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.     

Kinetic and spectroscopic studies of an intermediate in the reaction of the diimine complex trisferrozineiron(II) with hydroxide ion in water and in aqueous methanol

Summary Kinetic and spectroscopic evidence is presented to support the postulate of a ligand-substituted intermediate in the reaction of the trisferrozineiron(II) anion with hydroxide ion in water and in aqueous methanol.     

Measurement of traffic noise shielding provided by buildings

This paper presents a comparison between some current prediction methods for traffic noise shielding provided by buildings and the actual measured attenuations in typical residential areas. Generally, it was found that the method developed by the Department of Environment in the UK gives a reasonably accurate prediction of attenuation by shielding in fairly simple situations. In more complex situations, and particularly where a receiving position is close to a significant shielding structure, such as building, the attenuation obtained is underpredicted by the DOE method, thus the design facade levels for the rear of a building are overpredicted; however, in some other situations, the DOE method overpredicts the attenuation obtained. The attenuations measured for individual noise events under nominally identical conditions are shown to have large variations in attenuation.     

Accurate analysis of multitone signals using a DFT

Optimum data windows make it possible to determine accurately the amplitude, phase, and frequency of one or more tones (sinusoidal components) in a signal. Procedures presented in this paper can be applied to noisy signals, signals having moderate nonstationarity, and tones close in frequency. They are relevant to many areas of acoustics where sounds are quasistationary. Among these are acoustic probes transmitted through media and natural sounds, such as animal vocalization, speech, and music. The paper includes criteria for multitone FFT block design and an example of application to sound transmission in the atmosphere.     

Instantaneous, stoichiometric generation of powerfully reducing states of protein active sites using Eu(II) and polyaminocarboxylate ligands

Addition of an equivalent of a polyaminocarboxylate ligand (L) to a solution of a redox protein and the aqua Eu2+ ion results in the instantaneous in situ generation of a very powerful reductant Eu(II)-L that can rapidly drive an electron stoichiometrically onto a redox centre having an extremely negative reduction potential (lower than -1 V): this is exemplified by straightforward generation of the super-reduced state of the Fe-protein of nitrogenase.     

Measurable cardinals and the cardinality of Lindelöf spaces

We obtain from the consistency of the existence of a measurable cardinal the consistency of “small” upper bounds on the cardinality of a large class of Lindelöf spaces whose singletons are Gδ sets.