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A simple molecular thermodynamic theory of hydrophobic hydration

机译:疏水水合的简单分子热力学理论

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A recently developed microscopic model for associating fluids that accurately captures the thermodynamics of liquid water [Truskett et al., J. Chem. Phys. 111, 2647 (1999)] is extended to aqueous solutions with nonpolar species. The underlying association model incorporates the highly directional and open nature of water's hydrogen-bond netowrk, and, as a result, captures a number of the distinguishing properties of liquid water such as the density anomaly. The model for aqueous mixtures developed herein predicts many of the thermodynamic signatures of hydrophobic hydration without resorting to empirical temperature-dependent parameters. The predicted solubility of nonpolar species is slight over a wide range of temperatures, and exhibits a minimum as a function of temperature, in accord with experiment. Hydration is opposed by a dominant entropy and favored by the enthalpy at low temperatures. At elevated temperatures these roles are reversed. Furthermore, the hydration entropies for hydrophobes of varying size converge over a very narrow temperature range. Comparison with experimental and simulation dta for nonpolar solutes in water shows that the theory tends to exaggerate the solute's transfer heat capacity at low temperature, and hence solubility minima and entropy convergence are predicted to occur at lower temperatures than observed. Our results support the emerging view that hydrophobic effects can be attributed in large part to the equation of state for pure water.
机译:最近开发的用于关联流体的微观模型可以精确地捕获液态水的热力学[Truskett等,化学杂志,1986年。物理111,2647(1999)]扩展到具有非极性物质的水溶液。潜在的关联模型结合了水的氢键网络的高度定向性和开放性,因此捕获了液态水的许多区别属性,例如密度异常。本文开发的水性混合物模型可预测疏水水合的许多热力学特征,而无需依靠经验依赖温度的参数。根据实验,非极性物质的预测溶解度在很宽的温度范围内很小,并且随温度的变化呈现最小值。水合与主要的熵相反,而低温时的焓则有利。在升高的温度下,这些作用相反。此外,各种尺寸疏水物的水合熵在非常窄的温度范围内收敛。与水中非极性溶质的实验和模拟dta的比较表明,该理论倾向于夸大低温下溶质的传热能力,因此,预计在低于观察到的温度下会出现最低的溶解度和熵收敛。我们的研究结果支持了这样一种新观点,即疏水作用在很大程度上可以归因于纯水的状态方程。

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