Chemistry:Silver cyanide

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Silver cyanide
Silver cyanide
Names
IUPAC name
Silver cyanide
Other names
Argentous cyanide
Identifiers
3D model (JSmol)
ChemSpider
EC Number
  • 208-048-6
RTECS number
  • VW3850000
UNII
UN number 1684
Properties
AgCN
Molar mass 133.8856 g/mol
Appearance colorless, gray (impure) crystals
Odor odorless
Density 3.943 g/cm3
Melting point 335 °C (635 °F; 608 K) (decomposes)
0.000023 g/100 mL (20 °C)
5.97×10−17[1]
Solubility soluble in concentrated ammonia, boiling nitric acid, ammonium hydroxide, KCN
insoluble in alcohol, dilute acid
−43.2·10−6 cm3/mol
1.685
Structure
hexagonal
linear
Thermochemistry
84 J·mol−1·K−1[2]
146 kJ·mol−1[2]
Hazards
Main hazards toxic
GHS pictograms GHS05: CorrosiveGHS06: ToxicGHS09: Environmental hazard
GHS Signal word Danger
H290, H300, H310, H315, H318, H330, H410
P234, P260, P262, P264, P270, P271, P273, P280, P284, P301+310, P302+350, P302+352, P304+340, P305+351+338, P310, P320, P321, P322, P330, P332+313, P361, P362, P363, P390, P391
NFPA 704 (fire diamond)
Flammability code 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g. canola oilHealth code 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasReactivity code 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g. calciumSpecial hazards (white): no codeNFPA 704 four-colored diamond
1
3
1
Flash point 320 °C (608 °F; 593 K)
Lethal dose or concentration (LD, LC):
123 mg/kg (oral, rat)
Related compounds
Other anions
AgCl
Other cations
NaCN
Copper(I) cyanide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

Silver cyanide is the chemical compound with the formula AgCN. It is a white salt that is precipitated upon treatment of solutions containing Ag+ with cyanide, which is used in some schemes to recover silver from solution. Silver cyanide is used in silver-plating.

Structure

The structure of silver cyanide consists of -[Ag-CN]- chains in which the linear two-coordinate Ag+ ions are bridged by the cyanide ions,[3] typical of silver(I) and other d10 ions. This is the same binding mode as seen in the more famous case of Prussian blue. These chains then pack hexagonally with adjacent chains offset by +/- 1/3 of the c lattice parameter. This is the same as the structure adopted by the high temperature polymorph of copper(I) cyanide. The silver to carbon and silver to nitrogen bond lengths in AgCN are both ~2.06 Å[4] and the cyanide groups show head-to-tail disorder.[5]

Reactions

AgCN precipitates upon the addition of sodium cyanide to a solution containing Ag+. On the addition of further cyanide, the precipitate dissolves to form linear [Ag(CN)2](aq) and [Ag(CN)3]2−(aq). Silver cyanide is also soluble in solutions containing other ligands such as ammonia or tertiary phosphines.

Silver cyanides form structurally complex materials upon reaction with other anions.[6] Some silver cyanides are luminescent.[7]

Uses

"Cyanidation" is widely used in the isolation of silver from its ores. Partial purification of silver compounds is usually effected by froth flotation. The silver ion is then separated from the skimmed froth with cyanide, yielding a solution of [Ag(CN)2]. The silver metal can then be plated out by electrolysis of such solutions.[8]

Both AgCN and KAg(CN)2 have been used in silver-plating solutions since at least 1840 when the Elkington brothers patented their recipe for a silver-plating solution. A typical, traditional silver-plating solution would contain 15-40 g·L−1 KAg(CN)2 , 12-120 g·L−1 KCN and 15 g·L−1 K2CO3.[9]

See also

  • List of compounds with carbon number 1

References

  1. John Rumble (June 18, 2018) (in English). CRC Handbook of Chemistry and Physics (99 ed.). CRC Press. pp. 5–189. ISBN 978-1138561632. 
  2. 2.0 2.1 Zumdahl, Steven S. (2009). Chemical Principles 6th Ed.. Houghton Mifflin Company. p. A23. ISBN 978-0-618-94690-7. 
  3. Bowmaker, Graham A.; Kennedy, Brendan J.; Reid, Jason C. (1998). "Crystal Structures of AuCN and AgCN and Vibrational Spectroscopic Studies of AuCN, AgCN, and CuCN". Inorg. Chem. 37 (16): 3968–3974. doi:10.1021/ic9714697. PMID 11670511. 
  4. Hibble, S. J.; Cheyne, S. M.; Hannon, A. C.; Eversfield, S. G. (2002). "Beyond Bragg scattering: the structure of AgCN determined from total neutron diffraction". Inorganic Chemistry 41 (5): 1042–1044. doi:10.1021/ic015610u. PMID 11874335. 
  5. Bryce, David L.; Wasylishen, Roderick E. (2002). "Insight into the Structure of Silver Cyanide from 13C and 15N Solid-State NMR Spectroscopy" (in en). Inorganic Chemistry 41 (16): 4131–4138. doi:10.1021/ic0201553. ISSN 0020-1669. PMID 12160400. 
  6. Urban, Victoria; Pretsch, Thorsten; Hartl, Hans (2005-04-29). "From AgCN Chains to a Fivefold Helix and a Fishnet-Shaped Framework Structure" (in en). Angewandte Chemie International Edition 44 (18): 2794–2797. doi:10.1002/anie.200462793. ISSN 1433-7851. PMID 15830404. 
  7. Omary, Mohammad A.; Webb, Thomas R.; Assefa, Zerihun; Shankle, George E.; Patterson, Howard H. (1998). "Crystal Structure, Electronic Structure, and Temperature-Dependent Raman Spectra of Tl[Ag(CN)2]: Evidence for Ligand-Unsupported Argentophilic Interactions" (in en). Inorganic Chemistry 37 (6): 1380–1386. doi:10.1021/ic970694l. ISSN 0020-1669. PMID 11670349. 
  8. Etris, S. F. (2010). "Silver and Silver Alloys". Kirk-Othmer Encyclopedia of Chemical Technology. pp. 1–43. doi:10.1002/0471238961.1909122205201809.a01.pub3. ISBN 978-0471238966. 
  9. Blair, Alan (2000). "Silver plating" (in en). Metal Finishing 98 (1): 298–303. doi:10.1016/S0026-0576(00)80339-6.