FLUCTUATION THEORY OF HYDROGEN-BONDING IN NEAR-CRITICAL FLUIDS

Recent experiments indicate that the number of hydrogen bonds in solut ions increases in the critical region of the solvent. This effect can be explained by the density fluctuations near the critical point. A th eory of this unusual effect is developed. The theoretical predictions are compared with the experimental data on hydrogen bonding between pe rfluoro-tert-butanol and dimethyl ether in supercritical sulfur hexafl uoride. The theory requires no adjustable parameters and is in excelle nt agreement with the experimental data. Possible applications of this effect for hydrogen-bonding solutions and polymer mixtures are discus sed.