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Carbonic difluoride


Gas phase ion energetics data

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Data compilation copyright by the U.S. Secretary of Commerce on behalf of the U.S.A. All rights reserved.

Data evaluated as indicated in comments:
HL - Edward P. Hunter and Sharon G. Lias
L - Sharon G. Lias

Data compiled as indicated in comments:
B - John E. Bartmess
LL - Sharon G. Lias and Joel F. Liebman
LLK - Sharon G. Lias, Rhoda D. Levin, and Sherif A. Kafafi
RDSH - Henry M. Rosenstock, Keith Draxl, Bruce W. Steiner, and John T. Herron

View reactions leading to CF2O+ (ion structure unspecified)

Quantity Value Units Method Reference Comment
IE (evaluated)13.04 ± 0.03eVN/AN/AL
Quantity Value Units Method Reference Comment
Proton affinity (review)666.7kJ/molN/AHunter and Lias, 1998HL
Quantity Value Units Method Reference Comment
Gas basicity637.0kJ/molN/AHunter and Lias, 1998HL
Quantity Value Units Method Reference Comment
Deltaf(+) ion649.kJ/molN/AN/A 
Quantity Value Units Method Reference Comment
DeltafH(+) ion,0K653.kJ/molN/AN/A 

Ionization energy determinations

IE (eV) Method Reference Comment
13.035 ± 0.030PIBuckley, Johnson, et al., 1995LL
13.04PEThomas and Thompson, 1972LLK
13.02PEBrundle, Robin, et al., 1972LLK
13.2 ± 0.1EIWorkman and Duncan, 1970RDSH
14.6 ± 0.1EIThynne and MacNeil, 1970RDSH
13.6PEJohnson, Powis, et al., 1979Vertical value; LLK

Appearance energy determinations

Ion AE (eV) Other Products MethodReferenceComment
C+36. ± 1.2F+O?EIThynne and MacNeil, 1970RDSH
CF+27.0 ± 0.3?EIThynne and MacNeil, 1970RDSH
CFO+14.736 ± 0.012FPIBuckley, Johnson, et al., 1995LL
CFO+14.9 ± 0.2FPIJohnson, Powis, et al., 1979LLK
COF+16.0 ± 0.1FEIThynne and MacNeil, 1970RDSH
CF2+25.6 ± 0.3OEIThynne and MacNeil, 1970RDSH
F+38. ± 1.?EIThynne and MacNeil, 1970RDSH
O+35. ± 1.?EIThynne and MacNeil, 1970RDSH

De-protonation reactions

CF3O- + Hydrogen cation = Carbonic difluoride

By formula: CF3O- + H+ = CF2O

Quantity Value Units Method Reference Comment
Deltar1380. ± 8.4kJ/molG+TSHuey, Dunlea, et al., 1996gas phase; Agrees with G2 calculation: Segovia and Ventura, 1997, Burk, Koppel, et al., 2000, Chyall and Squires, 1996; B
Deltar1454. ± 7.9kJ/molG+TSTaft, Koppel, et al., 1990gas phase; In conflict with Huey, Dunlea, et al., 1996. Bracketing here may be for CF3O- + AH -> CF2=O + HF + A-.; B
Deltar<1431. ± 7.5kJ/molD-EAHuey, Dunlea, et al., 1996gas phase; EA > NO3; B
Deltar1405.1kJ/molAcidLarson and McMahon, 1983gas phase; These relative affinities are ca. 10 kcal/mol weaker than threshold values (see Wenthold and Squires, 1995) for donors greater than ca. 27 kcal/mol in free energy. This discrepancy has not yet been resolved, though the stronger value appears preferable.; B
Quantity Value Units Method Reference Comment
Deltar1351. ± 6.7kJ/molIMRBHuey, Dunlea, et al., 1996gas phase; Agrees with G2 calculation: Segovia and Ventura, 1997, Burk, Koppel, et al., 2000, Chyall and Squires, 1996; B
Deltar1425. ± 6.3kJ/molIMRBTaft, Koppel, et al., 1990gas phase; In conflict with Huey, Dunlea, et al., 1996. Bracketing here may be for CF3O- + AH -> CF2=O + HF + A-.; B
Deltar1377. ± 5.0kJ/molH-TSLarson and McMahon, 1983gas phase; These relative affinities are ca. 10 kcal/mol weaker than threshold values (see Wenthold and Squires, 1995) for donors greater than ca. 27 kcal/mol in free energy. This discrepancy has not yet been resolved, though the stronger value appears preferable.; B

References

Go To: Top, Gas phase ion energetics data, Notes

Data compilation copyright by the U.S. Secretary of Commerce on behalf of the U.S.A. All rights reserved.

Hunter and Lias, 1998
Hunter, E.P.; Lias, S.G., Evaluated Gas Phase Basicities and Proton Affinities of Molecules: An Update, J. Phys. Chem. Ref. Data, 1998, 27, 3, 413-656, https://doi.org/10.1063/1.556018 . [all data]

Buckley, Johnson, et al., 1995
Buckley, T.J.; Johnson, R.D.; Huie, R.E.; Zhang, Z.; Kuo, S.C.; Klemm, R.B., Ionization energies, appearance energies, and thermochemistry of CF2O and FCO, J. Phys. Chem., 1995, 99, 4879. [all data]

Thomas and Thompson, 1972
Thomas, R.K.; Thompson, H., Photoelectron spectra of carbonyl halides and related compounds, Proc. R. Soc. London A:, 1972, 327, 13. [all data]

Brundle, Robin, et al., 1972
Brundle, C.R.; Robin, M.B.; Kuebler, N.A.; Basch, H., Perfluoro effect in photoelectron spectroscopy. I. Nonaromatic molecules, J. Am. Chem. Soc., 1972, 94, 1451. [all data]

Workman and Duncan, 1970
Workman, G.L.; Duncan, A.B.F., Electronic spectrum of carbonyl fluoride, J. Chem. Phys., 1970, 52, 3204. [all data]

Thynne and MacNeil, 1970
Thynne, J.C.J.; MacNeil, K.A.G., Ionisation and dissociation of carbonyl fluoride and trifluoromethyl hypofluorite by electron impact, Intern. J. Mass Spectrom. Ion Phys., 1970, 5, 95. [all data]

Johnson, Powis, et al., 1979
Johnson, K.M.; Powis, I.; Danby, C.J., The fragmentation of COCl2+ and COF2+ ions studied by the photoelectron-photoion coincidence technique, Int. J. Mass Spectrom. Ion Phys., 1979, 32, 1. [all data]

Huey, Dunlea, et al., 1996
Huey, L.G.; Dunlea, E.J.; Howard, C.J., Gas-Phase Acidity of CF3OH, J. Phys. Chem., 1996, 100, 16, 6504, https://doi.org/10.1021/jp953058m . [all data]

Segovia and Ventura, 1997
Segovia, M.; Ventura, O.N., Density functional and G2 study of the strength of the OH bond in CF3OH, Chem. Phys. Lett., 1997, 277, 5-6, 490-496, https://doi.org/10.1016/S0009-2614(97)00860-9 . [all data]

Burk, Koppel, et al., 2000
Burk, P.; Koppel, I.A.; Rummel, A.; Trummal, A., Can O-H acid be more acidic than its S-H analog? A G2 study of fluoromethanols and fluoromethanethiols, J. Phys. Chem. A, 2000, 104, 7, 1602-1607, https://doi.org/10.1021/jp993487a . [all data]

Chyall and Squires, 1996
Chyall, L.J.; Squires, R.R., The Proton Affinity and Absolute Heat of Formation of Trifluoromethanpl, J. Phys. Chem., 1996, 100, 16435. [all data]

Taft, Koppel, et al., 1990
Taft, R.W.; Koppel, I.J.; Topsom, R.D.; Anvia, F., Acidities of OH Compounds, including Alcohols, Phenols, Carboxylic Acids, and Mineral Acids, J. Am. Chem. Soc., 1990, 112, 6, 2047, https://doi.org/10.1021/ja00162a001 . [all data]

Larson and McMahon, 1983
Larson, J.W.; McMahon, T.B., Strong hydrogen bonding in gas-phase anions. An ion cyclotron resonance determination of fluoride binding energetics to bronsted acids from gas-phase fluoride exchange equilibria measurements, J. Am. Chem. Soc., 1983, 105, 2944. [all data]

Wenthold and Squires, 1995
Wenthold, P.G.; Squires, R.R., Bond dissociation energies of F2(-) and HF2(-). A gas-phase experimental and G2 theoretical study, J. Phys. Chem., 1995, 99, 7, 2002, https://doi.org/10.1021/j100007a034 . [all data]


Notes

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