Shock E L
Department of Earth and Planetary Sciences, Washington University, St. Louis, Missouri 63130, USA.
Am J Sci. 1995 May;295(5):496-580. doi: 10.2475/ajs.295.5.496.
Experimental standard partial molal volumes, heat capacities, and entropies as well as apparent standard partial molal enthalpies and Gibbs free energies of mono- and dicarboxylic acids and their anions at low temperatures and pressures are used to generate correlations for predicting the same properties at high temperatures and pressures for 59 carboxylic and 18 hydroxyacid species with the revised Helgeson-Kirkham-Flowers (HKF) equation of state. Predicted equilibrium dissociation constants are compared with experimental values from the literature and tabulated as functions of pressure and temperature for 25 carboxylic acids and nine hydroxyacids. Close agreement between independent predictions and experimental data supports the generality of the computational techniques and the accuracy of predicted data. These results allow incorporation of a wide variety of organic acids into quantitative interpretations of geochemical processes.
利用一元和二元羧酸及其阴离子在低温低压下的实验标准偏摩尔体积、热容、熵以及表观标准偏摩尔焓和吉布斯自由能,通过修正的Helgeson-Kirkham-Flowers(HKF)状态方程,建立相关性以预测59种羧酸和18种羟基酸在高温高压下的相同性质。将预测的平衡解离常数与文献中的实验值进行比较,并将其制成25种羧酸和9种羟基酸的压力和温度函数表。独立预测结果与实验数据之间的高度吻合支持了计算技术的通用性和预测数据的准确性。这些结果使得能够将多种有机酸纳入地球化学过程的定量解释中。