Thermochemical parameters of the chloronitrophenol isomers: A combined experimental and theoretical investigation

• Tipo: Artigo em Revista Científica Internacional
• Data: 2007

Autores

Victor M F Morais (Autor) ICBAS; Margarida S Miranda (Autor) Outra; Agostinha A R Matos (Autor) FCUP

Revista

Título: Journal of Chemical & Engineering Data

Vol. 52

Páginas: 627-634

ISSN: 0021-9568

Editora: American Chemical Society

Indexação

ISI Web of Knowledge - 17 Citações

Scopus - 16 Citações

Classificação Científica

FOS: Ciências da engenharia e tecnologias > Engenharia química

Outras Informações

ID Authenticus: P-004-BH3

DOI: 10.1021/je6005218

Abstract (EN): The standard (p degrees = 0.1 MPa) molar enthalpies of formation of 2-chloro-4-nitrophenol, 4-chloro-2-nitrophenol, and 4-chloro-3-nitrophenol in the solid phase, Delta H-f degrees(m)(cr), at T = 298.15 K, were derived from the standard molar enthalpies of combustion measured by rotating-bomb combustion calorimetry, in oxygen. Enthalpies of fusion of the solid compounds were measured by differential scanning calorimetry. The standard molar enthalpies of sublimation, at T = 298.15 K, were measured by Calvet microcalorimetry. Summing the obtained Delta H-f degrees(m) (cr) and Delta H-g(cr)degrees(m) values, it was possible to derive the values of the standard molar enthalpies of formation in the gaseous phase, at T = 298.15 K: Delta H-f degrees(m)(4-chloro-3-nitrophenol, g) = -(108.8 +/- 3.7) kJ.mol(-1). Density functional theory calculations were also performed for all possible chloronitrophenol isomers using the B3LYP functional and the 6-31G** basis set. These calculations allowed the estimation of the standard molar enthalpies of formation in the gaseous phase for all isomers including those not studied experimentally. Identical DFT calculations were also carried out for the respective phenoxyl radicals and phenoxide anions which allowed the estimation of the O-H homolytic bond dissociation energies and gas-phase acidities.

Idioma: Inglês

Tipo (Avaliação Docente): Científica

Nº de páginas: 8