Silver compounds

Silver is a relatively unreactive metal, although it can form several compounds. The common oxidation states of silver are (in order of commonness): +1 (the most stable state; for example, silver nitrate, AgNO3); +2 (highly oxidising; for example, silver(II) fluoride, AgF2); and even very rarely +3 (extreme oxidising; for example, potassium tetrafluoroargentate(III), KAgF4). The +3 state requires very strong oxidising agents to attain, such as fluorine or peroxodisulfate, and some silver(III) compounds react with atmospheric moisture and attack glass. Indeed, silver(III) fluoride is usually obtained by reacting silver or silver monofluoride with the strongest known oxidizing agent, krypton difluoride.

Oxides and chalcogenides

Oxides

Silver and gold have rather low chemical affinities for oxygen, lower than copper, and it is therefore expected that silver oxides are thermally quite unstable. Soluble silver(I) salts precipitate dark-brown silver(I) oxide, Ag2O, upon the addition of alkali. (The hydroxide AgOH exists only in solution; otherwise it spontaneously decomposes to the oxide.) Silver(I) oxide is very easily reduced to metallic silver, and decomposes to silver and oxygen above 160 °C. This and other silver(I) compounds may be oxidized by the strong oxidizing agent peroxodisulfate to black AgO, a mixed silver(I,III) oxide of formula AgIAgIIIO2. Some other mixed oxides with silver in non-integral oxidation states, namely Ag2O3 and Ag3O4, are also known, as is Ag3O which behaves as a metallic conductor.

Other chalcogenides Silver(I) sulfide, Ag2S, is very readily formed from its constituent elements and is the cause of the black tarnish on some old silver objects. It may also be formed from the reaction of hydrogen sulfide with silver metal or aqueous Ag+ ions. Many non-stoichiometric selenides and tellurides are known; in particular, AgTe~3 is a low-temperature superconductor.

Halides

The only known dihalide of silver is the difluoride, AgF2, which can be obtained from the elements under heat. A strong yet thermally stable and therefore safe fluorinating agent, silver(II) fluoride is often used to synthesize hydrofluorocarbons. In stark contrast to this, all four silver(I) halides are known. The fluoride, chloride, and bromide have the sodium chloride structure, but the iodide has three known stable forms at different temperatures; that at room temperature is the cubic zinc blende structure. They can all be obtained by the direct reaction of their respective elements. As the halogen group is descended, the silver halide gains more and more covalent character, solubility decreases, and the color changes from the white chloride to the yellow iodide as the energy required for ligand-metal charge transfer (X−Ag+ → XAg) decreases. The fluoride is anomalous, as the fluoride ion is so small that it has a considerable solvation energy and hence is highly water-soluble and forms di- and tetrahydrates. The other three silver halides are highly insoluble in aqueous solutions and are very commonly used in gravimetric analytical methods. All four are photosensitive (though the monofluoride is so only to ultraviolet light), especially the bromide and iodide which photodecompose to silver metal, and thus were used in traditional photography. The reaction involved is:

X− + hν → X + e− (excitation of the halide ion, which gives up its extra electron into the conduction band) Ag+ + e− → Ag (liberation of a silver ion, which gains an electron to become a silver atom) The process is not reversible because the silver atom liberated is typically found at a crystal defect or an impurity site, so that the electron's energy is lowered enough that it is "trapped".

Other inorganic compounds

White silver nitrate, AgNO3, is a versatile precursor to many other silver compounds, especially the halides, and is much less sensitive to light. It was once called lunar caustic because silver was called luna by the ancient alchemists, who believed that silver was associated with the Moon. It is often used for gravimetric analysis, exploiting the insolubility of the heavier silver halides which it is a common precursor to. Silver nitrate is used in many ways in organic synthesis, e.g. for deprotection and oxidations. Ag+ binds alkenes reversibly, and silver nitrate has been used to separate mixtures of alkenes by selective absorption. The resulting adduct can be decomposed with ammonia to release the free alkene. Yellow silver carbonate, Ag2CO3 can be easily prepared by reacting aqueous solutions of sodium carbonate with a deficiency of silver nitrate. Its principal use is for the production of silver powder for use in microelectronics. It is reduced with formaldehyde, producing silver free of alkali metals:

Ag2CO3 + CH2O → 2 Ag + 2 CO2 + H2 Silver carbonate is also used as a reagent in organic synthesis such as the Koenigs-Knorr reaction. In the Fétizon oxidation, silver carbonate on celite acts as an oxidising agent to form lactones from diols. It is also employed to convert alkyl bromides into alcohols. Silver fulminate, AgCNO, a powerful, touch-sensitive explosive used in percussion caps, is made by reaction of silver metal with nitric acid in the presence of ethanol. Other dangerously explosive silver compounds are silver azide, AgN3, formed by reaction of silver nitrate with sodium azide, and silver acetylide, Ag2C2, formed when silver reacts with acetylene gas in ammonia solution. In its most characteristic reaction, silver azide decomposes explosively, releasing nitrogen gas: given the photosensitivity of silver salts, this behaviour may be induced by shining a light on its crystals.

2 AgN3 (s) → 3 N2 (g) + 2 Ag (s)

Coordination compounds

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