title: Experimental and computational study on the molecular energetics of 2-pyrrolecarboxylic acid and 1-methyl-2-pyrrolecarboxylic acid.
abstract: This paper reports a combined thermochemical experimental and computational study of 2-pyrrolecarboxylic acid and 1-methyl-2-pyrrolecarboxylic acid. Static bomb combustion calorimetry and Knudsen mass-loss effusion technique were used to determine the standard (p degrees = 0.1 MPa) molar enthalpies of combustion, Delta(c)H(m) degrees, and sublimation, Delta(cr)(g)H(m) degrees, respectively, from which the standard (p degrees = 0.1 MPa) molar enthalpies of formation, in the gaseous phase, at T = 298.15 K, were derived. The values obtained were -(286.3 +/- 1.7) and -(291.6 +/- 1.7) kJ x mol for 2-pyrrolecarboxylic acid and 1-methyl-2-pyrrolecarboxylic acid, respectively. For comparison purposes, the gas-phase enthalpies of formation of these two compounds were estimated by G3(MP2)//B3LYP and MP2 approaches, using a set of gas-phase working reactions; the results are in excellent agreement with experimental data. G3(MP2)//B3LYP computations were also extended to the calculation of N-H bond dissociation enthalpies, gas-phase acidities and basicities, proton and electron affinities and adiabatic ionization enthalpies. Moreover, the results are also discussed in terms of the energetic effects of the addition of a carboxylic and of a methyl groups to the pyrrole ring and compared with structurally similar compounds.
authors: Centro de Investigação em Química, Department of Chemistry, Faculty of Science, University of Porto, Rua do Campo Alegre, 687, P-4169-007 Porto, Portugal.
authors: Ana Filipa L O M
authors: AF
authors: Santos
authors: Manuel A V
authors: MA
authors: Ribeiro da Silva
mesh_terms: D002151:Calorimetry; D002264:Carboxylic Acids / Q000737:chemistry*; D003198:Computer Simulation; D005740:Gases / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D044367:Phase Transition; D011392:Proline / Q000031:analogs & derivatives* / Q000737:chemistry; D011758:Pyrroles / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: C545390:1-methyl-2-pyrrolecarboxylic acid; D002264:Carboxylic Acids; D005740:Gases; D011758:Pyrroles; C002986:2-pyrrolecarboxylic acid; D011392:Proline