Solvation spectra. Part 38.—E.s.r. spectra of m-dinitrobenzene anions in water + t-butyl alcohol mixtures: asymmetric hydration
Abstract
In pure aqueous solution m-dinitrobenzene anions are markedly asymmetric, the e.s.r. spectrum exhibiting strong coupling to one nitrogen atom and weak coupling to the other. This is attributed to an asymmetric solvation rather than to ion-pairing and from variations in the e.s.r. line-widths it is shown that the mean life-time of the units increases from about 0.8 µs at 291 K to 4.5 µs at 282 K. Addition of t-butyl alcohol in low concentration caused a slight initial increase in the lifetime of the asymmetrical solvate, but concentrations greater than about 0.04 mol fraction caused a rapid decrease in life-time. m-Dinitrobenzoate dianions behaved similarly but a generalized broadening rendered quantitative studies unsatisfactory. These results are discussed in terms of current theories for the structure of water + alcohol solutions.
Please wait while we load your content...
