Hydrogen cyanide

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Hydrogen cyanide
General
Systematic name	Hydrogen cyanide
Other names	Hydrocyanic acid prussic acid, formonitrile formic anammonide carbon hydride nitride cyclon
Molecular formula	HCN
SMILES	C#N
Molar mass	27.03 g/mol
Appearance	Colorless gas or pale blue highly volatile liquid
CAS number	[74-90-8]
Properties
Density and phase	0.687 g/cm3, liquid.
Solubility in water	Completely miscible.
Melting point	-13.4°C (259.75 K, 7.88°F)
Boiling point	26°C (299.15 K, 78.8°F)
Acidity (pKa)	9.2 - 9.3
Structure
Molecular shape	Linear
Dipole moment	2.98 D
Hazards
MSDS	External MSDS
Main hazards	Highly toxic, highly flammable.
NFPA 704	4 4 2
Flash point	−17.78 °C
Autoignition	538 °C
R/S statement	R: R12, R26, R27, R28, R32. S: S1, S2, S7, S9, S13, S16, S28, S29, S45.
RTECS number	MW6825000
Supplementary data page
Structure and properties	n, εr, etc.
Thermodynamic data	Phase behaviour Solid, liquid, gas
Spectral data	UV, IR, NMR, MS
Related compounds
Other anions	Hydrogen fluoride
Other cations	Sodium cyanide Potassium cyanide
Related compounds	Cyanogen Cyanogen chloride trimethylsilyl cyanide
Except where noted otherwise, data are given for materials in their standard state (at 25°C, 100 kPa) Infobox disclaimer and references

Hydrogen cyanide is a chemical compound with chemical formula HCN. A solution of hydrogen cyanide in water is called hydrocyanic acid. Hydrogen cyanide is a colorless, very poisonous, and highly volatile liquid that boils slightly above room temperature at 26 °C. HCN has a faint, bitter, almond-like odor that some people are unable to detect due to a genetic trait.^[1] Hydrogen cyanide is weakly acidic and partly ionizes in solution to give the cyanide anion, CN^–. The salts of hydrogen cyanide are known as cyanides. HCN is a highly valuable precursor to many chemical compounds ranging from polymers to pharmaceuticals.

Contents 1 Production and synthesis 2 Reactions 3 Occurrence and applications 4 HCN and the origin of life 5 Hydrogen cyanide as a chemical weapon 6 Sources 7 See also 8 External links

[edit] Production and synthesis

Currently hydrogen cyanide is produced in large quantities by three processes. In the year 2000, 1615 million pounds (732,552 tons) were produced in the US.[3] The most important process for the production of hydrogen cyanide is the Andrussov oxidation invented by Leonid Andrussow in which methane and ammonia react in the presence of oxygen at about 1200 °C over a platinum catalyst:^[2]

CH₄ + NH₃ + 1.5O₂ → HCN + 3H₂O

The energy needed for the reaction is provided by the part oxidation of methane and ammonia.

Of lesser importance is the Degussa process (BMA process) in which no oxygen is added and the energy must be transferred indirectly through the reactor wall:^[3]

CH₄ + NH₃ → HCN + 3H₂

This reaction is akin to steam reforming, the reaction of methane and water. In another process, practiced at BASF, formamide is heated and split into hydrogen cyanide and water:

CH(O)NH₂ → HCN + H₂O

In the laboratory, small amounts of HCN are produced by the addition of acids to cyanide salts of alkali metals:

H⁺ + NaCN → HCN + Na⁺

This reaction is sometimes the basis of accidental poisonings because the acid converts a nonvolatile cyanide salt into the gaseous HCN.

[edit] Reactions

HCN adds to ketones and aldehydes to give cyanohydrins. Amino acids are prepared by this reaction; the essential amino acid methionine is manufactured by this route.The cyanohydrin of acetone is a precursor to methyl methacrylate.^{[citation needed]}

In hydrocyanation, HCN adds to alkenes to give nitriles. This reaction is employed to manufacture of adiponitrile, the precursor to Nylon 66.

[edit] Occurrence and applications

Cyanide is used in tempering steel, dyeing, explosives, engraving, capital punishment, the production of acrylic resin plastic, and other organic chemical products (eg: historically: formic acid). The less toxic ethyl acetate (C₄H₈O₂) has now largely replaced the use of cyanide in insect killing jars.

Fruits that have a pit, such as cherries and apricots, bitter almonds and apples, from which almond oil and flavoring are made, contain small amounts of cyanohydrins such as mandelonitrile (CAS#532-28-5). Such molecules slowly release hydrogen cyanide.^[4],[5] Some millipedes release hydrogen cyanide as a defense mechanism^[6], as do certain insects such as some burnet moths. Hydrogen cyanide is contained in the exhaust of vehicles, in tobacco and wood smoke, and in smoke from burning nitrogen-containing plastics. Cyanide may be a cause of morbidity and mortality in fires.^{[citation needed]}

100g of crushed apple seeds can yield 217mg of Amygdalin which can generate ~10mg of HCN.^{[citation needed]}

[edit] HCN and the origin of life

Hydrogen cyanide has been discussed as a precursor to amino acids and nucleic acids. It is possible, for example, that HCN played a part in the origin of life. Leslie Orgel, among many researchers, has written extensively on the condensation of HCN.^[7] Although the relationship of these chemical reactions to the origin of life remains speculative, studies in this area have led to discoveries of new pathways to organic compounds derived from condensation of HCN.^[8]

[edit] Hydrogen cyanide as a chemical weapon

An HCN concentration of 300 parts per million in air will kill a human within a few minutes. The toxicity is caused by the cyanide ion, which prevents cellular respiration. Hydrogen cyanide (under the brand name Zyklon B) was perhaps most infamously employed by the Nazi regime in mid-20th century as a method of mass murder.

Hydrogen cyanide is commonly listed amongst chemical warfare agents which cause general poisoning.^[9] As a substance listed under Schedule 3 of the Chemical Weapons Convention as a potential weapon which has large-scale industrial uses, manufacturing plants in signatory countries which produce more than 30 tonnes per year must be declared to, and can be inspected by, the OPCW.

Although there have been no verified instances of this compound being used as a weapon, it has been reported that hydrogen cyanide may have been employed by Iraq in the war against Iran and against the Kurds in northern Iraq during the 1980s^[10].

In 1995 a device was discovered in a restroom in the Kayabacho Tokyo subway station consisting of bags of sodium cyanide and sulfuric acid with a remote controlled motor to rupture them in what was believed to be an attempt to produce toxic amounts of hydrogen cyanide gas by the Aum Shinrikyo cult^[11] . In 2003, Al Qaeda reportedly planned to attack the New York City Subway using hydrogen cyanide gas but aborted the attack for unknown reasons. ^[12]

Hydrogen cyanide gas in air is explosive at concentrations over 56,000 ppm^[13].

[edit] Sources

1. ^ Online Mendelian Inheritance in Man, Cyanide, inability to smell
2. ^ L. Andrussow (1935). "The catalytic oxydation of ammonia-methane-mixtures to hydrogen cyanide.". Angewandte Chemie 48: 593-595. 
3. ^ F. Endter (1958). "Die technische Synthese von Cyanwasserstoff aus Methan und Ammoniak ohne Zusatz von Sauerstoff". Chemie Ingenieur Technik 30 (5): 281-376. DOI:10.1002/cite.330300506. 
4. ^ J. Vetter (2000). "Plant cyanogenic glycosides". Toxicon. 38: 11-36. DOI:10.1016/S0041-0101(99)00128-2. 
5. ^ D. A. Jones (1998). "Why are so many food plants cyanogenic?". Phytochemistry 47: 155-162. DOI:10.1016/S0031-9422(97)00425-1. 
6. ^ M. S. Blum, J. P. Woodring (1962). "Secretion of Benzaldehyde and Hydrogen Cyanide by the Millipede Pachydesmus crassicutis (Wood)". Science 138: 512 - 513. DOI:10.1126/science.138.3539.512. 
7. ^ Matthews, C. N. "The HCN World: Establishing Protein-Nucleic Acid Life via Hydrogen Cyanide Polymers" Cellular Origin and Life in Extreme Habitats and Astrobiology (2004), 6 (Origins : Genesis, Evoluation and Diversity of Life), 121-135.
8. ^ Al-Azmi, A.; Elassar, A.-Z. A.; Booth, B. L. "The Chemistry of Diaminomaleonitrile and its Utility in Heterocyclic Synthesis" Tetrahedron (2003), 59, 2749-2763. CODEN: TETRAB ISSN:0040-4020
9. ^ Hydrogen Cyanide. Organization for the Prohibition of Chemical Weapons. Retrieved on October 7, 2006.
10. ^ http://www.bt.cdc.gov/agent/cyanide/basics/facts.asp
11. ^ Chronology of Aum Shinrikyo's CBW Activities (pdf).
12. ^ http://www.time.com/time/magazine/article/0,9171,1205478,00.html
13. ^ [1]

• Institut national de recherche et de sécurité (1997). "Cyanure d'hydrogène et solutions aqueuses". Fiche toxicologique n° 4, Paris:INRS, 5pp. (PDF file, in French)

[edit] See also

• Cyanide

[edit] External links

• International Chemical Safety Card 0492
• Hydrogen cyanide and cyanides (CICAD 61)
• National Pollutant Inventory - Cyanide compounds fact sheet
• NIOSH Pocket Guide to Chemical Hazards
• European Chemicals Bureau
• Department of health review
• OSHA: HCN Health Guidelines
• Links to external chemical sources

This article forms part of the series Chemical warfare
Blood agents:	Cyanogen chloride (CK) – Hydrogen cyanide (AC)
Blister agents:	Lewisite (L) – Sulfur mustard gas (HD, H, HT, HL, HQ) – Nitrogen mustard gas (HN1, HN2, HN3)
Nerve agents:	G-Agents: Tabun (GA) – Sarin (GB) – Soman (GD) – Cyclosarin (GF) – GV | V-Agents: VE – VG – VM – VX | Novichok agents
Pulmonary agents:	Chlorine – Chloropicrin (PS) – Phosgene (CG) – Diphosgene (DP)
Incapacitating agents:	Agent 15 (BZ) – KOLOKOL-1
Riot control agents:	Pepper spray (OC) – CS gas – CN gas (mace) – CR gas	v • d • e