The influence of temperature in the range 75-180 degrees C on the solvation
properties of pressurized water is studied by use of chromatography for a
varied group of compounds on a porous polymer sorbent PLRP-S 100, The solva
tion parameter model is used as the basis of a quantitative comparison of t
he influence of temperature and solvent composition variation on the elutio
n strength and selectivity of the mobile phase. The predominant influence o
f increasing temperature on the solvation properties of water is to reduce
its cohesion and capacity for hydrogen-bond interactions. Even at 189 degre
es C, however, hot water retains sufficient of its room temperature propert
ies to remain a relatively weak eluting solvent in reversed-phase chromatog
raphy compared with aqueous mixtures of miscible organic solvents. Changes
in selectivity accompanying composition variation for acetonitrile, methano
l, and propan-2-ol are quantitatively different from those demonstrated for
temperature variation of pressurized water, indicating that for method dev
elopment the two processes are complementary rather than redundant.