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含环己烷和环己烷 - d12混合物热扩散中的普遍同位素效应

Universal isotope effect in thermal diffusion of mixtures containing cyclohexane and cyclohexane-d12.

作者信息

Wittko G, Köhler W

机构信息

Physikalisches Institut, Universität Bayreuth, 95440 Bayreuth, Germany.

出版信息

J Chem Phys. 2005 Jul 1;123(1):014506. doi: 10.1063/1.1948368.

Abstract

The Soret coefficients S(T) of the liquids acetone, benzene, benzene-d1, 1,3,5-benzene-d3, benzene-d5, benzene-13C6, benzene-d6, n-hexane, toluene, 1,2,3,4-tetrahydronaphthalene, isobutylbenzene, and 1,6-dibromohexane have been measured in protonated and perdeuterated cyclohexane by a transient holographic grating technique. It has been found that S(T) can be either positive or negative and even change its sign as a function of concentration. The isotope effect DeltaS(T)=-0.99 x 10(-3) K(-1), which is the change of S(T) after isotopic substitution of cyclohexane, neither depends on concentration nor on the nature of the mixing partner. Only in the case of the polar acetone is DeltaS(T) approximately 30% larger but still concentration independent. Based on the experimental findings, some general conclusions about the dependence of the Soret coefficient on molecular properties are drawn.

摘要

已通过瞬态全息光栅技术在质子化和全氘代环己烷中测量了丙酮、苯、苯 - d1、1,3,5 - 苯 - d3、苯 - d5、苯 - 13C6、苯 - d6、正己烷、甲苯、1,2,3,4 - 四氢萘、异丁基苯和1,6 - 二溴己烷等液体的索雷特系数S(T)。研究发现,S(T) 可以为正或为负,甚至会随浓度变化而改变符号。同位素效应ΔS(T)= -0.99×10⁻³ K⁻¹,即环己烷同位素取代后S(T) 的变化,既不依赖于浓度,也不依赖于混合伙伴的性质。只有在极性丙酮的情况下,ΔS(T) 大约大30%,但仍然与浓度无关。基于实验结果,得出了一些关于索雷特系数对分子性质依赖性的一般性结论。

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