Improvements in the Manufacture of Explosives.
Year: 1886

page_text: Date of Application, 14th July, 1886.
Complete Left, 7th Mar., 1887
Complete Accepted, 7th Apr., 1887
Improvements in the Manufacture of Explosives.
I, CARL ROTH of Berlin in the Empire of Germany, Chemist do hereby declare
the nature of this Invention to be as follows :-
This Invention relates to a process for the production of components or constituents
for explosives by chlorating and nitrating coal tar and the products thereof.
Out of the components or constituents which form explosives when mixed with
substances containing oxygen, only the nitrated hydro carbons and hydroxyl com-
pounds of the aromatic group or sulpho acids have hitherto been employed-See
Sprengel "On a new class of explosives which are non-explosive during their
manufacture storage and transport" and the Bulletin de la Société chimique francaise
1873 XX No. 10 p. 257 with reference to the nitro substances as explosive components
and with regard to the sulpho acids see Bröckmann, "Explosive Stoffe" p. 207 note.
On the other hand aromatic compounds which contain simultaneously one or more
nitro groups and chlorine have not heretofore been employed as explosive components
mixed with substances containing oxygen. The advantage obtained by the intro-
duction of chlorine and nitro groups into the tar itself or its products is that the acid
constituent chlorine exerts a loosening effect on the nitro groups and accordingly
enables the same to react more readily in the presence of substances yielding oxygen
that is to say enables the combination to burn more readily than when nitro groups
only are present. The dynamic effect is also considerably increased as has been proved
by numerous experiments by the addition of the gaseous chlorine in nitro combination
probably in consequence of the increase in the volume of
gas.
Compounds formed as aforesaid or mixtures of such compounds are obtained
according to this invention either by nitrating chlorated substances or by chlorating

page_text: nitro products or by the action of mixtures which produce a nitrating and a chlorating
action at the same time preferably mixtures of nitric and hydrochloric acids.
1st example-One part of benzol chloride is gradually introduced into a mixture
composed of about three parts of concentrated nitric acid of 1.52 sp. gr. and about
six parts of concentrated sulphuric acid the vessel being artificially cooled during the
operation if required and after the evolution of nitrous vapour has ceased the reaction
is completed by the application of heat. After the addition of water a crystalline
product of from yellow to brown colour according to the degree of purity of the
benzol chloride separates and can be cleansed from the adhering acid by washing with
a copious supply of water and afterwards dried.
2nd example Chlorine is introduced into phenol heated to about fifty degrees
centigrade until the weight is increased by about one half. The semi fluid
crystalline mass is then introduced in small portions into three times its weight
of nitric acid of about 14 sp. gr. the vessol being cooled during the operation.
The brownish product which is separated by the addition of water is then
gradually introduced into a mixture of about three parts of nitric acid of 1.52 sp. gr.
and about five parts of concentrated sulphuric acid and the reaction is completed by
the heat of a water bath. A brownish yellow partially fluid crystalline mass is thus
obtained which is washed and the moisture evaporated by a gentle heat.
3rd example About one part of napthaline is gradually introduced into a warmed
mixture of about five parts nitrate of soda and about six parts concentrated sulphuric
acid and after the most violent reaction is concluded is gently heated with this mixture
during from about three to four hours. About one part of the washed yellowish brown
product is then carefully mixed with about 0-8 parts of chlorate of potash and about
five parts of concentrated hydrochloric acid are then allowed to flow by degrees into
the mixture. The chlorine is freed by applying a gentle heat to the vessel-The final
product being cleared of the adhering salt by washing with water forms when dried
an easily melted orange yellow crystalline mass of about 1-4 sp. gr.
4th example About twelve pounds (6 Kilos) of nitric acid of 145 sp. gr. are
heated with about four pounds of sodium chloride during about one hour to from
about sixty to sixty five degrees centigrade in an apparatus provided with means for
cooling or condensing. About two pounds (1 Kilo) of naphthaline in small portions
are then added to the mixture and towards the conclusion of the reaction the whole is
gently heated. The reddish mass which separates and is freed from salt by washing
is then introduced into about three parts of nitric acid of about 1.52 sp. gr. and about
six parts of concentrated sulphuric acid and digested with the acid mixture for several
hours in the apparatus hereinbefore referred to-The brownish yellow product obtained
after treatment with water is of a crystalline nature and of a sp. gr. of about 1.4.
5th example About four parts of the fraction of coal tar which goes over at a
temperature of between 190 and 210 degrees centigrade is gradually introduced into
a mixture composed of about ten parts of nitric acid of about 1-4 sp. gr. and about
five parts of hydrochloric acid at about 24 per cent the vessel being cooled during the
operation. Every part of the oily product which after a time becomes crystalline is
gradually incorporated with a mixture composed of about three parts of nitric acid
of about 1.52 sp. gr. and about seven parts of concentrated sulphuric acid and the
reaction is completed by heat-The product obtained after washing and drying forms
a brown greasy mass becoming crystalline at about ten degrees Centigrade.
6th example About five parts of coal tar are caused to flow in a fine stream or jet
into a mixture composed of about fifteen parts of nitric acid of 1-45 sp. gr. and about
12 parts of hydrochloric acid at 24 per cent. After the more violent evolution of gas
has ceased the reaction is maintained by the application of heat. Every part of the
plastic product of the reaction is then introduced into a mixture of about five parts
of nitric acid of 1.52 sp. gr. and about fifteen parts of sulphuric acid and digested
with the acid mixture for several hours. The final product after washing and drying
forms a brown amorphous powder.
The analysis of the product obtained according to the last example shows the

page_text: proportion of Chlorine contained to be 8.3 per cent; the proportion in the other
products varies from 10 to 21 per cent.
In order to effect the explosion each part of the nitro chlorine product is mixed
according to the carbon or hydrogen present, with from about 2 to 3.5 parts a suitable
substance containing Oxygen the various forms of nitre being chiefly employed for
this purpose and the mixture is then detonated by a suitable flash such as that produced
by fulminate of mercury. Especially powerful effects are obtained with the mixture
of about one part of the chloro nitro product (obtained as specified in example 4)
with about two parts of nitrate of potash.

page_text: I, CARL ROTH, of Berlin, in the Empire of Germany, Chemist, do hereby declare
the nature of this invention and in what manner the same is to be performed, to be
particularly described and ascertained in and by the following statement :-
My invention consists in a process for producing new and powerful explosives by
means of the mixture, with oxygen-yielding substances, of compounds obtained from
coal-tar or from fractional products of the same, by incorporating thereinto both
chlorine and nitrogen.
Of the carbon-compounds which, when mixed with oxygen-yielding substances,
form explosives, only the nitrated hydro-carbons and hydroxyl compounds of the
aromatic group, and certain nitrated sulpho-acids have hitherto been employed. (With
reference to the nitro-compounds as components of explosives see "Sprengel, on a new
class of explosives which are non-explosive during their manufacture, storage and
transport," and the "Bulletin de la Société Chimique francaise," 1873, XX, No. 10,
p. 257; and with regard to the sulpho-acids see "Bröckmann, Explosiv-Stoffe," p. 207,
note.) No use, however, has heretofore been made, for the same purpose, of aromatic
compounds containing both nitrogen and chlorine.
The advantage attained by the introduction of chlorine as well as nitrogen into the
tar itself, or its fractional products, is that the chlorine exerts a loosening effect on
the atomic groups containing the nitrogen, and accordingly enables the said groups to
react more readily on the oxygen-yielding substances, that is to say, it enables the
compound to burn more readily than when nitro-groups only are present. As has
been proved by numerous experiments, the dynamic effect is also considerably increased
by the introduction of chlorine into the nitro-compounds, probably in consequence of
the increase in the volume of the combustion-gas by the chlorine, when set free.
Compounds constituted as aforesaid, or mixtures of such compounds with each
other, are obtained either by nitrating chlorated substances, or by chlorating nitro-
products, or by the action of agents which produce a nitrating and a chlorating effect
at the same time, preferably of a mixture of nitric and hydrochloric acids. The
following are some examples of the modes of producing the said compounds.
1st Example One part of benzol chloride is gradually introduced into a mixture
composed of three parts of highly concentrated nitric acid of 1.52 sp. gr. and six
parts of concentrated sulphuric acid, the vessel being artificially cooled during the
operation if required, and, after the evolution of nitrous vapour has ceased, the reaction
is completed by the application of heat. After the addition of water a crystalline
product separates out, which, according to the degree of purity of the benzol chloride,

page_text: has a colour varying between yellow and brown. This product is cleansed from the
adhering acid by washing with a copious quantity of water, and afterwards dried.
2nd Example Chlorine is introduced into phenol, heated to fifty degrees centigrade,
until the weight is increased by one half. The semi-fluid crystalline mass is then
introduced in small portions into three times its weight of nitric acid of 14 sp. gr.,
the vessel being cooled during the operation. The brownish product which is separated
out by the addition of water, is thereupon gradually introduced into a mixture of
three parts of nitric acid of 1.52 sp. gr. and five parts of concentrated sulphuric acid,
and the reaction is completed by the heat of a water bath. A brown-yellow, partially
fluid crystalline mass is thus obtained, which is washed and the moisture evaporated
by a gentle heat.
3rd Example-One part of naphthaline is gradually introduced into a warmed
mixture of five parts of nitrate of soda and six parts of concentrated sulphuric acid,
and, after the most violent reaction is concluded, is gently heated with this mixture
during three or four hours. One part of the washed yellowish-brown product having
then been carefully mixed with 0.8 parts of chlorate of potash, 5 parts of concentrated
hydrochloric acid are allowed to flow by degrees into the mixture, and a gentle heat is
applied to the vessel. The final product is freed from the adhering salt by washing
with water and dried, and then forms an easily-melting orange-yellow crystalline mass
of about 14 sp. gr.
4th Example Twelve pounds of nitric acid of 1·45 sp. gr. are heated with four
pounds of sodium chloride during about one hour, to sixty or sixty-five degrees centi-
grade and subsequently cooled. Two pounds of naphthaline in small portions are
then added to the mixture, and, towards the conclusion of the reaction, the whole is
gently heated. The reddish mass which separates out, having been freed from salt by
washing, is introduced into three parts of nitric acid of 1.52 sp. gr. and six parts of
concentrated sulphuric acid, and digested with the acid mixture for several hours.
The brownish yellow product obtained after treatment with water is of a crystalline
nature and of a sp. gr. of about 1.4.
5th Example Four parts of the fractional distillate of coal tar which goes over at
a temperature of between 190 and 210 degrees centigrade, are gradually introduced
into a mixture composed of ten parts of nitric acid of 1-4 sp. gr. and five parts of
hydrochloric acid of 24 per cent, the vessel being cooled during the operation. One
part of the oily product, which after a time becomes crystalline, is gradually
incorporated into a mixture composed of three parts of nitric acid of 1.52 sp. gr. and
seven parts of concentrated sulphuric acid, and the reaction is completed by heat.
The product obtained after washing and drying, forms a brown greasy mass, becoming
crystalline at about ten degrees centigrade.
6th Example Five parts of coal-tar are caused to flow in a fine stream or jet into
a mixture composed of fifteen parts of nitric acid of 1.45 sp. gr. and twelve parts of
hydrochloric acid of 24 per cent. After the more violent evolution of gas has ceased,
the reaction is promoted by heat. One part of the plastic product of the reaction is
then introduced into a mixture of five parts of nitric acid of 1.52 sp. gr. and fifteen
parts of sulphuric acid, and digested with the acid mixture for several hours. The
final product obtained after washing and drying, forms a brown amorphous powder.
The analysis of the product obtained according to the last example shows the
proportion of chlorine contained therein to be 8.3 per cent. The proportion in the
other products varies from 10 to 21 per cent.
The described methods of producing the said compounds containing chlorine and
nitrogen, do not, however, in themselves form any part of my invention. Other
compounds of the same character, obtained by different processes may therefore also
be employed.
In order to produce the explosive matter, one part of the said chlorated and
nitrated compounds is mixed, according to the quantity of carbon and of hydrogen
present therein, with from 2 to 3.5 parts of oxygen-yielding substances, preferably
with nitre in its various forms, for instance with nitrate of soda, of potash or of

page_text: ammonia. Especially powerful effects have been obtained with the mixture of one
part of the chloro-nitro-compound produced according to example 4, with two parts
of nitrate of potash.
Having now particularly described and ascertained the nature of this invention and
in what manner the same is to be performed, I declare that what I claim is:
1. The process of producing explosives by the mixture, with oxygen-yielding
substances, of compounds obtained from coal-tar or from fractional products of the
same, by incorporating into the tar or the said fractional products, both chlorine and
nitrogen, substantially as herein before specified.
2. As an article of manufacture, an explosive composed of an oxygen-yielding
substance and of a compound or compounds obtained from coal-tar or from fractional
products of the same, by the incorporation thereinto of both chlorine and nitrogen,
substantially as described.