Potassium cyanide

Potassium cyanide
Names
IUPAC name
Potassium cyanide
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.005.267
EC Number 205-792-3
RTECS number TS8750000
UNII
UN number 1680
Properties
KCN
Molar mass 65.12 g/mol
Appearance White crystalline solid
deliquescent
Odor faint, almond-like
Density 1.52 g/cm3
Melting point 634.5 °C (1,174.1 °F; 907.6 K)
Boiling point 1,625 °C (2,957 °F; 1,898 K)
71.6 g/100 ml (25 °C)
100 g/100 mL (100 °C)
Solubility in methanol 4.91 g/100 mL (20 °C)
Solubility in glycerol soluble
Solubility in formamide 14.6 g/100 mL
Solubility in ethanol 0.57 g/100mL
Solubility in hydroxylamine 41 g/100 mL
Acidity (pKa) 11.0
37.0·10−6 cm3/mol
1.410
Thermochemistry
127.8 JK1mol1
131.5 kJ/mol
Hazards
Safety data sheet ICSC 0671
GHS pictograms
GHS signal word Danger
H290, H300, H310, H330, H370, H372, H410
P260, P264, P273, P280, P284, P301+310
NFPA 704
0
4
0
Flash point Non-flammable
Lethal dose or concentration (LD, LC):
5 mg/kg (oral, rabbit)
10 mg/kg (oral, rat)
5 mg/kg (oral, rat)
8.5 mg/kg (oral, mouse)[1]
US health exposure limits (NIOSH):
PEL (Permissible)
TWA 5 mg/m3[2]
REL (Recommended)
C 5 mg/m3 (4.7 ppm) [10-minute][2]
IDLH (Immediate danger)
25 mg/m3[2]
Related compounds
Other anions
Potassium cyanate
Potassium thiocyanate
Other cations
Sodium cyanide
Related compounds
Hydrogen cyanide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
N verify (what is YN ?)
Infobox references

Potassium cyanide is a compound with the formula KCN. This colorless crystalline salt, similar in appearance to sugar, is highly soluble in water. Most KCN is used in gold mining, organic synthesis, and electroplating. Smaller applications include jewelry for chemical gilding and buffing.[3]

Potassium cyanide is highly toxic. The moist solid emits small amounts of hydrogen cyanide due to hydrolysis, which smells like bitter almonds.[4] Not everyone, however, can smell this; the ability to do so is a genetic trait.[5]

The taste of potassium cyanide has been described as acrid with a burning sensation.[6]

Production

KCN is produced by treating hydrogen cyanide with aqueous solution of potassium hydroxide, followed by evaporation of the solution in a vacuum:[7]

HCN + KOH → KCN + H2O

or by treating formamide with potassium hydroxide:

HCONH2 + KOH → KCN + 2H2O

About 50,000 tons of potassium cyanide are produced yearly.[3]

Historical production

Prior to 1900, before the invention of the Castner process, potassium cyanide was the most important source of alkali metal cyanides.[3] In this historical process, potassium cyanide was produced by decomposing potassium ferrocyanide:[8]

K4[Fe(CN)6] → 4 KCN + FeC2 + N2

Structure

In aqueous solution, KCN is dissociated into hydrated potassium (K+) ions and cyanide (CN) ions. The common form of solid KCN, stable at ambient pressure and temperature, has the same cubic crystal structure as sodium chloride, with each potassium ion surrounded by six cyanide ions, and vice versa. Despite the cyanide ions being diatomic, and thus less symmetric than chloride, they rotate so rapidly, their time-averaged shape is spherical. At low temperature and high pressure, this free rotation is hindered, resulting in a less symmetric crystal structure with the cyanide ions arranged in sheets. [9][10]

Applications

KCN and sodium cyanide (NaCN) are widely used in organic synthesis for the preparation of nitriles and carboxylic acids, particularly in the von Richter reaction. It also finds use for the synthesis of hydantoins, which can be useful synthetic intermediates, when reacted with a carbonyl compound such as an aldehyde or ketone in the presence of ammonium carbonate.

KCN is used as a photographic fixer in the wet plate collodion process.[11] The KCN dissolves silver where it has not been made insoluble by the developer. This reveals and stabilizes the image, making it no longer sensitive to light. Modern wet plate photographers may prefer less toxic fixers, often opting for the less toxic Sodium thiosulphate, but KCN is still used.

Potassium gold cyanide

In gold mining, KCN forms the water-soluble salt potassium gold cyanide (or gold potassium cyanide) and potassium hydroxide from gold metal in the presence of oxygen (usually from the surrounding air) and water:

4 Au + 8 KCN + O2 + 2 H2O → 4 K[Au(CN)2] + 4 KOH

A similar process uses NaCN to produce sodium gold cyanide (NaAu(CN2)).

Toxicity

Potassium cyanide is a potent inhibitor of cellular respiration, acting on mitochondrial cytochrome c oxidase, hence blocking oxidative phosphorylation. This prevents the body from oxidizing food to produce useful energy. Lactic acidosis then occurs as a consequence of anaerobic metabolism. Initially, acute cyanide poisoning causes a red or ruddy complexion in the victim because the tissues are not able to use the oxygen in the blood. The effects of potassium and sodium cyanide are identical, and symptoms of poisoning typically occur within a few minutes of ingesting the substance: the person loses consciousness, and brain death eventually follows. During this period the victim may suffer convulsions. Death is caused by cerebral hypoxia.

The lethal dose(human) for potassium cyanide is 20 mg.[12] Its toxicity when ingested depends on the acidity of the stomach, because it must react with an acid to become hydrogen cyanide, the deadly form of cyanide. Grigori Rasputin may have survived a potassium cyanide poisoning because his stomach acidity was unusually low.[13]

A number of prominent persons were killed or committed suicide using potassium cyanide, including members of the Young Bosnia and famous personalities in the Third Reich, such as Erwin Rommel, Hitler's longtime companion Eva Braun, Joseph Goebbels, Heinrich Himmler, and Hermann Göring. World War II era British agents (using purpose-made suicide pills), computer scientist Alan Turing, polymer chemist Wallace Carothers, 19th-Century German chemist Viktor Meyer,[14], and various religious cult suicides such as by the Peoples Temple, Danish writer Gustav Wied in 1914, and members of the LTTE involved in the assassination of Indian prime minister Rajiv Gandhi. Jason Altom, who was a promising graduate student in the lab of Nobel-Prizewinning chemist EJ Corey at Harvard. Slobodan Praljak, a Wartime general in Republic of Croatia, committed suicide by drinking from a vial containing potassium cyanide during the reading of his sentence in The Hague on International Criminal Tribunal for the former Yugoslavia (ICTY) on 29 November 2017.[15]

It is used by professional entomologists as a killing agent in collecting jars, as insects succumb within seconds to the HCN fumes it emits, thereby minimizing damage to even highly fragile specimens.

KCN can be detoxified most efficiently with hydrogen peroxide or with a solution of sodium hypochlorite. Such solutions should be kept basic whenever possible so as to eliminate the possibility of generation of hydrogen cyanide:[3]

KCN + H2O2 → KOCN + H2O

References

  1. "Cyanides (as CN)". Immediately Dangerous to Life and Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  2. 1 2 3 "NIOSH Pocket Guide to Chemical Hazards #0522". National Institute for Occupational Safety and Health (NIOSH).
  3. 1 2 3 4 Andreas Rubo, Raf Kellens, Jay Reddy, Joshua Wooten, Wolfgang Hasenpusch "Alkali Metal Cyanides" in Ullmann's Encyclopedia of Industrial Chemistry 2006 Wiley-VCH, Weinheim, Germany. doi:10.1002/14356007.i01_i01
  4. http://www.smh.com.au/news/world/suicide-note-reveals-taste-of-cyanide/2006/07/08/1152240534587.html
  5. Online Mendelian Inheritance in Man (OMIM) 304300
  6. "The only taste: Cyanide is acrid". hindustantimes.com. Hindustan Times.
  7. Pradyot Patnaik. Handbook of Inorganic Chemicals. McGraw-Hill, 2002, ISBN 0-07-049439-8
  8. Von Wagner, Rudolf (1897). Manual of chemical technology. New York: D. Appleton & Co. p. 474 & 477.
  9. Crystallography Open Database, Structure of KCN
  10. H. T. Stokes; D. L. Decker; H. M. Nelson; J. D. Jorgensen (1993). "Structure of potassium cyanide at low temperature and high pressure determined by neutron diffraction". Physical Review B. 47 (17): 11082–11092. doi:10.1103/PhysRevB.47.11082..
  11. J. Towler, MD. "The Silver Sunbeam (Facsimile 1864 edition, 1969)" pg 119
  12. John Harris Trestrail III. Criminal Poisoning - Investigational Guide for Law Enforcement, Toxicologists, Forensic Scientists, and Attorneys (2nd edition). pg 119
  13. John Emsley. The Elements of Murder: A History of Poison. pg 73
  14. http://listverse.com/2007/10/07/top-10-scientists-who-committed-suicide/
  15. "War criminal 'took cyanide' in Hague court". BBC News. 2017-12-01. Retrieved 2017-12-01.
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