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Solvated and Stabilized Electrons in Radiation-Chemical Processes
Dr. Klaus Eiben,
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Dr. Klaus Eiben
Institut für Strahlenchemie des Kernforschungszentrums, 75 Karlsruhe, Postfach 3640 (Germany)
Institut für Strahlenchemie des Kernforschungszentrums, 75 Karlsruhe, Postfach 3640 (Germany)Search for more papers by this authorDr. Klaus Eiben,
Corresponding Author
Dr. Klaus Eiben
Institut für Strahlenchemie des Kernforschungszentrums, 75 Karlsruhe, Postfach 3640 (Germany)
Institut für Strahlenchemie des Kernforschungszentrums, 75 Karlsruhe, Postfach 3640 (Germany)Search for more papers by this authorAbstract
The electrons solvated in metal-ammonia solutions are relatively stable; by contrast, hydrated electrons are very unstable and have been discovered only recently during radiolysis of water. They can be regarded as the simplest radicals. Radiation chemical production of solvated electrons has proved to be a particularly elegant method for the qualitative and quantitative investigation of the reactions between these electrons and numerous compounds, whose rates are partly controlled by diffusion. It has been possible in some cases to identify optically and ESR-spectroscopically the resulting short-lived products (radical-anions). The similarity between the physical and chemical properties of electrons solvated in solutions and those of electrons stabilized in the solid phase suggests that the two species are identical.
References
- 1
G. Stein,
Discussions Faraday Soc.
12, 227
(1952).
10.1039/df9521200227 Google Scholar
- 2 R. L. Platzman in: Basic Mechanisms in Radiobiology, Natl. Res. Council (U.S.), Publ. 305, 34 (1953).
- 3
W. Weyl,
Ann. Physik
197, 601
(1863).
10.1002/andp.18641970407 Google Scholar
- 4 E. Hayon and J. J. Weiss, Proc. 2nd Int. Conf. Peaceful Uses Atomic Energy (Genève) 29, 80 (1958).
- 5 N. F. Barr and A. O. Allen, J. Phys. Chem. 63, 928 (1959).
- 6 G. Czapski and H. Schwarz, J. Phys. Chem. 66, 471 (1962).
- 7 E. Collinson, F. S. Dainton, D. R. Smith, and S. Tazuke, Proc. chem. Soc. (London) 1962, 149.
- 8 D. Schulte-Frohlinde and K. Eiben, Z. Naturforsch. 17a, 445 (1962).
- 9 J. Jortner and B. Sharf, J. Phys. Chem. 66, 108 (1962).
- 10 E. J. Hart and J. W. Boag, J. Am. Chem. Soc. 84, 4090 (1962).
- 11 R. F. Gould: Solvated Electron. Advan. Chem. Ser. 50 (1965).
- 12 R. F. Gould: Radiation Chemistry I. Advan. Chem. Ser. 81 (1968).
- 13 R. F. Gould: Radiation Chemistry II. Advan. Chem. Ser. 82, (1968).
- 14 J. K. Thomas, Radiat. Res. Rev. 1, 183 (1968); and in M. Burton and J. L. Magee: Advances in Radiation Chemistry. Interscience, New York 1969, Vol. 1, p. 103.
- 15 D. C. Walker, Quart. Rev. (London) 21, 79 (1967).
- 16 F. S. Dainton, IUPAC Int. Symp. Free Radicals in Solution, Ann Arbor. Butterworth, London 1967, p. 15; and in S. Cleasson: Proc. Fifth Nobel-Symp. 1967, p. 1.
- 17 J. H. Baxendale, Curr. Top. Radiat. Res. 3, 1 (1967).
- 18 E. J. Hart, Actions Chim. Biol. Radiations 10, 1 (1966).
- 19 G. R. A. Johnson and G. Scholes: The Chemistry of Ionisation and Excitation. Taylor & Francis Ltd., London 1967.
- 20 M. Ebert, J. P. Keene, A. J. Swallow, and J. H. Baxendale: Pulse radiolysis. Academic Press, New York 1965.
- 21 J. E. Willard in P. Ausloos: Fundamentals of Radiation Chemistry. Interscience, New York 1968, p. 599.
- 22
U. Schindewolf,
Angew. Chem.
80, 165
(1968);
10.1002/ange.19680800502 Google ScholarAngew. Chem. internat. Edit. 7, 190 (1968).
- 23 J. Jortner, Radiat. Res., Suppl. 4, 24 (1964).
- 24 L. Onsager, Radiat. Res. Suppl. 4, 14 (1964).
- 25 P. N. Moorthy and J. J. Weiss [11], p. 180.
- 26 K. Eiben and D. Schulte-Frohlinde, Z. physik. Chem. N.F. 45, 20 (1965).
- 27 R. Schiller, J. Chem. Phys. 47, 2278 (1967); Nature 217, 1141 (1968).
- 28 M. J. Bronskill, R. F. Wolff, and W. J. Hunt, J. Phys. Chem. 73, 3762 (1969); M. J. Bronskill and W. J. Hunt, J. Phys. Chem. 73, 1175 (1969).
- 29 I. A. Taub and K. Eiben, J. Chem. Phys. 49, 2499 (1968).
- 30 B. G. Ershov, A. R. Pikaev, P. Ya. Glazunov, and V. I. Spitsyn, Dokl. Akad. Nauk SSSR 149, 163 (1963).
- 31 H. Hase and L. Kevan, J. Phys. Chem. 73, 3290 (1969).
- 32 H. Barzynski and D. Schulte-Frohlinde, Z. Naturforsch. 22a, 2231 (1967).
- 33 B. G. Ershov, J. E. Markarov, and A. K. Pikaev, Khim. Visok. Energ. 1, 472 (1967).
- 34 M. J. Blandamer, C. Shields, and M. C. R. Symons, J. Chem. Soc. 1965, 1127.
- 35 J. Zimbrick and L. Kevan, J. Chem. Phys. 47, 2364 (1967).
- 36 L. Kevan and D. H. Chen, J. Chem. Phys. 49, 1970 (1968).
- 37 J. P. Keene, Radiat. Res. 22, 1 (1964).
- 38 S. Arai and M. C. Sauer, J. Chem. Phys. 44, 2297 (1966).
- 39 K. D. Asmus and J. H. Fendler, J. Phys. Chem. 72, 4285 (1968).
- 40 W. C. Gottschall and E. J. Hart, J. Phys. Chem. 71, 2102 (1967).
- 41 A. C. Avery, J. R. Remko, and B. Smaller, J. Chem. Phys. 49, 951 (1968).
- 42 K. Eiben and I. A. Taub, Nature 216, 782 (1967).
- 43 W. A. Seddon, D. R. Smith, and P. E. Bindner, Can. J. Chem. 46, 1747 (1968).
- 44 E. M. Fielden and E. J. Hart, Radiat. Res. 33, 426 (1968).
- 45 R. Olinger, Diplomarbeit, Universität Karlsruhe 1968.
- 46 K. D. Asmus and J. H. Fendler, J. Phys. Chem. 73, 1583 (1969).
- 47 K. Eiben, Proc. Int. Symp. Physics on Ice, München. Plenum Publ. Corp., New York 1969, p. 184.
- 48 K. Eiben and I. A. Taub, to be published.
- 49
U. Schindewolf,
H. Kohrmann, and
G. Lang,
Angew. Chem.
81, 496
(1969);
10.1002/ange.19690811310 Google ScholarAngew. Chem. internat. Edit. 8, 512 (1969).
- 50 M. C. Sauer, S. Arai, and L. M. Dorfman, J. Chem. Phys. 42, 708 (1965).
- 51 A. Ekstrom and J. E. Willard, J. Phys. Chem. 72, 4599 (1968).
- 52 C. Chachaty, J. Chim. Phys. 64, 614 (1967).
- 53 D. R. Smith and J. J. Pieroni, Can. J. Chem. 45, 2723 (1967).
- 54 F. S. Dainton, G. A. Salmon, and U. F. Zucker, Chem. Commun. 1968, 1172.
- 55 F. Kiss, Collection Czech. Chem. Commun. 34, 938 (1969).
- 56 F. S. Dainton and G. A. Salmon, Proc. Roy. Soc. (London) A 285, 319 (1965).
- 57 D. M. J. Compton, J. F. Bryant, R. A. Cesena, and B. C. Gehman [20], p. 43.
- 58 B. Ward [12], p. 601.
- 58a R. C. Weast: Handbook of Chemistry and Physics. The Chemical Rubber Co., Cleveland, Ohio.
- 59 J. Jortner in G. Stein: Radiation Chemistry of Aqueous Systems. Interscience, New York 1968, p. 91.
- 60 U. Schindewolf, personal communication.
- 61 K. H. Schmidt and W. L. Buck, Science 151, 70 (1966).
- 62 F. S. Dainton and W. S. Watt, Proc. Roy. Soc. (London) A 275, 447 (1963).
- 63 J. Liu, K. Tsuji, and F. Williams, J. Am. Chem. Soc. 90, 2766 (1968).
- 64 J. P. Guarino and W. H. Hamill, J. Am. Chem. Soc. 86, 777 (1964).
- 65 M. A. Bonin, J. Liu, K. Tsuji, and F. Williams [13], p. 269.
- 66 F. S. Dainton, G. A. Salmon, and C. v. Sonntag, Proc. Roy. Soc. (London) A 313, 31 (1969).
- 67 L. Shields, J. Phys. Chem. 69, 3186 (1965).
- 68 M. Natori and T. Watanabe, J. Phys. Soc. Japan 21, 1573 (1966); M. Natori, J. Phys. Soc. Japan 24, 913 (1968); J. Phys. Soc. Japan 27, 1309 (1969).
- 69
E. Mollwo,
Z. Physik
85, 56
(1950).
10.1007/BF01330778 Google Scholar
- 70 J. E. Bennet, B. Mile, and A. Thomas, J. Chem. Soc. A 1967, 1393.
- 71 W. H. Hamill in E. T. Kaiser and L. Kevan: Radical Ions. Interscience, New York 1968, p. 321.
- 71a S. Noda, K. Fueki, and Z. Kuri, J. Chem. Phys. 49, 3287 (1968); Bull. Chem. Soc. Japan 41, 2882 (1968).
- 72 G. N. Lewis and D. Lipkin, J. Am. Chem. Soc. 64, 2801 (1942).
- 73 R. Marx, S. Leach, and M. Horani, J. Chim. Phys. 60, 726 (1963).
- 74 C. Schneider, Naturwissenschaften 55, 197 (1968).
- 75 K. Eiben and R. W. Fessenden, J. Phys. Chem. 72, 3387 (1968).
- 76 M. Anbar and E. J. Hart, Intern. J. Appl. Radiation Isotopes 18, 493 (1967).
- 77 A. Habersbergerova, J. Janovsky, and J. Teply, Radiat. Res. Rev. 1, 109 (1968).
- 78 G. R. Freeman, Actions Chim. Biol. Radiations 14, 73 (1970).
- 79
C. v. Sonntag,
Fortschr. Chem. Forsch.
13, 333
(1969).
10.1007/BFb0051137 Google Scholar
- 80 M. Haissinsky, Actions Chim. Biol. Radiations 11, 133 (1967).
- 81 K. Eiben and R. W. Fessenden, to be published.
- 82 H. A. Schwarz, J. Phys. Chem. 73, 1928 (1969).
- 83 T. T. Sworski, J. Am. Chem. Soc. 86, 5054 (1964).
- 84
P. Debye,
Trans. Electrochem. Soc.
82, 265
(1942).
10.1149/1.3071413 Google Scholar
- 85 E. J. Hart, S. Gordon, and E. M. Fielden, J. Phys. Chem. 70, 150 (1966).
- 86 K. N. Jha and G. R. Freeman, J. Chem. Phys. 48, 5480 (1968).
- 87 M. S. Matheson and J. Rabani, J. Phys. Chem. 69, 1324 (1965).
- 88 J. Jortner and J. Rabani, J. Phys. Chem. 66, 2081 (1962); G. Navon and G. Stein, J. Phys. Chem. 69, 1384 (1965).
- 89 F. S. Dainton and D. B. Peterson, Nature 186, 878 (1960).
- 90 F. S. Dainton, G. A. Salmon, and P. Wardman, Proc. Roy. Soc. (London), A 313, 1 (1969).
- 91 J. M. Warman, K. D. Asmus, and R. H. Schuler [13], p. 25.
- 92 J. Rabani, W. A. Mulac, and M. S. Matheson, J. Phys. Chem. 69, 53 (1965).
- 93 S. O. Nielson, P. Pagsberg, J. Rabani, H. Christensen, and G. Nilsson, Chem. Commun. 1968, 1523.
- 94 G. Beck, J. Radiat. Phys. Chem. 1, 361 (1969).
- 95 H. Smith: Organic Reactions in Liquid Ammonia. Interscience, New York 1963.
- 96 A. Szutka, J. K. Thomas, S. Gordon, and E. J. Hart, J. Phys. Chem. 69, 289 (1965).
- 97 R. W. Taft in M. S. Newman: Steric Effects in Organic Chemistry. Wiley, New York 1956, Chap. 13.
- 98 M. Anbar and E. J. Hart, J. Phys. Chem. 69, 271 (1965).
- 99 K. D. Asmus, A. Henglein, and G. Beck, Ber. Bunsenges. Phys. Chem. 70, 459 (1966).
- 100 K. D. Asmus, A. Henglein, M. Ebert, and J. P. Keene, Ber. Bunsenges. Phys. Chem. 68, 657 (1964).
- 101 E. J. Hart, S. Gordon, and J. K. Thomas, J. Phys. Chem. 68, 1271 (1964).
- 102 J. Lilie and A. Henglein, Ber. Bunsenges. Phys. Chem. 73, 170 (1969).
- 103 K. Eiben, unpublished.
- 104 K. D. Asmus, A. Wigger, and A. Henglein, Ber. Bunsenges. Phys. Chem. 70, 862 (1966).
- 105 L. M. Dorfman, N. E. Shank, and S. Arai [13], p. 58.
- 106 M. Anbar and E. J. Hart, J. Am. Chem. Soc. 86, 5633 (1964).
- 107 M. Anbar and E. J. Hart [11], p. 79.
- 108 W. V. Sherman, J. Am. Chem. Soc. 88, 1567 (1966).
- 109(a) C. L. Greenstock, M. Ng, and J. W. Hunt [11], p. 397; (b) G. Scholes, P. Shaw, R. L. Wilson, and M. Ebert [20], p. 151; (c) G. Scholes in G. Stein: Radiation Chemistry of Aqueous Systems. Interscience, New York 1968, p. 259.
- 110(a) W. M. Garrison, Curr. Top. Radiat. Res. 4, 43 (1968); (b) R. Braams, Radiat. Res. 27, 319 (1966) and [20], p. 171; (c) P. Neta and R. W. Fessenden, J. Phys. Chem., 74, 2263 (1970).
- 111 M. Anbar, Quart. Rev. (London) 22, 578 (1968).
- 112 J. K. Thomas, S. Gordon, and E. J. Hart, J. Phys. Chem. 68, 1524 (1964).
- 113 G. Meissner and A. Henglein, Ber. Bunsenges. Phys. Chem. 69, 3 (1965).
- 114 J. H. Baxendale, E. M. Fielden, and J. P. Keene, Proc. Roy. Soc. (London) A 286, 320 (1965).
- 115 A. S. Ghosh-Mazumdar and E. J. Hart [12], p. 193.
- 116 B. Cercek and M. Ebert, J. Phys. Chem. 72, 766 (1968).
- 117 M. Anbar, Z. B. Alfassi, and H. Bregman-Reisler, J. Am. Chem. Soc. 89, 1263 (1967).
- 118 R. A. Marcus [11], p. 138.
- 119 L. Kevan [109c], p. 21.
- 120 L. Kevan, Actions Chim. Biol. Radiations 13, 56 (1969).
- 121 B. G. Ershov and A. K. Pikaev [12], p. 1.
- 122 D. M. Brown and F. S. Dainton, Radiat. Res. Rev. 1, 241 (1968).
- 123 D. Schulte-Frohlinde and K. Vacek, Curr. Top. Radiat. Res. 5, 39 (1969).
- 124 D. Schulte-Frohlinde and K. Eiben, Atomstrahlung Med. Tech. 1964, 265; K. Eiben, Kernforschungszentrum Karlsruhe 293 (1965).
- 125 O. F. Khoshaev, B. G. Ershov, and A. K. Pikaev, Isv. Akad. Nauk SSSR, Ser. Khim 7, 246 (1968).
- 126 F. E. Gunter, J. Chem. Phys. 46, 3818 (1967).
- 127 G. Nilsson, H. C. Christensen, F. Fenger, P. Pagsberg, and S. O. Nielson [12], p. 71.
- 128 V. N. Shubin, V. A. Zhigunov, V. J. Zolotarevsky, and V. J. Dolin, Nature 212, 1002 (1966).
- 129
R. Livingstone,
J. Zeldes, and
E. H. Taylor,
Discussions Faraday Soc.
19, 166
(1955).
10.1039/df9551900166 Google Scholar
- 130(a) I. Eisele, R. Lapple, and L. Kevan, J. Am. Chem. Soc 91, 6504 (1969); (b) J. Zimbrick and L. Kevan, J. Am. Chem. Soc 89, 2483 (1967); (c) L. Kevan, D. R. Renneke, and R. J. Friauf, Solid State Commun. 6, 469 (1968).
- 131 W. A. Seddon and D. R. Smith, Can. J. Chem. 45, 3083 (1967).
- 132 J. Wendenburg, H. Möckel, A. Benzow, and A. Henglein, Z. Naturforsch. 21b, 632 (1966).
- 133 P. Balk, G. J. Hoijtink, and J. W. Schreurs, Rec. Trav. Chim. 76, 813 (1957).
- 134 J. A. Leone and W. S. Koski, J. Am. Chem. Soc. 88, 24 (1966).
- 135 H. Wieczorek and K. Eiben to be published.
