RUBIDIUM ION HYDRATION IN AMBIENT AND SUPERCRITICAL WATER

X-ray absorption fine structure (XAFS) measurements and analyses are p resented for Rb+ in supercritical water solutions. The structure of th e first hydration shell at ambient conditions is compared to that in t he supercritical region at a temperature of 424 degrees C and pressure s from 382 to 633 bar. For al reported studies, RbBr at a concentratio n of 0.5 molal was used. XAFS results show that there is a well-define d hydration shell around the cation even at 424 degrees C but at these high temperatures the extent of hydration of the Rb cation is reduced by about 40%. A slight contraction of this first shell distance by ab out 0.10 Angstrom is also observed under supercritical conditions. The reduction in the number of water-ion bonds is analogous to the reduct ion in the amount of water-water hydrogen bonding that has been observ ed by others under supercritical conditions. The reduction in waters-o f-hydration under supercritical conditions may also be in part due to formation of contact-ion pairs. (C) 1996 American Institute of Physics .