Hostname: page-component-7dd5485656-wjfd9 Total loading time: 0 Render date: 2025-10-31T07:00:06.509Z Has data issue: false hasContentIssue false
  • English
  • Français

Molecular Structure Effects on Diffusion of Cations in Clays

Published online by Cambridge University Press:  28 February 2024

Alanah Fitch ,
John Song  and
Jenny Stein
Alanah Fitch
Affiliation:
Department of Chemistry, Loyola University of Chicago, 6525 N. Sheridan Rd. Chicago, Illinois 60626
John Song
Affiliation:
Department of Chemistry, Loyola University of Chicago, 6525 N. Sheridan Rd. Chicago, Illinois 60626
Jenny Stein
Affiliation:
Department of Chemistry, Loyola University of Chicago, 6525 N. Sheridan Rd. Chicago, Illinois 60626
Get access Rights & Permissions [Opens in a new window]

Abstract

The roles of molecular structure and charge are examined in the transport of cations within montmorillonite clay films. The series of Ru(NH3)63+, Co(NH3)3+, Co(en)33+, Co(sep)3+ and Co(bpy)33+ are examined in detail via electrochemical and spectrochemical methods. The electrochemical signal is enhanced both in minimizing the time required to develop the signal and in the magnitude of the signal for Ru(NH3)63+. In addition, the potential for the observed reduction peak is shifted negative and the current peak associated with reduction disappears with rinsing of the clay film. These observations are characteristic of a compound that is held by simple electrostatic charge characteristics. In contrast, the compounds Co(NH3)3+, Co(en)33+ and Co(sep)3+, while showing rapid and enhanced signal development, eventually evolve a signal that is diminished with respect to the bare electrode, consistent with a hydrophobic mode of retention. The signal for Co(bpy)33+ is slow to be observed, is diminished with respect to the bare electrode and is shifted positive in potential, all hallmarks of a strong, non-electrostatic mode of binding within the clay.

Keywords

Clay-modified electrodesCo complexesDiffusionTransport

Information

Type
Research Article
Information
Clays and Clay Minerals , Volume 44 , Issue 3 , June 1996 , pp. 370 - 380
Copyright
Copyright © 1996, The Clay Minerals Society

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

Article purchase

Temporarily unavailable

References

Allen, A.D. and Senoff, C.V.. 1967. Preparation and infrared spectra of some ammine complexes of Ruthenium(II) and Ruthenium(III). Can J Chem 45: 1337–1341.CrossRefGoogle Scholar
Bakava, A., Espenson, J.H., Creaser, I.I. and Sargeson, A.M.. 1983. Kinetics of the superoxide radical oxidation of [Cobalt sepulchrate](2+). A flash photolytic study. J Am Chem Soc 105: 7264–7628.Google Scholar
Barone, F.S., Yanful, E.K., Quigley, R.M. and Row, R.K.. 1989. Effect of multiple contaminant migration on diffusion and adsorption of some domestic waste contaminants in a natural clayey soil. Can Geotech J 26: 189–198.CrossRefGoogle Scholar
Burba, J.L. III and McAtee, J.L. Jr. 1977. The orientation and interaction of ethylenediamine Copper(II) with Montmorillonite. Clays & Clay Miner 25: 113–118.CrossRefGoogle Scholar
Brown, G.M. and Sutin, N.. 1979. A comparison of the rates of electron exchange reactions of ammine complexes of Ruthenium(II)-(III) with the predictions of the adiabatic, outer-sphere electron transfer models. J Am Chem Soc 101: 883–892.CrossRefGoogle Scholar
Cloos, P. and Lauro, R.D.. 1972. Adsorption of Ethylenediamine (EDA) on Montmorillonite saturated with different cations II. Hydrogen—and ethylenediammonium-Montmorillonite and hydrogen bonding. Clays & Clay Miner 20: 259–270.CrossRefGoogle Scholar
Crooks, V.E. and Quigley, R.M.. 1989. Saline leachate migration through clay: A comparative laboratory and field investigation. Can J Geotech 21: 349–362.CrossRefGoogle Scholar
Doine, H. and Swaddle, T.W.. 1991. Pressure effects on the self-exchange rates of Cobalt(III/II) couples. Evidence for adiabatic electron transfer in the Bis(1,4,7-trithiacyclononane) and Sepulchrate Complexes. Inorg Chem 30: 1858–1862.CrossRefGoogle Scholar
Earley, J.E. and Fealey, T.. 1973. Hydroxide ion as a reducing agent for cations containing three ruthenium atoms in nonintegral oxidation states. Inorg Chem 12: 2, 323–327.Google Scholar
Eberson, I. and Ekstrom, M.. 1988. Electron transfer reactions in organic chemistry. XIV. The reactivities of some polyalkanes toward the outer sphere electron transfer reductants Co(II)sepculchrate and Co(II)W12O407–. Acta Chem Scand B42: 1113–121.Google Scholar
Edens, G.J., Fitch, A. and Lavy-Feder, A.. 1991. Use of isopotential points to elucidate ion exchange reaction mechanisms: Cr(bpy)33+ at Montmorillonite clay modified electrodes. J Electroanal Chem 307: 139–154.CrossRefGoogle Scholar
Endicott, J.F., Durham, B. and Kuma, K.. 1982. Examination of the intrinsic barrier to electron transfer in Hexaaquocobalt(III). Evidence for very slow outer-sphere self-exchange resulting from contributions of Frank-Condon and electronic terms. Inorg Chem 21: 2437–2444.CrossRefGoogle Scholar
Fischer, O. and Bezdek, J.. 1973. Study of the kinetics of electrode processes by means of electrolysis with constant current. XIX. Comparison of preceding and succeeding first order reactions. Coll Czech Chem Comm 38: 1907–1910.CrossRefGoogle Scholar
Fitch, A.. 1990. Apparent formal potential shifts in ion exchange voltammetry. J Electroanal Chem 284: 237–244.CrossRefGoogle Scholar
Fitch, A.. 1990. Clay-modified electrodes: A review. Clays & Clay Miner 38: 391–400.CrossRefGoogle Scholar
Fitch, A. and Edens, G.J.. 1989. Isopotential points as a function of an allowed cross reaction. J Electroanal Chem 267: 1–13.CrossRefGoogle Scholar
Fitch, A. and Du, J.. 1992. Diffusion layer in well ordered clay-modified electrodes. J Electroanal Chem 319: 409–414.CrossRefGoogle Scholar
Fitch, A., Du, J., Gan, H. and Stucki, J.W.. 1995. Effect of clay charge on swelling: A clay-modified electrode study. Clays & Clay Miner 43: 607–614.CrossRefGoogle Scholar
Fitch, A. and Fausto, C.L.. 1988. Insulating properties of clay films towards Fe(CN)63–. J Electroanal Chem 257: 299–303.CrossRefGoogle Scholar
Fitch, A., Lavy-Feder, A., Lee, S.A. and Kirsh, M.T.. 1988. Montmorillonite face surface associated Cr(bpy)33+ monitored electrochemical: M.T. J Phys Chem 92: 6667–6670.CrossRefGoogle Scholar
Fitch, A. and Lee, S.A.. 1993. Effect of clay charge on Cr(bpy)33+ reaction mechanism at clay-modified electrodes. J Electroanal Chem 344: 45–59.CrossRefGoogle Scholar
Fitch, A. and Subramanium, P.. 1993. Dual electroactive probes of clay film chemistry. J Electroanal Chem 362: 177–185.CrossRefGoogle Scholar
Fletcher, J.M., Greenfield, B.F., Handy, C.J., Scargill, D. and Woohead, J.L.. 1961. Ruthenium Red. J Chem Soc A 2000.CrossRefGoogle Scholar
Fripiat, J.J. and Helsen, J.. 1966. Kinetics of decomposition of cobalt coordination complexes on montmorillonite surfaces. Clays & Clay Miner 14: 163–9.CrossRefGoogle Scholar
Gahan, L.R., Healy, P.C. and Patch, G.J.. 1989. Synthesis of co-balt(III) cage complexes. J Chem Ed 66: 5, 445–446.Google Scholar
Goldsman, L.J., Damle, A.S., Northein, C.M., Greenfiield, L.T., Kingsbury, G.L. and Truesdale, R.L.. 1990. Clay liners for waste management facilities: Design, construction and evaluation, pollution tech. review. #178, Noyes Data Corp. p 1–9.Google Scholar
Goodall, D.C. and Quigley, R.M.. 1977. Pollutant migration from two sanitary landfill sites near Sarnia, Ontario. Can Geo-tech J 14: 223–236.CrossRefGoogle Scholar
Indelli, A. and Duatli, A.. 1986. Association of Co(sep)3+ ions with S2O32– ions. J Chem Soc Farad Trans I 82: 1429–1440.CrossRefGoogle Scholar
Johnson, R.L., Cherry, J.A. and Pankow, J.F.. 1989. Diffusive contaminant transport in natural clay: A field example and implications for clay-lined waste disposal sites. Env Sci Tech 23: 340–349.CrossRefGoogle Scholar
Kaneyoshi, M., Yamagish, A., Tanaguchi, M. and Aramata, A.. 1993. Adsorption and spectroscopic studies on the interaction of cobalt(III) chelate with clays. Clays & Clay Miner 41: 1–6.CrossRefGoogle Scholar
Das, Kanungo JL and Chakravarti, K.. 1973. Behavior of quarternary ammonium ions in the desorption of [Co(en)3]3 + from H-Coen3 Bentonite. J Ind Chem Soc 35: 295–9.Google Scholar
Knudson, M.I. Jr. and McAtee, J.L. Jr. 1973. The effect of cation exchange of tris(ethylenediamine cobalt(III) for sodium on nitrogen sorption by montmorillonite. Clays & Clay Miner 21: 19–26.CrossRefGoogle Scholar
Krenske, D., Abdo, S., Van Damme, H., Cruz, M. and Fripiat, J.J.. 1980. Photochemical and photocatalytic properties of adsorbed organometallic compounds. 1. Luminescence quenching of tris(2,2'-bypyridin)ruthenium(II) and -chromium(III) in clay membranes. J Phys Chem 84: 2447.CrossRefGoogle Scholar
Lee, S.A. and Fitch, A.. 1990. Conductivity of clay-modified electrodes: Alkali metal cation hydration and film preparation effects. J Phys Chem 94: 4998–5004.CrossRefGoogle Scholar
Maes, A., Schoonheydt, R.A., Cremers, A. and Uytterhoeven, J.B.. 1980. Spectroscopy of Cu(en)22+ on clay surfaces. Surface and charge density effects. J Phys Chem 84: 2795–2799.CrossRefGoogle Scholar
Mayer, U., Kotocova, A., Gutmann, V. and Gerger, W.. 1979. Outer-sphere effects on the redox properties of the system Co(en)33/VCo(en)32+. J Electroanal Chem 100: 885–883.CrossRefGoogle Scholar
Mott, H.V. and Weber, W.J. Jr. 1991. Factors influencing organic contaminant diffusivities in soil-bentonite cutoff barriers. Env Sci Tech 25: 1708–1715.CrossRefGoogle Scholar
Naegeli, R., Redepenning, J. and Anson, F.C.. 1986. Influence of supporting electrolyte concentration and composition on formal potentials and entropies of redox couples incorporated in nafion coatings on electrodes. J Phys Chem 90: 6227–6232.CrossRefGoogle Scholar
Quigley, R.M., Fernandez, F., Yanful, E., Helgason, T., Margaritis, A. and Whitby, J.L.. 1987. Hydraulic conductivity of contaminated natural clay directly below a domestic landfill. Can Geotech J 24: 377–383.CrossRefGoogle Scholar
Ramaraj, R. and Kaneko, M.. 1993. In-situ spectrocyclic voltammetric studies on Ru-red and Ru-brown complexes for water oxidation catalyst in homogeneous aqueous solution and in heterogeneous nafion membranes. J Molecular Catalysis 81: 319–332.CrossRefGoogle Scholar
Sahami, S. and Weaver, M.J.. 1981. Solvent effects on the kinetics of simple electrochemical reactions. Part I. Comparisons of the behavior of Co(III)/(II) trisethylenediamine and ammine couples with the predictions of dielectric continuum theory. J Electroanal Chem 124: 35–51.CrossRefGoogle Scholar
Sastri, V.S.. 1972. Studies on the disposition of carbonato group in cobalt(III) complexes. Inorg Chim Acta 6: 2, 264–266.Google Scholar
Sotomayor, J., Santos, H. and Pina, F.. 1991. Application of 59Co NMR to the investigation of interactions between cobalt sepulchrate and various counterions. Can J Chem 69: 567–569.CrossRefGoogle Scholar
Stahlerg, J.. 1994. Electrostatic retention model for ion-exchange chromatography. Anal Chem 66: 440–449.CrossRefGoogle Scholar
Stein, J.A. and Fitch, A.. 1995. Computerized system for dual electrode multi-sweep cyclic voltammetry: Its use in clay-modified electrode studies. Analytical Chem 67: 1322–1325.CrossRefGoogle Scholar
Subramanium, P. and Fitch, A.. 1992. Diffusional transport of solutes through clay: Use of clay-modified electrodes. Environ Sci Technol 26: 1775–1779.CrossRefGoogle Scholar
Swartzen-Allen, S.L. and Matijevic, E.. 1975. Colloid and surface properties of clay suspensions. II. Electrophoresis and cation adsorption of montmorillonite. J Coll Inter Sci 50: 1, 143–153.Google Scholar
Szalda, D.J., Creutz, C., Mahajan, D. and Sutin, N.. 1983. Electron-transfer barriers and metal-ligand bonding as a function of metal oxidation state. 2. Crystal and molecular structure of tris(2,2‘-bipyridine) cobalt(II) dichloride-2-water-ethanol and tris(2,2‘-bipyridine) Cobalt(I) chloride-water. Inorg Chem 22: 17, 2372–2379.CrossRefGoogle Scholar
Ugo, R. and Gillard, R.D.. 1967. Adducts of coordination compounds. IV—Nitric acid adducts of ammine complexes of trivalent metals. Inorg Chim Acta 1: 2, 311–314.Google Scholar
Velghe, F., Schoonheydt, R.A., Yutterhoeven, J.B., Peigner, P. and Lunsford, J.H.. 1977. Spectroscopic characterization and thermal stability of copper(II) ethylene-diamine complexes on solid surface. 2. Montmorillonite. J Phys Chem 81: 12, 1187–1194.Google Scholar
Wang, X.Q., Thibodeaux, L.J., Valsaraj, K.T. and Relble, D.D.. 1991. Efficiency of capping contaminated bed sediments in situ. 1. Laboratory-scale experiments on diffusion-adsorption in the capping layer. Env Sci Tech 25: 1578–1584.CrossRefGoogle Scholar
Wielgos, T. and Fitch, A.. 1990. Clay modified electrode ion exchange voltammetry. Electroanalysis 2: 449–454.CrossRefGoogle Scholar