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水溶液的性质:从冰点降低看化学和生物化学的多个方面。

The nature of aqueous solutions: insights into multiple facets of chemistry and biochemistry from freezing-point depressions.

机构信息

Department of Chemistry and Biochemistry, Long Island University, University Plaza, Brooklyn, New York 11201, USA.

出版信息

Chemistry. 2010 May 25;16(20):5942-60. doi: 10.1002/chem.200903063.

Abstract

Contrary to current widely held beliefs, many concentrated aqueous solutions of electrolytes and nonelectrolytes behave ideally. For both, the same simple equation yields mole fractions of water that are equal to the theoretical activities of water. No empirical activity coefficients or ad hoc parameters are needed. Thermodynamic hydration numbers and the number of particles produced per mole of solute are found by searching freezing-point depression measurements, as if asking the water, "How much available water solvent is left and how many solute particles are there?" The results answer questions currently under debate: Do solutes alter the nature of water outside their immediate surroundings? What is the number of ion pairs formed by various electrolytes and what affects extents of their formation? What are some factors that cause precipitation of proteins, latexes, and so forth from aqueous solutions upon addition of other solutes (Hofmeister series)? Which nonelectrolytes form aggregates in water and what are the implications? Why do different solutes affect viscosity differently? How do ion-selective channels in cell membranes function at the molecular level?

摘要

与当前普遍持有的观点相反,许多电解质和非电解质的浓水溶液表现出理想行为。对于这两种溶液,相同的简单方程可以得出水的摩尔分数,其等于水的理论活度。不需要经验活度系数或特定参数。通过搜索冰点降低测量值,可以找到热力学水合数和每摩尔溶质产生的粒子数,就好像在问水:“还剩下多少可用的溶剂水,有多少溶质粒子?”结果回答了目前正在争论的问题:溶质是否改变其周围环境以外的水的性质?各种电解质形成的离子对的数量是多少,以及哪些因素影响它们的形成程度?是什么因素导致蛋白质、乳胶等在加入其他溶质时(Hofmeister 序列)从水溶液中沉淀出来?哪些非电解质在水中形成聚集体,其影响是什么?为什么不同的溶质对粘度的影响不同?细胞膜中的离子选择性通道在分子水平上是如何发挥作用的?

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