Photolysis Of Methyl Nitrite Research Articles

Rate constants for the reaction of OH radicals with a series of alkanes and alkenes at 299 ± 2 K

AbstractUsing methyl nitrite photolysis in air as a source of hydroxyl radicals, relative rate constants for the reaction of OH radicals with a series of alkanes and alkenes have been determined at 299 ± 2 K. The rate constant ratios obtained are: relative to n‐hexane = 1.00, neopentane 0.135 ± 0.007, n‐butane 0.453 ± 0.007, cyclohexane 1.32 ± 0.04; relative to cyclohexane = 1.00, n‐butane 0.341 ± 0.002, cyclopentane 0.704 ± 0.007, 2,3‐dimethylbutane 0.827 ± 0.004, ethene 1.12 ± 0.05; relative to propene = 1.00, 2‐methyl‐2‐butene 3.43 ± 0.13, isoprene 3.81 ± 0.17, 2,3‐dimethyl‐2‐butene 4.28 ± 0.21. These relative rate constants are placed on an absolute basis using previous absolute rate constant data and are compared and discussed with literature data.

An Experimental Protocol for the Determination of OH Radical Rate Constants with Organics Using Methyl Nitrite Photolysis as an OH Radical Source

(1981). An Experimental Protocol for the Determination of OH Radical Rate Constants with Organics Using Methyl Nitrite Photolysis as an OH Radical Source. Journal of the Air Pollution Control Association: Vol. 31, No. 10, pp. 1090-1092.

Photodissociation of methyl nitrite in the vacuum ultraviolet. II. Excitation energy dependence of the NO fluorescent fragments

The production efficiency of NO excited fragments in A 2Σ+ v′=0,1,2,3, C 2Π v′=0, D 2Σ+ v′=0 states resulting from the photolysis of methyl nitrite in the far UV has been measured as a function of incident wavelength using the synchrotron radiation of the electron storage ring of Orsay as the source of excitation. The experimental energy threshold to produce each NO excited state is in agreement with a bond dissociation energy of CH3O–NO of 1.8 eV. The excitation spectra of electronically excited NO A 2Σ+, C 2Π, D 2Σ+ are discussed in relation with the absorption spectrum of the parent molecule. The vibrational energy distribution in NO A 2Σ+ v′=0,1,2 can be explained by a statistical energy partition between CH3O and NO products provided some restrictions on the activated modes of the CH3O fragment. NO A 2Σ+ v′=3 population shows an anomalous behavior which can be indicative of a half-collision effect due to the interaction of NO C 2Π and D 2Σ+ primary product with CH3O.

CH 3O( [formula omitted]2E) production from 266 nm photolysis of methyl nitrite and reaction with NO

The CH 3O( X 2E) radical produced by the 266 nm photolysis of CH 3ONO is characterized by laser-induced fluorescence. Using a flowing gas cell the reaction rate of CH 3O( X 2E) with NO is measured to be (2.08 ± 0.12) × 10 −11 cm 3 s −1 molecule −1 based upon disappearance of CH 3O and appearance of HNO detected by laser induced fluorescence. Upper limits for CH 3O reactions with CH 4, CO, N 2O, NH 3, CH 3OH, (CH 3) 3CH and CH 2CHCH 2CH 3 are reported. These reactions are all too slow to measure under our experimental conditions.

CH3O(X̄ 2E) production from 266 nm photolysis of methyl nitrite and reaction with NO

The CH3O(X̄ 2E) radical produced by the 266 nm photolysis of CH3ONO is characterized by laser induced fluorescence. Using a flowing gas cell the reaction rate of CH3O(X̄ 2E) with NO is measured to be (2.08 ± 0.12) × 10−11 cm3 s−1 based upon disappearance of CH3O and appearance of HNO detected by laser induced fluorescence. Upper limits for CH3O reactions with CH4, CO, N2O, NH3, CH3OH, (CH3)3CH and CH2CHCH2CH3 are reported. These reactions are all too slow to measure under our experimental conditions.

Photolysis of methyl nitrite: kinetics of the reaction of the methoxy radical with O 2

The near-UV photolysis of methyl nitrite in the presence of oxygen was investigated at pressures near 1 atm. The initial process is ▪ which occurs with a quantum yield of unity under the conditions used in this work. The primary products react further by a complex mechanism to yield a variety of products which include NO 2. HNO 3, HCHO and CH 3ONO 2. Methyl nitrate exhibits a strong dependence on O 2 and NO 2; this could be interpreted in terms of competition between the reactions ▪ The ratio k 4/ k 5 was determined by a computer simulation of the experimental data over a range of temoeratures and compositions and k 4 was evaluated using a literature value for k 5. By combining all the available data for k 4 over the temperature range 296-450 K the following Arrhenius expressions was derived. ▪

Photolysis of methyl nitrite in the presence of nitric oxide, nitrogen dioxide, and oxygen

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTPhotolysis of methyl nitrite in the presence of nitric oxide, nitrogen dioxide, and oxygenH. A. Wiebe, Alberto. Villa, T. M. Hellman, and Julian. HeicklenCite this: J. Am. Chem. Soc. 1973, 95, 1, 7–13Publication Date (Print):January 1, 1973Publication History Published online1 May 2002Published inissue 1 January 1973https://doi.org/10.1021/ja00782a002RIGHTS & PERMISSIONSArticle Views127Altmetric-Citations50LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (760 KB) Get e-Alerts Get e-Alerts

Photolysis of methyl nitrite

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTPhotolysis of methyl nitriteH. A. Wiebe and Julian. HeicklenCite this: J. Am. Chem. Soc. 1973, 95, 1, 1–7Publication Date (Print):January 1, 1973Publication History Published online1 May 2002Published inissue 1 January 1973https://doi.org/10.1021/ja00782a001RIGHTS & PERMISSIONSArticle Views237Altmetric-Citations49LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (651 KB) Get e-Alerts Get e-Alerts

Molecular‐modulation spectrometry: CH3ONO photolysis and detection of nitroxyl

AbstractThe method of molecular‐modulation spectrometry for studying photochemical reactions has been applied to methyl nitrite photolysis. The infrared absorption of the nitroxyl radical HNO has been observed in the gas phase at 3300 cm−1. Under the present experimental conditions the steady‐state concentration of HNO under steady illumination was 1.1 × 1012 particles/cc, and the observed modulation amplitude was 4.5 × 1010 particles/cc. At 25°C and 1 atm of nitrogen, the cross section for infrared absorption by HNO at 3300 cm−1 is 1.7 × 10−19 cm2. The rate constant ratio b/c equation image was found to be 8.0. From the literature value of the rate constant d equation image , the observed rate constant for the reaction equation image is e = (5 ± 1) × 10−11 cc/particle sec.

The photosynthesis of nitrosoformaldehyde and the identification of its spectrum

A transient spectrum previously thought to be that of methoxyl is produced by the flash photolysis of methyl nitrite (McGrath & McGarvey 1964 a, b ). We now find that the same spectrum is produced by flashing formaldeyhde, acetaldehyde, methyl formate or glyoxal in the presence of nitric oxide and excess of nitrogen as coolant, and attribute it to nitroso-formaldehyde. The spectrum consists of diffuse bands with centres at 2070, 2043, 2020 (?) 2000 and 1982 Å which possibly constitute a progression in the NCO bending mode. The reaction leading to the decay of the nitrosoformaldehyde in about 0.1 s has not been positively identified, and alternative possibilities are discussed.

Photolysis of Nitromethane and of Methyl Nitrite in an Argon Matrix; Infrared Detection of Nitroxyl, HNO

The photolysis of nitromethane in solid argon at 20°K gives methyl nitrite. All other products can be explained in terms of the secondary photolysis of methyl nitrite. This work provides a definitive basis for segregating the vibrational frequencies of the cis- and trans-isomers of methyl nitrite. The primary products of photolysis of methyl nitrite under these conditions are formaldehyde and nitroxyl, HNO. The identification of HNO, detected by its infrared spectrum for the first time, is confirmed by the band shifts occurring upon deuteration. The vibrational frequencies of HNO (1570 and 1110 cm-1) and DNO (1560 and 822 cm-1) correspond to a bent molecule with a double bond between the nitrogen and oxygen atoms, thus supporting the structure HNO over the possible arrangement HON. The bending force constant, 0.67·10-11 dyne-cm, suggests that the HNO angle is near 110°, larger than the earlier estimate of 102° based on electronic spectra.

The photolysis of methyl nitrite

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