Entropy deficiency production

The greater the specificity of energy disposal in an exothermic reaction, then the larger is its entropy deficiency. Values of A., and KS,. for some well-studied atom-transfer reactions are listed in Table 1 is the av age fraction of available energy that is released as product vibration, i.e. 

RRHO prior branching ratio is corrected for the difference in entropy deficiencies of the product internal energy and angular distributions. The information-theoretic branching ratios, F and F, are purely classical that is, differences in zero-point energies of the products... 

Following earlier studies of the oxidation of formic and oxalic acids by pyridinium fluoro-, chloro-, and bromo-chromates, Banerji and co-workers have smdied the kinetics of oxidation of these acids by 2, 2Tbipyridinium chlorochromate (BPCC) to C02. The formation constant of the initially formed BPCC-formic acid complex shows little dependence on the solvent, whilst a more variable rate constant for its decomposition to products correlates well with the cation-solvating power. This indicates the formation of an electron-deficient carbon centre in the transition state, possibly due to hydride transfer in an anhydride intermediate HCOO—Cr(=0)(0H)(Cl)—O—bpyH. A cyclic intermediate complex, in which oxalic acid acts as a bidentate ligand, is proposed to account for the unfavourable entropy term observed in the oxidation of this acid. 

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