Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
Whatisequilibrium?
Expressionsforequilibriumconstants,Kc;
CalculatingKcusingequilibriumconcentrations;
Calculatingequilibriumconcentrationsusinginitial
concentrationandKcvalue;
RelationshipbetweenKcandKp;
Factorsthataffectequilibrium;
LeChateliersPrinciple
What is Equilibrium?
ChemicalEquilibriuminNature:
(TheformationofstalagmitesandStalactites)
ChemicalEquilibrium
Considerthefollowingreactions:
CaCO3(s)+CO2(aq)+H2O(l)Ca2+(aq)+2HCO3(aq)..(1)
and
Ca2+(aq)+2HCO3(aq)CaCO3(s)+CO2(aq)+H2O(l)..(2)
Reaction(2)isthereverseofreaction(1).
Atequilibriumthetwoopposingreactionsoccuratthe
samerate.
Concentrationsofchemicalspeciesdonotchangeonce
equilibriumisestablished.
ExpressionforEquilibriumConstant
Considerthefollowingequilibriumsystem:
wA+xByC+zD
[C] y [D] z
Kc= [A]w [B] x
ThenumericalvalueofKciscalculatedusingthe
concentrationsofreactantsandproductsthatexistat
equilibrium.
ExpressionsforEquilibriumConstants
Examples:
N2(g)+3H2(g)2NH3(g);Kc=
[NH 3 ] 2
[N 2 ][H 2 ]3
[PCl 3 ][Cl 2 ]
PCl5(g)PCl3(g)+Cl2(g); Kc= [PCl 5 ]
CH4(g)+H2(g)CO(g)+3H2(g);
[CO][H 2 ]3
Kc= [CH 4 ][H 2 O]
CalculatingEquilibriumConstant
Example-1:
1.000 mole of H2 gas and 1.000 mole of I2 vapor are
introduced into a 5.00-liter sealed flask. The mixture is
heated to a certain temperature and the following reaction
occurs until equilibrium is established.
H2(g) + I2(g)
2HI(g)
CalculatingEquilibriumConstant
forreaction:H2(g)+I2(g)2HI(g)
H2(g) +I2(g)2HI(g)
Initial[],M:
0.200 0.200
Changein[],M:0.1580.158
Equilibrium[],M 0.0420.042
0.000
+0.316
0.316
Kc=
[HI]2
[H 2 ][I 2 ]
(0.316) 2
(0.042) 2
=57
CalculatingEquilibriumConstant
Example-2:
0.500 mole of HI is introduced into a 1.00 liter sealed flask
and heated to a certain temperature. Under this condition
HI decomposes to produce H2 and I2 until an equilibrium is
established. An analysis of the equilibrium mixture shows
that 0.105 mole of HI has decomposed. Calculate the
equilibrium concentrations of H2, I2 and HI, and the
equilibrium constant Kc for the following reaction:
H2(g)+I2(g)2HI(g),
CalculatingEquilibriumConstant
Thereaction:H2(g)+I2(g)2HI(g),proceedsfrom
righttoleft.
H2(g) +I2(g)2HI(g)
Initial[],M:
0.000 0.0000.500
Changein[],M:+0.0525+0.05250.105
Equilm[],M
0.0525 0.05250.395
(0.395) 2
Kc==56.6
(0.0525) 2
ExpressionandValueof
EquilibriumConstantforaReaction
TheexpressionforKdependsontheequation;
ThevalueofKappliestothatequation;itdoes
notdependonhowthereactionoccurs;
ConcentrationsusedtocalculatethevalueofK
arethosemeasuredatequilibrium.
Relationshipsbetweenchemicalequationsand
theexpressionsofequilibriumconstants
The expression of equilibrium constant depends on how the
equilibrium equation is written. For example, for the
following equilibrium:
2
[HI]
Kc
[H 2 ][I 2 ]
[H 2 ][I 2 ]
1/K c
2HI(g) H2(g) + I2(g); K c '
2
[HI]
And for the reaction: HI(g) H2(g) + I2(g);
[H 2 ][ I 2 ]
Kc "
2
[HI]
Kc ' 1
Kc
ExpressionandValuesof
EquilibriumConstantUsingPartialPressures
Considerthefollowingreactioninvolving
gases:
2SO2(g)+O2(g)2SO3(g)
(PSO3 ) 2
Kp= (P ) 2 (P )
SO2
O2
TheRelationshipbetweenKcandKp
Consider the reaction: 2SO2(g)+O2(g)2SO3(g)
[SO]2
Kc =
[SO 2 ]2 [O 2 ]
(PSO3 ) 2
and Kp =
(PSO2 ) 2 (PO2 )
(
RT)
K
(
RT)
c
2
2
2
[SO 2 ] ( RT) [O 2 ]( RT) [SO 2 ] [O 2 ]
RelationshipbetweenKcandKp
For reaction: PCl5(g) PCl3(g) + Cl2(g);
( PPCl5 )
[PCl 5 ]( RT)
[PCl 3 ][Cl 2 ]
( RT) 1 K C ( RT) 1
[ PCl 5 ]
RelationshipbetweenKcandKp
In general, for reactions involving gases such that,
aA + bB cC + dD
where A, B, C, and D are all gases, and a, b, c,
and d are their respective coefficients,
Kp = Kc(RT)n
and n = (c + d) (a + b)
(In heterogeneous systems, only the coefficients
of the gaseous species are counted.)
RelationshipbetweenKcandKp
For other reactions:
1.
2NO2(g) N2O4(g);
Kp = Kc(RT)-1
2.
Kp = Kc
3.
Kp = Kc(RT)-2
Homogeneous&HeterogeneousEquilibria
Homogeneousequilibria:
CH4(g)+H2O(g)CO(g)+3H2(g);
CO(g)+H2O(g)CO2(g)+H2(g);
Heterogeneousequilibria:
CaCO3(s)CaO(s)+CO2(g);
HF(aq)+H2O(l)H3O+(aq)+F(aq);
PbCl2(s)Pb2+(aq)+2Cl(aq);
EquilibriumConstantExpressionsfor
HeterogeneousSystem
Examples:
CaCO3(s)CaO(s)+CO2(g);
Kc=[CO2] Kp=PCO2;Kp=Kc(RT)
HF(aq)+H2O(l)H3O+(aq)+F(aq);
[H 3O ][ F - ]
Ka
[HF]
SolubilityEqilibrium
PbCl2(s)Pb2+(aq)+2Cl(aq);
Ksp=[Pb2+][Cl]2
(Kspiscalledsolubilityproduct)
For example,
Eqn(1): A + B C + D;
[C][D]
K1
[A][D]
Eqn(2): C + E B + F;
[B][F]
K2
[C][E]
[D][F]
[A][E]
= K1 x K2
Equilibrium Exercise #1
A flask is charged with 2.00 atm of nitrogen dioxide and
1.00 atm of dinitrogen tetroxide at 25 oC and allowed to
reach equilibrium. When equilibrium is established, the
partial pressure of NO2 has decreased by 1.24 atm. (a) What
are the partial pressures of NO2 and N2O4 at equilibrium?
(b) Calculate Kp and Kc for following reaction at 25 oC.
2 NO2(g) N2O4(g)
(Answer: Kp = 2.80; Kc = 68.6)
Equilibrium Exercise #3
1. The reaction: N2(g) + 3H2(g) 2NH3(g),
has equilibrium constant, Kc = 0.0602 at 500oC.
What is the equilibrium constant for the following reaction?
Equilibrium Exercise #4
If N2(g) + O2(g) N2O(g); Kc(1) = 2.4 x 10-18
and N2(g) + O2(g) 2 NO(g);
Kc(2) = 4.1 x 10-31
What is the equilibrium constant for the reaction?
ApplicationsofEquilibriumConstant
Foranysystemorreaction:
1. Knowingtheequilibriumconstant,wecanpredict
whetherornotareactionmixtureisat
equilibrium,andwecanpredictthedirectionof
netreaction.
Qc=Kcequilibrium(nonetreaction)
Qc<Kcanetforwardreaction;
Qc>Kcanetreversereaction
2. ThevalueofKtellsuswhetherareactionfavors
theproductsorthereactants.
[C] [ D]
aA + bB cC + dD; Qc
[A]a [ B]b
WhyisEquilibriumConstantImportant?
KnowingKcandtheinitialconcentrations,wecan
determinetheconcentrationsofcomponentsat
equilibrium.
Equilibrium Exercise #5
For the reaction:
H2(g) +
I2(g)
2 HI(g),
Initial [ ], M
0.1000
0.1000
Change [ ], M
-x
-x
Equilibrium [ ], M (0.1000 - x) (0.1000 - x)
0.0000
+2x
2x
[HI]2
(2 x ) 2
Kc
55.6
2
[H 2 ][ I 2 ] (0.100 - x )
EquilibriumExercise#6
For the reaction:
2 NO2(g) N2O4(g);
Kp = 1.27 at 353 K.
Equilibrium Exercise #7
The reaction:
PCl5(g) PCl3(g) + Cl2(g) has Kc = 0.0900.
A 0.1000-mol sample of PCl5 is placed in an empty
1.00-L flask and the above reaction is allowed to
come to equilibrium at a certain temperature. How
many moles of PCl5, PCl3, and Cl2, respectively, are
present at equilibrium?
(Answer: PCl5 = 0.0400 mol; PCl3 = Cl2 = 0.0600 mol)
Le Chteliers Principle
The Le Chtelier's principle states that:
when factors that influence an equilibrium are altered, the
equilibrium will shift to a new position that tends to
minimize those changes.
Ho = -92 kJ,
Equilibrium Exercise #8
Determine whether the following reactions favor
high or low pressures?
1. 2SO2(g) + O2(g) 2 SO3(g);
2. PCl5(g) PCl3(g) + Cl2(g);
3. CO(g) + 2H2(g) CH3OH(g);
4. N2O4(g) 2 NO2(g);
5. H2(g) + F2(g) 2 HF(g);
Equilibrium Exercise #9
1.
2.
3.
4.
5.
Ho = -180 kJ
Ho = -46 kJ
Ho = -108 kJ
Ho = +57 kJ
Ho = -270 kJ