GeneralandPhysicalChemistry

forEngineers
ClassDiscussionon
Part(IV)ChemicalKinetics

A/PChinWeeShong
DepartmentofChemistry
GeneralandPhysicalChemistryforEngineers
Email:chmcws@nus.edu.sg
byA/PChinWS,Chemistry
 Part(IV)ChemicalKinetics
1) Reactionrateanditsdetermination
Wewilldiscusstoday
a) Expressionsforreactionrate
b) Theratelawanddeterminationofits
components 2) Theoriesofchemicalkinetics
c) Theeffectoftemperature a) Collisiontheory
b) Transitionstatetheory

3) Reactionmechanism
a) Overallandelementaryreactions 4) Catalysis
b) Theratedeterminingstep a) Homogeneouscatalysis
c) Thesteadystateapproximation b) Heterogeneouscatalysis
c) Enzyme
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 Topic:Howdoweknowareactionisoccurring?
Weobserveaconsumptionofthereactant(s),and/orformationof
product(s)
A+BX
Henceinordertofindouttherateofreaction,wetrytomeasurethe
changeinconsumptionorformation:
Initialrate? d A d B d X
Rate
Averagerate? dt dt dt
Butthereactionmaynotbe1:1inratio:
aA +bB xX

1 d A 1 d B 1 d X
Rate
GeneralandPhysicalChemistryforEngineers a dt b dt x dt
byA/PChinWS,Chemistry
 Topic:Butjusthowhasthereactionoccurred?
Collisiontheory
Rateofreaction=numberof
collisionsperunittime
probabilityofacollisionwith
sufficientenergy
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Forareactiontooccur,thereacting
speciesmustcollidewithappropriate
orientationandthecollisionmustresult
insufficientenergy
WhenTincreases,thespeciesmove
fasterandthisleadstomorefrequent
collisions
WhenTincreases,thefractionof
collisionswithenergy>Ea alsoincreases
Ea
Boltzmann
distributionlaw
Fraction (f) e RT
 qSMS Q1
Comparingtworeactions(1)and(2)withactivationenergyEa1 &
Ea2 andreactionconstantk1 &k2 respectively.
Suggesthowk1 &k2 willbeaffectedbyincreasingTaccordingto
collisiontheoryifEa1is10timeslessthanEa2.
A. k1 isaffectedmuchmorethank2
B. k2 isaffectedmuchmorethank1
C. k1 andk2 areaffectedtothesameextent
SendSMSresponse:
1502q41<space>answer
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byA/PChinWS,Chemistry
 Answer
Ea

Arrheniusequation k A e RT

Ea

Fraction ofmolecularcollisionshavingsufficientenergy(f) e RT

ThesmallertheEa,thelesseristheeffectanincreasedThas
onincreasingf
HencetherateconstantisalsolessaffectedbyT

GeneralandPhysicalChemistryforEngineers
byA/PChinWS,Chemistry
 Topic:Butjusthowhasthereactionoccur?
abetterdescription
Theminimumenergypath
Transitionstatetheory
Reactionpathwayisthelowest
energypathway connectinga
chemicalreactanttoitsproduct
Alongthepathway,thereacting
speciespassthrougha(orseveral)
potentialmaximum
Structureatthismaximalpotential
isthetransitionstate
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 Topic:Transitionstatestructures
Thesearespecies
withpartialbonds
Unstableandcan
neverbeisolated

E Products

Reactants a

Rateofreaction=concentrationofactivatedcomplex
GeneralandPhysicalChemistryforEngineers frequencythecomplexfallsapartintotheproducts
(R1:Figure16.21).
byA/PChinWS,Chemistry
 Topic:ReactionMechanisms
Butthereactionpathwaymightgo
throughsomeintermediatestates

A B
ka
I
kb
X

Eachelementary Anysubstancethatare
stephasitsown productsinanearlystep,
transitionstate, butareactantinalaterstep
rateconstantandEa arecalledintermediates

Moleculeswithnormalbondsand (R1:Figure16.22B).

sometimescanbeisolated
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 qSMS Q2
ConsidertheoverallgasphasereactionofamoleculeA:
1)A Y
AtverylowP,thisreactionoccursbythefollowingmechanism:
2)A+A A*+A(slow) A*representsamoleculewith
3)A* Y(fast) sufficientenergytoovercomeEa

Whichofthefollowingstatementisincorrect?
A. Reaction1isunimolecular
B. Reaction2isbimolecular SendSMSresponse:
C. Reaction3isunimolecular 1502q42<space>answer
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byA/PChinWS,Chemistry
to76767
 Answers
Onlysteps2and3areelementarysteps
Step2isbimolecular;step3isunimolecular
Molecularityisthenumberofcollidingparticles
thatareinvolvedinanelementaryreaction
Trythis:
Showthattheproposedmechanismisconsistentwiththe
observedreaction(1),andsuggestalikelyratelawforthereaction.
Deducealikelyratelawfromaproposedmechanism
Theratelawisdeterminedbytheratedetermining
step
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 Topic:Theempiricalratelaw
Ingeneral,rate [someofthereactants],wecanexpressrates
ofreactionempirically: or[Product]

Reactionorderscannotbe
Rate k A B
n m
deducedfromtheoverall
equation
n andm aretheorder foreachreactant Determinedthrough
andaredeterminedbyexperiment,the plottingorcalculations
valuecanbeinteger,zeroorfraction. using:
Initialratemethod
Overallorderofthereaction=m+n Isolationmethod
etc
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 Firstorderreactions Secondorderreactions
ForA Ponly
d A d A
Rate kA Rate - k A
2

dt dt
d A
d A
Integratedratelaw: A t
Integratedratelaw: - kdt
kdt A 2

A0 A
d A
t0
A t
kdt
[A] [A]0 e -kt A0 A t0
2

1 1
ln[A]t =kt +ln[A]0 kt
[A]t [A]0
Plotln[A]t againsttgivesastraightline
Plot1/[A]t vstgivesastraightline
Unitsofk:s1 Unitsofk:Lmol1s1
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 qSMS Q3
Thehalflifeforthefirstorderradioactivedecayof14Cis
5730years.
Anarchaeologicalsamplecontainswoodthathadonly72%
ofthe14Cfoundinlivingtrees.Estimateitsage.

A. 5730years
B. 4125.6years
C. 2716years SendSMSresponse:
D. 1604.4years 1502q43<space>answer
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GeneralandPhysicalChemistryforEngineers
byA/PChinWS,Chemistry
 Answer
Firstorderkinetics ln2 ln2
5730 k
k 5730
[A][A]0 ekt
[14 C]
ln[A]t =kt +ln[A]0 [ C] [ C]0 e
14 14 -kt
14
0.72
[ C]0
ln2
t1/ 2
ln2 ln0.72 t
k 5730
t 2716 years
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 Steadystateapproximation
Product
A I P
ka kb
Reactant

Assumption:rateofchangeof
theintermediatearenegligibly
small
d I
Intermediate
0
dt
Steadystateapproximationis
validwhenkb >>ka i.e.I
formsslowlyandreacts
readilyso[I]stayslow andits
GeneralandPhysicalChemistryforEngineers
rateofchangeissmall
byA/PChinWS,Chemistry
 qSMS Q4
Kineticstudiesofhydrogenhalideformationshowthatthe
ratelawforHBr formation,H2(g)+Br2(g) 2HBr(g),is
rate=k[H2][Br2]1/2.Isthefollowingproposedmechanisms
consistentwiththeratelaw?
ratedeterminingstep
i. H2(g) 2H(g) [fast]
ii. H(g)+Br2(g)HBr(g)+Br(g)[slow]
iii. Br(g)+H(g) HBr(g)
SendSMSresponse:
Answer:YorN 1502q44<space>answer
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to76767
 Answer
Step(ii)istheratedeterminingstep,rate=k2[H][Br2]
Hisanintermediate,k1[H2]=k1[H]2
[H]=(k1/k1)1/2[H2]1/2
Substitutethisfor[H]intotheearlierequation:
Rate=k2[H][Br2]
=k2(k1/k1)1/2[H2]1/2[Br2]
=k[H2]1/2[Br2]
Thisdiffersfromtheempiricallydeterminedratelaw,hence
themechanismisnotconsistent withtheratelaw
GeneralandPhysicalChemistryforEngineers
byA/PChinWS,Chemistry
 Topic:Catalysis
AnalternativereactionpathwaythathasalowerEa thanthe
uncatalysted reactionandresultsinahigherreactionrateatthe
sameT
speedupboththeforwardandthereversereactions
Producethesameproduct
doesnotaffecttheequilibriumconstantwhichisonlya
functionofT

x Itinvolvesanalternativereactionpathwaybywhichthereactantsand
productsareallstabilized.
Reactionrateisincreasedasthetransitionstateoftheratedetermining
stepismorestabilised.
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 GetreadyforTopic(V).
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