Formation of chlorinated species through reaction of SO2 with NaClO2 powder and their role in the oxidation of NO and Hg0

This study examines gaseous chlorinated species generated from the reaction of sulfur dioxide (SO₂) with sodium chlorite powder (NaClO_2(s)) to obtain insight into the propensity of this process to enhance NO and Hg⁰ oxidation. A packed bed reactor containing NaClO_2(s) was used and the reaction temperature was set to 130 °C. Initially, we determined that the presence of SO₂ enhances the oxidation of NO and Hg⁰ by reaction with NaClO_2(s). We then introduced NO₂ into the gas mixture as a radical scavenger and determined that the chlorinated species generated by the reaction of SO₂ with NaClO_2(s) are OClO, Cl, ClO, and Cl₂. Based on these results, we suggest that such gaseous chlorinated ones are responsible for the enhancement of NO and Hg⁰ oxidation.     

1990 Government Agencies Directory

ABSTRACT

The kinetics of pentachlorophenol (PCP) ozonation in terms of the gaseous O₃ and dissolved PCP concentrations has been investigated. When the O₃ concentration in the gas phase was in the range of 10 to 40 g O₃/m³, the O₃ dissolved for a short time period was proportional to the gaseous O₃ concentration. In this range, the ozonation reaction was first order for each reactant and the overall reaction was second order. At 25 °C, in an aqueous solution, the reaction rate constant was estimated to be 10.048 L/mol-sec. The reaction rate was much greater than the mass-transfer rate, indicating that the reaction of O₃ and PCP was an interface reaction on the surface of gaseous O₃ bubbles. The final product of the PCP ozonation was oxalic acid, with the carbon yield of the reaction being 59.4%. The ozonation of PCP in the aqueous solution was not a radical reaction but a direct reaction between O₃ and PCP molecules under the conditions investigated in this study, since O₃ has a high selectivity toward PCP. The reaction rate increased with the reaction temperature up to 35 °C but decreased at temperatures greater than 35 °C due to the decreased solubility of O₃. The addition of H₂O₂ did not increase the reaction rate significantly.     

Pore Structure Effects on Ca-Based Sorbent Sulfation Capacity at Medium Temperatures: Activated Carbon as Sorbent/Catalyst Support

Abstract

The reaction between three different Ca-based sorbents and SO₂ were studied in a medium temperature range (473–773 K). The largest SO₂ capture was found with Ca(OH)₂ at 773 K, 126.31 mg SO₂?g Ca(OH)₂ ^?1, and the influence of SO₂ concentration on the sorbent utilization was observed. Investigations of the internal porous structure of Ca-based sorbents showed that the initial reaction rate was controlled by the surface area, and once the sul-fated products were produced, pore structure dominated. To increase the surface area of Ca-based sorbents available to interact with and retain SO₂, one kind of CaO/activated carbon (AC) sorbent/catalyst was prepared to study the effect of AC on the dispersion of Ca-based materials. The results indicated that the Ca-based material dispersed on high-surface-area AC had more capacities for SO₂ than unsupported Ca-based sorbents. The initial reaction rates of the reaction between SO₂ and Ca-based sorbents and the prepared CaO/AC sorbents/cata-lysts were measured. Results showed that the reaction rate apparently increased with the presence of AC. It was concluded that CaO/AC was the active material in the des-ulfurization reaction. AC acting as the support can play a role to supply O₂ to increase the affinity to SO₂. Moreover, when AC is acting as a support, the surface oxygen functional group formed on the surface of AC can serve as a new site for SO₂ adsorption.     

Influence of NO2 and dissolved iron on the S(IV) oxidation in synthetic aqueous solution

The influence of dissolved NO₂ and iron on the oxidation rate of S(IV) species in the presence of dissolved oxygen is presented. To match the conditions in the real environment, the concentration of iron in the reaction solution and trace gases in the gas mixture was typical for a polluted atmosphere. The time dependence of HSO₃⁻, SO₄²⁻, NO₂⁻ and NO₃⁻ and the concentration ratio between Fe(II) and total dissolved iron were monitored. Sulphate formation was the most intensive in the presence of an SO₂/NO₂/air gas mixture and Fe(III) in solution. The highest contribution to the overall oxidation was from Fe-catalysed S(IV) autoxidation. The reaction rate in the presence of both components was equal to the sum of the reaction rates when NO₂ and Fe(III) were present separately, indicating that under selected experimental conditions there exist two systems: SO₂/NO₂/air and SO₂/NO₂/air/Fe(III), which are unlikely to interact with each other. The radical chain mechanism can be initiated via reactions Fe(III)–HSO₃⁻ and NO₂–SO₃²⁻/HSO₃⁻.     

Probing the sensitivity of gaseous Br2 production from the oxidation of aqueous bromide-containing aerosols and atmospheric implications

This paper presents a global sensitivity and uncertainty analysis of the bromine chemistry included in the Model of Aqueous, Gaseous and Interfacial Chemistry (MAGIC) in dark and photolytic conditions. Uncertainty ranges are established for input parameters (e.g. chemical rate constants, Henry's law constants, etc.) and are used in conjunction with Latin hypercube sampling and multiple linear regression to conduct a sensitivity analysis that determines the correlation between each input parameter and model output. The contribution of each input parameter to the uncertainty in the model output is calculated by combining results of the sensitivity analysis with input parameters' uncertainty ranges. Model runs are compared using the predicted concentrations of molecular bromine since Br_2(g) has been shown in previous studies to be generated via an interface reaction between O_3(g) and Br_(surface)^? during dark conditions [Hunt et al., 2004]. Formation of molecular bromine from the reaction of ozone with deliquesced NaBr aerosol: evidence for interface chemistry. Journal of Physical Chemistry A 108, 11559–11572]. This study also examines the influence of an interface reaction between OH_(g) and Br_(surface)^? in the production of Br_2(g) under photolytic conditions where OH_(g) is present in significant concentrations. Results indicate that the interface reaction between O_3(g) and Br_(surface)^? is significant and is most responsible for the uncertainty in MAGICs ability to calculate precisely Br_2(g) under dark conditions. However, under photolytic conditions the majority of Br_2(g) is produced from a complex mechanism involving gas-phase chemistry, aqueous-phase chemistry, and mass transport.     

Influence of ozone, relative humidity, and flow rate on the deposition and oxidation of sulfur dioxide on yellow sand

To evaluate the influences of O₃, relative humidity (RH), and flow rate on the reaction between yellow sand and SO₂, the SO₂ deposition velocity and the oxidation state of sulfur were investigated by means of exposure experiments in a cylindrical flow reactor. Early in the reaction, the deposition velocity was not influenced by the RH or the presence of O₃; as the reaction progressed, however, the deposition velocity increased in the presence of O₃ and at high humidity. The oxidation of sulfur from S(IV) to S(VI) was also enhanced under these conditions. The amount of sulfur oxidation was positively correlated with the amount of deposited O₃. Furthermore, the SO₂ deposition velocity increased with increasing flow rate. However, changes in the flow rate had no noticeable effect on the amount of SO₂ oxidation.     

An important pathway for ozonolysis of alpha-pinene and beta-pinene in aqueous phase and its atmospheric implications

The aqueous ozonolysis of α-pinene and β-pinene was conducted under simulated tropospheric conditions at different pHs and temperatures. Three kinds of products, peroxides, carbonyl compounds, and organic acids, were well characterized, and the detection of these products provides effective evidence for understanding the atmospheric aqueous reaction pathway. We have two interesting findings: (1) the unexpected formation of methacrolein (MACR), with a yield of ～40%, in the α-pinene–O₃ aqueous reaction indicates a potentially new SOA formation pathway, because MACR is one of the important precursors of SOA; and (2) the surprisingly high yields of H₂O₂, ～60% for the α-pinene–O₃ reaction and ～100% for the β-pinene–O₃ reaction, indicates that H₂O₂ can be a significant contributor to the origin and transformation of oxidants in the atmosphere, especially in the humid regions. Moreover, we have determined the rate constant for aqueous reaction between MACR and H₂O₂ in pH 2 to 7 and obtained its upper limit as 0.13 M L^?1 s^?1. A mechanism concerning the formation of the species mentioned above is proposed, and it differs from that in the gas-phase reaction. We suggest that water plays a key role in the mechanism, by participating in the reactions as a direct reactant and by removing the excess energy of intermediates formed in the reactions.     

Heterogeneous photocatalytic effect of zinc oxide on photochemical smog formation reaction of C4H8-NO2-air

As a model of heterogeneous photochemical smog formation reaction, butene-NO₂-air systems in the presence of zinc oxide were experimentally studied using a flowing reaction system. Zinc oxide revealed a remarkable photocatalytic action which involved the production of hitherto unreported species such as cyano-compounds (HCN and CH₃CN) as well as a striking change in the distribution of the reaction products (aldehydes, ketones, epoxides, alkyl nitrates, HNO₃, CO, CO₂, etc.). It is confirmed that ZnO little affected the initial process of gas-phase photochemical reactions but interacted photocatalytically with the gas-phase reaction products.     

The photochemical formation and gas–particle partitioning of oxidation products of decamethyl cyclopentasiloxane and decamethyl tetrasiloxane in the atmosphere

Decamethyl cyclopentasiloxane (D₅) and decamethyl tetrasiloxane (MD₂M) were injected into a smog chamber containing fine Arizona road dust particles (95% surface area <2.6 μM) and an urban smog atmosphere in the daytime. A photochemical reaction – gas–particle partitioning reaction scheme, was implemented to simulate the formation and gas–particle partitioning of hydroxyl oxidation products of D₅ and MD₂M. This scheme incorporated the reactions of D₅ and MD₂M into an existing urban smog chemical mechanism carbon bond IV and partitioned the products between gas and particle phase by treating gas–particle partitioning as a kinetic process and specifying an uptake and off-gassing rate. A photochemical model PKSS was used to simulate this set of reactions. A Langmuirian partitioning model was used to convert the measured and estimated mass-based partitioning coefficients (K_P) to a molar or volume-based form. The model simulations indicated that >99% of all product silanol formed in the gas-phase partition immediately to particle phase and the experimental data agreed with model predictions. One product, D₄TOH was observed and confirmed for the D₅ reaction and this system was modeled successfully. Experimental data was inadequate for MD₂M reaction products and it is likely that more than one product formed. The model set up a framework into which more reaction and partitioning steps can be easily added.     

Surface chemistry of dihydromyrcenol (2,6-dimethyl-7-octen-2-ol) with ozone on silanized glass,glass, and vinyl flooring tiles

The surface-phase reaction products of dihydromyrcenol (2,6-dimethyl-7-octen-2-ol) with ozone (O₃), air, or nitrogen (N₂) on silanized glass, glass and vinyl flooring tile were investigated using the recently published FACS (FLEC (Field and Laboratory Emission Cell) Automation and Control System). The FACS was used to deliver ozone (100 ppb), air, or N₂ to the surface at a specified flow rate (300 mL min^?1) and relative humidity (50%) after application of a 2.0% dihydromyrcenol solution in methanol. Oxidation products were detected using the derivatization agents: O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA) and N,O-bis(trimethysilyl)trifluoroacetamide (BSTFA). The positively identified reaction products were glycolaldehyde, 2,6-dimethyl-5-heptenal, and glyoxal. The proposed oxidation products based on previously published VOC/O₃ reaction mechanisms were: 2,6-dimethyl-4-heptenal, 6-methyl-7-octen-2-one and the surface-specific reaction products: 6-methyl-6-hepten-2-one, 6-methyl-5-hepten-2-one, and 6-hydroxy-6-methylheptan-2-one. Though similar products were observed in gas-phase dihydromyrcenol/O₃ reactions, the ratio, based on peak area, of the reaction products was different suggesting stabilization of larger molecular weight species by the surface. Emission profiles of these oxidation products over 72 h are also reported.     

Effect of pH and Temperature on the Kinetics of Odor Oxidation Using Chlorine Dioxide

Abstract

Increasing public concerns over odors and air regulations in nonattainment zones necessitate the remediation of a wide range of volatile organic compounds (VOCs) generated in the poultry-rendering industry. Currently, wet scrubbers using oxidizing chemicals such as chlorine dioxide (ClO₂) are utilized to treat VOCs. However, little information is available on the kinetics of ClO₂ reaction with rendering air pollutants, limiting wet scrubber design and optimization. Kinetic analysis indicated that ClO₂ does not react with hexanal and 2-methylbutanal regardless of pH and temperature and implied that alde-hyde removal occurs primarily via mass transfer. Contrary to the aldehydes, ethanethiol or ethyl mercaptan (a model compound for methanethiol or methyl mercaptan) and dimethyl disulfide (DMDS) rapidly reacted with ClO₂. The overall reaction was found to be second and third order for ethanethiol and DMDS, respectively. Moreover, an increase in pH from 3.6 to 5.1 exponentially increased the reaction rate of ethanethiol (e.g., k ₂ = 25– 4200 L/mol/sec from pH 3.6 to 5.1) and significantly increased the reaction rate of DMDS if increased to pH 9 (k ₃ = 1.4 × 10⁶ L²/mol²/sec). Thus, a small increase in pH could significantly improve wet scrubber operations for removal of odor-causing compounds. However, an increase in pH did not improve aldehyde removal. The results explain why aldehyde removal efficiencies are much lower than methanethiol and DMDS in wet scrub-bers using ClO₂.     

Hg Reactions in the Presence of Chlorine Species: Homogeneous Gas Phase and Heterogeneous Gas-Solid Phase

Abstract

The kinetics of Hg chlorination (with HCl) was studied using a flow reactor system with an online Hg analyzer, and speciation sampling using a set of impingers. Kinetic parameters, such as reaction order (α), overall rate constant (k′ ), and activation energy (E _a), were estimated based on the simple overall reaction pathway. The reaction order with respect to C _Hg, k′, and E _a were found to be 1.55, 5.07 x 10^-2exp(-1939.68/T) [(μg/m³)^-0.55(s)^-1], and 16.13 [kJ/mol], respectively. The effect of chlorine species (HCl, CH₂Cl₂) on the in situ Hg capture method previously de-veloped²⁸ was also investigated. The efficiency of capture of Hg by this in situ method was higher than 98% in the presence of chlorine species. Furthermore, under certain conditions, the presence of chlorine enhanced the removal of elemental Hg by additional gas-phase oxidation.     

The effect of oxygen on chemical dechlorination of dieldrin using iron sulphides

The degradation of dieldrin by ferric sulphide (FeS₂) in aqueous solution was investigated when shielded against sunlight. An oxidative dechlorination process was observed under aerobic and anaerobic conditions; oxygen volume changed the degradation rate of dieldrin and the generation rate of reaction products. The dechlorination rate under microaerophilic conditions was fastest among the anaerobic to air oxygen concentrations. For this experiment, over 99% of the dieldrin was degraded, and 90% of the released chloride was detected after 30 d under 10 μmol oxygen. The major reaction products were different depending on the dose of oxygen. In the case of aerobic conditions, low molecular weight organic acids, such as formic acid, lactic acid, and oxalic acid, were generated as major reaction products. However, under anaerobic conditions, C₁₆H₂₂O₄ (dibutyl phthalate) and C₆H₁₃ClO (3-chloro-4-methyl-2-pentanol) were detected as reaction intermediates, and small amounts of succinic acid, malonic acid, and formic acid were also generated. These reactions proceed by FeS₂ interface reactions with H₂O under anaerobic condition, or O₂ under aerobic condition.     

催化臭氧化降解技术中的两个问题

探讨了有机物特性及中间产物H₂O₂在催化臭氧化中的作用。结果表明,有机物在自由基链反应过程中的特性直接影响催化臭氧化的降解效率。当目标有机物是对链反应具有促进作用的甲酸时,自由基引发反应可以明显提高甲酸的臭氧化效率。当目标有机物是对自由基链反应具有抑制剂作用的乙酸时,O₃和Fe²⁺/O₃对乙酸有着相似的降解效率。以上结果表明,自由基引发反应并不是臭氧化降解效率提高的充分条件。另外,当臭氧化过程有H₂O₂产生时,必须考虑类Fenton反应对臭氧化效率的影响。     

Degradation of Acid Orange 7 in aqueous solution by dioxygen activation in a pyrite/H2O/O2 system

Increasing attention has been paid to pyrite due to its ability to generate hydroxyl radicals in air-saturated solutions. In this study, the mineral pyrite was studied as a catalyst to activate molecular oxygen to degrade Acid Orange 7 (AO7) in aqueous solution. A complete set of control experiments were conducted to optimize the reaction conditions, including the dosage of pyrite, the AO7 concentration, as well as the initial pH value. The role of reactive oxygen species (ROS) generated by pyrite in the process was elucidated by free radical quenching reactions. Furthermore, the concentrations of Fe(II) and total Fe formed were also measured. The mechanism for the production of ROS in the pyrite/H₂O/O₂ system was that H₂O₂ was formed by hydrogen ion and superoxide anion (O₂ ^·?) which was produced by the reaction of pyrite activating O₂ and then reacted with Fe(II) dissolved from pyrite to produce ^·OH through Fenton reaction. The findings suggest that pyrite/H₂O/O₂ system is potentially practical in pollution treatment. Moreover, the results provide a new insight into the understanding of the mechanism for degradation of organic pollutants by pyrite.     

The oxidation of sulphur dioxide in electrolyte droplets

The rate of absorption of sulphur dioxide into deliquescent aerosols of MgCl₂, NaCl and (NH₄)₂SO₄ has been studied using a radioactive tracing technique. The amount of SO₂ absorbed was approximately linear in the calculated liquid water content of the aerosols and reached about 12 mg g⁻¹ water after a reaction time of 145 min. Over the range 1–20 ppm the reaction was zero order in gas phase SO₂ concentration. Additional metal catalysts (Mn²⁺, Fe³⁺) had relatively small effects on the oxidation rates whilst NO²⁺ (0–20 ppm) had a large effect on the initial rate but did not significantly increase the final amount of SO₂ absorbed. The rates of reaction are shown to be far higher than in pure water and significant reaction continues down to pH 1–2. A detailed model of ionic activities and equilibria in the droplets is developed to aid the interpretation of the results and the implications for natural aerosols such as sea salt assessed.     

Alumina-supported oxime for the degradation of sarin and diethylchlorophosphate

1-(4-Chlorophenyl))-N-hydroxymethanimine and cyclohexyl-N-hydroxymethanimine were synthesized and a well-established oxime, i.e., 2-[(hydroxyimino)methyl]-1-methylpyridinium chloride was purchased. Thereafter; all were loaded over Al₂O₃ using incipient wetness technique. The prepared systems were characterized using surface area analyzer, scanning electron microscope, energy dispersive X-ray spectrophotometer, Fourier transform infrared spectrophotometer and thermogravimetric analyzer. Kinetics of the degradation of sarin (GB) and simulant, i.e. diethylchlorophosphate (DEClP) was studied over synthesized oxime impregnated Al₂O₃ and results were compared with well reported oxime impregnated Al₂O₃. Kinetics of reaction was found to be following the pseudo first order reaction kinetics. The order of reactivity of the prepared systems was found to be cyclohexyl-N-hydroxymethanimine/Al₂O₃ > 1-(4-chlorophenyl)-N-hydroxymethanimine/Al₂O₃ > 2-[(hydroxyimino)methyl]-1-methylpyridinium chloride/Al₂O₃ > Al₂O₃. From the reaction kinetics it was observed that the reaction with DEClP was faster than with GB. Cyclohexyl-N-hydroxymethanimine/Al₂O₃ was found to be the most reactive system with half-life of 0.94 and 15 h for DEClP and GB respectively.     

Products and mechanisms of the gas-phase reactions of OH radicals and O3 with 2-methyl-3-buten-2-ol

Products of the gas-phase reactions of OH radicals (in the presence of NO) and O₃ with the biogenic organic compound 2-methyl-3-buten-2-ol have been investigated using gas chromatography with flame ionization detection (GC-FID), combined gas chromatography–mass spectrometry (GC-MS), gas chromatography with Fourier transform infrared detection (GC-FTIR), in situ FT-IR spectroscopy and in situ atmospheric pressure ionization tandem mass spectrometry (API-MS/MS). Formaldehyde, 2-hydroxy-2-methylpropanal and acetone were identified from both the OH radical and O₃ reactions, glycolaldehyde and organic nitrate (s) were also observed from the OH radical reaction, and the OH radical formation yield from the O₃ reaction was measured. The formaldehyde, 2-hydroxy-2-methylpropanal, glycolaldehyde, acetone and organic nitrate yields from the OH radical reaction were 0.29±0.03, 0.19±0.07, 0.61±0.09, 0.58±0.04 and 0.05±0.02, respectively, and the formaldehyde, 2-hydroxy-2-methylpropanal and OH radical formation yields from the O₃ reaction were 0.29±0.03, 0.30±0.06 (0.47 from FT-IR measurements) and 0.19 (uncertain to a factor of 1.5), respectively. Acetone was also observed from the O₃ reaction, but appeared to be formed from secondary reactions. Reaction mechanisms are presented and discussed.     

4种高级氧化法处理高浓度正丙醇废水的动力学比较

研究了1%和10%(V/V)模拟正丙醇废水在UV/TiO2体系、UV/H2O2体系、Fe2+/H2O2体系和UV/TiO2/Fe2+/H2O2体系等4种工艺条件下的降解动力学过程,对比了降解动力学特点及工艺参数对动力学常数的影响,优化工艺参数。结果表明,UV/TiO2体系和Fe2+/H2O2体系的降解过程可分为零级反应阶段和一级反应阶段,转折点分别在反应开始后2 h和氧化剂浓度为6.7 g/L,UV/H2O2体系和UV/TiO2/Fe2+/H2O2体系分别符合零级反应和一级反应规律;相同工艺参数条件下,6 h反应后,组合工艺UV/TiO2/Fe2+/H2O2体系在处理效率达85%,比前3个体系分别高52.0%、8.3%和32.0%,与UV/TiO2体系和Fe2+/H2O2体系的处理效率之和持平,其协同效应提高了速率常数,在目标物浓度降低时依然可维持较高降解速率。而目标物浓度提高10倍后,UV能量利用率提高35.5倍,氧化剂用量是Fe2+/H2O2体系的1/7.1。     

Regression modelling of hourly NOx and NO2 concentrations in urban air in London

Based on hourly measurements of NO_x NO₂ and O₃ and meteorological data, an ordinary least squares (OLS) model and a first-order autocorrelation (AR) model were developed to analyse the regression and prediction of NO_x and NO₂ concentrations in London. Primary emissions and wind speed are the most important factors influencing NO_x concentrations; in addition to these two, reaction of NO with O₃ is also a major factor influencing NO₂ concentrations. The AR model resulted in high correlation coefficients (R > 0.95) for the NO_x and NO₂ regression based on a whole year's data, and is capable of predicting NO₂ (R = 0.83) and NO_x (R = 0.65) concentrations when the explanatory variables were available. The analysis of the structure of regression models by Principal Component Analysis (PCA) indicates that the regression models are stable. The results of the OLS model indicate that there was an exceptional NO₂ source, other than primary emission and reaction of NO with O₃, in the air pollution episode in London in December 1991.