Selected ATcT [1, 2] enthalpy of formation based on version 1.124 of the Thermochemical Network [3]

This version of ATcT results was generated by additional expansion of version 1.122x [4] to include additional information relevant to the study of thermophysical and thermochemical properties of CH2 and CH3 using nonrigid rotor anharmonic oscillator (NRRAO) partition functions [5], the development and benchmarking of a state-of-the-art computational approach that aims to reproduce total atomization energies of small molecules within 10–15 cm^-1 [6], as well as the study of the reversible reaction C₂H₃ + H₂ ⇌ C₂H₄ + H ⇌ C₂H₅ [7]

Chloromethane

Formula: CH3Cl (l)

CAS RN: 74-87-3

ATcT ID: 74-87-3*590

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
-106.52	-102.56	± 0.16	kJ/mol

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

The 20 contributors listed below account only for 56.7% of the provenance of Δ_fH° of CH3Cl (l).
A total of 336 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
20.3	5520.1	CH3Br (g) → [CH3]+ (g) + Br (g)	Δ_rH°(0 K) = 12.834 ± 0.002 eV	Song 2001
12.4	5513.6	4 CH3Cl (g) → CCl4 (g) + 3 CH4 (g)	Δ_rH°(0 K) = 2.52 ± 0.30 kcal/mol	Karton 2017
3.5	5698.7	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
3.3	2245.1	2 H2 (g) + C (graphite) → CH4 (g)	Δ_rG°(1165 K) = 37.521 ± 0.068 kJ/mol	Smith 1946, note COf, 3rd Law
2.4	5504.1	CH3Cl (g) + 3/2 O2 (g) → CO2 (g) + H2O (cr,l) + HCl (aq, 600 H2O)	Δ_rH°(298.15 K) = -764.00 ± 0.50 (×1.915) kJ/mol	Fletcher 1971
1.4	5701.6	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
1.3	5699.7	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
1.3	5507.10	CH3Cl (g) + H (g) → CH4 (g) + Cl (g)	Δ_rH°(0 K) = -7296 ± 100 cm-1	Czako 2012
1.1	1162.1	[HBr]+ (g) → H (g) + Br+ (g)	Δ_rH°(0 K) = 31394.5 ± 20 (×1.957) cm-1	Haugh 1971, Norling 1935
1.0	5523.1	CH3Br (g) + H2 (g) → CH4 (g) + HBr (g)	Δ_rH°(523.15 K) = -18.062 ± 0.321 kcal/mol	Fowell 1965
0.9	5500.3	CH3Cl (g) → C (g) + 3 H (g) + Cl (g)	Δ_rH°(0 K) = 371.31 ± 0.35 kcal/mol	Karton 2017
0.9	1152.1	Cl2 (g) + 2 Br- (aq) → Br2 (cr,l) + 2 Cl- (aq)	Δ_rH°(298.15 K) = -91.29 ± 0.40 (×2.327) kJ/mol	Johnson 1963, as quoted by CODATA Key Vals
0.9	1152.2	Cl2 (g) + 2 Br- (aq) → Br2 (cr,l) + 2 Cl- (aq)	Δ_rH°(298.15 K) = -91.29 ± 0.80 (×1.164) kJ/mol	Sunner 1964, as quoted by CODATA Key Vals
0.8	5461.8	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	5983.8	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	5235.6	CCl4 (g) + 4 F (g) → CF4 (g) + 4 Cl (g)	Δ_rH°(0 K) = -160.16 ± 0.30 kcal/mol	Karton 2017
0.7	5500.5	CH3Cl (g) → C (g) + 3 H (g) + Cl (g)	Δ_rH°(0 K) = 371.34 ± 0.4 kcal/mol	Feller 2008
0.7	5729.6	3 CH3Cl (g) → CHCl3 (g) + 2 CH4 (g)	Δ_rH°(0 K) = -0.33 ± 0.9 kcal/mol	Ruscic W1RO
0.6	5516.10	CH3Cl (l) → CH3Cl (g)	Δ_rG°(243.750 K) = 0.489 ± 0.083 kJ/mol	Messerly 1940, 3rd Law, ThermoData 2004
0.6	5516.16	CH3Cl (l) → CH3Cl (g)	Δ_rG°(243.190 K) = 0.543 ± 0.083 kJ/mol	Ganeff 1948, 3rd Law, ThermoData 2004

Top 10 species with enthalpies of formation correlated to the Δ_fH° of CH3Cl (l)

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
97.8	Chloromethane	CH3Cl (g)	-74.73	-82.66	± 0.16	kJ/mol	50.4872 ± 0.0012	74-87-3*0
96.7	Chloromethane cation	[CH3Cl]+ (g)	1014.55	1007.78	± 0.16	kJ/mol	50.4867 ± 0.0012	12538-71-5*0
64.7	Bromomethane	CH3Br (g)	-20.91	-36.31	± 0.16	kJ/mol	94.9385 ± 0.0013	74-83-9*0
62.1	Bromomethane cation	[CH3Br]+ (g)	996.21	981.29	± 0.17	kJ/mol	94.9380 ± 0.0013	12538-70-4*0
60.2	Bromomethane	CH3Br (l)	-56.63	-59.65	± 0.17	kJ/mol	94.9385 ± 0.0013	74-83-9*590
-35.2	Hydrogen bromide	HBr (aq, 500 H2O)		-120.35	± 0.14	kJ/mol	80.9119 ± 0.0010	10035-10-6*833
-35.2	Hydrogen bromide	HBr (aq, 3000 H2O)		-120.64	± 0.14	kJ/mol	80.9119 ± 0.0010	10035-10-6*842
-35.2	Hydrogen bromide	HBr (aq, 2570 H2O)		-120.62	± 0.14	kJ/mol	80.9119 ± 0.0010	10035-10-6*952
-37.9	Bromoniumyl	[HBr]+ (g)	1097.79	1089.94	± 0.13	kJ/mol	80.9114 ± 0.0010	12258-64-9*0
-37.9	Hydrogen bromide	HBr (g)	-27.88	-35.73	± 0.13	kJ/mol	80.9119 ± 0.0010	10035-10-6*0

Most Influential reactions involving CH3Cl (l)

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
0.156	5516.16	CH3Cl (l) → CH3Cl (g)	Δ_rG°(243.190 K) = 0.543 ± 0.083 kJ/mol	Ganeff 1948, 3rd Law, ThermoData 2004
0.156	5516.10	CH3Cl (l) → CH3Cl (g)	Δ_rG°(243.750 K) = 0.489 ± 0.083 kJ/mol	Messerly 1940, 3rd Law, ThermoData 2004
0.129	5516.4	CH3Cl (l) → CH3Cl (g)	Δ_rG°(231.405 K) = 1.626 ± 0.091 kJ/mol	ThermoData 2004, 3rd Law
0.121	5516.14	CH3Cl (l) → CH3Cl (g)	Δ_rG°(273.130 K) = -2.049 ± 0.094 kJ/mol	Ganeff 1948, 3rd Law, ThermoData 2004
0.121	5516.12	CH3Cl (l) → CH3Cl (g)	Δ_rG°(228.426 K) = 1.879 ± 0.094 kJ/mol	Messerly 1940, 3rd Law, ThermoData 2004
0.085	5516.2	CH3Cl (l) → CH3Cl (g)	Δ_rG°(213.995 K) = 3.202 ± 0.112 kJ/mol	ThermoData 2004, 3rd Law
0.059	5516.6	CH3Cl (l) → CH3Cl (g)	Δ_rG°(299.231 K) = -4.216 ± 0.135 kJ/mol	ThermoData 2004, 3rd Law
0.054	5515.7	CH3Cl (l) → CH3Cl (g)	Δ_rH°(248.945 K) = 21.796 ± 0.14 kJ/mol	Messerly 1940, ThermoData 2004
0.054	5515.6	CH3Cl (l) → CH3Cl (g)	Δ_rH°(248.955 K) = 21.861 ± 0.14 kJ/mol	McGovern 1943, ThermoData 2004
0.020	5516.8	CH3Cl (l) → CH3Cl (g)	Δ_rG°(311.370 K) = -5.194 ± 0.159 (×1.445) kJ/mol	Hsu 1964, 3rd Law, ThermoData 2004
0.013	5515.2	CH3Cl (l) → CH3Cl (g)	Δ_rH°(298.15 K) = 20.18 ± 0.24 (×1.189) kJ/mol	ThermoData 2004
0.012	5515.9	CH3Cl (l) → CH3Cl (g)	Δ_rH°(283.948 K) = 20.181 ± 0.17 (×1.756) kJ/mol	Griffiths 1932, ThermoData 2004
0.004	5515.5	CH3Cl (l) → CH3Cl (g)	Δ_rH°(298.15 K) = 20.26 ± 0.5 kJ/mol	Manion 2002, Shorthose 1924, est unc
0.003	5515.3	CH3Cl (l) → CH3Cl (g)	Δ_rH°(292.24 K) = 20.71 ± 0.50 (×1.067) kJ/mol	Yates 1926, est unc
0.002	5515.1	CH3Cl (l) → CH3Cl (g)	Δ_rH°(298.15 K) = 20.5 ± 0.3 (×2.044) kJ/mol	Manion 2002
0.000	5516.13	CH3Cl (l) → CH3Cl (g)	Δ_rH°(273.130 K) = 21.348 ± 1.171 kJ/mol	Ganeff 1948, 2nd Law, ThermoData 2004
0.000	5516.9	CH3Cl (l) → CH3Cl (g)	Δ_rH°(243.750 K) = 22.107 ± 1.223 kJ/mol	Messerly 1940, 2nd Law, ThermoData 2004
0.000	5516.15	CH3Cl (l) → CH3Cl (g)	Δ_rH°(243.190 K) = 22.164 ± 1.235 kJ/mol	Ganeff 1948, 2nd Law, ThermoData 2004
0.000	5516.5	CH3Cl (l) → CH3Cl (g)	Δ_rH°(299.231 K) = 20.123 ± 1.403 kJ/mol	ThermoData 2004, 2nd Law
0.000	5516.3	CH3Cl (l) → CH3Cl (g)	Δ_rH°(231.405 K) = 22.544 ± 1.465 kJ/mol	ThermoData 2004, 2nd Law

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. 1.124 of the Thermochemical Network, Argonne National Laboratory, Lemont, Illinois 2022; available at ATcT.anl.gov [DOI: 10.17038/CSE/1885923]
4		Y. Ren, L. Zhou, A. Mellouki, V. Daële, M. Idir, S. S. Brown, B. Ruscic, Robert S. Paton, M. R. McGillen, and A. R. Ravishankara, Reactions of NO3 with Aromatic Aldehydes: Gas-Phase Kinetics and Insights into the Mechanism of the Reaction. Atmos. Chem. Phys. 21, 13537-13551 (2021) [DOI: 10.5194/acp2021-228]
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		T. L. Nguyen, D. H. Bross, B. Ruscic, G. B. Ellison, and J. F. Stanton, Mechanism, Thermochemistry, and Kinetics of the Reversible Reactions: C2H3 + H2 ⇌ C2H4 + H ⇌ C2H5. Faraday Discuss. , (Advance Article) (2022) [DOI: 10.1039/D1FD00124H]
8		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]
9		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 [8,9]).
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.