Nitric acid in acid rain

The nitric acid in acid rain forms by a more complicated mechanism 4NO(g) + 2H20(i)... 

This Case Study is specifically concerned with the origin, dispersal and probable consequences of acid rain. Acid rain is caused by sulfur release, mainly as SO2, from the combustion of coal in thermal power stations used to generate electricity (Figure 2.1). The SO2 is later converted to sulfuric acid in the atmosphere (see Section 5). Other industries, for example the smelting of sulfide ores in metal extraction, also contribute to SO in the atmosphere. Power stations also release nitrogen oxides, and a proportion of these appear as nitric acid in acid rain, though the significance of this contribution will not be explored here. 

A more constrained opportunity for nitrate bioremediation arose at the US-DoE Weldon Spring Site near St. Louis, Missouri. This site had been a uranium and thorium processing faciUty, and treatment of the metal had involved nitric acid. The wastestream, known as raffinate, was discharged to surface inpoundments and neutralized with lime to precipitate the metals. Two pits had nitrate levels that requited treatment before discharge, but heavy rains in 1993 threatened to cause the pits to overflow. Bioremediation by the addition of calcium acetate as a carbon source successfully treated more than 19 million liters of water at a reasonable cost (75). 

In the eastern United States, acid rain consists of 65% sulfuric acid, 30% nitric acid, and 5% other acids. In the West, windblown alkaline dusts buffer the acidity in rains occurring over many rural areas, whereas in urban areas 80% of the acidity is due to nitric acid (28). Average pH in rainfall over the eastern United States for the period April 1979-March 1980 was less than 5.0, with some areas less than pH 4.2 (29). The lowest annual pH recorded was 3.78 at De Bilt, The Netherlands, in 1967, and the lowest in an individual rainfall was 2.4 at Pitlochry, Scotland, on April li) 1974 (30). 

Nitric oxide (NO) is a minor but villainous component of the atmosphere. It is involved in the formation of both smog (Chapter 11) and acid rain (Chapter 14). You may be surprised to learn that small amounts of NO are also produced in the human body, where it has a generally beneficial effect. In particular, it has the ability to dilate blood vessels, lowering blood pressure and reducing the likelihood of strokes or heart attacks. Beyond that, NO is effective in treating what television commercials refer to as erectile dysfunction it increases blood flow to the penis. 

Neutron-to-proton ratio, 29-30 Newton, 457,635 Newton, Isaac, 136 Nickel hydroxide, 78 Nicotinic acid, 364-365 NIMBY syndrome, 526 Nitric acid acid rain and, 400 acid strength of, 567 commercial use, 76 copper penny dissolving in, 570 production, 570-571... 

Nitric acid occurs naturally, in traces, in the atmosphere in rain w from the electrical discharge of lightning and from nuclear expins. Indeed, the natural nitrates of the world have probably been formed by the action of naturally occurring nitric acid to the extent of 4-6 lbs of combined nitrogen per acre (Ref 30)... 

Acid rain affects plants by changing the conditions in the soil. For example, nitric acid deposits nitrates, which fertilize the land. The nitrates allow fast-growing weeds such as quack grass to replace valuable prairie species. If these species were to become extinct, their genetic material would no longer be available for agricultural research. 

All of these species are very soluble in a rain or cloud drop and are an important source of atmospheric aerosols. For ammonia and ammonium, the condensed phases (I and s) represent approximately two-thirds of the total atmospheric burden, whereas for nitric acid and nitrates, about two-thirds is in the gas phase (Soderlund and Svensson, 1976). 

Similarly, SO2 and SO3 (SOJ compounds are produced in combustion by the oxidation of sulfur compounds within the fuel source. SO , emitted into the atmosphere can be incorporated into aerosol particles and wet-deposited as corrosive sulfuric acid. Both NO , and SO , emissions contribute to acid rain content from wet deposition, due to their participation in the formation of nitric and sulfuric acid, respectively. 

N02 plays a major role in the chemical reactions which generate photochemical smog and ground-level ozone, as well as contributes to the acid rain effect. Nitrogen dioxide is a strong oxidizing agent, which reacts in the air to form corrosive nitric acid, as well as... 

According to Summers and Chang from NASA s Ames Research Center, Moffett Field (1993), the oxidation of Fe2+ to Fe3+ provided a possibility for the reduction of nitrites and nitrates to ammonia. This reaction would have been of great importance, as NH3 is required in many syntheses of biogenesis precursors. The authors assume that nitrogen was converted to NO in a non-reducing atmosphere, and thence to nitrous and nitric acids. These substances entered the primeval oceans in the form of acid rain , and here underwent reduction to NH3 with the help of Fe2+, thus raising the pH of the oceans to 7.3. Temperatures above 298 K favoured this reaction, which can be written as ... 

The carbonic acid produced in Equation (6.5) is a proton donor, so the solution contains more solvated protons than hydroxide ions, resulting in rain that is (overall) an acid. To make the risk of pollution worse, acid rain in fact contains a mixture of several water-borne acids, principally nitric acid, HNO3 (from nitrous oxide in water), and sulphurous acid, H2SO3 (an aqueous solution of sulphur dioxide). 

The toxicity characteristic leaching procedure may be subject to misinterpretation if the compounds under investigation are not included in the methods development or the list of contaminants leading to the potential for technically invalid results. However, an alternative procedure, the synthetic precipitation leaching procedure (SPLP, EPA SW-846 Method 1312) may be appropriate. This procedure is applicable for materials where the leaching potential due to normal rainfall is to be determined. Instead of the leachate simulating acetic acid mixture, nitric and sulfuric acids are utilized in an effort to simulate the acid rains resulting from airborne nitric and sulfuric oxides. 

Acid rain. Lakes in some areas of the world are now registering very low pH s because of excess acidity in rain. This was first noticed in Scandinavia and is now prevalent in eastern Canada and the northeastern U.S. Normal rainfall is 5.6 (because of CO2 in the air forming H2CO3). However, excessive use of fossil fuels (especially coal) with high sulfur and nitrogen content cause sulfuric and nitric acids in the atmosphere from the sulfur dioxide and nitrogen oxide products of combustion. Some rain in the Adirondack Mountains of upper New York State has been measured with a pH of 3.0. This problem is not specific to the chemical industry but should be of concern to all of us. 

This is an extremely important reaction to which we wiU refer throughout this book. It is responsible for all NO, formation in the atmosphere (the brown color of the air over large cities) as well as nitric acid and acid rain. This reaction only occurs in high-temperature combustion processes and in lightning bolts, and it occurs in automobile engines by free-radical chain reaction steps, which will be the subject of Chapter 10. It is removed from the automobile exhaust in the automotive catalytic converter, which wiU be considered in Chapter 7. 

Nitric acid is very soluble in water, so it dissolves in rain and other forms of precipitation and is carried to Earth s surface in the form of acid deposition. 

One reason that the term acid deposition is preferred to the term acid rain is that sulfuric and nitric acid formed by the processes described may return to Earth s surface in either a wet or a dry form. Wet deposition consists of acids dissolved in water, as occurs in acid rain or acid snow. Dry deposition occurs when acids or nonme-tallic oxides remain in gaseous form or adhere to solid particles, on which they are carried to the ground. About half of the components of acid deposition fall back to Earth in each of these two forms, wet and dry. 

The emission of toxic gases, sulfur oxides (80, ), and nitric oxides (NO ) from industrial plants has become a serious problem in many countries. Fig. 1 shows the sources of 80 and NO c emission, which are recognized as the origin of dry and wet deposition known as acid rain [1]. 

Fig. 1 also shows the chemical reaction mechanism of 80, and NO c in air for producing acid rain [2]. The radicals (O, OH, and HO2) produced in air play an important role in oxidizing 80, and to produce sulfuric acid and nitric acid, which are the main components of acid rain. 8ome of these reactions also occur in a reaction chamber of electron beam treatment of flue gas. 

Liming an acidic lake is similar to the process many people use to maintain a pH balance in their soil for lawn maintenance. Plants have an optimum pH range in which they strive. Acidic conditions often develop in soils for several reasons. Rain tends to leach away basic ions, weak organic acids develop from the carbon dioxide produced by decaying organic matter, and strong acids, such as nitric acid, can form when ammonium fertilizers oxidize. To neutralize these acids, different forms of lime such as quicklime, CaO, and slaked lime, Ca(OH)2, are used to neutralize the acid and increase the pH of the soil. Table 13.9 shows how much fertilizer is wasted when applied to... 

The principal cause of acid rain is the combustion of fossil fuels that produce sulfur and nitrogen emissions. The primary sources are electrical power plants, automobiles, and smelters. Power plants produce most of the sulfur emissions and automobiles most of the nitrogen emissions. Other sources of acid rain include nitrogen fertilizers, jet aircraft, and industrial emissions. Just as in our discussion of ozone, numerous reactions are involved in the formation of acid rain. The process can be understood by considering the transformation of sulfur and nitrogen oxides into their respective acidic forms sulfuric acid and nitric acid. Sulfur, present up to a few percent in fuels such as coal, is converted to sulfur dioxide when the fuel is burned. The sulfur dioxide reacts with water to produce sulfurous acid, H,SO ,, that is then oxidized to sulfuric... 

Acid rain arises from the oxidation of S02 and N02 in the troposphere to form sulfuric and nitric acids, as well as other species, which are subsequently deposited at the earth s surface, either in precipitation (wet deposition) or in dry form (dry deposition). The contribution of organic acids has also been recognized recently (see Chapter 8). These oxidation and deposition processes can occur over relatively short distances from the primary pollutant sources or at distances of a fOOO km or more. Thus both short-range and long-range transport must be considered. 

While nitric acid is one of the major contributors to acid deposition (more colloquially acid rain ), we treat its chemistry separately from that of sulfuric and organic acids discussed in the following chapter. The reason for treating it first is that the chemistry of... 

---