03. Gupta, Ram B.; Combes, James R.; Johnston, Keith P. Solvent effect on hydrogen bonding in supercritical fluids. J. Phys. Chem. (1993), 97(3), 707-15.

Abstract

A pronounced solvent effect on the H bonding of methanol and triethylamine is obsd. throughout the gate, supercrit., and liq. states in the relatively inert solvent SF6, based on FTIR spectroscopy. The free energy of H bonding is stabilized by a decrease in d.; i.e., the donor and acceptor are destabilized more than the complex as the solvation is reduced. Also,the H-bond energy becomes larger. The H-bonding lattice-fluid (LFHB) model is extended to treat this d. dependence, and the calcns. are in reasonable agreement with expt. Near the mixt. crit. point, the no. of H bonding encounters between the donor and acceptor is enhanced due to solute-solute clustering as expected on the basis of previous exptl. and computer simulation studies.

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