Thermodynamic Properties of γ- and δ-Lactones: Exploring Alkyl Chain Length Effect and Ring-Opening Reactions for Green Chemistry Applications
An extensive thermochemical study of γ-undecanolactone and δ-undecanolactone has been developed using two complementary calorimetric techniques. The combustion energy of each compound was determined by static-bomb combustion calorimetry, and the corresponding enthalpy of vaporization was determined...
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2025-01-01
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| author | Ana L. R. Silva Gastón P. León Vladimír Lukeš Erik Klein Maria D. M. C. Ribeiro da Silva |
| author_facet | Ana L. R. Silva Gastón P. León Vladimír Lukeš Erik Klein Maria D. M. C. Ribeiro da Silva |
| author_sort | Ana L. R. Silva |
| collection | DOAJ |
| description | An extensive thermochemical study of γ-undecanolactone and δ-undecanolactone has been developed using two complementary calorimetric techniques. The combustion energy of each compound was determined by static-bomb combustion calorimetry, and the corresponding enthalpy of vaporization was determined by high-temperature Calvet microcalorimetry, in which both properties of each compound are reported at <i>T</i> = 298.15 K. The standard molar enthalpy of formation in the gas phase of each lactone was derived by the combination of the experimental results. Additionally, high-level computational calculations were carried out, using composite ab initio G4 and G4(MP2) methods, as well as DFT M06-2X/6-311++G(d,p) approach, to estimate the corresponding enthalpy of formation in the gas phase. The experimental and computational results are in good agreement. The G4 and G4(MP2) methods show the best accordance with experimentally determined gas phase enthalpies of formation. The experimental results are discussed in terms of structural contributions to the energetic properties of the lactones studied, as well as to other alkylated γ- and δ-lactones, and empirical correlations are suggested for the estimation of the standard molar enthalpies of formation, at <i>T</i> = 298.15 K, for other alkylated γ- and δ-lactones, both in the liquid and gaseous phases, as well as for the respective enthalpies of vaporization. Finally, the thermochemistry of individual steps of lactone ring opening and successive decarboxylation mechanism, including the identification of transition states, was studied using the M06-2X/6-311++G(d,p) approach. |
| format | Article |
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| institution | Kabale University |
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| language | English |
| publishDate | 2025-01-01 |
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| series | Molecules |
| spelling | doaj-art-f3166e7db5ff434da0d8a34e1516e2112025-01-24T13:43:54ZengMDPI AGMolecules1420-30492025-01-0130239910.3390/molecules30020399Thermodynamic Properties of γ- and δ-Lactones: Exploring Alkyl Chain Length Effect and Ring-Opening Reactions for Green Chemistry ApplicationsAna L. R. Silva0Gastón P. León1Vladimír Lukeš2Erik Klein3Maria D. M. C. Ribeiro da Silva4Centro de Investigação em Química (CIQUP), Institute of Molecular Sciences (IMS), Department of Chemistry and Biochemistry, Faculty of Sciences, University of Porto, Rua do Campo Alegre, 4169-007 Porto, PortugalCentro de Investigação em Química (CIQUP), Institute of Molecular Sciences (IMS), Department of Chemistry and Biochemistry, Faculty of Sciences, University of Porto, Rua do Campo Alegre, 4169-007 Porto, PortugalInstitute of Physical Chemistry and Chemical Physics, Slovak University of Technology in Bratislava, Radlinského 9, 812 37 Bratislava, SlovakiaInstitute of Physical Chemistry and Chemical Physics, Slovak University of Technology in Bratislava, Radlinského 9, 812 37 Bratislava, SlovakiaCentro de Investigação em Química (CIQUP), Institute of Molecular Sciences (IMS), Department of Chemistry and Biochemistry, Faculty of Sciences, University of Porto, Rua do Campo Alegre, 4169-007 Porto, PortugalAn extensive thermochemical study of γ-undecanolactone and δ-undecanolactone has been developed using two complementary calorimetric techniques. The combustion energy of each compound was determined by static-bomb combustion calorimetry, and the corresponding enthalpy of vaporization was determined by high-temperature Calvet microcalorimetry, in which both properties of each compound are reported at <i>T</i> = 298.15 K. The standard molar enthalpy of formation in the gas phase of each lactone was derived by the combination of the experimental results. Additionally, high-level computational calculations were carried out, using composite ab initio G4 and G4(MP2) methods, as well as DFT M06-2X/6-311++G(d,p) approach, to estimate the corresponding enthalpy of formation in the gas phase. The experimental and computational results are in good agreement. The G4 and G4(MP2) methods show the best accordance with experimentally determined gas phase enthalpies of formation. The experimental results are discussed in terms of structural contributions to the energetic properties of the lactones studied, as well as to other alkylated γ- and δ-lactones, and empirical correlations are suggested for the estimation of the standard molar enthalpies of formation, at <i>T</i> = 298.15 K, for other alkylated γ- and δ-lactones, both in the liquid and gaseous phases, as well as for the respective enthalpies of vaporization. Finally, the thermochemistry of individual steps of lactone ring opening and successive decarboxylation mechanism, including the identification of transition states, was studied using the M06-2X/6-311++G(d,p) approach.https://www.mdpi.com/1420-3049/30/2/399γ-undecanolactoneδ-undecanolactoneenthalpy of formationenthalpy of vaporizationcombustion calorimetryCalvet microcalorimetry |
| spellingShingle | Ana L. R. Silva Gastón P. León Vladimír Lukeš Erik Klein Maria D. M. C. Ribeiro da Silva Thermodynamic Properties of γ- and δ-Lactones: Exploring Alkyl Chain Length Effect and Ring-Opening Reactions for Green Chemistry Applications Molecules γ-undecanolactone δ-undecanolactone enthalpy of formation enthalpy of vaporization combustion calorimetry Calvet microcalorimetry |
| title | Thermodynamic Properties of γ- and δ-Lactones: Exploring Alkyl Chain Length Effect and Ring-Opening Reactions for Green Chemistry Applications |
| title_full | Thermodynamic Properties of γ- and δ-Lactones: Exploring Alkyl Chain Length Effect and Ring-Opening Reactions for Green Chemistry Applications |
| title_fullStr | Thermodynamic Properties of γ- and δ-Lactones: Exploring Alkyl Chain Length Effect and Ring-Opening Reactions for Green Chemistry Applications |
| title_full_unstemmed | Thermodynamic Properties of γ- and δ-Lactones: Exploring Alkyl Chain Length Effect and Ring-Opening Reactions for Green Chemistry Applications |
| title_short | Thermodynamic Properties of γ- and δ-Lactones: Exploring Alkyl Chain Length Effect and Ring-Opening Reactions for Green Chemistry Applications |
| title_sort | thermodynamic properties of γ and δ lactones exploring alkyl chain length effect and ring opening reactions for green chemistry applications |
| topic | γ-undecanolactone δ-undecanolactone enthalpy of formation enthalpy of vaporization combustion calorimetry Calvet microcalorimetry |
| url | https://www.mdpi.com/1420-3049/30/2/399 |
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