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Ozone Chemistry

상태와 변화2016. 6. 27. 14:05

   

The Physics and Chemistry of Ozone

1.0 Introduction

The ozone molecule consists of three oxygen atoms that are bound together (triatomic oxygen, or O3). Unlike the form of oxygen that is a major constituent of air (diatomic oxygen, or O2), ozone is a powerful oxidizing agent. Ozone reacts with some gases, such as nitric oxide or NO, and with some surfaces, such as dust particles, leaves, and biological membranes. These reactions can damage living cells, such as those present in the linings of the human lungs. Exposure has been associated with several adverse health effects, such as aggravation of asthma and decreased lung function.

Ozone was first observed in the Los Angeles area in the 1940s. The ozone that the ARB regulates as an air pollutant is mainly produced close to ground (tropospheric ozone), where people live, exercise, and breathe. A layer of ozone high up in the atmosphere, called stratospheric ozone, reduces the amount of ultraviolet light entering the earth's atmosphere. Without the protection of the stratospheric ozone layer, plant and animal life would be seriously harmed. In this document, 'ozone' refers to tropospheric ozone unless otherwise specified.

Most of the ozone in California's air results from reactions between substances emitted from vehicles, industrial plants, consumer products, and vegetation. These reactions involve volatile organic compounds (VOCs, which the ARB also refers to as reactive organic gases or ROG) and oxides of nitrogen (NOx) in the presence of sunlight. As a photochemical pollutant, ozone is formed only during daylight hours under appropriate conditions, but is destroyed throughout the day and night. Therefore, ozone concentrations vary depending upon both the time of day and the location. Ozone concentrations are higher on hot, sunny, calm days. In metropolitan areas of California, ozone concentrations frequently exceed regulatory standards during the summer.

From the 1950s into the 1970s, California had the highest ozone concentrations in the world, with hourly average concentrations in Los Angeles peaking over 0.5 ppm and frequent "smog alerts". In the early 1970s, the ARB initiated emission control strategies that provided for concurrent and continuing reductions of both NOx and VOC from mobile sources and, in conjunction with the local air districts, stationary and area sources. Since then, peak ozone concentrations have decreased by more than 60 percent and smog alerts no longer occur in the Los Angeles area, despite more than a 35 percent increase in population and almost a doubling in vehicle miles traveled. However, most Californians still live in areas that do not attain the State's health-based standard (0.09 ppm for one hour) for ozone in ambient air.

This chapter discusses the processes by which ozone is formed and removed, background ozone, the role of weather, and spatial and temporal variations in ozone concentrations. In addition, this chapter includes discussions of research that the ARB has been conducting in the following areas that affect ozone concentrations: reactivity, weekend/weekday effect, and biogenic emissions. Subsequent sections of this chapter include ARB websites for more information. The ARB also conducts more general research in atmospheric processes that affect air pollution; information is available at http://www.arb.ca.gov/research/apr/past/atmospheric.htm#Projects .  For more extensive general information on the physics and chemistry of ozone, the reader is referred to Finlayson-Pitts and Pitts (2000), and Seinfeld and Pandis (1998).

1.1 Formation and Removal of Tropospheric Ozone

The formation of ozone in the troposphere is a complex process involving the reactions of hundreds of precursors. The key elements, as summarized in Finlayson-Pitts and Pitts (2000), and in Seinfeld and Pandis (1998), are discussed below.

1.1.1 Nitrogen Cycle and the Photostationary-State Relationship for Ozone

The formation of ozone in the troposphere results from only one known reaction: addition of atomic oxygen (O) to molecular oxygen (O2) in the presence of a third "body" (M). [M is any "body" with mass, primarily nitrogen or oxygen molecules, but also particles, trace gas molecules, and surfaces of large objects. M absorbs energy from the reaction as heat; without this absorption, the combining of O and O2 into O3 cannot be completed.]

O + O2 + M à O3 + M                    (1)

The oxygen atoms are produced primarily from photolysis of NO2 by the ultraviolet portion of solar radiation (hn).

NO2 + hn à NO + O                       (2)

Reaction 3 converts ozone back to oxygen and NO back to NO2, completing the "nitrogen cycle."

O3 + NO à NO2 + O2                            (3)

Reactions 1 and 3 are comparatively fast. Therefore, the slower photolysis reaction 2 is usually the rate-limiting reaction for the nitrogen cycle and the reason why ozone is not formed appreciably at night. It is also one of the reasons why ozone concentrations are high during the summer months, when temperatures are high and solar radiation is intense. The cycle time for the three reactions described above is only a few minutes. Ozone accumulates over several hours, depending on emission rates and meteorological conditions. Therefore, the nitrogen cycle operates fast enough to maintain a close approximation to the following photostationary-state equation derived from the above reactions.

[O3]photostationary-state = (k2/k3) x [NO2]/[NO]     (the brackets denote concentration)

The ratio of the rate constants for reactions 2 and 3, (k2/k3), is about 1:100. Assuming equilibrium could be reached in the ambient air and assuming typical urban pollution concentrations, a NO2 to NO ratio of 10:1 would be needed to generate about 0.1 ppm of ozone (a violation of the state one-hour ozone standard [0.09 ppm]). In contrast, the NO2 to NO emission ratio is approximately 1:10; therefore, the nitrogen cycle by itself does not generate the high ozone concentrations observed in urban areas. The net effect of the nitrogen cycle is neither to generate nor destroy ozone molecules. Therefore, for ozone to accumulate according to the photostationary-state equation, an additional pathway is needed to convert NO to NO2; one that will not destroy ozone. The photochemical oxidation of VOCs, such as hydrocarbons and aldehydes, provides that pathway.

1.1.2 The VOC Oxidation Cycle

Hydrocarbons and other VOCs are oxidized in the atmosphere by a series of reactions to form carbon monoxide (CO), carbon dioxide (CO2) and water (H2O). Intermediate steps in this overall oxidation process typically involve cyclic stages driven by hydroxyl radical (OH) attack on the parent hydrocarbon, on partially oxidized intermediate compounds, and on other VOCs. The Hydroxyl radical is ever-present in the ambient air; it is formed by photolysis from ozone in the presence of water vapor, and also from nitrous acid, hydrogen peroxide, and other sources. In the sequence shown below, R can be hydrogen or virtually any organic fragment. The oxidation process usually starts with reaction 4, from OH attack on a hydrocarbon or other VOC:

RH + OH à H2O + R                     (4)

This is followed by reaction with oxygen in the air to generate the peroxy radical (RO2).

R + O2 + M à RO2 + M                  (5)

The key reaction in the VOC oxidation cycle is the conversion of NO to NO2. This takes place through the fast radical transfer reaction with NO.

RO2 + NO à NO2 + RO                 (6)

R can also be generated by photolysis, which usually involves only VOCs with molecules containing the carbonyl (C=O) bond. The simplest VOC molecule that contains the carbonyl bond is formaldehyde (HCHO). Because formaldehyde enters into several types of reactions of importance for understanding ozone formation and removal, we will use it to help illustrate these reactions. The oxidation cycle for formaldehyde can be written in the following sequence of reactions.

OH + HCHO à H2O + HCO         (7)

HCO + O2 à HO2 + CO                 (8)

HO2 + NO à NO2 + OH                 (9)

Hydroperoxyl radical (HO2) is generated by reaction 8, and the hydroxyl radical (consumed in reaction 7) returns in reaction 9 to complete the cycle. In addition, reaction 9 produces the NO2 required for ozone formation, as described above. Also, the carbon monoxide (CO) generated by reaction 8 can react like an organic molecule to yield another hydroperoxyl radical.

OH + CO à H + CO2                           (10)

H + O2 + M à HO2 + M                  (11)

Another component that formaldehyde provides for smog formation is a source of hydrogen radicals.

HCHO + hn à H + HCO               (12)

The hydrogen atom (H) and formyl radical (HCO) produced by this photolysis reaction yield two hydroperoxyl radicals via reaction with oxygen, as shown in reactions 8 and 11.

The reactions above comprise the simplest VOC oxidation cycle. Actually, hundreds of VOC species participate in thousands of similar reactions.

1.1.3 The Nitrogen Dioxide and Radical Sink Reaction

Another reaction is central to a basic understanding of ozone formation: the NO2 plus radical sink reaction that forms nitric acid.

NO2 + OH + M à HNO3 + M         (13)

The previous discussion can be used to explain the typical pattern of ozone concentrations found in the urban atmosphere. Nitric oxide concentrations are relatively high in the early morning because the free radicals needed to convert the NOx emissions (which are primarily NO) to NO2 are not yet present in sufficient quantities. After sunrise, photolysis of formaldehyde (reaction 12) and other compounds starts the VOC oxidation cycle for the hundreds of organic gases present in the atmosphere. Subsequent NO to NO2 conversion by the peroxy radical (reaction 6) results in NO2 becoming the dominant NOx species. When the NO2 to NO ratio becomes large enough, ozone builds up. In the South Coast Air Basin (Los Angeles area), the highest ozone concentrations are observed in the San Bernardino Mountains, many miles downwind from the highest concentration of emission sources (freeways, power generating facilities, and oil refineries along the coast), because the reactions involving the organic gases are relatively slow. Meanwhile, NO2 concentrations decrease via the sink reaction 13.

Winds disperse and dilute both NOx and ozone. During the day, NOx is also diluted by the diurnal rising of the inversion layer, allowing for more mixing (see section 1.4 for further discussion). For ozone, however, the deepening mixing layer may cause its concentration to decrease on some days and increase on others. Although increased mixing almost always dilutes NOx, the effect of increased mixing on ozone concentrations depends upon whether higher concentrations of ozone are present aloft. Ozone that is trapped above the inversion layer overnight is available to increase the concentrations of ozone generated by the following day's emissions.

During the night, NO and ozone combine to form NO2 and oxygen via reaction 3 until either the NO or ozone is consumed. Nitrous acid or HONO is also present at night in polluted ambient air in California. Nitrous acid is produced from NO2 and water, and is also emitted from various combustion sources. Its levels are low during the day because sunlight breaks it down rapidly. At sunrise, sunlight causes gas-phase HONO to react rapidly to provide NO and OH, two key reactants in the formation of ozone. In this way, they help initiate ozone formation in the morning by being available to react with VOCs as soon as their emissions increase due to an increase in human activity.

Nitric acid (HNO3) was once thought to be a permanent sink for NOx and for radicals. However, nitric acid on surfaces may react with NO to regenerate NO2, which would increase the ozone-forming potential of NOx emissions.

   

1.1.4 Ratio of Volatile Organic Compounds to Nitrogen Oxides in Ambient Air

Although VOCs are necessary to generate high concentrations of ozone, NOx emissions can be the determining factor in the peak ozone concentrations observed in many locations (Chameides, 1992; National Research Council, 1991). VOCs are emitted from both natural and anthropogenic sources. Statewide, natural VOC sources dominate, primarily from vegetation. However, in urban and suburban areas, anthropogenic VOC emissions dominate and, in conjunction with anthropogenic NOx emissions, lead to the peak concentrations of ozone observed in urban areas and areas downwind of major urban areas.

The relative balance of VOCs and NOx at a particular location helps to determine whether the NOx behaves as a net ozone generator or a net ozone inhibitor. When the VOC/ NOx ratio in the ambient air is low (NOx is plentiful relative to VOC), NOx tends to inhibit ozone formation. In such cases, the amount of VOCs tends to limit the amount of ozone formed, and the ozone formation is called "VOC-limited". When the VOC/ NOx ratio is high (VOC is plentiful relative to NOx), NOx tends to generate ozone. In such cases, the amount of NOx tends to limit the amount of ozone formed, and ozone formation is called "NOx -limited". The VOC/ NOx ratio can differ substantially by location and time-of-day within a geographic area. Furthermore, the VOC/ NOx ratio measured near the ground might not represent the ratio that prevails in the air above the ground where most of the tropospheric ozone is generated.

   

1.1.5 Photochemical Reactivity

Photochemical reactivity, or reactivity, is a term used in the context of air quality management to describe a VOC's ability to react (participate in photochemical reactions) to form ozone in the atmosphere. Different VOCs react at different rates. The more reactive a VOC, the greater potential it has to form ozone. Examples of the more reactive VOCs in California's atmosphere include propene, m-xylene, ethene, and formaldehyde. The ARB has helped to pioneer an approach to ozone control that considers the reactivity of each VOC constituent. In California's urban areas, ozone formation tends to be limited by the availability of VOCs. Therefore, the reactivity-based regulatory approach has been applied in conjunction with reduction of NOx emissions. Reactivity-based regulations promote the control of those VOCs that form ozone most effectively, thereby guiding the affected industries (such as manufacturers of motor vehicle and consumer product formulators that use solvents) to choose the most cost-effective processes and designs to reduce VOC emissions. Further information is available from the ARB website, http://www.arb.ca.gov/research/reactivity/reactivityresearch.htm.

1.2 Background Ozone Concentrations in California

   

Contributions to background ground-level ozone concentrations include downward mixing of ozone from the stratosphere, and ozone formation due to photochemical reactions of locally emitted natural precursors. Lightning, wildfires, and transport are additional factors.

Although little mixing occurs between the troposphere and stratosphere, stratospheric ozone intrusion occasionally causes localized ozone increases, especially at high mountain locations. Most of this intrusion is due to "tropopause folding", which results from strong storms that draw stratospheric air down into the troposphere. In California, this tends to occur in spring. Because stable, stagnant conditions are necessary to support high ozone concentrations in urban California, this process generally does not contribute significantly to peak ozone concentrations. Stratospheric ozone intrusion is also due to general stratospheric subsidence. On a global basis, California is particularly prone to springtime stratospheric ozone intrusion from this process. However, this process is a relatively minor contributor to surface ozone concentrations in California, especially in the summer when ozone concentrations tend to be highest.

Another process leading to ground-level ozone arises from photochemical reactions involving natural precursors. Plants emit VOCs (see section 1.3), and soil microbes produce NOx that is vented into the air. Small amounts of NOx are also emitted from crops, apparently related to fertilizer application. Natural precursors may react with anthropogenic precursors to produce ozone concentrations that are of ambiguous origin. Where vegetation produces large amounts of VOCs, if anthropogenic NOx is also present, significant amounts of ozone can be produced.

Lightning contributes to the formation of ozone by heating and ionizing the air along the path of the discharge, thus forming the ozone precursor NOx. However, lightning tends to occur when meteorological conditions are not conducive to high ozone concentrations. Wildfires also contribute to ozone formation by producing NOx from combustion, and by distilling VOCs from vegetation. However, wildfires in California are not a major contributor to ozone pollution.

Finally, transport from outside of California contributes to in-state ozone concentrations. Cities in neighboring states and Mexico emit ozone precursors that impact California. In addition, urban plumes can be lofted high enough into the atmosphere to be entrained in global circulation and transported thousands of miles. In particular, ozone due to emissions in Asia, reaches California in springtime. However, this transport is not a major contributor to peak ozone concentrations in California because downward mixing of Asian ozone to the surface is precluded by the strong surface inversion usually present during high ozone episodes. Also, periods of effective long-range transport are generally restricted to spring, while high ozone concentrations due to local sources in California tend to occur in late summer and fall.

1.3 Effect of Vegetation on Ozone Concentrations

California's varied ecosystems interact with emissions related to human activity to influence ozone concentrations. Certain desert species, oaks, and pines emit substantial amounts of highly reactive VOCs, called biogenic emissions. Vegetation can either increase or decrease the ambient ozone concentration as the result of complex processes briefly described below.

Vegetation can reduce ozone concentrations by providing cooling and by removing pollutants. The shade provided by trees lowers ozone concentrations in several ways. It reduces the pollutant emissions from many sources (such as less evaporation of fuel from cooler parked vehicles). By cooling homes and offices, tree shade lowers emissions associated with electricity generation because less power is needed for air conditioning. In addition, cooling reduces the speed of chemical reactions in ambient air that lead to the formation of ozone.

Vegetation can also enhance the removal of ozone through deposition on plant surfaces. The surfaces of leaves and pine needles allow for deposition of ozone and NO2. Several different factors affect pollutant removal, such as how long a parcel of air is in contact with the leaf, and the total leaf area available for deposition. Also, rain tends to reduce ambient ozone concentrations by washing out atmospheric gases as well as gases deposited on leaves and needles.

   

Other processes involving vegetation can lead to higher concentrations of ozone. For example, trees and other types of vegetation emit biogenic VOCs, such as isoprene, pinenes, and terpenoid compounds. These biogenic VOCs can react with NOx emitted from sources such as cars and power plants to form ozone. Many biogenic VOCs are highly reactive (i.e., especially efficient in reacting to form ozone); some VOCs are even more efficient in forming ozone than those emitted from cars and power plants. In addition, VOCs can be emitted from decomposing leaves.

To help understand the complex mechanisms by which vegetation influences ambient ozone concentrations, the ARB established a "Biogenic Working Group" (BWG). The BWG has developed vegetation maps, leaf biomass databases, emission factors, and a California-specific "biogenic emissions inventory through geographic information systems" (BEIGIS) that has satisfactorily accounted for observed ambient ozone concentrations. The information developed by the BWG will help the ARB to better model ozone formation, and to better determine the relative importance of VOC and NOx control. Additional information is available from the ARB website, http://www.arb.ca.gov/research/ecosys/biogenic/biogenic.htm.

 1.4 Role of Weather in Ozone Air Quality

In the troposphere, the air is usually warmest near the ground. Warm air has a tendency to rise and cold air to sink, causing the air to mix, which disperses ground-level pollutants. However, if cooler air gets layered beneath warm air, no mixing occurs -- the air is stable or stagnant. The region in which temperature is so inverted is called an inversion layer. One type of inversion occurs frequently several thousand feet above the ground and limits the vertical dispersion of pollutants during the daytime. Another type of inversion occurs on most evenings very near the ground and limits the vertical dispersion of pollutants to a few hundred feet during the night. Pollutants released within an inversion tend to get trapped there. When the top of the daytime inversion is especially low [in elevation], people can be exposed to high ozone concentrations. Mountain chains, such as those downwind of California's coastal cities and the Central Valley, help to trap air and enhance the air quality impact of inversions. Cooler air draining into the state's valleys and 'air basins' also enhances inversion formation.

The direction and strength of the wind also affect ozone concentrations. Based on worldwide climate patterns, western coasts at California's latitude tend to have high-pressure areas over them, especially in summer. By preventing the formation of storms, and by promoting the sinking of very warm air, these high-pressure areas are associated with light winds and temperature inversions, both of which limit dispersion of pollutants.

Because tropospheric ozone forms as a result of reactions involving other pollutants, the highest concentrations tend to occur in the afternoon. The photochemical reactions that create ozone generally require a few hours (see section 1.1) after the emissions of substantial VOC emissions, and are most effective when sunlight is intense and air temperatures are warm. Ozone concentrations in California are usually highest in the summer. The prevailing daytime winds in summer are on-shore, bringing relatively clean air from over the ocean to the immediate coastal areas, but carrying emissions of ozone precursors further inland. With the climatically favored clear skies and temperature inversions that limit the vertical dispersion of pollutants, these emissions are converted into ozone, with the highest concentrations tending to occur at distances a few tens of miles downwind of urban centers (ARB 2002).

During the periods of the year when the sunlight is most intense, much of California experiences a high frequency of inversions, relatively low inversion heights, and low wind and rainfall. As a result, no other State has more days per year with such a high potential for unhealthy ozone concentrations.

Additional information on the effects of weather on air pollution is available from the following textbooks:

Ahrens, C.D. (1994), Meteorology Today, West Publishing Co., St. Paul, MN.

Neiburger, M., Edinger, J.G., and Bonner, W.D. (1982), Understanding our Atmospheric Environment, W.H. Freeman & Co., San Francisco, CA.

 1.5 Spatial and Temporal Variations of Ozone Concentrations

 1.5.1 Spatial Variations of Ozone Concentrations

   

Ambient ozone concentrations can vary from non-detectable near combustion sources, where nitric oxide (NO) is emitted into the air, to several hundreds parts per billion (ppb) of air in areas downwind of VOC and NOx emissions. In continental areas far removed from direct anthropogenic effects, ozone concentrations are generally 20 - 40 ppb. In rural areas downwind of urban centers, ozone concentrations are higher, typically 50 - 80 ppb, but occasionally 100 - 200 ppb. In urban and suburban areas, ozone concentrations can be high (well over 100 ppb), but peak for at most a few hours before deposition and reaction with NO emissions cause ozone concentrations to decline (Finlayson- Pitts and Pitts 2000, Seinfeld and Pandis 1998, Chameides et al. 1992, Smith et al. 1997).

   

Ozone concentrations vary in complex ways due to its photochemical formation, its rapid destruction by NO, and the effects of differing VOC/ NOx ratios in air. A high ratio of NOx emissions to VOC emissions usually causes peak ozone concentrations to be higher and minimum concentrations to be lower, compared to background conditions. Peak ozone concentrations are usually highest downwind from urban centers. Light winds carry ozone from urban centers, and photochemical reactions create ozone from urban emissions of VOC and NOx. Also, away from sources of NOx emissions, less NO is available to destroy ozone. Due to the time needed for transport, these peak ozone concentrations in downwind areas tend to occur later in the day compared to peak ozone concentrations in urban areas.

Due to the lack of ozone-destroying NO, ozone in rural areas tends to persist at night, rather than declining to the low concentrations (<30 ppb) typical in urban areas and areas downwind of major urban areas, that have plenty of fresh NO emissions. Ratios of peak ozone to average ozone concentrations are typically highest in urban areas and lowest in remote areas (ARB 2002). Within the ground-based inversions that usually persist through the night, ozone concentrations can be very low. In urban areas, emissions of NO near the ground commonly reduce ozone below 30 ppb. In rural areas, however, NO emissions are less prevalent and nighttime ozone may persist well above 30 ppb.

 1.5.2 Temporal Variations in Ozone Concentrations

Ambient ozone concentrations tend to vary temporally in phase with human activity patterns, magnifying the resulting adverse health and welfare effects. Ambient ozone concentrations increase during the day when formation rates exceed destruction rates, and decline at night when formation processes are inactive. This diurnal variation in ozone depends on location, with the peaks being very high for relatively brief periods of time (an hour or two duration) in urban areas, and being low with relatively little diurnal variation in remote regions. In urban areas, peak ozone concentrations typically occur in the early afternoon, shortly after solar noon when the sun's rays are most intense, but persist into the later afternoon, particularly where transport is involved. Thus, the peak urban ozone period of the day can correspond with the time of day when people, especially children, tend to be active outdoors.

In addition to varying during the day, ozone concentrations vary during the week. In the 1960s, the highest ozone concentrations at many urban monitoring sites tended to occur on Thursdays. This pattern was believed to be due to the carryover of ozone and ozone precursors from one day to the next, resulting in an accumulation of ozone during the workweek. In the 1980s, the highest ozone concentrations at many sites tended to occur on Saturdays and the "ozone weekend effect" became a topic of discussion. Since then, the weekend effect has become prevalent at more urban monitoring locations and the peak ozone day of the week has shifted to Sunday. Although ozone concentrations have declined on all days of the week in response to emission controls, they have declined faster on weekdays than on weekends. Thus, the peak ozone period of the week now tends to coincide with the weekend, when more people tend to be outdoors and active than during the week.

The causes of the ozone weekend effect and its implications regarding ozone control strategies have not yet been resolved. Almost all of the available data represent conditions at ground level, where the destruction of ozone by fresh emissions of NO is a major factor controlling ozone concentration. However, most ozone is formed aloft, and the air quality models used to analyze ozone formation have not demonstrated the ability to represent the ozone-forming system aloft with sufficient realism. In addition, several potentially significant photochemical processes are yet to be fully incorporated in simulation models. These deficiencies leave unresolved this fundamental question: does the ozone weekend effect occur because more ozone is formed (aloft) on weekend, because more ozone is destroyed (at the surface) on weekdays, or because ozone formation is more efficient on weekends? More information may be obtained from the ARB website, http://www.arb.ca.gov/aqd/weekendeffect/weekendeffect.htm .

Ozone concentrations also vary seasonally. Ozone concentrations tend to be highest during the summer and early fall months. In areas where the coastal marine layer (cool, moist air) is prevalent during summer, the peak ozone season tends to be in the early fall. Additionally, as air pollution controls have reduced the emissions of ozone precursors and the reactivity of VOCs, ozone concentrations have declined faster during times of the year when temperatures and the amount of sunlight are less than during the summer. Thus, the peak ozone season corresponds with the period of the year when people tend to be most active outdoors.

Also, ozone concentrations can vary from year to year in response to meteorological conditions such as El Niño and other variations in global pressure systems that promote more or less dispersion of emissions than typical. Although peak ozone concentrations vary on a year-to-year basis, peak ozone concentrations in southern California have been declining on a long-term basis, as anthropogenic emissions of VOC and NOx have declined. However, since the advent of the industrial revolution, global background concentrations of ozone appear to be increasing (Finlayson-Pitts and Pitts, 2000). This increase has implications regarding the oxidative capability of the atmosphere and potentially global warming processes (ozone is a strong greenhouse gas but is present at relatively low concentrations). Further discussion of these topics is beyond the scope of this document.

1.6 References

   

Ahrens CD. 1994. Meteorology Today, West Publishing Co., St. Paul, MN.

Air Resources Board/Planning and Technical Support Division. 2002. California Ambient Air Quality Data – 1980 – 2001. Sacramento, CA.: December. Data CD Number: PTSD-02-017-CD

Chameides WL, Fehsenfeld F, Rodgers MO, Cardelino C, Martinez J, Parrish D, Lonneman W, Lawson DR, Rasmussen RA, Zimmerman P, Greenberg J, Middleton P, Wang T. 1992. Ozone Precursor Relationships in the Ambient Atmosphere. Journal of Geophysical Research 97:6037-55.

Finlayson-Pitts BJ, Pitts JN. 2000. Chemistry of the Upper and Lower Atmosphere - Theory, Experiments, and Applications. Academic Press, San Diego, CA.

National Research Council. 1991. Rethinking the Ozone Problem in Urban and Regional Air Pollution, National Academy Press, Washington, DC.

Neiburger M, Edinger JG, Bonner WD. 1982. Understanding our Atmospheric Environment. W.H. Freeman & Co., San Francisco, CA.

Seinfeld JH, Pandis SN. 1998. Atmospheric Chemistry and Physics - from Air Pollution to Climate Change. John Wiley and Sons, New York, NY.

Smith TB, Lehrman DE, Knuth WR, Johnson D. 1997. Monitoring in Ozone Transport Corridors. Final report prepared for ARB/RD (contract # 94-316), July.

Source:

California Environmental Protection Agency

Air Resources Board

and

Office of Environmental Health and Hazard Assessment

Additional Resources:

Review of the California Ambient Air Quality Standard for Ozone

   

출처: <http://www.fraqmd.org/ozonechemistry.htm>

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Ozonolysis

상태와 변화2016. 6. 27. 13:46

Ozonolysis

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Ozonolysis is an organic reaction where the unsaturated bonds of alkenes, alkynes, or azo compounds are cleaved with ozone. Alkenes and alkynes form organic compounds in which the multiple carbon–carbon bond has been replaced by a carbonyl group[1][2][3] while azo compounds form nitrosamines.[4] The outcome of the reaction depends on the type of multiple bond being oxidized and the work-up conditions.

Contents

 [hide

Ozonolysis of alkenes[edit]

Alkenes can be oxidized with ozone to form alcohols, aldehydes or ketones, or carboxylic acids. In a typical procedure, ozone is bubbled through a solution of the alkene in methanol at 78 °C until the solution takes on a characteristic blue color, which is due to unreacted ozone. This indicates complete consumption of the alkene. Alternatively, various other chemicals can be used as indicators of this endpoint by detecting the presence of ozone. If ozonolysis is performed by bubbling a stream of ozone-enriched oxygen through the reaction mixture, the gas that bubbles out can be directed through a potassium iodide solution. When the solution has stopped absorbing ozone, the ozone in the bubbles oxidizes the iodide to iodine, which can easily be observed by its violet color.[5] For closer control of the reaction itself, an indicator such as Sudan Red III can be added to the reaction mixture. Ozone reacts with this indicator more slowly than with the intended ozonolysis target. The ozonolysis of the indicator, which causes a noticeable color change, only occurs once the desired target has been consumed. If the substrate has two alkenes that react with ozone at different rates, one can choose an indicator whose own oxidation rate is intermediate between them, and therefore stop the reaction when only the most susceptible alkene in the substrate has reacted.[6] Otherwise, the presence of unreacted ozone in solution (seeing its blue color) or in the bubbles (via iodide detection) only indicates when all alkenes have reacted.

After completing the addition a reagent is then added to convert the intermediate ozonide to a carbonyl derivative. Reductive work-up conditions are far more commonly used than oxidative conditions. The use of triphenylphosphine, thiourea, zinc dust, or dimethyl sulfide produces aldehydes or ketones while the use of sodium borohydride produces alcohols. The use of hydrogen peroxide produces carboxylic acids. Recently, the use of amine N-oxides has been reported to produce aldehydes directly.[7] Other functional groups, such as benzyl ethers, can also be oxidized by ozone. It has been proposed that small amounts of acid may be generated during the reaction from oxidation of the solvent, so pyridine is sometimes used to buffer the reaction. Dichloromethane is often used as a 1:1 cosolvent to facilitate timely cleavage of the ozonide. Azelaic acid and pelargonic acids are produced from ozonolysis of oleic acid on an industrial scale.

An example is the ozonolysis of eugenol converting the terminal alkene to an aldehyde:[8]

By carefully controlling the reaction/workup conditions, unsymmetrical products can be generated from symmetrical alkenes:[9]

   

Reaction mechanism[edit]

Carbonyl oxide (Criegee zwitterion)

In the generally accepted mechanism proposed by Rudolf Criegee in 1953,[10][11][12] the alkene and ozone form an intermediate molozonide in a 1,3-dipolar cycloaddition. Next, the molozonide reverts to its corresponding carbonyl oxide (also called the Criegee intermediate or Criegee zwitterion) and aldehyde or ketone in a retro-1,3-dipolar cycloaddition. The oxide and aldehyde or ketone react again in a 1,3-dipolar cycloaddition or produce a relatively stable ozonide intermediate (a trioxolane).

Evidence for this mechanism is found in isotopic labeling. When 17O-labelled benzaldehyde reacts with carbonyl oxides, the label ends up exclusively in the ether linkage of the ozonide.[13] There is still dispute over whether the molozonide collapses via a concerted or radical process; this may also exhibit a substrate dependence.

History[edit]

Ozonolysis was invented by Christian Friedrich Schönbein in 1840. Before the advent of modern spectroscopic techniques, it was an important method for determining the structure of organic molecules. Chemists would ozonize an unknown alkene to yield smaller and more readily identifiable fragments. The ozonolysis of alkenes is sometimes referred to as "Harries ozonolysis", because some attribute this reaction to Carl Dietrich Harries.[14]

Ozonolysis of alkynes[edit]

Ozonolysis of alkynes generally gives an acid anhydride or diketone product,[15] not complete fragmentation as for alkenes. A reducing agent is not needed for these reactions. The exact mechanism is not completely known.[16] If the reaction is performed in the presence of water, the anhydride hydrolyzes to give two carboxylic acids.

Ozonolysis of elastomers[edit]

The method was used to confirm the structural repeat unit in natural rubber as isoprene. It is also a serious problem, known as "ozone cracking" where traces of the gas in an atmosphere will cut double bonds in susceptible elastomers, including natural rubber, polybutadiene, Styrene-butadiene and Nitrile rubber. Ozone cracking creates small cracks at right angles to the load in the surfaces exposed to the gas, the cracks growing steadily as attack continues. The rubber product must be under tension for crack growth to occur.

Ozone cracking in Natural rubber tubing

Ozone cracking is a form of stress corrosion cracking where active chemical species attack products of a susceptible material. Ozone cracking was once commonly seen in the sidewalls of tires but is now rare owing to the use of antiozonants. Other means of prevention include replacing susceptible rubbers with resistant elastomers such as polychloroprene, EPDM or Viton.

See also[edit]

References[edit]

   

출처: <https://en.wikipedia.org/wiki/Ozonolysis>

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Ozonolysis

상태와 변화2016. 6. 27. 13:45

Ozonolysis

Table of contents

  • Introduction
  • Reaction Mechanism
  • References
  • Problems
  • Ozonolysis is a method of oxidatively cleaving alkenes or alkynes using ozone (O 3  O3 ), a reactive allotrope of oxygen. The process allows for carbon-carbon double or triple bonds to be replaced by double bonds with oxygen. This reaction is often used to identify the structure of unknown alkenes. by breaking them down into smaller, more easily identifiable pieces. Ozonolysis also occurs naturally and would break down repeated units used in rubber and other polymers. On an industrial scale, azelaic acid and pelargonic acids are produced from ozonolysis.

    Introduction

    The gaseous ozone is first passed through the desired alkene solution in either methanol or dichloromethane. The first intermediate product is an ozonide molecule which is then further reduced to carbonyl products. This results in the breaking of the Carbon-Carbon double bond and is replaced by a Carbon-Oxygen double bond instead.

    Reaction Mechanism

    Step 1:

    The first step in the mechanism of ozonolysis is the initial electrophilic addition of ozone to the Carbon-Carbon double bond, which then form the molozonide intermediate.  Due to the unstable molozonide molecule, it continues further with the reaction and breaks apart to form a carbonyl and a carbonyl oxide molecule.

    Step 2:

       

    The carbonyl and the carbonyl oxide rearranges itself and reforms to create the stable ozonide intermediate. A reductive workup could then be performed to convert convert the ozonide molecule into the desired carbonyl products.

    References

  • Vollhardt, K., Schore, N. Organic Chemistry: Structure and Function. 5th ed. New York, NY: W. H. Freeman and Company, 2007.
  • Shore, N. Study Guide and Solutions Manual for Organic Chemistry. 5th ed. New York, NY: W.H. Freeman and Company, 2007.

    Problems

    Answers

       

    출처: <http://chemwiki.ucdavis.edu/Core/Organic_Chemistry/Hydrocarbons/Alkenes/Reactivity_of_Alkenes/Ozonolysis>

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Performance Catalytic Ozonation over the Carbosieve in the Removal of Toluene from Waste Air Stream

   

Mohammad Reza Samarghandi (PhD)a, Seyed Alireza Babaee (MSc)a, Mohammad Ahmadian (MSc)b, Ghorban Asgari (PhD)a, Farshid Ghorbani Shahna (PhD)c, and Ali Poormohammadi (MSc)d*

a Research Center for Health Sciences and Department of Environmental Engineering, School of Public Health, Hamadan University of Medical Sciences, Hamadan, Iran

b School of Public Health, Kermanshah University of Medical Sciences, Kermanshah, Iran

c Department of Occupational Health Engineering, School of Public Health and Research Center for Health Sciences, Hamadan University of Medical Sciences, Hamadan, Iran

d Social Development & Health Promotion Research Center, Kermanshah University of Medical Sciences, Kermanshah, Iran

* Correspondence: Ali Poormohammadi (MSc), E-mail: apoormohammadi000@yahoo.com

Received: 13 October 2013, Revised: 17 February 2014, Accepted: 17 March 2014, Available online: 06 April 2014

   

Abstract

Background: Toluene is a volatile organic compound, one of 189 hazardous air pollutants (HAPs) and the most important pollutant found in most industries and indoor environments; owing to its adverse health, toluene must be treated before being released into the environment.

Methods: In this research study, a continuous-flow system (including an air compressor, silica gel filters and activated charcoal, impinger, an ozone generation and a fixed bed reactor packed with the carbosieve in size 1.8-2.3 mm, specific surface: 972 m2/g,) was used. This glass reactor was 0.7 m in height; at a distance of 0.2 m from its bottom, a mesh plane was installed so as to hold the adsorbent. Moreover, 3 l/min oxygen passed through this system, 0.43 g/h ozone was prepared. The flow rate of waste airstream was 300 ml/min. The efficiency of this system for removal of toluene was compared under the same experimental conditions.

Results: Under similar conditions, performance of catalytic ozonation was better in toluene removal than that of ozonation and carbosieve alone. On average, increasing the removal efficiency was 45% at all concentrations. When carbosieve and ozone come together, their synergistic effects increased on toluene degradation.

Conclusions: Catalytic ozonation is a suitable, high-efficient and available method for removing toluene from various concentrations of waste air stream. This process due to the short contact time, low energy consuming and making use of cheap catalysts can be used as a novel process for removing various concentrations of volatile organic compounds.

Keywords: atalytic Ozonation, Volatile Organic Compounds, Carbosieve, Toluene

   

Introduction

Volatile Organic Compounds (VOCs) are a major group of air pollutants emitted from various sources and pollute the air. They contain more than 300 compounds such as oxygenated hydrocarbons, aromatic hydrocarbons and halogenated hydrocarbons1-3. Benzene, toluene, ethyl benzene, xylene (BTEX) compounds are the most important and common chemical compounds of aromatic hydrocarbons and are considered as indices of VOCs. They are abundantly found in cities and industrial areas and have been classified as toxic priority pollutants. Their major problem in the atmosphere is the possibility of cancer and production of "Air Toxic" 4,5. Toluene or methyl benzene is one of volatile aromatic compounds which is very similar to benzene, but less volatile. This compound has a methyl branch on a benzene ring. Toluene is transparent, colorless and volatile liquid with obnoxious odor. As a solvent, toluene is highly used in oils, paints, resins, detergents and glues and pastes. It is also used in gasoline, petrol and other aviation fuels to raise octane number.

According to ACGIH, toluene is one of 189 hazardous air pollutants and is a primacy and prioritized pollutant which has been classified in A4 group of carcinogenic substances6-8. Due to various environmental and health effects of this compound, different methods (including adsorption, thermal and catalytic oxidation and advanced oxidation processes) have been examined to remove it from waste air stream9,10. In comparison with conventional treatment methods, Advanced Oxidation Processes (AOPs) are suitable methods for degradation of toxic air pollutants. Degrading pollutants by AOPs is based on production of free active radicals that have high oxidative power and are capable of changing most organic compounds to minerals. The radicals by attaching molecules of organic substances and taking their hydrogen ion, convert these compounds to minerals, during one or some steps.

Catalytic ozonation process (COP) is a new method of single ozonation process (SOP) that has recently been taken into consideration in air pollution control industry. In this process, to improve SOP efficiency, various substances are used as catalysts to accelerate degradation process, increase reaction time and be sure of non-presence of ozone residues in exhaust air11-15. So far some catalysts such as activated carbon, silica gel, metal oxides and various resins have been used in catalytic ozonation process to remove toluene from polluted air16-18.

According to capabilities of various carbon adsorbents in treating air pollutants, carbosieve, a kind of carbon-based adsorbent which is produced as a result of pyrolysis of synthetic polymers or some of petroleum compounds with high porosity and specific surface area (BET) and is mostly used to adsorb volatile hydrocarbons19,20.

In this study, the carbosieve was used as a non-polar catalyst and adsorbent in catalytic ozonation process.

   

Methods

Experimental Pilot

This empirical laboratory study was carried out as a pilot scale from December 2012 to May 2013. A laboratory-scale pilot was designed and launched at Hamadan Environmental Chemistry Laboratory (Figure 1), western Iran. Toluene liquid with purity of 99.5% was prepared from German Merck Company. Air containing polluted gas and ozone gas entered bottom of a reactor with a continuous flow. Considering the aim of this study the reaction conditions were closer to the actual conditions thus a dynamic system with continuous flow was used. Contaminant gas in the first of the reactor enters into the bottom of the reactor and exits from the other side (Due to the absence of gas leaks in the system). To prevent condensation of contaminants in the reactor, all parts of the reactor was placed in isothermal chamber. Input air before entering to the bed enter to the converging chamber and after passing through reticulated plate and finally enter to the catalyst bed.

This glass reactor was 0.7 m in height; at a distance of 0.2 m from its bottom, a mesh plane was installed so as to hold the adsorbent. Required air was supplied by a compressor equipped with oil trap. After the pressure was adjusted, the air passed through a combined column of silica gel and activated charcoal in order to dry and remove any organic contamination. To prepare toluene-containing air in given concentrations, Standard Atmosphere Production method was used in a dynamic way with the aid of an impinger21. In this system, the air, produced by a compressor and dried as well as cleaned before, was divided into two branches; calibrated rotameter and needle valve were used to control carefully in the air stream in each branch so as to achieve certain concentrations. In one branch, toluene vapors entered air stream through impinger-bubbler (by keeping temperature of toluene constant) and in the other branch, there was pure stream of air. These two branches lead to a single branch in which a standard stream of air with the given concentration of toluene was created. The reactor was placed in the isothermal chamber for controlling temperature in the reactor. Our concept from constant pressure was atmospheric pressure in the laboratory environment. Dynamic method was used to create standard atmosphere. Inert and contaminant gas at determined concentration enter to the system with a regulated and specific ratio. This works was performed by maintain impinger temperature (Containing liquid toluene due to its vapor pressure) by a hot water bath. Besides for keeping a steady flow and to avoid concentration fluctuations a baffled mixing chamber was used before entering flow to the main reactor. However, in practice, only minor changes in concentration levels (a few ppm) was existed. Therefore, input and output load in the system was reported as removal efficiency.

Ozone was made using an ozone-making machine, ARDA, model COG-OM. In this generator, ozone is produced through creating electrical discharge with alternating current in a sluice in presence of oxygen. Oxygen required for the ozone generator was supplied by an oxygen-making machine, model PORSA VF-3 with high purity level and the ability to adjust oxygen injection level. The amount of ozone produced by an ozone generator was measured according to Iodometry method in the presence of 2% potassium iodide solution after 10 min of contact22,23. As 3 l/min oxygen passed through this system, 0.43 g/h ozone was prepared. In ozonation unit, ozone gas entered toluene-containing waste air stream; to prevent and reduce the probable fluctuations and to equalize and fix equilibrium, a baffled mixing chamber is used before the reactor which contains adsorbent bed. After current exits this mixing chamber, it enters carbosieve-containing reactor as a catalyst and non-polar adsorbent bed. Prior to experiments, carbosieve was placed in a in an oven for 2 h at 400 °C and was dried completely in order to remove all probable pollution. Carbosieve used in this study was purchased from Air Tools Co. in Tehran. Then the surface area was measured by BET method. Ten g of Carbosieve were used at each stage of the experiment. Although changes in pressure drop has not been measured before and after bed but the system was designed in such a way do not create the pressure drop in the input stream.

   

Sample Analysis

Toluene concentration was measured before and after experiments in an air stream using 1501 NMAM (NIOSH Manual Analytic Method) and gas-chromatography device, model SHIMADZU 2010, equipped with flame ionization detector (FID) with a column length of 60 m, column internal diameter of 0.25 mm, film thickness of 0.25 mm and temperature range of 50 to 180 °C according to temperature programming. Optimum analysis conditions of gas chromatography was prepared with injection site temperature of 200 °C, detector temperature of 250 °C, carrier gas flow of approximately 30 ml/min, hydrogen gas flow of 30 ml/min and air stream of about 300 ml/min 24,25. Toluene vapors collected with activated charcoal tube using sampling pump accordance with Method 150124. After extracting the samples in carbon disulfide 1 μL of extracted sample was injected into the GC in quick time. Experiments were performed in normal ambient temperature (27 ±2 °C) and desirable atmospheric pressure and ventilation. In order to assess the accuracy of the analysis method, was injected three times into the capillary column of gas chromatograph and their mean was reported as the amount of that parameter. The efficiency of carbosieve bed, single ozonation and catalytic ozonation were examined and compared separately.

   

   

Performance Catalytic Ozonation over the Carbosieve in the Removal of Toluene from Waste Air Stream | Samarghandi | Journal of Research in Health Sciences

http://jrhs.umsha.ac.ir/index.php/JRHS/article/view/1182/html

화면 캡처: 2016-05-13 오전 8:58

   

   

Figure 1: Schematic diagram of the experimental setup

Results

Efficiency of carbosieve bed

Parameters affecting system efficiency including air flow discharge entering the reactor, adsorbent bed size, ozone level and relative humidity were kept constant at 3 l/min, 15g, 0.43 g/h and 5% respectively; only system efficiency was examined on various concentrations of toluene in range of 20 to 200 ppm. As toluene concentration increased, bed saturation time and absorbent breakpoint decreased. Results of carbosieve efficiency of toluene removal are shown in Figure 2 (A).

Ozone efficiency

Figure 2(B) shows the removal efficiency of toluene from waste air stream by the single ozonation process separately and without the presence of carbosieve. In this step, experiments conducted in various concentrations of toluene in range of 20-200 ppm and only ozone gas with 3 1/min input of pure oxygen to ozone-making machine and production of 0.43 g/h ozone was used, also other variables affecting system efficiency were kept constant as before. In this step, as concentration increased from 20 to 200 ppm, toluene removal efficiency decreased. In 20 ppm of toluene in the reactor inlet, the removal efficiency reached to 31%. On the other hand, in 200 ppm of toluene in the reactor inlet, ozone efficiency was about 16%. Therefore, the highest efficiency of process was observed in toluene concentration equal to 20 ppm and lowest removal efficiency was in toluene concentration equal to 200 ppm.

Efficiency of catalytic ozonation

Results of efficiency of catalytic ozonation are shown in Figure 3, 4. In this step, experiment was performed under the same conditions and efficiency of catalytic ozonation was examined in terms of toluene output concentration and adsorbent break point. In this step, efficiency of catalytic ozonation was examined on various concentrations of toluene in range of 20-200 ppm. In 20 ppm of toluene, the efficiency of catalytic ozonation in removal of this compound reached about 16 ppm (80%). On the other hand, in 200 ppm of toluene was observed 155 ppm (77.5%). Therefore, by increasing toluene concentration from 20 to 200 ppm, toluene removal efficiency decreased. Moreover, carbosieve saturation and break point were occurred significantly later than single carbosieve system.

   

Figure 2: (A) Efficiency of carbosieve bed in removing toluene from waste air stream (B) Ozone efficiency (single ozonation) on removal of toluene from waste air stream

   

   

Performance Catalytic Ozonation over the Carbosieve in the Removal of Toluene from Waste Air Stream | Samarghandi | Journal of Research in Health Sciences

http://jrhs.umsha.ac.ir/index.php/JRHS/article/view/1182/html

화면 캡처: 2016-05-13 오전 9:01

   

   

   

Figure 3: Efficiency of catalytic ozonation in removal of toluene from waste air stream

   

   

Performance Catalytic Ozonation over the Carbosieve in the Removal of Toluene from Waste Air Stream | Samarghandi | Journal of Research in Health Sciences

http://jrhs.umsha.ac.ir/index.php/JRHS/article/view/1182/html

화면 캡처: 2016-05-13 오전 9:02

   

   

Figure 4: Comparison between times of toluene emergence in carbosieve system with COP process in the different concentrations

   

   

Performance Catalytic Ozonation over the Carbosieve in the Removal of Toluene from Waste Air Stream | Samarghandi | Journal of Research in Health Sciences

http://jrhs.umsha.ac.ir/index.php/JRHS/article/view/1182/html

화면 캡처: 2016-05-13 오전 9:03

   

   

Figure 5: A schematic of toluene decomposition in the catalytic ozonation over the carbosieve

   

   

Performance Catalytic Ozonation over the Carbosieve in the Removal of Toluene from Waste Air Stream | Samarghandi | Journal of Research in Health Sciences

http://jrhs.umsha.ac.ir/index.php/JRHS/article/view/1182/html

화면 캡처: 2016-05-13 오전 9:03

   

   

Discussion

This study investigated the efficiency of catalytic ozonation process in treating toluene-containing air as one of hazardous air pollutants. Toluene removal was examined separately on carbosieve bed, single ozonation and catalytic ozonation.

Results revealed that removal efficiency by SOP process was, on average, less than 23% at given concentrations; that is, as the concentration increased from 20 ppm at the beginning of the system to 200 ppm, removal efficiency by SOP process decreased from 31% to 16%. In a similar study by Mousavi et al. on removal of xylene from waste air stream, xylene removal efficiency by ozone gas was about 10% 26. On removal of volatile organic compounds (VOCs) using catalytic ozonation that removal efficiency of volatile organic compounds using only ozone was low and thus would result in production of harmful byproducts27. Besides, obtained results are in accordance with the findings of Alvarez et al. on comparison between catalytic ozonation and activated carbon adsorption/ozone- regeneration processes for wastewater treatment28.

Decreased efficiency by SOP process is due to ozone low ability to oxidize aromatic compounds and alkenes and low retention time necessary for complete reaction between ozone and toluene as a result of continuity of the system29. According to obtained results while using carbosieve alone as concentration increased from 20 ppm to 200 ppm, adsorbent break point in the reactor outlet decreased from 10 h to 3 h (Figure 5). Accordingly, adsorbent beds including carbosieve remove the pollutants available in the air passing through absorbent due to early saturation, especially at high concentrations, necessity to reclamation and most lack of change in the nature of pollutants that have be(A) Efficiency of carbosieve bed in removing toluene from waste air stream (B) Ozone efficiency (single ozonation) on removal of toluene from waste air streams hazardous to the environment, making use of absorbents alone may be impractical.

In the present study, to remove restrictions of SOP process and to adsorb over carbosieve, the combinations of these two methods were used. Results of this study indicate that catalytic ozonation has a significant efficiency compared with separate adsorption methods over carbosieve and SOP process. This advantage is show in Figure 4. Accordingly, as concentration increased from 20 to 200 ppm, absorption break point and removal of toluene from hybrid reactor decreased from 12 to 6 h, while this time was between 3 and 10 h for carbosieve. ThusEfficiency of catalytic ozonation in removal of toluene from waste air stream was higher in hybrid reactor output and COP process under similar laboratory conditions. For example, for concentration of 200 ppm, toluene discharge time increased by 50% compared to carbosieve bed; on average, efficiency in COP process increased by 45% at all concentrations compared with SOP. In carbosieve system, after the bed was saturated at reactor outlet, output toluene concentration was equal to input concentration, while in COP process concentration of output toluene was less than input concentration after saturation; it reflects that combining carbosieve and ozone systems strengthens the effect of them and thus results in more molecular degradation of toluene passing over bed. Xylene removal level increased 22% in COP process compared to activated charcoal and ozone26. Similarly, Wung et al. revealed that toluene removal level increased 20% and 40% in COP process in comparison with zeolite adsorption and MCM-41 respectively. Furthermore, efficiency of ozonation alone in removal nitrobenzene from aqueous solution was about 25% and while was used of COP, the process efficiency reached to about 70%; these results are consistent with results of this seA schematic of toluene decomposition in the catalytic ozonation over the carbosieve">27,30.

Since ozone is adsorbed over adsorbent, carbosieve adsorbs ozone which rapidly decomposes to activated oxygen atoms over adsorbent bed due to its instability. In other words, carbosieve acts as a catalyst and decomposes ozone into activated oxygen atoms. Having specific surface area and high porosity, carbosieve creates a surrounding bed; in addition to increasing contact surface and collision of toluene and ozone molecules, carbosieve increases retention time for reaction and thus improves removal efficiency.

In reaction between ozone and positions of acid Luis of adsorbent, ozone is decomposed into activated oxygen atoms which decompose toluene into CO2 and H2O through attacking single connective bonds between carbon atoms (C-C) or connective bonds between carbon-hydrogen atoms (C-H). Since, in practice, reaction between toluene and ozone is not done completely and may result in production of intermediate compounds, these compounds are again adsorbed by carbosieve (due to its high specific surface) and are decomposed by ozone or by the produced activated radicals (Figure 5).

No intermediate compound was observed in COP process output26,27. In positions of acid Luis of adsorbents, toluene is decomposed into O2 and O• according to the following reactions:

(1)  O3 + CMS – s CMS – 3SO        

(2)  CMS-3SºCMS-3Sº-sO•+O2               

(3)  CMS- sO•+O32CMS- sO•+O2           

(4)   CMS- SO2 CMS- s+O2               

CMS-S and CMS-sO3, respectively, reflect positions of acid Luis and ozone molecules adsorbed over carbosieve. CMS-sO3 and CMS-sO• show types of carbosieve surface oxides. CMS-sO• can also react with water vapor available in the air entering the system and can produce activated hydroxyl radicals (OHº) which indirectly take part in decomposition and oxidation of toluene and thus improve removal efficiency.

(5)  CMS-S O•+H2O CMS-S(OH)2•

When toluene- and ozone-containing air passes over carbosieve, catalysed reactions of 1-5 occur and toluene is directly and indirectly removed from waste air stream by ozone and radicals resulted from ozone decomposition. In the following equations, R represents intermediate compounds produced during direct and indirect oxidation reactions.

Direct oxidation:        

(6) CMS- SO3+ C6H5CH3 CO2 + H2O + R    

(7) CMS- SC6H5CH3+O3 CO2 + H2O + R               

(8)  C6H5CH3 +O3 CO2 + H2O + R                                 

Indirect oxidation:

(9) CMS-S O•+ C6H5CH3 CO2 + H2O + R                     

     (10) CMS-S(OH•)2+ C6H5CH3 CO2 + H2O + R               

Since the system used in this study was operated in dry mode, hydroxyl radicals are less likely to be formed so they cannot have an important and vital role in toluene decomposition. In COP process, in addition to ozone and radicals resulted from its decomposition, oxygen molecules play a significant role in toluene decomposition. In the presence of oxygen, ozone decomposition rate increases for more toluene oxidation. In autoxidation processes, this molecule oxides radical intermediate compounds (R*) which are one of the reasons for deactivation of catalyst26,27,29,31,32.

(11) R• + O2RO•2→→→CO2, CO    

Conclusions

Removal of toluene from waste air stream, especially in higher concentrations, is more efficient by COP process than by adsorption system over carbosieve and SOP. This system can be one of promising alternatives for removing various concentrations of volatile organic compounds, especially toxic and hazardous volatile compounds, from waster air stream due to  low energy consuming, making use of cheap catalysts and applying adsorbents proportional to pollutant. COP process adsorbs and destroys pollutant simultaneously; in addition to ozone O3 (E= 2.08 v), this process uses activated hydroxyl radicals (OHº) (E= 2.80 v) and atomic oxygen O• (E= 2.42 v) resulted from catalyzed reactions over bed. This phenomenon lead to bed chemical reclamation, increased system operating time and decreased the cost of bed reclamation. Therefore, the main benefit of catalytic ozonation is that reaction time is shortened, causing decomposition and purification of volatile organic compounds from air stream in high concentrations of ozone gas and pollutant without removal of excess ozone concentrations at the reactor outlet. However, additional studies are required to develop techniques to enhance the oxidation activity and industrial application in greater scales.

   

Acknowledgments

This article is extracted from the Master's thesis. The authors would like to thank Hamadan University of Medical Sciences for the financially supporting of this research.

Conflict of interest statement

This study did not have any conflict of interest statement.

   

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  • Moussavi GR, Khavanin A, Mokarami HR. Removal of xylene from waste air stream using catalytic ozonation process. Iran J Health & Environ. 2010;3:239-250. [Persian]
  • Kwong CW, Chao YH, Hui KS, Wan MP. Removal of VOCs from indoor environment by ozonation over different porous materials. J Atmos Environ. 2008; 42:2300-2311.
  • Alvarez PM, Beltran FJ, Masa FJ, Pocostales JP. Comparison between catalytic ozonation and activated carbon adsorption/ozone-regeneration processes for wastewater treatment. Appl Catal B-Environ. 2009;92:393-400.
  • Li W, Oyama ST. Mechanism of ozone decomposition on a manganese oxide catalyst 2. steady-state and transient kinetic studies. J Am Chem Soc. 1998;120:9047-9052.
  • Zhao L, Ma J, Sun ZZ, Zhai XD. Catalytic ozonation for the degradation of nitrobenzene in aqueous solution by ceramic honeycomb- supported manganese. Appl Catal B-Environ. 2009; 92:393-400.
  • Einaga H, Ogata A, Benzene oxidation with ozone over supported manganese oxide catalysts: effect of catalyst support and reaction conditions. J Hazard Mat. 2009;164:1236-1241.

  • Li W, Gibbs GV, Oyama ST. Mechanism of ozone decomposition on a manganese oxide catalyst.1, in situ Raman spectroscopy and ab initio molecular orbital calculations. J Am Chem Soc. 1998;120:9041-9046.

       

    JRHS Office:

    School of Public Health, Hamadan University of Medical Sciences, Shaheed Fahmideh Ave. Hamadan, Islamic Republic of Iran

    Postal code: 6517838695, PO box: 65175-4171

    Tel: +98 81 38380292, Fax: +98 81 38380509

    E-mail: jrhs@umsha.ac.ir

       

    출처: <http://jrhs.umsha.ac.ir/index.php/JRHS/article/view/1182/html>

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Ozone Reaction

상태와 변화2016. 6. 27. 12:46

FIGURE 1. Overall removal efficiencies and the corresponding toluene decomposition fractions at various ozone inlet concentrations with NaX, NaY, and MCM-41 adsorbents. Experimental conditions: toluene, 1.5 ppmv; ozone, 0 - 80 ppmv; adsorbent mass, 2 g; residence time, 0.13 s; temperature, 23 - 25 ° C; error bars are 1 σ . 

   

출처: <https://www.researchgate.net/figure/23649745_fig1_FIGURE-1-Overall-removal-efficiencies-and-the-corresponding-toluene-decomposition>

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Carbon monoxide, CO

Carbon monoxide has a small linear molecule with a relatively short C-O bond, earlier described as a double bond but nowadays mostly as a triple bond. The valence electrons are slightly drawn towards oxygen, which makes the molecule polar.

Carbon monoxide molecule shown in two ways, from Wikipedia. The C-O triple bond has the unit pm (picometer) which means 10-12 m.

   

CO is an uncolored and non-smelling gas at room temperature. Carbon monoxide is highly toxic since it replaces O2 molecules in hemoglobin, causing suffocation after a short while, and the state continues even after a poisoned person is taken into fresh air. Carbon monoxide is flammable and easily forming CO2 in this reaction: 2CO(g) + O2(g) 2CO2(g) The gas is found in all types of burning, for example car exhaust gases or smoke from a fire. It is also found in cigarette smoke. Moreover, it has been used in wartime for killing people.

   

   

IR spectrum of carbon monoxide, CO

The IR spectrum of carbon monoxide has a major absorption band at 2100 cm-1 or 4.8 µm, due to unsymmetrical vibration modes.

   

Theoretical IR spectrum of carbon monoxide, CO. The spectrum was simulated at: http://spectralcalc.com/info/about.php.

   

   

The IR spectrum of CO below shows an exhaust gas mixture from an oldtime car without catalytical cleaning. Nowadays, modern car exhaust contains mostly CO2 and H2O - the CO concentration is very low.

IR spectrum of 1942 Packard exhaust, showing a mixture of hydrocarbons, water, carbon monoxide and carbon dioxide. The spectrum was found on Internet in a paper by Jane A. Ganske: http://chemeducator.org/sbibs/s0008006/spapers/860353jg.htm

   

출처: <http://www.senseair.com/senseair/gases-applications/carbon-monoxide/>

   

Carbon dioxide, CO2

Carbon dioxide has a perfectly linear molecule due to the C=O double bonds.

   

Carbon dioxide molecule and C=O bond distance, from Wikipedia. The unit pm (picometer) is 10-12 m.

CO2 is an uncolored and non-smelling gas at room temperature which, directly freezes into solid state below -78°C ("dry ice") at normal pressure. The concentration of CO2 in atmosphere is around 0.039 %, or 390 ppm (parts per million). The gas is active in the large carbon cycle since plants use CO2 for photosynthesis and living beings evaporate CO2 when they breath.

   

CO2 is regarded as non-toxic at low concentrations. At higher levels it may displace oxygen in a closed space and cause a risk for suffocation. Also it directly influences on human performance and capacity when the levels are >1 % (10 000 ppm). Carbon dioxide is a major greenhouse gas and due to its steadily increase mainly caused by fossile fuel combustion, it is believed to bring on global heating. All greenhouse gases are compared to each other using the unit CO2 equivalents expressed as the Global Warming Potential (GWP), which is the heat rise a certain amount of CO2 will cause during a period of 100 years. CO2 has by convention a GWP of 1. More powerful greenhouse gases are for example methane or dinitrogen oxide, which have a GWP of 25 and 298, respectively. The GWP value for a gas molecule depends on how stable it is, how strongly it absorbs IR radiation and where in the spectrum the absorption peaks are placed.

   

IR spectrum of CO2

The IR spectrum of carbon dioxide has a strong absorption band consisting of many overlapping peaks. This band, caused by unsymmetrical C=O stretching, is placed at 2300 cm-1 corresponding to a wavelength of 4.3 μm.

CO2 molecules in the atmosphere absorb emitted heat radiation from the earth at this wavelength and in that way decrease cooling especially during clear nights. The mechanism of the increasing amount of carbon dioxide and other more powerful greenhouse gases is that they block IR radiation from exiting from earth back to space.

   

Theoretical IR spectrum of CO2 calculated with the program Spectracalc found at: http://spectralcalc.com.

   

출처: <http://www.senseair.com/senseair/gases-applications/carbon-dioxide/>

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Methane

상태와 변화2016. 6. 27. 12:40

------------ Property Broker ------------

Model: mrthane.mol

   

ChemPropPro: Boiling Point = 0 Kelvin

ChemPropPro: Critical Pressure = 0 Bar

ChemPropPro: Critical Temperature = 0 Kelvin

ChemPropPro: Critical Volume = 0 cm^3/mol

ChemPropPro: Gibbs Free Energy = 0 kJ/mol

ChemPropPro: Heat Of Formation = 0 kJ/mol

ChemPropPro: Henry's Law Constant = -1.429

ChemPropPro: Ideal Gas Thermal Capacity = 0 J/(mol.K)

ChemPropPro: LogP = 1.09

ChemPropPro: Melting Point = 0 Kelvin

ChemPropPro: Mol Refractivity = 6.347 cm^3/mol

ChemPropPro: Vapor Pressure = 103322.998 Pascal

ChemPropPro: Water Solubility = 24.4 mg/L

ChemPropPro: Full Report:

   

************************************************************************

Data from database

************************************************************************

   

<Name of molecule><RE PUBLISHING CORP.,NY,(l989).

   

<**********

   

Log(p)........: 1.09

St..deviation.: 0.47

by Crippen's fragmentation: J.Chem.Inf.Comput.Sci.,27,21(1987).

   

Log(p)........: 1.09

St..deviation.: 0.49

by Viswanadhan's fragmentation: J.Chem.Inf.Comput.Sci.,29,163(1989).

   

   

Estimation using Broto's fragmentation method

C Non available value

Log(p) can't be calculated by Broto's method:

Eur.J.Med.Chem.- Chim.Theor.,19,71(1984).

   

************************************************************************

Estimation of Molar Refractivity

************************************************************************

   

MR............: 6.88 [cm.cm.cm/mol]

St..deviation.: 1.27

by Crippen's fragmentation: J.Chem.Inf.Comput.Sci.,27,21(1987).

   

MR............: 6.35 [cm.cm.cm/mol]

St..deviation.: 0.77

by Viswanadhan's fragmentation: J.Chem.Inf.Comput.Sci.,29,163(1989).

   

   

************************************************************************

Estimation of Henry's Constant (H)

************************************************************************

   

1. method: H = -1.229 log[unitless]

Estimation of mean error..: 0.0620

   

2. method: H = -1.260 log[unitless]

Estimation of mean error..: 0.200

   

ChemPropStd: Formal Charge = 0

ChemPropStd: Connolly Accessible Area = 147.937 Angstroms Squared

ChemPropStd: Connolly Molecular Area = 44.35 Angstroms Squared

ChemPropStd: Connolly Solvent Excluded Volume = 24.335 Angstroms Cubed

ChemPropStd: Exact Mass = 16.0313001284 g/Mol

ChemPropStd: Mass = 16.04246

ChemPropStd: Mol Weight = 16.04246

ChemPropStd: Ovality = 1.09208204264751

ChemPropStd: Principal Moment = 3.303 3.303 3.303

ChemPropStd: Elemental Analysis = C, 74.87; H, 25.13

ChemPropStd: m/z = 16.03 (100.0%), 17.03 (1.1%)

ChemPropStd: Mol Formula = CH4

ChemPropStd: Mol Formula HTML = CH<sub>4</sub>

CLogP Driver: Mol Refractivity = 0.641199946403503

CLogP Driver: Partition Coefficient = 1.1029999256134

GAMESS Interface: Cp = 8.194 cal/(mol K)

GAMESS Interface: Cv = 6.207 cal/(mol K)

GAMESS Interface: Enthalpy = 31.086 Kcal/Mol

GAMESS Interface: Entropy = 49.479 cal/(mol K)

GAMESS Interface: Gibbs Free Energy = 16.334 Kcal/Mol

GAMESS Interface: Internal Energy = 30.494 Kcal/Mol

GAMESS Interface: Dipole = 0 Debye

GAMESS Interface: Harmonic Zero Point Energy = 0 Kcal/Mol

GAMESS Interface: Kinetic Energy = 24925.5722 Kcal/Mol

GAMESS Interface: Potential Energy = -50009.9336 Kcal/Mol

GAMESS Interface: Total Energy = -25084.3614 Kcal/Mol

Charges (Lowdin Charges)-GAMESS Interface:

C(1) -0.378865

H(2) 0.094718

H(3) 0.094714

H(4) 0.094714

H(5) 0.094718

GAMESS Interface: Lowdin Populations (Lowdin Populations)-GAMESS Interface:

C(1) 6.378865

H(2) 0.905282

H(3) 0.905286

H(4) 0.905286

H(5) 0.905282

Charges (Mulliken Charges)-GAMESS Interface:

C(1) -0.773602

H(2) 0.193402

H(3) 0.193399

H(4) 0.193399

H(5) 0.193402

GAMESS Interface: Mulliken Populations (Mulliken Populations)-GAMESS Interface:

C(1) 6.773602

H(2) 0.806598

H(3) 0.806601

H(4) 0.806601

H(5) 0.806598

GAMESS Interface: Frequencies = 0 0.01 502.48 502.54 502.58 1558.71 1558.72 1558.76 1746.61 1746.64 2925.64 2995.23 2995.24 2995.27

GAMESS Interface: Polarizibility:

AXIAL COMPONENTS WITH BASE FIELD OF 0.0010

ENERGY-BASED DIPOLE-BASED

DIPOLE Z: 1.2028308E-05 1.2028008E-05

ALPHA XZ: 3.4799825E-04

ALPHA YZ: -2.4807436E-04

ALPHA ZZ: 1.2137664E+01 1.2137767E+01

BETA XZZ: 2.5549004E+01

BETA YZZ: 1.6897140E+01

BETA ZZZ: 8.9251628E-01 8.9302229E-01

GAM ZZZZ: 7.8841822E+01 8.3879350E+01

Molecular Topology: Balaban Index = 0

Molecular Topology: Cluster Count = 1

Molecular Topology: Molecular Topological Index = 0

Molecular Topology: Num Rotatable Bonds = 0 Bond(s)

Molecular Topology: Polar Surface Area = 0 Angstroms Squared

Molecular Topology: Radius = 0 Atom(s)

Molecular Topology: Shape Attribute = 0

Molecular Topology: Shape Coefficient = 0

Molecular Topology: Sum Of Degrees = 0

Molecular Topology: Sum Of Valence Degrees = 0

Molecular Topology: Topological Diameter = 0 Bond(s)

Molecular Topology: Total Connectivity = 1

Molecular Topology: Total Valence Connectivity = 1

Molecular Topology: Wiener Index = 0

-----------------------------------------

------------MM2 Minimization------------

Note: All parameters used are finalized (Quality = 4).

Iteration 2: Minimization terminated normally because the gradient norm is less than the minimum gradient norm

Stretch: 0.0000

Bend: 0.0000

Stretch-Bend: 0.0000

Torsion: 0.0000

Non-1,4 VDW: 0.0000

1,4 VDW: 0.0000

Total Energy: 0.0000 kcal/mol

Calculation completed

------------------------------------

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1. 엔탈피(enthalpy)

   

H = U + PV

엔탈피는 에너지 개념입니다. 단위역시 에너지의 단위인 J(줄) 이나 kJ로 나타난다.

어떤 물질이 있으면, 그 안에 수많은 원자들이 결합되어 있다. 그 각 원자 혹은 분자들이 움직이고 있고,

그 하나하나의 운동에너지의 총합, 또 각각 전기력으로 결합되어 있고, 그 결합에너지들의 합 등등..한

물체내의 모든 에너지의 총합을 그 물체의 내부에너지라 한다.

   

내부에너지의 경우, 부피가 일정한경우 온도를 증가시켜주면 가해준 열만큼 내부에너지가 증가한다.

즉 '가해준열량 = 늘어난 내부에너지' 의 공식이 성립합니다. 단 부피가 일정해야한다는 조건이 있죠.

하지만, 우리가 사는 실제현실에서는 부피가 일정한 경우보다는 압력이 일정한 경우가 더 많겠죠.

대기압은 언제나 1기압으로 일정하기 때문에 그래서 도입된게 엔탈피입니다.

   

엔탈피 역시 내부에너지와 비슷한 그 물체가 갖고있는 에너지의 개념이지만, 엔탈피의 경우에는 일정한

압력하에서 '가해준 열량 = 늘어난 엔탈피' 라는 공식이 성립합니다. 즉 내부에너지보다 엔탈피가 얼마나

증가했는지 감소했는지 측정하기가 더 쉽다는 말입니다.

   

압력은 대기압으로 고정되어 있을 때 가해준 열량만 계산하면 되기 때문입니다. 내부에너지를 계산하려면,

부피를 고정시킨다는건 어려운 일이니까.

   

2. 엔트로피(Entropy)

   

엔트로피(Entropy) = 에너지(Energy) + 변환(Tropy)

1865년 R.E.클라우지우스가 변화를 뜻하는 그리스어 τροπη에서 이 물리량을 엔트로피라 이름하였다.

   

이론적으로는 물질계가 흡수하는 열량 dQ와 절대온도 T와의 비 dS=dQ/T로 정의한다. 여기서 dS는 물질

계가 열을 흡수하는 동안의 엔트로피 변화량이다.

   

열기관의 효율을 이론적으로 계산하는 이상기관의 경우는 모든 과정이 가역과정이므로 엔트로피는

일정하게 유지된다.

   

일반적으로 현상이 비가역과정인 자연적 과정을 따르는 경우에는 이 양이 증가하고, 자연적 과정에

역행하는 경우에는 감소하는 성질이 있다. 그러므로 자연현상의 변화가 자연적 방향을 따라 발생하는가를

나타내는 척도이다.

   

대부분 자연현상의 변화는 어떤 일정한 방향으로만 진행한다. 즉, 자연현상의 변화는 물질계의 엔트로피가

증가하는 방향으로 진행한다. 이것을 엔트로피 증가의 법칙이라고 한다.

   

예를 들면, 온도차가 있는 어떤 2개의 물체를 접촉시켰을 때, 열 q가 고온부에서 저온부로 흐른다고 하면

고온부(온도 T1)의 엔트로피는 q/T1만큼 감소하고, 저온부(온도 T2)의 엔트로피는 q/T2만큼 증가하므로,

전체의 엔트로피는 이 변화를 통하여 증가한다. 역으로 저온부에서 고온부로 열이 이동하는 자연현상에

역행하는 과정, 예를 들면 냉동기의 저온부에서 열을 빼앗아 고온부로 방출하는 과정에서 국부적으로

엔트로피가 감소하지만, 여기에는 냉동기를 작동시키는 모터 내에서 전류가 열로 바뀐다는 자연적 과정이

필연적으로 동반하므로 전체로서는 엔트로피가 증가한다.

   

때때로 자연현상은 국부적으로 엔트로피가 감소하는 비자연적 변화를 따르는 것도 있지만, 그것에 관계되는

물질계 전체를 다루어 보면, 항상 엔트로피를 증가시키는 방향으로 현상이 변화한다. 이 이론은 자연현상이

일어나는 방향을 정하는 것으로서, 에너지보존법칙과 함께 열역학의 기본법칙으로서 중요하다.

   

이상기체에서 엔트로피가 증가하지 않는 것은 가역변화라고 하는 비현실적인 변화를 가정하고 있기 때문

이다.

   

엔트로피는 물질계의 열적 상태로부터 정해진 양으로서, 통계역학의 입장에서 보면 열역학적인 확률을

나타내는 양이다. 엔트로피 증가의 원리는 분자운동이 확률이 적은 질서 있는 상태로부터 확률이 큰

무질서한 상태로 이동해 가는 자연현상으로 해석한다. 예를 들면, 마찰에 의해 열이 발생하는 것은 역학적

운동(분자의 질서 있는 운동)이 열운동(무질서한 분자운동)으로 변하는 과정이다. 그 반대의 과정은

무질서에서 질서로 옮겨가는 과정이며, 이것은 자발적으로 일어나지 않는다.

   

일반적으로 열역학적 확률의 최대값은 온도가 균일한 열평형상태에 대응하는 것이다. 고찰하고 있는

물질계가 다른 에너지 출입이 없는 고립계인 경우에는 늦던 빠르던 전체가 열평형에 도달하여 모든

열과정이 정지하는 것이라고 생각된다.

   

Pasted from <http://www.chemeng.co.kr/site/bbs/board.php?bo_table=xstudy4&wr_id=81>

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