Silver cyanide

Silver cyanide is the chemical compound with the formula AgCN. It is a white solid that 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.

Silver cyanide
Names
IUPAC name
Silver cyanide
Other names
Argentous cyanide
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.007.317
RTECS number
  • VW3850000
UNII
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)
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[1]
Std enthalpy of
formation (ΔfH⦵298)
 146 kJ·mol−1[1]
Hazards
Main hazards toxic
R-phrases (outdated) 25-32-33-41-50/53
S-phrases (outdated) 7-26-45-60-61
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 code
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).
N verify (what is YN ?)
Infobox references

Structure

Its structure consist of -[Ag-CN]- chains in which the linear two-coordinate Ag+ ions are bridged by the cyanide ions, 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 ~2.09 Å[2] and the cyanide groups show head-to-tail disorder.[3]

Reactions

AgCN precipitates upon the addition of sodium cyanide to a solution containing Ag+. The precipitate dissolves upon the addition of further amounts of cyanide to form linear [Ag(CN)2]−(aq) and [Ag(CN)3]2−(aq) on the addition of further cyanide. 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.[4] Some silver cyanides are luminescent.[5]

Uses

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.[6]

See also

References
  1. Zumdahl, Steven S. (2009). Chemical Principles 6th Ed. Houghton Mifflin Company. p. A23. ISBN 0-618-94690-X.
  2. Hibble, S. J.; Cheyne, S. M.; Hannon, A. C.; Eversfield, S. G.“Beyond Bragg scattering: the structure of AgCN determined from total neutron diffraction” Inorganic Chemistry 2002, volume 41, pages 1042.
  3. Bryce, David L.; Wasylishen, Roderick E. (2002). "Insight into the Structure of Silver Cyanide from 13C and 15N Solid-State NMR Spectroscopy". Inorganic Chemistry. 41 (16): 4131–4138. doi:10.1021/ic0201553. ISSN 0020-1669.
  4. Urban, Victoria; Pretsch, Thorsten; Hartl, Hans (2005-04-29). "From AgCN Chains to a Fivefold Helix and a Fishnet-Shaped Framework Structure". Angewandte Chemie International Edition. 44 (18): 2794–2797. doi:10.1002/anie.200462793. ISSN 1433-7851.
  5. 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". Inorganic Chemistry. 37 (6): 1380–1386. doi:10.1021/ic970694l. ISSN 0020-1669.
  6. Blair, Alan (2000). "Silver plating". Metal Finishing. 98 (1): 298–303. doi:10.1016/S0026-0576(00)80339-6.
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