Kinetics of the initial reaction of nitrite ion in bisulfite solutions

Oblath, S.B.; Markowitz, Samuel S.; Novakov, T.; Chang, Shuenn‐Yih

doi:10.1021/j100222a005

Cited by 49 publications

(68 citation statements)

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“…This involves applying the rate expression for reaction (R1) with Henry's law and acid dissociation constants computed at 271 K (Supplementary Table 1). We find a fogwater nitrite (N(III), mainly as NO 2 − ) concentration of 2.2 μmol L −1 , which leads to an e-folding SO 2 lifetime of 3.8 h using the rate expression of Martin et al 28 extended to pH 5.7 but 79 h using the rate expression of Oblath et al 27 . The former would imply a major role of HONO as SO 2 oxidant while the latter would imply an insignificant role.…”

Section: Resultsmentioning

confidence: 80%

“…where k 1 = 142 M −3/2 s −1 . Another study by Oblath et al 27 gives a rate expression chemistry, as is frequently observed in polluted air masses 34,35 . The signature of the reaction (R1) taking place in Stage II would then be manifested by the step increase in N 2 O between the two Stages.…”

Section: Resultsmentioning

confidence: 95%

“…We observe fast sulfate production as RH increases over the course of the event, leading to extensive nighttime fog and low clouds, and find a concurrent increase of nitrous oxide (N 2 O). N 2 O is a product of aqueous-phase SO 2 oxidation by dissolved nitrous acid (HONO) [27][28][29] , and observations of HONO during the event support this sulfate formation mechanism. Most of the HONO appears in turn to be produced by aqueous-phase SO 2 oxidation by NO 2 , leading us to propose a two-step fog-enabled mechanism for sulfate formation during winter haze events.…”

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confidence: 95%

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Fast sulfate formation from oxidation of SO2 by NO2 and HONO observed in Beijing haze

et al. 2020

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Severe events of wintertime particulate air pollution in Beijing (winter haze) are associated with high relative humidity (RH) and fast production of particulate sulfate from the oxidation of sulfur dioxide (SO 2) emitted by coal combustion. There has been considerable debate regarding the mechanism for SO 2 oxidation. Here we show evidence from field observations of a haze event that rapid oxidation of SO 2 by nitrogen dioxide (NO 2) and nitrous acid (HONO) takes place, the latter producing nitrous oxide (N 2 O). Sulfate shifts to larger particle sizes during the event, indicative of fog/cloud processing. Fog and cloud readily form under winter haze conditions, leading to high liquid water contents with high pH (>5.5) from elevated ammonia. Such conditions enable fast aqueous-phase oxidation of SO 2 by NO 2 , producing HONO which can in turn oxidize SO 2 to yield N 2 O.This mechanism could provide an explanation for sulfate formation under some winter haze conditions.

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Section: Resultsmentioning

confidence: 80%

Section: Resultsmentioning

confidence: 95%

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confidence: 95%

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Fast sulfate formation from oxidation of SO2 by NO2 and HONO observed in Beijing haze

et al. 2020

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“…[1981] and Oblath et al [1981Oblath et al [ , 1982, who performed experi- ground atmosphere leading to a fall in H20 2 and HONO concentration with a corresponding decrease in the oxidation rate.…”

Section: Soz + Hono Reaction In Hzsomentioning

confidence: 99%

Uptake of gas‐phase SO₂ in aqueous sulfuric acid: Oxidation by H₂O₂, O₃, and HONO

Rattigan¹,

Boniface²,

Swartz³

et al. 2000

J. Geophys. Res.

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Abstract. Uptake of SO2(g) was measured as a function of sulfuric acid concentration in the range pH = 1 to 70 wt% H2SO 4 at 293 K. Uptake studies were carried out in the presence of solvated H202, 03, HONO, NO•, and HNO3. The studies yielded Henry's law coefficients for SO: which were in accord with previous measurements. The results provided first time determinations at high acidities of rate coefficients for the reaction of SO: with H20:, 03, and HONO in the solvated state. The observed SO:(g) uptake was consistent with bulk phase oxidation processes. The measured rate coefficients were used to evaluate the role of heterogeneous interactions with the selected species for aerosol formation in aircraft plumes. Calculations show that these interactions are insignificant compared to gas phase oxidation by the OH radical.

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“…The redox reaction of HONO and SO 2 results in S(VI) and HON, which undergoes fast secondary reactions such as dimerization /dehydration to result in N 2 O [16]. The Raschig mechanism (Scheme I) describes the reduction of HONO by bi-sulfite ion leading to an initial adduct nitroso-sulfonate ( ) which further reacts with an additional bi-Ϫ ONSO 3 sulfite ion to form hydroxylaminedisulfonate (HADS) or undergoes hydrolysis to form nitroxyl (HON) in a competitive reaction [20,21]. Nitroxyl is a key intermediate of N(+I) leading to nitrous oxide and its dehydrative dimerization to N 2 O occurs in solution, but the corresponding rate constant was not accurately estimated [22,23].…”

Section: Introductionmentioning

confidence: 99%

The heterogeneous formation of N2O in the presence of acidic solutions: Experiments and modeling

Pires¹,

Rossi²

1997

Int. J. Chem. Kinet.

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We investigated the heterogeneous processes that contribute towards the formation of N 2 O in an environment that comes as closely as possible to exhaust conditions containing NO and SO 2 among other constituents. The simultaneous presence of NO, SO 2 , O 2 , and condensed phase water in the liquid state has been confirmed to be necessary for the production of significant levels of N 2 O. The maximum rate of N 2 O formation occurred at the beginning of the reaction and scales with the surface area of the condensed phase and is independent of its volume. The replacement of NO by either NO 2 or HONO significantly increases the rate constant for N 2 O formation. The measured reaction orders in the rate law change depending upon the choice of the nitrogen reactant used and were fractional in some cases. The rate constants of N 2 O formation for the three different nitrogen reactants reveal the following series of increasing reactivity:indicating the probable se-NO Ͻ NO Ͻ HONO, 2 quential involvement of those species in the elementary reactions. Furthermore, we observed a complex dependence of the rate constant on the acidity of the liquid phase where both the initial rate as well as the yield of N 2 O are largest at of a H 2 SO 4 /H 2 O solution. The pH ϭ 0 results suggest that HONO is the major reacting N(III) species over a wide range of acidities studied. The N 2 O formation in synthetic flue gas may be simulated using a relatively simple mechanism based on the model of Lyon and Cole. The first step of the complex overall reaction corresponds to NO oxidation by O 2 to NO 2 mainly in the gas phase, with the presence of both H 2 O and active surfaces significantly accelerating NO 2 production. Subsequently, NO 2 reacts with excess NO to obtain HONO which reacts with S(IV) to result in N 2 O and H 2 SO 4 through a complex reaction sequence probably involving nitroxyl (HON) and its dimer, hyponitrous acid.

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Kinetics of the initial reaction of nitrite ion in bisulfite solutions

Cited by 49 publications

References 3 publications

Fast sulfate formation from oxidation of SO2 by NO2 and HONO observed in Beijing haze

Fast sulfate formation from oxidation of SO2 by NO2 and HONO observed in Beijing haze

Uptake of gas‐phase SO₂ in aqueous sulfuric acid: Oxidation by H₂O₂, O₃, and HONO

The heterogeneous formation of N2O in the presence of acidic solutions: Experiments and modeling

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Kinetics of the initial reaction of nitrite ion in bisulfite solutions

Cited by 49 publications

References 3 publications

Fast sulfate formation from oxidation of SO2 by NO2 and HONO observed in Beijing haze

Fast sulfate formation from oxidation of SO2 by NO2 and HONO observed in Beijing haze

Uptake of gas‐phase SO2 in aqueous sulfuric acid: Oxidation by H2O2, O3, and HONO

The heterogeneous formation of N2O in the presence of acidic solutions: Experiments and modeling

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Uptake of gas‐phase SO₂ in aqueous sulfuric acid: Oxidation by H₂O₂, O₃, and HONO