THERMODYNAMICS OF PROTON IONIZATION IN DILUTE AQUEOUS SOLUTION .7. DELTAH DEGREES AND DELTAS DEGREES VALUES FOR PROTON IONIZATION FROM CARBOXYLIC ACIDS AT 25 DEGREES
THERMODYNAMICS OF PROTON IONIZATION IN DILUTE AQUEOUS SOLUTION .7. DELTAH DEGREES AND DELTAS DEGREES VALUES FOR PROTON IONIZATION FROM CARBOXYLIC ACIDS AT 25 DEGREES
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DOI：
10.1021/ja00978a005
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发表时间：
1967-01-01
影响因子：
15
通讯作者：
HANSEN, LD
中科院分区：
文献类型：
--
作者：
CHRISTEN.JJ;IZATT, RM;HANSEN, LD
用量热法研究了25 ℃下14种一元酸和12种二元酸在水溶液中的质子电离。将所得的aH值与文献中的AG值相结合，计算出相应的AS值。汇编的AG，AH，和AS值报告在这里和文献中给出的质子电离从103单，二，和三羧酸。发现这103种羧酸的AG与50之间存在线性关系。给出了这种线性关系的影响进行了讨论。根据已发表的水溶液静电相互作用理论，考察了25种二元酸从第一步电离到第二步电离时AH 0和AS的变化。通过在柯克伍德和韦斯特海默的方法之后引入有效介电常数项到静电计算中，发现AH 0和AS 0的变化本质上主要是静电的。从所得到的相关性的偏差被视为二羧酸的非静电效应的措施。
A calorimetric study has been made of proton ionization from 14 mono- and 12 dicarboxylic acids in aqueous solution at 25 The resulting aH values are combined with literature AGvalues to calculate corresponding ASvalues. A compilation of AG, AH, and AS values reported here and in the literature is given for proton ionization from 103 mono-, di-, and tricarboxylic acids. A linear relationship is found between AG and 50 for these 103 carboxylic acids. The effects which giverise to this linear relationship are discussed. The changes in AH0 and AS from the first to the second step of ionization for 25 dicarboxylic acids have been examined in the light of published theories of electrostatic interactionin aqueous solutions. By introducing a term for the effective di-electric constant into the electrostatic calculations after the method of Kirkwood and Westheimer, the changes in AH0 and AS0 were found to be primarily electrostatic in nature. Deviations from the resulting correlations were taken as a measure of nonelectrostatic effects for dicarboxylic acids.