Methyl formate

• Formula: C₂H₄O₂
• Molecular weight: 60.0520
• IUPAC Standard InChI: InChI=1S/C2H4O2/c1-4-2-3/h2H,1H3 Copy

  
• IUPAC Standard InChIKey: TZIHFWKZFHZASV-UHFFFAOYSA-N Copy
• CAS Registry Number: 107-31-3
• Chemical structure:
  This structure is also available as a 2d Mol file or as a computed 3d SD file
  The 3d structure may be viewed using Java or Javascript.
• Other names: Formic acid, methyl ester; Methyl methanoate; HCOOCH3; Formiate de methyle; Methylester kyseliny mravenci; Methylformiaat; Methylformiat; Mravencan methylnaty; UN 1243; Methyl ester of formic acid; Methanoic acid methyl ester
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• Information on this page:
  • Gas phase thermochemistry data
  • Phase change data
  • Gas phase ion energetics data
  • IR Spectrum
  • Vibrational and/or electronic energy levels
  • Gas Chromatography
  • References
  • Notes
• Other data available:
  • Condensed phase thermochemistry data
  • Reaction thermochemistry data
  • Henry's Law data
  • Mass spectrum (electron ionization)
• Data at other public NIST sites:
  • Gas Phase Kinetics Database
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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

Constant pressure heat capacity of gas

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

Enthalpy of vaporization

Enthalpy of vaporization

Δ_vapH = A exp(-βT_r) (1 − T_r)^β
    Δ_vapH = Enthalpy of vaporization (at saturation pressure) (kJ/mol)
    T_r = reduced temperature (T / T_c)

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Antoine Equation Parameters

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

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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
LL - Sharon G. Lias and Joel F. Liebman
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 C₂H₄O₂⁺ (ion structure unspecified)

Ionization energy determinations

Appearance energy determinations

De-protonation reactions

C₂H₃O₂^- +  =

By formula: C₂H₃O₂^- + H⁺ = C₂H₄O₂

C₂H₃O₂^- +  =

By formula: C₂H₃O₂^- + H⁺ = C₂H₄O₂

IR Spectrum

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Data compiled by: Coblentz Society, Inc.

• GAS (100 mmHg, N2 ADDED, TOTAL PRESSURE 600 mmHg); DOW KBr FOREPRISM-GRATING; DIGITIZED BY NIST FROM HARD COPY (FROM TWO SEGMENTS); 2 cm^-1 resolution

Data compiled by: Tanya L. Myers, Russell G. Tonkyn, Ashley M. Oeck, Tyler O. Danby, John S. Loring, Matthew S. Taubman, Stephen W. Sharpe, Jerome C. Birnbaum, and Timothy J. Johnson

• liquid; Bruker Tensor 27 FTIR; 0.4821395 cm^-1 resolution

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

• gas

Vibrational and/or electronic energy levels

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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: Takehiko Shimanouchi

Symmetry:   C_s     Symmetry Number σ = 1

Source: Shimanouchi, 1972

Notes

Gas Chromatography

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

Kovats' RI, non-polar column, isothermal

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Kovats' RI, non-polar column, custom temperature program

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Kovats' RI, polar column, isothermal

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Normal alkane RI, non-polar column, temperature ramp

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Normal alkane RI, non-polar column, custom temperature program

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Normal alkane RI, polar column, custom temperature program

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References

Go To: Top, Gas phase thermochemistry data, Phase change data, Gas phase ion energetics data, IR Spectrum, Vibrational and/or electronic energy levels, Gas Chromatography, 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]

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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]

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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
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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]

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

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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]

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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]

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]

Waterstradt, Jung, et al., 1994
Waterstradt, E.; Jung, R.; Belling, T.; Muller-Dethlefs, K., Zero kinetic energy (ZEKE) photoelectron spectrum and coincident mass spectra of methyl formate, Ber. Bunsen-Ges. Phys. Chem., 1994, 98, 176. [all data]

Cannington and Ham, 1985
Cannington, P.H.; Ham, N.S., He(II) photoelectron spectra of esters, J. Electron Spectrosc. Relat. Phenom., 1985, 36, 203. [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]

Benoit, Harrison, et al., 1977
Benoit, F.M.; Harrison, A.G.; Lossing, F.P., Hydrogen migrations in mass spectrometry III-Energetics of formation of [R'CO₂H₂]⁺ in the mass spectra of R'CO₂R, Org. Mass Spectrom., 1977, 12, 78. [all data]

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Sweigart, D.A.; Turner, D.W., Lone pair orbitals and their interactions studied by photoelectron spectroscopy. I. Carboxylic acids and their derivatives, J. Am. Chem. Soc., 1972, 94, 5592. [all data]

Watanabe, Nakayama, et al., 1962
Watanabe, K.; Nakayama, T.; Mottl, J., Ionization potentials of some molecules, J. Quant. Spectry. Radiative Transfer, 1962, 2, 369. [all data]

Benoit and Harrison, 1977
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King, A.B.; Long, F.A., Mass spectra of some simple esters and their interpretation by quasi-equilibrium theory, J. Chem. Phys., 1958, 29, 374. [all data]

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VanRaalte, D.; Harrison, A.G., Ionization and dissociation of formate esters by electron impact, Can. J. Chem., 1963, 41, 2054. [all data]

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Graul, S.T.; Squires, R.R., On the Existence of Alkyl Carbanions in the Gas Phase, J. Am. Chem. Soc., 1988, 110, 2, 607, https://doi.org/10.1021/ja00210a054 . [all data]

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DePuy, C.H.; Grabowski, J.J.; Bierbaum, V.M.; Ingemann, S.; Nibbering, N.M.M., Gas-phase reactions of anions with methyl formate and N,N-dimethylformamide, J. Am. Chem. Soc., 1985, 107, 1093. [all data]

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Becerra, M.R.; Sánchez, E.F.; Domínguez, J.A.G.; Muñoz, J.G.; Molera, M.J., The use of gaseous and liquid n-paraffins in GC identification of oxidation products of acetondimethyl acetal, J. Chromatogr. Sci., 1982, 20, 8, 363-366, https://doi.org/10.1093/chromsci/20.8.363 . [all data]

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Notes

Go To: Top, Gas phase thermochemistry data, Phase change data, Gas phase ion energetics data, IR Spectrum, Vibrational and/or electronic energy levels, Gas Chromatography, References

• Symbols used in this document:
  

  AE	Appearance energy
  Cp,gas	Constant pressure heat capacity of gas
  IE (evaluated)	Recommended ionization energy
  Pc	Critical pressure
  Tboil	Boiling point
  Tc	Critical temperature
  Tfus	Fusion (melting) point
  ΔfH°gas	Enthalpy of formation of gas at standard conditions
  ΔrG°	Free energy of reaction at standard conditions
  ΔrH°	Enthalpy of reaction at standard conditions
  ΔvapH	Enthalpy of vaporization
  ΔvapH°	Enthalpy of vaporization at standard conditions
  ρc	Critical density

• Data from NIST Standard Reference Database 69: NIST Chemistry WebBook
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