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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
GeneralandPhysicalChemistryforEngineers
byA/PChinWS,Chemistry
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 Forareactiontooccur,thereacting
speciesmustcollidewithappropriate
orientationandthecollisionmustresult
insufficientenergy
WhenTincreases,thespeciesmove
Rateofreaction=numberof fasterandthisleadstomorefrequent
collisionsperunittime collisions
probabilityofacollisionwith
WhenTincreases,thefractionof
sufficientenergy
collisionswithenergy>Ea alsoincreases
Ea
Boltzmann
distributionlaw
Fraction (f) e RT

GeneralandPhysicalChemistryforEngineers
byA/PChinWS,Chemistry
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
GeneralandPhysicalChemistryforEngineers to76767
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
GeneralandPhysicalChemistryforEngineers
byA/PChinWS,Chemistry
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
GeneralandPhysicalChemistryforEngineers
byA/PChinWS,Chemistry
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
GeneralandPhysicalChemistryforEngineers
byA/PChinWS,Chemistry
to76767
Answers
Onlysteps2and3areelementarysteps
Step2isbimolecular;step3isunimolecular
Molecularityisthenumberofcollidingparticles
thatareinvolvedinanelementaryreaction
Trythis:
Showthattheproposedmechanismisconsistentwiththe
observedreaction(1),andsuggestalikelyratelawforthereaction.
Deducealikelyratelawfromaproposedmechanism
Theratelawisdeterminedbytheratedetermining
step
GeneralandPhysicalChemistryforEngineers
byA/PChinWS,Chemistry
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
GeneralandPhysicalChemistryforEngineers
byA/PChinWS,Chemistry
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
GeneralandPhysicalChemistryforEngineers
byA/PChinWS,Chemistry
qSMS Q3
Thehalflifeforthefirstorderradioactivedecayof14Cis
5730years.
Anarchaeologicalsamplecontainswoodthathadonly72%
ofthe14Cfoundinlivingtrees.Estimateitsage.

A. 5730years
B. 4125.6years
C. 2716years SendSMSresponse:
D. 1604.4years 1502q43<space>answer
to76767
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
GeneralandPhysicalChemistryforEngineers
byA/PChinWS,Chemistry
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
GeneralandPhysicalChemistryforEngineers
byA/PChinWS,Chemistry
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.
GeneralandPhysicalChemistryforEngineers
byA/PChinWS,Chemistry
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