The direct reduction of sulphur dioxide to elemental sulphur using coal has been studied utilizing models that simulate thermodynamic equilibrium. Comparison has been made between the computer models and process results. The results of the analysis indicate a discrepancy which may be attributable to the manner in which samples are taken for analysis. The actual process may be in thermodynamic equilibrium. 相似文献
Iodoperfluooralkylation of terminal alkenes and alkynes is effectively photo‐promoted by benzophenone 2 (BP) or the photoreducible copper(II) complex 1 . In particular, BP at 1 mol% in methanol upon 365 nm irradiation with a low‐pressure mercury lamp (type TLC=thin layer chromatography, 6 W) results in a fast reaction with excellent reaction yields. Complex 1 and BP 2 exhibited very similar reactivity, suggesting that the reactions involving 1 are likely to be governed by the benzophenone photoactivation processes, rather than copper(I)/(II) redox processes. Mechanistic investigations using transient absorption spectroscopy revealed that a deactivation pathway of the benzophenone triplet (3BP*) is via its reaction with the methanol solvent. We propose that the generated radicals, in particular .CH2OH, play a key role in the initiation step forming Rf. by reacting with RfI, Rf. then entering a radical chain cycle. 1H NMR studies provided evidence that a substantial amount (∼7% NMR yield) of the hemiacetal CH3OCH2OH is formed, i.e., the possible by‐product of the reaction between .CH2OH and RfI. Finally, DFT calculations indicate that a triplet‐triplet energy transfer (TTET) process from 3BP* to perfluorooctyl iodide (C8F17I) is unlikely or should be rather slow under the reaction conditions, consistent with the transient absorption studies.
The phenomenon of drag reduction in walled turbulent flows of polymer solutions is theoretically modeled. A new mechanistic model of a polymer molecule in a turbulent flow field is suggested. It is argued that the dominant forces on a polymer fiber in the turbulent flow field are elastic and centrifugal. According to this model, an additional route of dissipation exists, in which eddy kinetic energy is converted to polymer elastic energy by the centrifugal elongation of the rotated polymer, which in turn is viscously damped by the surroundings, when the polymer relaxes. A novel approach is then illustrated, where it is shown that this mechanistic model can be accounted for as a turbulent scale alteration, instead of addition, which enables the classical dimensional analysis of a turbulent boundary layer to apply. Using this dimensional analysis with the equivalent altered scale yields remarkable results. Correct-form velocity profiles are obtained, and Virk's asymptote and slope are predicted with no empirical constants. Drag-flow rate curves are also calculated, and compared favorably with Virk's experiments. The onset of drag reduction phenomenon is also explained by this model, and calculations of it are also compared with Virk's data. The parametric dependencies of the onset point agree well with Virk's conclusions. 相似文献
