Poole Colin F
Department of Chemistry, Wayne State University, Detroit, MI 48202, USA.
J Environ Monit. 2005 Jun;7(6):577-80. doi: 10.1039/b501776a. Epub 2005 Apr 22.
The solvation parameter model is used to characterize interactions responsible for adsorption at the gas-water interface for bulk water at 15 and 25 degrees C, snow at -6.8 degrees C, mineral-supported water films (alumina, calcium carbonate and quartz) at 15 degrees C, and dry soil at 15 degrees C. The mineral-supported water films and dry soil adsorption data are modeled at different relative humidities in the range 40-99%. The models produce satisfactory results with standard errors of the estimate of 0.12 to 0.17 for regression of the model predicted adsorption equilibrium constants against the experimental values (range for equilibrium constants -2 to -7 log units). The water surface is polar with a significant capacity for dipole-type and hydrogen-bonding interactions. In addition, it is strongly electron lone pair repulsive. Dispersion interactions favor adsorption at the water surface. Mineral-supported water films at relative humidities greater than 40% demonstrate adsorption properties similar to bulk water. The adsorption characteristics, however, depend on the relative humidity and the nature of the support. In the case of dry soil the adsorption properties at different relative humidities cannot simply be explained by adsorption of a water film covering the soil surface and the changes in adsorption characteristics with relative humidity are more complex than the mineral-supported water films.
溶剂化参数模型用于表征在15和25摄氏度的 bulk 水、-6.8摄氏度的雪、15摄氏度的矿物支撑水膜(氧化铝、碳酸钙和石英)以及15摄氏度的干燥土壤中,在气-水界面处负责吸附的相互作用。矿物支撑水膜和干燥土壤的吸附数据是在40%-99%范围内的不同相对湿度下进行建模的。对于模型预测的吸附平衡常数与实验值(平衡常数范围为-2至-7对数单位)的回归,模型产生了令人满意的结果,估计标准误差为0.12至0.17。水面是极性的,具有显著的偶极型和氢键相互作用能力。此外,它具有很强的电子孤对排斥力。色散相互作用有利于在水面上的吸附。相对湿度大于40%的矿物支撑水膜表现出与 bulk 水相似的吸附特性。然而,吸附特性取决于相对湿度和支撑物的性质。就干燥土壤而言,不同相对湿度下的吸附特性不能简单地用覆盖土壤表面的水膜吸附来解释,并且吸附特性随相对湿度的变化比矿物支撑水膜更为复杂。