STATISTICAL FACTORS IN THE CORRELATION OF RATE CONSTANTS AND EQUILIBRIUM CONSTANTS
STATISTICAL FACTORS IN THE CORRELATION OF RATE CONSTANTS AND EQUILIBRIUM CONSTANTS
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DOI：
10.1021/ja01552a035
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发表时间：
1958-01-01
影响因子：
15
通讯作者：
BENSON, SW
中科院分区：
文献类型：
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作者：
BENSON, SW
/ \ Lh。m= k/ k，其中k < r, k <，分别为平衡态和化学反应中反应物和生成物的对称数之比。这导致胺的“相对”碱强度发生了一些有趣的变化。对称修正可以从统计力学推导出来，与目前使用的一些更直观的方法等效。在Brónsted关系的情况下，将一般酸碱催化行为与酸强度相关联，它导致了k和ATion的对称修正的一致方法。指出了在其他“线性自由能关系”中需要这样的修正。
/\ Lh. m= k/K where K< r and K<, are the ratios of symmetry numbers for reactant and product species in equilibrium and chemical reaction, respectively. This leadsto some interesting changes in the “relative” base strengths of amines. The symmetry corrections are derivable from statistical mechanics and are equivalent to some of the more intuitive methods in current use. In the case of the Brónsted relation, correlating general acid-base catalytic behavior with acid strength, it leadsto a consistent method of assigning symmetry corrections to both k and ATion. The need for such corrections in other “linear free-energy relationships” is pointed out.