Chloromethane

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Condensed phase thermochemistry data

Go To: Top, Phase change data, Gas phase ion energetics data, Mass spectrum (electron ionization), 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:
DRB - Donald R. Burgess, Jr.
DH - Eugene S. Domalski and Elizabeth D. Hearing

Quantity Value Units Method Reference Comment
Δfliquid-102.4 ± 1.5kJ/molReviewManion, 2002derived from recommended ΔfHgas° and ΔvapH°; DRB
Quantity Value Units Method Reference Comment
liquid140.08J/mol*KN/AMesserly and Aston, 1940DH

Constant pressure heat capacity of liquid

Cp,liquid (J/mol*K) Temperature (K) Reference Comment
80.8293.15Awberg and Griffiths, 1940T = 243 to 303 K. Cp reported at 20°C = 1.598 J/g*K and at 30°C = 1.632 J/g*K.; DH
75.60249.67Messerly and Aston, 1940T = 12 to 249.67 K. Value is unsmoothed experimental datum.; DH
81.2298.Shorthose, 1924T = -30 to 40°C.; DH

Phase change data

Go To: Top, Condensed phase thermochemistry data, Gas phase ion energetics data, Mass spectrum (electron ionization), 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:
TRC - Thermodynamics Research Center, NIST Boulder Laboratories, Chris Muzny director
DRB - Donald R. Burgess, Jr.
DH - Eugene S. Domalski and Elizabeth D. Hearing
AC - William E. Acree, Jr., James S. Chickos
ALS - Hussein Y. Afeefy, Joel F. Liebman, and Stephen E. Stein

Quantity Value Units Method Reference Comment
Tboil247. ± 10.KAVGN/AAverage of 9 values; Individual data points
Quantity Value Units Method Reference Comment
Tfus182.KN/AAwbery, 1941Uncertainty assigned by TRC = 1.5 K; TRC
Tfus175.55KN/ATimmermans, 1921Uncertainty assigned by TRC = 0.4 K; TRC
Tfus176.5KN/ATimmermans, 1911Uncertainty assigned by TRC = 0.5 K; TRC
Quantity Value Units Method Reference Comment
Ttriple175.43KN/AMesserly and Aston, 1940, 2Uncertainty assigned by TRC = 0.07 K; from T vs 1/f in a calorimter, Resistance thermomter and thermocouple gave same temperature, temp. scale in previous publication; TRC
Ttriple175.44KN/AMesserly and Aston, 1940, 2Uncertainty assigned by TRC = 0.05 K; from T vs 1/f in adiabatic calorimeter, temp. meas. with resistance thermometer & two thermocouples, temp scale described in previous publication; TRC
Quantity Value Units Method Reference Comment
Ptriple0.008700barN/AMesserly and Aston, 1940, 2Uncertainty assigned by TRC = 0.000013 bar; TRC
Quantity Value Units Method Reference Comment
Tc416. ± 1.KAVGN/AAverage of 6 values; Individual data points
Quantity Value Units Method Reference Comment
Pc67.144barN/AMansoorian, Hall, et al., 1981Uncertainty assigned by TRC = 0.0067 bar; VP measured up to 408 K,; TRC
Pc66.7924barN/AHsu and McKetta, 1964Uncertainty assigned by TRC = 0.0405 bar; TRC
Pc66.80barN/ALeduc, 1909Uncertainty assigned by TRC = 2.0265 bar; TRC
Pc74.00barN/AVincent and Chappuis, 1886Uncertainty assigned by TRC = 3.0398 bar; TRC
Quantity Value Units Method Reference Comment
ρc7.1895mol/lN/AHsu and McKetta, 1964Uncertainty assigned by TRC = 0.006 mol/l; TRC
ρc7.33mol/lN/ACentnerszwer, 1904Uncertainty assigned by TRC = 0.1 mol/l; extrapolation of rectilnear diam. to Tc; TRC
Quantity Value Units Method Reference Comment
Δvap20.5 ± 0.3kJ/molReviewManion, 2002weighted average of several measurements plus a correction for non-ideality; DRB

Enthalpy of vaporization

ΔvapH (kJ/mol) Temperature (K) Method Reference Comment
21.535248.94N/AMesserly and Aston, 1940P = 101.325 kPA; DH
22.7235.N/ABeersmans and Jungers, 2010Based on data from 183. to 250. K.; AC
22.0263.N/AGaneff and Jungers, 2010Based on data from 198. to 278. K.; AC
22.0262.AStephenson and Malanowski, 1987Based on data from 247. to 310. K.; AC
21.8383.AStephenson and Malanowski, 1987Based on data from 368. to 416. K.; AC
21.0323.AStephenson and Malanowski, 1987Based on data from 308. to 373. K.; AC
23.5206.N/AThomson, 1946Based on data from 191. to 249. K.; AC
22.6234.N/AMesserly and Aston, 1940Based on data from 192. to 249. K.; AC
20.09293.CYates, 1926ALS
20.1293.CYates, 1926AC

Entropy of vaporization

ΔvapS (J/mol*K) Temperature (K) Reference Comment
86.51248.94Messerly and Aston, 1940P; DH

Antoine Equation Parameters

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

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Temperature (K) A B C Reference Comment
303. to 416.34.918581427.52945.137Hsu and McKetta, 1964Coefficents calculated by NIST from author's data.
198. to 278.4.22507951.561-23.468Ganeff and Jungers, 1948Coefficents calculated by NIST from author's data.
183. to 249.44.15454916.223-28.466Beersmans and Jungers, 1947Coefficents calculated by NIST from author's data.

Enthalpy of sublimation

ΔsubH (kJ/mol) Temperature (K) Reference Comment
31.6 ± 0.1151.Bah and Dupont-Pavlovsky, 1995Based on data from 130. to 172. K.; AC

Enthalpy of fusion

ΔfusH (kJ/mol) Temperature (K) Reference Comment
6.431175.44Messerly and Aston, 1940DH
6.42174.5Domalski and Hearing, 1996AC

Entropy of fusion

ΔfusS (J/mol*K) Temperature (K) Reference Comment
36.66175.44Messerly and Aston, 1940DH

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:


Gas phase ion energetics data

Go To: Top, Condensed phase thermochemistry data, Phase change data, Mass spectrum (electron ionization), 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
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 CH3Cl+ (ion structure unspecified)

Quantity Value Units Method Reference Comment
IE (evaluated)11.26 ± 0.03eVN/AN/AL
Quantity Value Units Method Reference Comment
Proton affinity (review)647.3kJ/molN/AHunter and Lias, 1998HL
Quantity Value Units Method Reference Comment
Gas basicity621.1kJ/molN/AHunter and Lias, 1998HL

Ionization energy determinations

IE (eV) Method Reference Comment
11.221SHochmann, Templet, et al., 1975LLK
11.28 ± 0.01PIWerner, Tsai, et al., 1974LLK
11.27EILossing, 1972LLK
11.29PERagle, Stenhouse, et al., 1970RDSH
11.26PEDewar and Worley, 1969RDSH
11.265 ± 0.003PINicholson, 1965RDSH
11.28PIDibeler and Walker, 1965RDSH
11.28 ± 0.01PIWatanabe, 1957RDSH
11.22 ± 0.01SPrice, 1936RDSH
11.29PEKimura, Katsumata, et al., 1981Vertical value; LLK
11.29PEUtsunomiya, Kobayashi, et al., 1980Vertical value; LLK
11.33PEUehara, Saito, et al., 1973Vertical value; LLK
11.30PEDixon, Murrell, et al., 1971Vertical value; LLK

Appearance energy determinations

Ion AE (eV) Other Products MethodReferenceComment
C+26.3 ± 0.1?EIReed and Snedden, 1956RDSH
CH+22.5 ± 0.06?EIReed and Snedden, 1956RDSH
CH2+14.6 ± 0.2HClEITsuda and Hamill, 1964RDSH
CH2Cl+12.96HEILossing, 1972LLK
CH2Cl+12.98 ± 0.07HEIMartin, Lampe, et al., 1966RDSH
CH3+13.87ClPIKrauss, Walker, et al., 1968RDSH
CH3+10.07Cl-PIDibeler and Walker, 1965RDSH
Cl+16.6 ± 0.05CH3EITsuda, Melton, et al., 1964RDSH

De-protonation reactions

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

Mass spectrum (electron ionization)

Go To: Top, Condensed phase thermochemistry data, Phase change 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: NIST Mass Spectrometry Data Center, William E. Wallace, director

Spectrum

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Collection (C) 2014 copyright by the U.S. Secretary of Commerce
on behalf of the United States of America. All rights reserved.
NIST MS number 18894

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References

Go To: Top, Condensed phase thermochemistry data, Phase change data, Gas phase ion energetics data, Mass spectrum (electron ionization), Notes

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

Manion, 2002
Manion, J.A., Evaluated Enthalpies of Formation of the Stable Closed Shell C1 and C2 Chlorinated Hydrocarbons, J. Phys. Chem. Ref. Data, 2002, 31, 1, 123-172, https://doi.org/10.1063/1.1420703 . [all data]

Messerly and Aston, 1940
Messerly, G.H.; Aston, J.G., The heat capacity and entropy, heats of fusion and vaporization and the vapor pressure of methyl chloride, J. Am. Chem. Soc., 1940, 62, 886-890. [all data]

Awberg and Griffiths, 1940
Awberg, J.H.; Griffiths, E., The specific heat of liquid methyl chloride, Proc. Phys. Soc. (London), 1940, 52, 770-776. [all data]

Shorthose, 1924
Shorthose, D.N., G. B. DSIR, Food Invest. Board, Spec. Rept., 1924, No. 19, 16pp. [all data]

Awbery, 1941
Awbery, J.H., Philos. Mag., 1941, 31, 247. [all data]

Timmermans, 1921
Timmermans, J., The Freezing Points of Organic Substances IV. New Exp. Determinations, Bull. Soc. Chim. Belg., 1921, 30, 62. [all data]

Timmermans, 1911
Timmermans, J., Researches on the freezing point of organic liquid compounds, Bull. Soc. Chim. Belg., 1911, 25, 300. [all data]

Messerly and Aston, 1940, 2
Messerly, G.H.; Aston, J.G., The Heat Capacity and Entropy, Heats of Fusion and Vaporization and the Vapor Pressure of Methyl Chloride, J. Am. Chem. Soc., 1940, 62, 886-90. [all data]

Mansoorian, Hall, et al., 1981
Mansoorian, H.; Hall, K.R.; Holste, J.C.; Eubank, P.T., The density of gaseous ethane and of fluid methyl chloride and the vapor pressure of methyl chloride, J. Chem. Thermodyn., 1981, 13, 1001-24. [all data]

Hsu and McKetta, 1964
Hsu, C.C.; McKetta, J.J., Pressure-Volume-Temperature Properties of Methyl Chloride, J. Chem. Eng. Data, 1964, 9, 1, 45-51, https://doi.org/10.1021/je60020a014 . [all data]

Leduc, 1909
Leduc, A., Compressibility of gases between 0 atm and 3 atm and at all temperatures, C. R. Hebd. Seances Acad. Sci., 1909, 148, 407. [all data]

Vincent and Chappuis, 1886
Vincent, C.; Chappuis, J., J. Phys. Theor. Appl., 1886, 5, 58. [all data]

Centnerszwer, 1904
Centnerszwer, M., An Application of the Method of Cailletet and Mathias to Determine Critical Volume., Z. Phys. Chem., Stoechiom. Verwandtschaftsl., 1904, 49, 199. [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]

Ganeff and Jungers, 2010
Ganeff, Jean M.; Jungers, Joseph C., Tensions de vapeur du système CH3Cl «63743» CH2Cl2, Bull. Soc. Chim. Belges, 2010, 57, 1-3, 82-87, https://doi.org/10.1002/bscb.19480570109 . [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]

Thomson, 1946
Thomson, George Wm., The Antoine Equation for Vapor-pressure Data., Chem. Rev., 1946, 38, 1, 1-39, https://doi.org/10.1021/cr60119a001 . [all data]

Yates, 1926
Yates, G.W.C., LXXIV. Latent heats of vaporization of ethyl and methyl chlorides, Philos. Mag., 1926, 2, 817-826. [all data]

Ganeff and Jungers, 1948
Ganeff, J.M.; Jungers, J.C., Tensions de Vapeur du Systeme CH3Cl - CH2Cl2, Bull. Soc. Chim. Belg., 1948, 57, 1-3, 82-87, https://doi.org/10.1002/bscb.19480570109 . [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]

Bah and Dupont-Pavlovsky, 1995
Bah, A.; Dupont-Pavlovsky, N., Vapor Pressure of Solid Chloromethane, J. Chem. Eng. Data, 1995, 40, 4, 869-870, https://doi.org/10.1021/je00020a028 . [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]

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]

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]

Werner, Tsai, et al., 1974
Werner, A.S.; Tsai, B.P.; Baer, T., Photoionization study of the ionization potentials fragmentation paths of the chlorinated methanes carbon tetrabromide, J. Chem. Phys., 1974, 60, 3650. [all data]

Lossing, 1972
Lossing, F.P., Free radicals by mass spectrometry. XLIV. Ionization potentials bond dissociation energies for chloro-and fluoromethyl radicals, Bull. Soc. Chim. Belg., 1972, 81, 125. [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]

Dewar and Worley, 1969
Dewar, M.J.S.; Worley, S.D., Photoelectron spectra of molecules. I. Ionization potentials of some organic molecules and their interpretation, J. Chem. Phys., 1969, 50, 654. [all data]

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

Dibeler and Walker, 1965
Dibeler, V.H.; Walker, J.A., Ion-pair process in CH3Cl by photoionization, J. Chem. Phys., 1965, 43, 1842. [all data]

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

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]

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]

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]

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]

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]

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]


Notes

Go To: Top, Condensed phase thermochemistry data, Phase change data, Gas phase ion energetics data, Mass spectrum (electron ionization), References