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Title

Molecular association of normal alkanoic acids with their thallium(I) salts: A new homologous series of fatty acid metal soaps

AuthorsFernández García, Marcos ; García, M. V.; Redondo, M. I.; Cheda, J. A. R.; Westrum Jr., E. F.; Fernández Martín, Fernando
KeywordsFourier transform infrared spectroscopy
Differential scanning calorimetry
Energy storage Materials
Lamellar structures
Transitions CH2 conformation-configuration-packing
Thermodynamics of phase
Hydrogen dialkanoates
X-ray diffraction
Raman
Nuclear magnetic resonance spectrometry
Thallium
Issue Date1997
PublisherAmerican Society for Biochemistry and Molecular Biology
CitationJournal of Lipid Research 38: 361- 372 (1997)
AbstractA new homologous series of thallium (I) hydrogen dialkanoates, fatty acid thallium soaps, from the dipropane up to the ditetradecane is reported for the first time. This association with 1:1 stoichiometry is the only one exhibited by the thallium derivatives. They have been prepared by solidification of molten mixtures with equimolar proportions of acid and corresponding neutral salt, although crystallization from an anhydrous ethanolic solution of the mixture has also been successful in getting pure compounds with largest chain lengths. Vibrational spectroscopies clearly characterize these crystalline compounds as very strong hydrogen bonding systems. Assignations of active modes in proton and carbon nuclear magnetic resonance spectrometry (NMR) (in ethanol) and infrared (IR) and Raman spectra (in solid state) are reported. According to X-ray diffraction (XRD) they have monomolecular lamellar structures with the acyl chains arranged up and down to the cation/H-bond network in a methyl-to-methyl fashion, and vertically oriented to the basal plane. The acyl chains present all-trans conformation and alternating configuration (perpendicular orthorhombic subcell), like the β'-phases of other kinds of lipids. Lamellar thickness is reported for the six room-temperature crystalline members. The molecular compounds present polymorphism, one crystal/crystal transition at temperatures close to the peritectical melting. Phase transition thermodynamics are also given and discussed with respect to their acid and salt parents. Their incongruent melting involves nearly 90% of the total enthalpic increments of both constituents' melting processes, making those compounds potential thermal energy storage materials.
URIhttp://hdl.handle.net/10261/115537
DOIhttp://dx.doi.org/10.1021/jo901389q.
Identifiersdoi: 10.1021/jo901389q.
issn: 0022-2275
Appears in Collections:(IF) Artículos
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