Abstract
The exact verbal definition of qualitative concepts is more often the province of philosophy than of physical science. However, the various definitions suggested for acids and bases have been closely linked with the development of physical chemistry and have often served to stimulate experimental work and to further our understanding of chemical processes, and we shall therefore devote some time to this subject. The definitions used in the remainder of this book will be those proposed by Brönstedl in 1923, namely, An acid is a species having a tendency to lose a proton, and a base is a species having a tendency to add on a proton. This can be represented schematically by A ⇌ B + H+, where A and B are termed a conjugate (or corresponding) acid-base pair.2 Before examining the consequences of this definition and its relation to more recent concepts we shall consider briefly the previous history of the terms ‘acid’ and ‘base’.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
J. N. Brönsted, Rec. Tray. Chim., 42, 718 (1923).
It is frequently stated that the acid-base definition given here was put forward almost simultaneously by Brönsted and by T. M. Lowry [Chem. and Ind.,42, 43 (1923)]. However, although Lowry’s paper undoubtedly contains many of the ideas underlying this definition, especially for bases, it does not contain an explicit definition, and it is nowhere made clear that Lowry at that time regarded NH4 as an acid or CH3CO; as a base. In fact, in a later paper [J. Chem. Soc.,2562 (1927)], Lowry himself writes, More novelty is to be found in the perfectly logical conclusion of Brönsted that the anion of an acid is also a base or proton acceptor, in view of the fact that it can combine with a proton to form a molecule of the undissociated acid’: hence it does not seem justifiable to regard Lowry as one of the originators of the definition. I am indebted to the late Professor E. A. Guggenheim for calling my attention to this point. It is also noteworthy that G. N. Lewis (Valency and the Structure of Atoms and Molecules,(Reinhold, New York, 1923, p. 141) gave the same acid-base definition, and wrote, `… we may regard the ammonium ion as an acid’. However, he did not follow up the consequences of this view, and preferred the alternative definition of acids with which his name is usually associated.
P. Walden, Salts, Acids, and Bases: Electrolytes: Stereochemistry, Cornell, New York, 1929.
J. L. Gay-Lussac, Gab., Ann. Phys., 48, 341 (1814).
E.g., A. Werner, Z. Anorg. Chem., 3, 267 (1893); 15, 1 (1897); Ber., 40, 4133 (1907).
G. N. Lewis, Valency and the Structure of Atoms and Molecules, Reinhold, New York, 1923.
See particularly D. P. N. Satchell and R. S. Satchell, Chem. Soc. Quart. Rev., 25, 171 (1971).
For summaries see: Symposium on Hard and Soft Acids and Bases, Chem. and Eng. News.,43, 90 (1965); R. G. Pearson, Science.,151, 172 (1966); Chem. in Britain,103 (1967): Survey Progr. Chem.,5, 1 (1970): M. J. Frazer, New Scientist,662 (1967).
J. O. Edwards, G. C. Morrison, V. F. Ross, and J. W. Schultz, J. Am. Chem. Soc., 77, 266 (1955).
T. P. Onak, H. Landesman, R. E. Williams, and I. Shapiro, J. Phys. Chem., 63. 1533 (1959): W. D. Phillips, H. C. Miller. and E. L. Muetterties, J. Am. Chem. Soc., 81, 4496 (1959); R. J. Thompson and J. C. Davis, Jr., Inorg. Chem., 4, 1464 (1965).
R. P. Bell, The Proton in Chemistry, Methuen, London, 1959, pp. 13, 93.
For details of the evidence and further references, see R. P. Bell, J. O. Edwards, and R. B. Jones in The Chemistry of Boron and its Compounds (ed. E. L. Muetterties ), Wiley, New York, 1966. pp. 209–221.
A. Hantzsch, Ber., 32, 575 (1899).
A. Hantzsch, Z. Elektrochem., 29, 244 (1923); 30, 202 (1924); Ber., 58, 953 (1925).
K. J. Pedersen, Kgl. Dansk Vid. Selsk. Math-fys. Medd., 12 No. 1 (1932); J. Phys. Chem., 38, 581 (1934).
Hantzsch, and most later workers, made measurements in the neighbourhood of 0°C.
M. Eigen and J. Schoen, Z. Elektrochem., 59, 483 (1955); M. Eigen and L. De Maeyer, Z. Elektrochem., 59, 986 (1955).
A. Hantzsch and M. Kalb, Ber., 32, 3116 (1899): J. G. Aston, J. Am. Chem. Soc., 52, 5254 (1930): 53, 1448 (1931).
A. Werner, Neuere Anchauungen auf dem Gebiete der anorganischen Chemie, 2nd edn., Veweg, Braunschweig, 1909, p. 218.
B. E. Conway, in Modern Aspects of Electrochemistry (ed. J. O’M. Bockris and B. E. Conway), No. 3, MacDonald, London, 1964, p. 43.
P. A. Giguère, Rev. Chim. Minérale, 3, 627 (1966).
A. Volmer, Annalen, 440, 200 (1924).
R. E. Richards and J. A. S. Smith, Trans. Faraday Soc.,47, 1261 (1951). See also Y. Kakiuchi, H. Shono, H. Matsu, and K. Kigoshi, J. Chem. Phys.,19, 1069 (1951); J. Phys. Soc. Japan,7, 102 (1952), for HClO4•H2O.
E. R. Andrew and N. D. Finch, Proc. Phys. Soc., B, 70, 980 (1957).
D. E. O’Reilly, E. M. Peterson, and J. M. Williams, J. Chem. Phys., 54, 96 (1971).
V. Luzzati, Acta Cryst.,4, 239 (1951); 6, 157 (1953); Y. K. Yoon and G. B. Carpenter, Acta Cryst.,12, 17 (1959); F. S. Lee and G. B. Carpenter, J. Phys. Chem.,63, 279 (1959); C. E. Nordman, Acta Cryst.,15, 18 (1962). A report [P. BourreMaladière, Compt. Rend.,246, 1063 (1958)] that H2SO4•H20 contains sulphuric acid molecules has been refuted by I. Taessler and I. Olovsson, [Acta Cryst.,B24, 299 (1968)], who found good evidence for H3O+ • HSO4.
D. E. Bethell and N. Sheppard, J. Chem. Phys., 21, 1421 (1953).
C. C. Ferriso and D. F. Hornig, J. Chem. Phys., 23, 1464 (1955).
D. J. Millen and E. G. Vaal, J. Chem. Soc., 2913 (1956).
J. T. Mullhaupt and D. F. Hornig, J. Chem. Phys., 24, 169 (1956); R. C. Taylor and G. L. Vidale, J. Am. Chem. Soc., 78, 5999 (1956).
H. G. Grimm, Z. Elektrochem., 31, 474 (1925).
J. Sherman, Chem. Rev., 11, 164 (1932).
V. Kondratiev and N. D. Sokolov, Zh. Fiz. Khim., 29, 1265 (1955); F. W. Lampe and J. H. Futtrell, Trans. Faraday Soc., 59, 1957 (1963).
S. I. Vetchinkin, E. I. Pshenichnov, and N. D. Sokolov, Zh. Fiz. Khim., 33, 1269 (1959).
Ref. 13, p. 59.
P F. Knewstubb and A. W. Tickner, J. Chem. Phys., 36, 674 (1962); 38, 464 (1963).
H. D. Beckey, Z. Naturforsch., 14a, 712 (1959); 15a, 822 (1960).
D. Van der Raalte and A. G. Harrison, Canad. J. Chem., 41, 3118 (1963); see also M. A. Haney and J. L. Franklin, J. Chem. Phys., 50, 2028 (1969).
V. L. Tal’rose and E. L. Frankevich, Dokl. Akad. Nauk S.S.S.R., 111, 376 (1956); J. Am. Chem. Soc., 80, 2344 (1958).
J. L. Beauchamp and S. E. Butterill, J. Chem. Phys., 48, 1783 (1968); see also J. Long and B. Munson, J. Chem. Phys., 53, 1356 (1970).
For a summary up to 1963, see J. L. J. Rosenfeld, J. Chem. Phys.,40, 384 (1964); Acta Chem. Scand.,18, 1719 (1964). It is interesting to note that theory predicts a positive t H of 40–60 kcal mol-1 for the reaction H3O++H+ H402+; the last species has never been detected experimentally.
D. M. Bishop, J. Chem. Phys., 43, 4453 (1965).
R. Gaspar, I. Tamassy-Lentei, and V. Kruglyak, J. Chem. Phys., 36, 740 (1962); J. W. Moskowitz and M. C. Harrison, J. Chem. Phys., 43, 3550 (1965).
A. C. Hopkinson, N. K. Holbrook, K. Yates, and I. G. Cszimadia, J. Chem. Phys., 49, 3596 (1968).
H. Goldschmidt and O. Udby, Z. Phys. Chem., 60, 728 (1907); H. Goldschmidt, Z. Elektrochem., 15, 4 (1909).
It is reasonable to assume by analogy that the ‘hydrogen ion’ in an alcohol ROH has the formula ROH, hence that the equilibrium can be written ROH; +H2O ROH+H3O+; however, this cannot be deduced from experiments in which the concentration of the alcohol is effectively constant.
G. Bredig, Z. Elektrochem., 18, 535 (1912); W. S. Miller, Z. Phys. Chem., 85, 129 (1913).
G. Nonhebel and H. B. Hartley, Phil. M1dag., 50, 734 (1925); L. Thomas and E. Marum, Z. Phys. Chem., 143, 213 (1929).
P. Gross, A. Jamöck, and F. Patat, Monatsh., 63, 124 (1933).
L. S. Bagster and B. D. Steele, Trans. Faraday Soc., 8, 51 (1912); L. S. Bagster and G. Cooling, J. Chem. Soc., 693 (1920).
M. Schneider and P. A. Giguère, Compt. Rend., B, 267, 551 (1968).
See, e.g., R. Suhrmann and F. Breyer, Z. Phys. Chem., 23B, 193 (1933).
M. Falk and P. A. Giguère, Canad. J. Chem., 35, 1195 (1957); 36, 1680 (1958).
C. G. Swain and R. F. W. Bader, Tetrahedron, 10, 182 (1960); C. G. Swain, R. F. W. Bader, and E. R. Thornton, Tetrahedron, 10, 200 (1960); W. R. Busing and D. F. Hornig, J. Phys. Chem., 65, 284 (1961).
M. Eigen and L. de Maeyer, Z. Elektrochem., 60, 1037 (1956); The Structure of Electrolytic Solutions (ed. W. J. Hamer ), Wiley, New York, 1959, p. 64.
M. Eigen, Angew. Chem., 75, 489 (1963).
B. E. Conway, J. O’M. Bockris, and H. Linton, J. Chem. Phys., 24, 834 (1956).
L. Hall, Phys. Rer., 73, 775 (1948).
T. Ackermann, Z. Phys. Chem (Frankfurt), 27, 253 (1961).
R. More O’Ferrall, G. W. Koeppl, and A. J. Kresge, J. Am. Chem. Soc., 93, 1 (1971).
E. G. Weidemann and G. Zundel, Z. Phys., 198, 288 (1967); G. Zundel, Angew. Chem. Internat. Edn., 8, 499 (1969).
K. Fajans and G. Joos, Z. Phys. Chem., 23, 1, 31 (1924).
E. Wicke, M. Eigen, and T. Ackermann, Z. Phys. Chem. (Frankfurt), 1, 340 (1954).
E. Glueckauf, Trans. Faraday Soc., 51, 1235 (1955).
R. P. Bell and K. N. Bascombe, Disc. Faraday Soc., 24, 158 (1957). A similar treatment for concentrated alkaline solution leads to a hydration number of 3 for the hydroxide ion; cf. G. Yagil and M. Anbar, J. Am. Chem. Soc., 85, 2376 (1963); R. Stewart and J. P. O’Donnell, Canad. J. Chem., 42, 1681 (1964).
A. H. Laurence, D. E. Campbell, S. E. Wiberley, and H. M. Clark, J. Phys. Chem., 60, 901 (1956); D. G. Tuck and R. M. Diamond, J. Phys. Chem., 65, 193 (1961).
E. Glueckauf and G. P. Kitt, Proc. Roy. Soc., A, 228, (1955).
J. Rudolph and H. Zimmermann, Z. Phys. Chem. (Frankfurt), 43, 311 (1964).
J. O. Lundgren and I. Olovsson, J. Chem. Phys., 49, 1068 (1968).
A. C. Pavia and P. A. Giguère, J. Chem. Phys., 52, 3551 (1970).
I. Olovsson, J. Chem. Phys., 49, 1063 (1968).
R. D. Gillard and G. Wilkinson, J. Chem. Soc., 1640 (1964).
A. S. Gilbert and N. Sheppard, J. Chem. Soc., D, 337 (1971).
J. M. Williams and S. W. Petersen, J. Am. Chem. Soc., 91, 776 (1969); D. E. O’Reilly, E. M. Peterson, C. E. Scheie, and J. M. Williams, J. Chem. Phys., 55, 5629 (1971).
P. Kebarle, Advances in Chemistry, 72 (Am. Chem. Soc., 1968 ), p. 24.
M. de Paz, J. J. Leventhal, and L. Friedman, J. Chem. Phys., 49, 5543 (1968).
M. de Paz, A. G. Giardini, and L. Friedman, J. Chem. Phys., 52, 687 (1970).
E. C. Baughan, J. Chem. Soc., 1403 (1940).
H. F. Halliwell and S. C. Nyburg, Trans. Faraday Soc., 59, 1126 (1963). These authors give a useful summary of earlier estimates of this quantity. Conway prefers a slightly higher value, but gives an upper limit of 267 kcal mol-1. See also N. A. Izmailov, Zh. Fiz. Khim., 34, 2414 (1960).
J. T. Edward and I. C. Wang, Canad. J. Chem., 40, 399 (1962): G. Yagil and M. Anbar, J. Am. Chem. Soc., 85, 2376 (1963).
J. L. Moruzzi and A. V. Phelps, J. Chem. Phys., 45, 4617 (1966).
Author information
Authors and Affiliations
Rights and permissions
Copyright information
© 1973 R. P. Bell
About this chapter
Cite this chapter
Bell, R.P. (1973). Acids, Bases, and the Nature of the Hydrogen Ion. In: The Proton in Chemistry. Springer, Boston, MA. https://doi.org/10.1007/978-1-4757-1592-7_2
Download citation
DOI: https://doi.org/10.1007/978-1-4757-1592-7_2
Publisher Name: Springer, Boston, MA
Print ISBN: 978-1-4757-1594-1
Online ISBN: 978-1-4757-1592-7
eBook Packages: Springer Book Archive