Journal of Applied Electrochemistry

, Volume 20, Issue 2, pp 269–280 | Cite as

Electrogenerative oxidation of model alcohols at packed bed anodes

  • John C. Card
  • Stephen E. Lyke
  • Stanley H. Langer
Article

Abstract

The electrogenerative oxidation of dissolved ethanol and 2-propanol in aqueous 1 to 3 M sulphuric acid electrolyte was investigated at several types of packed bed anodes in ion exchange membrane separated cells. The operation of these electrogenerative cells which incorporated a platinum-catalysed commercial oxygen gas-diffusion-type cathode is described. It appears that for dissolved normal primary alcohols composite Teflon-platinum fuel-cell-type electrodes favour aldehyde formation while ‘platinum on graphite’ electrodes favour carboxylic acid formation. Oxidation of dissolved 2-propanol could be controlled to give acetone exclusively.

Keywords

Graphite Platinum Aldehyde Acid Formation Carboxylic Acid 

Nomenclature

A

current accountability (see Equation 4) (%)

d

thickness of the packed bed (cm)

F

Faraday constant (C mol−1)

i

current density (A cm−2)

I

cell current (A)

κ

conductivity of the electrolyte (Ω−1 cm−1)

N

molar production rate (g mol s−1)

α

charge transfer coefficient

ɛ

void fraction

Φ

potential in the electroyte phase (V)

n

number of electrons passed in the electrode reaction

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References

  1. [1]
    R. L. Pesselman, T. M. Meshbesher, S. Floyd and S. H. Langer,Chem. Engng Commun. 38 (1985) 265.Google Scholar
  2. [2]
    S. H. Langer, J. C. Card and M. J. Foral,Pure Appl. Chem. 58 (1986) 895.Google Scholar
  3. [3]
    B. O. Palsson, S. Fathi-Afshar, D. F. Rudd and E. N. Lightfoot,Science 213 (1981) 513.Google Scholar
  4. [4]
    K. Park, P. N. Pintauro, M. M. Baizer and K. Nobe,J. Electrochem. Soc. 132 (1985) 1850.Google Scholar
  5. [5]
    C. Oloman and A. P. Watkinson,Can. J. Chem. Engng 54 (1976) 312.Google Scholar
  6. [6]
    F. Goodridge and M. A. Hamilton,Electrochim. Acta 25 (1980) 481.Google Scholar
  7. [7]
    R. C. Alkire and R. M. Gould,J. Electrochem. Soc. 127 (1980) 605.Google Scholar
  8. [8]
    M. W. Breiter ‘Electrochemical Processes in Fuel Cells’, Springer, New York (1969).Google Scholar
  9. [9]
    W. Vielstich, ‘Fuel Cells’, Wiley, New York (1970).Google Scholar
  10. [10]
    G. Sundholm,J. Electroanal. Chem. 31 (1971) 265.Google Scholar
  11. [11]
    R. A. Rightmire, R. L. Rowland, D. L. Boos and D. L. Beals,J. Electrochem. Soc. 111 (1964) 242.Google Scholar
  12. [12]
    A. R. Blake, A. T. Kuhn and J. G. Sunderland,ibid. 120 (1973) 492.Google Scholar
  13. [13]
    H. Matsui, T. Terazawa and T. Hisano,Nippon Kagaku Kaishi 10 (1974) 1861.Google Scholar
  14. [14]
    K. V. Rao,J. Electrochem. Soc. India 27 (1978) 211.Google Scholar
  15. [15]
    S. N. Raicheva, S. V. Kalcheva, M. V. Christov and E. I. Sokolova,J. Electroanal. Chem. 55 (1974) 213.Google Scholar
  16. [16]
    S. V. Kalcheva, M. V. Christov, E. I. Sokolova and S. N. Raicheva,ibid. 55 (1974) 231.Google Scholar
  17. [17]
    Idem 55 (1974) 223.Google Scholar
  18. [18]
    H. Matsui, T. Hisano and T. Terazawa,Nippon Kagaku Kaishi 5 (1983) 618.Google Scholar
  19. [19]
    J. Willsau and J. Heitbaum,J. Electroanal. Chem. 194 (1985) 27.Google Scholar
  20. [20]
    Idem, Electrochim. Acta 31 (1986) 943.Google Scholar
  21. [21]
    B. Beden, M.-C. Morin, F. Hahn and C. Lamy,J. Electroanal. Chem. 229 (1987) 353.Google Scholar
  22. [22]
    K. V. Rao and C. B. Roy,J. Indian Chem. Soc. 54 (1977) 1180.Google Scholar
  23. [23]
    E. Sokolova,Electrochim. Acta 20 (1975) 323.Google Scholar
  24. [24]
    K. D. Snell and A. G. Keenan,ibid. 27 (1982) 1683.Google Scholar
  25. [25]
    Idem 26 (1981) 1339.Google Scholar
  26. [26]
    M. V. Christov and E. I. Sokolova,J. Electroanal. Chem. 175 (1984) 183.Google Scholar
  27. [27]
    S. N. Raicheva, M. V. Christov and E. I. Sokolova,Electrochim. Acta 26 (1981) 1669.Google Scholar
  28. [28]
    C. Liang and T. C. Franklin,ibid. 9 (1964) 517.Google Scholar
  29. [29]
    G. Horanyi, P. Konig and I. Telcs,Acta Chim. (Budapest) 72 (1972) 165.Google Scholar
  30. [30]
    K. V. Rao and C. B. Roy,Indian J. Chem. 19A (1980) 840.Google Scholar
  31. [31]
    E. I. Sokolova and M. V. Christov,J. Electroanal. Chem. 175 (1984) 195.Google Scholar
  32. [32]
    T. M. Meshbesher, US Pat. No. 4 347 109 (August 31, 1982).Google Scholar
  33. [33]
    R. G. Haldeman, W. P. Colman, S. H. Langer and W. A. Barber,Adv. Chem. Ser. 47 (1965) 106.Google Scholar
  34. [34]
    H. P. Landi, US Pat. 3 527 616 (1970).Google Scholar
  35. [35]
    J. C. Card, M. J. Foral and S. H. Langer,Environ. Sci. Technol. 22 (1988) 1499.Google Scholar
  36. [36]
    E. Mentasti, M. C. Gennaro, C. Sarzanini, C. Balocchi and M. Savigliano,J. Chromatogr. 322 (1985) 177.Google Scholar
  37. [37]
    R. W. McCabe and P. J. Mitchell,Ind. Engng Chem. Prod. Res. Dev. 23 (1984) 196.Google Scholar
  38. [38]
    R. W. McCabe, C. L. DiMaggio and R. J. Madix,J. Phys. Chem. 89 (1985) 854.Google Scholar
  39. [39]
    C. N. Satterfield, ‘Mass Transfer in Heterogeneous Catalysis’, MIT Press, Cambridge, Mass. (1970).Google Scholar
  40. [40]
    E. J. Wilson and C. J. Geankoplis,Ind. Engng Chem. Fund. 5 (1966) 9.Google Scholar
  41. [41]
    H. L. Chum, A. K. Hauser and D. W. Sopher,J. Electrochem. Soc. 130 (1983) 2507.Google Scholar
  42. [42]
    Z. Ogumi, Z. Takehara and S. Yoshizawa,J. Electrochem. Soc. 131 (1984) 769.Google Scholar
  43. [43]
    Z. Ogumi, T. Kuroe and Z. Takehara,ibid. 132 (1985) 2001.Google Scholar
  44. [44]
    A. Streitwieser and C. H. Heathcock, ‘Introduction to Organic Chemistry’, MacMillan, New York (1976).Google Scholar
  45. [45]
    D. Swern (Ed.), ‘Organic Peroxides’, Vol. 1, Wiley, New York (1969).Google Scholar
  46. [46]
    B. I. Podlovchenko, T. D. Gladysheva, V. F. Stenin and V. I. Levina,Sov. Electrochem. 9 (1973) 1579.Google Scholar
  47. [47]
    V. M. Hollnagel and U. Lohse,Z. Physik. Chem. 232 (1966) 237.Google Scholar
  48. [48]
    R. Alkire and P. K. Ng,J. Electrochem. Soc. 121 (1974) 95.Google Scholar
  49. [49]
    T. Risch and J. Newman,ibid. 131 (1984) 2551.Google Scholar

Copyright information

© Chapman and Hall Ltd. 1990

Authors and Affiliations

  • John C. Card
    • 1
  • Stephen E. Lyke
    • 1
  • Stanley H. Langer
    • 1
  1. 1.Chemical Engineering DepartmentUniversity of WisconsinMadisonUSA

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