Prepared by

Associate Prof. Dr. Mohamad

Wijayanuddin Ali
Chemical Engineering Department
Universiti Teknologi Malaysia
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Duringandaccident,processequipmentcanreleasetoxicmaterials
veryquicklyandinsignificantenoughquantitiestospreadindangerous
cloudsthroughoutaplantsiteandthelocalcommunity.Afewexamples
are
Explosiveruptureofaprocessvesselduetoexcessive
pressurecausedbyarunawayreaction.

Ruptureofapipelinecontainingtoxicmaterialsathigh
pressure.

Ruptureofatankcontainingtoxicmaterialstoredaboveits
atmosphericboilingpoint.
Ruptureofatrainortrucktransportationtankfollowingan
accident.
Seriousaccidents(suchasBhopal)emphasizetheimportanceof
emergencyplanningandfordesigningplantstominimizetheoccurrence
andconsequencesofatoxicrelease.Toxicreleasemodelsareroutinely
usedtoestimatetheeffectsofareleaseontheplantandcommunity
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environments.
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Anexcellentsafetyprogramstrivestoidentifyproblemsbeforethey
occur.Chemicalengineersmustunderstandallaspectsoftoxicreleaseto
preventtheexistenceofreleasesituationsandtoreducetheimpactofa
releaseifoneoccurs.Thisrequiresatoxicreleasemodel.
Thereare3stepsinutilizingatoxicreleasemodel.
1. Identifythedesignbasis.Whatprocesssituationscanleadtoa
release,andwhichsituationistheworst?
2. Developasourcemodeltodescribehowmaterialsarereleased
andtherateofrelease.
3. Useadispersionmodeltodescribehowmaterialsspread
throughouttheadjacentrates.
Themainemphasisofthetoxicreleasemodelistoprovideatool
usefulforreleasemitigation.Thesourceanddispersionmodelspredictthe
areaaffectedandtheconcentrationofvaporthroughout.Thedesignbasis
isvaluableforeliminatingsituationsthatcouldresultinarelease.
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Various options are available based on the predictions of the toxic

releasemodel.Tonameafew,theseare
1. developanemergencyresponseplanwiththesurrounding
community;
2. developengineeringmodificationstoeliminatethesourceofthe
release;
3. enclosethepotentialreleaseandaddappropriateventscrubbers
orothervaporremovalequipment;
4. reduceinventoriesofhazardousmaterialstoreducethequantity
released;and
5. addareamonitorstodetectincipientleaksandprovideblock
valvesandengineeringcontrolstoeliminatehazardouslevelsof
spillsandleak.
Theseoptionsarediscussedinmoredetailonreleasemitigation.
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DesignBasis
The design basis describes the various scenarios leading to toxic
release; it looks for what can go wrong. For any reasonably complex
chemical facility, thousands of release scenarios are possible; it is not
practicabletoelucidateeveryscenario.Mosttoxicreleasestudiesstriveto
determinethelargestpracticablereleaseandthelargestpotentialrelease.
The largest practicable release considers releases having a reasonable
chanceforoccurrence.Thisincludespiperuptures,holesinstoragetanks
and process vessels, ground spills, and so forth. The largest potential
release is a catastrophic situation resulting in release of the largest
quantity of material. This includes compete spillage of tank contents,
rupture of large bore piping, explosive rupture of reactors, and so forth.
Table 1 contains examples of largest practicable and largest potential
releases.
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Development ofa proper design basis requires skill,experience, and

considerableknowledgeoftheprocess.Hazardsidentificationprocedures
areveryhelpful.
Thecompleteddesignbasisdescribes
1. whatwentwrong,
2. thestateofthetoxicmaterialreleased(solid,liquid,orvapor),
and
3. themechanismofrelease(rupturedpipe,holeinstorage
vessel,andsoon).
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Table1ExamplesofLargestPracticableandLargestPotentialReleases
Largest practicable release : large release with a reasonable chance to
occur.
Rupture of small bore piping, 1-inch maximum.
Partial flange gasket blowout of large diameter piping (for example, 50%
blowout of a 2-inch line resulting in an equivalent hole diameter of 1inch).
Failure of a ? -inch fusible plug on a 1-ton cylinder.
Generally limited release duration (15 minutes typical based on time
required for operator intervention to stop the leak).
Largest potential release : catastrophic release of maximum amount of
material.
Rupture of a 2 or 3 inch liquid line.
Tank truck rupture on a highway (3 or 4 inch hole size assumed, typical).
Typically, entire source vessel inventory spilled.
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Wateristreatedataswimmingpoolusinga100lbbottleofchlorine.The
chlorineisfedfromthebottlethrougha1/4inlinetothewatertreatment
facility.Areliefvalveonthetankpreventsexcessivepressurefrom
rupturingthetank.Chlorineisstoredinthebottleasaliquidunder
pressureandwillboilwhenthepressureisreduced.Identifytherelease
scenarios.

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Scenario1:
Thebottleofchlorineruptures,possiblyfromdropping
thetankwhileunloadingfromatruck.Theentirecontentsisspilled,with
afractionflashingimmediatelyintovaporandtheremainingliquid
formingaboilingpoolontheground.
Scenario2:
Aholeformsinthetankeitherbecauseofmechanical
ruptureorcorrosion.Ajetofflashingchlorineandaboilingpoolof
liquidchlorineforms.
Scenario3:
Thereliefvalvefailsopen,formingajetandpoolof
boilingchlorine.
Scenario4:
Thefeedlinetothetreatmentplantfailswithajetand
poolofboilingchlorine.
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Scenario 5 :

A fire develops around the chlorine tank, heating the

tankuntilthereliefvalveopens.
Scenario6:

Afiredevelopsaroundthechlorinetank,buttherelief

valvefailsclosed.Thetankpressurebuildsuntilitruptures,spillingthe
entiretankcontentsexplosively.
Thelargestpracticablereleasecouldbeeitherscenarios2,3,or4,
dependingontherateofmaterialreleasecomputedusinganappropriate
sourcemodel.Thelargestpotentialreleaseisscenario6,releasingthe
entiretankcontentsalmostimmediately.
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Thepurposeofthesourcemodelisto
1. Theformofmaterialreleased,solid,liquidorvapor;
2. Thetotalquantityofmaterialreleased;and
3. Therateatwhichitisreleased.
This information is required for any quantitative dispersion
modelstudy.

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Dispersion models describe the airborne transport of toxic

materials away from the accident site and into the plant and
community.Afterarelease,theairbornetoxiciscarriedawaybythe
windinacharacteristicplumeasshowninFigure1orapuff,shown
inFigure2.Themaximumconcentrationoftoxicmaterialoccursat
thereleasepoint(whichmaynotbeatgroundlevel).Concentrations
downwind are less, due to turbulent mixing and dispersion of the
toxicsubstancewithair.
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Figure1Characteristicplumeformedbyacontinuousreleaseofmaterial.
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Figure2Puffformedbynearinstantaneousreleaseofmaterial.
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A wide variety of parameters affect atmospheric dispersion of toxic

materials
Windspeed
Atmosphericstability
Groundconditions,buildings,water,trees
Heightofthereleaseabovegroundlevel
Momentumandbuoyancyoftheinitialmaterialreleased
As the wind speed increases, the plume in Figure 1 becomes longer
and narrower; the substance is carried downwind faster but is diluted
fasterbyalargerquantityofair.
Atmosphericstabilityrelatestoverticalmixingoftheair.Duringthe
daytheairtemperaturedecreasesrapidlywithheight,encouragingvertical
motions.Atnightthetemperaturedecreaseisless,resultinginlessvertical
motion. Temperature profiles for day and night situations are shown in
Figure3.Sometimesaninversionwilloccur.
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Figure 3 Air temperature as a function of altitude for day and night

conditions.Thetemperaturegradientaffectstheverticalairmotion.
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During and inversion, the temperature increases with height,

resultinginminimalverticalmotion.Thismostoftenoccursatnightas
thegroundcoolsrapidlyduetothermalradiation.
Groundconditionsaffectthemechanicalmixingatthesurfaceand
the wind profile with height. Trees and buildings increase mixing
whilelakesandopenareasdecreaseit.Figure4showsthechangein
windspeedversusheightforavarietyofsurfaceconditions.
The release height significantly affects ground level
concentrations. As the release height increases, ground level
concentrations are reduced since the plume must disperse a greater
distancevertically.ThisisshowninFigure5.

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Figure4Effectofgroundconditionsonverticalwindgradient.
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Figure5Increasedreleaseheightdecreasesthegroundconcentration.
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The buoyancy and momentum of the material released changes the

effective height of the release. Figure 6 demonstrates these effects.
After the initial momentum and buoyancy has dissipated, ambient
turbulentmixingbecomesthedominanteffect.
Twotypesofvaporclouddispersionmodelsarecommonlyused:the
plume and puff models. The plume model describes the steadystate
concentration of material released from a continuous source. The puff
model describes the temporal concentration of material from a single
release of a fixed amount of material. The distinction between the two
modelsisshowngraphicallyinFigures1and2.Fortheplumemodel,a
typicalexampleisthecontinuousreleaseofgasesfromasmokestack.A
steadystate plume is formed downwind from the smokestack. For the
puffmodel,atypicalexampleisthesuddenreleaseofafixedamountof
material due to the rupture of a storage vessel. A large vapor cloud is
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formedthatmovesawayfromtherupturepoint.
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Figure6Theinitialaccelerationandbuoyancyofthereleasedmaterial
affects the plume character. The dispersion models discussed in this
chapterrepresentonlyambientturbulence.
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The puff model can be used to describe a plume; a plume is

simply the release of continuous puffs. If, however, steadystate
plume information is all that is required, the plume model is
recommendedsinceitiseasiertouse.Forstudiesinvolvingdynamic
plumes (for instance the effect on a plume due to a change in wind
direction),thepuffmodelmustbeused.
Consider the instantaneous release of a fixed mass of material,
Qm*, into an infinite expanse of air (a ground surface will be added
later). The coordinate system is fixed at the source. Assuming no
reactionormoleculardiffusion,theconcentration,C,ofmaterialdue
tothisreleaseisgivenbytheadvectionequation.
C

u j C = 0
+
t
x j

(1)

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whereujisthevelocityoftheairandthesubscriptjrepresentsthe
summationoverallcoordinatedirections,x,y,andz.ifthevelocity,uj,
inEquation1issetequaltotheaveragewindvelocityandtheequation
issolved,onewouldfondthatthematerialdispersesmuchfasterthan
predicted. This is due to turbulence in the velocity field. If one were
able to specify the wind velocity exactly with time and position,
including the effects due to turbulence, Equation 1 would predict the
correctconcentration.Unfortunately,nomodelsarecurrentlyavailable
to adequately describe turbulence. As a result, an approximation is
used. Let the velocity be represented by an average (or mean) and
stochasticquantity;
u j u j u 'j

(2)

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where <uj> is the average velocity and uj is the stochastic

fluctuationduetoturbulence.Itfollowsthattheconcentration,C,will
alsofluctuateasaresultofthevelocityfield,so,
C C C'

(3)

where <C> is the mean concentration and C is the stochastic

fluctuation. Since the fluctuations in both C and uj are around the
averageormeanvalues,itfollowsthat,
' 0
(4)
' 0
SubstitutingEquation2and3intoEquation1andaveragingthe
resultovertime,yields,
C
t

x j

+ x

u 'j C ' = 0
j

(5)
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Theterms<uj>Canduj<C>arezerowhenaveraged(<<uj>C>=
<uj><C>=0),buttheturbulentfluxterm<ujC>isnotnecessarilyzero
andremainsintheequation.
Anadditionalequationisrequiredtodescribetheturbulentflux.The
usualapproachistodefineaneddydiffusivity,Kj(withunitsofarea/time),
suchthat

u C

K j

(6)

x j

substitutingEquation6intoEquation5yields,
C
t

x j

x j

C
K j

x j

(7)
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Iftheatmosphereisassumedtobeincompressible,

0

(8)

andEquation7becomes
C
C

uj

t
x j
x j

(9)

C
K j

x j

Equation 9, together with appropriate boundary and initial

conditions, formsthe fundamental basis for dispersion modelling.This
equationwillbesolvedforavarietyofcases.
The coordinate system used for the dispersion models is shown in
Figures7and8.Thexaxisisthecentrelinedirectlydownwindfromthe
release point and is rotated for different wind directions. The yaxis is
thedistanceoffofthecentrelineandthezaxisistheelevationabovethe
release point. The point (x,y,z) = (0,0,0) is at the release point. The
coordinates(x,y,0)arelevelwiththereleasepoint,andthecoordinates
(x,0,0)arealongthecentreline,orxaxis.
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Figure7Steadystate,continuouspointsourcereleasewithwind.Note
coordinate system : x is downwind direction, y is offwind direction ,
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andzisverticaldirection.
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Figure8Puffwithwind.Aftertheinitial,instantaneousrelease,thepuff
moveswiththewind.

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