Inhibition of the second limit of the hydrogen + oxygen reaction by hydrogen bromide

Clark, D. R.; Simmons, Robert F.; Smith, D. A.

doi:10.1039/tf9706601423

Cited by 21 publications

(21 citation statements)

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“…These CCSD(T) results were extrapolated to the infinite basis set limit via the 1/n 3 relation of Halkier et al [101] and with the inclusion of vibrational zero-point energy yield relative enthalpies at 0 K. The data, summarized in Table 2 [102,103,108,109]. Our rate constant is an order of magnitude lower than the value reported by Clark et al [21] at 773 K, but our present modeling of their results, discussed below, shows little sensitivity to the value of k 5 .…”

Section: Ab Initio Calculationsmentioning

confidence: 64%

“…Reported results are largely limited to data on the effect of HBr on the H 2 /O 2 system, i.e. explosion limits [20,21], flammability limits [30] and flame speeds [17,18]. Among the data obtained at medium temperatures, we have chosen to emphasize the batch reactor results from Clark et al [21].…”

Section: Resultsmentioning

confidence: 99%

“…In the forward direction, Dixon-Lewis and coworkers [30] estimated a value at 1000 K from data on the effect of HBr on the flame speed [30] of H 2 /air mixtures. Similarly, Clark et al [21] reported a value of k 7 at 773 K based on data on the effect of HBr on the second explosion limit [21] . There is some scatter in the batch reactor data, which rely on interpreting a complex kinetic system that conceivably is also affected by reactions on the reactor surface [107].…”

Section: Reaction Mechanismmentioning

confidence: 97%

“…A key chain-breaking step in bromine-inhibited combustion is believed to be the reaction between atomic bromine and the HO 2 radical [21,30],…”

Section: Reaction Mechanismmentioning

confidence: 99%

“…In flames, bromine appears to be the most effective halogen inhibitor, and bromine species have been reported to narrow the composition limits of inflammability [7][8][9][10][11] and to decrease flame speeds [12][13][14][15][16][17][18][19]. The inhibiting effect of bromine species has also been observed at lower temperatures in batch reactor [20,21] and flow reactor [22] experiments. However, static reactor experiments have shown that hydrogen bromide acts to catalyze the slow oxidation of hydrocarbons [5,[23][24][25][26][27][28][29].…”

Section: Introductionmentioning

confidence: 99%

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Inhibition of hydrogen oxidation by HBr and Br2

Dixon‐Lewis

Marshall

Ruščić

et al. 2012

Combustion and Flame

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The high-temperature bromine chemistry was updated and the inhibition mechanisms involving HBr and Br 2 were re-examined. The thermochemistry of the bromine species was obtained using the Active Thermochemical Tables (ATcT) approach, resulting in improved data for, among others, Br, HBr, HOBr and BrO. Ab initio calculations were used to obtain rate coefficients for selected reactions of HBr and HOBr, and the hydrogen/bromine/oxygen reaction mechanism was updated. The resulting model was validated against selected experimental data from literature and used to analyze the effect of HBr and Br 2 on laminar, premixed hydrogen flames. Our work shows that hydrogen bromide and molecular bromine act differently as inhibitors in flames. For HBr, the reaction HBr + H ⇀ ↽ H 2 + Br (R2) is rapidly equilibrated, depleting HBr in favor of atomic Br, which is the major bromine species throughout the reaction zone. The chain-breaking

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Section: Ab Initio Calculationsmentioning

confidence: 64%

Section: Resultsmentioning

confidence: 99%

Section: Reaction Mechanismmentioning

confidence: 97%

“…A key chain-breaking step in bromine-inhibited combustion is believed to be the reaction between atomic bromine and the HO 2 radical [21,30],…”

Section: Reaction Mechanismmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Inhibition of hydrogen oxidation by HBr and Br2

Dixon‐Lewis

Marshall

Ruščić

et al. 2012

Combustion and Flame

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The Reaction between Bromine and the Water Dimer and the Highly Exothermic Reverse Reaction

Wang

et al. 2015

J Comput Chem

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The entrance complex, transition state, and exit complex for the bromine atom plus water dimer reaction Br + (H2O)2 → HBr + (H2O)OH and its reverse reaction have been investigated using the CCSD(T) method with correlation consistent basis sets up to cc-pVQZ-PP. Based on the CCSD(T)/cc-pVQZ-PP results, the reaction is endothermic by 31.7 kcal/mol. The entrance complex Br⋯(H2O)2 is found to lie 6.5 kcal/mol below the separated reactants. The classical barrier lies 28.3 kcal/mol above the reactants. The exit complex HBr⋯(H2O)OH is bound by 6.0 kcal/mol relative to the separated products. Compared with the corresponding water monomer reaction Br + H2 O → HBr + OH, the second water molecule lowers the relative energies of the entrance complex, transition state, and exit complex by 3.0, 3.8, and 3.7 kcal/mol, respectively. Both zero-point vibrational energies and spin-orbit coupling effects make significant changes to the above classical energetics. Including both effects, the predicted energies relation to separated Br + (H2O)2 are -3.0 kcal/mol [Br···(H2O)2 ], 28.2 kcal/mol [transition state], 26.4 kcal/mol [HBr···(H2O)OH], and 30.5 kcal/mol [separated HBr + (H2O)OH]. The potential energy surface for the Br + (H2O)2 reaction is related to that for the valence isoelectronic Cl + (H2O)2 system but radically different from the F + (H2O)2 system.

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Study of the reactions of OH with HCl, HBr, and HI between 298 K and 460 K

Khamaganov

Orkin

Larin

2020

Int J of Chemical Kinetics

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The reactions between OH radicals and hydrogen halides (HCl, HBr, HI) have been studied between 298 and 460 K by using a discharge flow-electron paramagnetic resonance technique. The rate constants were found to be k HCl (298 K) = (7.9 ± 1.3) × 10 −13 cm 3 molecule −1 s −1 with a weak positive temperature dependence, k HBr (298-460 K) = (1.04 ± 0.2) × 10 −11 cm 3 molecule −1 s −1 , and k HI (298 K) = (3.0 ± 0.3) × 10 −11 cm 3 molecule −1 s −1 , respectively. The homogeneous nature of these reactions has been experimentally tested.

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Inhibition of the second limit of the hydrogen + oxygen reaction by hydrogen bromide

Cited by 21 publications

References 0 publications

Inhibition of hydrogen oxidation by HBr and Br2

Inhibition of hydrogen oxidation by HBr and Br2

The Reaction between Bromine and the Water Dimer and the Highly Exothermic Reverse Reaction

Study of the reactions of OH with HCl, HBr, and HI between 298 K and 460 K

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