Electrochemistry in Near - Critical and Supercritical Fluids . 2 . Water . Experimental Techniques and the Copper ( I I ) System
نویسندگان
چکیده
An electrochemical cell and electrode system for investigation of aqueous systems under nearand supercritical conditions is described. Cyclic voltammetry of 1.5% w/w KC1 and 6% w/w KBr solutions was investigated and log current vs. potential (Tafel) plots for the chlorine and hydrogen evolution reactions are given. A study of the Cu/Cu(I)/Cu(II) system in Na2S04 and KC1 solutions is described and the variation of the standard potentials of the half-reactions with temperature (to ca. 300 "C) is given. The diffusion coefficient for Cu(I1) was determined by chronoamperometry as a function of temperature (22-245 "C) and shown to increase from 5.4 X 10" cm2/s at 22 OC to 3 X cm2/s at 245 OC. The change of diffusion coefficient with temperature was larger than that predicted by the Stokes-Einstein equation at temperatures above 175 "C.
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