The dissociation energy of BrCl and the equilibrium constant for its formation reaction in the gas phase

Tellinghuisen, Joel

doi:10.1063/1.1531621

Cited by 5 publications

(8 citation statements)

References 21 publications

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“…Equations − were employed to separate the contributions of each substance to the overall absorption intensity in the curve, allowing the concentrations of the bromine, chlorine, and bromine chloride to be evaluated − . I 330 = ε C l 2 , 330 L C C l 2 + ε B r C l , 330 L C B r C l + ε B r 2 , 330 L C B r 2 I 375 = ε C l 2 , 375 L C C l 2 + ε B r C l , 375 L C B …”

Section: Resultsmentioning

confidence: 99%

“…Figure is the spectra of Br 2 , Cl 2 , and BrCl as they reacted with Hg 0 . The concentration of Cl 2 , BrCl, and Br 2 could also be calculated according to eqs − with their respective spectra − . The concentration of Cl 2 and BrCl in the gas phase decreased significantly as the Hg 0 oxidation proceeded, but Br 2 concentration increased unexpectedly.…”

Section: Resultsmentioning

confidence: 99%

“…Equations 4-6 were employed to separate the contributions of each substance to the overall absorption intensity in the curve, allowing the concentrations of the bromine, chlorine, and bromine chloride to be evaluated (16)(17)(18)(19)(20).…”

Section: Resultsmentioning

confidence: 99%

“…The reaction between chlorine and bromine in the cell was monitored in situ by a UV/vis spectrometer equipped with an optical fiber for UV-beam transmission and a detector in the range of 200-800 nm. The maximum UV absorbances for bromine, chlorine, and BrCl are at approximately 415, 330, and 375 nm, respectively (16)(17)(18)(19)(20).…”

Section: Methodsmentioning

confidence: 99%

“…Br 2 can be produced from bromide salt solutions by gas chlorine stripping in industrial processes, and the primary Br 2 gas often contains surplus Cl 2 . Meanwhile, chlorine can react with bromine to form the interhalogen, bromine chloride, BrCl , , so the primary bromine gas can be readily converted to BrCl without any pretreatment. Employing BrCl to oxidize Hg 0 would be a promising choice to obtain higher conversion efficiency and to reduce the use of bromine.…”

Section: Introductionmentioning

confidence: 99%

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Bromine Chloride as an Oxidant to Improve Elemental Mercury Removal from Coal-Fired Flue Gas

Liu

Chi

et al. 2009

Environ. Sci. Technol.

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The equilibria and kinetics of the reaction between bromine (Br(2)) and chlorine (Cl(2)) to form bromine chloride (BrCl) at various temperatures were determined. BrCl was employed to oxidize elemental mercury (Hg(0)) under simulated flue gas conditions. The removal of Hg(0) from the gas phase by a homogeneous gas-phase oxidation reaction and the heterogeneous reactions involving flyash were investigated. The second-order gas phase rate constant was determined to be 2.3(+/-0.2) x 10(-17) cm(3).molecules(-1).s(-1) at 373K. The reaction of Hg(0)/BrCl was significantly accelerated in the presence of flyash, and the estimated Hg(0) removal efficiency in the presence of 0.6 ppmv BrCl and 20 g/m(3) flyash was up to 90%. Unexpectedly, the major product was found to be HgCl(2), rather than HgBr(2), indicating that bromine in part acted as the accelerant in Hg(0) oxidation in BrCl/Br(2)/Cl(2) system by facilitating the formation of intermediates. As a result, bromine consumption is much less than if only bromine gas is utilized alone. These results were helpful not only for understanding the mechanism of Hg(0) removal in coal-fired flue gas but also in any atmosphere in which bromine and chlorine species coexist.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Bromine Chloride as an Oxidant to Improve Elemental Mercury Removal from Coal-Fired Flue Gas

Liu

Chi

et al. 2009

Environ. Sci. Technol.

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CsAr, CsXe, and RbXe B²Σ_1/2⁺ Interatomic Potentials Determined from Absorption Spectra and Calculations of Franck–Condon Factors for Free–Free Optical Transitions of Atomic Collision Pairs

et al. 2023

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Interatomic potentials for the B 2 Σ 1/2 + states of CsAr, CsXe, and RbXe have been determined through comparisons of experimental B ← X absorption spectra for alkali vapor−rare gas mixtures with calculations of the Franck−Condon factors (FCFs) associated with free−free transitions of thermal atomic pairs. Simulations of optical transitions of alkali-rare gas atomic pairs between the thermal and vibrational continua of the X 2 Σ 1/2 + and B 2 Σ 1/2 + states of the molecule, responsible for the blue satellites of the Cs and Rb D 2 resonance lines in a rare gas background, require the incorporation of ground-state J values above ∼400 into the FCF calculations and proper normalization of the free-particle wave functions. Absorption spectra computed on the basis of several X and B state interatomic potentials available in the literature were found to be sensitive to the height of the B 2 Σ 1/2 + state barrier, as well as the X 2 Σ 1/2 + state repulsive wall contour and the location of the van der Waals minimum. Other spectral simulations entailed iterative modifications to a selected B 2 Σ 1/2 + interatomic potential, again coupled with comparison to experimental B ← X spectra. Comparisons of calculated spectra with experiment yield a CsXe B 2 Σ 1/2 + potential, for example, exhibiting a barrier height of 76 cm −1 at 5.2 Å and yet is nearly flat at smaller values of internuclear separation (R). The latter contrasts with previous theoretical calculations of V B (R) in the vicinity of the barrier maximum. For the CsAr molecule, the B 2 Σ 1/2 + barrier height was found to be 221 cm −1 , which is within 3% of the value determined from pseudopotential calculations incorporating the spin−orbit effect. Reproducing Cs-rare gas experimental absorption spectra also requires the existence of a broad, shallow potential well lying beyond the B 2 Σ 1/2 + barrier that, for CsAr, has a dissociation energy (D e ∼ 24 cm −1 ) a factor of 3 larger than values predicted by theory. Similar results are obtained for the RbXe and CsXe complexes.

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Chemically Accurate Thermochemistry of Cadmium: An ab Initio Study of Cd + XY (X = H, O, Cl, Br; Y = Cl, Br)

Shepler

Peterson

2006

J. Phys. Chem. A

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Using a composite coupled cluster method employing sequences of correlation consistent basis sets for complete basis set (CBS) extrapolations and with explicit treatment of core-valence correlation and scalar and spin-orbit relativistic effects, the 0 K enthalpies of a wide range of cadmium-halide reactions, namely, Cd + (HCl, HBr, ClO, BrO, Cl2, BrCl, Br2) have been determined to an estimated accuracy of +/-1 kcal/mol. In addition, accurate equilibrium geometries, harmonic frequencies, and dissociation energies have been calculated at the same level of theory for all the diatomic (e.g., CdH, CdO, CdCl, CdBr) and triatomic (CdHCl, CdHBr, CdClO, CdBrO, CdCl2, CdBrCl, CdBr2) species involved in these reactions, some for the very first time. Like their mercury analogues, all of the abstraction reactions are predicted to be endothermic, while the insertion reactions are strongly exothermic with the formation of stable linear, Cd-centric complexes. With the exception of CdH and the reactions involving this species, the present results for the remaining Cd-containing systems are believed to be the most accurate to date.

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The dissociation energy of BrCl and the equilibrium constant for its formation reaction in the gas phase

Cited by 5 publications

References 21 publications

Bromine Chloride as an Oxidant to Improve Elemental Mercury Removal from Coal-Fired Flue Gas

Bromine Chloride as an Oxidant to Improve Elemental Mercury Removal from Coal-Fired Flue Gas

CsAr, CsXe, and RbXe B²Σ_1/2⁺ Interatomic Potentials Determined from Absorption Spectra and Calculations of Franck–Condon Factors for Free–Free Optical Transitions of Atomic Collision Pairs

Chemically Accurate Thermochemistry of Cadmium: An ab Initio Study of Cd + XY (X = H, O, Cl, Br; Y = Cl, Br)

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The dissociation energy of BrCl and the equilibrium constant for its formation reaction in the gas phase

Cited by 5 publications

References 21 publications

Bromine Chloride as an Oxidant to Improve Elemental Mercury Removal from Coal-Fired Flue Gas

Bromine Chloride as an Oxidant to Improve Elemental Mercury Removal from Coal-Fired Flue Gas

CsAr, CsXe, and RbXe B2Σ1/2+ Interatomic Potentials Determined from Absorption Spectra and Calculations of Franck–Condon Factors for Free–Free Optical Transitions of Atomic Collision Pairs

Chemically Accurate Thermochemistry of Cadmium: An ab Initio Study of Cd + XY (X = H, O, Cl, Br; Y = Cl, Br)

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CsAr, CsXe, and RbXe B²Σ_1/2⁺ Interatomic Potentials Determined from Absorption Spectra and Calculations of Franck–Condon Factors for Free–Free Optical Transitions of Atomic Collision Pairs