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Underpotential deposition of metals – Progress and prospects in modelling

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Abstract

Underpotential deposition (UPD) of metals is analysed from the perspective of phenomeno-logical and statistical thermodynamic considerations; the parameters influencing the UPD shift have been quantitatively indicated using a general formalism. The manner in which the macroscopic properties pertaining to the depositing ions and solvent dipoles and the nature of the metallic substrate influence the UPD process are highlighted; earlier correlations of the UPD shift with the work function differences are rationalised. Anion-induced phase transitions which manifest as sharp peaks in experimental cyclic voltammograms are discussed using statistical thermodynamic models.

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References

  1. Kolb D M, Prazasnyski M and Gerischer H 1974J. Electroanal. Chem. 54 25

    Article  CAS  Google Scholar 

  2. Kolb D M 1978Advances in electrochemistry and electrochemical engineering (eds) H Gerischer and C W Tobias (New York: John Wiley Interscience) vol. 11, p. 125

    Google Scholar 

  3. Aramata A 1997Modern aspects of electrochemistry (eds) J O'M Bockris, R E White and B E Conway (New York: Plenum) vol. 31, p. 181

    Google Scholar 

  4. Herrero E, Buller L J and Abruna H D 2001Chem. Rev. 101 1897

    Article  CAS  Google Scholar 

  5. Toney M and Melroy O R 1991Electrochemical interfaces — Modern techniques for in situ characterization (ed) H D Abruna (Berlin: VCH) p. 57

    Google Scholar 

  6. Gewirth A A and Niece B K 1997Chem. Rev. 97 1129

    Article  CAS  Google Scholar 

  7. Kötz R 1990Advances in electrochemical science and engineering (eds) H Gerischer and C W Tobias (Weinheim: VCH) vol. 1, p. 75

    Google Scholar 

  8. Lehmpfuhl G, Uchida Y, Zei M S and Kolb D M 1999Imaging of surfaces and interfaces (eds) J Lipkowski and P N Ross (New York: Wiley) p. 57

    Google Scholar 

  9. Leiva E 1996Electrochim. Acta 41 2185

    Article  CAS  Google Scholar 

  10. Blum L, Huckaby D A and Legault M D 1996Electrochim. Acta 41 2207

    Article  CAS  Google Scholar 

  11. Rikvold P A, Brown G, Novotny M A and Wieckowski A 1998Coll. Surf. A 134 3

    Article  Google Scholar 

  12. Adzic R R 2002Encyclopedia of electrochemistry (eds) A J Bard and M Stratmann (Weinheim: Wiley-VCH Verlag) vol. 1, p. 561

    Google Scholar 

  13. Jennings G K and Laibinis P E 1997J. Am. Chem. Soc. 119 5208

    Article  CAS  Google Scholar 

  14. Rikvold P A, Zhang J and Sung Y E 1996Electrochim. Acta 41 2175

    Article  CAS  Google Scholar 

  15. Brown G, Rikvold P A, Mitchell S J and Novotny M A 1999Interfacial electrochemistry: Theory, experiment and applications (ed.) A Wieckowski (New York: Marcel Dekker) p. 47

    Google Scholar 

  16. Blum L, Legault M D and Huckaby D A 1999Interfacial electrochemistry: Theory, experiment and applications (ed.) A Wieckowski (New York: Marcel Dekker) p. 19

    Google Scholar 

  17. Sanchez C and Leiva E 1999Electrochim. Acta 45 691

    Article  CAS  Google Scholar 

  18. Schmickler W 1999Annual reports on the progress of chemistry vol. 95 Section C (London: The Royal Society of Chemistry) p. 128

    Google Scholar 

  19. Sudha V and Sangaranarayanan M V 2002J. Phys. Chem. B106 2699

    Google Scholar 

  20. Bockris J O'M and Reddy A K N 2000Modern electrochemistry 2A 2nd edn (New York: Plenum) chapters 6 and 7

    Google Scholar 

  21. Trasatti S 1978Advances in electrochemistry and electrochemical engineering (eds) H Gerischer and C W Tobias (New York: John Wiley Interscience) vol. 10, p. 213

    Google Scholar 

  22. Bewick A and Thomas B 1976J. Electroanal. Chem. 70 239

    Article  CAS  Google Scholar 

  23. Leiva E P M 1993J. Electroanal. Chem. 350 1

    Article  CAS  Google Scholar 

  24. Takayanagi K, Kolb D M, Kambe K and Lehmpfuhl G 1980Surf. Sci. 100 407

    Article  CAS  Google Scholar 

  25. Sudha V and Sangaranarayanan M V 2003J. Phys. Chem. B107 3907

    Google Scholar 

  26. See for example, Conway B E, Gileadi E and Dzieciuch M 1963Electrochim. Acta 8 143

    Article  CAS  Google Scholar 

  27. Angerstein-Kozlowska H, Macdougall B and Conway B E 1972J. Electroanal. Chem. 39 287

    Article  CAS  Google Scholar 

  28. Gu R A, Cao P G, Sun Y H and Tian Z Q 2002J. Electroanal. Chem. 528 121

    Article  CAS  Google Scholar 

  29. Aurbach D and Gottlieb H 1989Electrochim. Acta 34 141

    Article  CAS  Google Scholar 

  30. Goren E, Chusid O and Aurbach D 1991J. Electrochem. Soc. 138 L6

    Article  CAS  Google Scholar 

  31. Badiali J P 1986Electrochim. Acta 31 149

    Article  CAS  Google Scholar 

  32. Schmickler W 1990Chem. Phys. 141 95

    Article  CAS  Google Scholar 

  33. Schmickler W 1996Chem. Rev. 96 3177

    Article  CAS  Google Scholar 

  34. Sanchez C and Leiva E 1998J. Electroanal. Chem. 458 183

    Article  CAS  Google Scholar 

  35. Hohenberg P and Kohn W 1964Phys. Rev. B136 864

    Article  Google Scholar 

  36. Kohn W and Sham L J 1965Phys. Rev. A140 1133

    Article  Google Scholar 

  37. Smith J R 1969Phys. Rev. 181 522

    Article  CAS  Google Scholar 

  38. Leiva E and Schmickler W 1995Electrochim. Acta 40 37

    Article  CAS  Google Scholar 

  39. Saradha R and Sangaranarayanan M V 1998J. Phys. Chem. B102 5468

    Google Scholar 

  40. Ashcroft N W 1966Phys. Lett. 23 48

    Article  CAS  Google Scholar 

  41. Lehnert W and Schmickler W 1991J. Electroanal. Chem. 310 27

    Article  CAS  Google Scholar 

  42. Roudgar A and Gross A 2003J. Electroanal. Chem. 548 121

    Article  CAS  Google Scholar 

  43. Barbec V, Kim M H, Christian S D and Dryhurst G 1979J. Electroanal. Chem. Interfacial Electrochem. 100 111

    Google Scholar 

  44. Elliott C M and Murray R W 1976Anal. Chem. 48 259

    Article  CAS  Google Scholar 

  45. de Levie R 1988Chem. Rev. 88 599

    Article  Google Scholar 

  46. Ising E 1925Z. Phys. 31 253

    Article  CAS  Google Scholar 

  47. Rangarajan S K 1977J. Electroanal. Chem. 82 93

    Article  CAS  Google Scholar 

  48. Sangaranarayanan M V and Rangarajan S K 1984J. Electroanal. Chem. 176 119

    Article  CAS  Google Scholar 

  49. Pushpalatha K and Sangaranarayanan M V 1997J. Electroanal. Chem. 425 39

    Article  CAS  Google Scholar 

  50. Bosco E 1994J. Electroanal. Chem. 379 509

    Article  Google Scholar 

  51. Denny R A and Sangaranarayanan M V 1995Chem. Phys. Lett. 239 131

    Article  Google Scholar 

  52. Glauber R J 1963J. Math. Phys. 4 294

    Article  Google Scholar 

  53. Kawasaki K 1966Phys. Rev. 147 224

    Article  Google Scholar 

  54. Mitchell S J, Brown G and Rikvold P A 2000J. Electroanal. Chem. 493 68

    Article  CAS  Google Scholar 

  55. Zhang J, Sung Y E, Rikvold P A and Wieckowski A 1996J. Chem. Phys. 104 5699

    Article  CAS  Google Scholar 

  56. Brown G, Rikvold P A, Novotny M A and Wieckowski A 1999J. Electrochem. Soc. 146 1035

    Article  CAS  Google Scholar 

  57. Gimenez M C, Del Popolo M G and Leiva E P M 1999Electrochim. Acta 45 699

    Article  CAS  Google Scholar 

  58. Machado E and Buendia G M 2004J. Magn. Magn. Mater. 272-276 249

    Article  CAS  Google Scholar 

  59. Onsager L 1944Phys. Rev. 65 117

    Article  CAS  Google Scholar 

  60. Ma S K 1976Modern theory of critical phenomena (ed.) W A Benjamin (Reading, MA: Addison Wesley)

    Google Scholar 

  61. Ranjbar Sh and Parsafar G A 1999J. Phys. Chem. B103 7514

    Google Scholar 

  62. Baker G A Jr and Graves-Morris P 1981Encyclopedia of mathematics (ed.) G C Rota (Reading, MA: Addison Wesley) vol. 13

    Google Scholar 

  63. Blum L and Huckaby DA 1991J. Chem. Phys. 94 6887

    Article  CAS  Google Scholar 

  64. Blume M, Emery V J and Griffiths R B 1971Phys. Rev. A4 1071

    Google Scholar 

  65. Tarasenko A A and Jastrabik L 1997J. Electroanal. Chem. 440 201

    Article  CAS  Google Scholar 

  66. Sivardiere J and Lajzerowicz J 1975Phys. Rev. A11 2101

    Google Scholar 

  67. Schultze J W and Dickertmann D 1976Surf. Sci. 54 489

    Article  CAS  Google Scholar 

  68. Rajendran L and Sangaranarayanan M V 1997J. Phys. Chem. B101 4583

    Google Scholar 

  69. Arun Prasad M and Sangaranarayanan M V 2004Electrochim. Acta 49 445

    Article  CAS  Google Scholar 

  70. Rama Kant and Rangarajan S K 1990J. Electroanal. Chem. 277 19

    Article  Google Scholar 

  71. Huckaby D A and Blum L 1991J. Electroanal. Chem. 315 255

    Article  CAS  Google Scholar 

  72. Tanaka T 2002Methods of statistical physics (Cambridge: University Press)

    Google Scholar 

  73. Fowler R and Guggenheim E A 1965Statistical thermodynamics (Cambridge: University Press)

    Google Scholar 

  74. Kikuchi R 1951Phys. Rev. 81 988

    Article  Google Scholar 

  75. Saradha R and Sangaranarayanan M V 1997Langmuir 13 5470

    Article  CAS  Google Scholar 

  76. Guidelli R 1981J. Electroanal. Chem. 123 59

    Article  CAS  Google Scholar 

  77. Schmickler W 1983J. Electroanal. Chem. 149 15

    Article  CAS  Google Scholar 

  78. Huckaby D A, Legault M D and Blum L 1998J. Chem. Phys. 109 3600

    Article  CAS  Google Scholar 

  79. Samant M G, Borges G L, Gordon J G, Melroy O R and Blum L 1987J. Am. Chem. Soc. 109 5970

    Article  CAS  Google Scholar 

  80. Tadjeddine A, Guay D, Ladouceur M and Tourillon G 1991Phys. Rev. Lett. 66 2235

    Article  CAS  Google Scholar 

  81. Omar I H, Pauling H J and Juttner K 1993J. Electroanal. Chem. Soc. 140 2187

    Article  CAS  Google Scholar 

  82. Inzelt G and Horanyi G 2000J. Electroanal. Chem. 491 111

    Article  CAS  Google Scholar 

  83. Wandlowski T 2002Encyclopedia of electrochemistry (eds) M Urbakh and E Gileadi (Weinheim: VCH-Wiley) vol. 1, p. 383

    Google Scholar 

  84. Nikitas P 1996Electrochim. Acta 41 2159

    Article  CAS  Google Scholar 

  85. Girija T C and Sangaranarayanan M V 2005J. Solid State Electrochem. (in press)

  86. Pauling L 1960The Nature of Chemical Bond 3rd edn (New York: Cornell Univ. Press) chapter 3

    Google Scholar 

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  1. Department of Chemistry, Indian Institute of Technology — Madras, 600 036, Chennai, India

    V. Sudha & M. V. Sangaranarayanan

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  1. V. Sudha
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Sudha, V., Sangaranarayanan, M.V. Underpotential deposition of metals – Progress and prospects in modelling. J Chem Sci 117, 207–218 (2005). https://doi.org/10.1007/BF02709289

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