- Applications of real-time FTIR spectroscopy to the elucidation of complex electroorganic pathways: electrooxidation of ethylene glycol on gold, platinum, and nickel in alkaline solution
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The electrooxidation pathways of ethylene glycol in alkaline aqueous solution on gold, platinum, and nickel electrodes are explored by means of real-time FTIR spectroscopy in conjunction with cyclic voltammetry. The former enables a quantitative assay of specific intermediates and products formed during the reaction evolution. The electrooxidation on gold features the successive formation of partially oxidized C2 solution species en route to oxalate and carbonate production. The latter species is produced predominantly via the formation of the dialdehyde, glyoxal, based on comparisons with electrooxidative spectral sequences for candidate intermediate species. In contrast, ethylene glycol electrooxidation on platinum exhibits markedly different kinetics and product distributions to those for the partially oxidized C2 species, inferring that at least carbonate production from ethylene glycol occurs largely through sequences of chemisorbed, rather than solution-phase, intermediates. Electrooxidation of ethylene glycol and higher polyols on nickel display a remarkably selective production of formate. This efficient oxidative C-C bond cleavage on nickel is displayed in somewhat different fashion for partially oxidized C2 reactants in that carbonate is predominantly formed. Some possible surface chemical factors responsible for these striking mechanistic differences are discussed.
- Chang, Si-Chung,Ho, Yeunghaw,Weaver, Michael J.
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p. 9506 - 9513
(2007/10/02)
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- Kinetics of Oxidation of Lactic , Mandelic and Glycollic Acids by Diperiodatonickelate(IV) in Alkaline Media
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The title reactions show first order dependence in and .The rate of oxidation increases with increase in and decreases with increase in .A probable mechanism involving an adduct formation between substrate and Ni(IV) and its slow decomposition in slow step is proposed.
- Chandraiah, U,Murthy, C. P.,Kandlikar, Sushama
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p. 162 - 163
(2007/10/02)
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- Kinetics of Oxidation of Primary and Secondary Alcohols by Diperiodatoargentate(III)
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Kinetics of oxidation of ethyl, isopropyl and benzyl alcohols, and glycollic and lactic acids by diperiodatoargentate(III) has been investigated in alkaline medium.The order in and is found to be one each.The reaction rates decrease with increase in and increase with increase in .The nature of reactive species in diperiodatoargentate(III) is discussed.A probable mechanism involving a two-electron transfer from the alcohol moiety to the Ag(III) species is proposed.
- Rao, P. Jaya Prakash,Sethuram, B.,Navaneeth Rao, T.
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p. 733 - 734
(2007/10/02)
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