Selected ATcT [1, 2] enthalpy of formation based on version 1.156 of the Thermochemical Network [3]

This version of ATcT results[3] was generated by additional expansion of version 1.148 to include species relevant to a recent study of the oxidation of ethylene [4] as well as new measurements that led to refining the thermochemistry of CF and SiF and their cations [5].

Methanol cation

Formula: [CH3OH]+ (g)

CAS RN: 12538-91-9

ATcT ID: 12538-91-9*0

SMILES: [CH3+]O

InChI: InChI=1S/CH4O/c1-2/h2H,1H3/q+1

InChIKey: GTZIRXXNRBNPPU-UHFFFAOYSA-N

Hills Formula: C1H4O1+

2D Image:

Aliases: [CH3OH]+; Methanol cation; Methanol ion (1+); CH3OH+

Relative Molecular Mass: 32.04131 ± 0.00090

Δ_fH°(0 K)	Δ_fH°(298.15 K)	Uncertainty	Units
856.95	846.62	± 0.32	kJ/mol

3D Image of [CH3OH]+ (g)

spin ON spin OFF

Top contributors to the provenance of Δ_fH° of [CH3OH]+ (g)

The 20 contributors listed below account only for 87.5% of the provenance of Δ_fH° of [CH3OH]+ (g).
A total of 28 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.

Contribution (%)	TN ID	Reaction	Measured Quantity	Reference
28.7	2933.1	CH3OH (g) → [CH3OH]+ (g)	Δ_rH°(0 K) = 10.853 ± 0.005 eV	Karlsson 1977
28.7	2933.2	CH3OH (g) → [CH3OH]+ (g)	Δ_rH°(0 K) = 10.846 ± 0.005 eV	MacNeil 1977, note unc3
7.1	2933.3	CH3OH (g) → [CH3OH]+ (g)	Δ_rH°(0 K) = 10.85 ± 0.01 eV	Berkowitz 1978
5.2	2939.2	CH3OH (g) + 3/2 O2 (g) → CO2 (g) + 2 H2O (cr,l)	Δ_rH°(298.15 K) = -182.72 ± 0.05 kcal/mol	Rossini 1932a, Domalski 1972, Weltner 1951, Rossini 1934a, note old units, mw conversion
1.7	2933.6	CH3OH (g) → [CH3OH]+ (g)	Δ_rH°(0 K) = 10.85 ± 0.02 eV	Baker 1971, est unc
1.7	2933.7	CH3OH (g) → [CH3OH]+ (g)	Δ_rH°(0 K) = 10.85 ± 0.02 eV	Cocksey 1971
1.7	2933.8	CH3OH (g) → [CH3OH]+ (g)	Δ_rH°(0 K) = 10.85 ± 0.02 eV	Watanabe 1954, Watanabe 1962
1.7	2933.9	CH3OH (g) → [CH3OH]+ (g)	Δ_rH°(0 K) = 10.83 ± 0.02 eV	Dewar 1969a, est unc
1.7	2933.10	CH3OH (g) → [CH3OH]+ (g)	Δ_rH°(0 K) = 10.83 ± 0.02 eV	Al-Joboury 1964, est unc
1.7	2933.5	CH3OH (g) → [CH3OH]+ (g)	Δ_rH°(0 K) = 10.84 ± 0.02 eV	Refaey 1968
1.5	2933.4	CH3OH (g) → [CH3OH]+ (g)	Δ_rH°(0 K) = 10.829 ± 0.015 (×1.414) eV	Omura 1969a
0.9	2989.1	[CH2OH]+ (g) → CH2O (g) + H+ (g)	Δ_rH°(0 K) = 704.98 ± 0.39 kJ/mol	Czako 2009
0.8	2936.8	[CH3OH]+ (g) → 4 H (g) + C (g) + O (g)	Δ_rH°(0 K) = 229.94 ± 0.50 (×1.61) kcal/mol	Matus 2007
0.7	2933.11	CH3OH (g) → [CH3OH]+ (g)	Δ_rH°(0 K) = 10.83 ± 0.03 eV	Warneck 1971
0.5	2971.7	CH3O (g) + H+ (g) → [CH3OH]+ (g)	Δ_rH°(0 K) = -166.78 ± 0.90 kcal/mol	Ruscic W1RO
0.4	2941.1	CH3OH (g) → CH4 (g) + O (g, singlet)	Δ_rH°(0 K) = 133.94 ± 0.17 kcal/mol	Nguyen 2015a
0.4	2934.7	CH3OH (g) → [CH3OH]+ (g)	Δ_rH°(0 K) = 10.886 ± 0.040 eV	Ruscic W1RO
0.4	2940.1	CH3OH (g) → CH3 (g) + OH (g)	Δ_rH°(0 K) = 90.12 ± 0.17 kcal/mol	Nguyen 2015a
0.4	3013.1	CH3OH (g) → CH2O (g) + H2 (g)	Δ_rH°(0 K) = 20.28 ± 0.17 kcal/mol	Nguyen 2015a
0.4	2943.1	CH3OH (g) → CH2 (g, triplet) + H2O (g)	Δ_rH°(0 K) = 81.77 ± 0.17 kcal/mol	Nguyen 2015a

Top 10 species with enthalpies of formation correlated to the Δ_fH° of [CH3OH]+ (g)

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.

Correlation Coefficent (%)	Species Name	Formula	Δ_fH°(0 K)	Δ_fH°(298.15 K)	Uncertainty	Units	Relative Molecular Mass	ATcT ID
40.5	Methanol	CH3OH (g)	-189.90	-200.79	± 0.13	kJ/mol	32.04186 ± 0.00090	67-56-1*0
39.5	Methanol	CH3OH (cr,l)	-235.15	-238.48	± 0.14	kJ/mol	32.04186 ± 0.00090	67-56-1*500
26.9	Hydroxymethylium	[CH2OH]+ (g)	717.80	709.86	± 0.17	kJ/mol	31.03337 ± 0.00088	18682-95-6*0
15.0	Methoxy	CH3O (g)	29.01	21.64	± 0.26	kJ/mol	31.03392 ± 0.00088	2143-68-2*0
15.0	Methoxide	[CH3O]- (g)	-122.38	-130.11	± 0.26	kJ/mol	31.03447 ± 0.00088	3315-60-4*0
13.1	Hydroxymethyl	CH2OH (g)	-10.07	-16.37	± 0.28	kJ/mol	31.03392 ± 0.00088	2597-43-5*0
10.3	Methyl nitrite	CH3ONO (g)	-55.42	-66.09	± 0.43	kJ/mol	61.0401 ± 0.0010	624-91-9*0
10.3	Methyl nitrite	CH3ONO (g, cis)	-55.42	-67.20	± 0.43	kJ/mol	61.0401 ± 0.0010	624-91-9*2
9.9	Water	H2O (cr,l)	-286.274	-285.802	± 0.022	kJ/mol	18.01528 ± 0.00033	7732-18-5*500
9.9	Water	H2O (l)		-285.802	± 0.022	kJ/mol	18.01528 ± 0.00033	7732-18-5*590

Most Influential reactions involving [CH3OH]+ (g)

Please note: The list, which is based on a hat (projection) matrix analysis, is limited to no more than 20 largest influences.

Influence Coefficient	TN ID	Reaction	Measured Quantity	Reference
0.347	2933.2	CH3OH (g) → [CH3OH]+ (g)	Δ_rH°(0 K) = 10.846 ± 0.005 eV	MacNeil 1977, note unc3
0.347	2933.1	CH3OH (g) → [CH3OH]+ (g)	Δ_rH°(0 K) = 10.853 ± 0.005 eV	Karlsson 1977
0.216	4031.7	CH3CH2OH (g) + [CH3OH]+ (g) → [CH3CH2OH]+ (g) + CH3OH (g)	Δ_rH°(0 K) = -0.479 ± 0.036 eV	Ruscic W1RO, Bodi 2012
0.103	2959.6	[CH2OH2]+ (g) → [CH3OH]+ (g)	Δ_rH°(0 K) = 7.38 ± 1.2 kcal/mol	Ruscic W1RO
0.088	2959.5	[CH2OH2]+ (g) → [CH3OH]+ (g)	Δ_rH°(0 K) = 7.36 ± 1.3 kcal/mol	Ruscic CBS-n
0.088	2959.3	[CH2OH2]+ (g) → [CH3OH]+ (g)	Δ_rH°(0 K) = 7.20 ± 1.3 kcal/mol	Ruscic G4
0.086	2933.3	CH3OH (g) → [CH3OH]+ (g)	Δ_rH°(0 K) = 10.85 ± 0.01 eV	Berkowitz 1978
0.076	2959.2	[CH2OH2]+ (g) → [CH3OH]+ (g)	Δ_rH°(0 K) = 7.06 ± 1.4 kcal/mol	Ruscic G3X
0.064	4031.3	CH3CH2OH (g) + [CH3OH]+ (g) → [CH3CH2OH]+ (g) + CH3OH (g)	Δ_rH°(0 K) = -0.491 ± 0.066 eV	Ruscic G4
0.058	2959.4	[CH2OH2]+ (g) → [CH3OH]+ (g)	Δ_rH°(0 K) = 6.64 ± 1.6 kcal/mol	Ruscic CBS-n
0.058	4031.6	CH3CH2OH (g) + [CH3OH]+ (g) → [CH3CH2OH]+ (g) + CH3OH (g)	Δ_rH°(0 K) = -0.549 ± 0.068 (×1.022) eV	Ruscic CBS-n
0.039	4031.2	CH3CH2OH (g) + [CH3OH]+ (g) → [CH3CH2OH]+ (g) + CH3OH (g)	Δ_rH°(0 K) = -0.484 ± 0.084 eV	Ruscic G3X
0.035	4031.5	CH3CH2OH (g) + [CH3OH]+ (g) → [CH3CH2OH]+ (g) + CH3OH (g)	Δ_rH°(0 K) = -0.564 ± 0.089 eV	Ruscic CBS-n
0.021	2933.9	CH3OH (g) → [CH3OH]+ (g)	Δ_rH°(0 K) = 10.83 ± 0.02 eV	Dewar 1969a, est unc
0.021	2933.6	CH3OH (g) → [CH3OH]+ (g)	Δ_rH°(0 K) = 10.85 ± 0.02 eV	Baker 1971, est unc
0.021	2933.5	CH3OH (g) → [CH3OH]+ (g)	Δ_rH°(0 K) = 10.84 ± 0.02 eV	Refaey 1968
0.021	2933.8	CH3OH (g) → [CH3OH]+ (g)	Δ_rH°(0 K) = 10.85 ± 0.02 eV	Watanabe 1954, Watanabe 1962
0.021	2933.10	CH3OH (g) → [CH3OH]+ (g)	Δ_rH°(0 K) = 10.83 ± 0.02 eV	Al-Joboury 1964, est unc
0.021	2933.7	CH3OH (g) → [CH3OH]+ (g)	Δ_rH°(0 K) = 10.85 ± 0.02 eV	Cocksey 1971
0.019	2933.4	CH3OH (g) → [CH3OH]+ (g)	Δ_rH°(0 K) = 10.829 ± 0.015 (×1.414) eV	Omura 1969a

References

1		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]
2		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 21^st Century. J. Phys. Conf. Ser. 16, 561-570 (2005) [DOI: 10.1088/1742-6596/16/1/078]
3		B. Ruscic and D. H. Bross, Active Thermochemical Tables (ATcT) values based on ver. 1.156 of the Thermochemical Network (2024); available at ATcT.anl.gov
4		N. A. Seifert, B. Ruscic, R. Sivaramakrishnan, and K. Prozument, The C2H4O Isomers in the Oxidation of Ethylene J. Mol. Spectrosc. 398, 111847/1-8 (2023) [DOI: 10.1016/j.jms.2023.111847]
5		U. Jacovella, B. Ruscic, N. L. Chen, H.-L. Le, S. Boyé-Péronne, S. Hartweg, M. Roy-Chowdhury, G. A. Garcia, J.-C. Loison, and B. Gans, Refining Thermochemical Properties of CF, SiF, and Their Cations by Combining Photoelectron Spectroscopy, Quantum Chemical Calculations, and the Active Thermochemical Tables Approach Phys. Chem. Chem. Phys. 25, 30838-30847 (2023) [DOI: 10.1039/D3CP04244H]
6		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]
7		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]

Formula

The aggregate state is given in parentheses following the formula, such as: g - gas-phase, cr - crystal, l - liquid, etc.

Uncertainties

The listed uncertainties correspond to estimated 95% confidence limits, as customary in thermochemistry (see, for example, Ruscic [6] and Ruscic and Bross[7]).
Note that an uncertainty of ± 0.000 kJ/mol indicates that the estimated uncertainty is < ± 0.000₅ kJ/mol.

Website Functionality Credits

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/.

Acknowledgement

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.