Reaction of Limonene with F<sub>2</sub>: Rate Coefficient and Products

Bedjanian, Yuri; Romanías, Manolis N.; Morin, Julien

doi:10.1021/jp509498a

Cited by 3 publications

(3 citation statements)

References 22 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Experiments were carried out in a low pressure discharge flow reactor using a modulated molecular beam mass spectrometer with electron impact ionization as the detection method [7][8][9]. The flow reactor operated at temperatures T = 297 -833 K and nearly 2 Torr total pressure of Helium and consisted of an electrically heated Quartz tube (45 cm length and 2.5 cm i.d.)…”

Section: Methodsmentioning

confidence: 99%

Kinetic study of the F2 + C2H4 reaction: Disagreement between theory and experiment resolved?

Bedjanian

2019

Chemical Physics Letters

Self Cite

View full text Add to dashboard Cite

Reaction F 2 + C 2 H 4  F + C 2 H 3 F (1) has been studied using a discharge flow reactor combined with an electron impact ionization mass spectrometer. The reaction rate constant was determined either from kinetics of the reaction product, F-atom, formation or from the kinetics of F 2 consumption in excess of C 2 H 4 : k 1 = (7.94 ± 2.06) × 10-12 exp(-(3867 ± 120)/T) cm 3 molecule-1 s-1 at T= 297-833 K. The reaction activation energy, 7.7 ± 0.3 kcal mol-1 , is consistent with current theoretical prediction for the reaction barrier height and seems to solve the long-standing problem of the divergence between theory and experiment.

show abstract

Section: Methodsmentioning

confidence: 99%

Kinetic study of the F2 + C2H4 reaction: Disagreement between theory and experiment resolved?

Bedjanian

2019

Chemical Physics Letters

Self Cite

View full text Add to dashboard Cite

show abstract

“…So, on the one hand, molecular fluorine manifests relatively high reactivity with respect to some closed‐shell molecules and, on the other hand, it relatively slowly reacts with chemically active species, such as halogen and oxygen atoms. It was demonstrated, for example, that reactions of F 2 with organosulfur compounds, CH 3 SCH 3 and CH 3 SSCH 3 , and with limonene are barrierless reactions . Unexpectedly high (for reaction between two closed‐shell molecules) value, 1.6 × 10 −11 cm 3 molecule −1 s −1 at 298 K, was reported for the rate constant of the reaction of F 2 with CH 3 SCH 3 .…”

Section: Introductionmentioning

confidence: 99%

“…In addition to general interest, the information on these reactions is of practical interest for laboratory studies of chemical systems where bromine and fluorine are simultaneously present in their molecular and/or atomic form. For example, Br 2 is frequently used (as in the present work) as a fluorine atom scavenger

\begin{matrix} true \\ right normalF + normalB r_{2} \to BrF + Br \end{matrix}

to detect and/or measure the absolute concentrations of F‐atoms .…”

Section: Introductionmentioning

confidence: 99%

Kinetics and Products of the Reactions of F₂ with Br‐Atom and Br₂

Bedjanian

Romanías

2018

Int J of Chemical Kinetics

Self Cite

View full text Add to dashboard Cite

Reactions of F 2 molecules exhibit unusual features, manifesting in high reactivity of F 2 with respect to some closed-shell molecules and low reactivity toward chemically active species, such as halogen and oxygen atoms. The existing data base on the reactions of F 2 being rather sparse, kinetic and mechanistic studies (preferably over a wide temperature range) are needed to better understand the nature of the specific reactivity of fluorine molecule. In the present work, reactions of F 2 with Br atoms and Br 2 have been studied for the first time in an extended temperature range using a discharge flow reactor combined with an electron impact ionization mass spectrometer. The rate constant of the reaction F 2 + Br → F +BrF (1) was determined either from kinetics of the reaction product, BrF, formation or from the kinetics of Br consumption in excess of F 2 : k 1 = (4.66 ± 0.93) × 10 −11 exp(−(4584 ± 86)/T) cm 3 molecule −1 s −1 at T = 300-940 K. The rate constant of the reaction F 2 + Br 2 → products (2), k 2 = (9.23 ± 2.68) × 10 −11 exp(−(8373 ± 194)/T) cm 3 molecule −1 s −1 , was determined in the temperature range 500-958 K by monitoring both reaction product (FBr) formation and F 2 consumption kinetics in excess of Br 2 . The results of the experimental measurements of the yield of FBr (1.02 ± 0.07 at T = 960 K) combined with thermochemical calculations indicate that F+Br 2 F forming channel of reaction (2) is probably the dominant one, at least, at highest temperature of the study. C

show abstract

Experimental and Theoretical Study of the Reaction of F2 with Thiirane

Bedjanian,

Roose,

Vallet

et al. 2024

Molecules

View full text Add to dashboard Cite

The kinetics of the F2 reaction with thiirane (C2H4S) was studied for the first time in a flow reactor combined with mass spectrometry at a total helium pressure of 2 Torr and in the temperature range of 220 to 800 K. The rate constant of the title reaction was determined under pseudo-first-order conditions, either monitoring the kinetics of F2 or C2H4S consumption in excess of thiirane or of F2, respectively: k1 = (5.79 ± 0.17) × 10−12 exp(−(16 ± 10)/T) cm3 molecule−1 s−1 (the uncertainties represent precision of the fit at the 2σ level, with the total 2σ relative uncertainty, including statistical and systematic errors on the rate constant being 15% at all temperatures). HF and CH2CHSF were identified as primary products of the title reaction. The yield of HF was measured to be 100% (with an accuracy of 10%) across the entire temperature range of the study. Quantum computations revealed reaction enthalpies ranging from −409.9 to −509.1 kJ mol−1 for all the isomers/conformers of the products, indicating a strong exothermicity. Boltzmann relative populations were then established for different temperatures.

show abstract

Reaction of Limonene with F₂: Rate Coefficient and Products

Cited by 3 publications

References 22 publications

Kinetic study of the F2 + C2H4 reaction: Disagreement between theory and experiment resolved?

Kinetic study of the F2 + C2H4 reaction: Disagreement between theory and experiment resolved?

Kinetics and Products of the Reactions of F₂ with Br‐Atom and Br₂

Experimental and Theoretical Study of the Reaction of F2 with Thiirane

Contact Info

Product

Resources

About

Reaction of Limonene with F2: Rate Coefficient and Products

Cited by 3 publications

References 22 publications

Kinetic study of the F2 + C2H4 reaction: Disagreement between theory and experiment resolved?

Kinetic study of the F2 + C2H4 reaction: Disagreement between theory and experiment resolved?

Kinetics and Products of the Reactions of F2 with Br‐Atom and Br2

Experimental and Theoretical Study of the Reaction of F2 with Thiirane

Contact Info

Product

Resources

About

Reaction of Limonene with F₂: Rate Coefficient and Products

Kinetic study of the F2 + C2H4 reaction: Disagreement between theory and experiment resolved?

Kinetic study of the F2 + C2H4 reaction: Disagreement between theory and experiment resolved?

Kinetics and Products of the Reactions of F₂ with Br‐Atom and Br₂