Methyl formate
- Formula: C2H4O2
- Molecular weight: 60.0520
- 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 ion energetics data
Go To: Top, Gas Chromatography, 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
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)
Quantity | Value | Units | Method | Reference | Comment |
---|---|---|---|---|---|
IE (evaluated) | 10.835 | eV | N/A | N/A | L |
Quantity | Value | Units | Method | Reference | Comment |
Proton affinity (review) | 187.0 | kcal/mol | N/A | Hunter and Lias, 1998 | HL |
Quantity | Value | Units | Method | Reference | Comment |
Gas basicity | 179.6 | kcal/mol | N/A | Hunter and Lias, 1998 | HL |
Ionization energy determinations
IE (eV) | Method | Reference | Comment |
---|---|---|---|
10.835 | TE | Waterstradt, Jung, et al., 1994 | LL |
~10.7 | PE | Cannington and Ham, 1985 | LBLHLM |
10.99 | PE | Kimura, Katsumata, et al., 1981 | LLK |
10.85 ± 0.05 | PE | Benoit, Harrison, et al., 1977 | LLK |
10.85 | PE | Sweigart and Turner, 1972 | LLK |
10.815 ± 0.005 | PI | Watanabe, Nakayama, et al., 1962 | RDSH |
11.0 | PE | Cannington and Ham, 1985 | Vertical value; LBLHLM |
10.85 | PE | Benoit and Harrison, 1977 | Vertical value; LLK |
10.3 | PE | Rao, 1975 | Vertical value; LLK |
Appearance energy determinations
Ion | AE (eV) | Other Products | Method | Reference | Comment |
---|---|---|---|---|---|
CHO+ | 12.91 ± 0.07 | CH3O | PIPECO | Nishimura, Zha, et al., 1987 | LBLHLM |
CHO+ | 13.47 ± 0.05 | CH3O | EI | Haney and Franklin, 1969 | RDSH |
CHO2+ | 15.9 | CH3 | EI | King and Long, 1958 | RDSH |
CH2+ | 19.8 | ? | EI | King and Long, 1958 | RDSH |
CH2O+ | 13.6 | ? | EI | King and Long, 1958 | RDSH |
CH3+ | 13.27 ± 0.24 | HCO2 | PIPECO | Nishimura, Zha, et al., 1987 | LBLHLM |
CH3+ | 13.71 | ? | EI | Haney and Franklin, 1969 | RDSH |
CH3O+ | 12.23 | CHO | EI | Haney and Franklin, 1969 | RDSH |
CH4O+ | 11.47 ± 0.05 | CO | PIPECO | Nishimura, Zha, et al., 1987 | LBLHLM |
CH4O+ | 11.5 ± 0.1 | CO | EI | VanRaalte and Harrison, 1963 | RDSH |
C2H3O2+ | 12.3 | H | EI | King and Long, 1958 | RDSH |
De-protonation reactions
C2H3O2- + =
By formula: C2H3O2- + H+ = C2H4O2
Quantity | Value | Units | Method | Reference | Comment |
---|---|---|---|---|---|
ΔrH° | <384.00 | kcal/mol | CIDT | Graul and Squires, 1988 | gas phase; B |
ΔrH° | <391.75 ± 0.90 | kcal/mol | G+TS | DePuy, Grabowski, et al., 1985 | gas phase; HO- + DCO2CH3 -> (M-D)-. ΔHf(MeO- + CO) = -59.7 kcal/mol; B |
Quantity | Value | Units | Method | Reference | Comment |
ΔrG° | <384.00 | kcal/mol | IMRB | DePuy, Grabowski, et al., 1985 | gas phase; HO- + DCO2CH3 -> (M-D)-. ΔHf(MeO- + CO) = -59.7 kcal/mol; B |
C2H3O2- + =
By formula: C2H3O2- + H+ = C2H4O2
Quantity | Value | Units | Method | Reference | Comment |
---|---|---|---|---|---|
ΔrH° | 391.2 ± 4.1 | kcal/mol | G+TS | DePuy, Grabowski, et al., 1985 | gas phase; B |
Quantity | Value | Units | Method | Reference | Comment |
ΔrG° | 384.1 ± 4.0 | kcal/mol | IMRB | DePuy, Grabowski, et al., 1985 | gas phase; B |
Gas Chromatography
Go To: Top, 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
Kovats' RI, non-polar column, isothermal
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
Column type | Active phase | I | Reference | Comment |
---|---|---|---|---|
Capillary | SE-30 | 386. | Chretien and Dubois, 1978 | Program: not specified |
Kovats' RI, polar column, isothermal
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
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
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
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 ion energetics data, Gas Chromatography, Notes
Data compilation copyright by the U.S. Secretary of Commerce on behalf of the U.S.A. All rights reserved.
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]
Sweigart and Turner, 1972
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
Benoit, F.M.; Harrison, A.G.,
Predictive value of proton affinity. Ionization energy correlations involving oxygenated molecules,
J. Am. Chem. Soc., 1977, 99, 3980. [all data]
Rao, 1975
Rao, C.N.R.,
Lone-pair ionization bands of chromophores in the photoelectron spectra of organic molecules,
Indian J. Chem., 1975, 13, 950. [all data]
Nishimura, Zha, et al., 1987
Nishimura, T.; Zha, Q.; Meisels, G.G.,
Unimolecular dissociation of energy-selected methyl formate ion,
J. Chem. Phys., 1987, 87, 4589. [all data]
Haney and Franklin, 1969
Haney, M.A.; Franklin, J.L.,
Excess energies in mass spectra of some oxygen-containing organic compounds,
J. Chem. Soc. Faraday Trans., 1969, 65, 1794. [all data]
King and Long, 1958
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]
VanRaalte and Harrison, 1963
VanRaalte, D.; Harrison, A.G.,
Ionization and dissociation of formate esters by electron impact,
Can. J. Chem., 1963, 41, 2054. [all data]
Graul and Squires, 1988
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]
DePuy, Grabowski, et al., 1985
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]
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/technicalseries1997-01-011.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
Go To: Top, Gas phase ion energetics data, Gas Chromatography, References
- Symbols used in this document:
AE Appearance energy IE (evaluated) Recommended ionization energy ΔrG° Free energy of reaction at standard conditions ΔrH° Enthalpy of reaction at standard conditions - Data from NIST Standard Reference Database 69: NIST Chemistry WebBook
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