Browsing by Author "Spitzer, Jan J."

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Theory of electrolytes. Part 3.—On the number density of ions in the Debye–Hückel ionic atmosphere
(Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1978, 74 (09-12), 1978) Spitzer, Jan J.
A new derivation of the number of ions in various fractions of the Debye–Hückel ionic cloud is presented. The results provide an estimate of how many ions are involved in many-body long-range (ion–atmosphere) interactions in ionic solutions.
Theory of electrolytes. Part 4.—Model of polarisable dielectric spheres. “Structure” around ions in solution in relation to ionic solvation and activity coefficients
(Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1978, 74 (09-12), 1978) Bennetto, H. Peter; Spitzer, Jan J.
In a modification of the previous model, the representation of solvated ions as polarisable spheres of dielectric gives realistic activity coefficients. Predictions of the new treatment are examined for three types of non-spherical ionic cloud. Each specific structure of the ionic cloud leads to a characteristic family of curves which can be distinguished by the size and dielectric constant of the ion–solvent complex. A rôle for ionic solvation in promoting lattice-like structures in solutions is suggested. Further analysis of electrostatic contributions to the non-ideal part of the chemical potential reveals an incomplete cancellation of ionic self-energies and interaction energies, which leads to the upturn of activity coefficients at higher concentrations.
Theory of Electrolytes: Part 2.—Tests of the Model of Polarisable Spheres, with some Implications for “ Structure ” in Solutions
(Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1977, 73 (07), 1977) Bennetto, H. P.; Spitzer, Jan J.
Predictions of the polarised-sphere theory of electrolytes are compared with experimental results for 1:1, 1:2 and 1:3 electrolytes in water. The theory gives a good account of activity coefficients for a large number of electrolytes in dilute solution (κa < 0.5), and the partial molal enthalpies for 1:1 electrolytes are also accommodated. A limited survey of the results for hydrochloric acid in a number of solvents shows the applicability of the theory for a wide range of the dielectric constant. The significance of ion-size parameters is discussed in relation to the polarisation of solvated ions, and further developments of the electrostatic model are considered in the light of present limitations. An outline is given of a new approach to the phenomenon of “structure” in solutions.