Positive and negative ion-molecule reactions and the proton affinity of ethyl nitrate

Kriemler, P.; Buttrill, S. E.

doi:10.1021/ja00708a004

Cited by 35 publications

(12 citation statements)

References 2 publications

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“…Only few available data can be found concerning the PA of organic nitrates, which were calculated using ab initio quantum mechanical methods exclusively. The PA of organic nitrates has been estimated to be 740 kJ mol −1 for methyl nitrate (Lee and Rice, 1992), 753 kJ mol −1 for ethyl nitrate (Kriemler and Buttrill, 1970), 748 kJ mol −1 for methyl peroxynitrate (Ravelo and Francisco, 2007) and 759-773 kJ mol −1 for peroxyacetyl nitrate (Tureček, 2000). These studies show that the PA of organic nitrates is higher than that of water, so that proton transfer reaction may occur.…”

Section: Experimental Strategymentioning

confidence: 88%

Measurement of alkyl and multifunctional organic nitrates by proton-transfer-reaction mass spectrometry

et al. 2017

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Abstract. A commercial PTR-TOF-MS has been optimized in order to allow the measurement of individual organic nitrates in the atmosphere. This has been accomplished by shifting the distribution between different ionizing analytes, H3O+∕ H3O+(H2O)n or NO+∕ NO2+. The proposed approach has been proven to be appropriate for the online detection of individual alkyl nitrates and functionalized nitrates. It has been shown that hydroxyl and ketonitrates have a high affinity towards NO+, leading to the formation of an adduct that allows the easy identification of the organic nitrate (R) from the R–NO+ ion signal. The recorded sensitivities for both ionization modes correspond to detection limits of tens of ppt min−1 in the case of hydroxy- and ketonitrates. Alkyl nitrates exhibit a moderate affinity towards NO+ ionization leading to detection units of few hundreds of ppt and the highest sensitivity in H3O+ mode was obtained for the water adducts signals. However, this method exhibits much lower capabilities for the detection of peroxyacetyl nitrates with detection limits in the ppb range.

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Section: Experimental Strategymentioning

confidence: 88%

Measurement of alkyl and multifunctional organic nitrates by proton-transfer-reaction mass spectrometry

et al. 2017

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“…On the basis of the above considerations, we have undertaken a joint mass spectrometric and theoretical study aimed at ascertaining whether gas-phase protonation of C 2 H 5 ONO 2 gives isomeric ions of structure 1 and 2, establishing their relative stability and reevaluating the PA of ethyl nitrate by experimental and theoretical methods more reliable than the "bracketing" technique 18 employed in earlier measurements. 16,19 Methodology Structural Analysis. The techniques employed include mass-analyzed ion kinetic energy (MIKE) and collisionally activated dissociation (CAD) spectrometry.…”

Section: Introductionmentioning

confidence: 99%

Gas-Phase Proton Affinity of Nitric Acid and Its Esters. A Mass Spectrometric and ab Initio Study on the Existence and the Relative Stability of Two Isomers of Protonated Ethyl Nitrate

et al. 1996

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The protonation of C 2 H 5 ONO 2 has been studied in the gas phase by the joint application of mass spectrometric and ab initio theoretical methods. The MIKE and CAD spectra of (C 2 H 5 ONO 2 )H + ions from various sources and their reactivity toward selected nucleophiles, investigated by FT-ICR mass spectrometry, point to the existence of two protomers, the C 2 H 5 OHNO 2 + ion-dipole complex (1c) and the covalently bound C 2 H 5 -ONOOH + species (2c), and to the tendency of the latter to isomerize into 1c in the presence of neutral C 2 H 5 -ONO 2 . The BE of NO 2 + to C 2 H 5 OH, independently measured by the kinetic and the equilibrium methods, amounts to 22.2 ( 2 kcal mol -1 at 298 K, leading to a PA of C 2 H 5 ONO 2 of 178.4 ( 2.6 kcal mol -1 , referred to the protonation at the ethereal oxygen. The computational results at the G2(MP2) level of theory show that protomers 1c and 2c have the same stability at 298 K and that at the same temperature the 2c f 1c isomerization is characterized by a ∆G°change of ca. -3 kcal mol -1 . The PA of C 2 H 5 ONO 2 is computed to be 177 ( 2 kcal mol -1 at 298 K, irrespective of whether protonation occurs at the ethereal O or at the NO 2 group, in excellent agreement with the experimental value. The results are discussed in connection with the general problem concerning the preferred protonation site and the PA trend along the RONO 2 homologous series. It is shown that entirely different factors control the local PA of the RO and the NO 2 groups.

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“…The electrons involved in the reactions 6 and 7 are probably secondary electrons brought to near thermal energies by collisions with the major gas. NO; and C2H30-were the two major ions observed by Kriemler and Butrill (9) in the low pressure mass spectra of ethyl nitrate obtained with low energy electrons. The 0; ion and hydrates observed in the present work were probably produced in third body electron capture by oxygen (lo), i.e., reaction 8.…”

Section: Resultsmentioning

confidence: 77%

Kinetics and Rate Constants of Reactions Leading to Hydration of and in Gaseous Oxygen, Argon, and Helium Containing Traces of Water

Payzant¹,

Cunningham²,

Kebarle³

1972

Can. J. Chem.

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The rate constants for the forward and reverse components of gas phase reactions:were measured with a pulsed electron beam, time resolved detection high pressure mass spectrometer at 300 OK. O,, Ar, and He at pressures from 1-7 Torr were used as third gas M. The forward reactions were found to be third order and the reverse reactions second order. Establishment of the equilibria could also be observed.

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Positive and negative ion-molecule reactions and the proton affinity of ethyl nitrate

Abstract: Chemiluminescence from thermal decomposition of dibenzal diperoxide in the presence of aromatic fluorescent compounds was studied. The emitting species was identified as the lowest excited singlet state of the

Cited by 35 publications

References 2 publications

Measurement of alkyl and multifunctional organic nitrates by proton-transfer-reaction mass spectrometry

Measurement of alkyl and multifunctional organic nitrates by proton-transfer-reaction mass spectrometry

Gas-Phase Proton Affinity of Nitric Acid and Its Esters. A Mass Spectrometric and ab Initio Study on the Existence and the Relative Stability of Two Isomers of Protonated Ethyl Nitrate

Kinetics and Rate Constants of Reactions Leading to Hydration of and in Gaseous Oxygen, Argon, and Helium Containing Traces of Water

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