Initial state and transition state solvation effects in the cobaltitungstate oxidation of iodide in binary aqueous solvent mixtures

Summary Rate constants are reported for 12-tungstocobaltate(III) [CoW₁₂O₄₀]^5– oxidation of iodide in water and in binary aqueous solvent mixtures containing up to 40% methanol, 40% acetonitrile, or 60% dimethyl sulphoxide. From these kinetic results, solubility measurements on potassium 12-tungstocobaltate(III), and published data on Gibbs free energies of transfer of appropriate ions, it has been deduced that the dominant factor in determining the marked decrease in rate observed on going from water into the binary aqueous solvent mixtures is destabilisation of the transition state for the electron-transfer reaction.     

Polymerization of methyl acrylate in aqueous media

The polymerization of methyl acrylate in water and in dilute, aqueous, soap solutions, initiated by potassium peroxydisulfate, has been investigated, a dilatometric method being used to follow the conversion. It has been shown that small amounts of an anionic soap increase the rate of reaction while a cationic soap has the reverse effect. The change of molecular weight with conversion has also been examined as well as the effect of the exclusion of oxygen from the system.     

Galerkin methods applied to some model equations for non-linear dispersive waves

The application of a dissipative Galerkin scheme to the numerical solution of the Korteweg de Vries (KdV) and Regularised Long Wave (RLW) equations, is investigated. The accuracy and stability of the proposed schemes is derived using a localised Fourier analysis. With cubic splines as basis functions, the errors in the numerical solutions of the KdV equation for different mesh-sizes and different amounts of dissipation is determined. It is shown that the Galerkin scheme for the RLW equation gives rise to much smaller errors (for a given mesh-size), and allows larger steps to be taken for the integrations in time (for a specified error tolerance). Also, the interaction of two solitons is compared for the KdV and RLW equations, and several differences in their behaviour are found.     

Static moments of the first excited states of 32, 34S and 204, 206Pb

The reorientation effect in Coulomb excitation has been used to measure the following static quadrupole moments: $\text{Q}{}_2\text{+ (}{}^{32}\text{S}\text{) = ?0.066 ± 0.017}\text{b}\text{, Q}{}_2\text{+ (}{}^{34}\text{S}\text{) = 0.026 ± 0.023}\text{b}\text{, Q}{}_2\text{+ (}{}^{204}\text{Pb}\text{) = 0.19 ± 0.14}\text{b}$. Interference effects from higher excited states have been included in the analysis, with the signs of the E2 matrix elements taken from an anharmonic model. The value obtained for $\text{Q}{}_2\text{+ (}{}^{32}\text{S}\text{)}$ is in disagreement with two previous measurements. We attribute the discrepancy to the smaller internucleon separation distances involved in the previous experiments, which can cause deviations from Coulomb excitation cross sections. The other quadrupole moments have not been measured previously. The B (E2: 0⁺ → 2⁺) measured were: $\text{0.0305 ± 0.0016 e}{}^2\text{·}\text{b}{}^2\text{(}{}^{32}\text{S}\text{), 0.025 ± 0.004 e}{}^2\text{·}\text{b}{}^2\text{(}{}^{34}\text{S}\text{),}\text{and}\text{0.166 ± 0.009 e}{}^2\text{·}\text{b}{}^2\text{(}{}^{204}\text{Pb}\text{)}$. From the angular distribution of the de-excitation γ-rays of the Pb nuclei following recoil into vacuum, we have determined the following $\text{g-}\text{factors}\text{: ¦g}{}_2\text{+ (}{}^{204}\text{Pb}\text{)¦ < 0.08}$ (two standard deviations), $\text{¦g}{}_2\text{+ (}{}^{206}\text{Pb}\text{)¦ = 0.07}{}^{\mathrm{+\; 0.07}}{}_{\mathrm{?\; 0.03}}$. Our value of $\text{g}{}_2\text{+ (}{}^{206}\text{Pb}\text{)}$ is in agreement with a previous measurement.