阳离子标准熵、水合焓与配分函数的相关性

Studies on the Correlativities of Partition Function with Standard Entropy and Hydrated Enthalpy of Cations

根据独立共同可别粒子体系的熵与配分函数关系 ,建立 70种固体化合物中阳离子标准熵 [S0m/( J· mol- 1· K- 1) ]与其相对原子质量 ( Ar,i)、电子层数 ( ni)的数学模型 :S0m=- 0 .5 1 +3.5 9· ( 1 .5 ln Ar,i) 1.4 - 0 .31 ( ln ni) 2 ,R=0 .9996.对于独立共同不可别粒子体系的焓与配分函数的关系 ,建立 5 1种金属离子水合热 [Δh Hm/( k J· mol- 1) ]与其基态能量 (εi)的回归方程为 :-Δh Hm=46.93+ 5 2 5 .49εi,R=0 .992 0 .以上模型的计算值与实验值都基本吻合 .

Based on the relationship between partition function and entropy in statistical thermodynamics for a distinguishable particle system, the atomic weight (A_(r,i)) and electronic shell number(n_i) of ground state atom i has an excellent correlativity with the standard entropies \{[S^0_m/(J·mol^(-1)·K^(-1))]\} of 70 cations in solid compounds: S^0_m=(-0.51)+(3.59)·((1.5\}ln A_(r,i))^(1.4)-\{0.31(ln\} n_i)~2, R=(0.999 6.) Based on the relationship between enthalpy and partition function for an indistinguishable particle system, the linear regression equation between ground state energies (ε_i) and hydrated enthalpies[-Δ_hH_m/(kJ·mol^(-1))] of 51 metal ions is drawn up: -Δ_hH_m=46.93+525.49ε_i, R=(0.992 0). The calculated values of S^0_m, (Δ_hH_m) basically tally with the experiment values.