S. Wasmus et W. Vielstich, INFLUENCE OF ACETONITRILE, DIMETHYLSULFOXIDE AND LEAD ON THE ELECTROOXIDATION OF SMALL ORGANIC-MOLECULES - AN ONLINE MASS-SPECTROSCOPY STUDY, Journal of electroanalytical chemistry [1992], 359(1-2), 1993, pp. 175-191
The electro-oxidation of HCOOH in 0.05 M H2SO4 was investigated in an
electrolyte containing Pb2+ or acetonitrile. The catalytic effect caus
ed by the simultaneous presence of lead and acetonitrile is higher tha
n that of acetonitrile or lead alone. The influence of acetonitrile on
the electro-oxidation of formamide and dimethylformamide at a painted
Pt electrode in 0.05 M H2SO4 was also investigated. At potentials bel
ow 0.6 V/RHE the oxidation of formamide is catalysed by the presence o
f acetonitrile in the electrolyte; however, the electro-oxidation of d
imethylformamide is inhibited under these conditions. The electro-oxid
ation of HCOOH was also investigated in the presence of dimethylsulpho
xide (DMSO). It was found that DMSO inhibits the oxidation of formic a
cid. The addition of Pb2+ to the DMSO-containing electrolyte is able t
o compensate for the inhibitory effect of DMSO. Nevertheless, the orig
inal catalytic effect of lead is not obtained in the presence of DMSO.
In contrast with formic acid, the electro-oxidation of methanol at a
painted Pt electrode in an electrolyte containing 0.05 M H2SO4+0.1 M C
H3OH is inhibited by the presence of acetonitrile. Furthermore, the in
hibitory effect of the same concentration of DMSO is stronger than tha
t of acetonitrile.