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11th12thstdstandardClassOrganicInorganicPhysicalChemistryHighersecondaryschoolCollegeNotes

TemperatureDependanceOfRateConstant
PostedOn:12.03.201602:09am

Itisacommonobservationthatratesofreactionsincreasewithincreaseintemperatureofthereactionmixture.Keepingtheconcentrationof
thereactantsconstant,therateisfoundtobetwotimesitsinitialvalue,whenmeasuredatatemperature10Kgreaterthantheinitial
temperature.

TEMPERATUREDEPENDANCEOFRATECONSTANT

Itisacommonobservationthatratesofreactionsincreasewithincreaseintemperatureofthereactionmixture.
Keeping the concentration of the reactants constant, the rate is found to be two times its initial value, when
measuredatatemperature10Kgreaterthantheinitialtemperature.However,theexactvalueoftherateconstant
determinedatvarioustemperatureispredictedbyusingArrheniusequation.Thisexpressionisobeyedbymostof
thereactions.Arrheniusequationisgivenas
k=AeEa/RT

wherek=rateconstant,Ea=activationenergy,A=frequencyfactor,R=gasconstant,T=temperatureinKelvin.
Ifk1andk2aretherateconstantsmeasuredattwodifferentT1andTtemperaturesrespectively,thenEa can be
determinedasfollows:
ArrheniusequationfortwodifferenttemperaturesT1andT2are:
logk1=logA(Ea/2.303RT1)
logk2=logA(Ea/2.303RT2)
wherek1andk2aretherateconstantsattemperatureT1andT2respectively.
logk2logk1=(Ea/2.303RT2)+(Ea/2.303RT1)
log(k2/k2)=Ea/2.303R(T2T1/T1T2)
IfR=1.987cals.mol1,thenunitofEis103k.cal.
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IfR=1.987cals.mol ,thenunitofEis10 k.cal.

Also,aplotoflogkagainst1/TvaluesgivesastraightlinewithslopevalueequalstoE a/2.303Randintercept
valueequalstologA.WhenEaisapositivevalue,andifT2>T1thenk2>k1.Thatis,rateconstantvalueathigher
temperatureisgreaterthanrateconstantvalueatlowertemperature.Undersuchconditions,plotoflogkagainst
1/Tgivesanegativeslopestraightline.Fromtheslopeofthestraightline,Eacanbecalculated.

Reactantmoleculescomeintocontactthroughcollisionsfortransformationintoproductmolecules.Since,notall
collisions are successful in producing the product molecules, all colliding molecules must possess certain
minimumenergycalledasthethresholdenergywhichisneededtomakethecollisionseffectiveandsuccessful.
The additional energy required by the molecules to attain the threshold energy in addition to the energy of
collidingmoleculesiscalledasactivationenergyEa.Thus,activationenergy=thresholdenergyEnergyof
collidingmolecules.Generally,thisEavalueishigherthanthepotentialenergiesofreactantsandproducts.Thus,
Eaisconsideredasanenergybarrierthatmustbecrossedbythereactantmoleculesbeforegettingconvertedto
actualproductmolecules.

Potential energy diagram of a reaction. The molecular state present at the Ea position in the potential energy
diagram,isconsideredastheintermediateproduct(or)thetransitionstate.ThusEa,isalsotheenergyrequiredto
formtheactivatedstateortheintermediate,whichisnecessarytoformtheproducts.Eaisacharacteristicvalueof
areaction.Therate,rateconstant,andtheirtemperaturedependancearedeterminedbythevalueofEa.Higherthe
valueofEa,sloweristherateofthereaction.

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