物理化学学报 >> 2006, Vol. 22 >> Issue (12): 1478-1483.doi: 10.3866/PKU.WHXB20061209

研究论文 上一篇    下一篇

拓扑量子方法估算液相链烷烃导热率

高硕;曹晨忠   

  1. (中南大学化学化工学院, 长沙 410083; 湖南科技大学化学化工学院, 湖南 湘潭 411201)
  • 收稿日期:2006-06-06 修回日期:2006-07-19 发布日期:2006-12-06
  • 通讯作者: 曹晨忠 E-mail:czcao@hnust.edu.cn

A Topological-Quantum Method for the Estimation of the Thermal Conductivity of Liquid Alkanes

GAO Shuo;CAO Chen-Zhong   

  1. (Central South University, Changsha 410083, P. R. China; Hunan University of Science and Technology, Xiangtan 411201, P. R. China)
  • Received:2006-06-06 Revised:2006-07-19 Published:2006-12-06
  • Contact: CAO Chen-Zhong E-mail:czcao@hnust.edu.cn

摘要: 用烷烃分子C—C键和C—H键键邻接矩阵特征根衡量分子中价电子被束缚的强弱程度, 以该参数和烷烃的支化参数以及温度为变量, 对含有5~24个碳原子的液相烷烃在较大温度范围内的导热率建立一个4参数拟合方程: λ=0.7568−0.2728(ΣX1CC)/NC—C+1.5171(ΣX1CH)/NC—H+7.4×10−5ΣSij+2.0966T −0.4 该模型用于导热率估算, 其标准偏差仅为0.0033 W•m−1•K−1, 相对平均误差仅为2.11%. 用上述方程对拟合集以外的9个烷烃分子的导热率进行预测, 其预测的相对平均误差仅为1.64%, 该预测精度在实验误差范围内. 因此, 此方程可用于化工设计中估算还未经实验测定的液相烷烃的导热率.

关键词: 拓扑量子方法, 键邻接矩阵, 特征根, 导热率, 烷烃

Abstract: The strength that the nucleus attracts the valence electrons in alkane molecules can be scaled by the eigenvalues of the bond orbital-connection matrices of C—C and C—H bonds. Using the above two kinds of eigenvalues, the branching parameter of alkane molecules and temperature parameter, a four-parameter equation was developed to fit the thermal conductivity λ of a training set with 45 alkanes bearing 5 to 24 carbon atoms: λ=0.7568−0.2728(ΣX1CC)/NC—C+1.5171(ΣX1CH)/NC—H+7.4×10−5ΣSij+2.0966T −0.4 The standard error between the estimation values by above equation and the experimental values is only 0.0033 W•m−1•K−1 and the relative average error is only 2.11%. Further, the thermal conductivities of 9 another alkanes excluded in the training set were predicted with the obtained model, and the predicted relative average error is only 1.64%, which is within the experimental uncertainties. Therefore it is expected that this model can be used to estimate and predict the thermal conductivity of liquid alkanes whose λ values have not been measured by experiments.

Key words: Topological-quantum method, Bond-connecting matrix, Eigenvalue, Thermal conductivity, Aalkane