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Formic acid

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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
LBLHLM - Sharon G. Lias, John E. Bartmess, Joel F. Liebman, John L. Holmes, Rhoda D. Levin, and W. Gary Mallard
LLK - Sharon G. Lias, Rhoda D. Levin, and Sherif A. Kafafi
RDSH - Henry M. Rosenstock, Keith Draxl, Bruce W. Steiner, and John T. Herron
LL - Sharon G. Lias and Joel F. Liebman

Quantity Value Units Method Reference Comment
IE (evaluated)11.33 ± 0.01eVN/AN/AL
Quantity Value Units Method Reference Comment
Proton affinity (review)742.0kJ/molN/AHunter and Lias, 1998HL
Quantity Value Units Method Reference Comment
Gas basicity710.3kJ/molN/AHunter and Lias, 1998HL

Ionization energy determinations

IE (eV) Method Reference Comment
11.31PITraeger, 1985LBLHLM
11.329 ± 0.002SBell, Ng, et al., 1975LLK
11.16 ± 0.03PIWarneck, 1974LLK
11.314 ± 0.002PIKnowles and Nicholson, 1974LLK
11.3PEWatanabe, Yokoyama, et al., 1973LLK
11.33PEWatanabe, Yokoyama, et al., 1973, 2LLK
11.35 ± 0.03PEThomas, 1972LLK
11.16 ± 0.03PIMatthews and Warneck, 1969RDSH
11.33PEBrundle, Turner, et al., 1969RDSH
11.05 ± 0.03PIVilesov, 1960RDSH
11.05 ± 0.01PIWatanabe, 1957RDSH
11.33SPrice and Evans, 1937RDSH
11.5PEVon Niessen, Bieri, et al., 1980Vertical value; LLK
11.34PEBenoit and Harrison, 1977Vertical value; LLK
10.7PERao, 1975Vertical value; LLK
11.51PEKimura, Katsumata, et al., 1975Vertical value; LLK

Appearance energy determinations

Ion AE (eV) Other Products MethodReferenceComment
C+22.7 ± 0.5O+H2OEIStepanov, Perov, et al., 1988LL
CHO+12.76OHPITraeger, 1985LBLHLM
CHO+13.0 ± 0.1OHPIGolovin, Akopyan, et al., 1979LLK
CHO+12.79 ± 0.03OHPIWarneck, 1974LLK
CHO+12.79 ± 0.03OHPIMatthews and Warneck, 1969RDSH
CHO2+12.4 ± 0.1HPIGolovin, Akopyan, et al., 1979LLK
CHO2+12.26HPIAkopyan and Villem, 1976LLK
CHO2+12.29 ± 0.03HPIWarneck, 1974LLK
HO+17.97 ± 0.06HCOPIWarneck, 1974LLK
O+20.0 ± 0.5CO+H2EIStepanov, Perov, et al., 1988LL

De-protonation reactions

HCO2 anion + Hydrogen cation = Formic acid

By formula: CHO2- + H+ = CH2O2

Quantity Value Units Method Reference Comment
Deltar1449. ± 5.0kJ/molD-EAKim, Bradforth, et al., 1995gas phase; dHacid(0K) = 344.67±0.62 kcal/mol; B
Deltar1445. ± 9.2kJ/molG+TSCaldwell, Renneboog, et al., 1989gas phase; B
Deltar1445. ± 9.2kJ/molG+TSFujio, McIver, et al., 1981gas phase; value altered from reference due to change in acidity scale; B
Deltar1444. ± 12.kJ/molG+TSCumming and Kebarle, 1978gas phase; B
Deltar1423. ± 19.kJ/molEIAEMuftakhov, Vasil'ev, et al., 1999gas phase; B
Quantity Value Units Method Reference Comment
Deltar1419. ± 6.3kJ/molH-TSKim, Bradforth, et al., 1995gas phase; dHacid(0K) = 344.67±0.62 kcal/mol; B
Deltar1415. ± 8.4kJ/molIMRECaldwell, Renneboog, et al., 1989gas phase; B
Deltar1416. ± 8.4kJ/molIMREFujio, McIver, et al., 1981gas phase; value altered from reference due to change in acidity scale; B
Deltar1415. ± 8.4kJ/molIMRECumming and Kebarle, 1978gas phase; 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]

Traeger, 1985
Traeger, J.C., Heat of formation for the formyl cation by photoionization mass spectrometry, Int. J. Mass Spectrom. Ion Processes, 1985, 66, 271. [all data]

Bell, Ng, et al., 1975
Bell, S.; Ng, T.L.; Walsh, A.D., Vacuum ultraviolet spectra of formic and acetic acids, J. Chem. Soc. Faraday Trans. 2, 1975, 71, 393. [all data]

Warneck, 1974
Warneck, P., Heat of formation of the HCO radical, Z. Naturforsch. A:, 1974, 29, 350. [all data]

Knowles and Nicholson, 1974
Knowles, D.J.; Nicholson, A.J.C., Ionization energies of formic and acetic acid monomers, J. Chem. Phys., 1974, 60, 1180. [all data]

Watanabe, Yokoyama, et al., 1973
Watanabe, I.; Yokoyama, Y.; Ikeda, S., Vibrational structures in the photoelectron spectrum of formic acid, Chem. Phys. Lett., 1973, 19, 406. [all data]

Watanabe, Yokoyama, et al., 1973, 2
Watanabe, I.; Yokoyama, Y.; Ikeda, S., Lone pair ionization potentials of carboxylic acids determined by He(I) photoelectron spectroscopy, Bull. Chem. Soc. Jpn., 1973, 46, 1959. [all data]

Thomas, 1972
Thomas, R.K., Photoelectron spectroscopy of hydrogen-bonded systems: spectra of monomers, dimers and mixed complexes of carboxylic acides, Proc. R. Soc. London A:, 1972, 331, 249. [all data]

Matthews and Warneck, 1969
Matthews, C.S.; Warneck, P., Heats of formation of CHO+ and C3H3+ by photoionization, J. Chem. Phys. 5, 1969, 1, 854. [all data]

Brundle, Turner, et al., 1969
Brundle, C.R.; Turner, D.W.; Robin, M.B.; Basch, H., Photoelectron spectroscopy of simple amides and carboxylic acids, Chem. Phys. Lett., 1969, 3, 292. [all data]

Vilesov, 1960
Vilesov, F.I., The photoionization of vapors of compounds whose molecules contain carbonyl groups, Dokl. Phys. Chem., 1960, 132, 521, In original 1332. [all data]

Watanabe, 1957
Watanabe, K., Ionization potentials of some molecules, J. Chem. Phys., 1957, 26, 542. [all data]

Price and Evans, 1937
Price, W.C.; Evans, W.M., The absorption spectrum of formic acid in the vacuum ultra-violet, Proc. Roy. Soc. (London), 1937, A162, 110. [all data]

Von Niessen, Bieri, et al., 1980
Von Niessen, W.; Bieri, G.; Asbrink, L., 30.4 nm He(II) photoelectron spectra of organic molecules. Part III. Oxo-compounds (C,H,O), J. Electron Spectrosc. Relat. Phenom., 1980, 21, 175. [all data]

Benoit and Harrison, 1977
Benoit, F.M.; Harrison, A.G., Predictive value of proton affinity. Ionization energy correlations involving oxygenated molecules, J. Am. Chem. Soc., 1977, 99, 3980. [all data]

Rao, 1975
Rao, C.N.R., Lone-pair ionization bands of chromophores in the photoelectron spectra of organic molecules, Indian J. Chem., 1975, 13, 950. [all data]

Kimura, Katsumata, et al., 1975
Kimura, K.; Katsumata, S.; Yamazaki, T.; Wakabayashi, H., UV photoelectron spectra and sum rule consideration; out-of-plane orbitals of unsaturated compounds with planar-skeleton structure, J. Electron Spectrosc. Relat. Phenom., 1975, 6, 41. [all data]

Stepanov, Perov, et al., 1988
Stepanov, A.N.; Perov, A.A.; Kabanov, S.P.; Simonov, A.P., Formation of long-lived, highly excited atoms during dissociative excitation of CH3CN, CH3CH2OH, CH3COOH, HCOOH, and C4H4S molecules on electron impact, Russ. J. Phys. Chem., 1988, 22, 81. [all data]

Golovin, Akopyan, et al., 1979
Golovin, A.V.; Akopyan, M.E.; Vilesov, F.I.; Sergeev, Y.L., Ion-electron coincidence study of the photoionization of formic and acetic acids, Khim. Vys. Energ., 1979, 13, 200. [all data]

Akopyan and Villem, 1976
Akopyan, M.E.; Villem, Ya.Ya., Ion-molecule reactions in the photoionization of formic and acetic acid vapors, High Energy Chem., 1976, 10, 24. [all data]

Kim, Bradforth, et al., 1995
Kim, E.H.; Bradforth, S.E.; Arnold, D.W.; Metz, R.B.; Neumark, D.M., Study of HCO2 and DCO2 by Negative Ion Photoelectron Spectroscopy, J. Chem. Phys., 1995, 103, 18, 7801, https://doi.org/10.1063/1.470196 . [all data]

Caldwell, Renneboog, et al., 1989
Caldwell, G.; Renneboog, R.; Kebarle, P., Gas Phase Acidities of Aliphatic Carboxylic Acids, Based on Measurements of Proton Transfer Equilibria, Can. J. Chem., 1989, 67, 4, 661, https://doi.org/10.1139/v89-092 . [all data]

Fujio, McIver, et al., 1981
Fujio, M.; McIver, R.T., Jr.; Taft, R.W., Effects on the acidities of phenols from specific substituent-solvent interactions. Inherent substituent parameters from gas phase acidities, J. Am. Chem. Soc., 1981, 103, 4017. [all data]

Cumming and Kebarle, 1978
Cumming, J.B.; Kebarle, P., Summary of gas phase measurements involving acids AH. Entropy changes in proton transfer reactions involving negative ions. Bond dissociation energies D(A-H) and electron affinities EA(A), Can. J. Chem., 1978, 56, 1. [all data]

Muftakhov, Vasil'ev, et al., 1999
Muftakhov, M.V.; Vasil'ev, Y.V.; Mazunov, V.A., Determination of electron affinity of carbonyl radicals by means of negative ion mass spectrometry, Rapid Commun. Mass Spectrom., 1999, 13, 12, 1104-1108, https://doi.org/10.1002/(SICI)1097-0231(19990630)13:12<1104::AID-RCM619>3.0.CO;2-C . [all data]


Notes

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