Methyl formate

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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 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-336.9kJ/molN/AGladii, Starchevskii, et al., 1990Value computed using ΔfHliquid° value of -365.9 kj/mol from Gladii, Starchevskii, et al., 1990 and ΔvapH° value of 29.0 kj/mol from Hine and Klueppet, 1974.; DRB
Δfgas-349.0kJ/molN/AGuthrie, 1974Value computed using ΔfHliquid° value of -378.0 kj/mol from Guthrie, 1974 and ΔvapH° value of 29.0 kj/mol from Hine and Klueppet, 1974.; DRB
Δfgas-362.kJ/molCmHine and Klueppet, 1974ALS
Δfgas-355.5kJ/molCcrHall and Baldt, 1971ALS

Constant pressure heat capacity of gas

Cp,gas (J/mol*K) Temperature (K) Reference Comment
44.06100.Chao J., 1986p=1 bar. Recommended S(T) and Cp(T) values are in close agreement with statistical values calculated by [ Vay P.-M., 1971] (discrepancies in S(T) do not exceed 1.3 J/mol*K) and value of S(298.15 K)=286.10 J/mol*K determined from high accuracy ab initio calculation [ East A.L.L., 1997].; GT
49.84150.
54.18200.
61.45273.15
64.38 ± 0.09298.15
64.61300.
77.56400.
90.29500.
101.57600.
111.26700.
119.53800.
126.61900.
132.681000.
137.891100.
142.381200.
146.241300.
149.581400.
152.481500.

Condensed 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 as indicated in comments:
ALS - Hussein Y. Afeefy, Joel F. Liebman, and Stephen E. Stein
DH - Eugene S. Domalski and Elizabeth D. Hearing

Quantity Value Units Method Reference Comment
Δfliquid-365.9kJ/molEqkGladii, Starchevskii, et al., 1990ALS
Δfliquid-378.0kJ/molCmGuthrie, 1974Heat of hydrolysis; ALS
Δfliquid-391.kJ/molCmHine and Klueppet, 1974ALS
Δfliquid-386.1kJ/molCcrHall and Baldt, 1971ALS
Quantity Value Units Method Reference Comment
Δcliquid-972.61 ± 0.59kJ/molCcrHall and Baldt, 1971Corresponding Δfliquid = -386.1 kJ/mol (simple calculation by NIST; no Washburn corrections); ALS

Constant pressure heat capacity of liquid

Cp,liquid (J/mol*K) Temperature (K) Reference Comment
120.57298.75Zabransky, Hynek, et al., 1987T = 293 to 299 K. Unsmoothed experimental datum.; DH
119.7298.15Fuchs, 1979DH
95.5297.Hall and Baldt, 1971DH
121.3288.Mehl, 1934DH
130.298.Berthelot and Ogier, 1881T = 286 to 302 K. Cp given as 0.516 cal/g*K.; DH

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
DRB - Donald R. Burgess, Jr.
AC - William E. Acree, Jr., James S. Chickos

Quantity Value Units Method Reference Comment
Tboil305. ± 1.KAVGN/AAverage of 20 values; Individual data points
Quantity Value Units Method Reference Comment
Tfus173.2KN/ATimmermans, 1935Uncertainty assigned by TRC = 2. K; TRC
Tfus173.4KN/ATimmermans, 1911Uncertainty assigned by TRC = 0.3 K; TRC
Quantity Value Units Method Reference Comment
Tc487.2KN/AMajer and Svoboda, 1985 
Tc487.2KN/AYoung, 1910Uncertainty assigned by TRC = 1. K; TRC
Tc487.2KN/AYoung and Thomas, 1893Uncertainty assigned by TRC = 1. K; TRC
Tc523.7KN/ADe Heen, 1888Uncertainty assigned by TRC = 20. K; TRC
Tc485.2KN/ANadezhdin, 1887Uncertainty assigned by TRC = 2. K; TRC
Quantity Value Units Method Reference Comment
Pc60.04barN/AYoung, 1910Uncertainty assigned by TRC = 0.6079 bar; TRC
Pc60.075barN/AYoung and Thomas, 1893Uncertainty assigned by TRC = 0.40 bar; TRC
Pc62.47barN/ANadezhdin, 1887Uncertainty assigned by TRC = 2.0265 bar; TRC
Quantity Value Units Method Reference Comment
ρc5.818mol/lN/AYoung, 1910Uncertainty assigned by TRC = 0.08 mol/l; TRC
ρc5.818mol/lN/AYoung and Thomas, 1893Uncertainty assigned by TRC = 0.07 mol/l; TRC
Quantity Value Units Method Reference Comment
Δvap29. ± 2.kJ/molAVGN/AAverage of 6 values; Individual data points

Enthalpy of vaporization

ΔvapH (kJ/mol) Temperature (K) Method Reference Comment
27.92304.7N/AMajer and Svoboda, 1985 
29.6292.AStephenson and Malanowski, 1987Based on data from 279. to 305. K.; AC
28.4320.AStephenson and Malanowski, 1987Based on data from 305. to 443. K.; AC
28.7 ± 0.1293.CCihlár, Hynek, et al., 1976AC
27.9 ± 0.1305.CCihlár, Hynek, et al., 1976AC
27.4 ± 0.1313.CCihlár, Hynek, et al., 1976AC
30.1283.BGBaldt and Hall, 1971Based on data from 261. to 305. K.; AC

Enthalpy of vaporization

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

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Temperature (K) A (kJ/mol) β Tc (K) Reference Comment
293. to 314.46.090.3119487.2Majer and Svoboda, 1985 

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
294. to 304.90.250976.524-278.54Nelson, 1928Coefficents calculated by NIST from author's data.

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:


References

Go To: Top, Gas phase thermochemistry data, Condensed phase thermochemistry data, Phase change data, Notes

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

Gladii, Starchevskii, et al., 1990
Gladii, S.L.; Starchevskii, M.K.; Pazderskii, Yu.A.; Moiseev, I.I., Chemical equilibrium in the methyl formate-water-methanol-formic acid system, J. Appl. Chem. USSR, 1990, 63, 106-111. [all data]

Hine and Klueppet, 1974
Hine, J.; Klueppet, A.W., Structural effects on rates and equilibria. XVIII. Thermodynamic stability of ortho esters, J. Am. Chem. Soc., 1974, 96, 2924-2929. [all data]

Guthrie, 1974
Guthrie, J.P., Hydration of carboxamides. Evaluation of the free energy change for addition of water to acetamide and formamide derivatives, J. Am. Chem. Soc., 1974, 96, 3608-3615. [all data]

Hall and Baldt, 1971
Hall, H.K., Jr.; Baldt, J.H., Thermochemistry of strained-ring bridgehead nitriles and esters, J. Am. Chem. Soc., 1971, 93, 140-145. [all data]

Chao J., 1986
Chao J., Thermodynamic properties of key organic oxygen compounds in the carbon range C1 to C4. Part 2. Ideal gas properties, J. Phys. Chem. Ref. Data, 1986, 15, 1369-1436. [all data]

Vay P.-M., 1971
Vay P.-M., Tables of thermodynamic functions for gaseous methyl formate and methyl acetate, J. Chim. Phys. Physico-Chim. Biol., 1971, 68, 1757-1758. [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]

Zabransky, Hynek, et al., 1987
Zabransky, M.; Hynek, V.; Finkeova-Hastabova, J.; Vesely, F., Heat capacities of six liquid esters as a function of temperature, Coll. Czech. Chem. Comm., 1987, 52, 251-256. [all data]

Fuchs, 1979
Fuchs, R., Heat capacities of some liquid aliphatic, alicyclic, and aromatic esters at 298.15 K, J. Chem. Thermodyn., 1979, 11, 959-961. [all data]

Mehl, 1934
Mehl, W., Die spezifische Wärme einiger flüssiger Kältemittel, Z. ges. Kalte-Ind., 1934, 41, 152-153. [all data]

Berthelot and Ogier, 1881
Berthelot, M.; Ogier, J., Recherches sur les ethers formiques, Ann. chim. et phys., 1881, 23(5), 201-209. [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]

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

Young, 1910
Young, S., The Internal Heat of Vaporization constants of thirty pure substances, Sci. Proc. R. Dublin Soc., 1910, 12, 374. [all data]

Young and Thomas, 1893
Young, S.; Thomas, G.L., The vapour pressures, molecular volumes, and critical constants of ten of the lower esters, J. Chem. Soc., 1893, 63, 1191. [all data]

De Heen, 1888
De Heen, P., Research on Physics and Theory of Liquids, Experimental Part Paris, 1888. [all data]

Nadezhdin, 1887
Nadezhdin, A., Rep. Phys., 1887, 23, 708. [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]

Cihlár, Hynek, et al., 1976
Cihlár, J.; Hynek, V.; Svoboda, V.; Holub, R., Heats of vaporization of alkyl esters of formic acid, Collect. Czech. Chem. Commun., 1976, 41, 1, 1-6, https://doi.org/10.1135/cccc19760001 . [all data]

Baldt and Hall, 1971
Baldt, J.H.; Hall, H.K.K., Jr., Thermochemistry of strained-ring bridgehead nitriles and esters, J. Am. Chem. Soc., 1971, 93, 140-145. [all data]

Nelson, 1928
Nelson, O.A., Vapor Pressures of Fumigants: II---Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Secondary Butyl and Isobutyl Formates 1, Ind. Eng. Chem., 1928, 20, 12, 1382-1384, https://doi.org/10.1021/ie50228a035 . [all data]


Notes

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