Determine Rate Law by Method of Initial Rates

4/11/2016
ChemTeam:Kinetics:determineratelawbymethodofinitialrates
Determineratelawbymethodofinitialrates
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Problem#1:Ratedatawereobtainedforfollowingreaction:
A+2B>C+2D
Exp.
InitialA InitialB Init.RateofFormation

(mol/L) (mol/L)
ofC(Mmin1)
0.10
0.10
3.0x104
0.30
0.30
9.0x104
0.10
0.30
3.0x104
0.20
0.40
6.0x104
Whatistheratelawexpressionforthisreaction?
Solution:
1)compareexp.1andexp.3.AremainsconstantandBistripled.Theratefrom1to3
remainsconstant.Conclusion:Bisnotintheratelawexpression.
2)compareexp1toexp2.TheconcentrationofAtriples(andwedon'tcarewhat
happenstoB).Theratetriples.Conclusion:firstorderinA.
3)wecanalsoshowfirstorderinAbycomparingexp1toexp4.TheconcentrationofA
doublesandtheratedoubles.Remember,Bisnotpartoftheratelaw,sowedon'tpayany
attentiontoitatall.
rate=k[A]
Problem#2:ForthereactionA+B>products,thefollowinginitialrateswerefound.Whatisthe
ratelawforthisreaction?
Trial1:[A]=0.50M[B]=1.50MInitialrate=4.2x103M/min
Solution:
1)OrderwithrespecttoA:
Lookattrial1andtrial2.BisheldconstantwhileAtriples.Theresultisthattherate
triples.Conclusion:Aisfirstorder.
http://www.chemteam.info/Kinetics/WSKineticsmethodofinitialrates.html
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2)OrderwithrespecttoB:
Lookattrials2and3.ThekeytothisisthatwealreadyknowthattheorderforAisfirst
order.
Bothconcentrationsweredoubledfrom2to3andtherategoesupbyafactorof4.Since
Aisfirstorder,weknowthatadoublingoftherateisduetotheconcentrationofAbeing
doubled.
So,welookattheconcentrationchangeforB(adoubling)andtheconsequentrate
change(anotherdoublingremembertheoverallincreasewasafactorof4thinkof4as
beingadoubleddoubling).
Conclusion:theorderforBisfirstorder.
Theratelawisrate=k[A][B]
Comment:theabovemannerofmakingtherateorderdeterminationforBabitmorecomplexisa
commontechnique.Lookforittobeusedonyourtest!
Problem#3:Thefollowingdatawereobtainedforthischemicalreaction:A+B>products
Exp.

(mmol/L) (mmol/L) ofproducts(mMmin1)
4.0
6.0
1.60
2.0
6.0
0.80
4.0
3.0
0.40
(a)Determinetheratelawforthisreaction.
(b)Findtherateconstant.
Solution:
1)Lookatexperiments2and1.From2to1,weseethatAisdoubled(whileBisheld
constant).Adoublingoftheratewithadoublingoftheconcentrationshowsthatthe
reactionisfirstorderwithrespecttoA.
2)Nowcompareexperiments1and3.TheconcentrationofAisheldconstantwhilethe
concentrationofBiscutinhalf.WhenBiscutinhalf,theoverallrateiscutbyafactor
of4(whichisthesquareof2).ThisshowsthereactionissecondorderinB.
3)Theratelawisthis:rate=k[A][B]2
4)Notethatthecomparisonin(2)canbereversed.ConsiderthattheconcentrationofBis
doubledasyougofromexp.3toexp.1.Whentheconcentrationisdoubled,therategoes
upbyafactorof4(whichis22).
5)Wecanuseanysetofvaluestodeterminetherateconstant:
rate=k[A][B]2
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1.60mMmin1=k(4.0mM)(6.0mM)2
k=0.011mM2min2
theunitsonkcanberenderedinthismanner:
k=0.067L2mmol2min1
Problem#4:Thefollowingdatawereobtainedforthechemicalreaction:A+B>products
Exp.

(mol/L) (mol/L)
ofproducts(Ms1)
0.040
0.040
9.6x106
0.080
0.040
1.92x105
0.080
0.020
9.6x106
(a)Determinetheratelawforthisreaction.
(b)Findtherateconstant.
(c)Whatistheinitialrateofreactionwhen[A]o=0.12Mand[B]o=0.015
Solution:
1)Examineexps.2and3.AremainsconstantwhileBisdoubledinconcentrationfrom3
to2.Theresultofthischangeisthattherateofthereactiondoubles.Weconcludethat
thereactionisfirstorderinB.
2)Nowwelookatexps1and2.BremainsconstantwhiletheconcentrationofA
doubles.Asaresultofthedoubledconcentration,theratealsodoubles.Conclusion:the
reactionisfirstorderinA.
3)Theratelawforthisreactionis:
rate=k[A][B]
4)Wecanuseanysetofdatatocalculatetherateconstant:
rate=k[A][B]
9.6x106Ms1=k(0.040M)(0.040M)
k=0.0060M1s1
Comment:rememberthatM1s1isoftenwrittenasLmol1s1.
5)Weusetherateconstantalongwiththedatainpart(c)ofthequestion:
rate=(0.0060M1s1)(0.12M)(0.015M)
rate=1.08x105Ms1
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Problem#5:ConsiderthereactionthatoccurswhenaClO2solutionandasolutioncontaining
hydroxideions(OH)aremixed,asshowninthefollowingequation:
2ClO2(aq)+2OH(aq)>ClO3(aq)+ClO2(aq)+H2O(l)
WhensolutionscontainingClO2andOHinvariousconcentrationsweremixed,thefollowingrate
datawereobtained:
Determination#1:[ClO2]o=1.25x102M[OH]o=1.30x103M
InitialrateforformationofClO3=2.33x104Ms1
(a)Writetherateequationforthechemicalreaction.
(b)Calculatetherateconstant,k.
(c)Calculatethereactionrateforthereactionwhen[ClO2]o=8.25x103Mand[OH]o=5.35x
102M.
Solution:
1)Compare#1and#2.TheconcentrationofClO2doubles(hydroxideremainsconstant)
andtherategoesupbyafactoroffour(thinkofitastwosquared).Thismeansthe
reactionissecondorderwithrespecttoClO2.
2)Compare#2and#3.Theconcentrationofhydroxideisdoubledwhilethe[ClO2]
remainsconstant.Theratedoubles,showingthatthereactionisfirstorderinhydroxide.
3)Theratelawis:rate=k[ClO2]2[OH]
4)Calculationfortherateconstant:
1.87x103Ms1=k(2.50x102M)2(2.60x103M)
k=1.15x103M2s1
Oftentherateconstantunitisrenderedthusly:L2mol2s1.
Notethattheoverallorderoftheratelawisthirdorderandthatthisis
reflectedintheunitassociatedwiththerateconstant.
5)Calculationforpart(c):
rate=(1.15x103M2s1)(8.25x103M)2(5.35x102M)
rate=4.19x103Ms1
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Problem#6:2A+B>C+D
Thefollowingdataaboutthereactionabovewereobtainedfromthreeexperiments:
Exp. [A]
[B]
Initialrateof
formationofC
0.6 0.15
6.3x103
0.2
0.6
2.8x103
0.2 0.15
7.0x104
Calculatetherateexpressionintermsof[A]forexperiment1.
Solution:
rate1/rate3=k1[A1]x[B1]y/k3[A3]x[B3]y
k'swillcanceland[B]willcancel
rate1/rate3=[A1]x/[A3]x
0.0063/0.0007=(0.6)x/(0.2)x
9=0.6x/0.2x
9=3x
rate=k[A]2
Comment:notethat,withasecondorder,whentheconcentrationincreasesbyafactorof3,therate
goesupbyafactorof9(whichis32).
Problem#7:Determinetheproperformoftheratelawfor:
CH3CHO(g)>CH4(g)+CO(g)
Exp. [CH3CHO] [CO] Rate(Ms1)
1
0.30
0.20
0.60
0.10
0.30
0.067
0.10
0.20
0.067
Solution:
1)Noteexperiments2and3.The[CH3CHO]remainsconstantwhilethe[CO]changes.
However,nochangeofthereactionrateisobserved.Fromthis,weconcludethatCOis
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notpartoftheratelaw.
2)Examineexperiment3comparedtoexperiment1.from3to1,the[CH3CHO]triples
andtherategoesupbyafactorof9(whichis32).Conclusion:thereactionissecond
orderinCH3CHO.
3)Therateexpressionisthis:rate=k[CH3CHO]2
Problem#8:Determinetheratelaw,includingthevaluesoftheordersandratelawconstant,forthe
followingreactionusingtheexperimentaldataprovided.
Q+X>products
Trial
[Q]
[X]
Rate
0.12M 0.10M 1.5x103M/min
0.24M 0.10M 3.0x103M/min
0.12M 0.20M 1.2x102M/min
Solution:
1)Examinetrials1and2.[X]isheldconstantwhile[Q]isdoubled(from1to2).Asa
result,theratedoubles.WeconcludethatthereactionisfirstorderinQ.
2)Examinetrials3and1.TheconcentrationofQdoesnotchangefrom3to1butthe
concentrationforXisdoubled.Whenthishappens,weobserveaneightfoldincreasein
therateofthereaction.WeconcludethatthereactionisthirdorderinX.Thisarisesfrom
thefactthat23=8.Inmoredetail:
rate3/rate1=k3[Q3]x[X3]y/k1[Q1]x[X1]y
k'swillcanceland[Q]willcancel
rate3/rate1=[X3]x/[X1]x
0.012/0.0015=(0.20)x/(0.10)x
8=0.20x/0.10x
8=2x
x=3
Comment:notethat,withathirdorder,whentheconcentrationincreasesbyafactorof2,
therategoesupbyafactorof8(whichis23).
3)valueoftherateconstant:
rate=k[Q][X]3
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0.012Mmin1=k(0.12M)(0.20M)3
k=12.5L3mol3min1
Notethatthisreactionisoverallfourthorder.
Problem#9:Withthefollowingdata,usethemethodofinitialratestofindthereactionorderswith
respecttoNOandO2.:
Initialreaction
Trial [NO]o [O2]o
rate,M/s
1
0.020
0.010
0.028
0.020
0.020
0.057
0.040
0.020
0.227
Solution:
1)DoublingO2doublesreactionrate(trials2and1).
2)DoublingNOincreasesreactionrate8x(trials2and3).
3)Conclusion:firstorderO2,thirdorderNO.
Problem#10:Forthefollowingreaction:
A+B>2C
itisfoundthatdoublingtheamountofAcausesthereactionratetodoublewhiledoublingtheamount
ofBcausesthereactionratetoquadruple.Whatisthebestratelawequationforthisreaction?
(a)rate=k[A]2[B]
(b)rate=k[A][B]
(c)rate=k[A][B]2
(d)rate=k[A]1/2[B]
Theratedoublingwhentheconcentrationisdoubledisahallmarkoffirstorder.Therategoingupby
afactorof4(withistwosquared)whentheconcentrationisdoubledisahallmarkofsecondorder.
Answerchoice(c)isthecorrectanswer.
Here'sanansweronYahooAnswerstoaproblemliketheonesabove.
BonusProblem:Aratelawis1/2orderwithrespecttoareactant.Whatistheeffectontheratewhen
theconcentrationofthisreactantisdoubled?
Solution:
Letusexaminetheeffectontherate(symbolizedasR)aswedoubletheconcentrationfromstepto
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step:
R=k[1]0.5=1
R=k[2]0.5=1.4
R=k[4]0.5=2
R=k[8]0.5=2.8
R=k[16]0.5=4
OneanswerIfoundonYahooAnswerswasthis:
Thereactionrateisnotdoubledwhenyoudoubletheconcentration.Noticethatwhenthe
concentrationchangedfrom2to8,theRwentfrom1.4to2.8.Sowhentheconcentration
isquadrupled,theRdoubles.
Iwouldaddtotheabovebysaying:
Whentheconcentrationdoubles,therategoesupbyafactorwhichisthesquarerootof
two.
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Determine Rate Law by Method of Initial Rates

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Determine Rate Law by Method of Initial Rates

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InitialA InitialB Init.RateofFormation

InitialA InitialB Init.RateofFormation

InitialA InitialB Init.RateofFormation

0.12M 0.10M 1.5x103M/min

0.24M 0.10M 3.0x103M/min

0.12M 0.20M 1.2x102M/min

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