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Enthalpies of formation of four isoxazole derivatives in the solid and gas phases: application to the study of chemical equilibria

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Abstract

Calorimetry provides an accurate and reliable method to determine the enthalpies of formation of organic molecules in the gas phase. From the experimental formation enthalpies and the absolute entropies, obtained by theoretical calculations, it is possible to perform Gibbs energy calculations. This thermodynamic function is widely used to describe various thermodynamic processes, such as chemical equilibrium, and allows the calculation of equilibrium constants. The specific standard combustion energies of 3,5-dimethylisoxazole-4-carboxylic acid, 5-methylisoxazole-3-carboxylic acid, 5-amino-3-methylisoxazole, and 3-amino-5-methylisoxazole were determined by using a combustion calorimeter. The sublimation enthalpies of the compounds were determined by means of the Knudsen effusion technique. From these values, the molar standard enthalpy of formation in gaseous phase of each compound was calculated. Theoretical calculations at the G3 and G4 levels were performed, and a study of the molecular and electronic structure of these compounds was carried out. The calculated enthalpies of formation are in very good agreement with the experimental values. From both the experimental and theoretical results, five gas phase chemical equilibria were studied: one of isomerization, two of CO2 loss, and two of NH3 loss. The equilibrium constants for each process were calculated, which allow prediction of the direction of the chemical process from a thermodynamic viewpoint.

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Acknowledgements

Thanks are due to VIEP-BUAP for financial support through FLSH-NAT15-G project. G. P. thanks CONACYT for his grant (321454).

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Authors and Affiliations

  1. Facultad de Ciencias Químicas, Benemérita Universidad Autónoma de Puebla, 14 sur y Av. San Claudio, C.P, 72570, Puebla Pue, Mexico

    Gastón Perdomo, Henoc Flores, E. Adriana Camarillo & M. Patricia Amador

  2. Instituto de Química Física “Rocasolano”, CSIC, Serrano 119, 28006, Madrid, Spain

    Rafael Notario

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  1. Gastón Perdomo
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  2. Henoc Flores
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  3. Rafael Notario
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Corresponding author

Correspondence to Henoc Flores.

Electronic supplementary material

G3- and G4-calculated energies, at T = 0 K, E 0, and enthalpies at T = 298 K, H 298, in Hartrees; values of the combustion experiments of benzoic acid to T = 298.15 K, p° = 0.1 MPa; typical values of the combustion experiments for 35dmi4c to T = 298.15 K, p° = 0.1 MPa; typical values of the combustion experiments for 5mi3c to T = 298.15 K, p° = 0.1 MPa; typical values of the combustion experiments for 5a3mi to T = 298.15 K, p° = 0.1 MPa; typical values of the combustion experiments for 3a5mi at T = 298.15 K, p° = 0.1 MPa; effusion experimental results of 35dmi4c at T med = 343.7 K; experimental effusion results of 5mi3c at T med = 343.7 K; experimental effusion results of 3a5mi at T med = 297.3 K; experimental effusion results of 5a3mi at T med = 313.7 K; experimental values of temperature, intercept, slope, and enthalpy of sublimation at T med for compounds studied; experimental values of vapor pressure for the compounds studied; areas and clausing factors of the cell effusion holes; G3- and G4-calculated enthalpies at T = 298 K, and experimental enthalpies of formation in the gas phase for the molecules used as references in isodesmic reactions; formation enthalpies in gas phase of each isodesmic reaction for each compound studied. The values were obtained using Gaussian-n theories at G3 and G4 levels; the absolute entropies of each element used to calculate the variation of entropy of each compound; Cartesian coordinates of the compounds studied.

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Perdomo, G., Flores, H., Notario, R. et al. Enthalpies of formation of four isoxazole derivatives in the solid and gas phases: application to the study of chemical equilibria. Struct Chem 28, 1111–1123 (2017). https://doi.org/10.1007/s11224-017-0923-1

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  • DOI: https://doi.org/10.1007/s11224-017-0923-1

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