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Studies on the zeolites. Part VIII. A theory of the vapour pressure of the zeolites, and of the diffusion of water or gases in a zeolite crystal1

Published online by Cambridge University Press:  14 March 2018

Max H. Hey
Max H. Hey*
Affiliation:
Mineral Department of the British Museum of Natural History
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Extract

The behaviour of the zeolites on dehydration, and their capacity for absorbing other gases and vapours in place of the water removed, have formed the subject of numerous investigations, qualitative and quantitative, of various degrees of accuracy. In only a few cases have attempts been made to fit an equation to the experimental data. Of these equations, those proposed by O. Weigel, G. F. Hüttig, and O. Schmidt are quite inadequate, as is readily seen by a trial with the more extensive data now available. On the other hand, E. Rabinowitsch derived an equation which proved capable Of reproducing the experimental data and is very similar to the equation now proposed, but derived in a quite different way.

Type
Research Article
Information
Mineralogical magazine and journal of the Mineralogical Society , Volume 24 , Issue 150 , September 1935 , pp. 99 - 130
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 1935

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Footnotes

1

Parts I–VII, Min. Mag., 1930–1934, vols. 22–23

References

Page 99 Note 2 Other than a Freundlich isotherm, an empirical type of equation which will almost always represent the data over a limited range.

Page 99 Note 3 Weigel, O., Sitzungsber. Gesell. Naturwiss. Marburg, 1924, p. 107 Google Scholar [M.A. 4-373]; Hüttig, G. F., Fortschr. Chem. Phys. und Physikal. Chem., 1924, vol. 18, no. 1,Google Scholar and Kolloid-Zeits., 1924, vol. 35, p. 337 [M.A. 5-82]; Schmidt, O., Zeits. Physikal. Chem., 1928, vol. 133, p. 263 Google Scholar [M.A. 5-81].

Page 99 Note 4 Rabinowitsch, E., Zeits. Physikal. Chem., Abt. B, 1932, vol. 16, p. 50 Google Scholar [M.A. 5-355].

Page 99 Note 5 The similarity is not immediately apparent, but is readily disclosed by substituting (1- x) for Q/Qm and writing the equation logarithmically.

Page 101 Note 1 It is not necessary to consider more than the surface layer, since, in equilibrium, the influence of deeper layers on condensation and on evaporation must necessarily balance.

Page 101 Note 2 That is, a molecule approaching a given vacant lattice position is at first repelled, and only on reaching a certain point {which it will not reach, against the repulsion, unless it has the necessary energy η) is it attracted into the lattice position.

Page 102 Note 1 Strictly, the mean velocity is , where Φ denotes the Gaussian error function. If N∊/RT is large, the second expression is negligible.

Page 102 Note 2 Compare Lennard-Jones, J. E., Trans. Faraday Soc., 1932, vol. 18, p. 351 Google Scholar, who concludes, in a very similar problem, that the factor X can be neglected.

Page 103 Note 1 That is, the heat evolved when one gram-mol, of water vapour combines with an infinite amount of zeolite of degree of dehydration x, exclusive of the external work involved.

Page 105 Note 1 The reality of lattice shrinkage has been repeatedly demonstrated by X-ray and specific gravity measurements.

Page 105 Note 2 In some types of structure (e.g. chabazite) lattice shrinkage does not appear to affect the water-bearing channels.

Page 105 Note 3 Strictly, both E0 and a probably vary slightly with temperature, but the variation is in general too small to be detected with the range of experimental temperatures normally available. The variation in D due to thermal expansion is negligible.

Page 105 Note 4 Taylor, W. H. and Jackson, R., Zeits. Krist., 1933, vol. 86, p. 53 Google Scholar [M.A. 5-354].

Page 110 Note 1 More strictly, this applies to the high-temperature modification, metascolecite ; scolecite itself has a more volatile group of 16 and a less volatile group of 8 molecules.

Page 116 Note 1 Friedel, G., Bull. Soc. Franç. Min., 1896, vol. 19, p. 363.Google Scholar

Page 116 Note 2 Wyart, J., Recherches sur les zéolites. Thèse Fac. Sci. Univ. Paris, 1933 Google Scholar [M.A. 5-354] ; Bull. Soc. Franç. Min., 1933, vol. 56, p. 103.

Page 116 Note 3 Chilton, D. and Rabinowitsch, E., Zeits. Physikal. Chem., Abt. B, 1932, vol. 19, p. 107 Google Scholar [M.A. 5-356].

Page 116 Note 4 Grandjean, F., Bull. Soc. Franç. Min., 1910, vol. 33, p. 5.Google Scholar

Page 116 Note 5 Simon, F., Zeits. Physikal. Chem., 1928, vol. 132, p. 456 Google Scholar [M.A. 5-81] ; also Zeits. Elektrochem., 1928, vol. 34, p. 528 [M.A. 5-82].

Page 117 Note 1 Aharoni, J. and Simon, F., Zeits. Physikal. Chem., Abt. B, 1929, vol. 4, p. 175 Google Scholar [M.A. 5-81].

Page 117 Note 2 Friedel, G., Bull. Soc. Franç. Min., 1899, vol. 22, p. 5.Google Scholar

Page 117 Note 3 Tiselius, A. and Brohult, S., Zeits. Physikal. Chem., Abt. A, 1934, vol. 168, p. 248 Google Scholar [M.A. 6-126].

Page 117 Note 4 Rabinowitsch, E., Zeits. Physikal. Chem., Abt. B, 1932, vol. 16, p. 50 Google Scholar [M.A. 5-355].

Page 118 Note 1 Tammann, G., Zeits. Physikal. Chem., 1897, vol. 27, p. 325;Google Scholar Ann. Phys. Chem. (Wiedemann), 1897, vol. 63, p. 16.

Page 118 Note 2 Löwenstein, E., Zeits. Anorg. Chem., 1909, vol. 63, p. 69.CrossRefGoogle Scholar

Page 119 Note 1 Balarew, D., Zeits. Anorg. Chem., 1926, vol. 156, p. 238;Google Scholar ibid., 1927, vol. 163, p. 137 ; Kolloid-Zeits., 1929, vol. 48, p. 63.

Page 119 Note 2 Linck, G. and Jung, H., Zeits. Anorg. Chem., 1924, vol. 137, p. 407;CrossRefGoogle Scholar Jung, H., ibid., 1925, vol. 142, p. 73;Google Scholar Feitknecht, W., Helv. Chim. Acts, 1931, vol. 14, p. 85;CrossRefGoogle Scholar Onorato, E., Periodico Min. (Roma), 1932, vol. 3, p. 73;Google Scholar Gallitelli, P., ibid., 1933, vol. 4, p. 132;Google Scholar Caspari, W. A., Nature, 1934, vol. 133, p. 648.CrossRefGoogle Scholar The objections of Gaubert, P. (Bull. Soc. Franç. Min., 1934, vol. 57, p. 252)Google Scholar cannot be accepted as valid [M.A. 6-58].

Page 119 Note 3 Lange, W. and Lewin, G., Ber. Deut. Chem. Gesell., 1930, vol. 63B, pp. 2156 CrossRefGoogle Scholar, 2954; Lange, W. and Krueger, G., Zeits. Anorg. Chem., 1933, vol. 216, p. 49 CrossRefGoogle Scholar; Lange, W., ibid., 1934, vol. 219, p. 305.Google Scholar

Page 119 Note 4 The isothermal data for H2S for -60.6°C. are not in agreement with the isotherm for O°C. and the isobar for 760 ,mm., the observed pressures being much too high ; they have therefore been rejected. Calorimetric measurements gave for H2S, Qx = 9.94 X 103 cals., or E = 9.9 x 103 cals.

Page 122 Note 1 Sameshima, J., Bull. Chem. Soc. Japan, 1929, vol. 4, p. 96 CrossRefGoogle Scholar [M.A. 5-79].

Page 122 Note 2 Weigel, O. and Steinhoff, E., Zeits. Krist., 1925, vol. 61, p. 125 Google Scholar [M.A. 2-528].

Page 122 Note 3 Weigel, O. and Bezner, E., Sitzungsber. Gesell. Naturwiss. Marburg, 1927, vol. 62, p. 57 Google Scholar [M.A. 5-78].

Page 122 Note 4 Baba, T., Bull. Chem. Soc. Japan, 1930, vol. 5, p. 190 CrossRefGoogle Scholar [M.A. 5-79].

Page 123 Note 1 Simon, F., Zeits. Elektrochem., 1928, vol. 34, p. 528 Google Scholar [M.A. 5-82].

Page 123 Note 2 Hartwig, W., Zeits. Krist., 1931, vol. 78, p. 173 Google Scholar [M.A. 5-29] (analcime); Lengyel, B., Zeits. Physik, 1932, vol. 77, p. 133 CrossRefGoogle Scholar [M.A. 5-355] (chabazite).

Page 123 Note 3 Taylor, W. H., Zeits. Krist., 1930, vol. 74, p. 1 Google Scholar [M.A. 4-369] ; Taylor, W. H., Meek, C. A., and Jackson, W. W., ibid., 1933, vol. 84, p. 373 Google Scholar [M.A. 5-354] ; Taylor, W. H. and Jackson, R., ibid., 1933, vol. 86, p. 53 Google Scholar [M.A. 5-354] ; J. Wyart, loc. cit.

Page 124 Note 1 It need hardly be mentioned that the results here obtained for the diffusion of water in a zeolitic hydrate will apply to the diffusion of the volatile component in any zeolitic compound.

Page 124 Note 2 The activation energy, μ, for migration within the lattice is likely to be considerably less than the activation energy, ∊, for escape from the lattice.

Page 127 Note 1 Tiselius, A., Nature, 1934, vol. 133, p. 212 CrossRefGoogle Scholar; Zeits. Physikal. Chem., Abt. A, 1934, vol. 169, p. 425 [M.A. 6-126].

Page 128 Note 1 Tiselius found the diffusion to be faster normal to t(201) and s(2̄01) than normal to c (001) ; according to Gaubert, P. (Bull. Soc. Franç. Min., 1929, vol. 52, p. 162 Google Scholar [M.A. 4-377]) the opposite is the ease.