The thermodynamic properties of 4-pentenoic acid

• Published in: Russian Journal of Physical Chemistry A 2008-09, Vol.82 (9), p.1521-1526
• Main Authors: Emel’yanenko, V. N., Verevkin, S. P., Burakova, E. N., Roganov, G. N., Georgieva, M. K.
• Format: Article
• Language: English
• Subjects: Chemical Thermodynamics and Thermochemistry; Chemistry; Chemistry and Materials Science; Physical Chemistry
• ISSN: 0036-0244; 1531-863X
• DOI: 10.1134/S0036024408090215

The enthalpy of formation of liquid 4-pentenoic acid was determined by combustion calorimetry. The vapor pressure and enthalpy of vaporization of the compound were measured by the transfer method over the temperature range 289–324 K. Conformational analysis was performed. The equilibrium structure, fundamental vibrations, moments of inertia, and total energy of the stablest acid conformers were calculated by the B3LYP/6-311G( d, p ) and G3MP2 quantum-chemical methods. The experimental IR spectrum and calculated vibrational frequencies were used to assign IR bands. The thermodynamic properties of monomeric 4-pentenoic acid in the ideal gas state were calculated over the temperature range 0–1500 K. Additive and quantum-chemical methods were used to estimate the Δ f H °(g) and Δ vap H ° values. Close agreement between the calculation results and experimental data was obtained. It was shown that additive and quantum-chemical methods could be used for estimating the enthalpies of formation and vaporization of nonconjugated alkenoic acids.