Kinetics and Mechanisms of Aqueous Ozone Reactions with Bromide, Sulfite, Hydrogen Sulfite, Iodide, and Nitrite Ions

Liu, Qian; Schurter, Lynn M.; Muller, Charles E.; Aloisio, Simone; Francisco, Joseph S.; Margerum, Dale W.

doi:10.1021/ic000919j

Cited by 207 publications

(238 citation statements)

References 31 publications

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“…Thereby, the rate of ozone loss from the gas phase is described as a pseudo-first order process (Eq. 1), where k g,p,O 3 is the first order rate coefficient, and t is the exposure time between the gas and the aerosol surface (Liu et al, 2001). Then, the rate coefficient can be related to the uptake coefficient, γ , on the aerosol using Eq.…”

Section: Resultsmentioning

confidence: 99%

The effect of fatty acid surfactants on the uptake of ozone to aqueous halogenide particles

Rouvière

Ammann

2010

Atmos. Chem. Phys.

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Abstract. The reactive uptake of ozone to deliquesced potassium iodide aerosol particles coated with linear saturated fatty acids (C 9 , C 12 , C 15 , C 18 and C 20 ) was studied. The experiments were performed in an aerosol flow tube at 293 K and atmospheric pressure. The uptake coefficient on pure deliquesced KI aerosol was γ = (1.10±0.20)×10 −2 at 72-75% relative humidity. In presence of organic coatings, the uptake coefficient decreased significantly for long straight chain surfactants (≥C 15 ), while it was only slightly reduced for the short ones (C 9 , C 12 ). We linked the kinetic results to the monolayer properties of the surfactants, and specifically to the expected phase state of the monolayer formed (liquid expanded or liquid condensed state). The results showed a decrease of the uptake coefficient by 30% for C 12 , 85% for C 15 and 50% for C 18 in presence of a monolayer of a fatty acid at the equilibrium spreading pressure at the air/water interface. The variation among C 12 , C 15 and C 18 follows the density of the monolayer at equilibrium spreading pressure, which is highest for the C 15 fatty acid. We also investigated the effect of organic films to mixed deliquesced aerosol composed of a variable mixture of KI and NaCl, which allowed determining the resistance exerted to O 3 at the aqueous surface by the two longer chained surfactants pentadecanoic acid (C 15 ) and stearic acid (C 18 ). For these, the probability that a molecule hitting the surface is actually transferred to the aqueous phase underneath was β C 15 = 6.8 × 10 −4 and β C 18 = 3.3 × 10 −4 , respectively. Finally, the effect of twocomponent coatings, consisting of a mixture of long and short chained surfactants, was studied qualitatively.

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Section: Resultsmentioning

confidence: 99%

The effect of fatty acid surfactants on the uptake of ozone to aqueous halogenide particles

Rouvière

Ammann

2010

Atmos. Chem. Phys.

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“…The aqueous phase oxidation reaction NO 2 Ϫ ϩ O 3 3 NO 3 Ϫ ϩ O 2 was used in the present work. This is a very rapid reaction (5.83 ϫ 10 5 M Ϫ1 s Ϫ1 ) that quickly goes to completion, and previous studies by Liu et al showed that this was a oxygen atom transfer reaction (37). In addition, their ab initio calculations showed that the reaction pathway proceeded through an adduct conformation where the NO 2 Ϫ only abstracted the terminal atom (37) from the ozone molecule (Fig.…”

mentioning

confidence: 77%

The role of symmetry in the mass independent isotope effect in ozone

Michalski

Bhattacharya

2009

Proc. Natl. Acad. Sci. U.S.A.

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Understanding the internal distribution of ''anomalous'' isotope enrichments has important implications for validating theoretical postulates on the origin of these enrichments in molecules such as ozone and for understanding the transfer of these enrichments to other compounds in the atmosphere via mass transfer. Here, we present an approach, using the reaction NO 2 ؊ ؉ O3, for assessing the internal distribution of the (7) and non-mass-dependent (NOMAD) (8, 9).The most thoroughly studied MIF system is that of ozone formation. Ozone generated by electric discharge or UV photolysis can produce ⌬ 17 O values of 30-40‰ (‰ ϭ parts per thousand). There have also been numerous studies that have experimentally quantified the pressure and temperature dependence of the isotopic enrichments (10, 11). Most recently, the transfer of the ⌬ 17 O anomaly from ozone to other compounds during oxidation reactions (via atom transfer, e.g., mass balance) has been used to elucidate chemical oxidation pathways in modern atmospheres (16-21). These include ⌬ 17 O observations in atmospheric nitrate, sulfate, CO 2 , and N 2 O. ⌬ 17 O variations in atmospheric nitrate and sulfate are intriguing because they have opened the possibility of using these ⌬ 17 O variations in ice cores as a proxy for paleo-oxidation chemistry (22,23). Modeling such transfer reactions, however, requires knowledge of the internal distribution of the ⌬ 17 O anomaly, i.e., how much is contained in the central versus terminal atoms of ozone, because many atmospheric oxidations are thought to occur through terminal-only transition states.Theories as to the origin of the MIF effect have taken many turns (7,8,24,25), and some theories seem more adept at handling specific experimental cases than others. Most have symmetry as the main, albeit ad hoc, causal mechanism for producing MIF. Recent work by Marcus and coworkers (26-28) is perhaps the most thorough treatment, and they have suggested that nonstatistical RRKM effects arise because of differences in the rovibronic coupling efficiency of the asymmetric molecule when compared with the symmetric isomer. Recent NO 2 spectroscopic data appear to bear the theory out (29), but the uncertainties in that study remain significant, and no mass spectrometer isotope data on the unimolecular decay of NO 2 are available. Because the basis of the ozone MIF theory is symmetry driven, it is implied that the anomalous enrichment must be contained in the terminal atoms of ozone. To be clear, there maybe overall isotopic enrichment (␦ 18 O, ␦ 17 O) distributed throughout the molecule based on isotopologue zero-point energy differences (30), but the 17 O excess (⌬ 17 O) is expected to be only in the terminal position. Others, however, have argued against the symmetry theory (31-33) and have placed anomalous enrichments, even negative ⌬ 17 O values (34), throughout ozone in an attempt to reconcile experimental observations. Precise and accurate measurements of ozone's ⌬ 17 O internal distribution is therefore needed to test the symmet...

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“…37 In this case, K L and R L depends on the enhancement (or reaction) factor (E) according to Eq. 12 34 :…”

Section: Ozone Absorption In a Concentrated Sulfite Solution: Gas-phamentioning

confidence: 99%

“…37 z is the stoichiometric number equal to 1 for the sulfite oxidation in sulfate. The enhancement factor E was calculated according to the Danckwerts' surface renewal theory through Eq.…”

Section: Ozone Absorption In a Concentrated Sulfite Solution: Gas-phamentioning

confidence: 99%

Assessment of a Stirred-Cell Reactor Operated Semicontinuously for the Kinetic Study of Fast Direct Ozonation Reactions by Reactive Absorption

Dang

Biard

Couvert

2016

Ind. Eng. Chem. Res.

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A jacketed stirred-cell reactor, operated semi-continuously, was used to assess the kinetics of fast ozonation reactions by reactive absorption. The method was applied to the direct ozone reaction with resorcinol. A high resorcinol concentration was used to reach a steady state and to neglect the byproducts accumulation. Thus, the mass-transfer rate, and consecutively the reaction rate, were deduced from the ozone mass balance in the gas phase. The gas-phase and liquid-phase mass-transfer coefficients were previously measured directly through the ozone absorption in appropriated conditions. The results emphasized the high sensitivity of the reaction rate constant to the ozone physicochemical properties, especially its solubility, which is controversial in the literature. Therefore, several correlations used to calculate the ozone solubility in water were considered to calculate the second-order reaction rate constant, which varied from 3.57-4.68 10 5 L mol -1 s -1 at 20°C to 9.50-12.2 10 5 L mol -1 s -1 at 35°C. The activation energy was in the range 35-59 kJ mol -1 depending on the considered ozone solubility correlation. A sensitivity analysis is provided to assess the influence of the experimental conditions and ozone physicochemical properties on the model. Finally, the applicability of this method is thoroughly discussed.2

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Kinetics and Mechanisms of Aqueous Ozone Reactions with Bromide, Sulfite, Hydrogen Sulfite, Iodide, and Nitrite Ions

Cited by 207 publications

References 31 publications

The effect of fatty acid surfactants on the uptake of ozone to aqueous halogenide particles

The effect of fatty acid surfactants on the uptake of ozone to aqueous halogenide particles

The role of symmetry in the mass independent isotope effect in ozone

Assessment of a Stirred-Cell Reactor Operated Semicontinuously for the Kinetic Study of Fast Direct Ozonation Reactions by Reactive Absorption

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