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pH changes at near-electrode surfaces

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Abstract

Anodic or cathodic processes in which protons are released or consumed, respectively, lead to local pH changes at the electrode surface. The phenomenon is important in several branches of metal finishing, in corrosion, electro-organic synthesis and other branches of applied electrochemistry, as well as being a factor which can invalidate mechanistic investigations. The concept of ‘pHs’ (near-surface pH) is examined, as are the experimental techniques which have been used to measure it. Many of these are inherently weak. Published results are shown to be largely discrepant, both in respect of the magnitude of the effect and even its incidence. Attempts to treat the phenomenon theoretically are briefly summarized.

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References

  1. A. Brenner, ‘Electrodeposition of Alloys’, Academic Press, New York (1963).

    Google Scholar 

  2. B. A. Cooke, in Industrial Electrochemical Processes' (edited by A. T. Kuhn) Elsevier, Amsterdam (1971) pp. 417–66.

    Google Scholar 

  3. F. Beck,Farbe u. Lack 72 (1966) 218.

    Google Scholar 

  4. Y. Nakamura and K. Kamata,Bull. Chem. Soc. Jap. 43 (1970) 663.

    Google Scholar 

  5. E. Bardal,Corros. Sci. 9 (1969) 887.

    Google Scholar 

  6. A. Almar-Naess,Corros. Sci. 6 (1966) 205.

    Google Scholar 

  7. J. E. Castle and R. T. Tremain,Surf. interfacial anal. 1 (1979) 49.

    Google Scholar 

  8. B. Fedoronko,Adv. Carbohydr. Chem. 29 (1974) 107.

    Google Scholar 

  9. A. Bin Kassim and C. L. Rice,J. Chem. Soc. Farad. Trans. I77 (1981) 683.

    Google Scholar 

  10. H. Dahms,J. Electroanal. Chem. 8 (1964) 5.

    Google Scholar 

  11. S. G. Mairanovskii, in ‘Progress in Polarography’ Vol. 3 (edited by P. Zuman) Wiley Interscience, New York (1972) pp. 330–364.

    Google Scholar 

  12. J. O'M Bockris, D. Drazic and A. R. Despic,Electrochim. Acta 3 (1961) 325.

    Google Scholar 

  13. D. Winkelman,Korrosion (Weinheim)11 (1959) 58.

    Google Scholar 

  14. H. J. Engel and P. Forchammer,Corros. Sci. 5 (1965) 479.

    Google Scholar 

  15. H. Dahms and I. M. Croll,J. Electrochem. Soc. 112 (1965) 771.

    Google Scholar 

  16. N. Koura,Denki Kagaki 47 (1979) 738.

    Google Scholar 

  17. A. T. Kuhn and J. B. Yussof,J. Appl. Electrochem. 9 (1979) 765.

    Google Scholar 

  18. M. Hayes, A. T. Kuhn and W. Patefield,J. Power Sources 2 (1977) 121.

    Google Scholar 

  19. V. A. Panov, Z. A. Kravchenko,Sov. Electrochem. 10 (1974) 1427.

    Google Scholar 

  20. M. D. Birkett and A. T. Kuhn,Electrochim. Acta 22 (1977) 1427.

    Google Scholar 

  21. M. S. Chernovyants and A. I. Zolotov,Zh. Prikl. Khim. 43 (1970) 698.

    Google Scholar 

  22. A. Knoedler and K. W. Neugebohren,Metalloberflaeche 24 (1970) 78.

    Google Scholar 

  23. A. G. Ives and J. R. B. Gilbert, paper presented at 103rd Annual Meeting AIME Dallas February 1974.

  24. H. Gunther, R. Wetzel and L. Muller,Electrochim. Acta 24, (1979) 237.

    Google Scholar 

  25. V. N. Varypaev and V. P. Zinyuk,Sov. Electrochem. 12 (1976) 301.

    Google Scholar 

  26. N. T. Kudrayavstev, M. M. Yarlykov and M. M. Mel'nikova,Zh. Prikl. Khim. 38 (1965) 545.

    Google Scholar 

  27. V. S. Kublanowski,Teor. Eksp. Khim. 11 (1975) 128.

    Google Scholar 

  28. R. P. Slizhis and Yu. Yu. Matulis,Liet. TSR Mokslu. Akad. Darb.,B1 (1964) 45.

    Google Scholar 

  29. V. M. Gershov, B. A. Purin and G. A. Ozol'-Kalnin',Elektrokhimiya 8 (1972) 673.

    Google Scholar 

  30. T. M. Ovchinnikova, A. L. Rotinyan and L. A. Taran,Russ. J. Phys. Chem. 36 (1962) 1031.

    Google Scholar 

  31. S. S. Savelev,Electrokhimiya 10 (1974) 888.

    Google Scholar 

  32. S. S. Savelev,Sov. Electrochem. 11 (1975) 518.

    Google Scholar 

  33. V. M. Gershov and B. A. Purin,Izvest. Akad. Nauk. Latv. SSR, No. 5, (1971) 528.

    Google Scholar 

  34. R. U. Bondar, V. G. Bazdhrev,Zh. Prikl. Khim. 46 (1973) 1996.

    Google Scholar 

  35. V. V. Orekhova and F. K. Andryushenko,Zasch Metall. 10 (1974) 463.

    Google Scholar 

  36. A. G. Ives, J. W. Edington and G. P. Rothwell,Electrochim. Acta 15 (1970) 1797.

    Google Scholar 

  37. V. M. Nagirnyi, R. U. Bondar and V. V. Stender,J. Appl. Chem. USSR 40 (1961) 777.

    Google Scholar 

  38. V. S. Kublanowskii and V. N. Belinskii,Sov. Electrochem. 12 (1976) 1322.

    Google Scholar 

  39. N. A. Schwab and D. P. Zosimovich,Sov. Progr. Chem. 35 (1969) 35.

    Google Scholar 

  40. R. P. Slizhis,Galvanotechnik 61 (1970) 653.

    Google Scholar 

  41. B. M. Matov and B. R. Lazarenko,Elektronnaya Obrabotka Materialov 3 (1969) 44.

    Google Scholar 

  42. A. I. Levin and S. A. Puschkareva,Russ. J. Phys. Chem. 36 (1962) 1034.

    Google Scholar 

  43. A. J. Bard,J. Electroanal. Chem. 3 (1962) 117.

    Google Scholar 

  44. G. S. Collins, H. B. Hamzah and A. T. Kuhn,J. Chem. Tech. Biotechnol. 30 (1980) 423.

    Google Scholar 

  45. T. M. Ovchinnikova and A. L. Rotinyan,Russ. J. Phys. Chem. 37 (1962) 228.

    Google Scholar 

  46. R. P. Slizhis and Yu. Yu. Matulis,Tr. Akad. Nauk. SSR, B1 (1964) 45.

    Google Scholar 

  47. A. L. Rotinyan and T. M. Ovchinnikova, ‘Determination of Acidity in Cathode Layer’, Techn. Nonferrous Metal Publishing House, Leningrad (1962).Chem. Abs. 58 6452.

    Google Scholar 

  48. R. Piontelli and B. Rivolta,Zh. Elektrochem. 59 (1955) 64.

    Google Scholar 

  49. S. I. Berezina, G. A. Vozdvizhenskii and G. P. Dezider'ev,DAN SSSR 77 (1961) 53.

    Google Scholar 

  50. S. I. Berezina and G. S. Vozdvizhenskii,Zh. Prikl. Khim. 24 (1951) 832.

    Google Scholar 

  51. S. I. Berezina, A. Sh. Shaleev, G. S. Vozdvizhenskii, N. T. Grechukhina and G. P. Dezider'ev,Zh. F. Khim. 29 (1955) 237.

    Google Scholar 

  52. H. Vogt,Electrochim. Acta 25 (1980) 527.

    Google Scholar 

  53. M. Kh. Kadyrov, A. I. Golubev, L. I. Koschechkina and M. S. Shekhivatov,Elektrokhimiya 7 (1971) 94.

    Google Scholar 

  54. D. J. G. Ives and G. J. Janz, ‘Reference Electrodes. Theory and Practice’, Academic Press, New York (1961) Ch. 6.

    Google Scholar 

  55. E. I. Storchai and A. I. Turkovskaya,Zasch. Metall. 1 (1965) 118.

    Google Scholar 

  56. J. T. Stock, W. C. Purdy and L. M. Garcia,Chem. Revs. 58 (1958) 611.

    Google Scholar 

  57. R. G. Bates, ‘Determination of pH. Theory and Practice’, Wiley-Interscience, New York (1973) Ch. 10.

    Google Scholar 

  58. V. L. Kheifets, A. L. Rotinyan and T. M. Ovchinnikoca,J. Appl. Chem. USSR (Eng. Transl.)28 (1955) 457.

    Google Scholar 

  59. A. I. Levin and A. I. Falicheva,Zh. Prikl. Khim. 29 (1956) 1673.

    Google Scholar 

  60. A. I. Levin and S. A. Pushkareva,ibid. 31 (1958) 1040.

    Google Scholar 

  61. T. M. Ovchinnikova, L. A. Taran and A. L. Rotinyan,Russ. J. Phys. Chem. 36 (1962) 1031.

    Google Scholar 

  62. M. V. Simonova and A. L. Rotinyan,Zh. Prik. Khim. 37 (1964) 1951.

    Google Scholar 

  63. R. U. Bondar', I. V. Gamali and V. V. Stender,J. Appl. Chem. USSR (Eng. Transl.)40 (1967) 988.

    Google Scholar 

  64. D. P. Zosimovich, N. A. Shvab and V. N. Belinskii,Ukr. Khim. Zh. 35 (1969) 486.

    Google Scholar 

  65. V. G. Mairanovskii, A. A. Engovatov, N. T. Ioffee, V. A. Korsunov and E. I. Korsunova,Sov. Electrochem. 12 (1976) 807.

    Google Scholar 

  66. R. U. Bondar', V. G. Bazdyrev and I. V. Gamali,J. Appl. Chem. USSR (Eng. Transl.)461 (1973) 2119.

    Google Scholar 

  67. J. A. Henricks,Trans. Amer. Electrochem. Soc. 82 (1942) 113.

    Google Scholar 

  68. G. S. Vozdvizhenski,Zh. Prikl. Khim. 20 (1947) 913.

    Google Scholar 

  69. R. G. Golovchanskaya and G. A. Selivanova,Itogi Nauk. Elektrokhim. 96 (1968) Moscow 1970 96–111.Chem. Abs. 74 8847e.

    Google Scholar 

  70. R. M. Lazorenko-Manevich and L. A. Sokolova,Elektrokhimya 14 (1978) 1779.

    Google Scholar 

  71. A. G. Samarcev,Zh. Phys. Chem. A168 (1934) 45.

    Google Scholar 

  72. C. S. Lin, R. W. Moulton and G. L. Putnam,Ind. Eng. Chem. 45 (1953) 640.

    Google Scholar 

  73. G. Hansen,Z. Techn. Physik. 12 (1931) 436.

    Google Scholar 

  74. W. Kinder,Optik 1 (1946) 413.

    Google Scholar 

  75. H. Schardin.Z. Instrum. 53 (1933) 396.

    Google Scholar 

  76. Idem, ibid. 53 (1933) 424.

    Google Scholar 

  77. J. Winckler,Rev. Sci. Instrum. 19 (1948) 307.

    Google Scholar 

  78. G. Wranglen,Acta Chem. Scan. 12 (1958) 1543.

    Google Scholar 

  79. W. R. Wolfe, H. Chessin, E. Yeager and F. Horvorka,J. Electrochem. Soc. 101 (1954) 590.

    Google Scholar 

  80. N. Ibl, Y. Barrada and G. Trumpler,Hel. Chim. Acta 37 (1954) 583.

    Google Scholar 

  81. R. S. Cooper,J. Electrochem. Soc. 105 (1958) 506.

    Google Scholar 

  82. L. P. Stephenson, Doctoral Dissertation, University of Illinois, Urbana, Illinois, USA (1953).

    Google Scholar 

  83. T. Yannakopoulos and A. Brenner,J. Electrochem. Soc. 105 (1958) 521.

    Google Scholar 

  84. A. Brenner,Proc. Am. Electroplat. Soc. 95 (1940).

  85. Idem, ibid. 28 (1941) 28.

    Google Scholar 

  86. A. Brenner and E. G. Wranglen,Sartryck ur Svens. Kemisk. Tidskrift 67 (1955) 81.

    Google Scholar 

  87. A. K. Graham, S. Heiman and H. J. Read,Proc. Am. Electroplat. 95 (1939).

  88. H. J. Read and A. K. Graham,Trans. Electrochem. Soc. 78 (1940) 279.

    Google Scholar 

  89. K. Maejima,J. Min. and Metallurg. Inst. Japan 75 (1954) 857;Idem, ibid. 75 (1959) 1045.

    Google Scholar 

  90. W. L. Kheifets, A. L. Rotinyan and T. M. Ovchinnikova,J. Appl. Chem. USSR 28 (1955) 457.

    Google Scholar 

  91. R. K. Flatt, R. W. Wood and P. A. Brook,J. Appl. Electrochem. 1 (1971) 35.

    Google Scholar 

  92. C. Y. Chan, K. H. Khoo, T. K. Lim and A. T. Kuhn,Surface Technol. 15 (1982) 383.

    Google Scholar 

  93. N. Ibl and U. Braun,Chimia 21 (1967) 395.

    Google Scholar 

  94. L. B. Harris,J. Electrochem. Soc. 120 (1973) 1034.

    Google Scholar 

  95. V. S. Kublanowski, A. V. Gorodyskii and V. V. Pototskaya,Sov. Electrochem 13 (1977) 368.

    Google Scholar 

  96. R. Y. Bek and L. I. Borodikhina,Sov. Electrochem. 14 (1978) 121.

    Google Scholar 

  97. O. V. Kurov and R. K. Melekhov,Zhassch Metall. 15 (1979) 314.

    Google Scholar 

  98. N. Lukomski and K. Bohnenkamp,Werkstoff Korros. 30 (1979) 482.

    Google Scholar 

  99. K. Koichi,Keikinzoku 29 (1979) 563.

    Google Scholar 

  100. N. D. Tomashov,Bevord. Bunsenges. 84 (1980) 383.

    Google Scholar 

  101. B. I. Bairachnyi,Zh. Prik. Khim. 52 (1979) 870.

    Google Scholar 

  102. Yu. A. Kovalenko and N. Ya Kovarski,Zh. Prikl. Khim. 52 (1979) 1646.

    Google Scholar 

  103. T. Inui,Kinzoku Hyomen Gijutsu 32 (1981) 568.

    Google Scholar 

  104. J. Matulis and R. Slizys,Electrochim. Acta 9 (1964) 1177.

    Google Scholar 

  105. G. H. Kelsall, Personal Communication.

  106. F. Ovari,Hung. J. Indust. Chem. 10 (1982) 511.

    Google Scholar 

  107. A. Turnbull and M. K. Gardner,Brit. Corros. J. 16 (1981) 140.

    Google Scholar 

  108. Idem, J. Electrochem. Soc. 129 (1982) 1412.

    Google Scholar 

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Authors and Affiliations

  1. Institute of Dental Surgery, Eastman Dental Hospital, Grays Inn Road, WC1X 8LD, London, UK

    A. T. Kuhn

  2. Department of Chemistry, University of Malaya, Kuala Lumpur, Malaya

    C. Y. Chan

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  1. A. T. Kuhn
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  2. C. Y. Chan
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Kuhn, A.T., Chan, C.Y. pH changes at near-electrode surfaces. J Appl Electrochem 13, 189–207 (1983). https://doi.org/10.1007/BF00612481

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