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Gaussian M-062x/6-31+g (d,p) Calculation of Standard Enthalpy, Entropy and Heat Capacity of Some Fluorinated Alcohol’s and Its Radicals at Different Temperatures
American Journal of Physical Chemistry
Volume 9, Issue 4, December 2020, Pages: 101-111
Received: Oct. 20, 2020; Accepted: Dec. 8, 2020; Published: Dec. 28, 2020
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Hebah Abdel-Wahab, Department of Chemistry and Environmental Science, New Jersey Institute of Technology, Newark, New Jersey, United States
Joseph Bozzelli, Department of Chemistry and Environmental Science, New Jersey Institute of Technology, Newark, New Jersey, United States
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Thermochemical properties of fluorinated alcohols are needed for understanding their stability and reactions in the environment and in thermal process. Structures and thermochemical properties of these species were determined by the Gaussian M-062x/6-31+g (d,p) calculation. Contributions of entropy, S°298, and heat capacities, Cp(T) due to vibration, translation, and external rotation of the molecules were calculated based on the vibration frequencies and structures obtained from the M-062x/6-31+g (d,p) density functional method. Potential barriers are calculated using M-062x/6-31+g (d,p) density functional method and are used to calculate rotor contributions to entropy and heat capacity using integration over energy levels of rotational potential. Enthalpies of formation for 19 fluorinated ethanol and some radicals were calculated with a popular ab initio and density functional theory methods: the Gaussian M-062x/6-31+g (d,p) via several series of isodesmic reactions. The recommended ideal gas phase ΔHf298 ° (kcal mol−1) values calculated in this study are the following: -101.74 ± 0.72 for CH2FCH2OH; -113.51 ±1.39 for CH3CHFOH; -50.66 ± 0.75 for C•HFCH2OH; -56.05±0.62 for CH2FCH•OH; -45.00±1.31 for CH2FCH2O•; -59.61±1.20 for CH2•CHFOH; -67.99± 1.29 for CH3CF•OH; -58.76±1.20 for CH3CHFO•; -154.12±1.72 for CH2FCHFOH; -155.26±1.67 for CF2HCH2OH; -174.53±1.54 for CH3CF2OH; -104.07 ± 1.45 for CH2FC•FOH; -105.63±1.74 for C•HFCFHOH; -99.08±1.57 for CH2FCHFO•; -102.34±1.74 for CHF2C•HOH; -102.23±1.57 for C•F2CH2OH; -98.86±1.57 for CHF2CH2O•; -119.41±1.74 for CH2•CF2OH; -110.56±1.62 for CH3CF2O•. Entropies (S298° in cal mol−1 K−1) were estimated using the M-062x/6-31+g (d,p) computed frequencies and geometries. Rotational barriers were determined and hindered internal rotational contributions for S298°- 1500°, and Cp(T) were calculated using the rigid rotor harmonic oscillator approximation, with direct integration over energy levels of the intramolecular rotation potential energy curves.
Computation, Gaussian, Thermochemical, Enthalpy, Entropy
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Hebah Abdel-Wahab, Joseph Bozzelli, Gaussian M-062x/6-31+g (d,p) Calculation of Standard Enthalpy, Entropy and Heat Capacity of Some Fluorinated Alcohol’s and Its Radicals at Different Temperatures, American Journal of Physical Chemistry. Vol. 9, No. 4, 2020, pp. 101-111. doi: 10.11648/j.ajpc.20200904.13
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