Chemistry102

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)

When1.000molCOand3.000molH2 areplacedina10.00Lvesselat927 Candallowedtocometo

equilibrium,themixtureisfoundtocontain0.387molH2O. Howmanymolesofeachsubstanceare
presentatequilibrium?

CH4 (g) + H2O(g)

CO(g)+3 H2 (g)

Initial

1.000

3.000

0.387

3(0.387)

+0.387

+0.387

+0.387

+0.387

0.387mol

0.387mol

Equilibrium (1.0000.387) (3.0001.161)

Equilibrium

0.613mol

1.839mol

Example2:
Considerthefollowingdynamicequilibrium:

CO2(g) +
H2O(g)
H2(g)

Supposeyoustartwithagaseousmixturecontaining1.00molofCOand1.00molofH2O.
Whenequilibriumisreachedat1000 C,themixturecontains0.43molH2.
Whatisthemolarcompositionoftheequilibriummixture?
CO(g) +

CO2 (g)+ H2 (g)

CO(g)+ H2O (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)

When1.00molCOand3.00molH2 areplacedina10.0Lvesselat927 Candallowedtocometo

equilibrium,themixtureisfoundtocontain0.387molH2O. Calculatetheequilibriumconstantfor
thisreaction.

CH4 (g)+ H2O (g)

CO(g)+3H2 (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)

A2.00Lflaskwasfilledwith0.0400molSO2 and0.0200molO2. Atequilibrium,at900K,the

flaskcontained0.0296molSO3. ObtainthevalueofKc.
MolarityofSO2 =

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 =

CS2(g)+ H2O (g)+H2 (g)

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.

CS2 (g) +4H2O (g)

CH4 (g)+2H2S(g)

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)

Equilibrium Concs: 0.010M

K c=

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)

Equilibrium Concs: 0.0613M0.184 M

K c=

CH4 (g)+ H2O(g)

0.0387M0.0387M

[CH 4 ][H 2O] (0.0387M)(0.0387M)

=
=3.93
[CO][H 2]3
(0.0613M)(0.184M)3

13

Chemistry102

Chapter14

Example1:
TheEquilibriumConstantforthereactionbelowequals4.0x1013 at250C.

2 NO2(g)

(a)Doestheequilibriummixturecontainpredominantlyreactantsorproducts?
2NO(g)+O2(g)

(b) If[NO]=[O2]=2.0x10-6 Matequilibrium,whatistheequilibrium

concentrationof[NO2]?
K c =

[NO 2]2
[NO 2 ]2 =K c [NO]2[O 2]
[NO]2[O 2]

[NO 2 ]2 = K c[NO]2 [O 2]= (4.0x1013 )(2.0x106 ) 2 (2.0x10+) =1.8x102 M

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 =

[CH 4 ][H 2O] (1.00x103 M)(1.00x103M)

=
=6.25
[CO][H 2]
(2.00x102 M)(2.00x102 M)3
Qc =6.25

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

[H 2 ]4[CS2] (1.12M) 4(1.43M)

Qc=
=
=1.02
[CH 4 ][H 2S]2 (1.26M)(1.32M)2

Qc =1.02

Kc =3.59

Qc Kc

Notatequilibrium

(b)Ifnotatequilibrium,inwhichdirectionwillthereactiongotoreachequilibrium?
Qc < Kc
Reactionwillgototheright
Forwardreactionisfavored
Formationofproductsisfavored

16