Molecular association of normal alkanoic acids with their thallium(I) salts: a new homologous series of fatty acid metal soaps.
A 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, through 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 beta'-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 these compounds potential thermal energy storage materials.
Fernández-García
M
M
Departamento de Química Física I, Universidad Complutense, Madrid, Spain.
García
M V
MV
Redondo
M I
MI
Cheda
J A
JA
Fernández-García
M
M
Westrum
E F
EF
Fernández-Martín
F
F
D000438:Alcohols / Q000737:chemistry; D000473:Alkanes / Q000737:chemistry*; D002152:Calorimetry, Differential Scanning; D002244:Carbon / Q000737:chemistry; D002264:Carboxylic Acids / Q000737:chemistry*; D005227:Fatty Acids / Q000737:chemistry*; D006860:Hydrogen Bonding; D009682:Magnetic Resonance Spectroscopy; D012915:Soaps / Q000737:chemistry*; D017550:Spectroscopy, Fourier Transform Infrared; D013059:Spectrum Analysis, Raman; D013696:Temperature; D013793:Thallium / Q000737:chemistry*; D013816:Thermodynamics; D014961:X-Ray Diffraction
D000438:Alcohols; D000473:Alkanes; D002264:Carboxylic Acids; D005227:Fatty Acids; D012915:Soaps; D002244:Carbon; D013793:Thallium