Jenkins H Donald Brooke, Glasser Leslie
Department of Chemistry, University of Warwick, Coventry, West Midlands, UK.
Inorg Chem. 2006 Feb 20;45(4):1754-6. doi: 10.1021/ic051359x.
The lattice energy of an ionic crystal, U(POT), can be expressed as a linear function of the inverse cube root of its formula unit volume (i.e., Vm(-1/3)); thus, U(POT) approximately 2I(alpha/Vm(1/3) + beta), where alpha and beta are fitted constants and I is the readily calculated ionic strength factor of the lattice. The standard entropy, S, is a linear function of Vm itself: S approximately kVm + c, with fitted constants k and c. The constants alpha and beta have previously been evaluated for salts with charge ratios of 1:1, 1:2, and 2:1 and for the general case q:p, while values of k and c applicable to ionic solids generally have earlier been reported. In this paper, we obtain alpha and beta, k and c, specifically for 2:2 salts (by studying the ionic oxides, sulfates, and carbonates), finding that U(POT)[MX 2:2]/(kJ mol(-1)) approximately 8(119/Vm(1/3) + 60) and S degree [MX 2:2]/(J K(-1) mol(-1)) approximately 1382V(m) + 16.
离子晶体的晶格能U(POT)可表示为其化学式单元体积立方根倒数(即Vm(-1/3))的线性函数;因此,U(POT)≈2I(α/Vm(1/3)+β),其中α和β为拟合常数,I为晶格中易于计算的离子强度因子。标准熵S是Vm本身的线性函数:S≈kVm + c,k和c为拟合常数。之前已针对电荷比为1:1、1:2和2:1的盐以及一般情况q:p评估了常数α和β,而适用于离子固体的k和c值此前已有报道。在本文中,我们专门针对2:2盐(通过研究离子氧化物、硫酸盐和碳酸盐)得到了α和β、k和c,发现U(POT)[MX 2:2]/(kJ mol(-1))≈8(119/Vm(1/3)+60)且S°[MX 2:2]/(J K(-1) mol(-1))≈1382Vm + 16。