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CHE594 ChemicalReactionEngineering
Dr.SALAMA.MOHD / 2877079 PhoneNumber:0355436343/019

Fogler

5th

Reference edition,Levenspiel 3rd edition

TOPIC1 Introductionto ChemicalReactionEngineering

Classificationofreactions Definitionofreactionrate
Elementaryandnonelementaryreaction Molecularityandorderofreaction Kineticmodelsfornonelementaryreaction

Temperaturedependenttermofrateequation

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Whatisachemicalreaction? The h change h of fasubstance b intoanewsubstance b which h h hasnew/differentchemicalidentity i.e acid+metal atypeofsalt 2HCl+2Mg 2MgCl+H2 2HCl+2Na2NaCl+H2 Mg(OH)2 +2HCl MgCl2 +2H2O
Raw material
Chemical reaction

Product

changesinphysicaleffecti.e.emissionofheat, formationofprecipitation,colourchange,etc.

Inindustrialchemicalprocess,thetypical situation it ti of fchemical h i lprocessis i shown h below: b l

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ClassificationofReactions Generally,chemicalreactionscanbeclassified intohomogeneous andheterogeneous reactions. Homogeneousreaction isareactionthattake placeinonephasealone.i.e.reaction between2gases,2liquids,2solids Heterogeneousreaction isareactionthatthat requiresthepresenceofatleast2phases(or more)toproceedatcertainreactionrate.i.e. reactionbetweengasandliquid,gasandsolid, liquidandsolid

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Variablesthataffectrateofreaction Inhomogeneoussystemsthe temperature,pressure,andcomposition areobviousvariables. Inheterogeneous,theproblembecomes morecomplex.Materialmayhaveto movefromphasetophaseduring reaction;hence,therate ofmasstransfer canbecomeimportant.

IDEALREACTORS

Batch

Mixed Flow Reactor (MFR)

Plug Flow Reactor (PFR)

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DefinitionofReactionRate

Simplyput,reactionratescanbedefinedas speedofreactions. Somereactionscanbevery,veryslowi.e. Sewagetreatmentplants Somereactionscanbevery,veryfasti.e. Reactionsinrocketengines Therateofareactioncanbeexpressedas therateofdisappearance ofareactantor astherateofappearance ofaproduct

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Considerthisreaction
A B
-rA rB
= the rate of a disappearance of species A = the rate of formation of species B

By definition, the reaction rate is the increase in molar concentration of a product of a reaction per unit time time.
(EQ2)

(EQ3)

Considerthisreaction
4molesofAreactedwith8molesofBtoproduce4molesofCand4molesofD

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Iftherateofchangeisinnumberofmoles reaction ,the ofcomponentiduetoreaction, rateofreactioninvariousformscanbe defined:

basedonunitvolumeofreactingfluid
(EQ4)

basedonunitmassofsolidinfluidsolid

systems
(EQ5)

basedonunitinterfacialsurfaceintwofluidsystems
orbasedonunitsurfaceofsolidingassolidsystems
(EQ6)

basedonunitvolumeofsolidingassolidsystems
(EQ7)

basedonunitvolumeofreactor,ifdifferentfromthe ratebasedonunitvolumeoffluid
(EQ8)

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Inhomogeneoussystems thevolumeoffluidinthe reactorisoftenidenticaltothevolumeofreactor.Insuch acaseV and dVr areidentical id ti land dE Eqs.4and d8areused d interchangeably. Inheterogeneoussystems alltheabovedefinitionsof reactionrateareencountered,thedefinitionusedinany particularsituationoftenbeingamatterofconvenience. FromEqs.4to8theseintensivedefinitionsofreaction ratearerelated l dby: b

(EQ9)

Elementaryreaction
Elementaryreactions:therateofequationcorrespondstoa stoichiometricequations H2+I22HIrH2=k[H2][I2] Considerasinglereactionwithstoichiometric equation TherateofdisappearanceofAisgivenby

Suchreactioniscalledelementaryreaction

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Nonelementaryreaction
Nonelementaryreactions:nodirectcorrespondence betweenstoichiometryandrate Whenthereisnodirectcorrespondencebetweenstoichiometry andrate,thenwehavenonelementaryreactions.Theclassical exampleofanonelementaryreactionisthatbetweenhydrogen andbromine, whichhasarateexpression

MolecularityandOrderofReaction
Themolecularityofanelementaryreactionisthenumberof moleculesinvolvedinthereaction,andthishasbeenfoundto havethevaluesofone,two,oroccasionallythree. Notethatthemolecularityrefersonlytoanelementary reaction. Letussay,materialsA,B,...,D,canbeapproximatedbyan expressionofthefollowingtype:

aA+bB+cC+dD

product

Themolecularity showsthe powerortheorderofthe reaction

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Elementary reactions are often represented by an equation q showing g both the molecularity y and the rate constant. For example

Th rateof The fequation i is: i

Considerthisreaction

RateofequationthatreferstoB RateofequationthatreferstoD RateofequationthatreferstoT

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Butfromstoichiometry pointofview,theequation willbe

Hence, Hence

Anonelementaryreactionisone whosestoichiometry doesnot matchitskinetics.Forexample,

Nonelementaryreactionalwaysinvolveintermediate andmultiplereactions However,itisdifficulttoquantifytheconcentration ofintermediatesinceitexistsonlyforfewminutes.

Typesofintermediatecanbegroupedintofree radicals,ionsandpolarsubstances,molecules, transitioncomplexes,nonchainreactionsandchain reactions

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SingleandMultipleReaction
Singlereaction asinglestoichiometric equationandsingle rateequationrepresenttheprogressofreaction Multiplereaction morethanonestoichiometric equation representtheobservedchangesandmorethanonekinetic expressionneededtofollowthechangingcompositionofall reactioncomponents
Seriesreactions Parallelreactions AR S R A S
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KineticsModelfor NonelementaryReaction

Testingofkineticmodels

Whatisthepossiblereactionmechanism?

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Since stoichiometry of A and B are symmetrical therefore just interchange A and B in the model and set k2 = 0 and we will get:

TemperatureDependentTerm ofaRateofEquation

TemperaturedependencyonArrheniusLaw
Formanyreactions,andparticularlyelementary reactions,therateexpressioncanbewrittenasa productofatemperaturedependenttermanda compositiondependentterm,or
ri =1 (temperaure).2 (composition) k 2 (composition) =k.

ArrheniusLaw

Thisispracticallywellpresentedby

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Therateofequation/theratelawisanalgebraic equation thatdepends onreacting q p gmaterialsand reactionconditions.Itisindependent ofthetype ofreactor(batchorcontinuous).

kisrateconstantwhichistemperaturedependent

Atthesameconcentration,butattwodifferent temperatures Arrhenius temperatures, Arrhenius'lawindicatesthat

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Itcanbeconcludedthat
1. FromArrhenius' h 'law l aplot l of fln l k vs 1/T / givesastraight h line, l withlargeslopeforlargeE andsmallslopeforsmallE (slope=E/R). Reactionswithhighactivationenergiesarevery temperaturesensitive;reactionswithlowactivation energiesarerelativelytemperatureinsensitive. k0doesnotaffectthetemperaturesensitivity.

2.

3.

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ActivationEnergyandTemperatureDependency
Thetemperature p dependency p yofreactionsis determinedbytheactivationenergyandtemperature levelofthereaction,asillustrated

EXERCISE
Milk is pasteurized if it is heated to 63oC for 30 min, but if it is heated to 74 74C C it only needs 15 s for the same result. Find the activation energy of this sterilization process.

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Given,

The rate is inversely proportional to the reaction time, meaning that the rate is so:

EXERCISE
1. Inthehomogeneousgasphasereaction,statethe relationshipbetweenrCH4 andrO2.
3 CH 4 + O2 HCOOH + H 2O 2

2. Forthereactionof 1 N 2 + 3 H 2 , NH 3 ,determinetherate 2 2 law.

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