An experimental study of the gas-phase kinetics of reactions with hydrated hydronium(1+) ions(n = 1-3) at 298 K

Böhme, Diethard K.; Mackay, G. I.; TANNER, S. D.

doi:10.1021/ja00508a003

Cited by 85 publications

(73 citation statements)

References 6 publications

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“…The energy then increases as the reaction proceeds to the transition state and this transition state has a lower electronic energy than the reactants [16]. These theoretical results are in agreement with the experimental ones [5,6] which may be represented by potential-energy profiles with a double minimum [3,40].…”

Section: S N 2 Reactions Through Ab Initio Calculationssupporting

confidence: 86%

Theoretical approach of the chemical reactivity: The S_N2 reaction

Serre

1984

Int J of Quantum Chemistry

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Section: S N 2 Reactions Through Ab Initio Calculationssupporting

confidence: 86%

Theoretical approach of the chemical reactivity: The S_N2 reaction

Serre

1984

Int J of Quantum Chemistry

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“…This value is somewhat less than that reported in the literature 14,. 15 Spanel and Smith's14 reported rate coefficient of k = 2.7 × 10 −9 cm 3 s −1 was assumed to be the same as the collision rate coefficient calculated using the parameterised trajectory method16 and this is usually a good assumption for exoergic proton transfer reactions. The reason for the choice of H 3 O + as the preferred precursor ion for C 2 H 5 OH analysis is that it yielded a less complicated analysis than did O 2 + .…”

Section: Methodsmentioning

confidence: 88%

Alcohol in breath and blood: a selected ion flow tube mass spectrometric study

Wilson

Freeman

McEwan

et al. 2001

Rapid Comm Mass Spectrometry

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In this paper we compare the amounts of ethanol in breath and in blood after ingestion of whisky using analysis by selected ion flow tube mass spectrometry (SIFT-MS). Blood ethanol concentrations were also obtained using standard hospital forensic procedures for blood alcohol analyses. We demonstrate the quantitative nature of SIFT-MS analysis by correlating the observed alcohol content of the headspace above 5-mL amounts of venous blood and aqueous solution to which known trace amounts of alcohol have been added. This procedure provides a Henry's Law coefficient for ethanol in aqueous solution at 298 +/- 3 K of 209 +/- 7 mol/kg*bar. We also demonstrate that measurement of the ethanol concentration in the alveolar portion of a single breath using the SIFT-MS technique gives an accurate measure of blood alcohol and could obviate the need for blood samples in forensic processing. The storage performance of breath samples in Mylar bags with a volume greater than 1 L has been shown to maintain the mixture integrity for ethanol but not for some other species.

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“…(H20),, Ions with the Oxygen-Bearing Organics. 24 showed that four of these molecules (viz, methanol, acetaldehyde, ethanol, and acetone) undergo fast switching reactions with H30+.-(H2O)1,2,3 ions. k = k, (see Table 1).…”

Section: Resultsmentioning

confidence: 99%

Reactions of Hydrated Hydronium Ions and Hydrated Hydroxide Ions with Some Hydrocarbons and Oxygen-Bearing Organic Molecules

Španěl¹,

Smith²

1995

J. Phys. Chem.

111

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The rate coefficients and ion products have been determined at 300 K for the reactions of H30+*(H20)0,1,~,3 positive ions and OH-(H20)o,l ,2 negative ions with six hydrocarbons and six oxygen-containing organic species using a selected ion flow tube ( S a ) for the positive ions and a flowing afterglow (FA) for the negative ions. This study was initiated in support of a major development program of the SIFT and FA as chemical ionization devices for the analysis of trace gases in air and especially of human breath and the vapors emitted by fruits and food products. The H30+ and OH-ions mostly react with the molecules, MH, via proton transfer, producing respectively MH2+ and M-ions, which is ideal for gas analysis. The hydrated hydronium ions and the hydrated hydroxide ions are largely unreactive with the hydrocarbons included in this study, but they are very reactive with the oxygen-containing organic molecules undergoing ligand switching reactions producing mostly MH2+ and M-hydrates. The details of the reactions (e.g. the number of H20 molecules either ejected from the intermediate complexes or remaining associated with the MH2+ and MH-"core ions") are controlled largely by the reaction energy as far as this can be determined. The utility of the reactions of these hydrated ions as chemical ionization agents in atmospheric trace gas analysis is alluded to. Additionally, new FA data on the three-body association reactions of OH-and OH-*H2O with C02 are presented.

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An experimental study of the gas-phase kinetics of reactions with hydrated hydronium(1+) ions(n = 1-3) at 298 K

Cited by 85 publications

References 6 publications

Theoretical approach of the chemical reactivity: The S_N2 reaction

Theoretical approach of the chemical reactivity: The S_N2 reaction

Alcohol in breath and blood: a selected ion flow tube mass spectrometric study

Reactions of Hydrated Hydronium Ions and Hydrated Hydroxide Ions with Some Hydrocarbons and Oxygen-Bearing Organic Molecules

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An experimental study of the gas-phase kinetics of reactions with hydrated hydronium(1+) ions(n = 1-3) at 298 K

Cited by 85 publications

References 6 publications

Theoretical approach of the chemical reactivity: The SN2 reaction

Theoretical approach of the chemical reactivity: The SN2 reaction

Alcohol in breath and blood: a selected ion flow tube mass spectrometric study

Reactions of Hydrated Hydronium Ions and Hydrated Hydroxide Ions with Some Hydrocarbons and Oxygen-Bearing Organic Molecules

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Product

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Theoretical approach of the chemical reactivity: The S_N2 reaction

Theoretical approach of the chemical reactivity: The S_N2 reaction