Silver oxalate, thermal decomposition

Kabanov, A. A. etal., Russ. Chem. Rev., 1975, 44, 538-551 Application of electric fields to various explosive heavy metal derivatives (silver oxalate, barium, copper, lead, silver or thallium azides, or silver acetylide) accelerates the rate of thermal decomposition. Possible mechanisms are discussed. 

Benton and Cunningham [77] found that the rate of thermal decomposition of silver oxalate may be increased by previously exposing it to ultra-violet radiation. 

During the thermal decomposition of silver oxalate, fragments of metallic silver are formed. This has been confirmed by conductivity measurements (Macdonald and Sandison [78]) or by X-ray examination (Griffith [79]). 

Tompkins [80] investigated the thermal decomposition of silver oxalate at 110— 130°C. Its decomposition, in his opinion, is similar to that of barium azide. 

Silver oxalate is a colourless, crystalline substance which on heating undergoes an exothermic decomposition. The reaction begins at a little over 100 °C and easily becomes explosive. It was noticed quite early that samples prepared in the presence of an excess of oxalate were less stable thermally than those prepared using stoichiometric amounts of oxalate and silver ions. The thermal decomposition of silver oxalate into silver and C02 has subsequently been studied under varying conditions of preparation, decomposition environment and preirradiation.258,259... 

Many kinetic studies of the thermal decomposition of silver oxalate have been reported. Some ar-time data have been satisfactorily described by the cube law during the acceleratory period ascribed to the three-dimensional growth of nuclei. Other results were fitted by the exponential law which was taken as evidence of a chain-branching reaction. Results of both types are mentioned in a report [64] which attempted to resolve some of the differences through consideration of the ionic and photoconductivities of silver oxalate. Conductivity measurements ruled out the growth of discrete silver nuclei by a cationic transport mechanism and this was accepted as evidence that the interface reaction is the more probable. A mobile exciton in the crystal is trapped at an anion vacancy (see barium azide. Chapter 11) and if this is further excited by light absorption before decay, then decomposition yields two molecules of carbon dioxide ... 

The difficulties of interpreting the observations reported for the thermal decomposition of silver oxalate have been discussed [65]. Isothermal data for freshly prepared salt at 399 K were sufficiently irreproducible for different experiments to fit different rate expressions during the acceleratory process, for example, either the power law, or the exponential law. In the second half of reaction (i.e. tt> 0.5), however, data were more reproducible and results were satisfactorily described by the contracting volume equation. 

Certain acid dyes [67] stabilize silver oxalate by forming surface compounds, while other dyestufis accelerate the decomposition because their redox properties enhance the ease of electron transfer from the oxalate ion to the silver. The influences of incorporated cadmium, copper and other ions on the rate of thermal decomposition, and on the concentration and mobility of interstitial silver ions, have been reviewed [46,68]. 

Oxalic and malonic acids, as well as a-hydroxy acids, easily react with cerium(IV) salts (Sheldon and Kochi, 1968). Simple alkanoic acids are much more resistant to attack by cerium(IV) salts. However, silver(I) salts catalyze the thermal decarboxylation of alkanoic acids by ammonium hexanitratocerate(IV) (Nagori et al., 1981). Cerium(IV) carboxylates can be decomposed by either a thermal or a photochemical reaction (Sheldon and Kochi, 1968). Alkyl radicals are released by the decarboxylation reaction, which yields alkanes, alkenes, esters and carbon dioxide. The oxidation of substituted benzilic acids by cerium(IV) salts affords the corresponding benzilic acids in quantitative yield (scheme 19) (Hanna and Sarac, 1977). Trahanovsky and coworkers reported that phenylacetic acid is decarboxylated by reaction with ammonium hexanitratocerate(IV) in aqueous acetonitrile containing nitric acid (Trahanovsky et al., 1974). The reaction products are benzyl alcohol, benzaldehyde, benzyl nitrate and carbon dioxide. The reaction is also applicable to substituted phenylacetic acids. The decarboxylation is a one-electron process and radicals are formed as intermediates. The rate-determining step is the decomposition of the phenylacetic acid/cerium(IV) complex into a benzyl radical and carbon dioxide. 

---