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

Hebah Abdel-Wahab; Joseph Bozzelli

doi:doi:10.11648/j.ajpc.20200904.13

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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

Hebah Abdel-Wahab, Joseph Bozzelli

Published in American Journal of Physical Chemistry (Volume 9, Issue 4)

Received: 20 October 2020 Accepted: 8 December 2020 Published: 28 December 2020

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Abstract

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.

Published in	American Journal of Physical Chemistry (Volume 9, Issue 4)
DOI	10.11648/j.ajpc.20200904.13
Page(s)	101-111
Creative Commons	This is an Open Access article, distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution and reproduction in any medium or format, provided the original work is properly cited.
Copyright	Copyright © The Author(s), 2020. Published by Science Publishing Group

Keywords

Computation, Gaussian, Thermochemical, Enthalpy, Entropy

References

[1]	Wallington, T. J.; Schneider, W. F.; Worsnop, D. R.; Nielsen, O. J.; Sehested, J.; Debruyn, W. J.; Shorter, J. A. The Environmental Impact of CFC Replacements HFCs and HCFCs. Environ. Sci. Technol. 1994, 28, 320A−326A.
[2]	Wang H., Castillo A., Bozzelli J. W., Thermochemical properties enthalpy, entropy, and heat capacity of C1-4 fluorinated hydrocarbons. J. Phys. Chem. 2015.
[3]	Schneider, W. F.; Wallington, T. J. Ab Initio Investigation of the Heats of Formation of Several Trifluoromethyl Compounds. J. Phys. Chem. 1993, 97, 12783−12788.
[4]	Wang, H.; Castillo, Á.; Bozzelli, J. W. Thermochemical Properties Enthalpy, Entropy, and Heat Capacity of C1−C4 Fluorinated Hydrocarbons: Fluorocarbon Group Additivity. J. Phys. Chem. A 2015, 119, 8202−8215.
[5]	El-Taher, S. Ab Initio and DFT Investigation of Fluorinated Methyl Hydroperoxides: Structures, Rotational Barriers, and Thermo chemical Properties. J. Fluorine Chem. 2006, 127, 54−62.
[6]	Wang H., Bozzelli J. W., Thermochemical properties and Bond Dissociation Energy for Fluorinated Methanol and fluorinated methyl hydroperoxides,. J. Phys. Chem. 2016.
[7]	Ruscic, B., Active Thermochemical Tables: Sequential Bond Dissociation Enthalpy of Methane, Ethane, and Methanol and related Thermochemistry. J. Phys. Chem. A 2015, 119, 7810-7837.
[8]	Burke, S. M.; Simmie, J. M.; Curran, H. J. Critical Evaluation of Thermochemical Properties of C1 −C4 Species: Updated Group Contributions to Estimate Thermochemical Properties. J. Phys. Chem. Ref. Data 2015, 44, 013101.
[9]	Chase, M. W. J. NIST-JANAF Thermochemical Tables. J. Phys. Chem. Ref. Data. 1998, Monograph 9, 1-1951.
[10]	Luo, X.; Fleming, P. R.; Rizzo, T. R. Vibrational Overtone Spectroscopy of the 4 νOH+νOH′ Combination Level of HOOH via Sequential Local Mode −local Mode Excitation. J. Chem. Phys. 1992, 96, 5659−5667.
[11]	Bodi, A.; Kercher, J. P.; Bond, C.; Meteesatien, P.; Sztáray, B.; Baer, T. Photoion Photoelectron Coincidence Spectroscopy of Primary Amines RCH 2NH₂ (R = H, CH₃, C 2H₅, C 3H₇, i-C3H₇): Alkylamine and Alkyl Radical Heats of Formation by Isodesmic Reaction Networks. J. Phys. Chem. A 2006, 110, 13425−13433.
[12]	Wang, H.; Bozzelli, J. W. Thermochemical Properties (ΔfH (298 K), S (298 K), C p(T)) and Bond Dissociation Energies for C1−C4 Normal Hydroperoxides and Peroxy Radicals. J. Chem. Eng. Data 2016, 61, 1836−1849.
[13]	Csontos, J.; Rolik, Z.; Das, S.; Kállay, M. High-Accuracy Thermochemistry of Atmospherically Important Fluorinated and Chlorinated Methane Derivatives. J. Phys. Chem. A 2010, 114, 13093 −13103.
[14]	Math is Fun Advanced, 2017, Standard Deviation and Variance, 12/2019, {https://www.mathsisfun.com/data/standard-deviation.html}
[15]	NIST Computational Chemistry Comparison and Benchmark Database. NIST Standard Reference Database Number, Release 16a; Johnson, R. D., III, Ed.; NIST: Gaithersburg, MD, 2013.
[16]	Sheng, C. Elementary, Pressure Dependent Model for Combustion of C1, C2 and Nitrogen Containing Hydrocarbons: Operation of A Pilot Scale Incinerator and Model Comparison. Ph. D. dissertation; New Jersey Institute of Technology, 2002.
[17]	Becke, A. D. Density-functional Thermochemistry. III. The Role of Exact Exchange. J. Chem. Phys. 1993, 98, 5648−5652.
[18]	Lay, T. H.; Krasnoperov, L. N.; Venanzi, C. A.; Bozzelli, J. W.; Shokhirev, N. V. Ab Initio Study of α-Chlorinated Ethyl Hydro510peroxides CH₃CH₂OOH, CH₃CHClOOH, and CH₃CCl₂OOH: Conformational Analysis, Internal Rotation Barriers, Vibrational Frequencies, and Thermodynamic Properties. J. Phys. Chem. 1996, 513100, 8240−8249.
[19]	NIST Computational Chemsitry Comparison and Benchmark Database, NIST Standard Reference Database Number 101, Release 16a; Johnson, R. D. III, Ed.; NIST: Gaithersburg, MD, http://cccbdb. nist. gov (accessed Aug 2013).
[20]	Myrna H. M., Minh T. N., David A D, Minh T. N., Theoretical Prediction of the Heats of Formation of C₂H₅O* Radicals Derived From Ethanol and of the Kinetics of beta-C-C Scission in the Ethoxy Radical, J. Phys. Chem. A 2007, 111, 1, 113–126.
[21]	Density Functional theory, 2019, Density Functionals from the Truhlar Group, University of Minnesota, 11/25/2019, https://comp.chem.umn.edu/info/DFT.htm

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Hebah Abdel-Wahab, Joseph Bozzelli. (2020). 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, 9(4), 101-111. https://doi.org/10.11648/j.ajpc.20200904.13

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ACS Style

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. Am. J. Phys. Chem. 2020, 9(4), 101-111. doi: 10.11648/j.ajpc.20200904.13

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AMA Style

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. Am J Phys Chem. 2020;9(4):101-111. doi: 10.11648/j.ajpc.20200904.13

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@article{10.11648/j.ajpc.20200904.13,
  author = {Hebah Abdel-Wahab and Joseph Bozzelli},
  title = {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},
  journal = {American Journal of Physical Chemistry},
  volume = {9},
  number = {4},
  pages = {101-111},
  doi = {10.11648/j.ajpc.20200904.13},
  url = {https://doi.org/10.11648/j.ajpc.20200904.13},
  eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ajpc.20200904.13},
  abstract = {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.},
 year = {2020}
}

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TY  - JOUR
T1  - 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
AU  - Hebah Abdel-Wahab
AU  - Joseph Bozzelli
Y1  - 2020/12/28
PY  - 2020
N1  - https://doi.org/10.11648/j.ajpc.20200904.13
DO  - 10.11648/j.ajpc.20200904.13
T2  - American Journal of Physical Chemistry
JF  - American Journal of Physical Chemistry
JO  - American Journal of Physical Chemistry
SP  - 101
EP  - 111
PB  - Science Publishing Group
SN  - 2327-2449
UR  - https://doi.org/10.11648/j.ajpc.20200904.13
AB  - 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.
VL  - 9
IS  - 4
ER  -

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Author Information

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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APA Style

Hebah Abdel-Wahab, Joseph Bozzelli. (2020). 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, 9(4), 101-111. https://doi.org/10.11648/j.ajpc.20200904.13

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ACS Style

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. Am. J. Phys. Chem. 2020, 9(4), 101-111. doi: 10.11648/j.ajpc.20200904.13

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AMA Style

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. Am J Phys Chem. 2020;9(4):101-111. doi: 10.11648/j.ajpc.20200904.13

Copy | Download

@article{10.11648/j.ajpc.20200904.13,
  author = {Hebah Abdel-Wahab and Joseph Bozzelli},
  title = {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},
  journal = {American Journal of Physical Chemistry},
  volume = {9},
  number = {4},
  pages = {101-111},
  doi = {10.11648/j.ajpc.20200904.13},
  url = {https://doi.org/10.11648/j.ajpc.20200904.13},
  eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ajpc.20200904.13},
  abstract = {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.},
 year = {2020}
}

Copy | Download

TY  - JOUR
T1  - 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
AU  - Hebah Abdel-Wahab
AU  - Joseph Bozzelli
Y1  - 2020/12/28
PY  - 2020
N1  - https://doi.org/10.11648/j.ajpc.20200904.13
DO  - 10.11648/j.ajpc.20200904.13
T2  - American Journal of Physical Chemistry
JF  - American Journal of Physical Chemistry
JO  - American Journal of Physical Chemistry
SP  - 101
EP  - 111
PB  - Science Publishing Group
SN  - 2327-2449
UR  - https://doi.org/10.11648/j.ajpc.20200904.13
AB  - 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.
VL  - 9
IS  - 4
ER  -

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