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GIFT OF
MICHAEL REE&E




A TREATISE ON CHEMISTRY.



TEEATISE ON CHEMISTRY.



BY

H. E. ROSCOE F.R.S. AND C. SCHOKLEMMER F.R.S.

PROFESSORS OF CHEMISTRY IN THE VICTORIA UNIVERSITY, OWENS COLLEGE, MANCHESTER.



VOLUME III.
THE CHEMISTRY OF THE HYDROCARBONS AND THEIR DERIVATIVES,

on

ORGANIC CHEMISTRY.
PART I.



'' Chyinia, alias Alchemia et Spagirica, est ars corpora vel mixta, vel composita,
vel aggregaf.a etiam in principia sua resolvtndi, aut ex principiis in talia
combinandi." STAHL, 1723.




NEW YORK:
D. APPLETON AND COMPANY,

1, 3, AND 5 BOND STREET,
1890.



CONTENTS.



VAGI

HISTORICAL INTRODUCTION 3

Early Ideas on Organic Chemistry ....... 5

Lavoisier's Researches ....... 7

Berzelius' Investigations * ... 9

Compound Radicals . .11

Dumas' Theory of Substitutions . . ... . .15

Dumas' Theory of Chemical Types 16

Isolation of the Radicals . . . . . .19

Theories of Types and Radicals 22

Gerhardt's Theory of Types . 24

Williamson's Views 27

Theory of Mixed Types 30

Definitions of Organic Chemistry 33

Hydrocarbons and their Derivatives . 37

Homologous Series 39

ULTIMATE ORGANIC ANALYSIS 40

Lavoisier's Method of Analysis . . . . - . . . .41

Saussure, Thenard, and Berthollet's Method 43

Gay-Lussac and Thenard's Method 43

Berzelius' Method 45

Liebig's Method 48

Gas Combustion Furnaces . . 53

Combustion in Current of Oxygen 55

Combustion of Nitrogenous Bodies 58

Combustion of Bodies containing Sulphur 59

Organic Analysis by means of Platinum 60

Determination of Nitrogen 64

Will and Varrentrapp's Method 66

Liebig's Relative Method 67

Bunsen's Relative Method .......;. 68

Dumas' Absolute Method 70

Simpson's Method 71

Determination of Chlorine, Bromine, and Iodine .... 75

Determination of Sulphur 78

Determination of Phosphorus . 79

Determination of other Elements . 79

Determination of Oxygen ......... 80



vi CONTENTS.



CALCULATION OF ANALYSES 80

Percentage Composition 80

Calculation of Formulae ... 82



DETERMINATION or VAPOUR DENSITY . 84

Dumas' Method 84

Gay-Lussac's Method . . . 87

Hofmann's Method . 89

Victor Meyer's Methods 94

DETERMINATION OF MOLECULAR FORMULAE 103

Empirical and Rational Formulae .112

Constitutional Formulae . . . 114

Saturated and Non-Saturated Compounds 117

ISOMERISM . . . 119

t

CLASSIFICATION OF THE CARBON COMPOUNDS ... 128



HYDROCARBONS OF THE PARAFFIN SERIES 130

Constitution of the Paraffins 135

Preparation of the Paraffins 136

Application of the Paraffins . 140

Origin of Petroleum 142

American Oil-wells 145



FRACTIONAL DISTILLATION . . . . 147

Distillation of Mixtures . . . . . . . 153



THE COMPOUNDS OF THE MONAD ALCOHOL RADICALS . . . .154

Alcohols and Ethereal Salts, nature of . . . . . . 154

Haloid and Simple and Mixed Ethers 155

Sulphine Compounds and Sulphonic Acids 158

Compound Ammonias . 159

Hydrazine Compounds . 161

Cyanides of Alcohol Radicals 162

Cyanates and Isocyanates 163

Compound Ureas, or Carhamides, &c. . . . . . . . 165

Nitro-Paraffins . . 167

Compounds of Alcohol Radicals with Metals 168

THE ALCOHOLS AND THEIR DERIVATIVES 169

Primary Alcohols and Fatty Acids 169

Primary Alcohols 171

Aldehydes . . . . .172

Haloid Compounds of the Acid Radicals 173

Ethereal Salts, or Compound Ethers 174



CONTENTS. vii



PAGE

Anhydrides, or Oxides of the Acid Radicals 176

Thio- Anhydrides, or Sulphides of the Acid Radicals .... 176

Amides 177

Substitution-Products of the Fatty Acids 178

SYNTHESIS OF THE PRIMARY ALCOHOLS AND THE FATTY ACIDS . .179

Lieben and Rossi's Method . . . 180

Fraiikland and Duppa's Method ........ ISO

SECONDARY ALCOHOLS AND KETONES 182

TERTIARY ALCOHOLS 186

THE METHYL GROUP 190

Methane, or Methyl Hydride 190

Methyl Alcohol 194

Methyl Oxide, or Di-Methyl Ether 200

Ethereal Salts of Methyl 202

Sulphur Compounds of Methyl . . . . . . . .212

Selenium Compounds of Methyl 216

Tellurium Compounds of Methyl 217

Nitrogen Bases of Methyl 218

Cyanogen Compounds of Methyl . 224

Nitro-Compounds of Methyl 227

Phosphorus Compounds of Methyl 229

Arsenic Compounds of Methyl 234

Compounds of Methyl with Antimony 243

Compounds of Methyl with Boron . . . . . . .244

Compounds of Methyl with Silicon 245

Metallic Compounds of Methyl 245

Other Derivatives of Methyl 253

THE FORMYL GROUP 266

Formic Aldehyde . 266

Formic Acid , 269

The Formates 274

THE ETHYL GROUP . 279

Ethane 279

Ethyl Alcohol 282

Alcoholometry ........... 301

Ethyl Ether, or Ethyl Oxide - . 323

The Ethereal Salts of Ethyl, or Ethyl Compound Ethers . . .342

Sulphur Compounds of Ethyl 379

Compounds of Ethyl and Selenium 397

Compounds of Ethyl and Tellurium . 399

Nitrogen Bases of Ethyl . 401

Cyanogen Compounds of Ethyl 413

Ethylated Ureas 419



viii CONTENTS.



PAGE

Ethyl Semicarbazides 421

Ethylated Thio-Ureas 422

Nitro-Compounds of Ethyl 423

Phosphorus Bases of Ethyl 431

Arsenic Compounds of Ethyl 440

Antimony Compounds of Ethyl . . ... - . . .443

Bismuth Compounds of Ethyl . .447

Boron Compounds of Ethyl . . 448

Silicon Compounds of Ethyl . . 450

Compounds of . Ethyl with the Metals- 455

Acetyl Compounds * . . . .473

Acetic Acid 483

The Acetates, or the Salts and Ethers of Acetic Acid . . . .496

Oxides of Acetyl 509

Haloid Compounds of Acetyl . 513

Sulphur Compounds of Acetyl 515

Nitrogen Compounds of Acetyl . .517

Acetonitril and its Derivatives . 521

Substitution- Products of Acetic Acid .... 533



COMPOUNDS CONTAINING THREE ATOMS OF CAEBON, OR THE PROPYL

GROUP 548

Primary Propyl Alcohol . . . . . . , .548
Propionic Aldehyde and Propionic Acid ...... 556

Secondary Propyl Alcohol 563

Acetone, or Dimethyl Ketone , 569



COMPOUNDS CONTAINING FOUR ATOMS OP CARBON, OR THE BUTYL GROUP 576

Normal Butane and its Derivatives 577

Primary Butyl Compounds 584

Secondary Butyl Compounds 4 ....... 581

Isobutine and its Derivatives . . 583

Primary Isobutyl Compounds . . . . . . . . 583

Tertiary Butyl Compounds .586

The Butyric Acids .......... 590

Isobutyryl Compounds . . . . . . . . . 597



COMPOUNDS CONTAINING FIVE ATOMS OF CARBON, OR THE PENTYL GROUP 602

Normal Pentane and its Derivatives 603

Isopentane and its Derivatives 606

The Amyl Compounds . . . 611

Tetramethyl Methane and its Derivatives . 617

The Pentoic or Valeric Acids 617



COMPOUNDS CONTAINING Six ATOMS OF CARBON, OR THE HEXYL GROUP . 625

Normal Hexane and its Derivatives . 625

Isohexane and its Derivatives 631

Methyl-Diethyl Methane and its Derivatives 631



CONTENTS.



PAGE

Tetramethyl Ethane and its Derivatives 631

Trimethyl-Ethyl Methane and its Derivatives .... 633

The Hexoic or Caproic Acids 334



COMPOUNDS CONTAINING SEVEN ATOMS OF CARBON, on THE HEPTYL

GROUP . .639

Normal Heptane and its Derivatives ....... 639

Isoheptane and its Derivatives . . . , . . . .643

Triethyl Methane and its Derivatives 644

The Heptoic Acids . . . . . . . . . .646



COMPOUNDS CONTAINING EIGHT ATOMS OF CARBON, OR THE OCTYL GROUP 650

Normal Octyl Compounds ......... 650

Tetramethyl Butane and its Derivatives ...... 654

Tertiary Octyl Compounds 655

Hexmethyl Ethane .......... 656

The Octoic Acids 656



COMPOUNDS CONTAINING NINE ATOMS OF CARBON, OR THE NONYL GROUP 658
The Nonoic Acids 659



COMPOUNDS CONTAINING TEN ATOMS OF CARBON, OR THE DECATYL GROUP 662
The Capric, or Decatoic Acids , 664



COMPOUNDS CONTAINING ELEVEN ATOMS OF CARBON, OR THE HENDECATYL

GROUP 605



COMPOUNDS CONTAINING TWELVE ATOMS OF CARBON, OR THE DODECATYL

GROUP ... 667



COMPOUNDS CONTAINING THIRTEEN ATOMS OF CARBON, OR THE TRIDE-

CATYL GROUP ... 669



COMPOUNDS CONTAINING FOURTEEN ATOMS OF CARBON, OR THE TETRA-

DECATYL GROUP .....



COMPOUNDS CONTAINING FIFTEEN ATOMS OF CARBON, OR THE PENTA-

DECATYL GROUP . 670



COMPOUNDS CONTAINING SIXTEEN ATOMS OF CARBON, on THE HEC-

DECATYL GROUP . 671



CONTENTS.



PAGE

COMPOUNDS CONTAINING SEVENTEEN ATOMS OF CARBON .... 677
COMPOUNDS CONTAINING EIGHTEEN ATOMS OF CARBON .... 678

COMPOUNDS CONTAINING FROM NINETEEN TO TWENTY-FOUR ATOMS OF

CARBON . . . 681

The Waxes 681

General Properties of the Fatty Acids .... . . .684

Soap ....'.-:. . . . . . .688



OKGANIC CHEMISTRY.




ORGANIC CHEMISTRY,

OR THE CHEMISTRY OF THE HYDROCARBONS AND THEIR
DERIVATIVES.



HISTOEICAL INTRODUCTION.

I MANY of the most important chemical facts known to the
ancients have their place in the Organic portion of our science.
Thus, for example, the only acid with which the ancients were
acquainted was an organic substance, viz., vinegar or dilute
acetic acid, and the name of this body and the idea of acidity
were expressed by closely related words, of 09, acetus, vinegar ;
and ofy<?, acid its, acid. 1

Again, the first reagent of any kind which we find described
is also an organic body, namely the extract of gall-nuts with
which, as Pliny states, the ancients were accustomed to ascer-
tain whether verdigris was adulterated with green vitriol.

The first rude attempts at distillation were also made with
an organic body, viz., turpentine ; whilst the first salts which
were artificially prepared were organic ones, being those ob-
tained by the action of vinegar on the alkalis. The mode
of preparing soap by the action of fats upon the alkalis was
also known in early times. In addition to a knowledge of
the fats and oils, the ancients were acquainted with various
resins, and colouring matters, as well as with sugar and gum.
They likewise understood the preparation of \\ine from
grape-juice, and certain nations, especially the Egyptians,
Gauls and Germans, were accustomed to prepare beer from
malted grain.

i See Vol. ii. part i. r . 32.



HISTORICAL INTRODUCTION.



As the direction in which the science first developed itself
was that of alchemy, the object of which was the conversion of
the baser metals into gold and silver, it is natural that attention
was in the first place paid rather to the properties of mineral
substances than to those of organic bodies. Nevertheless im-
provements in general chemical processes, especially that of
distillation, gradually led to the discovery of definite organic
compounds such as spirit of wine (aqua mice] and certain of the
essential oils. The action of heat upon bodies when air is ex-
cluded was also studied in early times. . Thus the products of the
dry distillation, as we now term this process, of bodies such as
cream of tartar were investigated, and the action of acids upon
spirits of wine and other organic substances was likewise examined.

Later on, towards the sixteenth century, the cultivators of
this science, as we have seen, 1 exhibited activity mainly in two
directions, in the first place in the prosecution of the branch
science of metallurgy, and secondly, in the development of iatro-
chemistry. In these branches, and especially in the latter, it
was, however, the inorganic division of the science which made
the most rapid strides, because, in opposition to the practice of
the old school, the use of metallic preparations as medicines
was largely introduced. At the same time the study of organic
compounds, and especially of the active principles of organic
bodies, was not entirely neglected. Thus during this period
ben zoic acid, succinic acid, wood-vinegar, milk-sugar, and various
ethers were discovered.

In the succeeding epoch, when the true function of chemistry
had become fully recognised, inorganic compounds still claimed
the more immediate attention of chemists, not only because
they are more stable than organic bodies, but also because in
the latter case it had not as yet proved possible, as it had
in the case of inorganic bodies, to determine their composition
by synthesis as well as by analysis.

2 From this period it is that we may date a distinct separation
of mineral chemistry from that portion of the science which is
concerned with the study of substances formed in vegetable
and animal organisms. For a long time chemical compounds
were grouped together according to their physical properties,
and the common names at present in use for many substances
remind one of this bygone classification. Thus, for instance,
olive oil and other vegetable and animal oils were placed

1 Vol. i. p. 8, "Historical Introduction."



EARLY IDEAS ON ORGANIC CHEMISTRY.



together with oil of vitriol and with oleum tartari (deliquesced
carbonate of potash). Alcohol again (spirit of wine) was classed
with stannic chloride (fuming spirit of Libavius), with ammonia
(spirit of hartshorn), and with nitric acid (spirit of nitre), &c.
Common butter was placed in the same group as antimony
trichloride (butter of antimony) and other semi-solid metallic
chlorides. Colourless solid bodies which were soluble in water,
and possessed a peculiar taste were all classed together as salts,
even sugar being placed in this group.

3 In the year 1675 Nicolas Lemery published his Cours de
Chymie. In this work the aim of chemistry is defined to be
a knowledge of the various substances "qui se rencontrent
dans n n mixte," understanding by this term aU growing
or increasing natural products. Lemery distinguished these
bodies as mineral, vegetable, and animal products. In the first
group he placed the metals, minerals, earths, and stones ; in the
second, plants, resins, the different kinds of gums, fungi, fruits,
acids, juices, flowers, mosses, manna, and honey; and under
the third head he described the various parts of animal bodies.

Although Lemery's system of classification was generally
accepted, the founders of the phlogistic theory endeavoured to
show that the observed differences depended on a variation in
the composition of the bodies classed under each head. Thus
Becher in 1669 had argued that the same elements occur in
the three natural kingdoms, but that they are combined together
in a simpler manner in mineral substances than they are in
vegetable and animal bodies. Stahl, on the other hand, asserted
in 1702, that in vegetable as well as in animal substances the
watery and combustible principles predominate, and that these
make their appearance when such an organic substance is heated
out of contact with air, water and combustible charcoal being
farmed.

At this time, as well as during the preceding period, the
investigation of organic compounds was carried on mainly with a
view either to the preparation of medicines, or to the improve-
ment of technical processes, such as that of dyeing. Only
towards the close of the phlogistic period did organic chemistry
begin to make real progress, and it is from this time forward
that the scientific investigation of organic bodies can be said
to have commenced.

4 The early ideas of van Helmholt and afterwards of Stahl,
that all organic substances can be resolved by the action of



6 HISTORICAL INTRODUCTION.

heat into their ultimate constituents, viz., aqueous and com-
bustible principles, were successfully combated by Boyle, who,
in the Sceptical Chemist (1661), proved that this is not the case,
inasmuch as the application of heat leads to different results
according as air is permitted to have access or not, and that the
various residues thus obtained in no way merit a uniform de-
signation. The general reception of Boyle's views was slow but
sure. Still it was not until Lavoisier's discovery in 1775 of the
composition of carbon dioxide, and Cavendish's determination
of that of water, that the fact of the existence of carbon and
hydrogen in alcohol was ascertained (1784).

5 Amongst the early organic researches of a truly scientific
character those of Scheele deserve the first mention, for he
either discovered nearly all the most important vegetable
acids, or suggested methods for their discrimination. Thus,
he showed that the acid from lemons differs from that from
grapes, whilst that contained in apples differs again from
both of these. He proved that a fourth distinct acid i*
found in wood-sorrel, and pointed out that this can LJ
obtained artificially by heating sugar with nitric acid. He
likewise obtained gallic acid from gall-nuts, uric acid from
urine, and lactic acid from sour cow's milk. By the oxidation
of milk-sugar he prepared mucic acid, a substance altogether
different from the acid obtained from cane-sugar. In the pre-
paration of these and other acids Scheele employed methods
many of which are in use at the present day. Scheele also
showed that fatty oils and the solid fats contain the common
principle glycerin, termed by him the sweet spirit of oils. This,
he says, is connected with sugar not only on account of its sweet
taste, but also because, like sugar, it is oxidized to oxalic acid
by nitric acid.

Scheele's friend Bergman also assisted the progress of
organic chemistry, whilst Rouelle who distinguished himself
by researches on the hitherto neglected division of animal
chemistry, discovered urea and hippuric acid.

6 Investigations such as these drew general attention to
the subject of organic chemistry, and Lavoisier having estab-
lished the true principle upon which the process of com-
bustion depends, turned his mind to this interesting branch
of the science, and ascertained the ultimate composition of
certain organic compounds. He came to the conclusion that
vegetable bodies are chiefly composed of carbon, hydrogen, and



LAVOISIER'S RESEARCHES.



oxygen, "whilst the compounds of the animal kingdom contain
in addition to these elements, nitrogen and not unfrequently
phosphorus. 1

The Lavoisierian system of chemistry was essentially the
chemistry of oxygen and its compounds, and hence attention
was naturally directed to the question whether a given com-
pound is capable of combining, like an element, with oxygen,
or whether it was already combined with this element. To
that portion of a substance which combines with oxygen,
Lavoisier, at the suggestion of Guyton de Morveau, gave the
name of la base or le radical. This might either be an elemen-
tary substance, such as carbon, " le radical de 1'acide carbonique,"
or a compound, such as, " le radical oxalique, tartarique," &c.

Respecting the difference between organic and inorganic
compounds, he states that the oxidizable or acid-forming radicals
of the mineral kingdom are almost always simple ; those of the
vegetable and especially of the animal kingdom are however
generally composed of two substances, carbon and hydrogen,
and these frequently contain nitrogen as well, and some-
times phosphorus. 2

The observation that the elements can form different oxides
led to the supposition that this might likewise be the case
with organic radicals. Thus for example sugar was considered
to be a neutral oxide, "d'un radical hydro-carboneux," whilst
oxalic acid was supposed to be its higher oxide.

Amongst his more important investigations in the domain of
organic chemistry Lavoisier's research on fermentation deserves
especially to be mentioned, not only because he was the first
to point out that sugar is decomposed into carbonic acid and
alcohol, but especially because, in connection with this particular
reaction, he for the first time enunciated the principle which
underlies the whole of our science, viz., that the weight of the
products of any chemical change are equal to the sum of the
weights of the materials taking part in that change, and hence
that all chemical decompositions may be expressed by equations,
the truth of which can be ascertained by the analysis of the
original compound, and controlled by that of the products of
decomposition.

On this point Lavoisier's own words may be quoted : " We
may consider the substances submitted to fermentation and the

1 Lavoisier's Elements of Chemistry (1787), Kerr's Translation, pp. 173, 174.
1 Ibid, p. 261.

119



HISTORICAL INTRODUCTION.



products resulting from that operation as forming an algebraic
equation ; and, by successively supposing each of the elements in
this equation unknown, we can calculate their values in succes-
sion, and then verify our experiments by calculation and our
calculations by experiment, reciprocally. I have often success-
fully employed this method for correcting the first results of my
experiments, and so to direct me in the proper road for repeating
them, to advantage." 1

It must, however, be especially borne in mind that Lavoisier
did not distinguish organic chemistry as a special branch of the
science ; still less did he, as has been stated, define this portion
of chemistry as the chemistry of compound radicals. 2 Thus for
example he arranged all the acids together, dividing them like
Lemery into mineral, vegetable, and animal. His more im-
mediate followers also adopted this course, and it was at that
time only occasionally that we find organic bodies classed
together in a group.

7 By degrees, as substances common to both the animal and
the vegetable world were discovered, the distinction between
animal and vegetable chemistry disappeared, and the consequent
fusion, widening the area covered by the general term organic,
gradually led to a distinct separation into Inorganic and Organic
chemistry. At the same time no exact limit could be said
to exist between these two divisions of the science. One
reason for this was that several compounds were found to exist
which from their origin must be considered as organic, but which
yielded on analysis results proving that they exactly obey the
laws of constant and multiple proportion, laws supposed at that
time to apply only to compounds belonging to the mineral king-
dom. In the majority of instances, on the other hand, organic
bodies appeared not to obey these laws.

8 For the purpose of obtaining more satisfactory informa-
tion on this question, Berzelius, in 1814, proposed to investigate
the composition of such substances more accurately than had
hitherto been done. That this was much needed is clear when
we remember that Proust, so late as 1803, stated that acetic
acid contained nitrogen, and that Dal ton changed his formula
for alcohol from 2 C + H + O in 1803, to 3 C + H in 1810.

With this view Berzelius improved the processes of organic
analysis, and then ascertained that all organic compounds,

1 Lavoisier, Elements, p. 197.

8 Kopp, Entwickelung der Chemie in der ncuerem Zeit, p. 521.



THE INVESTIGATIONS OF BERZELIUS.



although in most cases possessing a somewhat complicated
composition, obey the laws of constant and multiple pro-
portions applicable to inorganic compounds. Agreeing with
the views of Lavoisier, Berzelius explained the difference
existing between these two great divisions by stating that
whilst in inorganic nature every oxidized compound contains
a simple radical, organic bodies consist of oxides of compound
radicals. In the case of vegetable substances the radical usually
consists of carbon and hydrogen, whilst in the case of animal
substances it consists of carbon, hydrogen, and nitrogen. 1

9 Berzelius, however, did not experimentally investigate these
compound radicals, although the discovery of cyanogen by
Gay-Lussac in 1815 served as an excellent example of the
existence of such a series of bodies. The cyanogen com-
pounds were, however, at that time almost invariably placed
amongst inorganic bodies, for, as has been stated, the limit
between inorganic and organic chemistry was not clearly defined.
Thus Gmelin in 1817, in the first edition of his great handbook,
states that a clear distinction ought to be made between the
two classes of compounds, but that this distinction can be more
readily felt than strictly defined. He laid down that Inorganic
compounds are characterised by their binary constitution, the
most simple consisting of compounds of two elements, a basic
oxide or an acid (that is what we now term an acid-forming
oxide), which can again unite to form a binary compound of a
higher order, namely, a salt. Organic bodies, on the other hand,
are at least ternary compounds, or are composed of three simple
substances, generally united together in less simple proportions
than is the case in inorganic bodies. Accordingly, Gmelin
describes marsh gas, olefiant gas, cyanogen, &c., in the inorganic
portion of his handbook. He likewise adds that organic com-
pounds cannot, like inorganic compounds, be artificially built up
from their elements.

About the same time Berzelius again enforced this distinction
between inorganic and organic bodies, asserting, like Gmelin,
that the first could, whilst the latter could not, be artificially
produced. He assumed that in living structures the elements



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