Methane, bromo-

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Gas phase 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 by: Hussein Y. Afeefy, Joel F. Liebman, and Stephen E. Stein

Quantity Value Units Method Reference Comment
Δfgas-8.2 ± 0.2kcal/molEqkFerguson, Okafo, et al., 1973 
Δfgas-9.0 ± 0.32kcal/molChydAdams, Carson, et al., 1966 
Δfgas-8.97 ± 0.35kcal/molChydFowell, Lacher, et al., 1965 

Phase change 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:
BS - Robert L. Brown and Stephen E. Stein
TRC - Thermodynamics Research Center, NIST Boulder Laboratories, Chris Muzny director
ALS - Hussein Y. Afeefy, Joel F. Liebman, and Stephen E. Stein
DH - Eugene S. Domalski and Elizabeth D. Hearing
AC - William E. Acree, Jr., James S. Chickos
CAL - James S. Chickos, William E. Acree, Jr., Joel F. Liebman, Students of Chem 202 (Introduction to the Literature of Chemistry), University of Missouri -- St. Louis

Quantity Value Units Method Reference Comment
Tboil276.6KN/AFarchan Laboratories, 1990BS
Tboil276.6KN/AMajer and Svoboda, 1985 
Tboil277.5KN/AMcKenna, Tartar, et al., 1953Uncertainty assigned by TRC = 0.3 K; TRC
Tboil277.65KN/AGrosse, 1937Uncertainty assigned by TRC = 1. K; TRC
Quantity Value Units Method Reference Comment
Ttriple179.47KN/AEgan and Kemp, 1938Crystal phase 1 phase; Uncertainty assigned by TRC = 0.02 K; TRC
Quantity Value Units Method Reference Comment
Δvap5.554kcal/molN/AMajer and Svoboda, 1985 
Δvap5.6kcal/molCAdams, Carson, et al., 1966ALS

Enthalpy of vaporization

ΔvapH (kcal/mol) Temperature (K) Method Reference Comment
5.7151276.71N/AEgan and Kemp, 1938, 2P = 101.325 kPA; DH
5.715276.6N/AMajer and Svoboda, 1985 
6.02262.N/ABeersmans and Jungers, 2010Based on data from 203. to 277. K.; AC
5.88281.A,EStephenson and Malanowski, 1987Based on data from 201. to 296. K. See also Li and Rossini, 1961.; AC
6.17238.N/AKudchadker, Kudchadker, et al., 1979Based on data from 223. to 278. K.; AC
5.72 ± 0.06276.66VEgan and Kemp, 1938, 3ALS
6.05263.N/AEgan and Kemp, 1938, 2Based on data from 203. to 278. K.; AC

Entropy of vaporization

ΔvapS (cal/mol*K) Temperature (K) Reference Comment
20.65276.71Egan and Kemp, 1938, 2P; DH

Antoine Equation Parameters

log10(P) = A − (B / (T + C))
    P = vapor pressure (atm)
    T = temperature (K)

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Temperature (K) A B C Reference Comment
203. to 276.84.263031069.708-25.771Beersmans and Jungers, 1947Coefficents calculated by NIST from author's data.

Enthalpy of fusion

ΔfusH (kcal/mol) Temperature (K) Reference Comment
1.43179.5Domalski and Hearing, 1996See also Kafarov, Dorokhov, et al., 1987.; AC

Entropy of fusion

ΔfusS (cal/mol*K) Temperature (K) Reference Comment
0.650173.8Domalski and Hearing, 1996CAL
7.96179.5

Enthalpy of phase transition

ΔHtrs (kcal/mol) Temperature (K) Initial Phase Final Phase Reference Comment
0.113173.78crystaline, IIcrystaline, IEgan and Kemp, 1938, 2DH
1.429179.47crystaline, IliquidEgan and Kemp, 1938, 2DH

Entropy of phase transition

ΔStrs (cal/mol*K) Temperature (K) Initial Phase Final Phase Reference Comment
0.650173.78crystaline, IIcrystaline, IEgan and Kemp, 1938, 2DH
7.96179.47crystaline, IliquidEgan and Kemp, 1938, 2DH

In addition to the Thermodynamics Research Center (TRC) data available from this site, much more physical and chemical property data is available from the following TRC products:


Henry's Law 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 by: Rolf Sander

Henry's Law constant (water solution)

kH(T) = H exp(d(ln(kH))/d(1/T) ((1/T) - 1/(298.15 K)))
H = Henry's law constant for solubility in water at 298.15 K (mol/(kg*bar))
d(ln(kH))/d(1/T) = Temperature dependence constant (K)

H (mol/(kg*bar)) d(ln(kH))/d(1/T) (K) Method Reference Comment
0.15 QN/A missing citation give several references for the Henry's law constants but don't assign them to specific species.
0.0044360.XN/A 
0.19 LN/AValue at T = 293. K.
0.163100.LN/A 
0.16 VN/A 

Gas phase ion energetics 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 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 CH3Br+ (ion structure unspecified)

Quantity Value Units Method Reference Comment
IE (evaluated)10.541 ± 0.003eVN/AN/AL
Quantity Value Units Method Reference Comment
Proton affinity (review)158.7kcal/molN/AHunter and Lias, 1998HL
Quantity Value Units Method Reference Comment
Gas basicity152.5kcal/molN/AHunter and Lias, 1998HL

Ionization energy determinations

IE (eV) Method Reference Comment
10.54SBaig, Connerade, et al., 1982LBLHLM
10.53PEKimura, Katsumata, et al., 1981LLK
10.53EIHolmes, Fingas, et al., 1981LLK
10.5 ± 0.2EIKaposi, Riedel, et al., 1976LLK
10.54 ± 0.01PITsai, Baer, et al., 1975LLK
10.5 ± 0.2EIKaposi, Riedel, et al., 1975LLK
10.541SHochmann, Templet, et al., 1975LLK
10.53PERagle, Stenhouse, et al., 1970RDSH
10.54PEPotts, Lempka, et al., 1970RDSH
10.53 ± 0.015PEHashmall and Heilbronner, 1970RDSH
10.53PIKrauss, Walker, et al., 1968RDSH
10.528 ± 0.005PINicholson, 1965RDSH
10.53 ± 0.01PIWatanabe, 1957RDSH
10.53 ± 0.02EIFrost and McDowell, 1957RDSH
10.541 ± 0.003SPrice, 1936RDSH
10.54PEAndrews, Dyke, et al., 1984Vertical value; LBLHLM
10.53PEUtsunomiya, Kobayashi, et al., 1980Vertical value; LLK
10.53PEUehara, Saito, et al., 1973Vertical value; LLK
10.70PEDixon, Murrell, et al., 1971Vertical value; LLK

Appearance energy determinations

Ion AE (eV) Other Products MethodReferenceComment
Br+15.8 ± 0.5CH3EIKaposi, Riedel, et al., 1976LLK
Br+15.8 ± 0.5CH3EIKaposi, Riedel, et al., 1975LLK
Br+14.7 ± 0.05CH3EITsuda, Melton, et al., 1964RDSH
HBr+15.9 ± 0.3CH2EIKaposi, Riedel, et al., 1976LLK
HBr+15.9 ± 0.3CH2EIKaposi, Riedel, et al., 1975LLK
C+22.9 ± 0.5H+H2+BrEIKaposi, Riedel, et al., 1976LLK
C+22.9 ± 0.5H+H2+BrEIKaposi, Riedel, et al., 1975LLK
CBr+18.8 ± 0.3H+H2EIKaposi, Riedel, et al., 1976LLK
CBr+18.8 ± 0.3H+H2EIKaposi, Riedel, et al., 1975LLK
CH+21.7 ± 0.3H2+BrEIKaposi, Riedel, et al., 1976LLK
CH+21.7 ± 0.3H2+BrEIKaposi, Riedel, et al., 1975LLK
CH+21.41?EIReed and Snedden, 1956RDSH
CHBr+16.3 ± 0.5H2EIKaposi, Riedel, et al., 1976LLK
CHBr+16.3 ± 0.5H2EIKaposi, Riedel, et al., 1975LLK
CH2+14.7 ± 0.5HBrEIKaposi, Riedel, et al., 1976LLK
CH2+14.7 ± 0.5HBrEIKaposi, Riedel, et al., 1975LLK
CH2+14.9 ± 0.2HBrEITsuda and Hamill, 1964RDSH
CH2Br+13.4 ± 0.3HEIKaposi, Riedel, et al., 1976LLK
CH2Br+13.4 ± 0.3HEIKaposi, Riedel, et al., 1975LLK
CH2Br+12.12 ± 0.09HEIMartin, Lampe, et al., 1966RDSH
CH3+12.77BrPITraeger and McLoughlin, 1981LLK
CH3+12.8 ± 0.3BrEIKaposi, Riedel, et al., 1976LLK
CH3+12.80 ± 0.03BrPITsai, Baer, et al., 1975LLK
CH3+12.8 ± 0.3BrEIKaposi, Riedel, et al., 1975LLK
CH3+9.60 ± 0.05Br-EIWilliams and Hamill, 1968RDSH
CH3+12.77BrPIKrauss, Walker, et al., 1968RDSH

De-protonation reactions

CH2Br- + Hydrogen cation = Methane, bromo-

By formula: CH2Br- + H+ = CH3Br

Quantity Value Units Method Reference Comment
Δr396.7 ± 2.5kcal/molEndoHierl, Henchman, et al., 1992gas phase; HO- + MeBr:6.0±2.3 kcal/mol endo. "Better than Ingemann and Nibbering, 19852" 2.0 kcal would not show barrier; B
Δr394.3 ± 4.6kcal/molEIAERogers, Simpson, et al., 2010gas phase; B
Δr392.7 ± 3.1kcal/molG+TSIngemann and Nibbering, 1985, 2gas phase; B
Quantity Value Units Method Reference Comment
Δr389.7 ± 3.4kcal/molH-TSHierl, Henchman, et al., 1992gas phase; HO- + MeBr:6.0±2.3 kcal/mol endo. "Better than Ingemann and Nibbering, 19852" 2.0 kcal would not show barrier; B
Δr385.8 ± 3.0kcal/molIMRBIngemann and Nibbering, 1985, 2gas phase; B

References

Go To: Top, Gas phase thermochemistry data, Phase change data, Henry's Law data, Gas phase ion energetics data, Notes

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

Ferguson, Okafo, et al., 1973
Ferguson, K.C.; Okafo, E.N.; Whittle, E., Bond dissociation energies from equilibrium studies Part 4.-The equilibrium Br2 + CH4 = HBr + CH3Br. Determination of D(CH3-Br) and ΔHf°(CH3Br,g), J. Chem. Soc. Faraday Trans. 1, 1973, 69, 295-301. [all data]

Adams, Carson, et al., 1966
Adams, G.P.; Carson, A.S.; Laye, P.G., Thermochemistry of reductions caused by lithium aluminium hydride. Part 4.-Heat of formation of methyl bromide, Trans. Faraday Soc., 1966, 62, 1447-1449. [all data]

Fowell, Lacher, et al., 1965
Fowell, P.; Lacher, J.R.; Park, J.D., Reaction heats of organic compounds. Part 3.-Heats of hydrogenation of methyl bromide and ethyl bromide, Trans. Faraday Soc., 1965, 61, 1324-1327. [all data]

Farchan Laboratories, 1990
Farchan Laboratories, Research Chemicals Catalog, Farchan Laboratories, Gainesville, FL, 1990, 91. [all data]

Majer and Svoboda, 1985
Majer, V.; Svoboda, V., Enthalpies of Vaporization of Organic Compounds: A Critical Review and Data Compilation, Blackwell Scientific Publications, Oxford, 1985, 300. [all data]

McKenna, Tartar, et al., 1953
McKenna, F.E.; Tartar, H.V.; Lingafelter, E.C., Studies of hemiacetal formation in alcohol - aldehyde systems: II refraction studies, J. Am. Chem. Soc., 1953, 75, 604-7. [all data]

Grosse, 1937
Grosse, A.V., Refractive Indices at Low Temperatures, J. Am. Chem. Soc., 1937, 59, 2739-41. [all data]

Egan and Kemp, 1938
Egan, C.J.; Kemp, J.D., Methyl Bromide. The Heat Capacity, Vapor Pressure, Heats of Trans- ition, Fusion and Vaporization. Entropy and Density of the Gas, J. Am. Chem. Soc., 1938, 60, 2097. [all data]

Egan and Kemp, 1938, 2
Egan, C.J.; Kemp, J.D., Methyl bromide. The heat capacity, vapor pressure, heats of transition, fusion and vaporization. Entropy and density of the gas, J. Am. Chem. Soc., 1938, 60, 2097-2101. [all data]

Beersmans and Jungers, 2010
Beersmans, J.; Jungers, J.C., Synthèse et Étude des Chlorure, Bromure et Iodure de Deutérométhyle, Bull. Soc. Chim. Belges, 2010, 56, 5-8, 238-250, https://doi.org/10.1002/bscb.19470560506 . [all data]

Stephenson and Malanowski, 1987
Stephenson, Richard M.; Malanowski, Stanislaw, Handbook of the Thermodynamics of Organic Compounds, 1987, https://doi.org/10.1007/978-94-009-3173-2 . [all data]

Li and Rossini, 1961
Li, J.C.M.; Rossini, F.D., Vapor Pressures and Boiling Points of the l-Fluoroalkanes, l-Chloroalkanes, l-Bromoalkanes, and l-Iodoalkanes, C 1 to C 20 ., J. Chem. Eng. Data, 1961, 6, 2, 268-270, https://doi.org/10.1021/je60010a025 . [all data]

Kudchadker, Kudchadker, et al., 1979
Kudchadker, A.P.; Kudchadker, S.A.; Shukla, R.P.; Patnaik, P.R., Vapor pressures and boiling points of selected halomethanes, J. Phys. Chem. Ref. Data, 1979, 8, 2, 499, https://doi.org/10.1063/1.555600 . [all data]

Egan and Kemp, 1938, 3
Egan, C.J.; Kemp, J.D., Methyl bromide. The heat capacity, vapor pressure, heats of transition, fusion and vaporization. Entropy and density of the gas, J. Am. Chem. Soc., 1938, 60, 2097-21. [all data]

Beersmans and Jungers, 1947
Beersmans, J.; Jungers, J.C., Synthese et Etude des Chlorure, Bromure et Iodure de Deuteromethyle, Bull. Soc. Chim. Belg., 1947, 56, 5-8, 238-250, https://doi.org/10.1002/bscb.19470560506 . [all data]

Domalski and Hearing, 1996
Domalski, Eugene S.; Hearing, Elizabeth D., Heat Capacities and Entropies of Organic Compounds in the Condensed Phase. Volume III, J. Phys. Chem. Ref. Data, 1996, 25, 1, 1, https://doi.org/10.1063/1.555985 . [all data]

Kafarov, Dorokhov, et al., 1987
Kafarov, V.V.; Dorokhov, I.N.; Vetokhin, V.N.; Volkov, L.P., Dokl. Phys. Chem., 1987, 298, 77. [all data]

Hunter and Lias, 1998
Hunter, E.P.; Lias, S.G., Evaluated Gas Phase Basicities and Proton Affinities of Molecules: An Update, J. Phys. Chem. Ref. Data, 1998, 27, 3, 413-656, https://doi.org/10.1063/1.556018 . [all data]

Baig, Connerade, et al., 1982
Baig, M.A.; Connerade, J.P.; Hormes, J., Autoionisation resonances in the 4p(Π) spectrum of methyl bromide, J. Phys. B:, 1982, 15, 5. [all data]

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]

Holmes, Fingas, et al., 1981
Holmes, J.L.; Fingas, M.; Lossing, F.P., Towards a general scheme for estimating the heats of formation of organic ions in the gas phase. Part I. Odd-electron cations, Can. J. Chem., 1981, 59, 80. [all data]

Kaposi, Riedel, et al., 1976
Kaposi, O.; Riedel, M.; Vass-Balthazar, K.; Sanchez, G.R.; Lelik, L., Mass-spectrometric determination of thermochemical data of CHBr3 and CBr4 by study of their electron impact and heterogeneous pyrolytic decompositions, Acta Chim. Acad. Sci. Hung., 1976, 89, 221. [all data]

Tsai, Baer, et al., 1975
Tsai, B.P.; Baer, T.; Werner, A.S.; Lin, S.F., A photoelectron-photoion coincidence study of the ionization and fragment appearance potentials of bromo- and iodomethanes, J. Phys. Chem., 1975, 79, 570. [all data]

Kaposi, Riedel, et al., 1975
Kaposi, O.; Riedel, M.; Sanchez, G.R., Mass-spectrometric study of electron-impact and heterogeneous pyrolytic decomposition of methyl bromide, Acta Chim. Acad. Sci. Hung., 1975, 85, 361. [all data]

Hochmann, Templet, et al., 1975
Hochmann, P.; Templet, P.H.; Wang, H.-t.; McGlynn, S.P., Molecular Rydberg transitions. I. Low-energy Rydberg transitions in methyl halides, J. Chem. Phys., 1975, 62, 2588. [all data]

Ragle, Stenhouse, et al., 1970
Ragle, J.L.; Stenhouse, I.A.; Frost, D.C.; McDowell, C.A., Valence-shell ionization potentials of halomethanes by photoelectron spectroscopy. I. CH3Cl, CH3Br, CH3I. Vibrational frequencies and vibronic interaction in CH3Br+ and CH3Cl+, J. Chem. Phys., 1970, 53, 178. [all data]

Potts, Lempka, et al., 1970
Potts, A.W.; Lempka, H.J.; Streets, D.G.; Price, W.C., Photoelectron spectra of the halides of elements in groups III, IV, V and VI, Phil. Trans. Roy. Soc. (London), 1970, A268, 59. [all data]

Hashmall and Heilbronner, 1970
Hashmall, J.A.; Heilbronner, E., n-Ionization potentials of alkyl bromides, Angew. Chem. Intern. Ed., 1970, 9, 305. [all data]

Krauss, Walker, et al., 1968
Krauss, M.; Walker, J.A.; Dibeler, V.H., Mass spectrometric study of photoionization. X. Hydrogen chloride and methyl halides, J. Res. NBS, 1968, 72A, 281. [all data]

Nicholson, 1965
Nicholson, A.J.C., Photoionization-efficiency curves. II. False and genuine structure, J. Chem. Phys., 1965, 43, 1171. [all data]

Watanabe, 1957
Watanabe, K., Ionization potentials of some molecules, J. Chem. Phys., 1957, 26, 542. [all data]

Frost and McDowell, 1957
Frost, D.C.; McDowell, C.A., Studies of the ionization of molecules by electron impact. II. Excited states of the molecular ions of methane and the methyl halides, Proc. Roy. Soc. (London), 1957, A241, 194. [all data]

Price, 1936
Price, W.C., The far ultraviolet absorption spectra and ionization potentials of the alkyl halides. Part I, J. Chem. Phys., 1936, 4, 539. [all data]

Andrews, Dyke, et al., 1984
Andrews, L.; Dyke, J.M.; Jonathan, N.; Keddar, N.; orris, A., The first bands in the photoelectron spectra of the CH2Br, CD2Br, CHBr2, and CH2I free radicals, J. Phys. Chem., 1984, 88, 1950. [all data]

Utsunomiya, Kobayashi, et al., 1980
Utsunomiya, C.; Kobayashi, T.; Nagakura, S., Photoelectron angular distribution measurements for some aliphatic alcohols, amines, halides, Bull. Chem. Soc. Jpn., 1980, 53, 1216. [all data]

Uehara, Saito, et al., 1973
Uehara, Y.; Saito, N.; Yonezawa, T., Ionization potentials of trifluoromethyl and methyl halides by photoelectron spectroscopy and calculations by extended Hucket and CNDO/2 methods, Chem. Lett., 1973, 495. [all data]

Dixon, Murrell, et al., 1971
Dixon, R.N.; Murrell, J.N.; Narayan, B., The photoelectron spectra of the halomethanes, Mol. Phys., 1971, 20, 611. [all data]

Tsuda, Melton, et al., 1964
Tsuda, S.; Melton, C.E.; Hamill, W.H., Ionization- efficiency curves for molecular and fragment ions from methane and the methyl halides, J. Chem. Phys., 1964, 41, 689. [all data]

Reed and Snedden, 1956
Reed, R.I.; Snedden, W., Studies in electron impact methods. Part 6.-The formation of the methine and carbon ions, J. Chem. Soc. Faraday Trans., 1956, 55, 876. [all data]

Tsuda and Hamill, 1964
Tsuda, S.; Hamill, W.H., Structure in ionization efficiency curves near threshold from alkanes and alkyl halides, J. Chem. Phys., 1964, 41, 2713. [all data]

Martin, Lampe, et al., 1966
Martin, R.H.; Lampe, F.W.; Taft, R.W., An electron-impact study of ionization and dissociation in methoxy- and halogen- substituted methanes, J. Am. Chem. Soc., 1966, 88, 1353. [all data]

Traeger and McLoughlin, 1981
Traeger, J.C.; McLoughlin, R.G., Absolute heats of formation for gas phase cations, J. Am. Chem. Soc., 1981, 103, 3647. [all data]

Williams and Hamill, 1968
Williams, J.M.; Hamill, W.H., Ionization potentials of molecules and free radicals and appearance potentials by electron impact in the mass spectrometer, J. Chem. Phys., 1968, 49, 4467. [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 chemistry of alpha-thio carbanions, Can. J. Chem., 1985, 62, 2273. [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]

Ingemann and Nibbering, 1985, 2
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]


Notes

Go To: Top, Gas phase thermochemistry data, Phase change data, Henry's Law data, Gas phase ion energetics data, References