Kinetics of the oxidation of hypophosphorous and phosphorous acids by chromium(VI)

The kinetics of the chromic acid oxidation of hypophosphorous and phosphorous acids have been reported. The evaluation of the equilibrium constants of the intermediate complexes shows that the complex in the former case is more stable than in the latter. The ΔH and ΔS values associated with these eq...

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Published inJournal of inorganic & nuclear chemistry Vol. 35; no. 3; pp. 901 - 908
Main Authors Sengupta, Kalyan K., Chakladar, J.K., Chatterjee, A.K.
Format Journal Article
LanguageEnglish
Published Elsevier B.V 01.03.1973
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Summary:The kinetics of the chromic acid oxidation of hypophosphorous and phosphorous acids have been reported. The evaluation of the equilibrium constants of the intermediate complexes shows that the complex in the former case is more stable than in the latter. The ΔH and ΔS values associated with these equilibrium constants have been calculated. The energy and entropy of activation for the slow step has also been evaluated. Unlike the H3PO3Cr(VI) reaction, a catalytic effect of pyridine has been noticed on the H3PO2Cr(VI) reaction. The suggested mechanism is based on the formation of phosphonium ion in the slow rate determining step.
ISSN:0022-1902
1878-1225
DOI:10.1016/0022-1902(73)80460-9