Electrohydrodimerization (EHD) of ethylcinnamate (EC) on mercury takes place both from hydrotropic solutions of tetraethylammonium-p-toluenesulphonate (TEA-PTS) and from dilute aqueous solutions of the strong surfactant Triton X-100. In both cases the one-electron reduction wave due to hydrodimer formation satisfies the requirements for a rate-determining homogeneous coupling of the electrochemically generated anion radicals. The kinetics of EC EHD on liquid gallium is identical with that on mercury at the same temperature of 31°C in hydrotropic solutions of TEA-PTS; conversely, in aqueous Triton X-100 it is faster than on mercury and satisfies the requirements for a rate-determining heterogeneous radical-radical coupling. This behaviour is explained by a stronger adsorptivity of EC and its intermediate reduction products on gallium than on mercury, so that Triton X-100 does not succeed in displacing these species completely from the electrode surface. The general trend consisting in a higher adsorptivity of organic compounds with conjugated double bonds and/or aromatic rings on gallium than on mercury is explained on the basis of the difference in hydrophilicity between these two metals.

A comparative kinetic investigation of ethylcinnamate electrohydrodimerization on mercury and liquid gallium / G. Pezzatini; S. Becagli; M. Innocenti; R. Guidelli.. - In: JOURNAL OF ELECTROANALYTICAL CHEMISTRY. - ISSN 1572-6657. - STAMPA. - 444:(1998), pp. 261-269.

A comparative kinetic investigation of ethylcinnamate electrohydrodimerization on mercury and liquid gallium

PEZZATINI, GIOVANNI;BECAGLI, SILVIA;INNOCENTI, MASSIMO;GUIDELLI, ROLANDO
1998

Abstract

Electrohydrodimerization (EHD) of ethylcinnamate (EC) on mercury takes place both from hydrotropic solutions of tetraethylammonium-p-toluenesulphonate (TEA-PTS) and from dilute aqueous solutions of the strong surfactant Triton X-100. In both cases the one-electron reduction wave due to hydrodimer formation satisfies the requirements for a rate-determining homogeneous coupling of the electrochemically generated anion radicals. The kinetics of EC EHD on liquid gallium is identical with that on mercury at the same temperature of 31°C in hydrotropic solutions of TEA-PTS; conversely, in aqueous Triton X-100 it is faster than on mercury and satisfies the requirements for a rate-determining heterogeneous radical-radical coupling. This behaviour is explained by a stronger adsorptivity of EC and its intermediate reduction products on gallium than on mercury, so that Triton X-100 does not succeed in displacing these species completely from the electrode surface. The general trend consisting in a higher adsorptivity of organic compounds with conjugated double bonds and/or aromatic rings on gallium than on mercury is explained on the basis of the difference in hydrophilicity between these two metals.
444
261
269
G. Pezzatini; S. Becagli; M. Innocenti; R. Guidelli.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2158/319879
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