Photolysis of cellulose and related compounds by 253.7 nm light. I. Rates of gas production from hydrocellulose

The initial stages of the photolysis of cellulose under vacuum can be followed by the gas production. A photolysis cell is described which allows a rigorous temperature control and gives a reproducible photolysis surface of the solid carbohydrate sample. A mass spectrometer was used to analyze the gases. To measure accurately the small amounts produced in a small volume requires careful calibration of this instrument, together with a fixed routine for the experimental procedure. Using this apparatus, we have photolyzed hydrocellulose under vacuum with 253.7 nm light. Only H₂, CO, and CO₂ were evolved, the rate of H₂ production increasing to a constant value, that of CO increasing more slowly without becoming constant, and that of CO₂ decreasing rapidly to a constant value. No induction periods were observed. The gas evolution was not caused by residual O₂ or CO₂ adsorbed on the polymer, but the rates were altered by leaving the photolyzed sample under vacuum overnight or heating the unphotolyzed sample under vacuum at 100°C. The rates of gas production increased markedly when the light filter was changed to allow a combined photolysis by 253.7 and 184.9 nm light. The results illustrate that stringent precautions must be taken to filter off the latter line in polymer photolyses with Hg arc light if the results are to be meaningfully interpreted in terms of 253.7 nm light photolysis. On photolyzing hydrocellulose previously boiled in NaOH solution, a larger H₂ production rate and a smaller CO₂ rate (compared with untreated hydrocellulose) were observed. It is suggested that this standard alkali treatment is the reason for the differences between our results and the results of the photolysis of cellulose reported in the literature.     

A photoelectrochemical study of the anodic oxidation of lead in alkaline solution

The oxidation of lead in sodium tetraborate and in sulphuric acid solution has been studied. The analysis of photocurrent spectra has shown that tetragonal PbO is formed in both electrolytes. Evidence for photoemission from the metal substrate into the anodic oxide film is presented and discussed. The photocurrent behaviour is related to changes in electrode impedance which accompany the interconvertion of PbO and PbO₂.     

Methane hydrate formation and decomposition: structural studies via neutron diffraction and empirical potential structure refinement

Neutron diffraction studies with hydrogen/deuterium isotope substitution measurements are performed to investigate the water structure at the early, medium, and late periods of methane clathrate hydrate formation and decomposition. These measurements are coupled with simultaneous gas consumption measurements to track the formation of methane hydrate from a gas/water mixture, and then the complete decomposition of hydrate. Empirical potential structure refinement computer simulations are used to analyze the neutron diffraction data and extract from the data the water structure in the bulk methane hydrate solution. The results highlight the significant changes in the water structure of the remaining liquid at various stages of hydrate formation and decomposition, and give further insight into the way in which hydrates form. The results also have important implications on the memory effect, suggesting that the water structure in the presence of hydrate crystallites is significantly different at equivalent stages of forming compared to decomposing. These results are in sharp contrast to the previously reported cases when all remaining hydrate crystallites are absent from the solution. For these systems there is no detectable change in the water structure or the methane hydration shell before hydrate formation and after decomposition. Based on the new results presented in this paper, it is clear that the local water structure is affected by the presence of hydrate crystallites, which may in turn be responsible for the "history" or "memory" effect where the production of hydrate from a solution of formed and then subsequently melted hydrate is reportedly much quicker than producing hydrate from a fresh water/gas mixture.     

Enhanced quantum-well photoluminescence in InGaAs/InGaAsP heterostructures following excimer-laser-assisted surface processing

The influence of excimer-laser-assisted surface processing on quantum-well photoluminescence (QW PL) has been investigated in InGaAs/InGaAsP heterostructures capped with a thin layer of In_0.53Ga_0.47As. The PL mapping measurements carried out on samples before they were processed in a rapid thermal annealer indicated no significant differences in the QW PL signal intensity measured at the excimer-laser-processed sites and in their vicinity. However, a large difference in the QW PL signal, with its intensity significantly enhanced at the laser-processed sites, was observed after 10 s of rapid thermal annealing (RTA) at 750 °C. The largest contrast in the PL signal (an intensity difference up to about 100%) was obtained for a site processed with 50 pulses and a laser fluence of 123 mJ/cm². The changes in the QW PL signal intensity have been found to coincide with the changes in the surface chemical composition that were detected with Auger electron spectroscopy. The main difference concerns the development of a GaO_x layer on the laser-processed In_0.53Ga_0.47As surface.     

High-spin structure of yrast-band in 78Kr

Lifetime of levels up to 22⁺, have been measured in ⁷⁸Kr and an oblate shape is assigned to the ground state using the CSM and the configuration dependent shell correction calculations. Calculations further show that ⁷⁸Kr is highly γ-soft nucleus. The experimental Q _t values coupled with theoretical calculations indicate an oblate shape for ⁷⁸Kr at low spins and triaxial shape at higher spins