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In [[chemistry]], '''catalysis''' is a process that uses a substance to accelerate the rate of a [[chemical reaction]] through an uninterrupted and repeated cycle of elementary steps until the last step regenerates the catalyst in its original form.  The substance that does this is known as a '''''catalyst'''''. It is usually present in relatively small amounts and none of it is consumed in the process.<ref name=NAP>{{cite book|author=Commission on Physical Sciences, Mathematics, and Applications (CPSMA), [[National Academies]]|publisher= National Academies Press|title=Catalysis Looks to the Future|edition=|year=1992|id=ISBN 0-309-04584-3}} Available online at [http://www.nap.edu/openbook.php?record_id=1903&page=1 Executive Summary]</ref>
__NOTOC__
[[File:Crude oil-fired power plant.jpg|thumb|right|225px|Industrial air pollution source]]
Atmospheric dispersion modeling is the mathematical simulation of how air pollutants disperse in the ambient atmosphere. It is performed with computer programs that solve the mathematical equations and algorithms which simulate the pollutant dispersion. The dispersion models are used to estimate or to predict the downwind concentration of air pollutants emitted from sources such as industrial plants, vehicular traffic or accidental chemical releases.  


Many substances can act as catalysts, including: [[metal]]s, [[chemical compounds]] (e.g., metal [[oxide]]s, [[sulfide]]s, [[nitride]]s), [[organometallic]] complexes, and [[enzyme]]s. Although a catalyst may be a [[gas]], [[liquid]] or [[solid]], most catalysts used in industrial chemical reactions are in the form of porous pellets. Since not all parts of a solid catalyst participate in the catalysis cycle, those parts that do participate are referred to as ''active sites''. A single porous pellet may have 10<sup>18</sup> active catalytic sites.<ref name=NAP/>
Such models are important to governmental agencies tasked with protecting and managing the ambient air quality. The models are typically employed to determine whether existing or proposed new industrial facilities are or will be in compliance with the National Ambient Air Quality Standards (NAAQS) in the United States or similar regulations in other nations. The models also serve to assist in the design of effective control strategies to reduce emissions of harmful air pollutants. During the late 1960's, the Air Pollution Control Office of the U.S. Environmental Protection Agency (U.S. EPA) initiated research projects to develop models for use by urban and transportation planners.<ref>J.C. Fensterstock et al, "Reduction of air pollution potential through environmental planning", ''JAPCA'', Vol. 21, No. 7, 1971.</ref>


This article does not discuss [[Enzyme|enzymatic]] or [[biochemical]] catalysis (for information on those types of catalysis, see the [[enzyme]], [[biochemistry]] and [[organocatalysis]] articles).
Air dispersion models are also used by emergency management personnel to develop emergency plans for accidental chemical releases. The results of dispersion modeling, using worst case accidental releases and meteorological conditions, can provide estimated locations of impacted areas and be used to determine appropriate protective actions. At industrial facilities in the United States, this type of consequence assessment or emergency planning is required under the Clean Air Act (CAA) codified in Part 68 of Title 40 of the Code of Federal Regulations.


{{Image|Catalysis.png|right|290px|Fig. 1: The catalysis cycle and its elementary steps.}}
The dispersion models vary depending on the mathematics used to develop the model, but all require the input of data that may include:
==The catalysis mechanism==


Figure 1 depicts the steps in a typical catalysis cycle. As depicted, the reactant [[molecule]]s A and B are reacted to yield product P. The catalysis cycle starts with the bonding of reactant molecules A and B to the catalyst. A and B then react, while bound to the catalyst, to yield product P which is also bound to the catalyst. In the last step, the catalyst is regenerated by product P separating from the catalyst. The regenerated catalyst then begins cycle again by bonding with two more reactant molecules. <ref name=Chork>{{cite book|author=I. Chorkendorff and J. W. Niemantsverdriet|title=Concepts of Modern Catalysts and Kinetics|edition=2nd Edition|publisher=Wiley-VCH|year=2007|id=ISBN 3-527-31672-8}}</ref> 
* Meteorological conditions such as wind speed and direction, the amount of atmospheric turbulence (as characterized by what is called the "stability class"), the ambient air temperature, the height to the bottom of any inversion aloft that may be present, cloud cover and solar radiation.
* The emission parameters such the type of source (i.e., point, line or area), the mass flow rate, the source location and height, the source exit velocity, and the source exit temperature.
* Terrain elevations at the source location and at receptor locations, such as nearby homes, schools, businesses and hospitals.
* The location, height and width of any obstructions (such as buildings or other structures) in the path of the emitted gaseous plume as well as the terrain surface roughness (which may be characterized by the more generic parameters "rural" or "city" terrain).


{{Image|Catalysis reaction paths.png|right|234px|Fig. 2: Catalyst effect on a hypothetical chemical reaction.<ref name=Clark1>[http://www.chemguide.co.uk/physical/basicrates/catalyst.html#top The Effect of Catalysts on Reaction Rates] From a website provided by Jim Clarke, retired Head of Chemistry and then Head of Science at [[Truro School]] in [[Cornwall]], [[United Kingdom]].</ref>}}
Many of the modern, advanced dispersion modeling programs include a pre-processor module for the input of meteorological and other data, and many also include a post-processor module for graphing the output data and/or plotting the area impacted by the air pollutants on maps. The plots of areas impacted usually include isopleths showing areas of pollutant concentrations that define areas of the highest health risk. The isopleths plots are useful in determining protective actions for the public and first responders.


In [[chemistry]], '''''activation energy'''''<ref>A term introduced in 1889 by the Swedish scientist [[Svante Arrhenius]]</ref> is the [[Energy (science)|energy]] that must be overcome in order for a chemical reaction to occur. Activation energy may also be defined as the minimum energy required to start a designated chemical reaction. It is denoted by '''''E<sub>a</sub>''''' in units of [[Joule|kilojoules]] per [[mole]] (kJ/mol). It may be thought of as the ''energy barrier'' that must be overcome to start a chemical reaction.
The atmospheric dispersion models are also known as atmospheric diffusion models, air dispersion models, air quality models, and air pollution dispersion models.


For a chemical reaction to proceed at a reasonable rate, there should exist an appreciable number of reactant species (molecules, [[atom]]s, [[ion]]s, etc.) with energy equal to or greater than the activation energy of the reaction.<ref name=Clark1/> A catalyst does not lower the activation energy for a reaction, instead it provides an alternative path for the reaction that has a lower activation energy. The catalyst changes the [[chemical kinetics]] of a reaction but not the [[chemical thermodynamics]].
==Atmospheric layers==


Figure 2 depicts how a catalyzed reaction follows a lower activation energy path than the higher activation energy path followed by the same reaction when it is not catalyzed. Overall, both the catalyzed path and the uncatalyzed path have the same change in [[Internal energy#Gibbs free energy|Gibbs free energy]] between the reactants and the reaction product.  
Discussion of the layers in the Earth's atmosphere is needed to understand where airborne pollutants disperse in the atmosphere. The layer closest to the Earth's surface is known as the ''troposphere''. It extends from sea-level up to a height of about 18 km and contains about 80 percent of the mass of the overall atmosphere. The ''stratosphere'' is the next layer and extends from 18 km up to about 50 km. The third layer is the ''mesosphere'' which extends from 50 km up to about 80 km. There are other layers above 80 km, but they are insignificant with respect to atmospheric dispersion modeling.


The energy diagram in Figure 2 illustrates several important points:<ref name=Chork/>
The lowest part of the troposphere is called the ''atmospheric boundary layer (ABL)'' or the ''planetary boundary layer (PBL)'' and extends from the Earth's surface up to about 1.5 to 2.0 km in height. The air temperature of the atmospheric boundary layer decreases with increasing altitude until it reaches what is called the ''inversion layer'' (where the temperature increases with increasing altitude) that caps the atmospheric boundary layer. The upper part of the troposphere (i.e., above the inversion layer) is called the ''free troposphere'' and it extends up to the 18 km height of the troposphere.


*The presence of the catalyst provides an alternative reaction path, which is definitely more complex (see Figure 1), but energetically much more favorable.
The ABL is the most important layer with respect to the emission, transport and dispersion of airborne pollutants. The part of the ABL between the Earth's surface and the bottom of the inversion layer is known as the ''mixing layer''. Almost all of the airborne pollutants emitted into the ambient atmosphere are transported and dispersed within the mixing layer. Some of the emissions penetrate the inversion layer and enter the free troposphere above the ABL.
*The activation energy of the catalyzed reaction is significantly smaller than that of the uncatalyzed reaction. Hence, the rate of the catalyzed reaction is much faster.
*Since the overall change in Gibbs free energy is the same for the catalyzed reaction as for the uncatalyzed reaction, the [[reaction equilibrium constant]] is not affected by the catalyst. As noted above, the catalyst does not change the chemical thermodynamics of the reaction. Thus, if a reaction is thermodynamically unfavorable, the catalyst cannot change that situation.


The term "turn over frequency" (TOF) is used quite commonly in the technical literature to characterize the activity of catalysts. However, the definition of TOF in the literature is not consistent and varies quite widely. For example, two of the definitions in the literature are:
In summary, the layers of the Earth's atmosphere from the surface of the ground upwards are: the ABL made up of the mixing layer capped by the inversion layer; the free troposphere; the stratosphere; the mesosphere and others. Many atmospheric dispersion models are referred to as ''boundary layer models'' because they mainly model air pollutant dispersion within the ABL. To avoid confusion, models referred to as ''mesoscale models'' have dispersion modeling capabilities that can extend horizontally as much as  a few hundred kilometres. It does not mean that they model dispersion in the mesosphere.


* Moles of product formed per second per mole of catalyst<ref>{{cite book|author=Hideo Kurosawa and Akio Yamamoto|title=Fundamentals of Molecular Catalysis|edition=1st Edition|publisher=Elsevier Science|year=2003|id=ISBN 0-444-50921-6}}</ref>
==Gaussian air pollutant dispersion equation==
* Moles of reactants converted per second per active site.<ref name=Chork/>


In both of the above definitions, the unit of time is sometimes designated as an hour rather than a second.
The technical literature on air pollution dispersion is quite extensive and dates back to the 1930s and earlier. One of the early air pollutant plume dispersion equations was derived by Bosanquet and Pearson.<ref>C.H. Bosanquet and J.L. Pearson, "The spread of smoke and gases from chimneys", ''Trans. Faraday Soc.'', 32:1249, 1936.</ref> Their equation did not assume Gaussian distribution nor did it include the effect of ground reflection of the pollutant plume.


Another catalytic activity term is the [[katal]], an [[SI]] derived unit, which is used mostly in biochemistry to characterize the activity of enzymes.<ref>{{cite journal|author=R. Dybkaer|title=Unit "katal" for Catalytic Activity (IUPAC Technical Report)|journal=Pure Appl. Chem.|volume=73|issue=6| pages=927-931|date=2001|id= |url=http://media.iupac.org/publications/pac/2001/pdf/7306x0927.pdf}}</ref>
Sir Graham Sutton derived an air pollutant plume dispersion equation in 1947<ref>O.G. Sutton, "The problem of diffusion in the lower atmosphere", ''QJRMS'', 73:257, 1947.</ref><ref>O.G. Sutton, "The theoretical distribution of airborne pollution from factory chimneys", ''QJRMS'', 73:426, 1947.</ref> which did include the assumption of Gaussian distribution for the vertical and crosswind dispersion of the plume and also included the effect of ground reflection of the plume.


==Types of catalysis==
Under the stimulus provided by the advent of stringent environmental control regulations, there was an immense growth in the use of air pollutant plume dispersion calculations between the late 1960s and today. A great many computer programs for calculating the dispersion of air pollutant emissions were developed during that period of time and they were commonly called "air dispersion models". The basis for most of those models was the '''Complete Equation For Gaussian Dispersion Modeling Of Continuous, Buoyant Air Pollution Plumes''' shown below:<ref name=Beychok>{{cite book|author=M.R. Beychok|title=Fundamentals Of Stack Gas Dispersion|edition=4th Edition| publisher=author-published|year=2005|isbn=0-9644588-0-2}}.</ref><ref>{{cite book|author=D. B. Turner| title=Workbook of atmospheric dispersion estimates: an introduction to dispersion modeling| edition=2nd Edition |publisher=CRC Press|year=1994|isbn=1-56670-023-X}}.</ref>


Catalysis can be categorized into two main types: heterogeneous and homogeneous. In heterogeneous catalysis, the catalyst is in one phase<ref>If a boundary exists between the catalyst and the reaction system (i.e., the reactants and the products), then the system has two phases. In this context, a phase is different from the most familiar [[Chemistry#states of matter|states of matter]]: solid, liquids and gases. For example, if a liquid catalyst and a liquid reaction system were mutually insoluble, a boundary would exist between the catalyst and the reaction system. That would constitute two phases in the context of catalysis whereas it would be considered as being one state of matter, namely a liquid.</ref> while the reactants and products are in a different phase or, for some cases, two different phases. In homogeneous catalysis, the catalyst is in the same phase as the reactants and the products.<ref name=Clark2>[http://www.chemguide.co.uk/physical/basicrates/catalyst.html#top Types of Catalysis] From a website provided by Jim Clarke, retired Head of Chemistry and then Head of Science at Truro School in Cornwall, United Kingdom.</ref>


'''''Heterogeneous catalysis'''''&thinsp;<ref name=Clark2/><ref name=Explained>[http://www.chemistryexplained.com/Bo-Ce/Catalysis-and-Catalysts.html Chemistry Explained] Chemistry Encyclopedia</ref><ref name=Silesian>[http://www.kataliza.chemia.polsl.pl/makro-ic-wyk12.pdf Catalyst Lecture 12] Faculty of Chemistry, [[Silesian University of Technology]], [[Poland]]</ref>
<math>C = \frac{\;Q}{u}\cdot\frac{\;f}{\sigma_y\sqrt{2\pi}}\;\cdot\frac{\;g_1 + g_2 + g_3}{\sigma_z\sqrt{2\pi}}</math>


Typical examples of heterogeneous catalysis involve a solid catalyst with the reactants as either liquids or gases. Separation of the products from the catalyst is relatively easy. However, the catalyst in heterogeneous catalysis is often less selective than in homogeneous catalysis.
{| border="0" cellpadding="2"
|-
|align=right|where:
|&nbsp;
|-
!align=right|<math>f</math> 
|align=left|= crosswind dispersion parameter
|-
!align=right|&nbsp;
|align=left|= <math>\exp\;[-\,y^2/\,(2\;\sigma_y^2\;)\;]</math>
|-
!align=right|<math>g</math>
|align=left|= vertical dispersion parameter = <math>\,g_1 + g_2 + g_3</math>
|-
!align=right|<math>g_1</math>
|align=left|= vertical dispersion with no reflections
|-
!align=right|&nbsp;
|align=left|= <math>\; \exp\;[-\,(z - H)^2/\,(2\;\sigma_z^2\;)\;]</math>
|-
!align=right|<math>g_2</math>
|align=left|= vertical dispersion for reflection from the ground
|-
!align=right|&nbsp;
|align=left|= <math>\;\exp\;[-\,(z + H)^2/\,(2\;\sigma_z^2\;)\;]</math>
|-
!align=right|<math>g_3</math>
|align=left|= vertical dispersion for reflection from an inversion aloft
|-
!align=right|&nbsp;
|align=left|= <math>\sum_{m=1}^\infty\;\big\{\exp\;[-\,(z - H - 2mL)^2/\,(2\;\sigma_z^2\;)\;]</math>
|-
!align=right|&nbsp;
|align=left|&nbsp; &nbsp; &nbsp; &nbsp; &nbsp; <math>+\, \exp\;[-\,(z + H + 2mL)^2/\,(2\;\sigma_z^2\;)\;]</math>
|-
!align=right|&nbsp;
|align=left|&nbsp; &nbsp; &nbsp; &nbsp; &nbsp; <math>+\, \exp\;[-\,(z + H - 2mL)^2/\,(2\;\sigma_z^2\;)\;]</math>
|-
!align=right|&nbsp;
|align=left|&nbsp; &nbsp; &nbsp; &nbsp; &nbsp; <math>+\, \exp\;[-\,(z - H + 2mL)^2/\,(2\;\sigma_z^2\;)\;]\big\}</math>
|-
!align=right|<math>C</math>
|align=left|= concentration of emissions, in g/m³, at any receptor located:
|-
!align=right|&nbsp;
|align=left|&nbsp; &nbsp; &nbsp; &nbsp; &nbsp; x meters downwind from the emission source point
|-
!align=right|&nbsp;
|align=left|&nbsp; &nbsp; &nbsp; &nbsp; &nbsp; y meters crosswind from the emission plume centerline
|-
!align=right|&nbsp;
|align=left|&nbsp; &nbsp; &nbsp; &nbsp; &nbsp; z meters above ground level
|-
!align=right|<math>Q</math>
|align=left|= source pollutant emission rate, in g/s
|-
!align=right|<math>u</math>
|align=left|= horizontal wind velocity along the plume centerline, m/s
|-
!align=right|<math>H</math>
|align=left|= height of emission plume centerline above ground level, in m
|-
!align=right|<math>\sigma_z</math>
|align=left|= vertical standard deviation of the emission distribution, in m
|-
!align=right|<math>\sigma_y</math>
|align=left|= horizontal standard deviation of the emission distribution, in m
|-
!align=right|<math>L</math>
|align=left|= height from ground level to bottom of the inversion aloft, in m
|-
!align=right|<math>\exp</math>
|align=left|= the exponential function
|}


A few specific examples of heterogeneous catalysis are:<ref name=Clark2/><ref name=Explained/><ref name=Silesian/>
The above equation not only includes upward reflection from the ground, it also includes downward reflection from the bottom of any inversion lid present in the atmosphere.
*The [[catalytic converter]]s in automobiles convert exhaust gases such as [[carbon monoxide]] (CO) and [[nitrogen oxides]] (NOx) into more harmless gases like [[carbon dioxide]] (CO<sub>2</sub>) and [[nitrogen]] (N<sub>2</sub>). Metals (solids) like [[platinum]] (Pt), [[palladium]] (Pd) and [[rhodium]] (Rh) are used as the catalyst. The metals are deposited as thin layers onto a ceramic honeycomb. This maximizes the surface area and keeps the amount of metal used to a minimum.


*The large-scale industrial processes for manufacturing [[sulfuric acid]] (H<sub>2</sub>SO<sub>4</sub>) involve using solid [[vanadium pentoxide]] (V<sub>2</sub>O<sub>5</sub>) as the catalyst to convert gaseous [[sulfur dioxide]] (SO<sub>2</sub>) into gaseous [[sulfur trioxide]] (SO<sub>3</sub>).  
The sum of the four exponential terms in <math>g_3</math> converges to a final value quite rapidly. For most cases, the summation of the series with '''''m''''' = 1, '''''m''''' = 2 and '''''m''''' = 3 will provide an adequate solution.


*The catalytic hydrogenation of liquid [[Hydrocarbon|unsaturated hydrocarbons]] ([[Hydrocarbon|alkenes]]) by reacting them with gaseous [[hydrogen]] (H<sub>2</sub>) to produce liquid [[Hydrocarbon|saturated hydrocarbons]] ([[hydrocarbon|alkanes]]) uses metals like [[platinum]] (Pt) and [[palladium]] (Pd) as the catalyst. This is an example of three-phase catalysis, the catalyst being a solid and one of the reactants being a gas while another reactant and the product are liquids.
<math>\sigma_z</math> and <math>\sigma_y</math> are functions of the atmospheric stability class (i.e., a measure of the turbulence in the ambient atmosphere) and of the downwind distance to the receptor. The two most important variables affecting the degree of pollutant emission dispersion obtained are the height of the emission source point and the degree of atmospheric turbulence. The more turbulence, the better the degree of dispersion.


'''''Homogeneous catalysis'''''&thinsp;<ref name=Clark2/><ref name=Explained/><ref name=Silesian/>
Whereas older models rely on stability classes for the determination of <math>\sigma_y</math> and <math>\sigma_z</math>, more recent models increasingly rely on Monin-Obukhov similarity theory to derive these parameters.


Typical examples of homogeneous catalysis have the catalyst, reactant and products all present as a gas or contained in a single liquid phase. Separation of the products from the catalyst is relatively difficult. However, the catalyst in homogeneous catalysis is often more selective than in heterogeneous catalysis.
==Briggs plume rise equations==


A few examples of homogeneous catalysts are:<ref name=Clark2/><ref name=Explained/><ref name=Silesian/>
The Gaussian air pollutant dispersion equation (discussed above) requires the input of ''H'' which is the pollutant plume's centerline height above ground level. ''H'' is the sum of ''H''<sub>s</sub> (the actual physical height of the pollutant plume's emission source point) plus Δ''H'' (the plume rise due the plume's buoyancy).


*The depletion of [[ozone]] (O<sub>3</sub>) in the [[Earth's atmosphere|ozone layer]] of the [[Earth's atmosphere]] by [[chlorine]] [[free radical]]s (Cl'''·''') is a an example where everything is present in a gas phase. The chlorine free radicals, derived from the slow breakdown of man-made [[chlorofluorohydrocarbon]]s (CFCs) like CCl<sub>2</sub>F<sub>2</sub> released into the atmosphere, acts both as a reactant and the catalyst in converting gaseous ozone to gaseous oxygen (O<sub>2</sub>).
[[File:Gaussian Plume.png|thumb|right|333px|Visualization of a buoyant Gaussian air pollutant dispersion plume]]


*The production of an [[ester]] by reacting a [[carboxylic acid]] with an [[alcohol]] involves the use of sulfuric acid as the catalyst and is an example where everything is contained in a liquid phase. This reaction is known a [[Fischer esterification]], named after the [[German]] chemist Hermann Emil Fischer (1852 - 1919).
To determine Δ''H'', many if not most of the air dispersion models developed between the late 1960s and the early 2000s used what are known as "the Briggs equations." G.A. Briggs first published his plume rise observations and comparisons in 1965.<ref>G.A. Briggs, "A plume rise model compared with observations", ''JAPCA'', 15:433–438, 1965.</ref> In 1968, at a symposium sponsored by CONCAWE (a Dutch organization), he compared many of the plume rise models then available in the literature.<ref>G.A. Briggs, "CONCAWE meeting: discussion of the comparative consequences of different plume rise formulas", ''Atmos. Envir.'', 2:228–232, 1968.</ref> In that same year, Briggs also wrote the section of the publication edited by Slade<ref>D.H. Slade (editor), "Meteorology and atomic energy 1968", Air Resources Laboratory, U.S. Dept. of Commerce, 1968.</ref> dealing with the comparative analyses of plume rise models.  That was followed in 1969 by his classical critical review of the entire plume rise literature,<ref>G.A. Briggs, "Plume Rise", ''USAEC Critical Review Series'', 1969.</ref> in which he proposed a set of plume rise equations which have become widely known as "the Briggs equations".  Subsequently, Briggs modified his 1969 plume rise equations in 1971 and in 1972.<ref>G.A. Briggs, "Some recent analyses of plume rise observation", ''Proc. Second Internat'l. Clean Air Congress'', Academic Press, New York, 1971.</ref><ref>G.A. Briggs, "Discussion: chimney plumes in neutral and stable surroundings", ''Atmos. Envir.'', 6:507–510, 1972.</ref>


==Inhibitors, promoters and poisons==
Briggs divided air pollution plumes into these four general categories:
* Cold jet plumes in calm ambient air conditions
* Cold jet plumes in windy ambient air conditions
* Hot, buoyant plumes in calm ambient air conditions
* Hot, buoyant plumes in windy ambient air conditions


Briggs considered the trajectory of cold jet plumes to be dominated by their initial velocity momentum, and the trajectory of hot, buoyant plumes to be dominated by their buoyant momentum to the extent that their initial velocity momentum was relatively unimportant.  Although Briggs proposed plume rise equations for each of the above plume categories, '''''it is important to emphasize that "the Briggs equations" which become widely used are those that he proposed for bent-over, hot buoyant plumes'''''.


==Applications==
In general, Briggs's equations for bent-over, hot buoyant plumes are based on observations and data involving plumes from typical combustion sources such as the flue gas stacks from steam-generating boilers burning fossil fuels in large power plants.  Therefore the stack exit velocities were probably in the range of 20 to 100 ft/s (6 to 30 m/s) with exit temperatures ranging from 250 to 500 °F (120 to 260 °C).


==History==
A logic diagram for using the Briggs equations<ref name=Beychok/> to obtain the plume rise trajectory of bent-over buoyant plumes is presented below:
[[Image:BriggsLogic.png|none]]
:{| border="0" cellpadding="2"
|-
|align=right|where:
|&nbsp;
|-
!align=right| Δh
|align=left|= plume rise, in m
|-
!align=right| F<sup>&nbsp;</sup> <!-- The HTML is needed to line up characters. Do not remove.-->
|align=left|= buoyancy factor, in m<sup>4</sup>s<sup>−3</sup>
|-
!align=right| x
|align=left|= downwind distance from plume source, in m
|-
!align=right| x<sub>f</sub>
|align=left|= downwind distance from plume source to point of maximum plume rise, in m
|-
!align=right| u
|align=left|= windspeed at actual stack height, in m/s
|-
!align=right| s<sup>&nbsp;</sup> <!-- The HTML is needed to line up characters. Do not remove.-->
|align=left|= stability parameter, in s<sup>−2</sup>
|}
The above parameters used in the Briggs' equations are discussed in Beychok's book.<ref name=Beychok/>


Catalysts had been used in the laboratory before 1800 by [[Joseph Priestly]] in [[England]]and by the [[Netherlands|Dutch]] chemist [[Martinus van Marum]], both of whom made observations on the [[dehyrogenation]] of [[alcohol]] with metal catalysts. However, it seems that  both of them regarded the metal merely as a source of heat.
==References==
{{reflist}}


Some the chemists involved in catalysis during the 1800's were:
== Further reading==


*In 1806, the [[France|French]] chemists Charles Bernard Désormes and his son-in-law Nicolas
*{{cite book | author=M.R. Beychok| title=Fundamentals Of Stack Gas Dispersion | edition=4th Edition | publisher=author-published | year=2005 | isbn=0-9644588-0-2}}
Clément made perhaps the first attempt to propose a theory of catalysis based on the catalytic
effect of nitrogen oxides in the [[lead chamber process]] for the manufacture of sulfuric acid.<ref>C. B. Désormes and N. Clément (1806), ''Annals Chim.'' '''59''' (329)</ref>


*In 1813, the [[France|French]] chemist [[Louis Jacques Thénard]] discovered that [[ammonia]] is entirely decomposed into [[nitrogen]] and [[hydrogen]] when passed over various red-hot metals.
*{{cite book | author=K.B. Schnelle and P.R. Dey| title=Atmospheric Dispersion Modeling Compliance Guide  | edition=1st Edition| publisher=McGraw-Hill Professional | year=1999 | isbn=0-07-058059-6}}


*[[Humphry Davy|Sir Humphrey Davy]], a [[Great Britain|British]] chemist, who discovered the use of platinum as a  catalyst in 1817,<ref>H. Davy (1817), ''Phil. Trans. Roy. Soc.'' '''107''' (77)</ref>.
*{{cite book | author=D.B. Turner| title=Workbook of Atmospheric Dispersion Estimates: An Introduction to Dispersion Modeling | edition=2nd Edition | publisher=CRC Press | year=1994 | isbn=1-56670-023-X}}


*In 1823, [[Johann Wolfgang Döbereiner]], a chemistry professor at the [[University of Jena]] in [[Germany}} demonstrated that hydrogen ignited spontaneously in the presence of a platinum sponge.<ref>J. W. Döbereiner (1823), ''Ann. Phys.'' '''74 (269)</ref><ref>J. W. Döbereiner (1823), ''Ann. Chim.'' '''24 (91)</ref>  He  then applied his work  to construct a ''fire stick'' (or "Feuerzeug" in [[German language|German]]) which was a fire lighter based on hydrogen and a catalyst of platinum sponge that became a commercial success in the 1820s.
*{{cite book | author= S.P. Arya| title=Air Pollution Meteorology and Dispersion | edition=1st Edition | publisher=Oxford University Press | year=1998 | isbn=0-19-507398-3}}


*In 1836, the [[Sweden|Swedish]] chemist [[Jöns Jakob Berzelius]], considered to be one of the "fathers of modern chemistry",  coined the phrase ''catalyzed processes'' to describe reactions that are accelerated by substances that remain unchanged after the reaction.<ref>{{cite book|author=Keith J. Laidler and John H. Meiser|Physical Chemistry|title=Physical Chemistry|edition=1st Edition|publisher=Benjamin-Cummings Publishing|year=1982| pages=p.423|id=ISBN 0-8053-5682-7}}</ref>
*{{cite book | author=R. Barrat| title=Atmospheric Dispersion Modelling | edition=1st Edition | publisher=Earthscan Publications | year=2001 | isbn=1-85383-642-7}}
In the 1880s, [[Wilhelm Ostwald]] at [[Leipzig University]] in [[Germany]] started a systematic investigation into reactions that were catalyzed by the presence of [[acid]]s and [[base]]s, and found that chemical reactions occur at finite rates and that these rates can be used to determine the strengths of acids and bases. For this work, Ostwald was awarded the 1909 [[Nobel Prize in Chemistry]].<ref>{{cite journal|author=M.W. Roberts|title=Birth of the catalytic concept (1800-1900)|journal=Catalysis Letters| volume=67|issue=1|year=2000|pages=1–4|url =http://www.springerlink.com/content/qm3732u7x7577224/fulltext.pdf}}</ref>


==References==
*{{cite book | author=S.R. Hanna and R.E. Britter| title=Wind Flow and Vapor Cloud Dispersion at Industrial and Urban Sites  | edition=1st Edition | publisher=Wiley-American Institute of Chemical Engineers | year=2002 | isbn=0-8169-0863-X}}
<references/>
 
*{{cite book | author=P. Zannetti| title=Air pollution modeling : theories, computational methods, and available software | edition= | publisher= Van Nostrand Reinhold | year=1990 | isbn=0-442-30805-1 }}

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Industrial air pollution source

Atmospheric dispersion modeling is the mathematical simulation of how air pollutants disperse in the ambient atmosphere. It is performed with computer programs that solve the mathematical equations and algorithms which simulate the pollutant dispersion. The dispersion models are used to estimate or to predict the downwind concentration of air pollutants emitted from sources such as industrial plants, vehicular traffic or accidental chemical releases.

Such models are important to governmental agencies tasked with protecting and managing the ambient air quality. The models are typically employed to determine whether existing or proposed new industrial facilities are or will be in compliance with the National Ambient Air Quality Standards (NAAQS) in the United States or similar regulations in other nations. The models also serve to assist in the design of effective control strategies to reduce emissions of harmful air pollutants. During the late 1960's, the Air Pollution Control Office of the U.S. Environmental Protection Agency (U.S. EPA) initiated research projects to develop models for use by urban and transportation planners.[1]

Air dispersion models are also used by emergency management personnel to develop emergency plans for accidental chemical releases. The results of dispersion modeling, using worst case accidental releases and meteorological conditions, can provide estimated locations of impacted areas and be used to determine appropriate protective actions. At industrial facilities in the United States, this type of consequence assessment or emergency planning is required under the Clean Air Act (CAA) codified in Part 68 of Title 40 of the Code of Federal Regulations.

The dispersion models vary depending on the mathematics used to develop the model, but all require the input of data that may include:

  • Meteorological conditions such as wind speed and direction, the amount of atmospheric turbulence (as characterized by what is called the "stability class"), the ambient air temperature, the height to the bottom of any inversion aloft that may be present, cloud cover and solar radiation.
  • The emission parameters such the type of source (i.e., point, line or area), the mass flow rate, the source location and height, the source exit velocity, and the source exit temperature.
  • Terrain elevations at the source location and at receptor locations, such as nearby homes, schools, businesses and hospitals.
  • The location, height and width of any obstructions (such as buildings or other structures) in the path of the emitted gaseous plume as well as the terrain surface roughness (which may be characterized by the more generic parameters "rural" or "city" terrain).

Many of the modern, advanced dispersion modeling programs include a pre-processor module for the input of meteorological and other data, and many also include a post-processor module for graphing the output data and/or plotting the area impacted by the air pollutants on maps. The plots of areas impacted usually include isopleths showing areas of pollutant concentrations that define areas of the highest health risk. The isopleths plots are useful in determining protective actions for the public and first responders.

The atmospheric dispersion models are also known as atmospheric diffusion models, air dispersion models, air quality models, and air pollution dispersion models.

Atmospheric layers

Discussion of the layers in the Earth's atmosphere is needed to understand where airborne pollutants disperse in the atmosphere. The layer closest to the Earth's surface is known as the troposphere. It extends from sea-level up to a height of about 18 km and contains about 80 percent of the mass of the overall atmosphere. The stratosphere is the next layer and extends from 18 km up to about 50 km. The third layer is the mesosphere which extends from 50 km up to about 80 km. There are other layers above 80 km, but they are insignificant with respect to atmospheric dispersion modeling.

The lowest part of the troposphere is called the atmospheric boundary layer (ABL) or the planetary boundary layer (PBL) and extends from the Earth's surface up to about 1.5 to 2.0 km in height. The air temperature of the atmospheric boundary layer decreases with increasing altitude until it reaches what is called the inversion layer (where the temperature increases with increasing altitude) that caps the atmospheric boundary layer. The upper part of the troposphere (i.e., above the inversion layer) is called the free troposphere and it extends up to the 18 km height of the troposphere.

The ABL is the most important layer with respect to the emission, transport and dispersion of airborne pollutants. The part of the ABL between the Earth's surface and the bottom of the inversion layer is known as the mixing layer. Almost all of the airborne pollutants emitted into the ambient atmosphere are transported and dispersed within the mixing layer. Some of the emissions penetrate the inversion layer and enter the free troposphere above the ABL.

In summary, the layers of the Earth's atmosphere from the surface of the ground upwards are: the ABL made up of the mixing layer capped by the inversion layer; the free troposphere; the stratosphere; the mesosphere and others. Many atmospheric dispersion models are referred to as boundary layer models because they mainly model air pollutant dispersion within the ABL. To avoid confusion, models referred to as mesoscale models have dispersion modeling capabilities that can extend horizontally as much as a few hundred kilometres. It does not mean that they model dispersion in the mesosphere.

Gaussian air pollutant dispersion equation

The technical literature on air pollution dispersion is quite extensive and dates back to the 1930s and earlier. One of the early air pollutant plume dispersion equations was derived by Bosanquet and Pearson.[2] Their equation did not assume Gaussian distribution nor did it include the effect of ground reflection of the pollutant plume.

Sir Graham Sutton derived an air pollutant plume dispersion equation in 1947[3][4] which did include the assumption of Gaussian distribution for the vertical and crosswind dispersion of the plume and also included the effect of ground reflection of the plume.

Under the stimulus provided by the advent of stringent environmental control regulations, there was an immense growth in the use of air pollutant plume dispersion calculations between the late 1960s and today. A great many computer programs for calculating the dispersion of air pollutant emissions were developed during that period of time and they were commonly called "air dispersion models". The basis for most of those models was the Complete Equation For Gaussian Dispersion Modeling Of Continuous, Buoyant Air Pollution Plumes shown below:[5][6]


where:  
= crosswind dispersion parameter
  =
= vertical dispersion parameter =
= vertical dispersion with no reflections
  =
= vertical dispersion for reflection from the ground
  =
= vertical dispersion for reflection from an inversion aloft
  =
           
           
           
= concentration of emissions, in g/m³, at any receptor located:
            x meters downwind from the emission source point
            y meters crosswind from the emission plume centerline
            z meters above ground level
= source pollutant emission rate, in g/s
= horizontal wind velocity along the plume centerline, m/s
= height of emission plume centerline above ground level, in m
= vertical standard deviation of the emission distribution, in m
= horizontal standard deviation of the emission distribution, in m
= height from ground level to bottom of the inversion aloft, in m
= the exponential function

The above equation not only includes upward reflection from the ground, it also includes downward reflection from the bottom of any inversion lid present in the atmosphere.

The sum of the four exponential terms in converges to a final value quite rapidly. For most cases, the summation of the series with m = 1, m = 2 and m = 3 will provide an adequate solution.

and are functions of the atmospheric stability class (i.e., a measure of the turbulence in the ambient atmosphere) and of the downwind distance to the receptor. The two most important variables affecting the degree of pollutant emission dispersion obtained are the height of the emission source point and the degree of atmospheric turbulence. The more turbulence, the better the degree of dispersion.

Whereas older models rely on stability classes for the determination of and , more recent models increasingly rely on Monin-Obukhov similarity theory to derive these parameters.

Briggs plume rise equations

The Gaussian air pollutant dispersion equation (discussed above) requires the input of H which is the pollutant plume's centerline height above ground level. H is the sum of Hs (the actual physical height of the pollutant plume's emission source point) plus ΔH (the plume rise due the plume's buoyancy).

Visualization of a buoyant Gaussian air pollutant dispersion plume

To determine ΔH, many if not most of the air dispersion models developed between the late 1960s and the early 2000s used what are known as "the Briggs equations." G.A. Briggs first published his plume rise observations and comparisons in 1965.[7] In 1968, at a symposium sponsored by CONCAWE (a Dutch organization), he compared many of the plume rise models then available in the literature.[8] In that same year, Briggs also wrote the section of the publication edited by Slade[9] dealing with the comparative analyses of plume rise models. That was followed in 1969 by his classical critical review of the entire plume rise literature,[10] in which he proposed a set of plume rise equations which have become widely known as "the Briggs equations". Subsequently, Briggs modified his 1969 plume rise equations in 1971 and in 1972.[11][12]

Briggs divided air pollution plumes into these four general categories:

  • Cold jet plumes in calm ambient air conditions
  • Cold jet plumes in windy ambient air conditions
  • Hot, buoyant plumes in calm ambient air conditions
  • Hot, buoyant plumes in windy ambient air conditions

Briggs considered the trajectory of cold jet plumes to be dominated by their initial velocity momentum, and the trajectory of hot, buoyant plumes to be dominated by their buoyant momentum to the extent that their initial velocity momentum was relatively unimportant. Although Briggs proposed plume rise equations for each of the above plume categories, it is important to emphasize that "the Briggs equations" which become widely used are those that he proposed for bent-over, hot buoyant plumes.

In general, Briggs's equations for bent-over, hot buoyant plumes are based on observations and data involving plumes from typical combustion sources such as the flue gas stacks from steam-generating boilers burning fossil fuels in large power plants. Therefore the stack exit velocities were probably in the range of 20 to 100 ft/s (6 to 30 m/s) with exit temperatures ranging from 250 to 500 °F (120 to 260 °C).

A logic diagram for using the Briggs equations[5] to obtain the plume rise trajectory of bent-over buoyant plumes is presented below:

BriggsLogic.png
where:  
Δh = plume rise, in m
F  = buoyancy factor, in m4s−3
x = downwind distance from plume source, in m
xf = downwind distance from plume source to point of maximum plume rise, in m
u = windspeed at actual stack height, in m/s
s  = stability parameter, in s−2

The above parameters used in the Briggs' equations are discussed in Beychok's book.[5]

References

  1. J.C. Fensterstock et al, "Reduction of air pollution potential through environmental planning", JAPCA, Vol. 21, No. 7, 1971.
  2. C.H. Bosanquet and J.L. Pearson, "The spread of smoke and gases from chimneys", Trans. Faraday Soc., 32:1249, 1936.
  3. O.G. Sutton, "The problem of diffusion in the lower atmosphere", QJRMS, 73:257, 1947.
  4. O.G. Sutton, "The theoretical distribution of airborne pollution from factory chimneys", QJRMS, 73:426, 1947.
  5. 5.0 5.1 5.2 M.R. Beychok (2005). Fundamentals Of Stack Gas Dispersion, 4th Edition. author-published. ISBN 0-9644588-0-2. .
  6. D. B. Turner (1994). Workbook of atmospheric dispersion estimates: an introduction to dispersion modeling, 2nd Edition. CRC Press. ISBN 1-56670-023-X. .
  7. G.A. Briggs, "A plume rise model compared with observations", JAPCA, 15:433–438, 1965.
  8. G.A. Briggs, "CONCAWE meeting: discussion of the comparative consequences of different plume rise formulas", Atmos. Envir., 2:228–232, 1968.
  9. D.H. Slade (editor), "Meteorology and atomic energy 1968", Air Resources Laboratory, U.S. Dept. of Commerce, 1968.
  10. G.A. Briggs, "Plume Rise", USAEC Critical Review Series, 1969.
  11. G.A. Briggs, "Some recent analyses of plume rise observation", Proc. Second Internat'l. Clean Air Congress, Academic Press, New York, 1971.
  12. G.A. Briggs, "Discussion: chimney plumes in neutral and stable surroundings", Atmos. Envir., 6:507–510, 1972.

Further reading

  • M.R. Beychok (2005). Fundamentals Of Stack Gas Dispersion, 4th Edition. author-published. ISBN 0-9644588-0-2. 
  • K.B. Schnelle and P.R. Dey (1999). Atmospheric Dispersion Modeling Compliance Guide, 1st Edition. McGraw-Hill Professional. ISBN 0-07-058059-6. 
  • D.B. Turner (1994). Workbook of Atmospheric Dispersion Estimates: An Introduction to Dispersion Modeling, 2nd Edition. CRC Press. ISBN 1-56670-023-X. 
  • S.P. Arya (1998). Air Pollution Meteorology and Dispersion, 1st Edition. Oxford University Press. ISBN 0-19-507398-3. 
  • R. Barrat (2001). Atmospheric Dispersion Modelling, 1st Edition. Earthscan Publications. ISBN 1-85383-642-7. 
  • S.R. Hanna and R.E. Britter (2002). Wind Flow and Vapor Cloud Dispersion at Industrial and Urban Sites, 1st Edition. Wiley-American Institute of Chemical Engineers. ISBN 0-8169-0863-X. 
  • P. Zannetti (1990). Air pollution modeling : theories, computational methods, and available software. Van Nostrand Reinhold. ISBN 0-442-30805-1.