A Combined Experimental and Computational Thermodynamic Study of the Isomers of Pyrrolecarboxaldehyde and 1-Methyl- pyrrolecarboxaldehyde

作者：Santos Ana Filipa L O M; Ribeiro da Silva Manuel A V

来源：Journal of Physical Chemistry B, 2011, 115(43): 12549-12557.

DOI：10.1021/jp2068057

The present paper reports an experimental calorimetric study of 2-pyrrolecarboxaldehyde and 1-methyl-2-pyrrolecarboxaldehyde, which aims to determine their standard (p(o) = 0.1 MPa) molar enthalpies of formation, in the gaseous phase, at T = 298.15 K. These values were derived from the standard (p(o) = 0.1 MPa) molar enthalpies of formation, in the condensed phase, Delta H-f(m)o (cr,l), at T = 298.15 K, obtained from the standard molar enthalpies of combustion, Delta H-f(m)o, measured by static bomb combustion calorimetry, and from the standard molar enthalpies of phase transition, Delta(g)(cr,l) H-m(o) at T = 298.15 K, obtained by high temperature Calvet micro-calorimetry. Additionally, the standard enthalpies of formation of these two compounds were estimated by computations based on standard ab initio molecular calculations at the G3(MP2)//B3LYP level. The estimated values are in very good agreement with experimental data, giving us support to estimate the gas-phase enthalpies of formation of the 3-pyrrolecarboxaldehyde and 1-methyl-3-pyrrolecarboxaldehyde that were not studied experimentally. N-H bond dissociation enthalpies, gas-phase acidities and basicities, proton and electron affinities, and adiabatic ionization enthalpies were also calculated. Furthermore, the molecular structure of the four molecules was established and the structural parameters were determined at the B3LYP/6-31G(d) level of theory.

• 出版日期2011-11-3