Measurements of the apparent rate constant for the reaction of iodine monoxide with chlorine monoxide to form iodine atoms

Larin, I. K.; Messineva, N. A.; Nevozhai, D. V.; Spasskii, A. I.; Trofimova, E. M.

doi:10.1007/bf02755367

Cited by 10 publications

(19 citation statements)

References 16 publications

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“…Figure 6 compares the present results with these previous studies, as well as the preliminary results from a new study by Blitz et al, 16 who employed a flash photolysis/laser induced fluorescence technique similar to that used here. Figure 6a is a comparison of results over a range of pressure, at temperatures close to 300 K. This shows that the present study is in very good agreement with the results of Daykin and Wine 13 and Blitz et al 16 between 20 and 760 Torr, and our RRKM fit extrapolates to be in satisfactory agreement with the low-pressure measurements of Maguin et al 14 In contrast, the studies of Jenkins and Cox 12 and Larin et al, 15 while in accord with each other, are about a factor of 2 lower than the other measurements. The possible reasons for the discrepancy with the study of Jenkins and Cox 12 have been discussed previously, 13,14 and we note that Larin et al 15 employed an indirect detection of IO (see above) which may have compromised the measurement of k 1 .…”

Section: Discussionsupporting

confidence: 89%

“…Maguin et al 14 studied the reaction in a low-pressure discharge-flow system at 298 K. In comparing with our work with N 2 as the third body, we have multiplied their values of k rec,0 measured in He by 2.2, as recommended by those authors. Finally, Larin et al 15 used a flow reactor with indirect detection of IO via reduction with NO to I, which was monitored by atomic resonance fluorescence.…”

Section: Discussionmentioning

confidence: 99%

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A Study of the Recombination of IO with NO₂ and the Stability of INO₃: Implications for the Atmospheric Chemistry of Iodine

Allan

Plane

2002

J. Phys. Chem. A

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The recombination reaction between IO and NO2 was studied over a large range of temperature (216−474 K) and pressure (20−760 Torr). IO, produced by the pulsed photolysis at 193 nm of NO2 to yield O in the presence of CF3I, was probed at 445.0 nm [IO(A2Π3/2 − X2Π3/2), (2,0)] and monitored by nonresonant LIF at 458.6 nm [IO(A2Π3/2 − X2Π3/2), (2,1)]. The resulting rate coefficients were then fitted by RRKM theory, using molecular parameters and a heat of formation for INO3 (Δ = 70 ± 16 kJ mol-1, best fit value 80 kJ mol-1) derived from quantum calculations at the B3LYP/6-311+g(2d,p) level. This yielded k rec,0 = (1.3 ± 0.2) × 10-30 (T/300 K)-(4.5±0.6) cm6 molecule-2 s-1, k rec, ∞ = (6.5 ± 1.0) × 10-12 (T/300 K)-(1.3±0.8) cm3 molecule-1 s-1, and F c = 0.57, over the experimental range of temperature and pressure. The RRKM calculations, in conjunction with measurements made at 474 K, were used to determine the rate of thermal dissociation of INO3 for the conditions of the lower atmosphere: k diss(240−305 K, 760 Torr) = 1.1 × 1015 exp(−12060/T) s-1, with an upper limit about a factor of 2 higher. The atmospheric significance of these results is discussed briefly.

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Section: Discussionsupporting

confidence: 89%

Section: Discussionmentioning

confidence: 99%

A Study of the Recombination of IO with NO₂ and the Stability of INO₃: Implications for the Atmospheric Chemistry of Iodine

Allan

Plane

2002

J. Phys. Chem. A

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“…21,22 I x O y are involved in new particles formation relevant to both atmospheric science 23−25 and nuclear reactor accidents. 6,8,9 For these two reasons, the kinetics and mechanisms of reactions involving IO 26 ments (IO + O 3 , 27 IO + IO and IO + NO, 28,29 IO + CHCl 2 CF 2 Cl and IO + HCOOH, 30 IO + ClO, 31 IO + HO 2 , 32 IO + CH 3 SCH 3 , 33 IO + CH 3 O 2 , IO + CF 3 O 2 , 27 IO + NO 3 34 ) or from theoretical calculations (IO + HO 2 and IO + CH 3 O 2 , 35,36 IO + CH 3 I, 37 IO + IO and IO + OIO 22 ).…”

Section: Introductionmentioning

confidence: 99%

“…Atmospheric chemistry ,, and containment chemistry is complex and challenging for iodine-containing species. Besides its implication in ozone depletion cycles, IO is known to play a key role in the formation of higher iodine oxides (I x O y ), which have drawn particular attention in recent studies. , I x O y are involved in new particles formation relevant to both atmospheric science − and nuclear reactor accidents. ,, For these two reasons, the kinetics and mechanisms of reactions involving IO have been studied in a number of laboratories either from experimental measurements (IO + O 3 , IO + IO and IO + NO, , IO + CHCl 2 CF 2 Cl and IO + HCOOH, IO + ClO, IO + HO 2 , IO + CH 3 SCH 3 , IO + CH 3 O 2 , IO + CF 3 O 2 , IO + NO 3 ) or from theoretical calculations (IO + HO 2 and IO + CH 3 O 2 , , IO + CH 3 I, IO + IO and IO + OIO).…”

Section: Introductionmentioning

confidence: 99%

A Density Functional Theory and ab Initio Investigation of the Oxidation Reaction of CO by IO Radicals

et al. 2016

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To get an insight into the possible reactivity between iodine oxides and CO, a first step was to study the thermochemical properties and kinetic parameters of the reaction between IO and CO using theoretical chemistry tools. All stationary points involved were optimized using the Becke's three-parameter hybrid exchange functional coupled with the Lee-Yang-Parr nonlocal correlation functional (B3LYP) and the Møller-Plesset second-order perturbation theory (MP2). Single-point energy calculations were performed using the coupled cluster theory with the iterative inclusion of singles and doubles and the perturbative estimation for triple excitations (CCSD(T)) and the aug-cc-pVnZ (n = T, Q, and 5) basis sets on geometries previously optimized at the aug-cc-pVTZ level. The energetics was then recalculated using the one-component DK-CCSD(T) approach with the relativistic ANO basis sets. The spin-orbit coupling for the iodine containing species was calculated a posteriori using the restricted active space state interaction method in conjunction with the multiconfigurational perturbation theory (CASPT2/RASSI) employing the complete active space (CASSCF) wave function as the reference. The CCSD(T) energies were also corrected for BSSE for molecular complexes and refined with the extrapolation to CBS limit while the DK-CCSD(T) values were refined with the extrapolation to FCI. The exploration of the potential energy surface revealed a two-steps mechanism with a trans and a cis pathway. The rate constants for the direct and complex mechanism were computed as a function of temperature (250-2500 K) using the canonical transition state theory. The three-parameter Arrhenius expressions obtained for the direct and indirect mechanism at the DK-CCSD(T)-cf level of theory is 1.49 × 10(-17) × T(1.77) exp(-47.4 (kJ mol(-1))/RT).

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“…The CAPRAM-HM3.0 now contains a more detailed representation of iodine oxide dimer formation and its chemical fate, − which might be important for new particle formation and early growth at coastal marine sites . Furthermore, the interaction of IO with ozone and reactive halogen species , as well as the reaction of I 2 with ozone , is implemented.…”

Section: Capram Halogen Module 30mentioning

confidence: 99%

Near-Explicit Multiphase Modeling of Halogen Chemistry in a Mixed Urban and Maritime Coastal Area

Hoffmann

Tilgner

Vogelsberg

et al. 2019

ACS Earth Space Chem.

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In the present study, detailed air-parcel model simulations have been carried out that focus on multiphase halogen chemistry and its impact on the air quality in polluted coastal areas under sea breeze conditions. To achieve this, an advanced halogen multiphase chemistry mechanism is developed, containing 846 gas-phase reactions, 61 uptake processes, and 442 aqueous-phase reactions. Simulations with and without cloud occurrence are performed and compared to control simulations without added marine multiphase chemistry. Overall, the simulations demonstrate the importance of marine multiphase chemistry for air quality in polluted coastal areas. In detail, the simulations indicate significant influence of Cl atoms on oxidation of volatile organic compounds, especially alkanes, alkenes, nonoxidized aromatic compounds, and alcohols. The NO3 radical is pointed out to be an important daytime oxidant contributing up to 29% on the average dimethyl sulfide daytime oxidation flux. Compared to the control simulations, ozone production rates decrease by 29 and 22%, depending on whether the air parcel is influenced by cloud chemistry or not. The NO and NO2 concentrations decrease by 15 and 10% and by 19 and 13% in the cloud-free and cloud simulations, respectively. Halogen nitrate hydrolysis leads to an increase of particulate nitrate of up to 5.6% in the cloud-free simulation. In contrast, particulate nitrate decreases by 6.6% in the cloud simulation, which is related to an increased sulfate formation, resulting in more gas-phase nitric acid. In-cloud sulfate formation increased by 9.1% when halogen multiphase chemistry is considered.

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Measurements of the apparent rate constant for the reaction of iodine monoxide with chlorine monoxide to form iodine atoms

Cited by 10 publications

References 16 publications

A Study of the Recombination of IO with NO₂ and the Stability of INO₃: Implications for the Atmospheric Chemistry of Iodine

A Study of the Recombination of IO with NO₂ and the Stability of INO₃: Implications for the Atmospheric Chemistry of Iodine

A Density Functional Theory and ab Initio Investigation of the Oxidation Reaction of CO by IO Radicals

Near-Explicit Multiphase Modeling of Halogen Chemistry in a Mixed Urban and Maritime Coastal Area

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Measurements of the apparent rate constant for the reaction of iodine monoxide with chlorine monoxide to form iodine atoms

Cited by 10 publications

References 16 publications

A Study of the Recombination of IO with NO2 and the Stability of INO3: Implications for the Atmospheric Chemistry of Iodine

A Study of the Recombination of IO with NO2 and the Stability of INO3: Implications for the Atmospheric Chemistry of Iodine

A Density Functional Theory and ab Initio Investigation of the Oxidation Reaction of CO by IO Radicals

Near-Explicit Multiphase Modeling of Halogen Chemistry in a Mixed Urban and Maritime Coastal Area

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Product

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A Study of the Recombination of IO with NO₂ and the Stability of INO₃: Implications for the Atmospheric Chemistry of Iodine

A Study of the Recombination of IO with NO₂ and the Stability of INO₃: Implications for the Atmospheric Chemistry of Iodine