Aqueous proton NMR chemical shifts induced by molal alkali halides have been re-examined and separated into two categories. The first, an upfield shift, has been quantitatively related to the change in hydrogen-bond fraction of the solvent as determined by others. The residue, a downfield shift, is anion dependent, cation independent, and directly proportional to effects induced in organic solutes present in the solvent in low concentration. For this latter effect, I−>Br−>Cl−>F− in inducing a downfield displacement; this order parallels certain Raman spectral changes reported for these solutions and is analogously attributed to charge-overlap effects.
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Glick et al. (1966) studied this question.
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