Chloromethane

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Reaction thermochemistry data

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Data compilation copyright by the U.S. Secretary of Commerce on behalf of the U.S.A. All rights reserved.

Data compiled as indicated in comments:
B - John E. Bartmess
M - Michael M. Meot-Ner (Mautner) and Sharon G. Lias
ALS - Hussein Y. Afeefy, Joel F. Liebman, and Stephen E. Stein

Note: Please consider using the reaction search for this species. This page allows searching of all reactions involving this species. A general reaction search form is also available. Future versions of this site may rely on reaction search pages in place of the enumerated reaction displays seen below.

Individual Reactions

Chlorine anion + Chloromethane = (Chlorine anion • Chloromethane)

By formula: Cl- + CH3Cl = (Cl- • CH3Cl)

Quantity Value Units Method Reference Comment
Δr43.5 ± 4.2kJ/molTDAsLi, Ross, et al., 1996gas phase; B
Δr49.0 ± 8.4kJ/molTDAsHiraoka, Mizuno, et al., 2001gas phase; B
Δr51.0 ± 8.4kJ/molIMRELarson and McMahon, 1984gas phase; B,M
Δr36.0 ± 0.84kJ/molTDAsDougherty, Dalton, et al., 1974gas phase; B,M
Δr63.6 ± 8.4kJ/molTDAsYamdagni and Kebarle, 1971gas phase; B
Quantity Value Units Method Reference Comment
Δr85.8J/mol*KN/ALarson and McMahon, 1984, 2gas phase; switching reaction(Cl-)t-C4H9OH, Entropy change calculated or estimated; French, Ikuta, et al., 1982; M
Δr64.0J/mol*KHPMSDougherty, Dalton, et al., 1974gas phase; Entropy change is questionable; M
Quantity Value Units Method Reference Comment
Δr24.3 ± 0.84kJ/molTDAsLi, Ross, et al., 1996gas phase; B
Δr20.3kJ/molTDAsHiraoka, Mizuno, et al., 2001gas phase; B
Δr26. ± 8.4kJ/molIMRELarson and McMahon, 1984gas phase; B,M
Δr17.2 ± 2.1kJ/molTDAsDougherty, Dalton, et al., 1974gas phase; B
Δr45.2 ± 8.4kJ/molTDAsYamdagni and Kebarle, 1971gas phase; B

CH2Cl- + Hydrogen cation = Chloromethane

By formula: CH2Cl- + H+ = CH3Cl

Quantity Value Units Method Reference Comment
Δr1672. ± 10.kJ/molEndoHierl, Henchman, et al., 1992gas phase; HO- + ClCH3: 8.8±2.3 kcal/mol endo; B
Δr1657. ± 13.kJ/molG+TSIngemann and Nibbering, 1985gas phase; B
Δr1659. ± 19.kJ/molEIAERogers, Simpson, et al., 2010gas phase; B
Δr1674. ± 8.4kJ/molIMRBPoutsma, Nash, et al., 1997gas phase; B
Δr1670. ± 17.kJ/molG+TSHenchman, Hierl, et al., 1985gas phase; HO- + MeCl: 0.38±0.1 eV endo; B
Quantity Value Units Method Reference Comment
Δr1628. ± 13.kJ/molIMREIngemann and Nibbering, 1985gas phase; B
Δr1641. ± 17.kJ/molIMRBHenchman, Hierl, et al., 1985gas phase; HO- + MeCl: 0.38±0.1 eV endo; B

(CH2Cl+ • Chloromethane) + Chloromethane = (CH2Cl+ • 2Chloromethane)

By formula: (CH2Cl+ • CH3Cl) + CH3Cl = (CH2Cl+ • 2CH3Cl)

Quantity Value Units Method Reference Comment
Δr24.kJ/molHPMSLuczynski, Malicki, et al., 1974gas phase; DG from graph, Entropy change is questionable; M
Quantity Value Units Method Reference Comment
Δr29.J/mol*KHPMSLuczynski, Malicki, et al., 1974gas phase; DG from graph, Entropy change is questionable; M

Free energy of reaction

ΔrG° (kJ/mol) T (K) Method Reference Comment
18.182.HPMSLuczynski, Malicki, et al., 1974gas phase; DG from graph, Entropy change is questionable; M

(CH4Cl+ • Chloromethane) + Chloromethane = (CH4Cl+ • 2Chloromethane)

By formula: (CH4Cl+ • CH3Cl) + CH3Cl = (CH4Cl+ • 2CH3Cl)

Quantity Value Units Method Reference Comment
Δr18.kJ/molHPMSLuczynski, Malicki, et al., 1974gas phase; DG from graph, Entropy change is questionable; M
Quantity Value Units Method Reference Comment
Δr4.6J/mol*KHPMSLuczynski, Malicki, et al., 1974gas phase; DG from graph, Entropy change is questionable; M

Free energy of reaction

ΔrG° (kJ/mol) T (K) Method Reference Comment
17.182.HPMSLuczynski, Malicki, et al., 1974gas phase; DG from graph, Entropy change is questionable; M

CH2Cl+ + Chloromethane = (CH2Cl+ • Chloromethane)

By formula: CH2Cl+ + CH3Cl = (CH2Cl+ • CH3Cl)

Quantity Value Units Method Reference Comment
Δr29.kJ/molHPMSLuczynski, Malicki, et al., 1974gas phase; DG from graph, Entropy change is questionable; M
Quantity Value Units Method Reference Comment
Δr-15.J/mol*KHPMSLuczynski, Malicki, et al., 1974gas phase; DG from graph, Entropy change is questionable; M

Free energy of reaction

ΔrG° (kJ/mol) T (K) Method Reference Comment
34.312.HPMSLuczynski, Malicki, et al., 1974gas phase; DG from graph, Entropy change is questionable; M

C3H7+ + Chloromethane = (C3H7+ • Chloromethane)

By formula: C3H7+ + CH3Cl = (C3H7+ • CH3Cl)

Quantity Value Units Method Reference Comment
Δr95.8kJ/molPHPMSSen Sharma and Kebarle, 1978gas phase; Entropy change is questionable; M
Quantity Value Units Method Reference Comment
Δr186.J/mol*KPHPMSSen Sharma and Kebarle, 1978gas phase; Entropy change is questionable; M

Methyl cation + Chloromethane = (Methyl cation • Chloromethane)

By formula: CH3+ + CH3Cl = (CH3+ • CH3Cl)

Quantity Value Units Method Reference Comment
Δr259.kJ/molPHPMSMcMahon, Heinis, et al., 1988gas phase; switching reaction(CH3+)N2, Entropy change calculated or estimated, uses MCA(N2) = 202. kJ/mol; Foster, Williamson, et al., 1974; M

Bromine anion + Chloromethane = (Bromine anion • Chloromethane)

By formula: Br- + CH3Cl = (Br- • CH3Cl)

Quantity Value Units Method Reference Comment
Δr45.6 ± 4.2kJ/molTDAsLi, Ross, et al., 1996gas phase; B
Quantity Value Units Method Reference Comment
Δr20.3 ± 0.84kJ/molTDAsLi, Ross, et al., 1996gas phase; B

CN- + Chloromethane = (CN- • Chloromethane)

By formula: CN- + CH3Cl = (CN- • CH3Cl)

Quantity Value Units Method Reference Comment
Δr42.7 ± 4.2kJ/molTDAsLi, Ross, et al., 1996gas phase; B
Quantity Value Units Method Reference Comment
Δr20.5 ± 0.84kJ/molTDAsLi, Ross, et al., 1996gas phase; B

CH3Cl2- + 2Chloromethane = C2H6Cl3-

By formula: CH3Cl2- + 2CH3Cl = C2H6Cl3-

Quantity Value Units Method Reference Comment
Δr46.44kJ/molN/AHiraoka, Mizuno, et al., 2001gas phase; B
Quantity Value Units Method Reference Comment
Δr16.5kJ/molTDAsHiraoka, Mizuno, et al., 2001gas phase; B

C2H6Cl3- + 3Chloromethane = C3H9Cl4-

By formula: C2H6Cl3- + 3CH3Cl = C3H9Cl4-

Quantity Value Units Method Reference Comment
Δr35.1kJ/molN/AHiraoka, Mizuno, et al., 2001gas phase; B
Quantity Value Units Method Reference Comment
Δr8.95kJ/molTDAsHiraoka, Mizuno, et al., 2001gas phase; B

C3H9Cl4- + 4Chloromethane = C4H12Cl5-

By formula: C3H9Cl4- + 4CH3Cl = C4H12Cl5-

Quantity Value Units Method Reference Comment
Δr31.8kJ/molN/AHiraoka, Mizuno, et al., 2001gas phase; B
Quantity Value Units Method Reference Comment
Δr5.61kJ/molTDAsHiraoka, Mizuno, et al., 2001gas phase; B

C4H12Cl5- + 5Chloromethane = C5H15Cl6-

By formula: C4H12Cl5- + 5CH3Cl = C5H15Cl6-

Quantity Value Units Method Reference Comment
Δr25.9kJ/molN/AHiraoka, Mizuno, et al., 2001gas phase; B
Quantity Value Units Method Reference Comment
Δr3.5kJ/molTDAsHiraoka, Mizuno, et al., 2001gas phase; B

C5H15Cl6- + 6Chloromethane = C6H18Cl7-

By formula: C5H15Cl6- + 6CH3Cl = C6H18Cl7-

Quantity Value Units Method Reference Comment
Δr24.3kJ/molN/AHiraoka, Mizuno, et al., 2001gas phase; B
Quantity Value Units Method Reference Comment
Δr1.8kJ/molTDAsHiraoka, Mizuno, et al., 2001gas phase; B

C6H18Cl7- + 7Chloromethane = C7H21Cl8-

By formula: C6H18Cl7- + 7CH3Cl = C7H21Cl8-

Quantity Value Units Method Reference Comment
Δr20.1kJ/molN/AHiraoka, Mizuno, et al., 2001gas phase; B
Quantity Value Units Method Reference Comment
Δr2.6kJ/molTDAsHiraoka, Mizuno, et al., 2001gas phase; B

C7H21Cl8- + 8Chloromethane = C8H24Cl9-

By formula: C7H21Cl8- + 8CH3Cl = C8H24Cl9-

Quantity Value Units Method Reference Comment
Δr19.7kJ/molN/AHiraoka, Mizuno, et al., 2001gas phase; B
Quantity Value Units Method Reference Comment
Δr2.2kJ/molTDAsHiraoka, Mizuno, et al., 2001gas phase; B

C2H5+ + Chloromethane = (C2H5+ • Chloromethane)

By formula: C2H5+ + CH3Cl = (C2H5+ • CH3Cl)

Quantity Value Units Method Reference Comment
Δr128.kJ/molPHPMSSen Sharma and Kebarle, 1978gas phase; M
Quantity Value Units Method Reference Comment
Δr128.J/mol*KPHPMSSen Sharma and Kebarle, 1978gas phase; M

Lithium ion (1+) + Chloromethane = (Lithium ion (1+) • Chloromethane)

By formula: Li+ + CH3Cl = (Li+ • CH3Cl)

Quantity Value Units Method Reference Comment
Δr100.kJ/molICRStaley and Beauchamp, 1975gas phase; switching reaction(Li+)H2O, from graph; Dzidic and Kebarle, 1970 interpolated; M

C4H9+ + Chloromethane = (C4H9+ • Chloromethane)

By formula: C4H9+ + CH3Cl = (C4H9+ • CH3Cl)

Quantity Value Units Method Reference Comment
Δr35.kJ/molPHPMSSharma, Meza de Hojer, et al., 1985gas phase; M
Quantity Value Units Method Reference Comment
Δr80.8J/mol*KPHPMSSharma, Meza de Hojer, et al., 1985gas phase; M

CH6N+ + Chloromethane = (CH6N+ • Chloromethane)

By formula: CH6N+ + CH3Cl = (CH6N+ • CH3Cl)

Quantity Value Units Method Reference Comment
Δr44.8kJ/molPHPMSMeot-Ner, 1984gas phase; M
Quantity Value Units Method Reference Comment
Δr86.2J/mol*KPHPMSMeot-Ner, 1984gas phase; M

Hydrogen + Chloromethane = Methane + Hydrogen chloride

By formula: H2 + CH3Cl = CH4 + HCl

Quantity Value Units Method Reference Comment
Δr-80.8 ± 0.4kJ/molChydLacher, Emery, et al., 1956gas phase; ALS

References

Go To: Top, Reaction thermochemistry data, Notes

Data compilation copyright by the U.S. Secretary of Commerce on behalf of the U.S.A. All rights reserved.

Li, Ross, et al., 1996
Li, C.; Ross, P.; Szulejko, J.; McMahon, T.B., High-Pressure Mass Spectrometric Investigations of the Potential Energy Surfaces of Gas-Phase Sn2 Reactions., J. Am. Chem. Soc., 1996, 118, 39, 9360, https://doi.org/10.1021/ja960565o . [all data]

Hiraoka, Mizuno, et al., 2001
Hiraoka, K.; Mizuno, T.; Iino, T.; Eguchi, D.; Yamabe, S., Characteristic changes of bond energies for gas-phase cluster ions of halide ions with methane and chloromethanes, J. Phys. Chem. A, 2001, 105, 20, 4887-4893, https://doi.org/10.1021/jp010143n . [all data]

Larson and McMahon, 1984
Larson, J.W.; McMahon, T.B., Hydrogen bonding in gas phase anions. An experimental investigation of the interaction between chloride ion and bronsted acids from ICR chloride exchange equilibria, J. Am. Chem. Soc., 1984, 106, 517. [all data]

Dougherty, Dalton, et al., 1974
Dougherty, R.C.; Dalton, J.; Roberts, J.D., SN2 reactions in the gas phase: Structure of the transition state, Org. Mass Spectrom., 1974, 8, 77. [all data]

Yamdagni and Kebarle, 1971
Yamdagni, R.; Kebarle, P., Hydrogen bonding energies to negative ions from gas phase measurements of ionic equilibria, J. Am. Chem. Soc., 1971, 93, 7139. [all data]

Larson and McMahon, 1984, 2
Larson, J.W.; McMahon, T.B., Gas phase negative ion chemistry of alkylchloroformates, Can. J. Chem., 1984, 62, 675. [all data]

French, Ikuta, et al., 1982
French, M.A.; Ikuta, S.; Kebarle, P., Hydrogen bonding of O-H and C-H hydrogen donors to Cl-. Results from mass spectrometric measurement of the ion-molecule equilibria RH + Cl- = RHCl-, Can. J. Chem., 1982, 60, 1907. [all data]

Hierl, Henchman, et al., 1992
Hierl, P.M.; Henchman, M.J.; Paulson, J.F., Threshold Energies for the Reactions HO- + MeX - MeOH + X- measured by Tandem Mass Spectrometry: Acidities of MeCl and MeBr, Int. J. Mass Spectrom. Ion Proc., 1992, 117, 475, https://doi.org/10.1016/0168-1176(92)80109-E . [all data]

Ingemann and Nibbering, 1985
Ingemann, S.; Nibbering, N.M.M., Gas-phase acidity of CH3X [X = P(CH3)2, SCH3, F, Cl, Br, I] compounds, J. Chem. Soc. Perkin Trans. 2, 1985, 837. [all data]

Rogers, Simpson, et al., 2010
Rogers, N.J.; Simpson, M.J.; Tuckett, R.P.; Dunn, K.F.; Latimer, C.J., Vacuum-UV negative photoion spectroscopy of CH3F, CH3Cl and CH3Br, Phys. Chem. Chem. Phys., 2010, 12, 36, 10971-10980, https://doi.org/10.1039/c0cp00234h . [all data]

Poutsma, Nash, et al., 1997
Poutsma, J.C.; Nash, J.J.; Paulino, J.A.; Squires, R.R., Absolute Heats of Formation of Phenylcarbene and Vinylcarbene, J. Am. Chem. Soc., 1997, 119, 20, 4686, https://doi.org/10.1021/ja963918s . [all data]

Henchman, Hierl, et al., 1985
Henchman, M.; Hierl, P.M.; Paulson, J.F., Nucleophilic displacement vs. proton tranfer: The system OH-.(H2O)0,1,2 + CH3Cl in the relative energy range 0.03-5 eV, J. Am. Chem. Soc., 1985, 107, 2812. [all data]

Luczynski, Malicki, et al., 1974
Luczynski, Z.; Malicki, W.; Wincel, H., Positive Ion Reactions of Methyl Cloride in the Gas Phase, Int. J. Mass Spectrom. Ion Phys., 1974, 15, 3, 321, https://doi.org/10.1016/0020-7381(74)85009-6 . [all data]

Sen Sharma and Kebarle, 1978
Sen Sharma, D.K.; Kebarle, P., Binding Energies and Stabilities of Chloronium Ions from Study of the Gas - Phase Equilibria: R1+ + ClR2 = R1ClR2+, J. Am. Chem. Soc., 1978, 100, 18, 5826, https://doi.org/10.1021/ja00486a039 . [all data]

McMahon, Heinis, et al., 1988
McMahon, T.; Heinis, T.; Nicol, G.; Hovey, J.K.; Kebarle, P., Methyl Cation Affinities, J. Am. Chem. Soc., 1988, 110, 23, 7591, https://doi.org/10.1021/ja00231a002 . [all data]

Foster, Williamson, et al., 1974
Foster, M.S.; Williamson, A.D.; Beauchamp, J.L., Photoionization mass spectrometry of trans-azomethane, Int. J. Mass Spectrom. Ion Phys., 1974, 15, 429. [all data]

Staley and Beauchamp, 1975
Staley, R.H.; Beauchamp, J.L., Intrinsic Acid - Base Properties of Molecules. Binding Energies of Li+ to pi - and n - Donor Bases, J. Am. Chem. Soc., 1975, 97, 20, 5920, https://doi.org/10.1021/ja00853a050 . [all data]

Dzidic and Kebarle, 1970
Dzidic, I.; Kebarle, P., Hydration of the Alkali Ions in the Gas Phase. Enthalpies and Entropies of Reactions M+(H2O)n-1 + H2O = M+(H2O)n, J. Phys. Chem., 1970, 74, 7, 1466, https://doi.org/10.1021/j100702a013 . [all data]

Sharma, Meza de Hojer, et al., 1985
Sharma, D.M.S.; Meza de Hojer, S.; Kebarle, P., Stabilities of halonium ions from a study of gas-phase equilibria R+ + XR' = (RXR')+, J. Am. Chem. Soc., 1985, 107, 13, 3757, https://doi.org/10.1021/ja00299a002 . [all data]

Meot-Ner, 1984
Meot-Ner, (Mautner)M., The Ionic Hydrogen Bond and Ion Solvation. 1. -NH+ O-, -NH+ N- and -OH+ O- Bonds. Correlations with Proton Affinity. Deviations Due to Structural Effects, J. Am. Chem. Soc., 1984, 106, 5, 1257, https://doi.org/10.1021/ja00317a015 . [all data]

Lacher, Emery, et al., 1956
Lacher, J.R.; Emery, E.; Bohmfalk, E.; Park, J.D., Reaction heats of organic compounds. IV. A high temperature calorimeter and the hydrogenation of methyl ethyl and vinyl chlorides, J. Phys. Chem., 1956, 60, 492-495. [all data]


Notes

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