Oxidation of SO2 in aqueous droplets: Mass-transport limitation in laboratory studies and the ambient atmosphere

Despite numerous laboratory investigations, the aqueous phase oxidation of SO₂ remains ill-understood. A major reason for this is the failure to treat properly the combined problem of mass transport and chemical reaction. This problem has not been adequately addressed either by experiments with bulk solutions or by experiments with aqueous droplets that have been undertaken in order to circumvent the mass-transport problem associated with bulk solutions. The conclusions of these laboratory investigations conflict with each other and report reaction rates which are considerably different from those that would pertain to the same reactions in the ambient atmosphere.In this paper we apply the theoretical analysis that has been developed to describe mass transport and reaction of SO₂ in aqueous droplets (Schwartz and Freiberg, 1981) to an analysis of the data of two laboratory studies of this reaction system. It is shown that mass-transport limitation (both gas-phase and aqueous-phase) in the experiment of Barrie and Georgii (1976) may have reduced the measured rates by 20% to as much as an order of magnitude from the intrinsic rate. In the experiment of van den Heuvel and Mason (1963) gas-phase mass-transport limitation is shown to have prevented the steady-state reagent concentration from having been achieved in the contact times employed. Consequently, the rate constants derived from these data by Scott and Hobbs (1967) are too low.Application of the analysis of Schwartz and Freiberg (1981) to an examination of SO₂ oxidation in clouds and fogs indicates that the mass-transport limitation of the oxidation rate is not significant except under conditions of very high oxidation rates, e.g. at high ozone or H₂O₂ concentration.     

Behavior and stability of organic contaminant droplets in aqueous solutions

The behavior of several hydrophobic organic compounds (HOCs) in water at concentrations close to and above their maximum solubility values was studied. For this purpose, solutions of benzene, toluene, xylene, trichloroethylene (TCE) and a mixture of them were prepared in excess in freshwater and in saltwater, and solution stability was examined. High organic concentrations were found to remain stable in both freshwater and saltwater. In saltwater, for example, toluene and xylene concentrations remained as high as 14 and 26 times their solubilities, respectively, over a period of 6 days, while in freshwater, their concentrations remained 8 and 30 times their solubilities over the same period. This phenomenon is attributed to the presence of stable organic droplets, which were observed using optical microscopy. In addition, the transport of HOC droplets through sand is demonstrated, using an experimental system consisting of a saltwater source reservoir connected by a porous inactive sand layer to a freshwater collector reservoir.     

Estimate of the conversion rate of so2 to so2 from the da vinci flight data

The conversion rates of SO₂ to SO₄ are estimated from the Da Vinci flight data reported by Forrest et al. (1979). From the Da Vinci II data, an upper bound for the conversion rate over St. Louis County is estimated to be 3.6%h⁻¹ during the daytime. From the Da Vinci III data, the conversion rate in the St. Louis urban plume is estimated to be 4.2%h⁻¹ during the daytime.     

Electrochemical oxidation of sulfite ions in aqueous solutions

Gaseous pollutants that affect human health, destroy vegetation and damage materials and art treasures can be converted into harmless components by electrochemical reactions. Electrochemical gas purification methods can be applied basically in two steps. In the first step, gases to be removed are absorbed in an aqueous electrolyte. Then, in the second step, they can be converted into harmless components via electrochemical oxidation or electrochemical reduction. This study investigated the feasibility of electrochemical removal of sulfite ions arising from the absorption of sulfur dioxide in an aqueous electrolyte. The removal efficiency, current efficiency, and energy consumption were determined at different initial sulfite ion and electrolyte concentrations and applied currents. Furthermore, linear sweep voltammetry studies were performed using a graphite electrode in sulfuric acid. It has been concluded from all these experiments that sulfur dioxide can successfully be removed using an electrochemical method.     

Photo-fenton assisted reaction of dimethoate in aqueous solutions

The photo-Fenton reaction of an organophosphorus insecticide, dimethoate (O,O-dimethyl methylcarbamoylmethyl phosphorodithioate), was studied by following the identification and determination of the decomposition products and the total carbon removal rate. The reactions were performed in a batch recycle reactor, at room temperature, using UV radiation, H2O2 as oxidant, and FeCl3 x 6H2O as catalyst. The oxidation results were determined with a total organic carbon (TOC) analyzer and ion chromatography. The presence of reaction products was identified by gas chromatography-mass spectrometry (GC-MS). Apart from the sulfate, phosphate, and ammonium ions, the presence of dimethyl phosphite, N-methyl-acetamide, and formic acid was also detected. Excess of H2O2 concentration did not influence the reaction rate. The expression for the total carbon removal was assessed and the TOC removal rate constants were calculated.     

Photocatalytic oxidation of cyanide in aqueous solutions of poly(sodium styrenesulfonate-co-2-vinylnaphthalene)

Photosensitized by poly (sodium styrenesulfonate-co-2-vinylnaphthalene) (PSSS-VN) oxidation of cyanide in an aqueous solution was studied. The reaction was found to occur via photoinduced electron transfer from CN- to the polymeric chromophores. The process leads to formation of NCO-.     

Cu/La共掺杂TiO2光催化氧化水中的氨氮

采用水解-沉淀法制备了Cu/La共掺杂纳米TiO2催化剂,利用XRD、XPS和BET技术对其进行表征,并考察了在紫外灯下,共掺杂TiO2对氨氮的光催化氧化工艺条件。物相结构和比表面积测试结果表明,共掺杂催化剂具有较好的锐钛矿晶型,孔径分布为4～8 nm,Cu/La共掺杂TiO2La以La3+,Cu是以Cu2+、Cu+的形式掺杂进入TiO2的晶格。光催化实验表明:所得改性光催化剂对氨氮的去除及焦化废水的处理均具有较高的催化活性。     

CuAPO-5分子筛催化氧化水溶液中苯酚的性能

以水热晶化法合成了铜磷铝分子筛CuAPO-5,并用XRD、SEM,FT-IR,UV-Vis等对样品进行了表征,结果表明Cu²⁺进入到了AlPO₄-5分子筛骨架中。研究了以CuAPO-5为催化剂, H₂O₂为氧化剂对水溶液中苯酚的催化氧化性能。在苯酚初始浓度200 mg/L 、H₂O₂添加量1 200 mg/L、pH值5.0、处理温度80 ℃时,处理240 min时苯酚去除率达到100％,TOC去除率达81.76％,析出到溶液中Cu²⁺浓度仅为0.527 mg/L。温度从40 ℃上升到80 ℃时,苯酚的去除率及TOC去除率明显增大,表明温度对催化剂的活性影响显著,相比于均相催化剂骨架Cu催化过氧化氢分解需要更多的能量。重复性实验表明,催化剂性能稳定。     

Photocatalytic oxidation of NOx gases using TiO2: a surface spectroscopic approach

The bandgap of solid-state TiO2 (3.2 eV) enables it to be a useful photocatalyst in the ultraviolet (lambda < 380 nm) region of the spectrum. A clean TiO2 surface in the presence of sunlight therefore enables the removal of harmful NOx gases from the atmosphere by oxidation to nitrates. These properties, in addition to the whiteness, relative cheapness and non-toxicity, make TiO2 ideal for the many de-NOX catalysts that are currently being commercially exploited both in the UK and Japan for concrete paving materials in inner cities. There is need, however, for further academic understanding of the surface reactions involved. Hence, we have used surface specific techniques, including X-ray photoelectron spectroscopy and Raman spectroscopy, to investigate the NOx adsorbate reaction at the TiO2 substrate surface.     

不同高级氧化法对水中低浓度药物甲硝唑降解过程的比较

采用UV、H₂O₂、UV/H₂O₂、Fenton、UV/Fenton和UV/TiO₂方法,对水中低浓度的药物甲硝唑进行降解。通过HPLC和UV-Vis光谱得到的甲硝唑去除率。详细讨论了Fe²⁺、TiO₂和H₂O₂的初始浓度以及溶液的初始pH值对降解效率的影响。结果表明,UV/Fenton和UV/TiO₂ 2种系统对水中低浓度甲硝唑均有很好的去除效果,但前者的光催化效率更高。在甲硝唑浓度=6 μmol/L,H₂O₂和Fe²⁺的初始浓度分别为0.5 mg/L和2.94 μmol/L,pH=4的条件下,UV/Fenton方法对甲硝唑水溶液光催化的最佳效率为95.8%。     

Measurements of the oxidation rate of sulfur (IV) by ozone in aqueous solution and their relevance to SO2 conversion in nonurban tropospheric clouds

An experimental survey of the rate of oxidation of sulfur (IV) by ozone in aqueous solution at 25 C in the pH range 3.1 to 6.2 has been conducted using stopped-flow spectrophotometry. The rates obtained are faster than those reported by Penkett et al. (Atmospheric Environment (1979) 13, 123–137), but are in good agreement with an extension of the rates reported by Erickson et al. (Atmospheric Environment (1977) 11, 813–817). Comparison of the present data with reported rates of oxidation of sulfur (IV) by H₂O₂ in aqueous solution at typical pH levels encountered in non-urban tropospheric cloud water, and at representative concentrations of O₃ and H₂O₂, indicates the potential importance of O₃ as a contributor to the oxidative conversion of SO₂ to sulfate in clouds. However, several orders of magnitude extrapolation in O₃ concentration are required in applying the present results to the environment, and verification by an experimental technique employing more representative O₃ concentrations is desirable.     

Carbon catalysis in the aqueous oxidation of SO2 by NO2 and air

Sulfur Dioxide and an oxidant gas — air or NO₂ — were bubbled through aqueous suspensions of both washed and unwashed carbon black as well as through samples of wash water, which contained whatever soluble species were originally present on the carbon, and high-purity water. The sulfate yields obtained showed the washed and unwashed carbon to be equally catalytic for the oxidation of SO₂ to sulfate by both oxidants whereas little sulfate was generated in either the wash water or high-purity water in the absence of carbon. These results indicate that the sulfate yields produced in aqueous suspensions of the carbon studied are due to catalysis by the carbon particles rather than by soluble species dissolved from them.     

超声-过氧化氢-氧化铜组合技术催化氧化水中苯酚

研究了超声-H2O2-CuO组合技术对苯酚的降解效果。考察了苯酚初始浓度、溶液温度及鼓入空气对苯酚去除率的影响。实验结果表明,与未鼓入空气时相比,连续鼓气时苯酚的降解效果较好;初始浓度低,苯酚去除率高;溶液温度从20℃上升到55℃时,苯酚去除率随温度升高而增大,温度对该过程的影响主要表现为对催化剂的影响而不是对超声作用的影响。高效液相色谱分析表明,苯酚降解的中间产物主要为对苯二酚、邻苯二酚及其他有机小分子物质,最终产物为草酸、二氧化碳和水。     

超声-过氧化氢-氧化铜组合技术催化氧化水中苯酚

研究了超声-H2O2-CuO组合技术对苯酚的降解效果。考察了苯酚初始浓度、溶液温度及鼓入空气对苯酚去除率的影响。实验结果表明，与未鼓入空气时相比，连续鼓气时苯酚的降解效果较好；初始浓度低，苯酚去除率高；溶液温度从20％上升到55％时，苯酚去除率随温度升高而增大，温度对该过程的影响主要表现为对催化剂的影响而不是对超声作用的影响。高效液相色谱分析表明，苯酚降解的中间产物主要为对苯二酚、邻苯二酚及其他有机小分子物质，最终产物为草酸、二氧化碳和水。     

不同电极降解2-氯苯酚

采用电沉积法制备了4种钛基二氧化铅电极,并与商业化的钛基RuO2电极进行了对比。分别用XRD和阳极极化曲线对电极性能进行了表征,并以2-氯苯酚为目标污染物,考察了6种电极的电催化氧化性能。研究结果表明,以钛板为基体的系列电极的综合性能优于以钛网为基体的相应电极。以β-PbO2为活性外层的二氧化铅电极的综合性能优于以RuO2为活性外层的电极。6种电极对2-氯苯酚降解反应均遵循一级反应动力学规律。其中Ti/α-PbO2/β-PbO2电极析氧电位最高,电催化性能最好,对2-氯苯酚的去除率可达99.3%。     

The importance of liquid water concentration in the atmospheric oxidation of SO2

The concentration of condensed water available for aqueous chemical reactions is viewed as a fundamental parameter of the heterogeneous conversion of gaseous SO₂ to particulate sulfate. New results from a series of dispersed-phase experiments in a cloud chamber, in which the magnitude of this parameter was allowed to vary widely, demonstrate that the heterogeneous SO₂ conversion rate in hazes is generally limited by the small concentration of condensed water. This limitation precludes the heterogeneous oxidation pathway from being important in the atmosphere during haze episodes except under extreme conditions of high humidities and aerosol loadings. In clouds, on the other hand, the liquid water concentrations are relatively large, permitting chemically related factors, such as pH-dependent equilibria and oxidant abundances, to limit the SO₂ conversion rate.