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Clays and Clay Minerals

, Volume 19, Issue 6, pp 383–390 | Cite as

Mechanisms of Formation of Colored Clay-Organic Complexes. A Review

  • B. K. G. Theng
Article

Abstract

The interactions of clay minerals with organic compounds which give rise to the formation of colored complexes, are discussed. The color reactions of clays can be ascribed to a charge transfer between the mineral and the adsorbed species. The active sites on the clay are aluminums exposed at crystal edges and/or transition metal cations in the higher valency state at planar surfaces both of which can act as electron acceptors. The pH of the system, the nature of the solvent and that of the exchangeable cation, influence the rate of color development and the final intensity and quality of the color produced. Steric factors also play a part in reactions involving bulky organics. Some practical applications based on color reactions of clays with electron-donating organic substances are described.

Résumé

Les interactions des minéraux argileux avec les composés organiques qui donnent naissance à la formation de complexes colorés sont discutées. Les réactions colorées avec les argiles peuvent être attribuées à un transfert de charge entre le minéral et l’espèce adsorbée. Les sites actifs de l’argile sont les atomes d’aluminium exposés sur les bords des cristaux, et/ou, les cations métalliques de transition dans un état de valence élevée sur les surfaces basales, chacun d’eux pouvant agir comme accepteur d’électrons. Le pH du système, la nature du solvant et celle du cation échangeable, influencent la vitesse du développement de la coloration, et l’intensité et la qualité finales de la teinte produite. Des facteurs stériques jouent également un rôle dans les réactions se produisant avec les composés organiques encombrants. Un certain nombre d’applications pratiques fondées sur les réactions colorées des argiles avec les composés organiques donneurs d’électrons sont décrites.

Kurzreferat

Die gegenseitige Einwirkung von Tonmineralen und organischen Verbindungen, die zur Bildung farbiger Komplexe führen kann, wird erörtert. Die Farbreaktionen der Tone kann einem Ladungsübergang zwischen Mineral und adsorbiertem Stoff zugeschrieben werden. Die Aktivstellen am Ton sind exponiertes Aluminium an den Kristallkanten und/oder Übergangsmetallkationen in der höheren Valenzstufe an ebenen Flächen, welche beide als Elektronenakzeptoren wirksam sein können. Das pH des Systems, die Art des Lösungsmittels und die des austauschfähigen Kations beeinflussen die Geschwindigkeit der Farbentwicklung und die schliessliche Stärke und Qualität der erzeugten Farbe. Sterische Faktoren spielen gleichfalls eine Rolle bei Reaktionen mit umfangreicheren organischen Stoffen. Es werden einige praktische Anwendungen auf Grund von Farbreaktionen von Tonen mit elektronenabgebenden organischen Stoffen angeführt.

Резюме

Обсуждается характер взаимодействия глинистых минералов с органическими соединениями, которое приводит к образованию окрашенных комплексов. Цветная реакция глин может быть приписана перемещению заряда между минералом и адсорбированным веществом. Активными центрами на поверхности глины являются атомы алюминия, выходящие на грани кристаллов и/или катионы переходных металлов в высоко валентном состоянии на плоских поверхностях; оба типа центров могут вести себя как акцепторы электронов. На скорость появления окраски, ее конечную интенсивность и характер влияют рН системы, природа растворителя и обменных катионов. Стерические факторы также играют роль при реакциях с объемными органическими молекулами. Описаны некоторые примеры практического применения методики, основанного на цветных реакциях глин с злектронно-донорными органическими соединениями.

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References

  1. Benesi, H. A. (1956) Acidity of catalyst surfaces—I. Acid strength from colors of adsorbed indicators: J. Am. Chem. Soc. 78, 5490–5494.CrossRefGoogle Scholar
  2. Benesi, H. A. (1967) Acidity of catalyst surfaces—II. Amine titration using Hammett indicators: J. Phys. Chem. 61, 970–973.CrossRefGoogle Scholar
  3. Bloch, J. M., Charbonneile, J. and Kayser, F. (1953) The oxidizing power of montmorillonite: C.r. hebd. Séanc. Acad. Sci. Paris 237, 57–59.Google Scholar
  4. Bloch, J. M. and Kayser, F. (1953) Formation of pigments and traces of aromatic amines in the presence of montmorillonite as a catalyst: Chim. lad. Paris 70, 58–63.Google Scholar
  5. Bozassa, V. L. (1944) On the adsorption of some organic dyes by clays and clay minerals: Am. Mineralogist 29, 235–241.Google Scholar
  6. Briegleb, G. (1961) Elektronen-Donalor-Acceptor Komplexe. Springer-Verlag, Berlin.CrossRefGoogle Scholar
  7. Brown, G. (Editor) (1961) The X-Ray Identification and Crystal Structures of Clay Minerals. 2nd Edn., Mineralogical Society London.Google Scholar
  8. Dodd, C. G. (1955) Dye adsorption as a method of identifying clays: Clays and Clay Technology, Calif. Div. of Mines Bull. 169, 105–111.Google Scholar
  9. Dodd, C. G. and Ray, S. (1960) Semiquinone cation adsorption on montmorillonite as a function of surface acidity: Clays and Clay Minerals 8, 237–251.CrossRefGoogle Scholar
  10. Doner, H. E. and Mortland, M. M. (1959) Benzene complexes with copper(II) montmorillonite: Science 166, 1406–1407.CrossRefGoogle Scholar
  11. Endell, J., Zorn, R. and Hofmann, U. (1941) The benzidine test for montmorillonite: Angew. Chem. 54, 376–377.CrossRefGoogle Scholar
  12. Flockhart, B. D., Leith, I. R. and Pink, R. C. (1969) Electron transfer at alumina surfaces—II. Electrondonor properties of aluminas: Trans. Faraday Soc. 65, 542–551.CrossRefGoogle Scholar
  13. Fripiat, J. J. (1964) New research methods in soil chemistry: Trans. Intern. Congr. Soil Sci. 8th Bucharest 1, 171–192.Google Scholar
  14. Fripiat, J. J., Jelli, A., Poncelet G. and André J. (1965) Thermodynamic properties of adsorbed water molecules and electrical conduction in montmorillonites and silicas: J. Phys. Chem. 69, 2185–2197.CrossRefGoogle Scholar
  15. Green, B. K. (1950) Pressure-sensitive record material: U.S. Pat. 2, 505, 470.Google Scholar
  16. Greene-Kelly, R. (1955) Sorption of aromatic compounds by montmorillonite—I. Orientation studies: Trans. Faraday Soc. 51, 412–424.CrossRefGoogle Scholar
  17. Grim, R. E. (1968) Clay Mineralogy. 2nd Edn., pp. 407–410. McGraw-Hill, New York.Google Scholar
  18. Hasegawa, H. (1961) Spectroscopic studies on the color reaction of acid clay with amines—I: J. Phys. Chem. 65, 292–296.CrossRefGoogle Scholar
  19. Hasegawa, H. (1962) Spectroscopic studies on the color reaction of acid clay with amines—II. The reaction with aromatic tertiary amines: J. Phys. Chem. 66, 834–836.CrossRefGoogle Scholar
  20. Hasegawa, H. (1963) Spectroscopic studies on the color reaction of acid clay—III. The coloration with polyenes and poiyacenes: J. Phys. Chem. 67, 1268–1270.CrossRefGoogle Scholar
  21. Hauser, E. A. and Leggett, M. B. (1940) Color reactions between clays and amines: J. Am. Chem. Soc. 62, 1811–1814.CrossRefGoogle Scholar
  22. Haxaire, A. and Bloch, J. M. (1956) The mechanism of adsorption by montmorillonite of azotized organic molecules: Bull. Soc. Frc. Min. Crist. 79, 464–475.Google Scholar
  23. Hendricks, S. B. and Alexander, L. T. (1940) A qualitative test for the montmorillonite type of clay minerals: J. Am. Soc. Agron. 32, 455–458.CrossRefGoogle Scholar
  24. Kranz, F. H. (1963) Pressure-sensitive copying sheets: U.S. Pat. 3, 079, 271.Google Scholar
  25. Krüger, D. and Oberlies, F. (1941) Catalytic oxidation of amines at the surface of negative adsorbents—II. Realization of a different course of the reaction in the oxidation of dimethylaniline and some of its homoiogs on bentonite and on other surfaces: Chem. Ber. 74B, 1711–1719.CrossRefGoogle Scholar
  26. Krüger, D. and Oberlies, F. (1943) Structure and color reactions of montmorillonite earths: Naturwissenschaften 31, 92.CrossRefGoogle Scholar
  27. Meunier, P. (1942) The action of montmorillonite clay on vitamin A and the phenomenon of mesomerism in the carotenoid group: C.r. hebd. Séanc. Acad. Sci. Paris 215, 470–473.Google Scholar
  28. Meunier, P. (1943) Action of acid clays on aromatic amines. Coloration and electromeric effect: C.r. hebd. Séanc. Acad. Sci. Paris 217, 449–451.Google Scholar
  29. Michaels, A. S. (1958) Deflocculation of kaolinite by alkali polyphosphates: Ind. Eng. Chem. 50, 951–958.CrossRefGoogle Scholar
  30. Mielenz, R. C. and King, M. E. (1951) Identification of clay minerals by staining tests: Proc. Am. Soc. Test. Mater. 51, 1213–1233.Google Scholar
  31. Mortland, M. M. (1968) Protonation of compounds at clay mineral surfaces: Trans. Intern. Congr. Soil Sci., 9th Adelaide 1, 691–699.Google Scholar
  32. Mortland, M. M. (1970) Clay-organic complexes and interactions: Advan. Agron. 22, 75–117.CrossRefGoogle Scholar
  33. Mortland, M. M. and Pinnavaia, T. J. (1971) Formation of copper(II) arene complexes on the interlamellar surfaces of montmorillonite: Nature 229, 75–77.CrossRefGoogle Scholar
  34. National Cash Register Company (1963) Pressure-sensitive copying paper: Ger. Pat. 1,152,429.Google Scholar
  35. National Cash Register Company (1965) Recording papers with attapulgite: Neth. Pat. 6,505,671.Google Scholar
  36. Norrish, K. (1954) The swelling of montmorillonite: Discuss. Faraday Soc. 18, 120–134.CrossRefGoogle Scholar
  37. Page, J. B. (1941) Unreliability of the benzidine color reaction as a test for montmorillonite: Soil Sci. 51, 133–140.CrossRefGoogle Scholar
  38. Papariello, G. J. and Janish, M. A. M. (1966) Diphenylpicrylhydrazyl as an organic analytical reagent in the spectrophotometric analysis of phenols: Analyt. Chem. 38, 211–214.CrossRefGoogle Scholar
  39. Ritzerfeld, W. and Ritzerfeld, G. (1961) Prints from matrices having a color supply of triphenylmethane dyes: Ger. Pat 1,119,302.Google Scholar
  40. Schenk, G. (1968) Organic Functional Group Analysis: Theory and Development: pp. 70–94. Pergamon Press, Oxford.CrossRefGoogle Scholar
  41. Solomon, D. H. (1968) Clay minerals as electron acceptors and/or electron donors in organic reactions: Clays and Clay Minerals 16, 31–39.CrossRefGoogle Scholar
  42. Solomon, D. H., Loft, B. C. and Swift, J. D. (1968a) Reactions catalysed by minerals—IV. The mechanism of the benzidine blue reaction on silicate minerals: Clay Minerals 7, 389–397.CrossRefGoogle Scholar
  43. Solomon, D. H., Loft, B. C. and Swift, J. D. (1968b) Reactions catalysed by minerals—V. The reaction of leuco dyes and unsaturated organic compounds with clay minerals: Clay Minerals 7, 399–408.CrossRefGoogle Scholar
  44. Takahashi, H. (1955) The effect of layered water on the color reaction of benzidine or other similar compounds with montmorillonite: Bull. Chem. Soc. Japan 28, 5–9.CrossRefGoogle Scholar
  45. Theng, B. K. G. and Walker, G. F. (1970) Interactions of clay minerals with organic monomers: Israel J. Chem. 8, 417–424.CrossRefGoogle Scholar
  46. Vedeneeva, N. E. (1950) The mechanism of the color reaction of benzidine with montmorillonite: Kolloid Zh. 12, 17–24.Google Scholar
  47. Walling, C. (1950) The acid strength of surfaces: J. Am. Chem. Soc. 72, 1164–1168.CrossRefGoogle Scholar
  48. Weil-Malherbe, H. and Weiss, J. (1948) Color reactions and adsorption of some aluminosilicates: J. Chem. Soc. 2164–2169.Google Scholar
  49. Weiss, A. (1963) Mica-type layer silicates with alkylammonium ions: Clays and Clay Minerals 10, 191–224.CrossRefGoogle Scholar
  50. Weiss, J. (1938) Note on some free radicals from benzidine and its derivatives: Chem. Ind. 57, 517–518.CrossRefGoogle Scholar
  51. White, D. and Cowan, C. T. (1960) Aromatic amine derivatives of montmorillonite: Trans. Br. Ceram. Soc. 59, 16–21.Google Scholar
  52. Zechmeister, L. and Sandoval, A. (1945) The coloration given by vitamin A and other polyenes on acid earths: Science 101, 585.CrossRefGoogle Scholar

Copyright information

© The Clay Minerals Society 1971

Authors and Affiliations

  • B. K. G. Theng
    • 1
  1. 1.Soil Bureau, D.S.I.R.Lower HuttNew Zealand

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