Sulfur trioxide atmospheric oxidation

The oxidation catalyst (OC) operates according to the same principles described for a TWO catalyst except that the catalyst only oxides HC, CO, and H2. It does not reduce NO emissions because it operates in excess O2 environments. One concern regarding oxidation catalysts was the abiUty to oxidize sulfur dioxide to sulfur trioxide, because the latter then reacts with water to form a sulfuric acid mist which is emitted from the tailpipe. The SO2 emitted has the same ultimate fate in that SO2 is oxidized in the atmosphere to SO which then dissolves in water droplets as sulfuric acid. 

Sulfur oxides (SO,) are compounds of sulfur and oxygen molecules. Sulfur dioxide (SO2) is the predominant form found in the lower atmosphere. It is a colorless gas that can be detected by taste and smell in the range of 1, (X)0 to 3,000 uglm. At concentrations of 10,000 uglm , it has a pungent, unpleasant odor. Sulfur dioxide dissolves readily in water present in the atmosphere to form sulfurous acid (H SOj). About 30% of the sulfur dioxide in the atmosphere is converted to sulfate aerosol (acid aerosol), which is removed through wet or dry deposition processes. Sulfur trioxide (SO3), another oxide of sulfur, is either emitted directly into the atmosphere or produced from sulfur dioxide and is readily converted to sulfuric acid (H2SO4). 

Sulfur forms several oxides that in atmospheric chemistry are referred to collectively as SOx (read sox ). The most important oxides and oxoacids of sulfur are the dioxide and trioxide and the corresponding sulfurous and sulfuric acids. Sulfur burns in air to form sulfur dioxide, S02 (11), a colorless, choking, poisonous gas (recall Fig. C.1). About 7 X 1010 kg of sulfur dioxide is produced annually from the decomposition of vegetation and from volcanic emissions. In addition, approximately 1 X 1011 kg of naturally occurring hydrogen sulfide is oxidized each year to the dioxide by atmospheric oxygen ... 

Acid rain is caused primarily by sulfur dioxide emissions from burning fossil fuels such as coal, oil, and natural gas. Sulfur is an impurity in these fuels for example, coal typically contains 2-3% by weight sulfur.1M Other sources of sulfur include the industrial smelting of metal sulfide ores to produce the elemental metal and, in some parts of the world, volcanic eruptions. When fossils fuels are burned, sulfur is oxidized to sulfur dioxide (SO2) and trace amounts of sulfur trioxide (SC>3)J21 The release of sulfur dioxide and sulfur trioxide emissions to the atmosphere is the major source of acid rain. These gases combine with oxygen and water vapor to form a fine mist of sulfuric acid that settles on land, on vegetation, and in the ocean. 

Sulfur dioxide, sulfur trioxide, and various oxides of nitrogen are generated by coal-burning power plants. They dissolve in water in the atmosphere to produce the acid rain downwind of industrial centers. 

The primary cause of acid rain is industrial and automotive pollution. Each year in industrialized countries, large power plants and smelters that burn sulfur-containing fossil fuels pour millions of tons of sulfur dioxide (S02) gas into the atmosphere, where some is oxidized by air to produce sulfur trioxide (S03). Sulfur oxides then dis-l solve in rain to form dilute sulfurous acid and sulfuric acid ... 

Renewable energy processes do not generate sulfur dioxide, but coal-burning power plants do therefore, sulfur oxides (just as C02) are present in the atmosphere, contributing to acid rain and other hazards. The predominant form of sulfur oxide in the atmosphere is sulfur dioxide (S02) itself. Some sulfur trioxide (S03) is also formed in combustion processes, but it rapidly hydrolyzes to sulfuric acid, which is considered to be a particulate matter. In the United States, the ultimate air quality goals (secondary standards) for sulfur dioxide are 60 pg/m3 (0.02 ppm) annual arithmetic average and 260 pg/m3 (0.1 ppm) maximum 24 h concentration, which are not to be exceeded more than once a year. 

Sulfur dioxide from the combustion of sulfur-containing fossil fuels (e.g., diesel oil and coal) is oxidized in the atmosphere to form sulfur trioxide that reacts with water to form sulfuric acid. 

In the last 150 years the anthropogenic emission of sulfur has increased dramatically, primarily due to combustion processes [1]. In the 1950s anthropogenic emission surpassed natural emission and the atmospheric sulfur cycle is one of the most perturbed biogeochemical cycles [1,2]. The oceans are the largest natural source of atmospheric sulfur emissions, where sulfur is emitted in a reduced form, predominantly as dimethyl sulfide (DMS) and to a much lesser extent carbonyl sulfide (OCS) and carbon disulfide (CS2) [3]. Ocean emitted DMS and CS2 are initially oxidised to OCS, which diffuses through the troposphere into the stratosphere where further oxidation to sulfur dioxide (SO2), sulfur trioxide (SO3) and finally sulfuric acid (H2SO4) occurs [1-4]. 

However, this reaction is very slow in the absence of a catalyst. One of the mysteries during early research on air pollution was how the sulfur dioxide produced from the combustion of sulfur-containing fuels is so rapidly converted to sulfur trioxide in the atmosphere. It is now known that dust and other particles can act as heterogeneous catalysts for this process (see Section 15.9). In the preparation of sulfur trioxide for the manufacture of sulfuric acid, either platinum metal or vanadium(V) oxide (V205) is used as a catalyst, and the reaction is carried out at approximately 500°C, even though this temperature decreases the value of the equilibrium constant for this exothermic reaction. 

Most of the sulfur dioxide in the troposphere is produced when coal and oil that contain high concentrations of sulfur are burned in power plants. The sulfur dioxide that forms is oxidized to sulfur trioxide (SO3) when it combines with either O2 or O3 in the atmosphere. When SO3 reacts with moisture in the air, sulfuric acid is formed. 

The oxides of sulfur create global pollution problems because they have longer lifetimes in the atmosphere than the oxides of nitrogen. Some of the SO2 and SO3 in the air originates from biological processes and from volcanoes, but much comes from the oxidation of sulfur in petroleum and in coal burned for fuel. If the sulfur is not removed from the fuel or the exhaust gas, SO2 enters the atmosphere as a stable but reactive pollutant. Further oxidation by radicals leads to sulfur trioxide ... 

Sulfates are discharged into water from mines and smelters, and from kraft pulp and paper mills, textile mills, and tanneries. Atmospheric sulfur dioxide, formed by the combustion of fossil fuels and by metallurgical roasting processes, may contribute to the sulfate content of surface waters. Sulfur trioxide, produced by the photolytic or catalytic oxidation of sulfur dioxide, combines with water vapor to form dilute sulfuric acid, which falls as acid rain . The environmental fate and transport of sulfate are inextricably linked to the physical and chemical processes active in the earth s sulfur cycle. 

Although some sulfuric acid is emitted directly by fuel-burning equipment, most of the sulfur in fuel is oxidized to and emitted as sulfur dioxide (S02). Sulfur dioxide contains sulfur in the ( + IV) oxidation state and dissolves in water to form sulfurous acid (H2S03), a relatively weak acid. In the presence of hydroxyl radicals in the atmosphere, sulfur dioxide is oxidized to sulfur trioxide (S03), which contains sulfur in the (+VI) oxidation state. Sulfur trioxide reacts with water to form H2S04, a strong acid. 

Sulfur oxides, in the form of sulfur dioxide (SO-) sulfur trioxide (SO-), sulfuric acid (H-SO ) and sulfates (SO ). Most of these pollutants are emitted to the atmosphere as sulfur dioxide, which is chemically converted by oxidation to SO- and sulfates in the air. Both particulate matter from smoke and sulfur oxides are known to be components in the smogs of London. They are mainly the result of combustion of coal. 

The major source of sulfur oxides in the atmosphere is the burning of sulfur-containing coal in power plants. As this type of coal burns in a furnace, sulfur dioxide gas, SO2, is produced. The SO2 escapes into the atmosphere, where it reacts with more oxygen to form sulfur trioxide, SO3. 

Alternately, on roasting FeS in the presence of limited air, the first product is ferrous sulfate. (Ferrous sulfate occurs as the mineral melanterite or copperas, from the atmospheric oxidation of native pyrites.) However, on roasting with fnrther air, it converts to ferric oxide pins sulfur dioxide and sulfur trioxide, depending npon the reaction conditions. 

---