Methane

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Reaction thermochemistry data

Go To: Top, Gas phase ion energetics data, Vibrational and/or electronic energy levels, References, Notes

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
MS - José A. Martinho Simões
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.

Reactions 1 to 50

CH3- + Hydrogen cation = Methane

By formula: CH3- + H+ = CH4

Quantity Value Units Method Reference Comment
Δr416.74 ± 0.70kcal/molD-EAEllison, Engelking, et al., 1978gas phase; B
Δr418.0 ± 3.5kcal/molCIDTGraul and Squires, 1990gas phase; B
Δr>404.18 ± 0.10kcal/molG+TSBohme, Lee-Ruff, et al., 1972gas phase; B
Δr414.80kcal/molN/ACheck, Faust, et al., 2001gas phase; FeBr3; ; ΔS(EA)=9.3; B
Quantity Value Units Method Reference Comment
Δr408.66 ± 0.80kcal/molH-TSEllison, Engelking, et al., 1978gas phase; B
Δr409.9 ± 3.6kcal/molH-TSGraul and Squires, 1990gas phase; B
Δr>396.10kcal/molIMRBBohme, Lee-Ruff, et al., 1972gas phase; B
Δr407.30kcal/molN/ACheck, Faust, et al., 2001gas phase; FeBr3; ; ΔS(EA)=9.3; B

(CH5+ • Methane) + Methane = (CH5+ • 2Methane)

By formula: (CH5+ • CH4) + CH4 = (CH5+ • 2CH4)

Quantity Value Units Method Reference Comment
Δr5.3 ± 0.3kcal/molPHPMSHiraoka and Mori, 1989gas phase; M
Δr5.9kcal/molPHPMSHiraoka and Kebarle, 1975gas phase; M
Δr1.5kcal/molHPMSField and Beggs, 1971gas phase; Entropy change is questionable; M
Quantity Value Units Method Reference Comment
Δr24.9cal/mol*KPHPMSHiraoka and Mori, 1989gas phase; M
Δr24.4cal/mol*KPHPMSHiraoka and Kebarle, 1975gas phase; M
Δr7.2cal/mol*KHPMSField and Beggs, 1971gas phase; Entropy change is questionable; M

CH5+ + Methane = (CH5+ • Methane)

By formula: CH5+ + CH4 = (CH5+ • CH4)

Quantity Value Units Method Reference Comment
Δr6.9 ± 0.3kcal/molPHPMSHiraoka and Mori, 1989gas phase; M
Δr7.4kcal/molPHPMSHiraoka and Kebarle, 1975gas phase; M
Δr4.1kcal/molHPMSField and Beggs, 1971gas phase; Entropy change is questionable; M
Quantity Value Units Method Reference Comment
Δr22.1cal/mol*KPHPMSHiraoka and Mori, 1989gas phase; M
Δr20.8cal/mol*KPHPMSHiraoka and Kebarle, 1975gas phase; M
Δr12.4cal/mol*KHPMSField and Beggs, 1971gas phase; Entropy change is questionable; M

C2H5+ + Methane = (C2H5+ • Methane)

By formula: C2H5+ + CH4 = (C2H5+ • CH4)

Quantity Value Units Method Reference Comment
Δr5.50kcal/molPHPMSHiraoka, Mori, et al., 1993gas phase; M
Δr6.6kcal/molPHPMSHiroka and Kebarle, 1975gas phase; M
Δr2.4kcal/molHPMSField and Beggs, 1971gas phase; Entropy change is questionable; M
Quantity Value Units Method Reference Comment
Δr22.2cal/mol*KPHPMSHiraoka, Mori, et al., 1993gas phase; M
Δr23.4cal/mol*KPHPMSHiroka and Kebarle, 1975gas phase; M
Δr8.6cal/mol*KHPMSField and Beggs, 1971gas phase; Entropy change is questionable; M

(Cobalt ion (1+) • 2Methane) + Methane = (Cobalt ion (1+) • 3Methane)

By formula: (Co+ • 2CH4) + CH4 = (Co+ • 3CH4)

Quantity Value Units Method Reference Comment
Δr11.kcal/molSIDTKemper, Bushnell, et al., 1993gas phase; Entropy change calculated or estimated; M
Quantity Value Units Method Reference Comment
Δr20.cal/mol*KN/AKemper, Bushnell, et al., 1993gas phase; Entropy change calculated or estimated; M

Enthalpy of reaction

ΔrH° (kcal/mol) T (K) Method Reference Comment
9.8 (+1.2,-0.) CIDArmentrout and Kickel, 1994gas phase; guided ion beam CID; M

Free energy of reaction

ΔrG° (kcal/mol) T (K) Method Reference Comment
0.7477.SIDTKemper, Bushnell, et al., 1993gas phase; Entropy change calculated or estimated; M

Cobalt ion (1+) + Methane = (Cobalt ion (1+) • Methane)

By formula: Co+ + CH4 = (Co+ • CH4)

Quantity Value Units Method Reference Comment
Δr19.8cal/mol*KSIDTKemper, Bushnell, et al., 1993gas phase; ΔrS(530 K); M

Enthalpy of reaction

ΔrH° (kcal/mol) T (K) Method Reference Comment
21.5 (+1.6,-0.) CIDHaynes and Armentrout, 1996gas phase; guided ion beam CID; M
21.5 (+1.4,-0.) CIDArmentrout and Kickel, 1994gas phase; guided ion beam CID; M
22.5 (+0.5,-0.) SIDTKemper, Bushnell, et al., 1993gas phase; ΔrS(530 K); M

(Cobalt ion (1+) • Methane) + Hydrogen = (Cobalt ion (1+) • Hydrogen • Methane)

By formula: (Co+ • CH4) + H2 = (Co+ • H2 • CH4)

Quantity Value Units Method Reference Comment
Δr22.9cal/mol*KSIDTKemper, Bushnell, et al., 1993gas phase; switching reaction(Co+).2H2, ΔrS(440 K); Kemper, Bushnell, et al., 1993, 2; M

Enthalpy of reaction

ΔrH° (kcal/mol) T (K) Method Reference Comment
17.4 (+0.8,-0.) SIDTKemper, Bushnell, et al., 1993gas phase; switching reaction(Co+).2H2, ΔrS(440 K); Kemper, Bushnell, et al., 1993, 2; M

(Cobalt ion (1+) • Hydrogen) + Methane = (Cobalt ion (1+) • Methane • Hydrogen)

By formula: (Co+ • H2) + CH4 = (Co+ • CH4 • H2)

Quantity Value Units Method Reference Comment
Δr21.8cal/mol*KSIDTKemper, Bushnell, et al., 1993gas phase; switching reaction(Co+)2H2, ΔrS(440 K); Kemper, Bushnell, et al., 1993, 2; M

Enthalpy of reaction

ΔrH° (kcal/mol) T (K) Method Reference Comment
22.6 (+1.2,-0.) SIDTKemper, Bushnell, et al., 1993gas phase; switching reaction(Co+)2H2, ΔrS(440 K); Kemper, Bushnell, et al., 1993, 2; M

Manganese, pentacarbonylmethyl- (g) = C5MnO5 (g) + Methane (g)

By formula: C6H3MnO5 (g) = C5MnO5 (g) + CH4 (g)

Quantity Value Units Method Reference Comment
Δr45.9 ± 3.6kcal/molPIMSMartinho Simões and Beauchamp, 1990The reaction enthalpy was derived from the appearance energy of Mn(CO)5(+), 224.8 ± 1.1 kcal/mol, using Mn(CO)5(Me) as the neutral precursor, together with the adiabatic ionization energy of Mn(CO)5 radical, 179. ± 3.3 kcal/mol Martinho Simões and Beauchamp, 1990; MS

(Cobalt ion (1+) • Methane) + Methane = (Cobalt ion (1+) • 2Methane)

By formula: (Co+ • CH4) + CH4 = (Co+ • 2CH4)

Quantity Value Units Method Reference Comment
Δr26.1cal/mol*KSIDTKemper, Bushnell, et al., 1993gas phase; ΔrS(500 K); M

Enthalpy of reaction

ΔrH° (kcal/mol) T (K) Method Reference Comment
22.9 (+1.2,-0.) CIDArmentrout and Kickel, 1994gas phase; guided ion beam CID; M
24.8 (+1.0,-0.) SIDTKemper, Bushnell, et al., 1993gas phase; ΔrS(500 K); M

(CH5+ • 2Methane) + Methane = (CH5+ • 3Methane)

By formula: (CH5+ • 2CH4) + CH4 = (CH5+ • 3CH4)

Quantity Value Units Method Reference Comment
Δr3.1 ± 0.2kcal/molPHPMSHiraoka and Mori, 1989gas phase; M
Δr4.1kcal/molPHPMSHiraoka and Kebarle, 1975gas phase; M
Quantity Value Units Method Reference Comment
Δr22.4cal/mol*KPHPMSHiraoka and Mori, 1989gas phase; M
Δr26.1cal/mol*KPHPMSHiraoka and Kebarle, 1975gas phase; M

(CH5+ • 3Methane) + Methane = (CH5+ • 4Methane)

By formula: (CH5+ • 3CH4) + CH4 = (CH5+ • 4CH4)

Quantity Value Units Method Reference Comment
Δr3.0 ± 0.2kcal/molPHPMSHiraoka and Mori, 1989gas phase; M
Δr3.9kcal/molPHPMSHiraoka and Kebarle, 1975gas phase; M
Quantity Value Units Method Reference Comment
Δr23.7cal/mol*KPHPMSHiraoka and Mori, 1989gas phase; M
Δr26.6cal/mol*KPHPMSHiraoka and Kebarle, 1975gas phase; M

Hydrogen bromide (g) + CH3BrMg (solution) = Methane (solution) + Br2Mg (solution)

By formula: HBr (g) + CH3BrMg (solution) = CH4 (solution) + Br2Mg (solution)

Quantity Value Units Method Reference Comment
Δr-65.61 ± 0.53kcal/molRSCHolm, 1981solvent: Diethyl ether; The enthalpy of formation was calculated using the assumptions and the auxiliary data in Holm, 1981, except for the organic compound, whose enthalpy of formation was quoted from Pedley, 1994; MS

(Cobalt ion (1+) • Methane) + Ethane = (Cobalt ion (1+) • Ethane • Methane)

By formula: (Co+ • CH4) + C2H6 = (Co+ • C2H6 • CH4)

Quantity Value Units Method Reference Comment
Δr25.9cal/mol*KSIDTKemper, Bushnell, et al., 1993gas phase; switching reaction(Co+).2CH4, ΔrS(480 K); M

Enthalpy of reaction

ΔrH° (kcal/mol) T (K) Method Reference Comment
28.4 (+1.3,-0.) SIDTKemper, Bushnell, et al., 1993gas phase; switching reaction(Co+).2CH4, ΔrS(480 K); M

C63H91CoN13O14P (solution) = Cyanocobalamin (solution) + Methane (solution)

By formula: C63H91CoN13O14P (solution) = C63H88CoN14O14P (solution) + CH4 (solution)

Quantity Value Units Method Reference Comment
Δr37.0 ± 3.1kcal/molKinSMartin and Finke, 1990solvent: Ethylene glycol; Please also see Martin and Finke, 1992. The reaction enthalpy relies on 41.0 ± 3.0 kcal/mol for the reaction activation enthalpy. The reaction refers to "base-on" cobalamine.; MS

C3H7+ + Methane = (C3H7+ • Methane)

By formula: C3H7+ + CH4 = (C3H7+ • CH4)

Quantity Value Units Method Reference Comment
Δr2.59kcal/molPHPMSHiraoka, Mori, et al., 1993gas phase; M
Δr3.4kcal/molPHPMSHiraoka and Kebarle, 1976gas phase; M
Quantity Value Units Method Reference Comment
Δr17.4cal/mol*KPHPMSHiraoka, Mori, et al., 1993gas phase; M
Δr20.cal/mol*KPHPMSHiraoka and Kebarle, 1976gas phase; M

Hydrogen iodide + Methane, iodo- = Methane + Iodine

By formula: HI + CH3I = CH4 + I2

Quantity Value Units Method Reference Comment
Δr-12.56 ± 0.13kcal/molEqkGolden, Walsh, et al., 1965gas phase; ALS
Δr-12.67 ± 0.05kcal/molEqkGoy and Pritchard, 1965gas phase; ALS
Δr-11.0 ± 1.3kcal/molCmNichol and Ubbelohde, 1952gas phase; ALS

(C2H5+ • 9Methane) + Methane = (C2H5+ • 10Methane)

By formula: (C2H5+ • 9CH4) + CH4 = (C2H5+ • 10CH4)

Quantity Value Units Method Reference Comment
Δr1.91kcal/molPHPMSHiraoka, Mori, et al., 1993gas phase; Entropy change calculated or estimated; M
Quantity Value Units Method Reference Comment
Δr22.cal/mol*KN/AHiraoka, Mori, et al., 1993gas phase; Entropy change calculated or estimated; M

(C3H7+ • 7Methane) + Methane = (C3H7+ • 8Methane)

By formula: (C3H7+ • 7CH4) + CH4 = (C3H7+ • 8CH4)

Quantity Value Units Method Reference Comment
Δr1.98kcal/molPHPMSHiraoka, Mori, et al., 1993gas phase; Entropy change calculated or estimated; M
Quantity Value Units Method Reference Comment
Δr22.cal/mol*KN/AHiraoka, Mori, et al., 1993gas phase; Entropy change calculated or estimated; M

(C4H9+ • 8Methane) + Methane = (C4H9+ • 9Methane)

By formula: (C4H9+ • 8CH4) + CH4 = (C4H9+ • 9CH4)

Quantity Value Units Method Reference Comment
Δr1.86kcal/molPHPMSHiraoka, Mori, et al., 1993gas phase; Entropy change calculated or estimated; M
Quantity Value Units Method Reference Comment
Δr20.cal/mol*KN/AHiraoka, Mori, et al., 1993gas phase; Entropy change calculated or estimated; M

(CH5+ • 8Methane) + Methane = (CH5+ • 9Methane)

By formula: (CH5+ • 8CH4) + CH4 = (CH5+ • 9CH4)

Quantity Value Units Method Reference Comment
Δr1.54kcal/molPHPMSHiraoka and Mori, 1989gas phase; Entropy change calculated or estimated; M
Quantity Value Units Method Reference Comment
Δr20.cal/mol*KN/AHiraoka and Mori, 1989gas phase; Entropy change calculated or estimated; M

(Cobalt ion (1+) • Water) + Methane = (Cobalt ion (1+) • Methane • Water)

By formula: (Co+ • H2O) + CH4 = (Co+ • CH4 • H2O)

Quantity Value Units Method Reference Comment
Δr27.0cal/mol*KSIDTKemper, Bushnell, et al., 1993gas phase; ΔrS(525 K); M

Enthalpy of reaction

ΔrH° (kcal/mol) T (K) Method Reference Comment
25.9 (+0.7,-0.) SIDTKemper, Bushnell, et al., 1993gas phase; ΔrS(525 K); M

(Hydronium cation • Methane) + Methane = (Hydronium cation • 2Methane)

By formula: (H3O+ • CH4) + CH4 = (H3O+ • 2CH4)

Quantity Value Units Method Reference Comment
Δr3.4kcal/molHPMSBennet and Field, 1972gas phase; Entropy change is questionable; M
Quantity Value Units Method Reference Comment
Δr8.1cal/mol*KHPMSBennet and Field, 1972gas phase; Entropy change is questionable; M

(Cobalt ion (1+) • Ethane) + Methane = (Cobalt ion (1+) • Methane • Ethane)

By formula: (Co+ • C2H6) + CH4 = (Co+ • CH4 • C2H6)

Quantity Value Units Method Reference Comment
Δr26.4cal/mol*KSIDTKemper, Bushnell, et al., 1993gas phase; ΔrS(490 K); M

Enthalpy of reaction

ΔrH° (kcal/mol) T (K) Method Reference Comment
24.4 (+1.1,-0.) SIDTKemper, Bushnell, et al., 1993gas phase; ΔrS(490 K); M

NH4+ + Methane = (NH4+ • Methane)

By formula: H4N+ + CH4 = (H4N+ • CH4)

Quantity Value Units Method Reference Comment
Δr3.6kcal/molHPMSBennet and Field, 1972, 2gas phase; Entropy change is questionable; M
Quantity Value Units Method Reference Comment
Δr15.5cal/mol*KHPMSBennet and Field, 1972, 2gas phase; Entropy change is questionable; M

Hydrogen bromide (g) + methyllithium (cr) = Methane (g) + Lithium bromide (cr)

By formula: HBr (g) + CH3Li (cr) = CH4 (g) + BrLi (cr)

Quantity Value Units Method Reference Comment
Δr-75.84 ± 0.48kcal/molRSCHolm, 1974Please also see Pedley and Rylance, 1977. The reaction enthalpy was quoted from Pedley and Rylance, 1977. See Liebman, Martinho Simões, et al., 1995 for comments; MS

2Hydrogen + Methylene chloride = Methane + 2Hydrogen chloride

By formula: 2H2 + CH2Cl2 = CH4 + 2HCl

Quantity Value Units Method Reference Comment
Δr-39.05 ± 0.30kcal/molChydLacher, Amador, et al., 1967gas phase; Reanalyzed by Cox and Pilcher, 1970, Original value = -40.07 ± 0.30 kcal/mol; At 250 C; ALS

Dimethylzinc (l) + (Sulfuric Acid • 100Water) (solution) = 2Methane (g) + (zinc sulphate • 100Water) (solution)

By formula: C2H6Zn (l) + (H2O4S • 100H2O) (solution) = 2CH4 (g) + (O4SZn • 100H2O) (solution)

Quantity Value Units Method Reference Comment
Δr-81.7 ± 0.2kcal/molRSCCarson, Hartley, et al., 1949Please also see Pedley and Rylance, 1977 and Cox and Pilcher, 1970, 2.; MS

(CH5+ • 4Methane) + Methane = (CH5+ • 5Methane)

By formula: (CH5+ • 4CH4) + CH4 = (CH5+ • 5CH4)

Quantity Value Units Method Reference Comment
Δr2.8 ± 0.2kcal/molPHPMSHiraoka and Mori, 1989gas phase; M
Quantity Value Units Method Reference Comment
Δr24.8cal/mol*KPHPMSHiraoka and Mori, 1989gas phase; M

(CH5+ • 5Methane) + Methane = (CH5+ • 6Methane)

By formula: (CH5+ • 5CH4) + CH4 = (CH5+ • 6CH4)

Quantity Value Units Method Reference Comment
Δr2.7 ± 0.2kcal/molPHPMSHiraoka and Mori, 1989gas phase; M
Quantity Value Units Method Reference Comment
Δr25.3cal/mol*KPHPMSHiraoka and Mori, 1989gas phase; M

(CH5+ • 6Methane) + Methane = (CH5+ • 7Methane)

By formula: (CH5+ • 6CH4) + CH4 = (CH5+ • 7CH4)

Quantity Value Units Method Reference Comment
Δr2.7 ± 0.2kcal/molPHPMSHiraoka and Mori, 1989gas phase; M
Quantity Value Units Method Reference Comment
Δr26.5cal/mol*KPHPMSHiraoka and Mori, 1989gas phase; M

(CH5+ • 7Methane) + Methane = (CH5+ • 8Methane)

By formula: (CH5+ • 7CH4) + CH4 = (CH5+ • 8CH4)

Quantity Value Units Method Reference Comment
Δr2.0 ± 0.2kcal/molPHPMSHiraoka and Mori, 1989gas phase; M
Quantity Value Units Method Reference Comment
Δr21.6cal/mol*KPHPMSHiraoka and Mori, 1989gas phase; M

(C2H5+ • 2Methane) + Methane = (C2H5+ • 3Methane)

By formula: (C2H5+ • 2CH4) + CH4 = (C2H5+ • 3CH4)

Quantity Value Units Method Reference Comment
Δr2.28kcal/molPHPMSHiraoka, Mori, et al., 1993gas phase; M
Quantity Value Units Method Reference Comment
Δr17.9cal/mol*KPHPMSHiraoka, Mori, et al., 1993gas phase; M

(C2H5+ • 3Methane) + Methane = (C2H5+ • 4Methane)

By formula: (C2H5+ • 3CH4) + CH4 = (C2H5+ • 4CH4)

Quantity Value Units Method Reference Comment
Δr2.26kcal/molPHPMSHiraoka, Mori, et al., 1993gas phase; M
Quantity Value Units Method Reference Comment
Δr18.4cal/mol*KPHPMSHiraoka, Mori, et al., 1993gas phase; M

(C2H5+ • 4Methane) + Methane = (C2H5+ • 5Methane)

By formula: (C2H5+ • 4CH4) + CH4 = (C2H5+ • 5CH4)

Quantity Value Units Method Reference Comment
Δr2.22kcal/molPHPMSHiraoka, Mori, et al., 1993gas phase; M
Quantity Value Units Method Reference Comment
Δr18.9cal/mol*KPHPMSHiraoka, Mori, et al., 1993gas phase; M

(C2H5+ • 5Methane) + Methane = (C2H5+ • 6Methane)

By formula: (C2H5+ • 5CH4) + CH4 = (C2H5+ • 6CH4)

Quantity Value Units Method Reference Comment
Δr2.21kcal/molPHPMSHiraoka, Mori, et al., 1993gas phase; M
Quantity Value Units Method Reference Comment
Δr19.4cal/mol*KPHPMSHiraoka, Mori, et al., 1993gas phase; M

(C2H5+ • 6Methane) + Methane = (C2H5+ • 7Methane)

By formula: (C2H5+ • 6CH4) + CH4 = (C2H5+ • 7CH4)

Quantity Value Units Method Reference Comment
Δr2.13kcal/molPHPMSHiraoka, Mori, et al., 1993gas phase; M
Quantity Value Units Method Reference Comment
Δr20.7cal/mol*KPHPMSHiraoka, Mori, et al., 1993gas phase; M

(C2H5+ • 7Methane) + Methane = (C2H5+ • 8Methane)

By formula: (C2H5+ • 7CH4) + CH4 = (C2H5+ • 8CH4)

Quantity Value Units Method Reference Comment
Δr2.10kcal/molPHPMSHiraoka, Mori, et al., 1993gas phase; M
Quantity Value Units Method Reference Comment
Δr21.0cal/mol*KPHPMSHiraoka, Mori, et al., 1993gas phase; M

(C2H5+ • 8Methane) + Methane = (C2H5+ • 9Methane)

By formula: (C2H5+ • 8CH4) + CH4 = (C2H5+ • 9CH4)

Quantity Value Units Method Reference Comment
Δr2.08kcal/molPHPMSHiraoka, Mori, et al., 1993gas phase; M
Quantity Value Units Method Reference Comment
Δr21.8cal/mol*KPHPMSHiraoka, Mori, et al., 1993gas phase; M

(C3H7+ • 2Methane) + Methane = (C3H7+ • 3Methane)

By formula: (C3H7+ • 2CH4) + CH4 = (C3H7+ • 3CH4)

Quantity Value Units Method Reference Comment
Δr2.26kcal/molPHPMSHiraoka, Mori, et al., 1993gas phase; M
Quantity Value Units Method Reference Comment
Δr18.4cal/mol*KPHPMSHiraoka, Mori, et al., 1993gas phase; M

(C3H7+ • 3Methane) + Methane = (C3H7+ • 4Methane)

By formula: (C3H7+ • 3CH4) + CH4 = (C3H7+ • 4CH4)

Quantity Value Units Method Reference Comment
Δr2.20kcal/molPHPMSHiraoka, Mori, et al., 1993gas phase; M
Quantity Value Units Method Reference Comment
Δr19.0cal/mol*KPHPMSHiraoka, Mori, et al., 1993gas phase; M

(C3H7+ • 4Methane) + Methane = (C3H7+ • 5Methane)

By formula: (C3H7+ • 4CH4) + CH4 = (C3H7+ • 5CH4)

Quantity Value Units Method Reference Comment
Δr2.20kcal/molPHPMSHiraoka, Mori, et al., 1993gas phase; M
Quantity Value Units Method Reference Comment
Δr20.9cal/mol*KPHPMSHiraoka, Mori, et al., 1993gas phase; M

(C3H7+ • 5Methane) + Methane = (C3H7+ • 6Methane)

By formula: (C3H7+ • 5CH4) + CH4 = (C3H7+ • 6CH4)

Quantity Value Units Method Reference Comment
Δr2.19kcal/molPHPMSHiraoka, Mori, et al., 1993gas phase; M
Quantity Value Units Method Reference Comment
Δr21.0cal/mol*KPHPMSHiraoka, Mori, et al., 1993gas phase; M

(C3H7+ • 6Methane) + Methane = (C3H7+ • 7Methane)

By formula: (C3H7+ • 6CH4) + CH4 = (C3H7+ • 7CH4)

Quantity Value Units Method Reference Comment
Δr2.16kcal/molPHPMSHiraoka, Mori, et al., 1993gas phase; M
Quantity Value Units Method Reference Comment
Δr21.8cal/mol*KPHPMSHiraoka, Mori, et al., 1993gas phase; M

(C4H9+ • 2Methane) + Methane = (C4H9+ • 3Methane)

By formula: (C4H9+ • 2CH4) + CH4 = (C4H9+ • 3CH4)

Quantity Value Units Method Reference Comment
Δr2.37kcal/molPHPMSHiraoka, Mori, et al., 1993gas phase; M
Quantity Value Units Method Reference Comment
Δr19.7cal/mol*KPHPMSHiraoka, Mori, et al., 1993gas phase; M

(C4H9+ • 3Methane) + Methane = (C4H9+ • 4Methane)

By formula: (C4H9+ • 3CH4) + CH4 = (C4H9+ • 4CH4)

Quantity Value Units Method Reference Comment
Δr2.36kcal/molPHPMSHiraoka, Mori, et al., 1993gas phase; M
Quantity Value Units Method Reference Comment
Δr20.0cal/mol*KPHPMSHiraoka, Mori, et al., 1993gas phase; M

(C4H9+ • 4Methane) + Methane = (C4H9+ • 5Methane)

By formula: (C4H9+ • 4CH4) + CH4 = (C4H9+ • 5CH4)

Quantity Value Units Method Reference Comment
Δr2.21kcal/molPHPMSHiraoka, Mori, et al., 1993gas phase; M
Quantity Value Units Method Reference Comment
Δr19.4cal/mol*KPHPMSHiraoka, Mori, et al., 1993gas phase; M

(C4H9+ • 5Methane) + Methane = (C4H9+ • 6Methane)

By formula: (C4H9+ • 5CH4) + CH4 = (C4H9+ • 6CH4)

Quantity Value Units Method Reference Comment
Δr2.09kcal/molPHPMSHiraoka, Mori, et al., 1993gas phase; M
Quantity Value Units Method Reference Comment
Δr19.3cal/mol*KPHPMSHiraoka, Mori, et al., 1993gas phase; M

(C4H9+ • 6Methane) + Methane = (C4H9+ • 7Methane)

By formula: (C4H9+ • 6CH4) + CH4 = (C4H9+ • 7CH4)

Quantity Value Units Method Reference Comment
Δr2.05kcal/molPHPMSHiraoka, Mori, et al., 1993gas phase; M
Quantity Value Units Method Reference Comment
Δr19.7cal/mol*KPHPMSHiraoka, Mori, et al., 1993gas phase; M

(C4H9+ • 7Methane) + Methane = (C4H9+ • 8Methane)

By formula: (C4H9+ • 7CH4) + CH4 = (C4H9+ • 8CH4)

Quantity Value Units Method Reference Comment
Δr1.99kcal/molPHPMSHiraoka, Mori, et al., 1993gas phase; M
Quantity Value Units Method Reference Comment
Δr20.1cal/mol*KPHPMSHiraoka, Mori, et al., 1993gas phase; M

Gas phase ion energetics data

Go To: Top, Reaction thermochemistry data, Vibrational and/or electronic energy levels, References, Notes

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

Data evaluated as indicated in comments:
HL - Edward P. Hunter and Sharon G. Lias
L - Sharon G. Lias

Data compiled as indicated in comments:
B - John E. Bartmess
LBLHLM - Sharon G. Lias, John E. Bartmess, Joel F. Liebman, John L. Holmes, Rhoda D. Levin, and W. Gary Mallard
LLK - Sharon G. Lias, Rhoda D. Levin, and Sherif A. Kafafi
RDSH - Henry M. Rosenstock, Keith Draxl, Bruce W. Steiner, and John T. Herron

View reactions leading to CH4+ (ion structure unspecified)

Quantity Value Units Method Reference Comment
IE (evaluated)12.61 ± 0.01eVN/AN/AL
Quantity Value Units Method Reference Comment
Proton affinity (review)129.9kcal/molN/AHunter and Lias, 1998HL
Quantity Value Units Method Reference Comment
Gas basicity124.4kcal/molN/AHunter and Lias, 1998HL

Ionization energy determinations

IE (eV) Method Reference Comment
12.61 ± 0.01PIBerkowitz, Greene, et al., 1987LBLHLM
12.6 ± 0.4EIChatham, Hils, et al., 1984LBLHLM
12.63 ± 0.02EIPlessis, Marmet, et al., 1983LBLHLM
13.6PEKimura, Katsumata, et al., 1981LLK
12.75 ± 0.02PEBieri, Burger, et al., 1977LLK
12.82 ± 0.02EISelim and El-Kholy, 1975LLK
12.6PEDebies and Rabalais, 1975LLK
12.6PIRabalais, Debies, et al., 1974LLK
12.8EIMorrison and Traeger, 1973LLK
12.64PEPotts and Price, 1972LLK
12.94 ± 0.04EIFinney and Harrison, 1972LLK
12.51PEBergmark, Rabalais, et al., 1972LLK
~12.51PERabalais, Bergmark, et al., 1971LLK
≤12.615 ± 0.010PIChupka and Berkowitz, 1971LLK
12.78PEPullen, Carlson, et al., 1970RDSH
12.75PEBrundle, Robin, et al., 1970RDSH
≤12.70EILossing and Semeluk, 1969RDSH
12.99 ± 0.05EIWilliams and Hamill, 1968RDSH
12.75 ± 0.05TEVillarejo, Stockbauer, et al., 1968RDSH
12.9CICermak, 1968RDSH
12.70PEBaker, Baker, et al., 1968RDSH
12.55 ± 0.05PIBrehm, 1966RDSH
12.704 ± 0.008PINicholson, 1965RDSH
12.71 ± 0.02PIDibeler, Krauss, et al., 1965RDSH
13.00 ± 0.02EIMelton and Hamill, 1964RDSH
13.6PEBieri and Asbrink, 1980Vertical value; LLK
13.6 ± 0.1PEBieri, Burger, et al., 1977Vertical value; LLK
13.60EIHarshbarger, Robin, et al., 1973Vertical value; LLK

Appearance energy determinations

Ion AE (eV) Other Products MethodReferenceComment
C+25. ± 2.?EIChatham, Hils, et al., 1984LBLHLM
C+19.56 ± 0.202H2EIPlessis, Marmet, et al., 1983LBLHLM
C+≤25.2?EIMorrison and Traeger, 1973LLK
CH+22.2 ± 0.4?EIChatham, Hils, et al., 1984LBLHLM
CH+19.11 ± 0.20H-+H2EIPlessis, Marmet, et al., 1983LBLHLM
CH+19.87 ± 0.20H+H2EIPlessis, Marmet, et al., 1983LBLHLM
CH+22.4H2+H?EIMorrison and Traeger, 1973LLK
CH2+15.1 ± 0.4H2EIChatham, Hils, et al., 1984LBLHLM
CH2+15.06 ± 0.02H2EIPlessis, Marmet, et al., 1983LBLHLM
CH2+15.16 ± 0.02H2PIMcCulloh and Dibeler, 1976T = 0K; LLK
CH2+15.3H2EIMorrison and Traeger, 1973LLK
CH2+15.19 ± 0.02H2PIChupka, 1968RDSH
CH2+15.16 ± 0.04H2PIDibeler, Krauss, et al., 1965RDSH
CH3+14.3 ± 0.4HEIChatham, Hils, et al., 1984LBLHLM
CH3+13.25 ± 0.08H-EIPlessis, Marmet, et al., 1983LBLHLM
CH3+14.01 ± 0.08HEIPlessis, Marmet, et al., 1983LBLHLM
CH3+14.30HPIPECOStockbauer, 1977LLK
CH3+14.324 ± 0.003HPIMcCulloh and Dibeler, 1976T = 0K; LLK
CH3+14.4HEIMorrison and Traeger, 1973LLK
CH3+14.30HEILossing and Semeluk, 1970RDSH
CH3+14.24 ± 0.05HEIWilliams and Hamill, 1968RDSH
CH3+13.50 ± 0.05H-PIChupka, 1968RDSH
CH3+14.320 ± 0.004HPIChupka, 1968RDSH
CH3+14.23 ± 0.05HPIBrehm, 1966RDSH
CH3+14.25 ± 0.02HPIDibeler, Krauss, et al., 1965RDSH
H+21.3 ± 0.3CH3EILocht, Olivier, et al., 1979LLK
H+24.0 ± 0.5CH3EIAppell and Kubach, 1971LLK

De-protonation reactions

CH3- + Hydrogen cation = Methane

By formula: CH3- + H+ = CH4

Quantity Value Units Method Reference Comment
Δr416.74 ± 0.70kcal/molD-EAEllison, Engelking, et al., 1978gas phase; B
Δr418.0 ± 3.5kcal/molCIDTGraul and Squires, 1990gas phase; B
Δr>404.18 ± 0.10kcal/molG+TSBohme, Lee-Ruff, et al., 1972gas phase; B
Δr414.80kcal/molN/ACheck, Faust, et al., 2001gas phase; FeBr3; ; ΔS(EA)=9.3; B
Quantity Value Units Method Reference Comment
Δr408.66 ± 0.80kcal/molH-TSEllison, Engelking, et al., 1978gas phase; B
Δr409.9 ± 3.6kcal/molH-TSGraul and Squires, 1990gas phase; B
Δr>396.10kcal/molIMRBBohme, Lee-Ruff, et al., 1972gas phase; B
Δr407.30kcal/molN/ACheck, Faust, et al., 2001gas phase; FeBr3; ; ΔS(EA)=9.3; B

Vibrational and/or electronic energy levels

Go To: Top, Reaction thermochemistry data, Gas phase ion energetics data, References, Notes

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

Data compiled by: Takehiko Shimanouchi

Symmetry:   Td     Symmetry Number σ = 12


 Sym.   No   Approximate   Selected Freq.  Infrared   Raman   Comments 
 Species   type of mode   Value   Rating   Value  Phase  Value  Phase

a1 1 Sym str 2917  A  ia 2917.0 gas
e 2 Deg deform 1534  A 1533 ia gas 1533.6 Observed through Coriolis interaction with ν4
f2 3 Deg str 3019  A 3018.9 gas 3019.5
f2 4 Deg deform 1306  C 1306.2 gas

Source: Shimanouchi, 1972

Notes

iaInactive
A0~1 cm-1 uncertainty
C3~6 cm-1 uncertainty

References

Go To: Top, Reaction thermochemistry data, Gas phase ion energetics data, Vibrational and/or electronic energy levels, Notes

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

Ellison, Engelking, et al., 1978
Ellison, G.B.; Engelking, P.C.; Lineberger, W.C., An experimental determination of the geometry and electron affinity of CH3, J. Am. Chem. Soc., 1978, 100, 2556. [all data]

Graul and Squires, 1990
Graul, S.T.; Squires, R.R., Gas-Phase Acidities Derived from Threshold Energies for Activated Reactions, J. Am. Chem. Soc., 1990, 112, 7, 2517, https://doi.org/10.1021/ja00163a007 . [all data]

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Check, Faust, et al., 2001
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Hiraoka, K.; Mori, T., Gas - Phase Stability and Structure of Cluster Ions CH5+(CH4)n with n = 1 - 9, Chem. Phys. Lett., 1989, 161, 2, 111, https://doi.org/10.1016/0009-2614(89)85040-7 . [all data]

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Hiraoka, K.; Kebarle, P., Energetics, Stabilities and Possible Structures of CH5+(CH4)n Clusters from Gas Phase Study of Equilibria CH5+(CH4)n - 1 + CH4 = CH5+(CH4)n for n = 1 - 5, J. Am. Chem. Soc., 1975, 97, 15, 4179, https://doi.org/10.1021/ja00848a005 . [all data]

Field and Beggs, 1971
Field, F.H.; Beggs, D.P., Reversible Reactions of Gas Phase Ions. III. Studies with Methane at 0.1-1.0 Torr and 77-300 K, J. Am. Chem. Soc., 1971, 93, 7, 1585, https://doi.org/10.1021/ja00736a003 . [all data]

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Kemper, P.R.; Bushnell, J.; Von Koppen, P.; Bowers, M.T., Binding Energies of Co+(H2/CH4/C2H6)1,2,3 Clusters, J. Phys. Chem., 1993, 97, 9, 1810, https://doi.org/10.1021/j100111a016 . [all data]

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Hiraoka, K.; Kebarle, P., Stabilities and Energetics of Pentacoordinated Carbonium Ions. The Isomeric C2H7+ Ions and Some Higher Analogues: C3H9+ and C4H11+, J. Am. Chem. Soc., 1976, 98, 20, 6119, https://doi.org/10.1021/ja00436a009 . [all data]

Golden, Walsh, et al., 1965
Golden, D.M.; Walsh, R.; Benson, S.W., The thermochemistry of the gas phase equilibrium I2 + CH4 «=» CH3I + HI and the heat of formation of the methyl radical, J. Am. Chem. Soc., 1965, 87, 4053-4057. [all data]

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Bennet and Field, 1972
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Bennet and Field, 1972, 2
Bennet, S.L.; Field, F.H., Reversible Reactions of Gaseous Ions. VI. The NH3 - CH4, H2S - CH4 and CF4 - CH4 Systems at Low Temperatures, J. Am. Chem. Soc., 1972, 94, 18, 6305, https://doi.org/10.1021/ja00773a009 . [all data]

Holm, 1974
Holm, T., J. Organometal. Chem., 1974, 77, 27. [all data]

Pedley and Rylance, 1977
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Liebman, Martinho Simões, et al., 1995
Liebman, J.F.; Martinho Simões, J.A.; Slayden, S.W., In Lithium Chemistry: A Theoretical and Experimental Overview Wiley: New York, Sapse, A.-M.; Schleyer, P. von Ragué, ed(s)., 1995. [all data]

Lacher, Amador, et al., 1967
Lacher, J.R.; Amador, A.; Park, J.D., Reaction heats of organic compounds. Part 5.-Heats of hydrogenation of dichloromethane, 1,1- and 1,2-dichloroethane and 1,2-dichloropropane, Trans. Faraday Soc., 1967, 63, 1608-1611. [all data]

Cox and Pilcher, 1970
Cox, J.D.; Pilcher, G., Thermochemistry of Organic and Organometallic Compounds, Academic Press, New York, 1970, 1-636. [all data]

Carson, Hartley, et al., 1949
Carson, A.S.; Hartley, K.; Skinner, H.A., Thermochemistry of metal alkyls. Part II.?The bond dissociation energies of some Zn?C and Cd?C bonds, and of Et?I., Trans. Faraday Soc., 1949, 45, 1159, https://doi.org/10.1039/tf9494501159 . [all data]

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Hunter and Lias, 1998
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Berkowitz, Greene, et al., 1987
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Chatham, Hils, et al., 1984
Chatham, H.; Hils, D.; Robertson, R.; Gallagher, A., Total and partial electron collisional ionization cross sections for CH4, C2H6, SiH4, and Si2H6, J. Chem. Phys., 1984, 81, 1770. [all data]

Plessis, Marmet, et al., 1983
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Kimura, Katsumata, et al., 1981
Kimura, K.; Katsumata, S.; Achiba, Y.; Yamazaki, T.; Iwata, S., Ionization energies, Ab initio assignments, and valence electronic structure for 200 molecules in Handbook of HeI Photoelectron Spectra of Fundamental Organic Compounds, Japan Scientific Soc. Press, Tokyo, 1981. [all data]

Bieri, Burger, et al., 1977
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Debies and Rabalais, 1975
Debies, T.P.; Rabalais, J.W., Calculated photoionization cross-sections and angular distributions for the isoelectronic series Ne, HF, H2O, NH3, and CH4, J. Am. Chem. Soc., 1975, 97, 487. [all data]

Rabalais, Debies, et al., 1974
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Morrison and Traeger, 1973
Morrison, J.D.; Traeger, J.C., Ionization and dissociation by electron impact. III. CH4 and SiH4, Int. J. Mass Spectrom. Ion Phys., 1973, 11, 289. [all data]

Potts and Price, 1972
Potts, A.W.; Price, W.C., The photoelectron spectra of methane, silane germane and stannane, Proc. R. Soc. London A:, 1972, 165. [all data]

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Baker, Baker, et al., 1968
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Dibeler, Krauss, et al., 1965
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Harshbarger, Robin, et al., 1973
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Notes

Go To: Top, Reaction thermochemistry data, Gas phase ion energetics data, Vibrational and/or electronic energy levels, References