Determination of Thermodynamic Equilibrium Constants in Mixed Solvents
Determination of Thermodynamic Equilibrium Constants in Mixed Solvents
复制标题
混合溶剂中热力学平衡常数的测定
DOI：
10.1021/ja01651a110
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发表时间：
1954
影响因子：
15
通讯作者：
W. Fernelius
中科院分区：
文献类型：
--
作者：
L. G. Uitert;W. Fernelius
已证明，通过对电池玻璃电极的刻度，H+，Cl~；饱和。以甘汞电极为浓度探针，利用Harned等人测定的氯化氢在水-二氧六环溶液中的稀溶液活度系数数据，可测定有机物质酸解离常数的2个近似热力学数值(对数中的±0.05)。3此外，pKv和gt；值与形成金属配位化合物的浓度数据一起，允许确定各种配位物种的形成(或稳定性)常数。4由于本报告所述的计算程序有些复杂，已收到要求提供简化的订正数据的请求。为此，提供了随附的图表和30℃时的数据表，可根据这些图表计算图表。(对于30℃以外的任何温度，必须准备不同的图表。)使用该图的步骤如下：(A)AD值的测定。-(1)选择要采用的水与二恶烷的比例，并计算存在的二恶烷的摩尔分数Ni。
It has been demonstrated1 that by calibrating the cell glass electrode; H+, Cl~; satd. calomel electrode as a concentration probe and by employing the dilute solution activity coefficient data for hydrogen chloride in water-dioxane solutions determined by Harned, et al., 2 approximate thermodynamic values (±0.05 in the log) for the acid dissociation con-stants (values) of the organic materials can be determined. 3 Further, the pKv> values together with concentration data for the formation of coor-dination compoundsof metals in which the acid anion functions as a ligand (chelate group) permit the determination of formation (or stability) con-stants for the various coordinated species. 4 Be-cause the calculation procedures as presented1 are somewhat complex, requests have been received that simplified correction data be made available. For this purpose, the accompanying graph and tables of data at 30 from which the graph may be calculated are provided.(For any temperature other than 30 a different graph must be prepared.) The procedure to employ the graph is as follows.(A) Determination of¿ Ad Values.—(1) Choose the water-dioxane ratio to be employed and calcu-late Ni, the mole fraction of dioxane present.