TNT, Trinitrotoluene Manufacture

I
TNT
TRINITROTOLUENES
AND
MONO- AND DINITBOTOLUENES
THEIR MANUFACTURE
AND PROPERTIES
BY
||1 Q. CAHLTON SMITH, B.S.

Jmnter fa Otiunl dumittr^, Botofl tfApplitt Boitntt,
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NEW YORK
D. VAN NOSTRAND COMPANY
26 PJLBK PL A OB .
1918
Reproduced by
DUOPAGE PROCESS
in the
U.S. of America
Micro Photo Division

Bell & Howell Company
Cleveland 12, Ohio
~TP
Copyright. 1918. by
D. VAN NO8TRAND COMPANY
.
* .*
_
. . 4
TO
BACBIFICSa AND LOVB

HAV* MAD IfT EDUCATION
813
i
ACKNOWLEDGMENT
THE writer wishes to thank all those who have

so
kindly aided him in the preparation of this book*
He is especially grateful for the valued comments
and criticisms offered by the members of the Staff of
the Department of Chemicid Engineering, Carnegie
Institute of Technology; for the facts which form the
basis of Chapter X, by Dr. Samuel Haythorn of the
Singer Memorial Laboratory, Allegheny General Hos-
pital; and for data on TNT
manufacture by Mr.
Robert M. Crawford of the Grasselli Powder Co.
The Chemical and Industrial Journals have been
consulted freely, and much valuable material has been
extracted therefrom.
Carnegie Inetitate of Technology,

PJL, iftay, 1918.
'
. .
TABLE OF CONTENTS
CHAPTER I
INTRODUCTION . *
CHAPTER II
HISTORICAL. 6
CHAPTER III
Tarn THEOET or IBB NITRATION OF TOLUENB. 20
CHAPTER IV
THB MANUFACTURE or TNT ............................ 29
CHAPTER V
Tarn PURIFICATION or TNT ............. ................ 2
CHAPTER VI
INSPECTION AMD TESTING or TNT ............. ... ...... . 61
CHAPTER VII
PsoFEmrns or m TRINITROTOLUENES ................... 77
CHAPTER VIII
PmotnaaoB or TH MONO- AND DINITROTOLUENJCS. ........ 05
CHAPTER IX
ACCIDENTS nr TNT PLANTS. 106
CHAPTER X
TNT DismAsis...... 112
vi
.
i
TRINITROTOLUENE
1
CHAPTER I
,
INTRODUCTION
THE almost universal adoption of trinitrotoluene
as the most efficient explosive in modern warfare; the
development and refinement of its manufacture,
and the interesting chemistry of its compounds, as
well as those of the lower nitro-derivatives of toluene
has prompted quite extensive research as to their
composition, structure, manufacture, properties and
uses. The fact that the results of these researches
have been varied; often quite contradictory; some-
what disconnected and expressed with some confusion
of terms would seem to warrant the publication of this
littlevolume in which an attempt is made to gather
together and correlate all accessible information on
the subject, both theoretical and practical.
Since the chemical name " trinitrotoluene
" is
rather mysterious to the non-scientific mind, and since
it is also much too lengthy for general use in this age
of efficiency, concentration and hustle, there have been

coined many abbreviations and substitutions of the
word. In general these terms are local only, but, by
2 TRINITROTOLUENE
use in specifications, etc., they have spread beyond the

territory in which they originated. little wonder is
caused, therefore, that the uninitiated should confuse

the several names now in vogue for trinitrotoluene,
" "
TNT
to be one substance,
and that he should think
" " to The entire list
trotyl be another, and so on.
of contractions and designation? is much too lengthy
to give in its entirety, but the more familiar ones are
these:
M
TNT "; the American contraction, and the one
usually used for trinitrotoluene in this country.
"
Trotyl "; this term is of English origin, and is
used almost exclusively in English specifications and

literature.
11
Tolite "; the French abbreviation.
"Trilite"; Spanish.
" " " "
Fullpulver-O2 or simply Fp-O2 is used by
the Germans to denote trinitrotoluene. This is, of
course, neither a contraction nor an abbreviation of
the name itself, but denotes merely a certain explosive
in accordance with the German system of classifica-
tion.
Someother terms are " Trinol," " tritol," " tri-
"
tolo and " coal tar salt," this last being the newest
designation for trinitrotoluene. By comparing the
above terms with the full word, the relation of most
of them is easily seen.
is just what its name implies

Trinitrotoluene a
triple nitrated toluene. Toluene, itself, is a liquid
prepared usually from coal tar, by distillation. This
isthe main source of this substance in North America,
although it isprepared in smaller amounts from arti-
ficial gas, the cracking of crude petroleum, etc.
INTRODUCTION 3
By treating toluene with nitric acid, three nitro-

groupe attach themselves to the molecule in this
CHs CHs
lOs
o NO*
+3HjO.
This particular trinitrotoluene is one of the six

isomeric compounds of that name, and is the one
formed by the commercial nitration of toluene. Chem-
ically it is the a, 1-2-4-6, or "symmetrical" tri-
nitrotoluene.
Trinitrotoluene belongs to the shattering class of
explosives known as the "brisants." The members
of this class possess great force, and upon exploding,
shatter the containing shell into small pieces, thus
doing more damage per shell.
The other well-known member of the brisant class
of explosives is picric acid, or trinitrophenol. Pre-
vious to the use of trinitrotoluene,_picric acid was used
largely as the explosive charge in shells. There are
several disadvantages in picric acid, however, which
trinitrotoluene does not have. Picric acid forms salts
(picrates) with a great number of the metals. These
picrates are very unstable, and are quite sensitive to
shock, thus giving rise to premature explosions which
often result fatally. Trinitrotoluene is very inactive
toward the greater number of the metals. Further-
more, picric acid has a high melting-point (122.5)
while the melting-point of trinitrotoluene is low enough
(80.6) that it may be poured into the shell in the
molten state without danger from fire.
.
TRINITROTOLUENE
On the other hand, trinitrotoluene is not quite as

powerful as picric acid, but its insensibility to shock,
together with the advantages cited above, have resulted
in its almost totally replacing the latter in warfare.
The nation to use trinitrotoluene in shells was the
first
Germans, who adopted il in 1904.

The great insensibility of trinitrotoluene as com-
pared to that of picric acid, is shown hi the following
table of minimum charges necessary for the detona-
tion of both explosives:
Detonator.
INTRODUCTION 5
" Macarite
"; TNT, 30 per cent; lead nitrate, 70
percent.
" Donarite 12 per cent; ^colcot. 0.2 per
"; TNT,
cent; ammonium nitrate, 80 per cent; flour, 4 per
cent; nitroglycerine, 3.8 per cent.
Dinitrotoluene is also used in conjunction with
other materials as an explosive. One such mixture is
" Cheddite-O2." The
analysis of the mixture is:
DNT, per cent; potassium chlorate, 79 per cent;
15
mononitronaphthalene, 1 per cent; castor oil, 5 per
cent.
One further mixture deserves mention because of
the use of DNT and TNT in the mixture. This
called
" The
explosive is triplastite." analysis is:
Mixture of DNT and TNT, 70 per cent; coLcot.,
1.2 per cent; lead nitrate, 28.8 per cent.
.
CHAPTER n
HISTORICAL
SOME doubt exists as to whom the honor of the dis-

covery of toluene is due. Dr. W. Wilson in an article
1850, (1) gives the credit of the discovery to

a French chemist, who obtained from balsam
,
of tolu a compound to which; he ascribed the name

" benjoen." From the above
article, Deville evi-
" "
dently did not analyze the benzoen but arbitrarily
assigned to it the formula CuHi.
" Eleventh Trea-
Beilstein and Kuhlberg, in their
tise on Isomers of the Toluene Series," (2) give the
honor to Pellet ier and Walters, also French chemists,
who obtained an oil from the distillation of pine resin,
and from which they separated a liquid which they
oil
"
called retinaptha." Their description of this liquid
"
is this: It is a very cbar liquid, . boiling at 108
. .
C., and it is not completely solidified at -20. The

results of three analyses indicate the formula CyHg."
(This is just half the molecular formula given by
"
Deville to his substance.) One could also give the
formula CuHie, but there is no definite ground for
such a statement. In fact, the vapor density is 3.23
the vapor density corresponding to the formula CrHg
would be 3.226."
From this statement it would seem that Pelletier
and Walters were already aware that a substance of the
6
HISTORICAL
formula (supposedly) CiJIia had been isolated, and

that, by determining the vapor density, they had proved
it to be just hah* this molecular weight, or CrH* On
the other hand, there is no reason why if they did
know of the previous discovery of this same substance
they should give it a new name. The dates on
which the above-mentioned men published their article
seems to point to Pelletier and Walters as the dis-
coverers their work was completed about 1838,
while Deville's work was published somewhere about
1841. Of
course, there is the possibility that Deville
completed his work some years before his results were
published.
In 1843, Berzelius technically accorded the discovery
"
of toluene to Deville by suggesting the name toluol
"
s
j
" toluene " for
or the compound, (3) the name being
derived from
" oil of tolu."
Some of the scientists of that period (probably
friends of Pelletier and Walters), did not approve of
9
Berzelius choice ofname for this substance, and
two of these, Muspratt and Hoffman, in a research
" Ber-
paper dated 1845, take occasion to remark:
(4)
'
zelius had proposed for this compound the name tol-
uol' or 'toluene/ names .which are not very well
;, chosen, but which we shall retain in the following dis-
cussion."
The " retinaptha "of Pelletier and Walters and the
" benzoen " of Deville were
proved to be the same sub-
stance by the preparation of the nitro-derivatives, and
by comparing the constants of those, and possibly the
acid nitro-derivativefl and corresponding toluidins.
Glenard and Boudalt, at about the ea me time, prob-
ably later than both Deville's and Pelletier and Wai-
,',*
8 TRINITROTOLUENE
"
tor'swork, isolated toluene from Dragon's blood." (5)
No further reference, and consequently no identifica-
tion of this substance, could be found. Glenard and
" "
Boudalt gave the name dracyl to the substance they
isolated. Following the methods of their predecessors
they proved the identity of dracyl and toluene.
Still another man, Cahours, during the years 1847-
48 isolated a substance from crude wood alcohol by

treating the alcohol with sulphuric acid. He called
" " "
this substance toluen," which is so near toluene
that naturally it would be supposed to be the same.
Cahours demonstrated, however, that the formula of
" "
toluen was Culls, which gives rise to a doubt as
to whether his product was really identical with tol-
uene. An abstract, dated 18-19, reads thus: (0)
"
Cahours has separated from crude wood alcohol
different oily hydrocarbons, some already ^nown;
some new. Toluen Culls is identical vith the toluene
of Deville. It distills between 108 and 112 C.
Cahours found the vapor density to be 3.27. Tlirough
treatment with nitric acid he obtained mono- and
dinitrotoluene, and from these, by reduction with
ammonium sulphide, the corresponding coiuidin and
nitrotoluiuin."
It is rather difficult to understand why Cahours
insisted on the formula CuHg after having determined
a vapor density of 3.27, which so closely cheeked
and Walter's determination.
Pelletier
About 1850, Mansfield, an English chemist, Iso-
lated toluene from coal tar. (7) This discovery of
Mansfield's practically ends the historical interest
in toluene, since has come to be the principal source
it
of this substance. One further method of obtaining

HISTORICAL
toluene will be cited, however, because of its scientific

interest In 1846, two German chemists, Tollens and
Fittig, prepared toluene synthetically from methyl
iodide and brombenzene. (8) This method was a
modification of Wurz' synthesis of the aliphatic hydro-
carbons, and it is interesting because the primary prod-
"
uct of the now commercially valuable Fittig's syn-
" was
thesis toluene, the basis of the greatest explosive
of modern times.
The earliest reference to be found concerning the
purification of coal tar toluene is contained in Wilson's
" The best method of
paper, (9) wherein he states:
obtaining pure toluene consists in collecting the part
which passes over between 100 and 120 C. and treat-
ing this with one-half its weight of concentrated sul-
phuric acid. I have not determined which substances
are removed in this process; the fact remains, however,
that a constant boiling-point is obtained more easily
through the use of sulphuric acid than without. The
boiling-point of pure toluene was found to be 110 C*
. . . Under all conditions a beries of protracted dis-
necessary to obtain this object."

tillations is
As seen from this statement, Wilson followed the
is
same method of procedure as is followed to-day in

order to effect the removal of the olefines from the
crude toluene. Modern plants, equipped with the
latest type of fractionating stills, with their compli-
cated columns, refluxes and fractional condensers are
fortunately not put to the same trouble in the puri-
fication of toluene as was Wilson.
The history of the discovery and preparation of
mononitrotoluene runs parallel with that of toluene,
since it was by the preparation of the former that toi-
10 TRINITROTOLUENE
uene was identified by the several chemists. Deville

prepared the mononitro toluene and also the sulphonate
"
of toluene. The nitro-compound he called protoni-
"
trobenzoen," and describes it in this manner: It
tastes like bitter almonds; smells suffocating at first
then penetrating. Its specific gravity is 1.18 at 16.
It boils at 225." The same chemist found the vapor
density to be 4.95. The vapor density as calculated
by him would be 7.87, basing the calculation on his
formula of Cull 6 for toluene. (10)
1
Berzelius, in a research paper published in 1843,

gives in detail the preparation of nitrotoluene. (11)
The results of a series of researches to prove its con-
stitution are mentioned also. Berzelius was misled
by his results, as was Deville. His final conclusion
"
states, Nitrotoluene can be considered as a nitride
of toluid oxide, Ci4Hi4O = N." The chemical proper-
ties of nitrotoluene were studied at length by Berzelius,
but he evidently arrived at no definite conclusion re-
garding these properties.
Dr. Wilson, in the same article to which reference
is made
above, makes this statement concerning nitro-
"
toluene: The changing of toluene to nitrotoluene is
carried out without difficulty in the i&ual manner.
The boiling-point of nitrotoluene lies between 220
and 225 C. This body boils without decomposition."
The last statement of Dr. Wilson, concerning the ability
of nitrotoluene to be distilled without decomposition,
confirmed experiments carried out by Glenard and
Boudalt. This question was a much mooted one at
this time, since other chemists had proved to tbeir
entire satisfaction that nitrotoluene could not be dis-
tilled without undergoing decomposition. Comment-*
HISTORICAL 11
ing on this question, BeilsteSn and Kuhlberg (12)

explain the decomposition of nitro toluene as being due
to the probable content of higher nitre-derivatives of
toluene. This we now know to be the truth, and the
firms who are purifying their nitrotoluene by distilla-
tion are very careful to remove all the higher nitro-
oompounds before attempting the distillation.
About this time, another chemist entered the field
of the This man was Jaworsky.
nitro-compounds.
He started out his work by preparing nitrotoluene,
which he claimed to be a solid, and not a liquid as
Deviile, Wilson, and others had thought it to be. (13)
Jaworsky represents about the best type of pure indus-
trial chemist to be found in this period of time. His
work on nitrotoluene had a great effect on the indus-
tries; so much the Paris Exposition of 1867
so, that at
there was exhibited a great quantity of beautifully
crystallized nitrotoluene. Whether this consisted of
the pure solid isomer of nitrotoluene or whether it
was a mixture of one or more nitrotoluenes and dini-
trotoluenes, is not known. Jaworsky was also the
first to produce toluidin the homologue of aniline
by the reduction of nitrotoluene with tin and hydro-
chloric acid. The immediate industrial result of
Jaworsky 's work was that the use of nitrotoluene as a
dyestuff base was firmly established.
" benzene "
Kekule, the great chemist whose ring
theory is now the basic law of the chemistry of the aro-
matic compounds, worked exhaustively with nitro-
toluene, and did much to clear the cloud caused by
Jaworsky 's contradiction of Deville's work. Kekule 's
work showed -to quote his words" At least it is quite
probable that the substance hitherto regarded as nitro-
12 TRINITROTOLUENE
toluene is. nothing else than a mixture of nitrotoluene
and nitrobenzene."
Summarizing the work of these earlier investiga-
tors of the nitrotoluenes, there is one fact that stands
out very clearly throughout all their work they had
no thought of the possible isomerism of nitrotoluene.
The results obtained by all the various work done by
these chemists was finally interpreted by Kekule as
meaning that nitrotoluene was a solid, and that the
liquid obtained by Deville and others was a liquid
only because of the admixture of nitrobenzene.
This cloud began to disappear with the work of
Rosenstill, who was the first to suggest the possibility
of the existence of nitrotoluene in different forms.
His work was later supplemented by Beilstein and
Kuhlberg, who found in Rosenstill's work the hint
that led to their isolation of the three isomeric nitre-
toluenes, and the classification and naming of these
compounds. The results of Beilstein und Kuhl-
berg's work was published in 1879, when, for the first
time, the true constitutions of the nitrotoluenes was
'
established.
It is very peculiar, indeed, that most of the bril-
liant earlier chemists, whose work did so much to lay
,the foundation of the present wonderful science,
wound up their work with a probable error. The
word " probable "is used intentionally, because in that
formative period of the chemistry of the aromatics,

with the constantly arising theories and hypotheses,
there may appear errors which are in reality not such,
but which were facts when viewed in the light of the
then accepted laws. Future discoveries have changed
many of these early ideas, and possibly it may be better
HISTORICAL 13
to state that they were led astray by statements and

hypotheses which later proved to be without founda-
tion. The particular point to which I refer is the
nomenclature used by Beilstein and Kuhlberg for the
nitrotoluenes. This may appear a small matter, but
when reference is made to the publications of these men,
and when these references are viewed in the light of
present day accepted facts, their nomenclature is con-
fusing. More so, because they made use of the terms
" " "
ortho," meta," and para," which are the same as
are used to-day. The meta and ortho isomeric nitro-
toluenes appear to be just reversed from those isomera
now regarded as meta and ortho. This view was not
due to Beilstein and Kuhlberg alone, for at least one
other scientist, V. von Richter, was of the same mind.
Von Richter states thus: (14) " Trinitrotoluene from
meta mononitrotoluene crystallizes in yellow needles
which melt at 82." Now, the meta mononitrotoluene,
according to modern orientation, will have the nitro-
group in position three. (Throughout this book the
methyl group in toluene will be considered as occupy-
ing position one.) The trinitrotoluene that has a melt-
ing-point of 82 (probably slightly incorrect), is the
symmetrical trinitrotoluene, with the nitro-groups in
positions 2-4-6. It would therefore be impossible for
this symmetrical trinitrotoluene to result from what
von Richter and Beilstein call meta nitrotoluene, unless
one nitro-group actually shifts its position in the mole-
cule which, as is known, is impossible with the con-
ditions existing as they do in the process of nitration.
Returning, now, to Beilstein and Kuhlberg, and
"
their Eleventh Treatise," there is found a detailed
summary of the constants of three nitrotoluenes:
14 TRINITROTOLUENE
HISTORICAL 15
After Beilstein and Kuhlberg completed their work

on the nitrotoluenes, they set about investigating tol-
uene to discover whether or not this substance existed in
isomeric forms, thinking thereby to explain the isom-
erism of the toluene derivatives. Their experiments
are interesting in the extreme, but are too lengthy to
discuss in this book. Suffice it to say that the results
of their research proved conclusively that toluene
existed in but one form.
In considering the discovery of dinitrotoluene, we
must again give the credit to Deville. His original
paper on the general subject of toluene and its nitra-
tion derivatives contains the statement that he pre-
"
pared the dinitro-compound, which he called binitro-
benzoen," in direct accordance with the scheme of
nomenclature he adopted. Deville gives the melting-
point of his preparation as 71. Therefore it is inferred
" "
that his binitrobenzoen was 1-2-4 dinitrotoluene.
(15)
Cf .hours also prepared a dinitrotoluene, but unfor-
tunately he did not leave any data as to which of the
isomers he obtained.
Beilstein and Kuhlberg prepared two di nitrotol-
uenes, but give the melting-point of but one of the two.
This was the same as that of Deville. The work of
Beilstein rnd Kuhlberg seems to have been mostly
on the raon on itro-com pounds of toluene, and the acidic
and basic compounds of mononitrotoluene.
Dr. O. Cunerth, in a paper dated 1874, (16) gives
probably the most comprehensive summary of the his-
tory and discovery of the dinitrotoluenes to be found.
His paper begins with this statement: " It is known
that in the nitration of toluene, two modifications are
16 TRINITROTOLUENE
obtained; the ortho and para." This statement is

further proof that Beilstein was mistaken in his no-
menclature.
The second dinitrotoluene was discovered by Rosen*
still, but he was not sure whether it was the 1-2-3,
tfee 1-2-5, or the 1-2-6 compound. Dr. Cunerth,
after much work, identified this dinitrotoluene as the
1-2-6 modification.
The 1-3-4 dinitrotoluene was discovered by Beil-
stein, who did this work independently of Kuhlberg
in 1873. It was then that Beilstein gave the names to
the three known dinitro toluenes. The 1-2-4 modi-
fication he called the ;
the 1-2-6, the 0; and the
l-o-4, the 7. This nomenclature is not strictly
adhered to, by modern chemists, the usual manner of

denoting a certain di- or trinitrotoluene being to state
the position occupied by the groups.
Iâmpricht is credited with the isolation of the next
dinitrotoluene. This was the 1-2-5 derivative, and
was discovered by Lampricht during experiments on
the action of fuming nitric acid on toluene.
The isolation of the remaining two modifications,
the 1-2-3 and the 1-3-5 is somewhat in doubt. The
sources of information at hand point to either Nolting
and Witte or to Bernthsen as the discoverers.
In considering the history of the trinitrotoluenes, it
is found that modern chemists enter the field. The first
three of these modifications were discovered quite early,
it is true,but the last three were discovered within the
past three years, and their discovery was due indirectly
to the great war. With the trinitrotoluenes, as with
the dinitro-, there are possible six isomers. The most
interesting of the six is the 1-2-4-6 or symmetrical
HISTORICAL 17
modification. Peculiarly enough, this was the first
'
discovered, very likely because it is the modification
present in the largest proportions in the nitration of
toluene.
The discoverer of the symmetrical trinitrotoluene
was Dr. J. Wilbrand, who, at the tune of his discovery,
was working at Gottingen University. Dr. Wil-
b rand's discovery was made in 1862 or 1863. Speaking
of his research, which led to the isolation of the sym-
"
metrical TNT,Dr. Wilbrand says: The preparation
of trinitrotoluene is very easy. Toluene is heated to
about boiling temperature with a mixture of fuming
nitric and sulphuric acidsfor a day. The acid mix-
ture is
agitated with water, and the residue is crystal-
lized after washing with water and drying with alcohol.
The analysis of trinitrotoluene is:
18 TRINITROTOLUENE
proved it to be symmetrical. (18) The melting-point

was found to be 82, in accordance with Dr. Wilbrand's
statement. !n the light of modern research, this melt-
ing-point appears too high. The correct melting-point
is probably 80.6.
The next trinitrotoluene to be isolated was the
1-2-3-6 modification. This was discovered by Paul
Hepp in 1882. (19) Hepp found the melting-point
of this trinitrotoluene to be 112.
The discovery of the 1 -2-3-6 compound was fol-
lowed very shortly by the discovery of the 1-2-4-5
modification by Beilstein, who isolated both the 1-2-3-6
and the l-~ -4-5 isomers the same year that Hepp
isolated the 1-2-3-6. Beilstein found the melting-
point of the 1-2-4-5 isomer to be 104 C.
The remaining three trinitrotoluenes have been
discovered in very recent times. In 1914, Giua and
Molinari discovered the 1-2-3-5 modification. (20)
The isolation of this compound was accomplished while
the discoverers were working on an industrial problem
with the oily substance resulting from the centrifugali-
zation of crude dinitrotoluene. It will be remembered
that Nolting and Witte woiked *iui this same sub-
stance in 1885. These latter investigators overlooked
this trinitrotoluene and also several dinitrotoluenes,
since Giua and Molinari found the following constitu-
ents in the oil.
Mono-.
HISTORICAL 19
Giua and Molinari give the melting-point of this

trinitrotoluene as 79.5.
The next trinitrotoluene to be isolated was the
1-3-4-5 modification. This was discovered by Korner
and Contardi in 1915. (21) Under what conditions,
or from what source this trinitrotoluene was dis-
covered is not known, since the original reference is
not at hand. The melting-point given by the dis-
coverers is 97.2.
The last trinitrotoluene, and the last of the fifteen
possible nucleus-substituted nitro-derivatives of toluene,
is supposed to have been discovered by Coparisow
during the latter part of the year 1915. (22) The

melting-point of this trinitrotoluene is 137.5.
The history of the nitro-derivatives of toluene is a
long one. There is interest at each step, however,
because of the periods of time involved, and because
of the great chemists who were concerned in the isola-
tion and constitution of these compounds. The mono-
nitrotoluenes formed the working subjects for the work-
ing out and proof of a considerable number of the basic
laws of orientation; a fact which is in itself of no little
interest.
.
CHAPTER HI
THE THEORETICAL WTRATI O N OF TOLUENE
.
IN this discussion of the theoretical nitration of
toluene, I shall make use of the ideal process the three-

stage. If either the one- or two-stage processes were
substituted, there would be changes in minor points

only, and I think the three-stage illustration will ren-
der the theory more clear.
The reactions of the first nitration of toluene are as
follows:
First stage:
CeHsCHa +HNO2 - CaH^CHaXNOa) +H2O.
There is also a possibility thai the reaction may go
forward in two steps, the first step being the sulpho-

nation of the toluene, and the second step the substitu-
tion of nitro-groups for the sulphonic groups:
CeH aCH 3 +H 2 S0 4 -* CeH 4 (CH 3 XS03 H) +H 2 O
and,
The reactions of the second stage consist first in

sulphonating the mononitro toluene, and then in nitrat-
ing the sulphonate:
20
THE THEORETICAL NITRATION OF TOLUENE 21
CH (CH,)(NO,) + HzSt)*
4
-> C5Hs(CH3)(NOa)(SOH) +H,O,

and
CH,(CH3)(NO,)(SO 8H) +HNO3
The third-stage reaction is similar to the second

stage:
SOaH) +H aO,
and
2(S03H) +HN08
-* CeH 2 (CH3)(N0 2 )3 + H 2 SO4 .
In each stage there may be the reactions of either

previous or later stages taking place, because of the
impossibility of absolute control.
The theory that sulphonation takes place before the
nitration can be accomplished may be the key to the
question as to why some mono- and dinitrotoluenes
and some are difficultly nitrated.
are easily nitrated,
The sulphonic group follows the laws of orientation
perhaps more closely than almost any other group,
and this explains why (assuming the sulphonation
theory) dilute nitric acid will not nitrate direct, but
will merely replace a sulphonic group. Therefore, if
the sulphonic group is not already in place, the nitro-
group cannot enter the molecule. So, if the previous
22 TRINITROTOLUENE
stage has resulted in the formation of isorners with the

groups in such positions that the sulphonic group cannot
enter the molecule easily, the isomer will be nitrated
only by very strong nitric acid, or by using some special
method of introducing the sulphonic group.
This solution to the question would seem to indicate
that in the first-stage nitration the sulphonation does
not take place, but that the toluene is nitrated directly
by the use of nitric acid.
Starting with toluene, purified as is considered neces-
sary for nitrations, the primary nitration is to mono-
nitrotoluene. The theoretically perfect nitration would
proceed in this manner:
CH3 CH3 CH a CH 3
ro2 2 ON,
NO2
This nitration, however, is never accomplished, for the
mononitrotoluene consists of all three isomeric forms.
The mononitrotoluene modifications are present in
the proportion of 38 per cent para, 60 per cent ort ho, and
2 to 4 per cent meta. (1) This result is exactly what
would be expected, because with the methyl group in
position 1, the tendency oi the nitro-groups is to enter
cither position 2 or position 4. This fact holds true
even with the more generally accepted view that the
first stage of the reaction consists in sulphonating the
toluene, because the sulphonic group behaves and
orientates just the same as the nitro-group, and with
the methyl group in position 1, the sulphonic group
will also enter either position 2 or position 4. The
nitre-group can then easily replace the sulphonic

group.
The formation of the small amount of meta nitro-
"
toluene explained thus by Holleman: (2)
is It is
apparent that there is an opposition between the ortho
and para derivatives on one hand, and the meta deriv-
atives on the other. Either the first two are the chief
products, or the last. Concerning the temperature
of the reaction, it has been proved that the quantity
of the by-products is the smaller, the lower the tem-
perature of nitration." This statement of Holleman
is based on earlier work by himself, and in a paper he
gives this tabulation : (3)
CONSTITUTION OF MIXTURE OF UNITS
Temp, of Nitration.
I
24 TRINITROTOLUENE
another nit ro- group, but still ort ho or para to the methyl
group. Of course, as in the first-stage nitration, a
small amount of the morion itrotoluene (especially
the meta) may, under the influence of conditions con-
cerning which we know nothing, attach nitro-groups
in other than the specified positions.
By the nitration of meta nitrotoluene there is formed
mainly the 1-3-4 dinitrotoluene. Some small amounts
of 1-2-3 and 1-3-6 (or 1-2-5) isomers also result from
this nitration. (4) In each of these cases it may be
noticed that the tendency of the nitro-group is to
resist the intruding prime nitro-group, which has
entered the molecule contrary to the laws governing
its action, because the second group will enter either
ortho or para to the methyl group. These isomeric
dinitrotoluenes, other than the 1-2-4, and the tri-
nitrotoluenes together with some unchanged mono-
nitrotoluene constitute the oil that separates from the
1-2-4 dinitrotoluene by centrifugalizing or cooling
and filtering. This oil is known in Germany as " Bini-
trotropfol." Nolting and Witte (5) state that this
oil constitutes about 7 per cent of the entire charge.
Various chemists have analyzed the oil, their analyses

being summarized and checked by Nolting and Witte,
who found, in addition to the substances isolated by
the others, some meta nitrotoluene. According to
Nolting and Witte, the analysis of this oil shows the
presence of 1-2-4 and 1-2-6 dinitrotoluenes, and
1-3 and 1-2 mononitrotoluenes. Giua and Molinari
(6) discovered some trinitrotoluenes in the oil which
were evidently overlooked by their predecessors.
Summarizing the products of the second stage, the
following nitro-derivatives m&y appear in the mix-
fare. This summary assumes no separation of the

binitrotropfol:
MNT.
26
.
TRINITROTOLUENE
(The German theory of nitration, advanced by Hepp, Edcalea, etc..

and the Italian theory, which is supported by Giua, Molinari, Copari-
so w, and others; differ at this point. The Germans assert that 1-3-4-5
TNT is formed from 1-3-4 DNT, while the Italian theorists state that
this is impossible. The statements gion in substantiation of both
theories are quoted at the end of this chapter.)
The trinitrotoluenes remain unchanged upon

attempts to further nitrate, unless too strong a nitrat-
ing mixture is used. In this case thay may be oxidized
to trinitrobenzoic acids or to tetranitromethane. (11)
All of the lower products of nitration must, of neces-
sity, be included in the products of the third-stage nitra-
tion, because a small amount of any or all of these may
have eâped nitration in all three stages. There is no
reason to suppose that any one of the nitration reactions
may have proceeded to completion, with the possible
exception of the nitration of 1-4 mononitrotoluene.
This particular nitrotoluene is the most easily nitrated
of the entire number, and from all reports, is never found
in the finished product. (12)
Summarizing the products which may be found in
the crude trinitrotoluene, the following formidable
list appears:
MNT.
THE THEORETICAL NITRATION OP TOLUENE 27
'
GERMAN
MNT.
28 TRINITROTOLUENE
'
the small amount of substance we had was a mixture/
The is, we have succeeded
truth in demonstrating that
from a mixture of the nitration products ofmet a
nitro toluene at least two trinitrotoluenes may be
isolated. . . . The first of these is a difficultly soluble
compound having a melting-point of 104 C. The

second, which I shall designate as the beta compound,
is an isomer of the first, and melts at 112 C." (13)
Giua's statement is much more brief and to the

|
point. He
says:
"
The direct nitration of toluene can give but three
trinitrotoluenes, these are the 1-2-4-6, the 1-3-4-6,
and the 1-2-3-4. Only through dinitrotoluidin can
the other three be formed. (14)
.
CHAPTER IV
THE MANUFACTURE OF TNT

1
THE complete manufacture of trinitrotoluene in-

volves the several processes of nitration, separation,
washing, and possibly purification.
crystallization
The experimental stage has been passed in every one of
these various divisions in the manufacture of this prod-
uct, until the modern plant runs as smoothly as a well-
oiled machine. The apparatus necessary to carry on
any one or TNT
all of the steps in the manufacture of
is now well standardized, and many excellent machines

are on the market for accomplishing the end toward
which every manufacturer works a pure product.
A detailed description of the necessary apparatus will
not be gone Into, but a brief outline of the requirements
to be fulfilled by the various machines will be given in
their respective places.
The first step in the manufacture of TNT is the
the nitration. This reaction is carried out in a large
vessel called the nitrator. This nitrator is generally
a cylindrical kettle or tank, built of either an acid-proof
cast metal or of boiler plate. The material of which
the nitrator is built should be thoroughly tested with
the acids of various concentrations met with in the
manufacture of the product. The nitrator must be
well equipped with cooling coils and heating coils so
placed that the temperature of the reacting mixture
29
30 TRINITROrrOLUENE
responds instantly to the operation of these coils. The

cooling is effected by the circulation of cold water
through one set of coils, and the heating coils must be
supplied with either superhea'<cd steam, or steam under
pressure. Some attempts have been made to build a
nitrating kettle with but one set of coils, this set serving
for both heating and cooling. So far as I am aware,
there has never been a really efficient nitratôr yet
built along the above line. The trouble with this
type of machine is that when cold water is waited, it
is wanted quickly, and sufficient time to manipulate
the several valves necessary on the above type of

machine is not to be had. In addition to the tem-
perature control coils, the nitratcr must be equipped
with a good agitating apparatus. This agitator is
just as necessary as the water and steam coils, and,
through keeping the mixture of toluene and acid uni-
form, aids in maintaining the temi>erature level. The
manufacture of TNT is essentially a problem in tem-
perature control. After the nitration is complete, the
rest of the process is easy. In order to check the opera-
tor of the nitrating kettle
it is well to install a recording
thermometer each unit. This eliminates error, and

in
causes the operator to be more careful, because he
knows that a mechanical watch is being kept on his
work.
I have noticed a
tendency in quite a number of TNT
plants to perform the nitration in a rather slip-shod
manner, and on remarking concerning it thfe reply
was made: " Well, its cheaper to use a little less acid
in the nitration and purify the product afterwards."
This policy is very, bad, it is both expensive and non-
efficient. It must be remembered that while TNT is
THE MANUFACTURE OF TNT 31
comparatively safe, it is made primarily to explode.

Now, the more care taken with the manufacture of
TNT the less explosions in the plant, and the more
explosions out of the plant.
There are three general processes for the nitration
of toluene to TNT. These are the one-stage, the two-
stage, and the three-stage. All of these are b?ing used
at present in North America, but the three-stage seems
to have the greatest preference. As the names imply,
the process involves either one, two or three separate
nitrations to carry the toluene to TNT. In some
respects, the names " one-stage," " two-stage," etc.,
are misleading, because in every preparation of TNT,
whether it be by the one-stage, the two-stage or the
three-stage process, there are three distinct nitrations.
With the one-stage process these three nitrations are
all effected with the one acid mixture and without
separation of the nitro-derivatives and the spent acid
until the TNT is completed. Similarly, the two-
stage and the three-stage processes accomplish the
same thing in either two or three different steps, each
step necessitating separation of the spent acid, and the
addition of fresh acid. It must not be supposed,
however, that the entire amount of the toluene is con-
verted to mononitrotoluene before any of the mono-
is nitrated to dinitro toluene, or that all of the mono-
nitrotoluene is nitrated to dinitrotoluene before the

di- is nitrated to TNT. This ideal result is not obtained
with even the three-stage process. No matter which
of the three processes is used, there will always be more
or less impurities existing at each stage in the form of
higher or lower nitration products.
The toluene which is to be used as the raw material
.
32 TRINITROTOLUENE
in the manufacture of TNT must be very pure. The

standard specifications now current in the United
States are as follows:
14
The first drop must distill not below 108 C.
"
95 per cent of the entire sample must distill with-
in 2.
"
The dry point must be below 112 C."
In addition, the toluene must be practically free
from defines or members of the di-olefine series. This
demands that the toluene be washed several times with
concentrated sulphuric acid to remove these com-
pounds. The laboratoi^- test for olcfines consists in
agitating some of the toluene with a certain percentage
of concentrated sulphuric acid. If olefines are present,
the acid layer will acquire a yellow to red color. This
color must not be deeper than whatever shade the cer-
tain plant has adopted as its standard.- The com-
parison standard colors consist of definite concentra-
tions of solutions of potassium dichromate, chromic
acid, etc.
The presence of olefines is dangerous because these
substances form nit no-compounds in the nitration proc-
ess, and these compounds are rather unstable. A fire
or even an explosion may possibly result if the toluene
is not freed from them. The presence of members of
the aliphatic or paraffin series is not nearly so detri-
mental as the presence of the olefines. These com-
pounds do not react on nitration, and with the three-
stage process they may be removed after the nitra-
tion to mouonitrotoluone.
As
stated in Chapter III, the ideal nitration of
toluene to TNT
would be toluene to 1-2 nitrotoluene,
to 1-2-4 dinitrotoluene, to 1-2-4-6 TNT. But this
is never accomplished. It is approached most nearly

with the three-stage process, in which process puri-
fication is possible at each step. In order to compare
the three processes, an outline of each is given.
NOTE. The acid mixtures given are approximate only. Each plant
haa determined just which mixture will give the best results, some of
these mixtures varying as much as 10 per cent. A statement of the
exact analysis of the mixed acid is therefore impossible.
The One-stage In the one-stage process,

Process.
but one acid mixture is used. This mixture consists
of 75 per cent sulphuric acid, and 25 per cent nitric
acid. The usual charge for this process is in the ratio
of one part toluene to twelve parts mixed acid. Each
kilogram of toluene requires, therefore, 3 kilograms
nitric acid and 9 kilograms sulphuric acid.
The toluene is added to the acid in the one-stage
process. The termination of the inlet pipe is in a kind

of well at the bottom of the nitrator, and the toluene is
nitrated beforeit can separate and spread about.
During the addition of the toluene the temperature

must not rise above 30 C. This addition requires
from two to two and one-half hours. After the addi-
tion is complete, the temperature of the mixture is
raised to 90 to 95 C., by means of the steam coils..
This temperature is maintained for two hours, during
which time the mononitrotoluene is nitrated to dinitro-
toluene. The temperature is then further increased to
" "
120, and is cooked for an additional two hours.
The nitration is now consiueied finished, and the charge
isready for separation, washing, and graining. In
many chemical plants a chemist tests the charge of
TNT, and the time of the final cooking is determined
by the solidification point of the mixed TNT and acid.
.
34 TRINITROTOLUENE
This principle of chemical control is adopted sometimes

in the two- and three-stage processes as well as in the
one-stage process. The yield of TNT
by the one-
stage process is 1.9 kilos per kilo toluene used.
The Two-stage Process. There are two possible
modifications of the two-stage process:
1. Nitration from toluene toMNT; separation and
purification of the monoiiitrotoluene, and nitration to

TNT.
2. Nitration to dinitrotoluene, separation of this
product from the spent acid, and further nitration to
TNT.
The second modification has been practically dis-
continued in this country, and will therefore not be
discussed.
The first stage of the other modification of tho two-
stage process requires a mixed acid which contains
30 per cent nitric acid, 55 per cent sulphuric acid,
and 15 per cent water. The proportions for the charge
are one part toluene to two and one-half parts acid
by weight. This process differs from the one stage
in that the toluene is placed in the nitrating kettle and
the Mixed acid is added. The addition of the acid is
carried out at a temperature not exceeding 40 C.,
and consumes one and one-half hours. The charge is
then heated to 60 for one hour, and the mononitro-
toluene is separated from the spent acid. At this point
of the process various procedures are adopted. The
mononitro toluene may be washed an:1 distilled, or it
may be separated from the impurities present by
solution. There has been much discussion as to
whether or not mononitrotoluene can be safely dis-
tilled. Recent investigations on the subject indicate
that it can be safely distilled providing there is no

trinitrotoluene present. In every case, however, the
distillation should be made under reduced pressure,
as this lessens the danger from explosions.
Following the purification of the mononitrotoluene,
or in case no purification has been made, following the
separation from the spent acid, the mononitrotoluene
is placed in the nitrator and is sulphonated with an
amount of sulphuric acid equal to three times the weight
of the mononitrotoluene. This requires about one-half
hour. The reaction mixture is then heated to 70 and
mixed acid containing 50 per cent each of nitric acid
and sulphuric acid, equal in weight to the sulphuric
acid used for sulphonating, is added through a period
of one hour. After the addition is complete the charge
is cooked at a temperature of 120 C. for two hours,
then separated, washed, etc.
The amount of acid necessary in the two-stage
process per kilogram toluene is 5.6 kilos sulphuric,
and 2.2 kilos nitric. The yield of TNT per kilo tol-
uene is 1.99 kilos.
Atwo-stage process has been proposed by Langen-
scheidt similar to the one outlined above, the main
difference being that the final cooking is done at 140 C.
Humphrey has made an especial study of this process,
and makes certain recommendations concerning its
use. (1) He recommends Langenscheidt's process,
but
his investigationshave shown that better yields of TNT
are produced by operating at a somewhat lower tem-
perature (120 to 125) than 140 as prescribed by
Langecscheidt, and maintaining the lower temperature
for a longer time than that specified for the high tem-
perature. The proportions of acids to toluene were

*
36 TRINITROTOLUENE
such that the water concentration in the final mixture

was about 4.4 per cent. The experimental data indi-
cate that the yield of TNT at a given temperature is
not a function of the water concentration of the reac-
tion mixture as assumed from
CH4CHS N02+2HN0 3 <= C6H 2CH3(NO 2 )3+2H 2O.
In his discussion Humphrey makes perfectly clear the

point that the above statement does not apply to either
very low or very high water concentrations, because
experiments have shown that with a very high water
concentration the nitro-group enters the side chain of
the toluene molecule, while with a low water concen-
tration, oxidation products, such as trinitrobenzoic
acids, result.
E. J. Hoffman, (2) has made a study of the effects
caused by the addition of the toluene to the acid, and
vice versa. In his experiments with the two-stage
method (nitrating first to mononitrotoluene and then
to TNT), he used an acid mixture of one part nitric
acid (gravity 1.42) to two parts sulphuric acid (gravity
1.84). When the toluene was added to the acids the
yieldwas 60 per cent mononitrotoluene and 40 per
cent dinitrotoluene. On the other hand, when the
acids were added to the toluene very little dinitrotol-
uene was formed. The temperature was more easily
controlled in the procedure, in which the toluene
first
was added to the acid. Providing the nitration product
is to be further nitrated to TNT, the presence of the
dinitrotoluene is not objectionable. Hoffman's yield

with this method was 75 per cent of TNT with a melt-
ing-point of 78 to 80 C.
The Three-stage Process. The firstrstage acid

for this process is composed of 70 per cent sulphuric
acid, 15 per cent nitric acid, and 15 per cent water.
The acid is run into the toluene, the addition generally
taking about two hours. The temperature during the
addition of the acid must not rise above 30 C. The
proportion of acid to toluene is three to one. Follow-
ing the acid addition the temperature is raised to 60 C.,
and is held at this point one and one-half hours. The
spent acid is then separated, and the mononit rotolucne
is either purified and nitrated to dinitrotoluene, or the

nitration is made without any purification other than
the separation of the spent acid.
The acid used hi the second stage contains 60 per
cent sulphuric, 25 per cent nitric, and 15 per cent water.
The acid is added to the mononitrotoluene at 75 C.,
one and one-half hours being consumed in the opera-
tion. After this addition has been made, the charge
is cooked at a temperature of 90 for one and one-half
hours. Then the spent acid is separated, and the dini-

trotoluene is ready for centrifugalization, or nitration
to TNT without purification.
The step in the third stage is the sulphonation
first
of the dinitrotoluene. Oleum (fuming sulphuric acid)

isused for this purpose in the majority of plants. The
acid may be added very .rapidly in the third stage,
since the temperature is 90 to 100. The acid analysis
shows 50 per cent each sulphuric and nitric. When
the addition is complete, the temperature is raised to
120 and the charge is cooked for one and one-half
hours. The nitration is then supposedly complete,
and the TNT is separated from the acid, and is ready
for washing. The yield of TNT per kilo toluene is
'
^38 TRINITROTOLUENE
2.2. The total acid necessary is 2 kilos nitric and

5 kilos sulphuric per kilo toluene.
The German process of manufacturing is of TNT
interest at this point, since the manufacture of this
product originated in this country. The two-stage
process is the one in greatest use in Germany, and in
many plants the mouonitrotoluene is separated, one
of the isomers being used in the dye plants, while the
other two are nitrated further to TNT. The first
stage of the German process consists in placing 90

liters of toluene in the nitrating kettle and adding
an equal volume of nitric acid (gravity 1.25) at a tem-
perature of 30 or lower.By using this acid alone,
the Germans claim that the separation of the ortho and
para mononitrotoluenes is effected more easily, and
that little or no TNT is present. The para isomer is
the one used for dyestuffs, and it is separated from the

ortho and the small amount of meta by cooling the
mixture to 10 C. At this temperature some of the
para mononitrotoluene separates out and may be
filteredoff. If a complete separation is desired, a
vacuum distillation of the mixture must be carried out.
For nitration to TNT only, no separation of the three
mononitrotoluenes is necessary.
The second stage of the German process is very
much like the American. The mononitrotoluene (500
kilograms) is placed in the nitrator and sulphonated
with 1400 kilos sulphuric acid at a temperature of
60 to 70. Then a mixture of 700 kilos of 100 per cent
sulphuric acid and 700 kilos ^8 run
Be*, nitric acid, is
in. The mixture is agitated until a sudden drop of the
temperature indicates the end of the reaction of nitra-
ting the mononitrotoluene to dinitrotoluene. The
temperature is then raised to 120, and held at this

point until the charge is finished as indicated by the
control analyses.
In some parts of Germany trinitrotoluene is made
from dinitrotoluene, which occurs as a by-product in
various processes of the manufacture of other materials.
In such a case, the dinitrotoluene is melted, sulphonated
with one and one-fourth its weight of oleum, nitrated
with three-fifths weight of nitric acid at tempera-
its
tures varying from 100 to 130, and finally separated
from the spent acid, washed and crystallized.
A good comparison of the three processes used in the
United States may be obtained from a summary of
these processes:
40 TMNITROTOLUENE
tion of the higher grade of product turned out, the three-
stage process may be said to be the best.

Many engineers have investigated to the extreme
the conditions necessary for the best yields and the best
product possible in the manufacture of TNT. Much
credit isdue one of these investigators, M. Coparisow,
because of the light his research has thrown upon the
nitration of toluene, and the cure for the troubles
encountered in this reaction. A summary of Copari-
sow's work is given here, it being taken from a recent
article. (3)
"
The mineral matter piesent during the process of
nitration may act cither as a catalyst or as a chemical
reagent, and this action may explain some of the
curious occurrences in the course of a nitration. Fur-
thermore, when mineral acids act upon the metal parts
of the apparatus, hydrogen may be set free, and may
reduce some of the nitro-compounds. Under the
working conditions a mi no groups may be diazotized
and nitrocresols, whose salts are highly
yielding cresols
explosive, and this action may explain some of the
heretofore mysterious accidents in TNT
plants. These
may be obtained as by-products, through the action of
the hydrogen, and the oxidizing action of the nitric
acid itself:"
"
1. Trinitrobenzoic acid and tetranitromethane.
These result from oxidation in case of overheating or
pressure. The intense odor of the tetranitromethane
is sometimes observed in the factories, but the trini-
acid, owing to its solubility, generally

etection."
"
2. Phenolic compounds. These, like cresols, may
result from the reduction of the nitro-compounds by the
nascent hydrogen which is generated by the action of

the acids upon the metal of the nitrator."
"3. Sulphonic acids. These compounds may result
when the quantity of sulphuric acid is too great;
i.e., when the mixture of acid contains too much sul-
phuric acid in proportion to the nitric acid."

In the process of the manufacture of TNT, Copari-
so w points out the following as being matters requiring
particular care and watchfulness:
"
The amount of nitric acid used must exceed the
1.
theoretical amount necessary by at least one-half

molecule."
"
2. The extent of the nitration should be regulated
more by the concentration of the acids, the temperature
and the duration of the nitration than by the actual
quantity of nitric acid present."
"3. The reaction product should not be kept in
contact with the spent acid longer than is absolutely
necessary."
"
The concentration of acid and the nature of the
4.
material in the plant should be such as to reduce their
action on one another to a minimum."
"
5. The raw
materials must be pure."
Coparisow further states that disposal may be made
of the residue from the mother liquor which residue
consists of a complex mixture of various dini trotoluenes
and nitrating this with a mixed
trinitrotoluenes by
acid containing only 15 per cent nitric acid. By this
" "
method, a liquid TNT is obtained, which has con-
siderable power, and has the property of gelatinizing
collodion cotton, the same as nitroglycerine does. This
liquid product is used in the manufacture of gelatinized
explosives.
42 TRINITROTOLUENE
Following the nitration of the TNT, either one of

two processes may be followed. The first of these
process ?s consist m " blowing " the charge of TNT plus
the spent acids to a separating pan, where the charge is
allowed to cool. On cooling, the TNT
crystallizes out,
and so separates from the spent acid. Water is usually
added to the mixture when it is blown, in order to more
completely precipitate the TNT from the acid solu-
tion. Mcllutchison and Wright (4) have investi-
gated the minimum amount of water necessary to
completely separate TNT from the mother liquor in
order to avoid unnecessary expense in the recovery of
the spent acids. It was found that the maximum pre-
cipitation of TNT
occurred on the addition of the acid
to 4-5 volumes of water. A greater dilution than
this, or the addition of the water to the acid was found
to be less effective. Following the separation, the spent
acid is drawn off to a tank, and may either form the
basis for the new nitrating acid, or may be sent to
the reclaiming plant for purification. The is TNT
transported to the washing plant by either manual
labor, or by melting and blowing through pipes or
troughs.
The second method of disposing of the completed
nitration mixture consists in cooling the products while
still in the nitrating kettle, and thus forcing out the
TNT from its acid solution. This procedure, of course,

more dissolved TNT in the spent acid, but
results in
the time saved in the separation is very great, since the
crystallization in pans requires about four days, while
the nitrator separation requires but a few minutes.
The nitrator separation is used especially in plants
where the spent acid goes into the next charge of
nitrating acids. Thus, the TNT in solution in the

spent acid is reclaimed, so the percentage dissolved does
not matter.
Even after this separation of the spent acid, there
still remains a considerable amount of acid in the TNT.
In order to obtain a marketable product, this acid must
all be washed out. To perform this operation, the
TNT is blown from the separating pan or, if the separa-
tion was made in the nitrator, from the nitrator to the
washing tanks. The washing is accomplished by means

of hot water (85 to 90 C.) Seven or eight changes of
water are necessary for the complete removal of the
acid.
The washing of TNT was originally for the sole pur-
i
pose of removing the acid and rendering the TNT neu-
tral to litmus. This process has been extended and
elaborated upon, until to-day, hi a modern plant, the
primary steps in the actual purification of the TNT are
carried out in the washing kettle. Various chemicals
have been tried in solution in the wash water. The
one great success in this line is sodium sulphite.
Besides acting as a neutralizing agent to the acid, the
sodium sulphite liquor exerts a solvent action on the
lower nitration products of toluene, and thus serves to
remove some of these impurities from the symmetrical
trinitrotoluene. The usual manner of using the
sodium sulphite wash is to give first about four washes
with hot water, then two washes with sodium sulphite
liquor, which contains 20 kilograms sodium sulphite
per 1000 liters water. This chemical wash is followed
by a slightly acidified water wash, and then with two
more pure water washes. Various other chemicals,
such as sodium carbonate, sodium bicarbonate, etc.,
-
44 TRINITROTOLUENE
have been used with more or less success. It has

been found that these more distinctly alkaline salts tend
to darken the TNT, and also tend to render it unstable.
There are, in fact, some sodium salts of TNT which
explode as low as 160 C.
The washing of TNT is, in short, a chemical engi-
neering problem which often taxes to the limit the re-

sources of the engineer. Practice has proved that the
most efficient washing apparatus is the most simple
in construction. As a matter of fact, the more simple
the entire TNT plant, the better the product, and the
most efficient the operation of the plant. One type of
washer, a very complicated îece of apparatus, built
of iron, containing a lead lining, and well supplied with
baffle walls, interior wells, and valves and syphons
galore,was at one time in use at a certain plant. This

machine was a model of the designer's art, but was
absolutely useless for the washing of TNT, since the
charge generally ^nished up by solidifying in the various
valves, wells, and syphons in and connected with the
machine. This necessitated dismantling the whole
apparatus, and the cleansing of each individual valve
and well with live steam. Plain wood tanks have
now replaced this machine, and are washing the TNT
perfectly, the entire tank costing less than a new lead
lining for the old type apparatus, and lasting from two
to three times as long. The agitation of the TNT and
water in this wood tank is done by means of compressed .
air or steam entering through small holes in a pipe run-
ning lengthwise on the bottom of the tank.

Since TNT is appreciably soluble in hot water, the
wash water from the washing machine contains a

comparatively large amount of dissolved TNT. In
order to reclaim this dissolved material the wash water

coming from the washers is run through a series of
tanks containing baffle walls to force the water to
travel a considerable distance. This is known as the
" TNT
labyrinth." Here the water cools, and the is
thrown out of solution. These labyrinths are cleaned

out periodically, and the recovered TNT is melted,
sieved, and if necessary treated with a nitrating acid
and finished in the ordinary way. In some cases this
reclaimed TNT (sometimes of inferior quality) is
mixed with good TNT("blending") and is thus
disposed of. The conscientious inspector of TNT
will
not allow this practice unlqss done under his personal
supervision. BlendedTNT possesses certain charac-
that pure
teristics TNT does not possess, and may thus
be detected.
Following the washing, the TNT is crystallized or
"
grained." From the washing tank or kettle the
molten TNT is run by gravity into the crystallizing
pan. This apparatus consists of a water-jacketed
horizontal pan, in the center of which is set a vertical
shaft carrying a brass or bronze arm. This shaft may
be driven by either c.verhead or bottom drive. The
under drive is preferable from the standpoint of safety,
because hi this manner of drive, all belts, gears and
motors are placed underneath the pan where the work-
men cannot come into contact with them. The under
drive furthermore lessens the possibility of contamina-
ting the TNT, which is being crystallized hi the pan,
with dropping oil or grease from the belt or gears, such
as might occur if the drive were of the overhead type.
The arm which is attached to the revolving shaft should
clear the sides and bottom of the pan by at least | inch.
.
46 TRINITROTOLUENE
This is necessary. to prevent friction between the arm

and the pan, and the possibility of ignition of the
TNT. The arm should be set in a sloping position
with the slope downward in the direction of rotation.
This slope causes the TNT to climb over the arm, and
greatly facilitates the graining of the material.
A second method of reducing the TNT to small
particles, and which is, as yet, quite new, depends upon
the rotation of a drum in the molten TNT. As the
drum revolves, a thin layer of TNT adheres to it, and
is scraped from the drum by a knife after about one-
half revolution. This machine decreases the time
necessary for the crystallization greatly. The process

"
is known as flaking."
The completion of the crystallization marks the end
of the process of manufacture of crude TNT. The only
operation left is the screening. This is done by shovel-
ing the TNTdirectly from the crystallizing apparatus
into an oscillating screen having 10 to 30 meshes per
inch. The TNT passing through the screen is packed
into boxes of 100 pounds each.
One of the problems confronting the pioneer chem-
ical engineers in the explosive field was the disposal
of the spent or waste acid from the nitrations. The
analysis of a typical spent acid shows the following
composition:
Nitric acid 3-12%

Water .... 10-30
Organic matter J-3
Sulphuric acid Balance
The disposal of this a/id in the earlier plants was accom-

plished by sending the acid directly from each uitra-
'
i
tion to the spent acid tank, and from this place to the
denitrifying plant. Modern practice utilizes the

spent
acid from one stage as the basis of the nitrating mix-
ture for the next preceding stage. This re-use is
along certain lines that are developed by the individual
plant. This method of using the spent acid over again
possesses the following advantages:
1. The saturation of each spent acid with organic
matter lessens the loss of the TNT

by solution.
2. A uniform spent acid is discarded by the nitra-
tion plant, thus enabling the denitrating plant to adopt
a standard practice, and to treat each batch of acid the
same.
The first step in the reclaiming of the spent acid is
the cooling and filtering of the acid. This removes a
large part of the organic matter. The removal of the
organic matter is very important, especially so if the
recovered nitric acid is to be used in the manufacture
of ammonium nitrate. Foreign material in the nitric
acid may result in an explosion. In the United States
alone, at least one explosion is known to have been
caused by such contamination.
Following the removal of the organic matter, the
acid goes to the denitrating plant. Here the nitric
acid separated from the sulphuric acid by blowing
is
air and steam through the mixture. The weak nitric

acid resulting from the solution from the denitrating
towers is used, as stated above, in the manufacture of
ammonium nitrate.
The reclaiming of the waste acid has been the object
of several patents granted in the United States and
foreign countries, the medium of separation being
solvents, for the most part. A British patent (5),
48 TRINITROTOLUENE
granted in 1914, separates the nitrotoluenes contained

in the waste acid by washing the acids with toluene or a
nitrated toluene which has been nitrated to a lower
degree than that of the products to be removed. If
the process be carried out at a suitable temperature,
the toluene or nitrotoluene used for the extractant
undergoes nitration in the process. Fresh nitric acid
may be added to the waste acids for this purpose.
Another process of extracting the organic matter
from the waste acids by solvent means was patented
in T915. (6) This process is made continuous by run-
ning together the waste acid and solvent, in suitable
proportions, into a mixing tank, while maintaining the
appropriate temperature and pressure. The mixture
flows from the mixing tank through an overflow pipe
into settling tanks, where the liquids divide into layers,
the nitrotoluenes formerly dissolved in the acids being
now dissolved in the solvent. Suitable solvents men-
tioned in the process are toluene, mononitrotoluenes,
etc.
A because of its
distillation process is interesting
uniqueness. In the operation of this process (7) the

wagtc acid is evaporated in a suitable container, and
the organic substances are removed from the gas and
vapors by passing these vapors through a chamber over
water. The part not absorbed by the water in this
chamber passes out into a condenser. The solidified
organic matter collects hi a readily accessible chamber,
and is removed from time to time.
A
peculiar use is made of the spent acid in some parts
of Russia. (8) The waste acid from the manufacture
of TNT contains 62 to 72 per cent sulphuric and 2 to
3 per cent nitric acid. This is used to prepare super-
phosphate from the Russian phosphate rock. The

superphosphate thus prepared is said to be much more
dry and more pulverulent than that made with sul-
phuric acid alone.
After the separation of the nitric acid from the solu-
tion, there remains a mixture of sulphuric acid and
water. This is concentrated by running slowly through
a series of pans, called a " cascade," which are heated
from beneath. Various other patented processes are
now coming into use for concentrating sulphuric acid
solutions. The acid coming from the concentrating
plant mixed with oleum to further reduce the water
is
J
content, and may be used hi nitr . "ng mixtures again.
Another use for the acid as it comes from the concen-
trating house is hi the manufacture of nitric acid.
Another problem which the engineer must meet is
that of transferring the TNT after it has been completed
by nitration to the various other stages of the manu-
facturing process. With the toluene, acids and other
raw materials comparatively easy, since these are
this is
in the liquid state.TNT, however, will solidify at
80 C. and must be kept above this temperature if it is
to be blown through pipes. Blowing consists in run-
ning the TNT in a molten state into a strong box called
a "blow-case," and then, by means of compressed
air, forcing it out through steam-jacketed pipes. Con-
siderable difficulty is experienced with this method of
transportation, because the TNT solidifies in the pipes
seemingly without the least reason. When such an
occurrence takes place, it is necessary to either wait
a considerable time until the TNT melts, which delays
the process; or else a section of the pipe must be cut
out, and the TNT removed mechanically. One very
50 TRINITROTOLUENE
good plan to overcome this difficulty is to run the TNT

through very short pipes, by gravity, or where a short
pipe is not feasible, a trough may be made, and sur-
rounded by steam pipes embedded in asbestos cement
or sand. Should the TNT solidify through accident,
the trough can be readily cleaned out without delay or
inconvenience.
The oily substance which separates on the second
stage of the three-stage process, called by the Germans
"
binitrotropfo!," is quite indifferent to attempts
made to nitrate it. The problem has been solved in
Italy, according to Giua, in this manner: (9)
The oil is treated with an anhydrous a id mixture,
within very narrow limits (1 :
2). With this treat-
ment, a product is formed, having a melting-point of
66 C., and which can be separated from the oily and
more difficultly nitrated portion by cooling to 40,
and allowing the oil to drain off. A second nitration
will yield a product which, on being washed, melted
and neutralized, melts at 80 C. This " tropf " oil
has always been regarded as useless in Italy, but in
Germany, where alcohol is used for crystallization,
" "
tropf oil is the starting-point for much of the TNT
produced. A single nitration of the oil does not give
a utilizable TNT if the latter is not crystallized from
some solvent, because 5 to 7 per cent of the oil remains

unnitrated under ordinary conditions. The use of
alcohol as a solvent from which to crystallize the is TNT
prohibited in Italy, because of the high tax on alcohol.
Denatured alcohol cannot be used, because the pyridine,
which used as a denaturant, darkens TNT. For
is
TNT industries in Italy use dinitrotolu-

this reason the
ene as the starting-point, and the dinitrotoluene is
centrifuged to separate the oil. By the above method

of nitrating, a great amount of this oil has been saved.
It will be seen from the foregoing description of the
complete manufacture of TNT that the modern fac-
tory must be much larger than a simple nitrating,
washing and crystallizing plant. The modern plant
must include, besides the TNT units: (a)Plant for
manufacturing nitric acid; (6) Sulphuric acid concen-
tration plant; (c) and filtering plant;
di nitrating
(d) ammonium nitrate plant, or other plant to utilize

the weak nitric acid that is recovered from the spent
acid.
Summing up the entire process, it is one of chemical

control from beginning to end from the testing of the
toluene from which the TNT
is made, to the analysis
of the acids recovered from the waste liquors. Chem-

ical control cannot be emphasized too greatly, and the
plant with the most highly developed chemical control
is the
plant that turns out the best product
'
'
'
CHAPTER V
THE PURIFICATION OF TNT
THE purification of TNT, while in reality a part of
its manufacture, may consist of any one of a number of
methods, most of which are equally good as a means of

" "
extracting the impurities in the TNT. There are
appearing every day new methods of purifying this
substance, and the number is now too great to treat
each method separately. It is thought wise, in view
of the fact that a differentiation is made between crude
and purified TNT, to treat the purification as a sepa-
rate subject, rather than to include it in the discussion
of the manufacture.
The product which results Irom the application of
the various processes outlined in the previous chapter
is known as "crude TNT." To define the word
" "
crude as applied to TNT
is rather difficult, since
a crude product is generally thought of as being a

product that is contaminated with foreign substances.
The purified product differs from the crude product in

that these foreign matters are removed. As a matter of
" "
fact, TI^T contains no real impurities, in the
crude
true sense of the word, because the impurities have been
removed in the washing of the crude product. There
are, it is true, other compounds of nitric acid and tol-
uene (the lower nitration products), in the TNT, and
52
THE PURIFICATION OF TNT 53
" "
these are the impurities meant when this term is
in connection with TNT.
By on " The Nitration of
referring to the chapter
"oluene" it is seen that TNT may contain mono-
nitrotoluene, dinitrotoluene and even other isomeric
trinitrotoluenes aside from the symmetrical TNT.
"
The common expressicJn TNT " (or its synonyms)
has become narrowed down mean that certain
to
trinitrotoluene isomer defined as the alpha, or 1-2-4-6
isomer. The melting-point of this particular trinitro-
toluene as determined by reputable authorities is
80.6 to 80.8 C. Now, if other trinitrotoluenes or any
mono- or dinitrotoluenes be mixed with the symmetrical
TNT, the melting-point will be either raised or lowered,
according to the specific nitrotoluene present. As a
general rule, the melting-point of the mixture is lower
than the melting-point of pure TNT, indicating the pres-
ence of some of the mono- and dinitrotoluenes. In
order to remove these compounds from the TNT,
many different methods of purification are resorted to.
The greater number of these methods depend upon the
solvent action of some substance upon the mononitro-
toluenes and the dinitrotoluenes. The more important
of these methods are outlined below.
1. The Purification by Alcohol. The crude TNT
is placed upon the filter medium of a vacuum filter.
An amount of 180 proof alcohol, equal in weight to
one-quarter the weight of the TNT, is added. This
mixture of TNT and alcohol is then agitated thoroughly,
and fresh alcohol, equal to one-half the weight of the
TNT is poured in on top of the mixture. The filter
pump is then started, and the alcohol is filtered off

until the top level of the alcohol layer is coincident
54 TRINITROTOLUENE
with the top of the TNT. At this point a further

amount of alcohol equal to one-quarter the weight of
the TNT is added, and the filter is sucked dry. The
TNT is dried by either a current of warm air, or by
vacuum. In the latter case, the filter must be so ar-
ranged that a vacuum may be effected in the upper
chamber.
The action of the first portion of alcohol added is
to dissolve the mononitrotoluencs and the dinitro-
toluenes. The second volume added dilutes this solu-
tion and dissolves any of the nitrotduenes which
escaped solution by the previous addition. The last
portion of alcohol serves to dissolve out any remaining
traces of the impurities, and also serves to wash the
TNT.
The cost of this method of purifying TNT is rather
high. Pure ethyl alcohol
preferable to denatured
is
alcohol, because of the action the denaturing agents

have on the TNT. The cost of the undenatured sol-
vent too high, however, to permit its use unless a
is
well-developed plan of solvent recovery is in operation,

so that practically none of the solvent is lost,
2. Purification by Sulphuric Acid. Hot sulphuric
acid, 100 per cent concentrated, possesses the property
of dissolving all three classes of the nitrotoluenes. Upon
such a solution, the trinitrotoluene crystallizes,
coolirig
but the mono- and dinitrotolucnes remain in solution.
This property of sulphuric acid forms the basis of an-
other method of purifying TNT. The solution of the
TNT in the sulphuric acid effected in steam-heated,
is
lead-lined vats. The liquor is then filtered and cooled.
The recrystallized TNT must be washed with several
changes of water to remove the acid. This method
of purifying TNT yield* a very light-colored product.

The loss of TNT is quite high, since about one-third
the total amount of TNT remains in solution. The
spent acid from this purification which contains the
dissolved mono- and dinitrotoluenes may be used
either as a sulphonating acid, or as the sulphuric acid
portion of a nitrating acid.
A
modification of the sulphuric acid process has
been patented (1) when applied to a mixture of mono-
nitrotoluenes and paraffin hydrocarbons. The nitra-
tion of the toluene is carried on carefully so as to take
it only as far as the mononitrotoluene. The mono-
nitrotoluene is dissolved in sulphuric acid, but any
paraffins that may be present will not dissolve, and will
form a separate layer. A separation of these two lay-
ers and the subsequent nitration of the sulphuric acid
solution of mononitrotoluene yields a very high grade
TNT. Thus a toluene containing a comparatively
large percentage of paraffins may be utilized in the
manufacture of TNT.
Carbon Tetrachloride and Alcohol. A mixture
3.
of carbon tetrachloride and alcohol exerts a marked
solvent action on the two lower nitro-compounds of
toluene, and this action forms the basis of a patent
granted for the purification of TNT. The proportions
of the solvent used vary, certain conditions requiring
particular concentrations of the two solvents. For the
. use of this solvent an especially designed filter is needed
which will allow the mixture of TNT and the solvent
to be thoroughly agitated directly on the filter medium.
The method of operation is practically the same as that
used for the purification by alcohol alone. The vacuum
filter is ao arranged that when the last layer of solvent
.
56 TRINITROTOLUENE
has been added, and the filter sucked dry, the apparatus
may be reversed and used as a vacuum drier. Hand-
ling of the TNT is thus reduced to a minimum. This
method is said to be very efficient, the loss being only
3 to 7 per cent. The cost per kilogram TNT is reported
to be about 6 cents.
4. Purification by Sodium Sulphite. One of the
cheapest and probably one of the best methods of
accomplishing the purification of TNT by solvent
means is by the use of a 20-per cent solution of sodium
sulphite. Various methods of using this solution have
been developed, the two best of these being given
'
The first method consists in agitating the TNT with

the hot sodium sulphite solution until the mono- and
dinitrotoluencsare in solution, then cooling and
allowing the TNT to solidify in the usual way. The
second method consists in adding the molten TNT to
the sulphite liquor in a very fine stream. The tem-
perature of the sulphite solution should not be so low
that any of the mono- or dinitrotoluenes may escape
solution, but, on the other hand, should not be higher
than the melting-point 01 the TNT. The TNT solidi-
fies in the form of small balls or pellets, and because
"
of this action, the process is known as pellet iiizing."
Of course, the solution used in the pelletilizing process
need not be sodium sulphite, as other solutions will
bring about the same result.
The use of sodium sulphite as a purifying agent
for TNT always necessitates a wash with 1 or 2 per
cent sulphuric acid after the sulphite treatment, in
order to remove the dark color whicli is imparted to
the TNT by the sulphite. Following the sulphuric
acid wash, two fresh water washes should be given.
The sodium sulphite method of purifying TNT is
very cheap; the figure given by one large producer of

A
TNT is cent per kilogram. This firm, it is said,
obtains the sulphite from the waste liquor of the hy-
droxide fusion in the manufacture of phenol. Assum-
ing the above statement to be true, the cost of purifica-
tion per kilogram TNT will be somewhat higher if it
were necessary to purchase the sulphite. The salt
need not be chemically pure for this purpose, but it
should not contain appreciable quantities of the
hydroxide, carbonate or other distinctly alkaline salts,
since these salts will darken the TNT so deeply
that the sulphuric wash may not restore the light
color.
5. Mechanical Purification.A very interesting
method of purifying TNT is in use at the plant of one
of the largest producers of TNT in the United States.
This process comes nearer to that used by the Germans
than does any other American process. It will be
remembered that in the second stage of the nitration
a mixture of mono- and dinitrotoluenes forms as an
oil. The procedure involved in this method is to
centrifuge the dinitrotoluene and in this manner remove
this oil. It is said that the oil obtained in this process
may be further nitrated to TNT, but according to

Giua and Molinari, and Nolting and Witte, the oil
consists mostly of meta mononitrotoluene and dinitro-
derivatives of the same. Will and others insist that
some of these derivatives at least are not capable of
being further nitrated without undergoing decomposi-
tion, ornot without great difficulty. The TNT formed
by the nitration of the thus purified dinitrotoluene
possesses a melting-point of 80 C.
58 TRINITROTOLUENE
6.Modified Solvent Process. Still another inter-

esting process is a modification of the sulphuric acid
solvent method. This method has gained favor with a
number of manufacturers because of its time-saving
qualities. The procedure with this method is to add
100 per cent hot sulphuric acid to the mixture of TNT
and spent acid immediately after the nitration is com-
pleted. The mono- and dinitrotoluenes together with
IT >st of the TNT dissolve in the sulphuric acid, the
mixture is cooled and TNT
filtered, and the recovered.
This process possesses the advantage of eliminating one
washing, and is '.bus to be preferred to the ordinary
sulphuric acid treatment as outlined above. The
spent acids may be used in subsequent nitrations, and
the dissolved organic matter recovered in this manner.
Many other solvents may be used to accomplish
the purification of TNT. The organic solvents such
as toluene, acetone, etc., find an especially wide
application. The method followed with these solvents
may be either a simple heating of the mixture of TNT
and solvent until the impurities dissolve, followed
by cooling and crystallization of the TNT, or it may
be a more elaborate scheme somewhat as outlined in
method 1 above. Well-developed processes have been
worked out for purifying TNT by solvent means
using nitrobenzene and nitrotoluene as the solvents.
The solvents may be purified for further use by dis-
tillation with steam. (2)
The recovery of the solvent is a very important con-
sideration in an efficient plant. This recovery must be
carried out with a great deal of care, since the concentra-
tion of the nitro-derivatives in the solvent increases
as the solvent is distilled off. if the distillation is
carried too far, the nitre-compounds may decompose

with explosive violence. Two cases are recalled where
explosions have resulted from an attempt to carry the
distillation of the solvent used for extract ing the mono-
ami dinitrotoluenes to a too-concentrated residue.
The solubility of the mono-, di- and trinitrotoluenes hi
the hot solvent is naturally greater than in the cold
solvent. Therefore, although the boiling solvent may
exhibit no signs of being saturated with the nitro-
compounds, it may be near the danger point. The
procedure followed by the writer in solvent recovery
is to distill the solvent until the volume of the recovered
solvent equal to one-half the volume of the solution

is
placed hi the still. At this point the distillation is

interrupted, and the residue, which is twice as concen-
trated as it originally was, is withdrawn from the still
and allowed to cool, when the excess of dissolved sub-

stances will be thrown out of solution. The mixture
is then filtered, and the concentration will be just the
same as at the start of the operation. To illustrate:
Suppose a volume of 1000 liters of solvent saturated
with 6 per cent dissolved nitrotoluenes is to be re-
covered; 500 liters, say, of the solvent are placed
in the still, and 250 liters distilled off. The residual
liquid in the still now contains 12 per cent dissolved
organic matter. On cooling, one-half this solute will
precipitate, and after mixture,
filtering the cold
the solvent concentration will be the same as it
-6 per cent. The remaining 250 liters
originally was,
may now be mixed with another 250 liters of the
fresh solutionand the process continued. It is not
probable that the concentration of the residue at the
point where the distillation is interrupted is very close
60 TRINITROTOLUENE
to the decomposition point, but with the operation

outlined it costs nothing to be on the safe side, and
practically 100 per cent solvent recovery, barring evap-

oration or carelessness, may be accomplished.
The which is used for the recovery of the sol-
still
vent may be a steam-jacketed still of almost any shape

for the lower boiling-point compounds. For those
solvents whose boiling-point is higher than that of
water a direct fired still, or one supplied with high
pressure steam, is necessary. In cases where simple
solvents such as alcohol or acetone are to be recovered
a simple still without any column will do very nicely.
If the solvent is complex; that is, if it is composed of a
mixture of two or more solvents, and these solvents
must be separated, a more complicated still with a
fractionating column is necessary. In this period
of modern engineering skill, a special still designed and
built expressly for the one particular purpose for which
the manufacturer desires it, can be bought for very little
more than a stock still, and will perform its work much
more satisfactorily.
.
CHAPTER VI
THE INSPECTION AND TESTING OF TNT

By K. K. STEVENS
Inspection. TNT is on the market in two grades,
primarily, crude and refined. The crude has not been

recrystallized from solvents, while the refined has. Of
thesetwo grades, there may be several other grades
based on the melting-point (M.P.) or usually the
solidification point (S.P.).
The crude TNT is the more common form in the
United States and when purchased by foreign govern-
ments is shipped crude and either refined or blended
with other substances. The greater bulk of TNT made,
up to very recently, has been shipped crude, possibly
only three plants in the United States manufacturing
the refined grade in any quantity. In the different
plants the product is obtained in lots of approximately
"
2200 pounds each, called runs."
The specifications usually call for containers, such
as cases or kegs, which hold from 60 to 100 pounds,
are lined with oiled paper, and numbered as to ship-
ment, "run" and case. The inspector may be ex-
pected to check the weights, and take samples for
analysis.
Sampling. Samples should represent lots of 4000
pounds, and for convenience a composite sample from
two runs is often taken. The cases are selected, opened,
ei
62 TRINITROTOLUENE
and the samples taken from different parts of the case,

mixed, and three 1-pounu bottles filled; one each for
buyer, seller, and referee, the latter's bottle being
sealed by the buyer's inspector.
Testing. Color should be light yellow for crude,
cream for refined.
Comment. The color changes rapidly when exposed
.
to strong light, sunlight changing it from yellow to

orange in fifteen to twenty minutes, although the deeper
shades of yellow .are not an indication of impurity.
The brownish grades should be inspected, though not
necessarily condemned in the crude grade without con-
firmatory tests.
In the refined grade the color may vary with the
solvent used in re-crystallizing, but should usually be
of a light cream, melting to a clear light brown, not
darkening appreciably at 100 C. for two hours.
Fineness. For crude, 90 per cent shall pass
through a 10-mesh sieve. For refined, 99 per cent
shall pass through a 12-mesh sieve. For exploders, all
shall pass through a 30-mesh sieve.
Comment. The crude may contain frequently 7 to
8 per cent of lumps larger than specified, but is usually
O.K., always being sieved before packing, and the' lumps
forming on the sides of the crystallizing tub have been
allowed, intentionally or accidentally, to get in the
sieved product.
Moisture. Moisture shall not be more than 0.10
per cent for crude or refined (some specifications allow
0.15 per cent) and shall be determined by drying
2 g. over sulphuric acid for twenty-four hours.
Comment. The method is efficient, and will remove
as much as 30 per cent moisture in the time specified.
INPSECTION AND TESTING OF TNT 63
Acidity. There must be no acidity. This deter-

mination is made by shaking 10 g., melted, with 100
c.c. boiling water (distilled) allowing to cool, pouring
off the water extract into a flask, and reserving; the
operation is repeated with 50 c.c. distilled water, adding

the second extract to the first. The combined extrac-
tion is titrated with N/20 caustic alkali, using phenol-
phi halein as indicator.
Other specifications less definite are as follows:
Shake 5 g. with 100 c.c. distilled water in a 100-o.c.
graduated cylinder one minute, adding blue litmus
paper and stand thirty minutes, with occasional shak-
ing. The paper must not show any acid reaction at the
end of this time.
One specification allows 0.03 per cent acid calcu-
lated as sulphuric.
Comment. The method of the first specification
seems better, although any sodium bicarbonate wash-
ing (not used at present) will give acid reaction at
this point, whereas methyl orange will give only the
mineral acids. The litmus paper shows acidity with
phenolic compounds as well as acids, but if the deter-
mination is carried out as specified, there will be no
color to the litmus paper, it having been completely
bleached, and any acid reaction is more or less doubt-
ful. The method may be modified as follows: Shake
5 g. with 400 c.c. distilled water one minute, filter,
stand 5 minutes and add the litmus papter; any acid
reaction will be detected in two minutes. The litmus
might be used instead of titrating in the first
method.
Insoluble matter must not exceed 0.15 per cent,
as determined by boiling 10 g. with 150 c.c. of 95 per
64 TRINITROTOLUENE
cent alcohol, collected on a weighed Gooch crucible,

washed with not more than 150 c.c. of 95 per cent al-
cohol, drying at 95 C. one hour and weighing.
Some specifications call for benzene as the solvent
and allow 0.10 per cent for refined, 0.15 per cent for
medium, and 0.20 per cent for crude.
Comment. The method is efficient.
Turbidity in the wash water is one cause for high
insoluble matter, and another cause is allowing the
TNT to stand too long in the lead-lined wash tanks,
the acid attacking the lead and forming lead salts.
Ash in crude TNT must not exceed 0.10 per cent,
determined by igniting 1 g. in a platinum crucible,
allowing to burn slowly and igniting completely, pre-
caution being taken to prevent loss of ash.
Comments. The sample should be heated, ignited
directly with the flame, and allowed to burn without
first melting; if melted and then heated further, the
sudden combustion will expel it from the crucible.

The size of the sample should be about 2 grams,
taking into consideration the low percentage of ash
present.
" "
The residue called insoluble matter
might be
conveniently used for the ash determination.
Some specifications call for sulphated ash, probably
to avoid loss of potassium or sodium salts during
ignition.
Ash in refined TNT for exploders must be less
than 0.05 per cent.
Nitrogen. Crude TNT
must contain not less than
18 per cent nitrogen determined by the Dumas combus-
tion method.
Refined TNT must contain not less than 18.20
INSPECTION AND TESTING OF TNT 65
per cent nitrogen determined by the Dumas combus-

tion method.
Comment. The Dumas method, standard for nitro-
gen, requires little comment, results being very satis-
factory, although it is necessary to make determina-
tions on a substance of standard nitrogen content.
The method requires from one and one-half to
three hours, and unless the chemist possesses several
furnaces, not very many determinations can be made
daily.
For the nitrogen determination on many organic
compounds, the Gunning-Arnold method or modifica-
tion of it has been used. The only modifications
reported to be satisfactory for trinitrotoluene or other
nitro-compounds are the zinc dust reduction by W. C.
Cope, U. 8. Bureau of Mines, and the use of nitron
as reagent by W. C. Cope and J. Barub. (1)'
The nitrogen determination is important, although
if the melting-point or solidification point is up to
specification, the nitrogen isseldom below.
In many instances it is common practice to average
several samples for the determination of nitrogen.
Diphenylamine Test. Crude TNT
shall contain
no products which will give the nitric acid reaction with
a sulphuric acid solution of diphenylamine. The deter-
mination is made by shaking with 50 c.c. distilled water
in a graduated glass-stoppered cylinder, standing fifteen
minutes, filtering and testing a few drops of the filtrate
by adding to the diphenylamine solution. No nitric
acid reaction should be obtained.
Comments. The blue color characteristic of this
reaction is readily recognized and the test is extremely
delicate.
66 TRINITROTOLUENE
Cure must be taken that vessels are free from traces

of nitric acid or nitrates.
Since other oxidizing agents, such as chlorine,
chlorates, bromates, etc., will respond to this test, it
is of more value, as a negative test, and fairly posi-
tive, because the oxidizing substances mentioned are

not likely to be found in trinitrotoluene. A pale blue
color is not confirmative; the color should be a deep
blue.
Melting-point The melting-point of crude TNT

must be 75.5 C. or higher.
NOTE. This is the mean, some specifications calling for a

melting-point of 74.5 C. others 70.5 C.
Medium TNT must have a melting-point of 79.5

to 81. 5 C.
Refined TNT for exploders must melt from 80
to 81.5 C.
Comments. Methods for obtaining melting-points
are not usually given in the specifications, but it is
absolutely necessary that a definite procedure and
definite apparatus be agreed upon. The following
points should be taken into consideration: calibration
and stem correction of thermometers, size of tubes,
amount of substance taken, rate of melting and vessel
of liquid to be used as bath.
The following is given by H. B. P. Humphries,
engineer:
Apparatus and Method. A beaker of 1500 c.c.
capacity should be filled three-quarters full of distilled
water, heated by an adjustable Bunsen burner, arranged
with a mechanical stirrer with the center of the blade
level with the thermometer bulb, clearing it by \ inch.
The thermometer should be graduated in tenths of a

degree, and lowered so that the bulb is one-third the
height of the beaker from the bottom and 1 inch from
the side.
Tubes should be made from thin walled 6-inch by
|-inch test tubes drawn out into A
inch internal
diameter, cut into 3-inch lengths, and sealed at
one end.
Set stirrer going and heat rapidly until temperature
is about 15 below the melting-point. Meanwhile
introduce a J to f-inch column of the powdered sample
(previously dried to remove moisture) into a tube
and tap and tamp down gently. Attach the tube to
the thermometer by a rubber ring so that the center
of the column of material is level with the center of
the thermometer bulb, and replace thermometer as
before. Reduce the heat so that the temperature
rises 1 in two or three minutes. The slower rate
should be adopted if several determinations are to be
made at the same time.
Readings. Note the temperature when:
(a) The first globule of melted material is observed ;
(6) The material is and half unmelted;
hah* molten
(r) The
melting is complete and the clear liquid
is obtained in the tube.
Record these readings, and call (b) the unconnected
melting-point.
Corrected M.P. Correct the readings for exposed
mercury stem as follows: While the thermometer is
registering the approximate melting-point, place a drop
of melted diphenylamine on the stem and allow to
flow down. For a small distance above the water
surface the diphenylamine will remain molten; above
68 TRINITROTOLUENE
this it will solidify. Note the point separating the

solid from molten diphenylamine.
Then, if JV-number of degrees of mercury stem ex-
posed above this point.
T. surrounding air temperature, and Tm melting-
point, the correction is, N(Tm -T.) xO.000154.
Add this correction to the recorded temperature
(6) for the corrected M.P.

The grading of the TNT being almost entirely de-
pendent upon this determination, the method should
be carefully followed.
Comments. The tubes above mentioned seem too
large in diameter, and a tube 1 mm. or less in diameter
would give a result closer to the real melting-point.
One quarter of an inch of the substance is enough,
because the higher the column, the more difficult it is
to decide when half is melted completely since this com-
pound does not always melt in one place in the tube r
but often at the top and bottom simultaneously and it

is left to the operator's judgment, at which point the
reading is to be taken.
The three readings are taken as a check upon each
other.
Solidifying-point. The uncertainty of the M.P.
is avoided to a great degree, when the solidify ing-point
is determined. Only one set of specifications gives the
method which is given by E. M. Weaver, Brig. General
U.S.A. and Chief of Coast Artillery, in his book on
"
Notes on Military Explosives."
Method. Place 200 to 250 g. TNT in a dry
porcelain dish of 15 cm. diameter and 500 c.c. capacity.
Melt below 90 C., remove heat and stir with thermom-
eter. The temperature falls gradually until TNT
INStECTION AND TESTING OF TNT 69
begins to crystallize, when it rises. Continue stirring

until the highest temperature is reached. This is the
solidifying-point.
Comments. This determination is more apt to give
consistent results, and is simple enough so that the
different operators usually check closely.
It is more accurate, since a larger sample is used,
and the point of taking the reading more defined than
in theM.P. determination.
The above method is followed, without adhering
to the size of the dish. The majority of chemists use
a smaller dish, or test tubes and beakers without
varying results.
Although the M.P. and S.P. are generally considered
the same, there is some difference, reports from differ-
ent chemists showing the S.P. to be in some instances
higher and in others lower than the M.P. Some
report identical results for the two.
The writer (Mr. Stevens) has noted that where the
M.P. was higher the TNT had been dried at 50 C.
and where lower, the undried sample had been used.
Further evidence is necessary for a decision on this
point.
Stability tests are not usually required on crude
material, although some specifications have required
it on refined as follows:
About 3 g. of the substance is placed in a 6-inch

test tube having a strip of potassium iodide starch
paper suspended on a glass hook which passes through
the stopper. The tube with contents is placed in a
bath and heated to 65 C., for from fifteen to thirty
minutes (depending on specification). No blue color
showing presence of nitrous acid should develop.
70 TRINITROTOLUENE
This last is the

"
Abel " heat test, usually used on
less stable nitro-compounds.
Since the above paper was written, many short

cuts and improvements have been made in the methods
of analysis. The more important of these are:
Diphenylamine Test. Much difficulty was encoun-
tered in this test, because of the low concentration
.of the oxidizing substances (nitric acid) and also
because of the dilution of the blue color when a
was obtained ; therefore the following mod-
positive test
was developed and adopted by at
ification least one
government as official.
The TNT is shaken with 50 c.c. distilled water in a
stoppered cylinder, allowed to stand fifteen minutes,
filtered, and 1 c.c. of the filtrate added to a similar
vTrhime of a 2-per cent solution of diphenylamine in
concentrated sulphuric acid; by pouring the filtrate
cautiously down the side of the tube. The two solu-
tions should not mix, but should form a two-layer
system. any nitric acid or other oxidizing substance
If
ispresent, a blue ring will develop at the junction of
the two layers. This modification is more delicate than
the original method, because when the two solutions
are kept apart, any blue that develops may be readily
seen, since it is concentrated at one point and not
diffused through the solution. This modification also
removes danger of bleaching the blue color by the heat
caused by the mixing of water and sulphuric acid.
While it is true that there is a slight amount of heat
generated at the junction of the two layers, yet this
heat is nothing near that which results from the
actual mixing of the two solutions.
A pale blue ring is really not significant because of

the extreme sensitiveness of the test. In fact water
often contains sufficient oxidizing agents to produce
a quite deep blue color. One case is recalled where
double water produced a test with diphenyla-
distilled
mine when the test was applied in the above manner.
To be absolutely sure of results, the water should be
distilled once in the ordinary manner, then should be
distilled with an alkaline solution of permanganate.
Even with this precaution, the water should always be
tested; or in other words a blank should be run along
with the determination.
Another possible source of error in the diphcnyla-
mine test is in the sulphuric acid used to make the test
solution. In many cases I have found the sulphuric
acid to contain sufficient oxidizing substances to turn
the entire test solution itself a deep blue. Obviously,
such a solution cannot give accurate results. The test
solution, when properly prepared is water white in
color.
Melting-point An excellent modification of the

apparatus used for the determination of the melting-
point which is described by the writer of the foregoing
methods of analysis of TNT, consists in enclosing the
thermometer, which of course carries the melting-point
tube, in a glass tube, closed at one end and which
extends into the heating bath as outlined above. This
tube should be long enough to enclose the thermometer
to such distance as the mercury column may rise. This
procedure provides an air bath for the mercury column;
the sample being included, and renders corrections for
the exposed stem really unnecessary, since with this
modification the correction is so small as to be negli-
72 TRINITROTOLUENE
.
gible. The adoption of the air bath for the thermome-

ter is furthermore an assurance that the chemist will
watch his determination very closely, for this reason:
The temperature of the water outside the air bath may
easily be 5 to 8 in advance of the temperature inside
the tube. If the water is heated too fast, therefore,
the temperature of the thermometer will rise speedily
above the melting-point of the TNT, and this rate of
rise will be too great for the operator to note the three
points which determine the melting-point. The rate

of rise of thethermometer is now officially per A
minute. This insures close watch upon the part of
the chemist, and if he be conscientious in his work,
the various determinations will check to A
Fur- .
thermore, the danger of superheating is eliminated by

the slower rate of heating. Concerning the three points
which are taken as the melting-point reading, it has
been said that these three temperatures are taken for the
purpose of insuring the operator's close attention during
the entire melting. One thin?: I have noticed is that
chemists are inclined to slight the melting-point deter-
mination; that is, to perform it in a "don't care"
manner. Anything or any modification that will
insure the chemist's attention, while not lessening the
accuracy of the method is well worth while in any lab-
oratory.
A new test that has recently been imposed on TNT
is an analysis of the ash for heavy metals, especially
lead. This determination is considered necessary be-
cause of the use of TNT
with picric acid. This latter
explosive forms an especially unstable compound with
lead, and for this reason the metal must not be present
even as traces. Lead may creep into TNT through
allowing the acid TNT

to stand in lead-lined tanks for
a considerable period of time, or through insufficient
washing. In connection with the above statement and
requirement an analysis of the ash of TNT which was
carried out for the purpose of determining the amount
of sodium present in the ash, is interesting. It was
found that some of the TNT offered for inspection was
quite unstable, even exploding on attempting to ash
it in the determination of the ash. It was suspected
that some sodium compound of the TNT existed in the
material, and that this was what was causing the
trouble. The possibility of the sodium compounds
remaining in the TNT
from insufficient washing after
the chemical wash was realized, and the determinations
were carried out in such a manner as to retain all the
Bodium in the ash. Some difficulty was encountered
from the tendency of the TNT to ignite suddenly
a miniature explosion, in fact and blow the entire
mass out of the crucible. This occurred, it was found,
at a temperature of about 155 C. Therefore a very
large crucible with a cover supported by a glass tri-
angle was tried, and was found to be perfectly satis-
factory. The ash analysis on two samples showed
the following percentages. (See page 74.)
The various compounds of sodium are the result of
the ignition (in ashing) upon the impure salts used in
washing. The iron and silicon no doubt result from
the action of the acid upon the nitrating kettle, which
is usually of a high silicon cast iron.
The washing in both
results indicate insufficient
cases, and the percentage of sodium is no doubt high
enough to cause the trouble encountered.
The Trauzl lead block test for TNT and other ex-
74 TRINITROTOLUENE
No.1. Sample weighed 500 grama

Ash weighed .1615 gram
Percentage of ash .0323
**
a measure of the power of the explosive to

plosives is
enlarge a hole in a certain size block of lead. The
method of performing this test consists first, in pre-
paring lead qylinders 200 mm. in height and 200 mm.
in diameter. In the axis of the cylinder is a hole
125 mm. deep and 25 mm. in diameter. These cylin-
ders are prepared from the finest grade of refined soft
lead. The casting is made in a mold which casts the
central hole as well as the cylinder, thus eliminating
errors from
drilling. For comparative tests on various
explosives, the blocks for the several tests should be
made from one melt and should be cast at the same
time. After casting, the blocks should be allowed to
stand until they have acquired a uniform temperature
of 15 to 20 C. The charge for the test is made up of
10 g. of the explosive, carefully weighed out, and then
wrapped in a piece of tin foil of the size and shape shown
in the illustration.
t?0mm:
This tin-foil wrapping should be made of foil weigh-

ing 80 to 100 g. per square meter. The charge is
wrapped in such a manner that a cartridge of the exact
size as the diameter of the hole is formed. After the
cartridge is completed, an electrically detonating charge

of 2 g. is inserted in the center of it, and the whole is
76 TRINITROTOLUENE
pressed into place in the lead block. Fine dry sharp

sand of 30 mesh or finer is tamped in on top of the car-
tridge to fill the hole. The charge is then fired, and
after firing, the lead block is inverted and any residue
isremoved with a brush. The hole is t lien filled with
water, the volume of the water measured, and the
volume of the original cavity is subtracted from the
final volume. The result expresses the power of the
explosive.
The Trauzl test is very good for explosives of the
TNT class. TNT itself gives a Trauzl test of 290 c.c.
This figure will vary somewhat with the lead used, and
with the operator.
Many other tests have been invented for the deter-
mination of the power of explosives. One of these
depends upon the amount of sand which is crashed
by the explosion a certain amount of the explosive.
of
Another depends upon the compression of a piece of
metal by the charge of explosive being placed on top
of the metal and then exploded. In all probability
the Trauzl test gives as good a comparative test as
any other method, and it is easily performed, is not
expensive, nor dangerous.
..
CHAPTER VII
THE PHYSICAL AND CHEMICAL PROPERTIES

OF TRINITROTOLUENE
THE physical and chemical properties of the first

three trinitrotoluenes the alpha, beta and gamma
are quite well known, since these isomers have been
known for some time,and have been prepared in suf-
ficient quantities to enable research, which has em-
braced many reactions, to be carried out. The last
three trinitrotoluenes the delta, epsilon and zeta
have been discovered in too recent years to enable the
scientist to reach definite conclusions concerning their
chemical reactions. Practically all that is known con-
cerning these last three isomers is the melting-point.
So far as the commercial manufacture of TNT is con-
cerned, the .chemical and physical properties of the
and gamma trinitrotoluenes are of vastly
alpha, beta,
more importance than the properties of the others,
because the first-mentioned isomers constitute prac-
tically 100 per cent of the TNT. Narrowing down the
relative importance still more, it is found that interest
has centered on but one of the six trinitrotoluenes
the alpha. This is because the alpha or symmetrical
trinitrotoluene forms about 98 per cent of the com-
mercial product and the reactions of this product are
77
78 TRINITROTOLUENE
governed Almost entirely by the reactions of the above-

mentioned isomer.
The structural formula of the six trinitrotoluenes
may be designated thus:
CH3
2 N,
Alpha Beta
O,
Gamma Delta
O2 N
NO 3 .
NC 2
.
CH3 CH3
0,N/\NO,
Zeta
i>
The
melting-point of the alpha trinitrotoluene has
been the subject of much discussion. The earlier
chemists determined the melting-point of this isomer,
and finally concluded that it melted at 82 C. More
re 'out research on this subject indicates that the true
mo. ting-point is lower than that figure. Many chem-
istsare loath to accept the lower melting-point because
in several cases TNT
has been prepared that melts
at just about 82. It must be remembered, however,
that the commercial product contains, aside from the
PROPERTIES OF THE TRINITROTOLUENES 79
alpha trinitrotoluene, varying quantities of both the

beta and gamma isomc^s. Moreover, the melting-
por-t of both these last isomers is considerably higher
than that of the alpha. It seems logical to assume,
in view of this fact, that the higher melting-point of
the product is due to the presence of the beta and
gamma trinitrotoluene. In any case if these two
isomers were present in the form of
"
impurities,"
they would certainly exert some influence on the melt-
ing-point, and since the highest melting-point that
has been obtained is 82 C., it is entirely logical to
assume that the melting-point of pure alpha trinitro-
toluene lower than this figure.
is
When the alpha trinitrotoluene was isolated, it

was the only one of the six that was known, and even
had there been present considerable amounts of the
beta, gamma, or other isomers, no means was at hand
for identifying them, or for separating them from the
alpha. It was under these conditions that the melting-
point of the first trinitrotoluene was determined, and
it seems to be a very evident fact that the melting-
point as determined by the earlier chemists was not

the melting-point of pure alpha trinitrotoluene, but
was a melting-point of a mixture of the isomeric tri-
nitrotoluenes. The melting-point as determined by
recent investigators varies from 80.5 to 80.85 C.
Comey jgives a melting-point of 80.5 to 80.6. (1)
Giua and Molinari state 80.65. (2) Rintoul's deter-
mination gives 80.8 to 80.85. (3) These determina-
tions are so close together that the mean of 80.65
may be adopted without any serious error, even con-
sidering the true melting-point to be at the lower or
higher extreme.
80 TRINITROTOLUENE
The complete table of melting-points of the six

trinitrotoluenes is:
Alpha... 80.66C.
Beta 112.
Gamma 104.
Delta 137.5
Epsilon... 97.2
Zeta 79.5
Each of the trinitrotoluenes crystallizes in definite

form. The forms of the first three have been deter-
mined. No references are at hand, however, to show
the crystalline structure of the last three isomers.
Alpha trinitrotoluene crystallizes in long yellow
needles, which belong to the monoclinic system and the
prismatic class.
Beta trinitrotoluene crystallizes in thin plates of a
dazzling white color, belonging to the assymetric
system.
The form of the gamma isomer, when
crystalline
crystallized from acetone, is rhombohedral crystals,
which possess sharp edges, and which belong to the
brachypinacoidal class.
The solubilities of the air ha, beta and gamma
trinitrotoluenes are very much the same. There are
slight variances, it is true, but these are so slight as
to be of no account; for instance, all three isomers are
very slightly soluble in cold water; slightly soluble
in cold alcohol ;
and very soluble in ether, acetone, hot.
glacial acetic acid, etc. Alpha trinitrotoluene is very
soluble in hot alcohol, while beta and gamma isomers
" "
are moderately soluble in the same substance. The
sgecific solubilities of alpha trinitrotoluene are:
Cold water, .021 per cent.

Cold alcohol, 1.6 per cent.
Hot alcohol, 10.0 per cent.
Cold 100 per cent sulphuric acid, 6.6 per cent.
Hot 100 per cent sulphuric acid, very soluble.
Ether, toluene, acetone, ligroin, etc., very soluble.
Preparation. The alpha TNT is prepared most
easily by the direct nitration of toluene. There are, of

course, varying amounts of the beta and gamma isomers
formed. These may be removed from the alpha isomer
by the means outlined under the preparation of the
beta and gamma trinitrotoluene in the following para-
graph.
For the preparation of the beta and gamma trini-
trotoluenes 100 parts concentrated nitric acid (which

has been distilled from twice its weight of concentrated
sulphuric acid) are placed in a flask. Two parts of
meta mononitrotoluene are then added cautiously.
After thefirst violent reaction is over, twenty-five parts
of concentrated sulphuric acid are added with cooling.

The mixture is then allowed to stand for twenty-four
hours, being heated during this time to boiling. The
boiling should not be violent, but should be rather quiet.
Upon cooling the reaction mixture the beta and gamma
trinitrotoluenes will separate out. The precipitated
mass is well washed with hot water, and then dissolved
in hot alcohol. Upon cooling, the gamma isomer crys-
tallizes first, and thus a crude separation may be made
in this fractional crystallization. To extract the
beta isomer from the mixture it may be agitated with
carbon bisulphide. The beta trinitrotoluene dissolves,
while the g^mm* remains as a residue. Upon evapora-
.
82 TRINITROTOLUENE
ting off the carbon bisulphide, the beta may be TNT

obtained in crystalline form. Both isomers may be
further crystallized by dissolving in hot alcohol and
cooling the solution slowly. The crystals thus formed
are very compact and pure. Any alpha may be TNT
separated from the other two isomers by fractional
precipitation from alcohol, the alpha being slightly
more soluble than the others.
Chemical Properties. There are many well-known
reactions in which the three first isomers participate.
Some of these reactions are little better than theoretical,
and for this reason will be omitted in this discussion.
The object in describing the few reactions given is to
include such reactions as may form a basis for the
separation of the trinitrotoluenes, or which may be of
interest to the manufacturer or user of TNT.
Thealpha, beta, and gamma trinitrotoluenes all
react with aniline, giving distinctive products. The
alpha trinitrotoluene compound with aniline is the
product of an additive reaction only. This compound
crystallizes in long glistening needles, dark violet in
color, and has a melting-point of 83 C. The crys-
tals themselves are the same physically as these formed
when trii;itrobenzene reacts with aniline, and therefore
cannot be used as a means of differentiating between
trinitrobenzene and trinitrotoluene. The reaction pro-
ceeds according to the following equation:
C 6H 2 CH 3 (NO 2 ) 3 -hCeHs NH 2
-> C 6H 2 CH 3 (NO 2 ) 3 CeH* NH
- - -
Beta and gamma trinitrotoluenes react with aniline,

but the product formed is not an additive compound
as in the case of alpha trinitrotoluene. Beta trinitro-

toluene is rather indifferent to the presence of aniline
at After a time the solution acquires a red color,
first.
and a vapor is given off. To accelerate the reaction,

the mixture is heated in a sealed tube for four or five
hours. During the heating a strong pressure develops
in the tube. On
opening the tube and removing the
contents, it is found that two distinct substances are
present: The first of these is a brownish fluid, and the
other is a faintly crystalline mass which also has a
brown Good crystals of the latter substance
color.
may be obtained by crystallizing from acetic acid,

the solution being decolorized with animal charcoal and
filtered before the crystallization is allowed to cool.
Two crystallizations give a very pure substance, which

crystallizes in short gold-colored needles, and which
melts at 94 C. This substance is beta-nitroto-
ludin.
Gamma trinitrotoluene reacts with aniline readily
in hot alcoholic solution. Boiling for several hours is
necessary to carry the reaction to completion. Orange-
colored crystals finally separate which are insoluble
in cold alcohol. The first mother liquor from this
crystallization reacts with hydrochloric acid giving a
gas. Hepp states that this gas is very likely the result
of the reaction of a diazo compound. The reactions
by both the beta and gamma forms of trinitrotoluene
and aniline are the same, but the beta form seems harder
to start. The reaction may be represented by the fol-
lowing equation:
CH 2 CH 3 (NO
-
2)a f 3C 6 H5
84 TRINITROTOLUENE
Dimethylaniline reacts with the three trinitrotolu-

enes in the same manner as the aniline, the resulting
products, of course, being dimethyl compounds.
These reactions divide the three trinitrotoluenes
into two distinct classes. Alpha trinitrotoluene con-
stitutes the one which one molecule of trini-
class, in
trotoluene reacts with but one molecule of aniline or
dimethylaniline while in the second class, one molecule
of either the beta or gamma trinitrotoluenes reacts
w.th three molecules of the base, forming decomposi-
tion products instead of one addition product. The
property of forming addition products seems to hinge
upon the symmetrical positions of the nitro-groups.
All .three of the above mentioned trinitrotoluenes
form compounds with the alkali hydroxides. 'As in
the case of the aniline reactions, a distinct difference
exists between the reaction of alpha trinitrotoluene
and that and gamma isomers. The alpha
of the beta
isoiner reacts with sodium hydroxide two molecules
of the former reacting with one of the latter forming
an unstable condensation product. Sodium salts of
this product are very unstable, also, and are sometimes
formed in the reaction:
2C6H* (NO 2 ) 3
-
CH 3 + NaOH
- (NO 2 3 C 6H 2 CH 2 CH 2
)
The beta and gamma isomers react in the ratio of

one molecule of the trinitrotoluene to one molecule of
sodium hydroxide. Instead of the product being a
condensation as with alpha trinitrotoluene; a deriva-
tive of en-sol is formed. The sodium salts of the dini-
trocresols have much the same properties .as the
.
picrates, beingvery unstable. These reactions explain

why the sodium compounds of TNT
explode with such
ease, and why care must be used in selecting the salt
used in the washing of the crude product. The reac-
tions of the beta and gamma isomers are, respectively:
C*H2 -(N0 2 )3-CH3+NaOH-

-> CeH 2 -
(N0 2) 2 (2-4) -CH 3 -OH(3).
(N0 2) 3 CHa + NaOH

(5).
It will be noted that hi each of these reactions the

nitro-group that is meta to another nitro- group and
ortho or para to the methyl group does not react.
This is exactly what would be expected from the orien-
tationof the nitro-group, because the meta
position to
the methyl group is the unnatural position for the nitro-
group, and with a basic substance such as NaOH it
would be expected that it would be the one affected.

Sodium hydroxide is not the only salt that will form
these unstablecompounds with the trinitrotoluenes.
Hepp (4) found that even the carbonates of the alkalies
gave precipitations of a dark brown substance on the
solution being treated with acid. He filtered this
mixture, and on extracting the residue with ether
"
obtained a small amount of an oil, which is probably
a dinitrocresol." Later Hepp identified his substance,
and proved conclusively that it was a dinitrocresol.
Alpha trinitrotoluene reacts with naphthalene in
benzol solution to form a needle like substance melting
at 97 to 98 C. Beta trinitrotoluene and gamma
86 TRINITROTOLUENE
trinitrotoluene also react with naphthalene. Beta

trinitrotoluene reacts rather difficultly, and the solu-
tion must be hot, and not too concentrated. The
gamma isomer reacts much easier than the beta, but
not quite so easily as the alpha. (5) The analysis of
of the three trinitrotoluene-naphthalene compounds
proves them to be addition compounds. The sub-
stance formed has the formula CeH2(NO2)3 CHa CioHg.
The color of all the addition compounds of trinitrotolu-
ene and naphthalene is yellowish-white. The melting-
points are: Alpha, 97 to 98 C.; beta, 100 C.; gamma,
88 to 89 C.
Anthracene reacts with all of the trinitrotoluenes
similarly to naphthalene, addition compounds being
formed.
A further reaction with sodium carbonate has been
discovered by Will. (6)He has obtained a reaction
between the beta and gamma isomers and 1 per cent
sodium carbonate solution in which reaction dinitro
tolyloxides are formed. The salts of this compound
are very explosive.
The reactions of all six isomeric trinitrotoluenes with
alcoholic ammoniumsulphide are known/* Aside from
the compounds formed, the color of the solutions
are different in each case, and form a very good
method of determining which trinitrotoluene is
present.
Alpha trinitrotoluene gives a deep red color.
Beta trinitrotoluene gives a greenish-yellow color.
Gamma trinitrotoluene gives a blue color.
Epsilon trinitrotoluene gives a rose red color.
Zeta trinitrotoluene gives an orange color.
This reaction, as described by Tiemann (7), pro-
ceeds thus, to use Tiemann's words:

"
If trinitrotoluene
(the alpha modification was used by Tiemann) is

covered with strong alcoholic ammonium sulphide,
a violent reaction takes place. The solution becomes
first red, then seethes gently as the trinitrotoluene dis-
solves. Soon a .nixture of sulphur and small yellow

crystals separate. Boiled down the mixture leaves a
residue which in dilute hydrochloric acid gives a basic
compound. This compound, when precipitated by
ammonia and crystallized from water,. forms small red
prisms, melting at 132 C. These crystals cannot
be sublimed without decomposition . . . Alcohol ex*
tracts from the residue left by the hydrochloric acid
treatment, a second compound, which, when freed from
sulphur forms small yellow crystals. . . . It is probable
that the compounds formed are respectively nitro-
diamidotoluol and dinitro toluol."
Sudborough (8) has succeeded in forming addition
compounds with alpha and beta naphthylamine and
alpha trinitrotoluene. These reactions take place
at moderate temperatures in alcoholic solutions.
Thiele and Escales (9) report that stilbcne deriva-
tives are formed by the reaction of alpha trinitrotoluene
and either benzaldehyde or piperidine. The reactions
probably proceed thus:
CHO
(NOa)3-CHi-CH CH-CoH*
:
The reaction with piperidine will not form a true

stilbene, but a hexahyclroazostiibene. These reac-
tions are important from a commercial standpoint, since
88 . TRINITROTOLUENE
the stilbenes- are the bases from which several im-

portant dyes are made.
Cohen and Dakin,(10) investigating more thor-
oughly the reaction discovered by Tiemann, to which
reference is made above, identified the product from
the reaction of ammonia and hydrogen sulphide on
trinitrotoluene as dinitrotolylhydroxylamine. Diui-
trotoluene also reacts similarly with this reagent. The
trinitrotoluene reaction takes place thus:
.
CH3 (NO2) 3 +H:zS +NH 4OH

CH 3 (NOa)* NHOH.
On oxidation trinitrotoluene yields trinitrobenzoic

acid. These ac*ds are important because Meyer's
esterification law was established by the preparation
of the symmetrical trinitrobenzoic acid. Until 1914,
but one of the acids the symmetrical was known.
In this year Giua discovered the second and third acids,
which he prepared from the beta and gamma trinitro-
toluenes. The trinitrobenzoic acids are named accord-
ing to the trinitrotoluene from which they are
prepared.
Heating results in the ultimate decomposition of
TNT. Verola(ll) found, while conducting experi-
ments to determine the vapor tension of TNT, that
beginning at 160 C. a steady evolution of gas took
place. He therefore investigated the behavior of the
substance at varying temperatures, measuring the gas
evolved. The quantity employed by Verola was 5 g.
The temperatures investigated were 160, 180, 201,
and 217.5. At 160 the TNT decomposed very slowly,
and a very slight volume of gas was given off. At 180

the decomposition increased, 8 cu.mm. of gas resulting.
The quantity of gas increased steadily until at 217.5
the volume of the gas was 200 cu.mm. per minute.
Upon heating the TNT higher, it was found that
still
very rapid decomposition took place at 281 to 286.

Verola determined that the reaction was exothermic.
As would be expected from the results obtained by
Verola, the heating of TNT lowers the melting-point
appreciably. Starting with TNT melting at 80.75
the results obtained by the same investigator summarize
thus:
5 hours heating at 180 gave M.P. of 78.

2J hours heating at 201 gave M.P. of 77.
} hour heating at 217.5 gave M.P. of 59.
Continuing his investigations at lower temperatures,

in order to find at what temperature TNT
began to
decompose. Verola heated TNT very long periods
at lower temperatures.
100 hours heating at 130 had no effect. '
80 hours heating at 150 gave a M.P. of 80.25.

177 hours heating at 150 gave a M.P. of 79.9.
From these figures it is evident that TNT

is quite
stable at temperatures below 130 C. The decomposi-

tion begins at 150, being very slight at this tempera-
ture, and increases rapidly with increased temperature,
until at 281 the decomposition takes place with
explosive violence.
The reaction of the burning of TNT differs from the
.
90 TRINITROTOLUENE
reaction of explosion. The former reaction takes place

thus:
2CeHa CH, (NO2) +21 oxygen->14CO, + SHjO +3N,.

-
In case the TNTis not supplied with a sufficient amount
of oxygen, very little carbon dioxide will be formed.

In most cases where TNT burns, the oxygen supply is
insufficient, and carbon results from the combustion.
When the first condition applies, the volume of the gases
are 1200 liters from 1.6 kg. of TNT.
The reaction according to which TNT explodes may
be represented thus:
-> 12CO+5H 2 +3N 2 + 2C

or ->12CO+2CH4+3N 2 +H 2
according to the conditions under which the explosion
takes place.
C. E. Bichtei (12) has analyzed the gases from TNT
under several conditions of explosion. From the com-
plete explosion of the material under atmospheric
pressure the gas gave the following analysis:
Per Cent
Carbon monoxide ................ 70. 5
Carbon dioxide .................. 3.7
Hydrogen ....................... 1.7
Nitrogen ........................ 19.9
Carbon ......................... 4.2
Under pressure, the explosion of TNT gives a dif-

ferent gas, including methane and considerably more
hydrogen:
PerCeni.
Carbon monoxide 59.01
Carbon dioxide. ..,.. 1.93
Methane 1 .97
Hydrogen 21.05
Nitrogen.. 16.05
The gases from the explosion of TNT

hi a lead block
(from Trauzl test) upon partial analysis gave these

figures: _ _,
Per Cent.
Carbon dioxide 20.60
Carbon monoxide 46 .02
Methane 1.40
Hydrogen.. 7.61
Hydrocarbons 1 .08
Some authorities state that in all probability gases

of entirely different constitution exist at the moment of
detonation than after being cooled for analysis. The
formation of methane and carbon dioxide may be
due to the heat of the gases at the moment succeeding
the explosion, at which moment the gases may, due to
the heat, be dissociated. As the gas cools, these
atoms recombine, but not hi their original
compounds.
The effect of daylight on TNT
very marked.
is
A sample of light cream TNT darkens to a deep brown

on exposure to strong sunlight for a few hours. This
action is, hi reality, a slight decomposition. Just
what the products of this decomposition are, is not
definitely known, but they may be separated from the
TNT itself by solution in acetone. (13)
Experiments to determine the sensitiveness of TNT
to shock have been carried out by von Schrotter. (14)
92 TRINITROTOLUENE .
In his report, he tabulates the results and compares

TNT to several other explosives:
Explosive.
Giua has studr^d the physical properties of mix-

tures of the dinitrotoluenes and the trinitrotoluenes.
He found that eutectics were formed hi the ratio of
three molecules of the lower nitration product to two
of the higher. Langenscheidt (16) has determined
the melting-points of a mixture of eymmetrical trinitro-
and alpha dinitrotoluenes hi varying proportions. His
results differfrom Giua, because they indicate that the
eutectic is formed in the ratio of one molecule of the
lower to one molecule of the higher melting-point.
Prr Cent
DNT.
94 TRINITROTOLUENE
The density of TNT varies directly with the pressure

applied. The following table shows the density at
various pressures (17) :
Pressure, Aim.
CHAPTER VIII
PROPERTIES OF THE MONO- AND DINITRO-

TOLUENES
The Mononitrotoluenes. There are three isomeric
mononitrotoluenes. The structural formulae of these
are:
CHa CHa CH3
ro 2
Ortholl I Metall I Paral
TO,
N0 2
The melting-points of two of the mononitrotol-
uenes, like that of thealpha trinitrotoluene, have been
under discussion for some time. Astromisslewsky (1)
has made an extended study of the ortho mononitro-
toluene to find out why this modification exhibits what
seems to be a double melting-point, which fact had been
noted by many preceding investigators. Astromis-
dewsky's reuilts proved that this mononitrotoluene
exists in two forms. One of these forms was designated
" "
as the alpha or labile modification. The melting-
point of this modification was determined to be
-10.56 C. To the second form Astromisslewsky
gave the name of Beta or "stable" modification,
having a melting-point of -4.14 C. The alpha form
seems to go over spontaneously to the Beta modifica-
96
TRINITROTOLUENE
tion. Extended research indicates that the transi-

tion point is close to the melting-point of the alpha
form.
Rintoul (2) has determined the correct melting-point
for para mononitrotoluene. After much trouble in puri-
fication and separation from. the accompanying ortho
and me* a forms, he finally determined the correct
melting-point to be 51.6 C. and not 54 C. as was pre-
viously supposed.
The corrected boiling- and melting-points of the
mononitro toluenes are:
1
MONO- AND DINTTROTOLUENES 97
toluene. A very good mixture for this purpose is

180 parts of toluene to a mixture of 315 parts concen-
trated sulphuric acid (sp.gr. 1.84) and 200 parts con-
centrated nitric acid (sp.gr. 1.44). The toluene is
placed in a vessel of suitable size and shape that is
equipped with a motor-driven stirrer, and the acid
mixture is added slowly. The temperature of the reac-
tion mixture should not rise above 30 C. The mix-
ture of nitrotoluenes from this nitration consists of all
three isomers, with the ortho greatly predominating.

The separation of the three isomers may be made by
repeated fractional distillation, provided the nitration
has been carried out at a temperature below 30. If
the temperature has risen above this point, there is
danger that some dinitro toluene or even trinitrotoluene
has been formed, and upon distilling the mixture may
explode.
A possibly better method of separating the isomeric
mononitro toluenes is one used by the firm of Meister,
Lucius & Bruning. This consists in cooling the
mixed nitrotoluenes to 4 to 10 , and removing
the liquid portion after about one-half the mixture has
crystallized. The separation may be effected by a
centrifuge. The liquid obtained by one crystalliza-
tion is practically pure ortho nitrotoluene. The result-
ing mixture of meta and para nitrotoluenes may be
separated by steam distillation. The para is very
volatile with steam, while the meta is but slightly so.
A considerable amount of para nitrotoluene may be
separated from the above residue, and easily enough
so that further methods of preparation would be super-
fluous. Avery small amount of the meta nitrotoluene
is present, also, but this amount is too small to be of
;
98 TRINITROTOLUENE
.
any value. A much method of preparing the

better
meta isomer is by the successive acetylization, nitra-
tion, saponificbtion, diazotizaticn, and finally boiling
with alcohol, of ortho- or para-toluidin. The amino
group is present and thus prevents the nitro-group
entering in its regulation position. Acetylization both
protects the amino group, and also renders it sus-
ceptible to diazotization, which procedure is necessary
for the removal of the amiiio group after the meta
nitro-compound has been formed. The reactions in

these various stages take place thus:
CH3 C*H NH 2 +C1 OC CH 3

-
4
- -
NH OC-CH3+HC1;
NH OC-CH3 +HON0 2
NH OC CH 3 +H 2 0;
CH3 CeH 3 -tt02 NH OC CH 3 +HCl(Aq)

.-CH3 -Celli-NOi-NHt HC1+CH 3COOH;
CHa CeH^-NOa-NHi-HCl-hHONO
-^CHaCeHa-NOz-N NC1+2H 2O; :
CH3 -CeH3 -NO2 -N NC1+HOC2 H 5

:
Chemical Properties. On oxidation, the mono-

nitrotoluenes are all converted to the corresponding
nitro-bensxric acid. This oxidation can best be carried
MONO- AND DINITROTOLUENES 99
out by boiling for a long time with an alkaline solution

of potassium ferricyanide.
Upon reduction, the mononitrotoluenes act differ-
ently, according to the metal used in the reduction.
If iron be used with hydrochloric acid, the correspond-
ing toluidin is produced, the reaction being analogous

to the preparation of aniline. If zinc and hydrochloric
acid is employed, a chlortoluidin is produced.
The reduction of the mononitrotoluenes to toluidins
by the use of iron and hydrochloric acid forms the basis
for a method of estimation of the para isomer hi crude
nitrotoluene. (3) A weighed amount of the mixed
toluidins is dissolved in ether, and then ethereal oxalic
acid is added. The toluidins all form compounds with
oxalic acid, and all but the para compound are soluble
in ether. The solution is then filtered, the residue
washed with ether, then dissolved in water and titrated
with N/10 sodium hydroxide, using phenolphthalein
as the indicator.
The sulphonation of the mononitrotoluenes offers
a qualitative test for ortho nitrotoluene, in that the
sulphonation product of this isomer gives no red color

when boiled with sodium hydroxide.
Green, Davies and Horsf all (4) have investigated
the products formed when podium hydroxide acts upon
the nitrotoluenes, especially the para isomer. They
have found that the first product of the reaction
is a dinitrosodistilbene, which then condenses to a
dinitroazodistiJbene, having the following composition:
N0 2
The reaction may also go to dini trodibenzy 1, accord-

100 TRINITROTOLUENE
ing to the temperature of the react it n and the oxidiz-

ing conditions, the formula being:
CH 2
(iiitro-groups in position 4-4).
'
If the reaction be started cold, and gradually heated up,

the product resulting is a dinitrostilbene:
NCVCeHi-CH CH-CeHi-NOa
:
(nitre-groups in position 4-4).

.
The action of light on the mononitrotoluenes was

investigated by Ciamician and Silber. (5) Their pro-
cedure involved the solution of the nitrotoluene in
alcohol. With this solution, it was found that light
transformed the nitrotoluenes into the corresponding
methyl quinaldine and the toluidin. This indicated
that light has a pronounced reducing action on the
nitrotoluenes, reducing the nitro-group to an amino
group.
The mononitrotoluenes form
addition products with
the inorganic salts. This property differs from the
trinitrotoluenes, which form their addition products
mostly with organic compounds. Walker and Spencer
(6) have produced an aluminium chloride compound
of mononitrotoluene, and Mascarelli (7) isolated an
addition compound of para nitrotoluene and mercuric
had the f07 mula NO 2 C 6 H 4 CH 3 HgCl 2
chloride, which .
This substance separates from alcohol in pale yellow

needles. Upon being heated, it softens at 105, begins
to melt at 150 and blackens at 222. The properties
of these compounds indicate that they are unstable.
MONO- AND DINTTROTOLUENES 101
"
Aninteresting application of the color reaction of

nitrotoluene with sodium hydroxide is made in detect-
ing traces of nitrotoluene in nitrobenzene. The latter
substance will not give a red color with sodium hydrox-
and by standardizing the colors, the test may be
ide,
made roughly quantitative. This reaction may, of
course, be applied to the detection of toluene in benzene
by first nitrating. (8)
Coparisow, in considering the results obtained

by many investigators on the reactions of para
mononitrotoluene reaches the following conclu-
sions: (9)
The reactive sensitiveness of nitro-groups toward
alkalies increases with the increase of the nitro-groups
in the molecule.
The sensitiveness and number of chemical changes
is greatly augmented by the presence of an alkyl
radical in the para position, facilitating, probably, the
formation of nitric esters. (R- NO
(OH) 2).
The reactivity of the molecule is very much in-
creased by the introduction of electronegative groups
in the ortho position to the alkyl radical.
Alkalies produce addition, substitution, and con-
densation products. Alkalies and alkali compounds
produce red colorations with alpha trinitrotoluene.
Coparisow found that when 5 c.c. of a saturated solu-
tion of potassium hydroxide in methyl alcohol, cooled
in solid carbon-dioxide-ether mixture, are added to
.166 g. of pure symmetrical trinitrotoluene, dissolved
in a mixture of pryidine and 5 c.c. methyl alcohol;
1 c.c.
the latter solution being kept cool in solid carbon-
dioxide-ether mixture, the color change took place at a
temperature as low as -65 C.
102 TRINITROTOLUENE
The Dinitrotoluenes. The structural formulae of

the six dinitro toluenes are as follows:
MONO" AND DINTTROTOLUENES 103
Delta, yellow needles from ligroin.

Epsilon, yellow needles from alcohol.
Zeta, very long needles when crystallized from carbon
disulphide.
Preparation. The alpha dinitro toluene is obtained
usually by the nitration of mononitrotoluene. It may
also be prepared by eliminating the amino group from
nitrotoluidin, first diazotizing, then forming the hydro-
chloride and saponifying.
The beta isomer is formed by eliminating the amino
group from dinitro-ortho-toluidin, as outlined above.
The gamma dinitrotoluene may be easiest pre-
pared by heating 2-3-1-4 dinitrotoluic acid with dilute
hydrochloric acid. The reaction goes in two steps :( 10)
(1) CH3-CeHi'(N02)2'COOH-fHCl(aq)
- CHa CcH 2 (N02)a COC1 ;
(2) CH3 -C6H2-(N02)2-COCl-fKOH
The delta modification may be formed from 1-4-3-6

dinitrotoluic acid as in the case of the gamma isomer.
Delta dinitrotoluene may also be formed by inter-
action of toluquinone dioxime and nitric acid. (11)
Epsilon dinitrotoluene is formed to a slight extent
when mononitrotoluene is further nitrated. It may
alsobe formed in the pure state by the elimination of
the amino group fromd initro-para-toluidin.
Zeta dinitrotoluene is prepared from the nitration
products of toluene.
Chemical Properties. The chemical properties of
the dinitrotoluenes have not been investigated nearly
TRINITROTOLUENE*
as thoroughly as have those of the mononitrotoluenes

and the trinitroluenes. This is possibly because the
dinitrotoluenes are merely an intermediate between the
mono- and trinitrotoluenes, and are important only as
such. While it is true that in some plants the dinitro-
compound forms the starting point for TNT, yet in
the vast majority of factories the raw material is
either toluene or mononitrotoluene.
The alpha dinitrotoluene will form addition prod-
ucts with naphthalene and anthracene just as the alpha
trinitrotoluene will do. The naphthalene product has
the following formula. (12)
This same DNT may be reduced by iron and aqueous

hydrochloric acid to tolylene m-diamine. Ammonium
monosulphide partially reduces alpha dinitrotoluene
in which reduction the para group is the one concerned.
Stannous chloride and alcohol exert the same action.
The product in each case is CeHa-CHs-NCVNI^.
Beta dinitrotoluene upon oxidation with ferricyanide
forms the corresponding dinitrobenzoic acid.
Some work has been done on the reduction of the
alpha and epsilon dinitrotoluenes by electrochemical
means. Brand and Lolier (13) have prepared from the
epsilon compound a 2-2-dinit ro-G-G-azoxy toluene and a
2-2-dinitro-3-hydroxy-6-6-azotoluene. The formation is
determined by the solution used. The alpha dinitro-
toluene gives similar substances.
The Omega Nitrotoluenes (Phenylnitrora ethanes).
Under various circumstances in the regulation manu-
facture of TNT a side-chain nitrated compound is
MONO- AND DmmiOTOLUENES 105
formed. These constitute the class of nitrotoluenes

known as the omega class. The first reference to the
preparation of one of these compoundsis made by
Holleman (14) in 1894, when he prepared an " exoni-
trotoluene." Hantszch (15) and Ponzio (16) have done
considerable work on the
properties of the omega nitro-
toluenes. The results of both these investigators
indicate that these nitro-compounds are very unstable.
Ponzio prepared the phenyldinitromethane, which
crystallized in large prisms. The crystals melted at
79 C., and upon heating were found to decompose vio-
lently at 130 or above. The products of the decom-
"
position of phenyldinitromethane are red vapors and
benzaldehyde." The same man prepared the potas-
sium derivative of the above-mentioned compound,
and found it to be less stable than the phenyldinitro-
methane itself. In fact, the alkali derivative exploded
when " slightly heated."
According to Neogi and Adhicary (17) omega
mononitrotoluene is readily prepared by the action of
mercurous nitrate or benzyl chloride. Heim (18) con-
cludes from a series of researches, that pure phenylnitro-
methane is not subject to spontaneous decomposition,
but a small amount of impurities may cause such
action. Korwalloff (19) has determined that this sub-
stance, on reduction, yields the corresponding aldehyde
and oxime.
CHAPTER IX
ACCIDENTS
i
TNT is considered the safest explosive that has ever

found a wide application in warfare. The manufacture
of this explosive is also comparatively safe, as long as
it is carried out with ordinary caution. There is no
doubt but that in the present rush to produce TNT in
the greatest possible quantities, and in the least pos-
sible tune, there is a tendency to be somewhat lax in
the enforcing of precautionary measures, and that there
is also a tendency to disregard the chemical properties
of the various products and by-products that result from

the manufacture of this product. The fact that TNT
isprimarily an explosive, makes certain the further fact
that there are certain conditions under which it must
explode. It is true that not many of these conditions
are known, but it certainly is not impossible that some
of these conditions can be produced in the plant where
the explosive is manufactured. It is no more impos-
sible that TNT will explode under conditions concern-
ing which we know nothing. These conditions may
just as well be brought about as the first kind. To be
on the safe side, then, it is up to the superintendent
of a plant to be certain thatno conditions exist in his
plant but those under which it is definitely known that
TNT will not explode. This will insure the safety of

the men, and the safety of the plant.
106
ACCIDENTS IN TNT PLANTS 107
Previous to 1914, there were in all less than a half-

dozen accidents reported in TNT plants. Within
the last year there have been not less than twenty
explosions and accidents in the United States alone.
It is true that not all of these have been due to the
detonation of TNT, but probably every one has been
due to carelessness on some employee's part. With con-
ditions as existed previous to the war, the manufacture
of TNT could be carried out with as great care as was
thought necessary, but with the total rearrangement
of conditions as they exist to-day, there is no doubt
but that in many cases certain details which, although
minor in nature, are really important, are not given the
attention they require.
The pre-war accidents in which TNT was concerned
were due in some cases, at least, to the action of some
substance other than the TNT. For instance: In
1909 an explosion occurred in the crystallizing room of a
TNT plant at Schoenbeck, Germany, in a long rotating
drum which was used for drying TNT crystals. In this
particular plant centrifuges were used to separate the
crystals from the alcohol used for the recrystallization.
It is thought that a hot bearing may have ignited the
alcohol vapors in the room, thus causing the explosion.
Experts differ on the subject. Some believe that the
explosion was due only to a mixture of air and alcohol
vapor, while others think that TNTdust was added to
the explosive mixture. In either case, the TNT did
not explod-j, since it was found that after the fire,
following the explosion, was extinguished, there re-
mained some unburned TNT in the drum. Further-
more, a wood sieve containing several hundred pounds
of TNT was burned, but the TNT did not explode.
108 TRINITROTOLUENE
A metallic container filled withTNT was blown 300

yards, but the explosive was only slightly melted on the
top. Another explosion took place in 1906 in the
storeroom of the Roberite factory situated at Witten.
The room was with TNT and ammonium nitrate.
filled
Forty-two persons were injured in this explosion.

Both of the above cases show that the explosions
were not due to the detonation of TNT alone, but to
the combined action of the TNT and some other sub-
stance.
Two further accidents are interesting, although not
much is known concerning the conditions surrounding
the explosions. In 190* an explosion of TNT
at the
factory of Letsch & Co., Huddcrsfield, caused the death
of five men. Another explosion in the washing plant
of a German factory in 1912 resulted in the death of
four men.
Even considering the high casualty rate of the pres-
ent, the explosives manufacture has a lower injury
and death rate than has railroading. Dr. W. G.
Hudson, the medical director of the E. I. Dupont
"
deNemours Co., " hit the nail on the head in his
"
recent paper on Safeguards in the Manufacture
of Explosives" when he said: "If explosives like
dynamite, smokeless powder and TNT were made
only by skilled chemists, under the best of laboratory
conditions, they would seldom, if ever, cause explosion
accidents. They are stable and safe explosives, and will
stand a far greater degree of rough handling than the
uninitiated have any idea of. But when such sub-
stances have to be produced in the immense quantities
required by present conditions, ordinary laboj[ must
be used, i\nd many of these men are unskilled and have
no speaking jcnowledgergf English. However careful

ôuTÊecEaste^ sjipervisnr And^foremen may be. it is
difficult indeed to guard against some one of these thou-
sands becomi n g careles^^r_^gUg^jLj,Oi?^8Aj^dtL
of_course, the results of an explosion are visited upon
~
all in the vicinity."
The problem of eliminating the explosive accidents
becomes then, one of making the plant fool-proof, or of
educating the foreigner. The first is impossible from
the very nature of the work. Aforeigner and even
some Americans may be told repeatedly to keep away
from any source of nitrous fumes, for instance, but
sooner or later the effect of the most stringent warning
wears off. The psychology of the employee of the
explosive plant another important factor in safety
is
work. The ordinary workman knows full well that he

is employed in an explosive plant, and that his work is
dangerous because an explosion may occur. There-

fore at the slightest unusual noise, or at the most
trivial occurrence which is out of the ordinary, he
immediately suspects trouble, becomes frightened,
loses his head, and often turns an absolutely harmless
situation intoa dangerous one. To cite an example:
The chemical engineer of a certain explosive plant
was one day inspecting the installation of. some acid
eggs that were placed in a concrete pit. He noticed
that the compressed air inlet valve leaked, thus allow-
ing air to enter the egg, forcing the acid out through
the discharge pipe which had, for some reason, been
disconnected about 2 feet from the egg. A
drop of the
acid had struck him in the face, and while wiping it
off with his handkerchief, he called to a nearby work-
man to shut off the compressed air valve more tightly.
110 TRINITROTOLUENE
The workman, immediately saw a sign of an accident,

became confused, and instead of turning off the air,
opened the valve wide, forcing the acid charge out of
the egg, and down on the man in the pit, burning him
very badly.
The plant officials are thus confronted with the great
problem of educating the workmen to keep a level
head at all times.
Aside from accidents of the above nature, there are
others the direct cause of wliich is carelessness on the
part of foremen or superintendents, who are either
ignorant of certain properties of their products, or who
are negligent in the performance of their duties. One
accident, due to a combination of these shortcoming?,
resulted from the too rapid mixing of spent acid from
one &tage of a nitration with fresh
nitric acid to prepare
the acid for the next nitration. Nitric acid on being
mixed with spent acid, tends to form a separate layer
apart from the spent acid unless it is thoroughly agi-
tated. In this instance, the two-layer system formed,
consequently the organic matter hi the spent acid
next to the layer of nitric acid was subjected to the
nitrating action of the latter. As the reaction pro-
ceeded, the mixture became warm, the heat hi turn
accelerated the nitrating reaction and so on. With
such an uncontrolled reaction taking place an ex-
plosion resulted. Nine times out of ten, the mixing
of the nitric acid with the spent acid may be carried
out without special precaution. The tenth time may
be the cause of an explosion. In this particular plant
the fortifying acid is always mixed in a particular man-
ner. The explosion taught a lesson in the effects of
disregarding minor details, and also concerning the
'
'
properties of spent acid, which should have been

determined before in the laboratory.
There is surely no step in the manufacture of TNT
which is entirely free from danger. Every step hi
the process should receive the utmost attention, and
minor details should be worked out with the same
care as the greater problems, rather than to " take a
"
chance that no accident will result.
,
'
']
'
.
.
.
;
CHAPTER X
TNT DISEASES '
THE problem of disease incident to the manufacture

of TNT has assumed great proportions in the last few
years. Before the manufacture of TNT grew so large,
an occasional sickness or death from poisoning caused
no great comment. Now, however, with the many
plants manufacturing this material, the number of
men and women who are constantly becoming afflicted
with diseases of various natures has grown to such a
large figure that many physicians are devoting their
entire tune to the conquering of TNT diseases.
To give some idea of the large number of persons who
are affected in one way or another, the following figures
are cited: Dr. Hamilton, in May, 1916, reported 703
cases of TNT poisoning, and 33 deaths resulting from
such poisoning. The Royal Society report of the same
year gives 181 cases of jaundice alone, which were
caused by TNT. The same report shows 52 deaths.
There has been considerable discussion among some
plant officials as to why the medical fraternity is unable
to check the TNT disease. I have followed quite
closely much of the research wcrk that has been done
on this problem, and I am of the opinion that the
physicians are doing everything hi their power to obtain

sufficient knowledge concerning the action of so TNT
they can, with the results obtained, lay the foundation
112
TNT DISEASES 113
for the treatment of disease resulting from the action

of TNT on the human body. When the recentness of
these diseases is considered; and when the vast amount
of work necessary to be carried out with such diseases
as tuberculosis, cancer, pneumonia and others, is con-
sidered, it seems that the medical profession is to be
congratulated for having progressed as far as they have
in the understanding of this sickness.
Many well-known physicians and pathologists have

worked on this subject. Drs. More, Panton, Feldman
and others have, by their researches, thrown much
light on the action of TNT in the body. At the present
time Dr. Samuel Haythorn, of the Singer Memorial
Laboratory, Allegheny General Hospital, is engaged
in a very extended series of researches to determine
the various ways hi which TNT
gains an entrance
into the body, and also to find out the effect of the TNT
on the various tissues and organs in the body. The
different ways in which TNT gets into the system has
been investigated by Dr. More, who reaches the con-
clusion that the most important means of entrance is
through the skin, by actual contact with the material.
In order to determine whether or not TNT has gone
through the system, use is made of Webster's test
which detects TNT, or possibly some product of its
action in the body, in the urine. Webster's test is
performed by placing 12} c.c. urine in a test tube, and
mixing with an equal amount of 20 per cent sulphuric
acid. The acidified urine is then extracted with ether,
the extraction being carried out most easily in a separa-
tory funnel, using 10 c.c. ether* The aqueous layer
is drawn off, and the ether is washed with water and
again separated, five c.c. of the ether extract is

TRINITROTOLUENE
-
then mixed with 10 c.c. of a 4 per cent solution of potas-

sium hydroxide in absolute alcohol. If TNT (or its
product) is present, a pink color appears, which quickly
changes to a purple and finally to a brown. The
question as to whether Webster's test detects TNT or
one of the products produced by the action of TNT
upon the system has never been definitely settled.
Dr. More has experimented upon the possibility of
TNT entering the body through the skin, by rubbing
some of the substance upon his hand, then washing
immediately. He reports that he obtained a positive
Webster's test on his urine for a period of ten days.
Dr. Haythorn has been unable to verify More's work,
in that he has been unable to secure a positive Webster's
test on his urine at all by apply ing TNT externally. Fur-
thermore, Haythorn allowed the TNT to remain in

contact with the skin for a considerable period of time
but was still not able to obtain a positive Webster
reaction. Guinea pigs whose skin had been rubbed
with TNT soon developed an eruption, at first not
serious, but which soon became co\ ercd with crusts.
Haythorn's next experiment consisted in subject-
ing rabbits and guinea pigs to the fumes of heated
TNT for several hours a day for over a month. In
this way the animals were under the same conditions as
men in the plants who ore forced to breathe fumes from
washing or crystallizing apparatus, or from any source
where the TNT is subjected to heat. The animals used
in this test showed no Webster reaction.
Haythorn then attempted t^> introduce TNT by
feeding the animals milk which contained dissolved
TNT. The animals rapidly lost weight, became list-
less and soon died, one of them in tliree days. The
TNT DISEASES 115
urine of these animals showed a strong positive Web-

ster's test. The liver, spleen and kidneys of one of
these animals were very dark hi color, due to the break-
ing up of the red blood cells, and the deposition of
the coloring matter in these organs.
From Dr. Haythorn's experiments, it seems that
the greatest danger from TNT
poisoning comes from
actually swallowing the material. More does not
agree with this. The effect of the TNT in the body
seems to be mostly on the liver, the poison almost
totally destroying the cellular portion of this organ.
Several blood tests on patients afflicted with TNT
poisoning shows that the substance hi many cases
attacks the red blood corpuscles, depositing the coloring
matter of these corpuscles hi the various organs such as
spleen and kidneys.
The differences hi the results obtained by the work
done by More and Haythorn, together with the fact
that in some plants TNT poisoning is quite prevalent,
while in others it is practically nil, has suggested that
the poisonous effects may not be due to TNT itself,

but to a pheny In itrome thane; that is, a toluene ni-
trated hi the side chain. It is known that these phen-
ylnitromethanes are very poisonous. It is also known
that hi some cases these compounds are formed dur-
ing the nitration of toluene; for instance, if the nitric
acid concentration of the acid mixture becomes very
low, or if the temperature rises very high. In this way,
some samples of TNT may contain the toxic phenyl-
nitromethanes, while other samples may be free from
them. This would explain the difference in toxic
effect of the various TNT
samples, and the variation
in results obtained.
116 TRINITROTOLUENE
There are six definite forms of TNT poisoning

known:
1. Dermatitis, or eruption of the skin. Often called
" TNT rash." This form of poisoning is caused by
contact with the TNT, and may usually be cured by
removing the cause.
2. Gassing. This condition is due more to the in-
halation of the nitrous fumes which occur during the
nitration of TNT
than to the itself.TNT
The wind
passages and lungs are often badly inflamed. Many
cases develop into pneumonia, while others recover
after a day or two of complete rest. In any case the
" "
patient who has been should be given atten-
gassed
tion by a physician. Ordinary methods, such
first-aid
as doses of dilute chloroform-alcohol mixtures, are
not sufficient.
3. Minor poisonings, which result from the handling
of TNT or receptacles which are covered with the sub-

stance. The effects differ from TNT dermatitis in
that the effects are internal as well as external. The
symptoms are dizziness, headache and sometimes
nausea. Men or women who are new to the work,
and whoare not accustomed to being a round TNT, are
especially subject to this form of poisoning from TNT.
The symptoms usually disappear after the person
becomes more accustomed to the presence of TNT.
Cases have beer known, however where the poison- >
ing has developed into a more serious form.

4. Severe Poisonings. After the symptoms of a
minor poisoning are displayed, there is a period in
which the subject feels perfectly well, no effects of
the TNT being noticeable. This neutral period inay,
in cases of extreme susceptibility, terminate in severe
TNT DISEASES 117
poisonings. The symptoms of the more severe cases

being loss of appetite, vomiting and constipation.
The severe poisonings from TNT
appear to be the result
of a cumulative action of the poison.
5. Toxic Jaundice. This is the most serious form
of TNT poisoning. It does not appear until at least
six weeks after the exposure to the explosive. Some
persons appear to be quite susceptible to the more
serious forms of TNT
poisoning, while others never
feel anything other than the minor effects that are
experienced upon the first exposure. There is yet a

third class who are not affected in any way by TNT.
Personally, I have often handled TNT until my hands

and forearms were stained a deep golden brown, and
have worked in an atmosphere filled with TNT dust
for hours, but I do not recall even a slight headache
or dizziness from such exposure.
Toxic jaundice is the direct result of what may be
termed " TNTliver." The yellow color of the skin
caused by the internal action of the TNT
persists
long after the stain by external contact wears off.
Furthermore, the color due to jaundice affects the entire
body, while the mechanical staining colors only those
parts which have been in contact with the TNT.
About 33 per cent of the cases of toxic jaundice are
fatal.
6. Anaemia. This disease is the result of the action
of TNT upon the erythrocytes or red blood corpuscles.
These corpuscles are disintegrated, and the coloring
matter is deposited in the kidneys and other organs,
causing these organs to assume a dark brown or black
color. Aa with toxic jaundice, not every person suffers
the same effects. Some cases are on record where an
118 TRINITROTOLUENE
.
actual increase in the number of red blood corpuscles

has resulted from TNT poisoning.
The summation of the researcn that has already
been done on TNT poisoning indicates that the solu-
tion of the problem consists more in prevention than
in treatment. The steps to be taken in prevention,
which have been suggested by the British Ministry of
Munitions are:
1. The employment of no persons under eighteen
years of age without special permission. This insures

the employment of none but mature men and women
and lessens liability from carelessness or indifference.
2. The rotation of work at two- week intervals;
thus removing the employee from contact with the
substance periodically.
3. The use of masks, gloves, and clean-laundered
overalls.
Large and well-ventilated workrooms,
4.
*V The
furnishing to every employee of free milk
and cocoa, and a weekly mcdiohl inspection.
The wisdom of requiring the employees to drink
milk has been severely questioned for this reason:
Milk contains primarily fats and casein. The fats are
capable of dissolving a large amount of TNT. There-
fore, should any of the explosive accidentally aJid its
way into the milk, or should there be any in the stomach

through swallowing dust in the factory, this will dis-
and will be absorbed by the
solve in the fats of the milk
blood. This action has been proved by Dr. Haythora,
who has performed several experiments upon rabbits
and guinea pigs with a solution of TNT in milk.
The very least that can be said concerning the toxic
action of TNT is that some persons are very susceptible
.
TNT DISEASES 119
to it. Minor poisonings should be treated as possible

cases of severe poisonings until all doubt of the severe
poisoning has been removed. A medical corps of
sufficient size to afford constant medical supervision
of the force of employees should be in constant attend-
ance at the plant. In this way any slight poisoning
or sickness will be checked before it has a chance to
develop into a more serious form.
.
:
.
.
'
REFERENCES
CHAPTER H
(1) Anallen, 77, 216.
"
(2) 155, 1-29.
(3)
" 64, 9.
(4)
" 54, 12.
(5)
" 77, 216.
"
(6) 76, 286.
"
(7) 77, 216.
"
(8) 131, 304.
"
(9) 77, 216
"
(10) 44, 306.
(11) Jahrea Berichte, 22, 360.
(12) Anallen, 155, 2.
"
(13) 128, ITS.
(14) Berichte Chem. GeeelL, 3, 202.
(15) Jahres Berichte, 22. 360. ^
:
(16) Anallen, 172, 221 <-
"
(17) 128,178
(18) Berichte, 16, 1596.
(19) Anallen, 215, 375.
(20) Chem. Zentr. 1914, II, 762.
(21) Atti. R. Accad. Lincci., 24, 1, &&.
"
(22) MarehaU, Exploeivcis" 26O-23L
CHAPTER in
(1) Proc. K. Accad. Metcnsch, Amsterdam, 1908, Vol. XI, 248.
(2) Organic Chemistry (Holleman) Ed. 1910, 486.
(3) Proc. K. Accad. Metenach, 1906, Vc4. XI, 248.
(4) Rec. traT. Chim. t 27, 208.
(5) Berichte, 18, 1336.
(6) Chem. Zentr^ 1914, II, 763.
121
122
.
REFERENCES
(7) Ammlen, 215, 344.

(8) Berichte, 1913, 658.
(9) Anallen, 217, 206.
Anallen, 225, 384.
(10) Berichte, 18, 306.
Anallen. 44, 307.
(11) fierichte, 1914, 707.
(12) Anallen, 155, 1-29.
(13) Anallen, 215, 344.
(14) Gau. Ital. Chim., 45 II, 32-44.
CHAPTER IV
(1) Journal Ind and Eng. Chem., 8, 998.

(2) Met. and Chem. Eng., 14, 467-8.
(3) Chem. News, 112, 247.
(4) J. Soc. Chem. Ind., 34, 781-2.
(5) British Patent No. 23,181, Nov. 27, 1914.
(6) British Patent No. 15,445, NOT. 2. 1915.
(7) U. S. A. patent No. 1,149,585, Aug. 10, 1915
(8) Ann. Inst. Agron. Moscow. 19, 56-9.
(9) Z. ges. Schicss-Sprengstoff, 10, 109-11.
..
CHAPTER V
(1) U. 8. A. patent, 1,225,321, May 8. 1917.
(2) British patent, 7047, May 11, 1915.
CHAPTER VI
(1) Journal Amer. Chem. Soc., 39, 504-14.
CHAPTER VII
(1) J. Ind. and Eng. Chem., 1910, 103.

(2) 1st Scienze Let., 46, 1913.
(3) J. Soc. Chem. Ind., 1915, 60.
(4) Anallen, 215, 344.
(5) Anallen, 215, 370.
(6) Berichte, 1914, 704.
(7) Berichte, Vol. Ill, 217.
(8) Trans. Lon. Chem. Soc., 79, 350.
(9) Berichte, 34, 2842.
REFERENCES 123

(11) Mem. Poud. Saltpetres, 16, 40-61.
CHAPTER VIII
(1) Zcit. Phys. Chem., 57, 341.

(2) J. Lon. Chem. Soc., 34, 60.
(3) Berichte, 36, 4260.
(4) Abst. Chem. Soc., 1907, 2076.
(5) Atti. R. Accad. Lincei, 14, II, 199.
(7) Atti. R. Accad. Lincei, 14, II, 199.
(8) Chem. Zeit., 30, 295.
(9) Chem. News, 112, 283-4.
(10) Berichte, 22, 2681.
(11) Berichte, 21, 428.
(12) Annalen, 215, 370.
(13) Berichte, 40, 3324 et seq.
(14) Rec. Trav. Chem., 14, 121-130.
(15) Berichte, 32, 607.
(16) Gaietta, 31, 133.
(17) Zeitachr. Anorg. Chem., 60, 270.
(18) Berichte, 43, 3417.
(19) J. Esw. Chem. Soc., 30, 960.
.
.
INDEX
Accidente 106
Acidity in TNT, determination of 63
Adda, table of 39
Action of inorganic salts on MNT 100, 101
of light onMNT . .V 100
of light on TNT. 91
of mineral matter on nitration 40
of nascent hydrogen on nitration 40, 41
Alkali carbonates, reaction with TNT 85, 86
hydroxides, reaction with TNT.. . *. 84
Aluminium explosive. . . 4
Ammonium nitrate 47
sulphide, reaction with TNT. 86, 88
Analysis of g?cs from the burning of TNT 90
of gases from explosion of TNT 91
of TNT 62
Anaemia from TNT. , 117
Aniline, reaction with TNT. 82,83
Ash in TNT, determination of. 64
'
B
Bcnzaldehyde, reaction with TNT. 87
Benxoen.... 6
BinitrotropfoL 24,60
Blending 45
Blood, effect of TNT upon the 115
Plow ease 49
126
INDEX
Boiling-point of the mononitrotoluenes 96

Burning of TNT, reaction of 90
Cheddite ; 5
Chemical control 34, 51
properties of dinitrotoluenes 103
of mononitrotoluenes 98
of trinitrotoluenes. 82
Color of TNT. ... 62
Constituents of crude TNT. 26
Constitution of TNT 17
Crystalline form of dinit rotoluenea. 102
of trinitrotoluenes 80
Crystallization 45
Denitrat ion of spent acid 47

Density of TNT. 94
Detection of toluene in bemene 1 101
Determination of para nitrotoluene 99
Detonators 4
Dimethylaniline, reaction with TNT.. 84
Dinit rocrcsols ; 85
Dinit rr> toluenes, action of naphthalene upon 104
and TNT, eutectic mixture 93
chemical properties of. 103
crystalline form of 102
history of 15
melting-points of isomerie 102
nitration of 21, 36, 27
oxidation of t 104
preparation of various 103
products of nitration of 27
reduction of 1O4
structural formula? of . . . 102
INDEX 127
PAOB
Dini t rotolui doxides 86
Di phenylo mine test 65,70
Disease in TNT plants, prevention of . . . 118
Donarite 5
Dracyl 8
'
F
Effect of breathing fumes from burning TNT 114
of breathing fumes from nitration 116
of heat TNT
on 88
of swallowing TNT . 114
of TNT on the blood 115
of TNT on the skin. 114,116
Exonitrotoluenes 105
Expire ion of TNT, reaction of. 90
Explosions 106
Explosive tests on TNT 92
Eutectic mixture of DNT and TNT 93
F
Factors affecting nitration 40
yield 41
Fineness of TNT, determination of 62
Flaking 46
Formation of DNT in first stage nitration 36
of phenolic compounds in nitration 40
of sulphonic compounds in nitration 41
Fortification of spent acid, precautions 110
Fumes from burning TNT, effect of 114
from nitration, effect of 116
Gases from the explosion of TNT, constituents of 91
Gas&ing 116
German process of nitration 38
128 INDEX
MM
Grainer ........................ . ....................... 46
Graining ............... . ...... .................. . ...... 45
Guncotton, aeuaitivenew of ____ .............. ........ ....
.
92
TNT ............. ....... ....... .....

Heat, effect of, on . 88
Heavy metals in TNT ................................... 72
Hydrogen, nascent, in nitration ....................... .... 40
i
Ideal nitration .......................................... 22
Impurities in TNT ........................ ............ . . 52
Insoluble residue in TNT, determination of ........ f ....... 63
Isomerism of the nitrot oluenes .............. . ............. 12
j
Jaundice ...................... ......................... 117
'
Labyrinth ................. ................. ............ 45

Langenscheidt process of nitration ........... ..... ........ 35
Light, action of, on mononitrotolueneB ..................... 100
on trinitrotoluene* .............. ......... 91
M
Macarite .......... ......................... . . .........
.* 5
Melting-point of dinitrotoluencs .......................... 102
of moncnit ro toluenes. .................... ... 96
of trinitrotoluenes. .......................... 80
of TNT, determination of ____ ....... . ..... 66, 71
Meta nitrotcluene ....... . ......................... 13, 23, 24
Mineral matter in nitration ........ . ..................... 40
Moisture in TNT, determination of ...................... 62
Mononitrotoluenes, action of inorganic salts on. ............. 100
of lighten ............. . ................... 100
of potassium ferricyanide on ..... ...... . ...... 98
of sodium hydroxide on ................... ... 101
INDEX 129
AM
MoDonitrotoIuenes, boiling-points of isomerio 96
chemical properties of 98
effect of temperature on formation of 23
history of 9
melting-points of isomerio 96
mtrat'onof 21,25
oxidation rf . 98
preparation of isomeric 96
products of the nitration of 25
reduction of 99
separation of * 97
specific gravity of 96
structural formulae of. . ... 95
N
Naphthalene reaction with dinitrotoluenes 104
with trinitrotoluenes 85
Naphthylamine, reaction with TNT 87
Nitration, factors affecting. 40
formation of DTN
in first stage of 36
formation of phenolic compounds in 40
formation of sulphonic compounds in 41
ideal 22
Langenscheidt process of 35
one-stage process of. 33
three-stage process of 37
two-stage process of ... 34
Nitwtor ,
29
O
One-stage process of nitration. ....'... 33
Orthonitrotoluene, test for W
Oxidation of dinitrotoluenes 104
of trinitrotoluenes. . % 88
'30 INDEX
Packing 61
Para nitrotol uene, determination of 99
Permonite , 4
Phenolic compounds in nitration . . 40
Phony Initromethanes 1O*
Picric acid 3
disadvantages of 3
A
sensitiveness of 92
Piperidine reaction with TNT 87
Plasteryl 4
Poisoning from TNT. 112
Potassium ferricyanide reaction with MNT. 98
Precautions in fortifying acids. 110
Preparation of dinitrotoluenea. 103
of trinitrotoluenes ..:.... 81
Prevention of TNT diseases 118
Products of nitration of dinitrotoluenes. 27
of mononitrotoluenes . . . . 25
Purification of trinitrotoluene by alcohol ... 53
by carbon tetrachloride mixture : 55
by mechanical means 57
by sodium sulphite 56
by sulphuric acid 54, 58
R
Rash, TNT 116
Reaction of burning of TNT . . . . 90
of explosion of TNT 90
Reduction of dinitrotoluene 101
of mononitrotoluene 99
Retinaptha 6
Rules for health in munition plants 118
.
8
Screening. .'..-. 46
Separation of mononitrotoluenea ..'..... 97
.
INDEX 131
Shock, sensitiveness to, of guncotton ...................... 02

of picric acid. ....... ........................ 02
TNT
of .................................... 02
Skin, effect of TNT on .............................. 114,116
Sodium salts of TNT ............................... 44,57,84
Solidifying point of TNT, determination of ..... .
........... 68
Solubilities of TNT .......................... . .......... 81
Solvent recovery, stills for ......................... .......60
Specific gravity of mononitrotoluenes ................... . 06
.
Spent acid, analysis of ................................... 46

dcnitration of ..................................... 47
effect of, on TNT ......... ; ............... . ....... 41
separation of TNT from ............. . ............. 47
utilization of ............................... ..... 48 .
Stabil i ty tests ......................... ........... ...... 60

Stilbene derivatives ................ . .................... 87
Structural formulae of dinitrotoluenes ............. ........ 102 .
of mononitrotoluenes ........ . .............. . 05

of trinitrotoluenes. . .......... ....... . ...... 78
.
Sulphonatkra theory ........... \ ......................... 21

Sulphonic acids, formation of ............................. 41
T
Test explosive 76
for orthonitrotoluene 90
for toluene in benzene 101
Trauzl lead block 73
Webster's 1*3
Tetranitromethane * 40
Theory of nitration, German 27
Italian 27
of sulphonation 21
Three-stage process of nitration. .'. 37

Thunderite. *
TNTampmia H7
TNT jaundice. W?
TNT nab "
132 INDEX
Toluene detection of, in beniene 101

from balsam of tola 6
from coal tar : . 8
from crude wood alcohol 8
from dragon's blood 7
from pne resin 6
history of , 7,
8
nitration of 20
specifications for. 32 j
synthetic 9
Trauil lead block test 73
Trinitrobenzoic acids 40
Trinitrotoluene, action of light on 91
analysis of 62
and DNT, eu tec tic mixture of 93
blending of 45
constitution of 17
crystallization of 45
density of : 94
effect of breathing fumes from burning 114
of breathing fumes from nitration of 1 16
on the blood of. 115
on the skin of 114, 1 1 6
on the system of 115
flaking 46
gases from burning 90
gases from explosion of 91
graining of 45
history of 17
inspection of 61
melting-points of isomerie 80
packing of rtl
poisoning from i!2

preparation of isomerie 81
purification of 52
reaction of 82
screening of .,%,%. 46
INDEX 133
MM
Trinitrotoluene, sensitiveness of. 92
separation of from spent acid 42
solubility of . 81
structural formula) of 78
washing of * ., 43
-
U
Utilisation of spent acids , 48
W
Washing of TNT , 43
Webster's test.. . 113
Yield, factors affecting 41

.
'
A SELECTED LIST OF BOOKS ON
CHEMISTRY AND CHEMICAL
TECHNOLOGY
FfcMfetedfty

26 Park Place New York
American Institute of Chemical Engineers. Transactions.

8vo. cloth. Issued annually. Vol. I., 1908, to Vol.
IX., 1916, now
ready. each, net, $6.00
Annual Report! on the Progress of Chemistry. Issued
annually by the Chemical Society. 8vo. cloth. Vol. I.,
1904, to Vol. XII., 1915, now ready, each, net, $2.00
ASCH. W., and ASCH, D. The Chemistry and
Silicates in
Commerce. Including the exposition of a hexite and
pentite theory and of a stereo-chemical theory of gen-
eral application. Translated, with critical notes and
additions, by Alfred B. Searle. Illus. 6J x 10. cloth.
476 pp. net, $6.00

ASHLEY, B. H. Chemical Calculations. Illustrated.
S /4 x 71/2. 286 pp.

l
cloth. net, $2.00
BAILEY, B. 0. The Brewer's Analyst. Illustrated. 8vo.
cloth. 423 pp. net, $5.00
BARKER, A. P., and MIDGLEY, E. Analysis of Woven

Fabrics. 85 illustrations. .
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BEADLE, C. Chapters on Papermaking. Illustrated.
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BEAUMONT, B. Color in Woven Design. treatise on A
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BECHHOLD, H. Colloidsin Biology and Medicine.

Translated by J. G. Bullowa. M.D. In Press.
BENNETT, HUGH 0. Tht Manufacture of Leather.

no illustrations. 8vo. cloth. 438 pp. net, $4.50
BERNTHSEN, A A
Text- book of Organic Chemistry.
English translation. Edited and revised by J. J. Sud-
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BERSCH, J. Manufacture of Mineral Lake Pigments.

Translated by A. C. Wright. 43 illustrations. 8vo.
BEVERIDGE, JAMES. Papennaker'a Pocketbook. Spe-

cially compiled for paper mill operatives, engineers,
che.nists and office officia s. Second and Enlarged
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BIRCHMORE. W H. The Interpretation of Gas Analyses.
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BLASDALE, W. C. Principles of Quantitative Analysis.
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BLUCHER, H Modern Industrial Chemistry. Trans-
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BLTTH, A. W. Foods: Their Composition and Analysis.
A manual for the use of analytical chemists, with an
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Poisons : Their Meets and Detection A manual for
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LIST OF CHEMICAL BOOKS
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B6CXMANN, p. Celluloid Its Haw Material,

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BOOTH, WILLIAM H. Water Softening and Treatment.
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BOURCART, E. Insecticides, Fungicides, and Weed

Killer*. Translated by D. Grant 8vo. cloth. 500 pp.
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BOUBBY, EXILE. A Treatise on Ceramic Industries.

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Alfred B. Searle. 308 illustrations. 12 mo. cloth.
488pp. net, $5.00
BBISLEE, F. J. An
Introduction to the Stndy of Fuel.
A text-book for those entering the engineering, chem-
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and technical
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BROWN. HAROLD. Rubber. Its Sources, Cultivation and
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BROWN. W.
'
A. The Portland Cement Industry.
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BBTJC2, EDWIN X. Detection of the Common Food
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BUSXETT, E. W.
Fire Assaying. A
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BYERS, HORACE 0.. and KNIGHT, HENRY 0. Notes

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CAVEN, R. It, and LANDER.
Systematic Inor-
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Law. A text-book for advanced students. Illustrated.
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CHRISTIE, W. W. Boiler-waters, Scale, Corrosion, Foam-
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CHURCH'S Laboratory Guide. manual of practical A
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cloth, 365 pp. net, $2.50

CORNWALL, H. B. Manual ofBlow-pipe Analysis.
Qualitative and quantitative. With a complete system
of determinative mineralogy. Sixth Edition, revised.
CROSS, C. F., BEVAN, E. J., and SINDALL, R. W.
Wood Pulp and Its Uses. With the collaboration of
W. X. Bacon. 30 illustrations. 121110. cloth. ,
281
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d'ALBE, E. E. F. Contemporary Chemistry. A survey

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DEERR, H. Cane Sugar. 280 illustrations. 6 /2 XQ^.
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EUMESNY. P., and NCYER, J. Wood Products, Dis-
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DIJNSTAN. A. E , and THOLE, F. B. A Text-book of
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DYSON, S. S., and CLABKSON, S. S. Chemical Works,

Their Design, Erection, and Equipment. 80 illustra-
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ELIOT, C.W., and STOBEB, F. H. A Compendious Man-

ual of Qualitative Chemical. Analysis. Revised with
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W. B. Lindsay. 111. 121110. cloth. 205 pp. net, $1.25
TTT.TJS, C. Hydrogenation of Oils, Catalysis and Catalyzers,

and the Generation of .Hydrogen. Second Edition, re-
vised and i dargtd. In Press
ENNIS, WILLIAM D. Linseed Oil and Other Seed Oils.
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336 pp. net, $4.00

EEHEN, W The Materials Used in Sizing. Their
F. A.
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JAY, IRVING W. The Chemistry of the Coal-tar Byes.
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F1KTU, J. B. Practical Physical Chemistry. 111. 5x7.

FISCHER, E. Introduction to the Preparation of Or-
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FO YE, J. C. Chemical Problems. Fourth Edition, revised
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FRANZEH, H. Exercises in Gas Analysis. Translated
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FRITSCH, J. The Manufacture of Chemical Manures.

Translated from the French, with numerous notes, by
Donald Grant 69 illus., 108 tables. 8vo. cloth. .
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GBOSSMANH, J. Ammonia and Its Compounds. Illus-
trated. .121110. cloth. 151 pp. net, $1.25
HALF,, WILLIAM J. Calculations in General Chemistry.
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HALT., CLARE H. Chemistry of Paints and Paint Ve-
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BERING, C , and GETMAN . F. H. Standard Tables of
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l l
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HILDITCH, T. P. A Concise History of Chemistry.
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HILL, C. W.
Laboratory Manual and Notes in Beginning:
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HOTT, W. F. Chemistry by Experimentation. Including
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firstyear course. In Press
HiJBNEB, JULIUS Bleaching and Dyeing of Vegetable
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HUDSON, Iron and Steel. An introductory text-
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HURST. GEO. H Lubricating Oils, Fats and Greases.
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HURST. and SIMMONS, W. H. Textile Soaps and

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HYDE. FREDERIC S. Solvents, Oils, Gums; Waxes and
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INGLE, HERBERT. Manual of Agricultural Chemistry.
Illustrated. 8vo. cloth.
388 pp. net, $3.00
JOHNSTON, J. F. W.
Elements of Agricultural Chem-
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12010. cloth. 502 pp. $2.60
JONES, HARRY C. A New Era in Chemistry. Some of
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The Nature of Solution. Edited by E. E. Reid.
Illustrated. 6x9. cloth. 406 pp. net,$3.50
XEMBLE. W. F., and UNDERHUL, C. R.* The Periodic
Law and the Hydrogen Spectrum. Illustrated. 8vo. .
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KERSHAW. J. B. C. Fuel, Water, and Gas Analysis, for
Steam Users. 50 ill. 8vo. cloth. 178 pp. net; $2.50
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F.R.S. 50 tables, 92 illustrations. 5#x8j4. cloth.
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KNOX, JOSEPH. Physico-chemical Calculations. 12010.
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The Fixation of Atmospheric Nitrogen. Illustrated.
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KOLLEB, T. A handbook of the manufac-

Cosmetics.
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8 D. VAN NOSTRA^D COMPANY'S
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Edition. 22 illustrations. 5#x8#. cloth. 336 pp
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KOPPE, 8. W. Glycerine. and
Its introduction, uses
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XREMANN, R The Application of Physico-chemical
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KRETSCHMAR. KARL. Yarn and Warp S&ng in All
Its Branches. Translated from the German by C.
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LAMBOBN, L I. Modern Soaps, Candles and Glycerin.

Cotton Seed Products. 79 illus. 8vo. cloth. 253 pp.
net, $3.00
LASSAR COHN. Introduction to Modern Scientific
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University Extension students and general readers.
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LETTS, Some Fundamental Problems in Chemis-
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LLOYD, STRAUSS I. Fertiliser Materials. In Press
LUNGE. GEORGE. Technical Methods of Chemical

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Technical Chemists' Handbook. Tables and meth-
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Coal, Tar and Ammonia. Fifth and Enlarged Edi-
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cloth. 1600 pp. net, $18.00
The Manufacture of Sulphuric Acid and Alkali.
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Sulphuric and Nitric Acid. Supplement to Vol. I.
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McOTTOSH, JOHN The Technology of Sugar. Third
G.
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6x8#. 54<>PP. $500
XcOTTOSH, JOmr G. The Manufacture of Varnish an*
10 D. VAN NOSTRAXD COMPANY'S
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66 illus. 216 pp. net, $4.00
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492 pp. net, $4 50
MARTIN, Triumphs and Wonders of Modern Chem-
0.
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Modern Chemistry and Its Wonders. A popular
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267 pp. $2.00
MELICK, CHARLES W. Dairy Laboratory Guide. 52
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MERCK, . Chemical Reagents : Their
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Second Edition, revised. 6x9. cloth. 2iopp. $1.00
MIERZINSKI, S. The Waterproofing of Fabrics. Trans-
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Second Edition, revised and enlarged. 29 illustrations.
5 \ "Vi. 140 pp. net, $2.50
MITCHELL, C A. Mineral and Aerated Waters in
illustrations. 8vo. cloth. 244 pp. net, $3.00
MITCHELL, C A and PRIDEAUX. R. M. Fibres Ustd

.,
in Textile, and Allied Industries. 66 illustrations.

8vo cloth. 208 pp net. $3.00
MTTNBY, A . Introduction to the Chemistry and

Physics of Building Materials. Illus. 8vo. cloth. 365
pp. ( Van Nostrand's Westminster Scries.) net, $2.00

MURKAY, J. A. Soils and Manures. 33 illustrations.
8vo. cloth. 367 pp. (Van Nostrand's Westminster

Series.) net $2.00
LIST OF CHEMICAL BOOKS u
HEAVE, O. B., and HEILBBON, L M. The Identifica-
tion of Organic Compounds. I2mc. cloth, in pp.
net, $1.25
NORTH, H. B. Laboratory Experiments in General
Chemistry. Second Edition, revised. 36 illustrations.
5;4 X 7#- cloth. 212 pp. net $1.00

OLSEN, J. C. A Textbook of Quantitative Chemical
Analysis by Gravimetric and Gasoinetric Methods.
Including 74 laboratory exercises giving the analysis
of pure salts, alloys, minerals and technical products.
Fifth Edition, rinsed and enlarged. Illustrated.
6^x924. cloth. 576pp. net, $3.50
PAKBY, ERNEST J. The Chemistry of Essential Oils

and Artificial Perfumes. Second Edition, thoroughly
revised end greatly enlarged. Illustrated. 8vo. cloth.
554 pp. net, $5.00
Food and Drugs. In 2 volumes. Illus. 8vo. cloth.

Vo!. I. The Analysis of Food and Drugs (Chemical
and Microscopical). 50 illus. 724 pp. net, $7.50
Vol. II. The Sale of Food and Drugs Acts, 1873-
1907. 184 pp. net, $3.00
FAJRTINGTON. JAMES K. A Text-book of Thermo-

dynamics (with special reference to Chemistry). 91
diagrams. 8vo. cloth. 550 pp. net, $4.00
Higher Mathematics for Chemical Students. 44

diagrams. I2mo. cloth. 272 pp. net, $2.00
PEKKDJ. F. X., and JAOOEBS, E. K. Textbook of Ele-

mentary Chemistry. 77 illustrations. 4?< x 7. cloth.
342 pp. net, $1.00
PLATTNER'S Manual of Qualitative a*d Quantitative

Analysis with the Blowpipe. Eighth Edition, revised.
Translated by Henry B. Cornwall, assisted by-John
H. Caswell, from the Sixth German Edition, by tried-
rich kolbeck. 87ill. 8va cloth. 4631$ net; $4.00
12 D. VAN NOSTRAXD LUMPAMY'S
1
POLLEYN 7. Dressings and Finishings for Textile

Fabrics xnd Their Application. Translated from the
Third German Edition by Chas. Salter. 60 illustra-
tions, evo. cloth. 279 pp. net, $3.00
POPE, F. Modern Research in Organic Chemistry.

GK
^0i diagrams. 121110. cloth. 336 pp. net, $2.25
PORRITT, B. D. The Chemistry of Rubber. 5 x 7 />.

l
cloth. }OO pp. (Van Nostrand's Chemical Mono-

graphs.) net, $0.75
POTTS, HAROLD Chemistry of the Rubber Industry.

.
8vo. clcth. 163 pp. net, $2.00

PRESCOTT A B. Organic Analysis. A manual of the
descriptive and analytical chemistry of certain carbon
compourds in common use. Sixth Edition. Illus-
trated. 8vo. cloth. 533 pp. $5.00
PRESCOT1, A B
and JOHNSON, 0. C. Qualitative
.
Chemical Analysis. Seventh Edition, revised and en-

larged by John C. Olsen, A.M., Ph.D. 6# x (>*/*.
PRESCOT7, A. B., and SULLIVAN, . C First Book in

QonJitauve Chemistry. For studies of witer solution
and mass action. Eleventh Edition, entirely reuvitten.
i2mo. cloth. 150 pp. net, $1.50
PRJDEAUX. . B. R. Problems in Physical Chemistry
with Practical Applications. 13 diagrams. 8vo. cloth.
323 pp. net, $2.00
RICHARDS, W. A , and NORTH, H. B. A Manual of

Cement Testing. For the use of engineers and chem-
ists in colleges and in the field. 56 illustrations.
121110. cloth. 147 pp. net. $1.50
HIuEAL, S. Glue and Glue Testing. Second Edition.

rt-7 !>(/ and enlarged. 14 illustrations.
cloth. 194 pp. net, $4 00
LIST OF CHEMICAL BOOKS 13
ROGERS, ALLEN (Editor). Industrial Chemistry. A.

manual for the student and manufacturer. Second
Edition, thoroughly revised and enlarged. Written
by a staff of eminent specialists. 304 illustrations.
6^x9^. cloth. io26pp. net, $5.00

ROGERS. ALLEN. Elements of Industrial Chemistry.
An abridgement of The Manual of Industrial Chem-
istry. 1
17 illustrations, I folding plate. /
l
$ 2 x 8.
521 pp. net, $3.00

A Laboratory Guide of Industrial Chemistry. Illus-
trated. 8vo. cloth. 170 pp. net, $1.50
KOHLAND, PAUL. The Colloidal and Crystalloidal State

of Matter. Translated by W. J. Britland and H. E.
Potts. I2tno. cloth. 54 pp. net, $1.25
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||1 Q. CAHLTON SMITH, B.S.

. : ::V .'. : :, : :..

Micro Photo Division

BACBIFICSa AND LOVB

THE writer wishes to thank all those who have

Carnegie Inetitate of Technology,

Tarn THEOET or IBB NITRATION OF TOLUENB. 20

of efficiency, concentration and hustle, there have been

use in specifications, etc., they have spread beyond the

caused, therefore, that the uninitiated should confuse

used almost exclusively in English specifications and

is just what its name implies

By treating toluene with nitric acid, three nitro-

This particular trinitrotoluene is one of the six

On the other hand, trinitrotoluene is not quite as

Germans, who adopted il in 1904.

SOME doubt exists as to whom the honor of the dis-

1850, (1) gives the credit of the discovery to

of tolu a compound to which; he ascribed the name

C., and it is not completely solidified at -20. The

formula (supposedly) CiJIia had been isolated, and

48 isolated a substance from crude wood alcohol by

of this substance. One further method of obtaining

toluene will be cited, however, because of its scientific

necessary to obtain this object."

same method of procedure as is followed to-day in

uene was identified by the several chemists. Deville

Berzelius, in a research paper published in 1843,

ing on this question, BeilsteSn and Kuhlberg (12)

toluene is. nothing else than a mixture of nitrotoluene

formative period of the chemistry of the aromatics,

to state that they were led astray by statements and

After Beilstein and Kuhlberg completed their work

obtained; the ortho and para." This statement is

adhered to, by modern chemists, the usual manner of

modification. Peculiarly enough, this was the first

proved it to be symmetrical. (18) The melting-point

Giua and Molinari give the melting-point of this

during the latter part of the year 1915. (22) The

IN this discussion of the theoretical nitration of

toluene, I shall make use of the ideal process the three-

substituted, there would be changes in minor points

CeHsCHa +HNO2 - CaH^CHaXNOa) +H2O.

There is also a possibility thai the reaction may go

forward in two steps, the first step being the sulpho-

CeH aCH 3 +H 2 S0 4 -* CeH 4 (CH 3 XS03 H) +H 2 O

The reactions of the second stage consist first in

-> C5Hs(CH3)(NOa)(SOH) +H,O,

CH,(CH3)(NO,)(SO 8H) +HNO3

The third-stage reaction is similar to the second

In each stage there may be the reactions of either

stage has resulted in the formation of isorners with the

nitre-group can then easily replace the sulphonic

CONSTITUTION OF MIXTURE OF UNITS

Various chemists have analyzed the oil, their analyses