链状分子状态方程的推导及热容的推算  

New Perturbation Theory Model for Chain- like Molecule Fluid and the Predicted Heat Capacity

作　　者：梁世强[1] 张秉坚[1] 路映红[1] 胡文暄[2] 金之钧[3] 

机构地区：[1]浙江大学化学系,杭州310027 [2]南京大学地球科学系,南京210093 [3]石油大学盆地与油藏研究中心,北京102200

出　　处：《物理化学学报》2001年第5期416-421,共6页Acta Physico-Chimica Sinica

基　　金：国家重点基础发展规划(973)项目! (G1999043309);国家自然科学基金资助项目! (29977018)&&

摘　　要：在 Barker- Henderson, Zhang以及 Wertheim等微扰理论的基础上 ,以方阱势硬球流体为参考体系 ,将 Zhang的解析表达方法与 Wertheim的链成键自由能的处理方法结合起来 ,推导出自由链接的链状分子流体的 Helmholtz自由能的解析表达式 ,并得到了压缩因子、内能、恒容热容等热力学性质的计算式 .计算结果与 MC(Monte Carlo)模拟结果吻合良好 .对 Zhang的解析表达式与 ' TPT- D' (二阶 Wertheim微扰理论 )的结合也作了推导和计算 .A model for the freely jointed square well chain fluid is developed based on the thermodynamic perturbation theory of Barker- Henderson,Zhang and Wertheim.The analytic representations of square- well monomer by Zhang are extended to obtain a series of representations for thermodynamic properties of square- well chain fluids using the incorporating structural information for square- well monomer of Wertheim's TPT1 model.The same work has been done using incorporating structural information for the diatomic square- well fluid of TPT- D model.The calculated results of compressibility factor,residual internal energy and constant- volume heat capacity of 4- mer,8- mer and 16- mer chain fluids are tested against the MC results and a careful comparison between the model from TPT1 and that from TPT- D has been made.The former agree with MC results much better than the later,especially for internal energy.To obtain the constant- volume heat capacity,NVT MC simulations have been performed.

关 键 词：链状分子 方阱势 微扰理论 热力学性质 分子流体 状态方程 热容 MONTE CARLO模拟 

分 类 号：O642[理学—物理化学]