The Chemistry of Powder and Explosives - Sciencemadness Dot Org

NITROGEN SULFIDE 439
acid, sulfur dioxide, free sulfur, and ammonia. 46 It melts with
sublimation at 178°, and explodes at a higher temperature which,
however, is variable according to the rate at which the substance
is heated. Berthelot found that it deflagrates at 207° or higher,
and remarked that this temperature is about the same as the
temperature of combustion of sulfur in the open air. Berthelot
and Vieille 47 studied the thermochemical properties of nitrogen
sulfide. Their data, recalculated to conform to our present notions
of atomic and molecular weight, show that the substance is
strongly endothermic and has a heat of formation of —138.8
Calories per mol. It detonates with vigor under a hammer blow,
but is less sensitive to shock and less violent in its effects than
mercury fulminate. Although its rate of acceleration is considerably
less than that of mercury fulminate, it has been recommended
as a filling for fuses, primers, and detonator caps, both
alone and in mixtures with oxidizing agents such as lead peroxide,
lead nitrate, and potassium chlorate. 48
Nitrogen selenide was first prepared by Espenschied 49 by the
action of ammonia gas on selenium chloride. His product was an
orange-red, amorphous powder which exploded violently when
heated and was dangerous to handle. Verneuil 50 studied the substance
further and supplied a sample of it to Berthelot and
Vieille 51 for thermochemical experiments. It detonates when
brought into contact with a drop of concentrated sulfuric acid
or when warmed to about 230°. It also detonates from friction,
from a very gentle blow of iron on iron, and from a slightly
stronger blow of wood on iron. It has a heat of formation of
— 169.2 Calories per mol, and, with nitrogen sulfide, illustrates
the principle, as Berthelot pointed out, that in analogous series
(such as that of the halides and that of the oxides, sulfides, and
selenides) "the explosive character of the endothermic compounds
becomes more and more pronounced as the molecular weight
becomes larger."
48 Van Valkenburgh and Bailor, /. Am. Chem. Soc, 47, 2134 (1925).
47 Berthelot, "Sur la force des matieres explosives," 2 vols., third edition,
Paris, 1883, Vol. 1, p. 387.
48 Claessen, Brit. Pat. 6057 (1913); Carl, U. S. Pat. 2,127,106 (1938).
49 Ann., 113, 101 (1860).
50 Bull. soc. chim., [2] 38, 548 (1882).
51 Berthelot, op. cit., p. 389.