A selected ion flow tube study of the reactions of various nitrogen containing ions with formic acid, acetic acid, and methyl formate

Jackson, Douglas; Stibrich, Nathan J.; McLain, J. L.; Fondren, L. Dalila; Adams, Nigel G.; Babcock, L

doi:10.1016/j.ijms.2005.09.001

Cited by 18 publications

(33 citation statements)

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“…In the dissociation reactions of propenal, where the molecule is not symmetric, the two major products occur in different proportions with HCO ϩ being the lesser product, which is reasonable since the double-bond is less likely to be positively charged. This trend of aldehydes (R-CHO) to form HCO ϩ in a lesser proportion to R ϩ in dissociative charge-transfer reactions has been seen in other molecules as well such as methyl formate, CH 3 OCHO© [18].…”

Section: Products and Product Structuresmentioning

confidence: 57%

“…To ensure a uniform flow into the flow tube, the vapors of these liquids were diluted in an isolated vessel to a 1% mix in He. Note that the dimerization of acetic©acid©was©accounted©for© [18]©in©reporting©rate coefficients for the switching reactions. The ternary reactions with NH 4 ϩ proceeded by successively associating one then two neutrals, X,…”

Section: Methodsmentioning

confidence: 99%

“…Most of the k b values are within experimental error (Ϯ30%) of the k theor values, indicating that the reactions usually proceed at the gas kinetic rate for true binary reactions. The atom abstraction reactions with NH 3 ϩ occur slightly slower and are slightly less than 100% efficient for various organic molecules© [18].© It© should© be© noted© that© NH 4 ϩ reacts with the neutrals significantly below the theoretical rate to form single association products and then upon further reactivity double association products as shown in Figure© 1.© Additionally,© the© k b value for these reactions varies as a function of He pressure indicating that ternary reactions, eq 1 and eq 2, were occurring. The values of the effective binary rate coefficient at a series of He pressures of the ternary association reactions of NH 4 ϩ with ethylene oxide and propenal were determined experimentally and three body rate coefficients, …”

Section: Rate Coefficientsmentioning

confidence: 99%

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Ion-molecule reactions of several ions with ethylene oxide and propenal in a selected ion flow tube

Jackson

Adams

Babcock

2007

J. Am. Soc. Mass Spectrom.

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The selected ion flow tube (SIFT) technique has been used to investigate the ion-molecule reactions of several ions with the neutral molecules ethylene oxide, CH 2 OCH 2 -c, and propenal, CH 2 CHCHO. Both molecules have been identified in hot-core star forming regions [1, 2]© and have significance to astrochemical models of the interstellar (ISM) and circumstellar medium (CSM). Moreover, the molecules contain functional groups, such as the epoxide group (ethylene oxide) and an aldehyde group, which are part of a conjugated -electron system (propenal) whose reactivities have not been studied in detail in gas-phase ion-molecule reactions. The larger recombination energy ions, Ar ϩ and N 2 ϩ , were reacted with the neutrals to give insight into general fragmentation tendencies. These reactions proceeded via dissociative charge-transfer yielding major fragmentation products of CH 3 ϩ and HCO ϩ for ethylene oxide and CH 2 CH ϩ and HCO ϩ for propenal. The amino acids glycine and alanine are of particular interest to astrobiology, especially if they can be synthesized in the gas phase. In an attempt to synthesize amino acid precursors, ethylene oxide and propenal were reacted with NH n ϩ (n ϭ 1-4) and HCNH ϩ . As might be expected from the proton detachment energies, NH ϩ , NH 2 ϩ , and HCNH ϩ reacted via proton transfer. NH 3 ϩ reacted with each molecule via H-atom abstraction to produce NH 4 ϩ , and NH 4 ϩ reacted via a ternary association. All binary reactions proceeded near the gas kinetic rate. Several associated molecule switching reactions were performed and implications of these reactions to the structures of the association products are discussed Ikeda et al. and Hollis et al. (J Am Soc Mass Spectrom 2007, 18, 445-452)

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Section: Products and Product Structuresmentioning

confidence: 57%

Section: Methodsmentioning

confidence: 99%

Section: Rate Coefficientsmentioning

confidence: 99%

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Ion-molecule reactions of several ions with ethylene oxide and propenal in a selected ion flow tube

Jackson

Adams

Babcock

2007

J. Am. Soc. Mass Spectrom.

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“…. with neutral amine species, CH 3 NH 2 and CH 3 CH 2 NH 2 (Jackson et al2005a,b); and b) reactions of positively charged ammonia and amine ion fragments, NH + 2 , NH + 3 , and HCNH + with neutral species, HCOOH, CH 3 COOH, and CH 3 OCHO (Jackson et al 2005b). …”

Section: Introductionmentioning

confidence: 99%

“…The reaction between the radical cation of ammonia and acetic acid was previously studied by selected ion flow tube experiments (Jackson et al 2005b). The authors concluded that NH + 3 reacts with CH 3 COOH via H atom abstraction giving NH + 4 + CH 2 COOH, this product being more thermodynamically stable than the CH 3 COO radical.…”

Section: Introductionmentioning

confidence: 99%

The reaction between NH₃⁺and CH₃COOH: a possible process for the formation of glycine precursors in the interstellar medium

Largo

Rayón

Largo

et al. 2010

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Context. The formation of glycine is strongly relevant to our understanding of the interstellar medium and is most accuretely studied computationally. Aims. We carry out a theoretical study of the reactions between the radical cation of ammonia and CH 3 COOH/CH 2 COOH as possible processes leading to glycine derivatives. Methods. The gas-phase reactions were theoretically studied using ab initio methods. We employed the second-order Moller-Plesset level in conjunction with the cc-pVTZ basis set. In addition, the electronic energies were refined by means of single-point calculations at the CCSD(T) level on the MP2/cc-pVTZ geometries with the aug-cc-pVTZ basis set. Results. We report accurate potential energy surfaces for the reactions considered in this work. The different intermediate species as well as the most relevant transition states for these reactions are characterized. Conclusions. Formation of protonated glycine from the reaction of NH + 3 with acetic acid is an exothermic (−9.15 kcal/mol at CCSD(T) level) barrier free process. However, the results obtained indicate that the hydrogen-transfer process forming NH + 4 and CH 2 COOH is clearly the dominating path, in agreement with the experimental evidence. The formation of ionized glycine from the reaction of product CH 2 COOH with NH + 3 is a quasi-isoenergetic (2.03 kcal/mol at CCSD(T) level) barrier free process that leads to a highly stable intermediate: protonated glycine.

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The Selective Role of Long‐Range Forces in the Stereodynamics of Ion–Molecule Reactions: The He⁺+Methyl Formate Case From Guided‐Ion‐Beam Experiments

et al. 2017

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Long‐range intermolecular forces play a crucial role in controlling the outcome of ion–molecule chemical reactions, such as those determining the disappearance of organic or inorganic “complex” molecules recently detected in various regions of the interstellar medium due to collisions with abundant interstellar atomic ions (e.g. H+ and He+). Theoretical treatments, for example, based on simple capture models, are nowadays often adopted to evaluate the collision‐energy dependence of reactive cross sections and the temperature dependent rate coefficients of many ion–molecule reactions. The obtained results are widely used for the modelling of phenomena occurring in different natural environments or technological applications such as astrophysical and laboratory plasmas. Herein it is demonstrated, through a combined experimental and theoretical investigation on a prototype ion–molecule reaction (He++methyl formate), that the dynamics, investigated in detail, shows some intriguing features that can lead to rate coefficients at odds with the expectations (e.g. Arrhenius versus anti‐Arrhenius behaviour). Therefore, this study casts light on some new and general guidelines to be properly taken into account for a suitable evaluation of rate coefficients of ion–molecule reactions.

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A selected ion flow tube study of the reactions of various nitrogen containing ions with formic acid, acetic acid, and methyl formate

Cited by 18 publications

References 28 publications

Ion-molecule reactions of several ions with ethylene oxide and propenal in a selected ion flow tube

Ion-molecule reactions of several ions with ethylene oxide and propenal in a selected ion flow tube

The reaction between NH₃⁺and CH₃COOH: a possible process for the formation of glycine precursors in the interstellar medium

The Selective Role of Long‐Range Forces in the Stereodynamics of Ion–Molecule Reactions: The He⁺+Methyl Formate Case From Guided‐Ion‐Beam Experiments

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A selected ion flow tube study of the reactions of various nitrogen containing ions with formic acid, acetic acid, and methyl formate

Cited by 18 publications

References 28 publications

Ion-molecule reactions of several ions with ethylene oxide and propenal in a selected ion flow tube

Ion-molecule reactions of several ions with ethylene oxide and propenal in a selected ion flow tube

The reaction between NH3+and CH3COOH: a possible process for the formation of glycine precursors in the interstellar medium

The Selective Role of Long‐Range Forces in the Stereodynamics of Ion–Molecule Reactions: The He++Methyl Formate Case From Guided‐Ion‐Beam Experiments

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The reaction between NH₃⁺and CH₃COOH: a possible process for the formation of glycine precursors in the interstellar medium

The Selective Role of Long‐Range Forces in the Stereodynamics of Ion–Molecule Reactions: The He⁺+Methyl Formate Case From Guided‐Ion‐Beam Experiments