Silver carbonate

Silver carbonate
Names


IUPAC name Silver(I) carbonate
Other names Argentous carbonate
Identifiers
CAS Number	534-16-7^Y
3D model (JSmol)	Interactive image
ChemSpider	83768^Y
ECHA InfoCard	100.007.811
EC Number	208-590-3
MeSH	silver+carbonate
PubChem CID	92796
UNII	V9WU3IKN4Q^N
CompTox Dashboard (EPA)	DTXSID9042384
InChI InChI=1S/CH2O3.2Ag/c2-1(3)4;;/h(H2,2,3,4);;/q;2+1/p-2^Y Key: KQTXIZHBFFWWFW-UHFFFAOYSA-L^Y InChI=1/CH2O3.2Ag/c2-1(3)4;;/h(H2,2,3,4);;/q;2+1/p-2 Key: KQTXIZHBFFWWFW-NUQVWONBAD
SMILES [Ag]OC(=O)O[Ag]
Properties
Chemical formula	Ag₂CO₃
Molar mass	275.75 g/mol
Appearance	Pale yellow crystals
Odor	Odorless
Density	6.077 g/cm³^[1]
Melting point	218 °C (424 °F; 491 K) decomposes from 120 °C^[1]^[4]
Solubility in water	0.031 g/L (15 °C) 0.032 g/L (25 °C) 0.5 g/L (100 °C)^[2]
Solubility product (K_sp)	8.46·10⁻¹²^[1]
Solubility	Insoluble in ethanol, liquid ammonia, acetates, acetone^[3]
Magnetic susceptibility (χ)	−80.9·10⁻⁶ cm³/mol^[1]
Structure
Crystal structure	Monoclinic, mP12 (295 K) Trigonal, hP36 (β-form, 453 K) Hexagonal, hP18 (α-form, 476 K)^[5]
Space group	P2₁/m, No. 11 (295 K) P31c, No. 159 (β-form, 453 K) P62m, No. 189 (α-form, 476 K)^[5]
Point group	2/m (295 K) 3m (β-form, 453 K) 6m2 (α-form, 476 K)^[5]
Lattice constant	a = 4.8521(2) Å, b = 9.5489(4) Å, c = 3.2536(1) Å (295 K)^[5] α = 90°, β = 91.9713(3)°, γ = 90°
Thermochemistry
Heat capacity (C)	112.3 J/mol·K^[1]
Std molar entropy (S^⦵₂₉₈)	167.4 J/mol·K^[1]
Std enthalpy of formation (Δ_fH^⦵₂₉₈)	−505.8 kJ/mol^[1]
Gibbs free energy (Δ_fG^⦵)	−436.8 kJ/mol^[1]^[4]
Hazards
Occupational safety and health (OHS/OSH):
Inhalation hazards	Irritant
GHS labelling:^[7]
Pictograms
Signal word	Danger
Hazard statements	H315, H319, H335
Precautionary statements	P261, P305+P351+P338
NFPA 704 (fire diamond)	^[6] 0 0 0
Lethal dose or concentration (LD, LC):
LD₅₀ (median dose)	3.73 g/kg (mice, oral)^[6]
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

Chemical compound

Silver carbonate is the chemical compound with the formula Ag₂CO₃. This salt is yellow but typical samples are grayish due to the presence of elemental silver. It is poorly soluble in water, like most transition metal carbonates.

Preparation and reactions

Silver carbonate can be prepared by combining aqueous solutions of sodium carbonate with a deficiency of silver nitrate.^[8]

{\ce {2 AgNO3(aq) + Na2CO3(aq) -> Ag2CO3(s) + 2 NaNO3(aq)}}

Freshly prepared silver carbonate is colourless, but the solid quickly turns yellow.^[9]

Silver carbonate reacts with ammonia to give the diamminesilver(I) ([Ag(NH₃)₂]⁺) complex ion. Like other diamminesilver(I) solutions, including Tollen's reagent, there is a possibility that explosive Silver nitride may precipitate out of the solution. Silver nitride was previously known as fulminating silver but due to confusions with silver fulminate it has been discontinued by the IUPAC.^[10]

With hydrofluoric acid, it gives silver fluoride.

The thermal conversion of silver carbonate to silver metal proceeds via formation of silver oxide:^[11]

{\ce {Ag2CO3 -> Ag2O + CO2}}

{\ce {2 Ag2O ->4 Ag + O2}}

Uses

The principal use of silver carbonate is for the production of silver powder for use in microelectronics. It is reduced with formaldehyde, producing silver free of alkali metals:^[9]

{\ce {Ag2CO3 + CH2O -> 2 Ag + 2 CO2 + H2}}

Organic synthesis

Silver carbonate is used as a reagent in organic synthesis.^[12] In the Fétizon oxidation, silver carbonate on Celite^[13] serves as an oxidising agent to form

aldehydes from primary alcohols

ketones from secondary alcohols

keto-alcohols from diols

ketones from hydroxymethyl compounds

In the Koenigs-Knorr reaction it is used to convert alkyl bromides to the methyl ethers. It is also employed to convert alkyl bromides into alcohols.^[8] As a base, it has been used in the Wittig reaction.^[14] and in C-H bond activation.^[15]

References

^ ^a ^b ^c ^d ^e ^f ^g ^h Lide, David R., ed. (2009). CRC Handbook of Chemistry and Physics (90th ed.). Boca Raton, Florida: CRC Press. ISBN 978-1-4200-9084-0.
^ Seidell, Atherton; Linke, William F. (1919). Solubilities of Inorganic and Organic Compounds (2nd ed.). New York City: D. Van Nostrand Company. p. 605.
^ Comey, Arthur Messinger; Hahn, Dorothy A. (February 1921). A Dictionary of Chemical Solubilities: Inorganic (2nd ed.). New York: The MacMillan Company. p. 203.
^ ^a ^b Anatolievich, Kiper Ruslan. "silver nitrate". chemister.ru. Retrieved 2014-07-21.
^ ^a ^b ^c ^d Norby, P.; Dinnebier, R.; Fitch, A.N. (2002). "Decomposition of Silver Carbonate; the Crystal Structure of Two High-Temperature Modifications of Ag₂CO₃". Inorganic Chemistry. 41 (14): 3628–3637. doi:10.1021/ic0111177. PMID 12099865.
^ ^a ^b "Silver Carbonate MSDS". saltlakemetals.com. Salt Lake City, Utah: Salt Lake Metals. Retrieved 2021-08-05.
^ Sigma-Aldrich Co., Silver carbonate. Retrieved on 2021-08-05.
^ ^a ^b McCloskey C. M.; Coleman, G. H. (1955). "β-d-Glucose-2,3,4,6-Tetraacetate". Organic Syntheses; Collected Volumes, vol. 3, p. 434.
^ ^a ^b Andreas Brumby et al. "Silver, Silver Compounds, and Silver Alloys" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2008. doi:10.1002/14356007.a24_107.pub2
^ Brumby, Andreas; Braumann, Peter; Zimmermann, Klaus; Brodeck, Francis; Vandevelde, Thierry; Goia, Dan; Renner, Hermann; Schlamp, Gunter; Zimmermann, Klaus; Weise, Wolfgang; Tews, Peter; Dermann, Klaus; Knodler, Alfons; Schroder, Karl-Heinz; Kempf, Bernd; Luschow, Hans; Peter, Cartrin; Schiele, Rainer (2008). Ullmann's Encyclopedia of Industrial Chemistry. p. 49. doi:10.1002/14356007.a24_107.pub2. ISBN 9783527306732. Retrieved 2020-12-24.
^ Koga, Nobuyoshi; Shuto Yamada; Tomoyasu Kimura (2013). "Thermal Decomposition of Silver Carbonate: Phenomenology and Physicogeometrical Kinetics". The Journal of Physical Chemistry C. 117: 326–336. doi:10.1021/jp309655s.
^ Ladd, Carolyn L. (2001). "Silver(I) Carbonate". Encyclopedia of Reagents for Organic Synthesis. pp. 1–10. doi:10.1002/047084289X.rn01865. ISBN 978-0-470-84289-8.
^ Fétizon, Marcel; Li, Yiming; Jiang, Xuefeng (2017). "Silver(I) Carbonate on Celite". Encyclopedia of Reagents for Organic Synthesis. pp. 1–19. doi:10.1002/047084289X.rs014.pub2. ISBN 978-0-470-84289-8.
^ Jedinak, Lukas et al. “Use of Silver Carbonate in the Wittig Reaction.” The Journal of Organic Chemistry 78.23 (2013): 12224–12228 https://doi.org/10.1021/jo401972a.
^ J. Org. Chem., 2018, 83 (16), pp 9312–9321 https://doi.org/10.1021/acs.joc.8b01284.