Computational and experimental studies of chemical ionization mass spectrometric detection techniques for atmospherically relevant peroxides

Messer, Benjamin; Stielstra, David E; Cappa, C. D.; Scholtens, Kurtis W.; Elrod, Matthew J.

doi:10.1016/s1387-3806(99)00260-2

Cited by 23 publications

(22 citation statements)

References 38 publications

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“…The rates of reactions (18) and (20) have been measured previously (k 18 ϭ 1.4 ϫ 10 Ϫ9 cm 3 molecule Ϫ1 s Ϫ1 and k 20 ϭ 1.4 ϫ 10 Ϫ10 cm 3 molecule Ϫ1 s Ϫ1 ) [22,23], reaction (16) has been used in our previous study of the CH 3 O 2 ϩ NO reaction [4], reaction (19) has been used in a previous study of the HO 2 ϩ BrO reaction [21], and reaction (17) had been predicted to be thermodynamically feasible on the basis of electronic structure calculations [24]. For the low-temperature studies, liquid-nitrogencooled silicone oil was used as the coolant for the jacketed flow tube, and the nitrogen carrier gas was precooled by passing it through a copper coil immersed in a liquid N 2 reservoir followed by resistive heating.…”

Section: Chemical Ionization Schemesmentioning

confidence: 99%

Direct kinetics study of the temperature dependence of the CH₂O branching channel for the CH₃O₂ + HO₂ reaction

Elrod

Ranschaert

Schneider

2001

Int J of Chemical Kinetics

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A direct kinetics study of the temperature dependence of the CH 2 O branching channel for the CH 3 O 2 ϩ HO 2 reaction has been performed using the turbulent flow technique with high-pressure chemical ionization mass spectrometry for the detection of reactants and products. The temperature dependence of the CH 2 O-producing channel rate constant was investigated between 298 and 218 K at a pressure of 100 Torr, and the data were fitted to the following Arrhenius expression:ϫ 10 Ϫ15 ϫ exp[(1730 Ϯ 130)/T] cm 3 molecule Ϫ1 s Ϫ1 .ϩ1.0 1.6 Ϫ0.7 Using the Arrhenius expression for the overall rate of the CH 3 O 2 ϩ HO 2 reaction and this result, the 298 K branching ratio for the CH 2 O producing channel is measured to be 0.11, and the branching ratio is calculated to increase to a value of 0.31 at 218 K, the lowest temperature accessed in this study. The results are compared to the analogous CH 3 O 2 ϩ CH 3 O 2 reaction and the potential atmospheric ramifications of significant CH 2 O production from the CH 3 O 2 ϩ HO 2 reaction are discussed.

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Section: Chemical Ionization Schemesmentioning

confidence: 99%

Direct kinetics study of the temperature dependence of the CH₂O branching channel for the CH₃O₂ + HO₂ reaction

Elrod

Ranschaert

Schneider

2001

Int J of Chemical Kinetics

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“…To obtain diagnostic species under CI conditions, some specific reagents have been used for inducing gas‐phase ion–molecule reactions. Methane (CH 5 +• )15 and oxygen (O 2 +• )16 were used in positive ion mode and negative ion CI experiments were performed with (i) O 2 −• (charge exchange),17 (ii) methane18 (electron capture) and (iii) F − (deprotonation) 12. Such gas‐phase reagents are alternatives for detecting, for instance, atmospheric peroxides.…”

Section: Introductionmentioning

confidence: 99%

Unusual atmospheric pressure chemical ionization conditions for detection of organic peroxides

Rondeau

Vogel²,

Tabet

2003

J. Mass Spectrom.

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Organic peroxides such as the cumene hydroperoxide I (M(r) = 152 u), the di-tert-butyl peroxide II (M(r) = 146 u) and the tert-butyl peroxybenzoate III (M(r) = 194 u) were analyzed by atmospheric pressure chemical ionization mass spectrometry using a water-methanol mixture as solvent with a low flow-rate of mobile phase and unusual conditions of the source temperature (< or =50 degrees C) and probe temperature (70-200 degrees C). The mass spectra of these compounds show the formation of (i) an [M + H](+) ion (m/z 153) for the hydroperoxide I, (ii) a stable adduct [M + CH(3)OH(2)](+) ion (m/z 179) for the dialkyl peroxide II and (iii) several protonated adduct species such as protonated molecules (m/z 195) and different protonated adduct ions (m/z 227, 389 and 421) for the peroxyester III. Tandem mass spectrometric experiments, exact mass measurements and theoretical calculations were performed for characterize these gas-phase ionic species. Using the double-well energy potential model illustrating a gas-phase bimolecular reaction, three important factors are taken into account to propose a qualitative interpretation of peroxide behavior toward the CH(3)OH(2) (+), i.e. thermochemical parameters (DeltaHdegrees(reaction)) and two kinetic factors such as the capture constant of the initial stable ion-dipole and the magnitude of the rate constant of proton transfer reaction into the loose proton bond cluster.

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“…As noted above, reaction Gibbs energies and equilibrium constants are available for Reaction (R1) (Bartmess, 2016). A more limited set of Gibbs energies and equilibrium constants are available for Reaction (R2) with H 2 O 2 as the analyte (Böhringer et al, 1984;Cappa and Elrod, 2001;Messer et al, 2000;O'Sullivan et al, 2018). Following Böhringer, we used known reaction enthalpies, H o R5 , or reaction Gibbs energies, G o R5 , of the ion protonation reaction (Reaction R5),…”

Section: Reaction Rate Coefficientsmentioning

confidence: 99%

“…Siddharth Iyer (personal communication, 2016) estimated the CH 3 OOH binding energy with I − is −60 kJ mol −1 . Messer et al (2000) also using ab initio methods examined the kinetics and energetics of H 2 O 2 and CH 3 OOH cluster ion formation with F − . They reported theoretical collision-limit rate coefficients of 1.42 × 10 −9 and 1.47 × 10 −9 , respectively, for reactions with F − (H 2 O) 3 .…”

Section: R2mentioning

confidence: 99%

An ion-neutral model to investigate chemical ionization mass spectrometry analysis of atmospheric molecules – application to a mixed reagent ion system for hydroperoxides and organic acids

et al. 2018

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Abstract. An ion-neutral chemical kinetic model is described and used to simulate the negative ion chemistry occurring within a mixed-reagent ion chemical ionization mass spectrometer (CIMS). The model objective was the establishment of a theoretical basis to understand ambient pressure (variable sample flow and reagent ion carrier gas flow rates), water vapor, ozone and oxides of nitrogen effects on ion cluster sensitivities for hydrogen peroxide (H2O2), methyl peroxide (CH3OOH), formic acid (HFo) and acetic acid (HAc). The model development started with established atmospheric ion chemistry mechanisms, thermodynamic data and reaction rate coefficients. The chemical mechanism was augmented with additional reactions and their reaction rate coefficients specific to the analytes. Some existing reaction rate coefficients were modified to enable the model to match laboratory and field campaign determinations of ion cluster sensitivities as functions of CIMS sample flow rate and ambient humidity. Relative trends in predicted and observed sensitivities are compared as instrument specific factors preclude a direct calculation of instrument sensitivity as a function of sample pressure and humidity. Predicted sensitivity trends and experimental sensitivity trends suggested the model captured the reagent ion and cluster chemistry and reproduced trends in ion cluster sensitivity with sample flow and humidity observed with a CIMS instrument developed for atmospheric peroxide measurements (PCIMSs). The model was further used to investigate the potential for isobaric compounds as interferences in the measurement of the above species. For ambient O3 mixing ratios more than 50 times those of H2O2, O3−(H2O) was predicted to be a significant isobaric interference to the measurement of H2O2 using O2−(H2O2) at m∕z 66. O3 and NO give rise to species and cluster ions, CO3−(H2O) and NO3−(H2O), respectively, which interfere in the measurement of CH3OOH using O2−(CH3OOH) at m∕z 80. The CO3−(H2O) interference assumed one of its O atoms was 18O and present in the cluster in proportion to its natural abundance. The model results indicated monitoring water vapor mixing ratio, m∕z 78 for CO3−(H2O) and m∕z 98 for isotopic CO3−(H2O)2 can be used to determine when CO3−(H2O) interference is significant. Similarly, monitoring water vapor mixing ratio, m∕z 62 for NO3− and m∕z 98 for NO3−(H2O)2 can be used to determine when NO3−(H2O) interference is significant.

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Computational and experimental studies of chemical ionization mass spectrometric detection techniques for atmospherically relevant peroxides

Cited by 23 publications

References 38 publications

Direct kinetics study of the temperature dependence of the CH₂O branching channel for the CH₃O₂ + HO₂ reaction

Direct kinetics study of the temperature dependence of the CH₂O branching channel for the CH₃O₂ + HO₂ reaction

Unusual atmospheric pressure chemical ionization conditions for detection of organic peroxides

An ion-neutral model to investigate chemical ionization mass spectrometry analysis of atmospheric molecules – application to a mixed reagent ion system for hydroperoxides and organic acids

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Computational and experimental studies of chemical ionization mass spectrometric detection techniques for atmospherically relevant peroxides

Cited by 23 publications

References 38 publications

Direct kinetics study of the temperature dependence of the CH2O branching channel for the CH3O2 + HO2 reaction

Direct kinetics study of the temperature dependence of the CH2O branching channel for the CH3O2 + HO2 reaction

Unusual atmospheric pressure chemical ionization conditions for detection of organic peroxides

An ion-neutral model to investigate chemical ionization mass spectrometry analysis of atmospheric molecules – application to a mixed reagent ion system for hydroperoxides and organic acids

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Direct kinetics study of the temperature dependence of the CH₂O branching channel for the CH₃O₂ + HO₂ reaction

Direct kinetics study of the temperature dependence of the CH₂O branching channel for the CH₃O₂ + HO₂ reaction