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EquilibriumProblemsAPLevel

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Problem#1:When0.0322molofNOand1.70gofbromineareplacedina1.00Lreactionvesselandsealed,
themixturereactsandthefollowingequilibriumisestablished:
2NO(g)+Br2(g)2NOBr(g)
At25.0Ctheequilibriumofnitrosylbromideis0.438atm.WhatistheKp?
Solution:
1)DeterminepressureexertedbyinitialamountofNO:
P=(nRT)/V
P=[(0.0322mol)(0.08206Latmmol1K1)(298K)]/1.00L
P=0.787415atm(keepingafewguarddigits)
2)DeterminepressureexertedbyinitialamountofBr2:
P=(nRT)/V
P=(gRT)/(molarmasstimesV)
P=[(1.70g)(0.08206Latmmol1K1)(298K)]/[(159.808gmol1)(1.00L)]
P=0.260135atm
3)DetermineequilibriumpressureofNO:
Fromthebalancedequation,theNO:NOBrratiois1:1.Therefore,0.438atmofNOreacted.
0.787415atm0.438atm=0.349415atm
4)DetermineequilibriumpressureofBr2:
Fromthebalancedequation,theBr2:NOBrratiois1:2.Therefore,0.438/2=0.219atmofBr2
reacted.
0.260135atm0.219atm=0.041135atm
5)WritetheKpexpressionandsolveit:
Kp=PNOBr2/[(PNO2)(PBr2)]
Kp=(0.438)2/[(0.349415)2(0.041135)]
Kp=38.2(to3sigfig.)
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Problem#2:A1.00Lvesselcontainsatequilibrium0.300molofN2,0.400molH2,and0.100molNH3.Ifthe
tempismaintainedconstant,howmanymolesofH2mustbeintroducedintothevesselinordertodoublethe
equilibriumconcentrationofNH3?
Solution:
1)SolvefortheKcfirst:
Kc=[NH3]2/([N2][H2]3)
x=(0.100)2/[(0.300)(0.400)3]
x=0.5208333
2)Createanewequilibriumexpressionwith[NH3]=0.200.Usethestoichiometryoftheequationtodetermine
the[N2]whenthe[NH3]isdoubled.Setx=[H2].Rememberthecube:
[N2]=0.250since0.050molesofN2arerequiredtomaketheadded0.100moleofNH3
0.52083=(0.200)2/[(0.250)(x)3]
x=0.675M
3)Thisisthe[H2]presentinthenewequilibriumconditions(remember,wearedetermininghowmuchH2got
added,whichiswhyitislargerthan0.400).Figureouthowmuchhadtohavebeenused(fromthebalanced
equation).Addthattotheequilibriumamount.Thisisthetotalinitial[H2]:
themolarratiobetweenNH3andH2is2:3therefore,0.15moleofH2gotusedupinmakingthe
added0.100molofNH3inthenewequilibrium
0.675+0.150=0.825M(thisistheinitialamountofH2intheequilibriumthateventually
produced0.200molofNH3)
4)Subtract0.400togettheamountofH2thatwasadded:
0.8250.400=0.425molofH2addedtopushthe[NH3]from0.100to0.200inthenew
equilibrium
Commentontheabovesolution:Ipostedtheaboveansweronsci.chemmanyyearsago.Igotthisresponse
(whichhasanerrorinit):
AftersolvingforKeqattheinitialconditions,Isettheammoniaconcentrationto0.200M,the
nitrogenconcentrationto0.250M,andthehydrogenconcentrationto(0.400+x)M.Afterplugging
thenewvaluesintotheexpressionforKeqandsolvingforx,mycalculationsyieldedavalueof
0.274746132241molesofhydrogenneeded.(aren'tTI85'swonderful).Thisisofcoursetoomany
sigfigsbutwhenpluggedintotheproblemitdoesagreewiththeoriginalKeqto10places.My
answerwouldthenbethat0.275molesofhydrogenareneededinordertodoubletheconcentration
oftheammoniaundertheconditionsgiven.(Myassumptionof0.250molesfornitrogenisbased
uponthebalancedequationandtheideathatittakes0.050molesofnitrogentomake0.100moles
ofammonia.)
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Someoneelsethenpostedthis
Andittakes0.15molesofH2tomaketheextra0.1molesofammonia.John[N.B.that'sme,the
ChemTeam!]gotitright.ThenumberyoucameupwithisthechangeinH2concentrationobserved
aftertheextrahydrogenisadded.However,0.15moloftheH2addedgoesintomakingtheextra
0.1molofammonia.ThefinalH2concentrationshouldbe0.4+x0.15,or0.25+x.
Problem#3:Nitricoxideandbromineatinitialpressuresof98.4and41.3torr,respectively,wereallowedto
reactat300.K.Atequilibriumthetotalpressurewas110.5torr.Thereactionisasfollows.
2NO(g)+Br2(g)2NOBr(g)
DeterminetheKp.
Solution:
1)SetupanICEbox:

PNO

PBr2

PNOBr

Initial
Change

98.4
2x

41.3
x

0
+2x

Equilibrium

98.42x

41.3x

+2x

2)Determinethevalueofx:
Atequilibrium,thesumofthepartialpressuresisequalto110.5torr.
(98.42x)+(41.3x)+2x=110.5
x=29.2torr
3)Atequilibrium,thepartialpressureswillbe:
NO:40.0torr
Br2:12.1torr
NOBr:58.4torr
4)DeterminetheKp:
Kp=(PNOBr)2/[(PNO)2(PBr2)]
Kp=(58.4)2/[(40.0)2(12.1)]
Kp=0.176torr1
5)Additionalproblem:WhatwouldKpbeifthepressureshadbeengiveninatmospheres?
0.176torr1x760torratm1=137atm1

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6)Additionalproblem(muchharder!):WhatwouldbethepartialpressuresofallthespeciesifNOandBr2,
bothataninitialpressureof0.300atm,wereallowedtocometoequilibriumatthistemperature?Sorry,no
solutionwillbeprovided.
Problem#4:Considerthefollowingequilibrium:
2CH3OH(g)CH3OCH3(g)+H2O(g)
IfKpis13.54,whatistheratiobetweenPCH3OHandPCH3OCH3?
Solution:
1)Letthethreepartialpressuresbe:
PCH3OH=x
PCH3OCH3=y
PH2O=y
ThekeyassumptionisthatPCH3OCH3=PH2O.Thiscomesfromassumingallthetwoproducts
camefromthemethanolreacting.Ifwedonotassumethis,thenwehavenosureknowledgeabout
thepartialpressuresofthetwoproductsandwecannotsolvetheproblem.
2)InsertvaluesintotheKpexpressionandsolve:
Kp=[(PCH3OCH3)(PH2O)]/(PCH3OH)2
13.54=[(y)(y)]/(x)2
3.68=y/x
3)However,wewishtheratioPCH3OH:PCH3OCH3
x/y=0.272
Problem#5:Considerthereaction:
H2+I22HI
whoseKeq=54.8.Ifanequimolarmixtureofthereactantsgivestheconcentrationoftheproducttobe0.500M
atequilibrium,determinetheconcentrationofhydrogen.
Solution:
1)Theequilibrumexpressionis:
Keq=[HI]2/([H2][I2])
2)Substitutingintothis,wehave:
54.8=(0.500)2/[(x)(x)]
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Comment:weknowtheequilibriumconcentrationsforH2andI2areequalbecauseofthefollowing
tworeasons:(1)theystartedoutequimolar(thatis,inequalamounts)and(2)theywereusedupina
1:1ratio(thatis,anequalrateofconsumptionforbothreactants)tomakeHI.
3)Seeingthetherighthandsideisaperfectsquare,wetakethesquarerootandproceedtotheanswer:
7.403=0.500/x
7.403x=0.500
x=0.0675M(tothreesigfig)
Problem#6:WhenNaFisaddedslowlytoasolutionthatis0.025MBa2+ and0.025MCa2+ whatwillthe
concentrationofcalciumbewhenthebariumjustbeginstoprecipitate?Ksp(BaF2)=1.0x107Ksp(CaF2)=
1.7x1010.
Solution:
1)Whatis[F]whenBaF2justbeginstoprecipitate?
1.0x107=(0.025)(x)2
x=0.0020M
2)Whatis[Ca2+ ]when[F]=0.0020M?
1.7x1010=(x)(0.0020)2
x=4.25x105M
Problem#7:ThesolubilityproductconstantforCu(IO3)2is1.44x107.Whatvolumeof0.0520MS2O32
wouldberequiredtotitratea20.00mLsampleofsaturatedsolutionofCu(IO3)2
Solution:
1)Determinemolesofiodatein20.00mL:
1.44x107=(x)(2x)2
x=0.003302M
[IO3]=0.006604M
0.006604mol/Ltimes0.02000L=1.3208x104mol
2)Determineiodate:thiosulfateratio:
IO3(aq)+6H+ (aq)+6S2O32(aq)>I(aq)+3S4O62(aq)+3H2O(aq)
Theiodate:thiosulfateratiois1:6
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3)Determinevolumeofthiosulfaterequired:
0.0520mol/L=1.3208x104mol/x
x=0.00254L=2.54mL(iftheratiowere1:1)
sinceratiois1:6,wedothis:
2.54x6=15.24mL(thisistheanswer)
4)Analternateapproach(fromYahooAnswers):
1moleofIO3reactswith6molesofS2O32
Assume1.00Lofsolutionpresent.Therefore:
molesofS2O32=6.604x104molx6=0.0396mol
numberofmoles=molarityxvolume
volume=0.0396/0.0520=0.762L=762mL
However,weonlytitrated20.00mL,so:
762x0.02=15.24mL
Problem#8:Brominechloride,BrCl,areddishcovalentgaswithpropertiessimilartothoseofCl2,may
eventuallyreplaceCl2asawaterdisinfectant.One(1.00)moleofchlorineandone(1.00)moleofbromineare
enclosedina8.05Lflaskandallowedtoreachequilibriumatacertaintemperature.
Cl2(g)+Br2(g)2BrCl(g)
Kc=11.57x102atthegiventemperature.WhatmassofCl2ispresentatequilibrium?
Solution:
1)DeterminemolaritiesofCl2andBr2:
[Cl2]=[Br2]=1.00/8.05=0.1242236M(I'llcarryseveralguarddigits)
2)SetupanICEbox:

[Cl2]

[Br2]

[BrCl]

Initial
Change

0.1242236
x

0.1242236
x

0
+2x

Equilibrium 0.1242236x 0.1242236x

+2x

3)Determinex:
Kc=[BrCl]2/([Cl2][Br2]
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11.57x102=(2x)2/[(0.1242236x)(0.1242236x)]
Therighthandsideisaperfectsquare.
0.340147=2x/(0.1242236x)
0.04225430.340147x=2x
0.0422543=2.340147x
x=0.01805626M
4)Determine[Cl2]atequilibrum:
0.1242236minus0.01805626=0.10616734M
5)DeterminemassofCl2presentatequilibrium:
MV=g/molarmass
(0.10616734mol/L)(8.05L)=x/70.906g/mol
x=60.6g(tothreesigfigs)
6)WecandetermineifthisisthecorrectanswerbyattemptingtorecovertheKc:
Kc=(0.03611252)2/[(0.10617)(0.10617)
Thecomputationislefttothereader.
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