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水的运动:热力学解释是否歪曲了现实?

Water movement: does thermodynamic interpretation distort reality?

作者信息

Essig A, Caplan S R

机构信息

Department of Physiology, Boston University School of Medicine, Massachusetts 02118.

出版信息

Am J Physiol. 1989 Mar;256(3 Pt 1):C694-8. doi: 10.1152/ajpcell.1989.256.3.C694.

DOI:10.1152/ajpcell.1989.256.3.C694
PMID:2923202
Abstract

In a recent theoretical analysis of water flow, Finkelstein (Water Movement Through Lipid Bilayers, Pores, and Plasma Membranes: Theory and Reality, 1987) has attacked the contributions of irreversible thermodynamics, stating that "the thermodynamic treatment of uphill water flow completely distorts reality." Instead he presents a mechanistic formulation. For a porous membrane, water flow is attributed to convection generated by a favorable hydrostatic pressure gradient within pores, even when in the presence of permeant solutes water moves against its chemical potential gradient; water flow may "drag", solute, to an extent determined by the solute partition coefficient, but the possibility that solute flow may drag water is excluded. We argue that this formulation violates the second law of thermodynamics. Water cannot move against its chemical potential gradient because of the influence of only part of the chemical potential gradient. Furthermore, the proposed mechanism requires that at one of the membrane-solution interfaces water must move against both its concentration gradient and the hydrostatic pressure gradient. Also considered by Finkelstein is the nature of the reflection coefficient sigma, a kinetic variable, which he concludes can be evaluated (in a porous membrane) by measurement of the (equilibrium) solute partition coefficient. We claim that in general it is not possible to evaluate a kinetic variable from measurements of equilibrium parameters alone. A valid kinetic analysis must incorporate the contribution of all coupled flows.

摘要

在最近一项关于水流的理论分析中,芬克尔斯坦(《水通过脂质双层、孔道和质膜的运动:理论与现实》,1987年)抨击了不可逆热力学的贡献,称“对水向上流动的热力学处理完全扭曲了现实”。相反,他提出了一种机械论的表述。对于多孔膜,水流归因于孔道内有利的静水压力梯度产生的对流,即使在存在渗透溶质的情况下水逆着其化学势梯度移动;水流可能会“拖动”溶质,其程度由溶质分配系数决定,但溶质流动可能拖动水的可能性被排除。我们认为这种表述违反了热力学第二定律。水不能仅因为化学势梯度的一部分的影响就逆着其化学势梯度移动。此外,所提出的机制要求在膜 - 溶液界面之一处水必须逆着其浓度梯度和静水压力梯度移动。芬克尔斯坦还考虑了反射系数σ的性质,它是一个动力学变量,他得出结论认为(在多孔膜中)可以通过测量(平衡)溶质分配系数来评估它。我们声称一般来说仅通过测量平衡参数不可能评估一个动力学变量。有效的动力学分析必须纳入所有耦合流的贡献。

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