Nitro-Explosives: A Practical Treatise

BURITE, BELLITE,

om Benzene-Toluene an

urite: Properties and

ecurite-Tonite No

monite-Sprengel's Ex

s-Melinite-Abel's Mixt

ition, Formula, Prepa

Composition, Manu

C_{6}H_{5}OH. The benzene hydro-carbons are generally colourless liquids, insoluble in water, but soluble in alcohol and ether. They generally distil without decomposition. They burn with a smoky flame, and have an ether

ordinary benzene of commerce contains thiophene (C_{4}H_{4}S), from which it may be freed by shaking with sulphuric acid. Its boiling point is 79° C.; specific gravity at 0° equals 0.9. It burns with

chemically pure by distilling a

omo-benzenes, are also known; and mono-chloro-, C_{6}H_{4}Cl(CH_{3}), and bromo-toluenes, together with di derivatives in the ortho, meta, and para

_____| | | | C_{6}H_{4}(CH_{3})NO_{2} Ortho-, meta-, and para- nitro-toluenes. | | B.P. 218°, 230°, and 234° C, Para compound solid. | |____________________________________________________________________| | | | C_{6}H_{3}(CH_{3}){2}NO{2} Nitro-xylene. Liquid. | |____________________________________________________________________| | | | C_{6}H_{2}(CH_{3}){3}NO{2} Nitro-mesitylene. Sol

s or pale yellow needles or prisms. Some of them, however, are of an intense yellow colour. Many of them explode upon bein

ne, the two nitro groups may be in the meta, ortho, or para position, the meta position being the most general (see fig., page 4). By recrystallising from alcohol, pure meta-di-nitro-benzene may be obtained in long c

nly necessary to bring the hydrocarbon into contact with strong nitric acid, when the reaction takes place, and one or more of the hydrogen atoms of

_{3} = C_{6}H_{5

itro-b

lecule of nitric acid, the

HNO_{3} = C_{6}H_{4}

tro-b

us acid, as nitro-glycerine is of glycerine. They are regarded as form

nitric to 2 parts sulphuric acid, and put in a beaker standing in cold water; then add 15 to 20 c.c. of benzene, drop by drop, waiting between each addition for the completion of the reaction, and shake well during the operation. When finished, pour contents of beaker into about a litre of cold water; the nitro-benzol will sink to the bottom. Decant the water, and wash the nitro-benzol two

nitric and sulphuric acids, say 50 c.c. of each, and without cooling add very slowly 10 c.c. of benzene from a pipette. After the action is over, boil the mixture for a short time, then pour into about half a litre of water, filter off the crystals th

he ground, beneath a line of shafting. Each cylinder is covered with a cast-iron lid having a raised rim all round. A central orifice gives passage to a vertical shaft, and two or more other conveniently arranged openings allow the benzene and the mixed acids to flow in. Each of these openings is surrounded with a deep rim, so that the whole top of the cylinder can be flooded with water some inches in depth, without any of it running into the interior of the nitrator. The lid overhangs the cylinder somewhat, and in the outer rim a number of shot- holes or tubes allow the water to flow down all over the outside of the cylinder into a shallow cast-iron dish, in which it stands. By means of a good supply of cold water, the top, sides, an

tch, to protect its surface from the action of the acids. The floor should be inclined to a drain, to save any nitro-benzol spilt. Fire hydrants should be placed at convenient places, a

f 1.845, and contains from 95 to 96 per cent. of mono- hydrate. A good mixture is 100 parts of nitric to 140 parts of sulphuric acid, and 78 parts of benzene; or 128 parts HNO_{3}, 179 of H_{2}SO_{4}, and 100 of benzene (C_{6}H_{6

nd cooling being kept up all the time. When all the acid is added the water is shut off, and the temperature allowed to rise a little, to about 100° C. When it ceases to rise the agitators are thrown out of gear, and the mixture allowed some hours to cool and settle. The acid is then drawn off, and the nitro-benzene is well washed with water, and sometimes distilled with wet steam, to recover a little unconverted benzene

e of the nitro- and di-nitro-benzol produced comes off at the high temperature which is attained, and a good condensing apparatus of stoneware must be used to prevent loss. The product is separated from the acids, washed with cold water and then with hot. It is slightly soluble in water, so that the washing waters must be kept and used over again. Finally it is allowed to settle, and run while still warm into iron trays, in whic

y be made by using a very large excess of the mixed acids. Nitro- benzene,

's principle), but which, when mixed, form a powerful explosive. The two substances are ammonium nitrate and chlorinated di-nitro-benzol. Nitro-naphthalene is also used. Nitrate of soda and sulphate of ammonium are allowed to be mixed with i

ve to shock; it must be used dry; it cannot be made to explode by concussion, pressure, friction, fire, or lightning; it does not freeze; it does not give off deleterious fumes, and it is to all intents and purposes flameless; and when properly tamped and fired by electricity, can be safely used in fiery mines, neither fine dust nor gases being

{2} + 9HN{4}NO_{3} =

he men jointly for the purpose of settling the question. The members of this committee were Dr N. Hannah, Dr D.J. Mouncey, and Professor H.B. Dixon, F.R.S., of Owens College. After a protracted investigation, a long and technical report was issued, completely vindicating the innocuousness of roburite when properly used. In the words of

certain explosives, one of which was roburite, were injurious to health. The trial comprised the chemical analysis of the air at the "intake," and of the vitiated air during the firing of the shots at the "return," and also of the smoky air in the vicinity of the shot-holes. Five pounds and a half of roburite were used in twenty-three shots. It had been asserted that the fumes from this explosive contained carbon-monoxide, CO, but no trace of this gas could be discovered after the explosion. On another occasion, however, when 4.

f the nitrate of ammonia, the finished explosive must be kept out of contact with the air, and for this reason the cartridges are waterproofed by dipping them in melted wax. Roburite is made in Germany, at Witten, Westphalia; and also at the English Company's extensive works at Gathurst, near Wigan, which have been at work now for some eighteen years, having started in 1888. These works are of considerable extent, covering 30 acres of ground, and are equal to an output of 10

no detonation whatever takes place. If roburite be mixed with gunpowder, and the gunpowder fired, the explosion simply scatters the roburite without affecting it in the least. In fact, the only way to explode roburite is to detonate it by means of a cap of fulminate, containing at least 1 gramme of fulminate of mercury. Secondly, its great safety for

3,220° C. With regard to the composition of the fumes formed by the explosion of roburite, Mr Orsman says: "With certain safety explosives-roburite, for instance-an excess of the oxidising material is added, namely, nitrate of ammonia; but in

ives, and shows the composition of the gases formed on explosion. The gases were collected after det

rench Commission that, when dry and finely powdered, ammonium nitrate succeeds in depreciating the heat of decomposition without reducing the power of the exp

_______________________

|

position

____________

e. |of Gas

O_{2}.| CO.

| |

____________|_______|___

| |

| Per |

ent. |cent.|

der- |

5 parts |

| 2,214 | 51.3 |

l 15 '' |

ite- |

rine 56.5 par

5 '' | 4,980 | 25

l 8.0 '' |

32.0 ''

e- | |

| 3,750 | 30

nitrate |

te- | |

trate, 86 par

nzol 14 '' | 4,780 |

ite | |

erine 25 par

' | 2,100 | 19 |

trate 34 ''

____________|_______|___

___________________|_____________|_____________|_____________| | | | | | |Nitro-glycerine | 3,200 | ... | ... | |Blasting gelatine | | | | | (8 per cent. gun-cotton)| 3,090 | 88 | 1,493 | |Dynamite | | | | | (25 per cent. s

hen it evaporates without exploding. If heated suddenly, it burns with a sooty flame, somewhat like tar, but if the source of heat is removed, it will cease burning, and assume a caramel-like structure. It absorbs very little moisture from the air after it has been pressed, and if the operation has been performed while the explosive is hot, the subsequent increase of weight is only 2 per cent. When subjected to the most powerful blow with a steel hammer upon an iron plat

powerful and extremely safe explosive; that it cannot be made to explode by friction, shock, or pressure, nor by electricity, fire, lightning, &c., and that it is specially adapted for use in coal mines, &c.; tha

is a yellow powder, with an odour of nitro-benzol. It was licensed in 1886. It sometimes co

10(NH{4}NO_{3}) = 6CO_

e presence of fire damp and coal dust.[A] The variety known as Flameless Securi

by S.B. Coxon, North

ng., 11

of Messrs Petry and Fallenstein, and consisted of nitro-benzol, thickened or gelatinised by the addition of some collodion-cotton, i

zol, 19.4

potash, 76

mony nitro-cotto

Smith, Jour. Soc. Che

ged, when the chlorate dissolves out, leaving a practical inexplosive residue.[A] It was found to be very sensitive to combined friction and percussion, and to be readily ignited by a glancing blow of wood u

ver, it be exposed to moist and dry air alternately, the chlorate cryst

s Explosive contains 10 per cent. of di-nitro-benzol, together with 85 per cent. of nitrat

nitric acid on toluene. According to H?ussermann, it is more advantageous to start with the ortho-para-di-nitro-toluene, which is prepared by allowing a mixture of 75 parts of 91 to 92 per cent. nitric acid and 150 parts of 95 to 96 per cent. sulphuric acid to run in a thin stream into 100 parts of para-nitro-toluene, while the latter is kept at a temperature between 60° to 65° C., and continually stirred. When the acid has all been run in, this mixture is heated for half an hour to 80° C., and allowed to stand till cold. The excess of nitric acid is then rem

al di-nitro-toluene melting at 60° to 64° C.; but when this is used, greater precautions must be exercised, for the reactions are more violent. Moreover, 10 per cent. more nitric acid is required, and the yield is 10 per cent. less. He also draws attention to the slight solubility of tri-nitro-toluene in hot water, and to the fact that it is decomposed by dilute alkalies and alkaline carbonates-facts which must be borne in mind in washing the substance. This material is neither difficult nor dangerous to make. It behaves as a very stable substance when exposed to the air under varying conditions of temperature (

It is composed of tri-nitro-toluol 11 parts, ammonium nitrate 93 parts, and moisture 1 part. This explosive must be used only when contained in a case of an alloy

and [beta] derivatives of nitro-naphthalene. It is the di-nitro-naphthalene that is chiefly used in explosives. It is contained in roburite, securite, romit, Volney's powder, &c. Fehven has patented an explosive consisting of 10 parts of nitro-naphthalene mixed with the crude ingredients of gunpowder as follows:-Nitro-

rbon. In this way a more intimate mixture is ensured between the particles of the components, and the explosive thus prepared can be fired by a small detonator, viz., by 0.54 grms. of fulminate. Favier's explosive also contains mono-nitro-naphthalene (8.5 parts), together with 91.5 parts of nitrate

and substituted di-nitro-naphthalene 11.5 per cent. for the mono-nitro-naphthalene, and used thin lead envelopes filled with loose powder slightly pressed in, in place of the compressed cylinders containing loose powder. The process of manufacture is shortly as follows:-132-3/4 lbs. of thoroughly dried nitrate of ammonium is placed in a mill pan, heated at the bottom with live steam, and ground for about twenty minutes until it becomes so dry that a slight dust follows the rollers; then 17-1/2 lbs. of thoroughly dry di-nitro-naphthalene is added, and the grinding continued for about ten minutes. Co

he charge, and keeping it in a fluid state), with frequent agitation, day and night, during the first three or four days, afterwards three or four times a day. In all fourteen days are occupied in the nitration process. It is then strained through an earthenware strainer, washed with warm water, drained, and dried. For the purpose of producing this material in a granulated condition, which is found more convenient for drying, and further nitrification, it is placed in a tub, and live steam passed through, until brought up to the boiling point (the tub should be about half full), cold water is then run in whilst violently agitating the contents until the naphthalene solidifies; it can then be easily drained and dried. For the further treatment to make di-nitro-naphthalene, 18 parts of nitro-naphthalene are placed in an earthenware pan, together

itted explosives. It contains about 75 per cent. of nitrate of ammonium, with the addition of nitrate of barium, wood meal, and starch. The gases resulting from detonation are chiefly water in the gaseous form, nitrogen, and a little carbon dioxide. It is granulated with the object of preventing missfires from ramming, to which nitrate of ammonium explosi

of the mixture being very often non-explosive bodies. This type of explosive is due to the late Dr Herman Sprengel, F.R.S. Following up the idea that an explosion is a sudden combustion, he submitted a variety of mixtures of oxid

nt of nitro-benzene to e

picric acid to 13 equ

of nitro-naphthalene to 41

violently with bisulphide of carbon, nitro-benzol, carboni

erhaps be regarded as belonging to the Sprengel class of explosives, otherwise this class is not manufactured or used in England. The principal members are known as Hellhoffite, consisting of a mixture of nitro-petroleum or nitro-tar oils and nitric acid, or of

one time a yellow gum from Botany Bay (Xanthorrhoea hastilis) was chiefly used. One part of phenol (carbolic acid), C_{6}H_{5}OH, is added to 3 parts of strong fuming nitric acid, slightly warmed, and when the violence of the reaction has subsi

l, where the crude picric acid crystallises out, and the acid liquid (which contains practically no picric acid, but only sulphuric acid, with some nitric acid) being poured down the drains. The crude picric acid is then dissolved in water by the aid of steam, and allowed to cool when most of the picric acid recrystallises. The mother liquor is transferred to a tank and treated with sulphuric acid, when

and p. phenols

= C_{6}H_{2}(NO_{2}){3}OH + H{2}

ea, Amer. Jour. Sci.

forming well crystallised yellow salts, which detonate violently when heated, some of them also by percussion. The potassium salt, C_{6}H_{2}(NO_{2})_{3}OK, crystallises in long needles very slightly soluble in water. The sodium, ammonium, and barium salts are, however, easily soluble in water. Picric acid, when heated, burns with a luminous and smoky fl

}|(NO_{2}

hree hydrogen atoms being displaced by the NO_{2} group.

_{3} = C_{6}H_{2}(NO

ries, and its heat of total combustion by free oxygen is equal to +618.4 cals. I

3}OH + O{10} = 12CO_

iberated, according to Berthelot, would be 130.6 cals., or 570 cals. per kilogramme. The reduced volume of the gases would be 190 litres per equivalent, or 829 litres per kilogramme. To obtain a total combustion of picric acid it is necessary to mix with it a

Bull. de la Soc. Chim. de Paris, xlix., p. 456) on the explosive decomposition of picric acid are also deserving of attention in this connection. If a small quantity of picric acid be heated in a moderate fire, in a crucible, or even in an open test tube, it will melt (at 120° C. commercial acid), then give off vapours which catch fire upon contact with air, and burn with a sooty flame, without exploding. If

lode with a curious characteristic noise. If the quantity be increased so that the temperature of the tube is materially reduced, no explosion will take place at once, but the substance will volatilise and then explode, though with much less violence than before, in the upper pa

e decomposition, there will be no explosion and no deflagration. If, however, the absorption is not sufficient to prevent deflagration, this may so increase the temperature of the surrounding

t be carefully kept from contact with nitrates, chlorates, or oxides. If only a little bit of lime or plaster become accidentally mixed with it, it may become highly dangerous. A local explosion may occur which might have the effect of causing the explosion of the whole mass. Picric aci

olved in some solvent (acetone or ether-alcohol). Sir F.A. Abel has also proposed to use picric acid, mixed with nitrate of potash (3 parts) and picrate of ammonia (2 parts) as a filling for shells. This substance requires a violent blow and strong confinement to explode it. I am not aware, ho

| Arms. | |___________________|_______________|___________________|___________| | | | | | | | Picrate of Potash | 55-50 | 16.4- 9.6 | 9 | 28.6-22.9 | | Saltp

edom from injurious action on the bores of guns, owing to the absence of sulphur. Brugère's powder is composed of ammonium picrate and nitre, the proportions being 54 per cent. picrate of ammonia and 46 per cent. potassic nitrate. It is stable, safe to manufac

and the Japanese Shimose are sai

picric acid into projectiles, the cast acid having a density of about 1.6. In this state it resists the shock produced by the firing of a cannon, when contained in a projectile, having an initial velocity of 600 metres. It is made in the following way:-The acid is fused in a vessel provided with a false bottom, heated to 130° to 145° C. by a current of steam under pressure, o

nol, such as sodium di-nitro-cresylate, known in the arts as victoria yellow. Naphthol, a phenol-like body obtained from naphthalene, under the same conditions, produces sodi

crystallises out upon cooling, which is similar to ammonium picrate. This salt is known as "Ecrasite," and has been used in Austria for charging shells. It is a bright yellow solid, greasy to the touch, melts at 100° C., is unaffected by moisture, heat, or cold, ignites when brought into contact with an incandescent body or open flame, burning harmlessly away unless strongly confined, and is insensitive to friction or concussion. It is claim

e fulminates are sal

eir constitution is not

Mr Kawakita (Chem. Soc.

of mercury and si

N AgO

\

O a

/

N A

.R.S., would prefer to write

H. | C

v. xxvi., p. 1403), assigns t

:

|

N.

(Ber., v. xxi

:

H

:

ally regarded as is

lowly to moderate the action. At first the mixture blackens from the separation of mercury, but this soon vanishes, and is succeeded by crystalline flocks of mercury fulminate which fall to the bottom of the vessel. During the reaction, large quantities of volatile oxidation products of alcohol, such as aldehyde, ethylic nitrate, &c., are evolved from the boiling liquid, whilst others, such as gl

}Hg = Hg + 2CO

.c. (= 66.96 litres for 284 grms.). Berthelot and Vicille have obtained

heated slowly, it explodes at 152° C., or if heated rapidly, at 187° C. It is often used mixed with potassium chlorate in

issolve in 36 parts of boiling water, and are with difficulty soluble in cold water. At above 100° C., or on the weakest blow, it explodes with fearful violence. Even when covered with water it is more sensitive than the mercury salt. It forms a very sensitive double salt with ammonia and several other metals. With hydrogen it forms the acid fulminate of silver. It is used in cr

Ag.CN, from whose aqueous solution nitric acid precipitates a white powder of hydric argentic fulminate, C(NO_{2})HAg.CN. All attempts to prepare fulminic acid, or nitro-aceto- nitrile, C(NO_{2})H_{2}CN, from the fulminates have failed. There is a fulmin

Its inflammation is so sudden that it scatters black powder on which it is placed without igniting it, but it is sufficient to place it in an envelope, however weak, for ignition to take place, and the more resisting the envelope the more violent is the shock, a circumstance that plays an important part in caps and detonators. The presence of 30 per cent. of water prevents decomposition, 10 per

ent some more alcohol is added, equal in volume to that which has already been added. This is added very gradually. The product obtained, which is mercury fulminate, is 112 per cent. of the mercury employed. Another method is to dissolve 10 parts of mercury in 100 parts of nitric acid of a gravity of 1.4, and when the solution has reached a temperature of 54° C, to pour it slowly through a glass funnel into 83 parts of alcohol. When the effervescence c

ur. The following is a common cap mixture:- 100 parts of fulminate of mercury and 50 parts of potassium nitrate, or 100 parts of fulminate and 60 parts of meal powder. Silver fulminate is also sometimes used in caps. There are eight siz

" " " 3 " 540 " " " " " " 4 " 650 " " " " " " 5 " 800 " " " " "

ary dynamite, 5, 6, or 7 for gun-cot

ntimony, the mixture being damped with a varnish consisting of 645 grains of shellac dissolved in a pint of methylated spirit. Abel's fuse (No. 1) consists of a mixture of sulphide of copper, phosphide of copper, chlorate of potash, and No. 2 o

same length, and so spaced apart as to exactly fit each point into a cap when inverted over a plate containing the blanks. The points are dipped into a vessel containing the cap composition, which has been previously moistened with methylated spirit. It is then removed and placed over the blanks, and a slight blo

tton, and 1 part chlorate. The water in which the fulminate is usually stored is first drained off, and replaced by displacement by methyl-alcohol. While the fulminate is moist with alcohol, the gun-cotton and chlorate mixtu

the operatives. There is equally just cause for apprehension in respect to the poisonous gases which are evolved during the solution of mercury in nitric acid, and especially during the subsequent treatment with alcohol. Many methods have been proposed for dealing with the waste products arising during the manufacture and manipulation o

with carpet, and the tables with felt. Felt shoes are also worn by the workpeople employed. All the tools and apparatus used must be kept very clean; for granulating, hair sieves are used, and the granulated mixture is afterwards dried on light

5 to 25 per cent. of pyroxyline, according to the stiffness or elasticity of the compound desired. Some solvent that dissolves the nitro-cotton is also used. The product thus formed is a kind of blasting gelatine, and should be in a pasty condition, in order that it may be mixed with fulminate of mercury. The solvent used is acetone, and the quantity of fulminate is between 75

. 34. METHOD OF PR

the detonator may be developed, but also to fix the fuse in the cap (Fig. 34). When the detonator, &c., is to be used under water, or in a damp situation, grease or tallow should be placed round the junction of the cap with the fuse, in order to make a water-tight joint. A cartridge is then opened and a hole made in its upper end, and

ion: FIG.

tension exploders. A charge having been prepared, as in Fig. 34, insert into the bore-hole one or more cartridges as judged necessary, and squeeze each one down separately with a wooden rammer, so as to leave no space round the charge, and above this insert the

FIG. 36.-ELEC