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131.
烷基极化效应与X=O键伸缩振动频率 总被引:2,自引:0,他引:2
烷基取代物R’X=0的X=0键伸缩振动频率ν与烷基R的极化效应指数PEI(R)的关系可表示为:ν=a bPEI(R)。研究结果表明,烷基的极化效应使X=0键的伸缩振动频率降低。 相似文献
132.
烯烃加成反应活性与烷基极化效应的关系 总被引:1,自引:0,他引:1
烯烃的自由基加成和亲电加成速率受不同的因素控制.对于仅仅含烷基取代的简单烯烃:(1)与OH自由基加成速率-log kOH可由π键上烷基极化效应指数的几何平均值GMPEIπ关联:-log kOH=a bGMPEIπ c(GMPEIπ)2; (2)与亲电试剂加成速率log k可由π键两端碳原子所连基团极化效应指数PEI(L)和PEI(S)关联:log k=a bPEI(L) cPEI(S),其中的PEI(L)和PEI(S)分别表示极化效应较大和较小的一端. 相似文献
133.
离子性指数、极化效应指数烷烃^13C NMR化学位移的 关系研究 总被引:5,自引:0,他引:5
定义了烷烃分子中碳原子的离子性指数(INI),用离子性指数(INI)、极化效应指数(PEI)及N^i~H(i=αβΥ)结构信息参数研究了烷烃的^13CNMR化学位移模型,结果表明,烷烃^13CNMR化学位移(CS)可用下式来定量描述:CS=194.6156-37.7394(INI)+98.6505(ΣPEI)+27.1630(INI/ΣPEI)-652.9106(ΣPEI/INI)+0.7735N^α~H+2.2468N^β~H-0.1742N^γ~H。用上式估算了304个碳原子的化学位移,平均绝对误差仅为0.77δ,标准差0.9860δ,预测值与实验值非常吻合。 相似文献
134.
From measurements performed on different polymeric glass-forming liquids using differential scanning calorimetry (DSC), we determined the values of the fragility index m according to the concept proposed by Angell. We calculated the average size of a cooperative rearranging region (CRR) at the glass transition i.e. z(Tg), according to the definition proposed by Solunov. This quantity is linked to the Kauzmann temperature which was determined from dielectric spectroscopy or viscosimetry measurements performed on different samples including three-dimensional polymeric networks and linear polymer families with variable lateral chain lengths. By using our experimental data and others collected in the literature in order to scan a large domain of fragility values, we show that the fragility index m, characterising the glass-forming liquid, can be correlated to z(Tg) which characterises the glass formed. 相似文献
135.
Densities,ρ, ultrasonic speeds, u, viscosities,η, and refractive indices, n, of pure benzene, benzyl alcohol (BA), benzonitrile (BN), benzoyl chloride (BC), chlorobenzene (CB) and their thirty six binary mixtures, with benzene as common component, were measured at 303.15 K over the entire mole fraction range. From these experimental data the values of deviations in ultrasonic speed, △u, isentropic compressibility, △ks,excess acoustic impedance, ZE, deviation in viscosity, Dh, and excess Gibbs free energy of activation of viscous flow, G*E, and partial molar isentropic compressibility, Kφ,20 of BA, BN, BC and CB in benzene were computed. The variation of these derived functions with composition of the mixtures suggested the increased cohesion
(molecular order) in the solution and that interaction (A-B)>(A-A) or (B-B).Moreover, theoretical prediction of ultrasonic speed, viscosity and refractive index of all the four binary mixtures was made on the basis of empirical and semi-empirical relations by using the experimental values of the pure components. Comparison of theoretical results with the experimental values was made in order to assess the suitability of these relations in reproducing the
experimental values of u, η and n. Also, molecular radii of pure liquids and the average molecular radii of binary mixtures were evaluated using the corresponding refractive indices of pure liquids and binary mixtures. The average molecular radii of binary mixtures were found to be additive with respect to mole fraction of the pure component. 相似文献
136.
Summary Gas chromatographic unified retention indices for 43 hydrocarbons (alkanes and cycloalkanes) are given for squalane and OV-101. Comparison of these values and unified retention index increments are presented as linear regression equations with high correlation coefficients and acceptable standard deviations. 相似文献
137.
在分子拓扑理论的基础上,提出一种新的拓扑指数——连接性指数~mG,其中。计算了12个系列94种分子的~0G、~1G值,发现~0G或~1G与这些化合物的Kovts指数具有很好的相关性。该模式计算方法简单,使用方便,预测结果理想。 相似文献
138.
高锰酸盐指数的灰色GM(1,1)预测 总被引:1,自引:0,他引:1
以中山市岐江河近7年的高锰酸盐指数监测数据为基础,采用灰色系统理论中的预测方法,建立了岐江河高锰酸盐指数的灰色预测模型。用该模型预测岐江河2006年、2007年、2008年高锰酸盐指数的值分别为5.3,5.4和5.4。 相似文献
139.
J. Canosa 《The Journal of chemical thermodynamics》2003,35(12):2021-2031
Density, refractive index and speed of sound at T=298.15 K and atmospheric pressure have been measured over the entire composition range for (dimethyl carbonate (DMC) + methanol + ethanol) and (DMC + methanol + 1-propanol). Excess molar volumes, changes of refractive index on mixing and deviations in isentropic compressibility for the above systems have been calculated. The calculated quantities are further fitted to the Cibulka equation to estimate the ternary fitting parameters. Standard deviations from the regression lines are shown. 相似文献
140.
The refractive index, n
D
, and density, ρ, of binary mixtures of monoalcohols + water, have been measured at a temperature of 298.15,K and atmospheric pressure. The variation of the refractive indices of these solutions has also been determined with temperature in the range T = (278.15 to 338.15) K and atmospheric pressure. A comparative study has been made of the refractive indices obtained experimentally and those calculated by means of the Lorentz-Lorenz [Theory of Electrons, Dover Phoenix (1952)] and Gladstone-Dale relations [Trans. R. Soc. London 148:887–902 (1858)]; in all cases, the Gladstone–Dale equation was seen to afford values similar to those obtained experimentally. Calculations have been made of the excess molar volumes, V
E, and the molar refraction deviations, ΔR, of these mixtures and the differences between the experimental values for refractive index and those obtained by means of the Gladstone–Dale equation. Values of V
E were compared with others in the literature. In all cases the V
E values were negative, and in all cases, except in the methanol + water, ΔR showed a maximum for x = 0.8. 相似文献