Piperidinium tetrathiotungstate as sulfur transfer reagent: synthesis of cyclic disulfides

Piperidinium tetrathiotungstate has been found to react with a number of 1,n-dihalo compounds to afford the corresponding cyclic disulfides in good yields, under mild reaction conditions. This new methodology has been used as a key step in the synthesis of (+/-)-lipoic acid (35) and asparagusic acid (37).

Non-Marcus energy gap dependence of electron transfer rate in contact ion pairs. Novel interplay between relaxation and reaction in solution

Electron transfer reactions between donor-acceptor pairs in solution and in organized media exhibit diverse behaviour. Recent experiments have indicated an interesting breakdown of the Marcus parabolic energy gap dependence in the normal regime for back electron transfer from contact ion pairs. A novel explanation of this breakdown has recently been proposed (M. Tachiya and S. Murata, J. Am. Chem. Sec., 116(1994) 2434) which attributes the breakdown to the interplay between the relaxation in the reactant well and the reaction. A particularly interesting aspect of the model is that it envisages the electron transfer in the normal regime to take place from a completely non-equilibrium condition. In this article a time dependent solution of the model is presented for the first time, after generalizing it to include a realistic initial population distribution. The decay of the contact ion pair population is completely non-exponential. This can be used to check the validity of the Tachiya-Murata model. The dynamics of electron transfer from the solvent separated ion pair, which seem to obey the Marcus relation, is exponential.

Quantum and non-Markovian effects in the electron transfer reaction dynamics in the Marcus inverted region

Electron transfer reactions in large molecules may often be coupled to both the polar solvent modes and the intramolecular vibrational modes of the molecule. This can give rise to a complex dynamics which may in some systems, like betaine, be controlled more by vibrational rather than by solvent effects. Additionally, a significant contribution from an ultrafast relaxation component in the solvation dynamics may enhance the complexity. To explain the wide range of behavior that has been observed experimentally, Barbara et al. recently proposed that a model of an electron transfer reaction should minimally consist of a low-frequency classical solvent mode (X), a low-frequency vibrational mode (Q), and a high-frequency quantum mode (q) (J. Phys. Chem. 1991, 96, 3728). In the present work, a theoretical study of this model is described. This study generalizes earlier work by including the biphasic solvent response and the dynamics of the low-frequency vibrational mode in the presence of a delocalized, extended reaction zone. A novel Green's function technique has been developed which allowed us to study the non-Markovian dynamics on a multidimensional surface. The contributions from the high-frequency vibrational mode and the ultrafast component in the non-Markovian solvent dynamics are found to be primarily responsible for the dramatic increase in charge transfer rate over the prediction of the classical theories that neglect both these factors. These, along with a large coupling between the reactant and the product states, may combine to render the electron transfer rate both very large and constant over a wide range of solvent relaxation rates. A study on the free energy gap dependence of the electron transfer rate reveals that the rates are sensitive to changes in the quantum frequency particularly when the free energy gap is very large.

Synthesis of epoxy-terminated polymers by radical polymerization using alpha-(t-butylperoxymethyl)styrene as chain transfer agent

Epoxy-terminated polystyrene has been synthesized by radical polymerization using alpha-(t-butylperoxymethyl) styrene (TPMS) as the chain transfer agent. The chain transfer constants were found to be 0.66 and 0.80 at 60 and 70 degrees C, respectively. The presence of epoxy end groups was confirmed by functional group modification of epoxide to aldehyde by treatment with BF3.Et(2)O. Thermal stability of TPMS was followed by differential scanning calorimetry and iodimetry. Thermal decomposition of TPMS in toluene follows first order kinetics with an activation energy of 23 kcal/mol. (C) 1996 John Wiley & Sons, Inc.

Effect of wall emissivities on radiation heat transfer in glass tank forehearths

In an earlier work, we had proposed a two-band, non-grey radiative transfer model for heat transfer in forehearths with simultaneous optically thick and thin approximations for molten glass interiors and at boundaries. Here using the same model, the radiative interaction of the top-crown and bottom-refractory walls with interior layers of shallow molten glass is studied by varying the wall emissivities. The forehearth exit temperature profiles for higher wall emissivities (0.9) show better conditioning of the glass for white flint glasses (optically thin).

The effect of surface mass transfer on buoyancy induced flow in a variable porosity medium adjacent to a vertical heated plate

The effect of surface mass transfer on buoyancy induced flow in a variable porosity medium adjacent to a heated vertical plate is studied for high Rayleigh numbers. Similarity solutions are obtained within the frame work of boundary layer theory for a power law variation in surface temperature,T Wpropx lambda and surface injectionv Wpropx(lambda–1/2). The analysis incorporates the expression connecting porosity and permeability and also the expression connecting porosity and effective thermal diffusivity. The influence of thermal dispersion on the flow and heat transfer characteristics are also analysed in detail. The results of the present analysis document the fact that variable porosity enhances heat transfer rate and the magnitude of velocity near the wall. The governing equations are solved using an implicit finite difference scheme for both the Darcy flow model and Forchheimer flow model, the latter analysis being confined to an isothermal surface and an impermeable vertical plate. The influence of the intertial terms in the Forchheimer model is to decrease the heat transfer and flow rates and the influence of thermal dispersion is to increase the heat transfer rate.

Theory of electron transfer processes via chemisorbed intermediates: Part II. Current-potential characteristics

Current-potential characteristics are obtained numerically for a lone-adsorbate-mediated anodic charge transfer at the electrode-solution interface. An increase in the overpotential leads to the appearance of maxima in the anodic current-potential plots instead of the extended activationless region (i.e. a saturation current at large positive overpotentials) predicted by the direct heterogeneous outer-sphere anodic charge transfer process. A detailed analysis of the dependence of current-potential profiles and other kinetic parameters on various system parameters is also presented.

Implications of the recent high statistics determination of the pion electromagnetic form factor in the timelike region

The recently evaluated two-pion contribution to the muon g - 2 and the phase of the pion electromagnetic form factor in the elastic region, known from pi pi scattering by Fermi-Watson theorem, are exploited by analytic techniques for finding correlations between the coefficients of the Taylor expansion at t = 0 and the values of the form factor at several points in the spacelike region. We do not use specific parametrizations, and the results are fully independent of the unknown phase in the inelastic region. Using for instance, from recent determinations, < r(pi)(2)> = (0.435 +/- 0.005) fm(2) and F(-1.6 GeV2) = 0.243(-0.014)(+0.022), we obtain the allowed ranges 3.75 GeV-4 less than or similar to c less than or similar to 3.98 GeV-4 and 9.91 GeV-6 less than or similar to d less than or similar to 10.46 GeV-6 for the curvature and the next Taylor coefficient, with a strong correlation between them. We also predict a large region in the complex plane where the form factor cannot have zeros.

Time-resolved resonance Raman spectroscopic investigations of the photochemistry of ubiquinone

Time-resolved resonance Raman spectroscopy has been used to investigate the photochemistry of ubiquinone in cyclohexane, water and ethanol. In water the absorption of a single 248 nm photon produces triplet ubiquinone which then oxidises water, via electron transfer, to form the ubiquinone radical anion. In ethanol, however, the triplet state reacts with the solvent via both electron and hydrogen-atom transfer, the latter process forming the semihydroquinone. Only in the less reactive solvent, cyclohexane, is triplet quinone observed. The Raman bands observed for each of the species are assigned on the basis of similarities of their spectra to other quinones.

Raman Spectroscopy of the Charge Transfer Complex (TTF)x C60 Br8

We report Raman studies on powder samples of the charge transfer complex (TTF)(x)C60Br8 at room temperature. The phonons show considerable softening with respect to the frequencies observed in the Raman spectrum of solid C60Br8. The strongest mode at 1464 cm(-1) in C60Br8 is red shifted to a doublet with peaks at 1414 and 1421 cm(-1), implying an average phonon softening Delta omega of -47 cm(-1). A comparison with the phonon softening of the corresponding A(g)(2) mode in alkali-doped C-60 (Delta omega similar to -36 cm(-1) for A(6)C(60), A = K, Rb or Cs) suggests that 8 electrons are transferred per C60Br8 molecule in the charge transfer complex. The mode at 503 cm(-1) in C60Br8 is shifted upwards, similar to that in A(6)C(60) compounds.

Sliding wear of YTZP ceramic against steel: observations on ceramic transfer and wear transition

Sliding tests were conducted, in air, of YTZP ceramic pins against steel discs at an applied pressure of 15.5 MPa over a speed range of 0.3 to 4.0 ms(-1). Pin wear was not detectable until 2.0 m s(-1), after which a finite but small wear rate was observed at 3.0 m s(-1), accompanied by a red glow at the contacting surface. A transition in wear behaviour and friction (mu) occurred at 4.0 ms(-1), increasing the former by over two orders of magnitude. Both mu and wear behaviour changed with time at 4.0 m s(-1). During initial periods mu was high and wear rate increased steadily with time accompanied by ceramic transfer onto the disc, which increased with time. When disc coverage exceeds a certain threshold value, mu decreased rapidly and the wear rate stabilized at a very high value. Metal transfer was not observed at any speed. High surface temperatures brought about significant adhesion between TZP and steel and this together with enhanced plastic deformation brought about a transition in wear behaviour.

Time-Resolved Photoluminescence and Microwave Conductivity at Semiconductor Electrodes: Depletion Layer Effects

Analytical expressions which include depletion layer effects on low-injection carrier relaxation are being presented for the first time here. Starting from the continuity equation for the minority carriers, we derive expressions for the output signal pertinent to time-resolved microwave and luminescence experiments. These are valid for the time domain that usually overlaps with the time scales of surface processes, such as charge transfer and trapping. Apart from the usual pulse form of illumination, theoretical expressions pertaining to other forms of illumination such as switch-on and switch-off transient modes, a periodic mode, and a steady state and their various inter-relationships are derived here. The expressions obtained are seen to be generalizations of existing flat-band low-injection results in the Limit of early or initial band bendings. The importance of the depletion layer as an experimental parameter is clearly seen in the limit of larger band bendings wherein it is shown, unlike the flat-band case, to exhibit pure exponential forms of carrier relaxation. Our results are consistent with the main conclusions of the numerical and experimental work published recently. Furthermore, this work provides the actual functional relationships between the applied potential and observed carrier decay. This should enable one to extract the surface kinetic parameters, after deciding on the dominant mode of carrier relaxation at the interface, whether charge transfer or trapping, by studying the potential dependence of the fate of relaxation.

Variation of Cu-O charge-transfer energies in YBa2Cu3O7-x thin films studied by photoemission spectroscopy

It is pointed out that the change in the oxidation state of Cu in YBa2CU3O7-x with increasing x vitiates the trend in the Cu(2p) satellite intensity and hence the Cu-O charge-transfer energy. When Y is partly replaced by Ca, however, the satellite intensity and T(c) decrease with the increase in Ca content or hole concentration, just as in other cuprates.

Gas-phase controlled mass transfer in a foam-bed reactor

Gas-phase controlled absorption of ammonia in foams made of solutions of sulphuric acid has been studied experimentally. Effects of gas-phase concentration of ammonia and type of surfactant on the performance of the foam-bed reactor are investigated. Gas-phase controlled absorption from a spherical bubble is anaylzed using the asymptotic value of Sherwood number (Sh = 6.58), for both negligible as well as significant changes in the volume of the bubble. The experimental data are shown to be in good agreement with the single-stage model of the foam-bed reactor using these asymptotic sub-models, as well as the diffusion-in-sphere analysis available in literature. Influence of effective diffusivity on the time dependence of fractional gas absorption has been found to be unimportant for foam columns with large times of contact. The asymptotic sub-models have been compared and use of the rigid-sphere asymptotic sub-model is recommended for foam columns of practical relevence.