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A Critique of Diffuse Double Layer Models Applied to Colloid and Surface Chemistry

Published online by Cambridge University Press:  28 February 2024

Murray B. McBride
Murray B. McBride*
Affiliation:
Department of Soil, Crop and Atmospheric Sciences, Cornell University, Ithaca, New York 14853
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Abstract

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The use of Derjaguin-Landau-Verwey-Overbeek (DLVO) theory in colloid science has continued to the present day in spite of the inability of this theory to explain, even qualitatively, numerous phenomena exhibited by clays and other colloidal materials. An alternative description of the fundamental forces involved in the formation of dispersions and gels was presented in 1938 by Langmuir, but was never widely accepted among colloid scientists. Recent experimental and theoretical work, particularly in Japan, has revived this alternative view, in which a long-range Coulombic attraction force appears to explain several phenomena, particularly transitions among ordered and disordered phases of colloidal particles in dilute salt solutions.

Examples are given from surface chemistry where rather complex models based on diffuse double layer theory are used to explain chemical adsorption behavior that often has a simpler explanation. It is argued that the rule of parsimony (Ockham's Razor) should be applied to complex models that appear to explain the data at hand before such models are taken to be generally valid. A satisfactory fit of model predictions to experimental data obtained under a very limited range of conditions does not prove the validity of the model. Thus, it is concluded that the DLVO theory and its modifications fail to meet the 2 criteria necessary to the acceptance of a theory: agreement with observations and simplicity.

Keywords

Clay DispersionClay SwellingDiffuse Double LayerDLVOElectrostatic Attraction TheoryInterparticle ForcesOckham's RazorSchiller LayersSmectites
Type
Research Article
Information
Clays and Clay Minerals , Volume 45 , Issue 4 , August 1997 , pp. 598 - 608
Copyright
Copyright © 1997, The Clay Minerals Society

References

Ackler, H.D. French, R.H. and Chiang, Y.-M., 1996 Comparisons of Hamaker constants for ceramic systems with intervening vacuum or water: From force laws and physical properties J Colloid Interface Sci 179 460–469 10.1006/jcis.1996.0238.CrossRefGoogle Scholar
Ajwa, H.A. and Tabatabai, M.A., 1995 Metal-induced sulfate adsorption by soils: II. Effects of metal type, valence and concentration Soil Sci 160 281–290 10.1097/00010694-199510000-00007.CrossRefGoogle Scholar
Barrow, N.J. Bowden, J.W. Posner, A.M. and Quirk, J.P., 1980 Describing the effects of electrolyte on adsorption of phosphate by a variable charge surface Aust J Soil Res 18 395–404 10.1071/SR9800395.CrossRefGoogle Scholar
Bolan, N.S. Syers, J.K. and Summer, M.E., 1993 Calcium-induced sulfate adsorption by soils Soil Sci Soc Am J 57 691–696 10.2136/sssaj1993.03615995005700030011x.CrossRefGoogle Scholar
Bolt, G.H. van Riemsdijk, W.H. et al. , Bolt, G.H. 1991 et al. , The electrified interface of the soil solid phase Interactions at the soil colloid-soil solution interface Dordrecht Kluwer 37–79 10.1007/978-94-017-1909-4_2.CrossRefGoogle Scholar
Bowden, J.W. Nagarajah, S. Barrow, N.J. Posner, A.M. and Quirk, J.P., 1980 Describing the adsorption of phosphate, citrate and selenite on a variable charge mineral surface Aust J Soil Res 18 49–60 10.1071/SR9800049.CrossRefGoogle Scholar
Bergmann, P. Löw-Beer, P. and Zocher, H., 1938 Beitrag zur Theorie der Schillerschichten Zeitschrift für Physikalische Chemie (Abt A) 181 301–314.Google Scholar
Braganza, L.F. Crawford, R.J. Smalley, M.V. and Thomas, R.K., 1990 Swelling of n-butylammonium vermiculite in water Clays Clay Min 38 90–96 10.1346/CCMN.1990.0380112.CrossRefGoogle Scholar
Brown, G.E. Parks, G.A. and Chisholm-Brause, C.J., 1989 In-situ X-ray absorption spectroscopic studies of ions at oxide-water interfaces Chimia 43 248–256.Google Scholar
Christenson, H.K., 1988 Non-DLVO forces between surfaces-solvation, hydration and capillary effects J Dispersion Sci Technol 9 171–206 10.1080/01932698808943983.CrossRefGoogle Scholar
Coper, K. and Freundlich, H., 1937 The formation of tactoids in iron oxide soils J Chem Soc, Faraday Trans 33 348–350 10.1039/tf9373300348.CrossRefGoogle Scholar
Dosho, S. Ise, N. Iwai, S. Kitano, H. Matsuoka, H. Nakamura, H. Okumura, H. Ono, J. Sogami, I. Uneo, Y. Yoshida, H. and Yoshiyama, T., 1993 Recent study of polymer latex dispersions Langmuir 9 394–411 10.1021/la00026a008.CrossRefGoogle Scholar
Engström, S. Wennerström, H. Mouritsen, O.G. and Fogedby, H.C., 1985 Fluctuation-induced forces between colloidal systems with many internal degrees of freedom: A model study of a one-dimensional Ising system Chemica Scripta 25 92–95.Google Scholar
Feibleman, J.K., 1972 Scientific method The Hague Martinus Nijhoff 10.1007/978-94-010-2758-8.CrossRefGoogle Scholar
Gast, R.G., Dixon, J.B. and Weed, S.B., 1977 Surface and colloid chemistry Minerals in soil environments Madison, WI Soil Sci Soc Am 27–73.Google Scholar
Goldberg, S. Forster, H.S. and Heick, E.L., 1993 Boron adsorption mechanisms on oxides, clay minerals, and soils inferred from ionic strength effects Soil Sci Soc Am J 57 704–708 10.2136/sssaj1993.03615995005700030013x.CrossRefGoogle Scholar
Goldberg, S. and Sposito, G., 1984 A chemical model of phosphate adsorption by soils: I. Reference oxide minerals Soil Sci Soc Am J 48 772–778 10.2136/sssaj1984.03615995004800040015x.CrossRefGoogle Scholar
Guldebrand, L. Jönsson, B. Wennerström, H. and Linse, P., 1984 Electrical double layer forces. A Monte Carlo study J Chem Phys 80 2221–2228 10.1063/1.446912.CrossRefGoogle Scholar
Hayes, K.F. Papelis, C. and Leckie, J.O., 1988 Modeling ionic strength effects on anion adsorption at hydrous oxide/solution interfaces J Colloid Interface Sci 125 717–726 10.1016/0021-9797(88)90039-2.CrossRefGoogle Scholar
Helyar, K.R. Munns, D.N. and Burau, R.G., 1976 Adsorption of phosphate by gibbsite: I. Effects of neutral chloride salts of calcium, magnesium, sodium, and potassium J Soil Sci 27 307–314 10.1111/j.1365-2389.1976.tb02001.x.CrossRefGoogle Scholar
Ise, N., 1986 Ordering of ionic solutes in dilute solutions through attraction of similarly charged solutes—A change of paradigm in colloid and polymer chemistry Angew Chem Int Ed Engl 25 323–334 10.1002/anie.198603231.CrossRefGoogle Scholar
Ise, N. and Smalley, M.V., 1994 Thermal compression of colloidal crystals: Paradox of the repulsion-only assumption Phys Rev B 50 22 16722–16725 10.1103/PhysRevB.50.16722.CrossRefGoogle ScholarPubMed
Israelachvili, J.N., 1985 Measurements of hydration forces between macroscopic surfaces Chemica Scripta 25 7–14.Google Scholar
Ito, K. Yoshida, H. and Ise, N., 1994 Void structure in colloidal dispersions Science 263 66–68 10.1126/science.263.5143.66.CrossRefGoogle ScholarPubMed
Jefferys, W.H. and Berger, J.O., 1992 Ockham’s Razor and Bayesian analysis Am Scientist 80 64–72.Google Scholar
Keren, R. and O’Connor, G.A., 1982 Effect of exchangeable ions and ionic strength on boron adsorption by montmorillonite and illite Clays Clay Miner 30 341–346 10.1346/CCMN.1982.0300504.CrossRefGoogle Scholar
Keren, R. and Sparks, D.L., 1994 Effect of pH and ionic strength on boron adsorption by pyrophyllite Soil Sci Soc Am J 58 1095–1100 10.2136/sssaj1994.03615995005800040013x.CrossRefGoogle Scholar
Kittrick, J.A., 1966 Forces involved in ion fixation by vermiculite Soil Sci Soc Am Proc 30 801–803 10.2136/sssaj1966.03615995003000060040x.CrossRefGoogle Scholar
Kjellander, R. Marcelja, S. Pashley, R.M. and Quirk, J.P., 1988 Double-layer correlation forces restrict calcium-clay swelling J Phys Chem 92 6489–6492 10.1021/j100334a005.CrossRefGoogle Scholar
Langmuir, I., 1938 The role of attractive and repulsive forces in the formation of tactoids, thixotropic gels, protein crystals and coacervates J Chem Phys 6 873–896 10.1063/1.1750183.CrossRefGoogle Scholar
Lear, P.R. and Stucki, J.W., 1989 Effects of iron oxidation state on the specific surface area of nontronite Clays Clay Miner 37 547–552 10.1346/CCMN.1989.0370607.CrossRefGoogle Scholar
Levine, S., 1946 On the interaction of colloidal particles. I. Particular application to parallel plates J Chem Soc, Faraday Trans 42A–B 102–117 10.1039/tf946420b102.CrossRefGoogle Scholar
MacEwan, D.M.C., 1948 Adsorption by montmorillonite, and its relation to surface adsorption Nature 162 935–936 10.1038/162935a0.CrossRefGoogle Scholar
Marcano-Martinez, E. and McBride, M.B., 1989 Calcium and sulfate retention by two oxisols of the Brazilian Cerrado Soil Sci Soc Am J 53 63–69 10.2136/sssaj1989.03615995005300010012x.CrossRefGoogle Scholar
McBride, M.B., 1994 Environmental chemistry of soils New York Oxford Univ Pr.Google Scholar
McBride, M.B., Dixon, J.B. and Weed, S.B., 1989 Surface chemistry of soil minerals Minerals in soil environments 2nd ed Madison, WI Soil Sci Soc Am 35–88.Google Scholar
McBride, M.B. and Stewart, B.A., 1989 Reactions controlling heavy metal solubility in soils Advances in soil science 10 1–56.CrossRefGoogle Scholar
Norrish, K., 1954 The swelling of montmorillonite Disc Faraday Soc 18 120–134 10.1039/df9541800120.CrossRefGoogle Scholar
Onsager, L., 1949 The effects of shape on the interaction of colloidal particles Ann NY Acad Sci 51 627–659 10.1111/j.1749-6632.1949.tb27296.x.CrossRefGoogle Scholar
Overbeek, J.T.h.G. and Kruyt, H.R., 1952 Stability of hydrophobic colloids and emulsions Colloid science, vol. 1. Irreversible systems New York Elsevier 302–341.Google Scholar
Pashley, R.M., 1981 DLVO and hydration forces between mica surfaces in Li+, Na+, K+, and Cs+ electrolyte solutions: A correlation of double-layer and hydration forces with surface cation exchange properties J Colloid Interface Sci 83 531–546 10.1016/0021-9797(81)90348-9.CrossRefGoogle Scholar
Rajan, S.S.S., 1978 Sulfate adsorbed on hydrous alumina, ligands displaced, and changes in surface charge Soil Sci Soc Am Proc 42 39–44 10.2136/sssaj1978.03615995004200010009x.CrossRefGoogle Scholar
Secor, R.B. and Radke, C.J., 1985 Spillover of the diffuse double layer on montmorillonite particles J Colloid Interface Sci 103 237–244 10.1016/0021-9797(85)90096-7.CrossRefGoogle Scholar
Slade, P.G. Quirk, J.P. and Norrish, K., 1991 Crystalline swelling of smectite samples in concentrated NaCl solutions in relation to layer charge Clays Clay Miner 39 234–238 10.1346/CCMN.1991.0390302.CrossRefGoogle Scholar
Schulthess, C.P. and Sparks, D.L.. Backtitration technique for proton isotherm modeling of oxide surfaces. Soil Sci Soc Am J 50:1406–1411.CrossRefGoogle Scholar
Smalley, M.V., 1990 Electrostatic interaction in macro-ionic solutions and gels Mol Phys 71 1251–1267 10.1080/00268979000102471.CrossRefGoogle Scholar
Smalley, M.V., 1994 Electrical theory of clay swelling Langmuir 10 2884–2891 10.1021/la00021a009.CrossRefGoogle Scholar
Sogami, I., 1983 Effective potential between charged spherical particles in dilute suspension Phys Lett 96A 199–203 10.1016/0375-9601(83)90704-1.CrossRefGoogle Scholar
Sogami, I. and Ise, N., 1984 On the electrostatic interaction in macroionic solutions J Chem Phys 81 6320–6332 10.1063/1.447541.CrossRefGoogle Scholar
Sogami, I.S. Shinohara, T. and Smalley, M.V., 1992 Adiabatic pair potential of highly charged plates in an electrolyte Mol Phys 76 1–19 10.1080/00268979200101121.CrossRefGoogle Scholar
Sposito, G., Huang, C.P. O’Melia, C.R. and Morgan, J.J., 1995 Adsorption as a problem in coordination chemistry. The concept of the surface complex Aquatic chemistry. Interfacial and interspecies processes Washington, DC ACS 33–57 10.1021/ba-1995-0244.ch002.CrossRefGoogle Scholar
Su, C. and Suarez, D.L., 1995 Coordination of adsorbed boron: A FTIR spectroscopic study Environ Sci Technol 29 302–311 10.1021/es00002a005.CrossRefGoogle Scholar
van Olphen, H., 1977 An introduction to clay colloid chemistry 2nd ed. New York J Wiley.Google Scholar
Verwey, E.J.W. and Overbeek, J.T.h.G., 1946 Long distance forces acting between colloidal particles J Chem Soc, Faraday Trans 42A–B 117–123 10.1039/tf946420b117.CrossRefGoogle Scholar
Viani, B.E. Roth, C.B. and Low, P.F., 1985 Direct measurement of the relation between swelling pressure and interlayer distance in Livermiculite Clays Clay Miner 33 244–250 10.1346/CCMN.1985.0330311.CrossRefGoogle Scholar
Williams, G.D. Moody, K.R. Smalley, M.V. and King, S.M., 1994 The sol concentration effect in n-butylammonium vermiculite swelling Clays Clay Miner 42 614–627 10.1346/CCMN.1994.0420514.CrossRefGoogle Scholar
Zhang, F. Zhang, Z.Z. Low, P.F. and Roth, C.B., 1993 The effect of temperature on the swelling of montmorillonite Clay Miner 28 25–31 10.1180/claymin.1993.028.1.03.CrossRefGoogle Scholar