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The evaluation and use of properties of individual ions in slution

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Abstract

A critical examination is given of extra-thermodynamic methods for evaluation of properties of individual ions in solution. The ways in which such data may be applied, or are required in various problems concerning specific properties of electrolyte solutions and in the fields of kinetics, electrochemistry, colloid and interfacial chemistry, are outlined. Special attention is given to the problem of evaluation of individual ionic thermodynamic functions for the hydration of ions but, in some cases, corresponding data for nonaqueous solutions are available for discussion and are of interest in a comparative way. The reliability of the various methods is assessed and estimates of numerical values for various individual ionic functions are tabulated. The question of scales of individual ionic radii, on which some of the derived data depend, is also examined. The dependence of various properties for anions and for cations on ionic radius is discussed and data are plotted comparatively. It is shown that for most, but not all, properties, the values for anions are more sensitive to increasing ionic radius than are the values for cations. This behavior, as well as the exceptions, is of theoretical interest. The significance of ion-specific behavior at interfaces is considered and the importance of interactions between ions of like sign of charge is indicated.

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References

  1. E. A. Guggenheim,J. Phys. Chem. 33, 842 (1929);34, 1540 (1930).

    Google Scholar 

  2. J. Tamamushi,Bull. Chem. Soc. Jpn. 47, 1921 (1974)

    Google Scholar 

  3. J. Keilland,J. Am. Chem. Soc. 59, 1675, (1937)

    Google Scholar 

  4. H. S. Frank,J. Phys. Chem. 67, 1554 (1963);Z. Phys. Chem. (Leipzig) 228, 364 (1965)

    Google Scholar 

  5. R. N. Goldberg and H. S. Frank,J. Phys. Chem. 76, 1758 (1972).

    Google Scholar 

  6. R. J. P. Williams,J. Bioenerg. 1, 215 (1970);Rep. Prog. Pure Appl. Chem. 54, 219 (1969).

    Google Scholar 

  7. A. Ikegami,J. Polym. Sci. Part A 2, 907 (1964); S. Lapanje, I. Haebig, H. T. Davis, and S. A. Rice,J. Am. Chem. Soc. 83, 1590 (1961).

    Google Scholar 

  8. I. M. Klotz, inThe Proteins, Vol. I, Pt. B, H. Neurath and K. Bailey, eds. (Academic Press, New York, 1953), p. 793.

    Google Scholar 

  9. B. Katz,Nerve, Muscle, and Synapse (Mc-Graw-Hill, New York, 1966).

    Google Scholar 

  10. B. E. Conway,Adv. Colloid Interface Sci. 8, 91 (1977).

    Google Scholar 

  11. E. J. W. Verwey,Rec. Trav. Chim. Pays-Bas 60, 887 (1941);61, 127 (1942).

    Google Scholar 

  12. A. D. Buckingham,Disc. Faraday Soc. 24, 151 (1957).

    Google Scholar 

  13. J. E. Desnoyers, M. Arel, G. Perron, and C. Jolicoeur,J. Phys. Chem.,73, 3347 (1969).

    Google Scholar 

  14. P. S. Ramanathan, C. V. Krishnan, and H. L. Friedman,J. Solution Chem. 1, 237 (1972); J. C. Rasaiah,J. Solution Chem. 2, 301 (1973).

    Google Scholar 

  15. R. H. Stokes and R. A. Robinson,J. Am. Chem. Soc. 70, 1870 (1948);Ann. N. Y. Acad. Sci. 51, 593 (1949).

    Google Scholar 

  16. B. E. Conway, H. Angerstein-Kozlowska, and W. B. A. Sharp,J. Chem. Soc. Faraday Trans. 74, 1373 (1978).

    Google Scholar 

  17. G. Zundel,Hydration and Intermolecular Interaction (Academic Press, New York, 1969).

    Google Scholar 

  18. E. V. von Dehmlow,Angew. Chem. 89, 521 (1977).

    Google Scholar 

  19. C. Gavach, P. Seta, and B. D'Epenoux,J. Electroanal. Chem. 83, 225 (1977).

    Google Scholar 

  20. K. Fajans,Verh. Dtsch. Phys. Ges. 21, 549; 709 (1919).

    Google Scholar 

  21. R. Parsons, inModern Aspects of Electrochemistry, J. O'M. Bockris and B. E. Conway eds. (Butterworths, London, 1954), Chapter 3.

    Google Scholar 

  22. J. E. B. Randles and D. Schiffrin,J. Electroanal. Chem. 10, 480 (1965).

    Google Scholar 

  23. B. E. Conway,J. Electroanal. Chem. 65, 491 (1975).

    Google Scholar 

  24. L. Onsager and N. N. T. Samaras,J. Chem. Phys. 2, 528 (1934); G. M. Bell and P. D. Rangecroft,Trans. Faraday Soc. 67, 649 (1971).

    Google Scholar 

  25. D. R. Rosseinsky,J. Chem. Soc., 785 (1962);Chem. Rev 65, 467 (1965); L. Benjamin and V. Gold,Trans. Faraday Soc. 50, 797 (1954).

  26. B. E. Conway and J. O'M. Bockris, inModern Aspects of Electrochemistry, J. O'M. Bockris and B. E. Conway, eds. (Butterworths, London, 1954), Chapter 2.

    Google Scholar 

  27. Water: A Comprehensive Treatise, Vol. 3, F. Franks, ed. (Plenum Press, New York, 1973).

    Google Scholar 

  28. J. D. Bernal and R. H. Fowler,J. Chem. Phys. 1, 515 (1933).

    Google Scholar 

  29. M. J. Blandamer and M. C. R. Symons,J. Phys. Chem. 67, 1304 (1963).

    Google Scholar 

  30. W. M. Latimer, K. S. Pitzer, and A. Slansky,J. Chem. Phys. 7, 108 (1939).

    Google Scholar 

  31. D. F. C. Morris,Struct. Bond. 4, 63 (1968).

    Google Scholar 

  32. W. M. Latimer, K. S. Pitzer, and C. Smith,J. Am. Chem. Soc. 60, 1839 (1938).

    Google Scholar 

  33. W. M. Noyes,J. Am. Chem. Soc. 84, 513 (1962).

    Google Scholar 

  34. F. Booth,J. Chem. Phys. 19, 391, 1327, 1615 (1949); D. C. Grahame,J. Chem. Phys. 21, 1054 (1951).

    Google Scholar 

  35. R. H. Stokes,J. Am. Chem. Soc. 86, 979 (1964).

    Google Scholar 

  36. K. J. Laidler and C. Pegis,Proc. Roy. Soc. London Ser. A 241, 80 (1957).

    Google Scholar 

  37. B. E. Conway, inModern Aspects of Electrochemistry Vol. 3, J. O'M. Bockris and B. E. Conway eds. (Butterworths, London, 1964), Chapter 2.

    Google Scholar 

  38. H. F. Halliwell and S. C. Nyburg,Trans. Faraday Soc. 59, 1126 (1963).

    Google Scholar 

  39. B. E. Conway and M. Salomon, inChemical Physics of Ionic Solutions, B. E. Conway and R. G. Barradas, eds. (Wiley, New York, 1966), Chapter 24, p. 541.

    Google Scholar 

  40. J. E. B. Randles,Trans. Faraday Soc. 52, 1573 (1956).

    Google Scholar 

  41. J. Kenrick,Z. Phys. Chem. 19, 625 (1896).

    Google Scholar 

  42. J. E. Desnoyers and C. Jolicoeur, inModern Aspects of Electrochemistry, Vol. 5, B. E. Conway and J. O'M. Bockris, eds. (Plenum Press, New York, 1969), Chapter 1.

    Google Scholar 

  43. J. O. Halford,J. Chem. Phys. 2, 694 (1934).

    Google Scholar 

  44. M. Eastman,J. Am. Chem. Soc. 50, 283; 292 (1928).

    Google Scholar 

  45. H. D. Crockford and J. R. Hall,J. Phys. Chem. 54, 731 (1950).

    Google Scholar 

  46. W. G. Breck and J. Lin,Trans. Faraday Soc. 61, 2223 (1965).

    Google Scholar 

  47. T. Ikeda,J. Chem. Phys. 40, 3412 (1965).

    Google Scholar 

  48. H. J. V. Tyrell and G. L. Hollis,Trans. Faraday Soc. 45, 411 (1949).

    Google Scholar 

  49. J. C. Goodrich, F. M. Goyan, E. E. Morne, R. G. Preston and M. B. Young,J. Am. Chem. Soc. 72, 4411 (1950).

    Google Scholar 

  50. F. H. Lee and Y. K. Tai,J. Chin. Chem. Soc. 8, 60 (1941).

    Google Scholar 

  51. R. W. Gurney,Ionic Processes in Solution (McGraw-Hill, New York, 1954), Chapter 10.

    Google Scholar 

  52. H. S. Frank and M. W. Evans,J. Chem. Phys. 13, 507 (1945).

    Google Scholar 

  53. C. M. Criss and J. W. Cobble,J. Am. Chem. Soc. 86, 5390 (1964).

    Google Scholar 

  54. D. H. Everett and W. F. K. Wynne-Jones,Proc. Roy. Soc. London Ser. A 140, 440 (1943).

    Google Scholar 

  55. C. Shin, I. Worsley, and C. M. Criss,J. Solution Chem. 5, 867 (1976).

    Google Scholar 

  56. C. Shin and C. M. Criss,J. Solution Chem. 7, 205 (1978).

    Google Scholar 

  57. A. Pasztor and C. M. Criss,J. Solution Chem. 7, 27 (1978).

    Google Scholar 

  58. Y. Choi and C. M. Criss,Faraday Disc. Chem. Soc., in press (1978).

  59. B. E. Conway, J. E. Desnoyers, and R. E. Verrall,Trans. Faraday Soc. 62, 2738 (1966);Z. Phys. Chem. (Leipzig) 230, 157 (1965).

    Google Scholar 

  60. G. Nemethy and H. A. Scheraga,J. Chem. Phys. 36, 3401 (1962).

    Google Scholar 

  61. C. Jolicoeur and J-C. Mercier,J. Phys. Chem. 81, 1119 (1977).

    Google Scholar 

  62. C. G. Malmberg and A. A. Maryott,J. Res. Nat. Bur. Stand. 56, 1 (1956).

    Google Scholar 

  63. L. Laliberté and B. E. Conway,Trans. Faraday Soc. 66, 3032 (1970).

    Google Scholar 

  64. B. E. Conway, J. E. Desnoyers, and R. E. Verrall,J. Phys. Chem. 75, 3031 (1971).

    Google Scholar 

  65. M. H. Panckhurst,Rev. Pure Appl. Chem. 19, 45 (1969).

    Google Scholar 

  66. B. E. Conway, D. M. Novak, and L. Laliberté,J. Solution Chem. 3, 683 (1974).

    Google Scholar 

  67. P. Debye,J. Chem. Phys. 1, 13 (1933).

    Google Scholar 

  68. J. Bugosh, E. Yeager, and F. Hovorka,J. Chem. Phys. 15, 592 (1947).

    Google Scholar 

  69. R. Zana and E. Yeager,J. Phys. Chem. 70, 954 (1966);71, 521 (1967).

    Google Scholar 

  70. F. Kawaizumi and R. Zana,J. Phys. Chem. 78, 1099 (1974).

    Google Scholar 

  71. F. Kawaizumi and R. Zana,J. Phys. Chem. 78, 627 (1974).

    Google Scholar 

  72. K. M. Kale and R. Zana,J. Solution Chem. 6, 733 (1977).

    Google Scholar 

  73. F. T. Gucker, C. L. Chernik, and R. Roy-Chowdhury,Proc. Nat. Acad. Sci. U.S.A. 55, 12 (1965).

    Google Scholar 

  74. D. S. Allam and W. H. Lee,J. Chem. Soc. A 5 (1966).

  75. L. A. Dunn, R. H. Stokes, and L. G. Hepler,J. Phys. Chem. 69, 2808 (1965).

    Google Scholar 

  76. H. S. Harned and B. B. Owen,The Physical Chemistry of Electrolytic Solutions, 3rd edn., (Reinhold, New York, 1958), p. 380.

    Google Scholar 

  77. J. G. Mathieson and B. E. Conway,J. Solution Chem. 3, 455 (1974).

    Google Scholar 

  78. P. Drude and W. Nernst,Z. Phys. Chem. 15, 79 (1894).

    Google Scholar 

  79. L. G. Hepler,J. Phys. Chem. 61, 1426 (1957).

    Google Scholar 

  80. E. Glueckauf,Trans. Faraday Soc. 64, 2423 (1968).

    Google Scholar 

  81. L. Laliberté and B. E. Conway,J. Phys. Chem. 72, 4317 (1968).

    Google Scholar 

  82. C. H. Collie, D. M. Ritson, and J. B. Hasted,J. Chem. Phys. 16, 1 (1948).

    Google Scholar 

  83. G. H. Haggis, J. B. Hasted, and T. J. Buchanan,J. Chem. Phys. 20, 1452 (1952).

    Google Scholar 

  84. R. W. Rampolla, R. C. Miller and C. P. Smyth,J. Chem. Phys. 30, 566 (1959).

    Google Scholar 

  85. J. A. Schellman,J. Chem. Phys. 25, 350 (1956).

    Google Scholar 

  86. P. D. Eley and M. G. Evans,Trans. Faraday Soc. 34, 1093 (1938).

    Google Scholar 

  87. R. N. Butler and M. C. R. Symons,Trans. Faraday Soc. 65, 945, 2559 (1969).

    Google Scholar 

  88. J. C. Hindman,J. Chem. Phys. 36, 1000 (1962).

    Google Scholar 

  89. A. K. Covington and K. E. Newman, inModern Aspects of Electrochemistry, Vol. 12, J. O'M. Bockris and B. E. Conway, eds. (Plenum Press, New York, 1977), Chapter 2.

    Google Scholar 

  90. H. Schneider, inSolute-Solvent Interactions, Vol. 2, J. F. Coetzee and J. D. Ritchie, eds. (Marcel Dekker, New York, 1976), p. 155.

    Google Scholar 

  91. J. Davies, S. Ormondroyd and M. C. R. Symons,J. Chem. Soc. Faraday Trans. 2 68, 686 (1972).

    Google Scholar 

  92. J. F. Hinton and E. S. Amis,Chem. Rev. 67, 367 (1967).

    Google Scholar 

  93. A. H. Narten,J. Phys. Chem. 74, 765 (1970); A. H. Narten and S. Lindenbaum,J. Chem. Phys. 51, 1108 (1969).

    Google Scholar 

  94. V. Gutmann,Electrochim. Acta 21, 661 (1976).

    Google Scholar 

  95. C. Treiner,Can. J. Chem. 55, 682 (1977).

    Google Scholar 

  96. E. Grunwald, G. Baughman, and G. Kohnstam,J. Am. Chem. Soc. 82, 5801 (1960).

    Google Scholar 

  97. O. Popovych,Anal. Chem. 46, 2009 (1974).

    Google Scholar 

  98. O. Popovych,Crit. Rev. Anal. Chem. 1, 73 (1970).

    Google Scholar 

  99. A. J. Parker and R. Alexander,J. Am. Chem. Soc. 89, 5549 (1967);90, 3313 (1968).

    Google Scholar 

  100. B. G. Cox, G. R. Hedwig, A. J. Parker, and D. W. Watts,Aust. J. Chem. 27, 477 (1974).

    Google Scholar 

  101. J. F. Coetzee and W. R. Sharpe,J. Phys. Chem. 75, 3141 (1971).

    Google Scholar 

  102. H. Strelow, inThe Chemistry of Non-aqueous Solvents, J. J. Lagowski, ed. (Academic Press, New York, 1966), Chapter 4.

    Google Scholar 

  103. N. A. Izmailov,Dokl. Akad. Nauk SSSR,126, 1033 (1959).

    Google Scholar 

  104. C. M. Criss and M. Salomon,J. Chem. Educ. 53, 263 (1976).

    Google Scholar 

  105. B. G. Cox and A. J. Parker,J. Am. Chem. Soc. 95, 402 (1973).

    Google Scholar 

  106. M. Salomon,J. Phys. Chem. 79, 2000 (1975).

    Google Scholar 

  107. M. Salomon and B. K. Stevenson,J. Phys. Chem. 77, 3002 (1973).

    Google Scholar 

  108. M. Salomon,J. Phys. Chem. 79, 1817 (1974);79, 429 (1975).

    Google Scholar 

  109. H. L. Friedman,J. Phys. Chem. 71, 1723 (1967).

    Google Scholar 

  110. K. Fajans,Naturwissenschaften 9, 729 (1921).

    Google Scholar 

  111. B. E. Conway,J. Solution Chem. 6, 23 (1977).

    Google Scholar 

  112. V. M. Goldschmidt,Nor. Vidensk. Akad. Oslo Skr. Math. Nat. Kl., No. 2 (1926).

  113. L. Pauling,The Nature of the Chemical Bond (Cornell Univ. Press, Ithaca, New York, 1960).

    Google Scholar 

  114. A. Landé,Z. Phys. 1, 191 (1920).

    Google Scholar 

  115. H. Witte and E. Wölfel,Z. Phys. Chem. N.F. 3, 296 (1955).

    Google Scholar 

  116. G. Schoknecht,Z. Naturforsch. Teil A 12, 983 (1957).

    Google Scholar 

  117. R. Hosemann,Freib. Forschungsh. B 37, 99 (1959).

    Google Scholar 

  118. V. Meisalo and O. Inkenen,Acta Cryst. 22, 58 (1967).

    Google Scholar 

  119. S. Gourary and F. J. Adrian,Solid State Phys. 10, 128 (1960).

    Google Scholar 

  120. R. F. W. Bader and P. M. Beddall,J. Chem. Phys. 56, 3320 (1972); R. F. W. Bader and G. R. Runtz,Mol. Phys. 30, 117 (1975); R. F. W. Bader,Acc. Chem. Res. 8, 34 (1975).

    Google Scholar 

  121. T. C. Waddington,Trans. Faraday Soc. 62, 1482 (1960).

    Google Scholar 

  122. F. J. Millero,Chem. Rev. 71, 147 (1971).

    Google Scholar 

  123. P. Mukerjee,J. Phys. Chem. 65, 740, 744 (1961).

    Google Scholar 

  124. A. Eucken,Z. Elektrochem. 51, 6 (1948).

    Google Scholar 

  125. M. Eigen and E. Wicke,Z. Elektrochem. 55, 354 (1951).

    Google Scholar 

  126. T. Ackermann,Disc. Faraday Soc. 24, 180 (1957).

    Google Scholar 

  127. J. Padova,J. Chem. Phys. 40, 691 (1964);39, 1552 (1963).

    Google Scholar 

  128. H. L. Friedman,Ionic Solution Theory (Wiley-Interscience, New York, 1962).

    Google Scholar 

  129. R. S. Ramanathan, C. V. Krishnan, and H. L. Friedman,J. Solution Chem. 1, 237 (1972).

    Google Scholar 

  130. E. Hückel,Phys. Z. 26, 93 (1925).

    Google Scholar 

  131. R.M. Diamond,J. Phys. Chem. 67, 2513 (1963); S. Lindenbaum and G. E. Boyd,J. Phys. Chem. 68, 911 (1964).

    Google Scholar 

  132. B. E. Conway and H. P. Dhar,J. Colloid Interface Sci. 48, 73 (1974).

    Google Scholar 

  133. B. E. Conway,Elektrokhimiya 12, 822 (1977).

    Google Scholar 

  134. D. C. Grahame,Chem. Rev. 41, 441 (1947).

    Google Scholar 

  135. G. J. Hills and R. Payne,Trans. Faraday Soc. 61, 316 (1965);61, 326 (1965).

    Google Scholar 

  136. N. J. Jarvis and M. A. Schieman,J. Phys. Chem. 72, 74 (1968).

    Google Scholar 

  137. P. Philip and C. Jolicoeur,J. Phys. Chem. 77, 3071 (1973); C. Jolicoeur and P. Philip,J. Solution Chem. 4, 3 (1975).

    Google Scholar 

  138. H. Kistenmacher, H. Popkie, and E. Clementi,J. Chem. Phys. 61, 799 (1974).

    Google Scholar 

  139. J. B. Russell and M. J. Sienko,J. Am. Chem. Soc. 79, 4051 (1957).

    Google Scholar 

  140. J. Paquette and C. Jolicoeur,J. Solution Chem. 6, 403 (1977).

    Google Scholar 

  141. W. M. Cox and J. H. Wolfenden,Proc. Roy. Soc. London Ser. A 145, 475 (1934).

    Google Scholar 

  142. M. Kaminsky,Z. Phys. Chem. N.F. 8, 173 (1956);Disc. Faraday Soc. 24, 171 (1957).

    Google Scholar 

  143. B. S. Krumgal'z,Zh. Fiz. Khim. 45, 2559 (1971).

    Google Scholar 

  144. B. S. Krumgal'z,Zh. Fiz. Khim. 47, 956 (1973).

    Google Scholar 

  145. D. F.-T. Tuan and R. M. Fuoss,J. Phys. Chem. 67, 1343, (1963).

    Google Scholar 

  146. N-P. Yao and D. N. Benion,J. Phys. Chem. 75, 1727 (1971).

    Google Scholar 

  147. E. R. Nightingale Jr., inChemical Physics of Ionic Solutions, B. E. Conway and R. G. Barradas, eds. (Wiley, New York, 1966), Chapter 7.

    Google Scholar 

  148. C. M. Criss, R. P. Held, and E. Luksha,J. Phys. Chem. 72, 2970 (1968).

    Google Scholar 

  149. C. M. Criss and M. Salomon, inPhysical Chemistry of Organic Solvent Systems, A. K. Covington and T. Dickinson, eds. (Plenum Press, New York, 1973), Part 4, Chapter 2.

    Google Scholar 

  150. C. M. Criss,J. Phys. Chem. 78, 1000 (1974).

    Google Scholar 

  151. J. E. Desnoyers, G. Perron, and N. Desrosiers,Can. J. Chem. 54, 2163 (1976).

    Google Scholar 

  152. C. Ostigny, J. C. Ahluwalia, G. Perron, and J. E. Desnoyers,Can. J. Chem. 55, 3368 (1977).

    Google Scholar 

  153. C. L. de Ligny, H. J. M. Denessen, and M. Alfenaar,Rec. Trav. Chim. Pays-Bas 90, 1265 (1971);91, 453 (1972);91, 965 (1972).

    Google Scholar 

  154. H. J. M. Nedermeijer-Denessen, C. L. de Ligny, and A. G. Remijnse,J. Electroanal. Chem. 77, 153 (1977).

    Google Scholar 

  155. K. J. Laidler,Can. J. Chem. 34, 1107 (1956).

    Google Scholar 

  156. K. J. Laidler and A. M. Couture,Can. J. Chem. 34, 1209 (1956);35, 202 (1957);35, 207 (1957).

    Google Scholar 

  157. B. E. Conway, R. E. Verrall, and J. E. Desnoyers,Z. Phys. Chem. (Leipzig) 230, 157 (1965).

    Google Scholar 

  158. E. Glueckauf,Trans. Faraday Soc. 60, 572 (1964).

    Google Scholar 

  159. W. M. Noyes,J. Amer. Chem. Soc. 86, 971 (1964).

    Google Scholar 

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Conway, B.E. The evaluation and use of properties of individual ions in slution. J Solution Chem 7, 721–770 (1978). https://doi.org/10.1007/BF00643580

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