The kinetics of ruthenium(III) catalyzed oxidation of the secondary amines-diethylamine, dipropylamine, di-isopropylamine and dibutylamine by chloramine-T (CAT) in aqueous perchloric acid medium has been studied. The reaction rate shows a first order dependence each on CAT, sec. -amine and Ru(III). The reaction rate shows an inverse fractional order dependence on acid concentration. Added halide ions and the reaction product, p-toluenesulphonamide have no effect on the reaction rate. Variation of ionic strength and dielectric constant of the medium has no influence on the reaction. The activation parameters have been evaluated. It was observed that the rate of oxidation of sec.-amine by CAT increases in the order DEA < DPA < DBA < DIPA. Also it was found that &UDelta; H* and &UDelta; S* are linearly related and an isokinetic relationship is observed with isokinetic temperature β as 394 K, indicating enthalpy as controlling factor. Mechanisms consistent with experimental rate law have been proposed.

The kinetics and mechanism of oxidation of D-glucose and D-mannose with bromamine-T in alkaline medium have been studied and the rate = kBAT] sugar]OH-](2), is observed. The rate of the reaction is influenced by a change in ionic strength of the medium and the dielectric effect is found to be positive. The latter enables the computation of d(AB), the size of the activated complex. Proton inventory studies are made for the reactions in H2O-D2O mixtures. Activation parameters are calculated from the Arrhenius plots. The product analyses indicates that the sugars are oxidized to a mixture of aldonic acids, consisting of arabinonic, ribonic, erythronic and glyceric acids. A mechanism consistent with the observed kinetics has been proposed.

Photolysis of aqueous solution of sodium salt of N-bromo-4-methylbenzenesulphonamide has been studied with a UV light source (lambda = 2537 Angstrom). The products have been identified by spectral studies. Conductometric and pH studies of acids (HCl, HClO4 and H2SO4) with the title compound have been performed. A suitable photolytic mechanism is suggested based on the observed results and the quantum yield for the photolytic decomposition is reported.

The kinetics of oxidation of dimethylsulphoxide (DMSO) by sodium N-bromobenzenesulphonamide or bromamine-B (BAB) has been studied in HClO4, HCl and NaOH media, at 35°C, with OsO4 as a catalyst in the latter medium. In acid medium, the rate shows a first order dependence on [BAB] and second order in [H+], but Is Independent of substrate concentration. Alkali retards the reaction (Inverse first order) and the rate is independent of oxidant concentration, but shows fractional order in [DMSO] and depends on (0sO4]2. The solvent isotope effect was studied by using D2O. Activation parameters have also been determined. Mechanisms proposed and the derived rate laws are consistent with the observed kinetics.

Distribution of isomorphous salts between aq. and solid phases in the title ternary systems was studied at different concns. of less sol. salt in the ternary systems. The results are explained by a proper choice of values of the parameters in the Abu Elamayem (1964) equations. These parameters characterize a given system over a wide range of concns. and can be effectively used in predicting the amt. of less sol. salt crystg. out of the 2 ternary systems. [on SciFinder(R)]