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Structure and Properties of Molten Metal Carboxylates

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Molecular Liquids: New Perspectives in Physics and Chemistry

Part of the book series: NATO ASI Series ((ASIC,volume 379))

Abstract

Long-chain metal carboxylates (soaps) have properties that are intermediate between those of ionic salts and aliphatic hydrocarbons. They form liquid phases at relatively low temperatures, with transition temperatures depending upon metal ion, hydrocarbon chain length, chain branching, unsaturation, etc. Typically, soaps of divalent metals form liquid phases around 400 K, whilst those of monovalent cations melt at rather higher temperatures. In many cases, intermediate liquid crystalline phases are observed between solid and liquid, and the presence of these suggests that aggregate structures may also be present in the melt. The phase behaviour of these systems will be briefly reviewed, with particular emphasis on information this may provide on the structure of the liquid phase. The case of the lead(II) carboxylates will be discussed in detail, both with respect to phase behaviour and the physical properties of the liquid. Information from transport properties, such as viscosity, together with data from multinuclear NMR and vibrational spectroscopy will be considered in relation to the structure and dynamics of the liquid phase, and the nature of any aggregate species present.

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References

  1. Gilmour, A. and Pink, R.C. (1953), ’Magnetic Properties and Structure of Copper Laurate’, J.Chem.Soc, 2198–2201.

    Google Scholar 

  2. Mitsuya, M. , Tanigucha, Y. and Akagi, M. (1983), ’The Structure of Vacuum Deposited Zinc Stearate Films’, J.Colloid Interface Sci., 92, 291–292.

    Article  CAS  Google Scholar 

  3. Bossert, R.G. (1950), ’The Metallic Soaps’, J.Chem.Ed., 27,10–15.

    Article  CAS  Google Scholar 

  4. Buono, F.J. and Feldman, M.L. (1979), ’Driers and Metallic Soaps’, in Kirk-Othmer Encyclopedia of Chemical Technology, vol.8, H.F. Mark, D.F. Othmer, C.G. Overberger and G.T. Seaborg (eds), Wiley, New York, 3rd edn., pp.34–49.

    Google Scholar 

  5. Ubbelohde, A.R. (1968), ’Some Problems Concerning Chemical Reactions in Ionic Melts’, Chem.Ind., 313–316.

    Google Scholar 

  6. Michels, H.J. and Ubbelohde, A.R. (1972), ’Melting Mechanisms of n-Alkylcarboxylates’ , J.Chem.Soc., Perkin Trans.2, 1879–1881.

    Google Scholar 

  7. Akanni, M.S., Okoh, E.K., Burrows, H.D. and Ellis, H.A.(1991), ’The Thermal Behaviour of Divalent and Higher Valent Metal Soaps: a Review’, Thermochim.Acta, accepted for publication.

    Google Scholar 

  8. Nagle, J.F. and Goldstein, M. (1985), ’Decomposition of Entropy and Enthalpy for the Melting Transition of Polyethylene’, Macromolecules, 18, 2643–2652.

    Article  CAS  Google Scholar 

  9. Burrows, H.D. (1990), ’The Phase Behaviour of Metal(II) soaps in One, Two and Three Component Systems’, in D.M. Bloor and E. Wyn-Jones (eds.), The Structure, Dynamics and Equilibrium Properties of Colloidal Systems, Kluwer Academic Publishers, Dordrecht, pp.415–426.

    Chapter  Google Scholar 

  10. Adeosun, S.O. and Sime, S.J. (1976), ’Properties of Molten Carboxylates. Part 4: A Quantitative Differential Thermal Analysis Study of Melting and Mesophase Formation in Some Lead(II) Carboxylates’, Thermochim.Acta, 17, 351– 359.

    Article  CAS  Google Scholar 

  11. Adeosun, S.O., Kehinde, A.O. and Odesola,G.A. (1979),’Electrical Conductance, Density, Viscosity and Thermal Behaviour of Lead(II) and Zinc(II) Salts of Some Unsaturated Fatty Acids’, Thermochim.Acta, 28, 133–142.

    Article  CAS  Google Scholar 

  12. Bazuin, C.G., Guillon, D., Skoulios, A.,Amorim da Costa, A.M., Burrows, H.D., Geraldes, C.F.G.C., Teixeira-Dias, J.J.C., Blackmore, E. and Tiddy, G.J.T. (1988), ’Thermotropic Polymorphism in Liquid Crystalline Lead(II) Alkanoates’, Liquid Crystals, 3, 1655–1670.

    Article  CAS  Google Scholar 

  13. Adeosun, S.O.and Sime, S.J. (1978), ’The Properties of Molten Carboxylates. Part 7: Odd-Even Variations in Melting and Mesophase Formation in the Lead(II) Carboxylates’, Thermochim.Acta, 27, 319–327.

    Article  CAS  Google Scholar 

  14. Ellis, H.A. (1986),’Thermotropic Phase Transitions in Some Lead(II) Carboxylates’, Mol.Cryst.Liq.Cryst., 139, 281–290.

    Article  CAS  Google Scholar 

  15. Amorim da Costa, A.M., Burrows, H.D., Geraldes, C.F.G.C.,Teixeira-Dias, J.J.C., Bazuin, C.G., Guillon, D., Skoulios, D., Blackmore, E., Tiddy, G.J.T. and Turner, D.L. (1986), ’Mesophase Formation in Lead(II) Decanoate’, Liquid Crystals, 1, 215–226.

    Article  Google Scholar 

  16. Wunderlich, B. (1989), ’The Detection of Conformational Disorder by Thermal Analysis’, Pure & Applied Chem., 61, 1347–1351.

    Article  CAS  Google Scholar 

  17. Cruz Pinto, J.J.C., Burrows, H.D., Geraldes, C.F.G.C., Miguel, M.G.M. and Pinheiro, T.J.T. (1991), ’A Kinetic Study of Phase Transitions in Some Even Chain Length Lead(II) Carboxylates’, manuscript in preparation.

    Google Scholar 

  18. Burrows, H.D., Geraldes, C.F.G.C., Miguel, M.G.M., Pinheiro, T.J.T. and Cruz Pinto, J.J.C. (1991), ’The Phase Behaviour of Some Mixtures of Lead(II) Carboxylates and Phosphatidylcholines’, Thermochim.Acta, accepted for publication.

    Google Scholar 

  19. Feio, G. , Burrows, H.D., Geraldes, C.F.G.C. and Pinheiro,T.J.T. (1991), ’Multinuclear NMR Studies of Lead(II) Soaps, II. 13’C and 1H Studies of Solid and Liquid Crystalline Phases’, Liquid Crystals, 9, 417–432.

    Article  CAS  Google Scholar 

  20. van der Ploeg, P. and Berendsen, H.J.C. (1983), ’Molecular Dynamics of a Bilayer Membrane’, Mol.Phys., 49, 233–248.

    Article  Google Scholar 

  21. Gruen, D.W.R. (1985), ’A Model for the Chains in Amphiphile Aggregates. 1. Comparison with a Molecular Dynamics Simulation of a Bilayer’, J.Phys.Chem., 89, 146–153.

    Article  CAS  Google Scholar 

  22. Burrows, H.D., Geraldes, C.F.G.C., Pinheiro, T.J.T., Harris, R.K. and Sebald, A. (1988), ,207Pb NMR of Lead(II) Soaps in Solid, Liquid-Crystalline and Liquid Phases’, Liquid Crystals, 3, 853–860.

    Article  CAS  Google Scholar 

  23. Adeosun, S.O. and Sime, S.J.(1979), ’Properties of Molten Carboxylates. Part 8. A.C. Impedance of Mesophases of Some Even Chain Length Lead(II) n-Alkanoates’ , J.Chem.Soc, Faraday Trans.1, 75, 953–961.

    Google Scholar 

  24. Ekwunife, M.E., Nwachukwu, M.V., Rinehart, F.P. and Sime,S.J. (1975), ’Properties of Molten Carboxylates. Part 1. Electrical Conductance and Molar Volumes of Some Molten Lead and Zinc Carboxylates’, 71, 1432–1446.

    CAS  Google Scholar 

  25. Doolittle, A.K. and Peterson, R.H. (1951), ’Preparation and Physical Properties of a Series of n-Alkanes’, J.Am.Chem.Soc., 73, 2145–2151.

    Article  CAS  Google Scholar 

  26. Allen, G. , Gee, G. and Wilson, G.J. (1960), ’Intermolecular Forces and Chain Flexibilities in Polymers. 1. Internal Pressure and Cohesive Energy Densities of Simple Liquids’, Polymer, 1, 456–466.

    Article  CAS  Google Scholar 

  27. Israelachvili, J.N. (1985), ’Intermolecular and Surface Forces’, Academic Press, London, p.138.

    Google Scholar 

  28. Miller, A.A. (1979), ’Conformational Properties of Liquid Polyethylene’, Macromolecules, 12, 651–655.

    Article  CAS  Google Scholar 

  29. Akanni, M.S. and Burrows, H.D. (1987), ’Surface Tensions of Some Molten Divalent Metal Carboxylates’, Thermochim.Acta, 115, 351–357.

    Article  CAS  Google Scholar 

  30. Obtained from data in CRC Handbook of Chemistry and Physics (1973/74), 54th edn., R.C. Weast (ed.), CRC Press Ohio, D 139.

    Google Scholar 

  31. Ekpe, V.J. and Sime, S.J. (1976), ’Properties of Molten Carboxylates. Part 2. The Viscosities of Some Molten Lead and Zinc Carboxylates’, J.Chem.Soc, Faraday Trans.1, 72, 1144–1149.

    Google Scholar 

  32. Barrer, R.M. (1943), ’Viscosities of Pure Liquids. 1. Non-polymerized Fluids’, Trans.Faraday Soc., 39, 48–59.

    Article  CAS  Google Scholar 

  33. Miguel, M.G.M. and Burrows, H.D. (1991), ’Luminescence Study of Fluidity in the L Mesophase and Liquid Phase of Lead(II) Decanoate’, Progr.Colloid Polym.Sci., 84, 223–226.

    Article  Google Scholar 

  34. Smit, B., Hilbers, P.A.J., Esselink, K., Rupert, L.A.M., van Os, N.M. and Schlijper, A.G. (1990), ’Computer Simulations of a Water/Oil Interface in the Presence of Micelles’, Nature, 348, 624–625.

    Article  CAS  Google Scholar 

  35. Feio, G. , Burrows, H.D., Geraldes, C.F.G.C. and Pinheiro,T.J.T. (1991),’Multinuclear NMR Studies of Lead(II) Soaps. III. Studies on the Liquid Phase and Solution with Reference to the Behaviour of the Corresponding Acids’, manuscript in preparation.

    Google Scholar 

  36. Pinheiro, T.J.T. (1989), ’Mesomorfismo Termotropico de Carboxilatos de Chumbo(II) e as suas Misturas com Fosfatidilcolinas’, M.Sc. Thesis, University of Coimbra.

    Google Scholar 

  37. Bloembergen, N. , Purcell, E.M. and Pound, P.V. (1948),’Relaxation Effects in Nuclear Magnetic Resonance Absorption’, Phys.Rev., 73, 679–712.

    Article  CAS  Google Scholar 

  38. See, for example, Chachaty, C, Wolkowski, Z., Piriou, F. and Lukacs, G. (1973), ’Substituent Effects on the 13C Relaxation Time along Aliphatic Chains. Application to a Prostaglandin’ , J.Chem.Soc., Chem.Comm., 951–952.

    Google Scholar 

  39. Chachaty, C. (1987), ’Applications of NMR Method to the Physical Chemistry of Micellar Solutions’, Progr. NMR Spectroscopy, 19, 183–222.

    Article  CAS  Google Scholar 

  40. Wennerstrom, H., Lindman, B.,Soderman, O., Drakenberg, T. and Rosenholm, J.B. (1979), 13C Magnetic Relaxation in Micellar Solutions. Influence of Aggregate Motion on T1’ , J.Am.Chem.Soc.,101, 6860–6864.

    Article  Google Scholar 

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Authors and Affiliations

  1. Departamento de Química, Universidade de Coimbra, 3049, Coimbra, Portugal

    Hugh D. Burrows

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  1. Hugh D. Burrows
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Editors and Affiliations

  1. Departamento de Química, Universidade de Coimbra, Coimbra, Portugal

    José J. C. Teixeira-Dias

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© 1992 Springer Science+Business Media Dordrecht

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Burrows, H.D. (1992). Structure and Properties of Molten Metal Carboxylates. In: Teixeira-Dias, J.J.C. (eds) Molecular Liquids: New Perspectives in Physics and Chemistry. NATO ASI Series, vol 379. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-2832-2_18

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  • DOI: https://doi.org/10.1007/978-94-011-2832-2_18

  • Publisher Name: Springer, Dordrecht

  • Print ISBN: 978-94-010-5258-0

  • Online ISBN: 978-94-011-2832-2

  • eBook Packages: Springer Book Archive

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