| Resumo: | The thermodynamic study of the phase transition (fusion and sublimation) of 2,2':5',2 ''-terthiophene and 3,2':5',3 ''-terthiophene is presented. The obtained data is used to evaluate the (solid + liquid) and (solid + gas) phase equilibrium, and draw the phase diagrams of the pure compounds near the triple point coordinates. For each compound the vapour pressures at different temperatures were measured by a combined Knudsen effusion method with a vacuum quartz crystal microbalance. Based on the previous results, the standard molar enthalpies, entropies and Gibbs energies of sublimation were derived at T = 298.15 K. For the two terthiophenes and for 3,3'-bithiophene, the temperature, and the molar enthalpies of fusion were measured in a power compensated differential scanning calorimetry. The relationship between structure and energetics is discussed based on the experimental results, ab initio calculations and previous literature data for 2,2'-bithiophene and 3,3'-bithiophene. The 3,2':5',3 ''-terthiophene shows a higher solid phase stability than the 2,2':5',2 ''-terthiophene isomer arising from the higher cohesive energy due to positioning of the sulphur atom in the thiophene ring. The higher phase stability of 3,3'-bithiophene relative to 2,2'-bithiophene isomer is also related to its higher absolute entropy in the solid phase associated with the ring positional degeneracy observed in the crystal structure of this isomer. A significant differentiation in the crystal phase stability between isomers was found.
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