Hydrocyanic acid, HCN, was discovered by Scheele in 1782 and first obtained

anhydrous by Gay Lussac, who heated mercury cyanide with hydrochloric acid,
and after passing the evolved gas over marble to remove HCl, and subsequently
drying, condensed the hydrocyanic acid in a freezing mixture.

This acid occurs in plants, very seldom in the free state, but generally as a
constituent of the glucoside amygdalin, which on hydrolysis yields hydrocyanic
acid, benzaldehyde, or bitter almond oil, and glucose, as follows:

C20H27NO11 + 2H2O = HCN + C6H5CHO + 2C6H12O6.

This hydrolysis occurs naturally by the agency of the enzyme emulsin; it is brought
about artificially by the action of dilute acids. Bitter almonds and laurel leaves are
the chief sources of amygdalin; and by distilling these products with water a dilute
solution of hydrocyanic acid is obtained.

Hydrogen cyanide has been synthesised from its elements by passing a mixture of
hydrogen and air through a carbon tube heated in an electric arc. The reaction is
endothermic, and, according to von Wartenberg, is represented by the following
thermal equation:

2C (graphite) + H2 + N2 = 2HCN - 59,700 calories.

The amount of hydrogen cyanide formed increases with temperature, as theory

indicates, and Wallis, by passing a mixture of nitrogen and hydrogen across the
carbon poles of the electric arc, whose temperature is about 3500 C., converted
33.6 per cent, of the gaseous mixture into hydrogen cyanide.

By means of an electric flame an even more striking result has been obtained; for
by employing a mixture of nitrogen and methane in the molecular proportion of 23:1, diluted with hydrogen so as to contain less than 10 per cent, of methane,
Muthmann and Schaidhauf have converted the methane quantitatively into
hydrogen cyanide. Lipinski also converted the whole of the methane in a mixture
of 8 to 34 per cent. CH4, 75 to 53 per cent. N2, and 16 to 12 per cent. H2 into
hydrogen cyanide by the passage of an alternating current at 2000 volts and 0.05 to
0.12 ampere between platinum terminals through 3.8 litres of the mixture for one
to three hours.

A less complete synthesis of hydrogen cyanide would be effected by causing

ammonia, in which nitrogen and hydrogen are already united, to react with carbon,
according to the equation

NH3 + C = HCN + H2.

Bergmann has shown that when ammonia is passed over carbon heated to about
1300 C., 90 per cent, of it is converted into HCN. The reaction is endothermic, its
heat being -39,500 calories. A modification of this reaction is that of Roeder and
Grunwald, who pass a mixture of ammonia, and nitrous oxide over heated carbon,
the reaction being:

2NH3 + N2O + 4C = 4HCN + H2O - 58,000 calories.

Owing to the heat of decomposition of nitrous oxide, which is endothermic, and

the heat of formation of steam, it is not necessary to heat the carbon to so high a
temperature as in the former case; indeed the yield of hydrogen cyanide is nearly
quantitative when the temperature of the carbon is but 450 C.

Hydrogen cyanide is also produced by the explosion of a mixture of acetylene and

nitrogen in a bomb:

C2H2 + N2 = 2HCN - 9400 calories,

and by the reaction between acetylene and ammonia at 300 C. in presence of a

catalyst:

C2H2 + 2NH3 = 2HCN + 3H2 - 33,000 calories.

Methane and nitrogen also yield hydrogen cyanide under the influence of the silent
electric discharge, or at 1000 C., the equation being:

2CH4 + N2 = 2HCN + 3H2 -103.5 calories.

Hydrogen cyanide is generally prepared, however, from potassium ferrocyanide or

a simple cyanide. In either case it is synthetic in origin, for ferrocyanide was
originally made by heating together a mixture of potassium carbonate, iron, and
nitrogenous organic matter, whilst cyanide is obtained either from the hydrogen
cyanide formed synthetically in gas manufacture or by passing ammonia over a
heated mixture of alkali carbonate, and carbon (Beilby's process). When powdered
potassium ferrocyanide is distilled with dilute sulphuric acid (1 part H2SO4 to 2
parts water) hydrocyanic acid is evolved according to the reaction:

2K4Fe(CN)6 + 3H2SO4 = 6HCN + K2Fe[Fe(CN)6] + 3K2SO4.

The vapour may be dried by passing it through calcium chloride tubes kept at 30
C. by immersion in warm water, and then condensed in a freezing mixture; or the
vapour may be at once passed into water if only a solution of the acid is required.

Practically anhydrous hydrocyanic acid may be obtained by dropping sulphuric

acid diluted with an equal volume of water on to 98 per cent, potassium cyanide.

Anhydrous hydrocyanic acid is also formed when mercuric cyanide, heated to 30

C., is decomposed by hydrogen sulphide.

Physical Properties of Hydrocyanic Acid

Anhydrous hydrogen cyanide is a colourless, mobile liquid having a smell of bitter

almonds, and is exceedingly poisonous. Owing to the danger of working with this
substance its physical properties have not been completely elucidated. Its density at
18 C. is 0.6969, and at 7 C. is 0.7058, whence the density at 0 C. has been
calculated to be 0.7115; its boiling-point at atmospheric pressure is 26.5 C. (Gay
Lussac); its vapour density at high temperature is 0.947 (air = 1) and 13.69 (H = 1);
at -15 C. it solidifies to a mass of white feathery crystals.

The heat of vaporisation of hydrogen cyanide is 210.7 calories per gram, or 5700
calories per gram molecule; this value is high on account of polymerisation. Rapid
evaporation causes a drop of the liquid on a glass rod to solidify.

The following thermal values have been determined by Berthelot and Thomsen:

Heat of formation HCN vapour: -30,500 calories

Heat of formation HCN liquid: -24,800 calories
Heat of formation HCN in solution: -24,400 calories
Heat of formation HCN from diamond: -30,200 calories
Heat of formation HCN from graphite: -29,850 calories

The heat of combustion at constant pressure is 159,300 calories (Berthelot) or

158,600 calories (Thomsen); the heat of aqueous solution is 400 calories
(Berthelot).

Liquid hydrogen cyanide dissolves many organic and inorganic substances.

Interesting results relating to the electric conductivity and chemical reactivity of
such solutions have been obtained by Kahlenberg and Schlundt.

Hydrogen cyanide mixes in all proportions with water, alcohol, and ether. Solution
in these cases is accompanied both by fall of temperature and diminution of
volume. No definite hydrate of hydrogen cyanide is known.
Chemical Properties of Hydrocyanic Acid

Hydrogen cyanide vapour burns with a violet flame of slight luminosity; both the
anhydrous liquid and its concentrated aqueous solution appear combustible. When
passed over heated copper oxide the vapour burns to carbon dioxide, water, and
nitrogen.

A polymer of hydrogen cyanide is slowly produced when an aqueous solution of

the latter is kept in presence of alkali carbonate or cyanide. Under these conditions
the liquid turns brown, and a black mass separates after some days, from which

ether extracts a substance which crystallises in colourless leaflets. This substance

possesses the composition (HCN)3, turns brown at 140 C. with partial
decomposition, and melts at 180 C. It is decomposed by being heated with baryta
water into carbonic acid, ammonia, and amino-acetic acid; it is therefore probably
the dinitrile of aminomalonic acid, NH2CH(CN)2.

That hydrogen cyanide is itself the nitrile of formic acid is shown by the fact that it
is resolved into this acid and ammonia when boiled with concentrated mineral
acids and alkalis:

HCN + 2H2O = HCOOH + NH3.

Hydrogen cyanide is reduced to methylamine, CH3NH2, by nascent hydrogen or

by hydrogen gas at 140 C. in presence of platinum black.

In sunlight chlorine converts hydrogen cyanide into cyanogen chloride; cyanogen

bromide and iodide are also produced, though less readily, from hydrogen cyanide
and the corresponding halogen according to the equation:

CNH + X2 = CNX + HX.

Hydrogen cyanide reacts with an organic carbonyl group, producing a cyanhydrin,

thus:

>CO + HCN = >C(CN)(OH)

whence by hydrolysis h hydroxyacid results:

>C(CN)(OH) + 2H2O = >C(COOH)(OH) + NH3

An aqueous solution of hydrogen cyanide is a very weak acid: hydrocyanic or

prussic acid.

A solution of the acid does not redden litmus; its soluble salts are largely
hydrolysed in aqueous solution, and are decomposed by atmospheric carbon
dioxide, so that they smell of hydrocyanic acid.

The electric conductivity of aqueous hydrocyanic acid has been measured by

Walker and Cormack at 18 C., with the following results:

0.0183

5.1210-5 0.08131

0.0262

7.3810-5 0.08133

0.0320

8.9410-5 0.08l33

16

0.0365

10.1910-5 0.08130

Mean 0.08132

The dissociation constant, which may be taken to be 1.310-9, shows the strength
of hydrocyanic acid to be only one-fortieth that of hydrogen sulphide and one twohundredth that of carbonic acid. From measurements of the hydrolysis of

potassium cyanide at 25 C. van Laar has found the value K=3.110-8, whilst by
measuring the potential between a silver electrode and a solution of potassium
silver cyanide at 18C. Morgan found K=2.610-8. The percentage degree of
electrolytic dissociation of hydrocyanic acid in decinormal solution is 0.011.

The catalytic influence of the cyanide ion in promoting the change of

benzaldehyde into benzoin has been studied by Stern, and the mechanism of the
addition of the elements of HCN to carbon compounds by Lap worth.
Cyanides

The cyanides of the alkali and alkaline earth metals are soluble in water and are
c.onsiderably ionised in solution. Other cyanides except mercuric cyanide are
insoluble.; Because of the weakness of hydrocyanic acid, mercuric cyanide shows,
to a greater degree than other mercuric salts, chemical inertness in solution owing
to feeble ionisation. Silver cyanide resembles silver chloride in physical properties;
it is a white, curdy precipitate, which, however, differs from the chloride by its
solubility in concentrated nitric acid. The solubility of silver cyanide in potassium
cyanide solution with the formation of KAg(CN)2, containing the anion Ag(CN)2',
illustrates an important general property of the cyanides, that of forming complex
cyanides. These are of different degrees of stability: from the least stable, as for
instance K2Ni(CN)4, dilute mineral acids reprecipitate the simple insoluble
cyanide; from the most stable, as for instance K4Fe(CN)6, the free, solid acid, e.g.
H4Fe(CN)6, is separated by mineral acid. The following list includes
representatives of the complex cyanides, which, like the ammines, are formed by
the members of the eighth and contiguous groups. These compounds will be dealt
with in detail under the respective metals.

Copper, silver, gold, and cadmium form the following complex cyanides:

K2Cu2(CN)4, K6Cu2(CN)8 KAg(CN)2

KAu(CN)2, HAu(CN)4 K2Cd(CN)4;

whilst chromium, manganese, and the metals of the eighth group form complex
cyanides of several different types, as the following table shows. Where the free
acid is known its formula appears.

H2M(CN)4 H4M(CN)6 H3M(CN)6

Cr

H4Cr(CN)6 K3Cr(CN)6

Mn

H4Mn(CN)6

Fe

H4Fe(CN)6 H3Fe(CN)6

Ni

K2Ni(CN)4

Co

H4Co(CN)6 H3Co(CN)6

Ru

H4Ru(CN)6

Rh

Pd

K2Pd(CN)4

Os

H4Os(CN)6

Ir

K4Ir(CN)6 H3Ir(CN)6

Pt

H2Pt(CN)4

K3Mn(CN)6

K3Rh(CN)6

Cyanogen Halides

Hydrogen cyanide, cyanogen halide, and a metallic cyanide may be formulated

respectively as:

H-CN, X-CN, M-CN or H-N=C, X-N=C, M-N=C.

The normal formulae, first given, have generally been preferred, because they
show the carbon atom to be quadrivalent, whilst the nitrogen atom is tervalent; but
there is a reason for preferring the iso formulae, in which hydrogen, halogen, or
metal is attached to nitrogen rather than to carbon.

The reactivity of halogen and hydrogen atoms attached to nitrogen is superior to

the reactivity of the same atoms attached to carbon; and a study of the cyanogen
halides shows them to possess all the characteristics of compounds having halogen
attached to nitrogen. This is borne out by such a reaction as the following:

C=N-Br + 2HI = C=N-H + HBr + I2,

which, being easy of achievement, is regarded as proving that bromine is attached

to nitrogen.

Now the cyanogen halides are readily formed from hydrocyanic acid and its salts,
which therefore in all probability have a similar composition, being iso
compounds, thus:

C=N-H and C=N-M.

Additive Compounds of Hydrogen Cyanide

When hydrogen chloride is passed into anhydrous hydrogen cyanide at - 10 C.,

and the solution is then heated to 35 C., the compound HCN.HCl is formed, and
crystallises on cooling. If hydrogen cyanide has the constitution :C:N-H, the
compound with HCl is . This compound is very hygroscopic and is decomposed by
water into formic acid and ammonium chloride, but may be sublimed. Another
compound, 2HCN.3HCl, exists which appears to be the hydrochloride of
dichlormethylformamidine, (NH=CH-NH-CHCl2).HCl.
Physiological Action of Hydrocyanic Acid

Hydrocyanic acid is one of the most powerful poisons known, and it is very rapid
in its action. An amount equal to 1/100000th part of the weight of its blood suffices
to kill a dog, and a few drops brought into a dog's eye kills the animal in thirty
seconds; 0.05 gram has proved a fatal dose for a man, though larger quantities have
been taken without fatal effects. The symptoms of poisoning by prussic acid are
headache, nausea, difficulty of breathing, palpitations, tetanic spasms affecting the
muscles of the jaws and limbs, paralysis, and insensibility.

The cause of the poisonous action of hydrocyanic acid and the soluble cyanides is
not known, but an analogy has been traced between this action and the inhibiting
effect of the same substance on catalysts such as ferments and colloidal metals.

Ammonia or chlorine water appears to serve as an antidote, though in neither case

is the chemical action understood.
Detection and Estimation

In cases of poisoning hydrocyanic acid is separated from the matter containing it

by distillation with tartaric acid. For the detection of small quantities of
hydrocyanic acid in aqueous solution several methods are available.

The cyanide may be converted into Prussian blue by boiling its solution with alkali
with the addition of ferrous and ferric salt. On acidifying ferric ferrocyanide
separates as a deep blue precipitate, or, if only a trace of cyanide was present,
shows a blue or green colour. By this test 1 part of cyanide in 50,000 can be
detected. Extremely dilute solutions of hydrogen cyanide containing as little as
0.00002 gram per c.c. may be made alkaline, evaporated to small bulk, and then
tested for in this way.
Conversion into nitroprusside, which gives a purple colour with alkali sulphide,
serves to detect 1 part of cyanide in 300,000.
By evaporation to dryness with yellow ammonium sulphide cyanide is converted
into thiocyanate, which gives a blood-red colour with ferric chloride. This test will
detect 1 part of cyanide in even 4,000,000 parts of solution.
Cyanide solution gives a deep red colour with picric acid.
Cyanide is estimated volumetrically by adding to its alkaline solution

standard silver nitrate solution until a permanent precipitate appears. One molecule
of silver nitrate then corresponds to two molecules of cyanide owing to the
formation of KAg(CN)2, according to the reaction:

AgNO3 + 2KCN = KAg(CN)2 + KNO3.

The estimation may be carried out gravimetrically by weighing the corresponding

silver cyanide, or by reducing it and weighing the metallic silver.