The standard electromotive forces of the reversible cells consisted of the Corning monovalent general cation selective electrode (M + ISE) and chloride selective electrode (Cl ISE), namely Cl --ISE｜RbCl( m ),H 2O(1- ...The standard electromotive forces of the reversible cells consisted of the Corning monovalent general cation selective electrode (M + ISE) and chloride selective electrode (Cl ISE), namely Cl --ISE｜RbCl( m ),H 2O(1- x ),DMF( x )｜M +-ISE have been measured, and the standard free energies of transfer(Δ S t ) of RbCl from H 2O to mixtures of H 2O DMF have been calculated, the standard transfer entropies(Δ S t ) have been also calculated from temperature coefficients of Δ G t of RbCl at seven temperatures from 283.15 K to 318.15 K. The behavior of change of Δ S t of RbCl with experimental temperature and mole fraction ( x ) of DMF in the mixed solvents and its influence on the structure of the mixed solvents were discussed on the basis of solvation theory ofelectrolyte solution.展开更多
Based on the partition function in statistical thermodynamics, atomic partit ion parameter fi =lg[(ni－1)0.5·Ar,i] is introduced in this paper. The fi has demonstrated good unitarity for all the ground state ato ...Based on the partition function in statistical thermodynamics, atomic partit ion parameter fi =lg[(ni－1)0.5·Ar,i] is introduced in this paper. The fi has demonstrated good unitarity for all the ground state ato ms, and excellent correlativity with the standard entropies (,J·mol－1·K －1) of 70 cations in solid compounds: = －10.247＋27.508 fi , r=0.996. A satisfactory curve equation is developed as follows: =6.229＋13.257 fi1.5, r= 0.999. On the basis of adjacency matrices and fi , a novel partition connectivit y index is developed for the study on the standard entropies of 64 S block compo unds. The linear regression equation is set up by the least square method: =－3 9.416＋33.9610H, r=0.985. The binary linear equation among and 0H, nM (princip al quantum number of the ground state atoms for S block) is drawn up: =－21.591 ＋32.0720H－31.013nM－1, R=0.990. The calculated values of basically tally w ith the experiment values. fi and 0H demonstrate that the method possesses the a dvantage of easy computation and clear physical significance.展开更多
文摘The standard electromotive forces of the reversible cells consisted of the Corning monovalent general cation selective electrode (M + ISE) and chloride selective electrode (Cl ISE), namely Cl --ISE｜RbCl( m ),H 2O(1- x ),DMF( x )｜M +-ISE have been measured, and the standard free energies of transfer(Δ S t ) of RbCl from H 2O to mixtures of H 2O DMF have been calculated, the standard transfer entropies(Δ S t ) have been also calculated from temperature coefficients of Δ G t of RbCl at seven temperatures from 283.15 K to 318.15 K. The behavior of change of Δ S t of RbCl with experimental temperature and mole fraction ( x ) of DMF in the mixed solvents and its influence on the structure of the mixed solvents were discussed on the basis of solvation theory ofelectrolyte solution.
文摘Based on the partition function in statistical thermodynamics, atomic partit ion parameter fi =lg[(ni－1)0.5·Ar,i] is introduced in this paper. The fi has demonstrated good unitarity for all the ground state ato ms, and excellent correlativity with the standard entropies (,J·mol－1·K －1) of 70 cations in solid compounds: = －10.247＋27.508 fi , r=0.996. A satisfactory curve equation is developed as follows: =6.229＋13.257 fi1.5, r= 0.999. On the basis of adjacency matrices and fi , a novel partition connectivit y index is developed for the study on the standard entropies of 64 S block compo unds. The linear regression equation is set up by the least square method: =－3 9.416＋33.9610H, r=0.985. The binary linear equation among and 0H, nM (princip al quantum number of the ground state atoms for S block) is drawn up: =－21.591 ＋32.0720H－31.013nM－1, R=0.990. The calculated values of basically tally w ith the experiment values. fi and 0H demonstrate that the method possesses the a dvantage of easy computation and clear physical significance.
