Selected ATcT [1, 2] enthalpy of formation based on version 1.130 of the Thermochemical Network [3]

This version of ATcT results[4] was generated by additional expansion of version 1.128 [5,6] to include with the calculations provided in reference [4].

Chloromethane

Formula: CH3Cl (g)

CAS RN: 74-87-3

ATcT ID: 74-87-3*0

SMILES: CCl

InChI: InChI=1S/CH3Cl/c1-2/h1H3

InChIKey: NEHMKBQYUWJMIP-UHFFFAOYSA-N

Hills Formula: C1H3Cl1

2D Image:

Aliases: CH3Cl; Chloromethane; Methyl chloride; Methyl monochloride; Monochloromethane; Carbon monochloride; Monochlorocarbon; RCRA U045; UN 1063; Freon 40; R 40; Artic; MeCl

Relative Molecular Mass: 50.4872 ± 0.0012

Δ_fH°(0 K)	Δ_fH°(298.15 K)	Uncertainty	Units
-74.75	-82.68	± 0.16	kJ/mol

3D Image of CH3Cl (g)

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Top contributors to the provenance of Δ_fH° of CH3Cl (g)

The 20 contributors listed below account only for 58.6% of the provenance of Δ_fH° of CH3Cl (g).
A total of 327 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
21.4	5947.1	CH3Br (g) → [CH3]+ (g) + Br (g)	Δ_rH°(0 K) = 12.834 ± 0.002 eV	Song 2001
13.1	5940.6	4 CH3Cl (g) → CCl4 (g) + 3 CH4 (g)	Δ_rH°(0 K) = 2.52 ± 0.30 kcal/mol	Karton 2017
3.7	6125.7	CH4 (g) + CH2Cl2 (g) → 2 CH3Cl (g)	Δ_rH°(0 K) = 1.03 ± 0.25 kcal/mol	Karton 2017, Karton 2011, Karton 2007, Karton 2006
2.5	2279.1	2 H2 (g) + C (graphite) → CH4 (g)	Δ_rG°(1165 K) = 37.521 ± 0.068 kJ/mol	Smith 1946, note COf, 3rd Law
2.3	5931.1	CH3Cl (g) + 3/2 O2 (g) → CO2 (g) + H2O (cr,l) + HCl (aq, 600 H2O)	Δ_rH°(298.15 K) = -764.00 ± 0.50 (×1.957) kJ/mol	Fletcher 1971
1.4	1196.1	[HBr]+ (g) → H (g) + Br+ (g)	Δ_rH°(0 K) = 31394.5 ± 20 (×1.795) cm-1	Haugh 1971, Norling 1935
1.4	6128.6	CH4 (g) + CCl4 (g) → CH3Cl (g) + CHCl3 (g)	Δ_rH°(0 K) = -3.24 ± 0.25 kcal/mol	Karton 2017, Karton 2011, Karton 2007, Karton 2006
1.4	6126.7	CH4 (g) + CHCl3 (g) → CH2Cl2 (g) + CH3Cl (g)	Δ_rH°(0 K) = -0.13 ± 0.25 kcal/mol	Karton 2017, Karton 2011, Karton 2007, Karton 2006
1.4	5934.10	CH3Cl (g) + H (g) → CH4 (g) + Cl (g)	Δ_rH°(0 K) = -7296 ± 100 cm-1	Czako 2012
1.1	5950.1	CH3Br (g) + H2 (g) → CH4 (g) + HBr (g)	Δ_rH°(523.15 K) = -18.062 ± 0.321 kcal/mol	Fowell 1965
1.0	5927.3	CH3Cl (g) → C (g) + 3 H (g) + Cl (g)	Δ_rH°(0 K) = 371.31 ± 0.35 kcal/mol	Karton 2017
0.9	5888.8	HCCCl (g) + CH4 (g) → HCCH (g) + CH3Cl (g)	Δ_rH°(0 K) = -2.17 ± 0.25 kcal/mol	Karton 2017, Karton 2011, Karton 2007, Karton 2006
0.8	1186.1	Cl2 (g) + 2 Br- (aq) → Br2 (cr,l) + 2 Cl- (aq)	Δ_rH°(298.15 K) = -91.29 ± 0.40 (×2.538) kJ/mol	Johnson 1963, as quoted by CODATA Key Vals
0.8	1186.2	Cl2 (g) + 2 Br- (aq) → Br2 (cr,l) + 2 Cl- (aq)	Δ_rH°(298.15 K) = -91.29 ± 0.80 (×1.269) kJ/mol	Sunner 1964, as quoted by CODATA Key Vals
0.8	6410.8	CO2 (g) + CCl4 (g) → 2 CCl2O (g)	Δ_rH°(0 K) = 11.18 ± 0.25 kcal/mol	Karton 2017, Karton 2011, Karton 2007, Karton 2006
0.8	5662.6	CCl4 (g) + 4 F (g) → CF4 (g) + 4 Cl (g)	Δ_rH°(0 K) = -160.16 ± 0.30 kcal/mol	Karton 2017
0.7	5927.5	CH3Cl (g) → C (g) + 3 H (g) + Cl (g)	Δ_rH°(0 K) = 371.34 ± 0.4 kcal/mol	Feller 2008
0.7	6156.6	3 CH3Cl (g) → CHCl3 (g) + 2 CH4 (g)	Δ_rH°(0 K) = -0.33 ± 0.9 kcal/mol	Ruscic W1RO
0.6	5889.8	HCCCl (g) + CH3Cl (g) → ClCCCl (g) + CH4 (g)	Δ_rH°(0 K) = 2.93 ± 0.25 kcal/mol	Karton 2017, Karton 2011, Karton 2007, Karton 2006
0.6	8938.1	S(O)(OH)2 (aq, 2500 H2O) + Br2 (cr,l) + H2O (cr,l) → OS(O)(OH)2 (aq, 2500 H2O) + 2 HBr (aq, 1250 H2O)	Δ_rH°(298.15 K) = -55.47 ± 0.11 (×2.768) kcal/mol	Johnson 1963

Top 10 species with enthalpies of formation correlated to the Δ_fH° of CH3Cl (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
98.8	Chloromethane cation	[CH3Cl]+ (g)	1014.53	1007.76	± 0.16	kJ/mol	50.4867 ± 0.0012	12538-71-5*0
97.8	Chloromethane	CH3Cl (l)	-106.55	-102.58	± 0.16	kJ/mol	50.4872 ± 0.0012	74-87-3*590
65.3	Bromomethane	CH3Br (g)	-20.89	-36.29	± 0.16	kJ/mol	94.9385 ± 0.0013	74-83-9*0
62.7	Bromomethane cation	[CH3Br]+ (g)	996.22	981.31	± 0.17	kJ/mol	94.9380 ± 0.0013	12538-70-4*0
60.7	Bromomethane	CH3Br (l)	-56.61	-59.63	± 0.17	kJ/mol	94.9385 ± 0.0013	74-83-9*590
-36.4	Hydrogen bromide	HBr (aq, 150 H2O)		-120.01	± 0.14	kJ/mol	80.9119 ± 0.0010	10035-10-6*829
-36.5	Hydrogen bromide	HBr (aq, 3000 H2O)		-120.60	± 0.14	kJ/mol	80.9119 ± 0.0010	10035-10-6*842
-36.5	Hydrogen bromide	HBr (aq, 2570 H2O)		-120.58	± 0.14	kJ/mol	80.9119 ± 0.0010	10035-10-6*952
-39.2	Bromoniumyl	[HBr]+ (g)	1097.83	1089.98	± 0.13	kJ/mol	80.9114 ± 0.0010	12258-64-9*0
-39.2	Hydrogen bromide	HBr (g)	-27.85	-35.69	± 0.13	kJ/mol	80.9119 ± 0.0010	10035-10-6*0

Most Influential reactions involving CH3Cl (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
0.986	5928.1	CH3Cl (g) → [CH3Cl]+ (g)	Δ_rH°(0 K) = 91057.0 ± 2.0 cm-1	Grutter 2011
0.961	5951.3	CH3Br (g) + HCl (g) → CH3Cl (g) + HBr (g)	Δ_rG°(449.3 K) = 10.036 ± 0.019 kJ/mol	Bak 1948, 3rd Law
0.268	5889.8	HCCCl (g) + CH3Cl (g) → ClCCCl (g) + CH4 (g)	Δ_rH°(0 K) = 2.93 ± 0.25 kcal/mol	Karton 2017, Karton 2011, Karton 2007, Karton 2006
0.256	5723.6	CH3Cl (g) → [CH2Cl]- (g) + H+ (g)	Δ_rH°(0 K) = 396.34 ± 0.90 kcal/mol	Ruscic W1RO
0.233	5940.6	4 CH3Cl (g) → CCl4 (g) + 3 CH4 (g)	Δ_rH°(0 K) = 2.52 ± 0.30 kcal/mol	Karton 2017
0.210	5722.1	CH3Cl (g) → CH2Cl (g) + 1/2 H2 (g)	Δ_rH°(0 K) = 193.72 ± 1.9 kJ/mol	Csontos 2010
0.195	6129.6	CH3Cl (g) + CCl4 (g) → CH2Cl2 (g) + CHCl3 (g)	Δ_rH°(0 K) = -4.27 ± 0.25 kcal/mol	Karton 2017
0.178	5888.8	HCCCl (g) + CH4 (g) → HCCH (g) + CH3Cl (g)	Δ_rH°(0 K) = -2.17 ± 0.25 kcal/mol	Karton 2017, Karton 2011, Karton 2007, Karton 2006
0.156	5943.16	CH3Cl (l) → CH3Cl (g)	Δ_rG°(243.190 K) = 0.543 ± 0.083 kJ/mol	Ganeff 1948, 3rd Law, ThermoData 2004
0.156	5943.10	CH3Cl (l) → CH3Cl (g)	Δ_rG°(243.750 K) = 0.489 ± 0.083 kJ/mol	Messerly 1940, 3rd Law, ThermoData 2004
0.138	6126.7	CH4 (g) + CHCl3 (g) → CH2Cl2 (g) + CH3Cl (g)	Δ_rH°(0 K) = -0.13 ± 0.25 kcal/mol	Karton 2017, Karton 2011, Karton 2007, Karton 2006
0.129	5943.4	CH3Cl (l) → CH3Cl (g)	Δ_rG°(231.405 K) = 1.626 ± 0.091 kJ/mol	ThermoData 2004, 3rd Law
0.129	6125.7	CH4 (g) + CH2Cl2 (g) → 2 CH3Cl (g)	Δ_rH°(0 K) = 1.03 ± 0.25 kcal/mol	Karton 2017, Karton 2011, Karton 2007, Karton 2006
0.121	5943.14	CH3Cl (l) → CH3Cl (g)	Δ_rG°(273.130 K) = -2.049 ± 0.094 kJ/mol	Ganeff 1948, 3rd Law, ThermoData 2004
0.121	5943.12	CH3Cl (l) → CH3Cl (g)	Δ_rG°(228.426 K) = 1.879 ± 0.094 kJ/mol	Messerly 1940, 3rd Law, ThermoData 2004
0.118	6128.6	CH4 (g) + CCl4 (g) → CH3Cl (g) + CHCl3 (g)	Δ_rH°(0 K) = -3.24 ± 0.25 kcal/mol	Karton 2017, Karton 2011, Karton 2007, Karton 2006
0.111	7923.4	HCCCH2Cl (g) + CH3 (g) → CH2CCH (g) + CH3Cl (g)	Δ_rH°(0 K) = -13.58 ± 0.9 kcal/mol	Ruscic W1RO
0.096	5743.4	CH2(Cl)OH (g) + CH4 (g) → CH3OH (g) + CH3Cl (g)	Δ_rH°(0 K) = 8.12 ± 0.85 kcal/mol	Ruscic W1RO
0.092	5753.4	CH(Cl)OH (g, syn-gauche) + CH4 (g) → CH2OH (g) + CH3Cl (g)	Δ_rH°(0 K) = 8.68 ± 0.85 kcal/mol	Ruscic W1RO
0.090	5758.4	CH2(Cl)O (g) + CH4 (g) → CH3O (g) + CH3Cl (g)	Δ_rH°(0 K) = 7.49 ± 0.85 kcal/mol	Ruscic W1RO

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. 1.130 of the Thermochemical Network. Argonne National Laboratory, Lemont, Illinois 2023; available at ATcT.anl.gov [DOI: 10.17038/CSE/1997229]
4		N. Genossar, P. B. Changala, B. Gans, J.-C. Loison, S. Hartweg, M.-A. Martin-Drumel, G. A. Garcia, J. F. Stanton, B. Ruscic, and J. H. Baraban Ring-Opening Dynamics of the Cyclopropyl Radical and Cation: the Transition State Nature of the Cyclopropyl Cation J. Am. Chem. Soc. 144, 18518-18525 (2022) [DOI: 10.1021/jacs.2c07740]
5		B. Ruscic and D. H. Bross Active Thermochemical Tables: The Thermophysical and Thermochemical Properties of Methyl, CH3, and Methylene, CH2, Corrected for Nonrigid Rotor and Anharmonic Oscillator Effects. Mol. Phys. e1969046 (2021) [DOI: 10.1080/00268976.2021.1969046]
6		J. H. Thorpe, J. L. Kilburn, D. Feller, P. B. Changala, D. H. Bross, B. Ruscic, and J. F. Stanton, Elaborated Thermochemical Treatment of HF, CO, N2, and H2O: Insight into HEAT and Its Extensions J. Chem. Phys. 155, 184109 (2021) [DOI: 10.1063/5.0069322]
7		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]
8		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]).
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.