Abstract
The formation of pyrophosphates from phosphorus monoamidates was studied by TGA associated with chromatographic techniques upto 320°. Above this temperature the salts decomposed completely. Other compounds were also formed: diamidophosphoric acid aryl esters, pyrophosphorus amidic acids, cyclohexylamine, phenols and a number of minor thermoproducts. The influence of substituents attached to the aromatic ring on the over-all rate of decomposition reaction showed the order: t-Bu > Me > H > Cl. Anomalous results were found for NO 2. Second order rate constants were measured. A mechanism in two steps is suggested for the reaction investigated. Initial formation of free phosphoramidic acid as proposed by Clark appears to be unnecessary. Pyrolysis stequiometric equation was proposed.
Published Version
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