CHARGE DEPENDENCE IN IONIC SOLVATION.
Abstract
Systems consisting of a single electrically neutral or ionic species in interaction with a large number of solvent molecules are treated in general quantum statistical mechanical terms. Such systems are assumed to have Hamiltonians, for each electronic state, which exhibit a dependence upon charge not exceeding quadratic. Changes in the Helmholtz free-energy, energy and entropy functions are determined formally for the process of ionic solvation due to Born. On the basis of a general argument that an electrically neutral species acquires a non-zero potential upon solvation, the changes in the cited thermodynamic functions are shown to be capable of taking on positive values. This behavior is in direct contrast with expectations from the Born expression for such changes. Semiempirical treatment of data available for solvation freeenergies of aqueous ions permits an estimate, of one volt, to be made of this potential. A possible experimental test of this result is described. (Author)
Document Details
- Document Type
- Technical Report
- Publication Date
- Oct 15, 1964
- Accession Number
- AD0607805
Entities
People
- Charles Guttman
- Sidney Golden
Organizations
- Brandeis University