.M
2.6
12-1 A.M ....
1.9
9-10 A.M... .
1.5
5- 6 P.M
3.1
1-2 A.M
1.9
10-11 A.M. ..
1.4
6- 7P.M....
2.8
2-3 A.M
1.9
11 A.M.-12M.
1.8
7- 8P.M....
2.5
3-4 A.M
1.8
12 M.-l P.M. .
1.8
8- 9P.M....
2.3
4-5 A.M
1.6
1-2 P.M
1.9
9-10 P.M....
2.0
5-6 A.M
1.6
2-3 P.M
2.1
10-11 P.M....
2.0
6-7 A.M ....
1.6
3-4 P.:M
2.3
111-12 P.M .. .
2.3
7-8 A.M
1.5
MANUAL OF CHEMISTRY.
The total of which, however, represents a quantity above tha
normal.
The absolute amount of urea eliminated in twenty-four hours
is increased by the exhibition of diuretics, alkalies, colchicum,
turpentine, rhubarb, alkaline silicates, and compounds of anti-
mony, arsenic, and phosphorus. It is diminished by digitalis,
caffein, potassium iodid, and lead acetate ; not sensibly affected,
by quinin.
In acute febrile diseases both the relative and absolute amounts
of urea eliminated augment, with some oscillations, until the
fever is at its height. There is, however, no constant relation
between the amount of urea eliminated and the body tempera-
ture. During the period of defervescence, the amount of urea,
eliminated in twenty-four hours is diminished below the normal ;
during convalescence it again sowly increases. If the malady
terminate in death the diminution of urea is continuous to the
end. In intermittent fever the amount of urea discharged is in-
creased on the day of the fever and diminished during the inter-
val. In cholera, during the algid stage, the elimination of urea,
by the kidneys is almost completely arrested, while the quantity
in the blood is greatly increased. When the secretion of urine is
again established, the excretion of urea is greatly increased (60-80
grams = 926-1235 grains a day), and the abundant perspiration is
also rich in urea. In cardiac diseases, attended with respiratory
difficulty, but without albuminuria, the elimination of urea is
diminished and that of uric acid increased. In nephritis, attended
with albuminuria, the elimination of urea at first remains nor-
mal ; later it diminishes, and the urea, accumulating in the
blood, has been considered by many as the cause of ursemic poi-
soning. It appears more probable, however, that the symptoms
of uraemia are due to the retention in the blood of alkaloidal
poisons normally excreted in small amount. The quantity of
urea in the urine is also diminished in all diseases attended with
dropsical effusions ; but is increased when the dropsical fluid is
reabsorbed. In true diabetes the amount of urea in the urine of
twenty-four hours is greater than normal. In chronic diseases
the elimination of urea is below the normal, owing to imperfect
oxidation.
To detect the presence of urea in a fluid, it is mixed with three
to four volumes of alcohol, and filtered, after having stood sev-
eral hours in the cold ; the filtrate is evaporated on the water-
bath, and the residue extracted with strong alcohol ; the filtered
alcoholic fluid is evaporated, and the residue tested as follows :
(1.) A small portion is heated in a dry test-tube to about 160*
(320° F.), until the odor of ammonia is no longer observed ; the
residue is treated with a few drops of caustic potassa solution and
DIAMIDS. 34:3
one drop of cupric sulfate solution. If urea be present, the
biuret resulting from its decomposition by heat causes the solu-
tion of the cupric oxid with a reddish-violet color. The same ap-
pearance is produced in solutions containing peptone.
(2.) A portion of the residue is dissolved in a drop or two of
H.jO, and an equal quantity of colorless concentrated HNO3
added ; if urea be present in sufficient quantity there appear
white, shining, hexagonal or rhombic, crystalline plates or six-
sided prisms of urea nitrate.
(3.) A portion dissolved in water, as in (2), is treated with a
solution of oxalic acid ; rhombic plates of urea oxalate crystallize.
Determination of Quantity of Urea in TJrine. — It must not
be forgotten that, in all quantitative determinations of con-
stituents of the urine, the question to be solved is not how much
of that constituent is contained in a given quantity of urine, but
how much of that substance the patient is discharging in a given
time, usually twenty-four hours. Quantitative determinations
are, therefore, in most cases, barren of useful results, unless the
quantity of urine passed by the patient in twenty-four hours is
known ; and, in view of diurnal variations in elimination, unless
the urine examined be a sample taken from the mixed urine of
twenty-four hours.
The process giving the most accurate results is that of Bunsen,
in which the urea is decomposed into COa and NH3, the former
of which is weighed as barium carbonate. Unfortunately, this
process requires an expenditure of time and a degree of skill in
manipulation which render its application possible only in a
well-appointed laboratory.
A process which is described in most text-books upon urinary
analysis, and which is much used by physicians, is that of Lie-
big. As this method is one, however, which contains more
sources of error than any other, and as it can only be made to
yield approximately correct results by a very careful elimination,
as far as possible, of those defects, it is not one which is adapted
to the use of the physician.
Probably the most satisfactory process in the hands of the
practitioner is that of Hiifner, based upon the reaction, to which
attention was first called by Knop, of the alkaline hypobromites
upon urea (p. 338) ; using, however, Dietrich's apparatus, or the
more simple modification suggested by Rumpf, in place of that
of Hiifner. The apparatus (Fig. 38) consists of a burette of 30-50
c.c. capacity, immersed in a tall glass cylinder filled with water,
and supported in such a way as to admit of being raised or low-
ered at pleasure. The upper end of the burette communicates
with the evolution bottle a, which has a capacity of 75 c.c., by
means of a rubber tube.
The reagent required is made as follows : 27 c.c. of a solution
of caustic soda, made by dissolving 100 grams NaHO in 250 c.c.
H2O, are brought into a glass-stoppered bottle, 2.5 c.c. bromin
are added, the mixture shaken, and diluted with water to 150 c.c.
The caustic soda solution may be kept in a glass-stoppered bottlu
MANUAL OF CHEMISTRY.
whose stopper is well paraffined, but the mixture must be made
up as required, a fact which, owing to the irritating character of
the Br vapor, renders the use of this reagent in a physician's
office somewhat troublesome. The Br is best measured by a
pipette of suitable size, having a compressible rubber ball at the
upper end.
To conduct a determination, about 20 c.c. of the hypobromite
solution are placed in the bottle a; 5 c.c. of the urine to be exam-
ined are placed in the short test-
tube, which is then introduced
into the position shown in the
figure, care being had that no
urine escapes. The cork with its
fittings is then introduced, the
pinch-cock 6 opened, and closed
again when the level of liquid in
the burette is the same as that
in the cylinder. The decompos-
ing vessel q is then inclined so
that the urine and hypobromite
solution mix; the decomposition
begins at once, and the evolved
N passes into the burette, Avhich
is raised from time to time so as
to keep the external and internal
levels of water about equal; the
CO2 formed is retained by the soda
solution. In about an hour (the
decomposition is usually complete
in fifteen minutes, but it is well to
wait an hour) the height is so ad-
justed that the inner and outer
levels of water are exactly even,
and the graduation is read, while
the standing of the barometer and
thermometer are noted at the same
time.
In calculating the percentage
of urea from the volume of N ob-
tained, it is essential that a cor-
rection should be made for differ-
ences of temperature and pressure,
without which the result from an
ordinary sample of urine ma}* be
vitiated by an error of ten per cent.
If, however, the temperature and
barometric pressure have been
noted, the correction is readily
made by the use of the table (see
Appendix B, III.), computed by Dietrich, giving the weight of
1 c.c. N at different temperatures and pressures.
In the square of the table in which the horizontal line of the
observed temperature crosses the vertical line of the observed
barometric pressure will be found the weight, in milligrams, of a
c.c. of N; this, multiplied by the observed volume of N, gives the
weight of N produced by the decomposition of the urea contained1
in 5 c.c. urine. But as 60 parts urea yield 28 parts N, the weight ol
N, multiplied by 2.14, gives the weight of urea in milligrams in
Fio 38.
DIAMIDS. 345
5 c.c. urine. This quantity, multiplied by twice the amount ot
urine in 24 hours, and divided by 10,000, gives the amount of
urea eliminated in 24 hours in grams. If the result be desired in
grains the amount in grams is multiplied by 15.434.
Example. — 5 c.c. urine decomposed ; barometer = 736 mm. ; ther-
mometer = 10°; burette reading before decomposition = 64.2 ; same
after decomposition = 32.6 : c.c. N collected = 31.6. From the
table 1 c.c. N at 10° and 736 mm BP weighs 1.1593. The patient
passes 1500 c.c. urine in 24 hours :
31.6 X 1.1593 = 36.6339 = milligr. N in 5 c.c. urine.
36.6339 X 2.14 = 78.3965 = milligr. urea in 5 c.c. urine.
78.3965 X 3000 OQ
1ft Q-.. = 23.019 = grams urea in 24 hours.
23.519 X 15.434 = 362.99 = grains urea in 24 hours.
In using this process it is well to have the urea solution as near
the strength of one per cent, as possible ; therefore if the urine
be concentrated, it should be diluted. Even when carefully con-
ducted, the process is not strictly accurate ; creatinin and uric
acid are also decomposed with liberation of N, thus causing a
slight plus error : on the other hand, a minus error is caused by
the fact that in the decomposition of urea by the hypobromite,
the theoretical result is never obtained within about eight per
•cent, in urine. These errors may be rectified to a great extent
by multiplying the result by 1.044.
A process which does not yield as accurate results as the pre-
ceding, but which is more easy of application, is that of Fowler,
based upon the loss o/ sp. gr. of the urine after the decomposition
of its urea by hypochlorite. To apply this method the sp. gr. of
the urine is carefully determined, as well as that of the liq. sodae
chlorinatse (Squibb's). One volume of the urine is then mixed
with exactly seven volumes of the liq. sod. chlor., and, after the
first violence of the reaction has subsided, the mixture is shaken
from time to time during an hour, when the decomposition is
complete ; the sp. gr. of the mixture is then determined. As the
reaction begins instantaneously when the urine and reagent are
mixed, the sp. gr. of the mixture must be calculated by adding
together once the sp. gr. of the urine and seven times the sp. gr.
of the liq. sod. chlor., and dividing the sum by 8. From the
quotient so obtained the sp. gr. of the mixture after decomposi-
tion is subtracted ; every degree of loss in sp. gr. indicates 0.7791
gram of urea in 100 c.c. of urine. The sp. gr. determinations
must all be made at the same temperature ; and that of the mix-
ture only when the evolution of gas has ceased entirely.
Finally, when it is only desired to determine whether the urea
is greatly in excess or much below the normal, advantage may
be taken of the formation of crystals of urea nitrate. Two sam-
ples of the urine are taken, one of 5 drops and one of 10 drops ;
the latter is evaporated, at a low temperature, to the bulk of the
former, and cooled ; to each, three drops of colorless HNO3 are
added. If crystals do not form within a few moments in the con-
centrated sample, the quantity of urea is below the normal ; if
346 MANUAL OF CHEMISTRY.
they do in the unconcentrated sample, it is in excess. In using-
this very rough method, regard must be had to the quantity of
urine passed in 24 hours ; the above applies to the normal amount
of 1200 c.c. ; if the quantity be greater or less, the urine must be
concentrated or diluted in proportion. The amorphous white
ppt. caused by HNO3 in albuminous urine must not be mistaken
for the crystalline deposit of urea nitrate.
COMPOUND UREAS.
These compounds, which are exceedingly numerous, may be
considered as formed by the substitution of one or more alcoholic
or acid radicals for one or more of the remaining H atoms of urea.
Those containing alcoholic radicals may be obtained, as urea is
obtained from ammonium isocyanate, from the cyanate of the
corresponding compound ammonium ; or by the action of NH3,
or of the compound ammonias, upon the cyanic ethers.
Those containing acid radicals have received the distinctive
name of ureids. Of these some are monureids, derived from a
single molecule of urea, others diureids, derived from two mole-
cules of urea. Among the monureids are the following :
NH-CO
Oxaly lurea = Parabanic acid— OC ( \ — C 3 H 2 N 2 O 3 —which
XNH-CO
is urea in which H2 has been replaced by the bivalent radical of
oxalic acid (G^^)=oxalyl. It is produced by oxidizing uric acid
or alloxan with hot HNO3, or may be formed synthetically from
pyruvic diureid.
NH-O-CO
Oxaluric acid— OC^ | —occurs in its ammonium salt,
XNH - CO
as a normal constituent, in small quantity, in human urine. It
may be obtained by heating oxalylurea with calcium carbonate.
It is a white, sparingly soluble powder, which is converted into
urea and oxalic acid when boiled with water or alkalies. Its
ammonium salt crystallizes in white, glistening, sparingly solu-
ble needles. Its ready conversion into urea and oxalic acid and
its formation from oxalylurea, itself a product of oxidation of
uric acid, render it probable that oxaluric acid is one of the many
intermediate products of the oxidation of the nitrogenous con-
stituents of the body.
Alloxan =Oxymalony lurea — ^^s-~^-C^^ — *s a Pr°duct of
the limited oxidation of uric acid. It has been found in the in-
testinal mucus in diarrhoea. It forms colorless crystals, readily
soluble in H2O. It turns red in air, and stains the skin red.
COMPOUND UREAS. 347
Violuric acid = Nitroso-malonylurea— OC ~ Q C = N. OH
— is produced, along with alloxan, by the action of nitric acid
upon hydurilic acid. It forms small, readily soluble, octahedral
crystals. It is a strong monobasic acid, whose salts are brilliantly
colored.
Dialuric acid = Tartronylurea— OC
basic acid produced by the reduction of alloxan. Nitrous acid
converts it into allantoln. By boiling with H3O it is converted
into tartronamic acid.
The diureids may be considered as consisting of two molecules
of urea united together by loss of hydrogen and interposition of
a group of proper valence (see formulae of uric acid, etc., be-
low). The best known of the group is :
Uric acid — Lithic acid — CsHoN^OsHs — 168. — It exists in the urine
of man and of the carnivora, and in that of the herbivora when,
during early life or starvation, they are for the time being carniv-
ora ; as a constituent of urinary calculi ; and, very abundantly, in
the excrement of serpents, tortoises, birds, mollusks, and insects,
also in guano. It is present in very small quantity in the blood
of man, more abundantly in that of gouty patients and in that
of birds. The so-called "chalk-stones " deposited in the joints of
gouty patients are composed of sodium urate. It also occurs in
the spleen, lungs, liver, pancreas, brain, and muscular fluid.
Although uric acid may be obtained from calculi, urine, and
guano, the source from which it is most readily obtained is the
solid urine of large serpents, which is composed almost entirely
of uric acid and the acid urates of sodium, potassium, and am-
monium. This is dried, powdered, and dissolved m a solution of
potassium hydroxid; the solution is boiled until all odor of NH3
has disappeared. Through the filtered solution COa is passed,
through a wide tube, until the precipitate, which was at first
gelatinous, has become granular and sinks to the bottom ; the
acid potassium urate so formed is collected on a filter, and
washed with cold H2O until the wash-water becomes turbid when
added to the first filtrate : the deposit is now dissolved in hot
dilute caustic potassa solution, and the solution filtered hot into
HC1. diluted with an equal volume of HaO. The precipitated
uric acid is washed and dried.
Uric acid, when pure, crystallizes in small, white, rhombic, rect-
angular or hexagonal plates, or in rectangular prisms, or in den-
dritic crystals of a hydrate, C^H^ 4O3,2H2O. As crystallized from
urine it is more or less colored with urinary pigments, and forms
rectangular or rhombic plates, usually with the angles rounded
so as to form lozenges, which are arranged in bundles, daggers,
crosses, or dendritic groups, sometimes of considerable size. It
is almost insoluble in HaO. requiring for its solution 1900 parts of
boiling H2O and 15.000 parts of cold H2O ; insoluble in alcohol
348 MANUAL OF CHEMISTRY.
and ether ; its aqueous solution is acid to test-paper ; cold HC1
dissolves it more readily than H2O, am1 on evaporation deposits
it in rectangular plates. It is tasteless and odorless.
When heated, it is decomposed without fusion or sublimation.
Its constitution has been recently established (see below), and
shows it to be the diureid of tartronic acid. Heated in Cl it yields
cyanuric acid and HC1. When Cl is passed for some time through
H2O holding uric acid in suspension, alloxan, parabanic and ox-
alic acids, and ammonium cyanate are formed. Similar decom-
position is produced by Br and I. It is simply dissolved by HC1.
It is dissolved by H2SO4 ; from a hot solution in which a deliques-
cent, crystalline compound, C5H4N4O3, 4H2SO4 is deposited ; it
is partly decomposed by H2SO4 at 140° (284° F.). It dissolves in
cold HNO3 with effervescence and formation of alloxan, alloxan-
tin, and urea ; with hot HNO3 parabanic acid is produced. So-
lutions of the alkalies dissolve uric acid with formation of neu-
tral urates. It is decomposed by sodium hypobromite, giving up
half of its N in the cold and the whole if heated. It reduces so-
lutions of CuSO4.
The synthesis of uric acid has been accomplished by heating
together a mixture of glycocol and urea at 230" (446° F)., and pu-
rifying the product. From this synthesis and from the products
of decomposition of uric acid its constitution has been established.
Its molecule consists of two urea remainders, CO(NH)2, united
unsymmetrically by a group of three carbon and one oxygen
•atoms, in the manner represented by the formula :
/NH-C-NH
00 II |
\NH-C CO
OC-NH
Uric acid is dibasic, forming two series of salts.
Ammonium urates. — The neutral salt, C5H2N4O.i(NH4)2, is un-
inown. The acid salt, C5H3N4O3(NH4), exists as a constituent of
the urine of the lower animals, and occurs, accompanying other
urates and free uric acid, in urinary sediments and calculi. Sedi-
ments of this salt are rust-yellow or pink in color, amorphous,
or composed of globular masses, set with projecting points, or
elongated dumb-bells, arid are formed in alkaline urine. It is
very sparingly soluble in H2O ; soluble in warm HC1, from which
solution crystalline plates of uric acid are deposited.
Potassium urates. — The neutral salt, C5H2N4O3K2, is obtained
"when a solution of potassium hydroxid, free from carbonate, is
COMPOUND UREAS. 3-19
saturated with uric acid ; the solution on concentration deposits
the salt in fine needles. It is soluble in 44 parts of cold HuO and
in 35 parts of boiling H2O. It is alkaline in taste, and absorbs
COa from the air.
The acid salt, CsHsJ^OsK, is formed as a granular (at first gelat-
inous) precipitate when a solution of the neutral salt is treated
with CO2. It dissolves in 800 parts of cold HaO and in 80 parts of
boiling H2O. The occurrence of potassium urates in urinary
sediments and calculi is very exceptional.
Sodium urates. — The neutral salt, CsEU^OaNaa, is formed
under similar conditions as the corresponding potassium salt. It
forms nodular masses, soluble in 77 parts of cold H2O and in 75
of boiling H2O ; it absorbs CO2 from the air.
The acid salt.CsHsI^OsNa, is formed when the neutral salt is
treated with CO2. It is soluble in 1200 parts of cold H2O and in
125 parts of boiling H2O. It occurs in urinary sediments and
calculi, very rarely crystallized. The arthritic calculi of gouty
patients are almost exclusively composed of this salt, frequently
beautifully crystallized.
Calcium urates. — The neutral salt, C5H2N4O3Ca, is obtained by
dropping a solution of neutral potassium urate into a boiling so-
lution of calcium chlorid until the precipitate is no longer redis-
solved, and then boiling for an hour. A granular powder, solu-
ble in 1500 parts of cold H2O and in 1440 parts of boiling HSO.
The acid salt, (CsHsN-iOa^Ca, is obtained by decomposing a
boiling solution of acid potassium urate with calcium chlorid so-
lution. It crystallizes in needles, soluble in 603 parts of cold HaO
and in 276 parts of boiling H2O. It occurs occasionally in urinary
sediments and calculi, and in "chalk-stones."
Lithium urates. — The acid salt, CsHaN-iOsLi, is formed by dis-
solving uric acid in a warm solution of lithium carbonate. It
crystallizes in needles, which dissolve in 60 parts of H2O at 50°
(122° F.) and do not separate when the solution is cooled. It i&
partly with a view to the formation of this, the most soluble of
the acid urates, that the compounds of lithium are given to
patients suffering with the uric acid diathesis.
Uric acid exists in the economy chiefly in combination as its
sodium salts ; it is occasionally found free, and from the probable
method of its formation it is difficult to understand how all the
uric acid in the economy should not have existed there free, at
least at the instant of its formation. It can scarcely be doubted
that uric acid is one of the products of the oxidation of the albu-
minoid substances — an oxidation intermediate in the production
of urea ; and that consequently diseases in which there is an ex-
cessive formation of uric acid, such as gout, have their origin in
defective oxidation.
350 MANUAL OF CHEMISTRY.
In human urine the quantity of uric acid varies with the
nature of the food in the same manner as does urea, and in about
the same proportion :
Urea. Uric Acid. Ul&2gSS^&L
Animal food 71.5 1.25 57.2
Mixed food 37.0 0.76 48.7
Vegetable food 26.0 0.50 52.0
Non-nitrogenized food 16.0 0.34 47.0
The mean elimination of uric acid in the urine is from one-
thirty-fifth to one-sixtieth of that of urea, or about 0.5 to 1.0 gram
(7.7-15.4 grains) in twenty-four hours. With a strictly vegetable
diet the elimination of twenty-four hours may fall to 0.3 gram
(4.6 grains), and with a surfeit of animal food it may rise to 1.5
gram (23 grains). The hourly elimination is increased after meals,
and diminished by fasting and by muscular and mental activity.
Deposits of free uric acid occur in acid, concentrated urines. In
gout the proportion of uric acid in the urine is diminished,
although, owing to the small quantity of urine passed, it may be
relatively great ; during the paroxysms the quantity of uric acid
is increased, both relatively and absolutely. The proportion of
uric acid in the blood is invariably increased in gout.
Uric acid may be recognized by its crystalline form and by the
murexid test. The substance is moistened with HNO3, which is
evaporated nearly to dryness at a low temperature ; the cooled
residue is then moistened with ammonium hydroxid solution.
If uric acid be present, a yellow residue — sometimes pink or red
when the uric acid was abundant — remains after the evaporation
of the HNO3, and this, on the addition of the alkali, assumes a
rich purplish-red color.
To detect uric acid in the blood, about two drachms of the
serum are placed in a flat glass dish and faintly acidulated with
acetic acid ; a very fine fibril of linen thread is placed in the
liquid, which is set aside and allowed to evaporate to the con-
sistency of a jelly ; the fibril is then examined microscopically.
If the blood contain uric acid in abnormal proportion, the thread
will have attached to it crystals of uric acid.
The best method for the determination of the quantity of uric
acid in urine is the following : 250 c.c. of the filtered urine are
-acidulated with 10 c.c. of HC1, and the mixture set aside for
twenty-four hours in a cool place. A small filter is washed, first
with dilute HC1 and then with H2O, dried at 100° (212° R), and
weighed. At the end of twenty-four hours this filter is moistened
in a funnel, and the crystals of uric acid collected upon it (those
which adhere to the walls of the precipitating vessel are best
separated by a small section of rubber tubing passed over the
COMPOUND UREAS. 351
•end of a glass rod, and used as a brush). No H2O is to be used in
this part of the process, the filtered urine being made use of to
bring all the crystals upon the filter. The deposit on the filter is
now washed with 35 c.c. of pure H2O, added in small portions at
& time ; the filter arid its contents are then dried and weighed.
The difference between this weight and that of the dry filter
alone is the weight of uric acid in 250 c.c. of urine. If from any
•cause more than 35 c.c. of wash- water have been used, Om^r-.043
must be added to this weight for every c.c. of extra wash-water.
If the urine contain albumen, this must first be separated by
adding two or three drops of acetic acid, heating to near 100°
(212° F.), until the coagulum becomes flocculent, and filtering.
Reducing agents convert uric acid into xanthin and then into
typoxanthin, which with guanin and adenin constitute a series
of leucomains, of great physiological interest. Their relations to
each other and to uric acid, of which they may all be considered
as products of reduction, will be understood by a comparison of
the formula of uric acid (p. 348) with the following :
.y =c— NH ,N=C-NH
OC | | HC/ j |
X
| |
-C C
NH-C CO
II I II I
HC-NH HC-NH
Xanthin. Hypoxanthin.
OC
/
X
.
HCC
-C C.NH XX-C C.
NH-C C.NH X-C C.NH
II I II I
HC-NH HC-NH
Guanin. Adenin.
Xanthin — Xanihic acid — Urous acid — CsILN^ — 152 — occurs
in a rare form of urinary calculus ; in the pancreas, spleen, liver,
thymus, and brain of mammals and fishes; and in human urine
after the use of sulfur baths or inunctions.
It is formed synthetically, either by the reduction of uric acid
by sodium amalgam, or by oxidation of guanin.
It is an amorphous, yellowish- white powder; very slightly
soluble in cold H2O. If dissolved in HNO3 and the solution
evaporated, xanthin leaves a yellowish residue, which turns red-
dish-yellow on the addition of potash solution, and violet-red
when heated.
By the action of methyl iodid upon its lead compound xanthin
is converted into theobromin, the natural alkaloid of cocoa, by
introduction of two methyl groups ; and by the introduction of
a third methyl group into caffein, the alkaloid of coffee.
352 MANUAL OF CHEMISTRY.
Xanthin calculi vary in size from that of a pea to that of a.
pigeon's egg. They are rather hard, brownish-yellow, smooth,
shining, arid made up of well-defined, concentric layers. Their
broken surfaces assume a waxy polish when rubbed.
Hypoxanthin—Sarcin— €5114X40 — 136 — occurs in the spleen,
muscular tissue, thymus, suprarenal capsules, brain, and other
animal tissues. In the urine it is present in very small quantity
in health, but in leucocythsemia it is increased in the urine and
has been found in the blood. It also occurs in numerous seeds
and pollen of plants, and is also produced during putrefaction of
albumen. It appears to be a product of decomposition of nuclein
(see p. 369). It may be obtained from the mother liquor of the
preparation of creatin (see p. 334). It is also found as a product
of the action of gastric juice, of pancreatic juice, or of dilute acids
upon fibrin. It is produced by the action of nitrous acid upon
adenin ; by the acton of sodium amalgam upon uric acid or upon
xanthin ; and, in small quantity, by the action of acids upon nu-
clein.
It is a white crystalline powder ; soluble in 300 parts of cold and
78 parts of boiling H2O. It dissolves in acids and alkalies. It is
decomposed by KHO at 200° (392° P.) into NH3 and potassium
cyanid; by H2O at 200° (392° P.) into CO2, formic acid and NH3;
and is oxidized to xanthin by HNO3.
It is probably, along with creatin, xanthin, guanin, and other
leucomaines, an intermediate product in the formation of uric
acid and urea in the processes of metabolism.
G-uanin— CsHeNsO — 151 — occurs in guano, in the excrements of
the lower animals, and in the pancreas, lungs, liver and other
organs of animals as well as in the young leaves and pollen of
certain plants. It has not been found in the urine. Like hypo-
xanthin and xanthin it is a product of decomposition of nuclein.
It is a white or yellowish, amorphous, odorless and tasteless solid ;
almost insoluble in H2O, alcohol and ether; readily soluble in
acids and alkalies, with which it forms compounds. It gives the
xanthin reaction with HNO3 and KHO. Nitrous acid oxidizes it
to xanthin. Potassium permanganate oxidizes it to urea, oxalic
acid and oxyguanin. Hydrochloric acid and potassium chlorate
oxidize it to COa, guanidin (p. 334), and oxalylurea (p. 346).
Adenin — CsH^Ns — is a leucomain of great physiological interest
recently separated from extract of pancreas, in which it is found
along with the bases described above by decomposition of nuclein.
It is widely distributed in both animal and vegetable kingdoms,
and has been found in tissues abounding in nucleated cells, in the
spleen, kidneys, lymphatic glands, and in the blood and urine in
leucocythsemia, as well as in yeast and in tea leaves.
COMPOUND UREAS. 353
Adenin crystallizes in nacreous plates or in long needles, con-
taining 3 Aq., which they lose only at 110° (230° F.) although they
become opaque at 53° (127°. 4 F.). Very soluble in hot H3O, it
requires 1086 parts of cold H2O for solution. The aqueous solu-
tion is neutral. It is insoluble in alcohol, ether and chloroform ;
readily soluble in acids and alkalies, with which it forms com-
pounds.
It resists oxidizing and hydrating actions obstinately. Nitrous
acid, however, converts it into hypoxanthin. Adenin is a poly-
mere of hydrocyanic acid, and when heated to 200° (392° F.) it pro-
duces potassium cyanid. It has not been obtained synthetically
from hydrocyanic acid, although the closely related xanthin and
niethylxanthin have been formed by heating hydrocyanic acid,
•water and acetic acid together under pressure.
Carnin — CTHfeNiOs+HaO— 196 + 18— is obtained from Liebig's
meat extract in chalky, microscopic crystals, readily soluble in
warm H2O. It forms compounds with acids and alkalies, similar
to those of hypoxanthin.
Heteroxanthin or Methylxanthin — Ct-,H,-,N,0.j — and ~ Paraxan-
thin=Dimethylxanthin — C^sN^O-i — the homologues of xanthin,
are leucomains existing in small quantity in urine.
Allantoin — C4H6N4O3 — is a diureid which occurs in the allantoic
fluid of the cow ; in the urine of sucking calves, in that of dogs
and cats when fed on meat, in that of children during the first
eight days of life, in that of adults after the ingestion of tan-
nin, and in that of pregnant women. It is produced artificially
by oxidizing uric acid, suspended in boiling H2O, with lead
dioxid.
It crystallizes in small, tasteless, neutral, colorless prisms ; spar-
ingly soluble in cold H2O, readily soluble in warm H2O. Heated
with alkalies it yields oxalic acid and NH3 ; and with dilute acids,
allanturic acid, C..H jN,0. .
Allantoin has been obtained synthetically by heating together
rnesoxalic acid, CsH^On, and urea.
Alloxantin— djHjNiOt— is a diureid crystallizing in small, bril-
liant, very sparingly soluble prisms, produced by the action of
reducing agents upon alloxan, whose action is less powerful than
that required to convert alloxan into dialuric acid.
Murexid— Ammonium purpurate — CeH4(NH4)N5O6 — is pro-
duced by oxidation of uric acid, of alloxan, and of a number of
other derivatives of uric acid with subsequent contact of ammo-
nium hydroxid. It is supposed to be the ammonium salt of a
hypothetical and non-isolated acid. The ammonium salt is of
a brilliant, but evanescent purple color. (See p. 350.)
Two vegetable alkaloids, theobromin and caffein, are diureids
, n — v_/ — n Jl
c( | 1
NTV- p pr\
OC^ | | '
HP ^~\ f^ (^Cl
II 1
HC-N.CH3
ii 1
HC-N.CH,
Theobromin.
Caffein.
354 MANUAL OF CHEMISTRY.
whose relations to each other and to the uric acid series will be
seen by comparison of their formulae with those on pp. 348, 351 :
H3C
Theobromin — C7H8N4Oa — occurs in the seeds of theobroma cacao
in the proportion of about two per cent. It is a colorless crys-
talline powder, bitter in taste ; difficultly soluble in water, alco-
hol, ether, and chloroform; soluble in acids, with which it forms
salts. When heated with chlorin water so that the fluid grad-
ually evaporates it leaves a red-brown residue, which turns to a
fine purple-violet with ammonium hydroxid.
Caffein— Thein— Guaranin— Caffeina (U. S.)— C8H10N4O2-i-Aq—
194+18— exists in coffee, tea, Paraguay tea, and other plants. It
crystallizes in long, silky needles ; faintly bitter ; soluble in 75
pts. H2O at 15° (59° F.); less soluble in alcohol and ether. Hot
fuming HNOs converts it into a yellow liquid, which after evap-
oration turns purple with NHjHO. It gives the same reaction
with chlorin water and ammonium hydroxid as theobroinin.
CARBAMIC ACIDS.
/ OH
Carbamic acid— OC(^NH- — is produced whenever NH3 and CO2
come in contact. It is formed during the combustion of organic
nitrogenized substances, and appears to exist in animal fluids,
particularly in blood serum. Its salts are much less stable than
its ethers. The latter are known as urethans.
Ethyl carbamate— TJrethan— OC5— is formed (1) by the
action of cyanogen chlorid on alcohol; (2) by the action of alcohol
upon urea nitrate under pressure at 120"-130° (248°-266° F.) ; (3)
lay the action of ethylcarbonic ether, CO3(C2H6)a, on alcohol. It
forms thin, large, transparent, crystalline plates, fusible at about
50° (122° F.) ; boils at 180° (356° F.), very soluble in alcohol and in
•water.
Chloral-urethan— ITralium — Somnal— C7H12C1303N (?)— is a prod-
uct obtained by the action of chloral upon urethan in the pres-
ence of ethylic alcohol. It is a very deliquescent, crystallizable
solid, readily soluble in alcohol ; decomposed by hot H2O into
TRIATOMIC ALCOHOLS.
•chloral and urethan. It is questionable whether this is a definite
•compound or a mere mixture.
/O C H
Phenyl-urethan. — OC' j^jj 5 — used as an antipyretic under the
name " euphorine" is a light white powder, having faintly aro-
matic odor and taste, almost insoluble in water, very soluble in
alcohol.
TBIATOMIC ALCOHOLS.
SERIES CnHnn + aOa.
These substances are known as glycerins or more properly
glycerols. Their relation to the uionoatomic and diatomic alco-
hols is shown by the following formulae:
CH2OH
I
CHOH
CH3
CH3
CH2OH
1
CHa
CH,
CH2
CH,
CH2OH
CH2OH
Propane.
Propyl alcohol.
Propyl glycol.
C
H2OH
Glycerin.
They are obtained by the saponification of their ethers, either
those existing in nature or those produced artificially.
They combine with acids to form three series of ethers, known
as monoglycerids, diglycerids, and triglycerids, formed by the
combination of one molecule of the alcohol with one, two, or
three molecules of a monobasic acid.
Glycerol — Glycerin — Propenyl Alcohol — G-lycerinum. (TJ. S.) —
C3H5(OH)3 — 92 — was first obtained as a secondary product in the
manufacture of lead plaster ; it is now produced as a by-product
in the manufacture of soaps and of stearin candles. It exists
free in palm-oil and in other vegetable oils. It is produced in
small quantity during alcoholic fermentation, and is consequently
present in wine and beer. It is much more widely disseminated
in its ethers, the neutral fats, iii the animal and vegetable king-
doms.
It has been obtained by partial synthesis, by heating for some
time a mixture of allyl tribromid, silver acetate and acetic acid,
and saponifying the triacetin so obtained.
The glycerol obtained by the process now generally followed —
the decomposition of the neutral fats and the distillation of the
product in a current of superheated steam — is free from the im-
purities which contaminated the product of the older processes.
The only impurity likely to be present is water, which may be
recognized by the low sp. gr.
Glycerol is a colorless, odorless, syrupy liquid, has a sweetish
taste ; sp. gr. 1.26 at 15° (59° F.). Although it cannot usually be
caused to crystallize by the application of the most intense cold,
356' MANUAL OF CHEMISTRY.
it does so sometimes under imperfectly understood conditions,,
forming small, white needles of sp. gr. 1.268, and fusible between
17° and 18° (62°. 6 and 64°. 6 P.). It is soluble in all proportions in
water and alcohol, insoluble in ether and in chloroform. The
sp. gr. of mixtures of glycerol and water increase with the propor-
tion of glycerol. It is a good solvent for a number of mineral and
organic substances (glycerites and glyceroles). It is not volatile
at ordinary temperatures. When heated, a portion distils un-
altered at 275°-280° (527°-536° F.), but the greater part is decom-
posed into acrolein, acetic acid, carbon dioxid, and combustible
gases. It may be distilled unchanged in a current of superheated
steam between 285° and 315° (545°-599° F.), and distils under ordi-
nary conditions when perfectly pure.
Concentrated glycerol, when heated to 150° (302° F.) ignites and
burns without odor and without leaving a residue, and with a
pale blue flame. It may also be burnt from a short wick.
Glycerol is readily oxidized, yielding different products with
different degrees of oxidation. Platinum-black oxidizes it, with
formation, finally, of H2O and CO2. Oxidized by manganese
dioxid and H2SO4, it yields CO2 and formic acid. If a layer of
glycerol diluted with an equal volume of H2O be floated on the
surface of HNO3 of sp. gr. 1.5, a mixture of several acids is
formed : oxalic, C2O4H2 ; glyceric, C3H6O4 ; formic, CHaOa ;
glycollic, C2H4O3 ; glyoxylic, C3H4O4 ; and tartaric, C4H6O«.
When glycerol is heated with potassium hydroxid, a mixture of
potassium acetate and formiate is produced. When glycerol,
diluted with 20 volumes of H2O, is heated with Br ; CO2, bromo-
form, glyceric acid, and HBr are produced. Phosphoric anhy-
drid removes the elements of H2O from glycerol, with formation
of acrolein (see p. 304). A similar action is effected by heating
with H2SO4, or with potassium hydrosulfate. Heated with
oxalic acid, glycerol yields CO2 and formic acid.
The presence of glycerol in a liquid may be detected as follows:
Add NaHO to feebly alkaline reaction, and dip into it a loop of
Pt wire holding a borax bead ; then heat the bead in the blow-
pipe flame, which is colored green if the liquid contain T£7 of
glycerol.
The glycerol used for medicinal purposes should respond to
the following tests : (1) its sp. gr. should not vary much from that
given above ; (2) it should not rotate polarized light ; (3) it should
not turn brown when heated with sodium nitrate ; (4) it should
not be colored by H2S ; (5) when dissolved in its own weight of
alcohol, containing one per cent, of H2SO4, the solution should
be clear ; (6) when mixed with an equal volume H2SO4, of sp. gr.
1.83, it should form a limpid, brownish mixture, but should not,
give off gas.
1CIDS DERIVED FROM GLYCEROLS. 357
ACIDS DERIVABLE FROM THE GLYCEROLS.
Three series of acids are derivable from the glycerols by sub-
stitution of O for H2 in the group CH2OH :
CHaOH
CH2OH
COOH
CH2,COOH
CHOH
CHOH
CHOH
CHS,COOH
CH..OH
COOH
COOH
CH2,COOH
Glycerin.
Glyceric acid.
Tartronic acid.
Tiicarballylic acid..
The terms of each series are triatomic ; those of the glyceric
series are monobasic, those of the tartronic series are dibasic, and
those of the tricarballylic series are tribasic.
Malic acid — C ,H, 0 — 134 — is the second term of the tartronic
series, and is therefore dibasic. It exists in the vegetable king-
dom ; either free or combined with K, Na, Ca, Mg, or organic
"bases ; principally in fruits, such as apples, cherries, etc. ; accom-
panied by citrates and tartrates.
It crystallizes in brilliant, prismatic needles ; odorless ; acid in
taste ; fusible at 100° (212° F.) ; loses HaO at 140° (284° F.) ; deli-
quescent ; very soluble in H»O and in alcohol. Heated to 175°-
180° (347°-356° F.), it is decomposed into H2O and maleic acid,
CiH,O i. The malates are oxidized to carbonates in the body.
TRIBASIC TCJNSATURATED ACIDS.
Aconitic Acid — C3H3(COOH)3 — exists in its Ca salt in the differ-
ent species of aconitum and of equisetum. It forms white,
crystalline crusts, or by slow crystallization white plates or
prisms ; odorless ; sour ; soluble in water, alcohol and ether ;
fuses at 186° (366°. 8 F.). Its salts are soluble and crystalline. It
is decomposed by heat into itaconic acid and CO2.
Citric acid— Acidum citricum (U. S., Br.)— C6H,O7 + Aq— 192+18
— is best considered in this place, although it is tetratomic, while
the other acids of the series are triatomic. It exists in the juices
of many fruits — lemon, strawberry, etc., and in cow's inilk in the
proportion of about 0.1#, as calcium citrate.
It is obtained from lemon-juice, which is filtered, boiled, and
saturated with chalk. The insoluble calcium citrate is separated
and decomposed with H2SO4, the solution filtered, and evaporated
to crystallization.
It crystallizes in large, right rhombic prisms, which lose their
aq at 100' (212° F.); very soluble in water, less soluble in alcohol,
sparingly soluble in ether; heated to 100° (212° F.) it fuses; at 175°
(347° F.) it is decomposed, with loss of H2O and formation of aco-
358 MANUAL OF CHEMISTRY.
nitic acid, C«H8O6 ; at a higher temperature CO2 is given off, and
itaconic acid, CsH6O4, and citraconic acid, C6H6O4, are formed.
Concentrated H2SO4 decomposes it with evolution of CO ; oxi-
dizing agents convert it into formic acid and CO2, or into acetone
and CO2, or into oxalic and acetic acids and CO2. It is tetratomie
and tribasic. In the body its salts are oxidized to carbonates.
Citric acid may be distinguished from tartaric and malic acid&
by the following reaction : Add glycerol, fuse in a porcelain cap-
sule, heat until acrolein is given off, dissolve in NH4HO. Expel
N«H4HO by heat, add two drops HNO3 — a green color, changing;
to blue when heated.
ETHERS OF GLYCEROL.
GLYCERIDS.
As glycerol is a triatomic alcohol, it contains three oxhydryl
groups which may be removed, combining with H from an acid
to form H2O, and leaving a univalent, bivalent, or trivalent re-
mainder, which may replace the H of monobasic acids to form,
three series of ethers. As, further, the OH groups differ from
each other in that two of them are contained in the primary
group CHaOH, the other in the secondary group CHOH, there
exist two isomeres of each mono- and di-glycerid :
CH2OH CH2— O— C2H30 CH2— O— C3H3O CH2— O— C,H3O
CHOH CHOH CH— O— C,H3O CH— O— C2H3O
CH2OH CH2OH CH2OH CH2— O— C2HSO
Glycerin. Manoacetin. Diacetin. Triacetin.
Of the many substances of this class, only a few, principally
those entering into the composition of the neutral fats, require
consideration here.
Tributyrin— C3H6(O,C4H7O)3— 302— exists in butter. It may
also be obtained by heating glycerol with butyric acid and
H2SO4. It is a pungent liquid, very prone to decomposition,
with liberation of butyric acid.
Trivalerin — C:iHr,(0,C.,H ,0) ; — 344 — exists in the oil of some mari-
time mammalia, and is identical with the phocenin of Chevreul.
Tricaproin— C3H5(O,C6Hi iO)3— 386 — Tricaprylin— C3HB(O,C8Hi 6O)»
— 470 — andTricaprin — C3H6(O,Ci0H19O)3 — 554 — exist in small quan-
tities in milk, butter, and cocoa-butter.
Tripalmitin — C3H6(O,Ci6H3iO)3 — 806 — exists in most animal and
vegetable fats, notably in palm-oil ; it may also be obtained by
heating glycerol with 8 to 10 times its weight of palmitic acid for
ETHERS OF GLYCEROL. 359
8 hours at 250° (482° F.). It forms crystalline plates, very spar-
ingly soluble in alcohol, even when boiling ; very soluble in ether.
It fuses at 50° (122° F.) and solidifies again at 46° (114°. 8 F.).
Trimargarin— C3H6(O,C17H330)3— 848— has probably been ob-
tained artificially as a crystalline solid, fusible at 60° (140° F.),
solidifiable at 52° (125°. 6 F.). The substance formerly described
under this name as a constituent of animal fats is a mixture of
tripalmitin and tristearin.
Tristearin— C3H5(O,Ci8H36O)3— 890— is the most abundant con-
stituent of the solid fatty substances. It is prepared in large
quantities as an industrial product in the manufacture of stearin
candles, etc., but is obtained in a state of purity only with great
difficulty.
In as pure a form as readily obtainable, it forms a hard, brittle,
crystalline mass ; fusible at 68° (154°. 4 F.), solidifiable at 61°
(141°. 8 F.) ; soluble in boiling alcohol, almost insoluble in cold
alcohol, readily soluble in ether.
Triolein— C3H5(O,CifH33O)3 — 884— exists in varying quantity in
all fats, and is the predominant constituent of those which are
liquid at ordinary temperatures ; it may be obtained from animal
fats by boiling with alcohol, filtering the solution, decanting
after twenty-four hours' standing ; freezing at 0° (32° F.), and ex-
pressing.
It is a colorless, odorless, tasteless oil ; soluble in alcohol and
ether, insoluble in water ; sp. gr. 0.92.
Trinitro-glycerol — Nitro-glycerol— C3H5(ONO2)3 — 227— used as
an explosive, both pure and mixed with other substances, in dyna-
mite, giant powder, etc , is obtained by the combined action of
H2SO4 and HNO3 upon glycerol. Fuming HNO3 is mixed with
twice its weight of H2SO4 in a cooled earthen vessel ; 33 parts by
weight of the mixed acids are placed in a porcelain vessel, and 5
parts of glycerol, of 31° Beaume", are gradually added with con-
stant stirring, while the vessel is kept well cooled ; after five
minutes the whole is thrown into 5-6 volumes of cold water ; the
nitro-glycerol separates as a heavy oil, which is washed with cold
water.
Nitro-glycerol is an odorless, yellowish oil ; has a sweetish
taste ; sp. gr. 1.6 ; insoluble in water, soluble in alcohol and ether;
not volatile ; crystallizes in prismatic needles when kept for some
time at 0° (32° F.); fuses again at 8° (46". 4 F.).
When pure nitro-glycerol is exposed to the air at 30° (86° F.) for
some time, it decomposes, without explosion and with production,
of glyceric and oxalic acids. When heated to 100° (212° F.) it
volatilizes without decomposition; at 185° (365° F.) it boils, giving
off nitrous fumes; at 217° (422°. 6 F.) it explodes violently; if
quickly heated to 257° (494°. 6 F.) it assumes the spheroidal form,
360 MANUAL OF CHEMISTRY.
and volatilizes without explosion. Upon the approach of flame at
low temperatures it ignites and burns with slight decrepitations.
When subjected to shock, it is suddenly decomposed into CO2 ;
N ; vapor of H2O, and O, the decomposition being attended with
a violent explosion.
In order to render this explosive less dangerous to handle, it is
now usually mixed with some inert substance, usually diatoma-
ceous earth, in which form it is known as dynamite, etc.
When taken internally, nitro-glycerin is an active poison, pro-
ducing effects somewhat similar to those of strychnin; in drop-
doses, diluted, it causes violent headache, fever, intestinal pain,
and nervous symptoms. It has been latterly used as a therapeu-
tic agent, and has been used by the homoeopaths under the name
of glonoin.
NEUTRAL OILS AND FATS.
These are mixtures in varying proportions of tripalmitin, tri-
stearin, and triolein, with small quantities of other glycerids,
coloring and odorous principles, which are obtained from animal
and vegetable bodies. The oils are fluid at ordinary tempera-
tures, the solid glycerids being in solution in an excess of the
liquid triolein. The fats, owing to a less proportion of the liquid
glycerid, are solid or semi-solid at the ordinary temperature of
the air. Members of both classes are fluid at sufficiently high
temperatures, and solidify when exposed to a sufficiently low
temperature. They are, when pure, nearly tasteless and odorless,
unctuous to the touch, insoluble in and not miscible with H2O,
upon which they float; combustible, burning with a luminous
flame. When rubbed upon paper they render it translucent.
When heated with the caustic alkalies, or in a current of super-
heated steam, they are saponified, i.e., decomposed into glycerin
and a fatty acid. If the saponification be produced by an alkali,
the fatty acid combines with the alkaline metal to form a soap.
Most of the fats and many of the oils, when exposed to the air,
absorb O, are decomposed with liberation of volatile fatty acids,
and acquire an acid taste and odor, and an acid reaction. A fat
which has undergone these changes is said to have become rancid.
Many of the vegetable oils are, however, not prone to this decom-
position. Some of them, by oxidation on contact with the air,
become thick, hard and dry, forming a kind of varnish over sur-
faces upon which they are spread ; these are designated as drying
or siccative oils. Others, although they become more dense on
exposure to air, become neither dry nor gummy ; these are known
as non-drying, greasy, or lubricating oils.
Under ordinary conditions, oils and melted fats do not mix
NEUTRAL OILS AND FATS. 361
with water, and, if shaken with that fluid, form a temporary
milky mixture, which, on standing for a short time, separates
into two distinct layers, the oil floating on the water. In the
presence, however, of small quantities of certain substances, such
as albumen, pancreatin (g.v.), ptyalin, etc., the milky mixture
obtained by shaking together oil and water does not separate
into distinct layers on standing; such a mixture, in which the fat
is held in a permanent state of suspension in small globules in a
watery fluid, is called an emulsion. Good emulsions may be
easily obtained by agitating an oil containing a trace of free oleic
acid with a very dilute solution of sodium carbonate and borax.
Fixed oils. — These substances are designated as " fixed," to dis-
tinguish them from other vegetable products having an oily ap-
pearance, but which differ from the true oils in their chemical
composition and in their physical properties, especially in that
they are volatile without decomposition, and are obtained by dis-
tillation, while the fixed oils are obtained by expression, with or
without the aid of a gentle heat.
Palm-oil is a reddish-yellow solid at ordinary temperatures,
has a bland taste and an aromatic odor. It saponifies readily,
and is usually acid and contains free glycerol liberated by spon-
taneous decomposition.
Rape-seed and colza oils, produced from various species of
Srassica, are yellow, limpid oils having a strong odor and dis-
agreeable taste.
Croton-oil — Oleum, tiglii (TJ. S.) — Oleum, crotonis (Br.) — varies
much in color and activity, according to its source ; that which
is obtained from, the East is yellowish, liquid, transparent, and
much less active than that prepared in Europe from the imported
seeds, which is darker, less fluid, caustic in taste, and wholly
soluble in absolute alcohol. Croton-oil contains, besides the gly-
cerids of oleic, crotonic and fatty acids, about four per cent, of a
peculiar principle called crotonol, to which the oil owes its vesi-
cating properties. It also contains an alkaloid-like substance,
also existing in castor-oil, called ricinin. None of these bodies,
however, are possessed of the drastic powers of the oil itself.
Peanut-oil — Ground-nut-oil — an almost colorless oil, very much
resembling olive-oil, in place of which it is frequently used for
culinary purposes, intentionally or otherwise. It is readily sapon-
ifiable, yielding two peculiar acids, arachaic and hypogaic (see
Olive-oil).
Cotton-seed-oil — Oleum gossypii seminis (TJ. S.) — a pale yellow,
bland oil, also resembling olive-oil, for which it is frequently sub-
stituted.
362 MANUAL OF CHEMISTRY.
Almond-oil — Oleum amygdalae expressum (TJ. S.) — Oleum amyg-
dalae (Br.) — a light yellow oil, very soluble in ether, soluble in.
alcohol; nearly inodorous; has a bland, sweetish taste. The
pure oil has no odor of bitter almonds.
Olive-oil — Oleum olives (TJ. S., Br.) — a well-known oil of a yel-
low or greenish-yellow color, almost odorless, and of a bland and
sweetish taste. The finest grades have a yellow tinge and a faint
taste of the fruit ; they are prepared by cold pressure ; they are
less subject to rancidity than the lower grades. Olive-oil is very
frequently adulterated, chiefly with poppy-oil, sesame-oil, cotton-
seed-oil and peanut-oil. The presence of the first is detected by
Pontet's reagent (made by dissolving 6 parts Hg in 7.5 parts of
HNO3 of 36° in the cold), which converts pure olive-oil into a solid
mass, while an oil adulterated with a drying oil remains semi-
solid. A contamination with oil of sesame is indicated by the
production of a green color, with a mixture of HNOs and H3SO.i.
Peanut-oil, an exceedingly common adulterant in this country,
is recognized by the following method : ten grams of the oil are
saponified ; the soap is decomposed with HC1 ; the liberated fatty
acids dissolved in 50 c.c. of strong alcohol; the solution precipi-
tated with lead acetate; the precipitate washed with ether; the
residue decomposed with hot dilute HC1 ; the oily layer separated
and extracted with strong alcohol; the alcoholic fluid, on evapo-
ration, yields crystals of arachaic acid, if the oil contains peanut-
oil. The most usual adulteration is with cotton-seed-oil, which
may be detected, if more than 5$ be present, as follows : 10 c.c.
each of the oil and of ethylic ether are agitated in a test-tube ;;
add 5 c.c. strong solution of neutral lead acetate, and then 5 c.c.
ammonium hydrate solution, and agitate again. In the presence
of cotton-seed-oil an orange-red color is produced, particularly in
the upper layer.
Cocoa-butter — Oleum theobromse (U. S., Br.) — is, at ordinary
temperatures, a whitish or yellowish solid of the consistency of
tallow, and having an odor of chocolate and a pleasant taste ; it
does not easily become rancid. The most reliable test of its
purity is its fusi rig-point, which should not be much below 33°
(91°.4 R).
Linseed-oil — Flaxseed-oil — Oleum lini (TJ. S., Br.) — is a dark,
yellowish-brown oil of disagreeable odor and taste. In it oleic
acid is, at least partially, replaced by linoleic acid, whose pres-
ence causes the oil, on exposure to air, to absorb oxygen and be-
come thick and finally solid. This drying power is increased by
boiling the oil with litharge (boiled oil).
Castor-oil — Oleum ricini (TJ. S., Br.) — is usually obtained by ex-
pression of the seeds, although in some countries it is prepared by
decoction or by extraction with alcohol. It is a thick, viscid,.
NEUTRAL OILS AND FATS. 363
yellowish oil, has a faint odor and a nauseous taste. It is more
soluble in alcohol than any other fixed vegetable oil, and is also
very soluble in ether. It saponifies very readily. Ammonia sep-
arates from it a crystalline solid, fusible at 66° (158°. 8 F.), ricino-
lamid. Hot HNO3 attacks it energetically, and finally converts
it into suberic acid.
Whale-oil — Train-oil — obtained by trying out the fat or blub-
ber of the " right whale " and of other species of balcence. It is of
sp. gr. 0.924 at 15° (59° F.); brownish in color; becomes solid at
about 0° ; has a very nauseous taste and odor. It is colored yel-
low by H2SO4 ; and is blackened by Cl.
Neat's-foot-oil — is obtained by the action of boiling H2O upon
the feet of neat cattle, horses, and sheep, deprived of the flesh
and hoofs. It is straw-yellow or reddish-yellow, odorless, not
disagreeable in taste, not prone to rancidity, does not solidify at
quite low temperatures ; sp. gr. at 15° (59° F.)=0.916. It is bleached,
not colored, by chlorin.
Lard-oil — Oleum adipis (U. S.) — obtained in large quantities in
the United States as a by-product in the manufacture of candles,
etc., from pig's fat. A light yellow oil, used principally as a
lubricant; is not colored by HaSCX, but is colored brown by a
mixture of H2SC>4 and HNO3.
Tallow-oil — obtained by expression with a gentle heat from the
fat of the ox and sheep. Sp. gr. 0.9003; light yellow in color.
Colored brown by H2SO4. Formerly this oil, under the trade
name of " oleic acid," was simply a by-product in the manufacture
of stearin candles ; of late years, however, it is specially prepared
for the manufacture of oleomargarine.
Cod-liver-oil — Oleum morrhuae (U. S., Br.) — is obtained from the
livers of cod-fish, either by extraction with water heated to about
80° (176° F.), or by hanging the livers in the sun and collecting
the oil which drips from them. There are three commercial vari-
eties of this oil : (a) Brown. — Dark brown, with greenish reflec-
tions ; has a disagreeable, irritating taste ; faintly acid ; does not
solidify at -13° (8°.6 F.). (6) Pale brown.— Of the color of Sherry
wine ; lias a peculiar odor and a fishy, irritating taste ; strongly
acid. (c)Pale. — Golden yellow; deposits a white fat at —13° (8°. 6-
F.); has a fresh odor, slightly fishy, and a not unpleasant taste,
without after-taste.
Pure cod-liver-oil, with a drop of H2SO4, gives a bluish-violet
aureole, which gradually changes to crimson, and later to brown.
A drop of fuming HNO3 dropped into the oil is surrounded by a.
pink aureole if the oil be pure. If the oil be largely adulterated
with other fish-oils, the pink color is not observed, and the oil
becomes slightly cloudy. Fresh cod liver-oil is not colored by
rosanilin.
364 MANUAL OF CHEMISTRY.
Cod-liver-oil contains, besides the glycerids of oleic, palmitic
and stearic acids, those of butyric and acetic acids; certain biliary
principles (to whose presence the sulfuric acid reaction given
above is probably due), a phosphorized fat of undetermined com-
position ; small quantities of bromin and iodin, probably in the
form of organic compounds ; a peculiar fatty acid called gadinic
acid, which solidifies at 60° (140° F.) ; and a brown substance called
gaduin or gadinin. It also contains two alkaloids: Asellin,
CaaHssN.!, and morrhuin, Ci9H27N3.
To which, if to any, of these substances cod-liver-oil owes its
value as a therapeutic agent is still unknown, although many
"theories have been advanced. Certain it is, however, that one of
the chief values of this oil is as a food in a readily assimilable form.
Solid Animal Fats. — Tho glycerids of stearic, palmitic, and oleic
acids exist, in health, in nearly all parts of the body ; in the fluids
in solution or in suspension, in the form of minute oil-globules;
incorporated in the solid or semi-solid tissues, or deposited in col-
lections in certain locations, as under the skin, enclosed in cells of
connective tissue.
The total amount of fat in the body of a healthy adult is from
2.5 to 5 per cent, of the body- weight, although it may vary con-
siderably from that proportion in conditions not, strictly speak-
ing, pathological. The approximate quantities of fat in 100 parts
of the various tissues and fluids, in health, are the following :
Urine ? Crystalline lens 2.0
Perspiration 0.001 Liver 2.4
Vitreous humor 0.002 Muscle 3.3
Saliva 0.02 Hair 4.2
Lymph 0.05 Milk 4.3
Sy no vial fluid 0.06 Cortex of brain 5.5
Amniotic fluid 0.2 Brain 8.0
Chyle -...0.3 Hen's egg 11.6
Mucus 0.4 White matter of brain. . . . 20.0
Blood 0.4 Nerve-tissue 22.1
Cartilage 1.3 Spinal cord 23.6
Bone 1.4 Fat-tissue 82.7
Bile 1.4 Marrow 96.0
The amount of fat, under normal conditions, is usually greater
in women and children than in men; generally greater in middle
than in old age, although in some individuals the reverse is the
<;ase; greater in the inhabitants of cold climates than in those of
hot countries.
In wasting from disease and from starvation the fats are rapidly
absorbed, and are again as rapidly deposited when the normal
•condition of affairs is restored.
Besides, as a result of the tendency to corpulence, which in
some individuals amounts to a pathological condition, fats may
NEUTRAL OILS AND FATS. 365-
accumulate in certain tissues as a result of morbid changes. This-
accumulation may be due either to degeneration or to infiltration.
In the former case, as when muscular tissue degenerates in con-
sequence of long disuse, the natural tissue disappears and is re-
placed by fat; in the latter case, as in fatty infiltration of the-
heart, oil-globules are deposited between the natural morpholog-
ical elements, whose change, however, may subsequently take
place by true fatty degeneration, due to pressure. The greater
part of the fat of the body enters it as such with the food. Not
unimportant quantities are, however, formed in the body, and
that from the albuminoid as well as from the starchy and saccha-
rine constituents of the food. By what steps this transformation
takes place is still uncertain, although there is abundant evidence
that it does occur.
Those fats taken in with the food are unaltered by the digestive
fluids, except in that they are freed from their enclosing mem-
branes in the stomach, until they reach the duodenum. Here,,
under the influence of the pancreatic juice, the major part is con-
verted into a fine emulsion, in which form it is absorbed by the
lacteals. A smaller portion is saponified, and the products of the
saponification, free fatty acids, soaps, and glycerol, subsequently
absorbed by lacteals and blood-vessels.
The service of the fats in the economy is undoubtedly as a pro-
ducer of heat and force by its oxidation ; and by its low power of
conducting heat, and the position in which it is deposited under
the skin, as a retainer of heat produced in the body. The fats
are not discharged from the system in health, except the excess
contained in the food over that which the absorbents are capable
of taking up, which passes out with the faeces; a small quantity
distributed over the surface in the perspiration and sebaceous,
secretion (which can hardly be said to be eliminated) ; and a mere
trace in the urine.
Butter. — The fat of milk, separated and made to agglomerate
by agitation, and more or less salted to insure its keeping. It
consists of the glycerids of stearic, palmitic, oleic, butyric, capric,
caprylic, and caproic acids, with a small amount of coloring mat-
ter, more or less water and salt, and casein. Good, natural but-
ter contains 80-90 per cent, of fat, 6-10 per cent, of water, 2-5 per
cent, of curd, and 3-5 per cent, of salt; fuses at from 32°. 8 to 34°. 9
(91°-94°.8 R).
Butter is adulterated with excess of water and salt, starch, ani-
mal fats other than those of butter, and artificial coloring mat-
ters.
Excess of salt and water are usually worked in together, the
former up to 14 per cent, and the latter to 15 per cent. To deter-
mine the presence of an excess of water, about 4 grams (60 grains)
of the butter, taken from the middle of the lump, are weighed in
366
MANUAL OF CHEMISTRY.
a porcelain capsule, In which it is heated over the water-bath, as
long as it loses weight ; it is then weighed again ; the loss of weight
is that of the quantity of water in the original weight of butter,
less that of the capsule. The proportion of salt is determined by
incinerating a weighed quantity of butter and determining the
chlorin in the ash by the nitrate of silver method (see Sodium
chlorid). Roughly, the weight of the ash may be taken as salt.
Starch is detected by spreading out a thin layer of butter, adding
solution of iodin, and examining under the microscope for purple
spots.
The detection of foreign fats in butter, formerly a most unsat-
isfactory problem to the analyst, has now become one which may
be answered with great certainty. All of the chemical processes
used are based upon a peculiar difference in the composition of
butter-fat from other animal and vegotabl > fats and oils. When
butter-fat is saponified, it yields from 5 to 8 per cent, of butyric
acid and its near homologues, which are soluble in HaO, and may
be distilled without suffering decomposition, and from 85.5 to 87.5
of stearic, palmitic, and oleic acids, which are neither soluble in
water nor capable of being distilled. The other fats and oils,
when saponified, yield mere traces of the vola-
tile or soluble fatty acids, and much larger
quantities (95.3 to 95.7 per cent.) of insoluble
acids. These variations are utilized directly in
some processes, such as those of Hehner and
Reichert, in which the percentage of fixed and
volatile acids are directly determined. In other
processes, such as those of Koettstorfer and
HUbl, advantage is taken of the different neu-
tralizing power of the two groups of acids.
Thus, as butyric acid, C4H8O2, and stearic acid,
CisHseOa, are each capable of neutralizing KHO,
molecule for molecule, it follows that their neu-
tralizing power is in proportion to their molec-
ular weights, and that 56 parts KHO will re-
quire for neutralization 88 parts of butyric
acid, or 284 parts of stearic acid. For descrip-
tions of processes the student is referred to
Allen, "Commercial Organic Analysis," 2d ed.,
II., pp. 145-160.
Methods for detecting admixture of foreign
fats by physical means are unreliable. One of
the best, which may be of service for pre-
liminary testing, is that of Angell and Hehner. A pear-shaped
bulb of thin glass is made of such size as to displace 1 c.c. water,
is weighted with mercury until it weighs 3.4 grams (52.5 grains),
and the pointed end closed by fusion. The butter to be tested
is fused in a beaker over the water-bath, and when quite fluid is
poured out into a test-tube about £ inch diameter and 6 inches
long, which is kept moderately warm and upright until the fat
has separated in a clear layer above the water, and then im-
mersed in water at 15° (59° F.) until the fat has solidified. The
test-tube is then arranged as shown in Fig. 39, the bulb being
laid upon the surface of the fat. The water in the beaker is now
heated until the globular part of the bulb has just sunk below
the surface of the fat, at which time the height of the thermo-
meter is noted ; this is the "sinking-point."
The sinking-point of pure butter is 34°. 3 to 36°.3 (93°.7-97°.3 F.),
that of oleomargarine is lower, that of butter adulterated with
other fats is higher.
FIG. 39.
NEUTRAL OILS AND FATS. 367
"Oleomargarine" is a product made in imitation of butter,
•which it resembles very closely in color, taste, odor, and general
appearance. Under the original patent, it is made from beef-fat,
which is hashed, steamed, and subjected to pressure at a carefully
regulated temperature. Under this treatment it is separated
into two fatty products, one a white solid, "stearine," the other
a faintly yellow oil, " oleo-oil." This oil is then mixed with milk,
the mixture colored and churned. The subsequent treatment of
the product is the same as that of butter. " Butterine," " suine."
«te., are products made, by modifications of the above process,
from beef or mutton tallow, lard, and cotton-seed-oil.
Butter is frequently, and oleomargarine is always, colored with
some foreign pigment, " butter color," which is usually a prepara-
tion of annoto.
Soaps — are the metallic salts of stearic, palmitic, and oleic acids :
those of K, Na, and NH4 are soluble, those of the other metals
insoluble. Those of Na are hard, those of K soft.
Soap is made from almost any oil or fat, the best from olive-oil,
or peanut, or palm-oil, and lard. The first step in the process of
manufacture is the saponification of the fat, which consists in
the decomposition of the glyceric ethers into glycerol and the
fatty acids, and the combination of the latter with an alkaline
metal. It is usually effected by gradually adding fluid fat to a
weak boiling solution of caustic soda, or potassa, to saturation.
Prom this weak solution the soap is separated by "salting,"
which consists in adding, during constant agitation, a solution
of caustic alkali, heavily charged with common salt, until the
soap separates in grumous masses, which float upon the surface
and are separated. Finally the soap is pressed to separate adher-
ing water, fused, and cast into moulds.
White Castile soap — Sapo (TT. S.), Sapo durus (Br.) — is a Na soap
made from olive-oil; strongly alkaline, hard, not greasy, very
soluble ; contains 21 per cent. H2O. Sapo mollis (Br.) is a K soap
made from olive-oil, and contains an excess of alkali and glycerol.
Yellow soap is made from tallow or other animal fat, and con-
tains about i its Aveight of rosin. Emplastrum plumbi (U. S., Br.)
is a lead soap, prepared by saponifying olive-oil with litharge.
The soaps are decomposed by weak acids, with liberation of
the fatty acid ; by compounds of the alkaline earths, with forma-
tion of an insoluble soap ; and in the same way by most of the
metallic salts.
368 MANUAL OF CHEMISTRY.
LECITHINS— NERVE-TISSUE.
Lecithin — is a substance first obtained from the yolk of hens*
eggs, and subsequently found to exist in brain-tissue, particularly
the gray substance, nerve-tissue, semen, blood-corpuscles, blood-
serum, milk, bile, and other animal tissues and fluids.
As obtained from brain-tissue lecithin is a colorless or faintly
yellowish, imperfectly crystalline solid, or sometimes of a waxy
consistency. It is very hygroscopic. It does not dissolve in HaO,
in which, however, it swells up and forms a mass like starch-
paste. It dissolves in alcohol or ether, very sparingly in the cold,
but readily under the influence of heat. It dissolves in chloro-
form and in benzene. Lecithin is very prone to decomposition,
particularly at slightly elevated temperatures. Its chlorid com-
bines with PtCl4 to form an insoluble yellowish chloroplatinate.
When an alcoholic solution of lecithin is brought into contact
with hot solution of barium hydroxid it yields barium glycero-
phosphate, barium stearate, and cliolin (see p. 276). This decom-
position indicates the constitution of lecithin and its relations to
the fats. Glycerophosphoric acid is phosphoric acid in which an
atom of hydrogen has been replaced by the univalent remainder
CH,OH— CHOH— CH2— left by the removal of OH from
glycerol :
/OH
O=P— OH
\O— CH2— CHOH— CH3OH.
In lecithin the remaining oxhydryl groups of the glycerol re-
mainder are removed by union with the basic hydrogen of two
molecules of stearic acid, and one of the two remaining basic
hydrogen atoms of the phosphoric acid is displaced by cholin. It
is obvious that the number of lecithins is not limited to one, but
that many may exist, and probably do, into whose composition
any one, or any combination of two, of the acids of the same
series as stearic acid may enter
/ O— N - CH2— CH2— OH
O=P— O— H
\O— CH2— CH(CieH36O2)— CH2(Ci8H36Oa).
Distearyl-lecithin.
Nerve-tissue, which is exceedingly complex in its chemical com-
position, and whose chemistry is still in a most rudimentary con-
dition, seems to contain similar constituents in its different parts,
which differ, however, materially in their quantitative composi-
tion.
The following substances have been obtained from cerebral
tissue :
LECITHINS — NERVE-TISSUE. 369
Mineral Substances Products of Decomposition.
Water. Glycerophosphoric acid.
Phosphates of Na, K, Ca, Mg. Oleophosphoric acid.
Ferric oxid. Volatile fatty acids.
Silicic oxid. Lactates.
Traces of sulfates, chlorids, and Hypoxanthin.
fluorids. Xanthin.
Creatin.
Albuminoids.
Substance related to myosin.
Soluble albuminoid, coagulable at 75° (167° F.).
Casein (?).
Organic Substances.
Elastin. Lecithin.
Neurokeratin. Fats (?).
Nuclein. Inosite.
Cerebrin. Cholesterin.
The composition of white and gray matter differs quantita-
tively, as shown below :
Gray White
Matter. Matter.
Albuminoids 55.37 24.72
Lecithin 17.24 9.90
Cholesterin and fats 18.68 51.91
Cerebrin 0.53 9.55
Extractive matters, insoluble in ether. . . 6.71 3.34
Salts 1.46 .0.57
Cerebrin is a substance deposited in the crystalline form from
hot ethero-alcoholic extracts of brain-tissue. It, is white, very
light, odorless, and tasteless ; insoluble in water or in cold alcohol
or ether. Its solutions are neutral. It does not contain phos-
phorus.
The substance known as protagon, described by Liebreich as
having been obtained from brain-tissue, would seem to exist there
notably in the white substance of Schwann. It appears to be a
compound formed by the union of lecithin with cerebrin.
Neurokeratin is a substance occurring principally in the gray-
matter, which is insoluble in all solvents, and is not acted upon
by digestive liquids.
Nuclein. — This name is applied to a phosphorized substance,
or more probably several such substances, existing in the nuclei
of animal and vegetable cells. The nucleins have been found in
pus. in the yolk of eggs, spermatic fluid, liver, brain, and casein,
in oleaginous seeds, and in many animal and vegetable tissues.
The nucleins from pus, spermatic fluid, and brain, and that from
yeast have been investigated.
370 MANUAL OF CHEMISTRY.
The nucleins are, when freshly precipitated, white, amorphous,
rather soluble in water, insoluble in acids and in the gastric
juice. They are extremely unstable and when decomposed yield
phosphoric acid, an albuminoid substance, xanthin, hypoxan-
thin, guanin, and adenin.
DIAMIDS OF THE TARTRONIC SERIES.
Corresponding to malic acid four amids are known:
Malamic acid — C4H7NO4 — is not known free, but exists as its
ethylic ether in malamethan.
Aspartic acid— C4H7NO4 — occurs in the molasses from beet-
sugar, and is produced by the decomposition of asparagin by
acids or alkalies. It crystallizes in sparingly soluble prisms.
Malamid — C4H8N2O3 — is produced in large crystals, by the ac-
tion of excess of NH3 on dry ethyl malate.
Asparagin — C,H-N,0: — is quite widely disseminated in vegeta-
ble nature, and is best obtained from asparagus, from the root
of the marsh-mallow, or from vetches. It crystallizes in ortho-
rhombic prisms with 1 Aq; sparingly soluble in water, odorless,
faintly nauseous in taste, faintly acid in reaction. Its solutions
are laevogyrous [a]j = 35°-38°.8. It enters into unstable combina-
tion with both acids and bases. It is converted into aspartic
acid and ammonia by heating with dilute mineral acids or alka-
line solutions. It is not oxidized by HNO3 unless the acid contain
nitrogen oxids, in which case it decomposes asparagin into malic
acid, N, and H2O.
THIRD SERIES OF HYDROCARBONS.
SERIES CnH2n_i.
The hydrocarbons of this series, above the first, form two iso-
meric series, designated as alpha and Beta. Those of the alpha
series are produced by heating the dibromids or diiodids of the
olefins with alcoholic solution of KHO. They have the general
formula HC~C — CnH2n+i. Those of the Beta series are pro-
duced by a variety of reactions, and have the general formula
H2C = C = CnHan.
Acetylene — Ethine — C2H2 — 26 — exists in coal-gas, and is formed
in the decomposition, by heat or otherwise, of many organic sub-
stances. It is best prepared by passing a slow current of coal-gas
through a narrow tube, traversed by induction sparks ; directing
the gas through a solution of cuprous chlorid ; and collecting and
decomposing the precipitate by HC1. It may be obtained by
direct synthesis from H and C, by producing the electric arc be-
tween carbon points in a glass globe filled with hydrogen.
It is a colorless gas, rather soluble in H2O ; has a peculiar, dis-
agreeable odor ; such as is observed when a Bunsen burner burns
within the tube. It forms explosive mixtures with O. It unites
•with N, under the influence of the electric discharge, to form hy-
TETRATOMIC ALCOHOLS. 37 1
<irocyanic acid. Mixed with Cl, it detonates violently in diffuse
daylight, without the aid of heat. It may be made to unite with
Itself to form its polymeres benzene, C«H6, styrolene, CeH8, and
uaphthydrene, CioHio.
Its presence may be detected by the formation in an ammo-
niacal solution of cuprous chlorid of a blood-red precipitate,
which is explosive when dry. It is probable that explosions
which sometimes occur in brass or copper pipes, through which
illuminating gas is conducted, are due to the formation of this
•compound.
Uluminating gas — is now manufactured by a variety of proc-
esses; thus we have gas made from wood, from coal, from fats,
from petroleum, and by the decomposition of H2O and subse-
quent charging of the gas with the vapor of naphtha. The typi-
cal process is that in which the gas is produced by heating bitu-
minous coal to bright redness in retorts. As it issues from the
retorts the gas is charged with substances volatile only at high
temperatures; these are deposited in the condensers or coolers,
and form coal- or gas-tar. From the condensers the gas passes
through what are known as "scrubbers" and "lime-purifiers," in
which it is deprived of ammoniacal compounds and other impu-
rities. As it comes from the condensers, coal-gas contains :
~* Acetylene. * Acenaphthalene. \ Cyanogen.
"* Ethylene. * Fluorene. •• Sulfocyanogen.
* Marsh-gas. * Propyl hydrid. • Hydrogen sulfid.
* Butylene. * Butyl hydrid. • Carbon disulfid.
* Propylene. f Hydrogen. f Sulfuretted hydro-
* Benzene. " Carbon monpxid. carbons.
* Styrolene. " Carbon dioxid. -j- Nitrogen.
* Naphthalene. f Ammonia. f Aqueous vapor.
In passing through the purifiers the gas is freed of the impuri-
ties to a greater or less extent, and, as usually delivered to con-
sumers, contains:
* Marsh-gas. f Hydrogen. f Carbon monpxid.
* Acetylene. f Nitrogen. \ Carbon dioxid.
* Ethylene. f Aqueous vapor. * Vapors of hydrocarbons.
TETRATOMIC ALCOHOLS.
SERIES CnH-m + aOi.
Very few of these compounds have yet been obtained. They
may be regarded as the hydrates of the hydrocarbons CnHan — a ; as
the glycols are the hydrates of the ethylene series.
CHOH-CHoOH
Erythrite — Phycite — I — is a product of decom-
CHOH-CH.OH
* Illuminating constituents. t Impurities. J Diluent.
372 MANUAL OF CHEMISTRY.
position of erythrin, C20H22Oi0, which exists in the lichens of
the genus rocella. It crystallizes in large, brilliant prisms ;
very soluble in H2O and in hot alcohol, almost insoluble in ether;
sweetish in taste; its solutions neither affect polarized light, nor
reduce Fehling's solution, nor are capable of fermentation. Its
watery solution, like that of sugar, is capable of dissolving a con-
siderable quantity of lirne, and from this solution alcohol precipi-
tates a definite compound of erythrite and calcium. By oxidation
with platinum-black it yields erythroglucic acid, C4H8O6. With
fuming HNO3 it forms a tetranitro compound, which explodes
under the hammer.
ACIDS DERIVABLE FROM ERYTHRITE.
Theoretically erythrite should, by simple oxidation, yield two
acids; one of the series CnH2nO5, and another of the series
CnH2n— 2Oe. Although both of these acids are known, only the
first, erythroglucic acid, has been obtained by oxidation of ery-
thrite :
CH2OH COOH COOH
CHOH CHOH CHOH
CHOH CHOH CHOH
CH2OH C(
CH2OH CH2OH COOH
Erythrite. Erythroglucic acid. Tartaric acid.
Tartaric acids — Acidum tartaricum (TJ. S., Br.) — C ,H, 0, — 150. —
There exist four acids having the composition C4H6O6, which
differ from each other only in their physical properties, and are
very readily converted into one another; they are designated as:
1st, Right ; 2d, Left ; 3d, Inactive tartaric acid ; 4th, Racemic
acid.
Right or dextrotartaric acid crystallizes in large, oblique,
rhombic prisms, having hemihedral facettes. Solutions of the
acid and its salts are dextrogyrous.
Lsevotartaric acid crystallizes in the same form as dextrotartaric
acid, only the hemihedral facettes are on the opposite sides, so
that crystals of the two acids, when held facing each other, ap-
pear like the reflections one of the other. Its solutions and those
of its salts are Isevogyrous to the same degree that corresponding
solutions of dextrotartaric acid are dextrogyrous. Racemic acid
is a compound of the two preceding; it forms crystals having no
hemihedral facettes, and its solutions are without action on po-
larized light. It is readily separated into its components. In-
active tartaric acid, although resembling racemic acid in its crys-
talline form and inactivity with respect to polarized light, differs
ACIDS DERIVABLE FROM ERYTHRITE. 373
essentially from that acid in that it cannot be decomposed into
right and left acids, and in the method of its production.
The tartaric acid which exists in nature is the dextrotartaric.
It occurs, both free and in combination, in the sap of the vine
and in many other vegetable juices and fruits. Although this is
probably the only tartaric acid existing in nature, all four varie-
ties may and do occur in the commercial acid, being formed dur-
ing the process of manufacture.
Tartaric acid is obtained in the arts from hydropotassic tartrate,
or cream of tartar (q.v.). This salt is dissolved in H2O and the
solution boiled with chalk until its reaction is neutral ; calcic and
potassic tartrates are formed. The insoluble calcic salt is sepa-
rated and the potassic salt decomposed by treating the solution
with calcic chlorid. The united deposits of calcium tartrate are
suspended in H3O, decomposed with the proper quantity of
H2SO4, the solution separated from the deposit of calcium sulfate,
and evaporated to crystallization.
The ordinary tartaric acid crystallizes in large prisms; very
soluble in H2O and alcohol; acid in taste and reaction. It fuses
-at 170° (338' F.); at 180° (356° F.) it loses H2O, and is gradually
converted into an anhydrid; at 200°-210° (392°-410° F.) it is de-
composed with formation of pyruvic acid, C3H4O3,and pyrotartaric
acid, C5HeO4 ; at higher temperatures CO3, CO, H2O, hydrocarbons
and charcoal are produced. If kept in fusion some time, two
molecules unite, with loss of HaO, to form tartralic or ditartaric
acid, C8H10O,i.
Tartaric acid is attacked by oxidizing agents with formation
of COa, Had), and, in some instances, formic and oxalic acids.
Certain reducing agents convert it into malic and succinic acids.
With fuming HNO3 it forms a dinitro-compound, which is very
unstable, and which, when decomposed below 36° (96°. 8 F.), yields
tartaric acid. It forms a precipitate with lime-water, soluble in
an excess of H2O. In not too dilute solution it forms a precip-
itate with potassium sulfate solution. It does not precipitate
with the salts of Ca. When heated with a solution of auric
chlorid it precipitates the gold in the metallic form. As its for-
mula indicates (see above), tartaric acid is tetratomic and dibasic.
It has a great tendency to the formation of double salts, such as
tartar emetic (Q.V.).
When taken into the economy, as it constantly is in the form
of tartrates, the greater part is oxidized to carbonic acid (carbon-
ates); but, if taken in sufficient quantity, a portion is excreted
unchanged in the urine and perspiration. The free acid is poi-
sonous in large doses.
374 MANUAL OP CHEMISTRY.
HEXATOMIC ALCOHOLS.
The known terms of this series are isomeric ; have the composi-
tion CeH^Oe. They are closely related to the carbohydrates.
Mannite — constitutes the greater part of manna, and also exists
in a number of other plants. It is also produced during the so-
called inucic fermentation of sugar, and during lactic fermenta-
tion. It crystallizes in long prisms, odorless, sweet, fuses at 166°
(330°.8 F.) and crystallizes on cooling; boils at 200° (392° F.), at
which temperature it is converted into mannitan, CcH^Os ; solu-
ble in H2O, very sparingly in alcohol. When oxidized it yields
first mannitic, then saccharic acid (g.v.), and finally, oxalic acid.
Organic acids combine with it to form compound ethers.
Dulcite — Melampyrite — Dulcose — Dulcin — exists in Melampy-
rum nemorosum. It forms colorless, transparent prisms, fuses at
182° (359°. 6 F.), is odorless, faintly sweet, neutral in reaction, and
optically inactive. It is subject to decompositions very similar
to those to which mannite is subject, yielding dulcitan, CeHiaOs.
CARBOHYDRATES.
~ These substances are composed of C, H, and O ; they all contain
C8, or some multiple thereof; and the H and O which they con-
tain are always in the proportion of H2 to O. Most of them
exist in nature either in animal or vegetable organisms or as the
products of fermentative processes.
Their constitution is stftll undetermined, although their reac-
tions would indicate that some are aldehydes, others alcohols,
and others ethers, while some are of mixed function. Indeed the-
synthesis of glucose has been recently accomplished in such
manner as to indicate that it is partly aldehyde, partly secon-
dary alcohol, and partly primary alcohol.
The carbohydrates are divisible into three groups, the mem-
bers of each of which are isomeric with each other :
I. GLUCOSES. II. SACCHAROSES. III. AMYLOSES.
n(C6HiaOe). nCdJI^On). n(CeH10O5).
-(-Glucose. -(-Saccharose. -(-Starch.
(Dextrose.) — Lactose. -j-Glycogen.
— Lsevulose. — Maltose. -f-Dextrin.
Mannitose. — Melitose. — Inulin.
+Galactose. -j-Melezitose. Tunicin.
Inosite. -f-Trehalose. Cellulose.
— Sorbin. -(-My cose. Gums.
— Eucalin. Synanthrose.
-f-Parasaccharose.
CARBOHYDRATES. 375
Glucoses, CcHisOo — 180.
Glucose — Grape-sugar — Dextrose — Liver-sugar— Diabetic sugar.
— The substance from which this group takes its name exists in
all sweet and acidulous fruits; in many vegetable juices; in
honey ; in the animal economy in the contents of the intestines,
in the liver, bile, thymus, heart, lungs, blood, and in small quan-
tity in the urine. Pathologically it is found in the saliva, per-
spiration, faeces, and largely increased in the blood and urine in
diabetes mellitus (see below). It may also be obtained by decom-
position of certain vegetable substances called glucosids (q.v.).
It is prepared artificially by heating starch or cellulose for 24
to 36 hours with a dilute mineral acid (HaSCX). Glucose obtained
by this method is liable to contamination with traces of arsenic,
which it receives from the HaSO4. Starch is also converted into
glucose by the influence of diastase, formed during the germina-
tion of grain.
Glucose crystallizes with difficulty from its aqueous solution, in
white, opaque, spheroidal masses containing 1 aq; from alcohol
in fine, transparent, anhydrous prisms. At about 60° (140° P.) in
dry air the hydrated variety loses H2O. It is soluble in all pro-
portions in hot H2O ; very soluble in cold H2O ; soluble in alcohol.
It is less sweet and less soluble than cane-sugar. Its solutions
are dextrogyrous : [a]D=4-52°.85.
At 170° (338° F.) it loses H2O and is converted into glucosan,
C,H, O . Hot dilute mineral acids convert it into a brown sub-
stance, ulmic acid, and, in the presence of air, formic acid. It
dissolves in concentrated KUSCh, without coloration, forming sul-
foglucic acid. Cold concentrated HNO3 converts it into nitre-
glucose. Hot dilute HNO3 oxidizes it to a mixture of oxalic and
oxysaccharic acids. With organic acids it forms ethers. Its solu-
tions dissolve potash, soda, lime, baryta, and the oxids of Pb and
Cu, with which it forms compounds. When its solutions are
heated with an alkali they assume a yellow or brown color, and
give off a molasses-like odor, from the formation of glucic and
melassic acids. Glucose in alkaline solution exerts a strong reduc-
ing action, which is favored by heat ; Ag, Bi, and Hg are precipi-
tated from their salts; and cupric are reduced to cuprous com-
pounds, with separation of cuprous oxid. In the presence of yeast,
at suitable temperatures, glucose undergoes alcoholic fermenta-
tion.
Physiological. — The greater part of the glucose in the economy
in health is introduced with the food, either in its own form or
as other carbohydrates, which by digestion are converted into
glucose. A certain quantity is also produced in the liver at the
expense of glycogen, a formation which continues for some time
24
376 MANUAL OB1 CHEMISTEY.
after death. In some forms of diabetes the production of glu-
cose in the liver is undoubtedly greatly increased. The quantity
of sugar normally existing in the blood varies from 0.81 to 1.231
part per thousand; in diabetes it rises as high as 5.8 parts per
thousand.
Under normal conditions, and with food not too rich in starch
and saccharine materials, the quantity of sugar eliminated as
such is exceedingly small. It is oxidized in the body, and the
ultimate products of such oxidation eliminated as CO2 and H2O.
Whether or no intermediate products are formed, is still uncer-
tain ; the probability, however, is that there are. The oxidation
of sugar is impeded in diabetes.
Where this oxidation, or any of its steps, occurs, is at present a
matter of conjecture merely. If, as is usually believed, glucose
disappears to a marked extent in the passage of the blood through
the lungs, the fact is a strong support of the view that its trans-
formation into CO2 and H2O does not occur as a simple oxidation,
as the notion that sugar or any other substance is " burned " in
the lung, beyond the small amount required by the nutrition of
the organ itself, is scarcely tenable at the present day.
So long r,s the quantity of glucose in the blood remains at or
below the normal percentage, it is not eliminated in the urine in
quantities appreciable by the tests usually employed. When,
however, the amount of glucose in the blood surpasses this limit
from any cause, the urine becomes saccharine, and that to an
extent proportional to the increase of glucose in the circulating
fluids. The causes which may bring about such an increase are
numerous and varied. Many of them are entirely consistent with
health, and the mere presence of increased quantities of sugar in
the urine is no proof, taken by itself, of the existence of diabetes.
Sugar is detectable by the ordinary tests in the urine under
the following circumstances :
Physiologically. — (1.) In the urine of pregnant women and dur-
ing lactation. It appears in the latter stages of gestation and
does not disappear entirely until the suppression of the lacteal
secretion. (2.) In small quantities in sucking children from eight
days to two and one-half months. (3.) In the urine of old per-
sons (seventy to eighty years). (4.) In those whose food contains
a large amount of starchy or saccharine material. To this cause
is due the apparent prevalence of diabetes in certain-localities, as
in districts where the different varieties of sugar are produced.
Pathologically. — (1.) In abnormally stout persons, especially in
old persons and in women at the period of the menopause. The
quantity does not exceed 8 to 12 grams per 1,000 c.c. (3.5-5.5 grains
per ounce), and disappears when starchy and saccharine food is
withheld. This form of glycosuria is liable to develop into true
CARBOHYDRATES. 377
^diabetes when it appears in young persons. (2.) In diseases at-
tended with interference of the respiratory processes — lung dis-
eases, etc. (3.) In diseases where there is interference with the
hepatic circulation — hepatic congestion, compression of the portal
vein by biliary calculi, cirrhosis, atrophy, fatty degeneration,
etc. (4.) In many cerebral and cerebro-spinal disturbances — gen-
eral paresis, dementia, epilepsy ; by puncture of the fourth ven-
tricle. (5.) In intermittent and typhus fevers. (6.) By the action
of many poisons — carbon nionoxid, arsenic, chloroform, curari;
by injection into an artery of ether, ammonia, phosphoric acid,
sodium chlorid, amyl nitrite, glycogen. (7.) In true diabetes the
elimination of sugar in the urine is constant, unless arrested by
suitable regulation of diet, and not temporary, as in the condi-
tions previously mentioned. The quantity of urine is increased,
sometimes enormously, and it is of high sp. gr. The elimination
of urea is increased absolutely, although the quantity in 1,000
c.c. may be less than that normally existing in that bulk of urine.
The quantity of sugar in diabetic urine is sometimes very large ;
an elimination of 200 grams (6.4 ounces) in twenty-four hours is
by no means uncommon ; instances in which the amount has
reached 400 to 600 grams (12.9-19.3 ounces) are recorded, and one
case in which no less than 1,376 grams (45 ounces) were discharged
in one day. The elimination is not the same at all hours of the
day; during the night less sugar is voided than during the day;
the hourly elimination increases after meals, reaching its maxi-
mum in 4 hours, after which it diminishes to reach the minimum
in 6 to 7 hours, when it may disappear entirely. This variation is
more pronounced the more copious the meal. It is obvious from
the above, that, in order that quantitative determinations of
sugar in urine shall be of clinical value, it is necessary that the
determination be made in a sample taken from the mixed urine of
twenty-four hours.
Analytical Characters. — A saccharine urine is usually abun-
dant in quantity, pale in color, of high sp. gr., covered with a
persistent froth on being shaken, and exhales a peculiar odor;
when evaporated it leaves a sticky residue. The presence of
glucose in urine is indicated by the following tests :
If the urine be albuminous, it is indispensable that the albumen
be separated before any of the tests for sugar are applied ; this is
done by adding one or two drops of dilute acetic acid, or, if the
urine be alkaline, just enough acetic acid to turn the reaction to
acid, and no more, heating over the water-bath until the albumen
has separated in flocks, and filtering.
(1.) When examined by the polariineter (see p. 25) it deviates
Ihe plane of polarization to the right.
(2.) When mixed with an equal volume of liquor potassse and
378 MANUAL OF CHEMISTRY.
heated, it turns yellow, and, if sugar be abundant, brown. A
molasses-like odor is observable on adding HNO3 (Moore's test).
(3.) The urine, rendered faintly blue with indigo solution and
faintly alkaline with sodium carbonate, and heated to boiling
without agitation, turns violet and then yellow if sugar be pres-
ent; on agitation the blue color is restored (Mulder-Neubauer
test).
(4.) About 1 c.c. of the urine, diluted with twice its bulk of
water, is treated with two or three drops of cupric sulfate solu-
tion and about 1 c.c. of caustic potassa solution; if sugar be pres-
ent the bluish precipitate is dissolved on agitation, forming a blue
solution. The clear blue fluid, when heated to near boiling, de-
posits a yellow, orange, or red precipitate of cuprous oxid if sugar
be present (Trommer's test). In the application of this test an
excess of cupric sulfate is to be avoided, lest the color be masked
by the formation of the black cupric oxid. Sometimes no precip-
itate is formed, but the liquid changes in color from blue to yel-
low. This occurs in the presence of small quantities of cupric
salt and large quantities of sugar, the cuprous oxid being held in
solution by the excess of glucose. In this case the test is to be
repeated, using a sample of urine more diluted with water. In
some instances, also, the reaction is interfered with by excess of
normal constituents of the urine, uric acid, creatinin, coloring
matter, etc., and instead of a bright precipitate, a muddy deposit
is formed. When this occurs the urine is heated with animal
charcoal and filtered; the filtrate evaporated to dryness; the
residue extracted with alcohol; the alcoholic extract evaporat-
ed; the residue redissolved in water, and tested as described
above.
(5.) Four or five c.c. of Fehling's solution (see p. 380) are heated
in a test-tube to boiling; it should remain unaltered. The urine
is then added, and the mixture boiled after each addition of 4-5
drops ; if it contain sugar, the mixture turns green, and a yellow
or red precipitate of cuprous oxid is formed, usually darker in
color than that obtained by Trommer's test. The absence of glu-
cose is not to be inferred until a bulk of urine equal to that of
the Fehling's solution used has been added, and the mixture
boiled from time to time without the formation of a precipitate.
This test is the most convenient and the most reliable for clinical
purposes.
(6.) A few c.c. of the urine are mixed in a test-tube with an
equal volume of solution of sodium carbonate (1 pt. crystal, car-
bonate and 3 pts. water), a few granules of bismuth subnitrate*
are added, and the mixture boiled for some time (until it begins
to " bump," if necessary). If sugar be present, the bismuth pow-
der turns brown or black by reduction to elementary bismuth
CAEBOIIYDRATES. otD
(Boettger's test). No other normal constituent of the urine reacts
with this test ; a fallacy is, however, possible from the presence of
some compound, which, by giving up sulfur, may cause the for-
mation of the black bismuth sulfid. To guard against this,
when an affirmative result has been obtained, another sample of
urine is rendered alkaline and boiled with pulverized litharge;
the powder should not turn black.
Nylander's test is a mere modification of Boettger's, in which
the Bi is used in solution. The test solution is made by dissolv-
ing 2.5 parts Bi (NO3)s and 4 parts of Rochelle salt in 100 parts of
a solution of NaHO of 8# strength. To use the reagent it is mixed
with one- tenth its volume of the urine and boiled. In the pres-
ence of glucose a black ppt. is formed. The same precautions
with regard to sulfur compounds are necessary.
(7.) A solution of sugar, mixed with good yeast and kept at 25°
(77° F.) is decomposed into CO3 and alcohol. To apply the fer-
mentation-test to urine, take three test-tubes, A, B, and C, place
in each some washed (or compressed) yeast, fill A completely with
the urine to be tested, .and place it in an inverted position, the
mouth below the surface of some of the same urine in another
vessel (the entrance of air being prevented, during the inversion,
by closing the opening of the tube with the finger, or a cork on
the end of a wire, until it has been brought below the surface of
the urine). Fill B completely with some urine to which glucose
has been added, and C with distilled water, and invert them in
the same way as A ; B in saccharine urine, and C in distilled water.
Leave all three tubes in a place where the temperature is about
25° (77° F.) for twelve hours, and then examine them. If gas have
collected in B over the surface of the liquid, and none in A, the
urine is free from sugar ; if gas have collected in both A and B,
and not in C, the urine contains sugar ; if no gas have collected
in B, the yeast is worthless, and if any gas be found in C, the
yeast itself has given off CO2. In the last two cases the process
must be repeated with a new sample of yeast.
Quantitative Determination of Glucose. — (1.) By the polarime-
ter. — The, filtered urine is observed by the polariscope (see p. 25)
and the mean of half a dozen readings taken as the angle of devi-
ation. From this the percentage of sugar is determined by the
formula p= .-, in which p= the weight, in grams, of glucose
52.85 X '
in 1 c.c. of urine; a=the angle of deviation; Z=the length of the
tube in decimetres. The same formula may be used for other
substances by substituting for 52.85 the value of [a]D for that sub-
stance. If the urine contain albumen, it must be removed before
determining the value of a.
(2.) By specific gravity ; Robert's method. — The sp. gr. of the
380 MANUAL OF CHEMISTRY.
urine is carefully determined at 25° (77° F.); yeast is then added,
and the mixture kept at 25° (77° F.) until fermentation is com-
plete ; the sp. gr. is again observed, and will be found to be lower
than before. Each degree of diminution represents 0.2196 gram
of sugar in 100 c.c. (1 grain per ounce) of urine.
(3.) By Fehling's solution. — Of the many formulae for Fehling's
.solutions, the one to which we give the preference is that of Dr.
Piffard. Two solutions are required:
I. Cupric sulfate (pure, crystals) 51.98 grams.
Water 500.0 c.c.
II. Rochelle salt (pure, crystals) 259.9 grams.
Sodium hydroxid solution, sp. gr. 1.12. 1000.0 c.c.
When required for use, one volume of No. I. is mixed with two
volumes of No. II. The copper contained in 20 c.c. of this mix-
ture is precipitated as cuprous oxid by 0.1 gram glucose.
To use the solution, 20 c.c. of the mixed solutions are placed in
a flask of 250-300 c.c. capacity, 40 c.c. of distilled water are added,
the whole thoroughly mixed and heated to boiling. On the other
hand, the urine to be tested is diluted with four times its volume
of water if poor in sugar, and with nine times its volume if highly
saccharine (the degree of dilution required is, with a little prac-
tice, determined by the appearance of the deposit obtained in the
qualitative testing) ; the water and urine are thoroughly mixed
and a burette filled with the mixture. A few drops of aqua am-
moniae are added to the Fehling's solution and the diluted urine
added, in small portions toward the end, until the blue color is
entirely discharged — the contents of the flask being made to boil
briskly between each addition from the burette. When the liquid
in the flask shows no blue color, when looked through with a
white background, the reading of the burette is taken. This
reading, divided by five if the urine was diluted with four vol-
umes of water, or by ten if with nine volumes, gives the number
of c.c. of urine containing 0.1 gram of glucose; and consequently
the elimination of glucose in twenty-four hours, in decigrams, is
obtained by dividing the number of c.c. of urine in twenty-four
hours by the result obtained above.
Example. — 20 c.c. Fehling's solution used, and urine diluted
with four volumes of water.
36 5
Beading of burette: 36.5 c.c. — —=7.3 c.c. urine contain 0.1
5
gram glucose. Patient is passing 2,436 c.c. urine in twenty-four
hours. ' ' =333.6 decigr.=33.36 grams glucose in twenty- four
7.3
hours.
The accuracy of the determination may be controlled by filter-
CARBOHYDRATES. 381
ing off some of the fluid from the flask at the end of the reaction ;.
a portion of the filtrate is acidulated with acetic acid and treated
with potassium ferrocyanid solution; if it turn reddish-brown
the reduction has not .been complete, and the result is affected
with a plus error. To another portion of the filtrate a few drops
of cupric sulfate solution are added and the mixture boiled ; if
any precipitation of cuprous oxid be observed, an excess of urine
has been added, and the result obtained is less than the true one.
This method, when carefully conducted with accurately pre-
pared and undeteriorated solutions, is the best adapted to clini-
cal uses. The copper solution should be kept in the dark, in a
well-closed bottle, and the stopper and neck of the No. II. bottle
should be well coated with paraffin.
(4.) Gravimetric method. — When more accurate results than are
obtainable by Fehling's volumetric process are desired, recourse
must be had to a determination of the weight of cuprous oxid
obtained by reduction. A small quantity of freshly prepared
Fehling's solution is heated to boiling in a small flask ; to it is
gradually added, with the precautions observed in the volumetric
method, a known volume of urine, such that at the end of the
reduction there shall remain an excess of unreduced copper salt.
The flask is now completely filled with boiling H3O, corked, and
allowed to cool. The alkaline fluid is separated as rapidly as
possible from the precipitated oxid, by decantation and filtration
through a small double filter, and the precipitate and flask re-
peatedly washed with hot H2O until the washings are no longer
alkaline ; a small portion of the precipitate remains adhering to>
the walls of the flask. The filter and its contents are dried and
burned in a weighed porcelain crucible ; when this has cooled,
the flask is rinsed out with a small quantity of HNO3 ; this is
added to the contents of the crucible, evaporated over the water-
bath, the crucible slowly heated to redness, cooled, and weighed.
The difference between this last weight and that of the crucible
-f- that of the filter-ash, is the weight of cupric oxid, of which 220
parts=100 parts of glucose.
Leevulose — Uncrystallizable sugar — forms the uncrystallizable
portion of the sugar of fruits and of honey, in which it is associ-
ated with glucose; it is also produced artificially by the pro-
longed action of boiling water upon inulin ; and as one of the?
constituents of inverted sugar.
Lsevulose is not capable of crystallization, but may be obtained
as a thick syrup; very soluble in water, insoluble in absolute
alcohol ; it is sweeter but less readily fermentable than glucose,
which it equals in the readiness with which it reduces cupro-
potassic solutions. Its prominent physical property, and that
to which it owes its name, is its strong left-handed polarization^
382 MANUAL OF CHEMISTRY.
£a>=-106° at 15° (59° F.). At 170° (338° F.) it is converted into
the solid, amorphous Isevulosan, C9H10O5.
Mannitose— is obtained by the oxidation of mannite. It is a
yellow, uncrystallizable sugar, having many of the characters of
glucose, but optically inactive.
Galactose — sometimes improperly called lactose — is formed by
the action of dilute acids upon lactose (milk-sugar) as glucose is
formed from saccharose. It differs from glucose in crystallizing
more readily, in being very sparingly soluble in cold alcohol, in
its action upon polarized light, [a]D=+83°.33, and in being oxi-
dized to mucic acid by HNO3. The substance called cerebrose,
obtained by the action of H2SO4 on cerebrin and other constitu-
ents of nerve-tissue, is identical with galactose.
Inosite — Muscle-sugar — exists in the liquid of muscular tissue,
in the lungs, kidneys, liver, spleen, brain, and blood; patholog-
ically in the urine in Bright's, diabetes, and after the use of dras-
tics in uraemia, and in the contents of hydatid cysts ; also in the
seeds and leaves of certain plants. What the source and function
of inosite in the animal economy may be is still a matter of con-
jecture.
It forms long, colorless, monoclinic crystals, containing 2 Aq,
usually arranged in groups having a cauliflower-like appearance.
It effloresces in dry air; has a distinctly sweet taste; is easily sol-
uble in water, difficultly in alcohol ; insoluble in absolute alcohol
and in ether ; it is without action upon polarized light.
The position of inosite in this series is based entirely upon its
•chemical composition, as it does not possess the other character-
istics of the group. It does not enter directly into alcoholic fer-
mentation, although upon contact with putrefying animal mat-
ters it produces lactic and butyric acids ; when boiled with barium
or potassium hydroxid, it is not even colored; in the presence of
inosite, potash precipitates with cupric sulfate solution, the pre-
cipitate being redissolved in an excess of potash ; but no reduc-
tion takes place upon boiling the blue solution.
The presence of inosite is indicated by the following reactions :
Scherer'ls. — Treated with HNO3, the solution evaporated to near
dryness, and the residue moistened with ammonium hydroxid and
calcium chlorid, and again evaporated ; a rose-pink color is pro-
duced. Succeeds only with nearly pure inosite. Qallois\ — Mer-
curic nitrate produces, in solutions of inosite, a yellow precipitate,
which, on cautious heating, turns red; the color disappears on
cooling, and reappears on heating.
Saccharoses, d.-H.^O,, — 342.
Saccharose — Cane-sugar — Beet-sugar — Saccharum (U. S.) — the
most important member of the group, exists in many roots, fruits,
CARBOH YD KATES. 383
and grasses, and is produced from the sugar-cane, Saccharum
officinarum, sorghum, Sorghum saccharatum, beet, Beta vul-
garis, and sugar-maple, Acer saccharinum.
For the extraction of sugar the expressed juice is heated in
large pans to about -100° (2123 F.); milk of lime is added, which
•causes the precipitation of albumen, wax, calcic phosphate, etc. ;
the clear liquid is drawn off, and " delimed " by passing a current
of COa through it ; the clear liquid is again drawn off and evap-
orated, during agitation, to the crystallizing-point ; the product
is drained, leaving what is termed raw or muscovado sugar, while
the liquor which drains off is molasses. The sugar so obtained
is purified by the process of " refining," which consists essentially
in adding to the raw sugar, in solution, albumen in some form,
-which is then coagulated, filtering first through canvas, afterward
through animal charcoal; the clear liquid is evaporated in
*' vacuum-pans," at a temperature not exceeding 72° (161°. 6 F.), to
the crystallizing-point. The product is allowed to crystallize in
earthen moulds; a saturated solution of pure sugar is poured
upon the crystalline mass in order to displace the uncrystallizable
sugar which still remains, and the loaf is finally dried in an oven.
The liquid displaced as above is what is known as sugar-house
.syrup.
Pure sugar should be entirely soluble in water; the solution
should not turn brown when warmed with dilute potassium
hydroxid solution ; should not reduce Fehling's solution, and
should give no precipitate with ammonium oxalate.
Beet-sugar is the same as cane-sugar, except that, as usually
met with in commerce, it is lighter, bulk for bulk. Sugar-candy,
or rock-candy, is cane-sugar allowed to crystallize slowly from a
•concentrated solution without agitation. Maple-sugar is a par-
tially refined, but not decolorized variety of cane-sugar.
Saccharose crystallizes in small, white, monoclinic prisms; or,
.as sugar-candy, in large, yellowish, transparent crystals; sp. gr.
1.60G. It is very soluble in water, dissolving in about one-third
its weight of cold water, and more abundantly in hot water. It
is insoluble in absolute alcohol or ether, and its solubility in
water is progressively diminished by the addition of alcohol.
Aqueous solutions of cane-sugar are dextrogyrous, [a]D=-f73°.8.
When saccharose is heated to 160° (320° F.) it fuses, and the
liquid, on cooling, solidifies to a yellow, transparent, amorphous
mass, known as barley-sugar ; at a slightly higher temperature,
it is decomposed into glucose and laevnlosan; at a still higher
temperature, H2O is given off, and the glucose already formed is
converted into glucosan ; at 210° (410° F.) the evolution of HaO is
more abundant, and there remains a brown material known as
caramel, or burnt sugar ; a tasteless substance, insoluble in strong
384 MANUAL OF CHEMISTRY.
alcohol, but soluble in H2O or aqueous alcohol, and used to com-
municate color to spirits ; finally, at higher temperatures, methyl
hydrid and the two oxids of carbon are given off; a brown oil,
acetone, acetic acid, and aldehyde distil over; and a carbona-
ceous residue remains.
If saccharose be boiled for some time with H2O, it is converted
into inverted sugar, which is a mixture of glucose and laevulose :
CiaHaaOn+HaO^iCoHjaOe+CeHisOe. With a solution of saccha-
rose the polarization is dextrogyrous, but, after inversion, it be-
comes Isevogyrous, because the left-handed action of the molecule
of Isevulose produced, [a]D= — 106°, is only partly neutralized by
the right-handed action of the glucose, [a]T)=-{-52°.85. This in-
version of cane-sugar is utilized in the testing of samples of sugar.
On the other hand, it is to avoid its occurrence, and the conse-
quent loss of sugar, that the vacuum-pan is used in refining — its-
object being to remove the H2O at a low temperature.
Those acids which are not oxidizing agents act upon saccharose
in three ways, according to circumstances: (1) if tartaric and
other organic acids be heated for some time with saccharose to
100°-120° (212°-248° F.), compounds known as saccharids, and
having the constitution of ethers, are formed; (2) heated with
mineral acids, even dilute, and less rapidly with some organic
acids, saccharose is quickly converted into inverted sugar; (3)
concentrated acids decompose cane-sugar entirely, more rapidly
when heated than in the cold; with HC1, formic acid and a
brown, flocculent material (ulmicacid?) are formed; with H2SO<,
SO2 and H2O are formed, and a voluminous mass of charcoal re-
mains. Oxalic acid, aided by heat, produces CO2, formic acid,
and a brown substance (humin?).
Oxidizing agents act energetically upon cane-sugar, which is a
good reducing agent. With potassium chlorate, sugar forms a
mixture which detonates when subjected to shock, and which
deflagrates when moistened with H2SO4. Dilute HNO3, when
heated with saccharose, oxidizes it to saccharic and oxalic acids.
Concentrated HNOa, alone or mixed with H2SO4, converts it into
the explosive nitre-saccharose. Potassium permanganate, in acid
solution, oxidizes it completely to CO2 and H2O.
Cane-sugar reduces the compounds of Ag, Hg, and Au, when
heated with their solutions ; it does not reduce the cupro-potassic
solutions in the cold, but effects their reduction when heated with
them, to an extent proportional to the amount of excess of alkali
present.
When moderately heated with liquor potassse, cane-sugar does
not turn brown, as does glucose ; but by long ebullition it is de-
composed by the alkalies much less readily than glucose, with
formation of acids of the fatty series and oxalic acid.
CARBOHYDRATES. 385
"With the bases, saccharose forms definite compounds called
sucrates (improperly saccharates, a name belonging to the salts
of saccharic acid). With Ca it forms five compounds. Calcium
hydroxid dissolves readily in solutions of sugar, with formation
of a Ca compound, soluble in H3O, containing an excess of sugar.
A solution containing 100 parts of sugar in 600 parts of H2O dis-
solves 32 parts of calcic oxid. These solutions have an alkaline
taste; are decomposed, with formation of a gelatinous precipi-
tate, when heated, and with deposition of calcium carbonate and
regeneration of saccharose, when treated with CO*. Quantities
of calcium sucrates are frequently introduced into sugars to in-
crease their weight — an adulteration the less readily detected, as
the sucrate dissolves with the sugar. Calcium sucrates exist in
the liq. calcis saccharatus (Br.).
Yeast causes fermentation of solutions of cane-sugar, but only
after its conversion into glucose. Fermentation is also caused by
exposing a solution of sugar containing ammonium phosphate to
the air.
During the process of digestion, probably in the small intestine,
cane-sugar is converted into glucose.
Lactose — Milk-sugar — Lactine — Saccharum lactis (U. S., Br.)—
has hitherto been found only in the milk of the mammalia. It
may be obtained from skim-milk by coagulating the casein with
a small quantity of HaSC^, filtering, evaporating, redissolving,
decolorizing with animal charcoal, and recrystallizing.
It forms prismatic crystals; sp. gr. 1.53; hard, transparent,
faintly sweet, soluble in 6 parts of cold and in 2.5 parts of boiling
HaO; soluble in acetic acid; insoluble in alcohol and in ether; its
solutions are dextrogyrous [a]D=+59°.3. The crystals, dried at
100° (212° P.), contain 1 Aq, which they lose at 150° (302° P.).
Lactose is not altered by contact with air. Heated with dilute
mineral or with strong organic acids, it is converted into galactose.
HNO3 oxidizes it to mucic and oxalic acids. A mixture of HNOs
and H2SO4 converts it into an explosive nitro-compound. With
organic acids it forms ethers. With soda, potash, and lime it forms
compounds similar to those of saccharose, from which lactose may
be recovered by neutralization, unless they have been heated to
100° (212° P.), at which temperature they are decomposed. It
reduces Pehling's solution, and reacts with Trommer's test.
In the presence of yeast, lactose is capable of alcoholic fermen-
tation, which takes place slowly, and, as it appears, without pre-
vious transformation of the lactose into either glucose or galac-
tose. On contact with putrefying albunafnoids it enters into
lactic fermentation.
The average proportion of lactose in different milks is as fol-
lows: Cow, 5.5 per cent.; mare, 5.5; ass, 5.8; human, 5.3; sheep,
25
386 MANUAL OF CHEMISTRY.
4.2; goat, 4.0. When taken internally, it is converted into galac-
tose by the pancreatic secretion; when injected into the blood,
it does not appear in the urine, which, however, contains glucose.
Maltose — a sugar closely resembling glucose in many of its
properties, is formed along with dextrin during the conversion of
starch into sugar by the action of diastase and of the oryptolytes
Fio. 40.
of the saliva and pancreatic juice. It crystallizes as does glucose,
but differs from that sugar in being less soluble in alcohol and in
exerting a dextrogyratory power three times as great.
Amyloses, n(C6H10O6) — nlQ2.
Starch — Amylum (TJ. S.) — the most important member of the
group, exists in the roots, stems, and seeds of all plants. It is
CARBOHYDRATES. 38T
prepared from rice, wheat, potatoes, maniot, beans, sago, arrow-
root, etc. The comminuted vegetable tissue is steeped for a con-
siderable time in H2O rendered faintly alkaline with soda; the
softened mass is then rubbed on a sieve under a current of water,
which washes out the starch granules ; the washings are allowed
to deposit the starch, which, after washing by decantation, is
dried at a low temperature.
Starch is a white powder, having a peculiar slippery feel, or it
appears in short columnar masses. The granules of starch differ
in size and appearance according to the kind of plant from which
they have been obtained. They are rounded or egg-shaped masses,
having at the centre or toward one end a spot, called the hilum,
around which are a series of concentric lines more or less well
marked. Differences in size, shape, and markings of starch gran-
ules are shown in Fig. 40.
Starch is not altered by exposure to air, except that it absorbs
moisture. Commercial starch contains 18 per cent, of H2O, of
'which it loses 8 per cent, in vacuo, and the remaining 10 per cent,
at 145° (293" F.). It is insoluble in alcohol, ether and cold water.
If 15 to 20 parts of HaO be gradually heated with 1 part of
starch, the granules swell at about 55° (131° F.), and at 80° (176°
F.) they have reached 30 times their original dimensions; their
structure is no longer distinguishable, and they form a trans-
lucent, gelatinous mass, commonly known as starch-paste. In
this state the starch is said to be hydrated, and, if boiled with
much EUO, and the liquid filtered, a solution of starch passes
through, which is opalescent from the suspension in it of undis-
solved particles. Cold dilute solutions of the alkalies produce
the same effects on starch as does hot water. Hydrated starch is
dextrogyrous, [a]D=4-216°. Dry heat causes the granules of starch
to swell and burst; at 200° (392° F.) it is converted into dextrin;
at 230° (446° F.) it forms a brownish-yellow, fused mass, composed
principally of pyrodextrin. Hydrated starch is converted into
dextrin by heating with HaO at 160° (320° F.), and, if the action
"be prolonged, the new product is changed to glucose.
The amount of starch contained in food vegetables varies from
about 5 per cent, in turnips to 89 per cent, in rice, as will be ob-
served in the table on page 388.
If starch be ground up with dilute HaSCX, after about half an
hour the mixture gives only a violet color with I (see below) ; if
now the acid be neutralized with chalk and the filtered liquid
evaporated, it yields a white, granular product, which differs
from starch in being soluble in H2O, especially at 50° (122° F.),
and in having a lower rotary power, [a]D=-|-2110. If the action
be prolonged, the value of [a]D continues to sink until it reaches
-(-73°. 7, when the product consists of a mixture of dextrin and
388
MANUAL OF CHEMISTRY.
glucose. Concentrated HNO3 dissolves starch in the cold, form-
ing a nitro-product called xylodin or pyroxam, which is insoluble
in H2O, soluble in a mixture of alcohol and ether ; explosive. HC1
and oxalic acid convert starch into glucose. When starch is heated
under pressure to 120° (248° F.) with stearic or acetic acid, coin-
pounds are formed which seem to be ethers, and to indicate that
starch is the hydrate of a trivalent, oxygenated radical, (C6H7O2)'".
Potash and soda in dilute solution convert starch into the soluble
modification mentioned above.
COMPOSITION OF VEGETABLE FOODS.
-
.
-i
£
I
8
e
ft
•° V
.
A
c8 ^
^
So*
JJ
d
e
"3
0 ®
1*
+3 „
|
Ig
*
~x
t>
j=
"3
"§
I -~
•£s
1
{*£
B
X
co
fl
0
8
o
f-
>
•5
Wheat, hard
22.75
58.62
9.50
3.50
2.61
3.02
Payen.
Wheat, hard
19 50
65.07
7.60
3.0
2.12
2.71
Payen
Wheat, hard
20.0
63.80
8.0
3.10
2.25
2.85
Payen
Wheat, semi-hard.
15.25
70.05
7.0
3.0
1.95
2.75
Payen.
Wheat, soft
12.65
76.51
6.05
2.80
1.87
2.12
Payen
Rye
12.50
64.65
14.90
3.10
2.25
2.60
Payen.
Barley
12.96
66.43
10.0
4.75
2.76
3.10
Payen.
Oats
1439
60.59
9.25
7.06
5.50
3.25
Payen
Maize .
12 50
67 55
40
5.90
6.80
1.25
Rice
7 55
88.65
1.0
1.10
0.80
0.90
Flour
14.45
1.25
1.60
68.48
14.22
Payen.
Flour
1080
2.0
1.70
70.50
15.0
Letheby.
Bread
8.10
1.60
2.30
51.0(1
37.0
Letheby.
Oatmeal
12.60
5.60
3.0
63.80
15.0
Letheby.
Buckwheat
13 10
64.90
3.50
3.0
2.50
13.0
Payen.
Quinoa seeds
22.86
56.80
5.74
5.05
9.53
Voelcker.
Ouinoa flour
190
60.0
5.0
16.6
Voelcker
Horse-bean
30.80
48.30
3.0
1 90
3.50
12.50
Payen.
Broad bean
29 65
55.85
1 05
2.0
3.65
8.40
Payen.
White bean
25.50
55.70
2.09
2.80
3.20
9.90
Payen.
Peas, dried
23.80
58.70
3.50
2.10
2.10
8.30
Payen.
Lentils
25.30
56.0
2.40
2.60
2.30
11.50
Payen.
Potato
2.50
20.0
1.09
1.04
0.11
1.26
74.0
Paven.
Potato
2.10
18.80
3.20
0.20
0.70
75.0
Letheby.
Sweet potato
1.50
16.05
10.20
0.45
0.30
2.60
67.50
1.10
Payen.
Carrots
1.30
8.40
6.10
0.20
1.0
8.3.0
Letheby.
Parsnip
1.10
9.60
5.80
0.50
1.0
82.0
Letheby.
Turnip
1.20
5.10
2.10
0.60
91.0
Letheby.
A dilute solution of I produces a more or less intense blue -violet
color with starch, either dry, hydrated, or in solution, the color
disappearing on the application of heat, and returning on cool-
ing. If to a solution of starch, blued by I, a solution of a neutral
salt be added, there separates a blue, flocculent deposit of the
so-called iodid of starch. lodin renders starch soluble in water,
and a soluble iodized starch, Amy him iodatum (U. S.), is obtained
by triturating together 19 pts. starch, 2 pts. water, and 1 pt. iodin,
and drying below 40° (104° F.).
Starch has not been found in the animal economy outside of the
CARBOHYDRATES. 38J>
alimentary canal, in which, as a prerequisite to its absorption, it
must be converted into dextrin and glacose. This change is par-
tially effected by the action of the saliva; more rapidly with hy-
drated than with dry starch, and more rapidly with the saliva of
some animals than that of others ; those of man and of the rabbit
acting much more quickly than those of the horse and dog. A '
great part of the starch taken with the food passes into the small
intestine unchanged; here, under the influence of a pancreatic
•cryptolyte, a further transformation into glucose, and of a portion
into lactic and butyric acids, takes place.
During the germination of grain, as in the process of malting,
a peculiar, nitrogenized substance is produced, which is known
as diastase. Under the influence of this body the starch is more
or less completely converted into glucose, in very much the same
^vay as the conversion occurs in the body.
This " diastatic " action, whether produced by vegetable or ani-
mal processes, does not take place by a simple conversion of starch
into glucose, by some such single reaction as that expressed by
•CoHioOs-f-HaC^CaHmOe, but by successive stages in which "solu-
ble starch " is first produced, then several bodies called dextrins,
then maltose, and finally glucose. (See Dextrin, p. 3£0.)
Glycogen occurs in the liver, the placenta, white blood-corpus-
cles, pus-cells, young cartilage-cells, in many embryonic tissues,
And in muscular tissue. During the activity of muscles the
amount of glycogen which they contain is diminished, and that
of sugar increased.
Pure glycogen is a snow-white, floury powder; amorphous,
tasteless, and odorless; soluble in HaO, insoluble in alcohol and
•ether. In H2O it swells up at first, and forms an opalescent solu-
tion, which becomes clear on the addition of potash. Its solu-
tions are dextrogyrous to about three times the extent of those of
glucose.
Dilute acids, ptyalin, pancreatin, extract of liver-tissue, blood,
diastase, and albuminoids convert glycogen into a sugar having
all the properties of glucose Cold HXO3 converts it into xyloidin ;
on boiling, into oxalic acid. Its solutions dissolve cupric hy-
droxid, which is, however, not reduced on boiling. lodin colors,
glycogen wine-red.
Concerning the method of formation of glycogen in the econ-
omy, but little is known with certainty ; there is little room for
doubting, however, that while the bulk of the glycogen found in
the liver results from modification of the carbohydrates, it may
he and is produced from the albuminoids as well. The ultimate
fate of glycogen is undoubtedly its transformation into sugar
under the influence of the many substances existing in the body
capable of provoking that change. This transformation is con-
390 MANUAL OF CHEMISTRY.
tinuous in the liver during life, and is accomplished through the
same series of intermediary changes into dextrins and maltose as
in the case of the conversion of starch into sugar, except that
possibly the structure of the dextrins may be different.
Dextrin — British gum — a substance resembling gum arabic in
appearance and in many properties, is obtained by one of three
methods : (1) by subjecting starch to a dry heat of 175° (347° F.) ; (2)
by heating starch with dilute H2SO4 to 90° (194° F.) until a drop of
the liquid gives only a wine-red color with iodin ; neutralizing with
chalk, filtering, concentrating, precipitating with alcohol ; (3) by
the action of diastase (infusion of malt) upon hydrated starch.
As soon as the starch is dissolved the liquid must be rapidly
heated to boiling to prevent saccharification.
Commercial dextrin is a colorless, or yellowish, amorphous-
powder, soluble in H3O in all proportions, forming mucilaginous
liquids. When obtained by evaporation of its solution, it forms
masses resembling gum arabic in appearance. Its solutions are
dextrogyrous, and reduce cupro-potassic solutions under the in-
fluence of heat, to amounts varying with the method of formation
of the sample. It is colored wine-red by iodin. It is extensively
used as a substitute for gum acacia.
By the action of diastase upon starch, four dextrins are pro-
duced: 1st, Erythrodextrin, which is colored red by iodin, and
which is easily attacked by diastase; 3d, Achroodextrin a, not
colored by iodin; partially converted into sugar by diastase;
rotary power [a]D=+210°; reducing power (glucose= 100) =12; 3d,
Achroodextrin /?, not colored by iodin, nor decomposable in 24
hours by diastase ; rotary power -(-190° ; reducing power= 12; 4th,
Achroodextrin y, not colored by iodin, rior decomposed by dias-
tase; slowly con verted into glucose by dilute H^SCX; rotary power
=-)-150° ; reducing power=28.
An explanation of this series of transformations has been sug-
gested in the supposition that the molecule of starch consists of
50(Ci2HaoOio); that this is first converted into soluble starch
10(Ci3H2oOio), and that this is then converted into the different
forms of dextrin by a series of hydrations attended by simultane-
ous formation of maltose, of which the final result might be
representd by the equation :
i.oOio) + 8(H2O) = SCC^HsoCM -f SCC.JT^Oi,)
Soluble starch. Water. Achroodextrin. Maltose.
Cellulose — Cellulin — forms the basis of all vegetable tissues. It
exists, almost pure, in the pith of elder and of other plants, in
the purer, unsized papers, in cotton, and in the silky appendages
of certain seeds. Cotton, freed from extraneous matter by boil-
CARBOHYDRATES. 391
ing with potash, and afterward with dilute HC1, yields pure cel-
lulose, in which form it is now met with in commerce under the
name " absorbent cotton."
It is a white material, having the shape of the vegetable struc-
ture from which it was obtained ; insoluble in the usual neutral
solvents, but soluble in the deep-blue liquid obtained by dissolv-
ing copper in ammonia in contact with air.
Vegetable parchment, or parchment paper, is a tough material,
possessing many of the valuable properties of parchment, made
by immersing unsized paper for an instant in moderately strong
H2SO<, washing thoroughly, and drying.
Nitrocellulose. — By the action of HNO3 upon cellulose (cotton)
three different products of substitution may be obtained : mono-
nitro-cellulose, soluble in acetic acid, insoluble in a mixture of
ether and alcohol ; dinitro-cellulose, insoluble in acetic acid, solu-
ble in a mixture of ether and alcohol ; trinitro-cellulose, soluble
in both the above solvents. Gun-cotton or pyroxylin is composed
of varying proportions of these three derivatives. "When gun-
cotton is required as an explosive agent, the process is so man-
aged that the product shall contain the greatest possible propor-
tion of trinitro-cellulose, the most readily inflammable of the
three. When required for the preparation of collodion, for use
in medicine or in photography, dinitro-cellulose is the most valu-
able. To obtain this, a mixture is made of equal weights of HNO3
and HuSO* (of each about 5 times the weight of the cotton to be
treated) ; in this the cotton is immersed and well stirred for about
three minutes, after* which it is well stirred in a large vessel of
water, washed with fresh portions of water until the washings
are no longer precipitated by barium chlorid, and dried. Col-
lodion is a solution of dinitro-cellulose in a mixture of three vol-
umes of ether and one volume of alcohol. Celluloid is gun-cotton
and camphor compacted under pressure.
Lignin is an isomere of cellulose, which constitutes the greater
part of the " incrusting substance " of wood.
Gums — are substances of unknown constitution, existing in
plants; amorphous; soluble in water, insoluble in alcohol; con-
verted into glucose by boiling with dilute HaSO4.
Lichenin is obtained from various lichens by extraction with
boiling water, forming a jelly on cooling; it is oxidized to oxalic
acid byHNO3; is colored yellow by iodin; and is precipitated
from its solutions by alcohol.
Arabin is the soluble portion of gum arabic and gum Senegal —
Acacia (TJ. S.). To separate it, gum arabic is dissolved in water
acidulated with HC1, and precipitated by alcohol. It is a white,
amorphous, tasteless substance, which is not colored by iodin ; is
oxidized by HNO3 to mucic and saccharic acids ; is converted by
392 MANUAL OF CHEMISTRY.
HsSCh into a non-fermentable sugar, arabinose; and has the com-
position, CiaH-joOio+lAq.
Bassorin constitutes the greater part of gum tragacanth ; it is
insoluble in water, but swells up to a jelly in that fluid.
Cerasin is an insoluble gum exuded by cherry- and plum-trees ;
water acts upon it as upon bassorin.
CYCLIC HYDROCARBONS.
393
CYCLIC HYDROCARBONS AND THEIR DERIVATIVES.
AROMATIC SUBSTANCES.
It is among the compounds of this series that the most impor-
tant products of synthetic chemistry are to be found ; and it is in
dealing with them that theoretic chemistry has received the
widest applications.
Although many of these bodies occur in nature, by far the
greater number, including all the hydrocarbons except the mem-
bers of the paraffene and
terebenthene groups, are it?
artificial products. w
Although the members
of the acyclic and of the
cyclic families are not
readily converted into
each other, acyclic com-
pounds are frequently
grafted upon cyclic, and
cyclic compounds are fre-
quently decomposed with
formation of acyclic de-
rivatives, but in the lat-
ter case cyclic derivatives
are simultaneously pro-
duced.
Among the instances of
conversion of acyclic into
cyclic compounds is one
of interest as bearing
upon the constitution
and relationships of the
cyclic hydrocarbons, and as showing their pyrogenic origin.
We have seen that one of the constituents of coal-gas is acety-
lene, H — C=C — H. The central figure of the cyclic compounds
is benzene, C6H6, which is obtained principally from gas-tar ;
and whose molecule may clearly be considered as produced by
the union of three molecules of acetylene, 3C2Ha = C6H6. If we
represent three molecules of acetylene by 1, 2, 3, A or B, Fig. 41
(the larger circles representing the carbon, and the smaller the
hydrogen atoms), it is easy to conceive that by the action of heat
one of the three bonds uniting the two C atoms may be loosened,
and that the neighboring C atoms will then attach themselves to
each other, exchanging the valences thus liberated, and produce
a molecule of benzene. The arrangement A produces the "pris-
394 MANUAL OF CHEMISTRY.
matic formula," the arrangement B the "hexagonal formula'*
of benzene, usually represented in writing thus :
H
C
HC/XCH
HC. /CH
x/
C
H
!H
It is hardly necessary to mention that such formulae are merely
schematic, intending to represent the relations of the atoms, but
not intending to convey any idea of the shape of the molecule.
Although the hexagonal expression is more frequently met with
than the prismatic, and is in some respects more manageable, the
prismatic in some cases better explains the structure of the mole-
cule.
Although substances are known which contain a cyclic nucleus
made up of a number of C atoms less than six, all cyclic com-
pounds may be considered as derivable from benzene, and all con-
tain the benzene nucleus or benzene ring, C6He, more or less mod-
ified by addition, by substitution or by subtraction.
Some of the benzene derivatives are produced by simple graft-
ing of lateral, open-chain groups upon a benzene nucleus, as
shown at A, others by the union of two or more benzene rings
with each other as shown at B ;
H H H
7CX H H /c\/c\
HO C-C-C-H HC C CH
I IJ H H II
HC CH HC C CH
H H H
A. B.
and all the molecules so formed are capable of deeper modifica-
tion by further substitution of atoms or groups for the remaining
H atoms.
The prismatic formula given above may also be opened out,
and the molecule thus gain two, four, or six valences, thus :
\/ v/ \/
C C C
/\ /\ x /\ /
— c— c— — c— c— pc c/
-c-c- >c c/ )c c<
\/ ' \/ ^ / \/^
c c c
/\ /\ /\
MONOBENZENIC HYDROCARBONS. 395
Condensation and substitution may also occur in the benzene
ring itself, giving rise to compounds containing modified nuclei,
such as :
C=C
i
/\ I
-C C— C—
C—
XX
N
The benzenic hydrocarbons (and their derivatives) are divided
into groups according to the number of benzene nuclei, more or
less modified, which they contain. Thus we have :
Monobenzenic hydrocarbons — containing one benzene nucleus.
Dibenzenic hydrocarbons — containing two benzene nuclei.
Tribenzenic hydrocarbons — containing three benzene nuclei, etc.
MONOBENZENIC HYDROCARBONS.
SERIES CnHan-8
The hydrocarbons of this series are the starting-points from
which the major part of the cyclic compounds are obtainable or
derivable. Those at present known are :
Benzene C8H8 boils at 80°.4 (176°.7 F.)
Toluene C7HS boils at 110°.3 (230°.5 F.)
Xylene C8H10 boils at 142°.0 (287°.6 F.)
Cuniene C»H,» boils at 151°.4 (304°.5 F.)
Cymene C,0H14 boils at 175°.0 (347°.0 F.)
Laurene C,iHi« boils at 188°.0 (370°. 4 F.)
The terms above benzene may be obtained by a general reac-
tion, by treating a mixture of monobrombenzene, ether and the
bromid or iodid of the corresponding alcoholic radical with
sodium in excess :
C8H5Br + CH3Br + Naa = 2 NaBr + C8H5,CH,
Monobrom- Methyl Sodium. Sodium Methylbenzene.
benzene. bromid. bromid. Toluene.
The reaction is violent and small quantities only (30-40 grams)
can be operated on.
Benzene — Benzol— Phenyl Jiydrid — C8H6 — 78 — (not to be con-
founded with the commercial benzine, a mixture of hydrocarbons
of the series CnHan + s, obtained from petroleum) does not exist in
nature, but is produced in a number of reactions. It is obtained
by one of two methods, according as it is required chemically
pure or mixed with other substances.
396 MANUAL OF CHEMISTRY.
To obtain it pure, recourse must be had to the decomposition
of one of its derivatives, benzoic acid ; this substance is inti-
mately mixed with 3 pts. slacked lime, and the mixture heated to
dull redness in an earthenware retort, connected with a well-
cooled receiver ; the upper layer of distilled liquid is separated,
shaken with potassium hydroxid solution, again separated, dried
by contact with fused calcium chlorid, and redistilled over the
water-bath.
For use in the arts, and for most chemical purposes, benzene is
obtained from coal- or gas-tar, an exceedingly complex mixture,
•containing some forty or fifty substances, among which are :
Benzene.
Toluene.
Xylene.
Cuinene.
Phenol.
Cresvlol.
Pyridin.
Anilin.
Picolin.
Lutidin.
By a primary distillation of coal-tar the most volatile constitu-
ents, including benzene, are separated as light oil ; this is washed,
first with H2SO4, and then with caustic soda, and afterward re-
distilled ; that portion being collected which passes between 80°
and 85° (176°-185° F.). This is the commercial benzene, a product
still contaminated with the higher homologues of the same series,
from which it is almost impossible to separate it, but whose pres-
ence is necessary for the principal use to which benzene is put —
the manufacture of anilin dyes.
Benzene is a colorless, mobile liquid, having, when pure, an
agreeable odor ; sp. gr. 0.86 at 15° (59° F.) ; crystallizing at +4°. 5
(40°. 1 F.) ; boiling at 80°. 5 (176°. 9 F.) ; very sparingly soluble in
water, soluble in alcohol, ether, and acetone. It dissolves I, S, P,
resins, caoutchouc, gutta-percha, and almost all the alkaloids.
It is inflammable, and burns with a luminous, smoky flame.
Benzene unites with Cl or Br to form products of addition, or
of substitution ; the corresponding iodin compounds can only be
obtained by indirect methods. Sulfuric acid combines with
benzene to form a neutral substance, sulfo-benzid, when the
anhydrous acid is used, and phenyl-sulfurous acid with the or-
dinary H2SO4.
If fuming HNO3 of sp. gr. 1.52 be slowly added to benzene, a
HYDROCARBONS.
Cymene.
Naphthalene.
Acenaphthalene.
Fluorene.
Anthracene.
Retene.
Chrysene.
Pyrene.
PHENOLS.
Phlorylic.
Corallin.
Catechol.
BASES.
Collidin.
Leucolin.
Iridolin.
Cryptidin.
Acridin.
Coridin.
Rubidin.
Viridin.
MONOBENZENIC HYDROCARBONS. 397
reddish liquid is formed ; from which, on the addition of H2O a,
reddish -yellow oil separates, and is purified by washing with H2O
and with sodium carbonate solution, drying and rectifying. This
oily material is mononitro-benzene (see p. 417). If benzene be
boiled with fuming HNO3, or if it be dropped into a mixture of
HNO3 and HaSO4, so long as the fluids mix, a crystalline product,
dinitro-benzene, is formed.
The superior homologues of benzene include many isomeres.
As they are derivable from benzene by substitution of a hydro-
carbon radical or radicals CnH-m + i for one or more atoms of
hydrogen, the following isomeres may exist :
C8H4(CH3)a = Dimethylbenzene I p TT
C8H5(C2Ha) = Ethylbenzene $^*a">
C8H3(CH3)3 = Trimethylbenzene
C8H6(C3H7) = Propylbenzene }• = C.Hi,
C8H4(CH3)(C2H6) = Methylethylbenzene
CsH2(CH3)4 = Tetramethylbenzene
C«H4(C2H5)2 = Diethylbenzene
C8H6(C4H») = Butylbenzene
C8H3(CH3)2(C2H5) = Dimethylethylbenzene
C8H4(GH3)(C3H,) = Methylpropylbenzene
The number of isomeres among the higher terms of the series
is further increased by the occurrence of increasing numbers of
isomeres among the substituted radicals themselves, as-
CHa— CH2— CH3 and CH \§§J, etc. Further, when the number
of substituted groups is greater than one, different substances are
produced by the substitution of the same groups in positions
bearing different relations to each other in the benzene nucleus.
In the case of benzene itself there exist products of substitu-
tion containing 1, 2, 3, 4, 5, and 6 groups CH3iC2H5, etc. (or other
radicals or univalent atoms), or combinations of two or three of
those radicals or elements. In the case of the unisubstituted de-
rivatives, C6H6,CH3 ; C6H5,C2H5, etc., but one of each exists. Of
the bisubstituted, trisubstituted, and quadrisubstituted deriva-
tives three of each are known.
From the existence of but one unisubstituted derivative it is
obvious that it is immaterial in which of the CH groups this sub-
stitution occurs, and hence these six groups are equal to each
other in value. The existence of isomeres of the higher products
of substitution depends upon differences in the relative positions
of the substituted radicals or atoms to each other, their orienta-
tion, as it is called, and not to their absolute positions.
If we represent the molecule of benzene by a hexagon, leaving
out the H atoms for the sake of brevity, we may start from any
angle and number the angles, or positions, from 1 to 6 :
398 MANUAL OF CHEMISTRY.
1
6—0 0—2
5—0 0—3
In such a hexagon there are three possible positions with rela-
tion to each other, in which two atoms or radicals inay be placed.
They may be consecutive, i.e.. occupying two adjoining posi-
tions, as 1 — 2, 2 — 3, 3 — 4, 4 — 5, 5 — 6, or 6 — 1 ; as for instance in 1, in
which x may be a radical CnH-m + i, a univalent atom, or any
XXX
C C C
06 2Cx C6 2C C6 2C
05 30 05 3Cx 05 30
\4/ \4/ \4/
C C C
x
1. 2. 3.
univalent radical. Or the positions may be unsymmetrical, 1 — 3,
2 — 4, 3 — 5, 4 — 6, 5 — 1, as in 2. Or the substitution may be symmet-
rical, as in 3, occupying the diagonal positions 1 — 4, 2 — 5, 3 — 6.
In the case of trisubstituted derivatives in which the substi-
tuted radical or element is the same there may also be three posi-
tions, thus :
XXX
COO
/ix /IN /i\
C6 2Cx 06 2O 06 20
05 3Cx 05 3Cx xC5 3Cx
COO
x
4. 5. 6.
either consecutive as in 4 ; unsymmetrical as in 5 ; or symmetrical
as in 6.
The three series of bi- and tri-substituted derivatives of ben-
zene, whether the substitution be of a halogen or of any univ-
alent element or radical, are designated by the prefixes ortho,
meta, and para. Thus, in the figures above :
Nos. 1 and 4 = 1 — 2 = Ortho benzene.
Nos. 2 and 5 = 1 — 3 = Meta benzene.
Nos. 3 and 6 = 1 — 4 = Para benzene.
MONOBENZENIC HYDROCARBONS. 399
The distinction between the three groups is best made by the
relations between the bi- and tri-substituted derivatives. The
consecutive or ortho bisubstituted derivatives can produce by
further substitution two tri-derivatives, one consecutive, the other
unsymmetrical ; the urisymmetrical, or meta, can produce three
trisubstituted derivatives ; and the symmetrical, or para, can
produce but one trisubstituted derivative, an unsymmetrical.
In expressing the constitution of substituted derivatives it is
customary either to use the prefixes ortho, para, and meta, as ex-
plained above, or to designate the substance by the numerical
positions of the substituted atoms or radicals, considering the
substituted atom or group in the parent mono-substituted deriv-
ative as always occupying the position 1.
When, in a trisubstituted derivative, the substituted radicals
or atoms are not the same in kind, the number of possible isomeres
is further increased. Thus, there are six possible chloro-dibromo-
benzenes :
Br Br Br
c c c
/IN /IN /IN
C6 2C Br C6 2C Br C6 20 Cl
C5 3C Cl 05 30 05 30 Br
\4/ \4/ \4/
COO
01
1. 2. 3.
Br Br Br
COO
/IN /IN /IN
06 20 C6 2C 06 2C
O5 3O Br Cl 05 30 Br C5 30 Cl
\4/ \4/ \4/
COO
Cl Br
4. 5. 6.
of which 1 and 2 are derivable from orthobibromobenzene, 3, 4,
and 5 from metabibromobenzene, and 6 from parabibromoben-
zene. If, in place of two elements or radicals, we have three, the
number of trisubstituted derivatives is increased to ten.
The naming of such polysubstituted derivatives presents many
difficulties. Adherence to the principle that the name of a com-
pound shall indicate its constitution, involves the construction
of names which are frequently of unwieldy length. It is usual
to consider the characterizing group as occupying the position 1
in the hexagon, and to prefix the term ortho to the name of that
400 MANUAL OF CHEMISTKY.
radical or atom occupying one of the ortho-positions 2 and 6 with-
relation to the characterizing group ; meta to that occupying one
of the meta-positions 3 and 5 ; arid para to that occupying the
para-position 4.
Thus the substance having the constitution indicated by the
formula 1 is designated by the name orthonitroparabromo-phe-
OH
C OH OH
/IS C C
06 2C— NO, /1-S /IS
|| | C6 20 NO, O2NC6 2C
05 30 || | || |
\ 4 / 05 30— Br 05 30 Br
C \4/ \4/
C C
IT
1. 2. 3.
,1,
nol. But even this is not always sufficiently definite, for to each
of the substances 2 and 3, although differing in characters, the
name orthonitrometabromo-phenol applies. It has been sug-
gested, to avoid this difficulty, that the prefix allortho be used to
designate the second ortho-position 6, and the prefix allometa
to designate the second meta-position 5.
The name of No. 3 would thus become metabromoallorthonitro-
phenol.
When formulae are used, all confusion may be readily avoided,
even in the most complex substances, by the use of the numeral
corresponding to the position in the benzene chain, enclosed in
brackets. Thus, the formulae of 2 and 3 above may be written i
C6H3(OH)(NO2)(2)Br(3) ; and
C6H3(OH)Br(3)(NOs)<6).
In the case of the tetrasubstituted derivatives there are also-
three possible positions : consecutive, 1, 2, 3, 4 ; symmetrical, 1, 3,
4, 6, and unsymmetrical, 1, 3, 4, 5.
In these hydrocarbons and in other derivatives of benzene the
six atoms of carbon belonging to benzene constitute what is
known as the benzene nucleus, benzene ring, or the principal
chain ; while the substituted groups are designated as the lateral
chains.
Toluene— Toluol— Methyl-benzene— C6H6,CH3 — 92 — exists in the
products of distillation of wood, coal, etc., and as one of the con-
stituents of commercial benzene. It has been formed syntheti-
cally by acting upon a mixture of moiiobromo-benzene and methyl
iodid with sodium.
It is a colorless liquid, having a peculiar odor, differing some-
what from that of benzene ; boils at 110°. 3 (230°. 5 F.) ; does not.
HALOID DERIVATIVES. -±01
solidify at -203 (-4° F.); sp. gr. 0.872 at 15° (59° F.); almost in-
soluble in water, soluble in alcohol, ether, carbon disulfid. It
burns with a bright, but very smoky flame. It yields a number
of derivatives similar to those of benzene, among which may be
mentioned nitro-toluene and toluidin, the homologues of nitro-
benzene and anilin, which accompany those substances in the
commercial products ; cresylol, the superior homologue of car-
bolic acid, and benzylic alcohol.
Xylenes — Xylols — CsHi0. — Four isomeres are possible and are
known: ethyl-benzene, CeH5,C2H5 — andortho-(l — 2), meta- (1 — 8),
and para- (1 — 4), dimethyl-benzenes, C6H4(CH3)2. Ethylbenzene is
a colorless oil, boiling at 134° (273°.2 F.), obtained by fractional dis-
tillation of animal oil. The three dimethyl benzenes exist in coal-
tar and in the commercial xylene, which boils at 139° (282°. 2 F.),
70 ^ consisting of metaxylene, and paraxylene being present in
very small amount.
HALOID DERIVATIVES.
By the substitution of atoms of Cl, Br and I for the hydrogen
of the principal and lateral chains in benzene and its superior
homologues, a great number of substances are obtained, many
of them forming isomeric groups.
The chlorin derivatives of benzene are :
Monochloro-benzene— C6H6C1— liquid ; boils at 132° (269°. 6 F.) ;
sp. gr. 1.128 at 0° ; obtained by the action of Cl upon CeHo in the
cold, in the presence of a little I.
Orthodichloro-benzene— 1—2— liquid ; boils at 179° (354°.2 F.); sp.
gr. 1.328 at 0° ; obtained by the action of Cl on C6H6.
Metadichloro-benzene — 1 — 3 — liquid ; boils at 172° (341°. 6 F.) ; sp.
gr. 1.307 at 0D ; obtainable indirectly.
Paradichloro-benzene— 1—4— crystalline ; fuses at 56°. 4 (133°. 5
F.) ; boils at 170° (343°.4 F.) ; is the principal product of the action
of Cl on C8H6 in presence of I.
Metatrichloro-benzene — 1 — 2 — 4 — crystals ; fuses at 17" (62°. 6
F.) ; boils at 213" (415°.4 F.).
Paratrichloro-benzene — 1 — 3—5 — crystals ; fuses at 63°.4 (146°. 1
F.) ; boils at 208° (406°.4 F.).
Tetrachloro-benzene — 1 — 2—3 — 5 — crystals ; fuses at 50° (122° F.) ;
boils at 246° (474°. 8 F.).
Tetrachloro-benzene — 1—2 — 4 — 5 — crystals ; fuses at 137° (278°. 6
F.) ; boils between 243°-246° (469°. 4-474°. 8 F.).
Benzoyl chlorid — C6H5CH2C1 — is an example of the substitution
of a halogen in the lateral chain of a superior homologue of
benzene. It is obtained by the action of chlorin upon boiling
26
402 MANUAL OF CHEMISTRY.
toluene ; or of PC15 on benzole alcohol. It is a colorless liquid,
boils at 176° (348°. 8 R), and gives off pungent vapors which excite
the lachrymal secretion. It is readily oxidized to benzoic alde-
hyde or benzoic acid, and serves for the introduction of the
radical benzoyl, C6H6,CHa into other molecules.
PHENOLS.
The hydrocarbons of the benzene series, unlike those previously
considered, form two distinct kinds of hydrates, differing from
each other materially in their properties. The terms of one of
these series exhibit all the functions of the alcohols, and are
known as aromatic alcohols. The terms of the other series differ
in function from any substance thus far considered, and are
known as phenols. The difference between them and the aro-
matic alcohols is due to the fact that in the phenols the OH is
directly attached to a C atom, while in the alcohols it forms part
of the group of atoms CH2OH, characteristic of the alcohols :
H H
(i i
/K /K
H— C C— CHS H— C 0— CH2OH
I H I
H— C C— OH H— C C— H
c
/
H H
!Benzylic phenol. Benzylic alcohol.
The phenols differ from the alcohols in not furnishing by oxida-
tion corresponding aldehydes and acids ; in not dividing into
water and hydrocarbon under the influence of dehydrating agents;
in not reacting with acids to form ethers ; in combining to form
directly products of substitution with Cl and Br ; and in forming
with metallic elements compounds more stable than similar com-
pounds of the true alcohols. In short, the phenols appear to
have, besides an alcoholic function, more or less of the function
of acids.
Phenol — Phenyl hydrate— Phenic acid — Carbolic acid — Acidum
carbolicum (TJ. S., Br.) — C,H OH — 94 — exists in considerable quan-
tity in coal- and wood-tar, and in small quantity in castoreum,
and possibly in urine.
It is formed : (1) by fusing sodium phenylsulfid with an ex-
cess of alkali ; (2) by heating phenyl iodid with potassium hy-
droxid to 320° (608° R); (3) by heating together salicylic acid and
PHENOLS. 403
quicklime ; (4) by total synthesis from acetylene ; (5) by dry dis-
tillation of benzoin.
The source from which it is obtained is that portion of the prod-
uct of distillation of coal-tar which passes over between 150° and
200C (302°-392° F.). This is treated with a saturated solution of
potash, containing undissolved alkali ; a solid phenate is formed,
which is dissolved in hot H2O ; the liquid is allowed to separate
into two layers, the lower of which is drawn off and neutralized
with HC1 ; the phenol rises to the surface, is separated, washed
with water, dried over calcium chlorid, redistilled, crystallized at
— 10° (14° F.), and the crystals drained A "synthetic phenol"
is now made from benzene and from anilin, and seems to be more
nearly pure than the "natural" product.
Pure phenol crystallizes in long, colorless, prismatic needles,
fusible at 4(T-41° (104~-10o°.8 ?.), boiling at 181°.5 (258°.7 F.). It
has a peculiar, well-known odor, and an acrid, burning taste ;
very sparingly soluble in water, readily soluble in alcohol and in
ether ; sp. gr. 1.065 at 183 (64=.4 F.) ; neutral in reaction. On con-
tact with- the skin or with mucous surfaces, it produces a white
stain ; it coagulates, albuminoids, and is a powerful antiseptic.
It may be distilled without decomposition. It absorbs H2O
from, damp air to form a hydrate, which crystallizes in six-sided
prisms, fusible at 16° (60°.8 F.). Its vapor is reduced to benzene
when heated with Zn. It combines with H2SO4 to form phenyl-
sulfuric acids. It forms trinitrophenic acid (q.v.) with HNOs
of 36° B. When heated with H2SO4 and oxalic acid it forms
rosolic acid or corallin, which is a mixture from which the pig-
ments aurin, peonin, azulin, and phenicin are obtained.
Analytical Characters. — (1.) Its peculiar odor. (2.) Mix with
one-quarter volume of XH4HO ; add two drops sodium hypo-
chlorite solution, and warm ; a blue or green color. Add HC1 to
acid reaction ; turns red. (3.) Add two drops of liquid to a little
HC1, add one drop HNO3 ; a purple red color. (4.) Boil with
HNO3 as long as red fumes are given off. Neutralize with KHO ;
a yellow, crystalline precipitate. (5.) With FeSO4 solution ; a
lilac color. (6.) Float the liquid on H;,SO4, add powdered KNO3 ;
violet color. (7.) With excess of Br water ; a yellowish-white
precipitate.
Toxicology. — When taken internally, phenol is an active poison,
and one whose use by suicides has become quite common. When
it has been taken the mouth is whitened by its caustic action,
and there is a marked odor of carbolic acid in the breath. It is
eliminated by the urine, partly unchanged, and partly in the
form of colored derivatives, which color the urine greenish, brown-
ish, or even black. The treatment consists in the administration
of albumen (white of egg) and of emetics.
404 MANUAL OF CHEMISTRY.
To detect phenol in the urine, that liquor must not be distilled
with H2SO4, as sometimes recommended, as it contains normally
substances which by such treatment yield carbolic acid. The
best method consists in adding an excess of bromin water to about
500 c.c. of the urine ; on standing some hours, a yellowish pre-
cipitate collects at the bottom of the vessel; this is removed,
washed, and treated with sodium amalgam, when the character-
istic odor of phenol is developed. From other parts of the body,
phenol may be recovered by acidulating with tartaric acid ; dis-
tilling ; extracting the distillate by shaking with ether ; evapo-
rating the ethereal solution ; extracting the residue with a small
quantity of water, and applying to this solution the tests de-
scribed above.
Phenates. — Carbolates. — The hydrogen of the oxhydryl group
of phenol is replaceable by certain metals and by alcoholic radi-
cals to form phenates. When phenol and KHO are heated to-
gether, potassium phenate, C,,H,,OK, is formed. This, when
treated in alcoholic solution with HgCl2, produces mercuric phe-
nate, (C6H5O,)2Hg', a yellow, crystalline solid which has been used
in medicine.
The phenylic ethers may be obtained by heating potassium
phenate with the iodid of the alcoholic radical.
Methyl phenate — Anisol— C6H6,OCH3— is a colorless, thin liquid,,
boils at 152° (305°. 6 F.) without decomposition. Sulfuric acid
dissolves it. with formation of methyl-phenol sulfonic acid.
Ethyl phenate — Phenetol — C6H6,OC2H5 — is a colorless liquid,
boils at 172' (341°. 6 F.), having an aromatic odor.
Anisol and phenetol serve as the starting-points for the produc-
tion of the anisidins and phenetidins (q.v.).
Cresols — Cresylols — Cresylic acids — Benzylic or cresylic phe-
/CH
nols — C6H4^Qjj3 — 108. — Of the three possible compounds, two, the
para and ortho, accompany phenol in coal-tar, from which they
may be separated by fractional distillation. They are more
readily obtained pure from toluene.
Ortho-cresol (1—2) is a crystalline solid, fusible at 31°-31°.5 (87°. 8-
88°. 7 F.), which assumes a blue color with ferric chlorid.
Metacresol (1 — 3) is obtainable by the action of P2O5 on thymol.
It is a colorless liquid, whose odor resembles that of phenol, boils
at 201° (393°.8 F.), does not solidify at -75° (-103° F.).
Paracresol (1—4) is a crystalline solid, fusible at 36° (96°.8 F.),
boiling at 198° (388°. 4 F.), having a phenol-like odor ; colored blue
by ferric chlorid.
Creasote — Creasotum (U. S.) — is a complex mixture containing
phenol, cresol, creasol, CfHi0O2, guaiacol, C7H6O2 (see catechol),
and other substances, obtained from wood-tar and formerly ex-
PHENOLS. 405
tensively used as an antiseptic. It is an oily liquid, colorless
-when freshly prepared, but becoming brownish on exposure to
light ; it has a burning taste and a strong, peculiar odor ; it boils
at 203° (39?°.4 F.), and does not solidify at —27° (—16°. 6 F.).
Crude phenol is often substituted for creasote ; the two sub-
stances may be distinguished by the following characters : Phe-
nol gives a brown color with ferric chlorid and alcohol, while
creasote gives a green color; phenol dissolves in glycerin, in which
creasote is insoluble; phenol precipitates nitro-cellulose from col-
lodion, while creasote does not.
Xenols — Xylenols. — Theoretically there are six possible xenols
which are dimethyl phenols, C H^CHL )_OH; two derivable from
.orthoxylene, three from metaxylene and one from paraxylene.
They have all been produced synthetically. There are also three
possible xenols which are ethyl phenols, C6H4(C2H5)OH.
Thymol — Methyl-parapropyl-metaphenol — Cymylic phenol —
C6H.j(CH3)(i)(OH)(3)(C3H7)(4) — exists, accompanying cymene and
thymene, C10H16, in essence of thyme, from which it is obtained.
The essence contains about one-half its weight of thymol, which
is separated by agitation with a concentrated solution of caustic
soda ; separation of the alkaline liquid, which is diluted and
neutralized with HC1 ; thymol separates and is purified by rec-
tification at 230° (446° F.). It is also prepared synthetically from
cuminic aldehyde, CeH^CHOX^CsHT)^).
It crystallizes in large, transparent, rhombohedral tables; has
a peppery taste, and an agreeable, aromatic odor ; it fuses at 44°
(111°. 2 F.), and boils at 230° (446^ F.); is sparingly soluble in water,
very soluble in alcohol and ether. With the alkalies it forms
definite compounds, which are very soluble in water. Its reac-
tions are very similar to those of phenol.
Thymol is an excellent deodorizing and antiseptic agent, pos-
sessing the advantage over phenol of having itself a pleasant odor.
Aristol is a compound of thymol and iodin, properly belong-
ing among the dibenzenic compounds, produced by the action of
a solution of I in KI upon an aqueous solution of thymol in the
presence of KHO. It is an inodorous, yellowish red powder, in-
soluble in H8O, very sparingly soluble in alcohol, readily soluble
in ether and in chloroform. It is decomposed by heat and by
light and is said to be a non-poisonous antiseptic.
Carvacrol — Methyl-paraisopropyl-metaplienol — C6 H3 (C H3) (i>
(OH)f2)(CHs)2CH(4) — an isomere of thymol, whose constitution dif-
fers in the position of tne oxhydryl group, exists in many essential
oils and is obtained by the action of iodin upon camphor ; by
the action of potash in fusion upon cymene sulfonic acid, CioHi3
SO3H ; or by a transposition of the atoms of another isomere,
carvol, which exists in caraway oil. It is an oil, boiling at 233°-
335° (451°.4-455° F.). Heated with P2O5, it yields orthocresol.
406 MANUAL OF CHEMISTRY.
SUBSTITUTED PHENOLS.
We have seen above (p. 398) how three bi- and tri-substituted1
derivatives are derivable from benzene. Phenol is a unisubsti-
tuted derivative of the same substance and hence still contains
five H atoms which may be replaced by other elements or radicals,
to produce di- or tri- or poly-substituted derivatives of benzene,
which will be ortho, meta or para, etc., according to the relations
of the introduced groups to the OH, already existing in phenol,
or to the CnK*n + i and OH groups in its superior homologues.
Chlorophenols. — The three monochlorinated compounds are
obtainable from the corresponding chloranilins. Orthochloro-
phenol (1—2) is a colorless liquid, boils at 175°-176° (347°-348°.8 R),
converted into catechol by KHO. Metachlorophenol (1 — 3) is a
liquid, boiling at 214° (417°. 2 F.). KHO converts it into resorcin.
Parachlorophenol (1 — 4) is a crystalline solid, fusible at 37° (98°. 6
F.), converted into quinol by fusion with KHO. Di-, tri-, and
penta-chlorophenols are also known.
Bromophenols correspond in method of formation and properties
with the Cl derivatives.
lodophenols are formed by the action of iodin and KS upon
phenol in the presence of excess of alkali, or from the corre-
sponding amidophenols. Like the chlorin and bromin deriva-
tives, they yield the corresponding diphenol by the action of
KHO in fusion. A tri-iodophenol, formed by the action of solu-
tion of I in KS upon an alkaline solution of phenol, has been
proposed as a substitute for iodoform under the name annidalin.
Nitro-phenols— Mononitro-phenols— C6H4(NO2)OH— (1 —2), (1—3)
and (1—4) are formed by the action of HNO3 on C6H6OH. The
ortho compound (1 — 2) crystallizes in large yellow needles, spar-
ingly soluble, and capable of distillation with steam. The meta
and para compounds are both colorless, non-volatile, crystal-
line bodies. Two dmitro-phenols, CeHsOH^Os^-o and C6H3
OH(NO2)a(2-6), are obtained by the action of strong nitric acid on
phenol, or on ortho- or para-mononitro phenol. They are both
solid, crystalline substances, converted by further nitration into
picric acid.
Trinitro-phenols — CeH-^NO^aOH. — Two are known : (1.) Picric
acid — Carbazotic acid — Trinitro-phenic acid — (NO2) in 2 — 4 — 6. It
is formed by nitrification of phenol, or of 1 — 2 — 4 or 1 — 2 — G dini-
tro-phenols, and also by the action of HNO3 on indigo, silk, wool,
resins, etc. It crystallizes in brilliant, yellow, rectangular plates,
or in six-sided prisms ; it is odorless, and has an intensely bitter
taste, whence its name (from m/c/jof = bitter) ; it is acid in reaction ;
sparingly soluble in water, very soluble in alcohol, ether, and.
SUBSTITUTED PHENOLS. 40 i
benzene ; it fuses at 122°. 5 (252°. 5 F.), and may, if heated with
caution, be sublimed unchanged ; but, if heated suddenly or in
quantity, it explodes with violence. It behaves as a monobasic
acid, forming salts, which are for the most part soluble, yellow,
crystalline, and decomposed with explosion when heated.
Picric acid is valuable as a dye-stuff, coloring silk and wool
yellow ; as a staining medium in histological investigations ; and
as a reagent for the alkaloids, with many of which it forms
crystalline precipitates. It is also sometimes fraudulently added
to beer and to other food articles, to communicate to them either
a bitter taste or a yellow color.
ANALYTICAL CHARACTERS. — (1.) Its intensely bitter taste. (2.)
Its alcoholic solution, when shaken with a potassium salt, gives a
yellow, crystalline ppt. (3.) An ammoniacal solution of cupric
sulfate gives a green, crystalline ppt. (4.) Glucose, heated with
a dilute alkaline solution of picric acid, communicates to it a
blood-red color. (5.) Warmed with an alkaline solution of potas-
sium cyanid, an intense red color is produced (the same effect is
produced by ammonium sulfhydrate). (6.) Unbleached wool,
immersed in boiling solution of picric acid, is dyed yellow.
Nos. 1, 3, 5, and 6 are quite delicate.
When taken internally in overdose, it acts as a poison ; it may
be separated from animal fluids or from beer by evaporation to a
syrup, extracting with 95 per cent, alcohol, acidulated with
H2SO4 ; filtering ; evaporating ; and applying the tests to a solu-
tion of the residue.
Amido-phenols— C6H4,OH,NH3.— Three are known, ortho-,
ineta- and para-, obtained by the action of reducing agents upon
the corresponding nitro-compounds. Their methylic ethers, C6H4,
O(CH3)NH2, are known as anisidins ; and their ethylic ethers,
C6H4,O(C2H5)NH3, as phenetidins.
By the action of glacial acetic acid upon paraphenetidin,
an aceto-derivative, para-acetphenetidin, C8H4,O(C2H5)(i),NH
(C2H3O)(4), is formed. It has been recommended as an antipyretic,
under the name phenacetine, and is a reddish, odorless, tasteless
powder, sparingly soluble in H2O, readily soluble in alcohol. Its
hot aqueous solution is colored violet, changing to ruby-red, by
chlorin water. The corresponding anisidin, para-acetanisidin ;
C6H4,O(CH3)(i),KrH(C2H3O)(4), has also been suggested as a thera-
peutic agent. It crystallizes in white, shining, tasteless, odorless
scales, fuses at 127° (260°.6 F.), sparingly soluble in HaO, readily
soluble in alcohol. •
408 MANUAL OF CHEMISTRY.
DIATOMIC PHENOLS.
Diatomic phenols are derived from the benzene series of hydro-
carbons by the substitution of two (OH) groups for two atoms of
hydrogen. In obedience to the laws of substitution already dis-
cussed, three such compounds exist, corresponding to each hydro-
carbon. Thus, in the case of benzene :
OH
OH OH |
C C /IS
/IS / 1 X C6 20
C6 2C— OH C6 20
II I I 05 30
C5 30 05 30— OH \4/
\4/ \4/ C
CO I
OH
Ortho. Meta. Para.
1-2 1-3 1-4
Catechol. Resorcinol. Quinol.
Catechol — Pyrocatechin — Oxyphenic acid — Orthodioxy-benzene
— C6H4(OH)2 — 1 — 2 — is obtained from catechin or from morintan-
nic acid by dry distillation; also by the action of KHO on ortho-
chlor- or orthoiodo-phenol, or by decomposing its methyl ether,
guaiacol, by HI at 200° (392° F.). It crystallizes in short, square
prisms; fuses at 104° (219°.2 F.), and boils at 245°.5 (473°.9 F.).
Readily soluble in water, alcohol, and ether. Its aqueous solu-
tion gives a dark green color with Fe2018 solution, changing to
violet on addition of NH4HO, NaHCO3, or tartaric acid.
Resorcinol — Resorcin — Metadioxy-benzene — CeH4(OH)2 — 1 — 3 —
is obtained by the action of fused KHO on parachlor- or iodo-
phenol. It is usually prepared by dry distillation of extract of
Brazil wood.
It forms short, thick, colorless and odorless, rhombic prisms.
Fuses at 104° (219°.2 F.), and boils at 271° (519°.8 F.). It is very
soluble in water, alcohol, and ether. Its aqueous solution is
neutral in reaction, and intensely sweet. With Fe2016 its solu-
tions assume a dark violet color, which is discharged by NH4HO.
Its ammoniacal solution, by exposure to air, assumes a pink
color, changing to brown and, on evaporation, green and dark
blue. Heated with phthalic anhydrid at 195° (383° F.) it yields
fluorescein (see page 410). It dissolves in fuming H2SO4, forming
an orange-red solution, which becomes darker, changes to green-
ish-black, then to pure blue, and finally to purple on being
warmed.
Resorcinol, heated with sodium nitrite and H2O to about 150°
TRIATOMIC PHENOLS. 409
•(302° F.) yields a blue pigment known as lacmoid, which behaves
like litmus with acids and alkalies, but is more sensitive.
Resorcinol has been recently used in medical practice.
Quinol — Hydroquinone — Paradioxy-benzene — C6H4(OH)2 — 1—4
— is formed by fusing paraiodo-phenol with KHO at 180° (356° F.),
by dry distillation of oxysalicylic acid or of quinic acid, and by
the action of reducing agents on quinone. It forms colorless,
rhombic prisms, which fuse at 169° (336=.2 F.). Readily soluble
in water, alcohol, or ether. Its aqueous solution is turned red-
brown by NH4HO. Oxidizing agents convert it into quinone.
Quinone — C6H4(OO)" — is the representative of a number of sim-
ilar compounds, derivable from the aromatic hydrocarbons. It
is produced by the oxidizing action of MnO2+H2SO4 or of dilute
chromic acid, upon quite a number of para-benzene derivatives;
but best by the limited oxidation of quinic acid.
It crystallizes in yellow prisms; fuses at 116° (240°. 8 F.); sub-
limes at ordinary temperatures; is sparingly soluble in cold, but
readily soluble in hot water and in alcohol or ether. It gives off
a peculiar, pungent odor, and stimulates the lachrymal secretion.
Reducing agents convert it into quinol.
There is no similar substance known corresponding either to
•catechol or to resorcinol.
Orsin — Dimetadioxy -toluene — C6H3(CH3)(1)(OH3)(3)(OH)(5)— exists
in nature in those lichens which are used as sources of archil and
litmus (Rocella tinctoria, etc.). It crystallizes in six-sided prisms ;
is sweet ; readily soluble in water, alcohol, or ether ; fuses at 58°
(136°. 4 F.). Its aqueous solution is colored violet-blue by Fe-iCl8.
It unites with NH3 to form a compound which absorbs O from
the air, and is converted into orcein, C7H7NO3 ; a dark red or
purple body, which is the chief constituent of the dye-stuff
known as archil, cudbear, French purple, and litmus.
TRIATOMIC PHENOLS.
The only compounds of this class at present known with cer-
tainty are two isotneric triatomic phenols, which owe the differ-
ences in properties existing between them to a different placing
of the OH groups. They are phloroglucin and pyrogallol.
Phloroglucin— C6H3(OH)3— 126— is obtained by the action of pot-
ash upon phloretin, quercitrin, maclurin (see Glucosids), catechin,
kino, etc. It crystallizes in rhombic prisms, containing 2 Aq ;
is very sweet ; very soluble in water, alcohol, and ether.
'PyrogaXlol—Pyrogallic acid— C6H3(OH)3— 126— is formed when
gallic acid (g.v.) is heated to 200° (3923 F.). It crystallizes in
MANUAL OF CHEMISTRY.
white needles ; neutral in reaction ; very soluble in water ; verjr
bitter ; fuses at 115° (239° F.) ; boils at 210° (410° F.) ; poisonous.
Its most valuable property is that of absorbing oxygen, for which
purpose it is used in the laboratory in the form of a solution of
potassium pyrogallate.
When pyrogallol is heated with half its weight of phthalic an-
hydrid for several hours at 190°-200° (374°-392° F.) it yields py-
rogallol phthalein, or gallein, a brown-red powder (or green crys-
tals) which dissolves with a brown color in neutral solutions,,
the color changing to red with a faint excess of alkali.
PHENOL DYES.
Aurin — C, ,H, ,0:i and Rosolic acid— C2oHi6O3— are substances ex-
isting in the dye obtained by the action of oxalic acid upon
phenol in presence of HaSCh, known as corallin or pceonin, which
communicates to silk or wool a fine yellow-red color.
Aurin crystallizes in fine, red needles from its solution in HC1.
It is insoluble in H2O, but soluble in HC1, alcohol, and glacial
acetic acid. It forms a colorless compound with potassium bi-
sulfite.
Phthaleins. — These substances are produced by heating the
phenols with phthalic anhydrid, C8H4O3, water being at the
same time eliminated.
Their constitution is that of a benzene nucleus, two of whose H
atoms have been replaced by two acetone groups (CO), whose re-
maining valences attach them to two phenol groups by ex-
change with an atom of hydrogen.
Thus phenol-phthalein, the simplest of the group, has the
/(*() rj TT (OH)
constitution C6H4(' «Q r^H (OH) Pnen°l-Pnthalein is a yellow,
crystalline powder, insoluble in water, but soluble in alcohol.
Its alcoholic solution, perfectly colorless if neutral, assumes a
brilliant magenta-red in the presence of an alkali. This property
renders phenol-phthalein very valuable as an indicator of re-
action.
Resorcin-phthalein — Fluorescein— C2oHi2O6 — bears the same re-
lation to resorcin that phenol-phthalein does to phenol, and is
obtained from resorcin by a corresponding method. It is a dark
brown crystalline powder, which dissolves in ammonia to form a
red solution, exhibiting a most brilliant green fluorescence. A
tetrabromo-derivative of fluorescein is used as a dye under the
name eosin.
ALPHENOLS.
AROMATIC ALCOHOLS.
The alcohols corresponding to this series of hydrocarbons have
the same composition as the corresponding phenols, from which
they differ in constitution, and in having the functions of true
alcohols. They yield on oxidation, first an aldehyde and then an
acid, and they contain the characterizing group of the primary
alcohols, CH2OH ; once if the alcohol be monoatomic, twice if
diatomic, etc. Thus :
C6H5,CH2OH = Benzylic alcohol.
C«H6,COH = Benzoic aldehyde.
C8H6,COOH = Benzoic acid.
As they contain the benzene nucleus, they are capable of yield-
ing isomeric products of further substitution, ortho, para, or
rneta, according to the position of the substituted atom or radical.
Benzylic alcohol— Benzoic alcohol— Benzyl hydrate-C6H6(CH2OH)
— 108 — does not exist in nature, and is of interest chiefly as cor-
responding to two important compounds, benzoic acid and ben-
zoic aldehyde (oil of bitter almonds). It is obtained by the action
of potassium hydroxid upon oil of bitter almonds, or by slowly
adding sodium amalgam to a boiling solution of benzoic acid.
It is a colorless liquid; boils at 206°. 5 (403°. 7 F.) ; has an aro-
matic odor ; is insoluble in water, soluble in all proportions
in alcohol, ether, and carbon disulfid. By oxidation it yields,
first, benzoic aldehyde, CeH5(COH) ; and afterward, benzoic acid,
CgH5(COOH). By the same means it may be made to yield
products similar to those obtained from the alcohols of the satu-
rated hydrocarbons.
ALPHENOLS.
•
These substances are intermediate in function between the
alcohols and the phenols, and contain both substituted groups
(OH) and CH2OH.
/ f*TT OTT
Saligenin, CsH^og3'"1-0-— 124— is obtained from salicin (q.v.) in
large, tabular crystals ; quite soluble in alcohol, water, and
ether. Oxidizing agents convert it into salicylic aldehyde, which
by further oxidation yields salicylic acid. It is also formed by
the action of nascent hydrogen on salicylic aldehyde.
412 MANUAL OF CHEMISTRY.
ALDEHYDES.
Benzole aldehyde— Benzoyl hydrid— C6H5(COH)— 106— is the
main constituent of oil of bitter almonds, although it does not
exist in the almonds (see p. 460) ; it is formed, along with hydro-
cyanic acid and glucose, by the action of water upon amygdalin.
It is also* formed by a number of general methods of producing
aldehydes ; by the dehydration of benzylic alcohol ; by the dry
distillation of a mixture in molecular proportions of calcium
benzoate and formate ; by the action of nascent hydrogen upon
benzoyl cyanid, etc.
It is obtained from bitter almonds. The crude oil contains,
besides benzoic aldehyde, hydrocyanic and benzoic acids and
cyanobenzoyl. To purify it, it is treated with three to four times
its volume of a concentrated solution of sodium bisulfite ; the
crystalline mass is expressed, dissolved in a small quantity of
water, and decomposed with a concentrated solution of sodium
carbonate — the treatment being repeated, if necessary.
It is a colorless oil, having an acrid taste and the odor of bitter
.almonds; sp. gr. 1.043; boils at 179°.4 (354°.9 F.) ; soluble in 30
parts of water, and in all proportions in alcohol and ether.
Oxidizing agents convert it into benzoic acid, a change which
occurs by mere exposure to air. Nascent hydrogen converts it
into benzylic alcohol. With Cl and Br it forms benzoyl chlorid
or broinid. H2SO4 dissolves it when heated, forming a purple-
red color, which turns black if more strongly heated.
When perfectly pure, benzoic aldehyde exerts no deleterious
action when taken internally ; owing, however, to the difficulty
of completely removing the hydrocyanic acid, the substances
usually sold as oil of bitter almonds, ratafia, and almond flavor,
are almost always poisonous, if taken in sufficient quantity.
They may contain as much as 10-15 per cent, of hydrocyanic acid,
although said to be "purified." The jyesence of the poisonous
substances may be detected by the tests given on page 292.
Salicylic aldehyde — Salicyl hydrid — Salicylal — Salicylous acid
— C6H.,(OH)COH — 122 — exists in the flowers of Spircea ulmaria,
and is the principal ingredient of the essential oil of that plant.
It is best obtained by oxidizing saliciri (q.v.).
It is a colorless oil ; turns red on exposure to air ; has an agree-
able, aromatic odor, and a sharp, burning taste ; sp. gr. 1.173 at
13°.5(56°.3F.); boils at 196°. 5 (385°. 7 F.) ; soluble in water, more
«o in alcohol and ether.
It is, as we should suspect from its origin, a substance of mixed
function, possessing the characteristic properties of aldehyde and
AROMATIC ACIDS. 413.
phenol. It produces a great number of derivatives, some of which
have the characters of salts and ethers.
Methyl-protocatechuic aldehyde — Vanillin — C6H3(OH)(OCH3)
COH — is the odoriferous, principle of vanilla. It is produced
artificially by oxidation of coniferin, Ci.H.jO,. a glucosid occur-
ring in coniferous plants. It crystallizes in needles, fuses at 80°
(176° F.) ; is sparingly soluble in water, readily soluble in alcohol
or ether. It has a pungent taste, and a faint odor of vanilla,
the latter more marked, when the substance is heated. On ex-
posure to air it becomes partially oxidized to vanillic acid C.H .O ;.
KETONES.
The ketones of this series are produced by the union of a ben-
zene nucleus with an alcoholic radical through a group (CO)" thus :
C6H5,CO,CH3. They are also called phenones.
Phenyl methyl ketone — Aceto-phenone — Hypnone — C6H6,CO,
CH3 — is obtained by distilling a mixture of calcium benzoate and
acetate ; or by the action of zinc-methyl upon benzoyl chlorid.
It forms large crystalline plates, fusible at 14° (57°. 2 F.). It has
been used as a hypnotic
ACIDS CORRESPONDING TO THE AROMATIC HYDRATES.
The acids possibly derivable from benzene by the substitution
of (COOH), or of (COOH) and (OH), for atoms of hydrogen, would
form, were they all known, a great number of series ; there are,
however, comparatively few of them which have been as yet
obtained, although the number of acid series known is greater
than that of corresponding alcohols. Each series of mono- and
diatomic alcohols furnishes a corresponding series of acids, thus :
r* ~u r<T4 r»TT r< TI /CHiOH f*, -rr /CH^OH
^«±l4xCHaOH ^«M4\OH
Benzole alcohol. Toluyl glycol. Saligenin.
CTT rT»nw r1 tr /COOH ^ TT /COOH
8 — \COOH \ OH
Benzole acid. Terephthalic acid. Salicylic acid.
By the progressive substitution of groups (COOH) for atoms of
hydrogen in benzene, we may obtain six series of acids, five of
which have been isolated :
C«HS(COOH) — CnH2n— sO3 Benzoic series.
C6H4(COOH)S— CnHw-ic^ Phthalic series.
C6H3(COOH)3— CnRim-nOs Trimellitic series.
C6H.,(COOH)4— CrtHan-i4O8 Prehnitic series.
C8H(COOH)5 — CnH2n-16Oio Wanting.
C6(COOH)S — CnK2H-,8Oi;i Mellitic series.
414 MANUAL OP CHEMISTRY.
There may also be three distinct series of bi- tri- and tetra- acids
produced by differences in orientation (see p. 397), according as
the groups COOH occupy consecutive, symmetrical or unsym-
metrical positions.
The alphenols, containing a single group (OH), are at present
represented by a single series :
C6H4(OH)(COOH)— CnH-m-sOa— Salicylic series.
Corresponding to unknown alphenols, containing a greater
number of (OH) groups, there are at present two series of acids
known :
C6H3(OH)!1(COOH)— CnHan-8O4— Veratric series,
and
C6H2(OH)3(COOH)—CnHan-8Os— Gallic series.
In each of these series the basicity is, as usual, equal to the
number of groups (COOH).
Benzole acid— Acidum benzoicum (TJ. S.)— C6H6(COOH) — 122 —
exists ready formed in benzoin, tolu balsam, castoreum, and
several resins. It does not exist in animal nature, so far as is at
present known ; in those situations in which it has been found,
it has resulted from decomposition of hippuric acid (g.u), or has
been introduced from without. When taken in moderate doses,
it does not pass out in its own form, but is converted into hip-
puric acid ; in excessive doses a portion is eliminated unchanged
in the urine. It is obtained from benzoin, or from the urine of
herbivorous animals ; and is formed in a variety of reactions.
It crystallizes in white, transparent plates ; odorless ; acid ;
fuses at 122° (251°.6 F.) ; sublimes at 145° (293° P.); boils at 240°
(464° F.) ; sparingly soluble in cold water ; soluble in hot water,
alcohol, and ether. Dilute HNO3 does not attack it. It dissolves
in ordinary HaSO4, and is precipitated unchanged by HaO. Its
salts are all soluble.
From it are produced many derivatives by the further substi-
tution of atoms or radicals for one or more of the atoms of H re-
maining in the C6H5 group.
Hippuric acid — Benzyl-glycocol — Benzyl-amido-acetic acid —
CH2,[NH(C«H6CO)],COOH— 179— is a constant constituent of the
urine of the herbivora, and of human urine to the extent of 0.29-
2.84 grams (4.5-43.8 grains) in 24 hours. It is more abundant with
a purely vegetable diet, after the administration of benzoic acid,
and in diabetes mellitus and chorea.
It crystallizes in transparent, colorless, odorless, bitter prisms ;
sparingly soluble in ; water ; fuses at 130° (266° F.). It dissolves
unchanged in HC1 ; but on boiling the solution it is decomposed
AROMATIC ACIDS. 415
into benzole acid and glycocol. The same decomposition is
effected by dilute H^SCN, HXO3, and oxalic acid, and by a fer-
ment developed in putrefying urine. Oxidizing agents convert
it into benzoic acid, benzauiid, and CO2.
The characters of hippuric acid are : (1) when heated in a dry
tube it fuses and gives off a sublimate of benzoic acid and an odor
of hydrocyanic acid ; (2) it gives a brown ppt. with ferric chlorid ;
(3) when heated with lime it gives off benzene and ammonia.
Salicylic acids — Oxybenzoic acids. — Three are known, ortho,
ineta and para. The Acidum salicylicum (U. S.), C6H4(OH)COOH,
is the ortho acid (1, 2)— 138. It was first obtained from essence of
spircea, which consists largely of salicylic aldehyde, and subse-
quently from oil of wintergreen (gaultherid), which contains
methyl salicylate, and also from salicin, a glucosid ; yielding sal-
icylic aldehyde. It is now obtained from phenol. This is fused,
and, while a current of dry CO2 is passed through it, small por-
tions of Na are added ; the sodium salicylate thus formed is dis-
solved in H2O and decomposed with HC1, when the liberated sal-
icylic acid is precipitated.
It crystallizes in fine white needles ; very sparingly soluble in
cold water, quite soluble in hot water, alcohol, and ether ; it fuses
at 158° (316°. 4 F.), and may be distilled with but slight decompo-
sition, if it be pure. Cl and Br form with it products of substi-
tution. Fuming HNO3 forms with it a nitro-derivative and, if
the action be prolonged, converts it into picric acid. With ferric
chlorid, its aqueous solution assumes a fine violet color.
The meta- and para- acids are obtained by fusing meta- or para-
chloro- bromo- or iodo-benzoic acid with KHO.
Salicylic acid and its salts (it is monobasic, although diatomic)
are extensively used in medicine, both externally as antiseptics
and internally in the treatment of rheumatism, etc. It is not
without caustic properties, and hence, when taken internally, it
should be largely diluted.
Phenyl salicylate— C6H4,OH,COO,CSH5 — has been used as an
antiseptic and antipyretic under the name salol. It is a white
crystalline powder, tasteless ; fusible at 42° (107°.4 F.) ; soluble in
H2O and in alcohol, ether and benzol. The corresponding ft
napht hoi (#.#.) compound, C6H4,OH,COO,C10H7, is a colorless, odor-
less, and tasteless substance, insoluble in H2O. It has been used
for the same purposes as salol under the names napthalol and
naphthol-salol.
Gallic acid — Acidum gallicum (U. S.) — C6H2(OH)3COOB[ — 170—
exists in nature in certain leaves, seeds, and fruits. It is best
obtained from gall-nuts, which contain its glucosid, gallotannic
acid (Q.V.). It can be obtained from salicylic acid.
It crystallizes in long silky needles with 1 Aq ; odorless ; acidu-
416 MANUAL OF CHEMISTRY.
lous in taste ; sparingly soluble in cold Avater, very soluble in hot
water and in alcohol ; its solutions are acid. When heated to
210°-215° (410°-419° F.) it yields CO2 and pyrogallol (q. v.). Its-
solution does not precipitate gelatin, nor the salts of the alkaloids,
as does tannin. It forms four series of salts.
SULFONIC ACIDS.
The sulfonic acids corresponding to the series CnH2n-6 are
derived from the hydrocarbons by the substitution of one or mor&
grdups (SO3H)' for one or more H atoms of the hydrocarbons.
They are produced by the action of fuming sulfuric acid upon
the hydrocarbons, and are mono-, bi- or polysubstituted, accord-
ing to the degree of concentration of the acid used, and the
temperature at which the action takes place. They are strong^
acids, forming soluble and crystalline salts. Their basicity varies
with the number of (SO3H) groups which they contain.
Benzo-monosulfonic acid — C6H6,SO3H— is formed by dissolving
benzene in weak fuming sulfuric acid at a slightly elevated tem-
perature, and diluting with H2O. It crystallizes in extremely
soluble, deliquescent plates with 1| Aq.
Three benzo-disulfonic acids — C6H4(SO3H)2 — ortho-, meta- and
para-, are known, also one benzo-trisulfonic acid — CeH3(SO3H)3.
Three tolu-sulfonic acids — C6H4CH3,SO3H — ortho-, meta-, and
para-, have been obtained. By the action of a mixture of ordi-
nary and fuming sulfuric acids upon toluene at a temperature
not exceeding 100° (212° F.), a mixture of the ortho- and para-
acids is produced. When this is treated with PC15, it is converted
into a mixture of para- and ortho-toluene sulfonic chlorids —
C,,H ,,CH: ,SO,.C1. The ortho-chlorid, when acted on by dry am-
monia and ammonium carbonate, is converted into ortho-toluene
sulfimid— Cf,H4,CH3,SO2NH2. This product, when oxidized by
potassium permanganate, is converted into benzyl-sulfonic
imid— C6H4,CO,SO2NH2 — or saccharin — an odorless, crystalline
powder, having great sweetening power, its sweet taste being
still detectable in a dilution of 1-50,000. Sparingly soluble in
water and in ether, readily in alcohol. Its solutions are acid in
reaction. When heated with Na2CO3 it is carbonized and gives
off an odor of benzene. It is not attacked by H2SO4.
Another series of sulfonic derivatives is obtained from the
phenols. Among them is :
Ortho-phenol sulfonic acid— Sozolic acid— Aseptol— C6H4,OH,
SO;H — which is prepared by the action of cold concentrated
H2SO4 upon phenol. It is a reddish, syrupy liquid, soluble in H2O
in all proportions, has a faint and not disagreeable odor. It pre-
NITRO-DERIVATIONS OF BENZENE. 417
vents fermentation and putrefaction, and is a non-poisonous,
non-irritant antiseptic. The salts of this and the corresponding
para- and meta-acids have been used as antiseptics and insecti-
cides, under the name of sulfo-carbolates, e.g., Sodii sulfo-carbo-
las (U. S.).
Salicyl sulfonic acid— C6H4,OH,COOH,SO3H— is a crystalline
solid formed by the action of strong H2SO4 on salicylic acid. It
is easily soluble in H2O. It has been recommended as a test for
albumin.
Diiodo phenol monosulfonic acid — C8H2l2,OH,SO3H — is used as
an antiseptic and astringent, in the form of its salts under the
name sozoiodol ; and Diiodo resorcin monosulfonic acid — C6
HI2,(OH)2(i-3),SO3H— is also used as an antiseptic having but slight
poisonous qualities, under the name picroL
NITRO-DERIVATIVES OF BENZENE.
By substitution of the univalent radical (NO2) for the hydro-
gen of benzene a series of substitution products are obtainable,
corresponding to the series of haloid derivatives, phenols, etc.
(see pp. 397-402).
Mono-nitro-benzene — Nitre-benzol — Nitre-benzene — Essence of
Mirbane — C6H5(NO2) — 123 — is obtained by the moderated action
of fuming HNO3, or of a mixture of HNO3 and H2SO4 on ben-
zene.
It is a yellow, sweet liquid, with an odor of bitter almonds ;
sp. gr. 1.209 at 15° (59° F.) ; boils at 213° (415°.4 F.) ; almost insol-
uble in water ; very soluble in alcohol and ether. Concentrated
H2SO4 dissolves, and, when boiling, decomposes it. Boiled with
fuming HNO3, it is converted into binitro-benzene. It is converted
into anilin by reducing agents.
It has been used in perfumery as artificial essence of bitter al-
monds ; but as inhalation of its vapor, even largely diluted with
air, causes headache, drowsiness, difficulty of respiration, cardiac
irregularity, loss of muscular power, convulsions, and coma, its
use for that purpose is to be condemned. Taken internally it is
an active poison.
Nitro-benzol may be distinguished from oil of bitter almonds
(benzoic aldehyde) by HaSO*, which does not color the former ;
and by the action of acetic acid and iron filings, which convert
nitro-benzene into anilin, whose presence is detected by the re-
actions for that substance (Q.V.).
27
418 MANUAL OF CHEMISTRY.
AMIDO-DEB-IVATIVES OF BENZENE.
These substances are derivable from benzene and its hoino-
logues by the substitution of one or more univalent groups (NH2)
(amidogen) for atoms of hydrogen. They may also be considered
as phenylamins, produced by the substitution of the univalent
radical phenyl (C6H5), or its homologues, derivable from the ben-
zene nucleus, for the hydrogen of ammonia. They all are strongly
basic in character.
Anilin — Amido-benzene — Amido-benzol — Phenylamin — Kyanol
C H )
—Cristallin — '6jj-5 - N — 93 — exists in small quantity in coal-tar
and is one of the products of the destructive distillation of indigo.
It is prepared by the reduction of iiitro-benzene by hydrogen :
C6H6(NO2) +3H2 = C6H5(NH2) + 2H2O ; the hydrogen being liber-
ated in the nascent state in contact with nitro-benzene by the
action of iron filings on acetic acid.
Pure anilin is a colorless liquid ; has a peculiar, aromatic odor,
•and an acrid, burning- taste ; sp. gr. 1.02 at 16° (60°. 8 F.) ; boils at
184°.8 (364°.6F.) ; crystallizes at -8° (17°.6 F.) ; soluble in 31 pts.
of cold water, soluble in all proportions in alcohol, ether, carbon
disulfid, etc. When exposed to air, it turns brown, the color of
the commercial "oil," and, finally, resinifies. It is neutral in re-
action. Oxidizing agents convert it into blue, violet, red, green,
or black derivatives. Cl, Br, and I act upon it violently to pro-
duce products of substitution. Concentrated H2SO4 converts it,
according to the conditions, into sulfanilic or disulfanilic acid.
With acids it unites, after the manner of the ammonia, without
liberation of H2O or H, to form salts, most of which are crystal-
lizable, soluble in water, and colorless, although by exposure to
air, especially if moist, they turn red. The sulfate has been used
medicinally. Potassium permanganate oxidizes it to nitro-ben-
zene. Heated with H2SO4 and glycerol it produces quinolin, and
substituted quinolins may be obtained by a similar reaction from
substituted anilins.
Anilin itself, when taken in the liquid form or by inhalation,
is an active poison, producing symptoms similar to those caused
by nitro-benzene (q.v.). Its salts, if pure, seem to have but slight
deleterious action.
Anilin may be recognized by the following reactions : (1.) With
a nitrate and H2SO4, a red color. (2.) Cold H2SO4 does not color
it alone ; on addition of potassium dichromate, a fine blue color is
produced, which, on dilution with water, passes to violet, and,
if not diluted, to black. (3.) With calcium hypochlorite, a violet
color. (4^ Heated with cupric chlorate, a black color. (5.)
Heated with mercuric chlorid, a deep crimson color. (6.) In very
DERIVATIVES OF AXILIN. 419
dilute solution (1 : 250,000), anilin gives a rose color with cblorid
of lime, followed by ammonium sulfhydrate.
Toluidins— C6H4(CH3)(NHo). — Three toluidins, ortho-, meta-
«.nd para-, are known as the superior homologues of anilin.
They occur in commercial anilin and play an important part in
the production of anilin colors.
Xylidins— Amido-xylenes— C6H3(CH3):j(NH2).— Six compounds
of this composition are known : two ortho-, derived from ortho-
^ylene, three meta-, derived from metaxylene, and one para-, de-
rived from paraxylene. Five of them exist in commercial xylidin.
The toluidins and xylidins yield products of substitution and
.addition similar to those of anilin.
Carbodiimids are substances having the general formula
in which R are two univalent radicals usually belonging to the
aromatic series. They are prepared from the sulfureids, by loss
of the elements of carbon oxysulfld, COS, by the action of heat
or of oxydants.
DERIVATIVES OF ANILIN.
By the substitution of other radicals or elements for the re-
maining hydrogen atoms of the benzene nucleus, or for the hy-
drogen atoms of the aiuidogen group, NH2, a great number of
-derivatives, including many isomeres, are produced.
In all of these derivatives the group (NHa) is considered as
occupying the position 1.
Chloranilins. — Three monochloranilins are known, of which
two, ortho- (1 — 2) and meta- (1 — 3), are liquid. The other, para-
{1 — 4), is solid and crystalline.
Four dichloranilins, 1—2 — 4, 1—2—5, 1—3—5, and 1—3 — 4, are
known, all solid and crystalline.
Two trichloranilins, 1 — 2 — 4—6 and 1—2 — 4 — 5, are known, both
solid and crystalline.
The corresponding bromanilins are also known ; also a tetra-
bromanilin, 1—2 — 3—4 — 6, and a pentabromanilin, C6(NHo)Br5.
Of the possible iodanilins, but four have been described : Meta-
moniodanilin (1 — 3) ; paramoniodanilin (1 — 4) ; the diiodanilin
(1—2—4) ; and the triiodanilin (1—2 4 6).
Nitranilins. — The three isomeres, ortho, meta-, and para-
mononitranilins, C6H4(NH2)(NO2), are formed by imperfect reduc-
tion of the dinitro-benzenes.
Two dinitranilins, CeHi(NH,XNO,), (1—2—4) and (1—2—6), are
known*.
A single trinitranilin, C.H^NHjXNOsJs (1—2—4—6), has been
obtained by the action of alcoholic ammonia upon the ethylic or
methylic ether of picric acid. It is also called picramid.
420 MANUAL OF CHEMISTRY.
Anilids. — These are compounds in which one of the H atoms of
the amidogen group has been replaced by an acid radical. Or
they may also be considered as amids, whose remaining hydrogen
has been more or less replaced by phenyl, C6H6.
Acetanilid— Antifebrin— Phenyl-acetamid— C6H6(NH, C2H3O)—
is obtained either by heating together anilin and glacial acetic
acid for several hours, or, better, by the action of acetyl chlorid
on anilin. It forms colorless, shining, crystalline scales ; fuses at
112°. 5 (234°.5 F.), and volatilizes unchanged at 295° (568° F.). It is-
sparingly soluble in cold water, soluble in hot water and in
alcohol.
When acetanilid is heated with an equal weight of ZnCl2,
flavanilin, a colored substance having a fine green fluorescence,
and soluble in warm dilute HC1, is produced.
By herbivorous animals acetanilid is eliminated as para-amido
phenol, C6H4,OH(1),NH2(4); by carnivorous animals partly in that
form, but mostly as orthoxy-carbanil, C,;H,.NO.COH.
By the further substitution of a group (CH3) in acetanilid,
methyl-acetanilid, or exalgine, C6H5,N,(CH3)C2H3O is produced.
It is formed by the action of methyl iodid upon sodium acetanilid,
C6H5,NNa,C2H3O. It is a crystalline solid, sparingly soluble in
H2O, readily in dilute alcohol. Its odor is faintly aromatic.
Three acettoluids, C6H4,CHs,NH,C2HsO, ortho, meta, and para,
are also known. The para- and meta- compounds seem to be
almost inert, while the ortho- compound is highly poisonous.
The "anilin dyes" now so extensively used, even those made
from anilin, are not compounds of anilin, but are salts of bases
formed from it, themselves colorless, called rosanilins (see p. 436).
Phenylamins— Phenylendiamins, etc. — Anilin is the simplest
representative of a large class of substances. It may be con-
sidered as benzene in which H has been replaced by NH2, thus:
C6HB,NH2. Its superior homologues, derivable from the supe-
rior homologues of benzene, each have at least three isomeres,
ortho-, meta- and para-, according to the orientation of the groups
NH2 and CnHan + i. Anilin may also be considered as ammonia in
which H has been replaced by phenyl, C6HB, thus being a primary
C1 TT )
monamin (see p. 274), ' b >• N. The remaining two H atoms may
be replaced by other radicals to form an almost infinite variety
of secondary and tertiary phenylamins, precisely as in the case
of the alcoholic monamins.
Again, it is clear that, considering anilin as amido-benzene, the
substitution of NH2 is not limited to the introduction of one such
group. There may be three phenylendiamins, C6H4(NH.j)2, or-
tho-, meta- and para-, three triamido benzenes, C6H3(NH2)3, etc^
AZO AND DIAZO DERIVATIVES. 421
"When it is remembered that each one of these compounds is
•capable of forming a large number of derivatives by further
substitution, and a series of salts, it is plain that the chemistry of
•these compounds would easily fill a volume.
HYDBAZINS.
The hydrazins are theoretically derivable from the group
H2N— NH2', diamidogen, by the substitution of acid, alcoholic,
•or phenylic radicals for one or more of the hydrogen atoms. They
may be primary, secondary, tertiary, or quaternary, as the sub-
stitution removes are two, three, or four of the H atoms. The sec-
ondary hydrazins may be symmetrical or unsyuimetrical, accord-
ing to the formulae RHN— N HR and R2N— NH2. They also form
compounds resembling the ammonium salts, known as azonium
compounds. In short, they play the part of compound ammonias.
The substituted groups may be acyclic as in ethyl-hydrazin,
CaHsHN — NH2, but in the majority it is a cyclic derivative as in
phenyl hydrazin.
These compounds are valuable reagents in synthetic chemis-
try. With the chlorids of the acid radicals they form amids;
they may produce compound ammonias; they form carbazic and
.sulfocarbazic acids with CO2 and CS2; by limited oxidation they
form tetrazones, substances having the formula R2N— N=N—
NR2, as the azo-compounds (see below) are produced from the
amins, etc. They also combine with ketones to form products of
•condensation.
Phenyl hydrazin— C6H5 — HN — NH2 — is obtained by the action
of zinc-dust and acetic acid on diazo-amidobenzene. It is a yellow
oil, sparingly soluble in v.'ater, soluble in alcohol and in ether,
possessed of strong reducing power, and acting as a jnonacid base
to form crystallized salts.
Phenyl-acetyl-hydrazin — Hydracetin— C6H5,HN— NH— C2H3O
— is produced by the action of acetyl chlorid, or of acetic anhy-
drid, upon phenyl hydrazin. It is a white, tasteless, odorless,
crystalline powder, sparingly soluble in H2O, readily soluble in
alcohol. It acts as a reducing agent. It is the active ingredient
in the antipyretic known as pyrodin.
AZO AND DIAZO DERIVATIVES.
The azo compounds are derivable from the aromatic hydrocar-
bons by loss of two H atoms from two molecules of the hydrocar-
bon, and union of the remainders through the intermediary of a
group ( — N = N — )". They are formed by the action of certain
reducing agents upon the nitro-derivatives, and may be considered
as intermediary products in the reduction of the nitro-derivatives
to amins. Thus in the case of benzene :
422
MANUAL OP CHEMISTRY.
Nitrobenzene.
r< TI -pj\
v^eHG — -Li \ f~\
Azoxybenzene.
CeHs— N/
Azobenzene.
H« =
+ Ha =
+
C8H6— N\n
C6H5— N/u
Azoxybenzene.
C6H5-]
C6H5NH\
CeHaNH/
Hydrazobenzene.
Azobenzene.
C6H6NH\
CeH6NH/'
Hydrazobenzene.
2[C6H(.(KH2)]
Anilin.
The diazo compounds consist of an univalent remainder of a»
aromatic hydrocarbon, united by the group ( — N = N — ) with a
haloid atom, or an acid residue : C6H6 — N = N — Br = Diazoberi-
zene bromid.
Phosphins, Stibins and Arsins. — As among the acyclic com-
pounds (see p. 299), there exist substances in which P, Sb, or As
takes the place of N, so among the cyclic derivatives there are
similar derivatives. Thus diphosphenyl — C6H5P=PC6H5, corre-
sponding to diazobenzene, C6H&N = NCeH6 ; Phenylphosphin —
CeHsPHs, corresponding to anilin, C6H6NHa; Triphenylstibin —
(C6H6)3Sb, and Triphenylarsin — (CeH6)3As, corresponding to tri-
methylamin, (CH3)sN.
PYRIDIN BASES.
These interesting substances, closely related to the vegetable
alkaloids, as well as to some of the alkaloids produced during
purtrefactive decomposition of animal matters, were first discov-
ered in 1846, as constituents of oil of Dippel = oleum animale =
oleum cornu cervi = bone-oil, an oil produced during the dry
distillation of bones, horns, etc., and as a by-product in the
manufacture of arnmoniacal compounds from those sources. They
also occur in coal-tar, naphtha, and in commercial ammonia,
methylic spirit, and fusel oil.
The pyridin bases at present known are :
Formula. Boiling-point. Sp.gr. at 22".
Pyridin C6H8N il5° 0.924
Picolin C9H7N 134° 0.933
Lutidin C7H8N 154° 0.945
Collidin C8H,,N 170° 0.953
Parvolin C9H13]Sr 188° 0.966
Coridin C10H16N 211° 0.974
Rubidin C,,H17N 230° 1.017
Viridin C]2H1SN 251° 1.024
It will be observed that these compounds are metameric with
PYRIDIN BASES. 423
the anilins, from which they differ in constitution, as shown by
the structural formulae of picolin and anilin :
NH, CH,
C C
/\ /\
H— C C— H H— C C— H
H-C C-H H-C C-H
V XN
C9H,N C,H7N
Anilin. Picolin.
They are all liquid at the ordinary temperature, behave as
tertiary monamins, react with several of the general reagents of
the alkaloids, and form chloroplatinates which are decomposed
by boiling water.
Pyridin — HC^r,TT~r,Tr^N — is obtained from oil of Dippel. It
^\ wXi. — v Jl #
is obtainable synthetically from piperidin, which is itself a de-
rivative of piperin, a constituent of black and white pepper (see
below); and also by the action of sodium in the presence of
methylene iodid, upon pyrrol (q. v.), as well as by other reactions.
It is a colorless, mobile liquid, having a peculiar, very pene-
trating odor. It boils at 115° (239° F.). It mixes with water in
all proportions. It is strongly alkaline, and combines with acids
as does NH3. Like all the bases of this series, it is very stable,
and withstands the action of such oxidizing agents as fuming
HNO3 and chromic acid. It forms crystalline salts.
PRODUCTS OF SUBSTITUTION OF PYRIDIN.
The products of substitution of pyridin, among which may be
included its superior homologues, are very numerous, and, by
reason of the introduction of the N atom in the benzene-chain,
form a greater number of isomeres tha,n are possible with the
symmetrical unaltered benzene-chain. Thus, while there is but
one monosubstituted derivative of the same univalent element or
radical in the case of benzene, there are three possible in the case
of pyridin, according as the substitution occurs in one of the
« or in a /3, or in the y position with reference to the N atom,
thus: y
C
(a')C C(a)
V/
N
424 MANUAL OF CHEMISTRY.
There are six each of bi- and tri-substituted derivatives, three
tetra-substituted derivatives and one penta-substituted. Fur-
ther, the double bonds with the chain may also be liberated, thus
forming a nucleus possessed of eleven in place of six valences,
such as exists in piperidin and its derivatives (see p. 425).
HOMOLOGATES OF PYRIDXN.
Picolins — C5H4N(CH3). — As pointed out above three picolins, a,
ft, and y are known, all of which exist in oil of Dippel and have
been produced synthetically.
Lutidins. — Theoretically there are three possible ethyl-pyridins,
C6H4N(C2H5), and six possible dimethyl-pyridins, C6H3N(CH3)2.
The former are all known, and three of the latter.
Collidins — C-HMN. — There are twenty-two possible collidins,
of which twelve are known. Of these several are the products
of decomposition of vegetable alkaloids, or are basic substances
existing in oil of Dippel, or formed during putrefactive changes.
Conyrin. — A basic substance produced by distilling coniln with
zinc chlorid, is a propyl pyridin. ft propyl pyridin is produced
from nicotin by passing its vapor through a red-hot tube. ,Two
isomeric collidins, probably methyl ethyl pyridins, are formed
by the action of fused KHO on cinchonin.
Aldehydin is a collidin of unknown constitution, formed by
heating aldehyde-ammonia in alcoholic solution to 120° (248° P.),
and by several other reactions, and exists also in the products of
rectification of alcohol. An oily ptomain product during the
putrefaction of gelatin in the presence of pancreas is a collidin of
undetermined constitution.
Parvolins — C9H]3N. — Theory indicates the existence of 57 par-
volins, of which five are known. One of these is a ptomain pro-
duced during the decomposition of mackerel and of horse-flesh.
It is an oily substance, slightly soluble in HaO, which, when
fresh, has an odor of hawthorn blossoms, but on exposure to
air becomes brown and resinous.
One of the coridins, Ci0Hi6N, has been obtained as a product of
putrefaction of fibrin and of jelly-fish during several months. It
is an alkaline oil, which has a poisonous action resembling that
of curara.
The pyridin bases exert a paralyzing action upon the central,
and to a less degree upon the peripheral, nervous system. They
are the antagonists of strychnin.
CARBOPYRIDIC ACIDS — PIPERIDIX. 425
CARBOPYRIDIC ACIDS.
These acids are derived from pyridin, in the same manner as
the benzoic and other series are derived from benzene (p. 413), by
the substitution of COOH for H, but differ from those acids in
presenting a greater number of isorueres.
Monocarbopyridic acids — C5H4N(COOH). — Three isoineric acids
having this composition corresponding to the three picolins
<p. 424) are known. The a acid, picolic acid, is a crystalline solid,
formed by oxidation of the corresponding picolin. The /3 acid,
nicotic acid, is formed by the oxidation of nicotin, of pilocarpin,
and of many artificial pyridin derivatives. The y acid, isonicotic
acid, is formed during the oxidation of many pyridin derivatives.
Dicarbopyridic acids — CpH3N(COOH)2. — The six acids whose ex-
istence is indicated by theory are all known. Among them are
quinolinic acid, formed by the oxidation of quinolin, and cin-
chomeric acid, produced by the oxidation of cinchonin, cinchoni-
•din or quinin.
PIPEBIDIN AND BELATED ALKALOIDS.
The researches made in recent years concerning the constitu-
tion of the vegetable alkaloids have proved that, with a few ex-
ceptions, they are derivatives either of a more or less modified
pyridin, or of quinolin, itself an addition product of pyridin and
benzene (see p. 447); and that many of the alkaloids may be con-
sidered as made up of a basic substance containing all the nitro-
gen of the alkaloid, a more or less modified pyridin or quinolin,
with a substance which is either an acid or a neutral substance.
The alkaloids of this class which are the most simple in constitu-
tion are those derived from :
Piperidin — CsHnN— which is a product of the action of KHO on
piperin (see below), and may also be obtained from pyridin by
the action of reducing agents, such as Sn+HCl. It is a colorless
liquid, having a strongly alkaline reaction and an ammoniacal
odor. When heated with methyl iodid it is converted into
methyl-piperidin. The composition of piperidin and its formation
from pyridin by reduction, as well as the fact that, on treatment
with silver oxid. it produces pyridin, prove it to be hexa hydro-
pyridin, or pyridin whose bonds have been released and satisfied
by hydrogen atoms (see below).
Coniin — C6H,,N — is the most simply constituted of the natural
vegetable alkaloids, and was the first to be produced by synthe-
sis. It exists in Conium maculatum, in which it is accompanied
by two other alkaloids, methyl-comin, CfS.t6N(CH.3), and con-
hydrin, C;,H17NO — the former a volatile liquid, the second a crys-
talline solid.
426 MANUAL OF CHEMISTRY.
Coniln is a colorless, oily liquid; has an acrid taste and a dis-
agreeable penetrating odor; sp. gr. 0.878; can be distilled when
protected from air; boils at 212° (413°. 6 F.) ; exposed to air it resin-
ifles ; it is very sparingly soluble in water, but is more soluble in
cold than in hot water ; soluble in all proportions in alcohol, sol-
uble in six volumes of ether, very soluble in fixed and volatile
oils.
The vapor which it gives off at ordinary temperatures forms a
white cloud when it comes in contact with a glass rod moistened
with HC1, as does NH3. It forms salts which crystallize with
difficulty. Cl and Br combine with it to form crystallizable com-
pounds; I in alcoholic solution forms a brown precipitate in
alcoholic solutions of conii'n, which is soluble without color in an
excess. Oxidizing agents attack it with production of butyric
acid (see below). The iodids of ethyl and methyl combine with
it to form iodids of ethyl- and methyl-coniln.
It has been obtained synthetically from a picolin by reactions
which show it to be a propyl piperidin. The relations of py-
ridin, piperidin, and coniln are shown by the following formulae t,
H H2 H2
c c c
/\ /\ /\
HC CH H2C CH2 H2C CH,
II I II II
HC CH H2C CH-, H3C CHCSH,
\7 \/ \/
N N N
H H
Pyridin. Piperidin. Coniln.
ANALYTICAL CHARACTERS.— (1.) With dry HC1 gas it turns
reddish-purple, and then dark blue. (2.) Aqueous HC1 of sp.
gr. 1.12 evaporated from conii'n leaves a green-blue, crystalline
mass. (3.) With iodic acid a white ppt. from alcoholic solutions.
(4.) With H2SO4 and evaporation of the acid : a red color,
changing to green, and an odor of butyric acid. (5.) When mixed,
with commercial nitrobenzene a fine blue color is produced,,
changing to red and yellow.
Paraconiin — C8Hi5N — is a synthetical product closely resem-
bling conii'n, obtained by first allowing butyric aldehyde and an
alcoholic solution of ammonia to remain some months in con-
tact at 30° (86° F.), when dibutyraldin is formed :
2(C4H8O) + NH3 = C8H17NO -f H,O
Butyric aldehyde. Ammonia. Dibutyraldin. Water.
The dibutyraldin thus obtained is then heated under pressure
to 150°-180° (302°-356° F.), when it loses water:
C8H1TNO = C8H15N + H20
Dibutyraldin. Paraconii'n Water.
PIPERIDIX AND RELATED ALKALOIDS.
A synthesis which, in connection with the decompositions of
(C«HT)' )
paraconiln, shows its rational formula to be (C4H7)' > ft.
H J
Atropin— Atropina (U. S.) — Atropia (Br.)— C^S.,3NO3.— Bella-
donna, stramonium, hyoscyamus, and duboisia contain five al-
kaloids : Atropin, hyoscyamin, hyoscin, belladonin, and daturin.
The first three are isoiueric with each other and the first two
possibly identical. The last two have been imperfectly studied.
Atropin forms colorless, silky needles, which are sparingly sol-
uble in cold water, more readily soluble in hot water, very soluble
in chloroform. It is odorless, but has a disagreeable, persistent,
bitter taste. It is distinctly alkaline, and neutralizes acids with
formation of salts. One of these, the sulfate — Atropinse sulphas,
TJ. S. — is a white, crystalline powder, readily soluble in water,
which is the form in which atropin is usually administered.
TOXICOLOGY. — It is actively poisonous, producing drowsiness,
dryness of the mouth and throat, dilatation of the pupils, loss of
speech, diplopia, dizziness, delirium, coma.
The treatment should consist in the administration of emetics
and the use of the stomach-pump.
ANALYTICAL CHARACTERS. — (1.) If a fragment of potassium
dichromate be dissolved in a few drops of H2SO4, the mixture
warmed, a fragment of atropin and a drop or two of H2O added,
and the mixture stirred, an odor of orange-blossoms is developed.
(2.) A solution of atropin dropped upon the eye of a cat produces
dilatation of the pupil. (3.) The dry alkaloid (or salt) is moist-
ened with fuming HNO3 and the mixture dried on the water-
bath. When cold it is moistened with an alcoholic solution of
KHO — a violet color which changes to red (Vitali). (4.) If a
saturated solution of Br in HBr be added to a solution of atropin
a yellow precipitate is formed which rapidly becomes crystalline,
and which is insoluble in acetic acid, sparingly soluble in H2SO*
and HC1.
CONSTITUTION. — If atropin is acted upon by baryta at 60" (140°
P.), or by caustic soda, or hydrochloric acid at 120°-130° (248°-266c>
F.) it is saponified, after the manner of an ether, into tropin and
tropic acid, according to the equation :
C17H23NO3 + H2O = C8H15NO -f- C9H10O3
Atropin. Tropin. Tropic acid.
but if the action of the reagents be prolonged tropic acid loses
H2O and produces a mixture of atropic acid, C9Hi.O.2, and isatropic
acid, C!.H,,O;. And if, during the action of HC1, the tempera-
ture rises to 180° (356° F.) the tropin also loses H»O and is con-
verted into tropidin, C-H^N.
428 MANUAL OF CHEMISTRY.
The relations of these bodies to each other and to piperidin are
•expressed by the following formulae :
H2 Ha H2
c c c
/\ /\ /\
H2C CHa H2C CH3 . H2C CH-CH
II II I I II
H2C CHa H2O CH2 H2O OH — OH
\/ \/ \/
N N N
H CHs CHs
Piperidin. Methyl-piperidin. Tropidin.
Ha H2
C C CeHs
/\ /\ I
H2C CH-CHOH H2C CH-CH. O.CO-CH
III III I
H2C CH-CH, H2C CH-CH CHaOH
\/ \/
N N
OHs OHs
Tropin. Atropin.
and atropin may be considered as formed by the union of tropin
with tropic acid, C«H6— CH^JJ^1, with loss of H2O. *
Tropin— C8H1BNO— is a crystalline solid, fusible at 62° (143°. 6 F.),
very soluble in water. It reacts with methyl iodid to produce a
methyltropin. Tropin has the poisonous qualities ot atropin,
but does not dilate the pupil.
Tropidin — CeHi3N— is a liquid having the odor of coniln, which
it also resembles in being more soluble in cold than in hot H2O. Its
bromid heated with excess of Br produces methyl dibromopyridin,
C5H2N (Br)2CH3, whose formation shows that it and its deriva-
tives, tropin and atropin, are derivatives of pyridin.
Tropeins are substances produced synthetically, as atropin is
produced from tropin and tropic acid, by the union of tropin
with other organic acids, such as benzoic, salicylic, etc.
Piperin — CnH19N03 — an alkaloid of black and white pepper,
and isomeric with morphin, is constituted somewhat similarly to
atropin. On saponiflcation by alcoholic soda it yields piperidin
{see above) and an acid, piperic acid, Ci2Hi0O4, whose constitution,
although partially known, is not completely established.
Piperin is a very feeble base, without alkaline reaction, insolu-
ble in dilute acids and only forming very unstable salts with con-
centrated acids. It crystallizes in monoclinic prisms.
Cocain — C17H2iNO4 — is another alkaloid of ethereal constitution,
containing a modified methyl-piperidin nucleus, whose consti-
tution is only partially known. It crystallizes in large, six-sided
OTHER SUBSTITUTED BENZENES. 429
prisms. Its taste is at first bitter, producing paralysis of the sense
of taste subsequently. It is strongly alkaline. Its chlorid, ex-
tensively used for the production of local anaesthesia, crystallizes
in well-formed prismatic needles, readily soluble in water.
When boiled with H2O it is saponified into benzyl-ecgonin, C,6
H NO,, and methylic alcohol. If the saponification be effected
by baryta or by concentrated mineral acids the decomposition is
more complete and ecgomn, C9H15N03, benzoic acid and methyl
alcohol are formed. Cocain may also be regenerated by acting
upon ecgonin with a mixture of methyl iodid and benzoic anhy-
drid, and, by substituting other alcoholic iodids for that of methyl,
other alkaloids homologous with cocain may be obtained. Ecgo-
nin not only combines with bases to form salts, but also with an-
hydrids to produce ethers. It is, therefore, both acid and basic
in character, and yields numerous products of derivation besides
cocain.
Besides cocain and benzyl-ecgonin, the leaves of erythroxy-
lon coca contain another alkaloid, hygrin, a very alkaline liquid
having an odor resembling that of trimethylamin.
ANALYTICAL CHARACTERS. — The reactions of cocain are not
very marked. (1.) Picric acid forms a yellow ppt. in concentrated
solutions. (2.) A solution of iodin in KI solution gives a fine red
precipitate in a solution containing 1 to 10,000 of cocain. (3.)
When cocain or one of its salts, dried at 100° (212° F.), is moistened
with fuming HNO3, evaporated to dryness, and the residue taken
up with alcoholic solution of KHO, a strong odor resembling
that of peppermint is developed, due to the formation of ethyl
benzoate.
Pilocarpin — CnH16N2O2 — occurs in jaborandi, along with two
other alkaloids, jaborin, C-H^NiOi (?), and pilocarpidin, doHn
N2O2, and an essential oil, consisting principally of pilocarpene,
CloH]6.
Pilocarpin is colorless, crystalline, readily soluble in water,
alcohol, ether, and chloroform. It is converted by heat into
jaborin; and by HNO3 or HC1 into a mixture of jaborin and jabo-
randin, CioH^NsOa. Like atropin, piperin, etc., it is ethereal in
constitution and is decomposed by KHO or NaHO into COa,
methylamin, butyric acid, and pyridin bases.
COMPOUNDS OF OTHER SUBSTITUTED BENZENES.
Pyridin is the simplest product which may be considered as
derived from benzene by the substitution 'of N for CH. Other
substances are known in which a further substitution of N has
more deeply modified the nucleus. Thus there exist three dia-
zins, a, [3, and y, containing two nitrogen atoms in the nucleus,
430 MANUAL OF CHEMISTRY.
two triazins, /3/3' and a/3, containing three, and one tetrazin, n/3y,
containing four.
The benzene nucleus may also be modified by the substitution
of oxygen, or of sulfur, producing compounds such as the fol-
lowing:
O O S
/\ /\ /\
HC CH2 HC CH HC CH
II I II II II II
HC CH HC CH HC CH
\/ \/ \/
c c c
H Ha H2
<x Furane. y Furane. y Thiane.
/CTT CH\
Pyrone (7)— Pyrocomane— °\CH=CH/CO~ is an oxidized de-
rivative of 7 furane, produced from comenic acid by the action of
heat and constituting the nucleus of couianic, chelidonic, and
meconic acids.
Comenic acid — C5H3O2(COOH) — is produced by the action of hot
H2O, of dilute acids, or of bromin water upon meconic acid. It
crystallizes in yellowish prisms, rather soluble in H2O. It is
monobasic. It is decomposed by heat into CO2 and pyrone.
Chelidonic acid — C5H2O2(OH)COOH — exists in chelidonium, in
combination with the alkaloids sanguinarin and chelidonin. It
is a crystalline solid, and a dibasic acid. Heat converts it into
comenic acid, which in turn yields pyrone.
Meconic acid — C5HO2(OH)(COOH)2 — is peculiar to opium, in
which it exists in combination with a part, at least, of the alka-
loids. It crystallizes in small prismatic needles; acid and astrin-
gent in taste; loses its Aq at 120° (248° F.); quite soluble in
water; soluble in alcohol; sparingly soluble in ether.
With ferric chlorid it forms a blood-red color, which is not dis-
charged by dilute acids or by mercuric chlorid ; but is discharged
by stannous chlorid and by the alkaline hypochlorites.
COMPOUNDS WITH PENTAGONAL NUCLEI.
CONDENSATION PRODUCTS OF BENZENE.
These compounds differ from the benzene derivatives in con-
taining pentagonal in place of hexagonal nuclei ; thus :
H
CON
/\ /\ /\
HC CH HC CH HC CH
II I II II II I
HC CH HC CH HC CH
\/ \/ \/
c c c
H Ha H
JJenzene. Furane. Pyridin.
COMPOUNDS WITH PENTAGONAL NUCLEI. 431
H, H
CON
/\ /\ /\
HC CH HC CH HC CH
II II . II II II II
HC-CH HC-CH HC-CH
Valylene. Furfuran. Pyrrol.
Furfuran — C4H4O — is a product of the distillation of fir-wood,
and is also formed from dehydrofurfuran, C4H6O, obtained from
erythrite.
Furfurol — Furfuraldehyde — C4H3O. CHO — was the earliest
known of the series. It is produced by the dry distillation of
sugar or of wood, or by the action of ZnCla or dilute H2SO4 on
bran. It is a colorless liquid, has an agreeable odor, boils at 162°
(323°. 6 F.), is soluble in water and in alcohol. Being an aldehyde
it undergoes the reactions common to those substances. With
urea and a trace of acid it develops a beautiful violet color, which
disappears after a time, while an insoluble, black, flocculent pre-
cipitate is formed.
/CH=CH
Pyrrol — HN ( • — accompanies the pyridin bases in oil
\Cjtl=v/.fci.
of Dippel, and is formed in a variety of reactions ; by the action
of baryta at 150° (303° F.) upon albumen ; by the dry distillation
of gelatin or of ammonium saccharate, etc.
It is a colorless, oily liquid, having the odor of chloroform. By
acting upon pyrrol with an ethereal solution of iodin, a quadri-
substituted derivative, tetriodopyrrol, C4HI4N, is obtained as
a brown powder, which has been used under the name iodol as a
substitute for iodoform in surgical practice.
The molecule of pyrrol may be further modified by the intro-
duction of further N atoms to produce :
H H H
N N N
/\ /\ /\
N«CH a'NaCH N N
II II II II II II
HC-CH £'N-CH N-CH
ft ft
a. Pyrazol. a /3 Pyrrodiazol. Pyrrotriazol.
and there may be two pyrazols, a and /?, and four pyrrodiazols,
a/3, a'/?, aa1, /3/3', varying according to the position of the N atoms.
As other substances may also be produced by substitution for
the hydrogen atoms or by liberation of the double bonds, the
pyrrol derivatives are very numerous. Among them is :
Antipyrin = Phenyl-dimethyl-pyrazolon — Ci iHi 2N2O — is ob-
tained by heating phenyl-methyl-pyrazolon with methyl iodid
and methyl alcohol in sealed vessels at 100° (212° F.); the first-
432 MANUAL OF CHEMISTRY.
named substance having been previously obtained by the action
by acetylacetic ether upon phenyl hydrazin.
The constitution and relations of antipyrin are shown by the
following formulae :
H H C6H5
N N N
/\ /\ /\
N CH . N CH CH3-N C— CH3
II II I II I II
HC-CH OC-CH OC-CH
a Pyrazol. Pyrazolon. Phenyl-dimethyl-pyrazolon,
antipyrin.
It constitutes a voluminous, reddish, crystalline powder ; read-
ily soluble in water, ether, alcohol, and chloroform. With nitroua
acid, or the nitrites (sp. seth. nitr.) in the presence of free acids, it
forms a green, crystalline, sparingly soluble nitro-derivative which
seems to be poisonous.
Its solution with Fe2Cl6 is colored deep red-brown, the color
being discharged by HsSCh. Nitrous acid colors dilute solutions
of antipyrin a bright green, which persists for several days at the
ordinary temperature. If the mixture be heated, and a drop of
fuming HNO3 added, the color changes to light red, then blood-
red, and the liquid deposits a purple oil on continued heating.
Addition of a drop of fuming HNO3 to a cold concentrated solu-
tion of antipyrin produces precipitation of small green crystals.
INCOMPLETE BENZENIC HYDROCARBONS.
SERIES OVHan-8 AND CnH2n— 10.
These may be considered as benzenic compounds which have
been rendered incomplete by loss of H2, either in the benzene
nucleus or in a lateral chain. Thus while ethylbenzerie is pro-
duced by the addition of a molecule of ethylene to a molecule of
benzene : C6H6,H + CH2,CH2 = C6H5,CH2,CH3 ; if acetylene be
substituted for ethylene, ethyl enbenzene is formed : C6H5,H +
OH, OH = CeH5,OH,CH2.
Styrolene — Cin.nam.ene — Ethylenbenzene — Phenylethene— C6H&
— CH = CH2 — 104 — exists ready formed in essential oil of styrax.
It is also formed by decomposition of cinnainic acid (<?.•«.), or, syn-
thetically, by the action of a red heat upon pure acetylene, a
mixture of acetylene and benzene, or a mixture of benzene and
ethylene. It is a colorless liquid, has a penetrating odor, recall-
ing those of benzene and naphthalene, and a peppery taste ; boils
at 143° (289°. 4 P.) ; soluble in all proportions in alcohol and water ;
neutral in reaction.
ALCOHOLS. 433
Phenyl-acetylene— Acetenyl-benzene — C6H5.C=CH— is formed
by heating acetophenone chloric! with KHO in alcoholic solution.
It is a colorless liquid, of an aromatic odor, boils at 140° (284° F.).
ALCOHOLS.
SERIKS CnH2n— 8O.
Cholesteric alcohol — Cholesterin — C26H43OH — 372 — is an alcohol,
although usually classed by physiologists among the fats, because
it is greasy to the touch and soluble in ether.
It occurs in the animal econornj', normally in the bile, blood
(especially that coming from the brain), nerve-tissue, brain.spleen,
sebum, contents of the intestines, rneconium, and faeces ; patho-
logically in biliary calculi, in the urine in diabetes and icterus,
in the fluids of ascites, hydrocele, etc., in tubercular and cancer-
ous deposits, in cataracts, in atheromatous degenerations, and
sometimes in masses of considerable size, in cerebral tumors. It
also exists in the vegetable world in peas, beans, olive-oil, wheat,
etc. It is best obtained from biliary calculi, the lighter-colored
varieties of which consist almost entirely of this substance.
Cholesterin crystallizes with or without Aq ; from benzene, pe-
troleum, chloroform or anhydrous ether, it separates in delicate,
colorless, silky needles, having the composition C28H44O ; from
hot alcohol, or a mixture of alcohol and ether, it crystallizes in
rhombic plates, usually with one obtuse angle wanting, having
the composition C26H44O + 1 Aq ; these crystals, transparent at
first, become opaque on exposure to air, from loss of Aq. It is
insoluble in water, in alkalies and dilute acids, difficultly soluble
in cold alcohol, readily soluble in hot alcohol, ether, benzene,
acetic acid, glycerol, and solutions of the biliary acids. It is
odorless and tasteless. When anhydrous it fuses at 145° (293° P.)
and solidifies at 137° (278°.6 F.) ; sp. gr. 1.046. It is laevogyrous,
[a]D = 31°. 6 in any solvent.
It combines readily with the volatile fatty acids. From its so-
lution in glacial acetic acid a compound having the composition
CseH44O,C2H4O:i separates in fine curved crystals, which are de-
composed on contact with water or alcohol ; when heated with
acids under pressure, it forms true ethers. Hot HNO3 oxidizes it
to cholesteric acid, C(,H10OS, which is also produced by the oxida-
tion of biliary acids ; a fact which indicates the probable exist-
ence of some relation between the methods of formation of cho-
lesterin and of the biliary acids in the economy.
Cholesterin may be recognized by the following reactions : (1.)
Moistened with HNO3, and evaporated to dryness, a yellow resi-
due remains, which turns brick-red on addition of NH4HO. (2.)
It is colored violet when a mixture of 2 vols. H2SO< (or HC1) and
28
434 MANUAL OF CHEMISTRY.
1 vol. ferric chlorid solution is evaporated upon it. (3.) When
H2SO4 is added to a CHC13 solution of cholesterin the liquid is
colored purple-red, changing during evaporation to blue, green
and yellow.
Cholesterin is accompanied in wool fat by an isomere, isocho-
lesterin.
Cholesterin combines with the fatty acids to form ethers, cor-
responding to the fats, and it probably exists in nature largely in
such combination. Lanolin is a neutral, fatty body consisting of
such cholesterids, or cholesterin ethei's, obtained from suint, or
wool fat. It is used as a vehicle in pharmacy, possessing two
advantages over the fats and over vaseline : it is rapidly absorbed
by the skin, and is iniscible with water in all proportions.
BI- AND POLYBENZOIC HYDROCARBONS.
Among the compounds already considered are several contain-
ing more than one benzene nucleus, but in them the union of the
two nuclei, as in the azo compounds, is through an element other
than carbon. In the compounds now to be considered two or
more benzene nuclei are united with each other, either directly,
or through the carbon of a linking lateral chain.
HYDROCARBONS WITH INDIRECTLY UNITED BENZENE
NUCLEI.
The simplest of the bi- and polybenzoic hydrocarbons are those
in which two or more benzene nuclei are combined with a linking
lateral chain. By the substitution of phenyl for the H of
methane four compounds can be produced :
Monophenylmethane. Triphenylmethane.
Toluene.
Diphenylmethane. Tetraphenylmethane.
Of these the first has been already considered, and the fourth
has not been isolated, although the corresponding ethane is
known.
Diphenylmethane — Benzyl-benzene — is produced by the action
of aluminium chlorid upon a mixture of benzyl chlorid and ben-
zene. It is a crystalline solid, fuses at 27° (80°. 6 F.) and boils at
262° (503°. 6 F.) ; soluble in alcohol, ether and chloroform ; has
an odor resembling that of the orange.
DERIVATIVES OF THE PHENYLMETHANES. 435
Triphenylmethane — is produced by the action of aluminium
•chlorid upon a mixture of benzene and chloroform. It is a
crystalline solid, fuses at 92° (197°.6 R); boils at 360° (680° F.) ;
soluble in ether, and in chloroform. It is converted into a tri-
nitro derivative by fuming HXO3, and this, in turn, is con verted
by nascent H into leuco-pararosanilin, CH,(C6H4,NH2)3 (see
below).
DERIVATIVES OF THE PHENTHLMETHANES.
Ketones — CO = (CnH2n— 7)2. — These substances are similar to the
phenones already described, but contain two benzene nuclei in
place of one. They are produced by the oxidation of the hydro-
carbons CnH2n— 14 ; by the action of P2O5 on a mixture of a
hydrocarbon CnHan— « with an acid CnH2n— 7CO,OH ; and by the
action of carbon oxychlorid upon a hydrocarbon CnH;m— e in the
presence of Al2Cle.
Benzophenone — Diphenyl-ketone — CO = (C«Hs)a — forms large
rhombic prisms ; fuses at 48° (118°. 4 F.) ; boils at 305D (581° F.) ;
insoluble in H2O, soluble in alcohol and ether. It is decomposed
by soda-lime into benzene and benzoic acid. Sodium amalgam
converts it into benzhydrol, or diphenylcarbinol, CH(OH) =
(C6H5)2, a secondary alcohol.
Amido-derivatives. — Among these substances are included some
of great industrial interest. Many of the bases, whose salts are
the brilliant pigments obtained from anilin and its homologues,
are amido-derivatives of triphenylmethane.
Amido-triphenylmethane — CH,(C6H6):,(C6H4NH!,) — is formed by
the action of benzhydrol upon anilin chlorid in the presence of
ZnCl3.
Diamido-triphenylmethane — CH,(C6H5)(C8H4,NH2)a — is pro-
duced by the action of anilin chlorid and benzoic aldehyde upon
each other in the presence of ZnClj. The salts of this base are
blue, and are decomposed by alkalies with liberation of the base,
which is a yellow, imperfectly crystalline solid, insoluble in
'water, soluble in benzene and in alcohol.
The base is converted by HgCl2 into the corresponding tertiary
alcohol, diamido-triphenyl carbinol, C(OH),(C6HB),(CsH4,NHj)»,
whose oxalate or chloro-zincate is malachite green.
Triamido-triphenylmethane — CH(C6H4.NH»)3— may be obtained
by the reduction of para-nitrobenzoic aldehyde by nascent hydro-
gen, and is also known as paraleucanilin. By the action of oxi-
dizing agents it is converted into a tertiary alcohol, pararosanilin,
or triamido-triphenyl carbinol, which is the type of quite a
number of important bodies, among which is rosanilin, or di-
436 MANUAL OF CHEMISTRY.
phenyltoluyl carbinol, whose chlorid or acetate is the brilliant
red dye known as anilin red, magenta, fuchsine. The relation
of these bodies to each other is shown by the following formulae :
/CeH5 /Ce
H— C— C6H5 H— O— C— CeHB.NH,
\C6H5 \C6H5,NEU
Triphenylmethane. Triamidophenyl carbinol.
Pararosanilin.
/C6H4,NH!1 ' /C6H6,NH2
H— C— CsH^NH,, H— O— C— C6H5,NH2
\C6H4,NH2 \C6H4,CH3,NHa
Triamidophenylmethane. Diamidophenyl amidptoluyl carbinol.
Paraleucanilin. Rosauilin.
The rosanilins are powerful triacid bases, are colorless, but
combine with acids to form brilliantly colored salts. Fuchsine
is industrially obtained from " anilin oil," which contains both
anilin and toluidin, neither of which in the pure state will pro-
duce a red color. The process consists essentially in heating the
oil with a mixture of nitro-benzene, hydrochloric acid and iron
filings. The product is a mixture of the chlorids of rosanilin and
pararosanilin, is in hard, green crystals, soluble in water and al-
oohol, to which it communicates a brilliant red color.
The rosanilins are capable of further modification by the sub-
stitution of various radicals for the hydrogen atoms in the ben-
zene nuclei, or in the groups NH2, and by variations in the posi-
tions in which such substitution occurs.
Hoffman's violet, obtained by heating rosanilin chlorid with.
methyl iodid, is trimethylrosanilin chlorid. By a further action
of methyl iodid, a brilliant green, iodin green, pentamethylrosan-
ilin chlorid, is produced. Lyons blue is triphenylrosanilin chlorid,
formed by heating rosanilin chlorid with excess of anilin.
HYDROCARBONS WITH DIRECTLY UNITED BENZENE
NUCLEI.
These hydrocarbons and their derivatives are divided into two
classes : 1. Those in which two or more benzene nuclei, each re-
taining its six C atoms, are attached together by loss of H2. 2.
Those in which two or more benzene nuclei are united in such
manner that each two possess two atoms of carbon in common,
as shown in the formulae of naphthalene and phenanthrene given,
below.
HYDROCARBONS. 437
H H H H
C— C C— C
/ X / X
Diphenyl — HC - C — C CH — is the simplest compound
\ / \ /
c=c c=c
H H H H
-uf the first class. It is obtained by the action of sodium upon
monobromobenzene, or by passing benzene through a red-hot
•tube. It crystallizes in large plates, fusible at 70°. 5 (159°. 8 F.) ;
boils at 254° (489°. 2 F.). Diphenyl and its superior homologues,
•ditoluyl, diphenylbenzene, etc., constitute the nuclei of a great
number of products of substitution, formed by the replacement
•of one or more of their H atoms by various radicals and elements,
=among them being many isomeres produced by differences of
orientation.
Dipyridyls — doHnKTa. — These substances bear the same re-
lation to pyridin that diphenyl does to benzene ; but, owing to
the presence of the N atom in the nucleus there are six possible
isomeres, varying with the position of the attachment, of which
four are known. The earliest described is that in which the at-
tachment is at the y position (see p. 423).
H H H H
C=C C=C
/ \ / \
Na /} C-C /? a N
X / '/ X /
C-C C-C
H H H H
This substance is formed by the action of sodium upon pyridin.
It is in crystalline needles, fusible at 114° (237° F.), which yield
isonicotic acid on oxidation. The a/3 and /3/J dipyridyls are formed
by the oxidation of phenanthrolins, and both yield nicotic acid
on oxidation. The fourth, probably aa, is formed by passing
vapor of pyridin through a red-hot tube. By the action of Zn+
HC1 the dipyridyls take up six H atoms to form substances,
CioHnN2, isonieric with nicotin (see nicotin below) and resem-
bling that alkaloid closely in chemical properties and in physi-
ological action. The one obtained from /3,3 dipyf idyl is a very
soluble and highly poisonous liquid, called nicotidin. That
from ;.y dipyridyl is a crystalline solid, soluble in H2O, less ac-
tively poisonous than nicotin, and called isonicotin.
Phenanthrene — Ci4Hi0 — isomeric with anthracene (Q.V.), may be
•considered as a diortho-derivative of diphenyl, or as produced by
the fusion of three benzene nuclei, the intermediate one of
•which has two C atoms in common with each of the extremes :
438 MANUAL OP CHEMISTRY.
OH = CH
/ \
CH— C C-CH
/ XXX
HC C— C CH
\ / \ /
CH = CH CH = CH
It crystallizes in brilliant, colorless plates, fusible at 99° (210". 2
F.), boils at 840° (644° F.), and sublimes readily at lower tempera-
tures. Soluble in hot alcohol, and in cold benzene and ether, the
solutions having a distinct blue fluorescence. It accompanies
anthracene in the crude product. It is formed synthetically.
Oxidizing agents convert it into phenanthroquinone, (C6H4)2(CO)2.
Naphthalene — C,0HS — 128 — is the simplest compound of the
second class (see above). It occurs in coal-tar. It has been formed
by a synthesis which indicates its constitution. Benzene and
ethylene, when heated together, unite to form, first, cinnamene
and afterward naphthalene. It is constituted by the fusion of
two benzol groups by two C atoms, thus :
H H
H— C C C— H
I II I .
H— C C C— H
XC/\C/
A
It crystallizes in large, brilliant plates ; has a burning taste and
a faint aromatic odor ; fuses at 80° (176° F.) and boils at 217°
(422°. 6 F.), subliming, however, at lower temperatures ; burns
with a bright, smoky flame ; insoluble in water, soluble in alcohol,
ether, and essences. It forms substitution compounds with Cl,
Br, I, HNOs, and H2SO4.
ALKALOIDS CONTAINING DIPYRIDYL OB PHENAN-
THRENE NUCLEI.
Although the constitution of nicotin and of morphin and its
congeners is not definitely established, sufficient has already been
determined to render it certain that nicotin contains a dipyridyl
nucleus and morphin a phenanthrene nucleus.
Nicotin — Ci0Hi4N2 — 162 — exists in tobacco in the proportion of
2-8 per cent.
It is a colorless, oily liquid, which turns brown on exposure to-
light and air; has a burning, caustic taste and a disagreeable,
penetrating odor; it distils at 250° (892° F.) ; it burns with a lumin-
OPIUM ALKALOIDS. 439
ous flame; sp. gr. 1.027 at 15° (59° F.); it is very soluble in water,
alcohol, the fatty oils, and ether ; the last-named fluid removes
it from its aqueous solution when the two are shaken together ; it
absorbs water rapidly from moist air. Its salts are deliquescent,
and crystallize with 'difficulty.
The oxidation of nicotin produces nicotic or /? monocarbopyri-
dic acid (see p. 435). When distilled with ZnCl2+CaO it yields
pyrrol, ammonia, methylamin, hydrogen, pyridic bases. When
heated to 250° (482° F.) it yields a collidin (p. 424) along with other
products. By limited oxidation it produces a substance, CioHio
N2, isodipyridin. These and other decompositions indicate that
nicotin is a piperidyl-pyridyl, that is, a piperidin nucleus com-
bined with a pyridyl, thus:
-'
;N, but the position of the
•v-' ••--•• #
attachment remains uncertain.
ANALYTICAL CHARACTERS. — (1.) Its ethereal solution, added
to an ethereal solution of iodin, separates a reddish-brown, resi-
noid oil, which gradually becomes crystalline. (2.) With HC1, a
violet color. (3.) With HNO3, an orange color.
TOXICOLOGY. — Nicotin is a very active poison. The free alkaloid
is probably capable of causing death in doses of two to three
drops, and was the first alkaloid to be separated from the cadaver
in a case of homicide. Most cases of poisoning from nicotin are
due to tobacco, usually resulting from its use in enemata.
When administered to dogs in doses of two to four drops, its
effects begin within half a minute to two minutes, and death en-
sues within one to five minutes. In the human subject tobacco
or its decoction causes nausea, vertigo, dilation of the pupils,
vomiting, syncope, diminution of the rapidity and force of the
heart. With large doses there are no subjective symptoms, the
victim falls unconscious instantly and dies within five minutes,
without convulsions, and with very few or only one deep sighing
respiratory act.
OPIUM ALKALOIDS.
The alkaloids of opium are considered in this place on account
of the relations of morphin and codein to phenanthrene, of which
hydrocarbon they may be considered as derivatives (see constitu-
tion of morphin, p. 444).
Opium is the inspissated juice of the capsules of the poppy.
It is of exceeding complex composition, and contains, besides a
neutral body called meconin (probably a polyatomic alcohol,
CioHioO4), a peculiar acid, meconic acid (q.v.), lactic acid, gum,
albumen, wax, and a volatile matter — no less than eighteen dif-
ferent alkaloids, one or two of which, however, are probably
440
MANUAL OF CHEMISTRY.
formed during the process of extraction, and do not pre-exist in
opium.
The following is a list of the constituents of opium, those
marki'd * being of medical interest :
Name.
Formula.
Per Cent, in
Smyrna
Opium.
Per Cent, in
Constanti-
nople Opium
* Meconic acid
C7H4O7
4.70
4.38
Lactic acid
C3H6O3
1.25
Meconin
0.08
0.30
* Morphin .... ...
Ci7H19NO3
10.30
4.50
Pseudomorphin
Ci7H19.NO4
Hydrocotarnin
Ci2Hi6NO3
* Codeln
C18H21NO3
0.25
1.52
* Thebal'n
Ci9H21NO3
0 15
Protopin
C20H19NO8
Rhseadin
C20H21NO6
Codamin
C«0H26NO4
Laudanin
C20H2B:NO4
Papaverin ....
C2iH2iNO4
1.00
Opianin
C2JH21NOi
Meconidin
C2iH23NO4
Cryptopiii.
C21H23NOB
Laudanosin
CaiH27NO4
* Narcotin
C22H23NO7
1.30
3.47
Lanthopin
* Narcetn
0.71
0.42
Morphin— Morphina (U. S.)—C17H19NO3+Aq—285-f-l8— crystal-
lizes in colorless prisms ; odorless, but very bitter ; it fuses at 120°
(248° F.), losing its Aq. More strongly heated, it swells up, be-
comes carbonized, and finally burns. It is soluble in 1,000 pts. of
cold water, in 400 pts. of boiling water; in 20 pts. of alcohol of
0.82, and in 13 pts. of boiling alcohol of the same strength; in 91
pts. of cold amyl alcohol, much more soluble in the same liquid
warm; almost insoluble in aqueous ether; rather more soluble in
alcoholic ether; almost insoluble in benzene; soluble in 860 pts.
of chloroform. All the solvents dissolve morphin more readily
and more copiously when it is freshly precipitated from solutions
of its salts than when it has assumed the crystalline form.
Morphin combines with acids to form crystallizable salts, of
which the chlorid, sulfate, and acetate are used in medicine. If
morphin be heated for some hours with excess of HC1, under
pressure, to 150° (302° F.), it loses water, and is converted into a
new base — apomorphin, C17H,7NO2.
By heating together acetic anhydrid and morphin, three modi-
OPIUM ALKALOIDS. 441
Hcations, a, |3, y, of acetyl-morphin, CnH, ,(C2H3O)NO3, are formed.
Similarly substituted butyryl-, benzoyl-, succinyl-, camphoryl-,
methyl-, and ethyl-morphin are also known.
Morphin is readily oxidized and is a strong reducing agent. It
reduces the salts of 'Au and Ag in the cold. It is oxidized by
atmospheric oxygen when it is in alkaline solution, as well as by
nitrous acid, potassium permanganate, potassium ferricyanid or
ammoniacal cupric sulfate, with the formation of a non-toxic com-
pound which has received the names oxymorphin, oxydimorphin,
dehydromorphin, and pseudoxnorphin (CnHleNO3)2l whose mole-
cule consists of two morphin molecules, united with loss of H2,
and which is an inferior degree of condensation to trimorphin
and tetramorphin, two amorphous, basic products of the action
of H2SO4 on morphin at 100° (212° F.). When morphin is distilled
with powdered Zn, the principal products of the reaction is
phenanthrene, accompanied by ammonia, trimethylamin, pyrrol,
pyridin, and a product having the formula CnHuN, probably
phenanthrene-quinolin.
The salts of morphin are crystalline. The acetate — Morphines
acetas, TJ. S. — Morphiae acetas, Br. — is a white crystalline pow-
der, soluble in 12 parts of water, which decomposes on exposure
to air, with loss of acetic acid. The chlorid — Morphinee hydro-
chloras, U. S. — is less soluble, but more permanent than the ace-
tate. The sulfate — Morphines sulfas, TJ. S. — Morphiee sulfas. Br.
— is the form in which morphin is the most frequently used in
medicine. It is a very light, crystalline, feathery powder; odor-
less, bitter, and neutral in reaction. It dissolves in 24 parts of
water. Its solutions deposit morphin as a white precipitate on
addition of an alkali. The crystals contain 5 Aq, which they lose
at 130° (266° P.).
ANALYTICAL CHARACTERS. — (1.) It is colored orange, changing
to yellow, by HNO3. (2.) A neutral solution of a morphin salt
gives a blue color with neutral solution of ferric chlorid. (3.) A
solution of molybdic acid in H^SO* (FrOhde's reagent) gives with
morphin a violet color, changing to blue, dirty green, and faint
pink. "Water discharges the color. (4.) Take two test-tubes.
Into one (a) put the solution of morphin, into the other (b) an
equal bulk of H2O. Add to each a granule of iodic acid and
agitate: a becomes yellow or brown, 6 remains colorless. To each
add a small drop of chloroform and agitate; the CHC13 in a is
colored violet, that in b remains colorless. Float some very
dilute ammonium hydroxid solution on the surface of the liquid
in a; a brown band is formed at the junction of the layers. (5.)
Moisten the solid material with HC1 to which a small quantity
of H2SC>4 has been added, and evaporate on the water-bath until
HC1 is expelled: a violet-colored liquid residue remains. Moisten
442 MANUAL OF CHEMISTRY.
this with HC1 and neutralize with solid sodium bicarbonate in
slight excess: a pink or rose color is produced, most distinctly
visible on the bubbles. Add a drop of H2O and a drop or two of
alcoholic solution of iodin: a green color is developed. This re-
action, known as the Pellagri test, is based upon the conversion
of morphin into apomorphin, and consequently reacts with that
alkaloid. (6.) Moisten the solid with concentrated H2SO4 and
heat cautiously until white fumes begin to be given off, cool and
touch the liquid with a glass rod moistened with dilute HNO3: a
fine blue violet color, changing to red and then to orange. If the
H2SO4 contains oxids of nitrogen, as it usually does, a violet tinge
will be produced before addition of HNO3, but then becomes much
more intense. This reaction, known as the Husemann, may be
applied by allowing the solid to remain in contact with H2SO*
for fifteen to eighteen hours in place of heating.
These are the most important tests for morphin, and affirmative
results with all of them prove the presence of that alkaloid. Other
tests have been suggested, among which are the following : (7.)
Solution of morphin acetate produces a gray ppt. when warmed
with ammoniacal silver nitrate solution ; and the filtrate turns
red or pink with HNO3. (8.) Auric chlorid gives a yellow ppt.,
turning violet-blue, with solutions of morphin salts. (9.) Add
solution of Fe2Cl6 (2-16) to solution of potassium ferricyanid (the
mixture must not assume a blue color), add morphin solution — a
deep blue color. (10.) Heat morphin with concentrated H2SO4
to 200° (392° F.) until green-black ; add a drop of the liquid cau-
tiously to water ; the solution turns blue. Shake a portion with
ether ; the ether turns purple. Shake another portion with chlo-
roform ; the chloroform turns blue. (11.) Warm the solid alkaloid
with concentrated H2SO4 ; add cautiously a few drops of alcoholic
solution of KHO (30$); a yellow color is produced, changing to
dirty red, then steel-blue, and sky-blue, and, with a further quan-
tity of KHO solution, cherry-red. (12.) A mixture of morphin
and cane-sugar (1 to 4) added to concentrated HnSO4 gives a dark
red color, which is intensified by a drop of bromin-water.
Codein— Codeina (TT. S.)—C18H2iNO3-f-Aq— 299+18— crystallizes
in large rhombic prisms, or from ether, without Aq, in octahedra ;
bitter; soluble in 80 pts. cold water; 17 pts. boiling water; very
soluble in alcohol, ether, chloroform, benzene; almost insoluble
in petroleum-ether.
Codein is the methyl ether of morphin, or its superior homo-
logue, and resembles that alkaloid in some of its reactions ; thus
under similar circumstances both form apomorphin, and morphin
may be converted into codein by the action of methyl iodid in
the presence of KHO. Codein, however, only contains one OH
group and forms a monoacetylic derivative with acetyl chlorid,.
while morphin produces a diacetylic.
OPIUM ALKALOIDS. 443
ANALYTICAL CHARACTERS.— (1.) Cold concentrated H2SO4
forms with it a coloress solution, which turns blue after some
days, or when warmed. (2. ) FrOhde's reagent dissolves it with a
dirty green color, which after a time turns blue. (3.) Chlorin-
water forms with it a colorless solution, which turns yellowish-red
with XH4HO.
Narcein— C23H29NO8-)-2Aq — 463+36— crystallizes in bitter, pris-
matic needles ; sparingly soluble in water, alcohol, and arnyl al-
cohol ; insoluble in ether, benzene, and petroleum-ether.
ANALYTICAL CHARACTERS. — (1.) Concentrated H2SO4 dissolves
it with a gray-brown color, which changes to red, slowly at ordi-
nary temperatures, rapidly when heated. (2.) FrOhde's reagent
colors it dark olive-green, passing to red after a time, or when
heated. (3.) lodin solution colors it blue-violet, like starch.
Narcotin — C22H23NO7 — 413 — crystallizes in transparent prisms,
almost insoluble in water and in petroleum-ether ; soluble in al-
cohol, ether, benzene, and chloroform. Its salts are mostly un-
crystallizable, unstable, and readily soluble in water and alcohol.
Narcotin is decomposed by H2O at 140° (284° F.), by dilute H2
SO4 or by baryta, with formation of opianic acid, C, nH; 0 . and
hydrocotarnin, doHisNOs. Reducing agents decompose it into
hydrocotarnin and meconin, C10Hi0O4. Oxidizing agents convert
it into opianic acid and cotarnin, Ci,HKNO' .
ANALYTICAL CHARACTERS. — (1.) Concentrated HaSO4 forms
with it a solution, at first colorless, in a few moments yellow, and
after a day or two, red. (2.) Its solution in dilute HaSO4, if grad-
ually evaporated until the acid volatilizes, turns orange-red,
bluish-violet and reddish- violet. (3.) FrShde's reagent dissolves
it with a greenish color, passing to cherry-red.
Thebain — Paramorphin — Ci9H21NO3 — 311 — crystallizes in white
plates; tasteless when pure; insoluble in water; soluble in al-
cohol, ether and benzene.
ANALYTICAL CHARACTERS. — (1.) With concentrated H2SO4 an
immediate bright red color, turning to yellowish-red. (2.) Its solu-
tion in chlorin-water turns reddish-brown with NH4HO. (3.)
With FrOhde's reagent same as 1.
Apomorphin — Ci-H17NO2 — is used hypodermically as an emetic
in the shape of the chlorid, Apomorph.in.8e hydrochloras, TJ. S. It
is obtained by sealing morphin with an excess of strong HC1 in a
thick glass tube, and heating the whole to 140° (252° F.) for two
to three hours. It is obtained also by the same process from
codeln. The free alkaloid is a white, amorphous solid, difficultly
soluble in water. The chlorid forms colorless, shining crystals,
which have a tendency to assume a green color on exposure to
light and air. It is odorless, bitter and neutral; soluble in 6.8
parts of cold water.
444: MANUAL OF CHEMISTRY.
Relations and Constitution of the Opium Alkaloids. — The alka-
loids of opium may be arranged in two groups : I., including those
which are strong bases, are highly poisonous and contain three
or four atoms of oxygen; II., those which are weak bases and
contain four to nine oxygen atoms. The six principal alkaloids
are equally divided between the two groups :
I. II.
Morphin Ci7Hi9NO3 Papaverin CaoHaiNCU
Codein Ci8H2iNO3 Narcotin C2sH23NO7
Thebain C19H2iNO3 Narcein .C»HMNOg
Although the syntheses of morphin and of codein have not
been realized, and although their constitution has not been defi-
nitely determined in all details, enough has been learned from
the products of decomposition of these complex molecules to in-
dicate that morphin is a derivative of phenanthrene and oxypy-
ridin, partly hydrogenated and containing two oxhydryl groups
in the same terminal phenanthrene ring, one probably phenolic,
the other alcoholic, and that codein is derivable from morphin
by substitution of CH3 for the hydrogen of one of the oxhydryl
groups, probably the phenolic. The structural formulae of mor-
phin and codein may be thus expressed :
OH OCH3
HOHC CH
I I
HaC C
CH, H
Morphin.
"the only points still remaining in doubt being the relative posi-
tions of the two OH groups in morphin, and the OH and OCH3
groups in codein, in the upper phenanthrene ring, in which both
exist.
Apomorphin is derived from both morphin and codein, by loss
of H2O, or of CH3HO, probably by a change of the superior ter-
minal of the formulae from I. or II. to III. :
SUBSTITUTION DERIVATIVES OF NAPHTHALENE.
OH OCH3 H
I I I
oc c
HOHC CH • HOHC CH OC CH
II II II
L U. IIL
Toxicology of Opium and its Derivatives. — Opium, its prepara-
tions and the alkaloids obtained from it, are all active poisons.
They produce drowsiness, stupor, slow and stertorous respiration,
contraction of the pupils, small and irregular pulse, coma, and
death. The symptoms set in from 10 minutes to 3 hours, some-
times immediately, sometimes only after 18 hours. Death has
occurred in from 45 minutes to 3 days, usually in 5 to 18 hours.
After 24 hours the prognosis is favorable. Death has been caused
in an adult by one-half grain of acetate of morphia, while 30
grains a day have been taken by those accustomed to its use
without ill effects.
The alkaloids of opium have not the same action. In soporific
action, beginning with the most powerful, they rank thus : Xar-
ce£n, morphin, codeln ; in tetanizing action : thebaln, papaverin,
narcotin, codeln, morphin ; in toxic action : thebaln, codeln, papa-
verin, narceln, morphin, narcotin.
The treatment should consist in the removal of unabsorbed
poison from the stomach by emesis and the stomach-pump, and
washing out of the stomach after injection into it of powdered
charcoal in suspension, or tea or coffee infusion. Cold affusions
should be used, and the patient should be kept awake.
After death the reactions for meconic acid and narcotin permit
of distinguishing whether the poisoning was by opium or its
preparations, or by morphin.
SUBSTITUTION DERIVATIVES OF NAPHTHALENE.
By the replacement of the hydrogen atoms of naphthalene by
other atoms or by radicals, substitution products are obtained
somewhat in the same manner as in the case of benzene (see pp.
397-400). In the case of naphthalene, however, the number of
H(a) H(a)
i !
C C
03)H— 70 C 02— H(/3)
0 0 03— H(/3)
0 C
5 4
H(«) H(a)
446 MANUAL OF CHEMISTRY.
isomeres is much greater than with benzene. In the structural
formula of naphthalene the positions 1, 4, 5, 8, although equal to
each other, are of different value from the positions 2, 3, 6, 7, also
equal to each other, as they are differently disposed with regard
to the carbon atoms x and y. There exist, therefore, two possible
unisubstituted derivatives of naphthalene for a single such de-
rivative of benzene, etc. If the substituted group occupy the
approximate positions 1, 4, 5, or 8, it is called an a-derivative ; if
it occupy the remote positions 2, 3, 6, or 7, it is a ^-derivative.
Naphthols — d0H7,OH — of which there are two :
a-Naphthol has been obtained by heating phenyl-isocrotonic
,acid ; also by boiling an aqueous solution of diazonaphthalene
nitrate with nitrous acid, or by fusing a-naphthalene-sulfonic acid
with KHO.
It crystallizes in colorless prisms ; fuses at 94° (201°. 2 F.); boils
at 280° (536° F.) ; is nearly insoluble in water, but soluble in alco-
hol and in ether, and gives a transient violet color with Fe2Cl8
and a hypochlorite.
fi-Naphthol—Isonaphihol — Hydronaphthol — is prepared indus-
trially by fusion of ^-naphthalene sulfonate of sodium with
NaHO, for the manufacture of a number of coloring matters,
among which are Campobello yellow and tropeolin. The com-
mercial product is in reddish-gray, friable, light masses. The
pure substance forms colorless, silky, crystalline plates, having
a faint, phenol-like odor, and an evanescent, sharp, burning taste.
It fuses at 123° (253°.4 F.), boils at 286° (514°.8 F.), and is sparingly
soluble in water, but readily soluble in alcohol and ether. Its
aqueous solutions are not colored violet by FeaClo. The pure
substance is a valuable antiseptic.
Naphth.ylam.ins — Amidonaphthalen.es — Ci 0H7, NH3. — Two are
known, corresponding in constitution to the naphthols. The a
modification is formed by the reduction of e-nitronaphthalene.
It crystallizes in flat needles, fuses at 50° (122° F.), boils at 300°
(572° F.), insoluble in water, soluble in alcohol and ether. Has a
disagreeable and persistent taste.
The /3-naphthylamin is produced by the action of ammonia on
/3-naphthol at 150°-160° (302°-320° F.). It forms crystalline
plates, fusible at 112° (233°.6 F.), boils at 294° (561°. 2 F.) ; dissolves
in hot H2O, forming a blue fluorescent solution. Both forms are
monacid bases, and form crystalline salts.
Compounds of addition are obtainable from naphthalene as
well as products of substitution. They are produced by the free-
ing of one or more of the double bonds in the positions 1 — 2 ; 3—4 ;
5 — 6 and 7 — 8. Among these products is tetrahydro /3naphthyl-
amin. CioH7,HJNH3, a very active mydriatic.
QUIXOLIN BASES. 417
QTTINOLIN BASES.
The bases of this group at present known are :
Quinolin ,.'... .C9H7N Pentahyrolin Ci3Hi5N
JLepidki CioH»N Isolin Ci4H17N
€ryptidin Ci.HnN Ettidin. C,6H19N
Tetrahyrolin C12H1SN Validin C,eHa,N
These bodies, which are closely related to the vegetable alka-
loids, bear the same relation to naphthalene that the pyridin
bases do to benzene, as will be understood by comparison of the
following formulae :
H H Ha Hy
II II
c c c c
/ \ / x / \ / \
HC C CH pHC C CH/3
I II I I B || Py |
HC C CH niHC C CH«
X / \ / X / \ /
C C C N
H H Ho
Naphthalene. Quinolin.
with those of anilin and picolin given on p. 423. As the molecule
of naphthalene may be considered as produced by the fusion of
two benzene nuclei, so quinolin may be regarded as resulting
from the union of a benzene with a pyridin nucleus.
They are obtained by the destructive distillation of the cin-
chonin, quinin, and other natural alkaloids, to which they are
closely related.
Quinolin— C9H7N— is a mobile liquid; boils at 238° (460°. 4 F.);
becomes rapidly colored on contact with air. It has an intensely
bitter and acrid taste, and an odor somewhat like that of bitter
almonds. It is sparingly soluble in water, readily soluble in al-
cohol and ether.
Quinolin is the nucleus of a vast number of products of substi-
tution, among which are many isorneres, due to differences in
orientation, according as the substitution occurs in the ortho,
meta or para positions in the benzene group B (see formulae above)
or in the «, /?, or y positions in the pyridin group Py.
Among the derivatives of quinolin are several synthetic prod-
ucts used as medicines and some vegetable alkaloids. Among
the synthetic products are :
ThsdHn=Tetrahydroparachinanisol — CioHnNO— is a derivative
of the paramethyl ether of quinolin. It is met with in the form
of sulfate and tartrate in the shape of crystalline powders. The
odor of the sulfate is similar to that of anisol (methyl phenate) ;
448 MANUAL OF CHEMISTRY.
that of the tartrate to that of coumarin. The taste of each is
bitter, acrid, and salty. Both salts are readily soluble in H2O, the
sulfate the more readily. Solutions of thallin salts assume, even
when very dilute, a magnificent emerald-green color with FeaCle
solution. A similar color is produced by AuCla and by AgNO3.
Ethylthallin — Ci2H17NO — is a derivative of thallin, whose chlo-
rid is hygroscopic ; readily forming solutions which are acid in re-
action, bitter in taste, and assume a red-brown color with Fe2Cl6.
Kairin — Methyloxyquinolin Tiydrid — Ci0H13NO — is more nearly
derived from quinolin than the substances previously mentioned.
Its chlorid is a crystalline, nearly white, easily soluble powder,
whose taste is at once bitter, aromatic, and salty.
Thallin, ethylthallin, and kairin are possessed of antiperiodic
and antipyretic properties.
CINCHONA ALKALOIDS.
The synthesis of the cinchona alkaloids has not been effected,
and their constitution is far from being established, yet it is cer-
tain that their molecules contain one and possibly two quinolin
groups.
Although by no means so complex as opium, cinchona bark
contains a great number of substances : quinin, cinchonin,
quiniain, cinchonidin, aricin; quinic, quinotannic, and quino-
mc acids ; cinchona red, etc. Of these the most important are
quinin and cinchonin.
Quinin— {Juinina (U. S.) — CsoH^NaOa-j-n Aq — 324-(-wl8 — exists
in the bark of a variety of trees of the genera Cinchona and China,
indigenous in the mountainous regions of the north of South
America, which vary considerably in their richness in this alka-
loid, and consequently in value ; the best samples of calisaya bark
contain from 30 to 32 parts per 1,000 of the sulfate ; the poorer
grades 4 to 20 parts per 1,000 ; inferior grades of bark contain from
mere traces to 6 parts per 1,000.
It is known in three different states of hydration, with 1, 2, and
3 Aq, and anhydrous. The anhydrous form is an amorphous,
resinous substance, obtained by evaporation of solutions in anhy-
drous alcohol or ether. The first hydrate is obtained in crystals
by exposing to air recently precipitated and well-washed quinin.
The second by precipitating by ammonia a solution of quinin
sulfate, in which H has been previously liberated by the action
of Zn upon H2SO4 ; it is a greenish, resinous body, which loses
H2O at 150° (302° F.). The third, that to which the following
remarks apply, is formed by precipitating solution of quinin salts
with ammonia.
It crystallizes in hexagonal prisms; very bitter; fuses at 57°
(134°. 6 F.); loses Aq at 100° (212° F.) and the remainder at 125°
QUINOLIN BASES. 449
(257° F.); becomes colored, swells up, and, finally, burns with a
smoky flame. It does not sublime. It dissolves in 2,200 pts. of
cold H2O, in 760 of hot H2O; very soluble in alcohol and chloro-
form ; soluble in amyl alcohol, benzene, fatty and essential oils,
and ether. Its alcoholic solution is powerfully Isevogyrous,
[a]D= — 270°. 7 at 18° (64°. 4 F.), which is diminished by increase of
temperature, but increased by the presence of acids.
ANALYTICAL CHARACTERS. — (1.) Dilute H2SO4 dissolves quinin
in colorless but fluorescent solution (see below). (2.) Solutions
of quinin salts turn green when treated with Cl and then with
NH3. (3.) Cl passed through H2O holding quinin in suspension
forms a red solution. (4.) Solution of quinin treated with Cl
water and then with fragments of potassium ferrocyanid be-
comes pink, passing to red.
SULFATE — Disulfate — Quininse sulfas (TJ. S.) — Quiniee sulfas
(Br.)— SO4(C2oH26N2O3)2-|-7 Aq— 746+126 — crystallizes in prismatic
needles ; very light ; intensely bitter ; phosphorescent at 100°
(212° F.) ; fuses readily ; loses its Aq at 120° (248° F.), turns red,
and finally carbonizes ; effloresces in air, losing 6 Aq ; soluble in
740 pts. H2O at 13° (55°.4 F.), in 30 pts. boiling H2O, and 60 pts.
alcohol. Its solution with alcoholic solution of I deposits brilliant
green crystals of iodoquinin sulfate.
HYDROSULFATE — Quinines bisulfas (TJ. S.)— SO4H(C20H26N2O2)
-f 7 Aq— 422+126 — is formed when the sulfate is dissolved in ex-
cess of dilute H2SO4. It crystallizes in long, silky needles, or in
short, rectangular prisms ; soluble in 10 pts. H2O at 15° (59° F.).
Its solutions exhibit a marked fluorescence, being colorless, but
showing a fine pale blue color when illuminated by a bright light
against a dark background.
IMPURITIES. — Quinin sulfate should respond to the following
tests : (1.) When 1 gram (15.4 grains) is shaken in a test-tube with
15 c.c. (4fl3) of ether, and 2 c.c. (32 m) of NH4HO; the liquids
should separate into two clear layers, without any milky zone
between them (cinchonin). (2.) Dissolved in hot H2O, the solu-
tion precipitated with an alkaline oxalate, the filtrate should not
ppt. with NH4HO (quinidin). (3.) It should dissolve completely
in dilute H2SO4 (fats, resins). (4.) It should dissolve completely
in boiling, dilute alcohol (gum, starch, salts). (5.) It should not
blacken with H2SO4 (cane-sugar). (6.) It should not turn red or
yellow with H2SO4 (salicin and phlorizin). (7.) It should leave
no residue when burnt on platinum foil (mineral substances).
By the action of alkaline hydroxids upon quinin, formic acid,
quinolin (see p. 447), and pyridin bases (see p. 422) are produced.
Concentrated HC1 at 140°-150° (284°-302° F.) decomposes quinin,
with separation of methyl chlorid and formation of apoquinin,
Cs H^NjOj. an amorphous base.
29
450 MANUAL OF CHEMISTRY.
Oxidizing agents produce from quinin oxalic acid and acids re-
lated to pyridin, notably pyridindicarbonic or cinchomeric acid,
C5H3N(COOH)2, which are also formed by oxidation of cinchonin.
Although cinchonin (see below) differs from quinin in composi-
tion by -j-O, and although the decompositions of the two bases
show them both to be related to the chinolin and pyridin bases,
attempts to convert cinchonin into quinin have resulted only in
the formation of other products, among which is an isomere of
quinin, oxycinchonin.
Methylquinin, C^H^NaOaCH.,, is a base which has a curare-like
action.
Cinchonin— Cinchonina (U. S.)—C19H221T2O— 294— occurs in Pe-
ruvian bark in from 2 to 30 pts. per 1,000. It crystallizes without
Aq in colorless prisms ; fuses at 150° (302° F.); soluble in 3,810 pts.
H2O at 10° (50° F.), in 2,500 pts. boiling H2O; in 140 pts. alcohol
and in 40 pts. chloroform. The salts of cinchonin resemble those
of quinin in composition ; are quite soluble in H2O and alcohol ;
are not fluorescent; permanent in air; phosphorescent at 100C
<212° F.).
Quinidin and Quinicin — are bases isomeric with quinin; the
former occurring in cinchona bark, and distinguishable from
quinin by its strong dextrorotary power ; the second a product
of the action of heat on quinin, not existing in cinchona.
Cinchonidin — a base, isomeric with cinchonin, occurring in cer-
tain varieties of bark; laevogyrous. At 130° (266° F.) H2SO4 con-
verts it into another isomere, cinchonicin.
INDIGO GROUP.
In this group are included a number of substances, derivable
from indigo-blue, which are evidently closely related to the ben-
zene group, as is shown by the number of benzene derivatives
which are obtained by their decomposition, but whose constitu-
tion is not yet definitely established. They are classified here
because some of the most perfectly studied seem to contain a nu-
cleus consisting of a hexagonal benzene ring attached to a pen-
tagonal pyrrol ring.
Indigotin — Indigo-blue — Ci6Hi0N2O2 — constitutes the greater
part of the commercial indigo. It does not exist preformed in
the plants from which it is obtained, whose juice is naturally
colorless, but is produced by decomposition of a glucosid con-
tained in them (see Indican, p. 451).
Indigotin may be obtained by the action of phosphorus tri-
chlorid on isatin ; or, in a nearly pure form, by cautiously sublim-
ing commercial indigo. It forms purple-red, somewhat metallic,
orthorhomb'.c prisms or plates, odorless, tasteless, neutral, insol-
INDIGO GROUP. 451
uble in water, ether, or dilute acids or alkalies. By dry distilla-
tion it yields anilin and other products. By moderate heating
'with dilute HNO3 it gives off gas and is converted into isatin.
Indigo sulfonic Acids. — When indigo is heated for some time
with fuming H2SO4 it dissolves. If the solution be diluted with
H2O, a blue powder, soluble in HaO, but insoluble in dilute acids,
is precipitated. This is indigo-monosulfonic or phcenicin-sul-
fonic acid— C16HaN2O,SO3H.
The nitrate from the last-mentioned precipitate contains
indigo-disulfonic, sulfindylic, or sulfindigotic acid — dsH.-N,
O3(SO3H)a — whose K and Na salts constitute soluble pastes known
in the arts as soluble indigo, or indigocarmine.
Isatin — CgH5NO2 — obtained by oxidation of indigo-blue, forms
shining, transparent, red-brown prisms. It is odorless, sparingly
soluble in water, readily soluble in alcohol.
Dioxindol — Hydrindic acid — CSH7NO2 — is formed by the action
of Na on isatin suspended in H2O. It forms yellow prisms, solu-
ble in H2O, and combines with both bases and acids.
Oxindol — GeH-NO — is obtained from dioxindol by reduction
with Xa amalgam in acid solution. It crystallizes in easily solu-
ble, colorless needles, and combines with acids and bases.
Indol — C»H7N — is produced by distilling oxindol over zinc-dust,
or by heating orthonitrocinnainic acid with KHO and Fe filings.
It crystallizes in large, shining, colorless plates, having the
odor of naphthylamin. It is a weak base, forming salts with
acids, which are, however, decomposed by boiling water. Its
aqueous solution, acidulated with HC1, is colored rose-red by
KXO2. It is converted into anilin by fused KHO.
It is one of the products of putrefaction of albuminoid sub-
stances, and is formed during the action of the pancreatic secre-
tion upon albuminoids. It is partly eliminated with the faeces
and partly reabsorbed.
In the intestine and faeces indol is invariably accompanied by
Skatol. C. H,N. its superior homologue, which may also be ob-
tained by the action of Sn and HC1 on indigo. It crystallizes in
brilliant plates, and is less soluble than indigo. The product ob-
tained from indigo has a penetrating but not disagreeable odor,
while that obtained from putrid albumin and from faecal or in-
testinal matter has a disgusting odor, probably due to the pres-
ence of foreign substances.
Indican — C^HsiNiT — is a glucosid existing in the different va-
rieties of indigo-producing plants, and also in the urine and blood
of man and the herbivora.
It is a yellow or light brown syrup, which cannot be dried
without decomposition, bitter and disagreeable to the taste, acid
in reaction, and soluble in water, alcohol, and ether.
452 MANUAL OF CHEMISTRY.
It is very prone to decomposition. Even slight heating decom-
poses it into leucin, indicanin, C2oH23NOi2, and indiglucin, C,-.H , ,,(X.
A characteristic decomposition is that when heated in acid solu-
tion, or under the influence of certain ferments (?), it is decom-
posed into indigo-blue and indiglucin, the latter a glucose :
2C26H3iNOi7 + 4H2O = CieHioNiO, + 6C,H,0O.
Indican. Water. Indigotin. Indiglucin.
ANTHRACENE GROUP.
SERIES CwH2n— 18.
Anthracene — CnH,,, — 178 — exists as a constituent of coal-tar,
and is obtained by expression from the substance remaining in
the still after the distillation of naphthalene, etc. The commer-
cial product thus obtained is a yellowish mass containing 50-80
per cent, of anthracene, the purification of which is a matter of
considerable difficulty. It has also been obtained synthetically,
by the action of the heat on benzyl toluene, and in other ways.
When pure, anthracene crystallizes in rhombic tables having a.
bluish fluorescence; fusible at 210° (410° P.) and boiling above 360°
(680° F.); its best solvents are benzene and carbon disulfid, in
which, however, it is only sparingly soluble.
The constitution of anthracene is that of two benzene nucleL
united through two of their C atoms by the group=CH — CH= ;
H(a) H(a)
I H(a?) <l
/C\ I /C\
03) H— C C— C— C C— H 03)
I II I II I
(/?) H— C C— C— C C— H (/3)
X / \n/
I H(y) V
H(a) H(a)
Oxidizing agents convert anthracene into anthraquinone. Re-
ducing agents decompose it into three hydrocarbons, C^Hso, CvH^,
and an oily hydrocarbon boiling above 360° (648° F.). Br and Cl at-
tack it violently, I more slowly, forming products of addition.
DERIVATIVES OF ANTHRACENE.
As may be inferred from the complex molecule of anthracene,
the number of possible derivatives of substitution and of addi-
tion, including many isomeres, is very great.
Anthraphenols— CnH9(OH). — Three are known, a and (3 anthrol,
TEREBEXTHIC SERIES. 453
«,nd anthranol. The two former are produced by the substitution
of OH for one of the H atoms a or ^ (see formula above) in anthra-
cene, the latter by the substitution of the same group in the posi-
tions x or y.
Anthraquinone — Ce'H.t('nQ^Ce'H.t — is formed by oxidation of
anthracene. It forms yellow needles, which fuse at 273° (523°. 4 F.).
It is not easily oxidized, but is converted into anthracene by suf-
iiciently active reducing agents.
Dioxyanthraquinone — Alizarin — C6H4 ^ QQ / C6H2 <f QJJ — is the
red pigment of the madder root (Rubia tinctoria). Artificial
alizarin has now almost completely displaced the natural product
in dyeing. It is obtained by the action of fused KHO on many
anthracene derivatives, the one generally used being anthraqui-
none-disulfonic acid, Ci4H6O2(SO3H)2.
Methylanthracene — Ci4H9,CH3 — is obtainable by synthesis, and
also by heating chrysophanic acid, emodin, or aloin with zinc-
dust.
Crysophanic Acid — Parietic Acid — Rheicacid — Rhein — Ci5Hi0O4
— is a derivative of methylanthracene, which exists in the lichens
Parmelia parietina and Squamaria elegans, in senna, and in
rhubarb, and obtainable to the extent of 80 per cent, from Goa
Chrysophanic acid crystallizes in golden, orange-yellow, inter-
laced needles. It is almost tasteless and odorless ; fuses at 162°
(291°. F.); almost insoluble in cold water, sparingly soluble in hot
water, alcohol, and ether, readily soluble in benzene. It forms a
red solution with H2SO4, from which it is deposited unchanged
by water. It also forms red solutions with alkalies. Reducing
agents convert it into methylanthracene.
Trioxymethylanthraquinone — Emodin — Ci4H4(CH3)(OH)3O2 —
occurs in the bark of Rhamnus frangula, and accompanies chry-
sophanic acid in rhubarb. It crystallizes in long, orange-red
prisms which fuse at 2<50° (482° F.), and yield methylanthracene
when heated with zinc-dust.
TEREBENTHIC SERIES.
In this series are included a number of isomeric hydrocarbons,
having the formula Ci0Hi6, or a simple multiple thereof, and their
products of derivation. The hydrocarbons are in some cases arti-
ficial products, but for the most part exist in nature in the differ-
ent turpentines, and volatile oils, or essences. When liquid they
.are called terpenes, when solid camphenes.
Turpentine — Terebenthina (TJ. S.) — is the common American
454 MANUAL OF CHEMISTRY.
turpentine, obtained from incisions in bark of Pinus palustris
and P. tceda, and may be taken as the type of many similar prod-
ucts obtained from other plants. It is a yellowish-white semi-
solid, having a balsamic odor, which is divided by distillation
into two products. One a liquid, an elceoptene : oil, or essence of
turpentine ; the other a solid, a stearoptene : rosin, or colophony.
The liquid product so obtained, oil of turpentine, in the case of
the American product consists chiefly of a hydrocarbon, CioHie,
called australene, and in the case of the French turpentine of an
isomeric body, called terebenthene.
These two bodies are obtained from the oils of turpentine by
mixing with an alkaline carbonate and subjecting them to frac-
tional distillation in vacuo over the water-bath. The differences
between them are principally in their physical properties. Aus-
tralene is dextrogyrous, (a)D=17°, boils at about 155° (311° F.). Tere-
benthene is Isevogyrous, (a)D= — 40°. 32, boils at 156°. 5 (313°. 7 F.), sp.
gr. 0.864 at 16° (60°. 8 F.). They are colorless, mobile liquids; have
the peculiar odor of turpentine ; burn with a smoky, luminous
flame. They absorb oxygen rapidly from the air, whether pure or
in the commercial essence, becoming thick, and finally gummy.
Oxidizing agents, such as HNO3, attack them energetically, caus-
ing them to ignite and burn suddenly, with separation of a large
volume of carbon. HC1 unites with them to form a number of com-
pounds, as do also HI and HBr — all the compounds having the odor
of camphor. When mixed with HNO3, diluted with alcohol, and
exposed to the air, they form terpin hydrate. Cl, Br and I form
compounds of substitution or of addition.
Oil of turpentine may be boiled without suffering decomposi-
tion, but if heated under pressure at 250°-300° (482°-572° F.) the
terpene is converted into two products, one liquid, boiling at 177°
(350°. 6 F.), isomeric with the terpene, called isoterebenthene ; the
other viscous, boiling at about 400° (752° F.), polymeric with the
first, C20H32, called metaterebenthene.
Sulfuric acid acts violently upon oil of turpentine when the
two liquids are agitated together, and the latter yields a number
of isomeric and polymeric derivatives. After standing 24 hours
the mixture separates into two layers. If the upper layer be dis-
tilled at about 250° (482° F.) it yields a mobile liquid, which, when
purified by contact with dilute H2SO4 and then with solution of
NaHO, and dried and subjected to fractional distillation, may
be separated into (1) Terebene, d0Hi6, a colorless, mobile liquid,
having a faint odor, optically inactive, boiling at 156° (312°. 8 F.)-
(2) cymene ; (3) a number of polymeres of terebenthene, among
which is Colophene, or Diterebene, C20H32, a colorless oil, having a
brilliant, indigo-blue fluorescence; boils at 300°-315° (572°-599° F.)^
sp. gr. 0.91 at 4° (39°. 2 F.).
TEREBENTHIC SERIES. 455
There exist a number of hydrates of the terpenes : Terpinol —
2 C H , ,H.O — produced by distilling terpin (see below) with very
dilute HaSCh, or terpene monochlorhydrate with H2O, or alcohol.
It is a colorless liquid, having the odor of hyacinth, boiling at
168° (234°.4 P.); sp. gr. 0.852.
Terpene hydrate — Ci0Hie,H20 — formed by distilling terpin with
HC1 ; or by allowing French oil of turpentine to remain for some
days in contact with alcohol and H3SO4. It is an oily liquid,
boils at 210°-214° (410°-417°.2 F.), suffering partial decomposition.
Terpin— Ci0Hi6,2H2O — is formed by the dehydration of terpin
hydrate (q.v.). It is crystalline, fusing at 103° (217°. 4 F.), capable
of sublimation, and boils at about 250° (482° F.). It absorbs H2O
eagerly to form terpin hydrate. It behaves like a diatomic al-
cohol, and is converted into terebenthene dichlorhydrate, by gas-
eous HC1, or by PC15. It is dehydrated by PaO6, and converted
into terebene and colophene.
Terpin hydrate — Ci,H1P,3H:0 — formed when oil of turpentine
remains for a long time in contact with HaO, the formation being
favored by the presence of a mixture of alcohol and dilute HNO2.
It exists in large, colorless, prismatic crystals, odorless, fuses at
about 100D (212° F.), sparingly soluble in H5O, soluble in alcohol
and in ether. It readily gives up H»O in dry air at 100° (212° F.),
and is then converted into terpin.
The Camphenes are solid, crystalline bodies, having odors re-
sembling that of camphor, formed by the action of the Na salts
of weak acids, at 200°-220° (392°-428° F.) upon the monochlorhy-
drates of the corresponding terebenes.
Isomeres of Terebenthene. — There exist a great number of bodies,
the products of distillation of vegetable substances, which are
known as essences, essential oils, volatile oils or distilled oils.
They resemble each other in being odorous, oily, sparingly solu-
ble in water, more or less soluble in alcohol and ether ; colorless
or yellowish, inflammable, and prone to become resinous on ex-
posure to air. They are not simple chemical compounds, but
mixtures, and in many of them the principal ingredient is a hy-
drocarbon, isomeric with terebenthene, and consequently having
the composition nCi0Hi6. Some contain hydrocarbons, others al-
dehydes, acetones, phenols, and ethers.
Of the numerous other hydrocarbons closely related to tereben-
thene, but two require further consideration as being the princi-
pal constituents of caoutchouc and gutta-percha.
Caoutchouc — India-rubber — is a peculiar substance existing in
suspension in the milky juice of quite a number of trees growing
in warm climates. It is, when pure, a mixture of two hydrocar-
bons—caoutchene, C10H1C, and isoprene, C5HS.
450 MANUAL OF CHEMISTRY.
The commercial article is yellowish-brown ; sp. gr. 0.919 to 0.942 ;
soft, flexible ; almost impermeable, but still capable of acting as a
dialyzing membrane when used in sufficiently thin layers. It is
insoluble in H2O and alcohol, both of which, however, it absorbs
by long immersion, the former to the extent of 25 per cent., and
the latter of 20 per cent., of its own weight; it is soluble in ether,
petroleum, fatty and essential oils ; its best solvent is carbon disul-
fld, either alone, or, better, mixed with 5 parts of absolute al-
cohol.
It is not acted upon by dilute mineral acids, but is attacked by
concentrated HNO3 and H2SO4, and especially by a mixture of
the two. Alkalies tend to render it tougher, although a solution
of soda of 40° B. renders it soft after an immersion of a few hours.
Cl attacks it after a time, depriving it of its elasticity, and ren-
dering it hard and brittle. When heated it becomes viscous at
145° (293° P.), and fuses at 170°-180° (347°-356° F.) to a thick liquid,
which, on cooling, remains sticky, and only regains its primitive
character after a long time. On contact with flame it ignites,
burning with a reddish, smoky flame, which is extinguished with
difficulty.
The most valuable property of india-rubber, apart from its
elasticity, is that which it possesses of entering into combination
with S to form what is known as vulcanized rubber, which is
produced by heating together the normal caoutchouc and S to
130°-150° (266°-302° F.). Ordinary vulcanized rubber differs mate-
rially from the natural gum in its properties ; its elasticity and
flexibility are much increased ; it does not harden when exposed
to cold; it only fuses at 200° (392° F.); finally, it resists the action
of reagents, of solvents, and of the atmosphere much better than
does the natural gum.
Frequently rubber tubing is too heavily charged with sulfur
for certain chemical uses, in which case it may be desulfurized
by boiling with dilute caustic soda solution.
Hard rubber, vulcanite, or ebonite, is a hard, tough variety of
vulcanized rubber, susceptible of a good polish, and a non-con-
ductor of electricity. It contains 20 to 35 per cent, of S (the ordi-
nary vulcanized rubber contains 7 to 10 per cent.).
Gutta-percha — is the concrete juice of Isonandra gutta. It is
a tough, inelastic, brownish substance, having an odor similar
to that of caoutchouc ; when warmed it becomes soft and may
be moulded, or even cast, so as to assume any form, which it re-
tains on cooling; it may be welded at slightly elevated temper-
atures, is a good insulating and waterproofing material. It is
insoluble in water, alkaline solutions, dilute acids, including
hydrofluoric, and in fatty oils; it is soluble in benzene, oil of tur-
pentine, essential oils, chloroform, and especially in carbon disul-
TEREBEXTHIC SERIES. 457
fid. A solution in chloroform is known as traumaticine, or Liq.
(jutta-perchae (U. S.), and is used to obtain, by its evaporation,
a thin film of gutta-percha over parts which it is desired to pro-
tect from the air. It is attacked by HXO3 and H2SO4.
When exposed to air and light, it is gradually changed from
the surface inward, assuming a sharp, acid odor, becoming hard
and cracked, and even a conductor of electricity.
Gutta-percha seems to be made up of three substances : Gutta,
C2oH32, 75-82 per cent., a white, tough substance, fusing at 150°
(302° F.), soluble in the ordinary solvents of gutta-percha, but
insoluble in alcohol and ether. Albane, C2oH32O2, 14-19 per cent.,
a white, crystalline resin, heavier than water, fusible at 160° (320D
F.); soluble in benzene, essence of turpentine, carbon disulfid,
ether, chloroform, and hot absolute alcohol; not attacked by
HC1. Fluviale, 4-6 per cent., C2oH3!!O, a yellowish resin, slightly
heavier than water, hard and brittle at 0° (32° F.), soft at 50° (122°
P.), liquid at 100° (212° F.) ; soluble in the solvents of gutta-percha.
Camphors and Resins. — The camphors are probably aldehydes
or alcohols corresponding to hydrocarbons related to tereben-
thene, although their constitution is still uncertain.
Common camphor — Japan camphor — Laurel camphor — Cam-
pholic aldehyde — Camphora (U. S., Br.) — Ci0Hi«O — 152. — Three
modifications are known, which seem to differ from each other
only in their action upon polarized light: (1.) Dextro camphor =
Camphora officinarum /obtained from Laurus camphora — [a]D=
-|-470. 4. (2.) Laevo camphor, obtained from Matricaria postla-
•nium — [a]D= — 47 D. 4. (3.) Inactive camphor, obtained from the
essential oils of rosemary, sage, lavender, and origanum.
The first is the ordinary camphor of the shops. It is a white,
translucent, crystalline solid; sp. gr. 0.986-0.996, hot and bitter in
taste; aromatic; sparingly soluble in H2O; quite soluble in ether,
acetic acid, methylic and ethylic alcohols, and the oils ; fuses at 175°
(347° F.) ; boils at 204° (399°.2 F.); sublimes at all temperatures.
It ignites readily and burns with a luminous flame. Cold HNO3
dissolves it, and from the solution H2O precipitates it unchanged.
Boiling HNOs, or potassium permanganate, oxidizes it to dextro
camphoric acid, C;, H; 0,. Concentrated H2SO4 forms with it a
black solution, from which H2O precipitates camphene. Distilled
with P2O5, it yields cymene, Ci0Hi4. Alkaline solutions, by long
heating under pressure, convert it into campnic acid, d ,,H , ,-O.j, and
"borneol. Cl attacks it with difficulty. Br unites with it to form
an unstable compound, which forms ruby-red crystals, having the
composition CioHi4OBr2. These crystals, when heated to 80'-90°
(176°-194" F.), fuse and give off HBr, there remaining an amber-
colored liquid, which solidifies on cooling, and yields, by recrys-
458 MANUAL OF CHEMISTRY.
tallization from boiling alcohol, long, hard, rectangular crystals of
monobromo camphor— Camphora monobromata (U. S.) — Ci 0H, 5OBr.
When vapor of camphor is passed over a mixture of fused potash
and lime, heated to 300°-400° (572°-752° F.), it unites directly with
the potash to form the K salt of campholic acid, doH^O..
Borneol — Borneo camphor — Camphol — Camphyl alcohol — Ci0HJ8
O — 154 — is usually obtained from Dryobalanops camphora, al-
though it may be obtained from other plants, and even artificially
by the hydrogenation of laurel camphor. The product from these
different sources is the same chemically, so far as we can deter-
mine, but varies, like the modifications of camphor, in its action
on polarized light.
It forms small, white, transparent, friable crystals ; has an odor
which recalls at the same time those of laurel camphor and of
pepper ; has a hot taste ; is insoluble in water, readily soluble in
alcohol, ether and ^acetic acid; fuses at 198° (388°. 4 F.), boils at
212° (413°.6F.).
It is a true alcohol, and enters into double decomposition with
acids to form ethers. When heated with P2O6, it yields a hydro-
carbon, borneene, Ci0Hi6. Oxidized by HNO3, it is converted into
laurel camphor.
Menthol — Menthyl alcohol — CioH20O — 156 — exists in essential oil
of peppermint. It crystallizes in colorless prisms; fusible at 36°
(96°. 8 F.); sparingly soluble in water; readily soluble in alcohol,
ether, carbon disulfid, and in acids. Corresponding to it are
a series of menthyl ethers.
Eucalyptol — Ci2H,0O — 180 — is contained in the leaves of Euca-
lyptus globulus ; it is liquid at ordinary temperatures, and boils at
175° (347° F.); by distillation with phosphoric anhydrid it yields'
eucalyptene, Ci2Hi8.
Resins — are generally the products of oxidation of the hydro-
carbons allied to terebenthene ; are amorphous (rarely crystal-
line) ; insoluble in water ; soluble in alcohol, ether, and essences.
Many of them contain acids.
They may be divided into several groups, according to the
nature of their constituents: (1.) Balsams, which are usually soft
or liquid, arid are distinguished by containing free cinnamic or
benzoic acid (q.v.). The principal members of this group are
benzoin, liquidambar, Peru balsam, styrax, and balsam tolii.
(2.) Oleo-resins consist of a true resin mixed with an oil, and usu-
ally with an oxidised product other than cinnamic or benzoic
acid. The principal members of this group are Burgundy and
Canada pitch, Mecca balsam, and the resins of capsicum, copaiva,
cubebs, elemi, labdanum, and lupulin. (3.) Gum-resins are mix-
tures of true resins and gums. Many of them are possessed of
TEREBENTHIC SERIES. 4591
medicinal qualities; aloes, ammoniac, asafcetida, ~bdellium, eu~
phorbium, galbanum, gamboge, guaiac, myrrh, olibanum, opop-
onax, and scammony. (4.) True resins are hard substances ob
tainable from the members of the three previous classes, and
containing neither essences, gums, nor aromatic acids. Such are
colophony or rosin, copal, dammar, dragon's blood, jalap, lac+
mastic, and sandarao, (5.) Fossil resins, such as amber, asphalt*,
and ozocerite.
460 MANUAL OF CHEMISTRY.
COMPOUNDS OF UNKNOWN CONSTITUTION.
GLTJCOSIDS.
Under this head are classed a number of substances, some of
them important medicinal agents, which are the products of veg-
etable or animal nature. Their characteristic property is that,
under the influence of a dilute mineral acid, they yield glucose,
phloroglucin or mannite, together with some other substance.
Under the supposition that glucose and its congeners are alcohols,
it is quite probable that the glucosids are their corresponding
ethers.
Amygdalin, C2oH27NOn — 457 — exists in cherry-laurel and in bit-
ter almonds, but not in sweet almonds. Its characteristic reac-
tion is that, in the presence of emulsin, which exists in sweet as
well as in bitter almonds, and of water, it is decomposed into
glucose, benzoic aldehyde, and hydrocyanic acid. The same re-
action is brought about by boiling with dilute H2SO4 or HC1.
Bitter almonds contain about 2 per cent, of amygdalin.
Digitalin. — The pharmaceutical products sold under the above
name, and obtained from digitalis, are mixtures in varying pro-
portions of several glucosids. Digitonin, C3iH62Oi7, an amorphous,
yellowish substance, very soluble in aqueous alcohol. Digitalin,
C6H8O2, the principal constituent of the French digitalin, is a col-
orless, very bitter, crystalline solid, insoluble in water, soluble in
alcohol. Digitalein, a white, intensely bitter, amorphous solid,
very soluble in water, soluble in alcohol. Digitoxin, CaiHesOr,
a colorless, crystalline solid, insoluble in water, sparingly soluble
in alcohol. It is not a glucosid, and is converted into toxiresin
by dilute acids.
The Abstractum digitalis (TT. S.) probably contains all the above,
the extraction of the first being more complete with weak alcohol,
that of the others with strong alcohol.
Glycyrrhizin. — A non-cry stallizable, yellowish, pulverulent prin-
ciple, obtained from liquorice; soluble with difficulty in cold
water, soluble in hot water, alcohol, and ether; bitter-sweet in
taste. By long boiling with dilute acids it is decomposed into
glucose and glycyrrhetin, Ci8H26O4.
Jalapin — C34H5cOio — 720 — is the active principle of scammony,
and exists also to a limited extent in jalap (see below). It is an
insipid, colorless, amorphous substance, which is decomposed by
dilute acids into glucose and jalapinol. The active ingredient of
jalap is not, as the name would imply, jalapin, but a resinous
.substance called convolvulin, which is insoluble in ether, odorless,
COMPOUNDS OF UNKNOWN CONSTITUTION. 461
and insipid. It is not attacked by dilute HsSCh, although the
concentrated acid dissolves it with a cariuine-red color, slowly
turning to brown ; in alcoholic solution it is decomposed by gase-
ous HC1 into glucose and convolvulinic acid.
Quinovin. — Quinovatic acid. — A bitter principle, possessed of
acid functions, obtained from the false bark, known as Cinchona
nova ; it is a glucosid, being decomposed by dilute acids into a
sugar resembling mannitan and quinovic acid.
Salicin — Salicinum (TJ. S.) — Ci3Hi807 — 286— occurs in the bark of
the willow (salix). It is a white, crystalline substance ; insoluble
in ether, soluble in water and in alcohol ; very bitter, its solutions
are dextrogyrous, [a]D = +55°. 8. Dilute acids decompose it into
glucose and saligenin (q.v.). Concentrated H2SO4 colors it red,
the color being discharged on the addition of water. When taken
into the economy it is converted into salicylic aldehyde and acid,
which are eliminated in the urine.
Santonin — Santonic acid — Santoninum (T7. S., Br.) — CirH,.0;, —
246. — A glucosid having distinct acid properties; obtained from
various species of Artemisia. It crystallizes in colorless, rectan-
gular prisms, which turn yellow on exposure to light ; odorless
and tasteless; insoluble in cold water, sparingly soluble in hot
water, alcohol, and ether ; its solutions are faintly acid in reac-
tion. Santonin, in solution, gives a chamois-colored precipitate
with the ferric salts, and a white precipitate with silver, zinc, and
mercurous salts ; no precipitate with mercuric salts.
Patients taking santonin pass urine having the appearance of
that containing bile, which, when treated with potash, turns
cherry-red or crimson, the color being discharged by an acid, and
regenerated on neutralization.
Solanin. — A glucosid, having basic properties, existing in differ-
ent plants of the genus /Solanum. It crystallizes in fine, white,
silky needles ; having an acrid, bitter taste ; insoluble in water,
and but sparingly soluble in ether and in alcohol. By the action
of hot dilute acids it is decomposed into glucose and a basic sub-
stance, solanidin. When not heated, solanin combines with
acids to form uncrystallizable salts. Cold concentrated HaSO*
colors it orange-yellow, and finally forms with it a brown solu-
tion ; HNO3 dissolves it, the solution being at first colorless, after-
ward rose-pink.
Strophanthin— C2oH34Oio — a glucosid from Strophanthus Kombg,
forms white, crystalline plates, bitter in taste, slightly soluble in
water, more soluble in alcohol, insoluble in ether, carbon disulfid
and benzene.
Tannins— Tannic acid — Ci4H10O9 — 322.— Quite a number of dif-
ferent substances of vegetable origin, principally derived from
barks, leaves, and seeds. They are amorphous, soluble in water.
462 MANUAL OF CHEMISTRY.
astringent, capable of precipitating albumen, and of forming im-
putrescible compounds with the gelatinoids. They are, with one
possible exception, glucosids.
Gallo-tannic acid — Acidum tannicum (U. S., Br.) — is the best
known of the tannins, and is obtained from nut-galls, galla (U. S.,
Br.), which are excrescences produced upon oak trees by the
puncture of minute insects. It appears as a yellowish, amor-
phous, odorless, friable mass ; has an astringent taste ; very solu-
ble in water, less so in alcohol, almost insoluble in ether ; its solu-
tions are acid in reaction, and on contact with animal tissues
give up the dissolved tannin, which becomes fixed by the tissue
to form a tough, insoluble, and non-putrescible material (leather).
A freshly prepared solution of pure gallo-tannic acid gives a
dark blue precipitate with ferric salts, but not with ferrous salts.
If, however, the solution have been exposed to the air, it is
altered by oxidation, and gives, with ferrous salts, a black color
(in whose production gallic acid probably plays an important
part), which is the coloring material of ordinary writing-ink.
Caffetannic acid — exists in saline combination in coffee and in
Paraguay tea. It colors the ferric salts green, and does not affect
the ferrous salts, except in the presence of ammonia ; it precipi-
tates the salts of quinin and of cinchonin, but does not precipi-
tate tartar emetic or gelatin. It is a glucosid, being decomposed
by suitable means into caffeic acid and mannitan.
Cachoutannic acid — obtained from catechu, is soluble in water,
alcohol, and ether. Its solutions precipitate gelatin, but not
tartar emetic ; they color the ferric salts grayish-green.
Morintannic acid — Maclurin — a yellow, crystalline substance,
obtained from fustic ; more soluble in alcohol than in water. Its
solutions precipitate green with ferroso-ferric solutions; yellow
with lead acetate ; brown with tartar emetic ; yellowish-brown
with cupric sulfate. It is decomposable into phoroglucin and
protocatechuic acid.
Quercitannic acid — is the active tanning principle of oak-bark ;
it differs from gallo-tannic acid in not being capable of conversion
into gallic acid, and in not furnishing pyrogallol on dry distilla-
tion. It forms a violet-black precipitate with ferric salts. The
tannin existing in black tea seems to be quercitannic acid.
Q,uinotannic acid — a tannin existing in cinchona barks, proba-
bly in combination with the alkaloids. It is a light yellow sub-
stance ; soluble in water, alcohol, and ether ; its taste is astringent,
but not bitter. Dilute H2SO4 decomposes it, at a boiling temper-
ature, into glucose and a red substance — quinova red.
ALKALOIDS.
463
ALKALOIDS.
The constitution of some of the substances belonging to this
•class has been more -or less definitely established, yet there re-
main many of whose chemical relations little is known. Those
whose constitution has been determined have been already con-
sidered.
The alkaloids are organic, nitrogenized substances, alkaline in
reaction, and capable of combining with acids to form salts in the
same way as does ammonia. They are also known as vegetable
or organic bases or alkalies. The similarity between the rela-
tion of the free alkaloids to their salts and that of ammonia to
the aminoniacal salts is shown in the following equations :
2XH,
Ammonia.
2Ci7H,.NO.
Morphin.
Sulfuric acid.
Sulfuric acid.
Ammouiuni sulfate.
(CiTH,.NO.),SO«
Morphium sulfate.
Classification.— The natural alkaloids are temporarily arranged
in two groups :
(1.) Those which are liquid and volatile, and consist of carbon,
hydrogen and nitrogen.
(2.) Those which are solid, crystalline, volatile with difficulty,
if at all, and consist of C, H, N and O.
General Physical Characters. — As a rule they are insoluble, or
nearly so, in water; more soluble in alcohol, chloroform, petro-
leum-ether, and benzene. Their salts are, for the most part, sol-
uble in water and insoluble or sparingly soluble in petroleum-
ether, benzene, ether, chloroform, and ainyl alcohol. All exert
a rotary action on polarized light :
Quinin
Vr]
— —126°. 7
Codein
'"]
— — 118°.2
Quinidin ..
a
— +250° 75
Narcein
i/
— — (3° 7
Cinchonin
(f
— +190° 4
Strychnin.
'i^
— — 132°.07
Cinchonidin ....
a
— — 144°.61
Brucin
'</'
— — 010.27
Morphin
ci
— _ 88°.4
Nicotin ,
d
— — 93°.5
Narcotin. .
a
= -103°. 5
Generally, combination with an acid diminishes their rotary
power; with quinin the reverse is the case. Free narcotin is
laevogyrous; its salts are dextrogyrous. They are all bitter in
taste.
General Chemical Reactions. — Potash, soda, ammonia, lime,
baryta, and magnesia precipitate the alkaloids from solutions of
their salts.
Phosphomotybdic acid forms a precipitate which is bright yel-
low, with anilin, morphin, veratrin, aconitin, emetin, atropin,
hyoscyamin, thein, theobromin, coniln, and nicotin; brownish-
MANUAL OF CHEMISTRY.
yellow with narcotin, codein, and piperin; yellowish- white with
quinin, cinchoniii and strychnin ; yolk-yellow with brucin.
The reagent is prepared as follows: Ammonium molybdate is-
dissolved in H2O, the solution filtered, and a quantity of hydro-
disodic phosphate \ in weight of the molybdate used is added,
and then HNO3 to strong acid reaction. The mixture is wanned;
set aside for a day; the yellow ppt. collected on a filter; washed
with H2O acidulated with HNO3 ; and while still moist transferred
to a porcelain capsule, to which the liquid obtained by exhaust-
ing the remainder on the filter with NH4HO is added. The fluid
is warmed and gradually treated with pulverized sodium carbon-
ate until a colorless solution is obtained. This is evaporated to-
dryness; a small quantity of sodium nitrate is added, and the
whole gradually heated to quiet fusion and until all NH3 is ex-
pelled. The residue is dissolved in warm H2O (1 to 10), acidulated
with HNO3, and decanted.
To use the reagent, a drop of the suspected liquid is placed on
a glass plate with a black background, and near it a drop of the
reagent; and the two drops are made to mix slowly by a pointed
glass rod.
Potassium iodhydrargyrate gives a yellowish precipitate with
alkaloidal solutions which are acid, neutral, or faintly alkaline in
reaction.
The reagent is obtained by dissolving 13.546 grams of mercuric
chlorid and 49.8 grams of potassium iodid in a litre of water.
The solution may be used for quantitative determinations.
The reagent is added from a burette to the solution of alkaloid
until a drop, filtered from the solution which is being tested, and
placed upon a black surface, gives no precipitate with a drop of
the reagent. Each c.c. of reagent used indicates the presence in
the volume of liquid tested of the following quantities of alka-
loids, in grams :
Aconitin 0.0267 Morphin 0.0200
Atropin 0.0145 Conim 0.00416
Narcotin 0.0213 Nicotin 0.00405
Strychnin 0.0167 Quinin 0.0108
Brucin 0.0233 Cinchonin 0.0102
Veratrin . . 0.0269 Quinidin 0.0120
Of course, the process can be used only in a solution containing
a single alkaloid.
Separation of Alkaloids from. Organic Mixtures and. from Each.
Other. — One of the most difficult of the toxicologist's tasks is the
separation from a mixture of organic material (contents of stom-
ach, viscera) of an alkaloid in such a state of purity as to render
its identification perfect. The difficulty is the greater if the
amount present be small, as is usually the case ; and if the search
be not confined to a single alkaloid, as frequently occurs. Some
of these substances, as strychnin, are detectable with much greater
facility and certainty than others.
ALKALOIDS. 465
Of the processes hitherto suggested, the best is that of Dragen-
dorff, devised for the detection of any alkaloid or poisonous or-
ganic principle present in the substances examined. It is very
exhaustive, and well adapted to cases frequently arising in
chemico -legal practice ; but, on the other hand, is too intricate to
be serviceable to the general practitioner.
An abridgement of this process may be of use to detect the
presence of the more commonly used alkaloids in a mixture of
organic material. The physician should, however, bear in mind
that, in cases liable to give rise to legal proceedings, these may
become seriously complicated by the analysis of any parts of the
body, dejecta, or suspected articles of food, etc., by any process
open to attack by the most searching cross-examination.
The substances to be examined are reduced to a fine state of
subdivision, and are digested for an hour or more in water acid-
ulated with H2SO4, at a temperature of 40° to 50° (104°-122° F.);
this is repeated three times, the liquid being filtered and the solid
material expressed. The united extracts are evaporated at the
temperature of the water- bath to a thin syrup ; this is mixed with
three or four volumes of alcohol, the mixture kept at about 35°
(95° F.) for 24 hours, cooled well and filtered; the residue being
washed with seventy per cent, alcohol. The alcohol is distilled
from the filtrate, and the watery residue diluted with H2O and
filtered.
The filtrate so obtained contains the sulfates of the alkaloids,
and from it the alkaloids themselves are separated by the follow-
ing steps :
A. The acid watery liquid is shaken with freshly rectified
petroleum-ether (which should boil at about 65°-70° (149°-158° F.),
and should be used with caution, as it is very inflammable) ; after
several agitations the ether layer is allowed to separate and is
removed ; this treatment is repeated so long as the ether dissolves
anything. The residue obtained by the evaporation of the ether
— Residue I. — is mostly composed of coloring matters, etc., which
it is desirable to i-emove.
B. The same treatment of the watery liquid is repeated with
benzene, which on evaporation yields Residue II. , which is, if
crystalline, to be tested for cantharidin, santonin, and digitalin
(q.v.); if amorphous, for elaterin and colchicin.
G. The acid, aqueous fluid is then treated in the same way
with chloroform to obtain Residue III., which is examined for
cinchouin, digitalin, and picrotoxin by the proper tests.
D. The watery fluid, after one more shaking with petroleum-
ether and removal of the ethereal layer, is rendered alkaline with
ammonium hydroxid and shaken with petroleum-ether at 40° (104°
F.), the ethereal layer being removed as quickly as possible while
still warm ; this is repeated two or three times, and repeated with
cold petroleum-ether, which is removed after a time. The warm
ethereal layers yield Residue IV. a ; the cold ones Residue IV. b.
The former is tested for strychnin, quinin, brucin, veratrin; the
latter for conitn and nicotin."
E. The alkaline, watery fluid is shaken with benzene, which,
on evaporation, yields Residue V., which may contain strychnin,
30
466 MANUAL OF CHEMISTRY.
brucin, quinin, cinchonin, atropin, hyoscyamin, physostigmln,
aconitin, codein, thebai'n, and narcetn.
F. A similar treatment with chloroform yields Residue VI.,
which may contain a trace of morphin.
G. The alkaline liquid is then shaken with amyl alcohol, which
is separated and evaporated; Residue VII. is tested for morphin,
solanin, and salicin.
H. Finally, the watery liquid is itself evaporated with pounded
glass, the residue extracted with chloroform, and Residue VIII.,
left by the evaporation of the chloroform, tested for curarin.
Volatile Alkaloids.
The most important alkaloids of this class are nicotin (see
p. 438), coniln (see p. 425), and sparteln.
Spartein — Ci5H26N2 — a colorless oil, whose odor resembles that
of anilin; extremely bitter in taste; sparingly soluble in water,
forming an alkaline solution. On exposure to air becomes brown
and resinous.
Fixed Alkaloids.
These are much more numerous than those which are volatile,
and form the active principles of a great number of poisonous
plants. The classification adopted for such of these alkaloids as
must still be included among the substances of unknown con-
stitution is a temporary one, based upon the botanic character
of the plants from which they are derived.
Alkaloids of the Loganiaceae. — Strychnin — Strychnina (U. S.;
— C2iH2oNoO2 — 334— exists in the seeds and bark of different van's
ties of strychnos.
It crystallizes on slow evaporation of its solutions in ortho-
rhombic prisms, by rapid evaporation as a crystalline powder;
very sparingly soluble in H2O and in strong alcohol ; soluble in
5 pts. chloroform. Its aqueous solution is intensely bitter, the
taste being perceptible in a solution containing 1 pt. in 600,000.
It is a powerful base ; neutralizes and dissolves in concentrated
H2SO4 without coloration; and precipitates many metallic oxids
from solutions of their salts. Its salts are mostly crystallizable,
soluble in H2O and alcohol, and intensely bitter. The acetate is
the most soluble. The neutral sulfate crystallizes, with 7 Aq,
in rectangular prisms. The iodids of methyl and ethyl react with
strychnin to produce the iodids of methyl or ethylstrychnium,
white, crystalline, basic substances, producing an action on the
economy similar to that of curare. When acted on by H2SC>4 and
potassium chlorate, with proper precautions, strychnic or igasuric
acid is formed.
ANALYTICAL CHARACTERS. — (1.) Dissolves in concentrated
H2SO4 without color. The solution deposits strychnin when di-
ALKALOIDS. 467
luted w th H2O, or when neutralized with magnesia or an alkali.
(2.) If a fragment of potassium dichromate (or other substance
capable of yielding nascent O) is drawn through a solution of
strychnin in H2SO4, it is followed by a streak of color; at first
blue (very transitory and frequently not observed), then a bril-
liant violet, which slowly passes to rose-pink, and finally to yel-
low. Reacts with ^J^TTO grain of strychnin. (3.) A dilute solution
of potassium dichromate forms a yellow, crystalline ppt. in
strychnin solutions ; which, when washed and treated with con-
centrated H2SO4, gives the play of colors indicated in 2. (4.) If a
solution of strychnin be evaporated on a bit of platinum foil, the
residue moistened with concentrated H2SO4, the foil connected
with the + pole of a single Grove cell, and a platinum wire from
the — pole brought in contact with the surface of the acid, a violet
color appears upon the surface of the foil. (5.) Strychnin and
its salts are intensely bitter. (6.) A solution of strychnin intro-
duced under the skin of the back of a frog causes difficulty of
respiration and tetanic spasms, which are aggravated by the
slightest irritation, and twitching of the muscles during the in-
tervals between the convulsions. With a small frog, whose sur-
face has been dried before injection of the solution, T^TJTT grain of
acetate of strychnin will produce tetanic spasms in 10 minutes.
(7.) Solid strychnin, moistened with a solution of iodic acid in
H2SO4, produces a yellow color, changing to brick-red and then to
violet-red. (8.) Moderately concentrated HNO3 colors strychnin
yellow in the cold. A pink or red color indicates the presence
of brucin.
TOXICOLOGY. — Strychnin is one of the most active and most
frequently used of poisons. It produces a sense of suffocation,
thirst, tetanic spasms, usually opisthotonos, sometimes einpros-
thotonos, occasionally vomiting, contraction of the pupils during
the spasms, and death, either by asphyxia during a paroxysm, or
by exhaustion during a remission. The symptoms appear in
from a few minutes to an hour after taking the poison, usually
in about 20 minutes ; and death in from 5 minutes to 6 hours,
usually within 2 hours. Death has been caused by i grain, and
recovery has followed the taking of 20 grains.
The treatment should consist of the removal of the unabsorbed
poison by the stomach-pump, injecting charcoal, and pumping it
out after about 5 minutes ; under the influence of chloroform if
necessary. Chloral hydrate should be given.
Strychnin is one of the most stable of the alkaloids, and may
remain for a long time in contact with putrefying organic matter
without suffering decomposition.
Brucin — C23H26N2O4-|-4Aq — 394-)- 72 — accompanies strychnin. It
forms oblique rhomboidal prisms, which lose their Aq in dry air.
468 MANUAL OF CHEMISTRY.
Sparingly soluble in H2O; readily soluble in alcohol, chloroform,,
and amyl alcohol ; intensely bitter. It is a powerful base and
most of its salts are soluble and crystalline. Its action on the
economy is similar to that of strychnin, but much less energetic.
ANALYTICAL CHARACTERS. — (1.) Concentrated HNO3 colors it
bright red, soon passing to yellow ; stannous chlorid, or colorless
NH4HS, changes the red color to violet. (2.) Chlorin-water,or CL
colors brucin bright red, changed to yellowish-brown by NH4HO.
Alkaloids of the Solanaceae. — Solanin — C43H71N"016 — 857 — ob-
tained from many species of /Solanum; crystallizes in small,
white, bitter, sparingly soluble prisms. Concentrated H2SO4
colors it orange-red, passing to violet and then to brown. It is
colored yellow by concentrated HC1. It dissolves in concen-
trated HNO3, the solution being at first colorless, but after a.
time becomes purple.
Hyoscyamin— C17H23NOS — occurs, along with another base, hy-
oscin, both isomeric with atropin, in Hyoscyamus niger. It
crystallizes, when pure, in odorless, white, silky needles whose
taste is very sharp and disagreeable, and which are very sparingly
soluble in water. As most commonly met with, it forms a
yellowish, soft, hygroscopic mass which gives off a peculiar, to-
bacco-like odor. It neutralizes acids. Its sulfate — Hyoscyaminee
sulfas, U. S.— forms yellowish crystals, very soluble in water,
hygroscopic, and neutral in reaction.
See Atropin (p. 427).
Alkaloids of the Aconites.— The different species of Aconitum
contain, probably, a number of alkaloids, but our knowledge of
them is as yet extremely imperfect. The substances described
as aconitin, lycoctanin, napellin are impure. It appears, how-
ever, that the principal alkaloids of aconitum napellus and of
A. ferox, although differing from each other, are both compounds
formed by the union of aconin, C26H39NOn, with the radical of
benzoic acid in the former, and with that of veratric acid in the
latter.
Aconitin — C33H43Ni2 (?) — the principal alkaloid of A. napellus,
is a crystalline solid, almost insoluble in water, and very bitter.
It is decomposed by H2O at 140° (284° F.) and by KHO into
aconin and benzoic acid. It is very poisonous.
Pseudo-aconitin—C36H49NO1 2 — occurs in A. ferox. It is a
crystalline solid, having a burning taste, and is extremely poison-
ous. On decomposition by H2O at 140° (284° F.) it yields aconin
and veratric acid.
Japaconitin — CoeHseNjOai — has been obtained from" the root of
A. japanicum, and is a crystalline solid which is decomposed by
alkalies into benzoic acid and japaconin, CnCH4,NO]o.
ALKALOIDS. 469
The color reactions described as characteristic of "aconitine"
are not due to the alkaloid.
TOXICOLOGY. — Aconite and "aconitin" have been the agents
used in quite a number of homicidal poisonings.
The symptoms usually manifest themselves within a few min-
utes ; sometimes are delayed for an hour. There is numbness and
tingling, first of the mouth and fauces, later becoming general.
There is a sense of dryness and of constriction in the throat. Per-
sistent vomiting usually occurs, but is absent in some cases.
There is diminished sensibility, with numbness, great muscular
feebleness, giddiness, loss of speech, irregularity and failure of the
heart's action. Death may result from shock if a large dose of
the alkaloid be taken, but more usually it is by syncope.
The treatment should be directed to the removal of unabsorbed
poison by the stomach-pump, and washing out of the stomach
with infusion of tea holding powdered charcoal in suspension.
Stimulants should be freely administered.
Alkaloids from other Sources. — Ergotin — d,0H.s,^N2O3 — and Ec-
bolin are two brown, amorphous, faintly bitter, and alkaline
alkaloids obtained from ergot. They are readily soluble in wyater
and form amorphous salts. The medicinal preparations known
as ergotin are not the pure alkaloid.
Colchicin — CnH19NO6 — occurs in all portions of Colchicum au-
tumnale and other members of the same genus. It is a yellowish-
white, gummy, amorphous substance, having a faintly aromatic
odor and a persistently bitter taste. It is slowly but completely
soluble in water, forming faintly acid solutions. It. forms salts
which are, however, very unstable.
Concentrated HNOs, or, preferably, a mixture of H2SO4, and
!XaNO3 colors colchicin blue-violet. If the solution be then di-
luted with H2O, it becomes yellow, and on addition of NaHO
solution, brick-red.
Veratrin. — Veratrina, U. S.— C32H62N2O8 — occurs in Veratrum of-
,flcinalis—Asagrcea officinal-is, accompanied by Sabadillin— C20H26
N2O;7 — Jervin — C3oH46N2O3 — and other alkaloids. The substance
to which the name Veratrina, U. S., applies is not the pure alka-
loid, but a mixture of those occurring in the plant.
Concentrated H2SC>4 dissolves veratrin, forming a yellow solu-
tion turning orange in a few moments, and then, in about half an
hour, bright carmine-red. Concentrated HC1 forms a colorless solu-
tion with veratrin, which turns dark red when cautiously heated.
Berberin— .ra/i«Ap/)«c;v7e— CauHi7NO4— occurs in Berberis vul-
garis, Cocculus palmatus, and many other plants. It crystallizes
in fine yellow needles or prisms; bitter in taste and neutral in
reaction. It is difficultly soluble in cold water, readilv soluble in
-±70 MANUAL OF CHEMISTRY.
Alcohol and in boiling water. It forms well-defined, crystalline,,
yellow salts.
Physostigmin — Eserin — Ci6H2iN3Oa — is an alkaloid existing in
the Calabar bean, Physostigma venenosum. It is a colorless,
amorphous solid, odorless and tasteless, alkaline and difficultly
soluble in water. It neutralizes acids completely, with formation
of tasteless salts. Its salicylate — Physostigminse salicylas, TJ. S.
— forms short, colorless, prismatic crystals, sparingly soluble in
water.
Concentrated H2SO4 forms a yellow solution with physostigmin
or its salts, which soon turns olive-green. Concentrated HNOS
forms with it a yellow solution. If a solution of the alkaloid in
H2SO4 be neutralized with NH4HO, and the mixture warmed, it
is gradually colored red, reddish-yellow, green, and blue.
Curarin— CseHssN (?) — is an alkaloid obtainable from the South
American arrow-poison, curare, or woorara. It crystallizes in
four-sided, colorless prisms, which are hygroscopic, faintly alka-
line, and intensely bitter.
Curarin dissolves in H2SO4, forming a pale violet solution, which,
slowly changes to red. If a crystal of potassium dichromate be
drawn through the H2SO4 solution, it is followed by a violet color-
ation, which differs from the similar color obtained with strychnin
under similar circumstances, in being more permanent, and in the
absence of the following pink and yellow tints.
Emetin — C28H4oN2O5 — an alkaloid existing in ipecacuanha
which crystallizes in colorless needles or tabular crystals, slightly
bitter and acrid ; odorless, and sparingly soluble in water.
It dissolves in concentrated H2SC>4, forming a green solution,
which gradually changes to yellow. With Fro'hde's reagent it
gives a red color, which soon changes to yellowisn-green and then
to green.
Ptomains. — This name, derived from 7rrw^a=that which is fallen
— i.e., a corpse — was first suggested by Selini to apply to a class of
substances, first distinctly recognized by him, which are produced
from albuminoid substances under the influence of putrefactive-
decomposition, and which are distinctly alkaloidal in character.
The ptomains are possessed of all of the distinguishing charac-
ters of the vegetable alkaloids. They are alkaline in reaction,
and combine with acids to form salts. Some are liquid, others-
are solid and crystalline. Some are actively poisonous, others are
practically inert. They behave toward the general reagents for
alkaloids in much the same way as do the vegetable alkaloids.
Although the names ptomains and cadaveric alkaloids are ap-
plied to alkaloids of animal origin, it is certain that such alkaloids
may be and are produced during life in the animal economy.
ALKALOIDS. 4T1
It was feared that, as alkaloidal substances in many respects
resembling those of vegetable origin are produced in the animal
body, not only after death, but during life, grave doubts would
be cast upon the results of analyses made to detect the presence
of poisonous vegetable alkaloids in the cadaver in cases of sus-
pected poisoning. Such fears were by no means groundless, as
there is abundant evidence that ptomains have been mistaken for
vegetable alkaloids in cheiiiico-legal analyses. The ptomains,
however, as well as the vegetable alkaloids, may be positively
identified by a careful analysis, based upon the use, not of a single
reaction, but of all known reactions for the alkaloid in question.
Therefore, it is possible to positively predicate the existence or
non-existence of a given vegetable alkaloid in a cadaver, but it
can only be done after a thorough and conscientious examination,
by all physiological and chemical reactions.
The ptomains have of recent years assumed great importance
to the physician by reason of their bearing upon the etiology of
disease, and sufficient experimental evidence has already been
obtained to warrant the belief that the method of action of many
of the known pathogenic bacteria is by their production of alka-
loidal poisons (see below).
One of the first of the putrid alkaloids to be formed in cadaveric
matter is cholin (see pp. 276, 361), which undoubtedly has its ori-
gin in the decomposition of the lecithins.
Mydalein is a putrid alkaloid, of undetermined composition,
forming a difficultly crystallizable, hygroscopic chlorid, which is
actively poisonous. Five milligrammes administered hypoder-
mically to a cat causes death after profuse diarrhoea and secretion
of saliva, violent convulsions, and paralysis, beginning with the
extremities and extending to the muscles of respiration.
Mydin — C6HnNO — is abase produced after continued putrefac-
tion at comparatively low temperatures. It is a powerful base
and a strong reducing agent, and has an ainmoniacal odor. It is
non-poisonous.
Mydatoxin— C6H12NO2 — is a strongly alkaline syrup, which pro
duces, when administered to animals, violent clonic spasms, fol-
lowed by paralysis and death.
An alkaloid, many of whose chemical reactions have been de-
termined, although its composition is unknown, has been obtained
from the internal organs, and dejecta of cholera victims, as well
as from cultures of the comma bacillus. This alkaloid, when ad-
ministered to animals, causes symptoms of poisoning and death.
From the cultures of the Koch-Eberth typhus bacillus an alka-
loid has been isolated — Typhotoxin, C7H,7NO« — which, when ad-
ministered to animals, causes paralysis, copious diarrhoea, and
death.
4l2 MANUAL OF CHEMISTRY.
Tetanin — CiaH3oN2O4 — is an alkaloid obtained from cultures of
a bacillus originating from a wound which had been the cause of
death by tetanus. It forms a deliquescent chlorid, and a very
soluble chloroplatiriate. The free base or its chlorid, when in-
jected into mice or guinea-pigs, causes clonic or tonic convulsions
of the greatest intensity, which terminate in death.
Mytilitoxin — C6H15NO2 — is an alkaloid obtained from poisonous
mussels, which, when administered to animals in small amount,
causes the same symptoms as are produced by the mussels.
JB'or other ptomains see Trimethylamiii, p. 275 ; Cholin, p. 276;
Muscarin and neurin, p. 277 ; Neuridin, pp. 277, 333 ; Diamins
and triamins, pp. 333 et seq.; Pyridin derivatives, pp. 424 et seq.
See also Toxalbumins, below.
ALBUMINOID SUBSTANCES.
PROTEIN BODIES.
The substances of this class are never absent in living vegetable
or animal cells, to whose "life" they are indispensable. They
are as yet the products exclusively of the organized world.
Physical Characters. — They are almost all uncrystallizable and
incapable of dialysis. Some are soluble in water, others only in
water containing traces of other substances, others are insoluble.
Their solutions are all Isevogyrous. Some are separated as solids
from their solutions, in a permanently modified form, by heat
and by certain reagents; a change called coagulation. When
once coagulated they cannot be redissolved. The temperature at
which coagulation by heat occurs varies with different albumi-
noids, and is of value in distinguishing them from one another.
Composition. — They consist of C, N, H, O, and usually a small
quantity of S, and form highly complex molecules, whose exact
composition is uncertain. Of their constitution nothing is defi-
nitely known, although there is probability that they are highly
complex amids, related to the ureids, and formed by the com-
bination of glycollamin, leucin, tyrosin, etc., with radicals of the
acetic and benzoic series.
Decompositions.— The study of the products of decomposition
of the albuminoids is of great importance, being the means by
which a knowledge of their constitution and chemical relation-
ships must be sought for.
Oxidizing agents attack the molecule of the albuminoids pro-
foundly, yielding products far removed from the original sub-
stance : A mixture of H2SO4 and manganese dioxid, or potassium
dichromate, produces aldehydes, and acids of the fatty and ben-
ALBUMINOID SUBSTANCES. 473
zoic series, hydrocyanic acid, and cyanids from the albuminoids.
When heated under pressure with Br and H2O they yield CO2,
oxalic and aspartic acids, amido-acids, and bromin derivatives of
the fatty and benzoic series. Potassium permanganate produces
from them urea, CO2, NHa and H2O.
Dilute acids decompose them into two substances : one insolu-
ble, amorphous, yellowish, called hemiprotein; the other soluble
in water, insoluble in alcohol, faintly acid, called hemialbumin.
A prolonged boiling with moderately concentrated H2SO4 de-
composes them, forming well-defined substances — glycocol, leu-
cin, tyrosin ; aspartic and glutamic acids.
Alkalies dissolve them more or less readily ; on boiling the so-
lution, part of the sulfur is converted into sulfid and hyposulfite.
Their alkaline solutions, when neutralized by acids, deposit
Mulder's protein. Concentrated alkalies decompose them into
amido-acids. By fusion with alkalies, alkaline cyanids are also
produced.
The action of hydrating agents, comparable with those by
which the fats are saponified, the compound ethers decomposed,
and the starches converted into sugar, have yielded the most im-
portant results. The most manageable reagent for the purpose
is barium hydroxid in the presence of H2O at elevated tempera-
tures under pressure. The product of the reaction gives off am-
monia and has the odor of fecal matter. It contains, if the albu-
minoid decomposed was gelatin, ammonia, carbon dioxid, oxalic
acid, acetic acid, and amido-derivatives. The last named belong
to two classes : leucins, glycocol, alanin, amidobutyric acid,
amidovaleric acid, caproic leucin — leucelns, which are amido de-
rivatives corresponding to pyrrol and related to the dimethyl
and trimethyl pyrrols existing in oil of Dippel. When the albu-
minoid decomposed by BaH2O2 is albumin the products of the
reaction are more complex. If the decomposition is effected at
100° (212° F.), there are produced, besides the substances obtained
from gelatin, glucoprotelns, having the formula CnH-mNaCh,
which are the first products of the hydration and some of which
by further hydration are decomposed into leucins and leucelns ;
and a substance crystallizing with difficulty, transparent, sweet
in taste, called diluceln, which on further hydration, at 180°
(356° F.), yields a glucoprotei'n and proteic acid. '
As a result of the study of the products of hydration of gelatin
and of albumen the empirical formula of the former has been deter-
mined to be C32H62NioOi2, and that of the latter C6oHiooNi6O2o.
Albuminoids are subject to a form of decomposition peculiar
to themselves and known as putrefaction, which has been the
subject of much careful study of recent years. Putrefaction is a
decomposition of dead albuminoid matter under the influence and
474 MANUAL OF CHEMISTRY.
as a result of the processes of nutrition of certain bacteria, and
attended by the evolution of more or less fetid products.
That putrefaction may occur certain conditions are necessary:
(1) The presence of living bacteria, or of their germs ; (2) the-
presence of air ; (3) the presence of moisture ; (4) a temperature
between 5° and 90° (41°-194° P.).
The bacteria which cause putrefaction are quite numerous,
and it is probable that the products are somewhat different with
different species. Their germs exist in the air, in the animal in-
testinal canal, and possibly in the pancreas. Although the bac-
teria causing putrefaction are anaerobic, putrefaction does not
progress in the absence of air, and in sealed vessels the process is-
either arrested or proceeds with extreme slowness. Albuminoids-
which have been deprived of moisture, either by drying or by
the action of dehydrating agents, such as strong alcohol, do not
enter into putrefaction unless water is supplied to them, when,
the process proceeds as usual. The temperature most favorable
to putrefaction is about 40° (104° F.). High or low temperatures-
arrest putrefaction or prevent it, the former, if sufficiently high, .
permanently (if the material be protected from new bacteria) by
destroying the vitality of the bacteria ; the latter, even if ex-
treme, only temporarily, and so long as the low temperature i»
maintained.
Putrefaction may, therefore, be prevented either (1) by the ac-
tion of agents or substances which interfere with the develop-
ment of bacteria (germicides and antiseptics); (2) by the exclusion
of air; (8) by the exclusion of water ; (4) by a temperature below
5° (41° P.) or above 90° (194° P.).
Germicides are substances or agents which destroy bacteria
and their germs. Mercuric chlorid and heat are germicides.
Antiseptics are substances which prevent or restrain putrefac-
tion. Antiseptics are either germicides, which prevent putrefac-
tion by destroying the organisms which cause it, or are agents
which interfere with the development of these organisms, with-
out destroying their vitality. The salts of aluminium are anti-
septic by reason of their chemical action on the albuminoids,
although their germicidal powers are slight.
Deodorizers, or air purifiers, are substances which destroy the
Odorous products of putrefaction.
Disinfectants are substances which restrain infectious diseases
by destroying or removing their specific poisons.
Putrefaction is attended by the breaking down and liquefac-
tion of the material if it be solid ; or its clouding and the forma-
tion of a scum upon the surface if it be liquid. The products of
putrefaction vary with the conditions under which it occurs.
The most prominent are : (1) Inorganic products such as N, H,
ALBUMINOID SUBSTANCES. 475
H2S, NH3, and simple organic compounds, such as CO2 and hy-
drocarbons ; (2) acids of the fatty series in great abundance, and
acids of the oxalic and lactic series ; (3) non -aromatic monamiris
and diamins, such as trimethylamiri, putrescin and certain of the
ptomalns; (4) aromatic products, among which are : (a) phenols,
such as tyrosin, oxyaromatic acids, phenol and cresol ; (b) phe-
nylic derivatives, such as phenyl acetic and phenyl propioriic
acids ; (c) indol, scatol, scatol-carbonic acid, etc. ; (d) ptomalns
of undetermined constitution, but belonging to the aromatic se-
ries ; pyridin derivatives.
Under certain imperfectly denned conditions, buried animal
matter is converted into a substance resembling tallow, and called
adipocere, which consists chiefly of palmitate, stearate, and oleate
of ammonium, phosphate and carbonate of calcium, and an un-
determined nitrogenous substance*
There occurs a decomposition of vegetable tissues under the
influence of warmth and moisture, which is known as erema-
causis, differing from putrefaction in that the substances decom-
posed are the carbohydrate instead of the azotized constituents,
and in the products of the decomposition, there being no fetid
gases evolved (except there be simultaneous putrefaction), and
the final product is a brownish material (humus or ulmin).
General Reactions. — The albuminoids all respond to a great
number of general reactions, which may be classified in three
groups: I. Color reactions; II. Precipitations in an insoluble
combination; alkaloidal reactions; III. Precipitations in a form
which permits of easy resolution in the primitive form.
I. (1.) A purple-red color when warmed to 70° (158° F.) with
Millon's reagent. The reagent is made by dissolving, by the aid
of heat, 1 pt, Hg in 2 pts. HNO3 of sp. gr. 1.42, diluting with 2
vols. H2O, and decanting after 24 hours. (2.) A yellow color with
HNO3; changing to orange with NH4HO (xanthoproteic reac-
tion). (3.) A purple color with Pettenkofer's test (q.v.). (4.)
With a drop or two of cupric sulfate solution and liquor potassse
a violet color. (5.) A solution of an albuminoid in excess of gla-
cial acetic- acid is colored violet and rendered faintly fluorescent
by concentrated H-,SO4. (6.) With Fro'hde's reagent (see Mor-
phin) solid albuminoids give a fine blue color. (7.) If an alkaline
solution of an albuminoid or a peptone be mixed with an alkaline
solution of diazobenzosulfonic acid a red-brown or orange color is
produced. If powdered Zii or sodium amalgam be added the
color becomes a brilliant red. (8.) Add to the albuminous liquid
two drops of an alcoholic solution of benzoic aldehyde, then some
H3SO4 diluted with an equal bulk of HSO, and finally a drop of
ferric sulfate solution: a dark blue color is produced either imme-
diately on warming, or slowly in the cold. (9.) Albumins dissolve
476 MANUAL OF CHEMISTRY.
in boiling concentrated HC1 (sp. gr. 1.19) with a violet-blue color,
and coagulated albumins are similarly colored by boiling HC1.
The color is the more distinct the purer the albuminoid. The
reaction may be applied to the albumin coagulated from urine
after collection on a filter and washing with water, alcohol, and
ether.
II. The albuminoids are precipitated in an insoluble form by:
1, the concentrated mineral acids, notably HNO3; 2, by potassium
ferrocyanid in presence of acetic acid ; 3, by certain organic acids
in the presence of concentrated solutions of NaCl or Na2SO4 ; 4,
by tannin in acid solution ; 5, by phosphomolybdic or phospho-
tungstic acid ; 6, by double iodid of potassium and mercury, or
double iodid of potassium arid bismuth, in acid solution ; 7, by
solutions of the salts of Pb, Cu, Ag, Hg, D; 8, by chloral, picric
acid, phenol or trichloracetic acid.
III. Some of the albuminoids are precipitated in a form capa-
ble of resolution by solutions of certain salts, notably by the sul-
fates and phosphates of the alkaline metals, ammonium and
magnesium.
Classification.— Until the constitution of the albuminoids shall
have been established, a rational classification of them will re-
main impossible. For the present a provisional arrangement of
the albuminoids of animal origin, based upon their solubilities,
is adopted. The vegetable albuminoids are conveniently classi-
fied by themselves. The division into albuminoids and gela-
tinoids formerly followed, and based upon the production of ar-
omatic derivatives by decomposition of the former and the
absence of such products in the case of the latter, has been
abandoned for the reason that benzoic acid and other aromatic
substances have been obtained by decomposition of gelatin.
The provisional classification is as follows :
1. ALBUMINS. — Soluble in pure water; coagulated by heat. —
Egg albumin ; serum albumin.
2. GLOBULINS. — Insoluble in pure water, but soluble in solu-
tions of neutral salts (NaCl, KC1, MgSO4, etc.); coagulated by
heat. — Vitelin, myosin, paraglobulin, fibrinogen.
3. FIBRINS. — Insoluble in pure water, swell in solutions of neu-
tral salts, and in dilute acids ; coagulated by boiling water. —
Blood fibrin.
4. COAGULATED ALBUMINOIDS. — Insoluble in water and in
saline solutions, only moderately swelled by the latter and by
dilute acids, not colored by iodin. — Produced from 1, 2, and 3 by
heat.
5. AMYLOID MATTER. — Insoluble in water, saline solutions or
dilute acids or alkalies, colored red-brown or violet by iodin.
6. ACID- ALBUMINS. — Insoluble in water, in dilute saline solu-
ALBUMINOID SUBSTANCES. 477
tions and in alcohol. When freshly precipitated readily soluble
in dilute acids or alkalies ; but insoluble when mixed with cal-
cium carbonate suspended in water.
7. ALKALI-ALBUMINS. — Very sparingly soluble in water and in
saline solutions; slightly soluble in hot alcohol. Shaken with
water and calcium carbonate they dissolve with displacement of
carbon dioxid.
8. ALBUMOSES OR PROPEPTONES. — Resemble the acid-albumins,
but dissolve in dilute solutions of NaCl. Precipitated in the cold
by HNO3, but redissolve on heating.
9. PEPTONES. — Very soluble in water, not coagulated by heat.
Are not precipitated by potassium ferrocyanid in the presence of
acetic acid, by Nad in excess in presence of an acid, by HNO3,
or by boiling with ferric acetate.
10. PROTEIDS. — May be decomposed into an albuminoid and
other substances. — Haemoglobins, casein, inucin, chondrin, and
some nucleins.
11. ALBUMINOIDS. — Insoluble, not dissolved by digestive secre-
tions.— Keratins, elastin, fibroin.
12. GELATINOUS SUBSTANCES. — Soluble in hot HtO without
modification. — Gelatin.
13. SPONQEOUS SUBSTANCES. — Dissolved by boiling water only
after modification. — Spongin, cornein.
The vegetable albuminoid substances have been much less
perfectly studied than those of animal origin. A crude classifica-
tion of them similar to that of the animal albuminoids is pro-
visionally made into four groups :
1. VEGETABLE ALBUMINS. — Soluble in H*0, coagulated by heat.
2. ALBUMINOIDS OF GLUTEN. — Insoluble in H^O and in abso-
lute alcohol; soluble in aqueous alcohol; coagulated by heat. —
Gluten-fibrin, gliadin, mucedin.
3. VEGETABLE CASEINS. — Insoluble in water and in saline
solutions ; soluble in dilute acids or alkalies ; coagulated by heat.
— Gluten-casein, legumin.
4. VEGETABLE GLOBULINS. — Similar to animal globulins, but
dissolve appreciably in pure water. Precipitated from aqueous
solution by Nad, but redissolved by an excess of the salt, and
again precipitated by a large excess.
I. ALBUMINS. — Egg albumin exists in solution, imprisoned in
a network of delicate membranes, in the white of egg. It is ob-
tained in an impure condition by cutting the whites of eggs with
scissors, expressing through linen, diluting with an equal volume
of water, filtering, and concentrating the filtrate at a temperature
below 40° (104° F.); mineral salts, which adhere to it tenaciously,
are separated by dialysis. It is a mixture of two kinds of pro-
teids. (1.) Those coagulable by heat. Of these, two are globu-
478 MANUAL OF CHEMISTRY.
lins (q. v.) precipitable by MgSO4. Their coagulation tempera-
tures are : oviglobulin a, 57°. 5 (135°. 5 F.); oviglobulin {1, 67°
(152°. 6 F.). Three are albumins which coagulate : a at 72° (161°. 6
F.), p at 76° (168° F.), and 7 at 82° (179°.6 F.). (2.) Peptones,
which increase in amount with the staleness of the egg.
Solutions of egg albumin are not precipitated by a small quan-
tity of HC1, but an excess of that acid produces a deposit which
is difficultly soluble in HC1, H2O, and salt solution. It is coag-
ulated by agitation with ether. Solutions of salts of Cu, Ag, and
Pb form precipitates with albumin, which contain definite pro-
portions of the metals. Egg albumin may be distinguished from
serum albumin by MaureFs reagent, which is a mixture of 25 cc.
NaHO solution, 5 cc. of a 3# solution of CuSO4 and 70 cc. glacial
acetic acid. Ten cc. of this reagent added to 2 cc. of the liquid
under examination precipitates egg albumin even from dilute
solution, but does not precipitate serum albumin.
When oxidized with potassium permanganate, egg albumin
yields a definite nitrogenized and sulfurated body, oxyprotein-
sulfuric acid, which is also produced from serum albumin, fibrin,
casein and conglutin, but not from peptones or propeptone ; and
by more energetic oxidation peroxyproteic acid. See Acid-albu-
mins and Alkali-albumins, below.
Serum-albumin exists in blood-serum, chyle, lymph, pericardial
fluid, the fluids of cysts and of transudations, in milk and, path-
ologically, in the urine. It is best obtained from blood-serum,
after removal of paraglobulin (q.v.), by a tedious process, and
only then in a state of doubtful purity. It is less abundant in
the blood of some animals than paraglobulin, but more abundant
in that of man.
Solutions of serum-albumin are laevogyrous [a]D = —56°; they
are not precipitated by CO2, by acetic or phosphoric acid, by ether
or by magnesium sulfate. They are precipitated by mineral
acids, tannic acid, metaphosphoric acid, and most metallic salts.
"When heated they become opalescent at 60° (140° F.), and coag-
ulate in the flocculent form at 72°-75° (161°.6-167° F.).
Human serum -albumin consists of three distinct proteids a, /?,
and 7, coagulating at 73° (163°.4 F.), 77° (170°. 6 F.), and 84° (183°.2
F.). The blood of some animals contains but two of these. They
are all precipitated, after removal of serum-globulin by saturation
with MgSO4, by saturation with ~NagSO4. Potassium acetate also
precipitates them without coagulation.
Detection and Determination of Albumin in TTrine. — If the urine
be not perfectly clear it is filtered ; if this do not render it per-
fectly transparent, it is treated with a few drops of magnesia mix-
ture (p. 120, note), arid again filtered. The filtrate, if alkaline, is
ALBUMINOID SUBSTANCES. 479
Tendered just acid by adding dilute acetic acid guttatim (nitric acid
should not be used, and the acidulation of alkaline urine is im-
perative). The urine is now heated to near boiling, and if a
cloudiness or precipitate be formed, HNO3 is added slowly to the
extent of about 10 drops. If heat produce a cloudiness, which
clears up completely on addition of H^O3, it is due to an excess
of earthy phosphates. If a cloudiness produced by heat do not
clear up (it may increase) on addition of HNO3, it is due to albu-
min.
Small quantities of albumin may sometimes be better detected
by Heller's test : A layer of HNO3 is placed in a test-tube, which is
then held at an angle, and the urine allowed to flow slowly upon the
surface of the HNO3 (Fig. 421) so as to form a distinct layer, with the
minimum of mixing of the two
liquids. The test-tube is then
brought to the vertical slowly,
and the point of junction of the
two liquids examined against a
dark background. If albumin
be present a white, opaque
band, whose upper and lower
borders are sharply defined, will
be seen at the line of junction
of the two liquids. When urates
are present hi excess, a white
band will be observed, but its
position will be rather above the
line of junction, and its upper
border will not be sharply de-
fined, but gradually diminished in density from below upward.
In non-albuminous urines there is usually a darkening, but never
an opacity at the line of junction.
QUANTITY. — The only method of determining the quantity of
albumin in urine, with an approach to accuracy, is gravimetric :
20-50 c.c. (5.4-13.5 fl 3 ) of the filtered urine (according as the qual-
itative testing shows albumin to be present in large or small
quantity) are diluted with an equal volume of water, and slowly
heated over the water-bath. As the boiling temperature is ap-
proached, 3-4 drops of dilute acetic acid are added. After the
urine has boiled for a few moments, and the coagulated albumin
has become flocculent, it is thrown upon a dried and weighed filter.
The coagulum is washed with boiling H2O, then with H2O acidu-
lated with HNO3, then with alcohol, and finally with ether. By
these washings impurities are removed, and the albumin is
caused to contract firmly. The filter and the albumin are dried at
110° (230° P.) until they cease to lose weight, and again weighed.
The difference between the two weighings is the weight of dry
albumin in the volume of urine used.
480 MANUAL OF CHEMISTRY.
II. GLOBULINS.— Vitelin exists in the yolk of egg and in the
crystalline lens. It is soluble in dilute solution of sodium chlorid,
from which it is precipitated by excess of H2O ; by heating to
75°-80° (167°-176° F.) ; and by alcohol. It is not precipitated by
solid sodium chlorid. It dissolves in weak alkaline solutions
without alteration, and in very dilute HC1 (1-1000), by which it
is quickly converted into syntonin.
Myosin — is one of the principal constituents of the muscular
fibre in rigor mortis. It is a faintly yellow, opalescent, distinctly
alkaline liquid, which, when dropped into distilled H2O, deposits
the myosin in globular masses, while the H2O assumes an acid
reaction. It is insoluble in H2O, easily soluble in dilute salt solu-
tion, from which it is precipitated by the addition of solid sodium
chlorid, or by a heat of 55°-60° (131 "-140° F.). Very dilute HC1
dissolves and converts it into syntonin.
Paraglobulin. — This substance has been described by various
authors under the names: plasmine (Denis), serum casein
(Panum), serum globuline, ftbrino-plastic matter (Schmidt), serin
(Denis). It exists in blood-serum, in pericardial fluid, hydrocele
fluid, lymph and chyle, and, accompanying serum-albumin, in
albuminous urine. It is obtained by diluting blood-serum, or
hydrocele fluid, with 10-15 volumes of ice-cold HaO, treatment of
the solution with strong current of CO2, and washing the collected
deposit with H2O as long as a portion of the filtrate precipitates
with acetic acid and potassium ferrocyanid, or with silver nitrate.
It is a granular substance, which gradually becomes more com-
pact; insoluble in H2O, sparingly soluble in H3O containing COa ;
soluble in dilute alkalies, in lime-water, in solutions of neutral
alkaline salts, in dilute acids. Its solution in very dilute alka-
line fluids is perfectly neutral and is not coagulated by heat, ex-
cept after faint acidulation with acetic or mineral acids ; it is
precipitated by a large volume of alcohol; its solutions are also
precipitated incompletely by dissolving sodium chlorid in them
to saturation, and completely by similar solution of magnesium
sulfate; this last method of precipitation is used for the sepa-
ration of paraglobulin from serum-albumin (see Fibrin).
Fibrinogen.— After the separation of paraglobulin from blood-
plasma, as described above, if the liquid be still further diluted,
and again treated with CO2, a substance is obtained which, al-
though closely resembling paraglobulin in many characters, is.
distinct from it, and, unlike paraglobulin, it cannot be obtained
from the serum separated from coagulated blood.
Paraglobulin and fibrinogen are both soluble in a solution of
sodium chlorid containing 5-8 per cent, of the salt; when the
degree of concentration of the salt solution is raised to 13-16 per
cent., the fibrinogen is precipitated, while the paraglobulin re-
ALBUMINOID SUBSTANCES. 481
mains in solution and is only precipitated, and then incompletely,
when the percentage of salt surpasses twenty (see Fibrin).
III. — FIBRIXS. — Fibrin is obtained when blood is allowed to
coagulate or is whipped with a bundle of twigs. When pure it
is at first a gelatinous, mass, which contracts to a white, stringy,
tenacious material, made up of numerous minute fibrils ; when
dried it is hard, brittle, and hygroscopic. It is insoluble in
water, alcohol, ether; in dilute acid it swells up and dissolves
slowly and incompletely. When heated with water to 72°
(161°. 6 F.), or by contact with alcohol, it is contracted, and is no
longer soluble in dilute acids, but soluble in dilute alkalies. In
solutions of many neutral salts of 6-10 per cent., it swells up and
is partially dissolved; from this solution it separates on the ad-
dition of water, or upon the application of heat to 73° (163°. 4 F.)r
or by acetic acid or alcohol. Moist fibrin has the property of de-
composing hydrogen peroxid with copious evolution of oxygen.
Fibrin does not exist as such in the blood, and the method of
its formation and of the clotting of blood has been the subject of
much experiment and argument; nor can the question be said to
be definitely set at rest. In the light of the researches of Denis,
Schmidt, and especially of Hammarsten, it may be considered as
almost proven that fibrin is formed from fibrinogen under favor-
able circumstances, and by a transformation which is not yet un-
derstood. Whether paraglobulin plays any part directly in the
formation of fibrin or not, is still an open question.
IV. — COAGULATED ALBUMINS — are obtained, as described
above, from the soluble varieties by the action of acids, heat,
alcohol, etc. They are insoluble in water, alcohol, solutions of
neutral salts; difficultly soluble in dilute alkaline solutions. In
acetic acid they swell up and dissolve slowly; from this solution
they are precipitated by concentrated salt solution. Concen-
trated HC1 dissolves them with formation of syntonin. By the
action of gastric juice, natural or artificial, they are converted
first into syntonin, then into peptone.
V. — AMYLOID — is a pathological product, occurring in fine
grains, resembling starch-granules in appearance, in the mem-
branes of the brain and cord, in waxy and lardaceous liver, and
in the walls of the blood-vessels. Its composition is that of the
albuminoids, from which it differs in being colored red by iodin;
violet or blue by iodin and H2SO.i. Soluble in HC1 with forma-
tion of syntonin; and in alkalies. It is not attacked by the
gastric juice, and is not as prone to putrefaction as the other
albuminoids.
VI. -VII.— ACID- ALBUMINS AND ALKALI-ALBUMINS — These
substances resemble each other so closely that they have been
considered by some writers as identical. They are, however, dis-
482 MANUAL OF CHEMISTRY.
tinct substances, and while acid-albumin may be readily trans-
formed into alkali-albumin by the action of alkalies, the reverse
transformation is not possible. The change of the albumin in
conversion into alkali-albumin is attended by the separation of
sulfur as alkaline sulfld and causes a deeper modification of the
molecule than that which occurs in the formation of acid-
albumin.
Alkali-albumins. — If a concentrated solution of caustic potash
be added to white of egg, a compact, translucent jelly is formed
in a few moments, and similar jellies are produced by other alka-
lies or from other albuminoids. These jellies dissolve in H2O,
and from these solutions the alkali-albumin is precipitated by
dilute acetic acid.
When freshly precipitated, alkali-albumin is in white flocks,
distinctly acid to litmus, not absolutely insoluble in H2O, but
still not sufficiently soluble to communicate to it an acid reac-
tion, and not more readily soluble in solution of NaCl. It is easi-
ly soluble in excess of caustic alkali solution or in solutions of
disodic phosphate or sodium carbonate. Solutions of alkali-al-
bumin in solutions containing a minimum of alkali are distinctly
acid in reaction, and are coagulated by a temperature somewhat
above 100° (212° F.), or by the addition of excess of NaCl. It is
probable that each albumin yields a different alkali-album in, and
also that different products may be obtained from the same albu-
min, as it has been observed that on dissolving precipitated al-
kali-albumin in an alkali four or five times each successive solu-
tion is attended by the formation of an alkaline sulfid.
Acid-albumins — Syntonins. — The term acid-albumin was first
applied to the product obtained by the simultaneous action of
a,n acid and a large excess of a neutral salt on an albuminoid, and
the term syntonin to the product similarly obtained from myo-
sin. The two terms are now indifferently applied to a product
obtained from an albuminoid by the action of an acid.
The acid-albumins are produced from the albuminoids by the
action of dilute acids, either added in solution or by passing air
charged with acid vapors through solutions of the albuminoids
or by floating dialysors containing albuminous solutions on di-
lute acid solutions. They are precipitated from their solutions
in the form of flocciilent jellies by alkalies, or, with a minimum
of free acid, by dilution with H2O.
They are white, gelatinous, translucent, soluble in HC1 1:1,000,
but less soluble after prolonged contact with H2O, soluble in al-
kaline solutions, and are precipitated from their solutions by
neutral salts, but not by heat. They are precipitated from alka-
line solutions by a current of COa.
yill. ALBUMOSES— PROPEPTONKS— are transitory products
ALBUMINOID SUBSTANCES. 483
produced during peptic and pancreatic digestion of albuminoids,
intermediate between the acid-albumins and the peptones. They
differ from the peptones in that they are precipitated by acetic
acid and sodium chlorid, by nitric acid and by many metallic
salts, and from the true albumins in the remarkable quality of
their precipitates, which dissolve when heated and reappear on
•cooling. It is probable that each albuminoid produces its own
aibumose.
Hemialbuxnose — Propeptone — is the product of the peptic di-
gestion of fibrin, and exists in abundance in the stomach during
the digestion of meat, as well as in the blood during digestion.
It has also been obtained from marrow, pancreas, spleen, liver,
kidneys, lungs, milk, spermatic fluid, and pathologically in the
urine in osteouialachia, scarlet fever, and nephritis.
By the peptic digestion of fibrin two products may be obtained ;
one: acid hemialbumose, which still contains 5% of acetic acid,
which is a yellowish powder, soluble in H2O and in hot dilute
-alcohol. It is precipitated from aqueous solution by excess of
solid NaCl. This precipitate redissolves in a small quantity of
hot HaO and is not precipitated on cooling. Neither pure hemi-
albuinose and salt water, nor acid hernialbumose and pure H2O
•exhibit this solubility, which requires the concurrent action of
hemialbumose, acid, and salt. By gradually adding NaCl to a
•clear solution* of acid hemialbumose in salt water an increasing
precipitation is produced, which disappears on addition of acid,
until the proportion of NaCl reaches 4%, when the alternation of
precipitation and solution ceases. Nitric acid forms a precipitate
in solutions of acid hemialbumose, which dissolves with an in-
tense yellow color on heating, and is deposited again on cooling.
It is precipitated by pyrogallic acid, the deposit redissolving on
heating. With KHO and CuSO4 it gives a violet color. Its solu-
tions precipitate with phospho-molybdic acid, tannin, and with
acetic acid and ferrocyanid. With Millon's reagent it gives a deep
red solution, except in presence of excess of NaCl.
If acid hemialbumose solution be exactly neutralized, concen-
trated, and dialysed, pure hemialbumose is obtained as a white
powder insoluble in H2O and in saline solutions.
Other albumoses are produced by the action of natural or arti-
ficial gastric juice upon egg albumin, upon globulins (globuloses),
upon vitellin (mtellosea) and upon casein (caseoses).
IX. — PEPTOXE— ALBUMIXOSE — is the product of the action of
the gastric and pancreatic juices upon albuminoids during the pro-
cess of digestion. It is soluble in H2O, insoluble in alcohol and in
ether. Its watery solution is neutral, not precipitable by acids or
alkalies, or by heat when faintly acid. Alcohol precipitates it in
white, casein-like flocks, which, if slowly heated to 90° (194° F.),
484: MANUAL OF CHEMISTRY.
while still inoist form a transparent, yellowish liquid, and, ort
cooling, an opaque, yellowish, glassy mass. It has a greater
power than other albuminoids of combining with acids and bases.
The most important character of peptone, in which it differs
from other albuminoids, is that it is readily dialyzable. Its pres-
ence in the blood has not been demonstrated, and it is probable
that immediately upon its entrance into the circulation it is con-
verted into albuminoids resembling, yet differing from, those from
which it was derived.
Peptone is produced by the action of many chemical reagents
upon albuminoids ; and also as one of the first products of putre-
faction. When produced by putrefaction, or by artificial diges-
tion, it is accompanied by peptotoxin, a crystallizable and actively
poisonous substance.
It has been claimed that the gastric digestion of different al-
buminoids produces, not a single substance, but a distinct pep-
tone for each albuminoid. If such be the case, and the present
state of our knowledge does not permit of a definite answer to the
question, these bodies are very closely related.
Peptone responds to the general reactions for the albuminoids-
(see p. 475), from which it may be distinguished by the biuret re-
action. If a mere trace of CuSO4 solution be added to a solution
of peptone and then KHO or NaHO solution, a purple or reddish-
violet color is produced. A similar appearance is produced with
acid albumins.
X. — PROTEIDS — Haemoglobin and its Derivatives — Hcemato-
crystallin. — The coloring matter of the blood is a highly complex
substance, resembling the albuminoids in many of its properties,
but differing from them in being crystallizable and in containing
iron.
Haemoglobin exists in the red-blood corpuscles in two conditions
of oxidation ; in the f orjii in which it exists in arterial blood it i»
loosely combined with a certain quantity of oxygen, and is known
as oxyhaemoglobin. The mean of many nearly concording an-
alyses shows its composition to be CeooHsfioN^FeSaO*!,. When
obtained from the blood of man and from that of many of the
lower animals, it crystallizes in "beautiful red prisms or rhombic
plates ; that from the blood of the squirrel in hexagonal plates ;
and that from the guinea-pig in tetrahedra. The crystals are
always doubly refracting. It may be diied in vacuo at 0° (32° F.) ;
if thoroughly dried below 0° (32° P.), it may be heated to 100°
(212° F.) without decomposition, but the presence of a trace of
moisture causes its decomposition at a much lower temperature.
Its solubility in water varies with the species of animal from
whose blood it was obtained ; thus, that from the guinea-pig is.
but sparingly soluble, while that from the pig is very soluble. It
ALBUMINOID SUBSTANCES. 485
is also dissolved unchanged by very weak alkaline solutions, but
is decomposed by acids or salts having an acid reaction.
Haemoglobin, or reduced haemoglobin, is formed from oxyhse-
moglobin in the economy during the passage of arterial into
venous blood ; and by the action of reducing agents, or by boiling
its solution at 40° (104° F.) in the vacuum of the mercury pump.
Oxyhseuioglobin is of a much brighter color than the reduced,
and has a different absorption spectrum. The spectrum of
oxyhaemoglobin varies with the concentration. In concentrated
solutions the light is entirely absorbed, in more dilute solutions
the spectrum 10, Fig. 16, is observed, and in still further dilutions
11, Fig. 16; in which the band at D is narrower, darker, and more
sharply defined than the other. In highly diluted solution the
band at D is alone visible. The spectrum of haemoglobin consists
of a single band much broader and fainter than either of the
oxyhaemoglobin bands (12, Fig. 16). (See p. 22.)
Haemoglobin, in contact with O or air, is immediately converted
into oxyhaemoglobin. With CO it forms a compound resembling
oxyhsemoglobin in the color of its solution, but in which the CO
cannot be replaced by O; for which reason haemoglobin, once
combined with CO, becomes permanently unfit to fulfil its func-
tion hi respiration (see p. 317).
When a solution of oxyheemoglobin is boiled, it becomes turbid,
and a dirty, brownish-red coaguluui is deposited ; the haemoglobin-
has been decomposed into an albuminoid (or mixture of albu-
minoids), called by Preyer globin, and haematin. The latter, at
one time supposed to be the blood-coloring matter, is a blue-black
substance, having a metallic lustre and incapable of crystalliza-
tion. It is insoluble in water, alcohol, ether, and dilute acids ; solu-
ble in alkaline solutions. It has the composition C68H70NtFeaOio.
Its alkaline solutions exhibit the spectrum 13, Fig. 16. Although
itself uncrystallizable, haematin combines with HC1 to form a
compound which crystallizes in rhombic prisms, and which is
identical with the earliest known crystalline blood-pigment,
lieeniin, or Teichmann's crystals.
When reduced haemoglobin is decomposed as above, in the
absence of oxygen, hsematin is not produced, but a substance
identical with that called reduced haematin, and called by Hoppe-
Seyler haemocromogen ; whose spectrum is shown in 14, Fig. 16.
If a solution of haemoglobin be exposed for some time to air it
changes in color from red to brownish, and assumes an acid re-
action ; it then exhibits the spectrum 15, Fig. 16, due to the pro-
duction of methaeinoglobin, probably a stage in the conversion of
haemoglobin into haematin and globin.
Milk casein — the most abundant of the albuminoids of the milk
of mammalia, closely resembles alkali albumins, from which it
486 MANUAL OF CHEMISTRY.
differs in being coagulated by rennet in the presence of sodium
phosphates, and in containing about 0.8% of phosphorus, which
it loses by prolonged boiling with H2O.
Casein, precipitated from cow's milk by acetic acid, and puri-
fied by washing with H2O, solution in very dilute NaHO, precipi-
tation with acetic acid, washing with alcohol and ether and dry-
ing, is a snow-white powder, almost insoluble in pure H2O,
soluble in alkalies and alkaline phosphates and carbonates. It
is distinctly acid in reaction and decomposes the carbonates of
Ca, Mg and Ba, suspended in H2O, with evolution of CO2. It also
dissolves in lime or baryta water, and the solutions so formed do
not coagulate when boiled.
Dilute acids precipitate casein from its solutions, the precipitate
being soluble in an excess. Casein is also coagulated from neu-
tral, acid, or alkaline solution by rennet (the product of the fourth
stomach of the calf) at 40° (104° F.) by a process which differs from
the precipitation by acids. If casein be precipitated by rennet
from boiled milk the coagulum, in place of being compact as it is
with unboiled milk, is light and finely flocculent. The coagulat-
ing action of rennet requires the presence of the mineral salts ex-
isting in milk, and is not manifested with milk which has been
subjected to dialysis nor with a solution of pure casein in soda or
in an alkaline phosphate. But a strong solution of casein in lime
water, after neutralization with phosphoric acid, is coagulated by
rennet more readily than milk.
The coagulation of casein is probably a decomposition into two
other albuminoids, one, more abundant, which constitutes the
coagulum (cheese), which is the more insoluble the greater the
proportion of calcium phosphate in the liquid from which it was
precipitated; the other soluble.
The casein in human milk and of mare's milk is very imper-
fectly coagulated in very fine flocks by acids and by rennet, in a
form very different from the dense coagulum obtained from cow's
milk. This difference is not due to the casein itself, which seems
to be identical in the different varieties of milk, but to the exist-
ence of a larger proportion of calcium salts in the milk of the
cow.
Milk. — The secretion of the mammary gland is water holding in
solution casein, albumin, lactose, and salts ; and fat and casein in
suspension. Cream consists of the greater part of the fat, with
a small proportion of the other constituents of the milk. Skim-
milk is milk from which the cream has been removed. Butter-
milk is cream from which the greater part of the fat has been
removed, and consequently is of about the same composition as
«kiin-milk.
The composition of milk differs in animals of different species:
ALBUMINOID SUBSTANCES.
48T
Human.
Cow.
Goat.
Sheep.
Ass.
Mare.
Cream
Condens-
ed Milk.
Water. . . .
88.35
84:28
86.85
83.30
89.01
90.45
45.99
25.68
Solids ....
11.65
15.72
13.52
16.60
10.99
9.55
54.01
74.32
Casein —
Albumin..
| 3.15 |
3.57
0.78
2.53
1.26
j- 5.73
3.57
2.53
6.33
16.83
Fat
3.87
6.47
4.34
6.05
1.85
1.31
43.97
10.27
Lactose. . .
4.37
4.34
3.78
3.96
|
j 5.43
3.28
44.33*
Salts
0.26
0.63
0.65
0.68
f
( 0.29
0.42
2.80
* Including 28.98 parts of cane-sugar.
The composition of cows' milk varies considerably, according
to the age, condition, breed, and food of the cow ; to the time and
frequency of milking; and to whether the sample examined is
from the first, middle, or last part of each milking.
Cows' milk is very frequently adulterated, both by the removal
of the cream and the addition of water. For ordinary purposes,
the purity of the milk may be determined by observing the sp.
gr. and the percentage of cream by the lactometer and creamoin-
eter, neither of which, used alone, affords indications which can
be relied upon. The sp. gr. should be observed at the tempera-
ture for which the instrument is made, as in a complex fluid such
as milk no valid correction for temperature is practical ; it ranges
in pure milk from 1027 to 1034, it being generally the lower in
milk which has been watered, and in such as is very rich in cream,
and the higher the less cream is present. The average sp. gr. is
1030 ; the average percentage of cream 13.
The percentage of cream is determined by the creamometer :
a glass tube about a foot long and half an inch in diameter, the
upper fifth (excluding about an inch from the top) being gradu-
ated into hundredths of the whole, the 0 being at the top. To
use it, it is simply filled to the 0 with the milk to be tested, set
aside for twenty hours and the point of separation between milk
and cream read off. It should be above eight per cent.
This method of determining the purity of milk, although suf-
ficient for ordinary purposes, should not be considered as afford-
ing evidence upon which to base legal proceedings ; in such cases
nothing short of a chemical determination of the percentage of
fats, and of solids not fat, should be accepted as evidence of the
impurity of milk.
Serum-casein — is a substance obtained from blood-serum diluted
with 10 volumes of H2O, freed from paraglobulin by COa, and
from albumin by acetic acid and heat. It is insoluble in salt
solutions, slowly soluble in a one-per-cent. solution of sodium
hydroxid. Such a solution is partially precipitated by COa, almost
completely by acetic acid, and completely by treating with excess
of powdered sodium chlorid ; incompletely soluble in dilute HC1.
488 MANUAL OF CHEMISTRY.
Gluten-casein — that portion of crude gluten (a soft, elastic,
grayish material best obtained from flour) which is insoluble in
alcohol, hot or cold ; Legumin — a sparingly soluble albuminoid
obtained from peas, beans, etc. ; and Conglutin— a substance
closely related to legurnin and to gliadin, but differing from them
in some characters, obtained from almonds, are three vegetable
albuminoids resembling casein.
They are insoluble in pure water, readily soluble in dilute alka-
line solutions, from which they are precipitated by acids and by
rennet.
Mucin — is a substance containing no S and .existing in the
different varieties of mucus, in certain pathological fluids, in the
bodies of mollusks, in the saliva, bile, connective tissues, etc. Its
solutions, like the fluids in which it occurs, are viscid. It is pre-
cipitated by acetic acid and by HNO3, but is dissolved by an ex-
cess of the latter; it dissolves readily in alkaline solutions, and
swells up in H2O, with which it forms a false solution. It is not
coagulated by heat.
Chondrin is the name given to a substance obtained from car-
tilaginous tissue and supposed to be distinct from gelatin. It is
probably'a mixture of gelatin and mucin.
XI. — ALBUMINOIDS. — Keratin — is the organic basis of horny
tissues, hair, nails, feathe/s, whalebone, epithelium, tortoise-
shell, etc. It is probably not a distinct chemical compound, but
a mixture of several closely related bodies.
Keratin, prepared by boiling quills in strong acetic acid for 24
hours, filtering and evaporating over the water-bath, is now used
as a coating for pills intended to pass through the stomach with-
out solution ; the coating being insoluble in the acid gastric se-
cretion, but soluble in the alkaline liquids of the intestine.
Elastin — is obtained from elastic tissues by successive treatment
with boiling alcohol, ether, water, concentrated acetic acid, dilute
potash solution, and water. It is fibrous, yellowish; swells up in
water and becomes elastic; soluble with a brown color in concen-
trated potash solution. It contains no S, and on boiling with
HaSO4 yields glycol.
Fibroin— Sericin — is obtained from silk by removal of fat, albu-
min, coloring matters, etc., by the proper solvents. It dissolves,
like cellulose, in ammonio-sulfate of copper solution. It does not
contain S, and resembles gelatin in its chemical composition.
XII.— GELATINOUS SUBSTANCES.— Collagen.— Bony tissue is
made up mainly of tricalcic phosphate, combined with an organic
material called ossein, which is a mixture of collagen, elastin, and
an albuminoid existing in the bone-cells. Collagen also exists in
all substances which, when treated with H2O, under the influence
of heat and pressure, yield gelatin. It is insoluble in cold HaO,
ALBUMINOID SUBSTANCES. 489
by prolonged boiling is converted into gelatin, which dis-
solves. It is dissolved by alkalies.
Gelatin — obtained as above, from ossein, exists in the commer-
cial product of that name, and in a less pure form in glue. When
pure it is an amorphous, translucent, yellowish, tasteless sub-
stance, which swells up in cold H3O, without dissolving, and
forms, with boiling H2O, a thick, sticky solution, which on cool-
ing becomes, according to its concentration, a hard glassy mass
or a soft jelly — the latter even when the solution is very dilute.
It is insoluble in alcohol and ether, but soluble, on warming, in
glycerin ; the solution in the last-named liquid forms, on cooling,
a jelly which has recently been applied to various contrivances
for copying writing. A film of gelatin impregnated with potas-
sium dichroruate becomes hard and insoluble on exposure to sun-
Jight.
TOXALBUMIXS — are bodies belonging among the albuminoid
substances and possessed of poisonous qualities. A few are the
products of the vegetable world, such as abrin, the poisonous
principle of jequJrity, but most of those which have been studied
are the products of bacterial action, putrefactive or pathogenic,
upon animal albuminoids. Some are true albumins, others albu-
moses, others peptones. The chemistry of these substances, which
are of great pathological interest, is still in its infancy. Among
them may be noted : (1), Myeoprotein — a product of putrefactive
bacteria ; (2), a substance bearing some relation to serum albumin
and supposed to be the poison of diphtheria; (3), an albuminoid
obtained from the cultures of the pneumonia bacillus; (4), an albu-
mose produced in the cultures of the anthrax bacillus; (5), Toxo-
peptone — a peptone found in cultures of the comma bacillus; (6),
-a toxalbumin found in cultures of the bacillus of tetanus.
490 MANUAL OF CHEMISTRY.
ANIMAL CRYPTOLYTES.
SOLUBLE ANIMAL FERMENTS.
Under this head are classed substances somewhat resembling1
the albuminoids, of unknown composition, occurring in animal
fluids, and having the power of effecting changes in other organic
substances, the method of whose action is undetermined.
Ptyalin — is a substance occurring in saliva, and having the
power of converting starch into dextrin and a sugar resembling
glucose (ptyalose), in liquids having an alkaline, neutral, or faintly
acid reaction.
Pepsin — is the cryptolyte of the gastric juice. Attempts to
separate it without admixture of other substances have hitherto
proved fruitless ; nevertheless, mixtures containing it and exhib-
iting its characteristic properties more or less actively have been
obtained by various methods. The most simple consists in mac-
erating the finely divided mucous membrane of the stomach in
alcohol for 48 hours, and afterward extracting it with glycerin ;
this forms a solution of pepsin, which is quite active, and resists
putrefaction well, and from which a substance containing the
pepsin is precipitated by a mixture of alcohol and ether.
If pepsin be required in the solid form, it is best obtained by
Brttcke's method. The mucous membrane of the stomach of the
pig is cleaned and detached from the muscular coat by scraping ;
the pulp so obtained is digested with dilute phosphoric acid at
38° (100°. 4 F.), until the greater part of it is dissolved ; the filtered
solution is neutralized with lime-water; the precipitate is col-
lected, washed with H2O, and dissolved in dilute HC1; to this
solution a saturated solution of cholesterin, in a mixture of 4 pts.
alcohol and 1 pt. ether, is gradually added ; the deposit so formed
is repeatedly shaken with the liquid, collected on a filter, washed
with H2O and then with dilute acetic acid, until all HC1 is re-
moved ; it is then treated with ether and H2O : the former dis-
solves cholesterin and is poured off, the latter the pepsin ; after
several shakings with ether the aqueous liquor is evaporated at
38° (100°. 4 F.), when it leaves the pepsin as an amorphous, gray-
ish-white substance; almost insoluble in pure H2O, readily
soluble in acidulated H3O ; probably forming a compound with
the acid, which possesses the property of converting albuminoids
into peptone.
The so-called Pepsina porci is either the calcium precipitate
obtained as described in the first part of the above method, or,
more commonly, the mucous membrane of the stomach of the
pig, scraped off, dried, and mixed with rice-starch or milk-sugar.
ANIMAL COLORING MATTERS. 491
Pancreatin. — Under this name, substances obtained from the
pancreatic secretion, and from extracts of the organ itself, have
been described, and to some extent used therapeutically. They
do not, however, contain all the cryptolytes of the pancreatic
juice, and in many instances are inert albuminoids. The actions
of the pancreatic juice are : (1) it rapidly converts starch, raw or
hydrated, into sugar ; (2) in alkaline solution — its natural reaction
— it converts albuminoids into peptone ; (3) it emulsifies neutral
fats ; (4) it decomposes fats, with absorption of HaO and liberation
of glycerin and fatty acids.
The pancreatic secretion probably contains a number of cryp-
tolytes— certainly two. The one of these to which it owes its
peptone-forming power has been obtained in a condition of com-
parative purity by Ktlhne, and called by him trypsin ; in aqueous
solution it digests fibrin almost immediately, but it exerts no
action upon starch.
The diastatic (sugar-forming) cryptolyte of the pancreatic juice
has not been separated, although a glycerin extract of the finely
divided pancreatic tissue contains it, along with trypsin.
ANIMAL COLORING MATTERS.
Biliary pigments. — There are certainly four, and probably
more, pigmentary bodies obtainable from the bile and from,
biliary calculi, some of which consist in great part of them.
Bilirubin — C _H ,N iO, — is, when amorphous, an orange-yellow
powder, and when crystalline, in red rhombic prisms. It is spar-
ingly soluble in H2O, alcohol, and ether; readily soluble in hot
chloroform, carbon disulfid, benzene, and in alkaline solutions.
When treated with HNO3 containing nitrous acid, or with a mix-
ture of concentrated HNO3 and H2SO4, it turns first green, then
blue, then violet, then red, and finally yellow. This reaction,
known as Grnelin's, is very delicate, and is used for the detection
of bile-pigments in icteric urine and in other fluids.
Biliverdin — C32H36N4O8 — is a green powder, insoluble in H2O,
ether, and chloroform, soluble in alcohol and in alkaline solutions.
It exists in green biles, but its presence in yellow biles or biliary
calculi is doubtful. It responds to Gmelin's test. In alkaline
solution it is changed after a time into biliprasin.
Bilifuscin — Ci6H20N2O4 — obtained in small quantity from hu-
man gall-stones, is an almost black substance, sparingly soluble
in H2O, ether, and chloroform ; readily soluble in alcohol and in
dilute alkaline solutions. Its existence in the bile is doubtful.
Biliprasin — Ci6H22N2O8 (?) — exists in human gall-stones, in ox-
gall, and in icteric urine. It is a black, shining substance, insol-
492 MANUAL OF CHEMISTRY.
uble in H2O, ether, and chloroform ; soluble in alcohol and in
alkaline solutions.
Urobilin— Hydrobilirubin — C32H4oN4O7. — Under the name uro'
bilin, Jaffe described a substance which he obtained from dark,
febrile urine, and which he regarded as the normal coloring mat'
ter of that fluid; subsequently he obtained it from dog's bile and
from human bile, from gall-stones and from faeces. Stercobilin,
from the faeces, is identical with urobilin.
Urinary pigments. — Our knowledge of the nature of the sub-
stances to which the normal urinary secretion owes its color is ex-
ceedingly unsatisfactory. Jaffe" in his discovery of urobilin shed
but a transient light upon the question, as that substance exists
in but a small percentage of normal urines, although they cer-
tainly contain a substance readily convertible into it. Besides the
substance convertible into urobilin, and sometimes urobilin
itself, human and mammalian urines contain at least one other
pigmentary body, uroxanthin, or indigogen. This substance was
formerly considered as identical with indican, a glucosid existing
in plants of the genus Isatis, which, when decomposed, yields,
among other substances, indigo-blue. Uroxanthin, however,
differs from indican in that the former is not decomposed by boil-
ing with alkalies, and does not yield any glucose-like substance
on decomposition ; the latter is almost immediately decomposed
by boiling alkaline solutions, and, under the influence of acids
and of certain ferments, yields, besides indigo-blue, indiglucin, a
sweet, non-fermentable substance, which reduces Fehling's solu-
tion.
Uroxanthin is a normal constituent of human urine, but is
much increased in the first stage of cholera, in cases of cancer of
the liver, Addison's disease, and intestinal obstruction. It has
also been detected in the perspiration.
In examining the color of urine it should be rendered strongly
acid with HNO3 or HC1, and allowed to stand six hours to liberate
combined pigment, and then examined by transmitted light in
a beaker three inches in diameter.
Melanin is the black pigment of the choroid, melanotic tumors,
and skin of the negro ; and occurs pathologically in the urine and
•deposited in the air-passages.
PART III.
LABORATORY TECHNICS.
CHEMISTRY is essentially a science of experiment ; and not only
is a knowledge of its truths much more rapidly and easily ac-
quired by the student through the actual performance of experi-
ment, than by any amount of reading or attendance upon
illustrated lectures; but it is even doubtful whether a thorough
knowledge of the facts and theories of the science can be obtained
in any other way than by personal observation.
A description of the various manipulations of the general
chemical laboratory would fill volumes. A short account of the
more prominent of those required in a study of rudimentary
chemistry, and in those processes of analysis which are likely to
be of service to the physician will, we believe, not be out of place
in a work of this nature.
GENERAL RULES.
"Cleanliness," said John Wesley, "is next to godliness." The
chemist, whatever his supply of godliness, must be thoroughly
imbued with the spirit of cleanliness ; not so much as regards
himself, for he who fears to soil his fingers is not of the material
whereof chemists are made, but as regards the vessels and reagents
which are his tools. Any substance foreign to the matter under
examination and the reagents used, whatever be its nature, is
dirt to the chemist.
Glass vessels should always be cleaned as soon as possible after
using, as foreign substances are much more readily removed then
than after they have dried upon the glass. Usually rinsing with
clear water, and friction with a probang or bottle brush is suffi-
cient; greasy and resinous substances may be removed with
KHO solution ; and other adherent deposits usually with HC1 or
HNO3 ; the alkali or acid being removed by clear water. After
washing, the vessels are drained upon a clean surface, and are
not to be put away unless perfectly bright.
Order and system are imperative, especially if several opera-
tions are conducted at the same time. If there be " a place for
494 MANUAL OF CHEMISTRY.
everything, and everything in its place," much time will be
spared. If a process be of such a nature that it requires a num-
ber of vessels, each vessel should be numbered with a small gum
label, or by scratching on the glass with a writing diamond, and
the notes of the operation should indicate the stage of the process
in each vessel.
The habit of taking full and systematic notes of experiments
and analyses in a book kept especially for the purpose, is one
which the student cannot contract too early. He will be sur-
prised, in looking over and comparing his notes, at the amount
of information he will have collected in a short time ; much of
which, had the memory been trusted to, would have been lost.
REAGENTS.
The stock of reagents required varies, of course, with the nature
of the work to be done ; from the small number required in urin-
ary analysis, to the array on the shelves of a fully-appointed
analytical laboratory.
The liquid reagents and solutions should always be kept in
glass-stoppered bottles (the 4£ § bottles, with labels blown in the
glass, serve very well). The solid reagents may be kept in cork-
stoppered or, preferably, glass-stoppered bottles. The ordinary
glass stoppers should never be laid upon the table, lest they take
up particles of foreign matter and contaminate the contents of
the bottle ; but should be held between the third and little fingers
of the right hand.
The reagents required for ordinary urinary analysis are :
Nitric acid, Ammonium hydroxid,
Sulfuric acid, Cupric sulfate,
Acetic acid, Fehling's solution,
Potassium hydroxid, Test papers.
Those required for ordinary qualitative analysis are :
Hydrochloric acid, Potassium ferricyanid,
Nitric acid, Potassium sulfocyanate,
Sulfuric acid, Potassium carbonate,
Acetic acid, Potassium chromate,
Hydrogen sulfid, Barium chlorid,
Ammonium sulfid, Calcium sulfate,
Ammonium hydroxid, Magnesium sulfate,
Potassium hydroxid, Cupric sulfate,
Ammonium chlorid, Argentic nitrate,
Ammonium carbonate, Mercuric chlorid,
Ammonium oxalate, Plumbic acetate,
Sodium carbonate, Ferric chlorid,
Hydro-disodic phosphate, Platinic chlorid.
Potassium ferrocyanid,
The chemicals must be C. P. (= chemically pure) ; and the solu-
tions must be made with distilled H2O. It is well to put corre-
LABORATORY TECHNICS.
495
spending numbers on each bottle and stopper to prevent their
becoming mixed in cleaning.
FIG. 43.
, GLASS TUBING.
The tubing used in making all usual connections and apparatus
is the soft German or American tubing. When the tube is to be
strongly heated, Bohemian
tubing must be used. The
fashioning of tubing of the
diameter generally used for
gas connections is a simple
matter.
Cutting into desired lengths
is accomplished by making a •
scratch with a triangular file at the desired point ; holding the tube
as shown in Fig. 43 ; and partly drawing, and partly bending it.
Larger glass surfaces may be cut in any required direction, by
first making a deep scratch with the file ; starting the break by
bringing in contact wi h scratched spot a piece of red-hot glass
tubing; and leading the break in the desired direction by apply-
ing a heated piece of J-inch iron wire, whose end is filed off
square, moved in the desired direction in ad-
vance of the crack. Cut ends of tubing should
always be rendered smooth by heating them,
to incipient fusion, or by trimming with a file.
Glass surfaces may be filed without danger
of breaking, if the file be moistened with a
saturated solution of camphor in oil of tur-
pentine. Holes may also be bored through
glass with the sharp edges of a broken rat-
tail file, kept moistened with the camphor-
turpentine mixture, the hole being started
from both surfaces and meeting in the middle.
Bending is done by heating the tube at the
desired point in an ordinary gas flame (not a
blow-pipe flame), without rotating it, until
softened ; removing from the flame and bend-
ing toward that surface which was nearest
the orifice of the gas-jet.
Closing. —For this and other operations with
glass tubing, the glass-blower's flame, ob-
tained with a burner (Fig. 44) which permits
of the injection of air into the gas flame, is required. To make
a test-tube a piece of tubing of the length of two test-tubes is
drawn out at the middle (see below). The small end of each
FIG. 44.
496
MANUAL OF CHEMISTRY.
piece is then heated and the superfluous glass removed by a warm,
glass rod, which is brought into contact for an instant and then
drawn away. The closed end is then heated, during rotation,
until soft, and rendered hemispherical by gently blowing into the
open end. The open end is then heated, and, while hot, formed
into a lip by a circular motion with a hot iron wire.
Drawing out consists in heating the tube at the point desired,
during rotation, and drawing it apart after removal from the
flame.
Joining. — Two pieces of tubing of different diameters may be
joined end for end if they be of the same kind of glass. The
ends of each are closed, heated, and blown out into thin bulbs.
The bulb is then broken off, the ends heated, pressed firmly to-
gether, and reheated during alternate pressure and drawing
apart, and gentle blowing into one end while the other is closed,
until an even joint is obtained.
Stirring-rods are made by cutting glass rods to the required
length and rounding the ends by fusion.
COLLECTION OF GASES.
Gases are collected over the pneumatic trough, by displace-
ment of air ; or over the mercurial trough.
In the pneumatic trough (Fig. 45) gases are collected over
FIG. 45.
water in bell jars filled with that liquid. This method of collec-
tion can only be used for insolublo or sparingly soluble gases.
LABORATORY TECHNICS.
497
If heat have been used in the generation of the gas, the disen-
gagement tube must be removed from the water before the heat
is discontinued, to avoid an explosion.
Soluble gases are collected over mercury or by upward or down-
ward displacement of air, according as they are without action
on Hg, or heavier or lighter than air.
SOLUTION.
As the particles of liquids can be brought into closer contact
than those of solids, reactions are usually facilitated by bringing
the reagents into solution or into fusion.
At a given temperature solution of a solid is more rapid the
greater the surface exposed to the
solvent, i.e., the greater the degree
of subdivision.
Ordinary salts are ground to pow-
der in Wedgwood or glass mortars.
Very hard substances are first coarse-
ly powdered in steel mortars, and
then finely ground in agate mortars.
Soft substances are best subdivided
either by hashing, as in the case of
muscular tissue, or by forcing through
the meshes of a fine sieve, as in the
case of white of egg, brain-tissue, etc.
When only certain constituents of
the substance are to be dissolved,
percolation may be resorted to. The
substance to be extracted is packed
in a percolator in such a manner that
the extracting liquid filters through
it slowly.
When the solvent is a volatile liquid
— ether, chloroform, carbon disulfid
—extraction is best accomplished in an apparatus such as that
shown in Pig. 46, in which the liquid is boiled in A ; the vapor
passing through a, &, is liquefied in the condenser and flows
back over the substance in B. The extract collects in A.
FIG.
PRECIPITATION— DECANTATION— FILTRATION-
WASHING.
When the conversion of an ingredient of a solution into an in-
soluble compound, and its separation from the liquid are desired,
both the liquid and the reagent should be in clear solution, and
498 MANUAL OF CHEMISTRY.
the latter should be added to the former, which has been warmed.
The vessel is then set in a warm place until the precipitate has
subsided, a few drops of the precipitant are added to the clear
liquid, and if no cloudiness be produced the precipitation is com-
plete. Precipitation should be effected in Erlenmeyer flasks
(Fig. 47) or in precipitating jars (Fig. 48), that the precipitate may
not collect on the sides, and may be readily detached by the
wash-bottle.
Precipitates are separated from the liquid in which they have
been formed by decantation or filtration.
Decantation consists in allowing the precipitate to subside,
and pouring off the supernatant liquid. It should always be
employed as a preliminary to nitration, and is sometimes used
FIG. 47. FIG. 48.
exclusively, when the precipitate is washed by repeatedly pour-
ing on clear water, and decanting it until it no longer contains
any solid matter.
In pouring liquid from one vessel to another it should be guided
by a glass rod, as shown in Fig. 49 ; the outer surface of the lip
of the pouring vessel having been slightly greased.
Filtration is resorted to more frequently than decantation.
Filters are made from muslin, paper, asbestos, or glass wool.
Muslin niters are only used for coarse nitration.
Paper niters are the most frequently used. For coarse work
the ordinary gray or German white paper is used ; but for ana-
lytic work a paper which leaves but a small amount of ash is re-
quired ; the best now in the market is Schleicher & Schtill's Nos.
597 and 589. The filter should be taken of such size that when
folded it will be smaller than the funnel in which it is to rest.
It is folded across one diameter, and again over the radius at
right angles to the first diameter ; one of the four layers of paper,
then seen at the circular portion of the filter, is separated from
the other three, in such a way as to form a cone. The filter so
formed is brought into the funnel, and, while held in position by
LABORATOEY TECHNICS.
499
a finger-nail over one of the folds, is wetted with water from the
wash-bottle. After the paper has been brought in contact with
the funnel by a glass rod, the liquid to be filtered is introduced,
•care being had not to overflow the filter, and to allow any super-
natant liquid in the precipitating jar to pass through, before
bringing the precipitate itself upon the filter. Funnels used
for filtering should have an angle of 60°, and a long stem, the
point of which is ground off at an acute angle.
Asbestos and glass wool plugs loosely introduced into the stem
FIG. 49.
of a funnel, are used in filtering such liquids as would destroy
paper.
For nitrations which take place slowly the filter-pump is now
extensively used. It is simply an appliance for exhausting the
air in the stem of the funnel, and thus taking advantage of at-
mospheric pressure. A simple and effective form of pump is that
shown in Fig. 50, in which the water (under 10 feet or more of
pressure) enters at a and aspirates the air from b through c.
When the pump is used a small cone of platinum foil must be
placed at the apex of the funnel to support the point of the filter,
which would otherwise be ruptured.
When the precipitate has been collected upon the filter, it must
be washed until free from extraneous matter. This is effected by
blowing into the tube a of the wash-bottle (Fig. 51), while the end
r>oo
or cm
of the tub* & 1* held *o a« to deliver a ^r««#g stream into th<; filter ;
care being had that the preei pitate i* not lo*t by «partfn#, over-
flowing, or creeping wp the side* of the funnel. The 6on»pleten«i»
of the washing i* «<rf to fa? guetated at, but i* to be judged by add'
ing reagent*, writable to the ea*e, to portion* of the filtrate until
they fail to catue a elouiline**.
If the fjVKKJpHttte adhere to wall* of the veM«el in trh^h
been formed, it way usually be det^;i«ed by ruMtintf with a
brujrfi, fortued by *\\\>\>in% a «iiort Mention of rubber to>^ over tbe
end of a «tirrir^'fod< or, if tl*i* fail, the preejpitaie i««*t be re-
di«wolved and repreeifrfteted by an approfj>riate solvent
are tM«ia0y eondaete^i of^ tl*e Nand- or
bath. The «and'ba4th i# ^wpty a Hat, iron ve*w«l, filled with *w*d
and heated. By it* «*e the heat i* wore eve»4y dMrit/wted th«//
wtth Hi* naked flame,
The water 4>ath, HMwally of the form «bown at « 1%, ^ i*
where fl»e temperature te to tw kept t^elow JX*T <Slx
«bonld alwuy* be tMied in evap<^ratin^ wV|« id* e/>ntainin^ organic
•iJtiiy, and «are «t^ouid be had that it d/>e« not t>«*'yy»«e dry,
In «•««* where it i* dewired to b</ii an a^««eotf# liquid in a gia**
thjw jw ftwpported on a pieee of wire ga««e and
501
..UMMX burner or spirit feunp brought under it . (F% 58), A
of sheet-iron may be substituted for the *is« gau«s with
vessel must Iv
In uMiUI
\\ ith
502
MANUAL OF CHEMISTEY.
Drying is always necessary as a preliminary to weighing1,
whether the substance is hygroscopic or not. It is usually effected
in water-ovens (Fig. 55), if a temperature of 100° (212° F.) be suf-
ficient; or in air-ovens, somewhat similarly constructed, if a,
higher temperature be desired. As a substance can never be ac-
curately weighed while it is warm, it is removed from the oven
and placed in the desiccator (Fig. 56), over HaSO4 or CaCl2, until
it has cooled.
In cases where the substance would be injured by elevation of
temperature, it is dried by allowing it to remain in the desiccator
until it ceases to lose weight.
Ignition has for its object the removal of organic matter by
FIG. 56.
FIG. 57.
burning, and is conducted in platinum or porcelain crucibles. If
a filter and precipitate are to be ignited, they are first well dried ;
as much as possible of the precipitate is detached and brought
into the crucible, placed upon a sheet of white paper ; the filter,
Avith adherent precipitate, is then rolled into a thin cone, around
which a piece of platinum wire is wound ; by means of the plati-
num wire the filter is held in the flame and burnt ; the remains of
the filter are then added to the contents of the crucible, which is-
supported in the position shown in Fig. 57, in which it is heated,
at first moderately, and the heat gradually increased to bright-
redness, at which it is maintained until no carbon remains. Be-
fore weighing, the crucible is to be cooled in the desiccator.
In igniting it must not be forgotten that mineral substances
LABORATORY TECHNICS.
503
may be modified or lost. Carbon at high temperature deoxidizes
easily reducible substances ; alkaline chlorids are partly volatil-
ized ; mineral bases combined with organic acids are converted
into carbonates. In every instance only that amount of heat
which is required is to be applied. In some cases it is well to ac-
celerate the oxidation by the addition of ammonium nitrate.
WEIGHING.
The balance (Fig. 58) should always be kept in a glass case, con-
taining a vessel with CaCla, and in a situation protected from the
fumes of the laboratory. The weights should be kept in a box
by or in the balance case, which is to be closed when not in use.
In weighing observe the following rules :
(1.) See that the balance is in adjustment before using, espe-
cially if more than one person use it. (2.) Always put the sub-
stance to be weighed in the same pan, usually the left-hand one,
*,nd the weights in the other. (3.) Never bring any chemical in
Contact with the pars, but have a pair of large watch-glasses of
MANUAL OF CHEMISTEY.
equal weight, one in either pan. Pieces of paper will not serve
the purpose. (4.) Always put the balance out of action before
adding anything to, or taking anything from, either pan. (5.)
Never weigh anything warm. (6.) In weighing a substance
which has been dried, do not consider the weight correct until
two successive weighings, with an intervening drying of a half-
hour, give identical results. (7.) In adding the weights, do so in
regular order from above downward. (8.) In counting the
FIG.
weights, reckon the amount first by the empty holes in the box,
and then tally in replacing the weights. (9.) Substances liable
to absorb moisture from the air are to be weighed in closed
vessels. Thus, when a filter and its adherent precipitate are to
be weighed together, they must be placed between the two watch-
glasses (Fig. 59) as soon as taken from the drying-oven; one of
the watch-glasses being used to support the filter in the oven.
MEASURING— VOLUMETRIC ANALYSIS.
The principle upon which volumetric analysis is based is that
by determining the volume of a solution of known strength, re-
quired to accurately neutralize another solution of unknown
strength, the amount of active substance in the latter may be
calculated.
If, for example, we have a solution of silver nitrate which con-
tains 170 grams to the litre, and we find that 12 c.c. of this solu-
tion precipitate all the chlorin from 10 c.c. of a solution of NaCl,
it follows that the NaCl solution contains 70.20 grains of that
substance per litre, because :
AgNO3 + NaCl = NaNOa + AgCl
170 58.5 85 143.5
and therefore each c.c. of the AgNO3 solution will accurately pre-
cipitate 0.0585 grm. NaCl; but as it has required 12 c.c. of the
AgNOs solution to neutralize 10 c.c. of the NaCl solution, the lat-
LABORATORY TECHNICS.
505
FIG. 60.
-ter contains 0.0585X12=0. 702 grm. NaCl, or 1,000 contain 0.702 X
100=70.20 grms. NaCl.
It is obvious, therefore, that the value of volumetric methods
depends, among other things, greatly upon the accuracy of the
standard solutions, as the solutions of known strength are called,
and upon the accuracy of the measurements of volume.
A standard solution containing in a litre of liquid a number of
grams of the active substance, equal to its molecular weight, is a
normal solution ; one containing ^ that amount is a
decinormal solution.
An indicator is a substance which, by some charac-
teristic reaction (end reaction), which will occur only
when the substance to be determined has been com-
pletely removed, indicates the point when a proper vol-
ume of the standard solution
has been added.
The apparatus required for
volumetric analysis consists of :
(1.) A litre-flask (Fig. 60); a
flask of such size that, when filled
to the mark on the neck, at the
temperature for which it has
been graduated, it contains ex-
actly 1,000 c.c. of water.
(2.) A burette, which is a glass
tube graduated into cubic centi-
metres, and having a stopcock or
pinch-cock at its lower extremity.
(3.) A series of pipettes (Fig. 61), which are glass tubes,
having bulbs blown upon them of such size that when
they are filled to a mark on the tube above the bulb,
they contain a given number of cubic centimetres.
(4.) Small beakers; stirring-rods; bottles for standard
solutions.
In making a standard solution the object to be at-
tained is to have a solution, one litre of which shall con-
tain a known quantity of the active material. If then
in the formula for the normal solution of silver nitrate :
Silver nitrate 170 grams.
Distilled water 1,000 c.c. \y
FIG. 61.
we weigh out the AgNO3 on the one hand, and measure
the H2O on the other, and mix the two, we will have, not what is
desired, a solution containing 170 grms. AgNO3 in 1,000 c.c., but a
solution of 170 grms. AgNO3 in 1,000-j-a? c.c. of liquid, in which
ic=the volume occupied by the AgNO3. Therefore, in making
506
MANUAL OF CHEMISTKY.
standard solutions, weigh out the active substances; introduce
them into the litre-flask ; and then fill that to the mark with HaO.
Too much caution cannot be used in having pure
chemicals and making accurate weighings in pre-
paring volumetric solutions; indeed, the great
disadvantage of the use of these methods by
physicians is that the solutions which they use
are carelessly prepared and, consequently, the
time which they spend in Obtaining inaccurate,
but seemingly accurate, results is worse than
thrown away.
To use a volumetric solution it is poured into
the burette, whose stopcock has been closed,
until above the 0 mark; the stopcock is then
slightly opened so as to expel all air from the
delivery tube. The float (Fig. 62) is now intro-
duced from above, and touched with a glass rod
to free' it from adhering air-bubbles; and the
solution allowed to flow out from below until
the mark on the float is opposite the 0 of the
burette. All is now ready for use ; a given quan-
tity of the solution to be analyzed is measured
into a pipette and placed in a beaker, a few drops
of the indicator solution are added, and the
standard solution allowed to flow in until the
end reaction is reached. The reading of the
FIG. 62. burette is then taken and the calculation made.
ANALYTICAL SCHEME. 50?
SCHEME FOB DETERMINING THE COMPOSITION OF
URINARY CALCULI.
1. Heat a portion on platinum foil :
a. It is entirely volatile 2
b. A residue remains 5
2. Moisten a portion with HNO3 ; evaporate to dryness at low-
heat ; add NH4HO :
a. A red color is produced 3
b. No red color is produced 4
3. Treat a portion with KHO, without heating :
a. An ammoniacal odor is observed. . Ammonium urate.
b. No ammoniacal odor Uric acid.
4. a. The HNO3 solution becomes yellow when evapo-
rated ; the yellow residue becomes reddish-yellow
on addition of KHO, and, on heating with KHO,
violet-red Xanihin.
b. The HNO3 solution becomes dark brown on evapo-
ration Cystin.
5. Moisten a portion with HNO3' ; evaporate to dryness at low
heat ; add NH4HO :
a. A red color is produced 6
6. No red color is produced. , 9
6. Heat before the blow- pipe on platinum foil :
a. Fuses 7
b. Does not fuse 8
7. Bring into blue flame on platinum wire :
a. Colors flame yellow Sodium urate.
b. Colors flame violet Potassium urate.
8. The residue from 6 :
a. Dissolves in dil. HC1 with effervescence ; the solu-
tion forms a white ppt. with ammonium oxa-
late Calcium urate.
b. Dissolves with slight effervescence in dil. H2SO4 ;
the solution, neutralized with NH4HO, gives a
white ppt. with HNa2PO4. . . .Magnesium urate.
9. Heat before the blow-pipe on platinum foil :
a. It fuses Ammonio-magnesian phosphate.
b. It does not fuse 10
10. The residue from 9, when moistened with H3O, is :
a. Alkaline 11
b. Not alkaline Tricalcic phosphate.
11. The original substance dissolves in HC1 :
a. With effervescence Calcium carbonate.
b. Without effervescence Calcium oxalate.
NOTK. — A fresh portion of the powdered calculus is to be
taken for each operation except where otherwise stated.
APPENDIX.
APPENDIX A.
ORTHOGRAPHY AND PRONUNCIATION OF CHEMICAL
TERMS.
IN 1887 a committee was appointed by the American Associa-
tion for the Advancement of Science, to consider the question of
securing uniformity in the spelling and pronunciation of chem-
ical terms. The work of this committee extended through the
four following years. As a result of widespread correspondence
a,nd detailed discussion at the annual meetings of the Chemical
Section of the American Association the following rules have
been formulated and adopted by the Association.
A circular embodying the substance of these rules has been
issued by the Bureau of Education at Washington, and distrib-
uted among chemists and teachers of chemistry, with a recom-
mendation of their general adoption.
GENERAL PRINCIPLES OF PRONUNCIATION.
1. The pronunciation is as much in accord with the analogy
of the English language as possible.
2. Derivatives retain as far as possible the accent and pro-
nunciation of the root word.
3. Distinctly chemical compound words retain the accent and
pronunciation of each portion.
4. Similarly sounding endings for dissimilar compounds are
avoided, hence -In, -Id, -ite, -ate.
ACCENT.
In polysyllabic chemical words the accent is generally on the
antepenult ; in words where the vowel of the penult is followed
by two consonants, and in all words ending in -ic, the accent is
on the penult.
PREFIXES.
All prefixes in strictly chemical words are regarded as parts of
compound words, and retain their own pronunciation unchanged
(as a'ceto-, a'nildo-, a'/o-, hy'dro-, I' so-, ni'tro-, nltro'so-).
512
MANUAL OF CHEMISTRY.
ELEMENTS.
In words ending in -ium, the vowel of the antepenult is short
if i (as irf'dium), or y (as dldy'mium), or if before two consonants
(as ca'lcium), but long otherwise (as tlta'nium, sele'nium, chro'-
mium).
alu'minum
e'rbium
me'rcury
so'dium
a'ntimony
flu'orln
moly'bdenum
strfi'ntium
a'rsfinic
gallium
nl'ckel
(shium)
ba'rium
germa'niuni
ni'trogen
su'lfur
bi'smuth (biz)
glu'cinum
6'smium
ta'ntalum
bo'ron
gold
6'xygen
tellu'riuin
bro'mln
hy'drogen
palla'dium
te'rbium
ca'dmium
I'ndium
ph6s'phorus
tha'llium
ca'lcium.
I'odln
pla'tinum
tho'rium
ca'rbon
iri'dium
pota'ssium
tin
ce'rium
iron
rho'dium
tlta'nium
ce'sium
la'nthanum
rubl'dium
tu'ngsten
chlo'rln
lead
ruthe'nium
ura'nium
chro'mium
ll'thium
sama'rium
vana'dium
co'balt
magne'sium
sea ndium
ytte'rbium
colu'mbiuin
(zhium)
sfile'nium
y'ttrium
co'pper
ma'nganese
silicon
zinc
dldy'mium
(eze)
silver
zirco'nium
Also : ammo'nium, phospho'nium, ha'logen, cya'nogen, aml'-
dogen.
Note in the above list the spelling of the halogens, cesium and
sulfur ; f is used in the place of ph in all derivatives of sulfur (as
sulfuric, sulfite, sulfo-, etc.).
TERMINATIONS IN -ic.
The vowel of the penult in polysyllables is short (as cya'nic,
fuma'ric, arsfi'nic, sill'cic, I6'dic, buty'ric), except (I) u when not
used before two consonants (as mercu'ric, pru'ssic), and (2) when
the penult ends in a vowel (as benzole, olelc); in dissyllables it is
long except before two consonants (as bo'ric, cl'tric). Exception:
ace'tic or ac&'tic.
The termination -ic, is used for metals only where necessary to
contrast with -ous (thus avoid aluminic, ammonic, etc.).
Fate, fat, far, mete, mSt, pine, pin, marine, note, n6t, mover
tube, tub, rlile, my, y = I.
' Primary accent ; " secondary accent. N. B. — The accent fol-
lows the vowel of the syllable upon which the stress falls, but
does not .indicate the division of the word into syllables.
ORTHOGRAPHY AND PRONUNCIATION. 513
TERMINATIONS IX -OUS.
The accent follows the general rule (as pia'tinous, su Ifurous,
ph6'sphorous, coba Itous). Exception : ace'tous.
TERMIXATIOXS ix -ate AXD -ite.
The accent follows the general rule (as a'cetate, va'nadate) : in
the following words the accent is thrown back : a'bietate, a'lco-
holate, a'cetonate, a'ntiinonlte.
TERMIXATIOXS IX -id (FORMERLY -ide).
Tlie final e is dropped in every case and the syllable pronounced
id (as chlo'rld, I'odld, hy'drid, 6'xld, hydr6'xld, su'lfld, a'uildv
a'nilld, umre'xld).
TERMIXATIOXS ix -ane, -ene, -ine, AXD -one.
The vowel of these syllables is invariably long (as me"thane,
e"thane, na'phthalene, a'nthracene, pro'plne, qul'none, a'cetone,
ke'tone).
A few dissyllables have no distinct accent (as benzene, xylene,
cetene).
The termination -ine is used only in the case of doubly unsatu-
rated hydrocarbons, according to Hofmann's grouping (as pro-
pine).
TERMIXATIOXS IX -in.
In names of chemical elements and compounds of this class,
which includes all those formerly ending in -ine (except doubly
ansaturated hydrocarbons), the final e is dropped, and the sylla-
ble pronounced -in (as chlo'rin, bro'min, etc., fi,'mln, a'nilln,
mo'rphtn, qul'nln (kwl'nln), vanl'llln, alloxa'ntln, absi'nthln,
euiu Istn, ca'ffeln, co'caln).
TERMIXATIOXS IX -ol.
This termination, in the case of specific chemical compounds,
is used exclusively for alcohols, and when so used is never fol-
lowed by a final e. The last syllable is pronounced -ol (as gly'col,
phe'nol, cre'sol, thy'mol (ti), gly'cerol, qul'nol. Exceptions : &lco-
hol, a rg61.
Fate, fat, far, mete, m6t, pine, pin, marine, note, n6t, move,
tube, tub, rule, my, y = I.
' Primary accent ; " secondary accent. N. B. — The accent fol-
lows the vowel of the s-yllable upon which the stress falls, but
does not indicate the division of the word into syllables.
514 MANUAL OF CHEMISTRY.
TERMINATIONS IN -Ole.
This termination is always pronounced -ole, and its use is lim-
ited to compounds which are not alcohols (as I'ndole).
TERMINATIONS IN -yl.
No final e is used ; the syllable is pronounced yl (as a'cetyl,
a'myl, ce'rotyl, ce'tyl, e"thyl).
TERMINATIONS IN -yde.
The y is long (as aldehyde).
TERMINATIONS IN -meter.
The accent follows the general rule (as hydro'meter, bar6'meter,
Iact6' meter). Exception : words of this class used in the metric
system are regarded as compound words, and each portion re-
tains its own accent (as c8'ntime"ter, mi'lliiue'ter, kl'lome"ter).
MISCELLANEOUS WORDS
which do not fall under the preceding rules.
Note the spelling : albumen, albuminous, albuminiferous, as-
bestos, gramme, radical.
Note the pronunciation : alkaline, a'lloy (n. and v.), a'llotropy,
a'llotropism, I'somerism, pdlymerism, appara'tus (sing, and plu.),
aqua regia, bary'ta, centigrade, co'ncentrated, crystallln or crys-
talline, electr61ysis, liter, m&'lecule, m616'cular, no'mencla/'ture,
ole'tiant, valence, u'niva'lent, bfvalent, trl'valent, qua'driva"-
lent, tl'trate.
A LIST OF WORDS WHOSE USE SHOULD BE AVOIDED IN FAVOR
OF THE ACCOMPANYING SYNONYMS.
For— Use —
sodic, calcic, zincic, nickelic, sodium, calcium, zinc, nickel,
etc., chlorid, etc. etc., chlorid, etc. (vid. ter-
minations in -ic supra).
arsenetted hydrogen arsin
antimonetted hydrogen stibin
phosphoretted hydrogen phosphin
sulfuretted hydrogen, etc hydrogen sulfid, etc.
Fate, fat, far, mete, mfit, pine, pin, marine, note, n6t, move,
tube, tub, rule, my, y = I.
' Primary accent ; " secondary accent. N. B. — The accent fol-
lows the vowel of the syllable upon which the stress falls, but
does not indicate the division of the word into syllables.
ORTHOGRAPHY AND PRONUNCIATION.
515
For — Use —
"beryllium ghicinum
niobium columbium
glycerin glycerol
hydroquinone
<& hydrochinon)quinol
pyrocatechin . . .catechol
resorcin, etc. . . .resorcinol, etc.
niannite mannitol
dulcite, etc dulcitol, etc.
benzol benzene
toluol, etc . . . .toluene, etc.
thein caffein
For— Use—
f urf urol f urf uraldehyde
fucusol fucusaldehyde
anisol methyl phenate
phenetol ethyl phenate
anethol methyl allylphe-
nol
alkylogens alkyl haloidc
titer (n.) strengthorstnnd-
ard
titer (v.) titrate
monovalent . . .univalent
divalent, etc. . .bivalent, etc.
quanti valence . valence
Fate, fat, far, mete, m8t, pine, pin, marine, note, n&t, move,
tube, tub, rule, my, y = I.
' Primary accent ; " secondary accent. N. B. — The accent fol-
lows the vowel of the syllable upon which the stress falls, but
does not indicate the division of the word into svllables.
APPENDIX B.-TABLES.
TABLE I.— SOLUBILITIES.
FRBSKNIUS.
W or w = soluble in H2O. A or a = insoluble in H2O ; soluble
in HC1, HNOs, or aquaregia. I or i = insoluble in H2O and acids.
W-A = sparingly soluble in H2O, but soluble in acids. "W-I =
sparingly soluble in H»O and acids. A-I = insoluble in H2O,
sparingly soluble in acids. Capitals indicate common substances.
Aluminium.
Ammonium.
Antimony.
Barium.
Bismuth.
Cadmium.
Calcium.
Chromium.
4*
1
I
O
Ferrous.
Ferric.
Acetate
W
W
Arsenate
Arsenite
w
a
a
a
a
A
a
a
Borate
Bromid
w a
Carbonate
Chlorate
a
W
A
A
a
A
a
A
A
A
a
Chlorid
w
Chroinate
Citrate
W
a
a
a
a
w-a
a
a
w
w
Cyanid .
w
Ferri,cyanid
Ferrocyanid . . .
Fluorid
Formate
w
W
w
w
w
w-a
a-i
w
w-a
w
w
A
w
i
i
W-a
Y
a
1
i
w-a
w
I
w
Hydrate
lodid
Malate
Nitrate
w
• *
• •
Oxalate . .
Oxid
a
W
a
a
a
a
A
w-a
A
w
a
a
a
Phosphate
Silicate
a
W3
w-a
w-a
a
a
W-A
a
a
a
a
a
Succinate
Sulfate...
w-a
W
w-a
w
w-a
w-a
w-a
w
Sulfid
Tartrate
1 (A12)(NH4)2(S04)4 = W; (A12)K2(SO4)4 = W. 2 As(NH4)Cl4 = W ;
Pt(NH4)Cl6 = W-I. 3 HNa(NH4>P04 = W ; Mg(NH4)PO4 = A.
4 Fe(NH4)2(S04)2 = W ; Cu(NH4)2(SO4)2 = W. ' C4H4O6K(NH4) =
W. 6 SbOCl = A. ' Sb2O3 = soluble in HC1, not inHNO3. 8 Sb2S3
= sol. in hot HC1, slightly in HNO3. 9 C4H4O8K(SbO) = W.
10BiOCl = A. » (BiO)N03 = A. « (Ora)K2(SO4)4 = W. I3 CoS =
easily sol. in HNO3, very slowly in HC1. 14 (C4H4O6)4(Fe2)K2 = W..
SOLUBILITIES.
51T
TABLE L— SOLUBILITIES.— Continued.
FRESEIflUS.
TV or \v = soluble in H2O. A or a = insoluble in H8O ; soluble
in HC1, HNO3, or aqua regia. I or i = insoluble in H2O and acids.
"W-A = sparingly soluble in H2O, but soluble in acids. W-I =
sparingly soluble in H2O and acids. A-I = insoluble in H3O,
sparingly soluble in acids. Capitals indicate common substances.
1
Magnesium.
i
i
Mercurous.
Mercuric.
Nickel.
I'otnssiurn.
in
Sodium.
Strontium.
Stannous.
Stannic.
d
d
N
Acetate
W
w
w
w-a
w
w
W
w
W
w
w
w
W
Arsenate
Arsenite
a
a
a
a
a
a
a
a
a
a
a
a
W
w
a
a
W
w
a
a
a
a
a
Benzoate
a
w
w
a
w-a
w
w-a
w
Borate
a
w-a
a
a
W
a
W
a
a
a
Bromid
w-i
w
w
a-i
w
w
W
a
W
w
w
Carbonate
Chlorate
A
w
A
w
A
w
a
w
w
A
w
W
W
a
w
w
w
A
w
w
A
w
Chlorid
W-I
W
W
A-T
W1*
W
W20
T
W
W
W
W
W
Chromate
Citrate
A-I
a
w
w
w
a
a
a
w-a
w-a
a
w
w
w
a
a
w
W
w-a
a
a
w
w-a
Cyanid
a
w
a
W
a-i
W
i
a
Ferricyanid —
Ferrocyanid . . .
Fluorid
w-a
a
a
w
w
a-i
i
a
a
--
w-a
i
i
w-a
W
w
i
i
w
w
w
w
w
n-i
w
a
a-i
w-a
Formate
w-a
w
w
w
w
w
w
w
w
w
w
w
Hydrate
a
A
a
a
W
W
w
a
a
a
lodid
W-A
w
w
A
A
w
W
i
w
w
w
w
w
Malate
w-a
w
w
a
w-a
w
w-a
w
w
w
w
w
Nitrate. ....
W
w
w
W
W
W
W
W
W
W
w
Oxalate
a
a
w-a
a
a
a
W
a
W
a
a
w
a
Oxid
A
A
A»*
A
A
A
W
a
W
W
a
A-T
A
Phosphate ....
Silicate
a
a*
a
a
a
a
a
a
a
w
W
a
W
w
a
a
a
a
a
a
Succinate
Sulfate
a
A-I
w
W
w
W
a
w-a
w-a
w
W
w
a
W-A
w
W
w-a
I
w
a
w-a
W
Sulfid
A
a
a
a
A18
A 19
W
a 21
W
w
a"
A 22
A «
Tartrate
a
w-a
w-a
w-a
a
a
W
a
w
a
a
a
15 MnOs = sol. in HC1 ; insol. in HNO3. 16 Mercurammonium
-chlorid = A. " Basic sulfate = A. JS HgS = insol. in HC1 and
in H-NOi, sol. in aq. regia. I9 See 13. 20 PtKCl. = W-A. 21 Only
soluble in HNO3. 2sSn sulfides= sol. in hot HC1 ; oxidized,
not dissolved, by HNO3. Sublimed SnCL only sol. in aq. regia.
*3 Easily sol. in HNO3, difficultly in HC1.
Au2S = insol. in HC1 and in HNO3, sol. in aq. regia. AuBr3,
AuCla, and Au(CN)3 = w ; AuI3 = a. PtSa - insol. in HC1, slightly
sol. in hot HNO3; sol. in aq. regia. PtBr4, PtCh, Pt(CN)4,
PtCN03)4, (CaO4)3Pt, Pt(SO4)a = w ; PtOa = a ; PtI4 = i.
.18
MANUAL OF CHEMISTRY.
TABLE II.— WEIGHTS AND MEASURES.
MEASURES OP LENGTH.
1 millimetre = 0.001 metre = 0.0394 inch.
1 centimetre =0.01 " = 0.3937 "
1 decimetre =0.1 " = 3.9371 inches.
1 METRE = 39.3708 "
1 decametre = 10 metres = 32.8089 feet.
1 hectometre = 100
1 kilometre = 1000
= 328.089
= 0.6214 mile.
Inch.
A -
Millimetres.
Inches
Centimetres.
Inches.
Centimetres
0.3819
2
= 5.08
9
= 22.86
0.7638
3
= 7.62
10
= 25.40
1.5875
4
= 10.16
11
= 27.94
3.175
5
= 12.70
12
= 30.48
6.35
6
= 15.24
18
= 45.72
12.7
7
= 17.78
24
= 60.96
25.4
8
= 20.32
36
= 91.44
MEASURES OF CAPACITY.
1
1
1
1
1
1
inillilitre =
centilitre =
decilitre =
LITRE =
decalitre
hectolitre
1
10
100
1000
c.c.
1C
u
u
= 0.001 litre =
= 0.01 " =
= 0.1 " =
= 10 litres =
= 100 " =
1 kilolitre
= 1000
0.0021 U. S. pint.
0.0211
0.2113
1.0567 quart.
2.6418 galls.
26.418
= 264.18
n.
c.c.
m.
c.c.
m.
c.c.
Fl?.
c.c.
1 =
0.06
26
= 1.60
51 =
3.14
5 =
147.81
2 =
0.12
27
= 1.66
52 =
3.20
6 =
177.391
3 =
0.19
28
= 1.73
53 =
3.26
7 =
206.96
4 =
0.25
29
= 1.79
54 =
3.32
—
236. 5a
O —
0.31
30
= 1.85
55 =
3.39
9 =
266.10
6 =
0.37
31
= 1.91
56 =
3.46
10 =
295.68
7 =
0.43
32
= 1.98
• 57 =
3.52
11 =
325.25
8 =
0.49
33
= 2.04
58 =
3.58
12 =
354.82
9 =
0.55
34
= 2.10
59 =
3.64
13 =
384.40
10 =
0.62
35
= 2.16
60 =
3.70
14 =
413.97
11 =
0.68
36
= 2.22
Fl7
15 =
443.54
12 =
0.74
37
= 2.28
A 1 J .
3r*tf\
16 =
473.11
13 =
14 =
0.80
086
38
39
= 2.34
= 2.40
=
2 =
.70
7.39
O.
1 =
Litres.
0.47
15 =
0.92
40
= 2.46
3 =
11.09
2 =
0.95
16 =
0.99
41
= 2.52
4 —
14.79
3 =
1.42
17 =
1.05
42
= 2.58
5 =
18.48
4 =
1.89-
18 =
1.11
43
= 2.66
6 =
22.18
5 =
2.3ft
19 =
1.17
44
= 2.72
7 =
25.88
6 =
2.84
20 =
1.23
45
= 2.77
=
29.57
7 =
3.31
21 =
1.29
46
= 2.84
n$.
8 =
3.79
22 =
1.36
47
= 2.90
1 =
29.57
9 =
4.26
23 =
1.42
48
= 2.96
2 =
59.14
10 =
4.73
24 =
1.48
49
= 3.02
3 =
88.67
11 =
5.20
25 =
1.54
50
= 3.08
4 =
118.24
12 =
5.67
WEIGHTS AND MEASURES.
519
WEIGHTS.
1 milligram =
0.001 gram =
0.015 grain Troy.
1 centigram =
0.01 " =
0.154 "
1 decigram =
0.1 " =
1.543 "
1 GRAM
=
15.432 grains
1 decagram =
10 grams =
154.324 "
1 hectogram =
100 " =
0.268 Ib.
1 kilogram =
1000 " =
2.679 Ibs.
Grains.
Grams.
Grains.
Grams.
Grains.
Grams. 1
Grams.
A =
0.001
21 =
1.361
47 =
3.046
1 =
31. 103
A =
0.002
22 =
1.426
48 =
3.110
2 =
62. 207
A =
0.004
23 =
1.458
49 =
3.175
3 =
93. 310
•
t —
0.008
24 =
1.555
50 =
3.240
4 =
124. 414
i —
0.016
25 =
1.620
51 =
3.305
5 =
155.517
i —
^ ~
0.032
26 =
1.685
52 =
3.370
6 =
186. 621
i =
0.065
27 =
1.749
53 =
3.434
7 =
217.724
2 =
0.130
28 =
1.814
54 =
3.499
248. 823
3 =
0.194
29 =
1.869
55 =
3.564
9 =
279. 931
4 =
0.259
30 =
1.944
56 =
3.629
10 =
311.035
5 =
0.324
31 =
2.009
57 =
3.694
11 =
342. 138
6 =
0.389
32 =
2.074
58 =
3.758
12 =
373. 250
7 =
0.454
33 =
2.139
59 =
3.823
8 =
0.518
34 =
2.204
60 =
3.888
Lbs.
Kilos.
9 =
0.583
35 =
2.268
1 =
0.373
10 =
0.648
36 =
2.332
3
2 =
0.747
11 =
0.713
37 =
2.397
1 =
3.888
3 =
1.120
12 =
0.778
38 =
2.462
2 =
7.776
4 =
1.493
13 =
0.842
39 =
2.527
3 =
11.664
5 =
1.866
14 -
0.907
40 =
2.592
4 =
15.552
6 -
2.240
15 =
0.972
41 =
2.657
5 =
19.440
7 —
2.613
16 =
1.037
42 =
2.722
6 =
23.328
8 =
2.986
17 =
1.102
43 =
2.787
7 =
27.216
9 =
3.359
18 =
1.166
44 =
2.852
8 =
31.103
10 =
3.733
19 =
1231
45 =
2.916
20 =
1 296
46 =
2.980
520
MANUAL OF CHEMISTRY.
«*
I-
lOOl
CO CO I
c
I-
oc
n
*
cc
I-
Q
O
i— i
cq
D
o
EH
M
CO
3
-M
w
I-
c
n
t-
*
i^
c
i-
t- r-t ZS O IO C5 -^
cscsaoZtSBH
K
t-
tt
l>
en
CO
0
CO
X
t-
ffi
I-
o
Ul
TABLE III.
521
^^ ^^ ww wy i-— u'fc' -.. » T— i s»J WJ iw w. v« "^ >iwJ ^^
TH o o Oi o oo QO t- i- o 1.1 « ^* -* cc so
^ O W Ci •
O »fj Oi "^ C5 CC GO 5O t- C! CO O IO C5 CO fr^ 90
l^
. ._ . , . b-
}
^w»«wi^»«« ^
&3
EH
—
JZ5
^—— ~ b»
HH
° O^OCOCOOO^OTHiOOC^O »
^ 50 O5 O5 00 GO t> t- t£> CO JO -^ rj< CO JO O5 C<? rH «ft gj
t- b. 3
3 M
d CH n
' pj -• jJCJClt— OTHQO^OlOO-^OOi— i-^CO .^
flE 10 OQOQOl^tiooiOO-^^MC.ICjTH j/j jj
W {5
H o
« o
w K ^ ^^^Zi^ZiZ:^^^^^^^^^ ^ a
« S
(^ v^^ w^ <-^ -^r t*"^ WJ 'i^' V* 'JU< U'J ^J>_^ -1*' f ^^ v^' 1:^
r. r^ S GOOOt-t^O^DOlO-^^MCiWi—r-lO I* 3
.i. "W T- Ir-li—li— It-Hi— iTHTHr-lTHT-lTiTHi— ir-Hi-H
^ ^ ^
° ODt-rPCOOt-^e-glOPCQOOgt.O ' ^
1^ GOC-t-OOLOib^^lOtMWOJr-lOO
b»
ffi
b»
b» b»
I
» 1" _ '* _ "
_ t^t^oiSo-^-^iococjoj^i— loodi _
b-
INDEX,
ABRIN, 489
Acenaphthalene, 396
Acetal, 271
Acetals, 271
Acetaldehyde, 267
Acetamid, 279
Acetanilid, 420
Acetonamins, 290
Acetone, 272
Acetones, 271
Acetophenone, 413
Acetoxims, 297
Acettoluids, 420
Acetyl, 255
chlorid, 262
hydrate, 255
hydrid, 267
methylid, 272
Acetylene, 227, 370
Acroodextrin, 390
Acid, acetic, 255
acetyl-acetic, 262
aconitic, 357
acrylic, 304
adipic, 327
allanturic, 353
amidoacetic, 280
amidobutyric, 282
ainidocaprpic, 282
amidppropionic, 282
angelic, 306
anthroquinone - disulfonic,
483
arachaic, 261, 361
arsenic, 126
arsenious, 123, 126
aspartic, 370
atropic, 427
auric, 148
azelaic, 327
benzo-disulfonic, 416
benzoic, 414
benzo-mpnosulfonic, 416
benzo-trisulfonic, 416
bilianic, 287
bisinuthic, 169
Acid, bpracic, 142
boric, 142
bromic, 88
butylactic, 313
butylforrnic, 259
butyric, 258
cachoutannic, 462
caffeic, 462
caffetannic, 462
camphic, 457
campholic, 458
capric, 260
caproic, 260
caprylic, 260
carbamic, 354
carbazptic, 406
carbolic, 402
carbonic, 313, 314, 318
cerotic, 266
chelidonic, 430
chenocholic, 286
chenptaurocholic, 286
chloric, 86
chlorous, 86
cholanic, 287
cholesteric, 433
choleic, 287
cholic, 286
cholonic, 285
chromic, 149
chrysophanic, 453
cinchomeric, 425, 450
citraconic, 331, 358
citric, 357
comenic, 430
convolvulinic, 461
cresylic, 404
crotonic, 305
cyanic, 295
cyanuric, 295
decylic, 260
dehydrocholeic. 287
dehydrpcholic, 287
delphinic, 259
deoxycholic, 287
deoxyglutanic, 327
524
INDEX.
Acid, dextrotartaric, 372
dialuric, 347
dichloracetic, 256
dichromic, 149
d i i o d o phenol moriosul-
fonic, 417
d i i o d o resorcin monosul-
fonic, 417
dilactic, 315
disulfanilic, 418
.disulfuric, 100
ditartaric, 373
dithionic, 97
elaidic, 307
erythroglucic, 372
ethalic, 261
ethyldiacetic, 273
ethylenolactic, 314
ethyl idenelactic, 314
ethylsulfoiiic, 265
ethylsulfuric, 264
ferric, 154
formic, 254
fulminic, 295
fulminuric, 295
fumaric, 330
gadinic, 364
gallic, 415
gallotannic, 462
glucic, 375
glyceric, 357
glycerophosphoric, 368
glycocholic, 284
glycolamic, 280
gly collie, 314
heptylic, 260
hexylic, 260
hippurio, 414
hydrazoic, 105
hydrindic, 451
hydriodic, 89
hydrobromic, 87
hydrochloric, 83
hydrocyanic, 291
hydroferricyanic, 296
hydroferrocyanic, 296
hydrofluoric, 79
hydrofluosilicic, 146
- hydrosulfuric, 92
hydrosulfurous, 97
hyocholic, 286
hyoglycocholic, 286
hyotaurocholic, 286
hypobromous, 87
hypochlorous, 86
hypogaic, 361
hyponitric, 107
hyponitrous, 108
Acid, hypophosphorous, 118
hyposulfurous, 97, 100
indigosulfonic, 451
iodic, 90
isatropric, 427
isethionic, 311
isethionuric, 311
isobilianic, 287
isobutylformic, 259
isobutyric, 259
isocholanic, 287
isocyanic, 295
isonicotic, 425
isopropylacetic, 259
isopropylformic, 259
isosuccinic, 330
isovaleric, 259
itacoriic, 331, 358
lactic, 314, 315
laevotartaric, 372
lauric, 260
laurostearic, 260
leucic, 283, 313
linoleic, 362
lithic, 347
malamic, 370
maleic, 330, 357
malic, 357
malonic, 329
margaric, 261
meconic, 430
melassic, 375
mellitic, 413
niesaconic, 331
metaboric, 142
metantirnonic, 139
metantimonous, 139
rnetaphosphoric, 120
metarsenic, 126
metastannic, 172
metatungstic, 147
methylcrotonic, 306
monochloracetic, 256
morintannic, 462
muriatic, 83
myristic, 261
nicotic, 425
nitric, 109
nitrohydrochloric, 84, 110
nitromuriatic, 84, 110
nitroso-nitric, 110
nitro-sulfonic, 107
nitrous, 108
nonylic, 260
Nordhausen, 100
octylic, 260
O3nanthylic, 260
oleic, 306
INDEX.
525
Acid, opianic, 443
orthoantimonic, 139
orthoarsenic, 126
orthoboric, 142
orthocarbonic. 314 •
orthophenol sulfonic, 416
orthophosphoric, 11!)
osmic, 147
oxalic, 327
oxaluric, 346
oxybeiizoic, 415
oxyphenic, 408
oxyprotein sulfuric, 478
oxyvaleric, 313
palmitic, 261
parabanic, 346
paraconic, 331
paralactic, 315
parietic, 453
pelargonic, 2GO
pentathionic, 97
perbromic, 88
perchloric, 86
periodic, 90
peroxyproteic, 478
phenic, 402
phenyl-sulfuric, 403
phenyl-sulfurou.s. 396
phlorylic, 396
phocenic, 259
phosphomolybdic, 146
phosphoric, 119
phosphorous, 119
phosphotungstic, 147
phthalic, 413
picolic, 425
picric, 406
pimelic, 327
pi peri c, 428
pivalic, 260
plumbic, 165
pneumic, 311
prehriitic, 413
propionic, 258
propylacetic, 259
propylformic, 258
proteic, 473
protocatechuic, 462
prussic, 291
pyridin-dicarbonic, 450
pyroantimonic. 139
pyroarsenic, 126
pyrobisinuthic, 169
pyroboric, 142
pyrogallic, 409
pyrol igneous. 255
pyrophosphoric, 120
pyrosulfuric, 100
Acid, pyrotartaric, 373
pyruvic, 373
quercitannic, 462
quinic, 448
quinolinic, 425
quinotannic, 462
quinovatic, 461
quinovic, 448
racemic, 372
rheic, 453
rocellic, 327
rosolic, 410
salicylous, 412
salicylic, 415
salicyl-sulforiic, 417
santonic, 461
sarcolactic, 314
sebacic, 327
silicotungstic, 147
sozolic, 416
stannic, 172
stearic, 261
suberic, 327
succinic, 329
sulfanilic, 418
sulftndigotic, 451
sulfindylic, 451
sulfocyanic, 295
sulfoglucic, 375
sulfovinic, 264
sulfoxyarsenic, 126
sulfuric, 98
sulfurous, 95, 07
sulfhydric, 92
tannic, 461
tartaric, 372
tartralic, 373
taurocarbamic, 311
taurocholic, 285
terephthalic, 413
tetraboric, 142
tetrathionic, 97
thiocyanic, 295
thiosulfuric, 100
toluo-sulfonic, 416
trichloracetic, 256
trichromic, 149
trimellitic, 413
trimethylacetic, 260>
trinitrophenic, 406
trithionic, 97
tropic, 427-428
ulmic, 375
uric, 347
urous, 351
valerianic. 259
vanillic, 413
veratric, 413
526
INDEX.
Acid, violuric, 347
xanthic, 351
Acids, 41
amido, 280
aromatic, 413
biliary, 284
carbamic, 354
carbopyridic, 425
diatomic and dibasic, 327
diatomic and monobasic, 31 3
fatty, 254
lactic, 314
mineral, 84
monobasic, 254
succinic, 329
sulfinic, 265
sulfonic, 265, 416
valerianic, 259
Aconin, 468
Aconitin, 468
Acridin, 396
Acrolein, 304
Actinic power, 26
Action on the economy
of acetic acid, 258
of aconitin, 469
of alcohol, 244
of ammonia, 196
of antimony, 141
of arsenic, 128
of atropin, 427
of barium, 204
of bismuth, 171
of carbolic acid, 403
of carbon dioxid, 322
of carbon disulfid, 327
of carbon morioxid, 317
of chloral, 269
of chloroform, 234
of chromium compounds,
150
of copper, 213
of ether, 254
of hydrocyanic acid, 292 -
of hydrogen sulfld, 94
of iodin, 89
of lead, 167
of mercury, 221
of mineral acids, 85
of nicotin, 439
of nitric acid, 111
of nitrogen monoxid, 106
of nitrogen tetroxid, 107
of opium, etc., 445
of oxalic acid, 328
of phenol, 403
of phosphoric acids, 120
of phosphorus, 114
Action on the economy
of potassium, 191
of silver, 193
of sodium, 191
of strychnin, 467
of sulfuric acid, 100
of zinc, 208
Adenin, 352
Adipocere, 475
After-damp, 231
Air, 102
ammonia in, 103
carbon dioxid in, 103, 319
confined, 322
solids in, 103
water in, 103
Alanin, 282
Albane, 457
Albumin, egg, 477
in urine, 478
serum, 478
vegetable, 477
Albumins, 476, 477
acid, 476, 481
alkali, 477, 481
coagulated, 476, 481
Albuminoid substances, 472
classification of, 476
general reactions of, 475
Albuminoids, 477, 488
of gluten, 477, 488
Albuminose, 483
Albumoses, 477, 482
Alcohol, 241
absolute, 243
allylic,302
am y lie, 249
benzoic, 411
benzylic, 411
butyl, 248
camphyl, 458
eery lie, 251
cetylic, 251
cholesteric. 433
ethylene, 310
ethylic, 241
isobutyl, 249
menthylic, 458
methylic, 240
propenyl, 355
propylic, 248
vinic, 241
vinyl, 302
wood, 240
Alcoholic beverages, 245
radicals, 229
Alcohols, 237
amylic, 239, 249
INDEX.
527
Alcohols, aromatic, 402, 411
butyric, 248
diatomic, 237, 310
hexatomic, 374
monoatomic, 237
primary, 238
secondary, 238
tertiary, 238
tetratomic, 371
triatomic, 355
Aldehyde, 267
acetic, 267
acrylic, 304
allylic, 304
ammonias, 267
benzoic, 412
butyric, 270
campholic, 457
crotonic, 305
formic, 267
furfur, 431
propionic, 270
salicylic, 412
Aldehydes, 266, 332, 412
Aldehydin, 424
Aldehydins, 290
Aldol, 305
Aldoxims, 297
Ale, 245
Algaroth, powder of, 139
Alizarin, 453
Alkali metals, 176
Alkaloids, 422, 425, 438, 448, 463
aconite, 468
cinchona, 448
detection of, 463
fixed, 466
opium, 439, 444
strychnos, 466
volatile, 466
Alkarsin, 300
Allantoin, 353
Allometa, 400
Allortho, 400
Allotropy, 15
Alloxan, 346
Alloxantin, 353
Allyl, 301
bromids, 303
chlorid, 303
hydrate, 302
iodid, 303
oxid, 302
sulfid, 302
sulfocyanate, 303
Allylic series, 301
Alphenols, 411
Alumina, 159
Aluminates, 160
Aluminium, 159
chlorid, 160
hydroxid, 159
oxid, 159
silicates, 161
sulfate, 160
Alums, 160
Amanitin, 277
Amidins, 290, 334
Amids, 278, 335
Amido acids, 280
benzene, 418
naphthalenes, 446
paraffins, 274
phenols, 407
Amidoxims, 297, 334
Am ins, 274, 332
Ammelid, 337
Ammonia, 104
Ammonias, compound, 274
Ammonium, 194
acetate, 196
acetylid, 267
bromid, 195
carbonates, 196
chlorid, 195
compounds, 194
hydrate, 105, 194
hydroxid, 105, 194
iodid, 195
nitrate, 195
purpurate, 353
sulfates, 195
sulfids, 195
sulf hydrate, 195
theory, 194
urates, 348
Amorphism, 10
Amphi-creatinin, 335
Amphoteric elements, 148
Amygdalin, 460
Amyl nitrate, 265
nitrite, 265
Amylene, 310
hydrate. 250
Amyloid, 476, 481
Amy loses, 386
Amylum, 386
Analysis, 31, 65
Analytical characters of alka-
loids, 463
of acetates, 256
of albumin. 478
of albuminoids, 475
of alcohol, 243
of aluminium, 161
of ammonium, 1%
528
INDEX.
Analytical characters of anilin,
418
of antimony, 134, 141
of arsenic, 131
of atropin, 427
of barium, 204
of bismuth, 170
of bromids, 87
of brucin, 468
of cadmium, 209
of calcium, 202
of carbolic acid, 403
of chlorids, 84
of chloroform, 234
of cholesterin, 433
of chromium, 150
of cobalt, 210
of cocain, 429
of codein, 443
of coniln, 426
of copper, 213
of cyanids, 292
of glucose, 377
of gold, 148
of hydrocyanic acid, 292
of hydrogen, 59
of hydrogen dioxid, 78
of iodids, 90
of iron, 158
of lead, 167
of leucin, 283
of lithium, 176
of magnesium, 206
of manganese, 151
of meconic acid, 430,
of mercury, 220
of niorphin, 441
of narcein, 443
of narcotin, 443
of nickel, 210
of nicotin, 439
of nitrates, 110
of oxalates, 328
of oxygen, 62
of ozone, 63
of phenol, 403
of phosphates, 120
of phosphorus, 115
of picric acid, 407
of potassium, 191
of quinin, 449
of silver, 193
of sodium, 183
of strychnin, 466
of sulfates, 100
of sulflds. 95
of sulfites. 97
of sulfur dioxid, 96
Analytical characters of the-
bain, 443
< of tin, 173
of tyrosin, 283, 284
of uric acid, 350
of zinc, 208
Analytical scheme for calculi.
597
Anhydrid, acetic, 362
antimonic, 139
antiuionous, 138
arsenic, 125
arsenious, 123
boric, 142
carbonic, 318
chlorous, 86
chromic, 149
glycollic, 314
hypochlorous, 86
molybdic, 146
. nitric, 108
nitrous, 107
phosphoric, 118
phosphorous, 118
plumbic, 165
silicic, 146
sulfuric, 96
sulfurous, 95
tungstic, 147
Anhydrids, 62, 262, 332
Anilids, 420
Anilin, 418
brom-, 419
chlor-, 419
derivatives, 419
dyes, 435
iod-, 419
nitr-, 419
red, 436
Anisidins, 404, 407
Anispl, 404
Annidalin, 406
Anode, 27
Anthracene, 452
Anthracite, 143
Anthranol, 453
Anthraphenols, 452
Anthraquinone, 453
Anthrol, 452
Antifebrin, 420
Antimony, 137
antimonate, 139
black, 140
butter of, 139
cinnabar, 141
crocus of, 140
crude, 140
glass of, 140
INDEX.
529
Antimony, intermediate oxid,
139
liver of, 140
pentachlorid, 140
pentasulfid, 140 •
pentoxid, 139
protochlorid, 139
trichlorid, 139
trioxid, 138
trisulfid, 140
Antimonyl, 138
Antipyrin, 431
Antiseptics, 474
Apomorphin, 440, 443, 444
Apoquinin, 449
Aqua ammoniae, 105, 194
chlori, 82
fortis, 109
regia, 110
Arabin, 391
Argol, 188
Aristol, 405
Aromatic series, 393
Arsenarnin, 122
Arsenia, 122
Arsenic, 121, 123
acids, 125
disulfid, 127
flour of, 123
oxids, 123
pentasulfid, 127
pentoxid, 125
sulfids, 127
tribromid, 128
trichlorid, 127
trifluorid, 127
triiodid, 128
trioxid, 123
trisulfld, 127
white, Ii3
Arsenical greens, 129
Arsin, 122
Arsins, 299, 422
Artiads, 38
Asellin, 364
Aseptol, 416
Asparagin, 370
Atom, 34
Atomic heat, 36
theory, 32
weight, 34
Atomicity, 38, 41, 312
Atropin, 427
Auric chlorid, 148
Aurin, 410
Auripisrmentum. 127
Australene, 454
Axes of crystals, 12
34
Azo-derivatives, 291, 421
Azoimid, 105
Azonium, 421
Azoparaffins, 291
Azote, 101
Azulin, 403
BAKIXG-POWDERS, 188
Balsams, 458
Barium, 203
carbonate, 204
chlorid, 203
hydroxid, 203
nitrate, 204
oxids, 203
sulfate, 204
Baryta, 203
Bases, 41
Basicity, 41, 312
Bassorin, 392
Beer, 245
Belladonin, 427
Benzene, 393, 395
amido-derivatives, 418, 420
haloid derivatives, 401
metadioxy, 408
nucleus, 393, 400
nitro-derivatives, 417
orthodioxy, 408
paradioxy, 409
ring. 393, 400
Benzhydrol, 435
Benzine, 232
Benzol, 395
Benzoline, 232
Benzophenone, 435
Benzoyl chlorid, 401
hydrid, 412
Benzyl hydrate, 411
hydrid, 412
Berberin, 469
Berylium, 158
Betain, 290
Betains, 290
Beverages, alcoholic, 245
Bile acids, 284, 288
pigments, 491
Bilifuscin, 491
Biliprasin, 491
Bilirubin, 491
Biliverdin, 491
Binary compounds, 31
Bismuth, 168
hydrates. 169
nitrate, 170 »
oxids, 169
trichlorid, 160
Bismuthyl, 168
530
INDEX.
Bismuthyl, carbonate, 170
nitrate, 170
Bleaching-powder, 198
Boiling-point, 18, 21
Bone, 199
ash, 199
black, 144
oil, 422
phosphate, 199
Borax, 182
Borneene, 458
Borneol, 457, 458
Boroglycerid, 142
Boron, 142
oxid, 142
Brandy, 248
Broinal, 270
Bromids, 87
Broinin, 86
Bromoform, 235
Brucin, 467
Butalanin, 282
Butaldehyde, 270
Butter, 365
Butterine, 367
CACODYLE, 300
Cadaverin, 333
Cadmium, 209
Caffein, 354
^•Calcium, 197
carbonate, 201
chlorid, 198
hydroxid, 198
monoxid, 197
oxalate, 202
phosphates, 199
sulfate, 198
u rates, 349
Calculi, 200, 202, 205, 507
Calomel, 216
Calorie, 20
Camphene, 457
Camphenes, 453, 455
Camphol, 458
Camphor, 457
Borneo, 458
Japan, 457
laurel, 457
monobromo, 458
Camphors, 457
Caouchene, 455
Caoutchouc, 455
Carbamid, 336
Carbamidoxim, 297
Carbamins, 294
Carbimid, 336
Carbinol, 240
Carbodiimids, 419
Carbohydrates, 374
Carbon, 143
compounds of, 222
dichlorid, 235, 309
dioxid, 318
disulfid, 326
monoxid, 316
oxids, 316
oxysulfld, 327
sulflds, 326
tetrabromid, 235
tetrachlorid, 235
trichlorid, 235, 236
Carbonyl chlorid, 316
Carbotriamin, 334
Carbylamins, 294
Carnin, 353
Carvacrol, 405
Carvol, 405
Casein, gluten, 477, 488
milk, 485
serum, 480, 487
Caseins, 477
vegetable, 477
Caseoses, 483
Catechol, 408
Cathode, 27
Cellulin, 390
Celluloid, 391
Cellulose, 390
Cerasin, 392
Cerebrin, 369
Cerebrose, 382
Ceruse, 167
Ceryl hydrate, 251
cerotate, 266
Cesium, 192
Cataceum, 266
Cetene, 266
Cetin, 266
Cetyl hydrate, 251
palmitate, 266
Chalk, 201
Charcoal, 143
animal, 144
Chemistry, 1
China wax, 265
Choral, 268
alcoholate, 269
butyric, 270
hydrate, 269
urethan, 354
Chloralamid, 279
Chloralid, 269
Chloralimid, 279
Chloranilins, 419
Chlorids, 84
INDEX.
531
Chlorin, 80
monoxid, 86
peroxid, 86
tetroxid, 86
trioxid, 86
•Chlorocarbon, 235
Chloroform. 233
{Jholesterids, 434
C holes terin, 433
€holin, 276, 3(i8, 471
Chondrin, 488
Chromium, 149
chlorids, 149
oxids, 149
sulfates, 150
Chrysarobin, 453
Chrysene, 396
Cicutin, 425
Cider, 247
Cinchonidin, 450
Cinehoiiin, 450
Cinnabar, 216
Cinnamene, 432
Classification, 52, 220
Clay, 61
Coagulated albumins, 476, 481
Coagulation, 472
Coal, 143
Cobalt, 210
Cocain, 428
Codein, 442
•Coke, 144
Colchicin, 469
Collagen, 488
Collidin, 424
Collodion, 391
Colloids, 17
Colophene, 454
Colophony, 454
Columbian), 146
Combination, 30
Combustion, 61
Composition, 50
Compounds, 31
binary, 31, 46
quaternary, 31
ternary, 31
Conglutin," 488
Conhydrin, 425
Conicin, 425
Coniferin, 413
Conil'n, 425
methyl, 425
Constitution, 50
Convolvulin, 460
Conyrin, 424
Copper, 210
acetates, 213
Copper, arsenite, 212
carbonates, 213
chlorids, 212
hydrates, 211
nitrate, 212
oxids, 211
sulfate, 212
sulfids, 211
Copperas, 155
Corallin, 410
Coridin, 424
Corrosives, 85
Corrosive sublimate, 217
Cosnioline, 232
Cotarnin, 443
Creasol, 404
Creaspte, 404
Creatin, 334
Creatinin, 335
Cresols, 404
Cresylols, 404
Cristallin, 418
Crith, 55
Croton chloral, 271
Crotonol, 361
Cruso-creatinin, 335
Cryptidin, 447
Cryptolysis, 242
Cryptolytes, 242, 490
Crystallization, 10
Crystalloids, 17
Cumene, 395
Cupric chlorid, 212
oxid, 211
nitrate, 212
sulfate, 212
sulfid, 211
Cuprous chlorid, 212
oxid, 211
sulfid, 211
Curarin, 470
Cyanamid, 296
Cyanids, 293
Cyanogen, 291
chlorids, 294
compounds, 291
hydrate, 294
hydrid, 291
Cymene, 395
Cymogene, 231
DA.TURIN, 427
Decantation, 497
Dehydromorphin, 441
Deliquescence, 16
Deodorizers, 474
Deoxidation, 58
Dextrin, 387, 389, 390
532
INDEX.
Dextrogyrous, 25
Dextrose, 375
Diallyl, 301
Dialysis, 17
Diamid, 105
Diamids, 335, 370
Diamins, 332
Diamond, 143
Diastase, 375, 389
Diazins, 429
Diazo-derivatives, 421
Dibromomethyl bromid, 235
Dichlormethyl chlorid, 233
Dichloromethane, 233
Dicyanogen, 291
Diethyl sulfate, 264
sultite, 265
Diffusion, 17, 58
Digitalein, 460
Digitalin, 460
Digitonin, 460
Digitoxin, 460
Diiodomethyl iodid, 236
Dilucein, 473
Dimethylamin, 275
Dimethyl arsin, 299
Dimethyl-benzene, 401
Dimethylia, 275
Dimethyl-xanthin, 353
Dimorphism, 14
Dioxindol, 451
Diphenyl, 437
Diphenyl-methane, 434
Dipyridyls, 437
Disinfectants, 474
Disocryl, 305
Diterebene, 454
Divisibility, 10
Drying, 502
Dulcite, 374
Dutch liquid, 309
Dynamite, 360
Dyslysin, 286
EBONITE, 456
Ecbolin, 469
Ecgonin, 429
benzyl, 429
Efflorescence, 15
Elastin, 488
Elayl, 308
Electricity, 27
Electrodes, 27
Electrolysis, 27
Electro-negative, 28
Electro-positive, 28, 29
Elements, 30
acidulous, 53, 79
Elements, amphoteric, 53, 148'.
basylous, 53, 176
classification of, 52, 54
typical, 53, 55
Eleoptene, 454
Elutriation, 202
Emetin, 470
Emodin, 453
Emulsin, 460
Emulsion, 361
Eosin, 410
Equations, 40
Equivalence, 38
Equivalents, 32
Eremacansio, 475
Ergotin, 469
Erythrin, 372
Erythrite, 371
Erythrodextrin, 390
Eserin, 470
Essence of bitter almonds, 405-
of garlic, 302
of mirbane, 417
of mustard, 403
Essences, 453, 455
Ethal, 251, 266
Ethene, 227, 308
chlorhydrin, 311
chlorid, 309
glycol, 310
oxid, 311
phenyl, 432
Ether, 251
acetic, 265
allylic, 302
ethylic, 251
hydrobromic, 236
hydrochloric, 236
hydriodic, 230
hyposulfurous, 264
niethylic, 251
muriatic, 236
nitric, 263
nitrous, 263
petroleum, 231
pyroacetic, 272
sulfuric, 251, 264
sulfurous, 204
Etherification, 251
Etherin, 264
Etherol, 2<>-t
Ethers, 251
compound, 262, 331
haloid, 232
hydrocyanic, 293
hyposulfurous, 264
mixed, 251
phenylic, 404
INDEX.
533
Ethers, simple, 251
sult'urous. 264
Ethine, 227. 370
.Ethyl acetate, 265
bromid, 236
carbauiate, 354
carbinol, 248
chlorid. 236
hydrate. 241
iodid, 236
mercaptol, 298
nitrate, 263
nitrite, 263
oxid, 251
pheuate, 404
sulfates, 264
sultids, 29?
sulfhydrate, 298
Ethylene, 227, 308
alcohol, 310
bichlorid, 309
glycol, 310
hydroxid, 310
oxid, 311
Ethylidene, 309
Etid'in, 447
Eucalyptene, 458
Eucalyptol, 458
Euphorine, 355
Evaporation, 500
Exalgin, 420
FATS, 360, 364
phosphorized, 368
Fenuentation. 241
Ferments, animal, 490
Ferric acetates, 156
bromid, 155
chlorid, 154
citrate, 157
ferrocyanid, 157
hydrates, 153
hydroxide, 153
iodid, 155
nitrates, 156
oxid, 153
phosphate, 156
pyrophosphate, 156
sulfates. 155
sulfld, 154
tartrate. 157
Ferrous acetate, 156
bromid, 155
carbonate, 157
chlorid, 154
ferricyanid, 158
hydrates, 153
iodid, 155
Ferrous lactate, 157
nitrate, 156
oxalate, 157
oxid, 153
phosphate, 156
sulfate, 155
sulfid. 154
tartrate, 157
Fibrin, 481
Fibrins, 476, 481
Fibrinogen, 480
Fibrinoplastic matter, 480
Fibroin, 488
Filtration, 74. 497
Fire-damp, 231
Flavanilin, 420
Fluids, 9
compressible. 9
incompressible, 9
Fluorescein. 408, 410
Fluorene. 396
Fluorin, 79
Fluviale, 457
Foods, vegetable, 388
Formal. 271, 310
Formaldehyde, 267
Formamid/279
Formulae, 40, 50
algebraic, 224
empirical, 40, 50
general, 224
graphic, 51
of constitution, 51
typical, 50
Formyl bromid, 235
chlorid, 233
iodid. 236
hydrid, 267
Freezing-point, 18, 20
Fuchsin, 436
Functions, 41, 228
Furane, 430
Furfuran. 431
Furfurol. 431
Fusel oil, 249
Fusing-point, 18
GADININ, 364
Gaduin, 364
Galactose, 382
Galena, 164
Gallein, 409
Gallium, 162
Galvanism, 27
Gasolene, 231
Gelatin, 489
sugar of. 280
Gelatinous substances, 477. 488
534
INDEX.
Germicides, 474
Gin, 248
Glauber's salt, 179
Gliadin, 477, 488
Globiri, 485
Globulin, 480
serum, 480
Globulins, 476, 480
vegetable, 477
Globuloses, 484
Glonoin, 860
Glucinium, 158
Glucoproteins, 473
Glucosan, 375
Glucose, 375
Glucoses, 375
Glucosids, 375, 460
Gluten, 477, 488
Glycerids, 355, 358
Glycerin, 355
ethers of, 358
Glycerins, 355
Glycerol, 355
ethers of, 358
Glycerols, 355
Glycin, 280
Glycocol, 280
benzvl, 414
Glycocols, 280
Glyeogen, 389
Glycol, 310
Glycolauiid, 280
Glycollid, 314
Glycols, 310
Glycyrrhetin, 460
Glycyrrhizin, 460
Go'ld, 148
trichlorid, 148
Grape-sugar. 375
Graphite, 143
Gravity, 2
specific, 3
Guaiacol, 404, 407
Guanidin, 334
Guanin, 352
Guaranin, 354
Gum, British, 390
Gum resins, 458
Gums, 391
Gun-cotton, 391
Gutta, 457
Gutta-percha, 456
Gypsum, 198
H JEM ATI N, 485
Hfematocrystallin, 484
Hijeiiiin, 485
Haemochromogen, 485
Haemoglobin, 484, 485
Haloid salts, 42
ethers, 232
Halogens, 79
Heat, atomic, 36
latent, 18
specific, 19
Hemialbumin, 473, 483
Hemihedral, 14
Hemiprotein, 473
Heteroxanthin, 353
Homologous series, 224
Hydracetiri, 421
Hydracids, 41
Hydrates, 41, 65
Hydrazin, 105
phenyl, 421
phenyl-acetvl, 421
Hydrazins, 290, 421
Hydrazobenzene, 422
Hydrobilirubiri, 492
Hydrocarbons, 226
first series, 229
second series, 308
third series, 370
acyclic, 227, 229
arborescent, 227, 229
benzenic, 227, 395
biberizenic, 434
cyclic, 227, 393
incomplete benzenic, 432
monobenzenic, 395
poly benzenic, 434
saturated, 229
terebenthic, 227, 453
Hydrocollidin, 424
Hydrocotarnin, 443
Hydrogen, 55
antimonid, 138
arsenids, 122
bromid, 87
chlorid, 83
cyanid, 291
dioxid, 77
fluorid, 79
heavy carburetted, 308
iodid, 89
light carburetted, 231
monosulfid, 92
nitrid, ]04
oxid, 64
peroxid, 77
phosphids, 117
silicid, 145
sulfid, 92
sulfuretted, 92
Hydrometer, 6
Hydronaphthol, 446,
INDEX.
535
Hydroquinone, 409
Hvdrosulphids. i>4
Hydroxids, 41, 65
Hydroxyl, 41, 65
Hydroxylamin, 105'
derivatives, 296
Hygrin, 429
Hyoscin, 427, 468
Hyoscyamin, 427, 468
Hypnone, 413
Hypoxanthin, 352
ICTHYOL, 299
Ignition, 502
Illuminating gas, 371
Imids, 335
Indestructibility of matter, 2
Indican, 451, 492
Indiglucin, 451, 492
Indigo, 450
blue, 450
carmine, 451
sulphonic acids, 451
Indigogen, 492
Indigotin, 450
Indium, 163
Indol, 451
Inosite, 382
lodids, 89
lodin, 88
chlorids, 99
lodoform, 236
lodol, 431
Iridium, 175
Iridolin, 396
Iron, 152
acetates, 156
bromids, 155
carbonate, 157
chlorids, 154
citrates, 157
compounds of, 153
ferricyanid, 158
ferrocyanid, 157
hydrates, 153
iodids, 155
lactate, 157
nitrates, 156
oxids, 153
phosphates, 156
pyrophosphate, 156
salts, 155
sul fates, 155
sulfids, 154
tartrates, 157
Isethionamid, 311
I sat in, 450, 451
Isocholesterin. 434
Isocyanids, 294
Isodipyridin, 439
Isolin, 447
Isomerism, 225
Isomorphism, 14
Isonicotin, 437
Isoparafflns, 229
Isoprene, 455
Isoterebenthene, 454
Isuretin, 297
Ivory black, 144
JABORAXDIX, 429
Jaborin, 429
Jalapin, 460
Jalapinol, 460 •
Japaconin, 468
Japaconitin, 408
Javelle water, 186
Jervin, 469
Jet, 143
KAIRIX, 448
Kaolin, 161
Kelp, 88
Keratin, 488
Kermes mineral, 140
Kerosene, 232
Ketones, 271, 413
aromatic, 413, 435
dimethyl, 272
King's yellow, 127
Kyanol, 418
LACMOID. 409
Lactid, 315
Lactin, 385
Lactose, 385
Lievogyrous, 25
Lsevulosan, 382
Ljevulose, 381
Lainp-black, 144
Lanolin, 434
Latent heat, 18
Laughing-gas, 106
Laurene, 395
Law of Ampere, 33
of Avogadro, 33
of definite proportions, 30
of Dulong and Petit, 36
of Gay Lussac, 33
of multiple proportions, 31
of Rapult, 19
of reciprocal proportions, 31
periodic, 162
Lead, 163
acetates, 166
black, 143
53G
INDEX.
Lead, carbonate, 167
chlorid, 165
chrouiate, 166
dioxid, 165
glycocholate, 285
iodid, 166
monoxid, 164
nitrates, 166
oxids, 164
peroxid, 165
protoxid, 164
puce oxid, 165
red, 165
sulfate, 166
sulfid, 165
Lecithins, 368
Legumin, 488
Lepidin, 447
Lethal, 266
Leucin, 282
Leucins, 473
Leuceins, 473
Leucolin, 396
Leucomains, 335, 351
Leuco-pararosanilin, 435
Lichenin, 391
Lignin, 391
Light, chemical effects of, 26
polarization of, 25
refraction of, 21
Lime, 197
chlorid of, 198
slacked, 198
water, 198
Liqueurs, 248
Litharge, 164
Lithium, 176
bromid, 176
carbonate, 176
chlorid. 176
hydroxid, 176
oxid, 176
urates, 349
Lubricating oils, 232
Lutidin, 424
Lycoctonin, 468
MACLURIX, 462
Magenta, 436
Magnesia, 205
alba, 206
Magnesium, 204
carbonates, 206
chlorid, 205
hydroxid, 205
oxid, 205
phosphates, 205
sulfate, 205
Malamid, 370
Maltose, 386
Manganese, 150
chlorids, 151
oxids, 150
salts, 151
Mannitan, 374
Mannite, 374
Mannitose, 382
Marsh-gas, 231
Massicot, 164
Matter, divisibility of, 10
impenetrability of, 2
indestructibility of, 2
states of, 9
weight of, 2
Measures, 518
Meconin, 439, 443
Melampyrite, 374
Melanin, 492
Melissin, 266
Melissyl palmitate, 266
Menthol, 458
Mercaptals, 298
Morcaptan, 298
Mercaptpls, 298
Mereaptids, 297
Mercurammonium chlorid, 218
Mercuric chlorid, 217
cyanid, 219
iodid, 219
oxid, 216
sulfld, 216
Mercurous chlorid, 216
iodid, 218
oxid, 215
Mercury, 215
chlorids, 216
formamid, 279
iodids, 218
oxids, 215
nitrates, 219
phenate, 404
sul fates, 220
sulfids, 216
Mesoparaffins, 229
Meta-, 398
Metachloral, 268
Metacresol. 404
Metallocyanids, 296
Metalloids, 52
Metals, 52
Metamerism, 225
Metaterebenthene, 454
Methaemoglobin, 485
Methal, 266
Methane, 231
series, 227
INDEX.
537
Methene chlorid, 233
glycol, 310
diiiiethylate, 310
Methenyl bromid, 235
chlorid, 233
iodid, 236
, Methyl acetanilid, 420
benzene. 400
bromid, 235
carbinol, 241
chlorid, 233
coniln, 425
glycocol, 281
guanidin, 334
hydrate, 240
hydrid, 231
hydrasulfid, 297
iodid, 236
mercaptan, 297
oxid, 251
phenate, 404
sulfids, 297
uramin, 334
xanthin, 353
Methylal, 271, 310
Methylaniin, 275
Methylanthracene, 453
Methylene bichlorid, 233
Methylia, 275
Methylquinin, 450
Milk, "486
Minium, 164
Mixtures, 31
Molecule, 34
Molybdenum, 146
Monamids, 278
Monamins, 274
Monochlonnethyl chlorid, 233
Mononitrobenzene, 417
Morphin. 440
Morrhuin, 364
Mucin, 488
Murexid, 353
Muscarin, 277
Mustard, oil of, 303
Mycoprotein, 489
Mydalein, 471
Mydatoxin, 471
My din, 471
Myosin. 480
Myricyl hydrate, 251
Myrosin, 303
Mvtilitoxin, 472
NAPELLIX. 468
Naphtha. 232
wood, 240
Naphthalene, 438, 445
Naphthalol, 415
Naphthols, 446
Naphthylamins, 446
Narcein, 443
Narcotin, 443
Nascent state, 58
Neoparaffins, 229
Nerve tissue, 368
Neuridin, 333
Neurin, 277
Neurokeratin, 369
Nickel, 209
Nicotidin, 437
Nicotin, 438
Niobium, 146
Nitrates, 110
Nitre, 185
Nitrils, 291, 293
Nitro-benzene, 417
benzol, 417
cellulose, 391
glycerin, 359
phenols, 406
Nitrogen, 101
bromid, 111
chlorid, 111
dioxid, 106
iodid, 111
nionoxid, 106
oxids, 105
pentoxid, 108
peroxid, 107
protoxid, 106
tetroxid, 107
trioxid, 107
Nitromethane, 273
Nitroparaffins, 273
Nitrosyl chlorid, 110
Nitrous fumes. 107
oxid, 106
Nomenclature, 46
Nuclein, 369
OCCLUSION, 58
Oils, 360
distilled, 455
essential, 455
fixed, 361
volatile, 453, 455
Olefiant gas, 308
Olefins, 227, 308
Olein, 306
Oleomargarine, 367
Oleoresins, 458
Opium, 439
Optically active bodies, 25
Organic substances, 222
Organo-uietallic substances, 300
538
INDEX.
Orientation, 897
Orpiment, 127
Orsein, 409
Orsin, 409
Ortho-, 398
Ortho-cresol, 404
Orthography, chemical, 511
Osmium, 147
Ossein, 488
Oviglobulin, 478
Oxacids, 41
Oxalylurea, 346
Oxhydryl, 41, 65
Oxids, 62
Oxims, 296
Oxiridol, 451
Oxyacids, 41
Oxycholin, 290
Oxycinchonin, 450
Oxydimorphin, 441
Oxygen, 59
Oxyhaemoglobin, 484
Oxymalonylurea, 346
Oxymorphin, 441
Oxyneurin, 290
Oxysalts, 41
Ozocerite, 232
Ozone, 62
PALLADIUM, 174
Pancreatin, 491
Para-, 398
Paraconiin, 426
Paracresol, 404
Paraffenes, 227
Paraffin, 232
Paraffins, 227, 229
sulfur derivatives, 297
Paraformaldehyde, 267
Paraglobulin, 480
Paraldehyde, 268
Paraleucanilin, 435
Paramorphin, 443
Pararosanilin, 435
Paraxanthin, 353
Paris green, 129, 212
Parvolin, 424
Pearlash, 187
Pentamethylendiamin, 333
Pentene, 310
Peonin, 410
Pepsin, 490
Peptones, 477, 483
Peptotoxin, 484
Perissads, 38
Petroleum, 231
ether, 231
Petrolatum, 232
Phenacetin, 407
Phenanthrene, 437
Phenanthoquinone, 43&
Phenates, 404
Phenetidins, 404, 407
Phenetol, 404
Phenicin, 403
Phenol, 402
benzylic, 404
cresylic, 404
cymylic, 405
dyes", 410
Phenols, 402
amido, 407, 420
benzylic, 404
bromo, 406
chloro, 406
cresylic, 404
diatomic, 408
iodo, 406
nitro, 406
substituted, 406
triatomic, 409
trinitro, 406
Phenones, 413
Phenyl, 418
acetamid, 420
acetylene, 433
amido derivatives, 435
hydrate, 402
hydrid, 395
methanes, 434
salicylate, 415
urethan, 355
Phenylamin, 418
Phenylamins, 418
Phenylendiamins, 420
Phloroglucin, 409
Phosgene, 316
Phosphamin, 117
Phosphates, 119
Phosphin, 117
Phosphins, 299, 422.
Phosphonia, 117
Phosphorus, 112
bromids, 121
chlorids, 120
fluorids, 121
iodids, 121
oxids, 118
oxychlorid, 120
pentachlorid, 120;
pentoxid, 118
trichlorid, 120
trioxid, 118
Phthalein, 410
phenol, 410
pyrogallol, 410;
INDEX.
539'
Phthalein resorcin, 410
Phthaleins, 410
Phycite, 371
Physostigmin, 470
Picnoiueter, 6
Picolin, 423, 424
Picramid, 419
Picrol, 417
Pilocarpene, 429
Pilocarpin. 429
Pilocarpidin, 429
Finite, 374
Piperidin, 423, 425
methyl, 425
Piperin, 423, 428
Plasmin, 480
Plaster-of -Paris, 198
Platinic chlorid, 174
Platinum, 174
Plumbago, 143
Plumbates, 165
Poisons, 85 -»
mineral, 136
Polarimetry, 25
Polymerisni, 225
Porcelain, 161
Porter, 245
Potash, 184. 187
Potassa, 184
Potassium, 184
acetate, 187
aluminate. 160
arsenite. 12!)
bromid, 185
carbonates, 187
chlorate. 186
chlorid, 185
cyanid, 190
dichromate, 186
ferricyanid, 1!H
ferrocyanid, 190
hydrate, 184
hypochlorite, 186
iodid, 185
myronate, 303
nitrate, 185
oxalates, 188
oxids, 184
permanganate, 187
phenate, 404
pyrosulfate, 186
sulfates. 186
sulfids, 184
sulfite, 186
tartrates, 188
urates, 348
Potato spirit, 249
Precipitation, 74, 497
Pronunciation of chemical
terms, 511
Proof spirit, 243
Propaldehyde, 270
Propeptones, 477, 482
Propylamin. 276
Propylhydrate, 248
Protagon, 369
Proteids, 477, 484
Protein, 473
bodies, 472
Prussian blue, 157
Pseudoaconitin, 468
Pseudomorphin, 441
Pseudonitrols, 273
Ptomains, 276, 333, 334, 424. 470'
Ptyalin. 490
Putrefaction, 473
Putrescin, 333
Pyrazol, 431
Pyrazolon. 432
Pyridin, 423
products of substitution of,.
423
Pyrites, 154, 211
Pyrocatechin, 408
Pyrocomane, 430
Pyrodiazol, 431
Pyrodextrin. 387
Pyrodin, 421
Pyrogallol, 409
Pyrone, 430
Pyrotriazol, 431
Pyroxam, 388
Pyroxylin, 391
Pyrrol', 431
QUERCITK, 374
Quick-lime, 197
Quinicin, 450
Quinidin, 450
Quinin, 448
Quinol, 409
Quinolin, 447
Quinone. 409
Quinova red, 462
Quinovin, 461
RADICALS, 49
Reagents, 494
Realgar. 127
Reduction. 58
Residues. 2N. 49
Resins, 457. 458
Resorcin, 408
Resorcin ol, 408
Retene, 396
540
INDEX.
Rhein, 453
Khigolene, 231
Rhodium, 175
Ricinin, 361
Rock crystal, 146
oil, 231
salt, 177
Rosanilin, 435
Rosin, 454
Kubidin, 422
Rubidium, 192
Rum, 248
Ruthenium, 175
SABADILLIN, 469
Saccharids, 384
{Saccharin, 416
Saccharose, 382
Saccharoses, 382
Sal ammoniac, 195
volatile, 196
Salaeratus, 182, 187
Salicin, 461
Salicylal, 412
Saligenin, 411
Salol, 415
Salt, Epsom, 205
common, 177
Glauber's, 179
of lemon, 188
of sorrel, 188
of tartar, 187
Rochelle, 189
rock, 177
Saltpetre, 185
Chili, 179
Salts, 41
acid, 48
basic, 49
bi, 48
double, 49
haloid, 42
neutral, 48
oxy, 42
sub, 49
Santonin, 461
Saponification, 263, 360, 367
Saprin, 333
Sarcin, 352
Sarcosin, 281
Scandium, 162
Scheele's green, 129, 212
Schweinfurth green, 129, 212
.Sea salt, 177
Secalin, 276
Selenium, 101
Sericin, 488
.Serin, 480
Serum albumin. 478
casein, 480, 487
globulin, 480
Silex. 146
Silicates, 146
Silicic acid, 146
Silicibromoform, 145
Silicichloroform, 145
Silicon, 145
chlorid, 145
Silver, 192
bromid, 193
chlorid, 193
cyanid, 193
iodid, 193
nitrate, 193
oxids, 192
Skatol, 451
Soaps, 367
Soda, 177, 182
Sodium, 177
acetate, 182
aluminate, 160
arsenite, 129
borates, 182
bromid, 179
carbonates, 182
chlorid, 177
glycocholate, 285
ydroxid, 177
hypochlorite, 182
hyposulfite, 180
io'did, 179
manganate, 182
nitrate, 179
oxids, 177
permanganate, 182
phosphates, 181
silicates, 180
sul fates, 179
sulflte, 180
sulfovinate, 264
thiosulfate, 180
tungstate, 147
urates, 349
Solanidin, 461
Solanin, 4(51, 468
Solubility, 516
Solution, 15, 497
chemical, 15
physical, 15
saturated, 16
simple, 15
supersaturated, 16
Somnal, 354
Sorbite, 374
Sozoiodol, 417
Spartein, 466
INDEX.
541
Specific gravity, 3
Spectroscopy, 21
Spermaceti, '251, 266
Spirits, 24?
methylated, 240
of wine. 241
pyroxylic, 240
Wood, 240
Spongeous substances, 477
Stannic compounds, 172
Stannous compounds, 172
Starch. 386
States of matter, 9
change of, 18
Stearoptenes, 454
Steel, 152
Stercobilin, 492
Stethal, 266
Stibamin. 138
Stibin, 138
Stibins, 299, 422
Stoichiometry, 44
Strontium. 203
Strophanthin, 461
Strychnin, 466
Styrolene, 432
Sublimation, 19
Sugar, beet. 382
candy, 383
cane, 382
diabetic, 375
of gelatin, 280
grape, 375
inverted, 384
of lead, 166
liver, 375
maple, 383
milk, 385
muscle, 382
tests for, 377
Suine, 367
Sulfates, 100
Sulfethylates, 298
Sulfids/94
Sulfites, 97
Sulfobases, 41
Sulfobenzid, 396
Sulfo-carbolates, 417
Sulfonal. 299
Sulfones, 298
Sulfur, 91
dipxid, 95
trioxid, 90
Superphosphate, 199
Supersaturation, 16
Symbols, 39
Synthesis, 31, 65
Syntonins, 482
TA2TXI3T, 461
Tantalum, 146
Tar, 396
Tartar, 188
emetic, 189
Taurin, 311
Technics, 493
Teeth, 200
Teichmann's crystals, 485
Tellurium, 101 *
Terebene, 454
Terebenthene. 454
dichlorhydrate, 455
Terpene hydrate, 4.J5
Terpenes, 453
Terpin, 455
hydrate, 454, 455
Terpinol, 455
Terra alba, 198
Test, biuret, 343, 483
Boettger's, 378
Fehling's, 378, 380
fermentation, 379
Fresenius' and von Babe's,.
135
Gallois'. 382
Gmelin's, 491
Heller's, 479
Marsh's, 133
Moore's, 377
Mulder-Neubauer's, 378
murexid, 348
Nylander's. 379
Pettenkofer's, 287
Reinsch's, 132
Scherer's, 283, 382
Trommer's, 37»
Tetanin, 472
Tetramethyl ammonium hy-
drate, 276
Tetramethylendiamin, 333
Tetramorphin, 441
Tetrazin, 430
Tetrazones, 421
Thallin, 447
ethyl, 448
Thallium, 197
Thebain, 443
Thein, 354
Theobromin. 35<1-
Thermometers, 20
Thialdin, 268
Thiane, 430
Thioalcohol. 298
Thioaldehydes, 27a
Thymol, 405
Tin. 172
chlorids, 172
.542
INDEX.
Tin, hydrates, 172
oxids, 17:3
Tincal, 182
Titanium, 171
Toluene, 400
Toluidins, 419
Toluol, 400
Toxalbumins, 480
Toxiresin, 460
Toxopeptone, 489
Traumaticine, 457
Trehalose, 374
Triamins, 332
Triazins, 430
Tributyrin, 358
Tricaprin, 358
Tricaproin, 358
Tricaprylin, 358
Trichloraldehyde, 268
Trimargarin, 359
Trimetnylamin, 275
Trimethyl glycocol, 282
Trimethylendiamin, 333
Trimethylia, 275
Trimorphin, 441
Trimorphism, 15
Trinitro-glycerol, 359
Trinitro-phenol, 406
Triolein, 359
Trioxymethane, 267
Tripalmltin, 358
Triphenyl methane, 435
Triple phosphate, 205
Tristearin, 359
Trithioaldehyde, 270
Trivalerin, 358
Tropeins, 428
Tropeolin, 446
Tropidin, 427, 428
Tropin, 427, 428
Trypsin, 491
Tungsten, 146
Turnbull's blue, 158
Turpentine, 453
Tutty, 207
Typhotoxin, 471
Typical elements, 55
Tyrosin, 283
URANIUM, 354
Uranium, 163
Urea, 336
determination of, 343
nitrate, 338
oxalate, 339
tests for, 342
Ureas, compound, 346
Ureids, 346
Urethan, 354
Urinary calculi, 507
pigments, 492
Urinometer, 6
Urobilin, 492
Uroxanthin, 492
VALENCE, 38
Valerene, 310
Yallidin, 447
Vanadium, 146
Vanadyl, 146
Vanillin, 413
Vapors, 10
Varech, 88
Vaselin, 232
Veratrin, 469
Verdigris, 213
Vermilion, 216
Vinegar, 256
wood, 240
Vinyl alcohol, 302
hydrate, 302
Viridin, 422
Vitelin, 480
Vitelloses, 483
Vitriol, blue, 212
green, 155
oil of, 98
white, 208
Volumetric analysis, 504
Vulcanite, 456
WASHING, 497
Water, 64
chlorids in, 69
glass, 181
hardness of, 68
impurities of, 68
metals in, 72
mineral, 75
natural, 66
nitrates and nitrites in, 71
of constitution, 66
of crystallization, 66
organic matter in, 69
oxygenated, 77
purification of, 73
solids in, 68, 73
Wax, 266
Weighing, 503
Weight, 2
absolute, 3
apparent, 3
atomic, 34
molecular, 37
relative, 3
specific, 3
INDEX. 543
"Weight, specific, of gases, 8 Xylenols, 405
of liquids, 5 Xylidins, 419
of solids, 4 Xyloidin, 388
of vapors, 8 Xylols, 401
Weights, 518
"Whiskey, 248 YVA^T 041
White-lead, 167 IE AST, 341
precipitate, 218
Wine, 246 Zl^C, 207
oil of, 264 butter of, 208
spirits of, 241 carbonates, 20?
Wolfram, 146 chlorid, 208
ethyl, 300
XANTHIN, 351 hydrate, 208
Xantho-creatinin, 335 oxid, 207
Xenols, 405 sulfate, 208
Xylenes, 401 Zirconium, 171
MEMORANDA.
MEMORANDA.
MEMORANDA.
MEMORANDA.
MEMORANDA.
MEMORANDA.
MEMORANDA.
MEMORANDA.
MEMORANDA.
MEMORANDA.
MEMORANDA.
MEMORANDA.
iMEMORANDA.
MEMORANDA.
MEMORANDA.
MEMORANDA.
-P
\o w
r> -H
c^ S
t*\
University of Toronto
Library
c<~\ o
o
a
1
-P W
CO -
rV t ^
DO NOT /f
REMOVE /
3 0)
THE //
X! -P
a CQ
H
O r-|
CARD
P^ «H
FROM ^
•v CD
M S
aJ 0
THIS V
-P ^
•H T;
S rH
0) <*>
o &
POCKET X
Acme Library Card Pocket
LOWE-MARTIN CO. LIMITED
Live Music Archive
Librivox Free Audio
Metropolitan Museum
Cleveland Museum of Art
Internet Arcade
Console Living Room
Books to Borrow
Open Library
TV News
Understanding 9/11