Abstract
Everyday laboratory experience suggests that, with very few exceptions, reactions between acids and bases are extremely fast, since no time lag is observable in the dissociation of acids or bases, buffer action, hydrolysis, etc. In fact, for many purposes proton-transfer reactions involving simple acids and bases are fast enough to be treated as equilibrium processes. However, there are two reasons why the rates of these processes are of interest. In the first place modern techniques have made it possible to measure the rates of extremely fast reactions, with half-times down to about 10−9 second, and hence to obtain information about the mechanism of such reactions. In the second place, when proton-transfer reactions are coupled with other chemical processes they may lead to slow observable changes, in particular to the catalysis of reactions by acids and bases. The latter type of approach is historically the older, but it is more logical to consider first the direct observation of reactions between simple acids and bases, as will be done in this chapter. Some general features of the experimental results will be described, but detailed consideration of the relations between rates, equilibria, and structures will be deferred until Chapter 10, so as to include the information obtained less directly from studies of acid-base catalysis, described in Chapters 8 and 9.
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References
Conference on Fast Reactions, Z. Elektrochem., 64, 1–204 (1960).
Technique of Organic Chemistry (ed. E. L. Friess, E. S. Lewis, and A. Weissberger), Vol. VIII B (Investigation of Rates and Mechanisms of Reactions), Interscience, 1963. This volume contains articles on most of the experimental techniques.
K. Tamm, Handbuch de Physik,Vol. XI (1), Springer, Heidelberg, 1961, p. 202 Ultrasonic methods).
E. F. Caldin, Fast Reactions in Solution, Blackwell, Oxford, 1964.
G. Czerlinski, Chemical Relaxation, Dekker, New York, 1966.
Fast Reactions and Primary Processes in Reaction Kinetics (5th Nobel Symposium) (ed. S. Claesson), Interscience, 1967.
J. N. Hague, Fast Reactions, Wiley, New York and London, 1971.
M. Eigen, Angew. Chem., 75, 489 (1963); Internat. Edn., 3, 1 (1964); Pure Appl. Chem., 6, 97 (1963).
M. Eigen, W. Kruse, G. Maas, and L. de Maeyer, Progr. Reaction Kinetics, 2, 285 (1964).
E. Grunwald. Progr. Phys. Org. Chem., 3, 317 (1965).
W J. Albery, Progr. Reaction Kinetics, 4, 353 (1966).
E. F. Caldin and J. E. Crooks, J. Sci. Instr., 44, 449 (1967); K. J. Ivin, J. J. McGarvey, and E. L. Simmons, Trans. Faraday Soc., 67, 97 (1971).
See, e.g., H. Koffer, Ber. Bunsengesell. Phys. Chem., 75, 1245 (1971).
R. G. Pearson, Disc. Faraday Soc., 17, 187 (1954).
W. R. Gilkerson, J. Chem. Phys., 27, 914 (1957).
R. P. Bell and R. R. Robinson, Trans. Faraday Soc., 58. 2358 (1962).
K. Bergmann, M. Eigen, and L. de Maeyer, Ber. Bunsengesell. Phys. Chem., 67, 819 (1963).
For a general account see H. Strehlow, Ref. 2: P. Delahay, New Instrumental Methods in Electrochemistry, Interscience, New York, 1954; H. Schmidt and M. von Stackelberg, Die neuartigen polarographischen Methoden, Verlag Chemie, Weinheim, 1962.
R. Brdicka, Coll. Tray. Chim. Czech., 12, 213 (1947).
H. W. Nürnberg, Fortschr. Chem. Forsch., 8, 241 (1967).
M. M. Kreevoy and C. A. Mead, J. Am. Chem. Soc., 84, 4596 (1962): Disc. Faraday Soc., 39, 166 (1965).
See, various authors, Disc. Faraday Soc., 39, 172–182 (1965).
For a general account, see H. Strehlow, Ref. 2, p. 865; J. A. Pople, W. G. Schneider, and H. J. Bernstein, High Resolution Nuclear Magnetic Resonance. McGraw-Hill, New York, 1959, especially Ch. 10; E. F. Caldin, Ref. 1, Ch. 11.
See, e.g., B. G. Cox, F. G. Riddell, and D. A. R. Williams, J. Chem. Soc., B, 859 (1970); B. G. Cox, J. Chem. Soc.,B, 1780 (1970).
R. A. Ogg, J. Chem. Phys., 22, 560 (1954); Disc. Faraday Soc., 17, 215 (1954).
T. J. Swift, S. B. Marks, and W. G. Sayre, J. Chem. Phys., 44, 2796 (1966); T. J. Swift and H. H. Lo, J. Am. Chem. Soc., 88, 2994 (1966); D. R. Clutter and T. J. Swift, J. Am. Chem. Soc., 90, 601 (1960).
For some collected results, see A. Loewenstein and T. M. Conner, Ber. Bunsengesell. Phys. Chem., 67, 280 (1963).
This section follows closely the treatment given by M. Eigen, Z. Phys. Chem. (Frankfurt), 1, 176 (1954); Angew. Chem. Internat. Edn., 3, 1 (1964).
A. Smoluchowski, Z. Phys. Chem., 92, 129 (1917).
L. Onsager, J. Chem. Phys., 2, 599 (1934).
P. Debye, Trans. Electrochem. Soc., 82, 265 (1942).
G. Brière and F. Gaspard, J. Chim. Phys., 64, 403 (1967).
G. C. Barker and D. C. Sammon, Nature, 213, 65 (1967).
M. Eigen and L. de Maeyer, Z. Elektrochem., 59, 986 (1955); G. Ertl and H. Gerischer, Z. Elektrochem., 65, 629 (1961); 66, 560 (1962).
a) R. P. Bell and D. M. Goodall, Proc. Roy. Soc., A, 294, 273 (1966); (b) D. M. Goodall and F. A. Long, J. Am. Chem. Soc., 90, 238 (1968); (c) R. P. Bell and D. J. Barnes, Proc. Roy. Soc., A, 318, 421 (1970); (d) M. L. Ahrens, M. Eigen, W. Kruse, and G. Maass, Ber. Bunsengesell. Phys. Chem., 74, 380 (1970).
H. Nürnberg, Ref. 20.
W. J. Albery and R. P. Bell, Proc. Chein. Soc., 169 (1963).
A. Hantzsch, Ber., 32, 575 (1899).
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Bell, R.P. (1973). The Direct Study of Rates of Simple Proton-Transfer Reactions. In: The Proton in Chemistry. Springer, Boston, MA. https://doi.org/10.1007/978-1-4757-1592-7_7
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DOI: https://doi.org/10.1007/978-1-4757-1592-7_7
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