Methyl formate

Formula: C₂H₄O₂
Molecular weight: 60.0520
IUPAC Standard InChI: InChI=1S/C2H4O2/c1-4-2-3/h2H,1H3
IUPAC Standard InChIKey: TZIHFWKZFHZASV-UHFFFAOYSA-N
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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Gas phase thermochemistry data

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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
Δ_fH°_gas	-80.52	kcal/mol	N/A	Gladii, Starchevskii, et al., 1990	Value computed using Δ_fH_liquid° value of -365.9 kj/mol from Gladii, Starchevskii, et al., 1990 and Δ_vapH° value of 29.0 kj/mol from Hine and Klueppet, 1974.; DRB
Δ_fH°_gas	-83.41	kcal/mol	N/A	Guthrie, 1974	Value computed using Δ_fH_liquid° value of -378.0 kj/mol from Guthrie, 1974 and Δ_vapH° value of 29.0 kj/mol from Hine and Klueppet, 1974.; DRB
Δ_fH°_gas	-86.6	kcal/mol	Cm	Hine and Klueppet, 1974	ALS
Δ_fH°_gas	-84.97	kcal/mol	Ccr	Hall and Baldt, 1971	ALS

Constant pressure heat capacity of gas

C_p,gas (cal/mol*K)	Temperature (K)	Reference	Comment
10.53	100.	Chao J., 1986	p=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/molK) and value of S(298.15 K)=286.10 J/molK determined from high accuracy ab initio calculation [ East A.L.L., 1997].; GT
11.91	150.
12.95	200.
14.69	273.15
15.39 ± 0.02	298.15
15.44	300.
18.54	400.
21.58	500.
24.276	600.
26.592	700.
28.568	800.
30.261	900.
31.711	1000.
32.957	1100.
34.030	1200.
34.952	1300.
35.750	1400.
36.444	1500.

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

Vibrational and/or electronic energy levels

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Data compiled by: Takehiko Shimanouchi

Symmetry: C_s Symmetry Number σ = 1

Sym.	No	Approximate	Selected Freq.		Infrared		Raman		Comments

Species		type of mode	Value	Rating	Value	Phase	Value	Phase

a'	1	CH3 d-str	3045	D	3045 M	gas	3030	liq.
a'	2	CH3 s-str	2969	D	2969 S	gas	2955 p	liq.
a'	3	CH str	2943	D	2943 S	gas
a'	4	C=O str	1754	C	1754 VS	gas	1717 p	liq.
a'	5	CH3 d-deform	1454	D	1454 W	solid solid
a'	6	CH3 s-deform	1445	D	1445 M	gas
a'	7	CH bend	1371	D	1371 W	gas	1379 p	liq.
a'	8	C-O str	1207	C	1207 VS	gas	1207	liq.
a'	9	CH3 rock	1166	D	1166 VS	gas	1157	liq.
a'	10	O-CH3 str	925	C	925 S	gas	912 p	liq.
a'	11	OCO deform	767	C	767 M	gas	765	liq.
a'	12	COC deform	318	D	318 M	gas
a	13	CH3 d-str	3012	D	3012 M	gas
a	14	CH3 d-deform	1443	E	1443 W	solid solid	1440	liq.
a	15	CH3 rock	1168	D	1168 M	gas
a	16	CH bend	1032	C	1032 M	gas	1030	liq.
a	17	C-O torsion	332	D	332 M	gas	332 p	liq.
a	18	CH3 torsion	130	D	130 VW	gas			MW: ν₁₃₂

Source: Shimanouchi, 1972

Notes

Very strong

Strong

Medium

Weak

Very weak

Polarized

Torsional Frequency calculated from microwave spectroscopic data.

3~6 cm^-1 uncertainty

6~15 cm^-1 uncertainty

15~30 cm^-1 uncertainty

Gas Chromatography

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

Kovats' RI, non-polar column, isothermal

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Column type	Active phase	Temperature (C)	I	Reference	Comment
Packed	Squalane	50.	376.	Becerra, Sánchez, et al., 1982	N2, Chromosorb W-AM; Column length: 6. m
Packed	Squalane	50.	377.	Becerra, Sánchez, et al., 1982	N2, Chromosorb W-AM; Column length: 6. m
Packed	Porapack Q	200.	369.	Goebel, 1982	N2
Packed	Apiezon L	120.	369.	Bogoslovsky, Anvaer, et al., 1978	Celite 545
Packed	Apiezon L	160.	373.	Bogoslovsky, Anvaer, et al., 1978	Celite 545
Packed	Apiezon L	70.	370.	Bogoslovsky, Anvaer, et al., 1978
Packed	SE-30	150.	386.	Ashes and Haken, 1974	Celaton (62-72 mesh); Column length: 3.7 m
Packed	Squalane	50.	373.	Mira and Sanchez, 1970	Chromosorb G
Packed	SE-30	150.	380.	Germaine and Haken, 1969	Celite 560; Column length: 3.7 m
Packed	Apiezon L	130.	362.	Wehrli and Kováts, 1959	Celite; Column length: 2.25 m
Packed	Apiezon L	70.	370.	Wehrli and Kováts, 1959	Celite; Column length: 2.25 m

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

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Column type	Active phase	I	Reference	Comment
Capillary	SE-30	386.	Chretien and Dubois, 1978	Program: not specified

Kovats' RI, polar column, isothermal

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Column type	Active phase	Temperature (C)	I	Reference	Comment
Packed	Carbowax 20M	75.	779.	Goebel, 1982	N2, Kieselgur (60-100 mesh); Column length: 2. m

Normal alkane RI, non-polar column, temperature ramp

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Column type	Active phase	I	Reference	Comment
Capillary	HP-5	401.1	Leffingwell and Alford, 2005	60. m/0.32 mm/0.25 μm, He, 30. C @ 2. min, 2. K/min, 260. C @ 28. min

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

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Column type	Active phase	I	Reference	Comment
Capillary	Methyl Silicone	386.	Du and Feng, 2008	Program: not specified
Capillary	Methyl Silicone	386.	N/A	Program: not specified
Capillary	SPB-1	407.	Flanagan, Streete, et al., 1997	60. m/0.53 mm/5. μm, He; Program: 40C(6min) => 5C/min => 80C => 10C/min => 200C
Capillary	SPB-1	407.	Strete, Ruprah, et al., 1992	60. m/0.53 mm/5.0 μm, Helium; Program: 40 0C (6 min) 5 0C/min -> 80 0C 10 0C/min -> 200 0C

Normal alkane RI, polar column, custom temperature program

View large format table.

Column type	Active phase	I	Reference	Comment
Capillary	Carbowax 400, Carbowax 20M, Carbowax 1540, Carbowax 4000, Superox 06, PEG 20M, etc.	757.	Waggott and Davies, 1984	Hydrogen; Column length: 50. m; Column diameter: 0.32 mm; Program: not specified
Capillary	Carbowax 400, Carbowax 20M, Carbowax 1540, Carbowax 4000, Superox 06, PEG 20M, etc.	779.	Waggott and Davies, 1984	Hydrogen; Column length: 50. m; Column diameter: 0.32 mm; Program: not specified
Capillary	Carbowax 20M	761.	Ramsey and Flanagan, 1982	Program: not specified

References

Go To: Top, Gas phase thermochemistry data, IR Spectrum, Vibrational and/or electronic energy levels, Gas Chromatography, Notes

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]

Shimanouchi, 1972
Shimanouchi, T., Tables of Molecular Vibrational Frequencies Consolidated Volume I, National Bureau of Standards, 1972, 1-160. [all data]

Becerra, Sánchez, et al., 1982
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]

Goebel, 1982
Goebel, K.-J., Gaschromatographische Identifizierung Niedrig Siedender Substanzen Mittels Retentionsindices und Rechnerhilfe, J. Chromatogr., 1982, 235, 1, 119-127, https://doi.org/10.1016/S0021-9673(00)95793-5 . [all data]

Bogoslovsky, Anvaer, et al., 1978
Bogoslovsky, Yu.N.; Anvaer, B.I.; Vigdergauz, M.S., Chromatographic constants in gas chromatography (in Russian), Standards Publ. House, Moscow, 1978, 192. [all data]

Ashes and Haken, 1974
Ashes, J.R.; Haken, J.K., Gas chromatography of homologous esters. VI. Structure-retention increments of aliphatic esters, J. Chromatogr., 1974, 101, 1, 103-123, https://doi.org/10.1016/S0021-9673(01)94737-5 . [all data]

Mira and Sanchez, 1970
Mira, J.M.; Sanchez, L.G., Polarity of the Gas Chromatographic Stationary Phases and Retention Indices of Aliphatic Esters, Ketones and Alcohols, Anal. Chim. Acta., 1970, 50, 2, 315-321, https://doi.org/10.1016/0003-2670(70)80071-X . [all data]

Germaine and Haken, 1969
Germaine, R.W.; Haken, J.K., Gas chromatography of homologous esters. Part 1. Simple aliphatic esters, J. Chromatogr., 1969, 43, 33-42, https://doi.org/10.1016/S0021-9673(00)99162-3 . [all data]

Wehrli and Kováts, 1959
Wehrli, A.; Kováts, E., Gas-chromatographische Charakterisierung ogranischer Verbindungen. Teil 3: Berechnung der Retentionsindices aliphatischer, alicyclischer und aromatischer Verbindungen, Helv. Chim. Acta, 1959, 7, 7, 2709-2736, https://doi.org/10.1002/hlca.19590420745 . [all data]

Chretien and Dubois, 1978
Chretien, J.R.; Dubois, J-E., Topological Analysis: A Technique for the Physico-Chemical Exploitation of Retention Data in Gas-Liquid Chromatography, J. Chromatogr., 1978, 158, 43-56, https://doi.org/10.1016/S0021-9673(00)89954-9 . [all data]

Leffingwell and Alford, 2005
Leffingwell, J.C.; Alford, E.D., Volatile constituents of Perique tobacco, Electron. J. Environ. Agric. Food Chem., 2005, 4, 2, 899-915. [all data]

Du and Feng, 2008
Du, X.; Feng, C., Correlativity research between topological dyeing index and gas chromatography retention index of fatty esters, J. Petrochem. Univ. (Chinese), 2008, 21, 1, 16-20. [all data]

Flanagan, Streete, et al., 1997
Flanagan, R.J.; Streete, P.J.; Ramsey, J.D., Volatile Substance Abuse, UNODC Technical Series, No 5, United Nations, Office on Drugs and Crime, Vienna International Centre, PO Box 500, A-1400 Vienna, Austria, 1997, 56, retrieved from http://www.odccp.org/pdf/technical_series₁997-01-01₁.pdf. [all data]

Strete, Ruprah, et al., 1992
Strete, P.J.; Ruprah, M.; Ramsey, J.D.; Flanagan, R.J., Detection and identification of volatile substances by headspace capillary gas chromatography to aid the diagnosis of acute poisoning, Analyst, 1992, 117, 7, 1111-1127, https://doi.org/10.1039/an9921701111 . [all data]

Waggott and Davies, 1984
Waggott, A.; Davies, I.W., Identification of organic pollutants using linear temperature programmed retention indices (LTPRIs) - Part II, 1984, retrieved from http://dwi.defra.gov.uk/research/completed-research/reports/dwi0383.pdf. [all data]

Ramsey and Flanagan, 1982
Ramsey, J.D.; Flanagan, R.J., Detection and Identification of Volatile Organic Compounds in Blood by Headspace Gas Chromatography as an Aid to the Diagnosis of Solvent Abuse, J. Chromatogr., 1982, 240, 2, 423-444, https://doi.org/10.1016/S0021-9673(00)99622-5 . [all data]

Notes

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Symbols used in this document:

C_p,gas Constant pressure heat capacity of gas

Δ_fH°_gas Enthalpy of formation of gas at standard conditions
Data from NIST Standard Reference Database 69: NIST Chemistry WebBook
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C_p,gas	Constant pressure heat capacity of gas
Δ_fH°_gas	Enthalpy of formation of gas at standard conditions

Methyl formate

Data at NIST subscription sites:

Gas phase thermochemistry data

Constant pressure heat capacity of gas

IR Spectrum

Vibrational and/or electronic energy levels

Symmetry: Cs Symmetry Number σ = 1

Notes

Gas Chromatography

Kovats' RI, non-polar column, isothermal

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

Kovats' RI, polar column, isothermal

Normal alkane RI, non-polar column, temperature ramp

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

Normal alkane RI, polar column, custom temperature program

References

Notes

Symmetry: C_s Symmetry Number σ = 1