Abstract
23Na and 81Br NMR spin-lattice relaxation times and signal half widths (Δ1/2) have been measured in 3-methylpyridine (3MP)/H2O/NaBr mixture along T = 294 and 301 K isotherms gradually increasing the mass fractions of salt (X) up to the phase separation boundary. The extreme narrowing condition and thus 1/T 1 = 1/T 2 = πΔ 1/2 was found to be valid in all cases. Discontinuous changes in slope of 1/T 1,2 = f(X) were detected, and then corresponding points on the phase diagram (X, T) were attributed to the borderline between the molecular-ionic solution and the area of enhanced mesoscopic structuring. A very strong relaxation effect was observed for 81Br nuclei reaching relaxation rates of 14,000 s–1. 23Na and 81Br NMR relaxation data together with calculations of quantum chemistry model of electrical field gradient tensor evidence the migration of 3-methylpyridinium at increasing X from the anions hydration shells towards cations. An interchange from migration to steady distribution regimes is observed for anions and vice versa for cations at the borderline of the structured phase.
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