Methane

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Gas phase thermochemistry data

Go To: Top, Phase change data, IR Spectrum, 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.
ALS - Hussein Y. Afeefy, Joel F. Liebman, and Stephen E. Stein
GT - Glushko Thermocenter, Russian Academy of Sciences, Moscow

Quantity Value Units Method Reference Comment
Δfgas-17.89kcal/molReviewChase, 1998Data last reviewed in March, 1961
Δfgas-17.8 ± 0.07kcal/molReviewManion, 2002adopted recommendation of Gurvich, Veyts, et al., 1991; DRB
Δfgas-17.8 ± 0.1kcal/molCcbPittam and Pilcher, 1972ALS
Δfgas-17.889 ± 0.075kcal/molCcbProsen and Rossini, 1945Hf derived from Heat of Hydrogenation; ALS
Δfgas-17.54 ± 0.26kcal/molCcbRoth and Banse, 1932Reanalyzed by Cox and Pilcher, 1970, Original value = -17.97 kcal/mol; ALS
Quantity Value Units Method Reference Comment
Δcgas-212.88 ± 0.09kcal/molCcbPittam and Pilcher, 1972Corresponding Δfgas = -17.80 kcal/mol (simple calculation by NIST; no Washburn corrections); ALS
Δcgas-212.798 ± 0.072kcal/molCcbProsen and Rossini, 1945Hf derived from Heat of Hydrogenation; Corresponding Δfgas = -17.883 kcal/mol (simple calculation by NIST; no Washburn corrections); ALS
Δcgas-213.14 ± 0.26kcal/molCcbRoth and Banse, 1932Reanalyzed by Cox and Pilcher, 1970, Original value = -212.07 ± 0.25 kcal/mol; Corresponding Δfgas = -17.54 kcal/mol (simple calculation by NIST; no Washburn corrections); ALS
Δcgas-212.753 ± 0.072kcal/molCmRossini, 1931Corresponding Δfgas = -17.928 kcal/mol (simple calculation by NIST; no Washburn corrections); ALS
Quantity Value Units Method Reference Comment
gas45.09 ± 0.10cal/mol*KN/AColwell J.H., 1963The calorimetric value is significantly higher than the statistically calculated entropy, 186.26 J/mol*K, which remains the best value for use in thermodynamic calculations [ Vogt G.J., 1976, Friend D.G., 1989, Gurvich, Veyts, et al., 1989]. Earlier the value of 185.3 J/mol*K was calculated from experimental data [ Giauque W.F., 1931]. The value of S(298.15 K)=185.94 J/mol*K was obtained by high accuracy ab initio calculation [ East A.L.L., 1997].; GT
Quantity Value Units Method Reference Comment
gas,1 bar44.515cal/mol*KReviewChase, 1998Data last reviewed in March, 1961

Constant pressure heat capacity of gas

Cp,gas (cal/mol*K) Temperature (K) Reference Comment
8.346 ± 0.060279.Halford J.O., 1957GT

Constant pressure heat capacity of gas

Cp,gas (cal/mol*K) Temperature (K) Reference Comment
7.954100.Gurvich, Veyts, et al., 1989p=1 bar. Because of more precise method of calculation, the recommended values are more accurate, especially at high temperatures, than those obtained by [ McDowell R.S., 1963] and often regarded as reference data [ Friend D.G., 1989].; GT
8.009200.
8.530298.15
8.547300.
9.711400.
11.14500.
12.61600.
14.01700.
15.32800.
16.52900.
17.631000.
18.621100.
19.521200.
20.331300.
21.061400.
21.721500.
22.311600.
22.841700.
23.331800.
23.781900.
24.1972000.
24.5772100.
24.9312200.
25.2632300.
25.5742400.
25.8682500.
26.1452600.
26.4102700.
26.6632800.
26.9052900.
27.1393000.

Gas Phase Heat Capacity (Shomate Equation)

Cp° = A + B*t + C*t2 + D*t3 + E/t2
H° − H°298.15= A*t + B*t2/2 + C*t3/3 + D*t4/4 − E/t + F − H
S° = A*ln(t) + B*t + C*t2/2 + D*t3/3 − E/(2*t2) + G
    Cp = heat capacity (cal/mol*K)
    H° = standard enthalpy (kcal/mol)
    S° = standard entropy (cal/mol*K)
    t = temperature (K) / 1000.

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Temperature (K) 298. to 1300.1300. to 6000.
A -0.16802820.50960
B 25.926702.692321
C -10.16290-0.505293
D 1.4012400.033028
E 0.162181-6.315060
F -18.36610-36.69520
G 37.9341153.63631
H -17.89510-17.89510
ReferenceChase, 1998Chase, 1998
Comment Data last reviewed in March, 1961 Data last reviewed in March, 1961

Phase change data

Go To: Top, Gas phase thermochemistry data, IR Spectrum, 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
DH - Eugene S. Domalski and Elizabeth D. Hearing
AC - William E. Acree, Jr., James S. Chickos

Quantity Value Units Method Reference Comment
Tboil111. ± 2.KAVGN/AAverage of 13 values; Individual data points
Quantity Value Units Method Reference Comment
Tfus85.7KN/AStreng, 1971Uncertainty assigned by TRC = 0.2 K; TRC
Tfus90.6KN/AVan't Zelfde, Omar, et al., 1968Uncertainty assigned by TRC = 0.3 K; TRC
Tfus91.2KN/ATimmermans, 1935Uncertainty assigned by TRC = 2. K; TRC
Tfus90.6KN/AClusius, 1929Uncertainty assigned by TRC = 0.2 K; TRC
Tfus90.5KN/AEucken and Karwat, 1924Uncertainty assigned by TRC = 0.2 K; TRC
Quantity Value Units Method Reference Comment
Ttriple90.67 ± 0.03KAVGN/AAverage of 25 out of 32 values; Individual data points
Quantity Value Units Method Reference Comment
Ptriple0.1154 ± 0.0006atmAVGN/AAverage of 20 out of 23 values; Individual data points
Quantity Value Units Method Reference Comment
Tc190.6 ± 0.3KAVGN/AAverage of 19 out of 23 values; Individual data points
Quantity Value Units Method Reference Comment
Pc45.5 ± 0.3atmAVGN/AAverage of 16 out of 21 values; Individual data points
Quantity Value Units Method Reference Comment
Vc0.09860l/molN/AAmbrose and Tsonopoulos, 1995 
Vc0.09852l/molN/AYounglove and Ely, 1987TRC
Vc0.100l/molN/ATerry, Lynch, et al., 1969Uncertainty assigned by TRC = 0.001 l/mol; TRC
Quantity Value Units Method Reference Comment
ρc10.1 ± 0.2mol/lAVGN/AAverage of 16 out of 17 values; Individual data points

Enthalpy of vaporization

ΔvapH (kcal/mol) Temperature (K) Method Reference Comment
2.03699.54N/AVogt and Pitzer, 1976P = 2.81 kPa Data from Frank and Clusius, 1937 and 39FRA/CLU.; DH
2.1101.N/AStock, Henning, et al., 2006Based on data from 92. to 110. K. See also Boublik, Fried, et al., 1984.; AC
2.1105.AStephenson and Malanowski, 1987Based on data from 90. to 120. K.; AC
2.0134.AStephenson and Malanowski, 1987Based on data from 115. to 149. K.; AC
2.1174.AStephenson and Malanowski, 1987Based on data from 148. to 189. K.; AC
1.95111.7N/AMajer and Svoboda, 1985 
2.1112.N/AOtt, Goates, et al., 1972Based on data from 91. to 127. K. See also Boublik, Fried, et al., 1984.; AC
2.0175.N/AOtt, Goates, et al., 1972Based on data from 91. to 190. K.; AC
1.9137.N/AReid, 1972AC
2.1175.N/AAmbrose, Counsell, et al., 1970Based on data from 100. to 190. K.; AC
2.0112.CHestermans and White, 1961AC
1.8130.CHestermans and White, 1961AC
1.4160.CHestermans and White, 1961AC
0.96180.CHestermans and White, 1961AC
2.0149.N/AHestermans and White, 1961Based on data from 109. to 189. K.; AC
2.0 ± 0.0299.N/AFrank and Clusius, 1939AC

Enthalpy of vaporization

ΔvapH = A exp(-αTr) (1 − Tr)β
    ΔvapH = Enthalpy of vaporization (at saturation pressure) (kcal/mol)
    Tr = reduced temperature (T / Tc)

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Temperature (K) 112. to 180.
A (kcal/mol) 2.416
α -0.22
β 0.388
Tc (K) 190.6
ReferenceMajer and Svoboda, 1985

Entropy of vaporization

ΔvapS (cal/mol*K) Temperature (K) Reference Comment
20.4599.54Vogt and Pitzer, 1976P; 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
90.99 to 189.993.9838443.028-0.49Prydz and Goodwin, 1972Coefficents calculated by NIST from author's data.
96.89 to 110.191.99682125.819-48.823Regnier, 1972Coefficents calculated by NIST from author's data.
93.04 to 107.843.79664403.106-5.479Cutler and Morrison, 1965Coefficents calculated by NIST from author's data.
110.00 to 190.54.21490516.68911.223Hestermans and White, 1961Coefficents calculated by NIST from author's data.

Enthalpy of sublimation

ΔsubH (kcal/mol) Temperature (K) Method Reference Comment
2.372.N/AStephenson and Malanowski, 1987Based on data from 53. to 91. K.; AC
2.272.N/ABondi, 1963Based on data from 54. to 90. K. See also Armstrong, Brickwedde, et al., 1955.; AC
2.3984.N/AJones, 1960Based on data from 79. to 89. K.; AC
2.363.A,MSTickner and Lossing, 1951Based on data from 48. to 78. K.; AC
2.3077.AStull, 1947Based on data from 67. to 88. K.; AC

Enthalpy of phase transition

ΔHtrs (kcal/mol) Temperature (K) Initial Phase Final Phase Reference Comment
0.0223620.53crystaline, IIcrystaline, IVogt and Pitzer, 1976Lambda transition.; DH
0.224590.67crystaline, IliquidVogt and Pitzer, 1976DH

Entropy of phase transition

ΔStrs (cal/mol*K) Temperature (K) Initial Phase Final Phase Reference Comment
1.08920.53crystaline, IIcrystaline, IVogt and Pitzer, 1976Lambda; DH
2.47690.67crystaline, IliquidVogt and Pitzer, 1976DH

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IR Spectrum

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

Data compiled by: Coblentz Society, Inc.

Data compiled by: NIST Mass Spectrometry Data Center, William E. Wallace, director


Mass spectrum (electron ionization)

Go To: Top, Gas phase thermochemistry data, Phase change data, IR Spectrum, 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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Additional Data

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Owner NIST Mass Spectrometry Data Center
Collection (C) 2014 copyright by the U.S. Secretary of Commerce
on behalf of the United States of America. All rights reserved.
Origin D.HENNEBERG, MAX-PLANCK INSTITUTE, MULHEIM, WEST GERMANY
NIST MS number 61313

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References

Go To: Top, Gas phase thermochemistry data, Phase change data, IR Spectrum, 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.

Chase, 1998
Chase, M.W., Jr., NIST-JANAF Themochemical Tables, Fourth Edition, J. Phys. Chem. Ref. Data, Monograph 9, 1998, 1-1951. [all data]

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]

Gurvich, Veyts, et al., 1991
Thermodynamic Properties of Individual Substances, 4th edition, Volume 2, Gurvich, L.V.; Veyts, I.V.; Alcock, C.B.;, ed(s)., Hemisphere, New York, 1991. [all data]

Pittam and Pilcher, 1972
Pittam, D.A.; Pilcher, G., Measurements of heats of combustion by flame calorimetry. Part 8.-Methane, ethane, propane, n-butane and 2-methylpropane, J. Chem. Soc. Faraday Trans. 1, 1972, 68, 2224-2229. [all data]

Prosen and Rossini, 1945
Prosen, E.J.; Rossini, F.D., Heats of combustion and formation of the paraffin hydrocarbons at 25° C, J. Res. NBS, 1945, 263-267. [all data]

Roth and Banse, 1932
Roth, W.A.; Banse, H., Die verbrennungs- und bildungswarme von kohlenoxyd und methan, Arch. Eisenhutten., 1932, 6, 43-46. [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]

Rossini, 1931
Rossini, F.D., The heats of combustion of methane and carbon monoxide, J. Res. NBS, 1931, 6, 37-49. [all data]

Colwell J.H., 1963
Colwell J.H., Thermodynamic properties of CH4 and CD4. Interpretation of the properties of solid, J. Chem. Phys., 1963, 39, 635-653. [all data]

Vogt G.J., 1976
Vogt G.J., Entropy and heat capacity of methane; spin-species conversion, J. Chem. Thermodyn., 1976, 8, 1011-1031. [all data]

Friend D.G., 1989
Friend D.G., Thermophysical properties of methane, J. Phys. Chem. Ref. Data, 1989, 18, 583-638. [all data]

Gurvich, Veyts, et al., 1989
Gurvich, L.V.; Veyts, I.V.; Alcock, C.B., Thermodynamic Properties of Individual Substances, 4th ed.; Vols. 1 and 2, Hemisphere, New York, 1989. [all data]

Giauque W.F., 1931
Giauque W.F., The entropies of methane and ammonia, Phys. Rev., 1931, 38, 196-197. [all data]

East A.L.L., 1997
East A.L.L., Ab initio statistical thermodynamical models for the computation of third-law entropies, J. Chem. Phys., 1997, 106, 6655-6674. [all data]

Halford J.O., 1957
Halford J.O., Standard heat capacities of gaseous methanol, ethanol, methane and ethane at 279 K by thermal conductivity, J. Phys. Chem., 1957, 61, 1536-1539. [all data]

McDowell R.S., 1963
McDowell R.S., Thermodynamic functions of methane, J. Chem. Eng. Data, 1963, 8, 547-548. [all data]

Streng, 1971
Streng, A.G., Miscibility and Compatibility of Some Liquid and Solidified Gases at Low Temperature, J. Chem. Eng. Data, 1971, 16, 357. [all data]

Van't Zelfde, Omar, et al., 1968
Van't Zelfde, P.; Omar, M.H.; LePair-Schroten, H.G.M.; Dokoupil, Z., Solid-liquid equilibrium diagram for the argon + methane system., Physica (Amsterdam), 1968, 38, 241-51. [all data]

Timmermans, 1935
Timmermans, J., Researches in Stoichiometry. I. The Heat of Fusion of Organic Compounds., Bull. Soc. Chim. Belg., 1935, 44, 17-40. [all data]

Clusius, 1929
Clusius, K., The specific heat of several condensed gases between 10deg. abs. and their triple point., Z. Phys. Chem., Abt. B, 1929, 3, 41. [all data]

Eucken and Karwat, 1924
Eucken, A.; Karwat, E., Determination of the heat content of several condensed gases, Z. Phys. Chem., Stoechiom. Verwandtschaftsl., 1924, 112, 467. [all data]

Ambrose and Tsonopoulos, 1995
Ambrose, D.; Tsonopoulos, C., Vapor-Liquid Critical Properties of Elements and Compounds. 2. Normal Alkenes, J. Chem. Eng. Data, 1995, 40, 531-546. [all data]

Younglove and Ely, 1987
Younglove, B.A.; Ely, J.F., Thermophysical Properties of Fluids II. Methane, Ethane, Propane, Isobutane, and Normal Butane, J. Phys. Chem. Ref. Data, 1987, 16, 577. [all data]

Terry, Lynch, et al., 1969
Terry, M.J.; Lynch, J.T.; Bunclark, M.; Mansell, K.R.; Staveley, L.A.K., The Densities of Liquid Argon, Krypton, Xenon, Oxygen, Nitrogen, Carbon Monoxide, Methane and Carbon Tetrafluoride Along the Orthobaric Liquid Curve, J. Chem. Thermodyn., 1969, 1, 413. [all data]

Vogt and Pitzer, 1976
Vogt, G.J.; Pitzer, K.S., Entropy and heat capacity of methane, spin-species conversion, J. Chem. Thermodynam., 1976, 8, 1011-1031. [all data]

Frank and Clusius, 1937
Frank, A.; Clusius, K., The entropy of methane, Z. Physik. Chem., 1937, B36, 291-300. [all data]

Stock, Henning, et al., 2006
Stock, Alfred; Henning, Fritz; Kuß, Ernst, Dampfdrucktafeln für Temperaturbestimmungen zwischen + 25° und - 185°, Ber. dtsch. Chem. Ges. A/B, 2006, 54, 5, 1119-1129, https://doi.org/10.1002/cber.19210540531 . [all data]

Boublik, Fried, et al., 1984
Boublik, T.; Fried, V.; Hala, E., The Vapour Pressures of Pure Substances: Selected Values of the Temperature Dependence of the Vapour Pressures of Some Pure Substances in the Normal and Low Pressure Region, 2nd ed., Elsevier, New York, 1984, 972. [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]

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]

Ott, Goates, et al., 1972
Ott, J. Bevan; Goates, J. Rex; Lamb, John D., Solid-liquid phase equilibria in water + ethylene glycol, The Journal of Chemical Thermodynamics, 1972, 4, 1, 123-126, https://doi.org/10.1016/S0021-9614(72)80015-6 . [all data]

Reid, 1972
Reid, Robert C., Handbook on vapor pressure and heats of vaporization of hydrocarbons and related compounds, R. C. Wilhort and B. J. Zwolinski, Texas A Research Foundation. College Station, Texas(1971). 329 pages.$10.00, AIChE J., 1972, 18, 6, 1278-1278, https://doi.org/10.1002/aic.690180637 . [all data]

Ambrose, Counsell, et al., 1970
Ambrose, D.; Counsell, J.F.; Davenport, A.J., The use of Chebyshev polynomials for the representation of vapour pressures between the triple point and the critical point, The Journal of Chemical Thermodynamics, 1970, 2, 2, 283-294, https://doi.org/10.1016/0021-9614(70)90093-5 . [all data]

Hestermans and White, 1961
Hestermans, P.; White, David, THE VAPOR PRESSURE, HEAT OF VAPORIZATION AND HEAT CAPACITY OF METHANE FROM THE BOILING POINT TO THE CRITICAL TEMPERATURE, J. Phys. Chem., 1961, 65, 2, 362-365, https://doi.org/10.1021/j100820a044 . [all data]

Frank and Clusius, 1939
Frank, A.; Clusius, K., Z. Phys. Chem. Abt. B, 1939, 42, 395. [all data]

Prydz and Goodwin, 1972
Prydz, R.; Goodwin, R.D., Experimental Melting and Vapor Pressures of Methane, J. Chem. Thermodyn., 1972, 4, 1, 127-133, https://doi.org/10.1016/S0021-9614(72)80016-8 . [all data]

Regnier, 1972
Regnier, J., Tension de Vapeur de L'Ethane Entre 80 et 135 K, J. Chim. Phys., 1972, 69, 942-944. [all data]

Cutler and Morrison, 1965
Cutler, A.J.B.; Morrison, J.A., Excess Thermodynamic Functions for Liquid Mixtures of Methane+Propane, Trans. Faraday Soc., 1965, 61, 429-442, https://doi.org/10.1039/tf9656100429 . [all data]

Bondi, 1963
Bondi, A., Heat of Siblimation of Molecular Crystals: A Catalog of Molecular Structure Increments., J. Chem. Eng. Data, 1963, 8, 3, 371-381, https://doi.org/10.1021/je60018a027 . [all data]

Armstrong, Brickwedde, et al., 1955
Armstrong, George T.; Brickwedde, F.G.; Scott, R.B., Vapor pressures of the methanes, J. RES. NATL. BUR. STAN., 1955, 55, 1, 39, https://doi.org/10.6028/jres.055.005 . [all data]

Jones, 1960
Jones, A.H., Sublimation Pressure Data for Organic Compounds., J. Chem. Eng. Data, 1960, 5, 2, 196-200, https://doi.org/10.1021/je60006a019 . [all data]

Tickner and Lossing, 1951
Tickner, A.W.; Lossing, F.P., The Measurement of Low Vapor Pressures by Means of a Mass Spectrometer., J. Phys. Chem., 1951, 55, 5, 733-740, https://doi.org/10.1021/j150488a013 . [all data]

Stull, 1947
Stull, Daniel R., Vapor Pressure of Pure Substances. Organic and Inorganic Compounds, Ind. Eng. Chem., 1947, 39, 4, 517-540, https://doi.org/10.1021/ie50448a022 . [all data]


Notes

Go To: Top, Gas phase thermochemistry data, Phase change data, IR Spectrum, Mass spectrum (electron ionization), References