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范特霍夫焓与量热焓之间的显著差异。II.

Significant discrepancies between van't Hoff and calorimetric enthalpies. II.

作者信息

Liu Y, Sturtevant J M

机构信息

Department of Chemistry, Yale University, New Haven, Connecticut 06520, USA.

出版信息

Protein Sci. 1995 Dec;4(12):2559-61. doi: 10.1002/pro.5560041212.

Abstract

Isothermal calorimetric titration of 18-crown-6 ether with BaCl2 in pure aqueous solution over the temperature range 7-40 degrees C gives precise binding constants and enthalpy changes. Nonlinear least-squares fitting of the binding constants to the integrated van't Hoff equation, including a temperature-independent change in heat capacity, leads to van't Hoff enthalpies that differ significantly from the observed calorimetric enthalpies. This perplexing discrepancy appears at present to be very widely occurring.

摘要

在7至40摄氏度的温度范围内,在纯水溶液中用氯化钡对18 - 冠 - 6醚进行等温滴定量热法,可得到精确的结合常数和焓变。将结合常数对积分范特霍夫方程进行非线性最小二乘拟合,包括与温度无关的热容变化,得到的范特霍夫焓与观察到的量热焓有显著差异。目前看来,这种令人困惑的差异非常普遍。

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