Selected ATcT [1, 2] enthalpy of formation based on version 1.202 of the Thermochemical Network [3]

This version of ATcT results[3] was generated by additional expansion of version 1.176 in order to include species related to the thermochemistry of glycine[4].

Methyl hydroperoxide

Formula: CH3OOH (g)

CAS RN: 3031-73-0

ATcT ID: 3031-73-0*0

SMILES: COO

InChI: InChI=1S/CH4O2/c1-3-2/h2H,1H3

InChIKey: MEUKEBNAABNAEX-UHFFFAOYSA-N

Hills Formula: C1H4O2

2D Image:

Aliases: CH3OOH; Methyl hydroperoxide; Methane hydroperoxide; Methyl hydrogen peroxide

Relative Molecular Mass: 48.0413 ± 0.0010

Δ_fH°(0 K)	Δ_fH°(298.15 K)	Uncertainty	Units
-114.82	-127.64	± 0.42	kJ/mol

3D Image of CH3OOH (g)

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Top contributors to the provenance of Δ_fH° of CH3OOH (g)

The 20 contributors listed below account only for 56.6% of the provenance of Δ_fH° of CH3OOH (g).
A total of 130 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
17.2	4541.9	CH3OOH (g) → C (g) + 4 H (g) + 2 O (g)	Δ_rH°(0 K) = 2184.34 ± 1. kJ/mol	Welch 2019, Welch 2018
4.2	4544.1	CH4 (g) + 2 H2O (g) → CH3OOH (g) + 2 H2 (g)	Δ_rH°(0 K) = 429.68 ± 2.00 kJ/mol	Klippenstein 2017
4.0	4545.10	CH3OOH (g) + H2O (g) → CH3OH (g) + HOOH (g)	Δ_rH°(0 K) = 34.25 ± 2.00 kJ/mol	Klippenstein 2017
3.6	4545.9	CH3OOH (g) + H2O (g) → CH3OH (g) + HOOH (g)	Δ_rH°(0 K) = 8.0 ± 0.5 kcal/mol	Matthews 2005, est unc
2.5	4643.6	CH3OO (g) → CH3 (g) + O2 (g)	Δ_rH°(0 K) = 30.40 ± 0.17 kcal/mol	Nguyen 2014a
2.2	4636.10	CH3OOH (g) → CH3OO (g) + H (g)	Δ_rH°(0 K) = 353.47 ± 2.0 kJ/mol	Klippenstein 2017
2.2	4636.9	CH3OOH (g) → CH3OO (g) + H (g)	Δ_rH°(0 K) = 353.60 ± 2. kJ/mol	Welch 2019, Welch 2018
2.2	4637.9	CH3OO (g) + HOOH (g) → CH3OOH (g) + HOO (g)	Δ_rH°(0 K) = 6.76 ± 2.0 kJ/mol	Klippenstein 2017
2.2	4639.6	CH3OO (g) + HOO (g) → CH3OOH (g) + O2 (g, triplet)	Δ_rH°(0 K) = -152.74 ± 2.0 kJ/mol	Klippenstein 2017
2.1	4645.6	CH3OOH (g) → [CH3OO]- (g) + H+ (g)	Δ_rH°(0 K) = 1553.64 ± 2 kJ/mol	Welch 2019, Welch 2018
2.0	4639.1	CH3OO (g) + HOO (g) → CH3OOH (g) + O2 (g, triplet)	Δ_rH°(0 K) = -36.14 ± 0.5 kcal/mol	Nguyen 2022
1.9	4547.6	CH3OOH (g) → CH3 (g) + HOO (g)	Δ_rH°(0 K) = 66.9 ± 0.7 kcal/mol	Farago 2015, est unc
1.6	3151.6	HC(O)OOH (g, cis) + CH4 (g) → CH3OOH (g) + CH2O (g)	Δ_rH°(0 K) = 125.37 ± 2.0 kJ/mol	Klippenstein 2017
1.5	3150.6	HC(O)OOH (g, cis) + CH3OH (g) → HC(O)OH (g, syn) + CH3OOH (g)	Δ_rH°(0 K) = -16.39 ± 2.0 kJ/mol	Klippenstein 2017
1.4	4634.9	[CH3OO]- (g) → C (g) + 3 H (g) + 2 O (g)	Δ_rH°(0 K) = 1942.76 ± 1. kJ/mol	Welch 2019, Welch 2018
1.3	4630.9	CH3OO (g) → C (g) + 3 H (g) + 2 O (g)	Δ_rH°(0 K) = 1830.74 ± 1. kJ/mol	Welch 2019, Welch 2018
1.1	4545.8	CH3OOH (g) + H2O (g) → CH3OH (g) + HOOH (g)	Δ_rH°(0 K) = 8.13 ± 0.9 kcal/mol	Ruscic W1RO
1.0	4683.6	CH3CH2OO (g, gauche) + CH3OOH (g) → CH3CH2OOH (g) + CH3OO (g)	Δ_rH°(0 K) = 0.81 ± 1.50 kJ/mol	Welch 2019, Welch 2018
0.9	4545.4	CH3OOH (g) + H2O (g) → CH3OH (g) + HOOH (g)	Δ_rH°(0 K) = 8.40 ± 1.0 kcal/mol	Ruscic G4
0.9	4545.7	CH3OOH (g) + H2O (g) → CH3OH (g) + HOOH (g)	Δ_rH°(0 K) = 8.41 ± 1.0 kcal/mol	Ruscic CBS-n

Top 10 species with enthalpies of formation correlated to the Δ_fH° of CH3OOH (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
66.1	Hydroxymethyleneoxonium	[CH2OOH]+ (g)	792.97	782.83	± 0.62	kJ/mol	47.0328 ± 0.0010	77144-12-8*0
35.3	Methylperoxy	CH3OO (g)	22.56	13.11	± 0.34	kJ/mol	47.0333 ± 0.0010	2143-58-0*0
27.9	Methylperoxy anion	[CH3OO]- (g)	-89.66	-99.81	± 0.45	kJ/mol	47.0339 ± 0.0010	35683-44-4*0
27.6	Ethyl hydroperoxide	CH3CH2OOH (g)	-142.47	-160.89	± 0.62	kJ/mol	62.0678 ± 0.0018	3031-74-1*0
25.7	Peroxyformic acid	HC(O)OOH (g)	-279.20	-288.33	± 0.63	kJ/mol	62.0248 ± 0.0012	107-32-4*0
25.7	Peroxyformic acid	HC(O)OOH (g, cis)	-279.20	-288.55	± 0.63	kJ/mol	62.0248 ± 0.0012	107-32-4*1
23.9	Hydroperoxymethyl	CH2OOH (g)	73.26	65.96	± 0.97	kJ/mol	47.0333 ± 0.0010	74087-87-9*0
15.8	Methyl hydroperoxide cation	[CH3OOH]+ (g)	833.8	819.7	± 2.0	kJ/mol	48.0407 ± 0.0010	112465-88-0*0
15.1	Phenyl hydroperoxide	C6H5OOH (g)	13.8	-5.2	± 2.1	kJ/mol	110.1106 ± 0.0049	36112-26-2*0
13.0	Vinyl hydroperoxide	CH2CHOOH (g, perp-syn)	-26.04	-38.32	± 0.69	kJ/mol	60.0520 ± 0.0017	66998-78-5*1

Most Influential reactions involving CH3OOH (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
0.931	4653.1	CH3OOH (g) → [CH2OOH]+ (g) + H (g)	Δ_rH°(0 K) = 11.647 ± 0.005 eV	Covert 2018
0.255	4542.5	CH3OOH (g) → [CH3OOH]+ (g)	Δ_rH°(0 K) = 9.821 ± 0.040 eV	Ruscic W1RO
0.176	8622.5	C6H5OOH (g) + CH3OO (g) → C6H5OO (g) + CH3OOH (g)	Δ_rH°(0 K) = 0.83 ± 0.85 kcal/mol	Ruscic W1RO
0.173	4541.9	CH3OOH (g) → C (g) + 4 H (g) + 2 O (g)	Δ_rH°(0 K) = 2184.34 ± 1. kJ/mol	Welch 2019, Welch 2018
0.163	4542.1	CH3OOH (g) → [CH3OOH]+ (g)	Δ_rH°(0 K) = 9.87 ± 0.05 eV	Li 2005, est unc
0.163	4542.6	CH3OOH (g) → [CH3OOH]+ (g)	Δ_rH°(0 K) = 9.84 ± 0.05 eV	Covert 2018, est unc
0.157	8622.1	C6H5OOH (g) + CH3OO (g) → C6H5OO (g) + CH3OOH (g)	Δ_rH°(0 K) = 1.15 ± 0.90 kcal/mol	Ruscic G3X
0.157	8622.4	C6H5OOH (g) + CH3OO (g) → C6H5OO (g) + CH3OOH (g)	Δ_rH°(0 K) = 0.51 ± 0.90 kcal/mol	Ruscic CBS-n
0.157	8622.2	C6H5OOH (g) + CH3OO (g) → C6H5OO (g) + CH3OOH (g)	Δ_rH°(0 K) = -0.09 ± 0.90 kcal/mol	Ruscic G4
0.141	4683.6	CH3CH2OO (g, gauche) + CH3OOH (g) → CH3CH2OOH (g) + CH3OO (g)	Δ_rH°(0 K) = 0.81 ± 1.50 kJ/mol	Welch 2019, Welch 2018
0.127	8622.3	C6H5OOH (g) + CH3OO (g) → C6H5OO (g) + CH3OOH (g)	Δ_rH°(0 K) = 1.17 ± 1.0 kcal/mol	Ruscic CBS-n
0.112	4690.6	[CH3CH2OO]- (g, gauche) + CH3OOH (g) → CH3CH2OOH (g) + [CH3OO]- (g)	Δ_rH°(0 K) = 1.48 ± 2.0 kJ/mol	Welch 2019, Welch 2018
0.110	3150.6	HC(O)OOH (g, cis) + CH3OH (g) → HC(O)OH (g, syn) + CH3OOH (g)	Δ_rH°(0 K) = -16.39 ± 2.0 kJ/mol	Klippenstein 2017
0.109	3151.6	HC(O)OOH (g, cis) + CH4 (g) → CH3OOH (g) + CH2O (g)	Δ_rH°(0 K) = 125.37 ± 2.0 kJ/mol	Klippenstein 2017
0.079	4683.7	CH3CH2OO (g, gauche) + CH3OOH (g) → CH3CH2OOH (g) + CH3OO (g)	Δ_rH°(0 K) = 2.34 ± 2.00 kJ/mol	Klippenstein 2017
0.076	4542.3	CH3OOH (g) → [CH3OOH]+ (g)	Δ_rH°(0 K) = 9.799 ± 0.073 eV	Ruscic G4
0.073	4652.5	CH2OOH (g) + CH3OH (g) → CH3OOH (g) + CH2OH (g)	Δ_rH°(0 K) = -1.65 ± 0.85 kcal/mol	Ruscic W1RO
0.067	4645.6	CH3OOH (g) → [CH3OO]- (g) + H+ (g)	Δ_rH°(0 K) = 1553.64 ± 2 kJ/mol	Welch 2019, Welch 2018
0.065	4652.1	CH2OOH (g) + CH3OH (g) → CH3OOH (g) + CH2OH (g)	Δ_rH°(0 K) = -1.71 ± 0.90 kcal/mol	Ruscic G3X
0.065	4652.2	CH2OOH (g) + CH3OH (g) → CH3OOH (g) + CH2OH (g)	Δ_rH°(0 K) = -1.44 ± 0.90 kcal/mol	Ruscic G4

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. 1.202 of the Thermochemical Network (2024); available at ATcT.anl.gov
4		B. Ruscic and D. H. Bross Accurate and Reliable Thermochemistry by Data Analysis of Complex Thermochemical Networks using Active Thermochemical Tables: The Case of Glycine Thermochemistry Faraday Discuss. (in press) (2024) [DOI: 10.1039/D4FD00110A]
5		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]
6		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 [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.

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.