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Thermochemistry of paracetamol

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Abstract

Combustion calorimetry, Calvet-drop sublimation calorimetry, and the Knudsen effusion method were used to determine the standard (p o = 0.1 MPa) molar enthalpies of formation of monoclinic (form I) and gaseous paracetamol, at T = 298.15 K: \( \Updelta_{\text{f}} H_{\text{m}}^{\text{o}} \left( {{\text{C}}_{ 8} {\text{H}}_{ 9} {\text{O}}_{ 2} {\text{N}},{\text{ cr I}}} \right) = - ( 4 10.4 \pm 1. 3){\text{ kJ}}\;{\text{mol}}^{ - 1} \) and \( \Updelta_{\text{f}} H_{\text{m}}^{\text{o}} \left( {{\text{C}}_{ 8} {\text{H}}_{ 9} {\text{O}}_{ 2} {\text{N}},{\text{ g}}} \right) = - ( 2 80.5 \pm 1. 9){\text{ kJ}}\;{\text{mol}}^{ - 1} . \) From the obtained \( \Updelta_{\text{f}} H_{\text{m}}^{\text{o}} \left( {{\text{C}}_{ 8} {\text{H}}_{ 9} {\text{O}}_{ 2} {\text{N}},{\text{ cr I}}} \right) \) value and published data, it was also possible to derive the standard molar enthalpies of formation of the two other known polymorphs of paracetamol (forms II and III), at 298.15 K: \( \Updelta_{\text{f}} H_{\text{m}}^{\text{o}} \left( {{\text{C}}_{ 8} {\text{H}}_{ 9} {\text{O}}_{ 2} {\text{N}},{\text{ crII}}} \right) = - ( 40 8.4 \pm 1. 3){\text{ kJ}}\;{\text{mol}}^{ - 1} \) and \( \Updelta_{\text{f}} H_{\text{m}}^{\text{o}} \left( {{\text{C}}_{ 8} {\text{H}}_{ 9} {\text{O}}_{ 2} {\text{N}},{\text{ crIII}}} \right) = - ( 40 7.4 \pm 1. 3){\text{ kJ}}\;{\text{mol}}^{ - 1} . \) The proposed \( \Updelta_{\text{f}} H_{\text{m}}^{\text{o}} \left( {{\text{C}}_{ 8} {\text{H}}_{ 9} {\text{O}}_{ 2} {\text{N}},{\text{ g}}} \right) \) value, together with the experimental enthalpies of formation of acetophenone and 4′-hydroxyacetophenone, taken from the literature, and a re-evaluated enthalpy of formation of acetanilide, \( \Updelta_{\text{f}} H_{\text{m}}^{\text{o}} \left( {{\text{C}}_{ 8} {\text{H}}_{ 9} {\text{ON}},{\text{ g}}} \right) = - ( 10 9. 2\,\pm\,2. 2){\text{ kJ}}\;{\text{mol}}^{ - 1} , \) were used to assess the predictions of the B3LYP/cc-pVTZ and CBS-QB3 methods for the enthalpy of a isodesmic and isogyric reaction involving those species. This test supported the reliability of the theoretical methods, and indicated a good thermodynamic consistency between the \( \Updelta_{\text{f}} H_{\text{m}}^{\text{o}} \)(C8H9O2N, g) value obtained in this study and the remaining experimental data used in the \( \Updelta_{\text{r}} H_{\text{m}}^{\text{o}} \) calculation. It also led to the conclusion that the presently recommended enthalpy of formation of gaseous acetanilide in Cox and Pilcher and Pedley’s compilations should be corrected by ~20 kJ mol−1.

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Acknowledgements

This study was supported by Fundação para a Ciência e a Tecnologia (FCT), Portugal. A PhD. grant from FCT is gratefully acknowledged by R. Picciochi (SFRH/BD/36029/2007).

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Authors and Affiliations

  1. Centro de Química Estrutural, Complexo Interdisciplinar, Instituto Superior Técnico, 1049-001, Lisbon, Portugal

    Ricardo Picciochi & Hermínio P. Diogo

  2. Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa, 1749-016, Lisbon, Portugal

    Manuel E. Minas da Piedade

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  1. Ricardo Picciochi
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  2. Hermínio P. Diogo
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Correspondence to Hermínio P. Diogo or Manuel E. Minas da Piedade.

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Picciochi, R., Diogo, H.P. & Minas da Piedade, M.E. Thermochemistry of paracetamol. J Therm Anal Calorim 100, 391–401 (2010). https://doi.org/10.1007/s10973-009-0634-y

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