Thermal and structural study of the crystal phases and mesophases in the lithium and thallium(i) propanoates and pentanoates binary systems: formation of mixed salts and stabilization of the ionic liquid crystal phase

F J Martínez Casado; M Ramos Riesco; I da Silva; A Labrador; M I Redondo; M V García Pérez; S López-Andrés; J A Rodríguez Cheda

doi:10.1021/jp1031702

Thermal and structural study of the crystal phases and mesophases in the lithium and thallium(i) propanoates and pentanoates binary systems: formation of mixed salts and stabilization of the ionic liquid crystal phase

J Phys Chem B. 2010 Aug 12;114(31):10075-85. doi: 10.1021/jp1031702.

Authors

F J Martínez Casado¹, M Ramos Riesco, I da Silva, A Labrador, M I Redondo, M V García Pérez, S López-Andrés, J A Rodríguez Cheda

Affiliation

¹ BM16-Laboratori de Llum Sincrotó (LLS), c/o European Synchrotron Radiation Facility, 38043 Grenoble, France.

PMID: 20684631
DOI: 10.1021/jp1031702

Abstract

The temperature and enthalpy vs composition phase diagrams of the binary systems [xC(2)H(5)CO(2)Li + (1 - x)C(2)H(5)CO(2)Tl], and [x(n-C(4)H(9)CO(2)Li) + (1 - x)n-C(4)H(9)CO(2)Tl], where x is the mole fraction, were determined by DSC. Both binary systems display the formation of one 2:1 mixed salt each (at x = 0.667) that appear as a peritectic (incongruent melting) at T(fus) = 512.0 K, and T(fus) = 461.1 K, with Delta(fus)H(m) = 13.76 and 8.08 kJ.mol(-1) for Li-Tl (I) propanoates, and n-pentanoate mixed salts, respectively. The thermotropic liquid crystal of the thallium(I) n-pentanoate transforms into a more stable liquid-crystal phase, which appears in the phase diagram between 380 and 488 K and for x = 0 up to x = 0.56. The crystal structure of thallium(I) propanoate and of the two mixed salts were obtained via X-ray synchrotron radiation diffraction measurements. These compounds present a bilayered structure similar to the two pure lithium salts previously found by our group.