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Tab. 7.2 (continued)
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7.3 Experimental and Data 69
Isodesmic Reactions
Target Specie
Reported ΔfH° () kcal mol
Standard Deviation over rxns .
–
kcal mol
–
CHFCHFOH + CHCH=CHCHOH
+CH
CF
–. –. –.
–.
–. –. – .
CHFOH + CH=CHCHOH
CHF
+ CHF
–. –. –.
–.
–. –. – .
Reported Δ
Standard Deviation over rxns .
kcal mol
H° () kcal mol
f
–
–
C•FCHFOH + CH=CHCHO•
+CHF
–. –. –.
–.
–. –. –.
CHFOH + CHCH=CHCHO• +
C•F
CH
CF
–. –. –.
–.
–. –. –.
Reported Δ
Standard Deviation over rxns .
kcal mol
H° () kcal mol
f
–
–
CHFC•FOH + CHCH=CHCHO• +
CH
CF
–. –. –.
–.
–. –. –.
ΔH°
Rxn ()
Hartrees
ΔH°
Rxn ()
Kcal/mole
ΔfH°
()
kcal mol
Error
–
kcal
mol
–.±.
–. –. –. ±.
. . –. ±.
–.±.
. . –. ±.
–. –. –. ±.
–.
±.
–. –. –. ±,
–
70 7 Enthalpy and Bond Dissociation Energy Values for Multifluorinated Ethanol
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Tab. 7.2 (continued)
Isodesmic Reactions
Target Specie
ΔH°
Rxn ()
Hartrees
ΔH°
Rxn ()
Kcal/mole
ΔfH°
()
kcal mol
Error
–
kcal
mol
CHFC•FOH + CHCHCH=CHCHO• +
CH
CHCF
–. –. –. ±.
–. –. –.
–.
–. –. –.
Reported Δ
Standard Deviation over rxns .
kcal mol
H° () kcal mol
f
–
CHFCHFO• +CH=CHCHO• + CHF
–
–. –. –. ±.
–.±.
–. –. –.
–.
–. –.
–.
CHFO• +CHCHCH=CHCHO• +
CHF
CH
CHCF
–. –. –. ±.
–. –.–.
–.
–. –. –.
Reported Δ
Standard Deviation over rxns .
kcal mol
H° () kcal mol
f
–
–
–.±.
CHFCFOH + CH=CHCHOH + CHF. . –. ±.
–. –. –.
–.
–. –. – .
FCFOH +CHCH=CHCHOH
CH
+CH
CF
–. –. –. ±.
–. –. –.
–.
–. –. – .
Reported Δ
Standard Deviation over rxns .
kcal mol
H° () kcal mol
f
–
C•HFCFOH + CH=CHCHO•+ CHF
–
. . –. ±.
–.±.
–. –. –.
–.
–. –. –.
–
Tab. 7.2 (continued)
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7.3 Experimental and Data 71
Isodesmic Reactions
Target Specie
C•HFCFOH + CHCH=CHCHO•+
CH
CF
–. –. –.
–.
–. –. –.
Reported Δ
Standard Deviation over rxns .
kcal mol
H° () kcal mol
f
–
CHFCFO• +CH=CHCHO• +CHF
–
–. –. –.
–.
–. –. –.
FCFO• +CHCH=CHCHO•+
CH
CH
CF
–. –. –.
–.
–. –. –.
Reported Δ
Standard Deviation over rxns .
kcal mol
H° () kcal mol
f
–
CFCFHOH + CH=CHCHOH+ CF
–
–. –. –.
–.
–. –. – .
CFHOH + CHCH=CHCHOH +
CF
CHF
CHF
–. –. –.
–.
–. –. – .
Reported Δ
Standard Deviation over rxns .
kcal mol
H° () kcal mol
f
–
CFC•FOH + CH=CHCHO•+CF
–
–. –. –.
–.
–. –. –.
ΔH°
Rxn ()
Hartrees
ΔH°
Rxn ()
Kcal/mole
ΔfH°
()
kcal mol
Error
–
kcal
mol
–. –. –. ±.
–.±.
–. –. –. ±.
–. –. –. ±.
–.±.
. . –. ±.
. . –. ±.
–.±.
. . –. ±.
–
72 7 Enthalpy and Bond Dissociation Energy Values for Multifluorinated Ethanol
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Tab. 7.2 (continued)
Isodesmic Reactions
Target Specie
CFC•FOH + CHCH=CHCHO•
CHF
+ CHF
–. – . –.
–.
–. –. –.
Reported Δ
Standard Deviation over rxns .
kcal mol
H° () kcal mol
f
–
CFCFHO• +CH=CHCHO•+CF
–
–. –. –.
–.
–. –. –.
CFHO• +CHCH=CHCHO• +
CF
CHF
CHF
–. –. –.
–.
–. –. –.
Reported Δ
Standard Deviation over rxns .
kcal mol
H° () kcal mol
f
–
CFHCFOH + CH=CHCHOH+ CF
–
–. – . –.
–.
–. –. – .
HCFOH + CHCH=CHCHOH+
CF
CHF
CHF
–. –. –.
–.
–. –. – .
Reported Δ
Standard Deviation over rxns .
kcal mol
H° () kcal mol
f
–
C•FCFOH + CH=CHCHO• +CF
–
–. –. –.
–.
–. –. –.
ΔH°
Rxn ()
Hartrees
ΔH°
Rxn ()
Kcal/mole
ΔfH°
()
kcal mol
Error
–
kcal
mol
. . –. ±.
–.±.
–. –. –. ±.
. . –. ±.
–.±.
. . –. ±.
. . –. ±.
–.±.
–.E– –. –. ±.
–
Tab. 7.2 (continued)
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7.3 Experimental and Data 73
Isodesmic Reactions
Target Specie
ΔH°
Rxn ()
Hartrees
ΔH°
Rxn ()
Kcal/mole
ΔfH°
()
kcal mol
Error
–
kcal
mol
C•FCFOH + CHCH=CHCHO• +
CHF
CHF
. . –. ±.
–. –. –.
–.
–. –. –.
Reported Δ
Standard Deviation over rxns .
kcal mol
H° () kcal mol
f
–
–
–.±.
CFHCFO• +CH=CHCHO• +CF –. –. –. ±.
–.–. –.
–.
–. –. –.
HCFO• +CHCH=CHCHO• +
CF
CHF
CHF
. . –. ±.
–. –. –.
–.
–. –. –.
Reported Δ
Standard Deviation over rxns .
kcal mol
H° () kcal mol
f
–
CFCFOH + CHCHCH=CHCHOH
CHF
+CF
CH
–
–.±.
. . –. ±.
–. –.–.
–.
–. –. – .
OH + CHCH=CHCHOH+
CF
CF
CHF
CF
. . –. ±.
–. –. –.
–.
–. –. – .
OH + CH=CFOH+ CHCHF
CF
CF
–. –. –. ±.
–. –.
–.–.
–. –. –.
–
74 7 Enthalpy and Bond Dissociation Energy Values for Multifluorinated Ethanol
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Tab. 7.2 (continued)
Isodesmic Reactions
Target Specie
Reported ΔfH° () kcal mol
Standard Deviation over rxns .
–
kcal mol
CFCFO• +CH= CHFO• +CHCF
–
ΔH°
Rxn ()
Hartrees
ΔH°
Kcal/mole
–. –. –. ±.
–. –. –.
–.
–. –. – .
O• +CHCHCH=CHCHO•
CF
CF
CHF
+CF
CH
–. –. –. ±.
–. –. –.
–.
–. –. –.
O• +CHCH=CHCHO•+
CF
CF
CHF
CF
. . –. ±.
–. –. –.
–.
–. –. –.
Reported Δ
Standard Deviation over rxns .
kcal mol
Hartrees, kcal mole
✶
SD Standard Deviation kcal mol
H° () kcal mol
f
–
-1
–
-1
Errors reported avg of sum of uncertainties in rxn’ s reference species
Rxn ()
ΔfH°
()
kcal mol
Error
–
kcal
–
mol
–.±.
–.±.
7.3.5 Bond Energies
The calculated BDE values in kcal/mol for methyl C–H, ethyl C–H, and hydroxyl O–H
bonds are listed in Tab. 7.3.
The difference in BDEs of products and reactants for hemolysis is called the BDE.
The BDE values don’t depend on the pathway by which it occurs; it doesn’t depend on
how bonds are formed or on how bonds break. Therefore, BDEs are state functions.
Energetics of chemical processes can be assessed using BDE values.
7.3 Experimental and Data 75
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Tab. 7.3: Bond dissociation energy (BDE) of tri-, tetra-, and penta-fluorinated ethanols using Gaussian
M-062x/6-31 + g (d,p) method of calculation.
Reactions Bond Dissociation Energy
a
(Kcal mol-)
✶
Error
Kcal mol
CFCH–HOH .± . ± .
CF
CH–HOH =H• + CFCH• OH
–. ±. . –.±.
O–H .±. ±.
CF
CH
CF
O–H =H• + CFCHO•
CH
–. ±. . –.±.
CHFOH .±. ±.
C–HF
C–HF
CHFOH =H• + C• FCHFOH
–.±. . –. ±.
C–HFOH .±. ±.
CHF
CHF
C–HFOH =H• + CHFC• FOH
–.±. . –.±.
CHFO–H .±. ±.
CHF
CHF
CHFO–H =H• + CHFCHFO•
–.±. . –.±.
HC–HFCF
HC–HFCF
OH .±. ±.
OH =H• + C• HFCFOH
–.±. . –.±.
FCFO–H .±. ±.
CH
CH
FCFO–H=H• + CHFCFO•
–.±. . –.±.
CF–HOH .±. ±.
CF
CF
CF–HOH=H• + CFCF• OH
–.±. . –.±.
CFHO–H .±. ±.
CF
CF
CFHO–H=H• + CFCFHO•
–.±. . –.±.
–HCFOH .±. ±.
CF
CF
–HCFOH=H• + CF• CFOH
–.±. . –.±.
HCFO–H .±. ±.
CF
CF
HCFO–H=H• + CFHCFO•
–.±. . –.±.
O–H .±. ±.
CF
CF
CF
O–H=H• +CFCFO•
CF
–.±. . –.±.
✶
Errors reported avg of sum of uncertainties in rxn’s reference specie
–
76 7 Enthalpy and Bond Dissociation Energy Values for Multifluorinated Ethanol
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7.4 Optimized Structures
The GaussView software has been utilized along with Gaussian output files to provide
a picture of the Gaussian M06-2x/6-31 + g (d,p) optimized structure for each molecule
in this chapter (Tab. 7.4).
Tab. 7.4: Optimized geometries for target tri-,
tetra-, and penta-fluorinated ethanols and
their related radicals calculated by Gaussian
M06-2x/6-31 + g (d,p) level of theory.
OH
CF
3CH2
F
F
CF3CH•OH
F
F
CF3CH2O•
F
H
C
H
C
O
C
H
F
C
F
H
H
O
H
O
C
C
F
F
H
Tab. 7.4 (continued)
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CHF
CHFOH
2
7.4 Optimized Structures 77
F
C•F2CHFOH
F
CHF2C•FOH
F
F
F
C
H
F
C
F
H
O
C
H
H
C
C
F
C
O
H
O
O
H
H
CHF2CHFO•
F
F
H
C
F
O
C
F
H
78 7 Enthalpy and Bond Dissociation Energy Values for Multifluorinated Ethanol
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Tab. 7.4 (continued)
CH
FCF2OH
2
H
F
C•HFCF2OH
H
CH2FCF2O•
H
F
F
C
H
C
F
O
C
H
F
C
O
H
F
F
C
O
H
F
C
F
CF3CFHOH
H
F
F
C
F
O
H
C
F
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