NMR probing of structural peculiarities in ionic solutions close to critical point

Abstract

(1)H, (23)Na, (35)Cl, (79)Br, and (81)Br NMR chemical shifts (delta) and signal half widths (Delta(12)) have been measured in aqueous electrolyte mixtures [tetrahydrofuran/H(2)ONaCl and 3-methylpyridine (3MP)H(2)ONaBr] at different mass fractions of salt (X) in the one-phase region, close to their lower critical solution points (T(CL)). Discontinuous changes in slope of delta=f(X) and Delta(12)=f(X) have been found in (23)Na and (81)Br NMR spectra of 3MP/water/NaBr solution at X approximately 0.1 and T=301 K. The dependency of (1)H NMR signals of 3MP is continuous over the whole investigated range of X=0.002-0.2, whereas changes in the slope of H(2)O chemical shifts are hardly noticeable. In the two-phase region, i.e., at T>T(CL), a doubling of all NMR signals has been observed. The sensitivity of NMR parameters depends more on composition of solution for anions (Cl(-) and Br(-)) than for cations (Na(+)). A very strong relaxation effect for (81)Br nuclei with relaxation rates reaching 14 000 s(-1) was observed. The results are interpreted in terms of ion-molecular clustering and changes in coherency of dipole configurations of water molecules during supramolecular restructuring of solutions.