Selected ATcT [1, 2] enthalpy of formation based on version 1.148 of the Thermochemical Network [3]This version of ATcT results[3] was generated by additional expansion of version 1.140 to include species relevant to a recent study of the role of atmospheric methanediol[4].
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Formic acid |
| Formula: HC(O)OH (g, anti) |
| CAS RN: 64-18-6 |
| ATcT ID: 64-18-6*2 |
| SMILES: C(=O)O |
| InChI: InChI=1S/CH2O2/c2-1-3/h1H,(H,2,3) |
| InChIKey: BDAGIHXWWSANSR-UHFFFAOYSA-N |
| Hills Formula: C1H2O2 |
2D Image: |
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| Aliases: HC(O)OH; Formic acid; Hydrogen carboxylic acid; Methanoic acid; HCOOH; OCHOH; O=CH-OH; H(C=O)OH; Formylic acid; Aminic acid |
| Relative Molecular Mass: 46.0254 ± 0.0010 |
| ΔfH°(0 K) | ΔfH°(298.15 K) | Uncertainty | Units |
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| -354.70 | -361.80 | ± 0.37 | kJ/mol |
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3D Image of HC(O)OH (g, anti) |
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Top contributors to the provenance of ΔfH° of HC(O)OH (g, anti)The 20 contributors listed below account only for 76.8% of the provenance of ΔfH° of HC(O)OH (g, anti).
A total of 79 contributors would be needed to account for 90% of the provenance.
Please note: The list is limited to 20 most important contributors or, if less, a number sufficient to account for 90% of the provenance. The Reference acts as a further link to the relevant references and notes for the measurement. The Measured Quantity is normaly given in the original units; in cases where we have reinterpreted the original measurement, the listed value may differ from that given by the authors. The quoted uncertainty is the a priori uncertainty used as input when constructing the initial Thermochemical Network, and corresponds either to the value proposed by the original authors or to our estimate; if an additional multiplier is given in parentheses immediately after the prior uncertainty, it corresponds to the factor by which the prior uncertainty needed to be multiplied during the ATcT analysis in order to make that particular measurement consistent with the prevailing knowledge contained in the Thermochemical Network.
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Contribution
(%) | TN
ID | Reaction | Measured Quantity | Reference | | 53.6 | 4576.1 | HC(O)OH (g, syn) → HC(O)OH (g, anti) | ΔrH°(0 K) = 1365 ± 30 cm-1 | Hocking 1976, Gurvich TPIS | | 4.4 | 4583.2 | HC(O)OH (cr,l) + 1/2 O2 (g) → CO2 (g) + H2O (cr,l) | ΔrH°(298.15 K) = -60.807 ± 0.074 kcal/mol | Lebedeva 1964 | | 3.0 | 4583.1 | HC(O)OH (cr,l) + 1/2 O2 (g) → CO2 (g) + H2O (cr,l) | ΔrH°(298.15 K) = -60.851 ± 0.089 kcal/mol | Sinke 1959 | | 2.9 | 4584.1 | HC(O)OH (cr,l) → HC(O)OH (g) | ΔrH°(298.15 K) = 46.30 ± 0.23 kJ/mol | Majer 1985 | | 1.0 | 3021.2 | HC(O)OH (g, syn) → [HCO]+ (g) + OH (g) | ΔrH°(0 K) = 12.81 ± 0.01 eV | Traeger 1985, AE corr | | 0.9 | 4584.2 | HC(O)OH (cr,l) → HC(O)OH (g) | ΔrH°(298.15 K) = 46.15 ± 0.40 kJ/mol | NBS Tables 1989 | | 0.9 | 4582.2 | HC(O)OH (g) → [HCO]+ (g) + OH (g) | ΔrH°(0 K) = 1235.7 ± 1.0 kJ/mol | Shuman 2010a, Bomble 2006 | | 0.9 | 4581.8 | HC(O)OH (g, anti) + CH4 (g) → CH2O (g) + CH3OH (g) | ΔrH°(0 K) = 29.70 ± 0.9 kcal/mol | Ruscic W1RO | | 0.8 | 4887.8 | CH3C(O)OH (g, syn) + HC(O)OH (g, anti) → CH3C(O)OH (g, anti) + HC(O)OH (g, syn) | ΔrH°(0 K) = 346 ± 200 cm-1 | Ruscic W1RO | | 0.8 | 4563.1 | HC(O)OH (g, anti) → [HC(O)OH]+ (g, syn) | ΔrH°(0 K) = 11.16 ± 0.03 eV | Warneck 1974 | | 0.8 | 4563.2 | HC(O)OH (g, anti) → [HC(O)OH]+ (g, syn) | ΔrH°(0 K) = 11.16 ± 0.03 eV | Matthews 1969 | | 0.7 | 4887.7 | CH3C(O)OH (g, syn) + HC(O)OH (g, anti) → CH3C(O)OH (g, anti) + HC(O)OH (g, syn) | ΔrH°(0 K) = 355 ± 210 cm-1 | Ruscic CBS-n | | 0.7 | 4887.4 | CH3C(O)OH (g, syn) + HC(O)OH (g, anti) → CH3C(O)OH (g, anti) + HC(O)OH (g, syn) | ΔrH°(0 K) = 395 ± 210 cm-1 | Ruscic G4 | | 0.7 | 4581.4 | HC(O)OH (g, anti) + CH4 (g) → CH2O (g) + CH3OH (g) | ΔrH°(0 K) = 29.55 ± 1.0 kcal/mol | Ruscic G4 | | 0.7 | 4581.7 | HC(O)OH (g, anti) + CH4 (g) → CH2O (g) + CH3OH (g) | ΔrH°(0 K) = 30.25 ± 1.0 kcal/mol | Ruscic CBS-n | | 0.6 | 4558.3 | HC(O)OH (g, syn) → C (g) + 2 H (g) + 2 O (g) | ΔrH°(0 K) = 479.81 ± 0.30 kcal/mol | Karton 2011 | | 0.6 | 4887.3 | CH3C(O)OH (g, syn) + HC(O)OH (g, anti) → CH3C(O)OH (g, anti) + HC(O)OH (g, syn) | ΔrH°(0 K) = 412 ± 225 cm-1 | Ruscic G3X | | 0.6 | 4584.3 | HC(O)OH (cr,l) → HC(O)OH (g) | ΔrH°(298.15 K) = 46.3 ± 0.5 kJ/mol | Konicek 1970 | | 0.6 | 4886.9 | CH3C(O)OH (g, syn) → CH3C(O)OH (g, anti) | ΔrH°(0 K) = 20.72 ± 0.50 kJ/mol | Feller 2018a, Lee 2021, est unc | | 0.6 | 4581.3 | HC(O)OH (g, anti) + CH4 (g) → CH2O (g) + CH3OH (g) | ΔrH°(0 K) = 29.74 ± 1.1 kcal/mol | Ruscic G3X |
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Top 10 species with enthalpies of formation correlated to the ΔfH° of HC(O)OH (g, anti) |
Please note: The correlation coefficients are obtained by renormalizing the off-diagonal elements of the covariance matrix by the corresponding variances.
The correlation coefficient is a number from -1 to 1, with 1 representing perfectly correlated species, -1 representing perfectly anti-correlated species, and 0 representing perfectly uncorrelated species.
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Correlation
Coefficent
(%) | Species Name | Formula | Image | ΔfH°(0 K) | ΔfH°(298.15 K) | Uncertainty | Units | Relative
Molecular
Mass | ATcT ID | | 52.0 | Formic acid | HC(O)OH (g, syn) |  | -371.03 | -378.35 | ± 0.21 | kJ/mol | 46.0254 ±
0.0010 | 64-18-6*1 | | 52.0 | Formic acid | HC(O)OH (g) |  | -371.03 | -378.32 | ± 0.21 | kJ/mol | 46.0254 ±
0.0010 | 64-18-6*0 | | 44.4 | Formic acid cation | [HC(O)OH]+ (g, syn) | O](../images/743.png) | 721.95 | 714.86 | ± 0.25 | kJ/mol | 46.0248 ±
0.0010 | 50614-05-6*1 | | 44.4 | Formic acid cation | [HC(O)OH]+ (g) | O](../images/2680.png) | 721.95 | 715.42 | ± 0.25 | kJ/mol | 46.0248 ±
0.0010 | 50614-05-6*0 | | 34.3 | Formic acid | HC(O)OH (cr,l) |  | -431.50 | -424.66 | ± 0.20 | kJ/mol | 46.0254 ±
0.0010 | 64-18-6*500 | | 15.0 | Formate | [HC(O)O]- (aq) | ![C(=O)[O-]](../images/2708.png) | | -425.47 | ± 0.45 | kJ/mol | 45.0180 ±
0.0010 | 71-47-6*800 | | 15.0 | Formic acid | HC(O)OH (aq) |  | | -425.47 | ± 0.45 | kJ/mol | 46.0254 ±
0.0010 | 64-18-6*800 | | 15.0 | Formic acid | HC(O)OH (aq, undissoc) |  | | -425.37 | ± 0.45 | kJ/mol | 46.0254 ±
0.0010 | 64-18-6*1000 | | 14.9 | Carbonic acid | C(O)(OH)2 (g, cis-cis) |  | -602.30 | -612.47 | ± 0.58 | kJ/mol | 62.0248 ±
0.0012 | 463-79-6*1 | | 14.9 | Carbonic acid | C(O)(OH)2 (g) |  | -602.30 | -611.62 | ± 0.58 | kJ/mol | 62.0248 ±
0.0012 | 463-79-6*0 |
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Most Influential reactions involving HC(O)OH (g, anti)Please note: The list, which is based on a hat (projection) matrix analysis, is limited to no more than 20 largest influences.
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Influence
Coefficient | TN
ID | Reaction | Measured Quantity | Reference | | 0.774 | 4576.1 | HC(O)OH (g, syn) → HC(O)OH (g, anti) | ΔrH°(0 K) = 1365 ± 30 cm-1 | Hocking 1976, Gurvich TPIS | | 0.145 | 4566.7 | [HC(O)OH]- (g, anti) → HC(O)OH (g, anti) | ΔrH°(0 K) = -1.183 ± 0.050 eV | Ruscic W1RO | | 0.117 | 4984.5 | CH3C(O)OCH3 (g, anti) + HC(O)OH (g, anti) → CH3C(O)OH (g, anti) + HC(O)OCH3 (g, anti) | ΔrH°(0 K) = -1.61 ± 0.85 kcal/mol | Ruscic W1RO | | 0.105 | 4984.2 | CH3C(O)OCH3 (g, anti) + HC(O)OH (g, anti) → CH3C(O)OH (g, anti) + HC(O)OCH3 (g, anti) | ΔrH°(0 K) = -1.38 ± 0.90 kcal/mol | Ruscic G4 | | 0.105 | 4984.1 | CH3C(O)OCH3 (g, anti) + HC(O)OH (g, anti) → CH3C(O)OH (g, anti) + HC(O)OCH3 (g, anti) | ΔrH°(0 K) = -1.37 ± 0.90 kcal/mol | Ruscic G3X | | 0.105 | 4984.4 | CH3C(O)OCH3 (g, anti) + HC(O)OH (g, anti) → CH3C(O)OH (g, anti) + HC(O)OCH3 (g, anti) | ΔrH°(0 K) = -1.54 ± 0.90 kcal/mol | Ruscic CBS-n | | 0.097 | 4566.4 | [HC(O)OH]- (g, anti) → HC(O)OH (g, anti) | ΔrH°(0 K) = -1.161 ± 0.061 eV | Ruscic G4 | | 0.097 | 4564.8 | HC(O)OH (g, anti) → [HC(O)OH]+ (g, anti) | ΔrH°(0 K) = 11.188 ± 0.040 eV | Ruscic W1RO | | 0.085 | 4984.3 | CH3C(O)OCH3 (g, anti) + HC(O)OH (g, anti) → CH3C(O)OH (g, anti) + HC(O)OCH3 (g, anti) | ΔrH°(0 K) = -1.47 ± 1.00 kcal/mol | Ruscic CBS-n | | 0.050 | 4566.3 | [HC(O)OH]- (g, anti) → HC(O)OH (g, anti) | ΔrH°(0 K) = -1.217 ± 0.085 eV | Ruscic G3X | | 0.045 | 5017.5 | HC(O)OH (g, anti) + CH3CH2OH (g) → HC(O)OCH2CH3 (g, anti) + H2O (g) | ΔrH°(0 K) = -4.88 ± 1.50 kcal/mol | Ruscic W1RO | | 0.043 | 4566.6 | [HC(O)OH]- (g, anti) → HC(O)OH (g, anti) | ΔrH°(0 K) = -1.190 ± 0.092 eV | Ruscic CBS-n | | 0.041 | 4887.8 | CH3C(O)OH (g, syn) + HC(O)OH (g, anti) → CH3C(O)OH (g, anti) + HC(O)OH (g, syn) | ΔrH°(0 K) = 346 ± 200 cm-1 | Ruscic W1RO | | 0.040 | 5017.4 | HC(O)OH (g, anti) + CH3CH2OH (g) → HC(O)OCH2CH3 (g, anti) + H2O (g) | ΔrH°(0 K) = -5.37 ± 1.60 kcal/mol | Ruscic CBS-n | | 0.040 | 5017.2 | HC(O)OH (g, anti) + CH3CH2OH (g) → HC(O)OCH2CH3 (g, anti) + H2O (g) | ΔrH°(0 K) = -4.91 ± 1.60 kcal/mol | Ruscic G4 | | 0.037 | 4887.7 | CH3C(O)OH (g, syn) + HC(O)OH (g, anti) → CH3C(O)OH (g, anti) + HC(O)OH (g, syn) | ΔrH°(0 K) = 355 ± 210 cm-1 | Ruscic CBS-n | | 0.037 | 4887.4 | CH3C(O)OH (g, syn) + HC(O)OH (g, anti) → CH3C(O)OH (g, anti) + HC(O)OH (g, syn) | ΔrH°(0 K) = 395 ± 210 cm-1 | Ruscic G4 | | 0.034 | 5017.1 | HC(O)OH (g, anti) + CH3CH2OH (g) → HC(O)OCH2CH3 (g, anti) + H2O (g) | ΔrH°(0 K) = -5.23 ± 1.72 kcal/mol | Ruscic G3X | | 0.032 | 4887.3 | CH3C(O)OH (g, syn) + HC(O)OH (g, anti) → CH3C(O)OH (g, anti) + HC(O)OH (g, syn) | ΔrH°(0 K) = 412 ± 225 cm-1 | Ruscic G3X | | 0.029 | 4564.4 | HC(O)OH (g, anti) → [HC(O)OH]+ (g, anti) | ΔrH°(0 K) = 11.143 ± 0.073 eV | Ruscic G4 |
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References
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1
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B. Ruscic, R. E. Pinzon, M. L. Morton, G. von Laszewski, S. Bittner, S. G. Nijsure, K. A. Amin, M. Minkoff, and A. F. Wagner,
Introduction to Active Thermochemical Tables: Several "Key" Enthalpies of Formation Revisited.
J. Phys. Chem. A 108, 9979-9997 (2004)
[DOI: 10.1021/jp047912y]
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2
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B. Ruscic, R. E. Pinzon, G. von Laszewski, D. Kodeboyina, A. Burcat, D. Leahy, D. Montoya, and A. F. Wagner,
Active Thermochemical Tables: Thermochemistry for the 21st Century.
J. Phys. Conf. Ser. 16, 561-570 (2005)
[DOI: 10.1088/1742-6596/16/1/078]
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3
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B. Ruscic and D. H. Bross,
Active Thermochemical Tables (ATcT) values based on ver. 1.148 of the Thermochemical Network (2023); available at ATcT.anl.gov |
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4
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T. L. Nguyen, J. Peeters, J.-F. Müller, A. Perera, D. H. Bross, B. Ruscic, and J. F. Stanton,
Methanediol from Cloud-Processed Formaldehyde is Only a Minor Source of Atmospheric Formic Acid
Natl. Acad. Sci. 120, e2304650120/1-8 (2023)
[DOI: 10.1073/pnas.2304650120]
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5
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B. Ruscic,
Uncertainty Quantification in Thermochemistry, Benchmarking Electronic Structure Computations, and Active Thermochemical Tables.
Int. J. Quantum Chem. 114, 1097-1101 (2014)
[DOI: 10.1002/qua.24605]
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6
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B. Ruscic and D. H. Bross,
Thermochemistry
Computer Aided Chem. Eng. 45, 3-114 (2019)
[DOI: 10.1016/B978-0-444-64087-1.00001-2]
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Formula
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The aggregate state is given in parentheses following the formula, such as: g - gas-phase, cr - crystal, l - liquid, etc.
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Uncertainties
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The listed uncertainties correspond to estimated 95% confidence limits, as customary in thermochemistry (see, for example, Ruscic [5] and Ruscic and Bross[6]).
Note that an uncertainty of ± 0.000 kJ/mol indicates that the estimated uncertainty is < ± 0.0005 kJ/mol.
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Website Functionality Credits
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The reorganization of the website was developed and implemented by David H. Bross (ANL).
The find function is based on the complete Species Dictionary entries for the appropriate version of the ATcT TN.
The molecule images are rendered by Indigo-depict.
The XYZ renderings are based on Jmol: an open-source Java viewer for chemical structures in 3D. http://www.jmol.org/.
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Acknowledgement
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This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences under Contract No. DE-AC02-06CH11357.
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