Experimental Organic Chemistry

EXPERIMENTAL
ORGANIC CHEMISTRY
BY
JAMES F. NORRIS
Professor of Organic Chemistry, Massachusetts Institute of Technology; Author
of "The Principles of Organic Chemistry," "A Textbook of Inorganic
Chemistry for Colleges," and Joint Author of "Laboratory
Exercises in Inorganic Chemistry"
SECOND EDITION
SECOND IMPRESSION
TOTAL ISSUE, 38,000
M c G R A W - H I L L BOOK C O M P A N Y , I N C .
NEW YORK: 370 SEVENTH AVENUE
LONDON: 6 & 8 BOUVERIE ST., E. C. 4
1924
COPYRIGHT, 1915, 1924, BY THE
MCGRAW-HILL BOOK COMPANY, INC.
PRINTED IN THE UNITED STATES OF AMERICA
THE MAPLE PRESS COMPANY, YORK, PA.

P R E F A C E T O T H E SECOND E D I T I O N
The appearance of the second edition of the author's "Text-
book of Organic Chemistry" made it advisable to prepare a
revision of this laboratory guide, in order that the references
given to the text should refer to the new edition of the latter.
Advantage has been taken of the opportunity to give improved
directions for a number of experiments and to incorporate new
material of importance. Some additions have been made to the
chapter on laboratory methods, and directions for a few new
preparations have been given. These include the preparation of
normal butyl chloride from the alcohol and aqueous hydrochloric
acid, of triphenylmethane directly from benzene, carbon tetra-
chloride, ether, and aluminium chloride, of an amylene from sec-
ondary amyl alcohol, and of a secondary alcohol from pentene-2.
The author will be glad to receive suggestions from teachers
who use the book with their classes.
JAMES F. NORRIS.
CAMBRIDGE, MASS.
April, 1924.
PREFACE TO THE FIRST EDITION
This book is designed primarily to be used as a laboratory
guide in connection with courses in organic chemistry in which
the student follows in the laboratory the subject as developed
in the class-room. An attempt has been made to furnish direc-
tions for experiments to illustrate the methods of preparation and
the chemical properties of the more important classes of organic
compounds. As a consequence, the student following the work
as given, comes in contact with many substances of importance
which are not handled by one whose laboratory work consists
solely in the preparation of a few compounds. For example,
directions are given in considerable detail for experiments
which illustrate the properties of fatty amines, hydroxy acids,
carbohydrates, fats, proteins, etc., subjects which receive scant,
if any, attention in many laboratory courses in organic chemistry.
Directions for a large number of preparations are also given.
These serve to illustrate the more important synthetic methods
and the different kinds of laboratory technique with which the
student should become acquainted. In connection with the
directions for the preparation of typical compounds, experiments
are given which illustrate the properties of the compounds made.
These experiments include in each case a study of the reactions
of the substance which are of particular value in the identification
of the characteristic group present.
No attempt has been made to introduce novel preparations;
the ones given are, in the main, those commonly used. These
have been selected on account of their simplicity and the fact
that they illustrate the principles to be taught; they are as novel
to the student as any that could be devised. Although the older
preparations are used, the laboratory details are, in many cases,
different from those commonly employed. The changes have
been the result of a detailed study of the preparations which,
in many cases, resulted in simplification and improvement. A
few new preparations are described; these are to illustrate, in
vii
viii PREFACE TO THE FIRST EDITION
most cases, the properties of compounds that have not been stud-
ied commonly in laboratory courses in organic chemistry.
A feature of the book is the introduction of directions for the
preparation of certain compounds on a very small scale. Stu-
dents often acquire the habit of careless work in the laboratory
practice in organic chemistry. Preparation-work on the small
scale serves to counteract this effect and to develop a technique
that is valuable. Such work is often necessary in the identifica-
tion of unknown compounds when a small amount only of the
substance is available. In many cases a crystalline derivative
whose melting-point can be determined, can be prepared in a
pure condition from but two or three drops of a substance.
Among the examples of work of this kind which are given are the
preparation of acetanilide from acetic acid, glyceryl tribenzoate
from glycerol, dinitrobenzene from benzene, and dibenzalacetone
from acetone. In order to facilitate such work, a section in the
first chapter is devoted to a consideration of the technique used
in the manipulation of small quantities of substances.
The final chapter of the book deals with the methods used to
identify organic compounds by a study of their chemical behavior
and physical properties. The method is outlined only, since the
pedagogical value of the work depends largely upon giving the
student opportunity to apply the knowledge he has gained
throughout the course in the study of the behavior of the typical
classes of organic compounds. It has been the experience of
the author for a number of years, that laboratory practice of this
kind undertaken at the end of the course, is of great value to the
student, on account of the fact that it gives him an opportunity
to review, correlate, and apply many of the facts he has learned.
The practical application of his knowledge is evident. When a
student has been able to identify definitely a number of com-
pounds which were unknown to him, he feels that he has gained
power in handling problems in organic chemistry.
A chapter of the book is devoted to detailed directions for
carrying out the simpler operations used in laboratory work in
organic chemistry. In order that the student may make use of
this information when it is necessary, references are given through-
out the book to the paragraph and page where the particular
process to be employed is described. It is impossible to repeat
PREFACE TO THE FIRST EDITION ix
in the laboratory directions details for these processes, and if the

student does not have these details before him he is apt to carry
out the operation in a careless manner. It is believed that a
definite reference to the place where the process is described may
be useful.
The book contains directions for more work than can be done
in a laboratory course of the usual length. An opportunity is
thus given the teacher to select the work that is best adapted to
the needs of his students. The method of numbering and letter-
ing the experiments makes it possible to assign readily the work
to be done by the class.
The author has consulted all the well-known texts on labora-
tory work in organic chemistry in the preparation of the book.
In writing the directions for the preparation of compounds on
a small scale, valuable help was obtained from S. P. Mulliken's
" T h e Identification of Pure Organic Compounds." A number
of experiments on fats, carbohydrates, and proteins have been
adapted, with the permission of the author, from a laboratory
manual in descriptive organic chemistry prepared for the use of
students of household economics, by Professor Alice F. Blood, of
Simmons College. The author wishes to express his thanks for
the courtesy shown in granting permission to make use of this
material.
All the figures in the book were prepared from drawings made
by the wife of the author; for this help and for assistance in read-
ing the proof he is deeply grateful.
The author will be pleased to have called to his attention any
mistakes which may be discovered by those who use the book;
any suggestions as to improved directions for the experiments
will also be gladly received.
JAMES F. NORRIS
BOSTON, MASS.
April, 1915.
CONTENTS
PAGE
PREFACE TO SECOND EDITION v
PREFACE TO FIRST EDITION vii
CHAPTER I.—LABORATORY METHODS 1

General directions, 1—Crystallization, 3—Distillation, 8—Ex-
traction, 21—Sublimation, 24—Drying agents, 25—Use of reflux
condenser, 26—Manipulation of sodium, 28—Manipulation of
small quantities of substances, 29—Determination of physical
properties, 32—Qualitative analysis, 39.
CHAPTER II.—GENERAL PROCESSES: HYDROCARBONS OF THE

METHANE SERIES 43
Methane, 44—Ethane, 46—Di-isoamyl, 46—Kerosene and gasoline,
47.
CHAPTER III.—UNSATURATED HYDROCARBONS 50

Ethylene, 50—Amylene, 51—Acetylene, 52.
CHAPTER IV.— ALCOHOLS 55
Methyl alcohol, 55—Ethyl alcohol, 57—Allyl alcohol, 60—
Secondary amyl alcohol, 61—Glycerol, 62.
CHAPTER V.—ACIDS 64
Formic acid, 64—Acetic acid, 65—Soap, 67—Oxalic acid, 69.
CHAPTER VI.—ETHERS, ESTERS, AND ANHYDRIDES 72
Ether, 72—Isoamyl-ethyl ether, 75—Acetic anhydride, 75—
Succinic anhydride, 77—Potassium ethyl sulphate, 78—Ethyl
acetate, 79—Isooamyl acetate, 80—Fats and oils, 81.
CHAPTER VII.—ALDEHYDES AND KETONES 84
Formaldehyde, 84—Acetaldehyde, 85—Acetone, 87.
CHAPTER VIII.—AMINES AND AMIDES 89
Methylamine, 89—Lecithin, 91—Acetamide, 91—Urea, 93.
CHAPTER IX.—CYANOGEN AND RELATED COMPOUNDS 95
Cyanogen, 95—Potassium cyanide, 95—Potassium ferrocyanide,
96—Potassium ferricyanide, 96—Methyl cyanide, 97—Iso-
cyanides, 98.
xi
xii CONTENTS
PAGE
CHAPTER X.—HALOGEN COMPOUNDS 99
Methyl iodide, 99—Ethyl bromide, 100—Ethyl iodide, 102—Iso-
amyl bromide, 103—Butyl chloride, 104—Chloroform, 105—
Ethylene bromide, 106—Acetyl chloride, 108.
CHAPTER XL—COMPOUNDS CONTAINING Two UNLIKE SUBSTITU-

ENTS 110
Trichloroacetic acid, 110—Lactic acid, 110—Tartaric acid, 111—
Citric acid, 113—Acotoacetic ester, 114—Chloral, 117.
CHAPTER XII.—CARBOHYDRATES 118
Dextrose, 118—General reactions of the sugars, 119—Sucrose,
121—Lactose, 121—Starches, 123—Dextrin, 126—Cellulose, 126—
Pentosans, 128.
CHAPTER XIII.—COMPOUNDS CONTAINING SULPHUR 129

Mercaptan, 129—Thiocyanates, 129—Xanthates, 129.
CHAPTER XIV.—URIC ACID AND RELATED COMPOUNDS 130
Uric acid, 130—Caffeine, 131.
CHAPTER XV.— AROMATIC HYDROCARBONS 132
Benzene, 132—Etbylbenzene, 134—Diphenylmethane, 136—Hexa-
phenylethane, 137—Naphthalene, 137.
CHAPTER XVI.—NITRO COMPOUNDS AND SULPHONIC ACIDS . . . 139
Nitrobenzene, 139—m-Dinitrobenzene, 141—Sodium benzene-
sulphonate, 142—Benzenesulphonyl chloride, 144—Benzenesul-
phonamide, 145—p-Toluenesulphonic acid, 145.
CHAPTER XVII.—HALOGEN DERIVATIVES or AROMATIC HYDRO-
CARBONS 147
Bromobenzene, 147—p-Dibromobenzene, 148—Properties of halo-
gen compounds, 148—Triphenylchloromethane, 150—Triphenyl-
methane, 151.
CHAPTER XVIII.—AROMATIC AMINES 153
Aniline, 153—Methylaniline, 156—Dimethylaniline, 156—Dis-
tinction between three types of amines, 157.
CHAPTER XIX.—DIAZO COMPOUNDS 158
Phenol, 158—Iodobenzene, 159—p-Tolunitrile, 159—Diazo-
aminobenzene, 161—Aminoazobenzene, 161- Phenylhydrazine,
162.
CHAPTER XX.—AROMATIC ALCOHOLS, PHENOLS, AND ETHERS . . 165
Benzyl alcohol, 165—Diphenylcarbinol, 166—Diphenylethylcar-
binol, 166—Phenol, 167—General reactions of phenols, 168—
Anisol, 168.
CONTENTS xiii
CHAPTER XXI.—AROMATIC ACIDS 170

Benzoic acid, 170—Benzanilide, 170—Benzamide, 171—p-Toluic
acid, 171—Cinnamic acid, 172—Terephthalic acid, 173—Di-
methyl terephthalate, 173.
CHAPTER XXII.—AROMATIC ALDEHYDES, KETONES, AND QUINONES 174
Benzaldehyde, 174—Benzophenone, 175—Benzophenoneoxime,
176—Quinone, 176—Anthraquinone, 178.
CHAPTER XXIII.—AROMATIC COMPOUNDS CONTAINING TWO OR
MORE UNLIKE GROUPS 179
o-Nitrophenol, 179—Eugenol, 180—Sulphanilic acid, 181—m-
Nitroaniline, 181—p-Nitroaniline, 182—Salicylic acid, 183—
Tannic acid, 184.
CHAPTER XXIV.—DYES AND DYEING 187
Methyl orange, 187—Malachite green, 188—Fluorescein, 189
Eosin, 190—Dyeing with congo, 190—Mordants, 191—Primuline,
191.
CHAPTER XXV.—HETEROCYCLIC COMPOUNDS 193
Thiophene, 193—Furfuraldehyde, 193—Pyridine, 193—Quinoline,
194—Alkaloids, 195.
CHAPTER XXVI.—PROTEINS 190
Detection of nitrogen, sulphur, and phosphorus, 196—Precipita-
tion reactions, 197—Color reactions, 198—Gelatin and wool, 199
—Salting out, 200—Hydrolysis of proteins, 200—Proteoses and
peptones, 201—Proteins of wheat, 201—Edestein, 202—Casein,
203—Textile fibers, 203.
CHAPTER XXVII.—THE IDENTIFICATION OF ORGANIC COMPOUNDS . 205
APPENDIX 211
INDEX 215
EXPERIMENTAL ORGANIC
CHEMISTRY
CHAPTER I
LABORATORY METHODS
1. General Directions to the Student.—Before beginning an

experiment read through to the end the directions which are to
be followed. Many mistakes which involve additional work can
be prevented by understanding beforehand just what is to be
done. The import of the experiment should be clear, and the
chemical reactions involved at each step should be understood
before the work is started.
References are given in each experiment to the section in the
author's textbook "The Principles of Organic Chemistry" in
which the chemical reactions involved are discussed. These
references are given in bold-face type thus, (SECTION 359).
References to paragraphs in this book are indicated thus, §64,
page 42.
Keep a clear and concise record of the laboratory work. The
notes should be written as soon as the experiment has been per-
forned, and care should be taken to have the original record,
made during the course of the experiment, of such a character
that it serves as the permanent record of the work. Notes
should not be taken on loose pieces of paper and afterward written
out in the notebook; they should be written carefully in good
English, and should state briefly what was done and what was
observed. It is necessary for the student to recognize what
the experiment is to teach—why he was asked to do it. If the
work consists in the preparation of some compound the details
for which are given in the laboratory guide, it is not advisable
to take time to copy these details in the notebook. References
to the pages in the book where the preparation is described should
2 EXPERIMENTAL ORGANIC CHEMISTRY
be given, and a statement made of the amounts of the substances

used. If any unexpected difficulties arose, or if any improve-
ment in the way of carrying out the preparation was used, these
facts should be noted. Write equations for all reactions taking
place in the experiment, and record the yield of the compound
obtained. The substance should be put in a clean, dry, glass-
stoppered bottle of appropriate size, and be labeled. The
student's name, the name, weight, and the boiling-point or
melting-point of the substance should be recorded on the label.
The boiling-point or melting-point should be that observed by the
student for the sample itself, and not the points recorded in the
book.
The student should use reasonable care in his manipulations.
He should endeavor to get as large a yield as possible of the
product sought, but should use judgment as to whether it is
advisable to spend a large amount of time to increase by a small
amount the yield of the product. The processes should not be
carried out in the manner used with a quantitative analysis—a
few drops may be lost here and there if they form but a very
small portion of the total amount formed, and their recovery
entails the expenditure of much extra time. It is not meant
by this that the student be careless; be should develop judgment
as to the relative value of a slightly higher yield of product and
the time required to obtain it.
2. Calculation of Yield.—The student should calculate in each
preparation the percentage yield obtained. From the chemical
equation for the reaction can be calculated the so-called theoretical
yield. The percentage of this obtained is called the percentage
yield. The latter is never equal to 100 per cent for many reasons.
It is often advisable to use an excess over the theoretical amount
of one of the substances used in the preparation. The student
should, before calculating the percentage yield obtained, deter-
mine whether an excess of one reagent has been employed.
When one substance used in a preparation is much more expensive
than the rest, it is customary to take the substances in such
amounts that the largest yield possible calculated from the more
expensive substance is obtained. For example, preparations
involving the use of iodine are so carried out that the largest
amount of the halogen possible is obtained in the substance
LABORATORY METHODS 3
prepared. In this case the test of the skill with which the prepara-
tion is carried out is determined by this fact; the percentage yield
should be calculated, accordingly, from the weight of iodine used.
3. Integrity in Laboratory Work.—The student should record
in his notebook his own observations only, and the results he
has obtained himself, unless there is a definite statement to the
contrary. If a student has carried out an experiment along
with another student a statement to this effect should be put
into the notes.
4. Cautions in Regard to Laboratory Work.—A student uses
in laboratory work in organic chemistry inflammable liquids and
substances like sodium and phosphorus which have to be handled
with great care. Unless care is exercised fires may happen.
The laboratory should be provided with buckets of sand and a
fire-extinguisher. A heavy woolen blanket should be near at
hand to be used in case the clothing catches fire.
Inflammable liquids such as ether, alcohol, and benzene should
not be poured into the jars provided for acids.
Only cold solutions should be extracted with ether, and the
process should be carried out at least twelve feet from a flame.
When carrying out a reaction in a test-tube, care should be
taken to hold the tube in such a position that if the contents
are violently thrown out, they will not come in contact with the
experimenter or any one in the neighborhood. If the odor of a
substance in the tube is to be noted, do not look down into the
tube. If this is done and a violent reaction takes place suddenly,
the material in the tube may be thrown into the eye.
CRYSTALLIZATION
5. When an organic compound has been prepared it must

be purified from the by-products which are formed at the same
time. In the case of solid substances crystallization is ordinarily
used for this purpose, although with certain compounds purifica-
tion can be more readily effected by sublimation or distillation,
processes which are described below.
Choice of Solvent.—The separation of two substances by
means of crystallization is based on the fact that they are present
in the mixture to be separated into its constituents in different
amounts, or on the fact that the two substances possess different
solubilities in the liquid used as a solvent. When it is desired

to purify a substance by crystallization a solvent should be
selected, if possible, in which the impurity is readily soluble,
and in which the substance sought is more or less difficultly
soluble. Purification is effected most easily when the sub-
stance to be purified is appreciably soluble in the hot solvent,
and much less soluble in it when cold. If the two conditions
stated above can be combined—and this is possible in many
cases—purification is readily accomplished.
The solvents most commonly used in crystallization are water,
alcohol, ether, benzene, petroleum ether, ligroin, carbon bisul-
phide, chloroform, acetone, and glacial acetic acid. In certain
cases hydrochloric acid, carbon tetrachloride, ethyl acetate,
toluene, and nitrobenzene have been found of particular value as
solvents.
In order to crystallize a compound the solubility of which is
not known, preliminary tests should be made with the solvents
enumerated above; about 0.1 gram or less of the substance should
be used in each test. The solid is placed in a small test-tube,
and the solvent is added a drop at a time and the tube is shaken.
After the addition of about 1 cc. of the liquid, if the substance
has not dissolved, the tube should be heated until the liquid
boils. If the substance does not dissolve, more liquid should be
added in small quantities until solution occurs. If a very large
amount of the liquid is required for solution, or the substance
proves insoluble, another solvent must be used. When solution
takes place the tube is cooled by running water. If the substance
separates, it is redissolved by heating, and the contents set aside
to cool slowly, when crystals will probably form.
If the substance does not separate to a considerable degree
when the hot solution is cooled, similar tests should be made
with other liquids. If none of the solvents can be used in this
way, either the substance must be obtained by spontaneous
evaporation, or a mixture of liquids must be used—a method
described below.
If the compound is to be crystallized by spontaneous evapora-
tion, cold saturated solutions, prepared by dissolving about 0.1
gram or less of the substance in a number of solvents, are poured
onto watch-glasses and left to evaporate slowly.
6. Some substances form solutions from which the first crystals

separate with difficulty. In such cases the solution is "seeded"
by adding a trace of the solid substance; a piece the size of the
bead of a small pin is sufficient. Crystallization of such sub-
stances can often be brought about by scratching with a glass
rod the side of the vessel containing the solution; the rough sur-
face so formed assists materially in the formation of the first
crystal, after which crystallization proceeds readily.
The liquid finally selected for the solvent should be one
which yields well-formed crystals, and does not evaporate too
slowly.
7. Use of Freezing Mixtures in Crystallization.—It often
happens that substances which do not separate from their hot
solutions when the latter are cooled with water, crystallize out
well when the solutions are allowed to stand for some time in a
freezing mixture. For this purpose, a mixture consisting of
equal weights of sodium chloride and finely divided ice or snow,
is commonly used; with snow, a temperature of -17° is obtained.
A mixture of equal weights of crystallized calcium chloride and
snow gives the temperature -48°. A convenient freezing mix-
ture is made by covering finely divided ice with commercial
concentrated hydrochloric acid.
8. Preparation of Crystals.—When a satisfactory solvent has
been selected, the material to be crystallized is placed in a beaker
and covered with the liquid. The mixture is heated to boiling
over a free flame or on a steam-bath if the solvent used is inflam-
mable. It is essential to avoid the presence of a free flame when
alcohol, benzene, ether, or petroleum ether are used as solvents.
The beaker is covered with a watch-glass, and the solvent is
added in small portions at a time until the substance to be
crystallized has passed into solution. It may happen that
a small amount of a difficultly soluble impurity is present; in
this case it is not advisable to add enough solvent to dissolve
the impurity.
When the substance to be crystallized has been dissolved, the
solution is filtered while hot through a fluted filter-paper into a
beaker. Crystallizing dishes should not be used. If the sub-
stance crystallizes out during the filtration, either a hot-water
funnel can be used, or enough of the solvent can be added to
prevent crystallization. In the latter case, and whenever an

excess of solvent has been used, it is advisable to concentrate
the solution to crystallization after filtration.
9. The solution is evaporated to crystallization by boiling it
gently. Tests are made from time to time to determine whether
crystals will form when the solution cools. This can be readily
done by placing a glass rod in the hot solution and then with-
drawing it; if crystals appear when the drop of the liquid which
adheres to the rod cools, the solution should be set aside and
covered with a watch-glass or
filter-paper. If crystals are not
formed, the evaporation should
be carried further.
A hot-water funnel is at times
very useful if crystals form dur-
ing the filtration. It consists
of a funnel surrounded by a
metal jacket in which is placed
water that can be heated to its
boiling-point by means of a
Bunsen burner. When inflam-
mable liquids are used as sol-
vents, the water should be
heated and the burner extin-
guished before filtration. Disregard of this precaution has fre-
quently led to fires.
10. It is advisable to cut off the stems of the funnels to be used
in the preparation of organic compounds. This eliminates the
clogging of the funnel as the result of crystallization of solids in the
stem. It also makes it unnecessary, in most cases, to use filter-
stands as the funnel can be supported by the beaker which is to
hold the filtrate; if the beaker is too large for this, the funnel can
be supported on a clay triangle placed on the beaker. The
arrangement represented in Fig. 1 is especially convenient for
filtering solutions which deposit crystals on cooling slightly.
During filtration the beaker is heated on the steam-bath or over
a flame; the vapor which rises heats the funnel. The latter
should be covered during filtration with a watch-glass to prevent
loss of heat from the liquid that it contains.
11. The Use of a Mixture of Two Liquids as the Solvent in

Crystallization.—It is advisable to use as a solvent in purifying
a substance a liquid in which the substance is readily soluble
when heated and difficultly soluble in the cold. If such a solvent
can not be found, a mixture of two miscible liquids is often used—
one in which the substance is readily soluble, and one in which
it is insoluble or difficultly soluble. In crystallizing a substance
in this way it is first treated with the hot liquid which dissolves
it; to the solution is then added the second liquid, also hot,
until the mixture begins to cloud. A little of the solvent is
added to clear up the solution, which is then covered to prevent
too rapid evaporation, and the mixture is set aside to crystallize.
Pairs of liquids which are valuable for crystallization in this
way are alcohol and water, alcohol and benzene, petroleum
ether and benzene, and alcohol and carbon disulphide.
12. Separation of Crystals.—The separation of crystals from
the mother-liquor is effected by filtration under diminished pres-
sure. A funnel is attached to a filter-bottle by means of a rubber
stopper. A perforated plate about 4 cm. in diameter is placed
in the funnel and covered with a circular piece of filter-paper
the diameter of which is about 6 mm. greater than that of the
plate. This paper is moistened with the solvent. The bottle
is connected with the suction-pump, and air is drawn through
the apparatus. The paper is fitted into place so that it covers
the joint between the filter-plate and funnel. If a crust has
formed around the beaker at the surface of the liquid from
which the crystals to be separated have formed, it should be
carefully removed, as it will probably contain some of the impuri-
ties present. The remaining solution and crystals are then
poured into the funnel, and the suction applied. When all the
liquid has been drawn off the solid should be pressed down
tightly with a spatula. The connection with the pump is broken,
and the solid on the funnel is moistened with some of the pure
solvent used for crystallization. The crystals are allowed to
absorb the solvent and to stay in contact with it for about half
a minute. The suction is then applied and the crystals drained
as fully as possible from the liquid. The filter-bottle is again
disconnected from the pump, and the crystals covered again with
the solvent, and washed as before. Crystals should never be
washed by pouring the solvent over them while the filter-bottle

is connected with the pump. If this is done a large amount of
liquid is required to wash the crystals, and there is great loss due
to the solution of the crystals in the solvent.
When the crystals have been freed by suction as much as
possible from the liquid used to wash them, they should be re-
moved to a porous plate and allowed to dry spontaneously in the
air.
13. In the preparation of many compounds tarry substances
are often obtained along with the compound desired. In this
case the crystals first obtained from solution are often mixed
with these substances. The tar may be removed by pressing
the crystals on a porous plate and allowing them to stand un-
disturbed for some time. The residue, from which the tar has
been largely removed as the result of absorption into the porous
plate, is transferred to a clean part of the plate and is moistened
with the solvent. The substance is left until the solution of the
tarry product clinging to the crystals is absorbed. A second
crystallization and treatment with the porous plate generally
yields a pure compound.
When the crystals are thoroughly dry a melting-point de-
termination (§49, page 33) should be made; if this is not sharp
the substance should be recrystallized.
14. Decolorization of Solutions.—If a substance contains
tarry materials which impart to it a color it can be purified usually
by boiling a solution of it for some time with bone-black, and
filtering the hot solution. The efficiency of the process and the
amount of bone-black required are markedly affected by the
quality of the latter. As an approximation about 1 gram should
be used for a solution of 250 cc. which is moderately colored.
DISTILLATION
15. Liquids are purified by distillation. The form of apparatus

ordinarily used is represented in Fig. 2. In setting up the ap-
paratus the details noted below should be considered.
The distilling flask should be supported by a clamp placed
above the side-arm, and the condenser by a clamp placed at its
middle point. The side-arm of the distilling flask should extend
for about one-half its length into the inner tube of the condenser.
16. Preparation of Corks.—Before being used corks should be

softened. This can be done by means of a press, which is made
for this purpose, or the cork can be rolled on the desk while it is
being pressed firmly by means of a block of wood. It is, in most
cases, not advisable to use rubber stoppers as they may be attacked
by the vapor of the liquid during distillation. Sharp cork borers
should be used to make the holes of such a size that the tubes to
pass through fit snugly. In boring corks it is advisable first
to push the borer with a rotary motion half way through the
FIG. 2.
cork, taking care that the hole is bored through the center of
the cork, the borer is then removed and a hole made from the
center of the other end of the cork to meet that first made. By
proceeding in this way the edges of the holes on the two sides of
the cork will be clean cut, and thus make a tight joint with the
tube to be passed through the hole; and the latter will run evenly
through the axis of the cork.
17. Position of the Thermometer.—The bulb of the thermom-
eter should be so placed that it is about 1 inch below the side-
arm of the distilling flask. If the liquid boils at such a point
that the end of the thread of mercury is hidden by the cork
during the boiling, the position of the thermometer can be shifted
downward, or the upper or lower end of the cork can be cut away.
The bulb should never be placed above the side-arm, since it
is essential that it be covered completely by the vapor during
the distillation.
18. Heating the Flask.—The best way of heating the distilling
flask is determined by the boiling-point of the liquid to be dis-
tilled. If the liquid has a low boiling-point, up to about 80° or
90°, the flask should be placed in a water-bath in such a position
that the level of the water is just below that of the liquid in the
flask. Toward the end of the distillation the flask should be
raised in order to prevent superheating the vapor of the liquid.
With very volatile liquids great care is necessary to prevent this
superheating.
Another method which is often used is to place the flask on
an asbestos board in which a hole is bored having a diameter
about one-half that of the flask. The smallest flame which will
furnish heat enough to boil the liquid is used. This method can
be used for distilling in general, whatever the boiling-point of
the liquid.
If a flask of 250-cc. capacity or greater is used, it is advisable
to support it on a wire gauze. This precaution is also advisable
when the burner is put in place, and the distillation allowed to
take place of itself. It is often better to hold the burner in the
hand and keep the flame in motion during the distillation. In
this way the process is more carefully watched and the rate of
distilling can be controlled.
The heating of the flask should be discontinued before all of the
liquid has distilled; it is customary to leave a residue of 2 to 5 cc.
in the flask.
19. Rate of Distillation.—The distilling flask should be heated
in such a way that the distillate falls in drops from the end of the
condenser at the rate of about one drop per second. Care
should be taken to avoid the rapid distillation of very volatile,
inflammable liquids, such as ether, alcohol, and carbon disulphide.
If such liquids are distilled very rapidly, a part of the vapor is
not condensed, and a fire may result when this vapor comes in
contact with a near-by flame. In order to prevent accidents
the method of collecting such liquids which is described in §34,
page 23, should be used.
20. Distillation of High-boiling Liquids.—When a liquid boils

above 150° an "air-condenser" should be used instead of the
kind shown in Fig. 2, which is supplied with a water-jacket.
If one of the latter type is used, the inner tube, cooled by running
water, is apt to crack when the vapor of the high-boiling liquid
comes in contact with it. The inner tube without a jacket is
used as an air-condenser. When a substance which boils at a
high temperature (above 300°) and solidifies readily is distilled,
it is customary to use no condenser, but to collect the distillate
directly at the end of the side-arm of the distilling flask. If,
FIG. 3. FIG. 4. FIG. 5.
in this case, or when an air-condenser is used, the distillate solidi-

fies before it reaches the receiver, the tube should be gently
heated by passing the flame of a burner slowly along its length.
It is necessary to prevent the filling of the side-arm of the flask
with solid; if this occurs and boiling is continued, the vapor
produced soon reaches a sufficient pressure to cause an explosion.
When this method is unsatisfactory on account of the high
melting-point of the substance, it is advisable to distil from a
retort. On account of the large diameter of the neck of the
retort, a considerable quantity of the solid can be collected in it.
Before the solid fills the neck at any point, the distillation is
stopped, the neck of the retort is heated, and the liquid collected
in a beaker; the distillation is then continued.
21. Fractional Distillation.—When it is necessary to separate

two or more liquids by distillation, special forms of distilling
flasks should be used. These are so constructed that they
decrease materially the time required to effect a separation. This
is accomplished by subjecting the vapor to gradual cooling before
it is finally condensed. In this way the less volatile constituents
of the vapor are condensed and returned to the flask, while the
more volatile parts pass on through the condenser. The types
of flasks used are illustrated by Figs. 3, 4, and 5.
FIG. 6. FIG. 7. FIG. 8. FIG. 9.
The arrangement represented in Fig. 5 is very efficient,

especially when a small amount of a liquid is to be fractionated.
After the liquid has been placed in the flask, a number of glass
beads tied together with a cotton thread are supported by the
thread, and the neck of the flask is filled to the place indicated
in the diagram with glass beads.
22. The more complicated arrangements are supplied as
tubes which are fitted by a cork to a round-bottomed flask.
Figures 6, 7, 8, and 9 illustrate the forms commonly used.
The most efficient form is that of Hempel, Fig. 9, which con-
sists of a tube filled with glass beads. The least efficient form
is that of Wurtz, Fig. 6. The efficiency of the Lebel-Henninger

tube, Fig. 7, and that of the Glinsky tube, Fig. 8, lie between the
two extremes stated.
Another simple form of apparatus, for fractionating low-boiling
liquids, which is especially valuable when small quantities only
are available, can be constructed from a Claissen flask and a test-
tube in the way illustrated in Tig. 10. The cold water enters
through the long tube in the test-tube and passes upward. By
FIG. 10. FIG. 11
regulating the flow of water the cooling effect on the vapor can be
varied. The principle of fractional condensation which is used
effects the separation of the vapor into low- and high-boiling con-
stituents. The combination of a still-head of this type with a
column containing short pieces of glass tubing about 15 mm.
long and 3 mm. internal diameter makes, perhaps, the most
efficient fractionating apparatus available for laboratory use.
It is illustrated in Fig. 11.
23. When a mixture of two liquids which boil at different
temperatures is distilled, the temperature of the vapor during
the distillation rises, in most cases, from the boiling-point of
one of the liquids to that of the other. The distillate which is

collected first contains a large proportion of the lower boiling
liquid, while that collected toward the end of the operation is
rich in the higher boiling liquid. In order to separate the two,
the mixture is subjected to what is called fractional distillation.
The process is carried out in the following way: The mix-
ture is distilled slowly, and the receiver in which the distillate
is collected is changed from time to time, as the boiling-point
of the liquid rises. In this way the mixture is separated into
what are called fractions. The number of fractions collected, and
the limits of the boiling-point of the various fractions, are deter-
mined by the difficulty of separating the mixture and the purity
of the products desired. The lowest boiling fraction is next
placed in a clean flask and distilled. When the temperature
reaches that of the upper limit of the fraction, the heating is
stopped, and the second fraction added to the flask. Distilla-
tion is then continued until the upper limit of this fraction is
reached, the distillate being collected in the appropriate receiver.
The process is continued in this way until all the fractions have
been distilled a second time. It will be found as a result of this
fractionation that the distribution of the liquid in the several
fractions is different from that obtained the first time. The
fractions which boil at temperatures near those of the boiling-
points of the constituents of the mixture increase in volume. By
repeating the process a sufficient number of times, practically
all of the liquid can be separated into its constituents.
In the following table are given the results of the fractional
distillation of a mixture of 50 cc. of methyl alcohol and 50 cc.
of water. The volumes of the fractions obtained after each of
six fractionations are recorded.
66°-68° 68°-78° 78°-88° 88°-98° 98°-100°
I 0.0 1.5 47.0 17.0 31.0

II 0.0 33.5 14.0 7.5 38.5
III 1.5 38.5 6.5 5.5 40.5
IV 15.0 24.5 5.0 3.0 43.5
V 25.0 16.0 2.5 1.0 44.5
VI 32.0 7.5 1.0 0.0 45.5
When the liquids form a constant-boiling mixture, they can

not be separated in pure condition by fractional distillation. The
boiling-point of a mixture of ethyl alcohol and water, which
contains 96 per cent by weight of the former, is lower than that
of pure alcohol. As a consequence, when a mixture of the two
substances is subjected to repeated fractional distillation, the
constant-boiling mixture is obtained. In order to prepare pure
alcohol it is necessary to remove the water from the mixture by
chemical means. Very few cases of this kind are met with in
the purification of organic compounds.
DISTILLATION UNDER DIMINISHED PRESSURE
24. Many substances which decompose when distilled at

atmospheric pressure, distil without decomposition when the
pressure is reduced. This results from the fact that the tempera-
ture at which a substance boils is markedly affected by the pres-
sure. For example, benzophenone boils at 306° at 760 mm.
pressure, and at 170° at 15 mm. pressure. The effect of change
in pressure on the boiling-point increases rapidly as the pressure
decreases. Stearic acid, for example, boils at 291° at 100 mm.,
at 232° at 15 mm., and at 155° under the best vacuum obtainable
with a mercury pump. A difference of 85 mm. in pressure from
100 mm. to 15 mm. causes a change in boiling-point of 59°,
whereas a difference of 15 mm. from 15 mm. to 0 mm. lowers
the boiling-point 77°.
Many substances which distill with partial decomposition at
atmospheric pressure can be distilled unchanged at the pressure
which can be obtained with a good water-pump. A convenient
arrangement of the apparatus required for distillation under
diminished pressure is represented by Fig. 12. A piece of glass
tubing drawn out to a fine opening is attached to the right arm
of the manometer, as indicated in the figure. This prevents the
mercury from being forced out of the tube when the cock (c) is
opened to admit air after the distillation has been completed.
The flask to contain the substance to be distilled is fitted with
a thermometer and a tube (a) which is drawn out to a fine open-
ing at one end; to the other end of the tube is attached a piece
of rubber tubing carrying a screw-clamp (b). This tube is pro-
vided to prevent violent bumping during the distillation. By
regulating the screw-clamp after the apparatus has been attached

to the vacuum-pump, a rapid stream of air-bubbles can be drawn
through the liquid. As the latter is heated the vapor formed
passes into the bubbles, and superheating and the consequent
bumping are largely avoided. The position of the tube is so
adjusted that the fine opening almost touches the bottom of the
flask. It is often advisable to replace the plain distilling flask,
like the one shown in Fig. 12, by one of the Claissen type (Fig.
FIG. 12.
10). If the latter is used and bumping occurs, the material in

the flask is not so apt to be forced over into the condenser.
25. Other modifications of the form of the tube to admit air
into the flask are often used. If the neck of the flask is small
and it is impossible to insert into it both the thermometer and a
glass tube of the ordinary diameter, the part of the tube which is
to pass through the cork is drawn out to a capillary, and is
inserted through a small hole made with a stout needle or the end
of a file. One end of the tube is left with such a diameter that
the rubber tubing and screw-clamp can be attached to it.
26. A second modification is often used on account of its con-
venience. It is illustrated in Fig. 13. A straight glass tube is
selected of such a diameter that the thermometer passes into it

easily. The tube is drawn out at one end to a small opening;
it is then cut off at the other end at such a point that when the
thermometer is placed in it and it is put into the flask,
the bulb of the thermometer is in the correct position
with regard to the side-arm of the flask. A piece of
rubber tubing provided with a screw-clamp is attached
to the upper end of the tube.
When liquids which boil at a very high temperature
are distilled, it is customary not to use an air-conden-
ser, but to connect the receiver directly with the side-
arm of the flask which contains the liquid to be distilled.
In assembling the distilling apparatus, a rubber
stopper may be used to attach the receiver to the con-
denser, provided care is taken to prevent the hot liquid
from coming in contact with the rubber. Great care
should be exercised in selecting the corks to be used;
these should be as free as possible from holes. After
the apparatus has been set up, small leaks can often
be closed by painting the corks with collodion.
A convenient arrangement of the manometer and
the connections between the pump and the receiver
is represented in Fig. 12. A number of forms of
manometers are used to register the pressure inside
the apparatus. A simple form which can be readily
made from a supply of mercury, a meter-stick, and
a piece of glass tubing is illustrated in the figure. In
order to determine the pressure in the apparatus the
readings on the scale opposite the levels of the mer-
cury in the manometer are subtracted, and this differ-
ence is subtracted from the height of the barometer.
It is necessary to insert an empty bottle between the
pump and the receiver. When the apparatus has been
evacuated, water may run back from the pump into FIG. 13.
the receiver as a result of a slight change in the pres-

sure of the water caused by the opening of a cock in the neigh-
borhood. The inserted bottle serves as a trap to catch this water.
At c is a stop-cock through which air can be let into the appar-
atus. This is of value at the end of a distillation, or in case the
boiling liquid begins to froth or bump violently. In the latter

case letting in a little air prevents the ejection of a part of the
contents of the flask into the receiver.
27. Method of Distillation.—Before introducing the liquid to
be distilled, the whole apparatus should be tested. The screw-
clamp b should be closed, and the receiver connected by a heavy-
walled tube to the pump. In no part of the apparatus should
rubber tubing be used which collapses under diminished pressure.
If no heavy tubing is available the connections can be made with
glass tubing joined by ordinary rubber tubing, the ends of the
glass tubes being brought together so that the connecting rubber
tubes can not collapse. When the apparatus has been connected
with the pump the pressure should be reduced to about 20 mm.
If this can not be done, either the pump is a poor one, or the
apparatus has not been well put together. The cause can be
determined as follows: First, test the pump by connecting it
directly with the manometer, making sure that there is not a
leak in the connecting tubes. Second, disconnect the tube at
d, and close it with a pinch-cock or glass rod. If the reduction
in pressure is sufficient it will show that all the connections from
the pump up to this point are tight. Next, disconnect the flask
from the condenser and connect it by means of the side-arm to
the pump and manometer. This will determine whether the
cork provided with the thermometer and the tube to admit air
is tight. It is probable that the leak will be found at this point.
If everything is tight, connect the flask with the condenser, and
the lower end of the latter with the pump. This will test the
tightness of the joint between the flask and condenser. The
apparatus is next completely adjusted, and tested again, when,
if no leak has been discovered up to this point and the pressure
can not be sufficiently reduced, it is evident that the connection
between that condenser and receiver is at fault.
When the apparatus has been found to be tight, the product
to be distilled is introduced into the flask, which should be filled
to not more than one-half its capacity. The suction is applied
and the screw-clamp b opened very slowly so that a stream of air-
bubbles passes through the liquid. The flask is heated by a
bath containing oil or, preferably, a low-melting alloy such as
Rose's or Wood's metal. It is often better to heat the flask by
means of a free flame as the amount of heat applied can be

quickly regulated. When a free flame is used it should be kept
in constant motion, and the surface of the liquid where it comes
in contact with the flask should be heated rather than the bottom
of the flask. This can be done by moving the flame around
the flask and letting it come in contact with the latter at the side
and not the bottom.
If frothing suddenly begins and there is a chance of the con-
tents of the flask rushing over into the receiver, such a result
can be prevented by opening the cock c which admits air to the
apparatus.
Special forms of apparatus have been devised to fractionate a
liquid by distillation under diminished pressure. It is often
simpler to use the apparatus described above, and change the
receiver when the limits of the fractions have been reached.
DISTILLATION WITH STEAM
28. Substances which are practically immiscible with water

and have an appreciable vapor pressure at 100°, can be readily
separated from those which have a very small vapor pressure
at this temperature by passing steam through the mixture.
The process which is of special value in separating organic com-
pounds from tarry materials formed in their preparation, is
carried out in an apparatus arranged as represented in Fig. 14.
The flask a is connected with a supply of steam; this can be con-
veniently generated in a kerosene can, which is supplied with a
long glass tube reaching to the bottom of the can, to act as a
safety-valve. Into the flask is put the substance to be distilled.
The flask should be set up at an angle as indicated in the dia-
gram. By placing the flask in this position any of the liquid
which is violently thrown up against the flask as the result of
the inrush of steam, will not be forced through the condenser
into the receiver. The tube through which the steam is led
should be so bent that its end almost touches the lowest point of
the flask in its inclined position. By this means the steam is
forced through the heavy liquid to be distilled, which is conse-
quently kept in motion. If the liquid is not stirred up by the
incoming steam distillation takes place very slowly.
29. The vapor issuing from the flask consists of a mixture of

steam and the volatile substance to be distilled. When this is
condensed, two layers are formed. The theory of the process is
briefly as follows: When a mixture of two immiscible liquids
is heated, each substance vaporizes independently of the other.
When the sum of the vapor pressures of the two liquids is equal
to the pressure of the atmosphere, the mixture distils. The
relation between the weight of the two substances obtained is
determined by their molecular weights and their vapor pressures
at the temperature of distillation. The case of nitrobenzene
Fig. 14.
and water is an example. When steam is passed into nitro-

benzene the mixture boils at 99°, when the atmospheric pressure
is 760 mm. At this temperature the pressure of water vapor is
733 mm., and of nitrobenzene 27 mm.; consequently the relation
between the weight of water and that of nitrobenzene is as
18 X 733 is to 123 X 27, or approximately 4 to 1. Although the
vapor pressure of nitrobenzene is small at 99°, its large molecular
weight compared with that of water leads to the result that about
one-fifth of the product obtained by distillation with steam con-
sists of nitrobenzene. When the vapor pressure of a compound is
as low as 10 mm. at 100°, it can be advantageously distilled with
steam. Orthonitrophenol can be conveniently separated from
paranitrophenol on account of the fact that the former has an
appreciable vapor pressure at 100°, and is consequently volatile

with steam.
30. When the vapor pressure of a substance increases rapidly
near 100°, the rate at which it distils can be markedly increased
by adding to the mixture of it and water a substance soluble in
water; the latter increases the boiling-point of the liquid. By
saturating the water with calcium chloride a marked rise in the
temperature at which distillation occurs can be effected, with the
consequent increase in the vapor pressure of the organic com-
pound undergoing distillation.
When the vapor pressure of a substance is appreciable only at a
temperature considerably above the boiling-point of water, it
may often be separated from less volatile compounds by distilla-
tion with superheated steam. In this case the flask containing
the substance is heated in an oil-bath, and steam which has been
passed through a hot coil of copper is conducted through it.
EXTRACTION
By extraction is meant the process of removing from a mixture,

usually an aqueous solution, one or more substances by shaking
with a liquid in which the substances to be removed are soluble.
Aniline, for example, is somewhat soluble in water; when the solu-
tion is shaken with ether a large part of the aniline is removed
from the water and passes into solution in the ether. As aniline
can be recovered much more readily from an ethereal solution
than from an aqueous solution, extraction, of such solutions is
made use of in the preparation of the compound. The liquid
used for extracting must be immiscible with the solution to be
extracted.
31. Method of Extraction.—In extracting a solution it is
shaken in a separatory funnel with a liquid in which the substance
to be extracted is readily soluble. The substances commonly
used for this purpose are ether, chloroform, benzene, petroleum
ether or ligroin, and carbon disulphide. Ether is generally
used as it is an excellent solvent for many organic compounds,
and, on account of its low boiling-point, it can be readily removed.
The disadvantages connected with the use of ether are its great
inflammability and the fact that it is somewhat soluble in water
and dissolves appreciable quantities of water. Water dissolves
approximately 10 per cent of its volume of ether. When large

volumes of aqueous solutions are extracted there is a loss of
ether, which is an expensive substance. This loss is decreased
by saturating the solution to be extracted with sodium chloride.
On account of the fact that ether dissolves about 2 per cent of
its volume of water, ethereal extracts have to be dried, in most
cases, before the ether is removed by evaporation.
32. The relation between the volume of an aqueous solution
to be extracted and the volume of the solvent used for extrac-
tion, is determined by the relative solubilities of the substances
to be extracted in water and the solvent used. If an aqueous
solution of a substance is extracted with ether, the amounts of
the substances found in the two liquids will be proportional to
the solubilities in the two solvents and to the amounts of the
latter. If the substance is equally soluble in water and in ether,
and the volumes of the two liquids are the same, after extraction
one-half of the substance will be found in the ether. If the
substance is twice as soluble in ether as in water, the relation
of the amount present in the ether will be to that present in the
water as two is to one, that is, two-thirds will be present in the
ether and only one-third in the water. By shaking the aqueous
solution with a second portion of ether, two-thirds of the sub-
stance present, that is two-thirds of one-third, or two-ninths, of
the original amount will be removed and one-ninth will remain
dissolved in the water. After three extractions but one twenty-
seventh of the substance will remain dissolved in the water.
In the above example a certain volume of a solution was
extracted three times, using each time a volume of ether equal to
that of the aqueous solution. The result would have been differ-
ent if the solution had been extracted with the three volumes of
ether in one operation. In this case the substances would have
been divided between the ether and the water in the ratio of
3 X 2 : 1 ; that is, one-seventh would have remained dissolved
in the water. As the result of extracting the solution with the
same volume of ether in three operations using one-third of the
solution each time, but one twenty-seventh remains dissolved
in the water. It is evident, therefore, that the most efficient
way to extract a substance is to shake the solution a number of
times with small amounts of the extracting agent.
33. The relation between the volumes of the extracting liquid

and of the solution, and the number of times the solution should
be extracted, vary widely with the relative solubility of the sub¬
stance to be extracted. In general, in the case of a substance
which is much more soluble in ether than in water, three extrac-
tions will be sufficient if a volume of ether equal to about one-
fourth of that of the aqueous solution is used. In order to de-
termine whether the extraction has been carried far enough, a
sample of the last ethereal extract should be evaporated on a
watch-glass on a steam-bath. The amount of the residue will
determine whether a fourth extraction is desirable.
If a large volume of liquid is to be extracted, a separatory
funnel of appropriate size is not available, the liquid can be
placed in a flask and shaken with ether; the major part of the
latter can be decanted off, and the rest separated in a small
separatory funnel.
34. Separation of the Extracted Substance.—If the substance
is a solid, and a small amount of the extracting liquid has been
used, the solution can be evaporated to dryness and the residue
crystallized. If it is desired to recover the ether or other solvent
used in the extraction, the solution should be placed in a flask
and the solvent distilled off on a water-bath as described below.
When the substance to be obtained from the solution is a liquid
which is to be finally distilled, it is necessary to dry the extract
before the removal of the solvent. The drying agent must be
selected according to the principles stated in §36, page 25. If
ether has been used, the solution should not be set aside to dry
in a thin-walled flask which has been stoppered; sufficient heat
is at times generated as the result of the union of the water and
the drying agent to break the flask. A bottle or distilling flask
should be used. It is not advisable to place the extract in a
beaker or other open vessel, as the solvent will be lost if the solu-
tion stands for some time.
When the solution is dry, the solvent can be removed by dis-
tillation. If ether or any other very volatile and inflammable
liquid is used, the flask containing the solvent should be heated
on a water-bath, and should be provided with a long water-
jacketed condenser and a special form of receiver. This is made
by attaching to the condenser, by means of a tightly fitting
stopper, an adapter, which, in turn, is attached in the same way

to a filter-bottle. The side-arm of the latter is provided with a
rubber tube of such length that it reaches nearly to the floor.
By taking these precautions accidents caused by fires are pre-
vented, as the only way in which ether vapor can escape from the
apparatus is through the rubber tube; as ether vapor is very heavy
and as any which escapes is delivered at the level of the floor,
there is little chance of its being ignited by any flames on the
laboratory desks. The receiver should be dry in order that the
ether which distils over may be used in transferring the residue
after the distillation to a flask of appropriate size for the final
distillation.
The dry ethereal extract is decanted, or, better, filtered from
the drying agent into the distilling flask, great care being taken
to prevent any heavy aqueous layer from getting into the flask.
Such a layer is frequently formed when potassium hydroxide is
used as a drying agent; the compound extracts water from the
ether and forms a saturated aqueous solution. The flask is next
tightly corked, attached to the condenser and receiver, and the
ether distilled off on a water-bath. When all the ether has evap-
orated the residue is poured into a flask of appropriate size for
distillation. As an appreciable amount of the substance adheres
to the larger flask from which the ethereal extract was distilled, it
should be washed out twice with a few cubic centimeters of the
ether which have been distilled off, and these washings added to
the flask from which the final distillation is to be made. In this
distillation the flask should be heated slowly at first until the
small amount of ether has been driven out. The final distilla-
tion should be made as described in §15.
35. Sublimation.—This process is of special value when it is
desired to separate a solid which is volatile from substances
which do not vaporize readily. It generally yields a very pure
substance, but it often leads to loss.
The process is most easily carried out between two watch-
glasses which fit closely. The substance which has been carefully
dried is placed in one of the glasses. This is covered with a piece
of filter-paper, in which a few small holes have been cut to allow
the passage of the vapor. The second glass, placed in an inverted
position, is fastened to the first by means of a specially constructed
clamp. The apparatus is heated slowly on a sand-bath and the

upper watch-glass is cooled by putting on it pieces of filter-paper
which are kept moist with cold water. It is necessary to keep
the upper watch-glass at a temperature lower than the melting-
point of the substance to be sublimed.
36. Drying Agents.—Many organic substances are prepared
in water solution or in their preparation are washed with water
to remove soluble impurities. In this case it is necessary to dry
them, if they are liquids, before they are distilled. It is necessary
to select as a drying agent a substance which does not react with
the compound to be freed from water. The substance generally
employed is anhydrous calcium chloride, which is commonly
used in a granular form; for many purposes the chloride which
has been fused in the form of sticks is preferable. Calcium
chloride forms addition-products with hydroxyl compounds
and should not be used as a drying agent for alcohols, phenols,
etc.
Alcohols are commonly dried with quicklime. Water is usu-
ally removed from basic substances by treating them with solid
potassium hydroxide. Anhydrous copper sulphate is an excellent
drying agent for most substances; another salt, anhydrous
sodium sulphate, is frequently used. It must be remembered
in the latter case that hydrated sodium sulphate loses its water
of crystallization at 33°; it is evident that the salt acts as a drying
agent only below this temperature.
The most powerful drying agents are sodium and phosphorus
pentoxide. The use of the former is evidently limited to those
substances which do not react with the metal. Sodium is used
to remove the last traces of water only, the substances being
previously dried with calcium chloride which removes most of
the water.
37. The drying agent should remain in contact with the
substances to be dried for from 2 to 3 hours, if the two are left
in contact at room temperature. If convenient, the mixture
should be set aside over night.
Whether the drying agent should be removed from the sub-
stance before it is distilled, is determined by the boiling-point
of the substance and the stability of the compound formed
between the water and drying agent. It is advisable, however,
except in the case of substances which boil below 80°, to remove

the drying agent before distillation.
The last traces of water may be removed from liquids which
boil above 200° by drawing a current of air through them while
they are gently heated.
38. Use of the Reflux Condenser.—It is often necessary to
heat together two or more substances for a number of hours. If
FIG. 15. FIG. 16.

all the substances boil above the room temperature an open vessel
provided with a reflux condenser is used. The arrangement
of the apparatus is shown in Figs. 15 and 16.
If it is desired to distil the product formed directly from the
flask, the arrangement represented in Fig. 16 may be used.
In this case the side-arm of the distilling flask is covered with a
cork into which a hole has been bored half through its length.
The side-arm is so placed that the liquid which condenses in it
returns to the flask. Heating with a reflux condenser is usually
carried out in a round-bottomed flask as shown in Fig. 15. If
the contents are apt to boil with bumping the flask is usually
heated on a sand-bath; otherwise a free flame and a wire gauze are

used. If the liquid boils above 150° an air-condenser is used
instead of a condenser provided with a water-jacket.
When it is necessary to heat with a reflux condenser substances
which destroy cork and rubber, a simple device can be used
which is represented in Fig. 17. A test-tube is selected which fits
loosely into a long-necked,
round-bottomed flask. The
tube is supplied with a rubber
stopper and tubes as shown in
the drawing. Water is passed
through the tube, which is
supported in the neck of the
flask by means of a clamp.
Such an arrangement can be
used conveniently instead of
that represented in Fig. 15.
A test-tube fitted in this
way can be used with a distill-
ing flask, if it is desired to
distill from the same flask after
refluxing.
In many syntheses hydro-
gen chloride or bromide is
given off. It is inadvisable
to let these gases get into the
room even when the appar-
atus is placed under a hood.
The top of the condenser FIG. 17.
should be provided with a tube
bent at two right angles. This tube should reach to within
about 1 inch of the surface of water contained in a flask supported
by a ring-clamp to the stand to which the condenser is attached.
If it is necessary to keep the contents of the flask dry during
the reaction, a straight drying tube containing calcium chloride
should be inserted between the condenser and the flask contain-
ing the water.
39. Prevention of Bumping.—When a substance boils irregu-
larly and "bumps," even boiling can often be obtained by placing
in the vessel a few pieces broken from a porous plate. The so-
called capillary boiling-tubes are also valuable. They can be
made by drawing out pieces of glass tubing to stout
capillary tubes; these are cut off at such a length that
they will reach from the bottom of the flask to well into
the neck. They are next put into the flame and melted
at such a point that the tube fuses together at about
0.5 cm. from one end. When this end is placed under
a liquid the small cavity is filled with air, and as the
liquid boils bubbles of vapor are formed at the end of
the tube and even boiling results. If the liquid cools
below its boiling-point after it has been heated some
time, the cavity at the end of the boiling-
tube becomes filled with liquid as the result
of the condensation of the vapor. In this
case the tube must be withdrawn and the
drop of liquid shaken from it, or a new
tube must be inserted.
40. Dropping Funnels.—A dropping fun-
nel like that shown in Fig. 18 is very useful.
With a funnel of this type it is possible to
observe at the point marked a the number
of drops which pass through the funnel. If
such a funnel is not available one can be
made from an ordinary separatory funnel
by attaching to its end a short calcium
FIG. 18. chloride drying tube as shown in Fig. 19,
and connecting the latter by means of a
glass tube to the apparatus to be used.
41. Manipulation of Sodium.—Sodium is used in the
preparation of a large number of organic compounds.
As the metal reacts rapidly with oxygen and with
water-vapor, it should not be allowed to stay in con-
tact with the air any longer than is necessary. When
sodium is to be cut with a knife or pressed into a wire,
the coating which covers the metal should be first care- FIG. 19.
fully removed and rejected; and the sodium should be
placed immediately under dry ether, if it is not to be used at once.
In many preparations in which sodium is used a part of the metal
is left unchanged at the end of the experiment. Great care must

be exercised in getting rid of the residue. It should not be left
in an unlabeled flask or bottle. Under no circumstances should
the product be allowed to come into contact with water. Small
quantities of alcohol should be added from time to time to the
sodium, until enough of the liquid is present to dissolve the
residue, or to make with it a thin paste. This mixture should
then be poured slowly into water, in order to prevent an accident
in case any sodium is enclosed within a mass of inert solid.
When sodium is used in a preparation, great care should be taken
to prevent water entering the vessel containing the metal, either
as the result of using a poorly fitting cork or a defective condenser.
T H E MANIPULATION OF SMALL QUANTITIES OP SUBSTANCES
In the identification of organic compounds it is generally

necessary to transform them into other compounds, the properties
of which are determined as an aid in the identification. It
often happens that but a few grams of a substance are available
for the purpose. The successful handling of such small quantities
requires careful work, and the student should have opportunity
to learn the special technique required.
42. Crystallization.—In the purification of small quantities
of substances by crystallization a solvent should be selected in
which the substance is more or less difficultly soluble, and care
should be taken to avoid an excess of the solvent. It is best not
to add enough of the solvent to dissolve the substance completely,
even at the boiling temperature. The hot solution should be
rapidly filtered. This can be done best under diminished pres-
sure. A filter-bottle is selected of such a size that it will hold
a 6-inch test-tube and permit a funnel being placed in the neck
of the bottle in the usual way. The funnel is fitted with a per-
forated plate and a circular piece of filter-paper which is cut
with a diameter about 8 mm. greater than the plate. The paper
is put in place and pressed down so that it covers the joint
between the plate and the funnel. A little of the liquid is poured
through the funnel and the suction applied. This serves to set
the paper firmly in place.
The liquid is poured out of the test-tube, which is then replaced
in the bottle. The funnel is put in place and the solution to be
filtered is poured into it. Under the diminished pressure, the

solution filters rapidly before the compound in solution can
crystallize out. The method of filtration described in §10,
page 6, is also to be recommended.
43. A filter-bottle provided with a perforated plate and test-
tube is used to separate crystals from the mother-liquor contain-
ing them. While connected with the suction-pump the mixture
of crystals and mother-liquor is poured slowly down a glass rod
onto the filter-paper. If a very small amount of crystals is to
be separated, care should be taken to collect them in a single spot
and not to spread them out over the entire plate. In this way the
crystals can be collected in a small mound, a few millimeters in
diameter, which can be readily removed from the paper when dry.
The crystals should be washed as directed in §12, page 7.
44. Distillation of Small Amounts of Liquids.—The liquid
should be distilled from a 5-cc. distilling flask. If this is not
available the neck of a broken distilling flask can be converted
into a serviceable piece of apparatus for this purpose by sealing
it at a point about 5 cm. from the side-tube. In distilling with
small flasks an asbestos shield as described in §18, page 10,
and a very small flame should always be used; a short thermome-
ter reduces the error arising from stem-exposure.
The boiling-point of 1 cc. of liquid can be determined in this
way. In heating the substance, the flame should be applied, at
first, in such a way that the vapor condenses in the flask just
before it reaches the side-tube. In this way the thermometer is
heated up to the temperature of the vapor before the latter is
driven over. If the distillation is carried on rapidly the small
amount of liquid will have distilled over before the thermometer
has been heated up to the temperature of the vapor. For a
method of determining the boiling-point of very small quan-
tities of a liquid see Smith and Menzies, J. Am. Chem. Soc.,
33, 897.
45. If it is necessary to distil fractionally a small amount of
liquid, a flask should be selected the side-arm of which is as far
away from the bulb as possible (see Fig. 4, page 11). Such a
flask can be furnished with an efficient fractionating column as
follows: Glass beads which pass snugly into the neck of the flask
are tied to the end of a cotton thread, or if necessary a fine
platinum wire. After the liquid had been introduced, the beads
arc: hung at the bottom of the neck of the flask, which is then
filled with more beads, just enough room being left for the ther-
mometer. A column of beads only a few centimeters high is
remarkably efficient in bringing about the separation of liquids
of different boiling-points through distillation (see Fig. 5, page 11).
46. Extraction of Small Amounts of Substances.—When
a small amount of substance is to be extracted the solution is
shaken with about an equal volume of ether or other solvent
in a test-tube. To separate the two liquids the upper layer is
drawn into a pipette. In order
to be able to see clearly the posi-
tion of the end of the pipette,
a long rubber tube is connected
with it so that the test-tube may
be held at the level of the eye
while the liquid is being drawn
up.
If a number of extractions are
to be made a simple apparatus
which can be made readily is of
value. This consists of a test-
tube with a side-arm placed at a
point slightly above the middle
of the tube. The tube is filled
with the liquid to be extracted
up to the side-arm, which is FIG. 20.
closed by the end of the forefinger. Ether is added, the tube

closed with the thumb, and the mixture shaken. A vessel to hold
the ether is placed under the side-arm; when the finger and thumb
are removed the ether runs out of the tube.
47. Preparation of Liquids on the Small Scale.—It is often
necessary to prepare small amounts of liquids, which are obtained
as the result of heating together two or more substances, and
subsequent distillation. An example is the preparation of ethyl
iodide by heating alcohol and hydriodic acid. A simplified
form of apparatus for such work is shown in Fig. 20.
The test-tube a is supported by a clamp; the test-tube which
serves as a condenser is surrounded by cold water contained in
a beaker. It is important that the tube from a should extend

nearly to the bottom of the condenser, in order that any vapor
which passes over may come in contact with the walls of the
tube, which are cooled by the water in the beaker. In using an
apparatus like this, the distillation should be made very slowly.
DETERMINATION OF PHYSICAL PROPERTIES
48. Calibration of Thermometers.—The thermometers pro-

vided for use in determining the physical properties of organic
compounds are usually far from accurate. If very exact measure-
ments are to be made, a high-grade thermometer should be
calibrated according to the methods described in books dealing
with physical measurements. For students' work in organic
chemistry, a cheap thermometer may be used provided it is cali-
brated with reasonable care. A thermometer which is accurate
to within 0.5° is satisfactory.
Although most thermometers register correctly at 0° and 100°,
it is well to make a calibration at these points. To determine the
reading at 0°, a beaker of 100 cc. capacity is filled with finely
chopped ice, and water is added until it reaches to within about
2 cm. of the surface of the ice. The thermometer is inserted into
the ice and water until the zero point is just above the surface, so
it can be seen. The reading on the thermometer is noted when
the mercury no longer falls. Care should be taken to have the
eye at the height of the top of the mercury column to avoid
parallax.
To calibrate the thermometer at higher temperatures it must
be heated in such a way that the entire mercury thread is exposed
to the vapor of a boiling liquid. This can be conveniently done
as follows: Attach to an 8-inch test-tube by means of a closely
fitting cork (not a rubber stopper) a short air-condenser. Place
in the tube about 10 cc. of water and support the tube and
condenser by means of a clamp over a wire gauze. Attach a
cotton thread to the thermometer, and lower it through the
condenser until the bulb is about 4 inches above the liquid. The
thermometer is held in place by tying the upper end of the thread
around a small piece of glass rod, which is then placed across
the end of the condenser. The water is boiled, and when the
entire thermometer is in the vapor, the position of the mercury

is noted.
The thermometer should be calibrated at higher temperatures
by determining the boiling-points of other liquids in the apparatus
described above. The latter should be thoroughly dried
and a fresh cork used to avoid the presence of water.
The substances which can be used conveniently are
aniline, naphthalene, and benzophenone. The boiling-
points of these substances at 760 mm. pressure are,
respectively, 183.7°, 218.1° and 306.1°. These are the
temperatures recorded when the entire thread of mercury
in the thermometer is exposed to the vapor
of the boiling liquid. The barometric pres-
sure should be noted and a correction made
of 0.1° for each 2.7 mm. of pressure; if the
observed pressure is less than 760 mm. the
correction should be added, and if greater
it should be subtracted. The substances
used should be pure; the aniline must be
redistilled, and the first part of the distillate
rejected, in order to free it from the small
amount of water that it usually contains.
The thermometer should be marked with
a number, and the corrections to be applied
recorded in the notebook.
49. Determination of Melting-points.—
A form of apparatus which can be con-
veniently used to determine melting-points
is represented by Fig. 21. It consists of a
100-cc. round-bottomed flask and a test-tube
which fits loosely into the neck of the flask.
A thermometer is supported in the test-tube
by a cork in which a slit has been cut so that
the graduations of the former are visible.
FIG. 21. The flask and test-tube are filled with pure
concentrated sulphuric acid to the heights
indicated in the drawing. If the sulphuric acid becomes brown
as the result of the introduction of traces of organic matter, a
tiny piece of a crystal of potassium nitrate will destroy the color.
The substance, the melting-point of which is to be determined,

is dried, usually in the air, and is powdered by rubbing it with
a spatula on a clean, porous tile. It is then placed in a small
capillary tube which has an internal diameter of about 1 mm.
50. Tubes for the determination of melting-points are conven-
iently made as follows: A piece of glass tubing of 5 mm. internal
diameter is softened by rotating it in a flame; it is removed from
the flame and after 2 seconds is slowly drawn out so that the tube
is elongated about 10 cm., and the tube formed has at its narrowest
point an external diameter of about 1.5 mm. The tube is again
heated and drawn out. The process is repeated until the tube is
of such a length it can not be conveniently handled. The appear-
ance of the tube so prepared is represented by Fig. 22.
The distance from a to c should be about 15 cm. The tube is
cut at a, c, e, etc. These pieces are then cut in the middle at
b, d, etc., and each piece sealed at these points by holding in a
flame. A number of tubes should be prepared at one time. In
order to avoid getting dust into the tubes, they should be kept in
a test-tube provided with a cork, or should be placed in a small
beaker with the open ends downward.
The substance to be melted is placed in a tube. This can be
done readily by pressing a little of the substance into the open
end of the tube with the aid of a spatula, grasping the tube by
the closed end, and drawing a file lightly over it. The vibrations
produced in this way cause the powder to fall in the tube. The
process is repeated until a layer of the substance from 0.5 to 1 cm.
thick has been formed.
The tube is attached to the thermometer by means of a rubber
band which is made by cutting off a piece of tubing about 2 mm.
in length from a rubber tube of such a diameter that it fits the
thermometer snugly when drawn over it. This band should be
placed at least 2 cm. above the surface of the acid.
51. In making a preliminary determination of an unknown
melting-point, the flask is heated cautiously with a free flame
in such a way that the thermometer rises at the rate of about
ten degrees per minute. The temperature should be noted at
which the substance first shows signs of melting and when it has
completely liquefied. As the thermometer is rapidly rising, this
result serves only as a guide for the determination of the melting-
point. When the apparatus has cooled to a number of degrees

below the temperature at which signs of melting were evident,
a new tube containing another sample of the substance is intro-
duced into the apparatus and the melting-point redetermined.
All melting-point determinations should be made with samples
which have not been melted. If the thermometer is at a high
temperature when it is removed from the bath, it should not
be cooled by placing it in cold water; if this is done the glass is
apt to crack. The tube is heated rapidly until the temperature
is at least ten degrees below that at which the substance melts.
The flame should be removed and the temperature allowed to
rise slowly. When the thermometer ceases to rise the flask
should be heated cautiously so that when the flame is removed
the temperature does not rise more than one degree. In the case
of a substance which melts without decomposition, the tempera-
ture should be allowed to rise at the rate of about two degrees per
minute for the last five degrees. An endeavor should be made to
have such control of the bath that the thermometer can be
forced up a degree at a time. The heating is continued until
the substance completely runs down the tube as a liquid. The
point at which this occurs and that at which the substance
begins to form in droplets should be recorded as the melting-
point of the sample studied. If these are separated by more
than one degree, the substance is more or less impure. If the sub-
stance shows signs of contracting or softening before it begins
to melt, the fact should be noted as it is an indication that it is
impure.
The determination of the melting-point should be repeated,
and great care taken to allow the temperature to rise very slowly
when the substance begins to melt. It may happen that the
substance melts within one degree, but that it appears to melt
over a considerable range of temperature on account of the fact
that the heat has been applied so rapidly that the thermometer
rises a number of degrees during the time required to melt the
substance.
When a substance appears to be pure and gives a sharp melt-
ing-point, a number of determinations should be made. If these
give the same result, the melting-point as determined may be
considered to be the correct one.
If a substance does not melt sharply it should be recrystallized,

and a second determination made. As a result of the purification
the melting-point obtained will probably be higher than before.
The process is repeated as long as the melting-point rises.
52. The melting-point determined as indicated is below the
true melting-point of the substance on account of the fact that
only part of the mercury is heated to the temperature of the
melting substance. A close approximation of the true melting-
point can be found by applying the correction which is found by
substituting in the formula N(t — t') 0.000154, in which N is the
number of degrees of mercury not heated directly by the acid in
the bath, t the observed temperature and t' the average tempera-
ture of the stem outside the bath. The correction, which is
added to the observed temperature, is, in the case of a bath like
that described, and when the usual form of thermometer which
registers up to 360° is used, about 1° at 100°, about 2° at 140°, 3°
at 170°, and 6° at 220°.
53. Determination of Boiling-points.—The determination of
the boiling-point of a substance is made during the final distilla-
tion in its purification. If 20 or more grams are distilled, the
boiling-point as determined in the apparatus described above
under distillation, may be considered to be correct. Care must
be taken, however, not to distil all of the liquid, as when this is
done the vapor toward the end of the distillation becomes super-
heated, and the thermometer does not register the true boiling-
point of the liquid.
54. If but a small amount of the substance has been prepared,
or the boiling-point of a small sample of an organic compound is
desired, the determination is best made in the manner described
below, which largely prevents superheating. About 10 cc. of
the liquid is placed in a 15-cc. flask provided with a thermometer
the bulb of which is placed just below the side-tube. The flask
is supported on an asbestos board in which has been carefully
cut by means of a sharp cork-borer of brass, a hole about 2 cm. in
diameter. The bottom of the flask should fit the hole tightly so
that the hot gases from the flame can not come in contact with
the upper part of the flask.
On account of the smallness of the flask, a large part of the
thermometer is not heated to the temperature of the vapor and
a correction should be made for stem exposure as described

above under the determination of melting-points. In order to
determine the mean temperature of the stem, a second ther-
mometer should be attached by means of rubber bands to the
one used to indicate the temperature of the vapors in the flask.
The bulb of the second thermometer should be placed at a point
half way below the upper end of the first thermometer and the
cork.
The condenser to be used is determined by the boiling-point
of the liquid (see §20, page 11). The flask should be heated by a
free flame of such a size that when it comes in contact with the
lower part of the flask it furnishes sufficient heat to keep the liquid
boiling at such a rate that about 0.5 cc. distils per minute. The
distillation should be stopped when the level of the liquid is
just below that of the asbestos-board that supports the flask.
If a very accurate determination of a boiling-point is to be
made, the substance should be distilled from a tube of such a
length that the thermometer can be heated by the vapor up to the
point where the top of the mercury column stands when the sub-
stance is boiling. When determined in this way no correction
for stem exposure is necessary.
55. As the boiling-point varies with the pressure, in recording
accurately determined boiling-points, both the pressure and the
temperature are stated. When the determination is made at a
pressure within 40 mm. of the normal pressure, 760 mm., a cor-
rection can be applied to the observed reading to reduce the
boiling-point to that of the substance at the normal pressure.
This correction is 0.1° for each 2.7 mm. pressure. If the observed
pressure is less than 760 mm., the correction should be added; if
greater, it should be subtracted. It is evident that this correc-
tion should not be applied if the substance does not boil sharply
and if every precaution has not been taken to have a pure sub-
stance and to eliminate the errors which commonly are present
in a boiling-point determination made in the ordinary way.
56. Determination of Specific Gravity.—The determination
of specific gravity is often made in the identification of organic
compounds. For this purpose results accurate to two units
in the third decimal place are sufficient; these may be obtained by
using as little as 1 cc. of a liquid. A convenient form of apparatus
for the determination is described by Mulliken. 1 It consists

of a 1-cc. pipette and a glass tube, closed at one end, into which
the former passes freely (see Fig. 23).
When the apparatus is weighed, it is stood on the pan of an
analytical balance and the loop of wire is placed over the hook
which supports the scale-pan. The apparatus is
calibrated as follows: The pipette and tube are cleaned,
dried, and weighed. The pipette is next filled to the
mark with distilled water, the temperature of which
is noted; any liquid adhering to the outside of the
pipette is removed. The pipette is put into the tube
and the water allowed to flow out into the latter.
The apparatus is weighed again. The increase in
weight is the weight of water, at the observed tem-
perature, which fills the pipette. In determining the
specific gravity of a substance the pipette is filled
with it as before and weighed, and the temperature of
the liquid is noted. The specific gravity is obtained by
dividing the weight of the substance by the weight of
the water. The result obtained is the specific gravity
at the temperature at which the substance was weighed,
compared with water at the temperature at which it
was weighed. As it is customary to refer specific
FIG. 23. gravities to water at 4°, the volume of the pipette
should be calculated for the weight of water which it
contains. In the following table are given the weights of 1 cc.
of water at temperatures from 14° to 30°.
Temp. Temp. Temp.
14° 0.9993 20° 0.9982 26° 0.9968
l6° 0.9989 22° 0.9977 28° 0.9963
18° 0.9986 24° 0.9973 30° 0.9957
The volume of the pipette may be determined by dividing the
weight of the water by the weight of 1 cc. of water at the tem-
perature at which the water was weighed.
In calculating the specific gravity of a substance the weight
observed is divided by the volume of the pipette; the result is
the specific gravity of the substance at the observed temperature
compared with water at 4°. If the number determined in this
1 Identification of Pure Organic Compounds, Vol. I.
way for a substance weighed at 18° was found to be 1.365, the

result would be expressed as 1.365 18°/4°.
If a number of determinations of specific gravity are to be
made, it is advisable to calibrate the pipette to hold 1 cc. If
this is done the observed weight of the substance which fills the
pipette is its specific gravity referred to water at 4°.
T H E QUALITATIVE ANALYSIS OF ORGANIC COMPOUNDS
57. Test for Metallic Elements.—About 0.1 gram of the sub-

stance is heated in a clean, dry, porcelain crucible. If it burns
with a flame or leaves a residue of carbon it is probably organic.
If the residue is black it should be heated until all the carbon has
burned off. If the original substance contained a metal there
will be left in the crucible after ignition either a metal, an oxide,
or a carbonate. This residue should be identified by the methods
of inorganic qualitative analysis. Organic compounds which
leave residues on ignition are usually metallic salts of acids.
If it is reasonably certain that the substance does not contain
a metal which is readily reduced by carbon, the ignition can be
made on a platinum foil.
If there is doubt as to whether the compound is organic, a
sample of it can be heated in a hard glass tube with powdered
copper oxide, and the evolved gas tested for carbon dioxide. If
the substance is volatile it is necessary to place a mixture of it
and copper oxide in the bottom of the tube and then add enough
of the oxide to make a layer at least 5 cm. thick. The tube
is carefully heated, beginning at the point farthest from the bot-
tom of the tube.
58. Test for Non-metallic Elements.—The substance to be
analyzed is first decomposed by heating it with metallic sodium,
and the resulting mixture, which may contain the following com-
pounds of sodium, is analyzed: chloride, bromide, iodide, phos-
phide, sulphide, cyanide, and sulphocyanide. The decomposi-
tion is accomplished as follows: A clean, dry 6-inch test-tube is
supported near the open end in a vertical position by means of
a clamp and iron stand. A piece of sodium equal in size to a
cube 3 mm. on each edge is cut and wiped free from oil by means
of a filter paper. Any deposit on the sodium should be rejected,
and the piece selected should have clean freshly cut surfaces on
all sides. The test-tube is warmed, and the sodium dropped in.
The burner is placed directly under the tube which is heated
until a layer of the sodium vapor about 1 cm. thick is formed.
The substance to bo analyzed is now dropped into the tube, care
being taken to have it fall directly onto the hot sodium without
coming into contact with the tube. If the substance is a liquid,
about 3 drops should be used. If it is a solid, a little should
be taken up on the end of a pen-knife or spatula and dropped into
the tube; a second portion should then be added. The flame is
removed immediately, and when the tube is cold, the lower end
of it should be broken off by tapping the tube with a pestle in a
clean, dry mortar. If, during the heating, some of the unde-
composed substance has settled on the upper part of the tube,
this part should be rejected; only the very end which contained
the sodium vapor should be used. About 2 cc. of alcohol is then
added to react with any excess of sodium present. When the
metal has ceased acting, the contents of the mortar are ground
with 20 cc. of distilled water, transferred to a small beaker,
heated to boiling, and filtered. If the decomposition has been
satisfactorily accomplished a colorless solution is obtained. If
this is not the case, a second fusion with sodium should be made,
and great care taken to introduce the substance directly into the
sodium vapor.
Separate portions of the filtrate are tested for non-metallic
elements as follows:
Test for Sulphur.—Add to about 2 cc. of a dilute solution of
sodium hydroxide 2 or 3 drops of a solution of lead acetate.
To the resulting mixture add about 5 cc. of the filtrate obtained
as described above. If sulphur is present, black lead sulphide
will be formed. If but a small amount of sulphur is present,
a yellow color may be produced without the formation of a pre-
cipitate. If this is the case, filter the solution after a few minutes,
and examine the paper for a precipitate of lead sulphide.
59. Test for Nitrogen.—Boil for a minute about 2 cc. of the
solution from the fusion with 5 drops of a 10 per cent solution
of sodium hydroxide and 5 drops of a solution of ferrous sulphate.
Cool, and add dilute hydrochloric acid drop by drop, until the
solution becomes acid and the precipitate of ferrous hydroxide
has dissolved. An excess should be avoided as the inaction

which lakes place if nitrogen is present—the formation of ferric
ferrocyanide—is more delicate in the absence of an excess of acid.
If a large amount of acid appears to be necessary, it is evident
that the original fusion did not completely destroy the organic
compound.
If a blue or green color does not develop on adding the acid,
a drop of ferric chloride should be added to the tube. It often
happens that enough ferric ferrocyanide is not formed to produce
the characteristic blue precipitate; the formation of a clear green
solution is ample proof of the presence of nitrogen. Such a
solution usually deposits a blue precipitate on standing.
60. Test for Halogens.—A preliminary test for halogen should
be made with some of the original substance. The so-called
Beilstein test is made as follows: A piece of stout copper wire is
bent around the end of a lead pencil to make a small loop at
one end. This end is then heated in a Bunsen flame until it no
longer imparts a color to the flame. The wire is allowed to cool,
and the clean end is inserted into the substance to be tested
if it is a liquid, or a bit of it, if solid, is supported in the loop on
the wire. It is then put into the flame. If a halogen is present
a green color is imparted to the flame. The test should be
repeated a number of times in order to have the conclusion
definite. A few nitrogen compounds give a green flame when
tested in this way.
If a halogen is found to be present the solution obtained from
the decomposition with sodium should be tested.
If sulphur and nitrogen have been found to be absent, about
1 cc. of the solution is acidified with nitric acid, and silver nitrate
is added. The color of the precipitate formed is an indication of
the halogen present, provided but one is present. If the pres-
ence of bromine or iodine is suspected, a second portion of the
original solution is acidified, and about 2 cc. of carbon disulphide
is added; chlorine water or a solution of sodium hypochlorite
is then added, drop by drop. If either sulphur or nitrogen is
present, it is necessary to boil the original solution for several
minutes with a few drops of dilute sulphuric acid to remove
hydrogen sulphide and hydrocyanic acid before the teats for
the halogens are applied.
61. Test for Phosphorus.—One cubic centimeter of the original

solution from the fusion is boiled for 1 minute with 3 cc. of
concentrated nitric acid. This treatment oxidizes the sodium
phosphide to sodium phosphate. The presence of the latter is
tested for by adding to the cooled solution twice its volume of
ammonium molybdate reagent. The tube is heated to such a
temperature that it can just be held in the hand, and is then set
aside. The formation of a yellow precipitate indicates phos-
phorus, provided arsenic is not present.
CHAPTER II
GENERAL PROCESSES: HYDROCARBONS OF THE METHANE
SERIES
62. Calibration of a Thermometer.—Calibrate a thermometer
at 0°, 100°, 183.7°, and 218.1° according to the method described
in §48, page 32.
63. Determination of Melting-points.—Determine the melting-
point of the substances furnished according to the directions
given in §49-52, pages 33-36.
64. Fractional Distillation.—Read the description of fractional
distillation in §21-23. Set up an apparatus for distillation like
that shown in Fig. 2, page 9. Use a 200-cc. distilling flask
and as receivers three 100-cc. flasks which are labeled, respectively,
I. 78°-82°; II, 82°-95°; and III, 95°-100°. Place 50 cc. of alcohol
and 50 cc. of water in the distilling flask, and heat the latter with
a flame of such a size that the liquid distils at the rate of about
1 drop per second. Collect the part which distils up to 82°
in the flask numbered I. When this point is reached replace this
receiver by flask I I , and collect the distillate in this flask until
the thermometer registers 95°. At this point use flask III as the
receiver. When nearly all the liquid has distilled, pour out the
small residue from the distilling flask and dry it, or use a clean
dry flask. Measure in a graduated cylinder the volumes of the
contents of the three receivers at the end of the first distillation,
and record the results in your notebook. (See the tabulation
on page 14.) Place in the distilling flask the liquid in receiver
I (the first fraction), and distil as before, collecting what boils
up to 82° in receiver I. When this point is reached, allow the
distilling flask to cool slightly, and then add to it the contents
of flask II. Replace the thermometer and distil. Collect what
passes over below 82° in flask I, and the part which boils between
82° and 95° in flask II. Remove the flame, and add to the dis-
tilling flask the contents of flask III. Replace the thermometer
and collect the distillate in the several receivers according to the
43
boiling-point. Measure and record the volumes of the three

fractions at the end of this second distillation. Repeat the
fractionation a third time and record the volumes of the fractions.
65. Qualitative Analysis of Organic Compounds.—Make
analyses of the substances furnished, following the directions
given in §58-61, pages 39-42.
66. Preparation of Methane from Sodium Acetate; Properties
of Methane (SECTIONS 17, 18).—( a ) Grind and mix thoroughly
in a mortar 8 grams of fused sodium acetate 1 and 8 grams of
soda-lime. 2 Transfer the mixture to an 8-inch test-tube pro-
vided with a rubber stopper fitted with a short piece of glass
tubing. Connect to the latter by means of a short piece of rubber
tubing a delivery-tube arranged to collect a gas over water.
Support the test-tube, by means of a clamp, in such a position
that the end containing the stopper is slightly lower than the
other end; this prevents any water given off during the heating
from running back into the hot tube and cracking it. Heat the
tube cautiously, keeping the flame in motion, in order to avoid
local overheating. (Eq.) 3 Collect three 250-cc. bottles of the
gas. Prepare a mixture of the gas with air by putting into a
fourth 250-cc. bottle 25 cc. of water; cover the bottle with a glass
plate, insert it in the pneumatic trough, and pass the gas into
the bottle until the water has just been replaced. C A U T I O N . —
Remove the delivery-tube from the water before the heating of
the tube is stopped. If during the heating the water begins to
go back into the test-tube, the breaking of the latter can be pre-
vented by separating the test-tube from the delivery-tube where
they are joined together.
1 Commercial fused sodium acetate is generally not anhydrous; it is well to
fuse it before use. If the compound is to be prepared from the hydrated salt
(CH3COONa.3H20) proceed as follows: Heat cautiously about 15 grams
of the crystalline salt contained in an iron pan over a small flame. Stir
continuously with a glass rod. The salt melts at first in its water of crystal-
lization; as the dehydration proceeds it solidifies, and, finally, when anhy-
drous, melts a second time. Care should be taken to avoid heating the
dehydrated salt much above its melting-point, as it undergoes decomposition
when strongly heated.
2The soda-lime can be replaced by an intimate mixture of 4 grams of
powdered sodium hydroxide and 4 grams of quicklime.

3 The abbreviation (Eq.) signifies that an equation for the reaction which
takes place should be written.

GENERAL PROCESSES 45
(b) Inflammability of methane.—Drop a lighted match into

one jar of the gas. Is soot produced? Why? (Eq.) What is
the color of the flame?
(c) Explosive mixture of methane and air.—Light the mixture
of methane and air. Explain the difference between the results
obtained in this case and in (b). (Eq.) Calculate the relation
between the volume of methane and the volume of oxygen in
the gas exploded. State the volumes which interact according
to the equation for the reaction.
(d) Methane and bromine.—Add one drop of bromine to a
bottle of the gas. This can be done conveniently by placing a
pipette, made from a piece of glass tubing drawn down to a
small bore at one end, into a bottle of bromine and placing the
finger over the end of the pipette, which is then withdrawn.
Cover the bottle with a glass plate, and allow it to stand for a
few minutes until the bromine has vaporized. Drop a lighted
match into the bottle. (Eq.) When the reaction is complete
breathe sharply across the mouth of the bottle, and test the gases
in the bottle with a piece of moist blue litmus paper.
(e) Methane and an oxidizing agent.—Make a dilute solution
of potassium permanganate by dissolving a crystal of the salt
in one-half a test-tube full of water. Add the solution to a bottle
of methane, replace the cover, and shake. Explain.
NOTES.—(a)1 Soda-lime is preferably used in experiments of this type

rather than sodium hydroxide, as the latter rapidly attacks glass at the tem-
perature at which the reaction takes place.
(b) The methane prepared in this way is not pure; it contains small
amounts of substances (acetone, for example) which impart a yellow color
to the flame. The reaction should be brought about at the lowest tempera-
ture at which it takes place, in order to reduce the amount of by-products
formed. Pure methane burns with a flame that is only slightly luminous.
(c) The violence of tho explosion is reduced by the fact that the oxygen
which reacts with the hydrocarbon is diluted with nitrogen. A mixture of
one volume of methane and two volumes of oxygen explodes with violence
when ignited.
(e) This test is of value in distinguishing hydrocarbons of the methane
series from other hydrocarbons which rapidly reduce an aqueous solution of
potassium permanganate. If reduction occurs it is due to the fact that the
methane is impure.
1 The letters used in the notes refer to the paragraphs under these letters
in the description of the experiments.

67. Preparation and Properties of Ethane: Grignard Reaction.

( a ) Into a dry 50-cc. Erlenmeyer flask fitted by means of a
cork to a return condenser, place 2 grams of magnesium powder
and a small crystal of iodine. Add through the condenser 5 cc.
of ethyl bromide and 10 cc. of ether dried over sodium. In
about 15 minutes when reaction ceases (Eq.) replace the condenser
by a two-holed stopper carrying a small separatory funnel and a
delivery-tube to collect a gas over water. Add water to the flask
drop by drop, through the funnel. (Eq.) Collect two 250-cc.
bottles of the gas.
(b) Inflammability of ethane.—Drop a lighted match into one
bottle of the gas and note the color of the flame.
(c) Ethane and oxidizing agents.—Test the second bottle of
gas to determine whether ethane can be readily oxidized. (See
experiment 66e, page 45.)
NOTE.—(a) A trace of iodine is usually added to the mixture of halide

and magnesium in effecting a Grignard synthesis, in order to hasten the
reaction. The reaction is similar to that by which methane is formed
from methyl iodide and magnesium. (See end of SECTION 17.)
68. Preparation and Properties of Di-isoamyl: Wurtz Syn-

thesis.—( a ) To 20 grams of isoamyl bromide contained in a
dry 100-cc. round-bottomed flask add 5 grams of sodium cut into
about six pieces. Connect the flask with a piece of glass tubing
about 3 feet long, to serve as a reflux condenser, and allow it to
stand over night. Connect the flask with an air condenser,
and distil with a smoky flame which is kept constantly in motion
to avoid local overheating. (Eq.) Redistil slowly the distillate
from a small flask, and save and weigh the fraction which boils
at 158°-161°. Isoamyl bromide boils at 118.6° and di-isoamyl
at 159°. CAUTION.—Read carefully §41, page 28. The flask
contains unused sodium, and water should not be put into it.
Add portions of 5 cc, of alcohol from time to time until the
evolution of hydrogen ceases, and there is enough of the liquid
to make a thin paste of it with sodium bromide; then pour
the contents of the flask cautiously into an open vessel con-
taining water. Do not pour water into the flask. Great care
should be taken in the disposal of sodium residues which should
be always treated in the manner just described; serious explo-
sions and accidents frequently happen as the result of a lack of

proper precautions.
Calculate the theoretical yield from the isoamyl bromide used
and the percentage obtained in the experiment.
(b) Di-isoamyl and bromine.—Add 2 drops of bromine to
about 2 cc. of di-isoamyl. Breathe across the tube. Is there
any evidence of substitution? Heat the contents of the tube
to boiling and test for hydrobromic acid as before. (Eq.)
(c) Di-isoamyl and sulphuric add.—Add 2 cc. of the hydro-
carbon to about 5 cc. of concentrated sulphuric acid, and shake
well. Allow the tube to stand a few minutes and observe the
contents. Do the two liquids mix?
(d) Di-isoamyl and nitric acid.—Repeat experiment (c) above
using concentrated nitric acid instead of sulphuric acid. Record
the results obtained.
NOTES.—(a) In carrying out the Wurtz synthesis the reaction is often

brought about in a solvent; the halide, or mixture of halides, is diluted with
about twice its volume of ether which has been dried over sodium. The
preparation described above should yield from 7 to 8 grams of the slightly
impure hydrocarbon.
(c and d) Concentrated sulphuric acid and nitric acid are valuable agents
for distinguishing between the paraffin hydrocarbons and many other classes
of compounds which dissolve in these reagents.
69. Composition of Kerosene (SECTIONS 24 and 28).—Distil

about 25 cc. of kerosene, using a small flask and a condenser.
(See Fig. 2, page 9.) CAUTION.—See that all corks fit tightly and
that the receiver is not near a flame. Note the temperature at
which the liquid begins to drop freely from the condenser and
when the last part is distilling over. Compare the boiling-points
obtained with those of the paraffin hydrocarbons, and state what.
compounds are present in the sample studied.
NOTE.—Crude petroleum is separated into various commercial products

according to the specific gravity of the distillates. These products are not
carefully fractionated and are mixtures.
70. Properties of Gasoline and Kerosene (SECTIONS 26 to

28).—( a ) Kerosene and acids and alkalies.—In separate test-
tubes shake about 5 cc. of distilled kerosene with 10 cc. each of
concentrated nitric acid, concentrated sulphuric acid, and a
dilute solution of sodium hydroxide. Note if heat is evolved

or if there is a change in color. Record your observations and
conclusions. Gasoline behaves in a similar way.
(b) Solubility of kerosene.—Test the solubility of about 2 cc.
of kerosene or 1 gram of paraffin in water, ether, alcohol, and
ligroin or petroleum ether. CAUTION.—Volatile inflammable
liquids such as ether, alcohol, and petroleum ether should not be
heated over a free flame. They can be heated conveniently by
immersing the vessel containing them in boiling water.
(c) Flash-point of gasoline.—Pass a burning match over a few
drops of gasoline placed on a watch-glass. What statement can
you make in regard to the flash-point of gasoline?
(d) Flash-point of kerosene.—This experiment should be car-
ried out in a place where there is no draft. Support a plain
beaker of 55-cc. capacity in a 100-cc. beaker by means of a triangle
made of copper wire, or a piece of pasteboard in which a hole has
been cut just large enough to allow the body of the small beaker to
pass. Fill the smaller beaker with kerosene and the larger
beaker with water. In each case the level of the liquid should
be within one-half inch of the top of the beaker. C A U T I O N . —
Have an asbestos-board or a watch-glass at hand with which to
smother the flame in case the kerosene takes fire during the
experiment. Insert a burning match into the kerosene. What
can you say of the flash-point of kerosene? Place the apparatus
on a wire gauze, and heat cautiously with a flame, the tip of which
should be about 3 inches below the gauze. Insert into the kero-
sene the bulb of a thermometer, which should be supported by a
clamp. The temperature of the oil should rise not faster than 2°
per minute. Attach by means of a rubber tube to the gas-cock
a blow-pipe or a piece of glass tubing drawn out to a fine opening.
The gas should be regulated to produce a flame about one-half
inch in length. When the temperature of the kerosene reaches
35°, pass the flame quickly over the surface of the oil, taking care
not to touch it. Repeat the test for every degree rise in tempera-
ture. Record the temperature at which the vapor of the oil
ignites; this is made evident by a slight flash which is more or
less difficult to see. As soon as the flash-point has been observed,
extinguish the flame under the apparatus. If the kerosene does
not flash before 48°, turn out the flame and consult the instructor.
Compare your results with the flash-point of kerosene required

by law (SECTION 29).
NOTE.—(a) Owing to the cracking of the paraffin oils in their distillation,

samples of the commercial products from petroleum often contain small
quantities of hydrocarbons which react with sulphuric acid and with nitric
avid. When these impurities have been removed by repeated shaking with
concentrated sulphuric acid, the resulting paraffin hydrocarbons show their
characteristic inertness.
CHAPTER III
UNSATURATED HYDROCARBONS
71. Preparation and Properties of Ethylene (SECTION 32).—
( a ) Weigh directly into an 8-inch test-tube 4 grams of phosphorus
pentoxide. Connect the test-tube by means of a closely fitting
cork with a reflux air-condenser; immerse the tube in cold water,
and pour 5 cc. of ethyl alcohol slowly into the condenser. The
alcohol should be added cautiously in small portions and the
test-tube shaken under water, as much heat is evolved when
alcohol comes in contact with phosphorus pentoxide. Support
the test-tube at an angle of about 45° with the table by means of
a clamp, and connect it with a delivery-tube arranged to collect
a gas over water. Heat the tube carefully until the mixture
becomes homogenous; then more strongly until a steady stream
of gas is evolved. Collect three 250-cc. wide-mouthed bottles
of the gas, and prepare an explosive mixture of ethylene and air.
This can be done by placing 20 cc. of water in a 250-cc. wide-
mouthed bottle, covering the latter with a glass plate, inverting
in a pneumatic trough, and displacing the water by ethylene.
(b) Inflammability of ethylene.—Throw a lighted match into a
bottle of ethylene. In order to facilitate the removal of the gas,
a stream of water should be poured into the bottle as the gas
burns. Note the color of the flame, and compare with results
obtained when methane was burned. (Explain.)
(c) Explosive mixture of ethylene and air.—Throw a lighted
match into the bottle containing the mixture of ethylene and air.
(d) Ethylene and bromine.—HOOD.—Add 2 drops of bromine to
a bottle of the gas. (See experiment 66d, page 45.) Replace
the glass cover and shake. When the color of bromine has
disappeared, observe carefully the contents of the bottle. Are
there drops of an oil present? (Eq.) Test the gas in the bottle
with moist blue litmus paper. Compare the results with those
obtained with methane.
50
UNSATURATED HYDROCARBONS 51
(e) Ethylene and oxidizing agents.—Dissolve a small crystal

of potassium permanganate in about 20 cc. of water, and add
a little of the solution to a bottle of the gas. Replace the cover
and shake. Explain the value of the test, and compare the
results with those obtained with methane. (See experiment
66e, page 45.)
(f) Test for unsaturated compounds in coal gas.—Collect over
water a bottle of illuminating gas. Add a dilute solution of
potassium permanganate in portions of 5 cc. to the bottle and
shake. What conclusions can be drawn as to the presence of
unsaturated hydrocarbons in illuminating gas? What are the
chief constituents of coal gas? Of water gas? Of what value are
the unsaturated hydrocarbons in these gases?
NOTE.—When sulphuric acid, which is commonly used as a dehydrating
agent in the preparation of ethylene, is employed, the reaction takes place at
a temperature very near that at which the alcohol chars; as a consequence,
carbon often separates, the mixture froths badly, and sulphur dioxide and
carbon dioxide are formed. The apparatus for the preparation in this way
is described under ethylene bromide (experiment 137, page 108).
72. Preparation of Ethylene from Ethylene Bromide (SECTION

32).—Into a 6-inch test-tube place about 2 cc. of ethylene bro-
mide, 2 cc. of alcohol, and about 0.5 gram of sheet zinc. Connect
the tube with a delivery-tube, warm gently until reaction begins,
and collect a test-tube full of the gas over water. (Eq.) Burn
the gas. (Eq.)
73. Preparation of an Amylene (Pentene-2).—Place in a 200-
cc. distilling flask 25 cc. of water, add 25 cc. of concentrated
sulphuric acid, and cool the mixture in running water. Add
next 22 grams of secondary amyl alcohol (see note) and connect
the flask with a long condenser through which a rapid stream of
cold water is passing. Attach to the condenser by means of a cork
an adapter, the open end of which extends as far as possible into a
flask. The latter is sunk into ice-water, contained in a beaker.
Close the distilling flask with a cork. It is necessary that all corks
fit tightly to prevent the loss of amylene which boils at 37°-39°.
Heat the flask on a boiling water-bath as long as anything distils.
The hydrocarbon is separated and placed in a distilling flask with
a little anhydrous calcium chloride. When all evidence of mois-
ture has disappeared it is distilled from a beaker containing water
heated to about 60°. The amylene is collected as before in a dry

flask surrounded by ice-water. Collect the product boiling from
36°-42°. Calculate the percentage yield and write the equation
for the reactions involved. The yield should be from 12 to 15
grams.
NOTE.—The alcohol to be used in this experiment is now made by the
Standard Oil Co. of New Jersey and is available commercially. Secondary
alcohols, of the general formula R2CHOH, lose water more readily than
primary alcohols, RCH2OH. For this reason sulphuric acid diluted with
water can be used. If the concentrated acid is used the unsaturated
hydrocarbon is polymerized to di- and tri-amylenes.
74. Properties of Unsaturated Hydrocarbons (SECTION 3 8 ) . —

( a ) Amylene and bromine.—Dissolve 1 cc. of amylene in 5 cc.
of carbon tetrachloride, and add gradually, as long as an evident
reaction takes place, a solution prepared by dissolving 2 cc. of
bromine in 50 cc. of carbon tetrachloride. (Eq.) Test for
evolved hydrobromic acid by breathing across the mouth of the
tube.
(b) Amylene and oxidizing agents.—Shake a few drops of amy-
lene with about 20 cc. of a dilute solution of potassium per-
manganate prepared by dissolving a crystal of the salt in one-
half a test-tube full of water. (Eq.)
(c) Test for unsaturated hydrocarbons in gasoline.—To 10 cc.
of gasoline contained in a dry test-tube add drop by drop a 5 per
cent solution of bromine in carbon tetrachloride. Note if hydro-
bromic acid is given off, by breathing across the mouth of the
tube. Add finally 2 cc. of the solution after it remains colored,
and divide the mixture into two portions; place one in your desk
the dark and the other in direct sunlight. Examine the tubes
in a few minutes. Explain the differences observed.
NOTE.—(c) Certain samples of gasoline consist essentially of saturated
hydrocarbons. Other samples, which are made from the products formed by
cracking crude oils, contain a large percentage of olefines.
75. Preparation and Properties of Acetylene (SECTIONS 41
to 43).—( a ) Support a dry 200-cc. distilling flask by means of a
clamp, and connect the side-arm of the flask with a delivery-
tube arranged to collect a gas over water. Fit a dropping funnel
into the neck of the flask by means of a cork. Place in the flask
about 10 grams of calcium carbide, and let water fall very slowly,
UNSATURATED HYDROCARBONS 53
drop by drop, from the funnel onto the carbide. (Eq.) Fill
four 250-cc. bottles with the gas generated, rejecting the first
bottle-full collected. W h y ? Prepare an explosive mixture of
acetylene and air by putting 15 cc. of water into a wide-mouthed
bottle, covering the bottle with a glass plate, inverting the bottle
in the pneumatic trough, and displacing the water by acetylene.
C A U T I O N . — D o not let acetylene escape freely into the air; the
gas has an unpleasant odor and is poisonous.
(b) Inflammability of acetylene.—Throw a lighted match into
a bottle of the gas. Is much soot deposited? Note the luminos-
ity of the flame and compare your results with those obtained
when methane and ethylene burned.
(c) Explosive mixture of acetylene and air.—Throw a lighted
match into a bottle containing the mixture of acetylene and air.
How does the explosion compare in intensity with those obtained
with methane and ethylene?
(d) Acetylene and oxidizing agents.—Apply the potassium per-
manganate test for unsaturation. (See experiment 66e, page 45.)
(e) Acetylene and bromine.—Add to a bottle of the gas about
5 drops of bromine. Replace the cover of the bottle and shake.
If the color does not disappear in a minute, add to the bottle a
few cubic centimeters of a dilute solution of sodium hydroxide
and shake. When the color has disappeared, observe the con-
tents of the bottle carefully. (Eq.) Note the odor of the prod-
uct formed. How could acetylene be obtained from this com-
pound? (Eq.)
(f) Test for the triple bond.—Test a bottle of the gas for a
compound containing a triple bond, using an ammoniacal solu-
tion of cuprous chloride which can be made as follows: Heat
together in a test-tube over a flame, a few pieces of copper oxide
and metallic copper with about 10 cc. of dilute hydrochloric
acid (sp. gr. 1.1). When the solution becomes colorless, cool,
decant off about 5 cc. of the liquid and add ammonia until the
solution is alkaline. Add this solution to a bottle of the gas;
cover the bottle and shake. (Eq.)
NOTES.—(a) The acetylene prepared in this way from commercial cal-
cium carbide contains impurities, such as hydrogen sulphide and phosphine.
If the gas is to be used to prepare other compounds, it should be purified
by passing it through a wash-bottle containing a solution of mercuric chlo-
ride in hydrochloric acid.
(c) It is easy to obtain an explosive mixture of air and acetylene as the

proportion of acetylene in such mixtures may vary between wide limits,
namely, from 3 to 82 per cent by volume. In the case of methane and
ethylene, the limiting volumes are from 5 to 13 per cent of the former and
from 4 to 22 per cent of the latter.
(f) This test applies only to compounds containing the C≡CH group;
the compounds must contain a hydrogen atom linked to a carbon atom which
is joined to a second carbon atom by a triple bond.
CHAPTER IV
ALCOHOLS
76. Properties of Methyl Alcohol (SECTION 56).—( a ) Inflam-
mability of methyl alcohol.—Pour about 1 cc. of methyl alcohol
into an evaporating dish and apply a burning match. (Eq.)
Note the appearance of the flame.
(b) Solubility of methyl alcohol.—Test the solubility of methyl
alcohol in water, ether, ethyl alcohol, petroleum ether, and ben-
zene. Use about 1 cc. of the alcohol in each test.
(c) Methyl alcohol as a solvent.—Test the solubility of anhy-
drous calcium chloride and sodium chloride in methyl alcohol.
(d) Methyl alcohol and sodium.—Add a piece of sodium the
size of a small pea to 5 cc. of methyl alcohol. (Eq.)
77. Tests for Methyl Alcohol.—(a) Methyl salicylate.—Mix
together in a test-tube about 0.2 gram of salicylic acid, 1 cc. of
concentrated sulphuric acid, and 1 cc. of methyl alcohol, and
warm gently. Note and describe the odor. The compound
formed is the methyl ester of a salicylic acid, HO.C 6 H 4 .COOCH 3 .
(b) Formaldehyde (SECTION 177).—Dissolve 5 drops of methyl
alcohol in 3 cc. of water. Wind a piece of stout copper wire
around a load pencil so that a closely coiled spiral about 2 cm.
in length is formed; leave about 20 cm. of the wire to serve as a
handle. Heat the spiral in the upper part of a Bunsen flame,
and plunge it while red hot into the solution of methyl alcohol.
Withdraw the spiral, cool the liquid under running water, and
heat again with the hot spiral. In this way the methyl alcohol
is oxidized by the hot copper oxide formed on the wire. Note the
odor of the liquid while hot. Cool the liquid, add 2 drops of a
0.5 per cent solution of resorcin and pour the resulting mixture,
slowly so the two liquids do not mix, down the side of an inclined
test-tube containing about 5 cc. of concentrated sulphuric acid.
78. Preparation of Ethyl Alcohol by Fermentation (SECTION
58).— ( a ) Dissolve 40 grams of commercial anhydrous glucose in
350 cc. of water in a 500-cc. bottle. Add one-fourth of a yeast
55
cake ground to a smooth paste with 50 cc. of water, and about

0.5 gram of Witte's peptone. 1 Close the bottle with a rubber
stopper through which passes one end of a glass tube bent in two
right angles to form three sides of a rectangle. The other end of
the tube passes to the bottom of a test-tube which is held in
place by means of cork along the side of which a groove is cut to
allow the escape of gas. The test-tube is one-half filled with a
solution of barium hydroxide. By using the apparatus arranged
in this way, any gas evolved must pass through the solution of
barium hydroxide before it escapes. Mark the bottle with
your name by means of a label, and set it in a warm place (about
30°). Examine the contents of the bottle at the next laboratory
exercise. Has the amount of yeast increased in quantity? What
gas has been evolved?
The product obtained is a dilute solution of ethyl alcohol which
contains small quantities of other substances. The alcohol
should be separated, and the amount formed in the reaction
determined as follows: Decant through a folded filter-paper,
taking care not to disturb the sediment of yeast, about 250 cc.
of the solution. While waiting for the solution to filter, weigh
to centigrams a clean dry 100-cc. flask, around the neck of
which has been pasted a narrow strip of paper to serve as a ref-
erence mark. Fill the flask up to the mark with distilled water,
and weigh again. Place exactly 200 cc. of the filtered solution
from the fermentation into a 500-cc. distilling flask, neutralize,
using litmus paper, with a dilute (10 per cent) solution of sodium
hydroxide, and distil into the weighed flask until the liquid fills
it exactly to the mark. (For the arrangement of the distilling
flask and condenser see Fig. 2, page 9.) Weigh the flask and
contents. Save the distillate for a later experiment. Calculate
the specific gravity of the distillate, which contains all the alcohol
that was present in 200 cc. of the product of fermentation. By
reference to a table of the specific gravity of aqueous solutions of
alcohol, calculate the weight of alcohol obtained from the 40
grams of glucose used in the experiment. What was the total
1 Yeast requires for its growth certain salts which are present in Witte's
peptone. If the latter is not available it may be replaced by 20 cc. of a
solution made by dissolving 10 grams each of potassium phosphate, magne-
sium chloride, and calcium nitrate in 1 liter of water.
ALCOHOLS 57
volume of the solution fermented? Calculate the theoretical

amount of alcohol obtainable from 40 grams of glucose and the
percentage of this (the yield) obtained in your experiment.
Write an equation for the reaction by which alcohol is formed
from glucose. W h y is the solution kept in a warm place during
fermentation? Why is the solution neutralized before distil-
lation? How could you determine whether an acid volatile
with steam was formed during the fermentation?
( b ) Place the dilute alcohol obtained in ( a ) above in a 200-cc.
distilling flask and distil off slowly about 50 cc. Add to this
distillate solid anhydrous potassium carbonate as long as the salt
dissolves.
(c) Test the product obtained in (a) or (b) by the iodoform
test. (Experiment 81b, page 59).
NOTES.—(a) If very accurate results are desired it is necessary to take

into account the temperature of the water in standardizing the contents of
the flask, and to note the temperature of the dilute alcohol. The specific
gravities of aqueous solutions of alcohol vary with the temperature. In the
analysis of beverages for alcohol the specific gravity is usually determined
by means of a hydrometer or a Westfall balance.
(b) The alcohol obtained in this way still contains water. It may be
rendered anhydrous by a second treatment with potassium carbonate and
with lime as described in experiment 80 below. The soluble monatomic
alcohols can be separated from not too dilute solutions in water by saturat-
ing them with potassium carbonate.
79. Properties of Ethyl Alcohol (SECTIONS 60, 64).—( a ) In-

flammability of alcohol.—Touch a lighted match to a few drops of
alcohol on a watch-glass.
(b) Solubility of alcohol.—Test the solubility of alcohol, using
about 5 cc. in each experiment, in water, benzene, kerosene, and
concentrated sulphuric acid.
(c) Test for water in alcohol.—Add to 5 cc. of commercial 95
per cent alcohol about 1 gram of anhydrous copper sulphate
which can be prepared by cautiously heating the crystalline salt
over a free flame in an evaporating dish. Note the change in
color. Explain. Repeat the experiment, using absolute alcohol.
For what purpose could this reaction be used?
(d) Place a crystal of potassium permanganate in about 5 cc.
of 95 per cent alcohol. Repeat, using absolute alcohol.
(e) Alcohol and sodium.—Add to about 5 cc. of absolute alcohol

a piece of sodium the size of a pea. Test the evolved gas.
(Eq.) Evaporate the solution on a water-bath. Dissolve the
resulting product in water and test the solution with litmus
paper. (Eq.)
(f) Alcohol and hydrobromic acid.—Place 2 cc. of alcohol and
10 cc. of hydrobromic acid (sp. gr. 1.49) in a test-tube supported
in a clamp and provided with a delivery-tube. (See Fig. 20,
page 31.) Let the second end of the tube pass to within 1 inch
of the bottom of a test-tube which is placed in a beaker containing
cold water. Heat the solution of alcohol and acid carefully
until about 5 cc. of liquid have distilled over. Examine the dis-
tillate. (Eq.)
(g) Alcohol and acetyl chloride.—HOOD.—In making the fol-
lowing test take care that the mouth of the test-tube is directed
away from you. Add acetyl chloride cautiously, drop by drop,
from a pipette to 2 cc. of alcohol in a test-tube, which is kept
cool by immersion in water, as long as reaction takes place.
Note the gas evolved. (Eq.) Pour the contents of the tube
cautiously into 5 cc. of cold water, and shake. Note the odor of
the product.
(h) Alcohol and acetic anhydride.—CAUTION.—The reaction
which takes place in this experiment is apt to occur with violence.
The experiment should be performed under the hood. In a test-
tube add 2 cc. of alcohol to 2 cc. of acetic anhydride. Is there
any evidence of action? Support the tube in a vertical posi-
tion by means of a clamp. Place a glass rod into concentrated
sulphuric acid, and then rub it against the neck of the bottle to
remove the drop that adheres. Put the rod with the trace of
acid into the mixture of alcohol and anhydride. Wait until the
mixture boils. (Eq.) Add the product to 5 cc. of cold water.
If the ester does not separate, saturate the aqueous solution with
sodium chloride. Note the odor of the product formed.
(i) Oxidation of alcohol.—Heat together about 1 cc. of alcohol,
5 cc. of a solution of potassium bichromate, and 5 cc. of dilute
sulphuric acid. Note the change in color and the production
of a characteristic odor. Write the equations for the reac-
tion, including the change which takes place in the potassium
bichromate.
ALCOHOLS 59
NOTE.—(h) Sulphuric acid serves as a valuable catalytic agent in bringing

about a reaction between alcohols and acid anhydrides.
80. Preparation of Absolute Alcohol (SECTION 60).—( a ) In a
500-cc. flask add quicklime broken into small lumps to 200 cc.
of 95 per cent alcohol until the pieces just project above the sur-
face of the liquid. Connect the flask with a reflux condenser
(§38, page 26), and heat to boiling on a water-bath for 1 hour.
Do not place the flask in the boiling water. Remove the bath,
and when the alcohol ceases boiling arrange the condenser for dis¬
tillation (Fig. 2, page 9). Distil from the water-bath and collect
the distillate in a filter-bottle, which is attached to the con-
denser by means of a cork stopper. In order to protect the
alcohol, which is hygroscopic, from the moisture in the air, con-
nect to the side-arm of the bottle by means of a piece of rubber
tubing a small drying-tube containing calcium chloride. Collect
the first 10 cc. in a small dry flask, and then adjust the filter-
bottle to receive the rest of the distillate. Keep the absolute
alcohol in a stoppered bottle for future use. Why is the first
part of the distillate rejected? Give a reason for the fact that
absolute alcohol can not be obtained from a mixture with water
by fractional distillation. What substance other than quicklime
could be used for freeing alcohol from water? Could phosphorus
pentoxide, concentrated sulphuric acid, or calcium chloride be
used? State a reason for your answer in each case.
( b ) Test portions of the first distillate, and of the absolute
alcohol obtained for water with anhydrous copper sulphate and
with potassium permanganate. (See experiment 79c and d, page
57).
81. Tests for Ethyl Alcohol (SECTIONS 64, 266).—( a ) Ethyl
acetate.—Warm gently together in a test-tube about 1 cc. of
alcohol, 1 cc. of glacial acetic acid, and 2 cc. of concentrated sul-
phuric acid. Note the odor. (Eq.)
(b) Iodoform test.—Add 5 drops of alcohol and about 1 cc. of
a dilute solution (10 per cent) of sodium hydroxide to 5 cc. of
water in a test-tube. Add to the mixture, drop by drop, a solu-
tion of iodine in potassium iodide 1 until a faint yellow color per-
sists after the solution is shaken. Heat the test-tube until it
1 This solution is made by dissolving 1 part of iodine and 5 parts of potas-
sium iodide in 15 parts of water.
feels warm to the hand (about 60°). If a precipitate does not

separate at once set the tube aside for a few minutes. Note
the odor and color of the precipitate.
NOTES.—(a) Tests which are based on the recognition of odors are not
reliable for the absolute identification of compounds. Whenever possible
the compound to be identified is converted into a solid substance, which
possesses a definite melting-point. For a test for ethyl alcohol based on
this principle see "The Identification of Pure Organic Compounds," by
S. P. Mulliken, Vol. I, page 168.
(b) A number of substances yield iodoform when treated with iodine
and sodium hydroxide. Isopropyl alcohol and acetone give the test imme-
diately in the cold.
82. Preparation and Properties of Allyl Alcohol (SECTIONS

85, 101).—( a ) Into a 500-cc. distilling flask, which is connected
with a condenser and receiver, place 50 grams of oxalic acid.
200 grams of glycerol and 0.5 gram ammonium chloride. Fit
into the neck of the flask by means of a stopper a thermometer so
placed that the bulb is near the bottom of the flask. Heat over
a wire gauze cautiously. Carbon dioxide is rapidly evolved and
the thermometer registers about 130° for some time. As the
temperature rises the evolution of gas slackens and finally ceases.
When the temperature reaches 195°, the receiver, which contains
a dilute aqueous solution of formic acid, is changed. At about
200° carbon dioxide is again evolved, and water and allyl alcohol
distil over. When the thermometer registers 260°, the distilla-
tion is stopped.
The distillate which contains the allyl alcohol is redistilled
slowly from a flask fitted in the usual way with a thermometer.
When the temperature reaches 103°, test from time to time about
2 cc. of the distillate for allyl alcohol by saturating it with solid
anhydrous potassium carbonate. When an oil no longer sepa-
rates, stop the distillation. Combine the products and saturate
the solution with solid anhydrous potassium carbonate. Sepa-
rate the layer of oil, and redistil. The allyl alcohol obtained in
this way boils at 87°-97° and contains water. Weigh the product
obtained and note its odor. The alcohol can be used for the ex-
periments described below. In order to obtain the alcohol in
dry condition, it should be placed in a flask and treated with
barium oxide until the pieces project from the surface of the
ALCOHOLS 61
liquid. The flask should then be connected with a return con-

denser and allowed to stand over night. It is necessary to use
the condenser, as the heat evolved in the union of the water and
oxide often heats the alcohol to boiling. The alcohol obtained
directly by distillation from the barium oxide boils at 96°-98°.
the yield of alcohol is about 40 per cent of the theoretical.
Ally] alcohol boils at 96.6° and has the specific gravity 0.872
at 0°.
(b) Test the solubility of allyl alcohol in water.
(c) Allyl alcohol and bromine.—HOOD.—To 1 cc. of allyl al-
cohol add bromine, drop by drop, as long as reaction occurs.
(Eq.)
(d) Allyl alcohol and acetyl chloride.—HOOD.—Add acetyl
chloride cautiously (see experiment 79g, page 58) to 2 cc. of
allyl alcohol until reaction ceases. (Eq.) Pour the product into
5 cc. of cold water. Shake and note the odor.
(e) Application of the iodoform reaction to allyl alcohol.—
determine whether allyl alcohol gives the iodoform reaction.
Carry out the test as in experiment 81b, page 59.
(l) Allyl alcohol and oxidizing agents.—HOOD.—Heat a mix-
ture of 1 drop of the alcohol, 5 cc. of a solution of potassium
bichromate, and 5 cc. of dilute sulphuric acid. Note the odor
of acrolein (SECTION 190), which is the aldehyde obtained by
the oxidation of allyl alcohol. (Eq.) Clean the tube under the
hood.
83. Preparation of Secondary Amyl Alcohol from an Amylene
(Pentene-2) (SECTION 81).—Pour 50 cc. of concentrated sulphuric
acid into 10 cc. of water, cool the mixture to 25°, and place it in
a 250-cc. bottle, the glass stopper of which fits tightly. Moisten
the neck of the bottle with a little of the acid so that when the
stopper is inserted and rotated, a gas-tight joint will be made.
Put in the bottle 25 cc. (16 grams) of pentene-2 (see experiment
73, page 51) and shake vigorously. As soon as there is the slight-
est indication of a rise in temperature, place the bottle under run-
ning water for a few seconds. Continue shaking and cooling in
this way until heat is no longer generated (2 to 3 minutes). After
the bottle has been shaken 5 minutes set it aside for another 5
minutes. At the end of this time the contents should be some-
what cloudy but should not separate into two distinct layers.
(Eq.) Pour the mixture slowly into 400 cc. of cold water and
after a few minutes filter it through a moistened filter paper, to
remove the insoluble oil, which should have a volume not greater
than about 2 cc. Place the aqueous layer, which contains the
alcohol formed, in a large flask connected with a condenser.
Distil off about 100 cc. of liquid. Dissolve about 10 grams of so-
dium hydroxide in the distillate, separate the oil, and place it in
a small distilling flask. Add 15 grams of sodium hydroxide and
attach to the flask by means of a cork a glass tube about 75 cm.
long. Place a cork over the side arm of the flask (see Figure 16,
page 26) and reflux gently for about 15 minutes. This process
serves to remove the water dissolved in the alcohol. Fit the
flask with a thermometer, attach it to a condenser, and distil.
The alcohol should boil between 115° and 119.5°. If much low-
boiling material is obtained the alcohol should be refluxed with
more sodium hydroxide to remove dissolved water which lowers
the boiling point.
The alcohol obtained is a mixture of pentanol-2 and pentanol-3.
(Eqs.) The former boils at 118.5°-119.5° and the latter at 116.5°.
The yield of mixed alcohols is about 60 per cent of the theoretical.
NOTE.—If concentrated sulphuric acid is used in this preparation, a large
part of the amylene is polymerized. If a more dilute acid is used than that
recommended, the reaction requires a longer time. Sodium hydroxide is
added to the distillate to precipitate the alcohol which is dissolved in the
water. Alcohols in general are less soluble in a solution of bases than in
water.
84. Properties of Glycerol (SECTIONS 93, 94, 190).—( a ) Solu-

bility of glycerol.—Test the solubility of glycerol in water, alcohol,
ether, petroleum ether, and benzene.
(b) Conversion of glycerol into acrolein.—Cover the bottom
of a test-tube with powdered acid potassium sulphate and then
add about 5 drops of glycerol. Heat strongly and note the
odor. (Eq.)
(c) Test for glycerol with borax bead.—Prepare a borax bead
in the usual way. Place the bead when cold into an aqueous
solution of glycerol, and then insert into a Bunsen flame. Note
the color of the flame. Glycerol liberates boric acid from borax.
(d) Test for glycerol with a solution of borax.—Make a dilute
solution (about 1 per cent) of borax in a test-tube. Add 2 drops
ALCOHOLS 63
of a phenolphthalein solution. What is the color? W h y ?

Add now a neutral aqueous solution of glycerol slowly until the
color is destroyed. Heat the solution to boiling and then cool.
(e) Test for glycerol by the preparation of glyceryl tribenzoate.—
To obtain a solid derivative of glycerol the melting-point of
which can be determined proceed as follows: Place in a small
flask 3 drops of glycerol, 1 cc. of benzoyl chloride, and 10 cc.
of a 10 per cent solution of sodium hydroxide. Cork the flask,
and shake vigorously for 10 minutes. At the end of this time
the compound formed will adhere to the sides of the flask. De-
cant off the liquid, and wash with cold water. Pour off as much
as possible of the latter, and add 10 cc. of alcohol. Heat on
the steam-bath, and filter the hot solution into a small flask.
Add 2 cc. of water, stopper the flask, and shake it vigorously
under running water. Filter off the crystals by suction, and wash
them with a mixture of 5 cc. of alcohol and 2 cc. of water. Let
the product, which is the tribenzoate of glycerol, (C 6 H 5 COO) 3 C 3 H 5,
dry in the air, and then determine its melting-point, which is
71°-72°. If the compound does not melt sharply, recrystallize
it from alcohol and water as before.
NOTES.—(b) If larger quantities of glycerol are used the acid potassium

sulphate should be replaced by phosphorus pentoxide; with this reagent
frothing is avoided and no sulphur dioxide is formed.
(d) Other polyatomic alcohols behave as glycerol does in this test.
Ammonium salts cause the disappearance of the color of the phenol¬
phthalein, but the color is not restored in this case by boiling.
(e) Alcohols in general are converted into esters of benzoic acid when
treated with benzoyl chloride as described in the test. (Baumann and
Schotten reaction, SECTION 547.) It should be noted that glycol gives an
ester which melts at 71°; it is evident, therefore, that the test is not appli-
cable in the presence of glycol.
CHAPTER V
ACIDS
85. Formation of Formic Acid by the Oxidation of Methyl

Alcohol (SECTION 100).—Place in a 100-cc. distilling flask, 5 grams
of powdered potassium bichromate, 20 cc. of water, and 5 cc. of
concentrated sulphuric acid. Cool the flask, and add slowly with
shaking 2 cc. of methyl alcohol drop by drop, keeping the flask
underwater. Place the flask for about 10 minutes in a beaker con-
taining boiling water. Distil off, using a condenser, about 10 cc.
of liquid. Apply to the distillate tests described in experiment
87b and c below. Write equations for all reactions involved.
86. Preparation of Formic Acid from Oxalic Acid (SECTION
100).—Into a 250-cc. distilling flask, provided with a condenser
and receiver, put 20 grams of anhydrous glycerol and 20 grams of
oxalic acid. Close the flask by a cork carrying a thermometer
which is so placed that the bulb is below the surface of the
glycerol. Heat cautiously with a small flame. Carbon dioxide
is given off at about 80°. Maintain the temperature at 105°-
110° until the evolution of gas has slackened. Cool the contents
of the flask to about 60°, add 20 grams more of oxalic acid, and
heat as before. Repeat the addition of oxalic acid until 80
grams in all of the acid have been used. After the last portion
of the acid has been added, allow the temperature to rise to 115°.
A dilute aqueous solution of formic acid is obtained. (Eq.)
87. Properties of Formic Acid (SECTION 100).—( a ) Odor of
formic acid.—Note the odor of the solution obtained in experi-
ment 86 above, and test the solution with blue litmus paper.
(b) Reduction of silver formate.—Neutralize 2 cc. of the dilute
solution of formic acid with ammonia. Add a few drops of a
solution of silver nitrate, and warm carefully. (Eq.)
(c) Reduction of mercuric formate.—Shake for about 1 minute
2 cc. of the distillate with 0.2 gram of mercuric oxide. Filter
the solution and heat it to boiling. The mercuric formate first
64
ACIDS 65
formed is reduced to mercurous formate, and finally to mercury.

(Eq.) This is a valuable test for formic acid.
(d) Reduction of mercuric chloride by formic acid.—To 5 cc.
of the distillate add 2 cc. of a solution of mercuric chloride and
heat. The mercuric chloride is reduced to mercurous chloride.
(Eq.)
(e) Decomposition of formic acid by sulphuric acid.—To 2 cc.
of the distillate add 2 cc. of concentrated sulphuric acid slowly
and heat gently. (Eq.) Apply a flame to the liberated gas.
If an inflammable gas is not obtained, repeat using 0.5 gram of
sodium formate.
(f) Oxidation of a formate.—Neutralize 1 cc. of the distillate
with a dilute solution of sodium hydroxide. Add, drop by drop,
a dilute (rose-colored) solution of potassium permanganate.
(Eq.) What is the significance of the result when compared
with the action of unsaturated hydrocarbons with potassium
permanganate? (See experiment 71e, page 51.)
(g) Salts of formic acid.—Dilute what is left of the distillate
with an equal volume of water and divide it in two portions;
boil one for about 5 minutes with an excess of lead oxide, and the
other with copper oxide. Filter the solutions while still hot and
set aside to crystallize.
88. Formation of Acetic Acid from Ethyl Alcohol (SECTION
107).—To 15 grams of coarsely powdered potassium bichromate
contained in a 200-cc. round-bottomed flask, add a mixture of
15 grams of concentrated sulphuric acid and 10 cc. of water.
Set the flask on a sand-bath and connect it with a reflux con-
denser through which a rapid stream of water is passing. Add
through the condenser slowly, in portions of 0.5 c c , 3 cc. of
alcohol. Shake after each addition and wait until the vigorous
reaction which takes place subsides before another addition of
alcohol is made. When all the alcohol has been added, heat to
boiling for 15 minutes. Change the condenser and distil off
about 10 cc. (Eq.) Observe the odor of the solution (see note)
and test it for acetic acid by experiment 91a and b below.
NOTE.—There is usually present in the distillate ethyl acetate and alde-
hyde, both of which have a characteristic odor. A mixture of potassium
bichromate and sulphuric acid (chromic acid) is an excellent oxidizing agent
to use in the preparation of acetic acid by oxidation, since acetic acid
is not readily oxidized by chromic acid.
89. Preparation of Glacial Acetic Acid (SECTION 103).—Melt

cautiously in an iron dish about 50 grams of anhydrous sodium
acetate. 1 Grind the salt to a coarse powder in a mortar; weigh
40 grams of the salt and place it in a 200-cc. distilling flask. Add
cautiously through a funnel, keeping the flask cold by immersion
in water, 25 cc. of concentrated sulphuric acid. Place a ther-
mometer in the flask in order to determine the temperature of
the vapor. Connect with a condenser and receiver, and distil
off the acetic acid. Weigh the acid obtained. Calculate the
theoretical amount which can be obtained from 40 grams of
sodium acetate, and the percentage yield of the experiment.
CAUTION.—Glacial acetic acid causes painful blisters when left
in contact with the skin.
90. Properties of Acetic Acid (SECTION 112).—( a ) Solubility of
acetic acid.—Test the solubility of acetic acid in water, alcohol,
ether, and benzene. Place about 10 cc. of the acid obtained in a
test-tube surrounded by chipped ice and water. Insert a ther-
mometer into the acid. If crystals do not form, scrape the side
of the tube with a glass rod. If the acid freezes, remove the tube,
stir with the thermometer, and note the temperature when the
acid is about one-fourth melted. 2 Pure acetic acid melts at 16.7°
and boils at 119°. One per cent of water lowers the melting-point
about 2.1°.
(b) Acetic acid and oxidizing agents.—Determine whether
acetic acid reduces solutions of potassium permanganate, silver
nitrate, and mercuric chloride. Compare the results with those
obtained with formic acid. (Experiment 87, page 64.)
(c) Add a few crystals of chromic acid to a mixture of 5 cc.
of glacial acetic acid and 2 cc. of water. Heat to boiling. Is the
chromic acid reduced?
(d) Formation of verdigris.—Stand a piece of copper foil in
a small beaker containing acetic acid; a part of the foil should
be under the liquid and a part exposed to the air. Examine
the foil at the next exercise. What is formed?
1 If the anhydrous salt is not available, dehydrate the crystalline salt for
this experiment according to the directions given in experiment 66a, page
44.
2 If the acid prepared does not freeze, determine the melting-point, as
described above, of a sample of glacial acetic acid.

ACIDS 67
91. Tests for Acetic Acid (SECTION 114).—( a ) Formation of

basic ferric acetate.—Add a few drops of a solution of ferric chlo-
ride to a solution of sodium acetate. Note the color. Heat the
solution to boiling. The neutral ferric acetate is converted into a
basic acetate. (Eq.) In using this test for the free acid it must
first be neutralized with sodium hydroxide.
(b) Formation of ethyl acetate.—Repeat the test involving the
formation of ethyl acetate given in experiment 81a, page 59.
(c) Conversion of acetic acid into acetanilide.—Place in a dry
test-tube 0.6 gram of anhydrous sodium acetate, 0.25 cc. of
concentrated sulphuric acid, 1 cc, of aniline. The substances
used should be measured accurately. Close the mouth of the
tube with a cork bearing a piece of glass tubing about 2 feet long.
Support the tube in a vertical position and heat it so the contents
boil gently for about 1 hour. Cool, dissolve the product in 25 cc.
of boiling water, filter hot, and set aside to crystallize. Deter-
mine the melting-point of the crystals. Acetanilide melts at
116°.
NOTE.—(c) The identification of a substance is best accomplished by

converting it into a solid which has a definite melting-point and can be
readily purified. In the case of acetic acid and its homologues the anilides
serve this purpose well (SECTION 497). They are formed as the result of
the elimination of water from the acid and aniline:
CH3COOH + C6H5NH2 = CH3CONHC6H5 + H2O
If the acid to be identified is dissolved in water it is neutralized with
sodium hydroxide and the solution evaporated to dryness. The salt is
cautiously heated over a free flame to drive out the water of crystallization;
it is then heated with aniline and enough concentrated sulphuric acid to set
free the organic acid. When salts are used the reaction is as follows:
CH3COONa + C6H5NH2.H2SO4 = CH5CONHC6H5 + NaHSO4 + H2O
92. Preparation and Properties of Soap: Saponification of Fat

(SECTION 123).—( a ) Weigh 35 grams of lard in a small beaker and
add slowly with constant stirring 9 grams of sodium hydroxide
dissolved in 9 cc. of water. Rest the beaker in a second beaker
containing boiling water and heat the mixture in this way for
from 45 to 60 minutes. Stir the mixture occasionally until it
hardens. The chief constituents of lard are the glyceryl esters
of palmitic, stearic, and oleic acids. Write equations for the
reactions which take place when these three substances are

heated with sodium hydroxide.
(b) Test for free alkali in soap.—Determine whether the soap
prepared in (a) above contains free alkali, as follows: Dissolve
a small piece of the soap in cold water and test the solution with
a solution of phenolphthalein.
(c) Hydrolysis of soap.—Shake vigorously a piece of Ivory soap
about the size of a large pea with 10 cc. of cold water. Filter and
test one-half of the solution with a solution of phenolphthalein.
How do you explain the difference between the result of this
experiment and that obtained with the soap you prepared?
Heat to boiling the other half of the solution of Ivory soap
and add phenolphthalein. Explain and write equations for
the reaction.
(d) Soft soap.—Cut the soap you prepared into thin shavings
and heat it with 400 cc. of water until it dissolves. Divide the
product into four parts. Put aside one of these and allow it to
cool. Describe the properties of the soft soap.
(e) Salting out of soap.—Precipitate one portion of the solu-
tion by adding slowly, with stirring, an equal volume of a satu-
rated salt solution. Filter off the precipitate and save the filtrate
for another experiment. Wash the precipitate with 50 cc. of
saturated salt solution, let it drain thoroughly, and finally spread
it on a watch-glass to dry. Test the soap for free alkali as in (b)
above. From what organic compound has the soap been sepa-
rated by this treatment?
(f) Solubility of soap.—Test the solubility of the purified soap
in water, in alcohol, and ether. This can be clone most readily
by shaking pieces of the soap with about 15 cc. of each of the
solvents, filtering, and evaporating the solvents on a water-bath.
If there is any residue from the ether, test it to determine whether
it is soap, or fat which has not saponified.
(g) Action of hard water and soap.—To determine the action
of hard water on a solution of soap, add to small portions of the
solution prepared in (d) above, solutions of calcium chloride and
magnesium sulphate. (Eq.) Test the solubility of the precipi-
tates in water. Explain the difference between the action of
sodium chloride and calcium chloride on a soap solution. Did
you note any difference in the action of the two salts on a dilute
ACIDS 69
solution of soap? What chemical compounds may be present in

natural hard water?
(h) Isolation of fatty acids from soap.—To the remainder of
the solution prepared in (d) above, add dilute hydrochloric acid
as long as a precipitate is formed. Of what does this precipitate
consist? (Eq.) Filter and wash with cold water; drain thor-
oughly and spread the precipitate on a watch-glass to dry. Test
the solubility of the precipitate in water, sodium hydroxide ( Eq. ) ,
other, and alcohol. Place a small piece of the precipitate in a
test-tube one-half full of water; heat to boiling and shake.
Describe the appearance. Cool and shake. What is the effect
of hot water on the acids? On the basis of their solubility,
state how you could separate into its constituents a mixture
which contained fat, fatty acids, and soap.
(i) Test for unsaturated acids in soap.—Dissolve about 1 gram
of the acids obtained in experiment (h) above in 5 cc. of carbon
tetrachloride and add, drop by drop, a solution of bromine in
carbon tetrachloride. Explain. (Eq.)
(j) Identification of glycerol in the product of the hydrolysis of
fat.—The presence of glycerol can be shown as follows: Neu-
tralize with dilute hydrochloric acid about 100 cc. of the solution
reserved in experiment (e) above; filter, evaporate the filtrate to
dryness, and stir the residue of salt and glycerol with about 20
cc. of alcohol. Decant off the liquid through a filter and evapo-
rate on the steam-bath. A sample of impure glycerol will be
left. Prove the presence of glycerol by applying two of the
tests given in experiment 84, page 62.
NOTES.—(e) If one precipitation does not free the soap from alkali,
redissolve it and precipitate again.
(f) Ether dissolves fat but does not dissolve soap; this solvent can be
used, therefore, to determine the presence of unsaponified fat in a sample
of soap.
93. Preparation and Properties of Oxalic Acid (SECTIONS 134,

136).—( a ) Heat on the steam-bath in an open 500-cc. flask 120
grams of concentrated nitric acid (sp. gr. 1.42) and 20 grams of
cane-sugar. As soon as brown fumes begin to be evolved, place
the flask in a hood, and let it stand until the rapid evolution
of oxides of nitrogen ceases. Evaporate on the steam-bath
until the volume of the liquid is reduced to about 30 cc. Set
aside to crystallize. Filter off the acid through a funnel provided

with a perforated plate, using no filter-paper. Dissolve the crys-
tals in the smallest amount of boiling water possible, and set
the solution aside to crystallize. Oxalic acid dissolves in 10.46
parts of water at 14.5c. Weigh the product obtained.
(b) Action of heat on oxalic acid.—Heat about 1 gram of oxalic
acid in a dry test-tube; continue the heating after the water of
crystallization has been driven off. Describe the result. Oxalic
acid, (COOH) 2 .2H 2 O, melts at 99°; the anhydrous acid sublimes
at 150-180°.
(c) Change of a formate to an oxalate.—Heat in a dry test-
tube about 1 gram of sodium formate. (Eq.) Apply a flame
to the gas evolved. Test the residue for an oxalate according
to experiment 94c below.
(d) Potassium tetroxalate.—Dissolve 5 grams of oxalic acid in
30 cc. of hot water. Neutralize exactly one-fourth of this solu-
tion carefully with a solution of potassium hydroxide ( 1 : 4 ) ;
combine the solutions and set aside to crystallize. (Eq.) When
cold, filter off the salt. Dissolve a little of the salt in water,
and try its effect on an iron-rust stain, also on a spot made with
an iron ink and an ink made from an aniline dye.
(c) Potassium ferric oxalate.—Add to a solution of ferric chlo-
ride a solution of potassium oxalate until a clear green solution
is formed. (Eq.) Moisten a piece of paper with the solution.
Test the paper for a ferrous salt by putting on it a drop of potas-
sium ferricyanide. Expose a piece of the paper to direct sunlight
for 1 minute and test again for a ferrous salt.
94. Tests for Oxalic Acid and Oxalates (SECTIONS 134, 136).—
(a) Oxalic acid and sulphuric acid.—Heat about 2 grams of oxalic
acid with about 5 cc. of concentrated sulphuric acid. (Eq.)
Pour some of the gas formed into a test-tube containing a solu-
tion of barium hydroxide, and shake. Ignite the gas which is
produced in the reaction. How could you prepare carbon mon-
oxide free from carbon dioxide by making use of this decomposi-
tion? What other acid yields carbon monoxide when heated
with sulphuric acid?
(b) Silver oxalate.—In a test-tube neutralize a solution of
oxalic acid with ammonia; if a slight excess of ammonia is added,
boil the solution until it is neutral to litmus. Cool and add a
ACIDS 71
solution of silver nitrate. A precipitate of silver oxalate is

formed. (Eq.) Heat to boiling. Compare the results with
those obtained with formic acid (experiment 87b, page 64).
(c) Precipitation of calcium oxalate.—To a solution of oxalic
acid add ammonia in slight excess, and then a solution of calcium
chloride. (Eq.) Test the solubility of the precipitate in a
solution of acetic acid and in dilute hydrochloric acid. How
would calcium carbonate act when treated with acetic acid?
(d) Reducing action of oxalic acid.—To a solution of oxalic
acid or an oxalate add dilute sulphuric acid and a solution of
potassium permanganate. (Eqs.)
(e) Repeat (d), using a solution of potassium bichromate in
place of one of potassium permanganate. (Eqs.)
CHAPTER VI
ETHERS, ESTERS, AND ANHYDRIDES
95. Preparation of Ether from Alcohol (SECTION 143).—( a )

CAUTION.—Ether is very inflammable and very volatile; as its
vapor readily ignites, vessels containing ether should not be
brought near a flame or allowed to stay in a warm place. Place
50 cc. of ethyl alcohol in a 500-cc. distilling flask and add slowly,
with constant shaking, 50 cc. of concentrated sulphuric acid.
Close the neck of the flask with a two-holed stopper bearing a
thermometer and a dropping funnel (Fig. 18, page 28), both of
which reach to the bottom of the flask.1 Place the flask on a
sand-bath and connect it by means of a tightly fitting stopper
with a long condenser, through which a rapid stream of cold
water is passing. Use as a receiver a filter-bottle which is con-
nected with the condenser by a tightly fitting stopper. Attach
to the side-arm of the filter-bottle a long rubber tube, which
extends almost to the floor. This tube serves to conduct the
vapor of the ether, which is very heavy, away from any flames
present on the desk. Heat the contents of the flask slowly.
When the temperature reaches 140°, and ether distils over, add
through the funnel 100 cc. of alcohol, allowing the latter to drop
at about the same rate as that at which the ether distils (about
2 drops per second). During the entire time the temperature of
the mixture in the flask should be maintained at 140°-145°.
Take the receiver from the immediate vicinity of any flames,
and transfer the contents to a separatory funnel. Shake the ether
with about one-fourth its volume of a solution of sodium hydroxide
Draw off the lower aqueous layer, which should still be alkaline,
add to the ether about one-fifth its volume of a cold mixture of
equal volumes of concentrated sulphuric acid and water. Shake
thoroughly, let the mixture stand until the two layers become
clear. Draw off the acid layer and run the ether into a distilling
1 If a dropping funnel is not available or if the tube of the funnel is not
long enough, arrange the apparatus as described in §40, page 28.
72
ETHERS, ESTERS, AND ANHYDRIDES 73
flask. Distil from a water-bath, and collect the distillate in a

receiver in the way described above. Record the boiling point
and the weight of the product obtained.
Ether boils at 35°. Write equations for the reactions which
take place when alcohol is treated with sulphuric acid, and when
the product of this reaction is heated with alcohol at about 140°.
What would happen if in the experiment the temperature were
allowed to rise as high as 180°?
(b) Absolute ether.—Shake in a separatory funnel 200 cc. of
commercial ether with one-fifth its volume of a cold mixture of
equal volumes of concentrated sulphuric acid and water. Let
the mixture stand until the two layers are clear. Separate the
acid layer and distil the ether in the way described in ( a) above.
Place the distillate in a dry bottle, add 5 grams of sodium in
the form of a wire or thin shavings. Insert a calcium chloride
tube in the neck of the bottle and allow it to stand until the evolu-
tion of hydrogen ceases. If the sodium becomes covered with a
coating of sodium hydroxide, the latter can be removed by press-
ing upon the metal with a stout glass rod, or fresh pieces of the
metal may be added from time to time. For most purposes the
ether purified in this way can be used without distillation; it can
be carefully decanted from the solid substances present. In
order to redistil it, the ether is transferred to a clean dry flask
containing about 1 gram of sodium shavings and distilled from a
water-bath, taking the precautions described in (a) above, and
using a carefully dried condenser and receiver. The first few
cubic centimeters which distil should be rejected, as they contain
the moisture present in the condenser tube and receiver.
NOTE.—(a) The ether is shaken with a solution of sodium hydroxide to

remove the sulphur dioxide formed as a result of the reduction of the
sulphuric acid by the alcohol or by the carbon that separates. The treat-
ment with sulphuric acid removes the alcohol and nearly all the water. The
method outlined above can be carried out more rapidly than the one com-
monly used, namely shaking with a solution of calcium chloride to remove
alcohol and then drying first with anhydrous calcium chloride and then with
sodium.
96. Properties of Ether (SECTIONS 143-147).—( a ) Volatility

of ether.—Place a few drops of ether in the palm of your hand
and breathe sharply across it. Explain the result.
(b) Inflammability of ether.—Place a few drops of ether on a

watch-glass and apply a lighted match.
(c) Explosive mixture of ether and air.—Hold for about 5
seconds the neck of an open bottle containing ether over an
empty wide-mouthed 250-cc. bottle, and then drop a lighted
match into the latter.
(d) Solubility of ether in water.—Test roughly the solubility of
ether in water as follows: Into a 100-cc. flask place 5 cc. of ether
and add 40 cc. of water. Close the flask with a stopper and shake
vigorously. Add water in portions of 5 cc. and shake each time,
until the ether has completely dissolved. State the solubility
you find as the result of your experiment.
(e) Solubility of water in ether.—Shake 10 cc. of ether with
10 cc. of water. Decant off the ether through a dry filter-paper
into a dry test-tube. Test the filtered ether for water by means
of anhydrous copper sulphate. (See experiment 79c, page 57.)
Is water soluble in ether?
(f) Solubilities of ether.—Test the solubility of ether in an
equal volume of alcohol, benzene, petroleum ether, dilute hydro-
chloric acid, concentrated hydrochloric acid, and a solution of
sodium hydroxide.
(g) Solubility of ether in sulphuric acid.—Add very cautiously
to 2 cc. of ether about 5 cc. of concentrated sulphuric acid. The
tube should be shaken under water to keep the mixture cold.
Is ether soluble in concentrated sulphuric acid? Pour the mix-
ture slowly into a test-tube containing cracked ice. Are two
layers formed? Explain. (See SECTION 145.)
(h) Reaction between ether and sulphuric acid.—Repeat experi-
ment (g), but warm the mixture gently over a free flame before
it is poured onto the ice. Are two layers formed? Explain.
(i) Ether and sodium.—Add a shaving of sodium to about
5 cc. of absolute ether. If a gas is evolved, wait until the evolu-
tion ceases and add a fresh piece of sodium. Explain the result.
If anhydrous ether is not available the experiment can be per-
formed with ordinary ether, but a number of additions of sodium
will be necessary before the metal does not react with the liquid.
Why?
(j) Decomposition of ether by hydriodic acid.—Mix in a test-
tube, kept cold by immersion in water, 1 cc. of ether and 3 cc.
of hydriodic acid (sp. gr. 1.7). lit the tube by means of a cork
to a delivery-tube bent at a right angle, (See Fig. 20, page 31.)
The end of the tube should extend nearly to the bottom of a
test-tube which is placed in cold water. Heat the mixture of acid
and ether carefully. When about one-third of the liquid has
distilled over, add a little water to the contents of the cold tube
and shake. Are there two liquids? Is one heavier than water?
97. Preparation of a Mixed Ether: Isoamyl Ethyl Ether ( S E C -

TION 144).—Place 50 grams of isoamyl alcohol in a 200-cc. round-
bottomed flask provided with a reflux condenser. Add slowly
through the condenser 6 grams of sodium cut in small pieces.
The alcohol may be heated slightly to hasten the reaction. When
all the sodium has dissolved, add cautiously through the con-
denser, as the reaction is apt to be a violent one, 30 grams of
ethyl bromide. Heat to boiling for 1 hour. (Eq.) Distil
directly from the flask, using a water condenser, and collect the
distillate in the following fractions: 80°-110°, 110°-114°, 114°-
120°, 120°-130°. Fractionate twice. (See §21-23, and experi-
ment 64, page 43.) Redistil the portion boiling at 110°-114°, and
collect and weigh the part which distils at 111°-113°. Deter-
mine the specific gravity of your product (§56, page 37), and
determine whether it dissolves in concentrated sulphuric acid.
Calculate the percentage yield of ether obtained from the ethyl
bromide used. The yield in the experiment should be about
50 per cent.
Isoamyl ethyl ether boils at 112°, and has the specific gravity
0.764 at 18°.
NOTE.—An excess of alcohol is used in the experiment to facilitate the
reaction between it and sodium. Sodium isoamylate is a solid which is
soluble in isoamyl alcohol. The sodium and ethyl bromide are used in the
proportion of one atomic weight of the former to one molecular weight of the
latter.
A C I D ANHYDRIDES
98. Preparation and Properties of Acetic Anhydride (SECTIONS

148, 149).—( a ) Place 50 grams of freshly fused sodium acetate 1
in a 250-cc. distilling flask. Connect the flask with a condenser
1For the preparation of fused sodium acetate see experiment 60a, page
44.
and a receiver, using for the latter a distilling flask which is

fitted tightly to the condenser by means of a stopper. Protect
the inside of the flask from moisture by connecting a drying tube
to the side-arm of the receiver. Insert in the neck of the flask
a cork bearing a separatory funnel which contains 40 grams of
acetyl chloride. Immerse the flask in cold water and add about
one-half of the acetyl chloride very slowly. The liquid should
not be allowed to get hot enough to boil. Disconnect the flask
from the condenser and shake it cautiously, while it is still in the
water. Replace the condenser and add the rest of the chloride.
If any liquid distils over during the addition of the acetyl chloride,
it should be returned to the distilling flask. Replace the separa-
tory funnel by a cork and distil, keeping the flame in motion to
avoid local over-heating. Add about 2 grams of fused sodium
acetate to the receiver and distil; note the boiling-point of the
liquid, and weigh the product obtained. (Eq.) Calculate the
theoretical yield, and the percentage of this obtained in the
experiment. If the substances from which the anhydride is
prepared are not brought together in the proportions represented
by the chemical equation, from which substances should the
theoretical yield be calculated? In the above experiment which
substance is used in excess? W h y ?
Acetic anhydride boils at 138°. The yield should be from 35
to 40 grams.
(b) Acetic anhydride and water.—Add about 1 cc. of acetic
anhydride to 5 cc. of water. Do the two liquids mix? Shake
the test-tube vigorously and finally warm gently. (Eq.)
(c) Acetic anhydride and sodium hydroxide.—Shake 2 cc. of
the anhydride with 5 cc. of a solution of sodium hydroxide. (Eq.)
(d) Acetic anhydride and alcohol.—Repeat experiment 79h,
page 58.
(e) Identification of acetic anhydride.—Add cautiously 2 cc.
of acetic anhydride to 2 cc. of aniline, and heat the mixture to
boiling. Pour the product while still hot into about 20 cc. of
cold water. Shake vigorously, decant off the water and wash
twice with cold water. Dissolve the product in boiling water,
avoiding an excess of the solvent. Filter hot through a fluted
filter-paper, and cool the solution in running water. Filter off
the crystals by suction (§12, page 7), dry them on a porous
plate and determine their melting-point. If the compound does

not melt sharply, it should be recrystallized from boiling water.
Acetanilide, the product of this reaction, melts at 116°, boils
at 304°, and crystallizes from hot water in colorless prisms.
(See note below and SECTION 497.)
'NOTES.—(a) The first distillate is redistilled from a small amount of

sodium acetate in order to convert any unchanged acetyl chloride into
anhydride.
(b, c, and d) These reactions apply in general to anhydrides and are
useful in their identification. The determination of the physical property
of the acids or esters formed is often made in the identification of anhy-
drides. Sulphuric acid is a valuable catalytic agent in the reaction which
takes place between alcohols and anhydrides.
(e) The chemical reaction in this test is analogous to that which takes
place between an anhydride and ammonia:
(CH3CO)2O + 2NH3 = CH3CO.NH2 + CH3COONH4

Aniline is related to ammonia; its formula is NH2C6H5. The reaction with
acetic anhydride takes place according to the following equation:
(CH3CO)2O + 2NH2C6H5 = CH3CO.NHC6H5 + CH3COONH3C6H5
In the case of ammonia, acetamide is formed; the product with aniline is

acetanilide, The second substance formed is the aniline salt of acetic acid;
this is soluble in water and is readily removed when the product of the
reaction is crystallized. The preparation of anilides in this way from acid
anhydrides is often effected in the identification of anhydrides. The
anilides are solids, which can be readily purified; as a consequence, an iden-
tification can be accomplished with a very small amount of a substance.
99. Preparation of Succinic Anhydride (SECTION 150).—

HOOD.—Heat to boiling for about one-half hour, in a dry round-
bottomed flask provided with a return condenser, a mixture of
10 grams of phosphorus oxychloride and 15 grams of succinic
acid. It is advisable to use a return condenser like the one illus-
trated in Fig. 17, page 27.
When the flask is cold, add 50 cc. of acetone and heat on the
steam-bath until the solid has dissolved. Filter hot and set
aside to crystallize. Filter off the crystals by suction (§12, page
7), and wash them with a few cubic centimeters of cold acetone.
Weigh the product and determine its melting-point. Calculate
the percentage yield.
Succinic anhydride melts at 120°; it may be recrystallized

from hot chloroform, in which it is difficultly soluble, or from
acetone.
NOTE.—Phosphorus oxychloride is used as a dehydrating agent in this
preparation. The reaction takes place according to the following equation:
2(CH2COOH)2 + POCl3 = 2(CH2CO)2O + HPO3 + 3HCl
ESTERS
100. Preparation of Potassium Ethyl Sulphate (SECTION 159).

(a) Pour into a small flask 20 cc. of ethyl alcohol, and add slowly
with constant shaking 10 cc. of concentrated sulphuric acid.
Connect the flask with a reflux condenser and heat on a boiling
water-bath for one-hour. Cool the liquid and pour it slowly
into 200 cc. of cold water. The solution contains ethyl sulphuric
acid, alcohol, and sulphuric acid. The acids are separated by
making use of the fact that barium ethyl sulphate is soluble in
water and barium sulphate is insoluble. Add to the solution,
with constant stirring, small quantities of barium carbonate 1 as
long as carbon dioxide is evolved. Filter in a porcelain funnel,
and wash the precipitate twice with about 20 cc. of hot water,
The filtered solution contains barium ethyl sulphate. Write
equations for all the reactions. Test 5 cc. of the solution for
barium in the usual way. (Eq.) Test the solution for a sul-
phate. Result? Heat about 5 cc. of the solution with about 1 cc.
of dilute hydrochloric acid. (Eq.)
(b) Conversion of barium ethyl sulphate into potassium ethyl
sulphate.—Heat the rest of the solution of barium ethyl sulphate
to boiling and add a solution of potassium carbonate until the
solution is slightly alkaline. (Eq.) Filter hot, wash the precipi-
tate twice with a small amount of hot water, and evaporate the
filtrate to crystallization (see §9, page 6) on the steam-bath.
When cold, filter off the crystals and wash them with a little
cold alcohol; dry on a porous tile. The salt can be recrystallized
from boiling alcohol.
101. Preparation of Ethyl Acetate from Alcohol and Acetic
Acid.—(SECTION 160).—Mix in a dry 200 cc. distilling flask 50
grams of alcohol, 60 grams of glacial acetic acid, and 4 cc. of
1 If barium carbonate is not available, calcium carbonate may be used.
concentrated sulphuric acid. Cover the side-arm of the flask

with a cork bored half way through its length. Connect the
flask with a reflux condenser, and heat to boiling for 30 minutes.
(See Fig. 16, page 26.) At the end of this time, arrange the
apparatus for distillation, using a water condenser and having a
thermometer to record the temperature of the vapor. Distil into
a flask; when the temperature registers 100°, collect separately
about 1 cc. of the distillate and add it to about 5 cc. of water.
If the mixture does not separate into two layers, stop the dis-
tillation. Shake the distillate in the flask with 30 cc. of water,
and add solid sodium carbonate until a drop of the ester is neutral
to moist litmus paper. Transfer to a separatory funnel, draw
off the water, and shake the ester twice with a saturated solution
of calcium chloride, using 50 cc. each time. Draw off the ester
into a distilling flask, add about one-fourth its volume of anhy-
drous calcium chloride, close the flask and cover the side-arm
with corks, and let stand for at least 1 hour. Distil from a
water-bath. Note the boiling-point and the weight of ester
obtained, and calculate the percentage yield from the acetic acid
used. Why from the acetic acid?
Ethyl acetate boils at 77°, has the specific gravity of 0.9028 18°/4°,
and is soluble in 17 parts of water at 17.5°. The yield should be
80 to 85 per cent of the theoretical.
NOTE.—The sulphuric acid used in the preparation serves as a catalytic
agent. The amount of alcohol used is that equivalent to the acid (equal
molecular proportions) plus that which combines with the sulphuric acid to
form ethyl hydrogen sulphate. The ester obtained in the first distillation
contains alcohol and acetic acid. The former is removed by shaking with
calcium chloride, and the latter by treatment with sodium carbonate.
102. Formation of Ethyl Acetate from Acetyl Chloride and
from Acetic Anhydride.—Consult your notes on experiments
79 g and h, page 58. If you have not carried out the experi-
ments, do so now.
103. Properties of Ethyl Acetate (SECTION 162).—( a ) Hydroly-
sis of ethyl acetate.—Place 25 cc. of ethyl acetate and a solution
of 14 grams of sodium hydroxide in 200 cc. of water in a round-
bottomed flask connected by a tightly fitting cork to a reflux
condenser. Place the flask in boiling water, and heat until
liquid ceases to flow back from the condenser (about three-
fourths of an hour). Transfer the liquid to a distilling flask, and

distil off 50 cc. into a small flask. Reserve for future study the
contents of the distilling flask. Add solid potassium carbonate
to the distillate in small portions. Close the flask and shake it.
Repeat the addition of the salt until a part of it remains undis-
solved. Pour the two layers into a separatory funnel, run off
the lower aqueous solution, and shake again with a small quantity
of dry potassium carbonate. Place the alcohol in a small distill-
ing flask, add about one-fourth its volume of anhydrous copper
sulphate, and allow the mixture to stand about 15 minutes with
occasional shaking. Distil the alcohol on a water-bath directly
from the flask, and note its boiling-point. Apply the iodoform
test to a few drops of the alcohol (experiment 81b, page 59).
Make the original aqueous solution obtained in the hydrolysis
strongly acid with dilute sulphuric acid (Eq.), and distil over
50 cc. What does the distillate contain? Prove your conclu-
sions by a suitable test. Explain how the procedure used in
this experiment serves to separate an acid and an alcohol. Is
the process one of general applicability?
(b) Ethyl acetate and concentrated sulphuric acid.—Add gradu-
ally with constant shaking, and keeping the mixture cool by
running water, 2 cc. of ethyl acetate to 4 cc. of concentrated sul-
phuric acid. Pour the solution very slowly, keeping the tube
cold, into 10 cc. of cold water. Will this test distinguish an
ester from an ether? From a saturated hydrocarbon?
Repeat the experiment, but heat the mixture for a minute
at about 100° before adding the solution to water. (Eq.)
(c) Ethyl acetate and hydriodic acid.—Repeat experiment 96j,
using ethyl acetate in place of ether. For what is the test used?
Will alcohol give a positive result?
104. Preparation of Isoamyl Acetate from Sodium Acetate.—
Place in a 750-cc. round-bottomed flask, provided with a return
condenser, 60 grams of finely powdered anhydrous sodium ace-
tate (see experiment 66 a ), and add through the condenser, very
slowly, 70 grams (38 cc.) of concentrated sulphuric acid. Add,
next, 65 grams of isoamyl alcohol. Heat on a wire gauze for one-
half hour. Connect the flask with a condenser arranged for
distillation, and distil as long as liquid passes over. Pour the
distillate into a separatory funnel, and wash it twice with an equal
volume of water. Separate the ester, and dry it over anhydrous

calcium chloride. Pour off the liquid and distil. Collect and
weigh the portion which boils at 137°-141°. Calculate the theo-
retical yield from the sodium acetate used, and the percentage
of this obtained. Test the solubility of isoamyl acetate in con-
centrated sulphuric acid.
Isoamyl acetate boils at 139°. The yield should be about
67 grams.
NOTE.—It is often advisable to prepare esters from salts rather than from
the free acids. The salts can be more readily obtained in an anhydrous con-
dition and, being solids, smaller quantities can be handled conveniently. In
the preparation of esters from salts, enough sulphuric acid must be added
to liberate the organic acid; equal molecular quantities must be used,
since acid sulphates are formed. A small excess of sulphuric acid should be
present to act as a catalytic agent. Enough of the alcohol is used to interact
with both the organic acid and the excess of sulphuric acid.
FATS AND OILS
105. Properties of Fats and Oils (SECTIONS 167-169).—( a )

Solubility of fats and oils.—Test the solubility of 1 gram of lard
and 1 cc. of olive oil in water, ether, alcohol, chloroform, and
petroleum ether.
(b) Extraction of fat.—Partly fill a small evaporating dish with
sand; pour 25 cc.of milk, into the dish and evaporate on the steam-
bath to dryness. Grind the residue and put it, together with
100 cc. of ether or petroleum ether, into a dry stoppered bottle.
At the next exercise filter off the ether into a beaker, and set
it aside to evaporate spontaneously. Examine the resulting
product. What is it?
(c) Saponification of a fat.—Read your notes on the saponi-
fication of lard (experiment 92a, page 67). If you have not
performed the experiment, do so now.
(d) Saponification of olive oil.—Warm together on the steam-
bath for 10 minutes 5 cc. of olive oil and 1 gram of sodium hy-
droxide dissolved in 20 cc. of alcohol. Pour the product into
water and add dilute sulphuric acid. (Eq.)
(e) Saponification of butter.—Saponify 15 grams of butrat
ment with lard (experiment 92a, page 67). As soon as the mix-
ture is thick and homogeneous, pour it into 15 cc. of water.
Transfer the solution of soap to a distilling flask, acidify with 25
cc. of sulphuric acid (1 part of acid to 4 of water), and distil over
about 15 cc. Test the distillate with litmus paper. Are the
volatile acids soluble in water? Note the odor of the solu-
tion. What causes the odor? Determine whether the oily
layer in the distilling flask contains acids. Find out if it is solu-
ble in alkalies. What happens when an acid is added to the alka-
line solution so formed?
(f) Test for unsaturated glycerides.—Dissolve 5 cc. of olive
oil or cotton-seed oil in 5 cc. of carbon tetrachloride, and add a
solution of bromine in carbon tetrachloride, drop by drop.
(g) Oils and concentrated sulphuric acid.—Add to 10 cc. of
olive oil or cotton-seed oil contained in a small beaker 5 cc. of
concentrated sulphuric acid. Stir with a thermometer and note
the rise in temperature. Repeat, using kerosene. Is there a
difference? Explain.
(h) Emulsification of oils.—In five test-tubes prepare the fol-
lowing mixtures: (1) 10 cc. of a 0.2 per cent solution of sodium
carbonate and 2 drops of neutral olive oil. (2) 10 cc. of a 0.2
per cent solution of sodium carbonate and 2 drops of rancid olive
oil. (3) 10 cc. of a warm solution of soap and 2 drops of the
neutral oil. (4) 10 cc. of white of egg solution and 2 drops of
neutral oil. (5) 10 cc. of water and 2 drops of neutral oil. Shake
the tubes very vigorously and let them stand for a few minutes.
Record the results in each case. Under what conditions is the
oil most perfectly emulsified?
Examine a drop of milk under a microscope.
NOTES.—(b) The fat can be extracted from milk in the usual way in a
separatory funnel with ether. In the analysis of foods, however, the prod-
uct is always dried before extraction. Milk can be dried as directed above,
or it can be absorbed on filter-paper which is then dried.
(d) If saponification is complete there should be no separation of oil
when the product is diluted with water.
(e) When this reaction is carried out quantitatively and 5 grams of fat
or oil are used, the number of cubic centimeters of a tenth normal solution of
sodium hydroxide required to neutralize the soluble volatile acids is called the
Reichert-Meissl number.
(g) The reaction illustrated in this test is the basis of a method used in
the analysis of oils. The number of degrees rise in temperature when 50
grams of an oil are treated with 10 cc. of sulphuric acid, in a vessel con-
structed in such a way as to avoid loss of heat by radiation, is called the
Maumené number of the oil.
(h) Oils which have become rancid contain free fatty acids. The latter
can be detected as follows: Dissolve in about 2 cc. of alcohol a drop
of phenolphthalein solution and 1 or 2 drops of a very dilute solution of
sodium hydroxide. To the resulting solution, which should have a light
pink color, add an alcoholic solution of the fat to be tested for free acid.
If the latter is present the color will disappear.
If a sample of rancid olive oil is not available for the experiment, mix
together the neutral oil and oleic acid in the proportion of 1 cc. of the former
to 1 drop of the latter, and shake 2 drops of the mixture with the solution
of sodium carbonate.
The factors which lead to the formation of emulsions are not definitely
known. The most permanent emulsions are formed when an insoluble
oil is shaken with a solution which contains a substance that interacts with
one of the constituents of the oil to produce a colloid. This occurs when an
oil containing free fatty acids is shaken with an aqueous solution of an
alkali. A layer of soap is formed around the particles of the oil, and it is
probable that a layer of oil may surround the colloidal particles of soap.
When a solution of egg albumin is shaken with olive oil, a layer of the coagu-
lated protein is formed around the drops of the oil and emulsification
takes place.
CHAPTER VII
ALDEHYDES AND KETONES
106. Formation and Properties of Formaldehyde (SECTIONS

176, 177).—( a ) Prepare a dilute solution of formaldehyde by
oxidizing methyl alcohol as directed in experiment 77b, page 55,
and make the following tests:
(b) Perform experiment 77b. Repeat the experiment, using
6 drops of a cold saturated alcoholic solution of gallic acid in place
of the solution of resorcin.
(c) Formaldehyde in milk.—Mix 2 cc. of the formaldehyde
solution prepared in ( a ) above with 5 cc. of milk, add 3 drops
of a solution of ferric chloride, hold the tube in a slanting posi-
tion, and pour down it slowly 5 cc. of concentrated sulphuric
acid in such a way that the acid forms a layer at the bottom of the
tube. Repeat the test with a sample of milk free from formalde-
hyde, which has been diluted with an equal volume of water.
(d) Reducing action of formaldehyde.—Clean a test-tube thor-
oughly by boiling a strong solution of sodium hydroxide in it,
and then washing with water. Place in the test-tube about 5 cc.
of a dilute solution of silver nitrate, and add a dilute solution of
ammonia, drop by drop, until the precipitate first formed is just
dissolved. Add about 1 cc. of the dilute solution of formalde-
hyde and put the tube into warm water.
(e) Formaldehyde and Schiffs reagent.—Add a few drops of
the solution of formaldehyde to 5 cc. of Schiff's reagent.
(f) Formaldehyde and Fehling's solution.—Add 1 cc. of the
dilute solution of the aldehyde to 5 cc. of Fehling's solution
and heat to boiling. The preparation of Fehling's solution is
described in the Appendix. (See note below and SECTION 188.)
(g) Polymerization of formaldehyde.—Evaporate on the steam-
bath 10 cc. of formalin (a 40 per cent solution of formaldehyde).
Heat some of the residue over a free flame and note cautiously
the odor.
(h) Formaldehyde and proteins.—Place in a solution of 1 cc.
of formalin and 5 cc. of water a thin piece of gelatin and let it
84
ALDEHYDES AND KETONES 85
stand for from 10 to 20 minutes. Place the gelatin in water

and heat to boiling. Try the action of boiling water on gelatin
which has not been in contact with formalin.
NOTES.—(b) In these teats very dilute solutions of formaldehyde should
be used, since strong solutions give precipitates which obscure the colors
that develop.
(c) A test similar to that described is made by pouring into the tube con-
taining the milk, so that two layers are formed, concentrated hydrochloric
acid containing a small amount of ferric chloride.
(e) It should be noted that alkalies or salts which give an alkaline reac-
tion produce a pink color with Schiff's reagent; it also becomes colored when
heated. The preparation of the reagent is described in the appendix.
(f) Fehling's solution is much used in testing for aldehydes. It consists
of a solution prepared by dissolving copper sulphate, sodium hydroxide, and
sodium potassium tartrate in water, the tartrate serving to keep in solution
the copper hydroxide, which would otherwise precipitate. The aldehyde
reduces the cupric compound in the alkaline solution to cuprous oxide.
107. Preparation of Acetaldehyde from Alcohol (SECTION
178).—A 500-cc. distilling flask containing 80 grams of powdered
potassium or sodium bichromate is closed by a cork bearing a
separatory funnel, and connected with a long condenser through
which a rapid stream of water below 15° passes. The con-
denser is attached to one end of an adapter the other end of
which extends to bottom of a receiver sunk to its neck in ice-
water. Drop in slowly through a funnel a cold mixture of 160 cc.
of water, 40 grams of alcohol, and 70 cc. of concentrated sul-
phuric acid. A vigorous reaction takes place; as this subsides the
mixture is run in more rapidly. The flask is shaken occasion-
ally to prevent the bichromate from forming a cake at the bottom.
When all the mixture has been added, and the action has ceased,
replace the funnel by a thermometer and heat the flask very
gently; remove the flame as soon as reaction sets up again. R e -
peat the heating in this way until reaction ceases when the flame
is withdrawn. Care should be taken to prevent the rise of the
thermometer beyond 65°. Place the distillate in a small distilling
flask provided with a long condenser and receiver cooled by ice-
water as described above, put the flask in water, and heat the
latter slowly up to 50°. Collect the portion which boils between
20° and 35°. Acetaldehyde boils at 21°. The product obtained
contains some water, but can be used for the experiments
described below.
108. Properties of Acetaldehyde (SECTIONS 179-185).—( a )

Aldehyde and sodium hydrogen sulphite.—Shake under water
2 cc. of the aldehyde prepared in the experiment just described
with 5 cc. of a saturated solution of sodium hydrogen sulphite.
(Eq.) Note the disappearance of the odor of aldehyde. Add
5 cc. of a strong solution of sodium carbonate and heat, noting
the odor. (Eq.)
(b) Aldehyde and bromine.—To 2 cc. of the aldehyde add
bromine, drop by drop, as long as the solution is decolorized.
The bromine should be added slowly as the reaction at first is
delayed. When the reaction is complete add about 10 cc. of
water. Does a heavy oil separate? (Eq.)
(c) Polymerization of aldehyde.—Dip a glass rod into con-
centrated sulphuric acid, and remove as much of the acid as
possible by shaking. Dip the rod into 2 cc. of aldehyde. Note
the reaction. (Eq.) Add 5 cc. of water.
(d) Aldehyde resin.—Boil a few drops of aldehyde in 5 cc. of
water with a few drops of a solution of sodium hydroxide. Note
the appearance and odor of the product. Repeat the test using
a solution of formaldehyde.
(e) Oxidation of aldehyde.—Add, in small portions, a dilute
solution of potassium permanganate to a solution of 2 cc. of
aldehyde in 5 cc. of water. (Eq.) Recall the action of an
unsaturated hydrocarbon with a solution of potassium perman-
ganate. Is the test with this salt a positive proof that a com-
pound contains a double or triple bond between carbon atoms?
How could you distinguish between a solution of an aldehyde and
one of ethylene?
(f) Reducing action of aldehyde.—Warm 5 drops of aldehyde
with 5 cc. of Fehling's solution.
(g) Tollen's reagent for aldehydes.—Test 3 drops of aldehyde
with an ammoniacal solution of silver nitrate as described in
experiment 106d, page 84, or without heating with Tollen's
reagent.1 (Eq.) Clean the test-tube to be used by boiling it
out with a solution of sodium hydroxide.
(h) Schiff's reagent and aldehydes.—Test a few drops of the
aldehyde with about 5 cc. of Schiff's reagent.1
1See Appendix.
ALDEHYDES AND KETONES 87
109. Formation of Acetaldehyde from an Acetate (SECTION

178).—Mix together 5 grams of sodium formate and 6 grams of
anhydrous sodium acetate in an 8-inch test-tube. Place the tube
in an inclined position and attach by means of a cork a delivery-
tube which dips under water contained in a test-tube. Heat for
a few minutes. Test the resulting solution of aldehyde with
Schiff's reagent.
KETONES
110. Formation of Acetone from an Acetate (SECTION 193).—

Place in an 8-inch test-tube 7 grams of calcium acetate and 7
grams of anhydrous sodium acetate which have been intimately
mixed by grinding together in a mortar. Clamp the tube in a
horizontal position and connect it with a condenser. Tap the
tube gently so that a channel is formed along its whole length.
Heat until the acetates glow, turning the tube from time to
time, so that all of the salts can be heated to a high temperature.
Redistil the liquid and determine its boiling-point.
Acetone boils at 56°. The yield is from 3 to 4 grams.
NOTE.—Sodium acetate is mixed with calcium acetate in this preparation
in order to facilitate the formation of acetone.
111. Properties of Acetone (SECTIONS 194, 200).—( a ) Acetone

and Schiff's reagent.—Add a few drops of acetone to 5 cc. of
Schiff's reagent. Examine the solution after it has stood some
time.
(b) Acetone and sodium hydrogen sulphite.—Mix 5 cc. of ace-
tone with 5 cc. of a saturated solution of sodium hydrogen sul-
phite; shake and cool. (Eq.)
(c) Acetone and Tollen's reagent.—Test a few drops of acetone
dissolved in 5 cc. of water with an ammoniacal solution of silver
nitrate or with Tollen's reagent.
(d) Conversion of acetone into iodoform.-—Apply the iodoform
test to a dilute solution of acetone. (See experiment 81b,
page 59.)
(e) Acetone and phosphorus pentachloride.—HOOD.—To 5 cc.
of acetone contained in a test-tube placed in cold water add, with
constant shaking, small quantities of phosphorus pentachloride
as long as any reaction takes place. Pour the contents of the
tube slowly into cold water. Does a heavy liquid separate?

(Eq.)
(f) Identification of acetone.—Acetone can be converted into
a solid compound which is valuable in its identification, especially
if the ketone is in a dilute aqueous solution. The substance pre-
pared is formed as the result of the interaction of acetone and
benzaldehyde, C 6 H 5 .CHO, in the presence of an alkali; it is
called dibenzalacetone. The reaction is as follows:
2C 6 H 5 .CHO + (CH 3 ) 2 CO = (C 6 H 5 .CH:CH) 2 CO + 2H2O
Place in a small flask 1 cc. of acetone, 4 cc. of water, 4 cc. of
benzaldehyde, 20 cc. of alcohol, and 5 cc. of a 10 per cent solution
of sodium hydroxide. Boil gently for 5 minutes. Cool and
shake. Filter off the crystals and wash them with 20 cc. of cold
alcohol. Recrystallize from 20 cc. of boiling alcohol. Let the
solution cool. Filter and wash with 10 cc. of cold alcohol. Dry
on a porous plate and determine the melting-point of the crystals.
Dibenzalacetone crystallizes in yellow plates and melts at
111°-112°.
CHAPTER VIII
AMINES AND AMIDES
112. Preparation of Methylamine from Acetamide (SECTION

204).—Place into a 1 liter flask 100 cc. of water and 36 grams of
fresh bleaching powder. Add 10 grams of acetamide dissolved
in 25 cc. of water in small portions and shake. Add slowly a
cold solution of 25 grams of sodium hydroxide in 100 cc. of water.
Arrange the apparatus to distil with steam (see Fig. 14, page 20),
and connect an adapter by means of a tightly fitting rubber
stopper with the end of the condenser. Place the end of the
adapter just below the surface of 50 cc. of cold water contained
in a beaker, and distil with steam. From time to time remove
the adapter, and test the distillate with litmus paper. Stop the
distillation when methylamine ceases to distil over. The yield
in this preparation, calculated from the methylammonium chlo-
ride obtained (see experiment 113d below), should be 70 per cent
of the theoretical.
NOTE.—In the preparation of methylamine by Hofmann's reaction,
bromine and potassium hydroxide are commonly used. The use of bleaching
powder, instead of these reagents, which form potassium hypobromite,
avoids the handling of large quantities of bromine, and reduces the cost of
the preparation. The amount of bleaching powder to be used is determined
by the percentage of available chlorine which it contains. The proportions
given above are based on a bleaching powder which contains about 35 per
cent of available chlorine.
113. Properties of Methylamine (SECTIONS 205-206).—( a )
Basic properties of a solution of methylamine.—Test the dis-
tillate obtained in the experiment just described with pink litmus
paper.
(b) Methylamine and solutions of metallic salts.—Add a little
of the distillate, drop by drop, as long as any change occurs, to
1 cc. of dilute solution of copper sulphate. Repeat with a solu-
tion of ferric chloride. Add ammonia to solutions of these salts.
Write equations for the reactions in the case of ammonia and of
methylamine; the reactions in the two cases are analogous.
89
(c) Carbylamine reaction.—HOOD.—Warm 1 cc. of the dis-

tillate with 2 drops of chloroform and 2 cc. of an alcoholic solu-
tion of potassium hydroxide, which may be prepared by heating
a little of the solid compound with alcohol and decanting off the
solution. (Eq.) Note the odor produced. Acidify the con-
tents of the tube before pouring into the sink.
(d) Methylammonium chloride.—Make the rest of the distil-
late slightly acidic with hydrochloric acid, and evaporate the
solution to dryness on the steam bath. Dissolve the salt in the
smallest possible amount of boiling absolute alcohol; a small
amount of ammonium chloride may be left as an insoluble residue.
To dissolve the salt, add to the beaker on a steam-bath about
25 cc. of the alcohol; cover with a watch-glass, and let the salt
digest with the hot alcohol for a few minutes. Filter through
a funnel from which the stem has been cut (see Fig. 1, page 6).
Continue the addition and digestion as long as the solvent
appears to dissolve the salt. About 100 cc. of alcohol will be
required. Cool the combined filtrates, and add an equal volume
of ether. Filter off the crystals by suction and dry them on a
porous plate. Determine the weight and the melting-point of the
methylammonium chloride obtained.
(e) Methylammonium chloride and alkalies.—Heat together in
a test-tube a very small amount of the salt with 2 cc. of a solu-
tion of sodium hydroxide. (Eq.) Note the odor of the gas.
(f) Inflammability of methylamine.—Place about 0.5 gram
of methylammonium chloride and an equal amount of lime
in a dry test-tube, and heat. Apply a flame to the gas. Does
it burn? Repeat with ammonium chloride. Does ammonia
burn in air?
(g) Methylammonium chlorplatinate.—Dissolve a small amount
of methylammonium chloride in a few drops of alcohol, and add,
drop by drop, a 10 per cent solution of platinic chloride. Repeat,
using a few drops of a strong aqueous solution of ammonium
chloride. The reactions in the two cases are analogous. Write
the equations for both reactions.
(h) Decomposition of methylammonium nitrite.—Mix in a test-
tube about 0.5 gram of methylammonium chloride with twice
its weight of sodium nitrite and about 5 cc. of water. Connect
the tube by means of a cork with a delivery-tube arranged to
AMINES AND AMIDES 91
collect a gas over water. Heat the solution gently and collect
two test-tubes full of the gas. (Eq.) Test the second tube for
nitrogen with a glowing splinter. Distil over about 3 cc. from
the tube into a second tube, surrounded by cold water. Test
the distillate for methyl alcohol (experiment 77b, page 55).
114. Isolation of Lecithin from Egg-yolk (SECTION 217).—
Grind the yolk of one hard-boiled egg with 50 cc. of ether. Filter
and wash the solid residue twice with 10 cc. of ether. Evaporate
off the ether on the steam-bath, or distil it off from a small
flask. Extract the residue twice with hot alcohol, using 10 cc.
each time. Pour off the alcohol from the heavy oil through a
small filter. Evaporate off the alcohol, dissolve the residue in
10 cc. of cold ether, and add 10 cc. of acetone. Stir until the
particles of the precipitated lecithin adhere together and form
a ball. Place the latter on a filter-paper. Describe its proper-
ties. Boil about one-fourth of the lecithin with about 10 cc.
of a 10 per cent solution of sodium hydroxide. Note the odor
of the gas evolved. What is it? Cool the solution. Is there
any evidence of the formation of a soap? Filter, dissolve the
precipitate in warm water and add dilute hydrochloric acid to
the solution. What is precipitated? Test a part of the lecithin
for nitrogen and for phosphorus (§§58, 59, 61, page 39).
NOTE.—Ether dissolves from egg-yolk, in addition to lecithin, some fat

and protein. The protein and a part of the fat are removed by extracting
the residue from ether with alcohol. The lecithin is finally separated by
adding acetone to an etheral solution of the lecithin and fat. The latter is
soluble in acetone while the lecithin is insoluble.
AMIDES
115. Preparation of Acetamide from Ethyl Acetate (SECTION

221).—Mix in a 250-cc. distilling flask 50 grams of ethyl acetate
and 100 cc. of a concentrated aqueous solution of ammonia
(sp. gr. 0.90). Close the flask with corks and let the mixture
stand over night, until the two layers first formed have dis-
appeared. (Eq.) Arrange the flask for distillation with a
thermometer and water condenser, and use as a receiver a
distilling flask or a filter-bottle, the side-arm of which is provided
with a tube which dips under water; the latter precaution is taken
to absorb the large quantity of ammonia which is given off in
the distillation. Distil carefully; collect the first part (about

10 cc.) of the distillate separately and test it for ethyl alcohol
When the thermometer registers 160°, replace the water-con-
denser by an air-condenser, change the receiver, using this time
a beaker, and collect what distils at 160°-225°. As the tempera-
ture rises the acetamide solidifies in the condenser to a crystalline
mass. which can be readily liquefied by warming the condenser
cautiously with a free flame. When the distillate is cold pour
off from the crystals in the receiver any liquid present, and dry
the crystals on a porous plate. Weigh the product obtained
and determine its melting-point. Calculate the percentage
yield obtained. The slightly impure acetamide may be purified
by a second distillation, or by crystallizing it from a mixture
of one volume of alcohol and two volumes of ether. If the
product obtained in the first distillation does not melt sharply,
recrystallize a small portion of it.
Acetamide melts at 82°, and boils at 222°. The yield obtained
in the preparation should be about 65 per cent of the theoretical.
NOTE.—The odor of the amide prepared as directed above is due to an

impurity which is present in small quantity. By a single recrystallization
the compound is obtained in an odorless condition.
116. Properties of Acetamide (SECTION 221).—( a ) Hydrolysis

of acetamide.—Mix about 0.5 gram of acetamide with about 5 cc.
of a solution of sodium hydroxide, shake and observe whether
the odor of ammonia is present. Heat the solution to boiling.
Is ammonia set free? (Eq.)
(b) Heat to boiling for 1 minute about 0.5 gram of acetamide
with 2 cc. of dilute sulphuric acid. Cool, and make alkaline with
a solution of sodium hydroxide. Does the solution smell of
ammonia? Explain.
(c) Mercury salt of acetamide.—Add an excess of a solution
of sodium hydroxide to 2 cc. of a solution of mercuric chloride.
(Eq.) Determine whether the precipitate dissolves when a little
acetamide is added. (Eq.) Test the solution for mercury with
hydrogen sulphide.
(d) Acetamide and nitrous acid.—To an aqueous solution of
acetamide add a few crystals of sodium nitrate and a few drops
of dilute sulphuric acid. (Eqs.)
AMINES AND AMIDES 93
117. Preparation of Urea from a Cyanate (SECTION 223).—

Dissolve 8 grams of potassium cyanate in 20 cc. of hot water
and 13 grams of ammonium sulphate in 20 cc. of hot water. Mix
the solutions and evaporate to dryness on the steam-bath. (Eq.)
Grind the product to a fine powder and dry on the steam-
bath for 15 minutes. Place the solid in a dry beaker and add
25 cc. of alcohol. Cover with a watch-glass, and let the mixture
digest just below the boiling-point of alcohol for a few minutes.
Decant off the liquid through a filter and digest a second time.
If the solution is colored, boil the combined filtrates with a little
bone-black. Filter and evaporate on the steam-bath to crystal-
lization (see §9, page 6). When the solution is cold, filter off
the crystals by suction (see §12, page 7) and dry them on a
porous plate. From the filtrate a second crop of crystals may
be gotten by evaporation and the addition of an equal column
of ether to the cold solution. Weigh the urea obtained and de-
termine its melting-point.
Urea melts at 132°, and can be crystallized from hot amyl
alcohol.
NOTE.—The blue substance formed at times in this preparation is probably
produced as the result of the following cause: Commercial potassium cya-
nate may contain potassium ferrocyanide. If this is the case, when a solu-
tion of the salt is evaporated in the air with ammonium sulphate containing
a trace of iron, Prussian blue is formed.
118. Properties of Urea (SECTIONS 223, 224).—( a ) Nitrate of
urea .—Dissolve a crystal of urea in a drop of water on a micro-
scope slide; place near this solution a drop of concentrated
nitric acid, and bring the two together by touching with a glass
rod. (Eq.) Examine the crystals under the microscope.
(b) Urea and oxalic acid.—Repeat (a) above but use a satu-
rated solution of oxalic acid in place of nitric acid. (Eq.)
(c) Hydrolysis of urea.—Treat about 0.5 gram of urea with
5 cc. of a solution of sodium hydroxide. Note whether ammonia
is given off. Explain. Boil the solution for a minute or two
and observe if ammonia is given off freely. (Eq.) Test the
vapor with litmus paper.
(d) Urea and nitrous acid.—Place in a test-tube 0.1 gram of
sodium nitrite and 10 cc. of water; in another tube put 0.1 gram
of sodium nitrite, 10 cc. of water and 0.2 gram of urea. Add to
each tube 1 cc. of dilute acetic acid. Compare the amount and
color of the gas given off in each case. (Eqs.)
(e) Urea and sodium hypobromite.—Prepare an alkaline solu-
tion of sodium hypobromite by adding 3 drops of bromine to
5 cc. of a dilute solution (10 per cent) of sodium hydroxide. Add
this solution to a dilute solution of urea. (Eq.)
(f) Urea and mercuric nitrate.—To a dilute solution of urea
add a 1 per cent solution of mercuric nitrate. A compound of
the formula CO(NH 2 ) 2 .Hg(NO 3 ) 2 .HgO is precipitated.
(g) Action of heat on urea: biuret (SECTION 224).—Heat cau-
tiously about 0.5 gram of urea in a dry test-tube; continue the
heating until a white opaque solid is formed. The residue is a
mixture of biuret and cyanuric acid (SECTION 249). Treat the
residue when cold with about 5 cc. of water, shake, pour off
the aqueous solution of biuret, and add 5 cc. of a solution of
sodium hydroxide and a few drops of a dilute (1 per cent) solu-
tion of copper sulphate.
Dissolve the residue insoluble in water in a little ammonia,
add a few cubic centimeters of a solution of barium chloride and
shake. A precipitate of barium cyanurate is formed.
NOTES.—(a) The nitrate of urea is difficultly soluble in cold water and in
nitric acid. This fact is made use of in the isolation of urea from urine.
(c) Ammonium salts can be distinguished from amides by means of sodium
hydroxide; the former yield ammonia in the cold.
(e) Ammonium salts give nitrogen when treated with a solution of
sodium hypobromite; they must, therefore, be absent when applying the
test to urea. This reaction is used in the clinical examination of urine for
urea.
(f) Many substances related to acid amides, for example the proteins,
give precipitates with solutions of mercuric salts.
(g) This test for biuret is not characteristic; it is given by many substances
in which there is a linking of atoms similar to that in biuret. The test is
useful in the study of proteins.
CHAPTER IX
CYANOGEN AND RELATED COMPOUNDS
119. Formation of Cyanogen (SECTION 233).—( a ) From mer-

curic cyanide.—CAUTION.—Cyanogen is a poisonous gas. Per-
form the experiment under a hood. Heat in a small dry test-tube
over a free flame about 0.5 gram of mercuric cyanide. Ignite
the gas generated. Note the unusual color of the different parts
of the flame. (Eq.)
(b) From copper sulphate and potassium cyanide.—CAUTION.—
Potassium cyanide is very poisonous. It should not be touched
with the fingers; use a spatula or handle small pieces with pin-
cers. HOOD.—Add to 5 cc. of a cold saturated solution of copper
sulphate a cold saturated solution of potassium cyanide until the
precipitate first formed dissolves. (Eq.) Heat to boiling. (Eq.)
and ignite the gas evolved. Add a solution of potassium iodide
to a solution of copper sulphate. (Eq.) Determine by an
appropriate test if iodine is liberated.
120. Formation of Potassium Cyanide from Potassium Ferro-
cyanide (SECTION 238).—Heat to a high temperature in a porce-
lain crucible about 1 gram of potassium ferrocyanide. (Eq.)
When cold add water, and heat to boiling. Pour off the solution
and test for a cyanide according to the next experiment.
121. Test for a Soluble Cyanide (SECTION 240).—To 1 cc. of
a dilute solution of potassium cyanide add 5 drops of a solution of
sodium hydroxide and 5 drops of a solution of ferrous sulphate;
heat to boiling, cool, and add dilute hydrochloric acid, drop by
drop, until the solution shows an acid reaction. If no color
develops add 3 drops of a solution of ferric chloride. Potassium
ferrocyanide is formed from the potassium cyanide and ferrous
sulphate; the ferrocyanide and the ferric salt then form Prussian
blue. (Eqs.)
NOTE.—It is usually not necessary to add ferric chloride, since the
ferrous sulphate contains enough ferric salt to give the reaction. An
excess of hydrochloric acid should be avoided since it interferes with the
formation of the ferric ferrocyanide.
95
122. Action of Cyanides on the Soluble Salts of Heavy Metals

(SECTION 238).—( a ) Add a few drops of a solution of potassium
cyanide to a solution of ferric chloride. (Eq.) Next add an
excess of potassium cyanide ( Eq. ) , acidify, and then add a solu-
tion of ferrous sulphate. (Eq.)
(b) Add a few drops of a solution of potassium cyanide to a
solution of silver nitrate ( E q . ) ; add an excess of the cyanide.
(Eq.) Determine if silver chloride is soluble in potassium cya-
nide. Precipitate some silver cyanide and determine its solu-
bility in nitric acid and in ammonia. How could you distinguish
silver chloride from silver cyanide?
123. Properties of Potassium Ferrocyanide (SECTION 240).—
( a ) Conversion into hydroferrocyanic acid.—Add concentrated
hydrochloric acid to about 10 cc. of a saturated solution of potas-
sium ferrocyanide as long as a precipitate is formed, (Eq.)
Pour off the liquid and place a part of the crystals on a porous
plate. They turn blue due to oxidation.
(b) Decomposition with strong sulphuric acid.—In a test-tube
moisten with 5 drops of water about 1 gram of powdered potas-
sium ferrocyanide and add 5 cc. of concentrated sulphuric acid.
Heat and apply a flame to the gas evolved, (Eq.)
(c) Ferrocyanides of heavy metals.—Add a solution of potas-
sium ferrocyanide to solutions of salts of ferric iron, silver, copper,
and mercury. (Eqs.)
124. Preparation of Potassium Ferricyanide from Potassium
Ferrocyanide (SECTION 241).—Dissolve 25 grams of potassium
ferrocyanide in 50 cc. of warm water and add bromine-water to
the solution until it no longer gives a blue color when a drop is
placed on paper treated with a solution of ferric chloride (Eq.)
About 175 cc. will be required. Evaporate to dryness in an
evaporating dish on a steam-bath. Grind the solid in a mortar.
add 10 cc. of cold water and grind again. Transfer the solid to
a suction-filter and remove the liquid. Disconnect the filter-
flask from the pump and add to the solid 10 cc. of cold water.
After 2 or 3 minutes draw off the liquid. This procedure serves to
remove most of the potassium bromide formed in the reaction
between the ferrocyanide and bromine,
Transfer the solid to a small beaker, add 50 cc. of water, heat to
boiling, and filter. Evaporate the filtrate on the steam-bath
CYANOGEN AND RELATED COMPOUNDS 97
until the surface of the liquid is just covered by a solid crust.

Set aside over night. Filter off and save the crystals, and let the
mother-liquor evaporate spontaneously to recover the salt in
solution.
125. Properties of Potassium Ferricyanide (SECTION 241).—
(a) Ferricyanides of heavy metals.—Add a solution of potassium
ferricyanide to solutions of salts of ferric iron, ferrous iron, silver,
copper, and mercury. (Eq.)
(b) Potassium ferricyanide as an oxidizing agent.—In a small
beaker dissolve 2 grams of lead nitrate in about 10 cc. of boiling
water, and add a solution of sodium hydroxide until the precipi-
tate first formed has dissolved. Next add a strong aqueous solu-
tion of 4 grams of potassium ferricyanide, and heat to boiling.
(Eq.) Filter off the precipitate, test the filtrate for a ferrocyanide
and determine if the precipitate is lead dioxide, PbO 2 . Add
hydrochloric acid to a little of the substance and heat. (Eq.)
NOTE.—(b) An alkaline solution of potassium ferricyanide is a valuable
mild oxidizing agent, which is frequently used in the oxidation of organic
compounds. The oxidizing power is equivalent to that represented in the
following equation:
2K3Fe(CN)6 + 2KOH = 2K4Fe(CN)6 + H2O + O
ALKYL CYANIDES
126. Preparation of Methyl Cyanide (SECTION 244).—Weigh

directly into a dry 100-cc. distilling flask 20 grams of phosphorus
pentoxide and add 20 grams of powdered acetamide; stir the
mixture and shake it. Close the flask with a cork bearing a
thermometer, connect with a condenser, and use a 25-cc. dis-
tilling flask as a receiver. Heat cautiously with a small flame,
kept constantly in motion, as long as any liquid distils. Add to
the distillate about 2 grams of phosphorus pentoxide, and
redistill, collecting the portion which boils at 80°-82°. Weigh the
distillate and calculate the percentage yield obtained.
Methyl cyanide (acetonitrile) boils at 81.6°. The yield
obtained in the above experiment should be 50-60 per cent
of the theoretical.
127. Hydrolysis of Methyl Cyanide (SECTION 244).—( a )
Heat about 1 cc. of methyl cyanide with a dilute solution of
sodium hydroxide, and note the odor of the gas evolved. (Eq.)
(b) In a small round-bottomed flask mix 3 cc. of water and 6

cc. of concentrated sulphuric acid; cool the mixture and add 5
grams of methyl cyanide. Connect the flask with a return con-
denser and boil gently for 15 minutes. (Eq.) Dilute with about
5 cc. of water and distil off about 5 cc. Test the distillate for
acetic acid. (See experiment 91, page 67.) Make a part of the
contents of the flask strongly alkaline with sodium hydroxide
and note the odor.
128. Formation of an Isocyanide (SECTION 246).—Repeat the
carbylamine test for primary amines (experiment 113c, page 90),
in which an isocyanide is formed, or apply the test to aniline,
C 6 H 5 NH 2 , which is a primary amine containing the phenyl
radical, C 6 H 5 ; phenyl isocyanide, C 6 H 5 NC, is formed. Proceed
as follows: HOOD.—Warm together 2 drops of aniline, 3 drops of
chloroform, and 2 cc. of an alcoholic solution of potassium
hydroxide. (Eq.) CAUTION.—As phenyl isocyanide has a very
disagreeable odor and is poisonous, the tube containing it should
be washed thoroughly under the hood.
CHAPTER X
HALOGEN COMPOUNDS
129. Preparation of Methyl Iodide from Methyl Alcohol

and Phosphorus Iodide (SECTIONS 55, 252).—In a 200-cc.
round-bottomed flask place 15 grams of methyl alcohol and 3.2
grams of red phosphorus. Have ready a reflux condenser with
cork attached. Place the flask in cold water and add in small
portions at a time 38 grams of iodine; the addition should take
about 10 minutes. If the contents of the flask begin to boil,
attach it to the reflux condenser; when reaction ceases add more
iodine. Finally attach the flask to the condenser and let it stand
for at least 4 hours (preferably over night). Distil through a
condenser from a water-bath, as long as any liquid passes over.
The receiver should be placed in cold water as methyl iodide is
very volatile. Wash the distillate by decantation with a dilute
aqueous solution of sodium hydroxide until the lower layer is
colorless, and then once with water. Separate the methyl
iodide carefully from the water using a separatory funnel, and
transfer it to a small distilling flask. Add about 10 grams of
anhydrous calcium chloride. Stopper the flask, place a cork
over the end of the side-arm, and set aside until the liquid is
quite clear. Place a thermometer in the flask, connect the latter
with a condenser, and distil from a water-bath. Note the boiling-
point and weight of the methyl iodide. Calculate the theoretical
yield from the iodine used (why iodine?), and the percentage of
this obtained.
Methyl iodide boils at 44°, and has the specific gravity 2.27
at 15°. The yield in the experiment should be about 80 per cent
of the theory.
NOTE.—An excess of the alcohol is usually taken in preparing alkyl halides
by the method illustrated above. The phosphorus and iodine are used in
the proportions necessary to form phosphorus tri-iodide, PI3. The chief
reaction which takes place is represented by the following equation:
3CH3OH + P + 3I = 3CH3I + P(OH)3
99
The hydriodic acid which is evolved is produced as the result of side-reac-

tions, which are described in the case of phosphorus trichloride in SECTION
65.
130. Properties of Methyl Iodide (SECTION 254).—( a ) Action

of light on methyl iodide.—Place in each of two small test-tubes
2 cc. of methyl iodide and close the tubes tightly with corks.
Put one tube in the desk in the dark, and allow the other to stand
in direct sunlight. At the end of an hour or two, examine the
two tubes. To remove the iodine set free, add a drop of mercury
or some copper wire and shake. The alkyl iodides should be
kept in well-stoppered bottles of brown glass.
(b) Methyl iodide and silver nitrate.—To a few drops of color-
less methyl iodide suspended in water add a solution of silver
nitrate and shake. Repeat, using a solution of methyl iodide in
alcohol and of silver nitrate in alcohol. (Eq.)
(c) Methyl iodide and sodium hydroxide.—Shake occasionally
during half an hour a mixture of 1 cc. methyl iodide and 5 cc.
of a dilute solution of sodium hydroxide. At the end of this
time neutralize with dilute nitric acid, filter, and test a part of
the filtrate for methyl alcohol according to experiment 77b,
page 55, and a part for an iodide. For other reactions of alkyl
halides, see the experiments with ethyl bromide below.
NOTE.—(a, b, and c) Methyl iodide is much more reactive than the other
alkyl iodides. Reactions analogous to those illustrated in the above experi-
ments take place with the higher iodides, but much more slowly. The
bromides are less reactive than the iodides; the chlorides are, in most cases,
very stable. Tertiary halides are much more reactive than the halides
derived from secondary and primary alcohols.
131. Preparation of Ethyl Bromide from Alcohol, Potassium

Bromide, and Sulphuric Acid (SECTION 252).—Add to a mixture
of 60 grams of alcohol and 50 cc. of water, contained in a 1-liter
flask, 100 cc. of concentrated sulphuric acid. Cool thoroughly
in running water, and add 100 grams of finely powdered potas-
sium bromide. Connect the flask by means of a bent glass tube
and a rubber stopper with a long condenser through which a rapid
stream of water is passing, and fit an adapter by means of a cork
to the end of the condenser. Use a 300-cc. Erlenmeyer flask as
a receiver, and place it in a beaker about one-half full of cold
water. Fill the receiver half full of water and adjust the con-
HALOGEN COMPOUNDS 101
denser so that the end of the adapter is below the surface of the
water. These precautions are taken because ethyl bromide is
a very volatile liquid (boiling-point 39°). Place a sand-bath
under the flask containing the reaction mixture, heat with a
large flame, and distil as rapidly as possible. As distillation
proceeds, the ethyl bromide drops to the bottom of the receiver,
and the aqueous part of the distillate finally overflows into the
beaker. Distil until drops of the insoluble bromide cease to
appear, About one hour is required for the distillation if it is
carried on rapidly.
Decant off most of the water from the ethyl bromide into a
beaker, add a dilute solution of sodium hydroxide, shake, and
decant. Wash again with water, and transfer to a separatory
funnel; run off the lower layer into a small dry distilling flask,
add anhydrous calcium chloride (about one-fourth the volume
of the bromide), and close the flask tightly with corks. Set
aside until the liquid is quite clear and no drops of water are
visible; if the calcium chloride appears moist, add more and set
aside again. Connect the flask with a long condenser and use
as a receiver a dry flask surrounded by ice-water. Distil from
a water-bath and collect the portion which boils at 35°-40°.
Calculate the theoretical yield from the potassium bromide used
(why from the bromide?) and the percentage yield obtained.
Write equations for all reactions. Why does the solution turn
red during the heating? (Eq.)
Ethyl bromide boils at 38.4° and has the specific gravity 1.47
at 13°. The yield in this preparation should be about 80 per
cent of the theoretical.
NOTE.—The ethyl bromide prepared in this way contains a small amount
of ether, from which it cannot be separated readily by distillation, since ether
boils at 35° and ethyl bromide at 38.4°. In separating the two substances
advantage is taken of the fact that ether is soluble in cold concentrated sul-
phuric acid, while ethyl bromide is not soluble. The bromide prepared
by the method given above can be purified by adding it slowly with con-
stant shaking, to an equal volume of concentrated sulphuric acid kept cold
by immersion in ice-water. After this treatment the liquids are separated
and the ethyl bromide shaken with water, dried, and distilled.
132. Properties of Ethyl Bromide (SECTIONS 254, 255).—( a )
Solubilities of ethyl bromide.—Using about 1 cc. in each test,
determine whether ethyl bromide dissolves in the following
liquids: water, alcohol, ether, petroleum ether, and cold con-

centrated sulphuric acid.
(b) Test for bromine in ethyl bromide.—Test ethyl bromide for
halogen with a copper wire (§60 page 41).
(c) Ethyl bromide and silver nitrate.—Shake about 2 cc. of
ethyl bromide with 5 cc. of water to remove any free hydro-
bromic acid which may be present. Separate the bromide by
means of a pipette and dissolve it in 5 cc. of an alcoholic solution
of silver nitrate. Is silver bromide precipitated? Stopper the
test-tube, and allow it to stand until the next laboratory exercise.
Is silver bromide precipitated? Compare the result with that
obtained with methyl iodide.
(d) Ethyl bromide and alcoholic potassium hydroxide.—Shake
a small piece of potassium hydroxide with 10 cc. of absolute
alcohol. Filter off the liquid and dissolve in it 2 cc. of ethyl
bromide. Boil for 1 minute. (Eq.) Dilute with water, acidify
with a dilute solution of pure nitric acid, and add a solution of
silver nitrate.
(e) Ethyl bromide and magnesium.—Just cover the bottom
of a test-tube with magnesium powder. Add 2 cc. of ethyl
bromide, 2 cc. of ether, and a very small piece of iodine; place
the tube in warm water for 1 minute. Cool and add a little
water. (Eq.)
(f) Ethyl bromide and sodium.—To 5 cc. of ethyl bromide in
a dry test-tube add a piece of sodium the size of a pea. Close
the tube with a cork carrying a small drying-tube containing
calcium chloride, and set aside. Examine in an hour. (Eq.)
NOTES.—(a) Some tertiary halides are decomposed when treated with
concentrated sulphuric acid.
(d) This reaction is useful as a test to distinguish alkyl halides from cer-
tain halogen derivatives of benzene and other hydrocarbons, which are not
decomposed readily by alcoholic potassium hydroxide. It is necessary to
use a solution of potassium or sodium hydroxide free from halogen com-
pounds. Since the alkalies usually contain chlorides, the solution is pre-
pared by using absolute alcohol in which sodium chloride and potassium
chloride are insoluble.
133. Preparation of Ethyl Iodide from Ethyl Alcohol and
Hydriodic Acid.—Place 60 grams of a strong solution of hydriodic
acid and water (the constant-boiling mixture, which contains 57
per cent hydrogen iodide, and has the specific gravity 1.7) in a
200-cc. distilling flask connected with a condenser through which

a rapid stream of cold water is passing. Connect an adapter
to the condenser and use as a receiver a flask surrounded by
water. Close the distilling flask with a stopper bearing a drop-
ping funnel (see Fig. 18, page 28), the end of which reaches to
the bottom of the flask. Heat the hydriodic acid to boiling, and
drop in through the funnel 10 grams of alcohol at about the same
rate as that at which the iodide distils over (about 1 drop per
second). Add water to the receiver, shake, and decant off the
water into a beaker. Separate the iodide by means of a separa-
tory funnel, place it in a small distilling flask, and add about
one-fourth its volume of anhydrous calcium chloride. Cover
the side-arm of the flask with a cork, and place one in the neck
of the flask. Let the iodide stand until it is quite clear, and distil
from a water-bath. Calculate the percentage yield obtained.
Ethyl iodide boils at 72.3°, and has the specific gravity 1.944
(14°). The yield in this preparation is about 90 per cent of the
theory, calculated from alcohol; a slight excess of the hydriodic
acid is used.
134. Preparation of Isoamyl Bromide from Isoamyl Alcohol
and Hydrobromic Acid.—Distil slowly from a 250-cc. distilling
flask, provided with a thermometer and connected with a water
condenser, a mixture of 30 grams of isoamyl alcohol and 115
grams of the constant-boiling mixture of hydrobromic acid and
water, which contains 48 per cent of hydrogen bromide and has
the specific gravity 1.49. Distil until the thermometer registers
124°. Add 100 cc. of water to the distillate, place the mixture in
a separatory funnel, and return to the distilling flask the oil,
which is a mixture of isoamyl bromide and unchanged alcohol.
Distil as long as an oil passes over. Put the liquid in the flask
in the bottle reserved for hydrobromic acid residues.
Separate the oil and shake it with an equal volume of concen-
trated sulphuric acid, which dissolves from the mixture the
unchanged alcohol and the isoamyl ether formed in a secondary
reaction. Separate the oil, wash it with water, and after drying
with calcium chloride pour it through a funnel containing a bit
of cotton-wool into a small distilling flask. Distil. Record the
boiling-point and the weight of the product, and calculate the
percentage yield from the weight of alcohol used.
Isoamyl bromide boils at 118°, and has the specific gravity

1.219 at 15°. The yield is about 66 per cent of the theoretical
calculated from the alcohol used.
NOTE.—It is frequently advantageous to prepare the alkyl bromides and
iodides from the alcohols and aqueous solutions of the halogen acids (the
so-called constant-boiling mixtures with water). This is particularly the
case when a very pure product is sought, or when an expensive synthetic
alcohol is used. In the latter case it is well, in order to increase the yield, to
use a large excess—two or three times the theoretical amount—of the acid;
the latter can be recovered readily. In making the lower alkyl halides, a
good yield can be obtained by using slightly more than the theoretical
amount of the halogen acid; in the case of the higher alcohols a large excess
is necessary. The alkyl halides prepared in this way are contaminated in
certain cases with a trace of an unsaturated hydrocarbon; this can be
removed by shaking them with a dilute solution of potassium permanganate.
135. Preparation of Normal Butyl Chloride (SECTION 252).—

In a 500-cc. flask dissolve in 95 grams of concentrated hydrochloric
acid 135 grams of anhydrous zinc chloride, keeping the mixture
cold to avoid loss of hydrogen chloride. Add next 37 grams of
normal butyl alcohol and connect the flask to a reflux condenser
or preferably use the form of apparatus represented in Fig. 17,
page 27. Boil the mixture gently for one hour. Separate the
upper layer, and place it with about an equal volume of con-
centrated sulphuric acid in a distilling flask. The side-arm of
the latter is closed by a cork and the neck connected with a
return condenser (see Fig. 16, page 26). The mixture is cau-
tiously heated so that the chloride boils gently. At the end of
one-half hour distil off the chloride using a water-condenser.
Wash the distillate with a dilute solution of sodium hydroxide,
separate it, and place it in a small distilling flask with a little
anhydrous calcium chloride. Set aside for a while and distil
collecting the portion boiling at 76°-78°. Weigh the chloride
and calculate the percentage yield, which should be about 66
per cent of the theoretical based on the weight of alcohol used.
Normal butyl chloride boils at 78° and has the specific gravity
0.907 at 0°.
NOTE.—It has been shown recently that alkyl chlorides can be prepared
from alcohols and hydrochloric acid in the presence of water, provided zinc
chloride is present. The metallic chloride probably acts as a catalytic agent
and not as a dehydrating agent, as has been assumed in the past. During
the reaction a part of the alcohol is converted into polymerization-products

which are removed with difficulty from the chloride by distillation. These
products are destroyed by hot concentrated sulphuric acid.
136. Preparation and Properties of Chloroform (SECTION 264).
(a) Place in a liter flask 150 grams of fresh bleaching powder and
400 cc. of water. Shake vigorously in order to break up the
lumps of bleaching powder, and connect the flask with a reflux
condenser. Through the condenser add, drop by drop, from a
separatory funnel a mixture of 12 grams of acetone and 50 cc. of
water. Arrange the flask for distillation with steam (see §28,
page 19) and distil as long as the chloroform comes over. Wash
the chloroform by decantation twice with water, separate, and
place it in a small dry distilling flask with anhydrous calcium
chloride. When the liquid is quite clear and no drops of water
are visible, distil from a water-bath, using a condenser. Weigh
the product, determine its specific gravity (§56, page 37), and cal-
culate the percentage yield obtained.
Chloroform boils at 61° and has the specific gravity 1.498 at
15°. The yield should be about 20 grams.
(b) Odor and solubility of chloroform.—Note the odor of chloro-
form and determine whether it is soluble in water, ether, alcohol,
benzene, petroleum ether, and concentrated sulphuric acid.
(c) Chloroform as a solvent.—Determine if the following sub-
stances are soluble in chloroform: iodine, butter, vaseline, olive
oil, a bit of black rubber tubing. In the latter case, let the
liquid stay in contact with the rubber for some time; then pour
off the liquid onto a watch-glass, and let it evaporate.
(d) Inflammability of chloroform.—Try to ignite some chloro-
form. Light a match and pour on the flame the vapor from
some chloroform which has been heated to boiling.
(e) Test for chlorine in chloroform.—Apply the test for halogen
with a copper wire (§60, page 41). Shake some chloroform with
a little water and test the aqueous solution with silver nitrate.
If silver chloride is formed wash the chloroform until the wash-
water no longer reacts with silver nitrate. Separate the chloro-
form with a pipette, dissolve it in alcohol and add an alcoholic
solution of silver nitrate.
Decomposition of chloroform in sunlight.—Place some chloro-
form which contains no free hydrochloric acid in a test-tube,
close the tube with a stopper, and allow it to stand several days in
a place where it will be in a strong light. Note the odor, shake
with water, and test the aqueous solution with silver nitrate.
(g) Chloroform and sodium hydroxide.—Heat a few drops of
chloroform for 1 minute with about 5 cc. of a very dilute solution
of sodium hydroxide free from chlorides. (Eq.) Test half of
the solution for chloride. Neutralize carefully the rest of the
solution with hydrochloric acid, add 5 drops of a dilute solution
of mercuric chloride and heat. (See note below and experiment
87d, page 65.)
(h) Carbylamine reaction (SECTION 206).—HOOD.—Warm
together 1 drop of aniline, which is a primary amine and has
the formula C 6 H 5 NH 2 , 1 drop of chloroform, and 1 cc. of an
alcoholic solution of potassium hydroxide. (Eq.) On account
of the very disagreeable odor produced, the test-tube should be
washed in the hood with concentrated hydrochloric acid.
(i) Oxidation of chloroform.—Heat together a few drops of
chloroform, a small crystal of potassium bichromate, and 2 cc.
of concentrated sulphuric acid. (Eq.) Cautiously note the
odor of the gas formed.
NOTE.—(a) The yield of chloroform is affected greatly by the quality of

the bleaching powder used. The acetone is added slowly as the reaction is a
vigorous one, and frothing is apt to occur if the flask becomes hot.
(g) The reaction between chloroform and sodium hydroxide is analogous
to that between the alkali and other halogen compounds. In this case the
three chlorine atoms are replaced by hydroxyl groups; the resulting com-
pound loses water and formic acid is produced:
CHCl3 + 3NaOH = CH(OH)3 + 3NaCl
HCOOH + NaOH = HCOONa + H2O.
137. Preparation of Ethylene Bromide (SECTION 32, 269).—

( a ) With phosphorus pentoxide as dehydrating agent.—Weigh
directly into a 200-cc. distilling flask 40 grams of phosphorus
pentoxide; close the side-arm of the flask with a stopper and
connect the flask with a reflux condenser (see Fig. 16, page 26).
Place the flask in cold water, and with constant shaking add
slowly through the condenser 30 grams of alcohol. Heat the flask

carefully with a free flame until the phosphorus pentoxide has
dissolved. Remove the condenser, place the flask on a wire
gauze at such a height that it can be heated with a burner,
close with a stopper, and connect with the absorption apparatus
which is arranged as follows: Fit three 8-inch test-tubes with
tightly fitting stoppers each containing two holes. The stoppers
should be covered with paraffin. This can be done by inserting
them into paraffin melted in an evaporating dish. As the appara-
tus must be tight it is advisable to use stoppers of rubber. Pre-
pare three tubes bent at a right angle of such a length that when
passed through the holes in the stoppers they will extend the
bottom of the test-tubes; also three shorter right-angle tubes
which just pass through the stopper. Put one long and one short
tube into each stopper, and connect the tubes in such a way that
a gas passing through the train when the test-tubes are in place,
will pass to the bottom of each test-tube through the long tube.
Put 10 cc. (30 grams) of bromine in each of two of the test-tubes,
and cover with a layer of water about 2 cm. high, which largely
prevents the volatilization of the bromine as the gas passes
through. The three test-tubes are now placed in beakers con-
taining cold water, and connected with the distilling-flask, the
empty tube which serves to condense any liquid which distils
over, being placed next to the flask. In order to prevent bromine
from getting into the air, connect a drying tube containing soda-
lime with the tube farthest removed from the distilling flask.
Test the apparatus to see if all joints are tight.
Heat the flask cautiously at first and then to such a temperature
that ethylene is given off freely. After the gas begins to come
off the apparatus needs little attention if it is so placed that the
flame is not in a draught; if this is the case, use a chimney so that
a steady heat may be obtained. Heat as long as ethylene is
formed; from one-half hour to an hour is usually sufficient. If
the bromine has not been used up when the ethylene ceases to be
evolved, remove the tubes containing ethylene bromide, and
under the hood transfer the liquids to a flask. Wash by decanta-
tion with a dilute solution of sodium hydroxide until the heavy oil
is colorless, and then once with water. Separate the bromide,
and dry it with calcium chloride. After standing an hour or
more, until the liquid is clear and no water is visible, filter through
a funnel, containing a bit of cotton wool, into a small distilling
flask. Distil, using a thermometer and water condenser, and
collect the fraction which boils at 130°-132°. Calculate the per-
centage yield both from the alcohol and bromine used.
Ethylene bromide melts at 8.4° and boils at 132°, and has the
specific gravity of 2.189 at 15°. The yield in this preparation
is about 55 grams.
(b) With sulphuric acid as dehydrating agent.—Mix cautiously
in a 1-liter, round-bottomed flask 90 cc. of alcohol and 135 cc.
of concentrated sulphuric acid; then add about 50 grams of
coarse sand and about 5 grams of aluminium sulphate. Place
the flask on a wire gauze and connect it by means of a tightly
fitting stopper, preferably one of rubber, with an absorbing train
of test-tubes like that described in (a) above. In this case use
four test-tubes which contain, respectively, beginning with the
one nearest the flask, 20 cc. of a dilute solution of sodium
hydroxide, 20 cc. of concentrated sulphuric acid, 10 cc. of bromine
covered with water, and 10 cc. of bromine covered with water.
Attach a drying tube containing soda-lime to the last tube.
Place all of the tubes in cold water. Make a test to determine if
all joints in the apparatus are tight.
Heat the flask at the lowest temperature at which ethylene is
freely evolved. It is very essential to avoid over-heating, which
results in frothing and the liberation of carbon. If this occurs,
the contents of the flask should be poured out and ethylene should
be prepared from a new mixture. When the bromine is decolor-
ized, treat the product as directed in (a) above.
The yield is about 55 grams.
NOTE.—Sand is added to the flask to distribute the heat more evenly and,
thus, to assist in preventing frothing. In the presence of aluminium sul-
phate, the decomposition of alcohol into ethylene takes place at about 140°,
whereas in the absence of the sulphate a temperature of about 180° is
required. At the lower temperature carbonization is not apt to occur.
ACYL CHLORIDES
138. Preparation of Acetyl Chloride (SECTION 274).—Connect

a 200-cc. dry distilling flask with a separatory funnel and a con-
denser; for use as a receiver, attach to the latter, by means of a
tightly fitting cork, a 200-cc. distilling flask or filter-bottle. Con-

nect to the side-arm of the receiver a drying tube containing cal-
cium chloride, which serves to protect the distillate from moisture.
As a large quantity of hydrochloric acid is set free during the
reaction between acetic acid and phosphorus trichloride, the dry-
ing tube should be fitted with a glass tube which reaches to just
above the surface of some water contained in a flask. When the
apparatus is arranged, place a water-bath containing cold water
in such a position that the bulb of the distilling flask is covered
with water. Put 50 grams of glacial acetic acid in the flask, and
run in slowly through the funnel 40 grams of phosphorus trichlo-
ride. The latter should be weighed and transferred to the funnel
in the hood. When the phosphorus trichloride has been added,
heat the water in the bath to 40°-50°, until the evolution of hydro-
chloric acid slackens and the liquid has separated into two layers;
then heat the water to boiling as long as any distillate comes over.
Redistil the distillate, using a thermometer, a condenser, and a
receiver protected from the air as directed above. Collect the
fraction which boils at 50°-55°. Weigh the product, and cal-
culate the theoretical yield and the percentage of this obtained.
Acetyl chloride boils at 51°. The experiment should yield
about 40 grams.
139. Properties of Acetyl Chloride (SECTION 275).—( a ) Acetyl
chloride and water.—Cautiously add about 0.5 cc. of acetyl chlor-
ide to 2 cc. of ice-water. Observe if two layers form, and then
shake carefully. (Eq.)
(b) Acetyl chloride and alcohol.—Cautiously add acetyl chlor-
ide, drop by drop, to 2 cc. of alcohol as long as reaction takes
place. Is hydrogen chloride given off? Pour the product into
5 cc. of water, shake and note the odor. (Eq.)
(c) Acetyl chloride and an amine.—Add to 5 drops of aniline,
C6H5NH2, acetyl chloride, drop by drop, until reaction ceases.
(Eq.) Add to the tube 10 cc. of water, heat to boiling, and filter
hot. Set the tube aside to cool.
CHAPTER XI
COMPOUNDS CONTAINING TWO UNLIKE SUBSTITUENTS
140. Preparation and Properties of Trichloroacetic Acid (SEC-

TION 290).—( a ) H O O D . — I n a 250-cc. flask place 25 grams of chloral
hydrate and add 15 cc. of fuming nitric acid (sp. gr. 1.5). Heat
the flask over a small flame until reaction begins; then remove the
flame. When the reaction has apparently ceased, heat gently
until the liquid becomes almost colorless. (Eq.) Transfer
the liquid to a small distilling flask and distil very slowly, using
an air-condenser. When the temperature reaches 150°, change
the receiver, using this time a small distilling flask, and collect
what comes over up to 200°. Redistil slowly and collect the frac-
tion boiling at 193°-195°. Weigh the product and calculate the
percentage yield.
Trichloroacetic acid melts at 55° and boils at 195°. The
amount obtained in this preparation should be about 10 to
12 grams.
(b) Dissolve in a test-tube about 1 gram of the acid in water,
and add 5 cc. of a dilute solution of sodium hydroxide. Attach
to the tube by means of a cork a piece of glass tubing about 3
feet long, clamp the tube over a wire gauze, and heat gently so
that the solution just boils. At the end of 5 minutes cool the
tube, examine the contents and note the odor. (Eq.)
141. Preparation and Properties of Lactic Acid (SECTION
298).—( a ) In a 750-cc. flask dissolve 50 grams of cane-sugar or
anhydrous glucose in 500 cc. of water; add 20 cc. of sour milk
and 20 grams of precipitated calcium carbonate. Set the flask
in a warm place (temperature about 40°) and allow the fermenta-
tion to proceed for one week. The flask should be taken at
least twice a day. At the end of the time add a small amount of
calcium carbonate, heat to boiling, filter, pour the solution into a
flat dish, and let it evaporate spontaneously. Filter off the solid
by suction, dissolve it in a small amount of boiling water, filter
110
TWO UNLIKE SUBSTITUENTS 111
if necessary, and set the solution aside to crystallize. Separate

the crystals as before and let them dry on a porous plate. The
yield is about 35 grams.
(b) Lactic acid and ferric chloride: test for an a-hydroxy acid.—
The solution of lactic acid required for this and the following
experiments can be made from lactic acid, or prepared from the
calcium lactate obtained in (a) above, as follows: Dissolve about
2 grams of the salt in 20 cc. of boiling water and add a dilute
solution of sulphuric acid, drop by drop, as long as a precipitate
is formed. If it is difficult to determine when the correct amount
of acid has been added, filter onto a watch-glass a few drops
of the solution and add to the filtrate a drop of sulphuric acid.
If an excess of sulphuric acid has been used, add to the original
solution a little of a solution of calcium lactate. When all the
calcium has been precipitated, warm the solution and filter. In
a small evaporating dish add to 5 cc. of the solution 1 drop of a
10 per cent aqueous solution of ferric chloride. Repeat the test,
using 5 cc. of water instead of the solution of the acid. Compare
the color in the two cases.
(c) Solubility of lactic acid.—Determine whether lactic acid
can be extracted from water by ether. Describe fully how you
made the test.
(d) Application of the iodoform reaction to lactic acid.—Deter-
mine whether lactic acid gives the iodoform reaction (experiment
81b, page 59).
NOTE.—(a) The sour milk used in the preparation contains the lactic
acid bacteria. The milk should be used before the curd has separated.
The latter is needed for the development of the bacteria during fermenta-
tion. Calcium carbonate is added to neutralize the lactic acid as it is
formed, since the fermentation stops if the acid accumulates. Toward the
end of the fermentation butyric acid is usually formed. The odor produced
is due to this cause. When the sugar has been fermented the calcium car-
bonate passes into solution. If there is a large residue at the end of a week
the milk was not satisfactory. The zinc salt of lactic acid is characteristic.
It can be prepared by digesting a strong solution of the acid with zinc car¬
bonate, filtering hot, and evaporating to crystallization.
142. Properties of Tartaric Acid and Tartrates (SECTIONS

310-314).—( a ) Behavior of tartaric acid and tartrates on heating.
Heat a little tartaric acid in a test-tube. Note the change in
appearance and the odor produced. What products are formed?

Repeat, using Rochelle salt.
(b) Tartaric acid and ferric chloride.—Apply the test for an
a-hydroxy acid as follows: Dissolve about 0.1 gram of tartaric
acid in 100 cc. of water. To 20 cc. of this solution add 1 drop of
a 10 per cent aqueous solution of ferric chloride. Compare the
color with that produced by adding 1 drop of ferric chloride to
20 cc. of water, and in a second tube to 20 cc. of water containing
1 drop of acetic acid. The depth of color can be more readily
observed by looking down the tubes placed on white paper.
(c) Potassium salts of tartaric acid.—Make a cold saturated
solution of tartaric acid by shaking an excess of the acid with
5 cc. of water. Decant off the liquid and acid, drop by drop, a
10 per cent solution of potassium hydroxide, until a crystalline
precipitate forms (Eq.); then add an excess of the solution of
potassium hydroxide. (Eq.)
(d) Calcium tartrate: test for tartrates.—Neutralize a solution
of tartaric acid or of cream of tartar with ammonia, and add
to the solution 1 cc. of a solution of calcium chloride. (Eq.)
If a precipitate of calcium tartrate does not appear, rub a glass
rod against the side of the tube under the surface of the liquid.
Filter off the precipitate, and pour 5 cc. of a solution of sodium
hydroxide through the filter into a clean test-tube. Heat the
filtrate to boiling. This behavior of tartaric acid is charac-
teristic, and is used in the identification of the acid and its
soluble salts.
(e) Reducing action of tartrates.—To a dilute solution of Rochelle
salt or sodium tartrate contained in a test-tube, which has been
cleaned by boiling in a solution of sodium hydroxide and washing
with water, add 1 cc. of a solution of silver nitrate. Dissolve the
precipitate by adding ammonia, drop by drop, avoiding excess,
and place the tube in hot water. Compare the results with those
obtained with formaldehyde (experiment 106d). Is the form-
ation of a silver mirror a positive test for an aldehyde?
(f) Fehling's solution.—Add to 1 cc. of a solution of copper
sulphate 5 cc. of a solution of sodium hydroxide (Eq.); then
add a solution of Rochelle salt or of sodium tartrate until the
precipitate dissolves. (Eq.) Repeat, using glycerine in place of
Rochelle salt. It is necessary to have a large excess of sodium
hydroxide. What organic compounds other than acids dissolve

copper hydroxide? Determine if Rochelle salt will dissolve the
hydroxides of iron and aluminium.
NOTES.—(b) This test for a-hydroxy acids must be made in the cold, as a
solution of ferric chloride alone develops a decided yellow tint on being
heated. In applying the test to an unknown substance a very dilute solu-
tion should be used, and the color developed should be compared with that
formed in a solution of equal concentration of an a-hydroxy acid (tartaric
acid). Many solutions of hydroxyl compounds when sufficiently concen-
trated give a yellow color with ferric chloride. The colors given by poly-
basic and ketonic acids are usually more intense or of a different shade from
those given by a-hydroxy acids.
(d) In making this test the calcium tartrate is usually filtered off before
solution in sodium hydroxide, since the carbonate that the alkali contains
produces a precipitate of calcium carbonate, which is insoluble. The
presence of ammonium salts should be avoided in making the test, as they
interfere with the precipitation of calcium tartrate.
143. Properties of Citric Acid and Citrates (SECTION 318).—

(a) Decomposition of citric acid by heat.—Heat a little citric acid
in a dry test-tube. Note the odor. What acids are present
among the products of decomposition when citric acid is heated?
(See SECTION 141.)
(b) Calcium citrate: test for citric acid.—Dissolve about 1 gram
of citric acid in about 50 cc. of water. Neutralize 5 cc. of the
solution with ammonia, avoiding an excess of the latter. If too
much has been added, add a little of the solution of the acid
until the reaction is neutral or slightly acidic. To the solution
of ammonium citrate add about 2 cc. of a 10 per cent solution
of calcium chloride. Is a precipitate formed? Compare the
behavior of tartrates. Heat the solution to boiling and set aside.
Examine in a few minutes. A precipitate of tricalcium citrate
is formed. Is the precipitate of tricalcium citrate crystalline?
Wash the salt by decantation three times with water, and deter-
mine its solubility in a solution of sodium hydroxide. Com-
pare the result with that obtained with tartrates. Preserve
the solution of citric acid for experiments (d) and (e) below.
(c) Presence of citric acid in lemon juice.—Test 5 cc. of lemon
juice or pineapple juice for citric acid as described above. Add
ammonia to the filtered juice but have it slightly acid when
making the test.
(d) Reducing power of citrates.—Neutralize 5 cc. of the solu-

tion of citric acid prepared in (b) above with sodium hydroxide,
add 1 cc. of a solution of silver nitrate, and then ammonia drop
by drop, until the precipitate is dissolved. Place the tube in
boiling water for two minutes. Is a mirror of silver formed?
(Compare with tartrates.) Heat the solution to boiling for two
minutes. Set aside and examine later.
(e) Reduction of ferric citrate by light.—Add to 5 cc. of a solution
of ferric chloride, until a clear green color is formed, a solution
of ammonium citrate, prepared by neutralizing a solution of
citric acid with ammonia. Moisten a piece of paper with the
solution, dry the paper in the dark in your desk and then expose
it to sunlight under a piece of thick paper in which a design has
been cut. At the end of 10 minutes place the paper in a dilute
solution of potassium ferricyanide. Write the formulas for all
the substances involved in the reactions, starting with ferric
chloride.
NOTE.—(b) In the presence of a large excess of sodium hydroxide, cal-
cium chloride gives a precipitate in the cold with solutions of alkali citrates.
Calcium citrate is soluble in acetic acid (calcium oxalate is insoluble).
144. Preparation of Acetoacetic Ester (SECTION 324).—( a )
The ethyl acetate to be used in this preparation must be dried
and distilled just before use. Place 250 cc. of ethyl acetate,
which should be neutral, in a 500-cc. flask, and add anhydrous
calcium chloride (about one-fourth of the volume of the ester).
Let the mixture stand over night or longer. Distil directly on
a water-bath from the calcium chloride, and collect the distillate
in a dry receiver which is protected from the moisture of the air.
Provide a reflux condenser for a 500-cc. flask, which has been
carefully dried, and set the flask in cold water. Add 200 grams
of the dried ethyl acetate and 20 grams of sodium in the form of
wire or very thin shavings (see §41, page 28). Connect the
condenser with the flask. When the evolution of hydrogen
ceases, heat the flask on a water-bath at such a temperature
that the contents boil gently. When all the sodium has dis-
solved, about 3 hours being required, cool the flask, and add
slowly a mixture of 1 part of concentrated hydrochloric acid and
4 parts of water, until the solution shows an acid reaction after
having been shaken thoroughly. Add an equal volume of a
saturated solution of sodium chloride, transfer to a separatory

funnel, and separate the ester as carefully as possible from water.
Shake the ester with a little anhydrous calcium chloride until it
becomes clear and no water can be seen, pour off from the drying
agent, and distil the liquid slowly from a flask provided with a
small Hempel tube (see Fig. 5, page 11). Discard the distillate
which boils up to 160°; collect the following fractions: 160°-175°,
175°-185°, 185°-200°. The fraction boiling at 175°-185° is
nearly pure acetoacetic ester. By redistilling the other fractions
a further quantity can be obtained, but as acetoacetic ester de-
composes slowly on boiling at atmospheric pressure, it is not
advisable to carry out an extended fractionation. If a better
yield is desired, the product of the reaction may be distilled under
diminished pressure.
Acetoacetic ester boils at 182° at 760 mm., 74° at 14 mm.,
and 88° at 29 mm. It has the specific gravity of 1.03 at 15°.
The yield in this preparation should be 35-40 grams.
(b) Compare the solubility of acetoacetic ester in water and
in a solution of sodium hydroxide. Explain.
(c) Dissolve a few drops of acetoacetic ester in 1 cc. of alcohol
and add a few drops of a solution of ferric chloride. What does
the result indicate?
145. Acetoacetic Ester Synthesis (SECTION 325).—(a) Prepara-
tion of ethylacetoacetic ester.—Into a 500-cc. flask place 60 cc. of
absolute alcohol. Weigh 4.6 grams of sodium and cut it into five
or six pieces. Hold the flask under running water and add one
piece of the metal. At the end of about a minute, when the vio-
lent reaction ceases, add the rest of the sodium and connect the
flask by means of a tightly fitting cork or rubber stopper with
a long reflux condenser through which a rapid stream of water
is passing. When the metal has dissolved add slowly through the
condenser 26 grams of acetoacetic ester, and then 24 grams of
ethyl bromide. Heat slowly to boiling on a water-bath until a
drop of the solution when mixed with a drop of water does not
show an alkaline reaction. Avoid too rapid heating at first, as
the reaction may become violent and ethyl bromide be lost.
The time required is about 2 hours. When the reaction is com-
plete, distil off the excess of alcohol on the water-bath, add 50
cc. of water to the residue, and shake until the salt has dissolved.
Separate the oil in a small separatory funnel, dry over calcium

chloride and distil. Collect the portion which boils at 192°-200°.
Calculate the percentage yield. Write equations for all the
reactions involved.
Ethylacetoacetic ester boils at 198°. The yield should be
about 22 grams.
(b) Hydrolysis.of ethylacetoacetic ester (SECTION 326).—Ketone
hydrolysis.—In a 500-cc. flask dissolve 10 grams of sodium hy-
droxide in 100 cc. of water, add 15 grams of ethylacetoacetic
ester, and connect with a reflux condenser. Place the flask in
a bath containing boiling water for 2 hours. Cool, place the
contents of the flask in a small separatory funnel, separate the
oil, and dry over calcium chloride. Pour off the oil from the
drying agent after a few hours and distil it. Collect what boils
at 198°-103°.
Methyl propyl ketone, the product of the reaction, boils at
102°, The yield obtained is about 60 per cent of the theoretical.
Acid hydrolysis.—In a small flask dissolve 5 grams of sodium
hydroxide in 15 cc. of water and add 5 grams of ethylacetoacetic
ester. Shake vigorously and connect the flask with a reflux
condenser. Place the flask in boiling water for 2 hours. At the
end of this time distil with steam (§28, page 19) until about
100 cc. of water have passed over. (What else passes over?)
Cool the flask through which steam has been passed, make the
contents acid to litmus with dilute sulphuric acid, and then add
about 50 cc. of the acid in excess to liberate the organic acids
formed in the hydrolysis. Distil again with steam into a clean
receiver until about 300 cc. of water have passed over. Note the
odor of this second distillate. Neutralize the latter with sodium
hydroxide and evaporate to dryness. The residue is a mixture of
sodium acetate and sodium butyrate. Put a little of the solid
on a watch-glass and add a few drops of concentrated sulphuric
acid. Note the odor. Add to this a few drops of alcohol, and
after warming gently note the odor.
The presence of butyric acid in this mixture can be shown in
another way as follows: Dissolve about 0.5 gram of the salt in
5 cc. of water. Acidify with dilute sulphuric acid, warm to
liberate any carbon dioxide present. Neutralize with ammonia,
and add a solution of calcium chloride. If a precipitate is formed,
it is calcium butyrate. Filter this off and heat the filtrate to

boiling. Since calcium butyrate is slightly less soluble in hot
water than in cold, the cold saturated solution deposits a pre-
cipitate when heated to boiling. Write equations for all reactions
involved in the experiment.
NOTE.—(a) If the solution of sodium acetoacetate and ethyl bromide
does not become neutral on boiling, it is evident that some of the latter has
been lost. This may result from too active boiling at first or there may have
been a leak in the stopper connecting the flask with the condenser. If
this occurs add more of the bromide and heat again.
146. Properties of Chloral (SECTIONS 329, 331).—( a ) Prepara-
tion from chloral hydrate.—Shake in a small test-tube about 3 grams
of chloral hydrate and 3 cc. of concentrated sulphuric acid. (Eq.)
Separate by means of a pipette the oil which floats on the sul-
phuric acid, and add it to one-half its volume of water. (Eq.)
(b) Test for the aldehyde group.—Determine whether chloral
hydrate forms a silver mirror with ammoniacal silver nitrate
(experiment 106d, page 84), and whether it produces a color
with Schiff's reagent.
(c) Decomposition of chloral hydrate by alkalies.—Dissolve
about 1 gram of chloral hydrate in water and add a solution of
sodium hydroxide. (Eq.) Test for chloroform.
CHAPTER XII
CARBOHYDRATES
147. Properties of Dextrose (SECTIONS 349-361).—( a ) Taste

and solubility of dextrose.—Taste equal amounts of dextrose
and cane-sugar. Determine whether dextrose is soluble in the
following liquids: water, alcohol, and ether.
(b) Presence of alcoholic hydroxyl groups in dextrose.—In a 100-
cc. bottle shake 10 cc. of a 10 per cent solution of dextrose with
2 cc. of benzoyl chloride and 25 cc. of a 10 per cent solution of
sodium hydroxide. Shake vigorously until the odor of the ben-
zoyl chloride disappears. Write the structural formula of the
compound formed.
(c) Dextrose and copper hydroxide.—Precipitate copper
hydroxide by adding 5 cc. of a solution of sodium hydroxide to
1 cc. of a solution of copper sulphate, and then add 5 cc. of a
strong solution of dextrose (about 20 per cent) and shake. It is
necessary to have a large excess of the alkali present. Compare
with experiment 142f, page 112. Heat the solution nearly to
boiling.
(d) Dextrose and alkalies.—Boil 10 cc. of a 10 per cent solution
of dextrose with 5 cc. of a solution of sodium hydroxide. Com-
pare the result with that obtained with aldehyde and sodium
hydroxide (experiment 108d, page 86).
(e) Dextrose and Schiff's reagent.—Determine whether dex-
trose produces a color with Schiff's reagent (experiment 108h,
page 86).
(f) Reducing action of dextrose: silver mirror.—Test a dilute
solution of glucose with an ammoniacal solution of silver nitrate
or with Tollen's reagent (experiment 106d, page 84).
(g) Reducing action of dextrose: Fehling's solution.—Test a
dilute solution of dextrose with Fehling's solution.
(h) Preparation of dextrosazone.—Dissolve 1 gram of dextrose
in 20 cc. of water and add 2 grams of phenylhydrazine hydro-
chloride, which should be colorless (see note), and 3 grams of
118
CARBOHYDRATES 119
hydrated sodium acetate. Heat the solution by placing the

flask in boiling water for 10 minutes. Cool under running water,
filter by suction, and wash the crystals with cold water. Redis-
solve the crystals in the smallest possible amount (about 20 cc.)
of boiling 50 per cent alcohol. Filter the hot solution, cool in
running water, filter off the crystals, and dry them on a porous
plate, and finally at 100°. Determine the melting-point of the
crystals in a bath, the temperature of which is rising rapidly, as
dextrosazone decomposes slowly when heated. The melting-
point of dextrosazone is 204°-205°.
NOTES.—(b) The insoluble compound formed is a pentabenzoate of

dextrose which is produced as the result of the replacement of the hydro-
gen atoms of the hydroxyl groups in dextrose by the benzoyl radical present
in benzoyl chloride, C6H5COCl. The test is an application of the Baumann-
Schotten reaction (see SECTION 547).
(c) Polyhydroxy alcohols and compounds related to them, such as the
sugars, dissolve the hydroxides of certain heavy metals, Compounds simi-
lar to that present in Fehling's solution (SECTION 311) are formed. The
sugars also form soluble compounds with calcium and barium hydroxides.
(e) Although many of the carbohydrates contain the aldehyde group,
they do not produce a color with Schiff's reagent.
(h) Phenylhydrazine and its salts decompose rapidly when exposed to
air and to light. Pure compounds must be used in the preparation of osa-
zones. The phenylhydrazine can be dissolved in an excess of acetic acid,
just before use, or the hydrochloride and sodium acetate may bo used. The
pure hydrochloride can be prepared as follows: Redistil the phenylhydra-
zine if it is colored. Dissolve the compound in 12 times its volume of
alcohol, and add pure concentrated hydrochloric acid as long as a precipi-
tate is formed. Filter off the precipitate by suction, and wash it with alco-
hol until it is colorless. Wash twice with ether. If the salt is not to be
used immediately, dry it in the air for half an hour, and then for 1 hour at
100°. Place the salt in a tightly stoppered bottle of brown glass.
MONOSACCHARIDES AND DlSACCHARIDES
148. General Reactions and Properties of the Sugars.—All

the experiments given in this section should be performed in
each case with samples of dextrose, levulose, maltose, lactose, and
sucrose.
( a ) Molisch reaction for carbohydrates (SECTION 386).—Place
a piece of the carbohydrate about the size of a mustard seed in
10 drops of water, and add 2 drops of a 10 per cent solution

of a-naphthol in chloroform. Allow 1 cc. of pure concentrated
sulphuric acid to flow, from a pipette, down the side of the
inclined tube so that two layers are formed. A pipette for this
purpose may be made by drawing out a piece of glass tubing to a
fine opening at one end. Observe what happens in a few seconds.
Shake and allow the mixture to stand 2 minutes; note the color,
Dilute with water, note the change, add an excess of ammonia,
and note the color.
(b) Solubility of sugars.—Determine whether the carbohy-
drates are soluble in water, in alcohol, and in ether. Dry test-
tubes should be used when the solubilities in alcohol and ether
are studied.
(c) Reduction of silver salts.—Determine whether dilute solu-
tions of the carbohydrates give a mirror with an ammoniacal
solution of silver nitrate or with Tollen's reagent. (See experi-
ments 106d, page 84, and 108g, page 86.)
(d) Reduction of Fehling's solutions.—Dissolve about 0.1 gram
of the carbohydrate in 5 cc. of water, and add 3 cc. of each of
the solutions which combined make Fehling's solution. (See
Appendix for the composition of this solution.) Heat to boiling.
(e) Fermentation of carbohydrates.—Fill fermentation-tubes
with 10 per cent solutions of the carbohydrates. Add to each 2
cc. of a mixture made by rubbing one-quarter of a yeast-cake
with 10 cc. of water. Label the tubes, and place them in a ther-
mostat at 30°-35° until the next exercise. Test the gas formed.
Which of the sugars are fermentated by common yeast?
(f) Formation of osazones.—Place in separate test-tubes 5 cc.
of 2 per cent aqueous solutions of the five carbohydrates; label
the tubes. Mix intimately 1.3 grams of colorless phenylhydra-
zine hydrochloride and 2 grams of crystallized sodium acetate.
Divide the mixture into 5 equal parts and put one of the parts
into each of the five tubes. Note the time, and place the tubes
in a beaker containing boiling water and heat for one-half hour.
Shake the tubes when the salts have dissolved in order to mix the
solution. Examine the tubes frequently and note the order in
which the precipitates first appear. At the end of one-half hour
place the tubes in a rack and see if any osazones crystallize out on
cooling slowly. Make a full record of the results of the experi-
CARBOHYDRATES 121
ment. Examine all the osazones under a high-power microscope,

and sketch the crystals.
(g) Summary of results.—Prepare a table in which are tabu-
lated the results of experiments a, b, c, d, e, and f above. State
how you could distinguish each one of the five sugars from the
others.
149. Properties of Sucrose (SECTIONS 366, 368).—( a ) Prepa-
ration of caramel.—Place about 2 grams of sucrose in a test-tube
and heat it for 15 minutes in an oil-bath at 210°. Taste the
product and determine if it is soluble in water.
(b) Sucrose and sulphuric acid.—Add to about 2 grams of
sugar 2 cc. of water and then 5 cc. of concentrated sulphuric
acid. If no marked change occurs heat gently. Repeat using
dextrose instead of sucrose.
(c) Sucrose and alkalies.—Heat 5 cc. of a solution (about 10
per cent) of sucrose with a solution of sodium hydroxide. Is the
solution highly colored? Compare with the results obtained
with dextrose. What conclusion can be drawn from the experi-
ment? What other tests lead to the same conclusion? (See
experiment 148c, d, f, page 120.)
(d) Formation of tricalcium saccharate.—Shake 10 cc. of a 20
per cent solution of sucrose with an excess of milk of lime, which
can be prepared by slaking a little quicklime and grinding the
calcium hydroxide with enough water to make a thin paste. Fil-
ter the solution and heat it to boiling. (Eq.)
(e) Inversion of sucrose.—Boil for 5 minutes a solution of
about 0.2 gram of sucrose in 10 cc. of water to which has been
added 1 cc. of dilute hydrochloric acid. Neutralize the solu-
tion with sodium hydroxide, and test for a reducing sugar with
Fehling's solution.
150. Isolation of Lactose from Milk (SECTION 371).—In a
beaker heat 200 cc. of milk to about 50°, and add a dilute
solution of acetic acid as long as a precipitate is formed (about
5 cc. of a 10 per cent solution of the acid). Stir until the casein
collects into a ball; remove this and neutralize the solution with
a dilute solution of sodium hydroxide. Make the solution
weakly acidic by adding 2 or 3 drops of very dilute acetic acid.
Heat the solution to boiling and add about 1 gram of precipi-
tated calcium carbonate. Stir thoroughly and filter hot. Evapo-
rate the solution to about 40 c c , cool, add 3 volumes of alcohol,

and filter. Set aside the solution in a shallow dish until the next
exercise. Filter off the crystals of lactose by suction and wash
them with alcohol. Dry the crystals in the air. Taste the sugar.
NOTE.—The procedure adopted in this experiment is designed to bring
about the precipitation of the proteins the milk contains. The solution is
heated with calcium carbonate before evaporation in order to neutralise
the free acid present, and thus largely prevent the hydrolysis of lactose
which takes place when the sugar is heated with water in the presence of
acids.
151. Oxidation of Lactose (see galactose, SECTIONS 359 and

319).—Heat 10 grams of lactose on the water-bath with about
four times its weight of concentrated nitric acid (28 cc.) until
the brown oxide of nitrogen is formed. Keep the mixture at
70°-80° until the evolution of gas ceases. Dilute the solution
with one-half its bulk of water and let it stand until cold. mucic
and oxalic acids crystallize out. Filter, save the filtrate, and
wash the crystals with warm alcohol to dissolve the oxalic acid,
and then twice with a small amount of cold water. Recrystallize
the residue, mucic acid, from a small amount of boiling water.
Neutralize the filtrate obtained above with solid potassium
carbonate, strongly acidify with glacial acetic acid, and let stand
until crystals of potassium hydrogen saccharate are formed.
Filter these off and recrystallize them from the smallest possible
amount of boiling water.
Dissolve a few crystals of mucic acid in a few drops of a solu-
tion of potassium hydroxide on a microscope slide. When the
solution has evaporated examine the crystals under the micro-
scope. The form of the crystals of potassium mucate is charac-
teristic. Describe their appearance.
When the ammonium salt of saccharic acid or of mucic acid is
heated, pyrrole is formed (SECTION 658). The latter imparts a
carmine-red coloration to a pine-wood shaving which has been
moistened with hydrochloric acid. Test the mucic acid obtained
in this way as follows: Mix 0.1 gram of the acid with 2 cc. of
ammonia and evaporate to dryness. Heat the residue strongly
in a test-tube; during the heating suspend in the tube a soft
pine splinter which has been soaked in concentrated hydrochloric
acid for a minute or two.
CARBOHYDRATES 123
POLYSACCHARIDES
152. Properties of Starches (SECTIONS 375, 376).—( a ) The

form of starch grains.-—Examine under the microscope and sketch
the following starches: potato, arrowroot, corn, rice, and wheat.
(b) Application of the Molisch test for carbohydrates.—Test a bit
of starch, filter-paper, and gum arabic as described in experiment
148a, page 119.
(c) Colloidal solutions: dialysis.—Select a piece of parchment-
paper, about 10 inches square, which contains no small holes.
Wet the paper thoroughly and form it into a bag of about 100 cc.
capacity; insert the neck of a small funnel into the mouth of the
bag and fix it in place by tying a string around it. Fill the bag
with water, dry it carefully on the outside, and hang it up for
a few minutes. If the bag leaks it must be discarded and a new
one made.
Prepare a starch solution as follows: Grind about 2 grams of
starch with 10 cc. of cold water, pour the mixture into 300 cc. of
boiling water, and set aside to cool. Pour the water out of the
parchment bag and fill it half full with the starch solution. Take
care not to spill any of the solution on the outside of the bag.
Suspend the bag in a beaker containing about 100 cc. of water.
The beaker should be of such a size that the water in it and that
in the solution in the bags are at approximately the same level.
Set aside until the next exercise and test the water outside the
bag for starch according to experiment (f) below.
Prepare a second bag and carry out a similar experiment, using
a 10 per cent solution of glucose. In this case test the water
outside the bag for glucose by Fehling's solution. Explain
dialysis and state why, by means of it, it is possible to separate
the polysaccharides from the sugars.
(d) Starch and Fehling's solution.—Wash about 2 grams of
starch by decantation twice. Shake up the residue with a little
water, and pour it into 200 cc. of boiling water. Test about 1 cc.
of this solution with Fehling's solution.
(e) Starch and alkalies.—Warm 5 cc. of the solution prepared
in (c) with 5 cc. of a solution of sodium hydroxide. Compare
the results with those obtained in the case of a monose (experi-
ment 147d, page 118).
(f) Starch and iodine.—Add to 5 cc. of the solution of starch

1 drop of a solution of iodine in potassium iodide. Heat the
solution to boiling, and then cool.
Shake up a little starch with cold water, filter and add a few
drops of iodine solution to the filtrate.
Test solutions of dextrose, sucrose, lactose, and dextrin with
a very dilute solution of iodine (light straw-yellow in color).
(g) Hydrolysis of starch: with an acid.—Boil in an Erlenmeyer
flask about 150 cc. of the starch solution prepared in (c) above
with 10 cc. of concentrated hydrochloric acid. Every 5 min-
utes pour out about 2 cc. of the solution, cool, and test with a
very dilute iodine solution. Describe the colors produced as
the hydrolysis progresses. When iodine produces no color in the
solution, neutralize about 5 cc. of it and test with Fehling's
solution.
(h) Hydrolysis of starch: with saliva.—A free flow of saliva is
easily obtained by chewing some insoluble substance such as
paraffin. Collect about 40 cc. in this way. Filter the saliva
through a wet filter. Test a portion of the saliva by allowing a
piece of red and of blue litmus paper to stay in contact with it
for 5 minutes.
Prepare 600 cc. of starch paste, using 25 grams of arrowroot
starch. (Do this in the usual way, by rubbing the starch with
a little cold water and pouring the suspension into boiling
water. Boil for 2 or 3 minutes.) Save one-third of the paste
for subsequent experiments. When the paste has cooled to 40°,
mix two-thirds of it with 25 cc. of the filtered saliva and watch
carefully for changes in consistency and opalescence of the mix-
ture. At 2-minute intervals remove a few drops to a porcelain
plate, and test with a very dilute iodine solution. Record the
time required for the solution to clear and to reach the point
where it no longer produces a color with iodine. Compare your
figures with those of your neighbors. Are the salivas equally
active?
Evaporate the solution in a casserole to about 100 cc. on the
steam-bath. (If this point is not reached at the end of the
exercise, leave the labeled casserole on the steam-bath in the care
of the instructor.) Filter out the small precipitate of car-
bonate and cellulose. Pour the solution into 3 volumes of
CARBOHYDRATES 125
alcohol to precipitate dextrins. Is the amount large? Filter.

Evaporate the alcohol and water on the steam-bath to a volume
of about 50 cc. What is the consistency of the residue? Try
the reducing power and make an osazone. What is the final
product of salivary digestion?
163. Conditions Influencing Salivary Digestion.—For the
following experiments dilute the filtered saliva with 5 volumes
of water and dilute the starch paste with an equal volume of
water.
( a ) Temperature.—In each of four test-tubes put 5 cc. of
starch paste. Keep two tubes at room temperature, chill the
third in ice-water, and warm the fourth in a 40° water-bath.
When the tubes have reached the temperature indicated, add
to the second, third, and fourth in quick succession 1 cc. each of
diluted saliva, and to the first 1 cc. of boiled, diluted saliva.
Maintain the tubes at their respective temperatures. Note the
time required for each to clear. Apply the iodine test at once
and at intervals of 5 minutes. After half an hour put the first
and third tubes in the 40° bath and continue the observations.
Compare the effect of high and low temperature on the enzyme.
(b) Acid and alkali.—Neutralize to litmus 5 cc. of filtered
saliva, using 0.4 per cent hydrochloric acid, and dilute with
5 volumes of water. Prepare a series of eight tubes containing
5 cc. each of hydrochloric acid of various percentage strengths:
0.2, 0.1, 0.05, 0.025, etc. To obtain these dilutions, measure
10 cc. of 0.2 per cent acid in a graduate, pour half into the first
tube, fill the graduate to the 10-cc. mark with water, mix, pour
half into the second tube, and so on. To each tube add 5 cc. of
starch paste, mix thoroughly, and add to each in quick succes-
sion 1 cc. of the neutralized saliva. Apply the same tests of
digestion as were used in previous experiments. What concen-
tration of acid is inhibitory? Compare your results with those
of your neighbors. Test each tube with litmus, and with congo
paper.
Plan and carry out a similar experiment to determine the effect
of alkali on ptyalin. Use 1 per cent sodium carbonate for the
highest concentration of alkali.
(c) Condition of starch.—Test the digestibility of raw starch,
Continue the experiment, using a little toluene for antiseptic.
till the following exercise. What do you infer as to the desira-

bility of cooking starchy foods thoroughly?
(d) Specificity.—Try the action of saliva on cane-sugar and
Irish moss. What criterion of digestion will you use?
154. Preparation and Properties of Dextrin (SECTION 377).—
Heat about 5 grams of starch for one-half hour at 220°-225° in an
oil-bath or air-bath. Pour the product into a mortar, add 2 cc. of
water, and notice the adhesive quality of the mixture. Add
25 cc. of water and grind with a pestle. If there is a residue of
starch which has not been converted into dextrin, filter through a
folded filter. Use 2 cc. of the solution to determine whether
the product reduces Fehling's solution. Test 2 cc. of the solu-
tion with a drop of iodine solution and note the color.
Add to the rest of the solution three times its volume of alcohol.
Filter off the precipitated dextrin and wash twice with alcohol.
Dissolve a little of the precipitate and test its reducing power with
Fehling's solution. Determine the color produced by iodine
solution. How does the color compare with that obtained dur-
ing the intermediate stages of the hydrolysis of starch by acid
(experiment 152g, page 124).
155. Properties of Cellulose (SECTIONS 380-382).—( a ) Solu-
bility in Schweitzer's reagent.—This reagent is a saturated solu-
tion of copper hydroxide in a concentrated solution of ammonium
hydroxide. It can be prepared as follows: Dissolve 5 grams of
copper sulphate in about 100 cc. of water, and add a solution of
sodium hydroxide as long as a precipitate is formed. Wash the
precipitate three times by decantation with 500 cc. of water,
and then filter through cotton; wash until the wash water is free
from sulphates. Press out as much water as possible from the
precipitate. Add to 10 cc. of concentrated ammonia (sp. gr. 0.90)
the copper hydroxide as long as it dissolves. Add pieces of filter
paper to the reagent as long as they dissolve, and filter through
glass wool. Pour the solution into dilute hydrochloric acid.
(b) Preparation of parchment-paper.—Pour slowly with stirring
50 cc. of concentrated sulphuric acid into 30 cc. of water. Cool
the solution to 15° to 20° and immerse in it strips of dry filter-
paper. At the end of 15 to 20 seconds remove the paper, and
wash it rapidly in running water; immerse the paper in a dilute
solution of ammonia, and wash again with water. Test the
CARBOHYDRATES 127
toughness of the paper and of a piece of wet filter-paper. Put

drop of a dilute solution of iodine in potassium iodide on the
paper. Hang up a piece of the paper to dry and examine it at
the next exercise.
(c) Hydrolysis of cellulose.—Grind in a mortar a pinch of cot-
ton-wool or a filter-paper with a few drops of concentrated sul-
phuric acid until a sticky mass is obtained; add 50 cc. of water
cautiously, and boil the resulting solution for 15 minutes. Neu-
tralize the solution with sodium hydroxide, and test for a reducing
sugar with Fehling's solution.
(d) Preparation of cellulose acetate (SECTION 381).—In a small
flask place 20 cc. of glacial acetic acid, 3 cc. of acetic anhy-
dride, 4 drops of pure concentrated sulphuric acid, and 0.5 gram
of cotton-wool. Press the cotton into the solution, and after a
few minutes stir it so that most of the air bubbles are removed.
Close the flask with a cork and let it stand over night or longer.
(Eq.) Pour the solution in a thin stream, and with stirring,
into 500 cc. of water. Filter, using a large funnel. Wrap
the cellulose acetate in a piece of cotton cloth (a towel), and
squeeze out as much water as possible; then set it aside until
dry. Put about one-half the dry product in a small beaker
or test-tube and add 10 cc. of chloroform. After standing some
time the acetate should pass into solution. Pour the solution
onto a watch-glass and let it evaporate slowly. When the
chloroform has evaporated, put some water into the watch-glass
and allow it to stand for a minute or two. Lift the edge of the
film and remove it slowly from the glass. Dry the film and
reserve it for a future test. Test the solubility of the rest of the
acetate in glacial acetic acid, in alcohol, and in ether.
(e) Preparation of cellulose nitrate.—Pour 10 cc. of concen-
trated sulphuric acid into 10 cc. of concentrated nitric acid. To
the hot mixture add 0.5 gram of cotton-wool. At the end of
3 minutes withdraw the nitrated cotton, and remove most of the
acid adhering to it by pressing it with a glass rod against the side
of the beaker. Put the cotton into a large amount of cold water.
Wash for a minute in running water. squeezing out the water
from time to time, and set aside to dry spontaneously. Hold a
small bit of the dry nitrate with tongs, and place it in a flame.
Test the solubility of a small amount of the product in alcohol.
Repeat using ether. In a test-tube cover some of the nitrate with

a mixture made of equal volumes of alcohol and ether. At the
end of a few minutes pour off the liquid onto a glass plate or
watch-glass and let the solution evaporate slowly. Remove the
film as in (d) above and dry. Place the edge of the film in a flame
and as soon as it begins to burn remove it. Note the rate at
which the film burns. Repeat using the film made from cellulose
acetate. Do you observe any difference?
156. Properties of Pentosans (SECTIONS 365, 382, 656).—
( a ) Tests for lignin.—Dissolve a few drops of aniline in a few
drops of dilute hydrochloric acid, and dilute with 5 cc. of water.
Pour one-half of the solution onto a piece of paper made from
wood-pulp (newspaper) and one-half onto a paper made from
linen. Repeat the tests using a solution of phloroglucinol in
dilute hydrochloric acid.
(b) Hydrolysis of pentosans.—Boil a little gum arabic or wheat
bran with 10 cc. dilute hydrochloric acid, and hold over the
tube a piece of paper which has been dipped into a dilute solu-
tion of aniline in acetic acid.
CHAPTER XIII
COMPOUNDS CONTAINING SULPHUR
157. Formation of Mercaptan (SECTION 391).—HOOD.—Warm

together about 1 gram of potassium ethyl sulphate, 1 gram of
sodium sulphide, and 2 cc. of water. (Eq.) Note the odor.
158. Preparation of Potassium and Mercuric Thiocyanates
(SECTION 401).—CAUTION.—Potassium cyanide is poisonous and
should not be handled with the fingers. Boil together 13 grams
of potassium cyanide, 6 grams of flowers of sulphur and 50 cc.
of water, until the sulphur has dissolved. (Eq.) Filter the
solution and evaporate to crystallization (§9, page 6). Cool,
filter off the crystals, dry them, and evaporate the mother-liquor
again to crystallization. Collect the crystals as before. Weigh
the product obtained.
Dissolve a few of the crystals in water, and add the solution
to a solution of ferric chloride.
Add a saturated solution of potassium thiocyanate to a satu-
rated solution of mercuric chloride; filter off the precipitate,
and press it into cones about 0.5 inch high and set aside to dry.
Apply a lighted match to the top of a dried cone.
159. Formation of Potassium Xanthate (SECTION 402).—
Make a saturated solution of potassium hydroxide in alcohol by
warming an excess of the alkali with 15 cc. of alcohol. Cool
the solution, decant off the clear liquid, and add 3 cc. of carbon
disulphide. (Eq.) Allow the solution to cool. Filter off the
crystals, wash them with a mixture of 5 cc. of alcohol and 5
cc. of ether and dry them. Dissolve a little of the compound
in water, and add a few drops of a solution of copper sulphate.
The brownish-black precipitate of cupric xanthate changes
immediately to yellow cuprous xanthate.
CHAPTER XIV
URIC ACID AND RELATED COMPOUNDS
160. Isolation of Uric Acid from Urine (SECTION 410).—Add

50 cc. of concentrated hydrochloric acid to 500 cc. of urine and
set aside in a cool place for 24 hours. Pour off the liquid from
the crystals of uric acid which adhere to the side of the vessel.
Collect the crystals, dissolve them in the smallest possible amount
of boiling water, boil with a little bone-black, and filter the solu-
tion hot. On cooling, colorless crystals of uric acid are obtained.
Examine them under the microscope and sketch the crystals.
161. Properties of Uric Acid (SECTION 410).—( a ) Solubility of
uric acid and its salts.—Shake up about 0.01 gram of uric acid
with about 5 cc. of water. Does the acid dissolve? Add a
dilute solution of sodium hydroxide, drop by drop, and shake.
When all the acid has dissolved add a slight excess of dilute
hydrochloric acid, heat to boiling, filter and set aside.
(b) To a dilute solution of uric acid in sodium hydroxide add
a little ammonia, some magnesia mixture, and ammoniacal silver
nitrate. The gelatinous precipitate formed is silver magnesium
urate. The insolubility of this salt is utilized in the separation
of uric acid from urine. The purine bases in urine give similar
insoluble salts.
(c) Reduction of silver nitrate by uric acid.—Dissolve a trace of
uric acid in a few drops of a solution of sodium carbonate, and
pour the solution upon a piece of paper moistened with silver
nitrate solution. The silver salt is reduced to metallic silver.
This reaction is known as Schiff's test for uric acid.
(d) Murexide test for uric acid.—On a small watch-glass moisten
a few crystals of uric acid with 2 or 3 drops of dilute nitric acid.
Evaporate to dryness on the steam-bath. Cool and add from
a glass rod a drop of ammonia. A similar color test is given by
other purines.
Repeat the test using bromine-water instead of nitric acid.
130
URIC ACID AND RELATED COMPOUNDS 131
162. Isolation of Caffeine from Tea (SECTION 418).—Boil

gently 10 grams of tea with 500 cc. of water for 15 minutes.
Filter through a folded filter, and precipitate the tannin by
adding) drop by drop, to the hot filtrate a 10 per cent solution
of lead acetate. When a precipitate is no longer formed, filter
the solution again, and evaporate it to about 75 cc. If a precipi-
tate has separated during the evaporation, filter again. Cool
the solution, and extract it with 30 cc. of chloroform. Separate
the chloroform and filter it through a dry paper. Set the solution
aside to evaporate spontaneously. Observe the appearance of
the crystals. Apply the murexide test to a few of the crystals.
Use in one experiment nitric acid, and in another bromine-water.
(See experiment 161d above.) Sublime the rest in watch-glasses.
(See §35, page 24.) Taste a little of the sublimed caffeine.
CHAPTER XV
AROMATIC HYDROCARBONS
163. Preparation of Benzene from Benzoic Acid (SECTION

427).—In a 6-inch evaporating dish place 10 grams of sodium
hydroxide and 25 cc. of water. Heat over a free flame and stir
until the sodium hydroxide dissolves; then stir in gradually 12
grams of benzoic acid. Evaporate to dryness over a free flame,
which is kept constantly in motion; this will take about 10
minutes. Grind the mixture of sodium benzoate and sodium
hydroxide in a mortar, and transfer it to an 8-inch test-tube.
Clamp the test-tube in an inclined position so that the mouth
of the tube is slightly lower than the other end; this will prevent
any water given off during the heating from running back into
the tube and cracking it. Connect the tube with a condenser
and receiver, and heat with a free flame kept constantly moving,
until no more liquid distils over. Measure the volume of the
benzene and calculate the number of grams and the percentage
yield obtained. Separate the benzene from the water, dry it
with calcium chloride, and distil, noting the temperature.
Benzene melts at 5.4°, boils at 80.4°, and has the specific
gravity 0.8736 (20°/4°). The yield should be about 6 grams.
NOTE.—By converting the benzoic acid into sodium benzoate in the pres-
ence of an excess of sodium hydroxide, an intimate mixture of the two sub-
stances is obtained. In this condition the compounds enter into reaction
more readily and at a lower temperature than does a mixture of the acid
and soda-lime; such mixtures are commonly used in the preparation of
hydrocarbons from acids.
The benzene prepared in this way contains a small amount of diphenyl,
which may be isolated from the residue left after the distillation of the hydro-
carbon. The residue on crystallization from alcohol yields crystals of di-
phenyl, which after two sublimations melt at 71°.
164. Properties of Benzene (SECTION 430).—( a ) Test for
thiophene in commercial benzene (SECTION 653).—To a few drops
of sulphuric acid add a crystal of isatin, about 5 cc. of crude
benzene, and shake.
132
AROMATIC HYDROCARBONS 133
Test for carbon disulphide in benzene.—Add to about 10 cc.

of crude benzene 2 drops of phenylhydrazine and set aside for
some time. If carbon disulphide is present, a crystalline pre-
-----ate of the formula (C 6 H 5 NH.NH 2 ) 2 .CS 2 will separate. If
crude benzene is not available add 1 drop of carbon disulphide
to 10 cc. of benzene, and test this mixture.
(c) Melting-point of benzene (SECTION 7).—Place about 50 cc.
of benzene in a flask, insert a thermometer so that the bulb is
covered, and place in a freezing mixture of ice and salt. When
the benzene has become solid, remove the flask, and allow the
mixture to melt partly. Note the temperature when about
one-fourth of the benzene is liquid. Pour off the liquid, melt
the benzene, and place the flask again in the freezing mixture,
and let it stay until the benzene is solid. Remove the flask and
determine the melting-point as before. Repeat until the melting-
point remains constant. Pure benzene melts at 5.4°.
(d) Inflammability of benzene.—Burn a few drops of benzene
in an evaporating dish. Is much soot formed?
(e) Benzene and sulphuric acid.—Shake 2 cc. of benzene with
about 5 cc. of pure concentrated sulphuric acid. Is the hydro-
carbon soluble? If the benzene is pure it will not markedly
color the acid.
Shake together about 2 cc. of benzene and 5 cc. of fuming
sulphuric acid (sp. gr. 1.89 at 20°) as long as heat is developed.
D o e s the hydrocarbon dissolve? (Eq.) Pour the mixture
slowly into a test-tube two-thirds full of ice. Does any insoluble
substance separate?
In order to compare the behavior of aromatic hydrocarbons
with that of the paraffins, repeat the above experiment using
petroleum ether or gasoline in place of benzene.
(f) Benzene and nitric acid.—CAUTION.—As the reaction may
become violent the mouth of the tube should be held away from
the experimenter. Repeat experiment (e) above with both ben-
zene and petroleum ether or gasoline, using fuming nitric acid
(sp. gr. 1.48) in place of fuming sulphuric acid. When this test
is applied to unknown substances, very small quantities should
be used at first, since fuming nitric acid reacts with certain sub-
stances with explosive violence.
(g) Test for a double bond in benzene.—Apply the test with a

solution of potassium permanganate. (See experiment 71e, page
51.)
(h) Benzene and bromine.—Add to about 10 cc. of benzene
1 cc. of a solution of bromine in carbon tetrachloride. Divide
the solution into two parts; place one in direct sunlight and the
other in the dark in your desk. Observe the two tubes after a
few minutes. Compare the results with those obtained with
gasoline (experiment 74c, page 52) and with amylene (experi-
ment 74a, page 52).
H O O D . — M i x 5 cc. of benzene with 2 cc. of bromine. Add a
small tack or clean piece of iron filings to the mixture. From
time to time shake the mixture and breathe across the mouth of
the tube. (Eq.) Let the mixture stand under the hood until
the next exercise and then pour it into water. Is the liquid
heavier than water? Explain.
NOTES.—(d) When aromatic compounds burn they produce a large

amount of soot. Soot is also formed when unsaturated compounds and
paraffin derivatives which contain alkyl radicals with four or more carbon
atoms are burned. The simpler paraffin derivatives do not produce soot
on burning. The behavior of an unknown substance on ignition is fre-
quently determined as a preliminary test in its identification. The test is
best made by putting some of the liquid or solid on a small roll of copper
gauze, to which a piece of wire is attached to serve as a handle.
(e and f) The determination of the behavior of substances with sulphuric
acid and with nitric acid is a valuable aid in their identification. Aromatic
compounds yield, in general, soluble sulphonic acids with fuming sulphuric
acid, and insoluble or difficultly soluble nitro-compounds with fuming
nitric acid.
(g) The unsaturation of benzene and other aromatic hydrocarbons is of
quite a different kind from that of ethylene. Aromatic hydrocarbons do not
readily react with potassium permanganate in the cold.
165. Preparation of Ethylbenzene: Fittig Synthesis (SEC-

TION 424).—( a ) In a round-bottomed one-half liter flask, which
is placed in a vessel containing cold water, put 200 cc. of ether
dried over sodium (see experiment 95b, page 73) and 27 grams
of sodium in the form of a wire or thin shavings. Connect the
flask by means of a tightly fitting stopper with a reflux condenser
through which water is passing. In order to guard against any
water entering the flask, wrap the stopper and the neck of the
flask with a towel. CAUTION.—Read §41, page 28, carefully.

When hydrogen is no longer evolved, add through the condenser
a mixture of 60 grams of bromobenzene and 60 grams of ethyl
bromide. At the end of about an hour turn off the water from
the condenser, and let the reaction proceed for at least over night.
Connect the flask with a condenser and receiver, and distil off
the ether on a water-bath. Distil the residue directly with a
large smoky flame, which is kept constantly in motion, as long
as any liquid passes over. Fractionate (see §23, page 13) the
product twice, and keep the fraction boiling at 133°-137°.
Calculate the percentage yield obtained from the bromobenzene
used. Add about 50 cc. of alcohol to the flask containing the
excess of sodium, and let the mixture stand at least one-half hour.
Ethylbenzene boils at 135°, and has the specific gravity 0.883
at 0°. The yield in the preparation should be 25 to 28 grams.
(b) Ethylbenzene may be considered as a substitution-product
of ethane and of benzene. Determine whether the hydrocarbon
shows the characteristic properties of a paraffin or an aromatic
hydrocarbon. State in your notes what tests were applied and
the results in each case.
NOTE.—(a) In the preparation of hydrocarbons by the Fittig synthesis

the halides used are often diluted with ether in order to moderate the reac-
tion; the volume of ether used ordinarily is twice that of the halogen com-
pounds. Benzene and petroleum ether are also used as diluents, especially
in the ease of very active substances, when it is desired to have the reaction
take place very slowly. When reaction takes place sluggishly, the mixture
without diluents can be heated on a water-bath or in an oil-bath. The
reaction between halides and sodium is catalyzed by a few drops of ethyl
acetate or methyl cyanide.
The rates at which the halides react with sodium are different, and, conse-
quently, an excess of the more reactive halide is used when a hydrocarbon
containing two radicals is prepared. In the preparation of ethylbenzene
the quantity of ethyl bromide required theoretically for 60 grams of bromo-
benzene is 41 grams; it has been found that a better yield is obtained if 60
grams of ethyl bromide are used. An excess of sodium is also used, as the
metal becomes coated with sodium bromide, and thus is prevented from fur-
ther action. The amount of sodium equivalent to 60 grams of bromo-
benzene and 60 grams of ethyl bromide is 21.5 grams; 27 grams of the metal
are used.
If all the substances used have not been carefully dried, the hydrogen
formed as the result of the reaction between sodium and water reduces
a part of the halides to hydrocarbons.
In the preparation of hydrocarbons containing two different radicals, the

product obtained is usually a mixture; in addition to ethylbenzene, some
diphenyl and butane are formed in the preparation described above.
166. Preparation of Diphenylmethane (SECTION 435).—As a

large amount of hydrochloric acid is formed in the preparation
the apparatus should be set up under a hood. In a 500-cc. flask
provided with a reflux condenser, place 120 grams of benzene
and an aluminium-mercury couple which is prepared as follows:
Cut up 2 grams of aluminium foil into strips about 1 inch by
0.5 inch and allow them to stay in a solution of mercuric chloride,
made by dissolving 1 gram of the salt in 200 cc. of water, for
8 to 10 minutes; a film of mercury is deposited on the aluminium.
Wash the couple thoroughly with water, then with alcohol, ether,
and finally with benzene. Into the upper end of the condenser
place a separatory funnel containing 60 grams of benzyl chloride;
allow the chloride to drop very slowly into the flask. At the end
of an hour heat the flask on a water-bath for about 15 minutes.
Pour the contents of the flask into an equal volume of water,
which contains a little sodium hydroxide, shake, separate the
benzene solution, and extract the aqueous layer once with a
little benzene. Combine the benzene solutions, and dry them
with calcium chloride. Pour off the solution into a distilling
flask, and distil, using a condenser, until the temperature of the
vapor reaches 150°. Remove the condenser, attach a short air
condenser, distil, and collect the fraction which boils at 250°-300°.
Redistil and collect the portion boiling at 255°-265°. Record
the weight obtained, and calculate the percentage yield from
the benzyl chloride. The yield should be about 35 grams.
Diphenylmethane melts at 26° and boils at 262°.
NOTE.—In the preparation of certain compounds by condensation as the

result of the elimination of chlorine and hydrogen, an aluminium-mercury
couple gives better results than aluminium chloride. It is probable that a
little aluminium chloride is first formed by the action of the metal on the
organic halogen compound; the presence of mercury makes the aluminium
more active.
167. Oxidation of Diphenylmethane to Benzophenone ( S E C -

TIONS 435, 487, 572).—In the identification of organic substances
they are frequently oxidized and the products isolated. The
following procedure is an example of one commonly used. Dis-

solve 5 grams of diphenylmethane in 10 cc. of glacial acetic acid
and add a solution of crystalline chromic anhydride prepared by
dissolving 4.5 grams of the anhydride in 5 cc. of water, and
adding 30 cc. of glacial acetic acid. Let the mixture stand for
half an hour, and then warm for an hour on the steam-bath.
Pour the product into 100 cc. of water, filter off the oil through
a moist filter paper, dissolve it in 20 cc. of hot alcohol, and add
cold water until the solution clouds. Set aside to crystallize.
If an oil separates, rub it against the side of the beaker with
a glass rod. A form of benzophenone which crystallizes with
difficulty, is produced as the result of the oxidation of diphenyl-
methane. If a sample of benzophenone is available a trace can
be used to seed the oil if it does not crystallize when rubbed
sharply against the beaker. Determine the melting-point of the
crystals. Benzophenone melts at 48°.
NOTE.—In oxidizing compounds with chromic anhydride, a slight excess

is used over that required for the oxidation. Two molecules of the anhy-
dride furnish three atoms of oxygen. If the compound which is insoluble in
water is to be oxidized, acetic acid is often used as a solvent. As chromic
anhydride is difficultly soluble in glacial acetic acid, it is first dissolved in a
little water and acetic acid added to the solution. Oxidation takes place
more readily in the presence of a small amount of sulphuric acid, which is
often used as a catalytic agent.
168. Formation of Hexaphenylethane (SECTION 439).—In a

test-tube put about 20 cc. of ethyl acetate or ether, 1 gram of
triphenylchloromethane and 5 grams of finely granulated zinc.
Close the tube with a tightly fitting cork, and shake frequently
during 10 minutes. Dissolve a little iodine in ethyl acetate.
Filter off the solution from the zinc rapidly through a fluted
filler-paper into two test-tubes; to one add the iodine solution
drop by drop. (Eq.) Shake the other solution in contact with
air, (Eq.) set the tube aside, and examine it in a few minutes.
169. Properties of Naphthalene (SECTIONS 446-448).—( a )
Solubility of naphthalene.—Test the solubility of naphthalene in
hot and in cold water, alcohol, and ether.
(b) Naphthalene and bromine.—Add bromine, drop by drop,
to a few crystals of naphthalene. Compare the ease of substitu-
tion in the case of this hydrocarbon with that of benzene.
(c) Compound of naphthalene and picric acid.—CAUTION.—

Picric acid stains the hands; it should be handled carefully.
Dissolve 0.1 gram of the hydrocarbon and 0.2 gram of picric acid
in 5 cc. of boiling alcohol. Allow the solution to cool spontane-
ously, and collect the yellow needles on a filter by suction (see
§42, page 29) and wash them three times with cold alcohol, using
1 cc. of alcohol each time. Dry the crystals on a porous tile for
half an hour in the air, and then determine their melting-point.
The compound of naphthalene and picric acid has the formula
C 1 0 H 8 .C 6 H 2 (NO 2 ) 3 OH; it melts at 150.5°.
NOTE.—(b) Naphthalene and bromine react readily without the presence

of a halogen carrier. The reaction can be used to prepare anhydrous hydro-
gen bromide.
(c) Picric acid, which is trinitrophenol, forms crystalline addition-prod-
ucts with a number of organic compounds; these are frequently made as an
aid in the identification of certain hydrocarbons. (See anthracene, SECTION
449.)
CHAPTER XVI
NITRO COMPOUNDS AND SULPHONIC ACIDS
170. Preparation of Nitrobenzene (SECTIONS 460, 462).—To

80 cc. of concentrated sulphuric acid, contained in a one-half
liter flask, add 70 cc. of concentrated nitric acid cautiously
with shaking. Keep the mixture cool by placing the flask in
cold water. To the cold mixture of acids add slowly and with
vigorous shaking 50 grams of benzene from a small flask in por-
tions of about 2 cc. The addition should take about one-half
hour. From time to time test the temperature of the mixture
which should be kept warm (40°-50°). If the temperature rises
above 50°, place the flask in cold water. When all the benzene
has been added, connect the flask with a reflux air-condenser and
place it in a water-bath the temperature of which is about 60°.
Shake the flask vigorously about every 5 minutes. At the end
of an hour cool the flask in running water, pour the contents into
a separatory funnel, and separate the upper layer of nitrobenzene
from the acids. Wash with about 100 cc. of water. As nitro-
benzene is heavier than water the lower layer is separated this
time and shaken vigorously with a dilute solution of sodium
hydroxide until the aqueous layer shows an alkaline reaction.
The nitrobenzene is finally washed again with water, tested for
free acid, which should not be present, separated, and warmed
on the steam-bath with about 10 grams of anhydrous calcium
chloride until the turbid liquid has become clear and no drops
of water are visible. Decant or filter the liquid into a distilling
flask, and distil using an air condenser. Reject the first part of
the distillate which contains benzene and is apt to be cloudy
due to the presence of a trace of water, and collect what distils
at 204°-208°. Calculate the percentage yield obtained from the
benzene.
Nitrobenzene boils at 207° (uncorrected), melts at 3°, and has
the specific gravity 1.204 at 20°/4°. The yield should be about
60-70 grams.
139
NOTE.—A low yield of nitrobenzene may be the result of one of the fol-
lowing causes: Either the nitration was effected at too low a temperature and
a quantity of benzene is recovered in the final distillation, or the tempera-
ture of the mixture reaches too high a point and a large amount of dinitro-
benzene is formed. In the latter case there will be an appreciable residue
in the flask when the temperature reaches 207° in the final distillation. This
result is apt to occur if the benzene is added too rapidly at first, and the mix-
ture of acid kept at too low a temperature; little nitration occurs, and when
the mixture is heated in the water-bath, the reaction takes place rapidly,
and the heat generated causes the temperature to rise above 60°, with the
result that dinitrobenzene is formed. The effect on the result of the tem-
perature at which nitration is carried out is marked, as can be seen by com-
paring with the above preparation that of dinitrobenzene described below.
It is necessary to wash the nitrobenzene free from nitric acid. If this is
not done, the acid which remains dissolved in the nitrobenzene will react
further with it when the product is distilled. Brown vapors of oxides of
nitrogen will be given off, dinitrobenzene will be formed, and an explosion
may occur. The residue of dinitrobenzene should not be distilled; it is apt
to decompose violently when the flask is nearly empty. It may be dissolved
out of the flask and crystallized from alcohol.
171. Properties of Nitrobenzene (SECTIONS 461, 469).—( a )
Solubility of nitrobenzene.—Describe the odor of nitrobenzene.
Determine whether nitrobenzene is soluble in alcohol, ether,
benzene, dilute hydrochloric acid, and a solution of sodium
hydroxide. Mix about 2 cc. of nitrobenzene with 5 cc. of con-
centrated sulphuric acid and pour the mixture into water. How
could you most readily separate into its constituents a mixture
of benzene and nitrobenzene?
(b) Reduction of nitrobenzene to aniline.—Place 2 cc. of nitro-
benzene and about 3 grams of granulated tin in an 8-inch test-
tube, and add with constant shaking, in portions of 1 cc., 5 cc.
of concentrated hydrochloric acid. The acid should be added
at such a rate that the tube becomes hot, but care should be
taken to avoid a violent reaction. Do not add the next portion
of acid until the solution begins to cool. Finally, boil the solu-
tion for about 3 minutes, shaking the tube constantly. Cool
under running water and add a strong solution of sodium hydrox-
ide (1:2) until the precipitate first formed has largely dissolved
(about 20 cc.). Remove with a pipette a few of the oily drops
which separate. Put 1 drop of the oil on a watch-glass and
place near it a drop of concentrated hydrochloric acid; bring
the drops together by touching them with a glass rod. (Eq.)
NITR0 COMPOUNDS AND SULPHONIC ACIDS 141
Aniline hydrochloride, C 6 H 5 NH 2 .HCl, is formed as a crystal-

line solid. Shake up a few drops of the aniline with 2 cc. of
water and add a few drops of bromine-water. Tribromoaniline,
Br 3 C 6 H 2 NH 2 , is precipitated.
(c) Reduction of nitrobenzene to phenylhydroxylamine (SECTION
506).—Dissolve 3 drops of nitrobenzene in 2 cc. of water and
2 cc. of alcohol, and add about 6 drops of a 10 per cent solution
of calcium chloride and a pinch of zinc dust. Heat to boiling
for one-half minute and filter. Add to the filtrate a strongly
ammoniacal solution of silver nitrate. The phenylhydroxyl-
amine, C 6 H 5 N H O H , formed as the result of the reaction reduces
the silver salt to metallic silver.
NOTES.—(a) Many nitro compounds are insoluble in sodium hydroxide
but impart a marked color to the solution of the alkali. Concentrated sul-
phuric acid is a valuable reagent to separate many nitro compounds from
substances which are insoluble in the acid. The change in appearance of
the nitrobenzene after solution and precipitation is due to the fact that when
a solution of an oil insoluble in water is poured into water, the oil separates
in minute globules which cause a milky appearance.
(b) The reduction of nitro compounds to amines, which are soluble in
dilute acids, is a reaction of importance in their identification. It should
be noticed, however, that substances other than nitro compounds can be
reduced to amines. Among these are hydroxylamines, and azo, hydrazo
and azoxy compounds (SECTIONS 509, 510). The test is, nevertheless, of
value in the identification of nitro compounds.
(c) Nitro compounds are reduced in neutral solution to hydroxylamine
derivatives; the reaction takes place more readily in the presence of a little
calcium chloride. The hydroxylamines reduce an ammoniacal solution of
silver nitrate. Nitroso, azo, and azoxy compounds behave in a similar
manner.
172. Preparation of m-Dinitrobenzene (SECTION 463).—To

5 grams of benzene contained in a 100-cc. flask, fitted with a
cork and a piece of glass tubing about 2 feet long to serve as a
reflux condenser, add slowly in small portions, shaking the flask
constantly, a cooled mixture of 18 cc. of concentrated nitric acid
and 30 cc. of concentrated sulphuric acid. The acid should be
added at first in portions of about 1 c c ; about 10 minutes are re-
quired for the addition of the mixture. After the main reaction
has ceased, remove the condenser and boil the mixture gently over
a free flame for 5 minutes. Cool the contents of the flask to
about 80° and pour the product slowly with stirring into about
1 42 EXPERIMENTAL ORGANIC CHEMISTRY
200 cc. of water. Filter by suction, and wash twice with water.
Dissolve the dinitrobenzene in 40 cc. of hot alcohol and set
aside to crystallize. Filter off the crystals by suction and wash
with 10 cc. of cold alcohol. Dry the crystals on a porous plate,
and determine their melting-point. By adding 10 cc. of water
to the filtrate a small additional amount of dinitrobenzene can
be obtained. Calculate the percentage yield.
m-Dinitrobenzene crystallizes in colorless, odorless needles,
which melt at 90°, and boil at 297°. It is readily soluble in hot
alcohol; it dissolves in about 28 parts of alcohol at 20°. The
yield in the preparation should be about 9 grams.
NOTE.—Small quantities of benzene and other hydrocarbons can be readily
identified by converting them into solid nitro derivatives the melting-points
of which can be determined. As little as 2 or 3 drops of benzene is sufficient
for the identification of the hydrocarbon in this way. In working with such
a small quantity proceed as follows: Mix 3 drops of benzene and 1 cc. each
of concentrated sulphuric acid and concentrated nitric acid. Boil the mix-
ture for one-half minute. Cool, and pour slowly into 10 cc. of water. Shake,
filter by suction (§42, page 29), and wash with water. Dissolve in a boiling
mixture of 4 cc. of water and 4 cc. of alcohol. Set aside to crystallize, filter,
wash with 5 cc. of cold 50 per cent alcohol, and dry on a porous plate. The
compound prepared in this way melts at 89°-89.5°.
SULPHONIC ACIDS
173. Preparation of Sodium Benzenesulphonate (SECTION

470).—In a 250-cc. flask place 50 grams of fuming sulphuric acid
which contains 8 to 10 per cent of sulphur trioxide (sp. gr. 1.90),
connect the flask with a reflux condenser, and add, drop by drop,
from a separatory funnel suspended in the condenser, 20 grams
of benzene. During the addition of the benzene, which should
take from 10 to 15 minutes, the flask should be shaken vigorously
every minute or two. If all the benzene does not dissolve after
continuous shaking for a few minutes, heat the mixture on a
water-bath until solution is complete.
The sulphonic acid formed can be separated in the form of a
salt by either of the methods described below. In the first
method ( a ), which in the case of benzenesulphonic acid is simpler,
advantage is taken of the fact that sodium benzenesulphonate
is insoluble in a solution of sodium chloride. The second method
(b) is the one commonly used to isolate sulphonic acids. It is
NITRO COMPOUNDS AND SULPHONIC ACIDS 143
based on the fact that the calcium salts of sulphonic acids are
soluble in water, whereas calcium sulphate is very difficultly
soluble. In certain cases it is advisable to prepare the barium
salts.
(a) Dissolve 65 grams of sodium chloride in 250 cc. of water,
and filter the solution if necessary. Measure off 200 cc. of the
solution, and reserve the rest for washing the crystals of sodium
benzenesulphonate. Pour into 200 cc. of the salt solution,
slowly and with stirring, the mixture of benzenesulphonic acid
and sulphuric acid. Filter off from the warm solution the di-
phenylsulphone, (C 6 H 5 ) 2 SO 2 , which separates, and cool the
filtrate in cold water, using ice if necessary. If crystals do not
separate, scratch the side of the vessel containing the solution
with a glass rod. Let the crystals stand with the mother-liquor
for about 15 minutes to insure the complete separation of the
salt. Filter by suction, and drain off as much of the liquid as
possible by pressing the solid down firmly with a spatula. Dis-
connect the filter-flask from the pump, and cover the salt with a
part of the sodium chloride solution which was reserved for this
purpose. When the liquid has penetrated into the solid, remove
it by the aid of the pump; repeat the washing with more of the
salt solution. Draw off as much of the liquid as possible, and
transfer the sodium benzenesulphonate to a porous plate to dry.
The compound prepared in this way contains about 0.5 per cent
of sodium chloride. Weigh the product and calculate the yield.
About 30 grams of sodium benzenesulphonate should be obtained.
(b) Pour the mixture of sulphuric acid and benzenesulphonic
acid into 500 cc. of water in a large evaporating dish, and heat
it to boiling. Add precipitated calcium carbonate, which has
been rubbed to a thick paste with water, until the solution no
longer shows an acid reaction. Filter through a cotton cloth
filter to separate most of the calcium sulphate, and wash the
precipitate with hot water. If a small amount of solid passes
through the filter the solution need not be refiltered, as the
precipitate will be removed in a later filtration. Evaporate the
solution to about one-half its volume, and add just enough of a
solution of potassium carbonate to precipitate the calcium and
convert the salt into potassium benzenesulphonate. If it is
difficult to determine when the calcium has just been precipitated,
filter off a few cubic centimeters of the solution from time to time,
and add to the filtrate a drop of the solution of potassium car-
bonate. An excess of potassium carbonate should be avoided,
for a sample of pure potassium benzenesulphonate is desired.
Filter off the calcium carbonate, wash it with a little hot water,
evaporate the solution to crystallization, and let it cool. Filter
off the crystals and dry them on a porous plate. The filtrate
on evaporation will yield a further quantity of the salt. Calcu-
late the percentage yield obtained.
Potassium benzenesulphonate crystallizes in lustrous plates,
which effloresce in the air. The salt is very soluble in water, and
melts above 300° with decomposition.
NOTE.—(b) The free sulphonic acid can be obtained from the calcium
salt by adding to its solution just enough sulphuric acid to precipitate the
calcium as sulphate, evaporating the solution to a small volume, and placing
it in a desiccator to evaporate over sulphuric acid. In the preparation of
free sulphonic acids in this way it is better to prepare the barium salt,
as barium sulphate is less soluble in water than calcium sulphate, and the
free acid is not contaminated with a small amount of sulphate.
174. Identification of a Sulphonic Acid by Conversion into

a Phenol (SECTION 477).—Melt about 1 gram of sodium hydroxide
in a small iron or porcelain crucible, and add to the fused mass
about 0.5 gram of sodium benzenesulphonate. Keep the mixture
just above its melting-point, and do not let it char. Stir occa-
sionally during 5 minutes. Cool, dissolve in water, acidify
with dilute hydrochloric acid, and note the odor produced.
Filter and add bromine water, drop by drop. Write equations
for all the reactions involved in the test.
175. Preparation of Benzenesulphonyl Chloride (SECTION
473).—Convert all of the salt of benzenesulphonic acid obtained
in experiment 173 above into benzenesulphonyl chloride as
follows: H O O D . Place the dry salt in a flask and add phos-
phorus pentachloride, which should be weighed in the hood, in
the proportion of 3 parts by weight of the salt to 4 parts by
weight of the chloride. Heat the mixture on the steam-bath,
with occasional shaking, for half an hour. Cool, and add to the
liquid about ten times its volume of ice-water. Shake about
every 10 minutes in order to facilitate the reaction of the phos-
phorus oxychloride present with water. At the end of an hour
NITRO COMPOUNDS AND SULPHONIC ACIDS 145
pour off the water and wash the oil twice with water by decanta-
tion. Separate the benzenesulphonyl chloride and calculate
The chloride can be used without further purification for the
experiments given below. If it is desired to preserve the chloride
for future use (see experiment 186, page 157), it should be taken
up in ether, dried over calcium chloride and distilled under
reduced pressure (§24, page 15) after the ether has been removed.
Benzenesulphonyl chloride is a colorless liquid which distils
at 246°-247° with decomposition, and undecomposed at 120°
under a pressure of 10 mm. It melts at 14.5°.
176. Preparation of Benzenesulphonamide (SECTION 474).—
Put into a test-tube about 1 cc. of benzenesulphonyl chloride
and add about 5 cc. of strong ammonia. Shake until a solid is
formed and the odor of the chloride has disappeared. Pour
off the liquid and wash twice with water by decantation. Add
about 20 cc. of water; heat to boiling until the substance has
dissolved. Filter, if necessary, and set the solution aside to
crystallize. When cold, filter by suction, wash with cold water,
and dry the amide for half an hour on a porous place. Deter-
mine the melting-point of the amide. If the crystals do not melt
sharply, recrystallize them from hot water.
Benzenesulphonamide crystallizes from hot water in needles,
which melt at 156°.
NOTE.—Sulphonamides are frequently made in the identification of sul-

phonic acids or their salts. The preparation can be carried out with small
quantities in a few minutes. Proceed as follows: Warm together in a test-
tube on a steam-bath about 0.5 gram of the salt with an equal volume of
phosphorus pentachloride, until the mixture liquefies. Cool, pour 5 cc. of
water into the tube, warm gently, and shake for about 1 minute. Pour off
the liquid and wash twice by decantation with 5 cc. of cold water. Add
6 cc. of ammonia and proceed as described in the experiment above.
177. Preparation of p-Toluenesulphonic Acid (SECTION 476).—

To 25 grams of toluene in a 200-cc. flask add 25 cc. of pure con-
centrated sulphuric acid, and place on the steam-bath. Allow
the mixture to stand until the toluene has dissolved. This will
require about 2 hours if the flask is shaken once in a while. Let
the solution cool; before it solidifies pour it, with stirring, into
100 cc, of pure concentrated hydrochloric acid. Heat the mix-
ture on the steam-bath until the solid dissolves. Set aside to

crystallize. Filter by suction, and wash the crystals with con-
centrated hydrochloric acid. Press the crystals to remove as
much of the mother-liquor as possible and dry them on a porous
plate. Weigh the toluenesulphonic acid and calculate the
percentage yield from the toluene used.
p-Toluenesulphonic acid crystallizes from water, in which it is
very soluble, in long colorless needles. It is less soluble in con-
centrated hydrochloric acid. It melts at 104°-105°. The yield
should be about 25 grams. The amide can be prepared by the
method described in experiment 176; it melts at 136°-137°.
CHAPTER XVII
HALOGEN DERIVATIVES OF AROMATIC HYDROCARBONS
178. Preparation of Bromobenzene (SECTION 481).—To 50

grams of benzene in a 200-cc. flask add 35 cc. (105 grams) of
bromine. Fit the flask with a cork stopper through which passes
a glass tube, bent twice at right angles. The longer arm of the
tube which passes through the cork should be about 2 feet long.
Place below the end of the shorter arm a flask containing 100 cc.
of water to absorb the hydrobromic acid formed in the reaction;
the end of the tube should be just above the surface of the water.
Put the flask containing the benzene and bromine in a pail or
large beaker containing ice-water, and add to the flask two
clean iron tacks or nails. Allow the reaction to proceed until the
next laboratory exercise. Wash the product with water, and
with a little sodium hydroxide if necessary, until any excess of
bromine has been removed. Place the liquid in a separatory
funnel, separate it, and dry it with anhydrous calcium chloride.
Fractionate three times, collecting the following fractions:
up to 120°, 120-150°, 150°-160°, 160°-200°. The fraction
boiling at 150°-160° is practically pure bromobenzene. Cal-
culate the molecular proportions in which the reacting substances
were used in the preparation and the percentage yield obtained.
Determine the specific gravity of the bromobenzene (§56, page 37).
The residue boiling above 200° contains p-dibromobenzene.
It may be poured while still hot onto a watch-glass, and crystal-
lized from alcohol. (See directions under the preparation of
dibromobenzene.)
Put the hydrobromic acid collected as a by-product in the
reaction into the bottle provided for hydrobromic acid residues.
This preparation yields a large amount of hydrobromic acid, as
one-half of the bromine used is converted into the acid. On
distillation the aqueous solution yields an acid than can be used
conveniently for the preparation of alkyl halides.
147
Bromobenzene boils at 156°, and has the specific gravity 1.491

at 20°. The yield in this experiment should be from 60 to 65
grams.
NOTE.—In order to obtain a good yield of bromobenzene, it is advisable to

keep the mixture of benzene and bromine cold during the reaction. The
product obtained consists of a mixture of benzene, bromobenzene, and
dibromobenzene. The effect of the temperature on the reaction is clearly
seen by comparing the method used in this preparation with that employed
to prepare dibromobenzene. See the experiment below.
179. Preparation of p-Dibromobenzene (SECTION 482).—HOOD.

To 5 grams of benzene in a small round-bottomed flask add
10 cc. of bromine. Close the flask with a cork through which
passes a piece of glass tubing about 3 feet long to serve as a reflux
condenser. Place the flask in the hood, drop into it a tack or
piece of clean iron filing, and allow the reaction to proceed
spontaneously to completion; this usually takes about 30 minutes.
Then heat the flask cautiously over a free flame for 2 minutes to
expel most of the excess of bromine. Add about 50 cc. of water
and heat to boiling, shaking vigorously. Cool until the dibromo-
benzene solidifies, and decant off the liquid. Repeat the wash-
ing with hot water twice, adding to the liquid the last time
about 50 cc. of a solution of sodium hydroxide. Cool and wash
the crystals once more with cold water, decant off the water,
add 75 cc. of alcohol and a little bone-black, and heat to boiling.
Filter the hot solution, and add 20 cc. of water. Set aside to
crystallize. Separate the crystals and determine their melting-
point. Calculate the percentage yield obtained.
p-Dibromobenzene crystallizes in colorless leaflets, which
melt at 89° and boil at 219°. The yield should be about 13 to
14 grams.
180. Properties of Aromatic Halogen Compounds (SECTION
4 7 9 ) . - ( a ) Solubility of halogen compounds.—Determine whether
bromobenzene is soluble in the following: Water, alcohol, ether,
concentrated sulphuric acid, dilute hydrochloric acid, and a
solution of sodium hydroxide.
(b) Inflammability of halogen compounds.—Wrap a strip of
copper gauze about 1 cm. wide around a piece of wire to serve
as handle, so that a roll a b o u t as thick as a lead pencil is formed.
HALOGEN DERIVATIVES 149
Pour a few drops of the liquid or place a few crystals on the gauze
and place it for an instant in a flame. Remove the gauze and
note whether soot is formed by holding the burning substance
in front of a piece of white paper. Determine whether the
following substances burn, and whether soot is produced:
Benzene, bromobenzene, dibromobenzene, benzyl chloride, ethyl
bromide, chloroform, carbon tetrachloride. What conclusions
can be drawn from the experiment? (See the note to experi-
ment 164d, page 134.)
(c) Comparison of the behavior of compounds containing the
halogen joined directly to the benzene ring with those containing the
halogen in a side-chain.—Read carefully SECTIONS 479, 480.
Compounds of the two classes behave differently with an alco-
holic solution of potassium hydroxide. In order that conclusive
results may be drawn from the test, it is necessary to have a solu-
tion of the alkali which is free from halogen. As all samples
of commercial potassium hydroxide contain potassium chloride,
prepare a solution by dissolving about 1 gram of the hydroxide
in 20 cc. of absolute alcohol; filter from the undissolved carbonate
and chloride and use the clear filtrate for the tests.1 Test a
part of the solution so prepared for a halide as follows: Dilute
with water, acidify with nitric acid, and add silver nitrate. Add
3 drops of benzyl chloride to 5 cc. of the alcoholic potassium
hydroxide solution, and boil gently for 2 minutes. Dilute with
water, acidify with pure dilute nitric acid, and add a few drops of
a solution of silver nitrate. Repeat the experiment, using
bromobenzene. In order not to confuse with silver bromide
the cloudiness produced when the bromobenzene is precipitated
from the alcoholic solution by the addition of water, add 3 drops
of bromobenzene to 5 cc. of alcohol and dilute with the amount
of water used in the test. Compare the appearance of the solu-
tion with the one which was heated. If the unchanged precipi-
tated organic halogen compound interferes with the observation
of the silver halide, it can be removed by shaking the solution
with ether, and adding the silver nitrate to the clear aqueous
solution.
1 A solution which can also be used for the test may be prepared by dis-
solving about 0.5 gram of clean sodium, free from any crust, in 20 cc. of alco-
hol and adding a few drops of water.
NOTE.—(c) In applying this test it is necessary to determine first whether

the compound contains any free halogen acid, which has been produced as
the result of decomposition on standing. Shake a little of the substance with
water, and test the aqueous solution with silver nitrate. If a precipitate is
formed, the halide must be washed with water until the latter gives no test
for halides.
181. Preparation and Properties of Triphenylchloromethane
(SECTION 488).—( a ) Attach to a 500-cc. flask b y means of a
stopper a small drying tube containing anhydrous calcium
chloride. Provide a beaker containing cold water into which
the flask can be sunk up to the neck and held in place by a wire.
Add to the flask 31 grams of carbon tetrachloride, 78 grams of
benzene, and 28 grams of anhydrous aluminium chloride in the
form of lumps.
Let the flask stand in the hood for at least 24 hours. In a
beaker place 100 grams of shaved ice or snow and add 100 cc. of
concentrated hydrochloric acid. Pour the mixture into the
flask, add 50 cc. of benzene, and shake the flask under running
water until two distinct layers are formed. Separate the upper
layer with the aid of a separatory funnel, and add to it about 5
grams of anhydrous calcium chloride. Shake the flask to bring
the drying agent in contact with any water present. In about
5 minutes filter the solution into a flask and distil on a boiling
water-bath as long as any liquid passes over. Pour the contents
of the flask into a beaker, add to the flask 100 cc. of petroleum
ether, and pour the latter into the beaker.
The next day filter off the crystals by suction. Disconnect the
flask from the pump, add 25 cc. of petroleum ether and in a few
minutes draw off the liquid adhering to the crystals. Repeat the
washing with another 25 cc. portion of petroleum ether. Spread
the crystals on a paper to dry and weigh them.
Triphenylchloromethane melts at 109°-111°. It can be crys-
tallized from boiling ligroin, in which it is readily soluble hot and
difficultly soluble cold. Since triphenylchloromethane is decom-
posed when heated with water, anhydrous solvents should be
used. The compound can be obtained in a very pure condition
by recrystallizing it from the boiling acetyl chloride. The yield
of the material obtained is 60 per cent of the theoretical. By
distilling off the solvent from the first crystallization, and adding
to the residue 50 cc. of petroleum ether, an additional quantity of
HALOGEN DERIVATIVES 1 51
triphenylchloromethane can be recovered which increases the

yield to 75 per cent.
NOTE.—If the dark red oil which separates at first in the reaction is decom-
posed at once by water, benzophenone chloride, (C6H5)2CCl2, is obtained.
This red oil, which is a molecular compound of benzophenone chloride and
aluminium chloride, reacts on standing with more benzene and is converted
into a substance of the composition (C6H5)2CCl.AlCl3, which is a crystalline
solid. Water decomposes this addition-product into its constituents.
(b) Reaction with water.—Powder about 0.1 gram of triphenyl-

chloromethane and shake it in a test-tube with water. Let the
mixture stand a few minutes and then test the aqueous solution
for hydrochloric acid with litmus paper and with silver nitrate.
(c) Reaction with sulphuric acid.—In a small beaker treat
about 2 grams of triphenylchloromethane with 5 cc. of concen-
trated sulphuric acid, and shake until solution is complete. Is
hydrogen chloride given off? Compare the results with those
obtained with ethyl bromide (experiment 132a, page 101). Pour
the solution into 50 cc. of water, filter off by suction the pre-
cipitate of triphenylcarbinol, wash with water, and dry it.
Add a small amount of the carbinol to a little concentrated sul-
phuric acid on a watch-glass. Grind thoroughly some of the
carbinol in a mortar with a little concentrated hydrochloric
acid for about 1 minute. Remove the product with a spatula
to a porous plate and let it dry. Add the compound to a little
concentrated sulphuric acid. Write equations for all reactions
which take place.
(d) Reaction with silver nitrate.—Dissolve a bit of triphenyl-
chloromethane in a little acetone and add an alcoholic solution
of silver nitrate. (Eq.)
(e) Reaction with metals.—Repeat experiment 168, page 137.
181a. Preparation of Triphenylmethane from Triphenylchloro-
methane.—When the addition-product of triphenylchloro-
methane and aluminium chloride is treated with ether, the
halogen atom in the former is replaced by hydrogen.
Attach to a 250-cc. flask, by means of a cork, a drying tube
containing anhydrous calcium chloride. Have ready a beaker
containing cold water into which the flask can be sunk up to the
neck and can be held in place by means of a wire. Add to the
flask 29 grams of carbon tetrachloride, 73 grams of benzene, and
25 grams of anhydrous aluminium chloride in the form of lumps.

Place the flask in the water and let it stand at least 24 hours.
Connect the flask with a return condenser, place it in water and
add through the condenser 30 grams of ether. Shake occasion-
ally and let the mixture stand at least 24 hours. Pour the
mixture onto 200 grams of ice and 5 cc. of concentrated hydro-
chloric acid. Add 100 cc. of carbon disulphide and shake until
two layers have formed. Separate and dry the oil with calcium
chloride. Filter into a flask and distil off the carbon disulphide.
Transfer the residue to a small flask and distil, using a short glass
tube as an air-condenser. Collect the fraction boiling between
330° and 356°. The distillate, which should weigh about 33
grams, is dissolved in 135 cc. of boiling alcohol. The solution is
stirred as it cools. When cold, filter off the triphenylmethane by
suction and wash twice with 10 cc. of cold alcohol. Weigh the
product after drying in the air, determine its melting-point, and
calculate the yield from the carbon tetrachloride used. The
yield should be about 60 per cent of the theoretical. Triphenyl-
methane melts at 92°.
CHAPTER XVIII
AROMATIC AMINES
182. Preparation of Aniline (SECTION 494).—Provide a 1-liter

flask with a cork and tubes arranged for distillation with steam
(§28, page 19); the tubes will be needed later in the prepara-
tion and should be ready for use. Place in the flask 25 grams of
nitrobenzene and 50 grams of granulated tin, and connect it with
a reflux air-condenser. Add to the mixture 125 cc. of concen-
trated hydrochloric acid in the following way: Add about 10 cc.
of the acid and shake vigorously. If reaction does not take
place in a minute or two, warm gently until there is an evolution
of hydrogen and the reaction produces sufficient heat to keep the
flask warm. When the reaction subsides, add another portion of
10 cc. of acid, and shake. Continue in this way until about
one-half the acid has been added. If the reaction becomes too
vigorous and there is chance of vapor escaping from the flask,
place the latter in cold water. Care must be taken not to keep
the flask so cold that the reaction does not proceed rapidly. The
last half of the acid may be added in portions of about 20 cc.
When all the acid has been added, heat the flask on a boiling
water-bath, shaking occasionally, until no drops of nitrobenzene
can be seen floating on the surface of the liquid. The odor of
nitrobenzene should also disappear. From 1/2 to 1 hour is
required to complete the reaction in this way. 1 Add to the
hot solution 50 cc. of water, place the flask in cold water, and
add a solution of 90 grams of sodium hydroxide in 150 cc. of
water until most of the precipitate first formed has dissolved and
the solution shows a strong alkaline reaction. The mixture
must not be cooled too strongly; it is necessary only to keep it
1 If the preparation can not be completed in one exercise it is well to stop
at this point; if the alkali to liberate the aniline is added, and the mixture
allowed to cool, it is necessary to heat the flask to boiling before the contents
are distilled with steam. The distillation requires about an hour.
153
from boiling in order to prevent loss of aniline. Distil with

steam. The aniline passes over at first as a colorless oil. As
the compound is somewhat soluble in water (about 1 part in 30),
the distillation should be continued after the drops cease to form;
change the receiver at this point and collect about 100 cc. of the
solution. Combine the two distillates and saturate the solution
with sodium chloride, using 20 grams of salt for each 100 cc. of
solution. Extract twice with ether using about 200 cc. each
time (§31, page 21). Separate the ether, place it in a bottle,
and add 3 or 4 sticks of potassium hydroxide. Stopper the
bottle and let the solution stand over night. Filter the solution
into a dry flask. The water extracted from the ethereal solution
forms with the potassium hydroxide a saturated solution of the
alkali; care should be taken not to allow this to get into the flask.
Distil off the ether on a water-bath (see §34, page 23). Trans-
fer the residue to a small dry flask, wash out the first flask with
a few cubic centimeters of the dry ether which has just been dis-
tilled off, and add the solution to the aniline. Distil over a free
flame using an air-condenser, heating cautiously until the small
amount of ether has come over, and collect the fraction boiling
at 180°-184°. Calculate the percentage yield obtained.
Aniline boils at 182° (183.7° corrected), and has the specific
gravity 1.024 at 16°. The yield should be from 85 to 90 per cent.
183. Properties of Aniline (SECTIONS 490, 494).—( a ) Solubility
of aniline.—Determine whether aniline is soluble in the following:
water, dilute sodium hydroxide, dilute hydrochloric acid, con-
centrated sulphuric acid, alcohol, and benzene.
(b) Salts of aniline.—Add 2 cc. of aniline to 5 cc. of water
and add 1 cc. of concentrated sulphuric acid. Heat to boiling
and set the solution aside to crystallize. (Eq.)
Heat together in a small beaker about 5 cc. of aniline, 5 cc. of
water, and 10 cc. of concentrated hydrochloric acid. When the
solution is cold, filter off the crystals by suction; do not wash
them with water in which they are very soluble. Dry the crystals
in a beaker on the steam-bath. The salt will be needed for the
following experiments.
(c) Double salts containing aniline.—Make a saturated solu-
tion of about 1 gram of aniline hydrochloride in a little water.
To one-half of the solution add a few drops of a solution of plati-
AROMATIC AMINES 155
num chloride, and to the other a few drops of saturated solution

of stannous chloride, and cool. (Eqs.)
(d) Base-forming property of aniline.—Make a saturated aque-
ous solution of aniline by shaking about 1 cc. of the amine with
16 cc. of water. Test the clear solution with litmus paper, and
add some of it to a solution of aluminium sulphate or chloride.
Compare the results with those obtained with methylamine
(experiment 113b, page 98). Explain.
(e) Hydrolysis of salts of aniline.—Dissolve a little aniline
hydrochloride in water and test the solution with litmus paper.
Is the result in accord with those obtained in (d) above? Explain.
(f) Reaction of salts of aniline with bases.—Add to a concen-
trated aqueous solution of aniline hydrochloride a solution of
sodium hydroxide. (Eq.)
(g) Aniline and acetyl chloride.-—Add acetyl chloride, drop
by drop, to 1 cc. of aniline as long as an evident reaction takes
place. Add about 15 cc. of water and heat to boiling, filter hot,
and cool in running water. (Eq.) Filter off the precipitate by
suction, wash twice with cold water, and dry the crystals on a
porous plate for half an hour. Determine the melting-point of
the crystals. Acetanilide melts at 112°. Amines are frequently
identified by converting them into acetyl derivatives.
(h) Aniline and bromine.—Add bromine-water, drop by drop,
to an aqueous solution of aniline until the solution becomes
yellow. Tribromoaniline, which is precipitated, crystallizes from
alcohol and melts at 116°.
(i) Aniline and nitrous acid.—Dissolve about 1 cc. of aniline
in 2 cc. of concentrated hydrochloric acid and 5 cc. of water.
Cool the solution in running water. Add a cold solution of about
0.5 gram of sodium nitrite in 5 cc. of water. Shake, and heat
gently. Observe that a gas is given off, and note the odor of
the solution. (Eq.)
(j) Aniline and ferric chloride.—Add to an aqueous solution of
aniline a few drops of a dilute solution of ferric chloride.
(k) Aniline and hypochlorites.—Add to a dilute aqueous solu-
tion of aniline a solution of bleaching powder or of sodium
hypochlorite.
(l) Aniline and potassium bichromate.—Mix on a watch-glass
a drop of aniline with 3 drops of concentrated sulphuric acid,
and add 2 drops of a solution of potassium bichromate. Note

the color, and heat on the steam-bath for a few minutes.
(m) Aniline and methyl iodide.—Mix together 3 cc. of aniline
and 2 cc. of methyl iodide, and let the mixture stand in a stop-
pered tube until the next exercise. (Eq.) Remove the crystals,
dry them on a porous plate, and then treat them with a strong
solution of sodium hydroxide. (Eq.) Note the odor. Is it like
that of aniline?
NOTES—(a) The solubility of many amines in dilute hydrochloric acid

serves to distinguish them from other nitrogen compounds. Amines which
contain a number of strongly negative groups are insoluble in the acid.
(g) Acetyl chloride is a useful reagent to distinguish primary and second-
ary amines from tertiary amines. Alcohols and phenols also react with
acetyl chloride.
(h) Many amines give a precipitate of an insoluble substitution-product
when treated with bromine water; certain phenols give a similar reaction.
184. Properties of Methylaniline (SECTIONS 491, 502).—( a )

Methylaniline and acetyl chloride.—Add acetyl chloride, drop
by drop, to about 1 cc. of methylaniline, add water, and heat to
boiling. Cool. (Eq.) The acetyl derivative formed melts at
102°.
(b) Methylaniline and nitrous acid.—Repeat experiment 183i,
page 155, using methylaniline in place of aniline. Is an oil
formed? Compare the results in the two experiments. (Eq.)
185. Properties of Dimethylaniline (SECTIONS 492, 504).—
(a) Dimethylaniline and acetyl chloride.—Repeat experiment
184a, page 156, and compare the results obtained when primary,
secondary, and tertiary amines are treated with acetyl chloride.
(b) Dimethylaniline and nitrous acid: nitroso-dimethylaniline.—
Dissolve 5 grams of dimethylaniline in a mixture of 10 cc. of
concentrated hydrochloric acid and 40 cc. of water. Cool the
mixture in ice-water, and add, slowly with stirring, a solution of
3 grams of sodium nitrite in 20 cc. of water. At the end of 15
minutes filter off the salt by suction, wash with dilute hydro-
chloric acid, and crystallize a little of it from warm (about 60°)
dilute hydrochloric acid. Shake up the rest with an excess of a
solution of sodium hydroxide. Dissolve a little of the precipi-
tate in ether, filter the solution, and let it evaporate. Boil some
of the free amine with sodium hydroxide, note the odor of the gas
AROMATIC AMINES 157
given off, and test it with moist litmus paper. Write equations
for all the reactions.
186. Use of Benzenesulphonyl Chloride in Distinguishing the
Three Types of Amines (SECTION 473).—Shake together for 2
or 3 minutes 0.5 cc. of aniline, 50 cc. of a strong aqueous solution
of sodium hydroxide (1 to 4) and 2 cc. of benzenesulphonyl
chloride. Warm gently until the odor of the chloride disappears.
Filter and add hydrochloric acid to the filtrate. (Eqs.)
Repeat the experiment using methylaniline and then dimethyl-
aniline. Test the solubility in dilute hydrochloric acid of the
substances separated in these two cases by filtration. Write
equations for all reactions, and state clearly how the reagent
serves to distinguish from one another the three classes of amines.
NOTE.—A few primary amines yield products with benzenesulphonyl

chloride which do not dissolve in a dilute solution of sodium hydroxide.
This is due to the fact that a difficultly soluble sodium salt is formed, which
is partially hydrolyzed. Such compounds are converted into sodium salts
by strong solutions of the base.
CHAPTER XIX
DIAZO COMPOUNDS
187. Preparation of Phenol from Aniline (SECTION 513).—

Prepare some iodo-starch paper for use as an indicator for nitrous
acid as follows: Grind about 1 gram of starch with a few cubic
centimeters of water and pour the mixture into 200 cc. of boiling
water. Cool the solution and dissolve in it a crystal of potassium
iodide. Insert pieces of filter-paper into the solution, and hang
them up to dry in a place free from acid vapors. The moist
paper can be used in the following preparation.
In a 500 cc. beaker pour 25 cc. of concentrated sulphuric acid
into 200 cc. of water, and add to the warm solution 20 grams of
aniline slowly and with vigorous stirring. Cool, and add 100
grams of ice. Dissolve 16 grams of sodium nitrite in 100 cc. of
water, and add the solution in small quantities, with stirring, to
the solution of aniline sulphate, until the amine has been diazo-
tized. This can be determined by testing the solution for nitrous
acid, which will be present when the nitrite has been added in
excess. The amount of nitrite which has been dissolved is a
slight excess over that required for the reaction. When the larger
portion of the nitrite has been added, stir vigorously, place a drop
of the solution on a piece of iodo-starch paper. If free nitrous
acid is present a blue spot will form. (Eq.) Continue the addi-
tion of nitrite until the solution, after thorough stirring and
standing 15 to 20 seconds, produces an immediate blue color with
the iodo-starch paper. Pour the solution of the diazonium salt
into a flask, and heat it at 40°-50° on a water-bath for half an hour.
Distil with steam (§28, page 19) and collect about 300 cc.of distil-
late. As long as any phenol distils over the distillate will give a
color with a solution of ferric chloride. Saturate the solution of
phenol with sodium chloride, and extract three times with ether,
using 100 cc. each time. Let the ether solution stand over night
with about one-fifth its volume of anhydrous sodium sulphate.
Filter the ether, and distil it off from a flask on a water-bath
158
DIAZO COMPOUNDS 159
(§34, page 23.) Wash the drying agent with some of the recov-
ered ether, and add this solution to the flask. Pour the residue
into a small flask, and distil using an air-condenser. Collect the
fraction boiling at 180°-183°. Calculate the percentage yield.
Phenol melts at 43°, boils at 183°; it is soluble in about 15 parts
of water at 16°. The yield in this preparation should be about
15 grams.
NOTE.—In the preparation of diazonium salts it is advisable to keep the

reaction-mixture cold during the addition of the nitrite solution, even in the
case when the resulting salt is to be decomposed by water; in this way the
formation of by-products is largely avoided.
A small amount of p-hydroxydiphenyl, C 6 H 5 . C 6 H 4 O H , is formed as the
result of the condensation of the diazonium salt with some of the phenol
formed in the reaction. The compound can be obtained by filtering the
hot solution from which the phenol has been distilled. On cooling, p-hy-
droxydiphenyl separates out in plates which melt at 164°.
188. Preparation of Iodobenzene from Aniline (SECTIONS 513,

483).—Mix together in a beaker 150 cc. of water, 12 cc. of con-
centrated sulphuric acid, and 10 grams of aniline. Cool the
solution, and add 100 grams of ice. Diazotize the solution by
adding a solution of 8 grams of sodium nitrite dissolved in 40 cc.
of water in the way described in the above experiment (prepara-
tion of phenol). Pour the solution of the diazonium salt into a
liter flask and add a solution of 22 grams of potassium iodide in
50 cc. of water. Place the flask in a water-bath heated to 70°-
80° until the evolution of nitrogen ceases. Make the solution
strongly alkaline by adding a solution of sodium hydroxide, and
distil with steam as long as an oil comes over. It is necessary
to have the end of the tube through which the steam enters the
flask pass to the bottom of the latter, so that the steam passes
through the heavy oil, and keeps it constantly in motion. Sepa-
rate the iodobenzene, and dry it with calcium chloride. Filter
it into a small flask and distil, using an air-condenser. Calculate
Iodobenzene boils at 188° (corrected). The yield should be
about 20 grams.
189. Preparation of p-Tolunitrile: Sandmeyer Reaction (SEC-
TION 513).—CAUTION.—In this preparation cuprous cyanide is
to be used. The compound is made from copper sulphate and
potassium cyanide. As the reaction involves the liberation of

cyanogen, a very poisonous gas, it should be carried out under
the hood with a good draught, and care should be taken not to
breathe any of the gas liberated. Care should be exercised also
in handling the potassium cyanide.
Dissolve 50 grams of copper sulphate in 200 cc. of hot water,
place the solution in a 2-liter flask on a water-bath heated to
boiling under the hood, and add in small portions a solution of
55 grams of potassium cyanide dissolved in 100 cc. of water.
Leave the solution heating on the water-bath, and prepare the
diazo compound as follows: Add 20 grams of p-toluidine to a
mixture of 45 cc. of concentrated hydrochloric acid and 100 cc.
of water, and stir. Place the vessel containing the solution in
cold water, add 100 grams of ice, and diazotize with a solution of
16 grams of sodium nitrite in 60 cc. of water, taking precaution
to avoid an excess of the nitrite solution. (See experiment 187
above.) HOOD.—Pour the diazo solution into the hot solution
of cuprous cyanide; add about 10 cc. at a time and shake vigor-
ously. Avoid running the solution down the side of the flask;
it should fall directly into the solution of the cyanide. This
precaution is taken to avoid as much as possible the formation of
cresol, CH 3 .C 6 H 4 .OH, as the result of the interaction of the
diazo compound with water. The addition of the diazo solution
should take about 15 minutes. Leave the flask on the water-
bath for about 15 minutes more, and when the evolution of nitro-
gen ceases, distil with steam under the hood. If the tolunitrile
solidifies in the condenser, turn off the water in the latter for a
short time; the steam will warm the water in the condenser, and
the nitrile will melt. Distil as long as an insoluble substance
comes over in appreciable amounts. If only a small amount of
cresol has been formed the nitrile will solidify in the receiver.
Separate the crystals and let them dry spontaneously on a
porous plate. As tolunitrile melts at 38°, the crystals should not
be put in a warm place. Weigh the crystals, and calculate the
percentage yield. Save the preparation for a future experiment.
If much cresol has been formed during the reaction the product
will not solidify. In this case, extract with a small amount of
ether, shake the ethereal solution with an equal volume of a solu-
tion of sodium hydroxide, and dry over calcium chloride. Pour
DIAZO COMPOUNDS 161
off the solution, distil off the ether, and distil, using an air-
condenser.
p-Tolunitrile melts at 38° and boils at 218°. The yield should
be about 13 grams.
190. Preparation of Diazoaminobenzene (SECTION 514).—Dis-
solve 10 grams of aniline in a mixture of 100 cc. of water and 20
cc. of concentrated hydrochloric acid. Add 100 grams of ice.
When the solution is cold add a solution of 8 grams of sodium
nitrite in 40 cc. of water. Dissolve 10 grams of aniline in a mix-
ture of 7 cc. of concentrated hydrochloric acid and 50 cc. of water,
and add 50 grams of ice. Pour the solutions of aniline hydro-
chloride slowly with stirring, into the solution of the diazo com-
pound. (Eq.) Dissolve 25 grams of hydrated sodium acetate in
50 cc. of water, and add the solution to the mixture. At the
end of half an hour, add about 300 cc. of water, stir, and filter
by suction; wash the precipitate with cold water. Press the
diazoaminobenzene on a porous plate, and let it stand until dry;
do not heat it. Weigh the product and calculate the percentage
yield.
Crystallize a little of the compound from petroleum ether as
follows: Digest for 2 or 3 minutes 2 grams of the diazoamino-
benzene with 100 cc. of petroleum ether, filter hot, evaporate to
about 50 c c , and set aside the solution to crystallize.
Diazoaminobenzene crystallizes in yellow plates, which melt
at 98°; it explodes when heated above its melting-point. It is
insoluble in water, and is soluble in benzene, ether, and alcohol.
The yield obtained in the above preparation is about 15 grams.
NOTE.—The sodium acetate is added to interact with the excess of hydro-

chloric acid present:
HCl + CH3COONa = NaCl + CH3COOH
The salt is frequently added to solutions containing strong acids when it
is desired to bring about a reaction which does not take place in the presence
of such acids.
191. Preparation of Aminoazobenzene (SECTION 515).—Mix

in a small beaker 10 grams of diazoaminobenzene, 20 grams of
aniline, and the aniline hydrochloride prepared as follows: Dis-
solve 5 cc. of aniline in 10 cc. of concentrated hydrochloric acid,
cool in running water, filter by suction, press on a porous plate.
Allow the salt to dry for about 5 minutes. Heat for 1 hour on
a water-bath the mixture so that the temperature of the latter is
between 50° and 60°; stir frequently. Dissolve the product in
50 cc. of glacial acetic acid, and pour the solution slowly into
400 cc. of water, stirring vigorously. After about 5 minutes
filter by suction, wash with water and set aside to dry.
Convert a part of the aminoazobenzene into the chloride as
follows: Dissolve 2 grams of the compound in 10 cc. of alcohol
and pour the solution into a boiling mixture of 20 cc. of concen-
trated hydrochloric acid and 200 cc. of water. Boil for 10 min-
utes and set aside to crystallize. Filter and wash the crystals
with water containing some hydrochloric acid.
Crystallize the rest of the aminoazobenzene as follows: Dis-
solve the substance in alcohol in the proportion of 1 gram of
aminoazobenzene to 10 cc. of alcohol. Heat to boiling and add
water until the solution begins to cloud; set aside to crystallize.
Filter off the crystals and wash them with a mixture of equal
volumes of alcohol and water.
Aminoazobenzene crystallizes in yellow prisms, melts at 127°,
and distils undecomposed above 360°. It crystallizes well from
hot water in which it is difficultly soluble.
192. Preparation and Properties of Phenylhydrazine (SECTION
517).—( a ) In a beaker pour slowly, with stirring, 20 grams of
aniline into 170 cc. of concentrated hydrochloric acid. Cool the
beaker to 0° in a freezing mixture of ice and salt, and add, drop
by drop, from a separatory funnel, a mixture of 20 grams of
sodium nitrite dissolved in 100 cc. of water, until a drop of the
solution when diluted with a few drops of water produces a blue
color with iodo-starch paper. (See experiment 187, page 158).
The mixture should be stirred during the addition of the sodium
nitrite. Dissolve 120 grams of hydrated stannous chloride in
100 cc. of water, cool the solution with ice-water, and pour it
slowly into the solution of the diazo compound. After an hour
filter off by suction the precipitate of phenylhydrazine hydro-
chloride, using a porcelain funnel or a filter-plate and hardened
filter-paper. Remove as much of the mother-liquor as possible
by pressing the crystals, and then transfer them to a flask and
add an excess of a solution of sodium hydroxide. Extract with
ether, dry over anhydrous potassium carbonate, and distil off
DIAZO COMPOUNDS 163
the ether. The resulting oil can be used for the following
experiments. If it is desired to keep the phenylhydrazine, it
should be distilled; as it decomposes slightly on distillation it
is better to distil it under diminished pressure (§24, page 15).
The compound can also be purified by freezing it and pouring
off the liquid which does not solidify.
Phenylhydrazine is nearly colorless when pure; it melts at
17.5°, boils at 242°, and has the specific gravity 1.097 at 23°.
The yield in this preparation should be about 10 grams.
(b) Conversion of phenylhydrazine into benzene.—Dissolve 35
grams of copper sulphate in 100 cc. of water in a 500 cc. flask
connected with a reflux condenser. Heat the solution to boiling,
remove the flame, and drop into the solution from a separatory
funnel suspended in the condenser 10 grams of phenylhydrazine
dissolved in 10 cc. of acetic acid and 50 cc. of water. As soon as
the phenylhydrazine has been added, arrange the condenser
for distillation, and distil as long as an oil comes over. Separate
the oil and shake it with anhydrous calcium chloride until no
drop of water can be seen, and the benzene is clear. Distil the
oil and note its boiling-point.
Benzene, the product of the reaction, boils at 80.4°. The
yield should be about 6 grams.
Add 2 drops of phenylhydrazine to Fehling's solution.
(c) Formation of a urea derivative from phenylhydrazine: phenyl-
semicarbazide.—Dissolve 1 cc. of phenylhydrazine in 1 cc. of
glacial acetic acid and 5 cc. of water, and add a solution of 0.5
gram of potassium cyanate dissolved in 2 cc. of water. Heat to
boiling, cool, and shake. Filter off the precipitate, wash with
cold water, and crystallize it from boiling water. Phenylsemi-
carbazide melts at 172°.
(d) Formation of a phenylhydrazone.—Dissolve 2 drops of
phenylhydrazine in 12 cc. of alcohol, and add 12 cc. of water.
Add to the solution 2 drops of benzaldehyde and boil for half a
minute. Cool, shake thoroughly, and filter by suction (§43,
page 30). Wash with 10 cc. of 50 per cent alcohol, and recrys-
tallize the precipitate from 25 cc. of boiling 50 per cent alcohol.
Cool, filter off the crystals, and wash them with 10 cc. of 50 per
cent alcohol. Dry the crystals, and determine their melting-
point.
Benzalphenylhydrazone is a white crystalline compound which

melts at 156°.
NOTES.—(b) The reaction between phenylhydrazine and copper sul-

phate takes place according to the following equation:
C6H5NH.NH2 + CuSO4 = C6H6 + N2 + Cu + H2SO4
(c) Phenylhydrazine is a derivative of ammonia, and its salts, therefore,
react in many cases like ammonium salts and the salts of amines. The
preparation of phenylsemicarbazide from phenylhydrazine salts is analogous
to the preparation of urea from ammonium salts; the equations for the two
reactions are similar. (See SECTION 223.)
NH4Cl + KCNO = NH4CNO + KCl
NH4CNO = NH2.CO.NH2
C6H5NH.NH2.HCl + KCNO = C6H5NH.NH3.CNO + KCl
C6H5NH.NH3CNO = C6H5NH.NH.CO.NH2
(d) Phenylhydrazine is a valuable reagent for identifying aldehydes.
The method of preparing the phenylhydrazones is illustrated by this experi-
ment.
CHAPTER XX
AROMATIC ALCOHOLS, PHENOLS, AND ETHERS
193. Preparation of Benzyl Alcohol from Benzaldehyde ( S E C -

TION 523).—Place in a 250-cc. bottle 20 grams of benzaldehyde
and a cold solution of 18 grams of potassium hydroxide in 12 cc.
of water. Close the bottle with a cork or a rubber stopper,
shake it vigorously until an emulsion is formed, and set aside
over night or longer. (Eq.) Add enough water to dissolve the
crystals of potassium benzoate formed, and extract the solution
three times with ether, using about 50 cc. each time. Save the
aqueous solution. Dry the ethereal solution with anhydrous
copper sulphate, distil off the ether (§34, page 23), and distil
the benzyl alcohol. Weigh the alcohol and calculate the per-
centage yield.
Benzyl alcohol boils at 206°. The yield in the preparation
should be about 7 grams.
Add an excess of hydrochloric acid to the filtered aqueous
solution of potassium benzoate, filter off the precipitate of benzoic
acid, and wash it with cold water. Crystallize the acid from
boiling water. Weigh the acid and calculate the percentage
yield.
Benzoic acid melts at 121.4°; it is soluble in 345 parts of water
at 20°, and in 17 parts at 100°.
194. Properties of Benzyl Alcohol (SECTION 523).—( a ) Benzyl
alcohol and hydrochloric acid.—Mix 2 cc. of benzyl alcohol and
4 cc. of concentrated hydrochloric acid. Heat the mixture slowly
and note any change produced. (Eq.) Observe the odor of the
substance formed.
(b) Oxidation of benzyl alcohol.—Mix together 1 cc. of concen-
trated nitric acid, 4 cc. of water, and 3 drops of benzyl alcohol.
Boil the mixture for about 2 minutes and note the odor from time
to time. The characteristic odor of benzaldehyde is first o b -
served, and then disappears as the aldehyde is oxidized further
to benzoic acid. Cool the solution in running water; if the oxi-
165
dation has progressed far enough benzoic acid will crystallize

out. (Eq.)
(c) Benzyl alcohol and acetyl chloride.—Add acetyl chloride,
drop by drop, to about 2 cc. of benzyl alcohol as long as evident
reaction takes place. Pour the product into cold water and
shake. (Eq.)
195. Preparation of Diphenylcarbinol from Benzophenone
(SECTION 524).—In a 500-cc. flask dissolve 15 grams of benzo-
phenone and 15 grams of potassium hydroxide in 150 cc. of
alcohol. Add 15 grams of zinc dust, connect the flask with a
reflux condenser and boil for 1 1/2 hours. (Eq.) Filter hot, add
water until the solution clouds, and set aside to crystallize.
Filter off the crystals by suction, and wash with dilute alcohol.
A second crop of crystals may be obtained from the filtrate.
Diphenylcarbinol melts at 67.5°-68°. The yield is nearly
theoretical.
Warm a few of the crystals with concentrated hydrochloric
acid. (Eq.)
196. Preparation of Diphenylethylcarbinol by the Grignard
Reaction (SECTION 426).—In a 200-cc. flask surrounded by cold
water and provided with a return condenser, place 5 grams of
magnesium powder, and add slowly through the condenser from
a separatory funnel a solution of 38 grams of ethyl iodide dis-
solved in 50 cc. of ether which has been dried over sodium. If
a reaction does not take place promptly, add a small crystal of
iodine. Toward the end of the reaction it may be necessary to
heat the flask by surrounding it with warm water. When the
magnesium has passed into solution add, drop by drop, through
the condenser, a solution of 10 grams of benzophenone in 10
grams of dry benzene. If the reaction ceases, place warm water
around the flask for a few minutes. Cool the reaction-mixture,
and pour it slowly into about 200 cc. of ice-water which contains
about 10 cc. of dilute sulphuric acid. Extract twice with ether,
using about 100 cc. each time. Shake the ether with a little
sodium hydroxide solution if it is colored by iodine. Filter the
ether solution, and distil off the ether; dissolve the residue in 50
cc. of hot petroleum ether and set the solution aside to crystal-
lize. Weigh the product and calculate the yield from the ben-
zophenone used.
AROMATIC ALCOHOLS, PHENOLS. AND ETHERS 167
Diphenylethylcarbinol melts at 95°. The yield should be from

10 to 12 grams.
PHENOLS
197. Properties of Phenol (SECTIONS 528, 529).—( a ) Solu-

bility of phenol.—-CAUTION.—Do not touch phenol; it causes pain-
ful blisters when brought into contact with the skin. Deter-
mine the solubility of phenol in the following: Water, a solution
of sodium hydroxide, and a solution of sodium carbonate. Use
about 1 gram of phenol in each case, and add the liquids in por-
tions of about 2 cc. until solution is complete; shake thoroughly
after each addition of the solvent.
(b) Acidity of phenol.—Test an aqueous solution of phenol
with litmus paper and with Congo paper. Test a dilute solution
of hydrochloric acid with the two indicators. Do you observe
a difference? A much higher concentration of hydrogen ions
is required to affect the coloring matter on the Congo paper than
to affect litmus. From the results obtained in experiment
( a ) above what conclusion can be drawn in regard to the relative
acidity of phenol and carbonic acid? Test a solution of picric
acid (trinitrophenol), acetic acid, benzoic acid, and salicylic acid,
with the two indicators.
(c) Phenol and acetyl chloride.—Add acetyl chloride, drop by
drop, as long as an evident reaction takes place, to about 0.5
gram of phenol. (Eq.) Pour the product into water and note
the odor.
(d) Phenol and ferric chloride.—Add a few drops of a dilute
aqueous solution of ferric chloride (1 part of the 10 per cent
reagent with 3 parts of water) to an aqueous solution of phenol.
(e) Identification of phenol by converting it into s-tribromophenol.
Dissolve about 0.1 gram of phenol in 5 cc. of water and add
an aqueous solution of bromine until a permanent yellow color
is formed. Filter off the precipitate and wash it with a solution of
sulphur dioxide or of acid sodium sulphite until there is a strong
odor of sulphur dioxide. Wash with water. Dissolve the com-
pound in 10 cc. of hot alcohol, filter, add 20 cc. of hot water, and
set aside to crystallize. Filter off the crystals and dry them on
a porous plate. Determine the melting-point of the crystals;
the 2, 4, 6-tribromophenol which is formed melts at 93°.
NOTES.—(d) If the ferric chloride solution contains much free acid it will
not give the usual test—the production of a marked color. If this occurs
make up a reagent for this and the following experiments as follows: Add to
a 10 per cent solution of ferric chloride a solution of sodium hydroxide, drop
by drop, until a permanent precipitate is just formed on shaking. If too
much alkali is added, a little of the solution of ferric chloride can be used to
almost dissolve it. Filter the solution, which should have a deep yellow
color and mix with three volumes of water.
(e) When bromine is added in excess to an aqueous solution of phenol, a
compound of the formula Br3C6H2.OBr, is formed, which is converted by
sulphur dioxide into tribromophenol, Br3C6H2.OH. On account of the great
insolubility of this compound in cold water, it is of value in detecting the
presence of phenol in dilute aqueous solutions. Salicylic acid, and a few
other compounds are converted into tribromophenol by bromine water.
198. General Reactions of Phenols (SECTION 540).—( a ) With

ferric chloride.—Add a dilute aqueous solution of ferric chloride
(see note to experiment 197d, above) to dilute aqueous solu-
tions of pyrocatechol, quinol, resorcinol, cresol, a-naphthol,
b-naphthol, and pyrogallol. If no color appears, dissolve a
little of the substance in alcohol and add a drop of ferric chloride
solution.
(b) With bromine water.—Add bromine water to the solutions
of the phenols listed above.
(c) Preparation of phthaleins from phenols (SECTION 558).—
Put in a dry test-tube about 0.1 gram of phenol, in a second tube
0.1 gram of resorcin, and in a third 0.1 gram of thymol. To
each tube add about 0.1 gram phthalic anhydride and 2 drops of
concentrated sulphuric acid. Place the tube for 3 minutes in an
oil-bath heated to 160°. Cool, add 5 cc. of a solution of sodium
hydroxide, and observe the color by transmitted and reflected
light. If the solution appears to be too concentrated, pour off a
little and dilute with water. (Eqs.)
NOTES.—(a) Most phenols give a color when treated with a solution of

ferric chloride. The reaction is valuable in testing for compounds of this
class.
(b) Most monhydroxy phenols which dissolve in water give a precipitate
when treated with bromine water.
199. Preparation and Properties of Anisol (SECTION 541).—

(a) Add to 50 cc. of methyl alcohol, contained in a 250-cc. flask,
2.5 grams of sodium; the metal should be cut into about half a
AROMATIC ALCOHOLS, PHENOLS, AND ETHERS 169
dozen pieces and added slowly, and the flask should be kept cold
by immersion in water. When the sodium has reacted, add to
the solution 10 grams of phenol and 20 grams of methyl iodide.
Attach a reflux condenser to the flask, and heat on a water-bath,
until a drop of the solution, when diluted with water, no longer
shows an alkaline reaction. The reaction is complete in about an
hour. Distil off the excess of methyl alcohol on a water-bath,
and add about 25 cc. of water to the residue. Extract with a
small amount of ether, dry the ethereal solution with calcium
chloride, and distil off the ether on a water-bath. Distil the
residue over a free flame. Calculate the percentage yield from
the phenol used.
Anisol boils at 155°. The yield is nearly the theoretical.
(b) Solubility of anisol.—Determine if anisol is soluble in the
following: dilute hydrochloric acid, dilute sodium hydroxide,
and cold concentrated sulphuric acid.
CHAPTER XXI
AROMATIC ACIDS
200. Preparation of Benzoic Acid from Benzyl Chloride ( S E C -

TION 546).—In a 500-cc. flask provided with a return condenser
like that shown in Fig. 17, page 27, place 20 grams of benzyl
chloride, 100 cc. of water, 40 cc. of concentrated nitric acid, and
half a dozen small pieces from a broken porous plate to prevent
bumping. Place the flask on a wire gauze and boil for about
4 hours. When the oxidation is complete, the oil, which at first
floats, becomes heavier than the aqueous solution, and when the
flame is removed for an instant sinks to the bottom of the flask.
Cool under running water, shaking vigorously to avoid the for-
mation of large lumps. Filter by suction and wash with cold
water. Dissolve the crystals in the smallest amount of boiling
water, about 900 cc., add 2 grams of bone-black, boil for 3 min-
utes, and filter hot; set aside over night to crystallize. Filter
off the crystals by suction, and wash with cold water. Let the
acid stand in the air until dry. Weigh and determine the
melting-point. If the acid does not melt sharply, sublime a
little of it (§35, page 24), and determine the melting-point again.
Calculate the percentage yield. How could you readily distin-
guish a solution of phenol from one of benzoic acid? How could
you distinguish a solid acid from a solid phenol? How could
you obtain pure benzoic acid from sodium benzoate?
Benzoic acid melts at 121.4° and boils at 249°. One hundred
parts of water at 17.5° dissolve 0.268 parts, and at 75° dissolve
2.19 parts of the acid. It is readily soluble in alcohol and in
ether. The yield should be about 14 grams.
NOTE.—In oxidizing aromatic compounds with nitric acid, the latter is
usually diluted with water in order to prevent nitration. An acid of the
specific gravity 1.15 is ordinarily used.
201. Identification of Benzoic Acid: Conversion into Benz-
anilide.—To definitely identify as benzoic acid an unknown sub-
stance which has the melting-point and physical properties of
170
AROMATIC ACIDS 171
this acid, it should be converted into a solid derivative, and

the properties of this compound determined. Benzanilide,
C 6 H 5 CO.NHC 6 H 5 , is conveniently prepared and melts sharply.
Proceed as follows: To about 0.2 gram of the acid in a dry test-
tube add about 0.4 gram of phosphorus pentachloride; warm and
stir the mixture until a homogeneous liquid is obtained. Cool,
shake with about 5 cc. of water, decant off the latter, and add
slowly about 1 cc, of aniline. Dissolve the product in a boiling
mixture of 25 cc. of alcohol and 25 cc. of water. Filter the
solution if necessary, cool, and filter off the crystals; wash with a
little dilute alcohol, and dry the compound at 100°. Determine
the melting-point. Benzanilide crystallizes in pearly, white
scales which melt at 160°.
202. Preparation of Benzamide (SECTION 549).—HOOD.—
Place in a small flask 5 grams of benzoic acid and 9 grams of
phosphorus pentachloride (weighed under the hood), and shake
and warm on the steam-bath until a clear liquid is formed. Cool,
and add the liquid to 150 grams of ice and 50 cc. of concentrated
ammonia in a beaker. Stir occasionally until the liquid has
changed to a solid. If the substance when pressed with a glass
rod appears to be plastic, the reaction is not complete; it must
be more or less granular. Filter by suction, wash with dilute
ammonia, and crystallize from the smallest possible amount of
boiling water (about 50 c c ) . Weigh the product and determine
its melting-point. A small amount of amide can be recovered
from the mother-liquor.
Benzamide melts at 128°-130°. The yield is about 4 grams.
Determine whether benzamide shows the properties of an acid
amide, and describe in your notes the test applied and the result
obtained.
203. Preparation of p-Toluic Acid from the Nitrile (SECTION
551).—Hydrolyze the tolunitrile obtained in experiment 189,
page 159, by heating it with sulphuric acid as follows: For each
gram of nitrile use 6 grams of concentrated sulphuric acid and
2 cc. of water. Heat on a sand-bath the mixture contained in a
flask provided with a wide-bore reflux condenser, until the acid
sublimes freely into the condenser. Cool, dilute with about 3
volumes of water, filter off the crystals, and wash them several
times with cold water. Dissolve the toluic acid in hot alcohol,
add about 1 gram of bone-black, and boil for 5 minutes. Filter

hot, and add boiling water until the solution clouds. Set aside
the solution to crystallize. Filter off the crystals, wash with cold
water, and dry on a porous plate. Determine the percentage
yield. A further amount of acid can be obtained from the
mother-liquor. Save the acid for a later experiment.
p-Toluic acid melts at 180° and boils at 275°. The yield of
acid is the theoretical, although some of it is lost in the purification.
204. Preparation of Cinnamic Acid by Perkin's Synthesis
(SECTION 553).—Place in a small round-bottomed flask provided
with a reflux air-condenser, in the end of which is a drying tube
containing calcium chloride, 20 grams of freshly distilled benzal-
dehyde, 30 grams of acetic anhydride, and 10 grams of freshly
fused and pulverized anhydrous sodium acetate. (See experiment
66, page 44.) Heat the mixture in an oil-bath at 170°-180°
for 8 hours. Pour the mixture into 500 cc. of water, place about
100 cc. of a 10 per cent solution of sodium carbonate in the flask,
and shake to dissolve most of the residue. Add this solution to
the mixture of water and cinnamic acid, heat to boiling, and add
solid sodium carbonate as long as anything dissolves and the
solution has a strong alkaline reaction. Stir vigorously during
the addition in order to bring the oil in contact with the sodium
carbonate. A small insoluble residue is left. Filter the solution
hot and add an excess of hydrochloric acid. Filter off the acid
when the solution has cooled, and wash it with cold water.
Dissolve the acid in boiling water, add about 2 grams of bone-
black, boil for 5 minutes, filter hot, and set aside to crystallize.
Weigh the acid, after drying on a porous plate, determine its
melting-point, and calculate the percentage yield from the sodium
acetate used.
Cinnamic acid melts at 134°; it is soluble in 3,500 parts of water
at 17° and in 100 parts at 100°. The yield is from 12 to 14 grams.
205. Properties of Cinnamic Acid (SECTION 553).—( a ) Test
for the double bond in cinnamic acid.—Dissolve about 0.5 gram
of the acid in carbon tetrachloride and add, drop by drop, a
solution of bromine in the same solvent. If no reaction takes
place in 1 minute, warm the solution gently. (Eq.) How
does the rate at which this reaction proceeds compare with the
rate with which ethylene and bromine react?
AROMATIC ACIDS 173
(b) Oxidation of cinnamic acid.—Stir about 0.1 gram of the

acid with about 5 cc. of cold 10 per cent solution of potassium
permanganate and note the odor. (Eq.) What acid would be
obtained by the further oxidation of cinnamic acid?
NOTE.—(a) The rate at which bromine is added to a double bond is
determined by the nature of the radicals linked to the carbon atoms joined
by the double bond; negative atoms or groups markedly retard the reaction.
In the case of certain compounds which contain four negative groups, for
example tetraphenylethylene, (C 6 H 5 ) 2 C = C ( C 6 H 5 ) 2 , addition does not take
place at all.
206. Preparation of Terephthalic Acid from p-Toluic Acid
(SECTION 561).—Dissolve 5 grams of the toluic acid prepared in
experiment 203 in a solution of 3 grams of sodium hydroxide
in 250 cc. of water. Heat the solution on a water-bath and add
a solution of 12 grams of potassium permanganate in 250 cc. of
water until the color of the permanganate persists after heating
for 5 minutes. Add to the hot solution enough alcohol to react
with the excess of permanganate, and filter hot. Wash the pre-
cipitate of manganese dioxide with a little hot water, and add
an excess of concentrated hydrochloric acid to the filtrate.
Filter off the terephthalic acid when the solution has cooled.
Weigh the acid and calculate the yield. Sublime a little of the
acid.
Terephthalic acid is almost insoluble in hot and cold water.
It sublimes without melting. It can be identified most readily
by converting it into its dimethyl ester as described below.
207. Preparation of Dimethyl Terephthalate.—In a dry test-
tube warm together on the steam-bath or in hot water about
0.2 gram of terephthalic acid and 0.6 gram of phosphorus penta-
chloride. (Eq.) Cool the mixture and add in small portions,
keeping the mixture cold in running water, 4 cc. of methyl
alcohol. (Eq.) Warm the mixture cautiously for a short time
until reaction is complete. Cool again, add 20 cc. of water, filter
by suction, and wash the precipitate with 10 cc. of water. Dis-
solve the dimethyl terephthalate in a boiling mixture of 8 cc.
of methyl alcohol and 2 cc. of water. Filter hot, using a small
funnel. Cool, filter off the crystals by suction, and wash them
with a mixture of 3 cc. of methyl alcohol and 3 cc. of water. Dry
the crystals on a porous plate and determine their melting-point.
Dimethyl terephthalate melts at 140°.
CHAPTER XXII
AROMATIC ALDEHYDES, KETONES, AND QUINONES
208. Properties of Benzaldehyde (SECTIONS 564-567).—( a )

Oxidation of benzaldehyde.—Leave a few drops of benzaldehyde
on a watch-glass exposed to the air for a few days. (Eq.)
Grind a pinch of starch with a few cubic centimeters of cold
water and pour the mixture into about 50 cc. of boiling water.
Cool, and dissolve in the solution a crystal of potassium iodide.
Divide the solution into two portions. Shake one of these with
2 drops of benzaldehyde and expose both to sunlight for some
time. Explain. (See SECTION 565.)
(b) Test for the aldehyde group in benzaldehyde.—Shake up
a few drops of benzaldehyde with about 15 cc. of water, and test
parts of the solution with Fehling's solution, Tollen's reagent,
and Schiff's reagent. Compare the results with those obtained
with acetaldehyde. For the test with phenylhydrazine see
experiment 192d, page 163. If this experiment has not been
performed, do it now.
(c) Benzaldehyde and sodium hydrogen sulphite.—Shake about
1 cc. of benzaldehyde with 5 cc. of a saturated solution of sodium
hydrogen sulphite. Filter off the crystals by suction and wash
them with a little alcohol until odorless. Dissolve the crystals
in warm water; to one-half of the solution add a solution of sodium
carbonate, and to the other dilute sulphuric acid. Explain the
cause of the appearance and odor produced.
(d) Benzaldehyde and sodium hydroxide.—Shake up a few drops
of benzaldehyde with a solution of sodium hydroxide, and then
warm the mixture. Is a resin formed? Compare the results
with those obtained in the case of acetaldehyde (experiment
108d, page 86). For the behavior of benzaldehyde with alkalies
see experiment 193, page 165.
(e) Benzaldehyde and ammonia: hydrobenzamide.—Mix to-
gether 3 cc. of benzaldehyde, 20 cc. of alcohol, and 10 cc. of a
concentrated solution of ammonia. Set aside the mixture until
174
AROMATIC ALDEHYDES, KETONES, AND QUINONES 175
the product which separates becomes solid. Heat on the steam-

bath, and add alcohol until the solid dissolves. Set aside to
crystallize. Determine the melting-point of the crystals. Com-
pare the behavior of formaldehyde, acetaldehyde, and benzalde-
hyde with ammonia.
Hydrobenzamide, (C 6 H 5 CH) 3 N 2 , crystallizes from alcohol in
octahedra which melt at 110°.
209. Preparation of Benzophenone (SECTIONS 572 and 425).
In a dry 500-cc. flask put 28 grams of benzene, 30 grams of an-
hydrous aluminium chloride in the form of lumps, and 27 grams
of benzoyl chloride. The aluminium chloride should not be
exposed to the air any longer than necessary, as it rapidly absorbs
moisture. Attach to the flask by means of a cork a small drying
tube containing anhydrous calcium chloride, place the flask
under a hood in a beaker containing water, and let the reaction
proceed for at least 24 hours. To determine whether the reaction
is complete, pour a few drops of the material into a few cubic
centimeters of water in a test-tube. Shake the tube and observe
whether the characteristic odor of benzoyl chloride is present.
If the chloride is present, the mixture should stand for several
hours and then be tested again. When benzoyl chloride can no
longer be recognized by its odor, pour into the flask rapidly a
mixture of 200 cc. of water, 100 grams of shaved ice or snow, and
50 cc. of concentrated hydrochloric acid. Shake under running
water until two layers are formed. Add 50 cc. of benzene and
separate the solution from the acid. Shake the former with a
solution of sodium hydroxide to remove any benzoic acid that
may be present. Dry the solution with calcium chloride and
filter it into a distilling flask, provided with a thermometer.
Distil, using a water condenser, until the temperature of the
vapor reaches 250°. Replace the water condenser by an air
condenser and collect in a weighed 200-cc. beaker the material
boiling between 285° and 305°. Record the weight of the distil-
late, which should change to a mass of crystals. Dissolve it
in warm alcohol (5 cc. for each gram of benzophenone) and add
to the cooled solution cold water until a permanent cloud is
formed. The volume of the water used should be about one-
third that of the alcohol. After standing over night, filter off
the crystals and add water to the filtrate as before. Weigh the
two crops of crystals, calculate the yield and determine the

melting-point of the crystals.
Benzophenone melts at 48°, and boils at 306.1° (corr.). The
yield in the preparation is about 25 grams.
210. Preparation of Benzophenoneoxime (SECTION 573).—In
a flask provided with a reflux condenser dissolve 5 grams of
benzophenone in 50 cc. of alcohol, and add a solution of 5 grams
of hydroxylamine hydrochloride in 15 cc. of water; to this add a
solution of 10 grams of sodium hydroxide in 15 cc. of water, and
heat the mixture on a water-bath for an hour. Pour the product
into about 200 cc. of water, filter if necessary, and add to the fil-
trate dilute sulphuric acid until the solution is just acidic to lit-
mus paper. After an hour filter off the benzophenoneoxime.
Weigh the product when dry and calculate the percentage yield,
which should be nearly theoretical. Recrystallize the oxime
from about 25 cc. of hot alcohol.
Benzophenoneoxime melts at 141°.
211. Beckmann's Rearrangement of an Oxime (SECTION
573).—In a small flask dissolve 2 grams of benzophenoneoxime
in 30 cc. of ether dried over sodium, and add slowly in small
portions 3 grams of finely divided phosphorus pentachloride.
At first it may be necessary to cool the solution; toward the end
of the reaction the mixture should be heated on the steam-bath
until the phosphorus pentachloride has dissolved. When this
has taken place, pour the ethereal solution with vigorous stirring
into 400 cc. of cold water. Stir until a solid has formed, and then
filter it off by suction and wash with cold water. Crystallize
the benzanilide from the smallest amount of boiling alcohol, and
determine the melting-point of the dried crystals. Write equa-
tions for the reactions involved in the rearrangement.
Benzanilide melts at 160°.
212. Preparation of Quinone (SECTION 577).—Mix is a large
beaker 250 cc. of water, 50 cc. of pure concentrated sulphuric
acid, and 50 grams of sodium bichromate or the equivalent weight
of potassium bichromate. When the salt has dissolved, set the
beaker in cold water and cool the solution to 20°. Mix in a
beaker 150 cc. of water and 10 grams of aniline; pour into the
mixture, with stirring, 10 cc. of pure concentrated sulphuric
acid. Cool the solution to 20° and add it, stirring vigorously,
AROMATIC ALDEHYDES, KETONES, AND QUINONES 177
in four portions to the solution of sodium bichromate. The

beaker in which the reaction takes place should be surrounded by
cold water and the temperature should be kept between 35° and
40°. About 6 to 8 minutes are required for the addition of the
solution of aniline sulphate. When this has been accomplished,
remove the beaker from the water and let it stand for about
15 minutes. Transfer the product to a large flask, and cool it in
running water to about 15°. Add to the flask 300 cc. of ether
and shake. Let the flask stand for a few minutes. In order to
facilitate the separation of the ether into a distinct layer, add to
it 25 cc. of acetone, and give to the flask a gentle rotary motion.
In a few minutes decant off carefully as much of the ether as
possible into a separatory funnel; if some of the aqueous layer
flows into the funnel it can be separated. Draw off the ethereal
solution, place it in a flask, and distil the ether off from a water-
bath through a long water-jacketed condenser (see §34, page
23). Extract the solution of quinone once more with this re-
covered ether, and evaporate it off as before. Crystallize the
residue of quinone from the smallest possible amount of boiling
ligroin, or distil it with steam in the ordinary way except that
no water is put into the flask containing the quinone. Dry
the crystals of quinone in a desiccator; the compound is volatile
at room temperature, and if left exposed to the air for a number
of hours an appreciable quantity is lost.
Quinone melts at 116°. The yield in this preparation is 5
to 6 grams.
213. Properties of Quinone (SECTION 577).—( a ) Reduction of
quinone.—Shake up a crystal of quinone with 10 cc. of water.
Note the odor and color of the solution; add to one-half of it a
solution of sodium hydrogen sulphite. (Eq.) To the other half
add a dilute solution of potassium iodide and a few drops of
dilute hydrochloric acid. (Eq.)
(b) Unsaturation of quinone.—Dissolve a few crystals of quin-
one in 5 cc. of carbon tetrachloride and add, drop by drop, a
solution of bromine in carbon tetrachloride. (Eq.)
(c) Formation of quinhydrone.—Make a saturated solution of
quinone in water and add to the solution, drop by drop, a strong
aqueous solution of hydroquinone. Examine the tube after about
1 minute. If crystals have not formed, repeat, using a more con-
centrated solution of hydroquinone. (Eq.) Add a solution of

ferric chloride to a strong solution of hydroquinone. (Eq.)
Add an ammoniacal solution of silver nitrate to an aqueous solu-
tion of hydroquinone.
214. Preparation of Anthraquinone (SECTION 579).—In a
250-cc. round-bottomed flask provided with a reflux condenser
place 5 grams of anthracene and 50 cc. of glacial acetic acid.
Heat the liquid to boiling over a wire gauze and add, drop by
drop, from a separatory funnel placed in the upper end of the
condenser, a solution made by dissolving 10 grams of chromic
acid anhydride in 10 cc. of water and then adding 25 cc. of glacial
acetic acid. Boil the solution for 10 minutes after the oxidizing
agent has been added, and then allow the mixture to cool spon-
taneously to the temperature of the room. Finally cool under
running water. Filter by suction, and wash the crystals twice
with a mixture of 2 volumes of water and 1 volume of glacial
acetic acid, using 20 cc. of the mixture each time. Finally wash
twice with water and allow the crystals to dry in the air.
Sublime a small amount of the dried anthraquinone (§35,
page 24), and crystallize a little from boiling alcohol.
Anthraquinone sublimes at about 250° in yellow needles
which melt at 273°. The yield in this preparation is 5 grams.
Boil together for about half a minute a trace of powdered
anthraquinone with a little zinc dust and 10 cc. of a solution of
sodium hydroxide. Filter the solution and shake it with air.
Anthraquinone is partly reduced by zinc and sodium hydroxide
to a red salt of the composition:
This salt is oxidized by air to anthraquinone. The reaction is

a valuable one in the identification of this substance.
Compare the properties of anthraquinone with those of benzo-
quinone. Does the former oxidize an acidified solution of potas-
sium iodide? Is it reduced by sulphurous acid?
NOTE.—After oxidation by chromic acid in acetic acid solution, the prod-
uct is usually precipitated by pouring the solution into water. In the case
of anthraquinone it is convenient to allow the mixture to cool as the com-
pound crystallizes well from glacial acetic acid.
CHAPTER X X I I I
AROMATIC COMPOUNDS CONTAINING TWO OR MORE UNLIKE

GROUPS
215. Preparation of o-Nitrophenol (SECTION 584).—( a ) In a

small beaker melt 20 grams of phenol on the steam-bath, and add
it slowly with stirring to a mixture of 30 cc. of pure concentrated
nitric acid and 100 grams of ice contained in a beaker. Stir
the mixture and then let it stand for at least 3 hours; if more con-
venient it can be set aside until the next laboratory exercise.
Decant off as much of the acid layer as possible through a funnel
containing a filter-paper, which serves to collect the part of the oil
that is suspended in water. Add about 200 cc. of water to the
oil, stir, and decant off the liquid as before. Repeat the washing
with 200 cc. of water. Place the filter-paper with the adhering
oil in a liter flask, arranged for steam distillation (see Fig. 14,
page 20). Wash the oil in the beaker into the flask using for
the purpose 200 cc. of water, which should be measured. (This
is done to facilitate the isolation of the p-nitrophenol which is not
volatile with steam.) Distil with steam as long as any oil or
solid condenses (about 30 minutes). If the oil solidifies in the
condenser, turn off the water from the latter; when the water in
the condenser becomes heated, the solid melts and runs into the
receiver. Filter, dry, and weigh the o-nitrophenol. Recrystal-
lize the product by dissolving it in 40 cc. of hot alcohol and adding
40 cc. of water; set aside over night to crystallize. Filter by
suction and wash with a small amount of cold alcohol. Heat the
filtrate to boiling and add an equal volume of water. Set aside
and collect as before.
o-Nitrophenol melts at 45°. The yield is from 7 to 8 grams.
( b ) The p-nitrophenol, which is not volatile with steam, may be
obtained from the residue in the flask as follows: Cool in running
water the solution in the flask to 40° and filter it rapidly through
a large funnel. The volume of the solution should be about 300
cc. Add 2 grams of bone-black to the filtrate and boil it for about
179
15 minutes. Filter hot, and place in cold water. The solution

should be cooled to at least 10°, and ice should be used if neces-
sary. If crystals do not form, scratch the side of the beaker with
a glass rod. After standing for about half an hour, filter off the
crystals by suction and wash them with a little cold water. The
yield is about 3 grams. By evaporating the mother-liquor to
dryness on the steam-bath and extracting the residue with
about 50 cc. of boiling benzene, about 2 grams more of the prod-
uct can be obtained.
p-Nitrophenol melts at 114°; it crystallizes well from benzene
in which it is readily soluble hot and difficultly soluble cold.
When pure it crystallizes readily from hot water.
Compare the conditions used in the nitration of phenol with
those used in making nitrobenzene (experiment 170, page 139),
dinitrobenzene (experiment 172, page 141), and nitroacetanilide
(experiment 219, page 182).
NOTE.—The yields are small in this preparation on account of the fact
that compounds other than o- and p-nitrophenol are formed; among these
are substances of a tarry nature from which it is difficult to separate the para-
compound. It is on this account that special precautions are necessary in
order to obtain p-nitrophenol in a crystalline condition,
216. Isolation of Eugenol from Cloves (SECTION 593).—Distil

25 grams of cloves with steam as long as an oil separates in the
condenser; during this time about 600 cc. of water will distil.
Give the vessel containing the mixture a rotary motion so that
the oil settles. Decant off most of the water, and pour the oil
into a test-tube. By means of a pipette transfer about one-half
the oil to a small test-tube, cover it with about 2 cc. of water, and
add a dilute solution of sodium hydroxide (10 per cent) as long as
it appears to dissolve the oil. (Eq.) Is a clear solution obtained?
Add to a few cubic centimeters of the alkaline solution, bromine-
water in excess. What does the reaction indicate? Divide the
rest of the alkaline solution into two equal portions. To one add
an excess of dilute hydrochloric acid. (Eq.) Set the two tubes
aside and examine them carefully at the next exercise for an oil.
Explain why sodium hydroxide did not dissolve the oil to a clear
solution.
Separate from water, by means of a pipette, the rest of the oil
obtained in the distillation with steam. Put it in a dry test-
AROMATIC COMPOUNDS 181
tube, avoiding getting water into the tube. Add about 2 cc.
of carbon tetrachloride, and filter into a dry test-tube through a
small funnel containing a paper moistened with carbon tetra-
chloride. Add a solution of bromine in carbon tetrachloride,
drop by drop. What does the behavior indicate?
217. Preparation of Sulphanilic Acid (SECTION 598).—In a
small round-bottomed flask containing 25 grams of aniline, pour
cautiously 80 grams of pure concentrated sulphuric acid. Heat
the mixture for from 4 to 5 hours in an oil-bath at 180°-190°.
In order to determine whether the reaction is complete, remove a
drop of the mixture on a glass rod, and mix it on a watch-glass
with a few drops of a solution of sodium hydroxide. If any
aniline sulphate is present in the mixture, the aniline will separate
as an oil; if sulphonation is complete, the sodium salt of sulph-
anilic acid, which is soluble in water, is formed. When the
reaction is complete, pour the product into about 300 cc. of cold
water. Filter, wash the precipitated sulphanilic acid with cold
water, dissolve it in boiling water, avoiding an excess of the latter,
add about 2 grams of bone-black, and boil for 5 minutes, stirring
occasionally. Filter the hot solution and set aside to crystal-
lize. Dry the crystals in the air; weigh them as soon as dry as
the acid slowly loses its water of crystallization on standing.
Calculate the percentage yield.
Sulphanilic acid crystallizes from water in plates, which con-
tain 2 molecules of water of crystallization; it is converted into
tribromoaniline by an excess of bromine water. The yield in
this preparation is about 25 grams.
218. Preparation of m-Nitroaniline (SECTION 600).—In a 100-
cc. flask dissolve 10 grams of m-dinitrobenzene in 50 cc. of hot
alcohol; cool the solution under running water so that small
crystals are formed, and add 10 cc. of a concentrated solution of
ammonia in water. HOOD.—Pass into the solution a rapid
stream of hydrogen sulphide as long as heat is evolved by the
reaction ( Eq. ) ; this requires about one-half hour. Heat on the
steam-bath for 10 minutes. Pour the product into 200 cc. of
water, filter by suction, and wash the precipitate with water.
Put the mixture of m-nitroaniline and sulphur into a beaker, add
100 cc. of water and 20 cc. of concentrated hydrochloric acid, stir,
and filter off the residue of sulphur by suction. Set the filtrate
aside. Determine whether all the nitroaniline has been extracted

from the sulphur by treating it on the filter with a little dilute
hydrochloric acid, and adding ammonia to the filtrate. To the
original filtrate from the sulphur add an excess of concentrated
ammonia. Cool in running water, filter off the precipitated
m-nitroaniline by suction, and wash it with a little cold water.
Dissolve the nitroaniline in the smallest amount of boiling water
(about 500 cc.), filter the hot solution, and set it aside to crys-
tallize. Filter off the crystals, wash them with a little cold
water, and dry on filter-paper. Calculate the percentage yield
and determine the melting-point of the product.
m-Nitroaniline crystallizes in yellow needles, which melt at
114°. The yield in this preparation is from 5 to 6 grams.
219. Preparation of p-Nitroaniline (SECTION 600).—Add slowly
in small amounts with stirring, 20 grams of finely powdered
acetanilide to 60 grams of fuming nitric acid (sp. gr. 1.52) con-
tained in a beaker surrounded by ice and concentrated commercial
hydrochloric acid. The temperature of the nitric acid should
not be allowed to rise above 10°. The addition of the acetanilide
requires about 20 minutes. When the substance has dissolved,
pour the solution into about 300 cc. of cold water, stir vigorously,
and filter by suction. p-Nitroacetanilide is precipitated, and
the ortho compound formed remains in solution. Wash the pre-
cipitate three or four times with hot water. Remove as much
water as possible by pressing the compound on the funnel, and
then crystallize it from boiling alcohol. Let the solution cool,
and filter off the crystals. By evaporating the filtrate to a small
bulk, a further amount of the anilide can be obtained. Deter-
mine the melting-point and yield of the p-nitroacetanilide
obtained.
p-Nitroacetanilide melts at 207°. The yield should be about
14 grams. The ortho compound can be obtained from the origi-
nal solution in dilute nitric acid by extraction with chloroform.
To obtain p-nitroaniline from the anilide proceed as follows:
H O O D . — I n a beaker covered with a watch-glass boil the p-nitro-
acetanilide with ten times its weight of dilute hydrochloric acid
(sp. gr. 1.12) for about 20 minutes. Cool the solution, add
about an equal volume of water and an excess of concentrated
ammonia. When the solution is cold, filter off the p-nitroaniline,
wash it with cold water, recrystallize from hot dilute hydrochloric

acid (1 vol. conc. HCl to 5 vols. H 2 O). Weigh the compound,
determine its melting-point, and calculate the percentage yield
from the p-nitroanilide used.
p-Nitroaniline melts at 147°.
220. Hydrolysis of the Salts of the Nitroanilines.—Prepare a
sample of aniline hydrochloride as follows: Mix together 1 cc.
of aniline and 1 cc. of concentrated hydrochloric acid. Cool
under running water, and place the solid which separates on a
porous plate. When the liquid has been absorbed pour a little
ether on the salt. Repeat the treatment with ether, and let the
salt dry in the air. Prepare samples of the hydrochlorides of
meta- and para-nitroanilines as follows: Mix together about 1
gram of the amine with 5 cc. of concentrated hydrochloric acid
and 5 cc. of water. Heat to boiling, and then cool in running
water. Filter the salt by suction, and wash the crystals with
10 cc. of alcohol and then with 10 cc. of ether. Dry the salts for
a few minutes on filter-paper.
Shake up a little of the three salts with about 2 cc. of water
and test the solutions for acid with litmus paper and with Congo
paper. Explain the results.
NOTE.—Litmus is much more sensitive to hydrogen ions than the dye on
Congo paper.
221. Properties of Salicylic Acid (SECTION 606).—( a ) Salicylic
acid and ferric chloride.—Add a dilute solution of ferric chloride
(see note to experiment 197d, page 168) to a dilute aqueous
solution of salicylic acid. To one-half of the solution add
dilute hydrochloric acid, drop by drop, and to the other half
dilute acetic acid. Add a drop of ferric chloride to an alcoholic
solution of salicylic acid. Repeat these tests with phenol and
compare the results.
(b) Salicylic acid and bromine.—Add bromine water to a solu-
tion of the acid. (Eq.)
(c) Formation of methyl salicylate.—Warm together on a watch-
glass about 0.05 gram of salicylic acid, 3 drops of methyl alcohol
and 3 drops of concentrated sulphuric acid. (Eq.) Note the
odor of the compound formed.
(d) Decomposition of salicylic acid on heating.—Heat rapidly
in a dry test-tube a little of the acid (Eq.) and note the odor.
(e) Detection of salicylic acid and benzoic acid in foods.—If the

sample to be tested is a liquid, acidify 100 cc. of it with 10 drops
of dilute sulphuric acid, and extract the solution twice with
ether or petroleum ether, using 50 cc. each time. If the material
contains a substance insoluble in water, grind 50 grams of it
with 100 cc. of water, and add enough of a dilute solution of
sodium hydroxide to make the mixture alkaline. Mix thor-
oughly, filter through 3 layers of cheese-cloth, acidify with dilute
sulphuric acid, and extract twice with ether or petroleum ether
using 50 cc. each time. Separate the ethereal extract and filter
it through a dry filter-paper. Shake 5 cc. of the extract with
5 cc. of water and add to the aqueous solution a dilute solution
of ferric chloride containing no free acid; if salicylic acid is pres-
ent, the characteristic color will develop. Evaporate the rest
of the ethereal extract to dryness, dissolve the residue in the
smallest possible amount of hot water. Let the solution cool,
and remove the crystals by means of a spatula to a porous plate.
When dry, determine their melting-point. Test a crystal with
ferric chloride as in (a) above. Dissolve a crystal in a drop of
ammonia, evaporate on the steam-bath, dissolve in a few drops
of water, and add a drop of a solution of ferric chloride. If
benzoic acid is present, a buff-colored precipitate of basic ferric
benzoate is formed.
222. Properties of Tannic Acid (SECTIONS 613, 614).—For
the following experiments make a 1 per cent solution of tannic
acid, by dissolving 0.5 gram of the acid in 50 cc. of water.
(a) Tannic acid and ferric chloride.—Add a few drops of a
dilute solution of ferric chloride (see note to experiment 197d,
page 168) to about 5 cc. of a solution of tannic acid. Dilute
some of the solution of the acid with 50 parts of water and add
a drop of ferric chloride.
(b) Tannic acid and the salts of heavy metals.—Add to a solu-
tion of the acid a solution of lead acetate. Repeat using copper
sulphate.
(c) Tannic acid and gelatin.—Dissolve about 0.1 gram of
gelatin in about 10 cc. of warm water, and add to one-half of the
cold solution a solution of tannic acid. Reserve the rest of the
solution for experiment (f) below.
(d) Reducing action of tannic acid.—Test a solution of the

acid with Fehling's solution. Add a solution of tannic acid to
an ammoniacal solution of silver nitrate.
(e) Oxidation of tannic acid by air.—Mix a little of the solu-
tion of the acid with a solution of sodium hydroxide and shake
the mixture in contact with air.
(f) Tannic acid in tea (SECTION 616).—Pour about 50 cc. of
boiling water onto about 1 gram of tea. After 2 minutes decant
off the clear solution; to 5 cc. of it add 2 drops of ferric chloride
solution. If the shade of the color produced can not be clearly
seen, dilute with water. Compare the color with that produced
by the gall-nut tannic acid in experiment ( a ) above. Add 5 cc.
of the solution to a dilute solution of gelatin. Compare the
behavior of the tannic acid from tea with that from gall-nuts.
To the rest of the tea-infusion add a dilute solution of lead
acetate, drop by drop, from a pipette as long as a precipitate
is formed.
Devise and carry out an experiment to determine whether the
amount of tannic acid present in a tea-infusion is greater when
the tea is steeped for 2 minutes, or when it is boiled with water
for 15 minutes.
(g) Preparation of a tannin ink: removal of ink-stains ( S E C -
TION 616).—Dissolve 1 gram of tannic acid in 10 cc. of hot water,
0.5 gram of ferrous sulphate in 5 cc. of hot water, and 0.05 gram
gum arabic in 5 cc. of hot water. Cool the solutions and mix
them. Write on a piece of paper with some of the ink, using a
new pen. Add a few drops of ferric chloride to a little of the
ink and write with the mixture. Compare result in the two cases.
Explain. Put the paper away, and examine the writing with the
two samples of ink at the next exercise. Explain.
Put on a piece of cotton cloth some of the iron ink and on an-
other piece some ordinary ink which probably contains a dye.
When the ink-spots are dry, cut each piece of cloth into three
parts in such a way that the pieces containing the iron ink can
be distinguished from those containing the dye. Wash the
pieces in water. Add a piece of each kind to a dilute solution
of oxalic acid. Explain the result. Add a piece of each kind to a
dilute solution of sodium hypochlorite. Place these pieces alter-
nately in the solution of oxalic acid and sodium hypochlorite

until the color is destroyed in both cases.
Prepare a 0.5 per cent solution of potassium permanganate by
dissolving about one-fourth gram of the salt in 50 cc. of water.
Add to the solution 5 drops of concentrated sulphuric acid.
Place in the solution pieces of cloth containing the two kinds
of ink. After about 2 minutes remove them, wash with water,
and place them in a strong solution of sodium hydrogen sulphite.
Repeat the treatment with the permanganate and sulphite until
the ink is destroyed. If ink is removed in this way the fabric
should be washed thoroughly in water, and then placed in a
dilute solution of ammonia.
NOTES.—(b) The formation of insoluble compounds from tannic acid
and the salts of metals is used in preparing mordants in dyeing. (See
experiment 228, page 191.)
(c) The use of tannin in tanning leather is based on the fact that it forms
a compound with the proteins in the hide, of which gelatine is an example.
(g) The removal of ink-spots from fabrics made of silk is best accom-
plished by means of potassium permanganate. If sodium hypochlorite is
used, the chlorine present attacks the material, and converts it into a chlorin-
ated product which has a faint yellow color that can not be readily destroyed.
A neutral solution of potassium permanganate oxidizes ink; the reaction
takes place more rapidly in a very faintly acid solution.
CHAPTER XXIV
DYES AND DYEING
223. Preparation of an Azo D y e : Methyl Orange (SECTION

629).—Dissolve 10 grams of sulphanilic acid and 3 grams of
anhydrous sodium carbonate in 150 cc. of water. To the solu-
tion first add 4 grams of sodium nitrite dissolved in 20 cc. of
water, and then a mixture of 7 cc. of concentrated hydrochloric
acid and 10 cc. of water. (Eq.) Dissolve 6 cc. of dimethylani-
line in a mixture of 20 cc. of water and 10 cc. of concentrated
hydrochloric acid. Cool the solution under running water, and
pour it slowly and with stirring into the diazotized sulphanilic
acid. (Eq.) Add a dilute solution of sodium hydroxide until
the solution is just alkaline; this can be seen by the change in
color. Add to the mixture 50 grams of salt dissolved in 150
cc. of water. In order to facilitate the separation of the dye,
heat the mixture to boiling until gas-bubbles disappear. Allow
the solution to cool to room temperature, and filter it with a large
funnel, without the use of suction. When the liquid no longer
passes through the filter-paper, transfer the precipitated dye ,
which is mixed with much water, to a funnel connected with
a filter-bottle and pump, and remove the last part of the solvent
by suction. It is well to proceed in the way described, and
not to attempt to filter by suction at first; in this case the paper
soon becomes clogged with the dye and filtration proceeds very
slowly.
The salt may be purified by recrystallization from hot water
(about 150 c c ) . Filter the boiling solution in the way described
in §10, page 6. The yield should be about 12 grams.
Dissolve a little methyl orange in water and add alternately
to the solution dilute hydrochloric acid and dilute sodium
hydroxide as long as a change in color is observed. (Eqs.)
Dissolve about 0.2 gram of methyl orange in about 10 cc. of
dilute hydrochloric acid, add about 1 gram of zinc dust and boil
187
the solution as long as any change takes place. Methyl orange,

like other azo dyes, is reduced to colorless compounds by hydro-
gen in acid solution at the N : N bond:
(CH 3 ) 2 NC 6 H 4 N:NC 6 H 4 SO 3 H + 4H = (CH 3 ) 2 NC 6 H 4 NH 2 +
H 2 NC 6 H 4 SO 3 H
224. Preparation of a Triphenylmethane D y e : Malachite

Green (SECTION 637).—Melt cautiously over a flame in a 6-inch
evaporating dish 7 grams of fused zinc chloride, as long as bubbles
are given off. Remove the flame and as the zinc chloride cools
rotate the dish slowly so that when cold the chloride covers an
area from 3 to 4 inches in diameter. Put into the dish 13 grams
of dimethylaniline and 5 grams of freshly distilled benzaldehyde.
Cover the dish with a watch-glass and heat on the steam-bath
for 4 hours. Stir the contents frequently with a glass rod, which
should be left in the mixture. Transfer the reaction-product
to a flask; the part that can not be poured out of the evaporating
dish can be treated repeatedly with hot water and thus removed.
Distil with steam as long as any oil passes over. Discard the
distillate.. Pour the water out of the flask and dissolve the mate-
rial sticking to the side of the flask in the smallest amount of
boiling alcohol. Filter the solution and set it aside to crystallize
over night. The leuco base which separates may form at first
as an oil, but on standing changes into masses of small crystals.
Filter off the solid, dry, and weigh it. The yield of leuco base,
C 6 H 5 CH[C 6 H 4 N(CH 3 ) 2 ] 2 , should be from 7 to 10 grams.
To convert the leuco base into the color base it is oxidized by
lead dioxide. The dye is finally obtained as the double chloride
of the color base and zinc chloride. Prepare the lead dioxide
as follows: Dissolve 8 grams of lead acetate in 50 cc. of water.
Mix thoroughly 20 grams of fresh bleaching powder with 300 cc.
of water and filter. Heat the solution of lead acetate, and add
the solution of bleaching powder slowly, keeping the solution
just below boiling. When all the lead has been precipitated and
the solid has changed to a deep brown color, stop heating and
let the precipitate settle. Pour off the liquid and wash the solid
three times by decantation, using about 500 cc. of water each
time.
DYES AND DYEING 189
Dissolve 5 grams of the leuco base in a mixture of 5 cc. of con-

centrated hydrochloric acid and 10 cc. of water. Pour this into
a large beaker containing 400 cc. of water and 100 grams of ice.
Stir, and add slowly, taking about 5 minutes for the operation,
the lead dioxide from which as much water as possible has been
removed by decantation. Next add a solution of 5 grams of
sodium sulphate in 25 cc. of water; this is to precipitate the lead
which has gone into solution as chloride. Filter, and to the fil-
trate add a solution of 5 grams of zinc chloride in 10 cc. of water.
To precipitate the dye add 50 grams of powdered salt, and stir
until the latter has dissolved. Filter with a large funnel, and
finally transfer the dye, which is mixed with much water, to a
funnel connected with a pump, and remove most of the solution
by suction. Wash once with a solution of salt. Transfer the
dye to a porous plate. When quite dry, weigh the compound.
Write equations, using graphic formulas, for all the reactions
involved in the preparation. The yield should be 7 grams.
226. Preparation of a Phthalein: Fluorescein (SECTIONS 639,
641).—Melt cautiously over a flame in a 6-inch evaporating dish,
5 grams of anhydrous zinc chloride, as long as bubbles are given
off. When the zinc chloride solidifies, add 10 grams of resorcin
and 7 grams of phthalic anhydride. Cover the dish with a watch-
glass, place it on a wire gauze, and heat very carefully over a
flame about 2 cm. high, the top of which is 2 or 3 cm. below
the gauze. (Eq.) The heating should be at such a rate that the
mixture produces bubbles slowly. In about 15 minutes, when
the bubbles cease to be formed and the mass becomes stiff, stop
the heating, and add to the dish, after it has cooled somewhat,
100 cc. of water and 20 cc. of concentrated hydrochloric acid.
Heat the mixture to boiling, and break up with a glass rod the
mass on the bottom of the dish. In a few minutes pour off the
liquid through a filter and grind the solid with a pestle. Add 100
cc. of water and 20 cc. of concentrated hydrochloric acid, and boil
again. Finally filter and wash with water. Let the fluorescein,
the insoluble residue, dry in the air. Weigh the product. The
yield should be about 12 grams.
Fluorescein can be crystallized by dissolving it in hot alcohol
or in hot glacial acetic acid, and adding water.
Dissolve a trace of fluorescein in a dilute solution of sodium

hydroxide and examine the solution by reflected and by trans-
mitted light.
226. Preparation of Eosin (SECTION 641).—In a small flask
cover 5 grams of fluorescein with 20 cc. of alcohol. Add slowly
in small portions, taking 10 minutes for the operation, 4 cc.
of bromine. Shake the flask frequently. When about one-half
of the bromine has been added most of the fluorescein passes
into solution as the dibrom-substitution-product; as the addi-
tion continues the tetrabrom-substitution-produet crystallizes
out. (Eq.) Allow the mixture to stand for an hour; filter and
wash twice with a small amount of cold alcohol. The yield is
about 7 grams.
Dissolve a little eosin in sodium hydroxide and examine the
solution by transmitted and by reflected light.
Salts of eosin are used for dyeing. Prepare some of the ammo-
nium salt as follows: Place in a desiccator about 25 cc. of con-
centrated ammonia. Place about a gram of powdered eosin on
a small watch-glass and support it on a triangle in the desiccator.
Cover the latter. At the next exercise test the solubility of the
substance on the watch-glass; if it has been completely converted
into the ammonium salt it will dissolve without a residue in water.
Dissolve some of the ammonium salt in a little water, and then
use the solution as ink, with a new pen.
Dissolve about 0.1 gram of the salt in 200 cc. of water and dye
a piece of silk by heating it with the solution for about 10 minutes.
DYEING
227. Dyeing with a Substantive D y e : Congo (SECTIONS 622,

625, 628).—The cotton to be used in this and the experiments
which follow should be heated for 10 minutes in a boiling solution
of 1 gram of sodium carbonate in 500 cc. of water. Prepare in
this way seven pieces of white cotton cloth about 6 inches square.
Wash the cotton three times with water and let it stand under
water until needed.
Dissolve 0.1 gram of Congo and 0.1 gram of sodium carbonate
in 500 cc. of water. Heat the solution to a temperature just
below boiling, and add pieces of white cotton cloth, woolen cloth,
DYES AND DYEING 191
and silk about 6 inches square. Stir occasionally to obtain even

dyeing. At the end of 10 minutes remove the fabrics and wash
in hot water as long as the dye is removed. Cut the pieces in two,
and place half of each material in a very dilute solution of hydro-
chloric acid. Let the samples stay in the air until dry.
228. Dyeing with an Adjective D y e : Mordants: Malachite
Green (SECTIONS 624, 637).—Mordant two pieces of boiled-out
cotton cloth (see previous experiment) by allowing them to stand
for 15 minutes in a cold solution of 0.2 gram of tannic acid in 200
cc. of water. Fix the tannic acid on one of the pieces by placing
the cloth without washing into a solution of 0.2 gram of tartar
emetic in 200 cc. of water, and allowing it to stand for 10 minutes.
Make a dye bath by dissolving 0.1 gram of malachite green in
500 cc. of water. Add to the bath a piece of boiled-out cotton
which has not been mordanted, the piece of cotton mordanted
with tannic acid from which most of the solution has been
removed by pressure, the piece of cotton cloth on which the tannic
acid was fixed by tartar emetic, a piece of wool, and a piece of
silk. Dye for 15 minutes at a temperature just below boiling.
Work the pieces over and over with a rod occasionally to obtain
even dyeing.
Wash the dyed material in boiling water as long as color is
removed. Dry. Compare the appearance of the three pieces of
cotton cloth. Why is the piece which was treated with tannic
acid and tartar emetic darker than the one mordanted with tannic
acid alone?
229. Dyeing with an Ingrain Color: Primuline (SECTION 625).
Dye three pieces of boiled-out cotton cloth (see experiment
227) in a solution of 0.2 gram of primuline and 0.2 gram of sodium
carbonate in 500 cc. of water, at a temperature just below boiling
for 15 minutes. Wash the cloth twice in about 500 cc. of water.
Prepare a diazotizing bath by dissolving 10 cc. of concentrated
hydrochloric acid in 500 cc. of cold water and then adding 0.2
gram of sodium nitrite. Place in the bath the three pieces of
cloth which have been dyed with primuline, and allow them to
stay 10 minutes. Stir occasionally. Prepare three baths in
which the diazotized primuline is to be developed. Dissolve 0.1
gram b-naphthol in 1 cc. of a 10 per cent solution of sodium
hydroxide, and add 100 cc. of water; dissolve 0.1 gram resorcinol
in 2 cc. of the sodium hydroxide solution and add 100 cc. of water;
dissolve 0.1 gram of phenol in 1 cc. of the sodium hydroxide solu-
tion and add 100 cc. of water.
Transfer the cloth from the diazo bath to a beaker containing
about 500 cc. of water and stir. Put one piece of cloth in each
of the developing solutions, and allow them to stay 5 minutes.
Wash the dyed cloth twice with water and dry.
CHAPTER XXV
HETEROCYCLIC COMPOUNDS
230. Formation of Thiophene (SECTION 654).—Shake together

in a test-tube 1 gram of red phosphorus and 2 grams of flowers
of sulphur. Heat the mixture over a free flame until action
begins. Prepare some sodium succinate by neutralizing 2 grams
of succinic acid with a strong solution sodium carbonate and
evaporating to dryness. HOOD.—Powder the residue and
grind it with the phosphorus sulphide. Place the mixture in an
8-inch test-tube which is fitted with a glass tube bent at two right
angles; the second bend of the tube should pass to the bottom of
a test-tube placed in a beaker containing ice and concentrated
hydrochloric acid. Heat under the hood the tube containing the
mixture of sodium succinate and phosphorus trisulphide as long
as anything distils. Note whether the oil is lighter or heavier
than water.
Add to a drop of the oil a trace of isatin and 1 cc. of concen-
trated sulphuric acid. Test a sample of commercial benzene and
one of benzene purified by crystallization from thiophene.
231. Formation of Furfuraldehyde (SECTION 656).—Boil a
small piece of gum arabic in a test-tube with 5 cc. of dilute sul-
phuric acid. Hold in the vapors escaping from the tube a piece
of paper which has been moistened with a solution of 2 drops of
aniline and 2 drops of glacial acetic acid in 2 cc. of water.
232. Properties of Pyridine (SECTIONS 659, 660).—( a ) Base-
forming property of pyridine.—Dissolve about 1 cc. of pyridine
in 5 cc. of water and test the solution with litmus paper.
Add a solution of pyridine to a solution of ferric chloride and to
one of aluminium chloride. (Eq.)
(b) Pyridine and mercuric chloride.—Add an aqueous solution
of pyridine to one of mercuric chloride. The crystalline pre-
cipitate has the composition HgCl 2 .C 5 H 5 N.
(c) Pyridine and oxidizing agents.—Determine whether pyri-
dine is oxidized by a solution of potassium permanganate, by
193
concentrated nitric acid, or by a mixture of potassium bichromate

and sulphuric acid.
(d) Behavior of pyridine as an amine.—Determine whether
pyridine is a primary, secondary, or tertiary amine. Describe
in detail the tests applied.
(e) Pyridine and methyl iodide.—Mix together in a test-tube
5 drops of pyridine and 5 drops of methyl iodide. Set aside
and examine after a few hours. (Eq.)
233. Preparation of Quinoline by Skraup's Synthesis ( S E C -
TION 662).—In a 1500-cc. flask place 15 grams of finely powdered
hydrated ferrous sulphate, 24 grams of nitrobenzene and 38
grams of aniline; add cautiously 100 grams of pure concentrated
sulphuric acid, and then, slowly with shaking, 120 grams of gly-
cerol. Connect the flask with a long reflux water-condenser, the
inner tube of which has a wide bore. Support the flask and con-
denser by means of damps. Do not use a gauze or bath, but heat
the flask directly, cautiously, with a free flame. In a short
time a vigorous reaction will begin, and a large amount of heat
is evolved; when this occurs remove the flame. When the
spontaneous boiling ceases, place a wire-gauze under the flask,
and heat to boiling for 2 hours. Cool the flask slightly, add about
100 cc. of water and distil with steam as long as an oil passes over.
This distillation serves to remove the excess of nitrobenzene.
Cool the flask under running water, and add a cold solution of 100
grams of sodium hydroxide in 150 cc. of water. Distil over
the quinoline with steam. When an oil no longer separates in
the condenser, stop the distillation.
The aqueous distillate contains the quinoline formed in the
reaction and a small amount of aniline. In order to separate the
latter, advantage is taken of the fact that aniline is converted
into a diazo compound by nitrous acid, whereas quinoline, being a
tertiary amine, is not affected by this reagent. When the aque-
ous solution containing the diazo compound is heated, the latter
is converted into a phenol. Quinoline can be readily separated
from phenol by distillation with steam from an alkaline solu-
tion, in which the phenol is present as the sodium salt and is,
therefore, non-volatile. To effect this separation treat the aque-
ous distillate as follows: Add to the distillate 10 cc. of concen-
trated sulphuric acid. There should be a small excess of acid
HETEROCYCLIC COMPOUNDS 195
over that required to dissolve the oil. Next add a few cubic
centimeters of a solution of sodium nitrite and stir vigorously.
Continue the addition until the solution smells strongly of the
oxides of nitrogen. The quinoline is liberated from its salt by
adding a solution of 40 grams of sodium hydroxide in 50 cc.
of water. Distil again with steam as long as an oil passes over.
Separate the oil, dry it with solid potassium hydroxide and dis-
til. By extracting with ether the aqueous solution, from which
the quinoline was finally separated, the yield can be slightly
increased.
Quinoline boils at 238°. The yield in this preparation is
about 38 grams.
NOTE.—The ferrous sulphate prevents rapid oxidation from taking place,
and, as a result, reduces the violence of the reaction.
ALKALOIDS
234. General Reactions of Alkaloids (SECTION 670).—Dis-

solve the amount of quinine sulphate that can be held on the
point of a pen-knife in about 20 cc. of water. Observe the
appearance of the solution. Add to 2 cc. of the solution drop by
drop, a dilute (1 per cent) solution of tannic acid. Repeat using
solutions of phosphomolybdic acid, picric acid, iodine in potas-
sium iodide, and potassium mercuric iodide. The last-named
solution can be prepared by adding an excess of a solution of
potassium iodide to a solution of mercuric chloride.
235. Test for an Alkaloid in Tobacco: Nicotine (SECTION
672).—In a small distilling flask boil together one cigarette, 25
cc. of water, and 2 cc. of dilute sulphuric acid. At the end of
10 minutes, add an excess of a solution by sodium hydroxide,
connect the flask with a condenser, and distil over about 10 cc.
of the solution. Test the distillate by adding to separate por-
tions of it, drop by drop, solutions of the following: mercuric
chloride, tannic acid, iodine in potassium iodide, and potassium
mercuric iodide.
CHAPTER XXVI
PROTEINS
236. Detection of Nitrogen, Sulphur, and Phosphorus in

Proteins.—The methods described below illustrate those com-
monly used in the analysis of proteins.
(a) Analysis for nitrogen by means of soda-lime.—HOOD.—
Heat about 0.1 gram of casein with five times its weight of soda-
lime in a dry test-tube over a small flame. Observe the odor
of the gases which escape, and test them with moist litmus paper.
(b) Analysis for phosphorus and sulphur by fusion with potas-
sium nitrate.—HOOD.—Fuse together cautiously in a small porce-
lain crucible about 0.1 gram of casein, 0.2 gram of potassium
nitrate, and 0.1 gram of anhydrous sodium carbonate. When
the mixture is colorless, let it cool; then add 10 cc. of water and
heat to boiling. The fusion has converted the phosphorus into
sodium phosphate. The acid radical is tested for in the usual
way. Acidify about 2 cc. of the solution with nitric acid, and
add a solution of ammonium molybdate. If no precipitate forms,
warm gently (about 60°) and set aside. A yellow precipitate
indicates the presence of phosphorus.
Acidify about 2 cc. of the solution from the fusion mixture,
which contains a sulphate if sulphur is present, with hydrochloric
acid, and add a solution of barium chloride. Heat the solu-
tion to boiling and set aside. Examine the tube for a white
precipitate.
(c) Analysis for sulphur by decomposition with sodium hydrox-
ide.—Boil about 0.1 gram of casein with 5 cc. of a 10 per cent
solution of sodium hydroxide to which a drop of lead acetate
solution has been added. If a black precipitate is not evident,
filter the solution through a paper and observe if a precipitate
is left on the paper. When proteins containing sulphur are
decomposed by sodium hydroxide, sodium sulphide is formed; the
latter is converted into lead sulphide by lead salts.
196
PROTEINS 197
(d) Analysis for nitrogen, phosphorus, and sulphur by fusion

with sodium.—Analyze a sample of dried egg-white for nitrogen,
phosphorus, and sulphur by the method commonly used in the
qualitative analysis of organic compounds (§58-61, page 39).
237. Precipitation Reactions of Proteins (SECTION 686).—The
protein solution to be used in the following experiments is pre-
pared as follows: Beat egg-white for a short time to break the
membranes, and squeeze it through cotton cloth. Mix with
ten times its volume of water and filter through paper. This
gives a solution which contains about 1 per cent of protein.
( a ) Strong mineral acids: Heller's test.—Put 2 cc. of egg-
white in a test-tube; incline the tube, and pour cautiously down
the side concentrated nitric acid in such a way that the acid
sinks to the bottom of the tube and two layers are formed.
Shake the tube. Is the precipitate dissolved? Dilute 2 cc. of the
egg-white solution with 100 cc. of water, and test 2 cc. of this
solution as before with nitric acid. Determine whether the pro-
tein is precipitated from the 1 per cent solution by dilute hydro-
chloric acid and by dilute acetic acid, and if it is soluble in an
excess of the acid.
(b) Salts of the heavy metals.—To 2 cc. of egg-white solution
add 1 drop of a solution of mercuric chloride. For what purpose
can this reaction be used?
Test in the same way the effect on the protein of a solution of
lead acetate, of silver nitrate, and of copper sulphate. To the
tube containing the precipitate with copper sulphate add 3 to 4
drops of a solution of sodium hydroxide, dilute, and note the
color.
(c) Alkaloidal reagents in acid solutions. Hydroferrocyanic
acid.—Add to 2 cc. of egg-white solution 5 drops of glacial acetic
acid and 1 drop of a solution of potassium ferrocyanide.
Tannic acid.—Add, drop by drop, to 2 cc. of egg-white solu-
tion a solution of tannic acid.
Picric acid.—Repeat with a solution of picric acid.
Potassium mercuric iodide.—Prepare the reagent by adding
to a few drops of a solution of mercuric chloride a solution of
potassium iodide until the precipitate first formed is dissolved.
Add to 2 cc. of egg-white solution a drop of dilute hydrochloric
acid and a drop of the reagent.
Bromine.—Add bromine-water to 2 cc. of the egg-white solu-

tion until a permanent yellow color is formed.
(d) Coagulation by alcohol.—Add to 5 cc. of the egg-white
solution twice its volume of alcohol. Set aside until the next
exercise. Filter and test the solubility of the precipitate in
water. To do this, wash the precipitate with water, and test
the solution for protein
(e) Heat coagulation.—Heat 2 cc. of the egg-white solution
to boiling. To 2 cc. of the egg-white solution add 1 or 2 drops
of a 0.5 per cent solution of acetic acid, and heat to boiling.
Compare the results in the two cases (see note below).
Determine the temperature of coagulation of egg-white as
follows: Add to 5 cc. of the protein solution 5 drops of a 0.5 per
cent solution of acetic acid. The mixture should be faintly acid
to delicate litmus paper. Put a thermometer in the solution,
and place the test-tube in cold water in a beaker; heat the water
and determine the temperature at which the solution clouds and
when the precipitate separates in flocks. Stir from time to time
with the thermometer.
NOTES.—(a) Heller's reaction is a very delicate test for most proteins;
peptones are not precipitated by nitric acid.
(c) A reaction with potassium ferrocyanide takes place only in acid solu-
tion; neutral salts interfere to some extent with the reaction. Peptones
are not precipitated by hydroferrocyanic acid.
(d) Alcohol precipitates proteins unchanged, but on standing the latter
are converted into a form which is insoluble in water.
(e) Egg-white is faintly alkaline. Complete precipitation takes place
only in faintly acid solution. The temperature at which coagulation takes
place depends to a large extent on the amount of acid and of salts present.
238. Color Reactions of Proteins (SECTION 686).—( a ) Biuret
reaction.—Add to 2 cc. of egg-white solution 2 cc. of a 10 per
cent solution of sodium hydroxide and 2 drops of a 1 per cent
solution of copper sulphate.
(b) Xanthoproteic reaction.—To 2 cc. of the egg-white solution
add 5 drops of concentrated nitric acid and heat to boiling.
Note the change in color. Cool the solution and make it alkaline
with ammonia or sodium hydroxide.
(c) Millon's reaction.—To 2 cc. of the egg-white solution add
5 drops of Mellon's reagent. Is a precipitate formed? Heat to
boiling.
PROTEINS 199
(d) Molisch reaction.—Add to 2 cc. of egg-white solution

3 drops of a solution of a-naphthol in chloroform; shake and
pour cautiously down the side of the test-tube concentrated
sulphuric acid so that two layers are formed. If no color is
produced, put the tube aside and examine in a few minutes.
(e) Sulphur reaction.—Add 1 drop of a solution of lead ace-
tate to 2 cc. of the egg-white solution and then a dilute solution
of sodium hydroxide until the precipitate is dissolved. Heat to
boiling.
(f) Hopkins-Cole reaction.—Add to 2 cc. of the egg-white
solution 5 drops of a solution of glyoxylic acid (see Appendix).
Pour down the side of the tube concentrated sulphuric acid so
that two layers are formed. If no color develops examine the
tube in a few minutes.
NOTES.—(a) Excess of copper sulphate must be avoided in making the

biuret test, since the color of the salt prevents the recognition of the color
produced in the reaction. The presence of ammonium salts interferes with
the test. In applying the reaction to solutions containing these salts a
large excess of sodium hydroxide must be present. Compounds which give
the biuret test must contain at least two —CO—NH— groups. The color
formed in the reaction varies in shade with the complexity of the molecules.
(b) The color is produced as the result of the formation of nitro-derivatives
of the compounds which contain a benzene ring, for example, tyrosine.
(c) The color produced in Millon's test is given by derivatives of benzene
in which a hydrogen in the ring has been replaced by a hydroxyl group. The
reaction serves as a test for the presence of tyrosine.
(d) If the Molisch test is positive, a carbohydrate is present in the protein
molecule.
(e) If sulphur is present a black precipitate or brown coloration is pro-
duced. If the result is in doubt the solution should be filtered and the paper
examined. The precipitate, which is lead sulphide, is formed as the result
of the decomposition of the cystine by the alkali.
(f) The color produced is due to the formation of a compound from the
glyoxylic acid in the reagent and the tryptophane in the protein. A similar
color is produced when sulphuric acid is added to a protein solution in the
presence of a trace of formaldehyde. The reaction is used as a test for
formaldehyde in milk.
239. Study of the Composition of Gelatin and of Wool.—

Apply the precipitation and color reaction of proteins to a solu-
tion of gelatin made by dissolving 1 gram of the substance in 100
cc. of hot water. Cool the solution before it is used. State what
conclusion can be drawn from the results as to the presence or

absence of certain amino-acids in gelatin.
Apply the color tests to a sample of wool.
240. Separation of Proteins by Salting Out (SECTION 679).—
(a) Separation of a globulin from an albumin by means of sodium
chloride.—Add to 10 cc. of the egg-white solution finely powdered
sodium chloride until the solution is saturated and a slight residue
of salt is obtained (3.6 grams for each 10 cc. of solution). The
globulin is precipitated. Filter the solution; add to the filtrate
2 to 3 drops of 0.5 per cent acetic acid, and heat to boiling. The
albumin which was in solution is coagulated.
(b) Separation of a globulin from an albumin by means of am-
monium sulphate.—Prepare a saturated solution of ammonium
sulphate by dissolving 8 grams of the salt in 10 cc. of water.
Add 10 cc. of this solution to 10 cc. of egg-white solution. In
this way the latter solution is one-half saturated with ammonium
sulphate, and the globulin is precipitated. Filter, and to one-
half of the filtrate add 2 drops of a 0.5 per cent solution of acetic
acid and boil. The albumin is coagulated. Saturate the other
half with solid ammonium sulphate; the albumin is precipitated.
Filter, and test the filtrate as before for protein.
241. Products of the Hydrolysis of Proteins.—( a ) Meta-
proteins.—In a test-tube place 10 cc. of the egg-white solution
and 1 cc. of a 10 per cent solution of sodium hydroxide. In a
second tube place 10 cc. of the egg-white solution and 1 cc. of
concentrated hydrochloric acid. Place the tubes in a beaker
containing about 300 cc. of water at 50°, and allow them to stand
from 15 to 20 minutes. The temperatures should not fall below
40°. The protein is partly converted into alkali-albumin and
into acid-albumin.
Boil 2 cc. of the solution in each tube. Is protein precipi-
tated? Add to 2 cc. of the alkali albumin a drop of dilute
hydrochloric acid. Is the precipitate soluble in dilute alkali?
Add to 2 cc. of the alkali albumin a drop of dilute hydrochloric
acid; heat to boiling. Is the precipitate soluble in dilute alkali
as before? Explain. Add to 2 cc. of the acid albumin a drop of
dilute alkali. Is the precipitate soluble in dilute acetic acid?
Add to 2 cc. of the solution of alkali albumin an equal volume of
a saturated ammonium sulphate solution. Is the protein
precipitated?
PROTEINS 201
(b) Proteoses and peptones.—Stir 2 grams of Witte's pep-

tone with 40 cc. of cold water, and filter from the small insoluble
residue.
Add to 2 cc. of the solution 2 to 3 drops of 0.5 per cent solu-
tion of acetic acid and boil. Are the proteins coagulated?
242. Separation of Proteoses and Peptones.—Saturate 20
cc. of the solution prepared in experiment 241b above with
ammonium sulphate (16 grams). Filter. Save the filtrate which
contains the peptones. Place the filter-paper containing the
precipitate in a beaker, and heat it with 25 cc. of water. Filter.
This filtrate contains the proteoses. Apply to the solution of
the peptones and to the solution of the proteoses the precipita-
tion and color reactions given above. Compare the results in
the two cases. In making the biuret test when ammonium salts
are present, a large excess of alkali must be added; add a strong
(1 to 1) solution of sodium hydroxide or about 10 cc. of a 10
per cent solution to 2 cc. of the solution to be tested.
243. The Proteins of Wheat (SECTION 690).—( a ) Protein
soluble in water (leucosin).—Shake up about 1 gram of bread
flour with 10 cc. of water, filter, and determine whether the
filtrate contains protein by applying three or four tests.
(b) Alcohol-soluble protein (gliadin).—Add 25 cc. of water to
75 cc. of alcohol. Pour the mixture onto about 20 grams of
bread flour. Stir occasionally during half an hour. Filter, and
evaporate the filtrate to dryness. Observe the properties of the
dried protein. Is it brittle? Moisten it with water and after
a few minutes note its properties. Is it elastic? Prove that it
is a protein by applying a number of tests.
(c) Separation of gluten.—Gluten is a mixture of glutenin
and gliadin. In a porcelain dish mix 50 grams of bread flour
with enough water to make a stiff dough (about 25 c c ) . Let the
mixture stand for half an hour. Add about 100 cc. of water and
work the dough, keeping it in the form of a ball. The starch
passes into suspension in the water. Pour off the water, and
add fresh water from time to time until all the starch is re-
moved. Note the properties of the gluten.
The two proteins present can be separated by extracting the
gliadin with 75 per cent alcohol. This is a tedious process.
Grind a small part of the gluten in a mortar repeatedly with 10
cc. portions of 75 per cent alcohol. Finally heat the residue with
some of the alcohol on the steam-bath. When all the gliadin has
been removed the protein is no longer elastic. Dissolve the glu-
tenin in dilute sodium hydroxide and apply a few of the protein
tests.
NOTE.—Wheat contains the following proteins: Soluble in water, leucosin,
about 0.4 per cent, and a proteose, about 0.3 per cent; soluble in 10 per
cent sodium chloride, edestin, about 0.6 per cent; soluble in 75 per cent
alcohol, gliadin, about 4.3 per cent; insoluble in neutral solvents, glutenin
from 4.0 to 4.5 per cent.
244. Isolation of a Crystalline Protein: Edestin from Hemp

Seed.—Grind in a mortar 25 grams of hemp seed; add the seed in
small quantities at a time, and see that each seed is crushed.
Dissolve 28 grams of sodium chloride in 700 cc. of water (4 per
cent solution of sodium chloride) and heat to 60°. Add the hemp
seed and stir frequently during 15 minutes. The temperature
of the solution should be kept between 58° and 60° during the
extraction of the protein. This can be accomplished by placing
a very small flame under the beaker. If the temperature rises
above 60°, the flame should be removed. Filter into a dry
beaker through a large hot water funnel containing water at 60°.
Cover the funnel with a watch-glass to prevent loss in heat from
the solution. Receive the first part of the filtrate in a small
beaker and return it to the funnel. Set the filtrate aside to cool
slowly. When the solution is cold, decant off most of the liquid
carefully and filter off the solid. Place a little of the suspended
solid on a glass slide, cover, and examine under a microscope.
Sketch the crystals. If crystals have not separated from the
solution before the end of the laboratory period, leave the solu-
tion in a cool place. Test the edestin crystals by applying the
following reactions: xanthoproteic, biuret, Hopkins-Cole, Mil-
lon, sulphur. Shake up some of the protein with 20 cc. of a
10 per cent solution of sodium chloride. Filter through a dry
paper into a dry test-tube. If the first part of the filtrate is
cloudy return it to the funnel. Pour some of the clear filtrate
into water. Determine whether the protein is coagulated by
heat, and whether it is salted out by sodium chloride and by
ammonium sulphate.
NOTE.—During the extraction of edestins it is necessary to avoid a
high temperature in order to prevent the coagulation of the protein.
PROTEINS 203
245. Isolation of Casein from Milk (SECTION 696).—To 50 cc.

of milk add 150 cc. of water and heat the mixture to 30°. Add
dilute acetic acid, drop by drop, as long as a precipitate is formed
(about 1 cc. of a 10 per cent solution). Stir vigorously. It is
necessary to avoid an excess of acid, since the latter dissolves
some of the protein. Filter, During the filtration test small
portions of the filtrate for protein by three or four color reactions.
Heat 10 cc. of the filtrate to boiling. What protein is pre-
cipitated? Filter this off, and test the filtrate for a sugar with
Fehling's solution, and for a phosphate with ammonium
molybdate.
Wash the precipitate of casein with 50 cc. of water; press out
as much water as possible, and then wash the precipitate twice
with 20 cc. of alcohol. Squeeze out the alcohol, and press
the casein between a number of pieces of filter-paper. Break
up the casein and let it dry in the air. Determine whether it is
soluble in water. To do this, grind in a mortar a little of the
solid with 10 cc. of water, filter, and test the filtrate for a protein
with concentrated nitric acid. If the filtrate is not clear, refilter
it through two filter-papers. Determine if casein is soluble in
sodium carbonate solution. Proceed as before; acidify the fil-
trate and test it for a protein.
Put into a mortar 10 cc. of water and 3 or 4 drops of a dilute
solution of sodium hydroxide. Test the solution with red
litmus paper. Next add some casein and grind it thoroughly in
the alkaline solution. Test the solution again with red litmus
paper. What conclusion can you draw in regard to the chemical
nature of casein. Filter the solution through a wet filter-paper,
and add to the filtrate a few drops of a solution of calcium
chloride. Explain.
T E X T I L E FIBERS
246. Appearance of Fibers.—Examine under a microscope a

fiber of each of the following: Silk, wool, cotton, mercerized
cotton, and linen.
247. Properties of Wool, Silk, and Cotton.—( a ) Effect of
burning.—Burn a thread of wool, of silk, and of cotton. Notice
the odor produced during the burning. Explain. At the end of
a few seconds blow out the flame and observe the appearance of
the charred residue.
(b) Action of sodium hydroxide.—For this and the following
experiments use pieces of the material about 1 inch square.
Place in a test-tube a piece of cotton, a piece of silk, and a piece
of wool; add about 10 cc. of a 10 per cent solution of sodium
hydroxide. Heat the solution to such a temperature that the
tube can just be held in the hand (about 65°); shake, and keep the
tube hot by heating it occasionally until the wool dissolves. Heat
to boiling for some minutes and note the effect. Explain the cause
of the difference in behavior of the animal and vegetable fibers.
(c) Action of concentrated hydrochloric acid.—Shake pieces of
cotton, silk, and wool with about 10 cc. of cold concentrated
hydrochloric acid. One of the pieces should dissolve.
Place a piece of cotton and a piece of wool in a mixture of 1 cc.
of concentrated hydrochloric acid and 5 cc. of water. Press out
as much of the solution as possible. Set aside to dry and examine
at the next exercise. Try to tear the material.
(d) Examination of wool and of silk for sulphur.—Add a few
drops of a solution of lead acetate to about 20 cc. of a 10 per cent
solution of sodium hydroxide. Divide the solution into two
portions. In one dissolve a piece of wool and in the other a
piece of silk.
(e) Action of Millon's reagent (SECTION 686).—Millon's reagent
is prepared by using the substances in the following proportions:
One gram of mercury is dissolved in 2 cc. of hot concentrated
nitric acid and the resulting solution diluted with 3 cc. of water.
Dilute 2 cc. of the reagent with 10 cc. of water, add to the solu-
tion pieces of cotton, silk, and wool, and heat to boiling.
(f) Test of textile fabrics.—Test the samples submitted, mak-
ing use of the results obtained in ( a ), ( b ), (c), (d), and (e) above.
The samples may consist of cotton, silk, or wool, or mixtures
of any two of the fibers. It is a common practice to make
fabrics in which the threads running in one direction are of
one material, and those running in another are of a different
material. Designs in pure silk are often woven into a fabric
made of mercerized cotton. These designs can be readily
developed by warming a sample of the material with Millon's
reagent.
CHAPTER XXVII
THE IDENTIFICATION OF ORGANIC COMPOUNDS
248. Throughout the laboratory course outlined in the pre-

vious chapters, the typical reactions of a number of important
classes of compounds have been illustrated by experiments.
These reactions are made use of in the identification of organic
compounds. Practice in such identifications is of great edu-
cational value, as it requires continuous thought on the part of
the student, is an excellent review of many facts which have
been learned, and has a practical significance.
No set analytical scheme is available as is the case in inor-
ganic qualitative analysis. The subject is more complicated than
the latter, and each compound requires special study. By the
application of a few simple tests it is often possible to determine
to what class a compound belongs. In order to facilitate the
work the student should prepare a table which summarizes the
behavior of certain typical compounds with a few important
reagents. To do this proceed as follows: Divide a large sheet
of paper into squares by drawing on it twenty horizontal and
fifteen vertical lines. Place in the first vertical column on the
left side of the paper the names of the following important classes
of compounds, using a square for each class: paraffin hydro-
carbons, unsaturated hydrocarbons, aromatic hydrocarbons,
alcohols, phenols, acids, ethers, anhydrides, esters, aldehydes,
ketones, amines, amides, nitriles, nitro compounds, halogen
compounds, sulphonic acids, carbohydrates. In the squares
that form the upper horizontal column write the following: water,
cold solution of sodium hydroxide, hot solution of sodium hydrox-
ide, solution of sodium carbonate, dilute hydrochloric acid, cold
concentrated sulphuric acid, acetyl chloride, sodium, bromine,
influence of substituents, influence of aromatic group, special
reactions, and remarks. State briefly, as far as possible, in the
appropriate squares, the behavior of the several classes of com-
pounds with the reagents listed. It will take time and study
205
to do this satisfactorily. The following references to the sections

in the text-book and to the laboratory experiments will be of
value in getting together the facts to be incorporated into the
table. It is important that any notes under the experiments
referred to should be read: paraffin hydrocarbons, 26, 27,
and experiment 70, page 47; unsaturated hydrocarbons, 38, 46,
and experiments 74 and 75, page 52; aromatic hydrocar-
bons, 429, and experiments 164d to h, page 133; alcohols, 74, 83,
and experiment 79, page 57; phenols, 540, and experiments 197,
198, page 167; acids, 124, and experiments 90, 91, page 66;
ethers, 147, and experiment 96, page 73; anhydrides, 152, and
experiment 98, page 75; esters, 173, and experiment 103, page
79; aldehydes, 188, and experiment 108, page 86; ketones, 200, and
experiment 111, page 87; amines, 213, 505, and experiments 113,
183, 184, 185, pages 89, 154, 156; amides, 231, and experiment
116, page 92; nitriles, 244, and experiment 127, page 97; alkyl
halides, 255, and experiment 132, page 101; acyl halides, 278, and
experiment 139, page 109; aryl halides, 480, and experiment 180,
page 148; carbohydrates, 386, and experiments 148, 152, 156,
pages 119, 123, 128; nitro compounds, 469, and experiment
171, page 140; sulphonic acids, 477, and experiment 174,
page 144.
249. The properties of the members of any class are in general
like those illustrated in the case of the simpler members, which
have been studied by the student. It is important to remember,
however, that increase in molecular weight generally leads to
decreased solubility and chemical activity. For example, the
anhydrides with low molecular weight of the homologues of
acetic acid react promptly with water, whereas those of high
molecular weight must be heated with water for some time to
bring about hydrolysis. It is also important to remember that
the presence of a second group in a compound often modifies
the properties which a characteristic group gives to i t ; for ex-
ample, monhydroxy phenols are insoluble in dilute hydrochloric
acid, but aminophenol dissolves in this reagent on account of
the presence of the amino group.
Before beginning to identify an unknown compound the
student should study SECTIONS 405 to 408 inclusive, and solve
problem 2 at the end of Chapter X V I I in the text-book. The
IDENTIFICATION OF ORGANIC COMPOUNDS 207
work should be done carefully with small amounts of the substance

to be studied. About 10 grams of a pure compound is ordinarily
enough for complete identification, including the preparation of
a derivative and the determination of its physical properties.
Solubilities can be determined with a crystal or a single drop.
The first substances given to the student should be practically
pure.
The work is begun by testing the purity of the sample to be
identified. If it is a liquid the substance should be distilled very
carefully from a small flask (§44, page 30). If the substance
is a solid its melting-point should be determined. Record the
result obtained, as it is to be used in the final identification. If
the substance is impure it should be purified before being studied
further. Burn some of the substance (experiments 164d, note,
and 180b, pages 134, 148,) and determine if possible if it is an
aromatic compound (experiment 164e and f, note). Next make
a qualitative analysis (§57-61, pages 39, 42). If any element
other than carbon, hydrogen, and oxygen is found, it is well to
make tests to discover in what group the element is present.
Study next the behavior of the substance with the reagents
given in the table prepared as described above, and test with
Tollen's and Schiff's reagent. If the substance appears to be a
carbohydrate, apply the Molisch test.
250. When the class or classes to which the compound belongs
and the melting-point or boiling-point have been determined,
consult large texts, or other reference books on organic chemistry,
which contain tables or lists of compounds with their physical
properties. Such books as Richter, "Organic Chemistry;" Beil-
stein, "Handbuch der Organischen Chemie;" Mulliken, "Identi-
fication of Pure Organic Compounds;" Chemiker Kalender;
Meyer and Jacobson, "Lehrbuch der Organischen Chemie;" and
Van Nostrand's "Chemical Annual" are useful. Take into con-
sideration compounds the melting-points of which lie within
about four degrees on either side of the point observed. Such a
range is necessary as the melting-points and boiling-points
recorded are at times far from accurate. When one or more
compounds are found the descriptions of which fit those of the
substance under study, find out what derivative which possesses
a satisfactory melting-point or boiling-point can be readily made.
It is best to prepare a solid whenever possible, since in this case

much smaller amounts of substance can be used. Look up the
properties of this derivative and its method of preparation, and
convert about 1 gram of the substance to be identified into the
derivative if the latter is a solid; if it is a liquid more will be
required. Before making the preparation read carefully pages
29 to 32, where the special technique of handling small quanti-
ties is described. Determine the melting-point or boiling-point
of the compound prepared; if this agrees with the number as
given, the identification of the original substance may be con-
sidered satisfactory.
In the case of certain compounds it is difficult to transform
them into other substances when only a small amount is avail-
able. In this case, if the compound is a liquid, it is often con-
venient to determine its specific gravity (§56, page 37) as an
aid in its identification. At times both the melting-point and
the boiling-point of a substance can be determined; these two
constants often will serve to identify a compound. For the iden-
tification of a substance it is necessary to have at least two phys-
ical constants agree with those which have been recorded; these
may be constants of the substance itself, or one may be a constant
of the substance and one of a compound into which it has been
converted. Reliance on one constant often leads to mistakes.
For example, o-chlorotoluene boils at 154° and m-chlorotoluene at
156°. It would be very difficult to identify either substance by
a determination of its boiling-point alone. The identification is
readily accomplished, however, by converting the compounds
into the corresponding benzoic acids; o-chlorobenzoic acid melts
at 137° and m-chlorobenzoic acid at 153°.
251. In the following list, the derivative which can be conven-
iently prepared, in most cases, from the several classes of com-
pounds is given. In some cases specific gravity determinations
are made, although it is preferable to convert the compound
into another substance if possible: paraffin hydrocarbons, specific
gravity; unsaturated hydrocarbons, addition-products with bro-
mine or hydriodic acid; aromatic hydrocarbons, solid nitrocom-
pounds (experiment 172, note, page 142), or addition-products
with picric acid (experiment 169c, page 138); alcohols, special
tests or solid esters of aromatic acids; phenols, bromine substi-
IDENTIFICATION OF ORGANIC COMPOUNDS 209
tution-products; monobasic fatty acids, solid anilides (experiment

91c, page 67), or esters; polybasic acids, characteristic salts;
aromatic acids, amides (experiment 202, page 171) or nitro-
derivatives; ethers, specific gravity or conversion into iodides
(experiment 96j, page 74); aromatic ethers, as above, or nitro-
derivatives; fatty anhydrides, anilides (experiment 98e, page
76); aromatic anhydrides, change to acids; esters, hydrolysis
and identification of the acid or alcohol formed; fatty aldehydes,
specific tests; aromatic aldehydes, nitroderivatives or special
tests; ketones, oximes (experiment 210, page 176), or special
tests (experiment 111f, page 88); fatty amines, salts with hydro-
chloric acid; aromatic amines, acetyl derivatives or special
tests; amides, change to acids; nitriles, change to acids; nitro
compounds, further nitration or reduction to amines; sulphonic
acids, amides; carbohydrates, special tests, osazones, behavior
with Fehling's solution, etc.
252. Study of Mixtures.—(See SECTION 408).—The mixture
should be treated in turn with twice its volume of water, dilute
hydrochloric acid, dilute sodium hydroxide, and concentrated
sulphuric acid. When sulphuric acid is used care must be taken
to keep the mixture cold. If the mixture is a liquid it should be
treated with solvents in a graduated cylinder. The volume of
the liquid should be noted before and after shaking with the
solvents; in this way it can be easily seen whether any of the mix-
ture dissolves. If this occurs the mixture should be treated
with small quantities of the solvent as long as any of its dissolves.
The several solutions should be examined separately. The water
solution should be carefully distilled. It is tested first with lit-
mus paper to determine whether an acid or an amine is present.
If an acid is present the solution should be neutralized with
sodium hydroxide before distillation. The acid will remain in
the flask as a sodium salt and other volatile substances will pass
over. The boiling-point should be carefully noted during the
whole distillation. If there is evidence of the presence of any-
thing in solution, tests should be applied to the distillate for the
classes of substances soluble in water.
The extract obtained by treatment with acid should be ren-
dered alkaline. If a basic substance has been removed it will be
precipitated; this should be separated and tested.
The extract obtained with sodium hydroxide is next treated

with dilute hydrochloric acid. If an acid or phenol is present
it will be precipitated, and is examined.
The concentrated sulphuric acid solution is poured very care-
fully onto twice its volume of cracked ice. Any substance which
is precipitated is washed with a little water, separated, and
examined. If two substances which belong to the same class of
compounds are present in a mixture, it is usually necessary to
separate them by fractional distillation.
A full record of all tests used should be placed in the note-
book. The observed physical properties (melting-point, boiling-
point or specific gravity) of the substance and of the compound
prepared from it should be given together with the physical
properties as recorded in the reference books.
APPENDIX
SCHIFF'S R E A G E N T
Dissolve about 0.2 gram of rosaniline in a small amount of

boiling water. Cool and add 15 cc. of a saturated solution of
sulphur dioxide in water, and allow the mixture to stand several
hours until it becomes colorless or pale yellow; then dilute to
200 cc. with water. The reagent should be kept in a well-stop-
pered bottle of dark glass.
TOLLEN'S R E A G E N T
Make an ammoniacal solution of silver nitrate by dissolving

10 grams of the salt in 100 cc. of a solution of ammonia prepared
by mixing equal volumes of concentrated ammonia (sp. gr. 0.9)
and water. When ready to make a test, mix a portion of this
solution with an equal volume of a 10 per cent aqueous solution
of sodium hydroxide. The test should be made in the cold.
The sodium hydroxide should be added immediately before
use; on standing or on heating, the mixture so prepared deposits
a black explosive precipitate.
FEHLING'S SOLUTION
Dissolve 34.64 grams of pure crystalline copper sulphate in

distilled water, and dilute to 500 cc. Dissolve 70 grams of
sodium hydroxide and 180 grams of pure Rochelle salt in 400 cc.
of water, and dilute to 500 cc. The solutions should be kept in
separate bottles until used. Fehling's solution is made by mixing
equal volumes of the two solutions. A solution prepared in this
way is of such a strength that 1 cc. of it will oxidize 0.005 gram
of dextrose.
MILLON'S REAGENT
Dissolve 10 grams of mercury in 20 cc. of hot concentrated

nitric acid, and dilute the resulting solution with 30 cc. of water.
211
HOPKINS-COLE REAGENT
In a large flask place 10 grams of powdered magnesium, cover

the latter with distilled water, and add slowly, keeping the mix-
ture cold, 250 cc. of a cold saturated solution of oxalic acid.
When the reaction is complete, filter, make the filtrate slightly
acid with acetic acid, and dilute to 1000 cc. with distilled water.
PREPARATION OF HYDROBROMIC A C I D
The constant-boiling mixture of hydrobromic acid and water

can be conveniently used to prepare alkyl bromides. The acid
boils at 126°, contains about 47.5 per cent of hydrogen bromide,
and has a specific gravity of about 1.48.
The acid can be prepared from potassium bromide or from
bromine.
(a) From potassium bromide.—In a 250 cc. distilling flask
pour slowly into 85 cc. of water 98 grams of pure concentrated
sulphuric acid. To the mixture add 119 grams of powdered
potassium bromide and distil slowly, using a water-jacketed
condenser. Collect the fraction boiling at 124°-126°. The yield
is 85 to 90 per cent of the theoretical.
(b) From bromine.—In a 200 cc. distilling flask place 162 cc.
of water and 10 grams of red phosphorus; cover the side-arm of
the flask with a cork (Fig. 16, page 26), connect the flask
with a return condenser, and place it in a water-bath so that it is
completely covered with cold water. Put 40 cc. of bromine in a
small separatory funnel, and support the latter in the condenser
at the top. Allow the bromine to flow into the flask slowly,
drop by drop. When all the bromine has been added, support
the flask on a wire gauze, connect it with a condenser and distil.
Collect the part which boils at 124°-126°. The yield is about
95 per cent of the theoretical.
PREPARATION OF HYDRIODIC A C I D
The constant-boiling aqueous solution of hydriodic acid can be

conveniently used for the preparation of alkyl iodides. The solu-
tion contains about 57 per cent of hydriodic acid, boils at 127°,
and has the specific gravity of 1.68 to 1.70. The exact composi-
tion varies with the pressure at which the acid is distilled. The
APPENDIX 213
solution is prepared as follows: In a 100 cc. distilling flask place

65 cc. of water and 70 grams of iodine. Put the flask in a water-
bath containing cold water, and force it down so that the whole
bulb of the flask is submerged. Hold the flask in place by means
of a clamp and ring-stand. Add 6.5 grams of red phosphorus.
Let the flask stand for about 5 minutes. Support it on a wire
gauze, connect with a condenser and distil. Collect what boils
at 126°-127°. The yield is about 95 per cent of the theoretical.
INDEX
A Aniline, preparation of, 153

properties of, 154
Acetaldehyde, 85-87 Anisol, 168
Acetamide, 91-92 Anthraquinone, 178
Acetanilide, 67, 76 Azo dye, 187
Acetic acid, glacial, 66
preparation of, 65 B
properties of, 66 Barium ethyl sulphate, 78
tests for, 67 Baumann and Schotten reaction, 63
Acetic anhydride, 75 Beckmann's rearrangement, 176
Acetoacetic ester, 114 Benzaldehyde, properties of, 174
synthesis, 115 Benzalphenylhydrazone, 163
Acetone, 87 Benzamide, 171
identification of, 88 Benzanilide, 170
Acetyl chloride, 108 Benzene, preparation of, 132
Acetylene, 52 properties of, 132-134
Acids, aromatic, 170 Benzenesulphonamide, 145
fatty, 64 Benzenesulphonic acid, 142
Acyl chlorides, 108 Benzenesulphonyl chloride, 144, 157
Albumin, 200 Benzoic acid, detection in foods, 184
Alcohol, see ethyl alcohol identification of, 170
Alcohols, 55 preparation of, 170
aromatic, 165 Benzophenone, 175
Aldehyde, see acetaldehyde from diphenylmethane, 136
Aldehydes, 84 Benzophenoneoxime, 176
aromatic, 174 Benzyl alcohol, 165
Alkaloidal reagents, 197 Biuret, 94
Alkaloids, 195 Boiling-points, determination of, 36
Allyl alcohol, preparation of, 60 Bone-black, use of, 8
properties of, 61 Bromine, test for, 41
Amides, 91 Bromobenzene, 147
Amines, 89 Bumping, prevention of, 27
aromatic, 153, 157 Butter, saponification of, 81
Aminoazobenzene, 161 Butyl chloride (normal), 104
Amyl alcohol (sec.), 61 Butyric acid, 116
Amylene, 51, 52
Analysis, 205 C
qualitative, 39 Caffeine, from tea, 131
Anhydrides, 75 Calcium oxalate, 71
Aniline, formation of, 140 Carbohydrates, 118
215
216 INDEX
Carbon disulphide, test for, 133 E

Casein, 203
Cellulose, 126 Edestin, 202
acetate, 127 Emulsification, 82
nitrate, 127 Eosin, 190
Chloral, 117 Esters, 78
Chlorine, test for, 41 properties of, 79
Chloroform, 105 Ethane, 46
Cinnamic acid, 172 Ether, absolute, 73
Citric acid, 113 preparation of, 72
Cloves, oil of, 180 properties of, 73
Coagulation of proteins, 198 Ethers, 72
Colloidal solutions, 123 properties of, 73
Condensers, reflux, 26 Ethyl acetate, preparation of, 78
Congo red, 190 properties of, 79
Cotton, 203 Ethylacetoacetic ester, 115
Crystallization, 3, 29 Ethyl alcohol, absolute, 59
Cyanides, 95
preparation of, 55
alkyl, 97 properties of, 57
test for, 95 tests for, 59
Cyanogen, 95 Ethyl-benzene, 134
bromide, 100-102
D iodide, 102
isoamyl ether, 75
Dextrin, 126 sulphuric acid, 78
Dextrosazone, 118 Ethylene, 50, 51
Dextrose, 118 bromide, 106
Dialysis, 123 Eugenol, 180
Diazo compounds, 158 Extraction, 21, 31
Diazoaminobenzene, 161
Dibenzalacetone, 88 F
Dibromobenzene, p, 148 Fat, saponification of, 67, 81
Digestion, salivary, 125 Fats, 81
Di-isoamyl, 46 Fehling's solution, 211
Dimethylaniline, 156 Fermentation, 55, 120
Dimethyl terephthalate, 173
Ferric citrate, 114
Dinitrobenzene, m, 141
Diphenyl-carbinol, 166 Flash-point, 48
Flour, composition of, 201
-ethycarbinol, 166 Fluorescein, 189
-methane, 136 Formaldehyde, 84
Distillation, 8, 30 Formic acid, 64
fractional, 12, 43 Furfuraldehyde, 193
under diminished pressure, 15
G
with steam, 19
Drying agents, 25 Gasoline, 47, 52, 106
Dyeing, 190 Gelatin, 184
Dyes, 187 composition of, 199
INDEX 217
Gliadin, 201 L
Globulin 200
Gluten, 201 Lactic acid, 110
Glycerol, 69 Lactose, 121, 122
properties of, 62 Lecithin, 91
Glyceryl tribenzoate, 63 Leucosin, 201
Grignard reaction, 46, 166
M
H Malachite green, 188, 191
Melting-points, determination of, 33
Halogen compounds, 99 Mercaptan, 129
aromatic, 148 Mercuric thiocyanate, 129
Halogens, test for, 41 Metals, tests for, 39
Heller's test, 197 Metaproteins, 200
Hemp seed, 202 Methane, preparation of, 44
Heterocyclic compounds, 193 properties of, 45
Hexaphenylethane, 137
Methyl alcohol, 55
Hopkins-Cole reaction, 199
-amine, 89
reagent, 212 -aniline, 156
Hydriodic acid, preparation of, 212 cyanide, 97
Hydrobenzamide, 174
iodide, 99, 100
Hydrobromic acid, preparation of,
orange, 187
212 salicylate, 55
Hydrocarbons, aromatic, 132 Milk, 203
saturated, 44, 47 formaldehyde in, 84
unsaturated, 50, 51, 52 Millon's reaction, 198
Hydroxy acids, test for, 113 reagent, 211
Mixture, analysis, 209
I Molisch reaction, 119, 199
Mordants, 191
Identification of compounds, 205 Mucic acid, 122
Iodine, test for, 41 Murexide test, 130
Iodobenzene, 159
Iodoform test, 59 N
Ingrain colors, 191
Naphthalene, 137
Ink, 185
Nicotine, 195
Isoamyl, acetate, 80
Nitroaniline, m, 181
bromide, 103
p, 182
ethyl ether, 75
Nitroanilines, salts of, 183
Isocyanides, 98
Nitro-acetanilide, 182
benzene, 139-141
K compounds, 139
-phenol, o and p, 179
Kerosene, 47 Nitrogen, test for, 40
Ketones, 87 test for in proteins, 196
218 INDEX
O S
Oils, 81 Saccharic acid, 122

emulsification of, 82 Salicylic acid, 183
Osazones, 120 detection of in foods, 184
Oxalic acid, preparation of, 69 Saliva, 125
properties of, 70 Salting out of proteins, 200
tests for, 70 Sandmeyer reaction, 159
Saponification, 67
P Schiff's reagent, 211
Schweitzer's reagent, 126
Paper, test of, 128 Silk, 203
Parchment-paper, 126 Silver oxalate, 70
Pentosans, 128 Skraup's synthesis, 194
Peptones, 201 Soap, 67
Perkin's synthesis, 172 Sodium, benzenesulphonate, 142
Phenol, preparation of, 158
manipulation of, 28
properties of, 167 Specific gravity, determination of, 37
Phenols, from sulphonic acids, 144 Starches, 123
reactions of, 168 Sublimation, 24
Phenyl-hydrazine, 162 Succinic anhydride, 77
-hydroxylamine, 141 Sucrose, 121
-semicarbazide, 163 Sugars, general properties of, 119
Phosphorus, test for, 42 Sulphanilic acid, 181
test for in proteins, 196 Sulphonic acids, 142
Phthaleins, 168 identification of, 144
Potassium benzene sulphonate, 143
Sulphur, compounds, 129
cyanide, 95 test for, 40
ethyl sulphate, 78 test for in proteins, 196
ferric oxalate, 70
ferricyanide, 96
ferrocyanide, 96 T
tetroxalate, 70
thiocyanate, 129 Tartaric acid, 111
xanthate, 129 Tannic acid, 184
Primuline, 191 Tea, 131, 185
Proteins, analysis of, 196 Terephthalic acid, 173
and formaldehyde, 84 Textile fibers, 203
color reactions of, 198 Thermometers, calibration of, 32
hydrolysis of, 200 Thiocyanates, 129
precipitation reactions of, 197 Thiophene, 193
Proteoses, 201 Tobacco, 195
Pyridine, 193 Tollen's reagent, 211
Toluenesulphonic acid, p, 145
Q Toluic acid, p, 171
Tolunitrile, p, 159
Quinoline, 194
Tribromophenol, s, 167
Quinone, 176
INDEX 219
Trichloroacetic acid, 110 W

Triphenylchloromethane, 150
Triphenylmethane, 151 Water, test for in organic com-
Triple bond, test for, 53 pounds, 57
Wheat, proteins of, 201
U Wool, 203
composition of, 199
Unsaturated compounds, test for, Wurtz synthesis, 46
52
Urea, 93 X
Uric acid, 130 Xanthates, 129
Xanthoproteic reactions, 198
V Y
Verdigris, 66 Yield, calculation of, 2

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EXPERIMENTAL

TOTAL ISSUE, 38,000

PRINTED IN THE UNITED STATES OF AMERICA

THE MAPLE PRESS COMPANY, YORK, PA.

in the laboratory directions details for these processes, and if the

CHAPTER I.—LABORATORY METHODS 1

CHAPTER II.—GENERAL PROCESSES: HYDROCARBONS OF THE

CHAPTER III.—UNSATURATED HYDROCARBONS 50

CHAPTER XL—COMPOUNDS CONTAINING Two UNLIKE SUBSTITU-

CHAPTER XIII.—COMPOUNDS CONTAINING SULPHUR 129

CHAPTER XXI.—AROMATIC ACIDS 170

1. General Directions to the Student.—Before beginning an

be given, and a statement made of the amounts of the substances

5. When an organic compound has been prepared it must

solubilities in the liquid used as a solvent. When it is desired

6. Some substances form solutions from which the first crystals

prevent crystallization. In the latter case, and whenever an

11. The Use of a Mixture of Two Liquids as the Solvent in

washed by pouring the solvent over them while the filter-bottle

15. Liquids are purified by distillation. The form of apparatus

16. Preparation of Corks.—Before being used corks should be

20. Distillation of High-boiling Liquids.—When a liquid boils

FIG. 3. FIG. 4. FIG. 5.

in this case, or when an air-condenser is used, the distillate solidi-

21. Fractional Distillation.—When it is necessary to separate

FIG. 6. FIG. 7. FIG. 8. FIG. 9.

The arrangement represented in Fig. 5 is very efficient,

is that of Wurtz, Fig. 6. The efficiency of the Lebel-Henninger

FIG. 10. FIG. 11

one of the liquids to that of the other. The distillate which is

66°-68° 68°-78° 78°-88° 88°-98° 98°-100°

I 0.0 1.5 47.0 17.0 31.0

When the liquids form a constant-boiling mixture, they can

DISTILLATION UNDER DIMINISHED PRESSURE

24. Many substances which decompose when distilled at

regulating the screw-clamp after the apparatus has been attached

10). If the latter is used and bumping occurs, the material in

selected of such a diameter that the thermometer passes into it

the receiver as a result of a slight change in the pres-

boiling liquid begins to froth or bump violently. In the latter

means of a free flame as the amount of heat applied can be

DISTILLATION WITH STEAM

28. Substances which are practically immiscible with water

29. The vapor issuing from the flask consists of a mixture of

and water is an example. When steam is passed into nitro-

appreciable vapor pressure at 100°, and is consequently volatile

By extraction is meant the process of removing from a mixture,

approximately 10 per cent of its volume of ether. When large

33. The relation between the volumes of the extracting liquid

stopper, an adapter, which, in turn, is attached in the same way

clamp. The apparatus is heated slowly on a sand-bath and the

except in the case of substances which boil below 80°, to remove

FIG. 15. FIG. 16.

heated on a sand-bath; otherwise a free flame and a wire gauze are

is left unchanged at the end of the experiment. Great care must

T H E MANIPULATION OF SMALL QUANTITIES OP SUBSTANCES

In the identification of organic compounds it is generally

filtered is poured into it. Under the diminished pressure, the

closed by the end of the forefinger. Ether is added, the tube

a beaker. It is important that the tube from a should extend