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Reactions in Supercritical Fluids

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Book cover Supercritical Fluids

Part of the book series: NATO ASI Series ((NSSE,volume 273))

Abstract

The reasons for carrying out chemical reactions in supercritical fluids are discussed. Most of these motivations relate to the physical behaviour exhibited in these media, in particular phase behaviour, diffusion rates and ‘anomalies’, and solvation effects. Examples are given of the use of phase and diffusion behaviour. The transition-state theory is developed for supercritical fluids and used to explain solvation effects in chemical reactions in the media. The possibilities of product control in supercritical fluids via diffusion and solvation effects are outlined. Finally the use the continuously varying solvent properties available in supercritical fluids for the fundamental study of reaction mechanisms is reviewed. Because of their environmental advantages, discussions focus upon the use of carbon dioxide and water as fluids.

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References

  1. Shaw, R. W.; Brill, T. B.; Clifford, A. A.; Eckert, C. A.; Franck, E. U. (1991) Chem. and Eng. News 1991, 69, 26.

    CAS  Google Scholar 

  2. Kramer, G. M.; Leder, F. US Patent 3,889,945, 1975.

    Google Scholar 

  3. Poliakoff, M.; Howdle, S. M; Healy, M. A.; Whalley, J. M. In Proc. Int. Symp. Supercritical Fluids, Vol. 2, Perrut, M. Ed.; Institut National Polytechnique de Lorraine, Nancy, France, 1988, Page 853.

    Google Scholar 

  4. Howdle, S. M.; Poliakoff, M. (1989) J. Chem. Soc. Chem. Comm. 1989, 77, 1099.

    Article  Google Scholar 

  5. Howdle, S. M.; Healy, M. A.; Poliakoff, M. J. Amer. Chem. Soc. 1990, 772, 4804.

    Article  Google Scholar 

  6. Howdle, S. M.; Grebenik, P.; Perutz, R. N.; Poliakoff, M. J. Chem. Soc. Chem. Comm. 1989, 77, 1517.

    Article  Google Scholar 

  7. Jobling, M.; Howdle, S. M.; Healy, M. A.; Poliakoff, M. J. Chem. Soc. Chem. Commun. 1990, 18, 1287.

    Article  Google Scholar 

  8. Baumgartner, H. J. US Patent 4,408,082, 1983.

    Google Scholar 

  9. Haar, L.; Gallagher, J. S.; Kell, G. S. NBS/NRC Steam Tables; Hemisphere, Washington, 1984, Page 266.

    Google Scholar 

  10. Patat, F. Monatsh. Chemie 1945, 77, 352.

    Google Scholar 

  11. Townsend, S. H. Ph.D. Thesis Univ. Delaware, U.S.A., 1989.

    Google Scholar 

  12. Penninger, J. M. L.; Kolmschate, J. M. M. In Supercritical Fluid Science and Technology; Johnston, K. P.; Penninger, J. M. L. Eds.; ACS Symposium Series 406; American Chemical Society, Washington D.C., 1988, Page 242.

    Chapter  Google Scholar 

  13. Lawson, J. R.; Klein, M. T. Ind. Eng. Chem. Fundam. 1985, 24, 203.

    Article  CAS  Google Scholar 

  14. Townsend, S. H.; Abraham, M. A.; Huppert, G. L.; Klein, M. T.; Paspek, S. C. Ind. Eng. Chem. Res. 1988, 27, 143.

    Article  CAS  Google Scholar 

  15. Modell, M. US Patent 4,338,199, 1982.

    Google Scholar 

  16. Schilling, W.; Franck, E. U. Ber. Bunsenges. Phys. Chem. 1988, 92, 631.

    CAS  Google Scholar 

  17. Tiltscher, H.; Wolf, H.; Schelchshorn, J. Ber. Bunsenges. Phys. Chem. 1984, 88, 897.

    Article  CAS  Google Scholar 

  18. Tiltscher, H.; Wolf, H.; Schelchshorn, J. Angew. Chem. Int. Ed. Engl. 1981, 20, 892.

    Article  Google Scholar 

  19. Marshall, W. L.; Franck, E. U. J. Phys. Chem. Ref. Data, 1981, 10, 295.

    Article  CAS  Google Scholar 

  20. Armellini, F. J.; Tester, J. W. In Proc. 2nd Int. Symp. Supercritical Fluids, McHugh, M. A. Ed.; Boston, U.S.A., May, 1991 Page 21.

    Google Scholar 

  21. Ehrlich, P. Mortimer, G. A. Adv. Polymer Sci. 1970, 7, 386.

    Article  CAS  Google Scholar 

  22. Krase, N. W.; Lawrence, A. E. US Patent 2,396,791, 1946.

    Google Scholar 

  23. Cottle, J. E. US Patent 3,294,772, 1966.

    Google Scholar 

  24. Bhise, V. S. US Patent 4,400,559, 1983.

    Google Scholar 

  25. Dumont, T; Barth, D.; Perrut, M. In Proc. 2nd Int. Symp. Supercritical Fluids, McHugh, M. A. Ed.; Boston, U.S.A., May, 1991, Page 150.

    Google Scholar 

  26. Dumont, T; Barth, D.; Corbier, C.; Branlant, G; Perrut, M. Biotech. Bioeng. 1992, 39, 329.

    Article  Google Scholar 

  27. Perrut, M. High Press. Biotech. 1992, 224, 401.

    CAS  Google Scholar 

  28. Dumont, T; Barth, D.; Perrut, M. J.Supercritical Fluids 1993, 6, 1.

    Article  Google Scholar 

  29. Brennecke, J. F. In Supercritical Fluid Engineering Science; Kiran, E.; Brennecke, J. F., Eds.,; ACS Symposium Series 514 American Chemical Society, Washington, D.C., 1993, Chapter 16.

    Google Scholar 

  30. Helling, R. K.; Tester, J. W. J. Energy and Fuels 1987, 7, 417.

    Article  Google Scholar 

  31. Bernard, P; Barth, D; Perrut, M. High Press. Biotech., 1992, 224, 451.

    CAS  Google Scholar 

  32. Russell, A. J.; Beckman, E. J. Enzyme Microb. Technol. 1991, 13, 1007.

    Article  CAS  Google Scholar 

  33. Taniguchi, M.; Kamihira, M.; Kobayashi, T. Agric. Biol. Chem. 1987, 51, 593.

    Article  CAS  Google Scholar 

  34. Kasche, V.; Schlothauer, R.; Brunner, G. Biotech. Lett. 1988, 10, 569.

    Article  CAS  Google Scholar 

  35. Butler, L. G. Enzyme Microb. Technol. 1979, 7, 253.

    Article  Google Scholar 

  36. Goldman, R.; Kedem, O.; Katchalski, E. Biochemistry 1971, 10, 165.

    Article  CAS  Google Scholar 

  37. Kobayashi, T.; Laidler, K. J. Biotech and Bioeng. 1974, 16, 77.

    Article  CAS  Google Scholar 

  38. Randolph, T. W.; Blanch, H. W.; Prausnitz, J. M.; Wilke, C. R. Biotech. Lett. 1985, 7, 325.

    Article  CAS  Google Scholar 

  39. van Eijs, A. M. M; de Jong, J. P. L.; Doddema, H. J.; Lindeboom, D. R. In Proc. Int. Symp. Supercritical Fluids, Vol. 1, Perrut, M. Ed.; Institut National Polytechnique de Lorraine, Nancy, France, 1988, Page 933.

    Google Scholar 

  40. Steytler, D. C.; Moulson, P. S.; Reynolds, J. (1991) Enzyme Microb. Technol. 1991, 13, 221.

    Article  CAS  Google Scholar 

  41. Marty, A.; Chulalaksananukul, W.; Willemot, R. M.; Condoret, J. S. Biotech. Bioeng. 1992, 39, 273.

    Article  CAS  Google Scholar 

  42. Wong, J. M.; Johnston, K. P. Biotech. Progr. 1986, 2, 2939.

    Article  Google Scholar 

  43. Randolph, T. W.; Blanch, H. W.; Prausnitz, M. A.I.Ch.E.J 1988, 34, 1354.

    Article  CAS  Google Scholar 

  44. Hammond, D. A.; Karel, M.; Klibanov, A. M.; Krukonis, V. J. Appl. Biochem. Biotech 1985, 11, 393.

    Article  CAS  Google Scholar 

  45. Dumont, T.; Barth, D.; Perrut, M. In Abstract Handbook of the 2nd Int. Symp. High-Pressure Chem. Eng. Erlangen, Germany, September, 1990.

    Google Scholar 

  46. Marty, A.; Chulalaksananukul, W.; Condoret, J. S.; Willemot R. M. Biotech. Let. 1990, 12, 11.

    Article  CAS  Google Scholar 

  47. Nakamura, K.; Chi, Y.M.; Yano, T. In Proc. Int. Symp. Supercritical Fluids, Vol. 1, Perrut, M. Ed.; Institut National Polytechnique de Lorraine, Nancy, France, 1988, Page 925.

    Google Scholar 

  48. Nakamura, K.; Chi, Y-M.; Yamada, Y.; Yano, T. Chem. Eng. Comm. 1986, 45, 207.

    Article  CAS  Google Scholar 

  49. Erickson, J. C. Ph.D Thesis M.I.T., U.S.A, 1988.

    Google Scholar 

  50. Kamihara, M.; Taniguchi, M.; Kobayashi, T. Agric. Biol Chem. 1987, 51, 413.

    Article  Google Scholar 

  51. Pasta, P.; Mazzola, G.; Carreaand G.; Riva, S. Biotech. Lett. 1989, 11, 643.

    Article  CAS  Google Scholar 

  52. Zaks, A.; Klibanov, A. M. Science 1984, 224, 1249.

    Article  CAS  Google Scholar 

  53. Carroll, J. C. Ph.D Thesis, University of Leeds, U.K., 1992.

    Google Scholar 

  54. Staszak, C. N.; Malinowski, K. C.; Killilea, W. R. Envirn. Prog. 1989, 6, 39.

    Article  Google Scholar 

  55. Symcox, R. O.; Erlich, P. J. Amer. Chem. Soc. 1962, 84, 531.

    Article  CAS  Google Scholar 

  56. Laird, R. K.; Morrell, A. G.; Seed, L. Disc. Faraday Soc. 1956, 22 126.

    Article  Google Scholar 

  57. Procaccia, I; Gitterman, M. Phys. Rev. Lett. 1981, 46, 1163.

    Article  CAS  Google Scholar 

  58. Procaccia, I; Gitterman, M. Phys. Rev. 1982, A25, 1137.

    Google Scholar 

  59. Patashinskii, A. Z.; Pokrovskii, V. I.; Feigelman, M. V. Sov. Phys. JETP 1982, 55, 851.

    Google Scholar 

  60. Milner, S. T.; Martin, P. C. Phys. Rev. 1986, A34, 1996.

    Google Scholar 

  61. Greer, S. C. Int. J. Thermophys. 1988, 9, 761.

    Article  CAS  Google Scholar 

  62. de Groot, S. R.; Mazur, P. Non-equilibrium thermodynamics North Holland, Amsterdam, 1962, Page 197.

    Google Scholar 

  63. Greer, S. C. Phys. Rev. 1985, A31, 3240.

    Google Scholar 

  64. Krichevskii, I. R.; Tsekhanskaya, Yu. V.; Polyakova, Z.A. Dokl. Phys. Chem. U.S.S.R. 1966, 166, 60.

    Google Scholar 

  65. Tsekhanskaya, Yu. V.; Mushkina, E. V. (1972) Russ. J. Phys. Chem. 1972, 46, 372.

    Google Scholar 

  66. Evans, M. G.; Polanyi, M. (1935) Trans. Faraday Soc. 1935, 31, 875.

    Article  CAS  Google Scholar 

  67. Glasstone, S.; Laidler, K. J.; Eyring, H. The Theory of Rate Processes 1st Edn., McGraw-Hill, New York, 1941.

    Google Scholar 

  68. Simmons, G. M.; Mason, D. M. Chem. Eng. Sci. 1972, 27, 89.

    Article  CAS  Google Scholar 

  69. Hamann, S. D. High Pressure Physics and Chemistry, Bradley, R.S. Ed., Vol. 2, Academic Press, New York, 1963, Page 163.

    Google Scholar 

  70. van Eldik, R.; Asano, T.; le Noble, W. J. Chem. Rev. 1989, 89, 549.

    Article  Google Scholar 

  71. Suvachittanont, S. J. Chem. Ed. 1983, 60, 150.

    Article  CAS  Google Scholar 

  72. le Noble, W. J. Prog. Phys. Org. Chem. 1967, 5, 207.

    Article  Google Scholar 

  73. Lawrance, G. A.; Stranks, D. R. Acc. Chem. Res. 1979, 12, 403.

    Article  CAS  Google Scholar 

  74. Langford, C. H.; Gray, H. B. Ligand Substitution Processes Benjamin, New York, 1965.

    Google Scholar 

  75. Troe, J. J. Phys. Chem. 1986, 90, 357.

    Article  CAS  Google Scholar 

  76. van Wasen, U.; Schneider, G. M.; J. Phys. Chem. 1980, 84, 229.

    Article  Google Scholar 

  77. Schroeder, J.; Troe, J. Chem. Phys. Let. 1985, 116, 453.

    Article  CAS  Google Scholar 

  78. Burshtein, A. I.; Khudyakov, I. V.; Yakobson, B. I. Prog. Reaction Kinetics 1984, 13, 221.

    CAS  Google Scholar 

  79. Hrnjez, B. J.; Mehta, A. J.; Fox, M. A.; Johnston, K. P. J. Amer. Chem. Soc. 1989, 111, 2662.

    Article  CAS  Google Scholar 

  80. Collins, N. A.; Debenedetti, P. G.; Sundaresan, S. A.I.Ch.E. J. 1988, 34, 1211.

    Article  CAS  Google Scholar 

  81. Johnston, K. P. Haynes, C. A.I.Ch.E. J. 1987, 33, 2017.

    Article  CAS  Google Scholar 

  82. Kirkwood, J. G. J. Chem. Phys. 1934, 2, 351.

    Article  CAS  Google Scholar 

  83. Laidler, K. J. Chemical Kinetics 2nd edn., McGraw Hill, New York, 1965, Page 227.

    Google Scholar 

  84. Kwart, H.; Silver, P. A. J. Org. Chem. 1975, 40, 3019.

    Article  CAS  Google Scholar 

  85. Paulaitis, M. E.; Alexander, C. Pure Appl. Chem. 1987, 59, 61.

    Article  CAS  Google Scholar 

  86. Ikushima, Y.; Saito, N.; Arai, M. Bull. Chem. Soc. Jpn., 1991, 64, 282.

    Article  CAS  Google Scholar 

  87. Ikushima, Y.; Saito, N.; Arai, M. J. Phys. Chem. 1992, 96, 2293.

    Article  CAS  Google Scholar 

  88. North, A. M. Reed, G. A. Trans. Faraday Soc. 1961, 57, 859.

    Article  CAS  Google Scholar 

  89. Neuman, R. C. Acc. Chem. Res. 1972, 5, 381.

    Article  CAS  Google Scholar 

  90. Peck, D. G.; Mehta, A. J.; Johnston, K. P. J. Phys. Chem. 1989, 93, 4297.

    Article  CAS  Google Scholar 

  91. Flarsheim, W. M.; Bard, A. J.; Johnston, K. P. J. Phys. Chem. 1989, 93, 4234.

    Article  CAS  Google Scholar 

  92. Kimura, Y.; Yoshimura, Y.; Nakahara, M. J. Chem. Phys. 1989, 90, 5679.

    Article  CAS  Google Scholar 

  93. Yoshimura, Y.; Kimura, Y. Chem. Phys. Let. 1991, 181, 517.

    Article  CAS  Google Scholar 

  94. Chapman, O. L.; Nelson, P. J.; King, R. W.; Trecker, D. J.; Griswold, A. Rec. Chem. Prog. 1967, 28, 167.

    CAS  Google Scholar 

  95. Hrnjez, B. J.; Mehta, A. J.; Fox, M. A.; Johnston, K. P. J. Am. Chem. Soc. 1989, 111, 2662.

    Article  CAS  Google Scholar 

  96. le Noble, W. J.; Tamura, K. Tetrahedron Let. 1977, 6, 495.

    Article  Google Scholar 

  97. Combes, J. R.; Johnston, K. P.; O’Shea, K. E.; Fox, M. A. In Supercritical Fluid Technology; ACS Symposium Series 488; Bright, F. V.; McNally, M. E. P., Eds., American Chemical Society, Washington, D.C., 1992.

    Google Scholar 

  98. Sigman, M. E.; Leffler, J. E. J. Org. Chem. 1987, 52, 3123.

    Article  CAS  Google Scholar 

  99. Suppes, G. J.; McHugh, M. A. I. & E.C Res. 1989, 28, 1146.

    Article  CAS  Google Scholar 

  100. Occhiogrosso, R. N.; McHugh, M. A. Chem. Eng. Sci. 1987, 42, 2478.

    Article  CAS  Google Scholar 

  101. Suppes, G. J.; Occhiogrosso, R. N.; McHugh, M. A. I. & E.C. Res. 1989, 28, 1152.

    Article  CAS  Google Scholar 

  102. Hippler, H.; Schubert, V.; Troe, J. (1984) J. Chem. Phys. 1984, 81, 3931.

    Article  CAS  Google Scholar 

  103. Hippler, H.; Luther, K.; Troe, J. Ber. Bunsenges. Phys. Chem. 1973, 77, 1104.

    CAS  Google Scholar 

  104. Otto, B.; Schroeder, J.; Troe, J. (1984) J. Chem. Phys. 81 202–213.

    Article  Google Scholar 

  105. Luther, K.; Troe, J. Chem. Phys. Let. 1974, 24, 85.

    Article  CAS  Google Scholar 

  106. Luther, K.; Schroeder, J.; Troe, J.; Unterberg, U. J. Phys. Chem. 1980, 84, 3072.

    Article  CAS  Google Scholar 

  107. Troe, J. J. Phys. Chem. 1986, 90, 357.

    Article  CAS  Google Scholar 

  108. Maneke, G.; Schroeder, J.; Troe, J.; Voss, F. Ber. Bunsenges. Phys. Chem. 1985, 89, 896.

    Article  CAS  Google Scholar 

  109. Kramers, H. A. Physica 1940, 7, 284.

    Article  CAS  Google Scholar 

  110. Squires, T. G.; Venier, G. C.; Aida, T. Fluid Phase Equil. 1983, 10, 261.

    Article  CAS  Google Scholar 

  111. Bright, F. V. Personal Communication.

    Google Scholar 

  112. Brennecke, J. F.; Tomasko, D. L.; Eckert, C. A. J. Phys. Chem. 1990, 94, 7692.

    Article  CAS  Google Scholar 

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  1. School of Chemistry, University of Leeds, Leeds, LS2 9JT, UK

    Anthony A. Clifford

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  1. Anthony A. Clifford
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  1. Department of Chemical Engineering, University of Maine, Orono, Maine, USA

    Erdogan Kiran

  2. Thermophysics Division, National Institute of Standards and Technology, Gaithersburg, Maryland, USA

    Johanna M. H. Levelt Sengers

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Clifford, A.A. (1994). Reactions in Supercritical Fluids. In: Kiran, E., Sengers, J.M.H.L. (eds) Supercritical Fluids. NATO ASI Series, vol 273. Springer, Dordrecht. https://doi.org/10.1007/978-94-015-8295-7_18

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  • DOI: https://doi.org/10.1007/978-94-015-8295-7_18

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