Solvation spectra. Part 32.—Variation in the e.s.r. linewidths of ClO2 and SO –2 in water-butyl alcohol mixtures
Abstract
Because of the dependence of the e.s.r. linewidths on T/η, the predominant relaxation mechanism for both ClO2 and SO–2 is taken to be the motional modulation of spin-rotational interactions. This is more efficient for ClO2 than for SO–2 in water, but the effect of added t-butyl alcohol is markedly different for the two isoelectronic radicals. Whereas the linewidth for SO–2 roughly follows T/η, as expected theoretically, that for ClO2 is independent of viscosity η in the 0-0.1 mol fraction region. These differences are discussed in terms of the clathrate theory of hydration.