Chinese Science Bulletin

, Volume 46, Issue 15, pp 1285–1288 | Cite as

Voltammetric studies on free radicals of lower fatty alcohols

  • Junfeng Song
  • Huafeng Fu
  • Wei Guo


In this work, both generation and reduction processes of the α-radicals of lower fatty alcohols were studied by voltammetry in lower fatty alcohols/peroxydisulfate/phosphate buffer system. Experimental results showed that such three reactions were successively completed at negative potential on mercury electrode surface: (i) sulfate radical anion SO 4 was generated electrochemically from one-electron reduction of peroxydisulfate ion S2O 8 2− , (ii) the SO 4 oxidized lower fatty alcohols to the corresponding α-radicals and (iii) the α-radicals were reduced in one-electron and one-proton addition to produce their own reduction waves. The apparent free energy ΔrGm of the α-radicals of lower straight-chain fatty alcohols such as methanol, ethanol, propanol, butanol and pentanol obtained were 107.09, 116.74, 122.53, 126.39 and 129.28 kJ · mol/L, respectively. The proposed method is more simple and convenient than the current approaches based on the radical-chain reaction for studying alcohol oxidation.


lower fatty alcohols alcohol α-radical peroxydisulfate sulfate radical anion voltammetry 


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  1. 1.
    Beylerian, N. M., Khachatrian, A. G., The mechanism of the oxidation of alcohols and aldehydes with peroxydisulphate ion, J. Chem. Soc., Perkin Trans 2, 1984, 1937.Google Scholar
  2. 2.
    Park, J. S. B., Wood, P. M., Gilbert, B. C. et al., EPR evidence for hydroxyl- and substrate-derived radicals in Fe(II)-oxalatehydrogen peroxide reaction: The importance of the reduction of Fe(III)-oxalate by oxygen-conjugated radicals to regenerate Fe (II) in reactions of carbohydrates and model compounds, J. Chem. Soc., Perkin Trans 2, 1999, 923.Google Scholar
  3. 3.
    Gilbert, B. C., Smith, J. R. L., Ward, S. R. et al., Kinetic EPR studies of the addition of carbohydrate-derived radicals to methacrylic acid, J. Chem. Soc., Perkin Trans 2, 1998, 1565.Google Scholar
  4. 4.
    Gilbert, B. C., Stell, J. K., Mechanisms of peroxide decomposition: An ESR study of the reactions of the peroxomonosulphate anion (HOOSO3) with TiIII, FeII, and α-oxygen-substituted radicals, J. Chem. Soc., Perkin Trans 2, 1990, 1281.Google Scholar
  5. 5.
    Fung, Y. S., Mo, S. Y., Determination of ethanol in beer by flow injection dual-pulse staircase voltammetric detection, Analyst, 1996, 121: 369.CrossRefGoogle Scholar
  6. 6.
    Memming, R., Mechanism of the electrochemical reduction of persulfates and hydrogen peroxide, J. Electrochem. Soc., 1969, 116(6): 785.CrossRefGoogle Scholar
  7. 7.
    Liu, Y. C., Zhang, F., Jing, Z. Q., Studies on nitroxides (X VII): The electrochemical behavior and self-decay reduction in aqueous solution, Acta Chimica Sinica (in Chinese), 1987, 45: 477.Google Scholar
  8. 8.
    Song, J. F., Fu, H. F., Guo, W., Determination of ethanol based on polarographic catalytic current of sulfate radical anion using ethanol as catalyst, Anal. Lett., 2000, 33(11): 2259.CrossRefGoogle Scholar
  9. 9.
    Pandey, P. C., Upadhyay, S., Upadhyay, B. C. et al., Ethanol bio-sensors and electrochemical oxidation of NADH, Anal. Biochem., 1998, 260: 195.CrossRefGoogle Scholar
  10. 10.
    Xie, Y. Q., Huber, C. O., Electrocatalysis and amperometric detection using an electrode made of copper oxide and carbon paste, Anal. Chem., 1991, 63: 1714.CrossRefGoogle Scholar

Copyright information

© Science in China Press 2001

Authors and Affiliations

  • Junfeng Song
    • 1
  • Huafeng Fu
    • 1
  • Wei Guo
    • 2
  1. 1.Institute of Electroanalytical ChemistryNorthwest UniversityXi’anChina
  2. 2.Department of ChemistryNorthwest UniversityXi’anChina

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