Methyl nitrite

Formula: CH₃NO₂
Molecular weight: 61.0400
IUPAC Standard InChI: InChI=1S/CH3NO2/c1-4-2-3/h1H3
IUPAC Standard InChIKey: BLLFVUPNHCTMSV-UHFFFAOYSA-N
CAS Registry Number: 624-91-9
Chemical structure:
This structure is also available as a 2d Mol file or as a computed 3d SD file
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Other names: Nitrous acid, methyl ester; CH3ONO; Methylester kyseliny dusite; Methyl ester of nitrous acid
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Other data available:
- Mass spectrum (electron ionization)
- Gas Chromatography
Data at other public NIST sites:
- Gas Phase Kinetics Database
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Gas phase thermochemistry data

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Data compiled by: Hussein Y. Afeefy, Joel F. Liebman, and Stephen E. Stein

Quantity	Value	Units	Method	Reference	Comment
Δ_fH°_gas	-15.64 ± 0.20	kcal/mol	Eqk	Ray and Gershon, 1962
Δ_fH°_gas	-16.8 ± 0.8	kcal/mol	Ccb	Geiseler and Thierfelder, 1961
Δ_fH°_gas	-14.93 ± 0.26	kcal/mol	Cm	Gray and Pratt, 1958	Measured by Baldrey, Lotzgesell and Style
Quantity	Value	Units	Method	Reference	Comment
Δ_cH°_gas	-179.7 ± 0.8	kcal/mol	Ccb	Geiseler and Thierfelder, 1961

Condensed phase thermochemistry data

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Data compiled by: Hussein Y. Afeefy, Joel F. Liebman, and Stephen E. Stein

Quantity	Value	Units	Method	Reference	Comment
Δ_fH°_liquid	-16.05 ± 0.20	kcal/mol	Eqk	Silverwood and Thomas, 1967
Δ_fH°_liquid	-20.33 ± 0.25	kcal/mol	Cm	Gray and Pratt, 1958	Measured by Baldrey, Lotzgesell and Style

Phase change data

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Data compiled as indicated in comments:
ALS - Hussein Y. Afeefy, Joel F. Liebman, and Stephen E. Stein
AC - William E. Acree, Jr., James S. Chickos

Quantity	Value	Units	Method	Reference	Comment
Δ_vapH°	5.40 ± 0.04	kcal/mol	V	Gray and Pratt, 1958	Measured by Baldrey, Lotzgesell and Style; ALS

Enthalpy of vaporization

Δ_vapH (kcal/mol)	Temperature (K)	Method	Reference	Comment
5.28	258.	A	Stephenson and Malanowski, 1987	Based on data from 218. to 273. K.; AC
6.26	190.	N/A	Rook, 1982	Based on data from 154. to 225. K.; AC

Reaction thermochemistry data

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Data compiled by: Hussein Y. Afeefy, Joel F. Liebman, and Stephen E. Stein

Note: Please consider using the reaction search for this species. This page allows searching of all reactions involving this species. A general reaction search form is also available. Future versions of this site may rely on reaction search pages in place of the enumerated reaction displays seen below.

Individual Reactions

0.76 + 0.62 + = + Methyl nitrite

By formula: 0.76NO₂ + 0.62N₂O₄ + CH₃NO₃ = N₂O₅ + CH₃NO₂

Quantity	Value	Units	Method	Reference	Comment
Δ_rH°	8.662	kcal/mol	Cm	Ray and Ogg, 1959	liquid phase

Methyl nitrite + = +

By formula: CH₃NO₂ + HCl = ClNO + CH₄O

Quantity	Value	Units	Method	Reference	Comment
Δ_rH°	2.14 ± 0.20	kcal/mol	Eqk	Ray and Gershon, 1962	gas phase

Methyl nitrite + = 2 +

By formula: CH₃NO₂ + HNO₃ = 2NO₂ + CH₄O

Quantity	Value	Units	Method	Reference	Comment
Δ_rH°	15.89	kcal/mol	Eqk	Silverwood and Thomas, 1967	gas phase

Gas phase ion energetics data

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Data evaluated as indicated in comments:
HL - Edward P. Hunter and Sharon G. Lias

Data compiled as indicated in comments:
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

Quantity	Value	Units	Method	Reference	Comment
Proton affinity (review)	190.9	kcal/mol	N/A	Hunter and Lias, 1998	HL
Quantity	Value	Units	Method	Reference	Comment
Gas basicity	183.2	kcal/mol	N/A	Hunter and Lias, 1998	HL

Ionization energy determinations

IE (eV)	Method	Reference	Comment
10.44	DER	Schroder, Sulzle, et al., 1994	LL
10.3	PE	Ogden, Shaw, et al., 1983	LBLHLM
10.38 ± 0.03	PIPECO	Gilman, Hsieh, et al., 1983	LBLHLM
10.38	PIPECO	Gilman, Hsieh, et al., 1983, 2	LBLHLM
10.38 ± 0.03	PI	Meisels, Hsieh, et al., 1980	LLK
11.0	PE	Bergmann and Bock, 1975	LLK
10.475 ± 0.007	PI	Nicholson, 1970	RDSH

Appearance energy determinations

Ion	AE (eV)	Other Products	Method	Reference	Comment
CH₃O⁺	10.82 ± 0.05	NO	EI	Burgers and Holmes, 1984	LBLHLM
CH₃O⁺	11.0 ± 0.2	NO	EI	Burgers and Holmes, 1984	LBLHLM
CH₃O⁺	10.69 ± 0.03	NO	PIPECO	Gilman, Hsieh, et al., 1983	LBLHLM
CH₃O⁺	10.69	NO	PIPECO	Gilman, Hsieh, et al., 1983, 2	LBLHLM
CH₃O⁺	10.96	NO	EI	Haney and Franklin, 1969	RDSH
NO⁺	10.83 ± 0.04	CH₃O	PIPECO	Gilman, Hsieh, et al., 1983	LBLHLM
NO⁺	10.83	CH₃O	PIPECO	Gilman, Hsieh, et al., 1983, 2	LBLHLM
NO⁺	10.83 ± 0.04	CH₃O	PE	Meisels, Hsieh, et al., 1980	LLK
NO⁺	10.917 ± 0.008	CH₃O	PI	Nicholson, 1970	RDSH
NO⁺	11.15	CH₃O	EI	Haney and Franklin, 1969	RDSH
NO⁺	11.07 ± 0.06	CH₃O	EI	Martin, Lampe, et al., 1966	RDSH

References

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

Ray and Gershon, 1962
Ray, J.D.; Gershon, A.A., The heat of formation of gaseous methyl nitrite, J. Phys. Chem., 1962, 66, 1750-1752. [all data]

Geiseler and Thierfelder, 1961
Geiseler, G.; Thierfelder, W., Bestimmung der bildungswarme des gasformigen methylnitrits, Z. Phys. Chem. (Neue Folge), 1961, 29, 248-257. [all data]

Gray and Pratt, 1958
Gray, P.; Pratt, M.W.T., 687. The thermodynamic functions of methyl nitrite and the potential barrier to free rotation., J. Chem. Soc., 1958, 3403-3412. [all data]

Silverwood and Thomas, 1967
Silverwood, R.; Thomas, J.H., Reaction between methanol and nitrogen dioxide. Part 1.-Low-temperature reaction and the thermodynamic constants of methyl nitrite, J. Chem. Soc. Faraday Trans., 1967, 63, 2476-2479. [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]

Rook, 1982
Rook, Frederick L., Preparation, vapor pressure, and infrared spectrum of methyl nitrite, J. Chem. Eng. Data, 1982, 27, 1, 72-73, https://doi.org/10.1021/je00027a022 . [all data]

Ray and Ogg, 1959
Ray, J.D.; Ogg, R.A., Jr., The heat of formation of methyl nitrate, J. Phys. Chem., 1959, 63, 1522-1523. [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]

Schroder, Sulzle, et al., 1994
Schroder, D.; Sulzle, D.; Dutuit, O.; Baer, T.; Schwarz, H., Further insight in the surprisingly complex unimolecular fragmentations of the methyl nitrite radical cation, J. Am. Chem. Soc., 1994, 116, 6395. [all data]

Ogden, Shaw, et al., 1983
Ogden, I.K.; Shaw, N.; Danby, C.J.; Powis, I., Competing dissociation channels of nitromethane and methyl nitrite ions and the role of electronic and internal modes of excitation, Int. J. Mass Spectrom. Ion Processes, 1983, 54, 41. [all data]

Gilman, Hsieh, et al., 1983
Gilman, J.P.; Hsieh, T.; Meisels, G.G., The unimolecular decomposition rates of energy selected methylnitrite and deuterated methylnitrite ions, J. Chem. Phys., 1983, 78, 3767. [all data]

Gilman, Hsieh, et al., 1983, 2
Gilman, J.P.; Hsieh, T.; Meisels, G.G., Competition between isomerization and fragmentation of gaseous ions. II. Nitromethane and methylnitrite ions, J. Chem. Phys., 1983, 78, 1174. [all data]

Meisels, Hsieh, et al., 1980
Meisels, G.G.; Hsieh, T.; Gilman, J.P., Ion fragmentation from noninterconverting electronic states, J. Chem. Phys., 1980, 73, 4126. [all data]

Bergmann and Bock, 1975
Bergmann, H.; Bock, H., Photoelectron spectra molecular properties, XLVI nitroso compounds - electron-rich molecules, Z. Naturforsch. B:, 1975, 30, 629. [all data]

Nicholson, 1970
Nicholson, A.J.C., Determination of bond dissociation energies from photoionization efficiency curves in Recent Developments in Mass Spectrometroscopy, ed. K Ogata and T. Hayakawa, Univ. Park Press, Baltimore, MD, 1970, 745. [all data]

Burgers and Holmes, 1984
Burgers, P.C.; Holmes, J.L., The generation of triplet methoxy cations, Org. Mass Spectrom., 1984, 19, 452. [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]

Martin, Lampe, et al., 1966
Martin, R.H.; Lampe, F.W.; Taft, R.W., An electron-impact study of ionization and dissociation in methoxy- and halogen- substituted methanes, J. Am. Chem. Soc., 1966, 88, 1353. [all data]

Notes

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Symbols used in this document:

AE	Appearance energy
Δ_cH°_gas	Enthalpy of combustion of gas at standard conditions
Δ_fH°_gas	Enthalpy of formation of gas at standard conditions
Δ_fH°_liquid	Enthalpy of formation of liquid at standard conditions
Δ_rH°	Enthalpy of reaction at standard conditions
Δ_vapH	Enthalpy of vaporization
Δ_vapH°	Enthalpy of vaporization at standard conditions

Data from NIST Standard Reference Database 69: NIST Chemistry WebBook
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