Abstract:
We have performed a study of structural, thermochemical and thermophysical properties of the (Z)-cinnamic acid neutral molecule and its corresponding oxyanion (formed by deprotonation of the carboxylic group). The thermophysical study (heat capacities, temperature and enthalpy of fusion) was made by DSC. The following intrinsic (gas-phase) thermochemical magnitudes have been experimentally determined: (i) standard enthalpy of formation, at T = 298.15 K, of the neutral molecule, ΔfHm0(g) = (-215.5 ± 3.2) kJ · mol-1, by combustion calorimetry and by the Knudsen effusion technique, (ii) deprotonation enthalpy, ΔacidH0(g) = (1416.4 ± 8.8) kJ · mol-1 and acidity, GA = (1386.7 ± 8.8) kJ · mol-1, by the EKM method using ESI-TQ Mass Spectrometry. From these results we have also derived the enthalpy of formation of the oxyanion, ΔfHm0(oxyanion, g) = (-303.5 ± 9.4) kJ · mol-1. A computational study, through density functional calculations at the B3LYP/6-311++G(d,p) level of theory, was used to check the good consistency of the experimental results. The global results show that (Z)-cinnamic acid is significantly less stable than the corresponding (E)-isomer, which can be related to the greater acidity of the (Z)-form found in both the gas and aqueous solution phases. © 2015 Elsevier Ltd. All rights reserved.
Registro:
Documento: |
Artículo
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Título: | Energetics of neutral and deprotonated (Z)-cinnamic acid |
Autor: | Dávalos, J.Z.; Lima, C.F.R.A.C.; Silva, A.M.S.; Santos, L.M.N.B.F.; Erra-Balsells, R.; Salum, M.L. |
Filiación: | Instituto de Quimica-Fisica rocasolano, CSIC, Serrano 119, Madrid, 28006, Spain CIHIDECAR, Departamento de Química Orgánica, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Buenos Aires, 1428, Argentina Centro de Investigação em Química, Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade Do Porto, Porto, P-4169-007, Portugal Department of Chemistry and QOPNA, University of Aveiro, Aveiro, P-3810-193, Portugal
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Palabras clave: | (Z)-cinnamic acid; B3LYP; EKM; Enthalpies of formation; G3; G4; Gas-phase acidity; Computation theory; Density functional theory; Gases; Mass spectrometry; Molecules; Positive ions; Solutions; Thermodynamic properties; B3LYP; Cinnamic acids; EKM; Enthalpies of formation; G3; G4; Gas-phase acidities; Enthalpy |
Año: | 2016
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Volumen: | 95
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Página de inicio: | 195
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Página de fin: | 201
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DOI: |
http://dx.doi.org/10.1016/j.jct.2015.12.014 |
Título revista: | Journal of Chemical Thermodynamics
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Título revista abreviado: | J Chem Thermodyn
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ISSN: | 00219614
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CODEN: | JCTDA
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Registro: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00219614_v95_n_p195_Davalos |
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Citas:
---------- APA ----------
Dávalos, J.Z., Lima, C.F.R.A.C., Silva, A.M.S., Santos, L.M.N.B.F., Erra-Balsells, R. & Salum, M.L.
(2016)
. Energetics of neutral and deprotonated (Z)-cinnamic acid. Journal of Chemical Thermodynamics, 95, 195-201.
http://dx.doi.org/10.1016/j.jct.2015.12.014---------- CHICAGO ----------
Dávalos, J.Z., Lima, C.F.R.A.C., Silva, A.M.S., Santos, L.M.N.B.F., Erra-Balsells, R., Salum, M.L.
"Energetics of neutral and deprotonated (Z)-cinnamic acid"
. Journal of Chemical Thermodynamics 95
(2016) : 195-201.
http://dx.doi.org/10.1016/j.jct.2015.12.014---------- MLA ----------
Dávalos, J.Z., Lima, C.F.R.A.C., Silva, A.M.S., Santos, L.M.N.B.F., Erra-Balsells, R., Salum, M.L.
"Energetics of neutral and deprotonated (Z)-cinnamic acid"
. Journal of Chemical Thermodynamics, vol. 95, 2016, pp. 195-201.
http://dx.doi.org/10.1016/j.jct.2015.12.014---------- VANCOUVER ----------
Dávalos, J.Z., Lima, C.F.R.A.C., Silva, A.M.S., Santos, L.M.N.B.F., Erra-Balsells, R., Salum, M.L. Energetics of neutral and deprotonated (Z)-cinnamic acid. J Chem Thermodyn. 2016;95:195-201.
http://dx.doi.org/10.1016/j.jct.2015.12.014