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
The 3d structure may be viewed using Java or Javascript.
Other names: Nitrous acid, methyl ester; CH3ONO; Methylester kyseliny dusite; Methyl ester of nitrous acid
Permanent link for this species. Use this link for bookmarking this species for future reference.
Information on this page:
Other data available:
- Mass spectrum (electron ionization)
- Gas Chromatography
Data at other public NIST sites:
- Gas Phase Kinetics Database
Options:
- Switch to calorie-based units

Data at NIST subscription sites:

NIST / TRC Web Thermo Tables, professional edition (thermophysical and thermochemical data)

NIST subscription sites provide data under the NIST Standard Reference Data Program, but require an annual fee to access. The purpose of the fee is to recover costs associated with the development of data collections included in such sites. Your institution may already be a subscriber. Follow the links above to find out more about the data in these sites and their terms of usage.

Gas phase thermochemistry data

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

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

Quantity	Value	Units	Method	Reference	Comment
Δ_fH°_gas	-65.44 ± 0.84	kJ/mol	Eqk	Ray and Gershon, 1962
Δ_fH°_gas	-70. ± 3.	kJ/mol	Ccb	Geiseler and Thierfelder, 1961
Δ_fH°_gas	-62.5 ± 1.1	kJ/mol	Cm	Gray and Pratt, 1958	Measured by Baldrey, Lotzgesell and Style
Quantity	Value	Units	Method	Reference	Comment
Δ_cH°_gas	-752. ± 3.	kJ/mol	Ccb	Geiseler and Thierfelder, 1961

Condensed phase thermochemistry data

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

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

Quantity	Value	Units	Method	Reference	Comment
Δ_fH°_liquid	-67.15 ± 0.84	kJ/mol	Eqk	Silverwood and Thomas, 1967
Δ_fH°_liquid	-85.1 ± 1.0	kJ/mol	Cm	Gray and Pratt, 1958	Measured by Baldrey, Lotzgesell and Style

Phase change data

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

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°	22.6 ± 0.2	kJ/mol	V	Gray and Pratt, 1958	Measured by Baldrey, Lotzgesell and Style; ALS

Enthalpy of vaporization

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

Reaction thermochemistry data

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

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°	36.24	kJ/mol	Cm	Ray and Ogg, 1959	liquid phase

Methyl nitrite + = +

By formula: CH₃NO₂ + HCl = ClNO + CH₄O

Quantity	Value	Units	Method	Reference	Comment
Δ_rH°	8.95 ± 0.84	kJ/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°	66.48	kJ/mol	Eqk	Silverwood and Thomas, 1967	gas phase

Gas phase ion energetics data

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

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)	798.9	kJ/mol	N/A	Hunter and Lias, 1998	HL
Quantity	Value	Units	Method	Reference	Comment
Gas basicity	766.4	kJ/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

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

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
The National Institute of Standards and Technology (NIST) uses its best efforts to deliver a high quality copy of the Database and to verify that the data contained therein have been selected on the basis of sound scientific judgment. However, NIST makes no warranties to that effect, and NIST shall not be liable for any damage that may result from errors or omissions in the Database.
Customer support for NIST Standard Reference Data products.