Temperature dependence of the total reaction rates for Cl+HI and Cl+HBr

Mei, Chang‐Chi; Moore, C. Bradley

doi:10.1063/1.435409

Cited by 64 publications

(8 citation statements)

References 17 publications

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“…We can also compare our results with the rapid reaction of Cl atoms with HI ( k 295 ≈ 1.5 × 10 -10 cm 3 s -1 ) , which displays a complex temperature dependence with the rate coefficient decreasing with increasing temperature above ≈ 300 K and displaying the reverse behavior at t < 300 K . In addition, the ratio of rate coefficient for Cl atoms with HI and DI also showed a pronounced temperature dependence and an increase in the translational energy of the Cl atom reduced the rate coefficient.…”

Section: Discussionmentioning

confidence: 57%

Kinetics of the Reaction of OH with HI between 246 and 353 K

Campuzano‐Jost

Crowley

1999

J. Phys. Chem. A

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The laser-flash photolysis technique combined with resonance fluorescence detection of OH was used to investigate the kinetics of the title reaction at temperatures between 246 and 353 K and at a total pressure of 75 ( 1 Torr Ar. Under these conditions the rate coefficient shows a negative temperature dependence which is described by k 4 (246-353 K) ) 7.0 -0.4 +1.9 × 10 -11 (T/298) -1.5(0.5 cm 3 s -1 . Both the large rate coefficient and trends in the reactivity of OH with HCl, HBr, and HI are suggestive of a reaction mechanism that proceeds without a significant activation barrier. The room temperature (294 K) rate constant is k 4 ) 6.5 -0.4 +2 × 10 -11 cm 3 s -1 , which is significantly larger than previous measurements. Reasons for this difference and the implications of the new rate coefficients for the lifetime of HI in the atmosphere are discussed.

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Section: Discussionmentioning

confidence: 57%

Kinetics of the Reaction of OH with HI between 246 and 353 K

Campuzano‐Jost

Crowley

1999

J. Phys. Chem. A

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“…The investigation of laser-flash-initiated reaction 1 in the Cl 2 /HBr flow system using infrared chemiluminescence (IRCL) from excited HCl formed in the reaction gave a curved Arrhenius relation, concave to the 1/ T axis. Its form is unusual in that only the high-temperature data (at 402 and 349 K) are responsible for the curvature.…”

Section: Discussionmentioning

confidence: 99%

“…Direct experimental studies of the temperature coefficients for reaction 1 are scarce, − and some of them are controversial. , Therefore, we have decided to proceed with our VLPR investigation of reaction 1 in the range 228−368 K. The results are presented in the following.…”

Section: Introductionmentioning

confidence: 99%

Temperature Coefficients of the Rate of Cl Atom Reaction with HBr in the 228−368 K Range at Millitorr Pressures

Dobis

Benson

1997

J. Phys. Chem. A

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Temperature coefficients for the kinetics of reaction Cl + HBr → HCl(v,j) + Br have been measured in the range 228−368 K using the very low-pressure reactor (VLPR) system. This experimental technique permits measurement of both the reactant consumption and product formation rates under second-order conditions and achieves mass conservation of 98 ± 2% for the overall chemical change in the reactor. Thermalization of vibrationally and rotationally excited HCl product is well attained in this system. A simple Arrhenius function describes the thermal rate constant as k = (1.99 ± 0.10) × 10-11 exp[−(710 ± 29)/RT] cm3/(molecule s). The measured activation energy is in good agreement with E a = 0.72 kcal/mol obtained from total energy balancing of energy partition among the reaction products, while the A factor indicates a bent configuration of the transition state.

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“…Ground-state I atoms are generated from the F + DI → I( 2 P 3/2 ) + DF reaction. As with the F + DCl reaction, the F + DI rate constant is not determined; however, the F + HI rate coefficient is k = 8 × 10 -11 cm 3 / (molecule s) and the F + DI rate coefficient is also likely to be in this range . Accordingly, the ground-state I density is taken as the initial DI density, [DI] 0 .…”

Section: Methodsmentioning

confidence: 99%

Temperature Dependence of the NCl(aΔ) + I (²P_3/2) Reaction from 300 to 482 K

1998

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The total quenching rate of NCl(a1Δ) metastables by ground-state I(2P3/2) atoms over the temperature range 297−473 K has been studied in a flow reactor. The room-temperature rate coefficient is (2.1 ± 0.4) × 10-11 cm3/(molecule s). In this temperature range, the temperature dependence for the total quenching rate is described by an Arrhenius expression of k(T) = 1.1 × 10-10 exp(−519 ± 143 K/T) cm3/(molecule s). The rate coefficient for the energy transfer of NCl(a1Δ) to I*(2P1/2) at 300 K is (1.5 ± 0.7) × 10-11 cm3/(molecule s), which is in good agreement with a previous measurement. The magnitude of the energy transfer rate implies a large fraction of the I(2P3/2) is converted to I*(2P1/2), and the NCl(a1Δ) + I(2P3/2) reaction is an efficient source of I*(2P1/2). Under the current experimental conditions, a simple kinetic model that simulated the experimental time histories of NF(a1Δ) and NCl(a1Δ) infers the Cl + N3 rate coefficient of (1.6 ± 0.4) × 10-11 cm3/(molecules s) and is slower than previously measured.

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Temperature dependence of the total reaction rates for Cl+HI and Cl+HBr

Cited by 64 publications

References 17 publications

Kinetics of the Reaction of OH with HI between 246 and 353 K

Kinetics of the Reaction of OH with HI between 246 and 353 K

Temperature Coefficients of the Rate of Cl Atom Reaction with HBr in the 228−368 K Range at Millitorr Pressures

Temperature Dependence of the NCl(aΔ) + I (²P_3/2) Reaction from 300 to 482 K

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Temperature dependence of the total reaction rates for Cl+HI and Cl+HBr

Cited by 64 publications

References 17 publications

Kinetics of the Reaction of OH with HI between 246 and 353 K

Kinetics of the Reaction of OH with HI between 246 and 353 K

Temperature Coefficients of the Rate of Cl Atom Reaction with HBr in the 228−368 K Range at Millitorr Pressures

Temperature Dependence of the NCl(aΔ) + I (2P3/2) Reaction from 300 to 482 K

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Temperature Dependence of the NCl(aΔ) + I (²P_3/2) Reaction from 300 to 482 K