Ion–molecule reactions of CoAr6+ with nitrogen oxides N2O, NO, and NO2: measuring absolute pressure by shock-freezing of the collision complex

Linde, Christian van der; Höckendorf, Robert F.; Balaj, O. Petru; Beyer, Martin K.

doi:10.1063/1.3432259

Cited by 7 publications

(4 citation statements)

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“…By electron ionization inside the ICR cell, the absence of the previously studied difluorobenzene in the trifluorobenzene reaction gas was confirmed, and vice versa. To determine the absolute pressure of the reaction gas in the ICR-cell, the recently introduced pressure calibration method 55,56 was employed, using ion-molecule reactions that proceed with collision rate.…”

Section: Experimental and Computational Detailsmentioning

confidence: 99%

Competition between Birch reduction and fluorine abstraction in reactions of hydrated electrons (H2O)n− with the isomers of di- and trifluorobenzene

Höckendorf

Balaj

Beyer

2011

Phys. Chem. Chem. Phys.

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The reactions of the isomers of di- and trifluorobenzene with hydrated electrons (H(2)O)(n)(-), n = 19-70, have been studied by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. While Birch reduction, i.e. H atom transfer to the aromatic ring, was observed for all studied isomers, a strong dependence on the substitution pattern was observed for fluorine abstraction. Nanocalorimetry combined with G3 calculations are used to analyze the thermochemistry of the reactions. Fluorine abstraction is at least 100 kJ mol(-1) more exothermic than Birch reduction, yet the latter is the dominant reaction pathway for all three difluorobenzene isomers. Fluorine abstraction and Birch reduction face activation barriers of comparable magnitude. The relative barrier height is sensitive to the substitution pattern. Birch reduction occurs selectively with 1,3- and 1,4-difluorobenzene in a nanoscale aqueous environment.

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Section: Experimental and Computational Detailsmentioning

confidence: 99%

Competition between Birch reduction and fluorine abstraction in reactions of hydrated electrons (H2O)n− with the isomers of di- and trifluorobenzene

Höckendorf

Balaj

Beyer

2011

Phys. Chem. Chem. Phys.

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“…Note that NO 2 , H 2 O and CH 3 OH stick to metal surfaces, and adsorption and desorption processes lead to additional uncertainties in the pressure measurement, as discussed in detail before. [31] Liquid reactants are subjected to several freeze-pump-thaw cycles to remove any dissolved gases, before being leaked into the vacuum system. Mass spectra are recorded after varying reaction delays to monitor the reaction kinetics.…”

Section: Experimental and Theoretical Methodsmentioning

confidence: 99%

“…The most likely explanation for these observations are problems with the pressure measurement, since controlling the pressure is difficult for both H 2 O and NO 2 , as also NO 2 is easily adsorbed to surfaces. [31] The corresponding rate coefficients are k abs (NO 2 ) = (16 � 10) • 10 À 10 cm 3 s À 1 and k abs (H 2 O) = (13 � 9) • 10 À 10 cm 3 s À 1 , respectively.…”

Section: Reactions Of N 2 H +mentioning

confidence: 99%

“…A possible explanation for this unexpectedly low rate coefficient could again be the pressure measurement, since water, too, sticks to surfaces which leads to significant error in the pressure measurement. [31] PTR with CH 3 OH. Proton transfer from ArH + to methanol yields, in addition to protonated methanol, reaction (7), also protonated formaldehyde, reaction (8).…”

Section: Reactions Of Arh +mentioning

confidence: 99%

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Proton Transfer Reactions from N₂H⁺ and ArH⁺ to Small Molecules

Münst

Barwa

Ončák

et al. 2023

Israel Journal of Chemistry

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Proton transfer reactions (PTR) are important for chemical ionization, especially in trace gas analysis in air. In an effort to extend their application to the analysis of high‐purity inert gases, we studied PTR of N2H+ and ArH+ with various reaction gases, viz. O2, N2, CH4, CO2, NO2, H2O and CH3OH. Oxygen, nitrogen, methane, carbon dioxide, and water undergo non‐dissociative proton transfer, where the original molecule remains intact. PTR to nitrogen dioxide leads to NO+ with release of neutral OH⋅. While PTR from N2H+ to methanol exclusively yields protonated methanol, the reaction with ArH+ exhibits dissociative proton transfer, due to its higher exothermicity. Products include methenium, protonated formaldehyde, and protonated methanol. The latter undergoes a slow secondary reaction to form protonated dimethyl ether. Within error limits, most reactions proceed at or close to collision rate. Quantum chemical calculations provide energetics and reaction pathways. In such highly exothermic proton transfer reactions, identification and quantification of trace compounds require detailed understanding of the fragmentation pathways and branching ratios.

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Carboxylierung von Methylacrylat durch das Kohlendioxid‐Radikalanion in Wasserclustern

et al. 2013

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Professor Wolfgang Domcke zum 65. Geburtstag gewidmet Mit dem wachsenden Interesse an der Verwendung von Kohlendioxid (CO 2 ) als C 1 -Baustein in der chemischen Synthese [1,2] und als Wasserstoff-Speichermaterial [3] haben die Mechanismen der CO 2 -Aktivierung auf molekularer Ebene große Aufmerksamkeit in Gasphasenstudien erlangt.[4] Für die Anwendung ist die Umsetzung von CO 2 mit Olefinen von besonderem Interesse.[2] Abhängig von den Reaktionsbedingungen erfolgt die Carboxylierung von Methylacrylat (MA, CH 2 =CHCOOCH 3 ) in elektrochemischen Synthesen [5][6][7] beträgt.[12] Diese Werte entsprechen Effektivitäten von F HSA = 114 % und F SCC = 60 %.Eine nanokalorimetrische Anpassung [10,13] (Abbildung 2 b,c) zeigt, dass während der Aufnahme von MA durchschnittlich (2.2 AE 0.5) Wassermoleküle aus dem Cluster verdampfen, was einer Reaktionsenthalpie von (À95 AE 22) kJ mol À1 entspricht. [14] Die Aufnahme von genau einem Abbildung 1. Massenspektren der Reaktion von CO 2 C À (H 2 O) n , n % 50-100, mit CH 2 =CHCOOCH 3 (MA) bei einem Druck von 7.5 10 À9 mbar nach a) 0 s, b) 7 s und c) 35 s Reaktionszeit.

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Ion–molecule reactions of CoAr6+ with nitrogen oxides N2O, NO, and NO2: measuring absolute pressure by shock-freezing of the collision complex

Cited by 7 publications

References 60 publications

Competition between Birch reduction and fluorine abstraction in reactions of hydrated electrons (H2O)n− with the isomers of di- and trifluorobenzene

Competition between Birch reduction and fluorine abstraction in reactions of hydrated electrons (H2O)n− with the isomers of di- and trifluorobenzene

Proton Transfer Reactions from N₂H⁺ and ArH⁺ to Small Molecules

Carboxylierung von Methylacrylat durch das Kohlendioxid‐Radikalanion in Wasserclustern

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Ion–molecule reactions of CoAr6+ with nitrogen oxides N2O, NO, and NO2: measuring absolute pressure by shock-freezing of the collision complex

Cited by 7 publications

References 60 publications

Competition between Birch reduction and fluorine abstraction in reactions of hydrated electrons (H2O)n− with the isomers of di- and trifluorobenzene

Competition between Birch reduction and fluorine abstraction in reactions of hydrated electrons (H2O)n− with the isomers of di- and trifluorobenzene

Proton Transfer Reactions from N2H+ and ArH+ to Small Molecules

Carboxylierung von Methylacrylat durch das Kohlendioxid‐Radikalanion in Wasserclustern

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Proton Transfer Reactions from N₂H⁺ and ArH⁺ to Small Molecules