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91.
The oxidation of 34 organic sulphides hy 2,2′-hipyridinium chlorochromate (BPCC) resulted in the formation of the corresponding
sulphoxides. The reaction is first order with respect to both BPCC and the sulphide, and is catalysed by hydrogen ions. The
hydrogen-ion dependence has the form:k
obs = a+b[H+]. The oxidation was studied in 19 different organic solvents. An analysis of the solvent effect by Swain’s equation showed
that the both cation-and anion-solvating powers of the solvents play important roles. The rates of oxidation meta- andp-substituted phenyl methyl sulphides were correlated with Charton’s LDR equation. The rates of theo-compounds showed excellent correlation with the LDRS equation. Oxidation of thep-compounds is more susceptible to the delocalizationeffect. Oxidation of themcompounds exhibited a greater dependence on the field effect. In the oxidation of theo-compounds, the contribution of delocalized effect is slightly more than that of the field effect. The oxidation of alkyl
phenyl sulphides is subject to both polar and steric effects of the alkyl groups. Polar reaction constants are negative, indicating
an electron-deficient sulphur centre in the rate-determining step. A mechanism involving formation of a sulphurane intermediate
in the slow step has been proposed. 相似文献
92.
Correlation spectroscopy as a tool for detecting losses of ligand elements in laser welding of aluminium alloys 总被引:1,自引:0,他引:1
T. Sibillano A. Ancona V. Berardi E. Schingaro P. Parente P.M. Lugar 《Optics and Lasers in Engineering》2006,44(12):1324-1335
The plasma plume induced during laser welding of metals is a mixture of metal vapour, coming from the vaporised weld pool surface and shielding gas. The influence of the shielding gas on the welded joints quality is not yet well understood and very few investigations, to the best of our knowledge, were addressed to study its role in case of welding of aluminium–magnesium alloys. In this paper we present a study of the dynamics of plasma plume produced in laser welding of 5xxx aluminium alloys by means of correlation spectroscopy. By our results we can correlate the influence of the welding speed, in case of ineffective gas shielding, to the loss of alloying elements. Finally, the results obtained are consistent with the EDX analysis performed in post-processing on the welded joints. 相似文献
93.
94.
Jingtao He 《European Polymer Journal》2003,39(7):1297-1310
In this work, correlations for the estimation of the infinite dilution activity coefficients of non-polar solvents in polystyrene (PS), poly(vinyl acetate) (PVAc), poly(n-butyl methacrylate) (PBMA), poly(dimethyl siloxane), poly(methyl methacrylate) (PMMA), poly(ethylene oxide) (PEO), poly(vinyl chloride) (PVC), polyisobutylene and polyethylene (PE), and that of polar solvents in PS, PVAc, PBMA, PMMA, PEO, PVC and PE are proposed. A total of 205 polymer/non-polar solvent systems with 1708 data points, and 118 polymer/polar solvent systems with 695 data points were used to develop the correlations. The overall average errors were 9.6% and 11.3%, respectively, significantly lower than other predictive models. Since the new correlations require only the connectivity indices of the solvents in the calculations, and the connectivity indices can be calculated easily once the molecular structure of the substance in question is known, they are easy to apply, and are useful for process design and development. 相似文献
95.
96.
97.
本文测定了三个3(或4)-取代苯甲亚氨酸乙酯(1)和八个N-氰甲基-3(或4)-取代苯甲亚氨酸乙酯(2)的~(13)C-NMR谱。归属了1 和2和各碳化学位移。求得了的取代基化学位移(substituent Chemical Shift,SCS)。碳-13化学位移与单取代苯的取代基化学位移(SCS)的相关分析表明:4-取代苯甲亚氨酸酯1 b~g和2b~e中,除C_(2,6)外,其他各芳碳的化学位移值与加和规则基本相符;3-取代苯甲亚氨酸酯1h~j和2f~h中,除C_1外,其他各芳碳的化学位移值与加和规则基本相符。另外,本文还进行了碳-13化学位移与σ_(I)/σ_(R)~O和F/M的双参数相关分析。 相似文献
98.
P. J. Solomon 《商业与工业应用随机模型》1989,5(2):153-164
The present paper describes an example of practical analysis of data from an application of visual analogue scales. Potentially useful and simple methods for analysing visual analogue scales are described for effective handling of complex data when the desire is to compare two or more groups of patients. Visual analogue scales were used to assess subjective tolerability in the International Prospective Primary Prevention Study in Hypertension, a large scale clinical trial. The methods are illustrated on the IPPPSH data. 相似文献
99.
100.
The solubility of tricin in water and ethanol mixtures was measured over the temperature range of (288.15 to 328.15) K. The concentrations of tricin in the aqueous mixtures were assayed by the ultraviolet spectrophotometric method. The experimental solubility data indicated that the solubility of tricin increases with an increase in temperature and an enrichment in ethanol content. The two models, including the modified Apelblat equation and λh equation were used to correlate the experimental solubility data. The calculated solubility of tricin shows good agreement with the experimental results. Additionally, the estimation of thermodynamic properties including the activity coefficients, dissolution enthalpy, and entropy were obtained from the experimental data. Within the studied temperature range the dissolution process of tricin is endothermic, and the driving force is the entropy. 相似文献