Further studies of chemical shifts in the nuclear resonances of caesium ions in solution

Abstract

An attempt is made to clarify the relation between the empirical logarithmic law and the theory developed by Halliday, Richards & Sharp (1969) to describe and account for the concentration dependence of the nuclear resonance frequency of the caesium ion in solution. It is shown that the range of validity of the empirical law is expected to diminish as the dielectric constant of the solvent falls, and nonlinear regression to a simplified form of the full theoretical equation is proposed as a preferable method of obtaining infinite dilution resonance frequencies. New experimental data are presented to test the predictions of the theory in respect to changes in (i) dielectric constant, (ii) temperature, (iii) ionic strength, and we conclude that the results provide substantial confirmation of the theory.