Chapter14
CHEMICALEQUILIBRIUM
Reactionsthatcangoinbothdirectionsarecalledreversiblereactions.
Thesereactionsseemtostopbeforetheygotocompletion.
Whentherateoftheforwardandreversereactionsbecomeequal,an equilibrium systemis
established.
Stepwiseviewtoanequilibriumsystem
Step1
A+B
C+DFast
NoReaction
C+D
A+B
C+D
A+B
C+D
Step2 Forwardreactionslowsdown.
Reversereactionstartsslowlyatfirst.
TherearefewerAandBmoleculesavailable. TherearefewCandDmoleculesavailable.
A+B
C+D
Step3 Forwardreactionslowsdownfurtherasthe
numberofAandBmoleculesdecreases.
A + B
Step4
A+B
C+D
Reversereactionspeedsupasthenumber
ofCandDmoleculesincreases.
forward
reverse
C +
RATEOFFORWARDREACTION=RATEOFREVERSEREACTION
Chemistry102
Chapter14
CHEMICALEQUILIBRIUM
CharacteristicsofaChemicalEquilibriumSystem:
1. AmixtureofReactantsandProductsispresent
2. Thecompositionofthereactionmixturenolongerchanges:
Concentrationofreactantsisconstant
Concentrationofproductsisconstant
NOTE:
Concentrationofreactants Concentrationofproducts
3. AChemicalEquilibriumisaDynamicEquilibriumbothreactions(forwardandreverse)
arestill goingon
4. TheDynamicEquilibriummaybecontrolled(shiftedtotherighttofavorproducts,orshifted
tothelefttofavorreactants) bychangingtheconditionsforthereaction.
DefinitionofChemicalEquilibrium:
Astatereachedbyareactionmixturewhentherateofforwardreactionandtherateof
reversereactionsbecomeequal.
Chemistry102
Chapter14
COMPOSITIONOFANEQUILIBRIUMMIXTURE
Inanequilibriummixture,theamountofonesubstanceisdeterminedexperimentally andthe
amountsoftheothersubstancesarecalculated.
Example1:
CO(g) +
CH4(g)
3H2(g)
H2O(g)
Initial
1.000
3.000
0.387
3(0.387)
+0.387
+0.387
+0.387
+0.387
0.387mol
0.387mol
0.613mol
1.839mol
Example2:
Considerthefollowingdynamicequilibrium:
CO2(g) +
H2O(g)
H2(g)
Supposeyoustartwithagaseousmixturecontaining1.00molofCOand1.00molofH2O.
Whenequilibriumisreachedat1000 C,themixturecontains0.43molH2.
Whatisthemolarcompositionoftheequilibriummixture?
CO(g) +
Initial
1.00mol
1.00mol
+x
+x
Equilibrium
(1.00x)
(1.00x)
+0.43
+0.43
Equilibrium
0.57mol
0.57mol
0.43mol
0.43mol
Chemistry102
Chapter14
Example3:
0.750molofN2 and2.250molofH2 areplacedintoareactionvesselat450 Cand10.0atm.
N2(g) +
3H2(g)
2NH3(g)
Whatisthecompositionoftheequilibriummixtureifyouobtain0.060molofNH3 fromit?
2NH3 (g)
N2 (g)+3H2 (g)
Initial
D
Equilibrium
Equilibrium
Chemistry102
Chapter14
THEEQUILIBRIUMCONSTANT
Considerthefollowingequilibriumsystem:
forward
N2O4(g)
2NO2(g)
reverse
NOTE:Bothforwardandreversereactionsareelementaryreactions.
AtEquilibrium:
Rate(forwardreaction) =Rate(reversereaction)
kf[N2O4]
= kr[NO2]2
k f [NO 2]2
=
=constant
k r [N 2O 4]
kf
=K c=equilibriumconstant
kr
impliesmolarconcentration
InGeneral:
aA
bB
K c=
cC
dD
[C]c [D]d
[A]a [B]b
[C],[D]= molarconcentrations(molarities)oftheproductsatequilibrium
[A],[B]= molarconcentrations(molarities)ofthereactantsatequilibrium
Thisrelationshipwaspostulatedbytwochemistsin1864andcalledthelawofmassaction.
Chemistry102
Chapter14
EQUILIBRIUMCONSTANT
TheEquilibriumConstant,Kc,isaconstantforaparticularreaction atagiventemperature.
NOTE:
1. Iftheoverallreactionoccursbyamultistepmechanism,onecanshowthatKc forthe
overallreactionequalsaproductofratiosof theindividual rateconstants.
2. ItiscommonpracticetowriteKc withoutunits
Example1:
Writetheequilibriumconstantexpressionfortheequation shownbelow:
2NH3(g)+ 4H2O(g)
2NO2(g)+ 7 H2(g)
Kc =
Example2:
TheEquilibriumConstantforareactionis:
K c=
[NH 3 ]4 [O 2]5
[NO]4 [H 2O]6
WhatistheEquilibriumConstantexpressionwhentheequationfor thisreactionishalvedandthen
reversed?
OriginalEquation:
4 NH3
4NO + 6 H2O
+ 5 O2
HalvedandReversed:
Kc =
Chemistry102
Chapter14
CALCULATINGKC FORREACTIONS
Molarconcentrations(molarities)ofproductsandreactantsatequilibrium mustbesubstituted
intheexpressionofKc
Example1:
CO(g) +
3H2(g)
CH4(g) +
H2O(g)
Initial
1.00mol
3.00mol
0.387
1.16
+0.387
+0.387
Equilibrium
0.613mol
1.84mol
0.387mol
0.387mol
CO:
H2 :
CH4:
H2O:
Equilibriumamounts:
0.613mol
1.84mol
0.387mol
0.387mol
K c=
EquilibriumConcentrations(M)
0.613mol/10.00L = 0.0613M
1.84 mol/10.00L = 0.184M
0.387mol/10.00L = 0.0387M
0.387mol/10.00L = 0.0387M
[H 2 O][CH 4] (0.387M)(0.387M)
=
=3.93
[CO][H 2]3
(0.0613M(0.184M)3
Example2:
An8.00Lreactionvessel at491 Ccontained0.650molH2,0.275molI2 and3.00molHI.
Assumingthatthesubstancesareatequilibrium,findthevalueofKc at491 C.
Theequilibriumis:
H2(g)
+
I2(g)
2HI(g)
MolesatEquilibrium:
0.650
0.275
MolaritiesatEquilibrium:
(moles/L)
0.650moles
8.00L
0.275moles
8.00L
MolaritiesatEquilibrium:
0.08125M
0.03438M
3.00
3.00moles
8.00L
0.375M
[HI]2
(0.375M)2
K c=
=
=50.3
[H 2 ][I2] (0.08125M)(0.03438M)
Chemistry102
Chapter14
Example3:
2H2(g)+ S2 (g)
H2S,acolorlessgasdissociatesonheating: 2H2S
When0.100molofH2Swasputina10.0Lvesselandheatedto1132 C,itgaveanequilibriummixture
containing0.0285molH2. WhatisthevalueofKc atthistemperature?
Note:
Itisconvenienttoexpressequilibriumamountsofreactantsandproductsinmolar
concentrations(molaritiesinmol/L)
MolarityofH2S=
MolarityofH2 =
2H2 (g)
2 H2S(g)
+S2 (g)
Initial
D
Equilibrium
Equilibrium
Kc =
Example4:
Inthecontactprocess,sulfuricacidismanufacturedbyfirstoxidizingSO2 toSO3,whichisthen
reactedwith water. ThereactionofSO2 withO2 is:
2SO2(g)+O2(g)
2SO3(g)
MolarityofO2 =
2SO3 (g)
2SO2 (g) +O2 (g)
Initial
D
Equilibrium
Equilibrium
Kc =
Chemistry102
Chapter14
GASPHASEEQUILIBRIA(KP)
GasPhaseEquilibriareferstoequilibriumsystemswhereallreactantsandproducts
aregases.
Concentrationsofgasescanbeexpressedintermsofpartialpressures,sincetheconcentration
ofagasisproportionaltoitspartialpressure.
Constantat
agiven
temperature
n mol
P
PV=nRT (
)=
V L
RT
n
1
molarconcentrationofagas= =P(
)
V
RT
Kp istheequilibriumconstantforagaseousreactionexpressedintermsofpartialpressures.
Kp hasavaluedifferentfromKc
Kp = Kc(RT)Dn
Dn=
sumofcoefficients
sumofcoefficients
of
of
gaseousproductsgaseousreactants
CO(g) +
3H2(g)
Example1:
K p=
PCH4 PH2O
PCO PH23
CH4(g) +
H2O(g)
Kc =3.92
(at1200K)
Dn=(1+1) (1+3)= 2
Kp = Kc(RT)Dn =3.92 [(0.0821)(1200)]-2 =4.04x10-4
Example2:
TheequilibriumconstantKc equals10.5forthefollowingreactionat227 C.
CO(g) +
CH3OH (g)
2H2(g)
WhatisthevalueofKp atthistemperature?
Dn=
Kp = Kc(RT)Dn =
Chemistry102
Chapter14
OTHEREQUILIBRIUMCONSTANT
Ifagivenchemicalequation canbeobtainedbytakingthesum ofotherequations,the
EquilibriumConstantfortheoverallequation equalstheproductoftheequilibriumconstants
oftheotherequations.
Koverall=K1K2
Example1:
Thefollowingequilibriaoccurat1200K
CO(g) +
CH4(g)
3H2(g)
H2O(g)
K1=3.92
CH4(g) +
CS2(g)
2H2S (g)
4H2(g)
K2 =3.3x104
CO(g)+
2H2S(g)
K1 =
K3 =???
[CH 4 ][H 2 O]
[CS2 ][H2]4
K
=
2
[CO][H 2 ]3
[CH 4 ][H 2S]2
K1K 2=
[ CH4 ][H 2 O]
[CS2 ][H2]4
x
=K3
[CO][ H2 ]3
[ CH4 ][H 2S]2
Theequilibriumconstantforan overallequationisequaltotheproductoftheequilibrium
constantsoftheindividualequations.
K3 =K1 xK2
Becauseanequilibriumcanbeapproachedfromeitherdirection,thedirectioninwhichwe
writethechemicalequationisarbitrary.Forexample,forthereactionshownbelow:
2NO2 (g)
N2O4 (g)
K c=
[NO2]2
=0.212(at100 o C)
[N 2 O 4]
Whenconsideringtheequilibriuminthereversedirection:
N2O4 (g)
2NO2 (g)
K c=
[N 2 O 4]
1
=
=4.72(at100 oC)
2
[NO 2]
0.212
Kfwd =1/Krev
10
Chemistry102
Chapter14
CLASSIFICATIONOFCHEMICALEQUILIBRIA
ChemicalEquilibriacanbeclassifiedaccordingtothephysicalstateofthereactantsand
productspresent:
I. HomogeneousEquilibrium
Anequilibriumthatinvolvesreactantsandproductsinasinglephase.
Example:Catalyticmethanation:
CO(g) + 3 H2(g)
CH4(g) + H2O(g)
II. HeterogeneousEquilibrium
Anequilibriuminvolvingreactantsandproductsinmorethanonephase
Example:
3Fe(s) +
K c=
4H2O(g)
[H 2]4
[H 2O]4
Fe3O4(s) + 4H2(g)
NOTE: Theconcentrationsofsolidsareomitted.
Reason:Theconcentrationofapuresolidorpure
liquidisaconstantatagiventemperature.
EquilibriumConstantexpression canbewrittenwithpuresolidsincluded:
[Fe 3O 4][H 2]4
K c=
[Fe]3 [H2O]4
[Fe]3
[H 2]4
Byrearrangement:
K c=
[Fe3O4]
[H2O]4
constant
factors
variable
factors
[Fe]3
[H 2]4
K 'c =
K c=
[Fe 3O 4]
[H 2O]4
Theconcentrationsofpuresolidsandliquidsareincorporatedin thevalueofKc.
Theconcentrationofsolventisalsoomittedfromtheexpressionof Kc fora
homogeneousreaction(ifconstant).
Theequilibriumisnotaffectedbypuresolids,pureliquids,or solvents.
11
Chemistry102
Chapter14
Examples:
IdentifyeachofthefollowingequilibriumsashomogeneousorheterogeneousandwriteKc
expressionsforeach:
1.
Fe(s)+H2O(g)
FeO(s)+H2 (g)
2.
3.
TiCl4 (l)
Ti(s)+2Cl2 (g)
4.
Given theequilibriumshownbelow,forwhichKp=0.0752at480 C:
4HCl(g)+O2 (g)
2Cl2 (g)+2H2O(g)
WhatisthevalueofKpforthereactionshownbelow:
Cl2 (g)+H2O(g)
2HCl(g)+O2 (g)
12
Chemistry102
Chapter14
MEANINGOFTHEEQUILIBRIUMCONSTANT
Themagnitudeoftheequilibriumconstantindicatestheextenttowhichtheforwardand
reversereactionstakeplace.
Kc >>>1
amountof
reactantsat
equilibrium
amountof
productsat
equilibrium
Productsarefavoredatequilibrium
N2(g) +
3H2(g)
2NH3(g)
0.010M
2.02M
[NH3]2
(2.02M)2
=
=4.1x108
[N 2][H 2]3 (0.010M)(0.010M)2
Kc <<<1
amountof
reactantsat
equilibrium
amountof
productsat
equilibrium
Reactantsarefavoredatequilibrium
2NO(g)
O2(g)
N2(g) +
Equilibrium Concs: 1.0M
K c=
1.0M
6.8x10-16 M
[NO]2
(6.8x1016 M)2
=
=4.6x1031
[N 2 ][O 2] (1.0M)(1.0M)
Kc 1 (0.5 10)
amountof
productsat
equilibrium
amountof
reactantsat
equilibrium
Neitherreactants,norproductsarepredominant
CO(g)+3 H2(g)
13
Chemistry102
Chapter14
Example1:
TheEquilibriumConstantforthereactionbelowequals4.0x1013 at250C.
2 NO2(g)
(a)Doestheequilibriummixturecontainpredominantlyreactantsorproducts?
2NO(g)+O2(g)
[NO 2]2
[NO 2 ]2 =K c [NO]2[O 2]
[NO]2[O 2]
2NO(g)
Equilibrium Concs:
O2(g)
2.0x10-6 M
2.0 x10-6 M
muchsmaller
2NO2(g)
1.8x10-2 M
muchlarger
Example2:
Sulfurdioxidereactswithoxygenat25 Ctoreachequilibrium.Kc forthisreactionatthis
temperatureis8.0x1035.
O2(g)
2SO3(g)
a) From themagnitudeofKc,whichreactionisfavored(forwardorreverse)when
equilibriumisestablished?
2SO2(g)
b) Ifanequilibriummixtureis1.0MSO3 andhasequalconcentrationsofSO2andO2,what
istheconcentrationofSO2 inthemixture? Doesthisresultagreewithwhatyouexpect
fromthemagnitudeofKc?
14
Chemistry102
Chapter14
PREDICTINGTHEDIRECTIONOFREACTION
Considerthefollowingreactionandthefollowingcompositionofgasmixture
present.
CO(g)+3 H2(g)
(1200K)
Composition
of gasmixture:
(NOTATEQUIL)
CH4(g) +
H2O (g)
Kc =3.93
0.0200M0.0200M0.00100M0.00100M
At1200Kandinthepresenceofacatalyst,whatwouldbemorelikely?
1.Wouldforwardreactionbefavored?(wouldproductsbefavored?)
OR
2.Wouldreversereactionbefavored?(wouldreactantsbefavored?)
Toanswerthis,anewquantityisintroduced:
Qc = theReactionQuotient
= hasthesameformasKc buttheconcentrationsusedtocalculateitsvaluearenot
equilibriumconcentrations.
Qc =
Kc =3.92
shoulddecreaseto
Forthereactionmixturetoreachequilibrium:Qc
Qc decreasesif:
3.92
[CH4],[H2O] decreases
[CO],[H2] increases
CO(g)+3H2(g)
CH4(g) +
H2O(g)
Thereactiongoestotheleft
Reversereactionisfavored
Formationofreactantsisfavored
Qc =0
Qc =
Kc
ForwardRxn
Reactants
ReverseRxn
Equilibrium
IncreasingQc
15
Products
Chemistry102
Chapter14
PREDICTINGTHEDIRECTIONOFREACTION
InGeneral:Forareactionmixturethatis NOTATEQUILIBRIUM:
aA
bB
[C]c [D]d
Qc= a b
[A] [B]
cC
dD
Compare:Qc to Kc
If:
Qc > Kc
Reactionwillgotheleft(
If:
Qc < Kc
Reactionwillgototheright(
If:
Qc =Kc
Reactionmixtureisatequilibrium(
)
)
Examples:
Thefollowingreactionhasanequilibriumconstant,Kc,equalto3.59at900 C,andthe
followingcompositionof reactionmixture:
CH4(g)+
2H2S(g)
1.26M
1.32M
(a)Isthereactionmixtureatequilibrium?
CS2(g) +
4H2(g)
1.43M
1.12M
Qc =1.02
Kc =3.59
Qc Kc
Notatequilibrium
(b)Ifnotatequilibrium,inwhichdirectionwillthereactiongotoreachequilibrium?
Qc < Kc
Reactionwillgototheright
Forwardreactionisfavored
Formationofproductsisfavored
16