Preparation, analysis, and atmospheric production of multifunctional organic nitrates

Muthuramu, K.; Shepson, P. B.; O’Brien, Jason

doi:10.1021/es00043a010

Cited by 88 publications

(85 citation statements)

References 18 publications

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“…Ethyl nitrate was prepared according to the procedure developed earlier in our lab (Ranschaert et al, 2000). 1-nitrato-2-butanol, 2-nitrato-1-butanol, 3-nitrato-2-butanol, and 2-methyl-2-nitrato-1-butanol were prepared according to a previous procedure (Muthuramu et al, 1993). All other organonitrates were prepared in situ in the reaction solutions by nucleophilic attack of nitrate on epoxide precursors (Darer et al, 2011).…”

Section: Syntheses Of Organonitrates and Organosulfatesmentioning

confidence: 99%

Thermodynamics and kinetics of the hydrolysis of atmospherically relevant organonitrates and organosulfates

2011

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Abstract. The presence of alcohol, organonitrate, and organosulfate species related to the gaseous precursor isoprene in ambient secondary organic aerosol (SOA) has stimulated investigations of the nature of SOA-phase chemical processing. Recent work has suggested that certain isoprene-derived organonitrates are able to efficiently convert to organosulfates and alcohols on ambient SOA. In order to better understand the structure activity relationships previously observed for the isoprene-derived organonitrates and organosulfates, the hydrolysis reactions of a number of monofunctional and difunctional organonitrates and organosulfates with varying carbon substitution properties were investigated. Nuclear magnetic resonance techniques were used to study the bulk phase aqueous reactions of these organonitrates and organosulfates in order to determine hydrolysis reaction rate and, in some cases, thermodynamics information. Electronic structure calculations were also carried out to determine the enthalpy of hydrolysis for these species, and for the previously studied isoprene-derived species. The results suggest that while organonitrates and organosulfates are thermodynamically unstable with respect to the corresponding alcohols at standard state, only the tertiary organonitrates (and perhaps some tertiary organosulfates) are able to efficiently hydrolyze on SOA timescales and acidities.

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Section: Syntheses Of Organonitrates and Organosulfatesmentioning

confidence: 99%

Thermodynamics and kinetics of the hydrolysis of atmospherically relevant organonitrates and organosulfates

2011

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“…One sample could be injected every 49 min. The GC-ECD inlet, sample loop, and column were conditioned (Muthuramu et al, 1993) with a large gas phase concentration of the synthesized isoprene nitrates to alleviate adsorptive losses of the INs during experiments. We found that blanks following these samples were free of INs, indicating that the uptake of the INs from "conditioning" samples was irreversible.…”

Section: Isoprene Nitrate Isomer Identificationmentioning

confidence: 99%

“…The ECD detects the isoprene nitrates with very good sensitivity. However, it responds slightly differently to different types of nitrates (Muthuramu et al, 1993) making calibrations difficult without standards, which up to now, have not been available for isoprene nitrates. A relative response experiment was conducted to determine the ECD detector response to an IN with respect to a readily available standard, isobutyl nitrate (IBN, Aldrich).…”

Section: Isoprene Nitrate Isomer Identificationmentioning

confidence: 99%

“…Calibration curves for the (1,2)-IN and for IBN are shown in Fig. 4 Muthuramu et al (1993). They determined relative response factors (with respect to IBN) for several hydroxy nitrates that ranged from 0.92 for 1-nitroxy-2-hydroxy butane to 2.70 for 2-nitroxy-3-hydroxy butane with an average value of 1.61 (±0.57).…”

Section: Isoprene Nitrate Isomer Identificationmentioning

confidence: 99%

“…They determined relative response factors (with respect to IBN) for several hydroxy nitrates that ranged from 0.92 for 1-nitroxy-2-hydroxy butane to 2.70 for 2-nitroxy-3-hydroxy butane with an average value of 1.61 (±0.57). For this work, we will assume that the relative response (to IBN) for all of the INs is 1.21, which falls within the uncertainty of the Muthuramu et al (1993) average value for the α, β-hydroxy nitrates.…”

Section: Isoprene Nitrate Isomer Identificationmentioning

confidence: 99%

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Isoprene nitrates: preparation, separation, identification, yields, and atmospheric chemistry

et al. 2010

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Abstract.Isoprene is an important atmospheric volatile organic compound involved in ozone production and NO x (NO+NO 2 ) sequestration and transport. Isoprene reaction with OH in the presence of NO can form either isoprene hydroxy nitrates ("isoprene nitrates") or convert NO to NO 2 which can photolyze to form ozone. While it has been shown that isoprene nitrate production can represent an important sink for NO x in forest impacted environments, there is little experimental knowledge of the relative importance of the individual isoprene nitrate isomers, each of which has a different fate and reactivity. In this work, we have identified the 8 individual isomers and determined their total and individual production yields. The overall yield of isoprene nitrates at atmospheric pressure and 295 K was found to be 0.070(+0.025/−0.015). Three isomers, representing nitrates resulting from OH addition to a terminal carbon, represent 90% of the total IN yield. We also determined the ozone rate constants for three of the isomers, and have calculated their atmospheric lifetimes, which range from ∼1-2 h, making their oxidation products likely more important as atmospheric organic nitrates and sinks for nitrogen.

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Products of the gas-phase reaction of the OH radical with 3-methyl-1-butene in the presence of NO

Atkinson

Tuazon

Aschmann

1998

Int. J. Chem. Kinet.

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The products of the gas-phase reaction of the OH radical with 3-methyl-1-butene in the presence of NO have been investigated at room temperature and total pressure 740 torr of air by gas chromatography with flame ionization detection, in situ Fourier transform infrared absorption spectroscopy, and direct air sampling atmospheric pressure ionization tandem mass spectrometry. The products identified and quantified by GC-FID and in situ FT-IR absorption spectroscopy were HCHO, 2-methylpropanal, acetone, glycolaldehyde, and methacrolein, with formation yields of and 0.70 Ϯ 0.06, 0.58 Ϯ 0.08, 0.17 Ϯ 0.02, 0.18 Ϯ 0.03, respectively. In addition, IR absorption bands due to organic nitrates were 0.033 Ϯ 0.007, observed, consistent with API-MS observations of product ion peaks attributed to the ␤-hydroxynitrates (CH 3 ) 2 CHCH(ONO 2 )CH 2 OH and/or (CH 3 ) 2 CHCH(OH)CH 2 ONO 2 formed from the reactions of the corresponding ␤-hydroxyalkyl peroxy radicals with NO. A formation yield of ca. 0.15 for these nitrates was estimated using IR absorption band intensities for known organic nitrates. These products account for essentially all of the reacted 3-methyl-1-butene. Analysis of the potential reaction pathways involved shows that H-atom abstraction from the allylic C9 H bond in 3-methyl-1-butene is a minor pathway which accounts for 5-10% of the overall OH radical reaction.

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Preparation, analysis, and atmospheric production of multifunctional organic nitrates

Cited by 88 publications

References 18 publications

Thermodynamics and kinetics of the hydrolysis of atmospherically relevant organonitrates and organosulfates

Thermodynamics and kinetics of the hydrolysis of atmospherically relevant organonitrates and organosulfates

Isoprene nitrates: preparation, separation, identification, yields, and atmospheric chemistry

Products of the gas-phase reaction of the OH radical with 3-methyl-1-butene in the presence of NO

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