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71.
72.
作为一种原位、快速、无损坏的中红外光谱分析技术,ATR-FTIR已在很多工程领域得到越来越多的应用,尤其是针对结晶过程溶液浓度的原位实时测量。水是一种常用的结晶溶剂,在中红外波段具有强吸收峰,并且在不同温度下具有光谱吸收差异性,因而不能忽略溶剂水和温度对溶液浓度的中红外光谱测量带来的影响。以朗伯-比尔定律为基础,提出采用溶液光谱减去相应温度下的溶剂光谱的方法,从而能准确地测量溶液浓度。以L-谷氨酸溶液结晶过程为例,对L-谷氨酸水溶液的原始光谱数据、溶液光谱扣除常温(25℃)溶剂水的光谱数据以及溶液光谱对应温度扣除溶剂水的光谱数据分别进行建模。结果表明,提出的对应温度差谱法能有效消除溶剂水峰对溶质光谱测量的干扰,明显地降低了溶液浓度光谱标定模型的预测误差。该方法对提高原位ATR-FTIR光谱检测精度的实际应用具有一定的参考价值。 相似文献
73.
《Physics and Chemistry of Liquids》2012,50(4):239-247
Abstract The electrical conductance of KC1 in glycerol solutions has been measured at concentrations between 1.5 mol m?3 and 353 mol m?3 at 22°C. The results are compared with the Fuoss paired ion model and fits to the data are obtained assuming a Gurney co-sphere having a radius in the approximate range 6 ± 10?10 m to 9 ± 10?10 m. The model leads to an estimate of ionic association which is less than that given by the theory of Bjerrum. 相似文献
74.
《Physics and Chemistry of Liquids》2012,50(6):665-673
Abstract Excess molar enthalpies for mixtures of each of the isomers of chlorobutane with each of the isomers of butanol were determined at the temperature 298.15 K and atmospheric pressure. Excess molar enthalpies are positive for all the mixtures. The results are discussed in terms of molecular interactions. 相似文献
75.
A pilot plant study of the radiation grafting of styrene to polyvinyl chloride) (PVC) latex is described. When correct extraction conditions are used less than 3% grafting took place. This is shown to be due to the low total radiation doses needed to polymerize the styrene in an emulsion system. A parallel study with PVC film did, however, lead to substantial true grafting. The G (radical) value for PVC film as determined by ESR was found to be 4.6. 相似文献
76.
Finding an efficient solution to linear bilevel programming problem: An effective approach 总被引:1,自引:0,他引:1
Multilevel programming is developed to solve the decentralized problem in which decision makers (DMs) are often arranged within a hierarchical administrative structure. The linear bilevel programming (BLP) problem, i.e., a special case of multilevel programming problems with a two level structure, is a set of nested linear optimization problems over polyhedral set of constraints. Two DMs are located at the different hierarchical levels, both controlling one set of decision variables independently, with different and perhaps conflicting objective functions. One of the interesting features of the linear BLP problem is that its solution may not be Paretooptimal. There may exist a feasible solution where one or both levels may increase their objective values without decreasing the objective value of any level. The result from such a system may be economically inadmissible. If the decision makers of the two levels are willing to find an efficient compromise solution, we propose a solution procedure which can generate effcient solutions, without finding the optimal solution in advance. When the near-optimal solution of the BLP problem is used as the reference point for finding the efficient solution, the result can be easily found during the decision process. 相似文献
77.
J. N. Spencer Eric S. Holmboe Daniel W. Firth Mindy R. Kirshenbaum 《Journal of solution chemistry》1981,10(10):745-756
Enthalpies of solution have been used to calculate transfer enthalpies for phenol, pyridine, and DMSO between the solvent cyclohexane and the solvents CCl4, benzene, and CHCl3. By use of model compounds, enthalpies due to interactions with phenol, pyridine, and DMSO have been determined. These enthalpies are used to calculate the effect of solvation relative to cyclohexane on hydrogen bonded complexes in CCl4 and benzene solvents. Correlations with enthalpies due to interactions and frequency shifts for the hydroxyl stretch in these solvents have also been made. 相似文献
78.
Banci L Bertini I Felli IC Sarrou J 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2005,172(2):191-200
CH(alpha) residual dipolar couplings (Deltardc's) were measured for the oxidized cytochrome b562 from Escherichia coli as a result of its partial self-orientation in high magnetic fields due to the anisotropy of the overall magnetic susceptibility tensor. Both the low spin iron (III) heme and the four-helix bundle fold contribute to the magnetic anisotropy tensor. CH(alpha) Deltardc's, which span a larger range than the analogous NH values (already available in the literature) sample large space variations at variance with NH Deltardc's, which are largely isooriented within alpha helices. The whole structure is now significantly refined with the chemical shift index and CH(alpha) Deltardc's. The latter are particularly useful also in defining the molecular magnetic anisotropy parameters. It is shown here that the backbone folding can be conveniently and accurately determined using backbone restraints only, which include NOEs, hydrogen bonds, residual dipolar couplings, pseudocontact shifts, and chemical shift index. All these restraints are easily and quickly determined from the backbone assignment. The calculated backbone structure is comparable to that obtained by using also side chain restraint. Furthermore, the structure obtained with backbone only restraints is, in its whole, very similar to that obtained with the complete set of restraints. The paramagnetism based restraints are shown to be absolutely relevant, especially for Deltardc's. 相似文献
79.
We study the exact multiplicity and ordering properties of positive solutions of the p-Laplacian Dirichlet problem
80.
Lu‐Feng Zou Kuang Shen Yao Fu Qing‐Xiang Guo 《Journal of Physical Organic Chemistry》2007,20(10):754-763
Experimental studies showed that sulfur radicals play the vital role in petroleum formation. 1 Sulfur‐ centered radicals also exhibit activities in antioxidant functions. Here we conduct a theoretical investigation of their precursor‐disulfides. By investigation into substituent effect on sulfur? sulfur bond dissociation enthalpies (S? S BDEs), we would like to find the most effective provider for sulfur radicals. In the present work, 50 alpha‐substituted disulfides and 16 para‐substituted aryl disulfides are studied systematically, with the general formula XS‐SX or HS‐SX. The substituent effect on S? S BDEs is found to be very eminent, ranging from 33.2 to 75.0 kcal/mol for alpha‐substituted disulfide, and from 43.7 to 59.7 kcal/mol for para‐substituted phenyl disulfides. We also evaluate the performance of 44 density functional methods to get an accurate prediction. A further study indicates that substituents play a major role in radical energies, instead of molecule energies, which is substantiated by the good linearity between XS‐SX bond dissociation enthalpy (BDE) and HS‐SX BDE. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献