1. Introduction

OJPC

Open Journal of Physical Chemistry

2162-1969

Scientific Research Publishing

10.4236/ojpc.2021.112002

OJPC-107976

Articles

Chemistry&Materials Science

Heat Capacity and Bond Dissociation Energy Calculations of Some Fluorinated Ethanol’s and its Radicals: CH3-xCH2FxOH, CH3CH2-xFxOH

Hebah

M. Abdel-Wahab

¹^*Joseph

W. Bozzelli

Department of Chemistry and Environmental Science, New Jersey Institute of Technology, Newark, New Jersey, USA

25032021

1102135326, October 202022, March 2021 25, March 2021

2014

This work is licensed under the Creative Commons Attribution International License (CC BY). http://creativecommons.org/licenses/by/4.0/

Structures and thermochemical properties of these species were determined by the gaussian M-062x/6-31 + G (D, P) calculation 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. Entropies (S298 ° in Cal · Mol ^- ¹ K ^- ¹ ) were estimated using the M-062x/6-31 + G (D, P) computed frequencies and geometries. 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. 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. Thermochemical properties of fluorinated alcohols are needed for understanding their stability and reactions in the environment and in thermal process.

Thermo-Chemistry Enthalpy Fluorinated Ethanol’s Thermochemical Properties

1. Introduction

Fluorinated hydrocarbons are used as refrigerants, in polymers, heat exchange ﬂuids, and as solvents. They are present in the atmosphere, lithosphere, and hydrosphere. Because of their less adverse effects on the stratospheric ozone layer, they are used in place of greenhouse gases [1]. Fluorinated hydrocarbons exist as compounds ranging from pure to oxidized intermediates resulting from oxidation in the environment. In order to study their reactivity in biological systems, lifetimes, and in the environment, it’s critical to understand the chemical and thermodynamic properties of ﬂuorocarbons and their breakdown intermediates.

The thermochemistry of fluorinated alcohols with one carbon atom was studied in the past and is in the literature [2]. In 2016, Hang Wang studied thermodynamic properties of fluorinated methanol using CBS-QB3, M06, M06-2X, WB97X, W1U, B3LYP, CBS-APNO and G4 Calculations. Small standard deviation suggests good error cancellation of work reactions and accuracy. M06-2x/6-31 + g (d, p) calculation had small values for standard deviations. It is an accurate method to calculate Enthalpy of fluorinated alcohols. It shows the second smallest standard deviation after CBS-QB3 method of calculation.

Halogenated compounds are highly stable, have low reactivity and are valued chemicals in industry [3]. Due to its widespread use and their persistence in the environment, they are of concern to the environment. In order to understand the oxidation and reduction reactions involving such molecules, their thermochemical properties must be studied [3].

1.1. Isodesmic and Isogyric Reaction

The enthalpy of formation of mono and di fluorinated ethanol’s and its radicals has been calculated using Gaussian M-062x/6-31 + g (d, p) method of calculation. In order to calculate the enthalpy of formation of ﬂuorinated ethanols using this method, we use the calculated enthalpies of formation in work reactions along with reference species.

The number of each type of bond must be conserved in the isodesmic reactions in order to cancel any systematic error in the molecular orbital calculations using this method. Calculations of enthalpies of formation are allowed to accuracies close to experimental values by the careful choice of the isodesmic reactions [2]. Standard enthalpy of formation for the reference species used in the isodesmic work reactions along with their uncertainties is listed in Table 1. Taking 1-fluoroethanol as an example, two isodesmic reactions (Table 2) are selected to determine the ΔHf298˚ of the target molecule, 1-fluoroethanol. Since the ΔHf298˚ values of all species but 1-fluoroethanol in 1 - 2 (Table 2) are known, the ΔHf298˚ of the target species 1-fluoroethanol is obtained from this data and the calculated ΔHrxn, 298˚. ΔHf298˚ calculated using two different reference molecules is within ±2 Kcal∙mol⁻¹.

1.2. Reference Species

Standard enthalpy of formation for the reference species used in the isodesmic work reactions along with their uncertainties is listed in Table 1. Table 2 provides one example on the method of Isodesmic Work Reactions used for the

Table 1 Reference Species in the Isodesmic Reactions Standard Enthalpy of Formation Values (kcal∙mol−1) [<xref ref-type="bibr" rid="scirp.107976-ref4">4</xref>]

Species	Δ_fH˚₍₂₉₈₎	Species	Δ_fH˚₍₂₉₈₎
CH₃F	−56.54 ± 0.07^a −56.62 ± 0.48^h	CH₃OOH CH₃CH₂OOH	−30.96 ± 0.67^b −38.94 ± 0.81^b
CH₃CH₂F	−65.42 ± 1.11^a	CH₃CH₂CH₂OOH	−44.03 ± 0.67^b
CH₃CH₂CH₂F	−70.24 ± 1.30^a	CH₃OO^•	2.37 ± 1.24^b
CH₂F₂	−108.07 ± 1.46^a −107.67 ± 0.48^h	CH₃CH₂OO^• CH₃CH₂CH₂OO^•	−6.19 ± 0.92^b −11.35 ± 1.24^b
CH₃CHF₂	−120.87 ± 1.62^a	CH₄	−17.81 ± 0.01^c
CH₃CH₂CHF₂	−125.82 ± 1.65^a	CH₃CH₃	−20.05 ± 0.04^c
CHF₃	−166.71 ± 1.97^h −166.09 ± 0.48^h	CH₃CH₂CH₃ CH₃CH₂CH₂CH₃	−25.01 ± 0.06ⁱ −30.07 ± 0.08ⁱ
CH₃CF₃	−180.51 ± 2.05^a	CH₃O^•	5.15 ± 0.08 ^c
CH₃CH₂CF₃	−185.48 ± 2.15^a	CH₃CH₂O^•	−3.01^d
CH₃^•	34.98 ± 0.02^c	OH	8.96 ± 0.01^c
CH₃CH₂^•	28.65 ± 0.07^c	CH₃OH	−47.97 ± 0.04^c
CH₃CH₂CH₂^•	24.21 ± 0.24^gj 24.18ⁱ	CH₃CH₂OH	−56.07 ± 0.05ⁱ
H	52.10^c	HOO^•	2.94^cj
O	59.57^c	HOOH	−32.39 ± 0.04^fj −32.37ⁱ

^aWang [2], ^bWang [4], ^cRuscic [5], ^dBurke [6], ^eChase [7], ^fLuo [8], ^gBodi [9], ^hPedley, ⁱATcT Tables [10], ^hCsontos [11]. ^jThe value we used in this study [4]

Table 2 Example for Enthalpy of Formation Calculations for 1-fluoroethanol using Isodesmic Reactions; using different reference molecules, Units in kcal∙mol−1.

Isodesmic Reactions	ΔH˚_Rxn₍₂₉₈₎ Hartrees	ΔH _Rxn₍₂₉₈₎ kcal/mol⁻¹	Δ_fH˚₍₂₉₈₎ CH_3−xCH₂F_xOH, CH₃CH_2-xF_xOH kcal∙mol⁻¹	Error kcal∙mol⁻¹	Equ. #
CH₂FCH₂OH + CH₄ = CH₃CH₂OH + CH₃F − 254.173115^a − 40.447961 − 154.926666 − 139.683801 Reference Values − 17.81 − 56.21 − 56.54 Kcal∙mol⁻¹	0.010609	6.657243	−101.6	±0.2	1
CH₂FCH₂OH + CH₃CH₃ = CH₃CH₂OH + CH₃CH₂F − 254.173115 − 79.717768 − 154.926666 − 178.963776 − 20.05 − 56.21 − 65.42	0.000441	0.276731	−101.9	±1.3	2
Reported Δ_fH˚ (298) kcal∙mol⁻¹			−101.7 ± 0.7
Standard Deviation over rxns			±0.1

^aHartrees, kcal∙mol⁻¹; *SD Standard Deviation kcal∙mol⁻¹ Errors reported avg of sum of uncertainties in rxn’s reference species.

calculation of the Standard Enthalpy of Formation Δ_fH˚ (298) for the fluoroethanols.

1.3. Computational Method

Composite calculations and series of Isodesmic Reactions are used to calculate enthalpy of formation of fluorinated ethanols. All calculations are performed using the Gaussian 16 program. The DFT method M06-2x is used to initially analyze optimized structures, frequencies, thermo energies and internal rotors of the molecules studied. It’s a Global-hybrid meta-GGA density functional approximation, GGA, generalized gradient approximation, in which the density functional depends on the up and down spin densities and their reduced gradient, meta GGA, in which the functional also depends on the up and down spin kinetic energy densities, hybrid GGA, a combination of GGA with Hartree-Fock exchange, hybrid meta GGA, a combination of meta GGA with Hartree-Fock exchange [12]. All reported values are for standard state of 298 K and 1 atm. We continue the calculation of ﬂuorinated alcohols in this study with this method, because the M-062x/6-31 + g (d, p) level of calculation have been applied to ﬂuoro hydrocarbons 6 with small reported standard deviations values.

2. Results and Discussion2.1. Entropy and Heat Capacity Values

Internal rotor contributions to calculated entropy and heat capacity at 298 - 1500 K were determined using the molecular mass of each molecule, number of optical isomers, symmetry of the molecule, electron degeneracy, moment of inertia, and vibrational frequencies values (Table3). The vibrational frequencies for the calculation of heat capacity and entropy at the M-062x/6-31 + g (d, p) level of calculation was scaled by a factor of 0.97 [13]. The moment of inertia values is shown in the Supplemental Information Tableprovided. To calculate the contributions of external rotor, vibration and transition to the calculated entropy and heat capacity, the “SMCPS” [14] program is used. It employs the rigid-rotor harmonic oscillator approximation using moment of inertia from optimized structure and frequencies. The “Rotator” [15] program by Lay et al. [16] is used to calculate internal rotor contributions from the corresponding internal rotor torsion frequencies. In this paper, a torsional potential curve presenting a ten-parameter Fourier series function is used to calculate the contribution of internal rotor. Parameters and detailed functions are shown in the Supplemental Information Tableprovided. Rotor [16] program is used to calculate thermodynamic functions from hindered rotations with arbitrary potentials.

Calculation of the Hamiltonian matrix of the internal rotor, and subsequent calculation of energy levels by direct diagonalization of the matrix are employed by this technique. Rotational barriers versus dihedral angle are presented as a potential curve. In this paper, the calculated torsional potential at discrete torsional angles.

V ( Φ ) = a 0 + ∑ a i cos ( i Φ ) + ∑ b j cos ( j Φ ) i , j = 1 − 10 (1)

The coefficients a i and b j are calculated to present the maxima and minima of the torsional potentials with a possibility to shift from the extreme angular positions.

Table 3 Monofluoro and Difluoro-Ethanol’s Ideal Gas phase Entropy and Heat Capacity obtained using M-062x/6-31 + g (d, p) level of theory (Cal∙mol−1∙K−1)

Species		S (298)	Cp (298)	Cp (400	Cp (500)	Cp (600)	Cp (800)	Cp (1000)	Cp (1500)
CH₂FCH₂OH	TVR Internal Rotor Total	64.74 3.84 2.02 70.60	13.23 3.24 3.15 19.62	17.12 3.48 3.33 23.94	20.72 3.43 3.04 27.20	23.75 3.22 2.66 29.62	28.18 2.68 2.05 32.91	31.11 2.23 1.69 35.03	35.06 1.62 1.30 37.98
CH₃CHFOH	TVR Internal Rotor Total	65.17 4.48 2.67 72.32	14.06 2.13 2.17 18.35	17.90 2.09 2.21 22.21	21.37 1.95 2.18 25.50	24.26 1.80 2.09 28.16	28.51 1.56 1.89 31.96	31.32 1.40 1.71 34.42	35.15 1.19 1.40 37.75
C•HFCH₂OH	TVR Internal Rotor Total	66.30 6.19 3.09 75.58	13.54 2.31 3.16 19.01	16.96 1.91 2.52 21.38	19.97 1.69 2.04 23.70	22.48 1.54 1.74 25.76	26.29 1.36 1.41 29.06	29.04 1.25 1.25 31.55	33.33 1.13 1.11 35.56
CH₂FCH•OH	TVR Internal Rotor Total	66.47 5.72 6.00 78.19	13.76 2.34 1.96 18.06	17.09 2.22 1.95 21.27	20.04 2.09 1.95 24.07	22.52 1.95 1.91 26.38	26.29 1.73 1.79 29.81	29.02 1.56 1.65 32.24	33.31 1.32 1.40 36.03
CH₂FCH₂O•	TVR Internal Rotor Total	75.30 6.08 81.38	20.44 2.20 22.64	23.66 1.96 25.62	26.27 1.7982 28.07	28.39 1.68 30.07	31.55 1.53 33.08	33.79 1.43 35.21	37.16 1.27 38.42
CH₂•CHFOH	TVR Internal Rotor Total	66.89 4.94 2.84 74.67	14.80 1.42 1.95 18.17	18.21 1.25 2.12 21.58	21.07 1.17 2.12 24.35	23.40 1.12 2.04 26.55	26.90 1.06 1.83 29.79	29.44 1.04 1.64 32.11	33.49 1.01 1.35 35.86
CH₃CF•OH	TVR Internal Rotor Total	66.56 4.91 1.71 73.18	13.94 1.97 2.60 18.50	17.25 1.75 3.17 22.17	20.17 1.57 3.22 24.96	22.62 1.44 3.01 27.07	26.38 1.27 2.43 30.08	29.11 1.18 1.99 32.28	33.38 1.08 1.45 35.92
CH₃CHFO•	TVR Internal Rotor Total	66.73 4.55 71.27	14.44 2.12 16.56	18.16 2.05 20.21	21.39 1.90 23.29	24.09 1.75 25.84	28.18 1.51 29.69	31.12 1.36 32.48	35.58 1.18 36.75
CH₂FCHFOH	TVR Internal Rotor Total	67.46 0.00 6.12 73.58	15.41 0.00 3.11 18.52	19.51 0.00 2.64 22.15	23.12 0.00 2.24 25.35	26.07 0.00 1.94 28.00	30.23 0.00 1.57 31.79	32.83 0.00 1.37 34.20	36.15 0.00 1.17 37.31
CF₂HCH₂OH	TVR Internal Rotor Total	62.94 4.98 2.23 70.15	12.00 3.36 3.21 18.57	15.54 3.20 3.17 21.91	18.95 2.97 2.81 24.72	21.90 2.72 2.44 27.06	26.43 2.26 1.91 30.60	29.57 1.93 1.60 33.10	34.06 1.48 1.27 36.81

CH₃CF₂OH	TVR Internal Rotor Total	68.41 4.53 1.58 74.52	16.53 2.13 2.45 21.11	20.74 2.08 3.09 25.91	24.23 1.93 3.28 29.44	27.01 1.77 3.14 31.93	30.87 1.53 2.60 35.01	33.29 1.38 2.14 36.80	36.37 1.18 1.53 39.08
CH₂FC•FOH	TVR Internal Rotor Total	69.58 6.18 3.15 78.90	15.15 3.28 1.91 20.34	18.76 2.51 1.96 23.22	21.84 2.07 1.91 25.82	24.36 1.80 1.83 27.99	28.05 1.50 1.65 31.19	30.59 1.34 1.50 33.43	34.38 1.16 1.27 36.81
C•HFCFHOH	TVR Internal Rotor Total	69.60 6.92 1.72 78.25	15.48 2.03 2.79 20.30	19.22 1.69 3.10 24.01	22.30 1.49 3.03 26.83	24.76 1.37 2.83 28.96	28.32 1.22 2.37 31.91	30.75 1.15 2.02 33.92	34.41 1.07 1.52 37.00
CH₂FCHFO•	TVR Internal Rotor Total	70.53 5.48 76.01	15.99 2.92 18.91	19.88 2.79 22.67	23.22 2.58 25.80	25.94 2.37 28.31	29.93 2.01 31.94	32.65 1.76 34.41	36.59 1.40 37.99
CHF₂C•HOH	TVR Internal Rotor Total	68.27 6.07 1.51 75.85	15.46 2.65 2.50 20.61	19.18 2.30 3.06 24.54	22.25 2.05 3.18 27.48	24.71 1.86 3.06 29.63	28.28 1.61 2.60 32.49	30.72 1.45 2.20 34.37	34.40 1.24 1.61 37.25
C•F₂CH₂OH	TVR Internal Rotor Total	69.57 6.18 3.46 79.21	15.16 2.68 2.45 20.29	18.73 2.38 2.04 23.15	21.81 2.11 1.75 25.66	24.32 1.89 1.55 27.76	28.03 1.5848 1.32 30.94	30.58 1.41 1.21 33.19	34.37 1.19 1.09 36.65
CHF₂CH₂O•	TVR Internal Rotor Total	70.02 5.78 75.79	15.31 2.51 17.82	18.91 2.41 21.32	22.14 2.26 24.40	24.87 2.10 26.97	29.03 1.83 30.86	31.94 1.63 33.57	36.19 1.34 37.53
CH₂•CF₂OH	TVR Internal Rotor Total	70.20 4.97 1.78 76.95	17.30 1.37 2.81 21.48	21.07 1.23 3.33 25.63	23.93 1.16 3.25 28.35	26.13 1.11 2.9407 27.25	29.24 1.06 2.30 32.61	31.38 1.04 1.87 34.29	34.69 1.01 1.38 37.09
CH₃CF₂O•	TVR Internal Rotor Total	70.14 4.84 5.78 80.75	16.85 2.08 2.51 21.44	20.78 1.89 2.41 25.08	23.99 1.70 2.26 27.94	26.55 1.54 2.10 30.20	30.30 1.35 1.83 33.47	32.87 1.23 1.63 35.73	36.66 1.11 1.34 39.11

Calculations of heat capacity and standard entropy based on benchmark database and the computational chemistry comparison for the M-062x/6-31 + g (d, p) calculation method, the vibrational frequencies were scaled by a factor of 0.987 [13]. Potential Energy profiles for mono and di fluorinated ethanol and their related radicals are listed in the Supplemental Information Tableprovided., the solid lines are the fit of Fourier series expansion, rotator contribution for barriers below 7 kcal∙mol⁻¹ were added to the SMCPS calculated entropy and heat capacity. Energies are in kcal∙mol⁻¹ (Table3).

2.2. Standard Enthalpy Values

Enthalpies of formation were determined from isodesmic work reactions from M-062x/6-31 + g (d, p) method of calculation. The standard enthalpy of formation for the reference species along with their uncertainties, which are used the isodesmic work reactions, Table 4, are listed in Table 1 in kcal∙mol⁻¹. The standard deviation was calculated [17] for all Enthalpies of formation values for all 19 ﬂuorinated ethanol and is included in Table 4. Details of the method of

Table 4 Standard Enthalpy of Formation using isodesmic reactions: Monofluoro and Difluoro-Ethanols using the M06-2x/6-31 + g (d, p) Level of Theory. Errors reported as sum of avg uncertainty in rxn’s reference specie

Isodesmic Reactions Target Specie	ΔH˚_Rxn₍₂₉₈₎ Hartrees	ΔH˚_Rxn₍₂₉₈₎ Kcal/mole¹	Δ_fH˚₍₂₉₈₎ kcal∙mol⁻¹	Error kcal∙mol⁻¹
CH₂FCH₂OH + CH₄ = CH₃CH₂OH + CH₃F −254.173115 −40.447961 −154.926666 −139.683801 −17.81 −56.21 −56.54	0.010609	6.657243	−101.6	±0.2
CH₂FCH₂OH + CH₃CH₃ = CH₃CH₂OH + CH₃CH₂F −254.173115 −79.717768 −154.926666 −178.963776 −20.05 −56.21 −65.42	0.000441	0.276731	−101.9	±1.3
Reported Δ_fH˚ (298) kcal∙mol⁻¹			−101.7 ± 0.7
Standard Deviation over rxns			±0.1
CH₃CHFOH + CH₃CH₂CH₃ = CH₃CH₂OH + CH₃CH₂CH₂F −254.19203 −118.990915 −154.926666 −218.237381 −25.02 −56.21 −70.24	0.018898	11.85867	−113.3	±1.5
CH₃CHFOH + CH₃CH₃ = CH₃CH₂OH + CH₃CH₂F −254.19203 −79.717768 −154.926666 −178.963776 −20.05 −56.21 −65.42	0.019356	12.14606	−113.7	±1.3
Reported Δ_fH˚ (298) kcal∙mol⁻¹			−113.5 ± 1.4
Standard Deviation over rxns			±0.2
C•HFCH₂OH + CH₃CH₂CH₃ = CH₃CH₂O• + CH₃CH₂CH₂F −253.518298 −118.990915 −154.268107 −218.237381 −25.02 −3.01 −70.24	0.003725	2.337471	−50.6	±1.4
C•HFCH₂OH + CH₄ = CH₃CH₂O• + CH₃F −253.518298 −40.447961 −154.268107 −139.683801 −17.81 −3.01 −56.54	0.014351	9.005382	−50.8	±0.1
Reported Δ_fH˚ (298) kcal∙mol⁻¹			−50.7 ± 0.8
Standard Deviation over rxns			±0.1
CH₂FCH•OH + CH₃CH₃ = CH₃CH₂O• + CH₃CH₂F −253.518298 −79.717768 −154.268107 −178.963776 −20.05 −3.01 −65.42	0.012436	7.803702	−56.2	±1.2
CH2FCH•OH + CH₄ = CH₃CH₂O• + CH₃F −253.518298 −40.447961 −154.268107 −139.683801 −17.81 −3.01 −56.54	0.022604	14.18421	−55.9	±0.1
Reported Δ_fH˚ (298) kcal∙mol⁻¹			−56.1 ± 0.6

Standard Deviation over rxns			±0.1
CH₂FCH₂O• + CH₃CH₂CH₃ = CH₃CHO• + CH₃CH₂CH₂F −253.509195 −118.990915 −154.268107 −218.237381 −25.02 −3.01 −70.24	−0.00538	−3.37474	−44.9	±1.4
CH₂FCH₂O• + CH₄ = CH₃O• + CH₃CH₂F −253.509195 −40.447961 −114.989112 −178.963776 −17.81 5.15 −65.42	0.004268	2.678208	−45.1	±1.2
Reported Δ_fH˚ (298) kcal∙mol⁻¹			−45.0 ± 1.3
Standard Deviation over rxns			±0.1
CH₂•CHFOH + CH₄ = CH₃O• + CH₃CH₂F −253.532134 −40.447961 −114.989112 −178.963776 −17.81 5.15 −65.42	0.027207	17.07264	−59.5	±1.2
CH₂•CHFOH + CH₃CH₃ = CH₃CH₂O• + CH₃CH₂F −253.532134 −79.717768 −154.268107 −178.963776 −20.05 −3.01 −65.42	0.018019	11.30708	−59.7	±1.2
Reported Δ_fH˚ (298) kcal∙mol⁻¹			−59.6 ± 1.2
Standard Deviation over rxns			±0.1
CH₃CF•OH + CH₃CH₃ = CH₃CH₂O• + CH₃CH₂F −253.542527 −79.717768 −154.268107 −178.963776 −20.05 −5.01 −65.42	0.028412	17.82879	−68.2	±1.2
CH₃CF•OH + CH₃CH₂CH₃ = CH₃CH₂O• + CH₃CH₂CH₂F −253.542527 −118.990915 −154.268107 −218.237381 −25.02 −5.01 −70.24	0.027954	17.54139	−67.8	±1.4
Reported Δ_fH˚ (298) kcal∙mol⁻¹			−68.0 ± 1.3
Standard Deviation over rxns			±0.2
CH₃CHFO• + CH₄ = CH₃O• + CH₃CH₂F −253.530783 −40.447961 −114.989112 −178.963776 −17.81 5.15 −65.42	0.025856	16.22487	−58.7	±1.2
CH₃CHFO• + CH₃CH₃ = CH₃CH₂O• + CH₃CH₂F −253.530783 −79.717768 −154.268107 −178.963776 −20.05 −3.01 −65.42	0.016668	10.45932	−58.8	±1.2
Reported Δ_fH˚ (298) kcal∙mol⁻¹			−58.8 ± 1.2
Standard Deviation over rxns			±0.2
CH₂FCHFOH + CH₄ = CH₃CH₂OH + CH₂F₂ −353.429924 −40.447961 −154.926666 −238.938973 −17.81 −56.21 −108.07	0.012246	7.684475	−154.2	±1.6
CH₂FCHFOH + CH₃CH₂CH₃ = CH₃CH₂OH + CH₃CH₂CHF₂ −353.429924 −118.990915 −154.926666 −317.498882 −25.02 −56.21 −125.82	−0.00471	−2.95494	−154.1	±1.9
Reported Δ_fH˚ (298) kcal∙mol⁻¹			−154.2 ± 1.7
Standard Deviation over rxns			±0.6
CF₂HCH₂OH + CH₄ = CH₃CH₂OH + CH₂F₂ −353.431533 40.447961 −154.926666 −238.938973 −17.81 −56.21 −108.07	0.013855	8.694137	−155.2	±1.6
CF₂HCH₂OH + CH₃CH₃ = CH₃CH₂OH + CH₃CHF₂ −353.431533 −79.717768 −154.926666 −278.225303 −20.05 −56.21 −120.87	−0.00267	−1.67419	−155.4	±1.8

Reported Δ_fH˚ (298) kcal∙mol⁻¹			−155.3 ± 1.7
Standard Deviation over rxns			±0.1
CH₃CF₂OH + CH₄ = CH₃CH₂OH + CH₂F₂ −353.462472 −40.447961 −154.926666 −238.938973 −17.81 −56.21 −108.07	0.044794	28.10864	−174.6	±1.6
CH₃CF₂OH + CH₃CH₂CH₃ = CH₃CH₂OH + CH₃CH₂CHF₂ −353.462472 −118.990915 −154.926666 −317.498882 −25.02 −56.21 −125.82	0.027839	17.46922	−174.5	±1.5
Reported Δ_fH˚ (298) kcal∙mol⁻¹			−174.5 ± 1.5
Standard Deviation over rxns			±0.1
CH₂FC•FOH + CH₄ = CH₃CH₂O• + CH₂F₂ −352.776406 −40.447961 −154.268107 −238.938973 −17.81 −3.01 −108.07	0.017287	10.84775	−104.1	±1.5
CH₂FC•FOH + CH₃CH₂CH₃ = CH₃CH₂O• + CH₃CH₂CHF₂ −352.776406 −118.990915 −154.268107 −317.498882 −25.02 −3.01 −125.82	0.000332	0.208333	−104.0	±1.4
Reported Δ_fH˚ (298) kcal∙mol⁻¹			−104.1 ± 1.5
Standard Deviation over rxns			±0.1
C•HFCFHOH + CH₄ = CH₃O• + CH₃CHF₂ −352.778474 −40.447961 −114.989112 −278.225303 −17.81 5.15 −120.87	0.01202	7.542658	−105.5	±1.7
C•HFCFHOH + CH₃CH₃ = CH₃O• + CH₃CH₂CHF₂ −352.778474 −79.717768 −114.989112 −317.498882 −20.05 5.15 −125.82	0.008248	5.175694	−105.8	±1.8
Reported Δ_fH˚ (298) kcal∙mol⁻¹			−105.6 ± 1.7
Standard Deviation over rxns			±0.2
CHF₂C•HOH + CH₄ = CH₃O• + CH₃CHF₂ −352.773245 −40.447961 −114.989112 −278.225303 −17.81 5.15 −120.87	0.006791	4.261414	−102.5	±1.7
CHF₂C•HOH + CH₃CH₃ = CH₃O• + CH₃CH₂CHF₂ −352.773245 −79.717768 −114.989112 −317.498882 −20.05 5.15 −125.82	0.003019	1.89445	−102.2	±1.8
Reported Δ_fH˚ (298) kcal∙mol⁻¹			−102.3 ± 1.7
Standard Deviation over rxns			±0.2
CH₂FCHFO• + CH₄ = CH₃CH₂O• + CH₂F₂ −352.768218 −40.447961 −154.268107 −238.938973 −17.81 −3.01 −108.07	0.009099	5.709704	−99.0	±1.5
CH₂FCHFO• + CH₃CH₃ = CH₃CH₂O• + CH₃CHF₂ −352.768218 −79.717768 −154.268107 −278.225303 −20.05 −3.01 −120.87	−0.00742	−4.65863	−99.2	±1.7
Reported Δ_fH˚ (298) kcal∙mol⁻¹			−99.1 ± 1.6
Standard Deviation over rxns			±0.1
C•F₂CH₂OH + CH₄ = CH₃CH₂O• + CH₂F₂ −352.773245 −40.447961 −154.268107 −238.938973 −17.81 −3.01 −108.07	0.014126	8.864192	−102.1	±1.5

C•F₂CH₂OH + CH₃CH₃ = CH₃CH₂O• + CH₃CHF₂ −352.773245 −79.717768 −154.268107 −278.225303 −20.05 −3.01 −120.87	−0.0024	−1.50414	−102.3	±1.7
Reported Δ_fH˚ (298) kcal∙mol⁻¹			−102.2 ± 1.6
Standard Deviation over rxns			±0.2
CHF₂CH₂O• + CH₄ = CH₃CH₂O• + CH₂F₂ −352.767873 −40.447961 −154.268107 −238.938973 −17.81 −3.01 −108.07	0.008754	5.493214	−98.8	±1.5
CHF₂CH₂O• + CH₃CH₃ = CH₃CH₂O• + CH₃CHF₂ −352.767873 −79.717768 −154.268107 −278.225303 −20.05 −3.01 −120.87	−0.00777	−4.87512	−99.0	1.7
Reported Δ_fH˚ (298) kcal∙mol⁻¹			−98.9 ± 1.6
Standard Deviation over rxns			±0.2
CH₂•CF₂OH + CH₄ = CH₃O• + CH₃CHF₂ −352.800434 −40.447961 −114.989112 −278.225303 −17.81 5.15 −120.87	0.03398	21.32276	−119.2	±1.7
CH₂•CF₂OH + CH₃CH₃ = CH₃O• + CH₃CH₂CHF₂ −352.800434 −79.717768 −114.989112 317.498882 −20.05 5.15 −125.82	0.030208	18.95579	−119.6	±1.8
Reported Δ_fH˚ (298) kcal∙mol⁻¹			−119.4 ± 1.7
Standard Deviation over rxns			±0.2
CH₃CF₂O• + CH₄ = CH₃CH₂O• + CH₂F₂ −352.786755 − 40.447961 −154.268107 −238.938973 −17.81 5.15 −108.07	0.027636	17.34184	−110.6	±1.5
CH₃CF₂O• + CH₃CH₂CH₃ = CH₃CH₂O• + CH₃CH₂CHF₂ −352.786755 −118.990915 −154.268107 −317.498882 −25.02 5.15 −125.82	0.010681	6.702424	−110.5	±1.8
Reported Δ_fH˚ (298) kcal∙mol⁻¹			−110.6 ± 1.6
Standard Deviation over rxns			±0.1

Hartrees, kcal∙mole⁻¹ *SD Standard Deviation kcal∙mol⁻¹ Errors reported avg of sum of uncertainties in rxn’s reference species.

standard deviation [19] and example calculation(s) are shown in the Supplemental Information table provided. The bond dissociation energy (BDE’s) of Monofluoro and Difluoro-Ethanol’s are also calculated in Table 5 with a small percent error, ranging from 0.2 - 0.8 Kcal/mol. A small value for percent error indicates accurate calculated values for BDB of these molecules.

2.3. Bond Energies

*Supplemental Information

Supplemental Information is available, Cartesian Coordinates; Z-matrixes, vibration frequencies, moments of inertia, the method of standard deviation, Optimized Geometries, and C-C and C-O internal rotors potential energy profile for target fluorinated ethanol and their related radicals are included.

Table 5 Bond Dissociation Energy (BDE’s) of Monofluoro and Difluoro-Ethanol’s

Reactions	Bond Dissociation Energy^a (Kcal∙mol⁻¹)	Error Kcal∙mol⁻¹
Reactions	BDE (this study)
H-CHFCH₂OH H-CHFCH₂OH = H• + •CHFCH₂OH −101.7 ± 0.1 52.1 −50.7 ± 0.09	103.1 ± 0.1	±0.2
CH₂FC-HHOH CH₂FC-HHOH = H• + CH₂FC•HOH −101.7 ±0.1 52.1 −56.1 ± 0.1	97.7 ± 0.1	±0.2
CH₂FCH₂O-H CH₂FCH₂O-H = H• + CH₂FCH₂O• −101.7 ± 0.1 52.1 −45.0 ± 0.1	108.8 ± 0.1	±0.2
H-CH₂CHFOH H-CH₂CHFOH = H• + •CH₂CHFOH −113.5 ± 0.2 52.1 −59.6 ± 0.1	106.0 ± 0.15	±0.3
CH₃C-HFOH H-CH₂CHFOH = H• + CH₃C•FOH -113.5 ±0.2 52.1 -68. ±0.2	97.6 ± 0.2	±0.4
CH₃CHFO-H CH₃CHFO-H = H• + CH₃CHFO• −113.5 ± 0.2 52.1 −58.8 ± 0.2	106.8 ± 0.2	±0.4
H-CHFCHFOH H-CHFCHFOH = H• + •CHFCHFOH −154.6 ± 0.6 52.1 −105.6 ± 0.2	101.1 ± 0.4	±0.8
CH₂FC-HFOH CH₂FC-HFOH = H• + CH₂FC• FOH −154.6 ± 0.6 52.1 −104.1 ± 0.1	102.6 ± 0.35	±0.7
CH₂FCHFO-H CH₂FCHFO-H = H• + CH₂FCHFO• −154.6 ± 0.6 52.1 −99.1 ± 0.1	107.6 ± 0.35	±0.7
CF₂-HCH₂OH CF₂-HCH₂OH = H• + • CF₂CH₂OH −155.3 ± 0.1 52.1 −102.3 ± 0.2	105.1 ± 0.15	±0.3
CF₂HCH-HOH CF₂HCHOH-H = H• + CF₂HC•OH −155.3 ± 0.1 52.1 −102.4 ± 0.2	105.0 ± 0.15	±0.3
CF₂HCH₂O-H CF₂HCH₂O-H = H• + CF₂HCH₂O• −155.3 ± 0.1 52.1 −98.9 ± 0.2	108.5 ± 0.15	±0.3
H-CH₂CF₂OH H-CH₂CF₂OH = H• + •CH₂CF₂OH −174.5 ± 0.1 52.1 −119.4 ± 0.2	107.2 ± 0.15	±0.3
CH₃CF₂O-H CH₃CF₂O-H = H• CH₃CF₂O• −174.5 ± 0.1 52.1 −110.6 ± 0.1	116.0 ± 0.1	±0.2

3. Conclusions

Thermodynamic properties of 19 mono and di-fluoro ethanols and their related radicals are calculated using the abinitio and Global-hybrid meta-GGA density function methods. Isodesmic work reactions are employed for cancellation of calculation errors. Multiple work reactions are utilized to calculate standard enthalpy of formation at the Gaussian M06-2X calculation level. Optimized geometries and frequencies are used to determine entropy and heat capacity with M06-2x/6-31 + g (d, p) level of calculation. Intermolecular torsion potential curves at the M-06-2x/6-31 + g (d, p) level of calculation are used to calculate hindered internal rotation contributions to heat capacity and entropy with a correction to the calculated heat capacity and entropy. The Thermochemical properties: Entropy, Heat Capacities at (298 - 1500 K), Standard Enthalpy of formation (298K), and the C—F and C—H Bond Dissociation Energies (BDEs) for Mono and Difluorinated Ethanols and Radicals: CH_3−xCHF_xOH, CH₃CH_2-xF_xOH have been calculated. The C-H bond energies range from 102.2 to 107.2 Kcal∙mol⁻¹ on the methyl carbons, and from 97.3 to 105.2 Kcal∙mol⁻¹ on the secondary ethyl carbons. The calculated values for C-H bond energies for fluorinated methyl carbons are higher than those of the fluorinated ethyl carbons. Calculated values for the O-H bond energies for 2-fluoroethanol are higher than those of O-H bond energies for 1-fluoroethanol and an intermediate calculated value for O-H bond energies for 1,2-difluoroethanol. Introducing a fluorine atom to either methyl or ethyl carbon increases O-H bond energy [18].

Acknowledgements

We acknowledge the NJIT Advanced Research Computing Services for significant help in providing the computer calculation software.

Conflicts of Interest

The authors declare no conflicts of interest regarding the publication of this paper.

Cite this paper

Abdel-Wahab, H.M. and Bozzelli, J.W. (2021) Heat Capacity and Bond Dissociation Energy Calculations of Some Fluorinated Ethanol’s and its Radicals: CH_3−xCH₂F_xOH, CH₃CH_2−xF_xOH. Open Journal of Physical Chemistry, 11, 13-53. https://doi.org/10.4236/ojpc.2021.112002

Supplemental Information

Table S1 Cartesian Coordinates in Angstroms for target fluorinated ethanol and their related radical’s geometries at the m062x/6-31 + g (d, p) level of theory

CH₂FCH₂OH		Cartesian Coordinates
Center Number	Atomic Number	X	Y	Z
1 2 3 4 5 6 7 8 9	6 9 1 1 6 1 1 8 1	0.000003116 0.000014524 −0.000005137 0.000001564 −0.000021746 −0.000002396 0.000005782 0.000005060 −0.000000767	−0.000001518 −0.000002341 −0.000003977 0.000000767 0.000030833 0.000010185 −0.000006013 −0.000028332 0.000000396	0.000020526 −0.000029060 0.000002345 0.000016765 0.000003239 0.000006184 −0.000000243 −0.000029361 0.000009605
CH₃CHFOH		Cartesian Coordinates
Center Number	Atomic Number	X	Y	Z
1 2 3 4 5 6 7 8 9	6 6 1 1 1 9 1 8 1	0.000021353 −0.000117652 −0.000017542 0.000002761 −0.000013646 0.000109835 0.000018820 0.000000477 −0.000004406	0.000006161 0.000027420 −0.000011156 −0.000007600 −0.000002428 0.000008063 −0.000022248 0.000011019 −0.000009231	−0.000053662 0.000072872 −0.000000420 0.000015768 0.000033080 −0.000042913 0.000004569 −0.000059799 0.000030505
C•HFCH₂OH		Cartesian Coordinates
Center Number	Atomic Number	X	Y	Z
1 2 3 4 5 6 7 8	6 9 1 6 1 1 8 1	−0.000020602 0.000008151 −0.000000850 0.000027899 −0.000003824 0.000008293 −0.000008585 −0.000010483	0.000003182 0.000053880 −0.000011335 −0.000023254 −0.000056264 0.000001847 −0.000003122 0.000035066	−0.000077408 0.000000565 0.000020759 0.000011757 −0.000008549 −0.000024269 0.000024031 0.000053114
CH₂FCH•OH		Cartesian Coordinates
Center Number	Atomic Number	X	Y	Z
1 2 3 4 5 6 7 8	6 9 1 1 6 1 8 1	0.000001249 0.000007760 −0.000003551 −0.000005664 −0.000037395 0.000001277 0.000037801 −0.000001476	−0.000000923 0.000016425 0.000003238 0.000000417 0.000046885 −0.000023053 −0.000035478 −0.000007512	−0.000001559 −0.000015375 −0.000020167 −0.000013020 0.000022542 0.000004842 −0.000015526 0.000038263

CH₂FCH₂O•		Cartesian Coordinates
Center Number	Atomic Number	X	Y	Z
1 2 3 4 5 6 7 8	6 9 1 1 6 1 1 8	0.000009752 −0.000007540 −0.000006175 −0.000001921 −0.000095473 0.000036312 0.000030627 0.000034418	0.000030682 0.000018428 −0.000009977 −0.000005002 −0.000015917 −0.000025722 0.000027608 −0.000020100	0.000120978 −0.000104164 −0.000011573 −0.000038255 0.000025447 0.000008467 −0.000011892 0.000010992
CH₂•CHFOH		Cartesian Coordinates
Center Number	Atomic Number	X	Y	Z
1 2 3 4 5 6 7 8	6 6 1 1 9 1 8 1	0.000014779 −0.000030495 0.000010354 −0.000018812 0.000041121 0.000011136 −0.000010627 −0.000017456	0.000033223 −0.000005099 −0.000009796 −0.000018702 0.000009214 −0.000017220 0.000005847 −0.000007665	−0.000005569 0.000010101 −0.000011520 −0.000000754 −0.000011106 0.000008038 0.000010223 0.000000588
CH₃CF•OH		Cartesian Coordinates
Center Number	Atomic Number	X	Y	Z
1 2 3 4 5 6 7 8	6 6 1 1 1 9 8 1	0.000001336 −0.000071306 −0.000014952 −0.000000203 −0.000029193 0.000068515 0.000028358 0.000017444	0.000012708 0.000036407 −0.000021374 0.000002487 0.000004057 0.000006342 −0.000032227 −0.000008399	−0.000046895 0.000029101 −0.000009157 0.000002208 0.000022548 −0.000002103 0.000010729 −0.000006430
CH₃CHFO•		Cartesian Coordinates
Center Number	Atomic Number	X	Y	Z
1 2 3 4 5 6 7 8	6 6 1 1 1 9 1 8	−0.000025583 −0.000004925 −0.000016576 −0.000010431 −0.000006608 0.000038154 0.000017550 0.000008419	0.000026726 −0.000017774 0.000000727 0.000004336 0.000007692 −0.000008832 −0.000008997 −0.000003878	0.000006931 −0.000022873 −0.000013731 0.000014687 −0.000003229 0.000013405 −0.000000815 0.000005626

CH₂FCHFOH		Cartesian Coordinates
Center Number	Atomic Number	X	Y	Z
1 2 3 4 5 6 7 8 9	6 6 9 1 1 9 1 8 1	−0.000209387 −0.000078791 0.000055970 0.000037582 0.000008069 0.000213499 −0.000002897 −0.000003076 −0.000020969	−0.000014742 −0.000026117 −0.000014001 0.000003431 −0.000003401 −0.000011196 0.000018025 0.000003947 0.000044055	−0.000046791 −0.000054220 0.000038779 0.000025080 0.000000786 0.000078222 −0.000024730 −0.000028849 0.000011724
CF₂HCH₂OH		Cartesian Coordinates
Center Number	Atomic Number	X	Y	Z
1 2 3 4 5 6 7 8 9	6 6 9 9 1 1 1 8 1	−0.000006264 0.000196771 −0.000177152 0.000058924 −0.000009820 −0.000016810 −0.000014380 −0.000035113 0.000003845	−0.000010001 −0.000004891 −0.000024722 0.000072953 0.000002957 −0.000024610 0.000016248 −0.000034435 0.000006502	−0.000015081 0.000062245 −0.000031629 −0.000005858 −0.000026980 0.000029199 −0.000024677 0.000010637 0.000002145
CH₃CF₂OH		Cartesian Coordinates
Center Number	Atomic Number	X	Y	Z
1 2 3 4 5 6 7 8 9	6 6 1 1 1 9 9 8 1	0.000056837 −0.000057651 0.000011317 0.000014600 −0.000001272 −0.000131047 0.000140461 −0.000014132 −0.000019113	−0.000094451 0.000098699 −0.000004093 −0.000025891 −0.000012112 −0.000088396 0.000063879 0.000020314 0.000042051	0.000110833 0.000001478 −0.000026345 −0.000015228 −0.000025019 0.000020206 0.000020905 −0.000026071 −0.000060759
CH₂FC•FOH		Cartesian Coordinates
Center Number	Atomic Number	X	Y	Z
2 3 4 5 6 7 8	6 9 1 1 9 8 1	0.000107121 −0.000086887 −0.000015313 0.000000240 0.000003934 0.000076030 0.000000747	0.000054590 −0.000026092 −0.000013867 −0.000001842 0.000030284 0.000051318 0.000022936	0.000053325 −0.000005448 −0.000003160 −0.000016239 0.000010058 −0.000056283 0.000051063

C•HFCFHOH		Cartesian Coordinates
Center Number	Atomic Number	X	Y	Z
1 2 3 4 5 6 7 8	6 6 9 1 9 1 8 1	−0.000058756 −0.000088748 0.000068251 0.000023870 0.000011825 −0.000011611 0.000047202 0.000007966	0.000023216 −0.000108788 0.000068970 0.000025841 −0.000021999 0.000023111 0.000013830 −0.000024181	0.000035904 −0.000099552 0.000065027 0.000034527 −0.000019250 −0.000006306 −0.000008891 −0.000001459
CH₂FCHFO•		Cartesian Coordinates
Center Number	Atomic Number	X	Y	Z
1 2 3 4 5 6 7 8	6 6 9 1 1 9 1 8	−0.000043639 0.000048716 −0.000022444 0.000001695 0.000003424 0.000023881 0.000006948 −0.000018580	0.000033246 −0.000026830 0.000006378 0.000020117 0.000009684 0.000019171 −0.000005119 −0.000056646	0.000009821 −0.000018036 −0.000008784 0.000006913 0.000001110 0.000030292 0.000004871 −0.000026187
CHF₂C•HOH		Cartesian Coordinates
Center Number	Atomic Number	X	Y	Z
1 2 3 4 5 6 7 8	6 6 1 8 1 1 9 9	0.000004676 0.000027275 −0.000013476 0.000006557 0.000018970 −0.000051957 −0.000013983 0.000021937	−0.000070251 −0.000132737 0.000008382 0.000005715 −0.000003557 −0.000006265 0.000033076 0.000165638	0.000051141 −0.000118944 0.000015950 −0.000023257 0.000007094 −0.000015262 0.000051050 0.000032227
CF₂•CFOH		Cartesian Coordinates
Center Number	Atomic Number	X	Y	Z
1 2 3 4 5 6 7 8	6 6 1 8 1 1 9 9	0.000045030 0.000001125 −0.000002716 −0.000050429 −0.000005831 −0.000015223 0.000011981 0.000016063	0.000052085 0.000036125 0.000001155 −0.000036049 −0.000009141 0.000001185 −0.000006184 −0.000039174	−0.000051151 0.000024114 0.000006275 0.000025853 −0.000009552 0.000012909 0.000002242 −0.000010691

CHF₂CH₂O•		Cartesian Coordinates
Center Number	Atomic Number	X	Y	Z
1 2 3 4 5 6 7 8	6 6 9 9 1 1 1 8	−0.000032920 −0.000030593 −0.000036099 −0.000006345 −0.000014790 0.000040237 0.000038791 0.000041718	−0.000119205 −0.000022551 0.000010735 −0.000017725 −0.000026477 0.000019571 0.000046905 0.000108747	0.000076072 −0.000053428 0.000025263 −0.000018129 0.000021461 −0.000021746 −0.000010985 −0.000018508
CH₂•CF₂OH		Cartesian Coordinates
Center Number	Atomic Number	X	Y	Z
2 3 4 5 6 7 8	6 1 1 9 9 8 1	−0.000001071 0.000004590 0.000019461 −0.000009537 −0.000017948 0.000001500 −0.000006214	−0.000001757 0.000002074 0.000007677 −0.000013694 0.000004296 0.000001265 −0.000001754	−0.000000838 0.000000801 −0.000000682 −0.000009305 0.000010263 0.000000690 −0.000000488
CH₃CF₂O•		Cartesian Coordinates
Center Number	Atomic Number	X	Y	Z
1 2 3 4 5 6 7 8	6 6 1 1 1 9 9 8	−0.000049808 0.000314370 −0.000001882 0.000007442 0.000007479 −0.000225548 −0.000008257 −0.000043796	0.000049564 −0.000446227 0.000003042 0.000003265 −0.000020681 0.000114125 0.000232988 0.000063924	0.000101113 −0.000322008 0.000019595 −0.000034062 0.000033341 0.000063416 0.000078418 0.000060187

Table S2 Frequencies for target fluorinated ethanol and their related radicals at the m062x/6-31 + g (d, p) level of theory (cm−1)

Target fluorinated ethanol	Frequencies (cm⁻¹)
CH₂FCH₂OH	153.7115 526.9463 1084.2017 1227.6058 1406.9769 1503.3220 3119.3826	318.4318 879.0892 1123.0654 1278.1133 1443.0414 3040.8126 3144.6188	395.2338 913.6087 1155.2746 1382.4638 1499.5695 3082.2806 3895.3665

CH₃CHFOH	222.4821 476.6613 967.7343 1207.0636 1408.6162 1496.5668 3162.1117	381.0906 591.2739 1083.1639 1299.2263 1481.8193 3074.8833 3168.6137	395.9003 882.7961 1139.5797 1395.3640 1491.1530 3098.4238 3905.4122
C•HFCH₂OH	117.2311 487.0844 1047.2118 1230.9543 1433.9762 3135.9012	305.3799 672.8813 1078.4074 1340.0387 1486.8167 3227.9702	387.2015 897.2987 1202.2847 1397.8007 3060.3820 3904.1459
CH₂FCH•OH	136.3261 469.7867 976.5181 1261.6997 1477.7581 3148.4826	293.7121 588.3163 1064.6622 1324.3255 1517.2468 3209.7826	372.9921 948.2198 1237.5557 1380.0377 3089.0157 3921.1700
CH₂FCH₂O•	138.8341 645.0346 095.1447 287.6953 436.1160 021.0190	326.2587 900.2694 1132.5555 1366.6408 1499.8795 3079.4857	461.7143 995.0829 1209.7403 1397.9225 2978.3111 3141.2839
CH₂•CHFOH	103.9492 464.4234 917.9447 1204.3179 1421.9543 3176.3175	354.4677 533.4936 973.1708 1292.9244 1501.7259 3301.9307	378.6019 615.0872 1082.8162 1375.2909 3093.4946 3902.4787
CH₃CF•OH	183.0404 446.3670 992.1200 1302.2104 1477.4645 3128.3197	339.6091 566.0359 1063.5695 1363.7386 1485.2396 3174.6193	381.8885 874.2810 1140.5736 1442.6873 3031.7545 3874.3729
CH₃CHFO•	234.8451 572.8867 1040.2264 1216.4848 1484.8041 3077.4025	359.2559 866.7266 1088.1878 1326.7171 1492.1170 3170.0581	443.1211 929.6382 1158.3501 1391.8028 2997.0767 3179.9978

CH₂FCHFOH	123.7297 442.3530 932.9529 1132.3163 1341.7047 1477.0191 3141.2603	253.3055 508.5501 1049.0131 1216.5809 1356.5333 1509.6783 3156.9890	341.9812 585.7551 1096.9489 1244.5656 1432.8601 3073.3252 3868.8911
CF₂HCH₂OH	261.5051 803.8978 1113.2025 1377.1368 1493.5768 3032.2176 3125.0745	333.1831 905.9089 1153.4006 1403.4215 1500.2248 3044.0073 3137.9412	429.7499 1069.3307 1280.2493 1433.7765 1525.4172 3104.6932 3910.0283
CH₃CF₂OH	213.0609 407.4641 584.5503 1000.3581 1301.5094 1488.5073 3175.9594	336.6797 552.4402 847.6087 1135.7264 1390.3411 1492.2192 3186.0332	378.8026 575.8400 959.8589 1204.1092 1483.7215 3086.0281 3866.1356
CH₂FC•FOH	109.4115 436.4869 917.0734 1135.9138 1365.0202 3049.1641	244.9232 472.3557 1055.3780 1244.9454 1448.3398 3148.5710	388.6686 575.6453 1102.3841 1336.2661 1502.9979 3871.9507
C•HFCFHOH	107.9351 416.6962 765.4796 1161.1762 1356.7224 3148.9051	257.2006 546.9238 916.4141 1227.5285 1403.4567 3254.0619	353.4210 646.1233 991.0405 1327.6897 1473.0076 3863.4809
CH₂FCHFO•	122.5173 426.8055 981.5646 1159.6593 1306.1655 3020.9800	253.1428 595.6816 1062.7404 1193.8858 1411.2155 3106.4335	406.6622 922.4453 1130.5318 1264.5276 1509.8582 3176.7438
CHF₂C•HOH	102.5287 498.7454 776.4400 1117.9847 1361.3396 3165.5275	255.5062 531.8669 943.7162 1203.9780 1407.7937 3252.1304	307.6957 588.6407 1040.6628 1346.8684 1499.6505 3846.9473

C•F₂CH₂OH	111.2059 439.8572 889.8898 1208.8861 1380.7274 3013.5503	240.3480 476.0825 1035.2006 1259.6672 1441.8811 3147.9499	355.7645 590.2258 1136.6153 1294.5087 1496.7631 3898.0279
CHF₂CH₂O•	128.4545 494.0758 1096.8914 1232.6325 1404.8759 3031.4094	257.5539 586.0455 1139.6268 1307.2674 1510.7673 3120.2437	433.4387 917.5567 1157.8405 1385.1305 1859.0406 3174.3851
CH₂•CF₂OH	90.5157 392.3412 593.9731 960.9120 1308.1224 3211.2694	313.8094 492.4899 597.4030 1070.4557 1403.4875 3342.0724	380.5941 547.1101 869.8795 1131.1978 1499.7334 3863.9788
CH₃CF₂O•	168.6127 534.8395 846.1077 1162.5612 1397.7811 3077.0770	340.9654 551.7060 915.5633 1220.2174 1466.2734 3170.5354	360.5945 557.0587 974.0145 1281.3277 1488.6608 3190.3722

Table S3 Moment of inertia for target fluorinated ethanol and their related radicals at the m062x/6-31 + g (d, p) level of theory (GHZ)

target fluorinated ethanol	Moment of inertia(GHZ)
CH₂FCH₂OH	15.7788859	5.5493007	4.6093694
CH₃CHFOH	10.0766267	8.3371985	5.1680915
C•HFCH₂OH	18.77997	5.13190	4.51693
CH₂FCH•OH	23.2409534	4.5476319	4.3485670
CH₂FCH₂O•	18.24036	5.23748	4.59279
CH₂•CHFOH	10.3760339	9.1250064	5.3599040
CH₃CF•OH	10.20355	9.05876	5.07651
CH₃CHFO•	10.7702750	8.5850705	5.3185779
CH₂FCHFOH	9.4161023	3.5112856	2.7600267
CF₂HCH₂OH	34.8864548	9.2467926	8.1783038
CH₃CF₂OH	9.4161023	3.5112856	2.7600267
CH₂FC•FOH	9.7798799	3.5506736	2.7289504
C•HFCFHOH	9.5295647	3.7425748	2.9008390
CH₂FCHFO•	10.2331738	3.5038934	2.8019184
CHF₂C•HOH	9.1000423	3.8971695	3.0141244
C•F₂CH₂OH	9.6401202	3.8114853	2.8520087
CHF₂CH₂O•	9.21258	3.85327	2.93914
CH₂•CF₂OH	5.7024545	5.2730634	5.1759614
CH₃CF₂O•	5.9149594	5.2219748	5.0070937

Optimized Geometries for target fluorinated ethanol and their related radicals at the m062x/6-31 + g (d, p) level of theory

Table S4 The method of standard deviation and example calculation

The standard deviation is calculated using the following formula (36): σ = 1 N ∑ i = 1 N ( x i − μ ) 2 where, x i is the mean; the average of the numbers, µ is the actual numbers to be calculated the standard deviation of, and 1 N ∑ i = 1 N ( x i − μ ) 2 is the variance. The standard deviation for standard enthalpy of formation for 1-fluroethanol is calculated to be ± 0.1. The calculation of standard deviation for this molecule is as follows: N = 2, µ₁ = −101.60, µ₂ = −101.86 Step 1, X_i = (−101.60 − 101.86)/2 = −101.73 Step 2, (X_i − µ₁) = (−101.73 + 101.60)² = 0.0169 (X_i − µ₂) = (−101.73 + 101.86)² = 0.0169 Step 3, 1/2 (0.0169 + 0.0169) = 0.0169 Step 4, square root of 0.0169 = 0.13 = ±0.1

References1

Wallington, T.J., Schneider, W.F., Worsnop, D.R., Nielsen, O.J., Sehested, J., Debruyn, W.J. and Shorter, J.A. (1994) The Environmental Impact of CFC Replacements HFCs and HCFCs. Environmental Science & Technology, 28, 320A-326A. https://doi.org/10.1021/es00056a714

Wang, H., Castillo, A. and Bozzelli, J.W. (2015) Thermochemical Properties Enthalpy, Entropy, and Heat Capacity of C1-C4 Fluorinated Hydrocarbons: Fluorocarbon Group Additivity. The Journal of Physical Chemistry A, 119, 8202-8215. https://doi.org/10.1021/acs.jpca.5b03912

Schneider, W.F. and Wallington, T.J. (1993) Ab Initio Investigation of the Heats of Formation of Several Trifluoromethyl Compounds. The Journal of Physical Chemistry, 97, 12783-12788. https://doi.org/10.1021/j100151a025

Wang, H. and Bozzelli, J.W. (2016) Thermochemical Properties and Bond Dissociation Energies for Fluorinated Methanol, CH3-xFxOH, and Fluorinated Methyl Hydroperoxides, CH3-xFxOOH: Group Additivity. The Journal of Physical Chemistry A, 120, 6998-7010.

Ruscic, B. (2015) Active Thermochemical Tables: Sequential Bond Dissociation Enthalpy of Methane, Ethane, and Methanol and Related Thermochemistry. The Journal of Physical Chemistry A, 119, 7810-7837. https://doi.org/10.1021/acs.jpca.5b01346

Burke, S.M., Simmie, J.M. and Curran, H.J. (2015) Critical Evaluation of Thermochemical Properties of C1-C4 Species: Updated Group Contributions to Estimate Thermochemical Properties. Journal of Physical and Chemical Reference Data, 44, Article ID: 013101. https://doi.org/10.1063/1.4902535

Chase, M.W.J. (1998) NIST-JANAF Thermochemical Tables (Journal of Physical and Chemical Reference Data). Monograph No. 9, 1-1951.

Luo, X., Fleming, P.R. and Rizzo, T.R. (1992) Vibrational Overtone Spectroscopy of the 4νOH + νOH’ Combination Level of HOOH via Sequential Local Mode-Local Mode Excitation. The Journal of Chemical Physics, 96, 5659-5667. https://doi.org/10.1063/1.462665

Bodi, A., Kercher, J.P., Bond, C., Meteesatien, P., Sztaray, B. and Baer, T. (2006) Photoion Photoelectron Coincidence Spectroscopy of Primary Amines RCH2 NH2 (R = H, CH3, C2H5, C3H7, i-C3H7): Alkylamine and Alkyl Radical Heats of Formation by Isodesmic Reaction Networks. The Journal of Physical Chemistry A, 110, 13425-13433. https://doi.org/10.1021/jp064739s

Wang, H. and Bozzelli, J.W. (2016) Thermochemical Properties (ΔfH°(298 K), S°(298 K), C p(T)) and Bond Dissociation Energies for C1-C4 Normal Hydroperoxides and Peroxy Radicals. Journal of Chemical & Engineering Data, 61, 1836-1849. https://doi.org/10.1021/acs.jced.5b01035

Csontos, J., Rolik, Z., Das, S. and Kallay, M. (2010) High-Accuracy Thermochemistry of Atmospherically Important Fluorinated and Chlorinated Methane Derivatives. The Journal of Physical Chemistry A, 114, 13093-13103. https://doi.org/10.1021/jp105268m

Expanding the Limits of Computational Chemistry, 2015-2019 (2020) Density Function Method. https://gaussian.com/dft

NIST Computational Chemistry Comparison and Benchmark Database, NIST Standard Reference Database Number 101, Release 16a; Johnson, R.D. III, Ed., NIST: Gaithersburg, MD. http://cccbdb.nist.gov

Sheng, C. (2002) 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, Newark.

Becke, A.D. (1993) Density-Functional Thermochemistry. III. The Role of Exact Exchange. The Journal of Chemical Physics, 98, 5648-5652. https://doi.org/10.1063/1.464913

Lay, T.H., Krasnoperov, L.N., Venanzi, C.A., Bozzelli, J.W. and Shokhirev, N.V. (1996) Ab Initio Study of α-Chlorinated Ethyl Hydro Peroxides CH3CH2OOH, CH3CHClOOH, and CH3CCl2OOH: Conformational Analysis, Internal Rotation Barriers, Vibrational Frequencies, and Thermodynamic Properties. The Journal of Physical Chemistry, 100, 8240-8249. https://doi.org/10.1021/jp952976h

Math Is Fun Advanced, 2017. Standard Deviation and Variance. https://www.mathsisfun.com/data/standard-deviation.html

Myrna, H.M., Minh, T.N., David, A.D. and Minh, T.N. (2007) 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. The Journal of Physical Chemistry A, 111, 113-126.