含醇二元物系过量焓的测定与缔合对过量焓的影响

Determination of Excess Enthalpies and Effectof Association on Excess Enthalpies of BinaryMixtures Containing Alkanols

用Calvet微量热仪测定了正辛烷—正辛醇、正辛烷—正庚醇、正辛烷-异丙醇及正壬烷-仲丁醇、正壬烷-异丙醇五个二元物系在297.95K、常压下的过量焓H^E数据.用纠正后的QCSM缔合溶液模型对烃-醇物系氢键缔合对过量焓的影响进行了研究.对AGSM基团贡献模型进行了改进,引入了一个“修正参数”.修正后的AGSM模型对短分子链的醇与烷烃的过量焓的预测结果有明显的改善.

The excess enthalpies of five binary systems, n-octane-n-octanol, n-hep-tanol, i-propanol and n-nonane-2-butanol, i-propanol, were determined at 297.95K and under atmospheric pressure with the Calvet microcalorimeter. With the corrected QCSM associatioaal solution model, the effect of hydrogen bond association on excess enthalpies of alkane-alkanol binary systems was investigated. The AGSM group contribution model was modified, and the modified parameters for AGSM model was proposed. The prediction of excess enthalpies with modified AGSM model for the systems containing shorter chain alkanols is better than with AGSM model.