It is shown that it is possible to carry out electrochemical reactions in poorly conducting and nonconducting media by means of bipolar electrolyses with dispersions. Polarization equations are predicted for highly simplified models based on the concept of the mixture potential, the surface reactions being assumed to be rate determining. Results for hydrogen evolution/oxidation and oxygen evolution/reduction show that the interpretation of polarization curves at high field strengths will have to take into account the effects of diffusion. The results also show that it should be possible to investigate, monitor, and modify heterogeneous catalyses of reactions in the liquid phase by means of the faradaic currents induced by the electric fields.
In situ infrared spectroelectrochemistry has been used to observe electrolyte/solvent breakdown processes in TBAF/acetonitrile at a platinum electrode. Anodic breakdown gives the adduct CH3CNBF3 as the major product. Cathodic breakdown gives the anion of 3-aminocrotonitrile as the major product in the absence of water, and the formation of this product is a consequence of reduction of hydrogen dissolved in the metal. In the presence of water the anion of acetamide is also formed, and breakdown commences at much less negative potentials.
' 7C35A71 CODES 'S SUBjECT TERMS (Continue on roverse if necessary an'd identify by biock number) ELD ;ROL' 5,8-GROuP * ~ Vibrational analysis, adsorption, platinum metal .9 A&SItRACT XCantinu* on reverse if necessary iand identify by block number) (L7~i c >___The vibrationail frequencies of carbon monoxide adsor ed on a platinum metal cx.electrode are obtained in terms of discrete pairwise mt ratomic interactions. 0~ On the one hand, we show that there is a linear dependence of the shift in * C..l frequency with uniform linear changes In the binding energy of carbon and oxygen to the surface. Experimental evidence suggests that there is a relationship LLJbetween the binding energy and the applied electrostatic potential; based on our-model, we suggest that the relationship is linear. As a result, we predict a ILlinear dependence of the frequency on electrochemical potential in accord with C73experiment. On the other hand, we demonstrate that the applicpat 6on of even a ~elatively large external electric field (of the order of-1-l 0 V/rn) has only a ~Inimus effect on the vibrational frequency shift. We conclude that the direct Uin~ffect of the electrostatic field is unlikely to account for the observed spectral shifts. 20. O$TRIISUTON0 AVAILAII ITYOP ABSTRACT 21 ABSTRACT SECI-RiTY CLASS.FiCATiON 63UNCLASSIFIEOUNt.'TEO 10 SAME AS RPT C3orIC USERS Unclassified 138 14AMI Of 46SPONSIBSLE NOIVIOUAL
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