9 Chemical

equilibria
 9.1 Chemical equilibrium

N2(g) + 3H2(g) 2NH3(g)

• Rates of the forward and reverse
reactions are equal
• There is no net change in the overall
composition of the reaction mixture
• Dynamic equilibrium
• ‘Reactants’ substances on the left
• ‘Products’ substances on the right
9.2 The equilibrium constant, K,
and the reaction quotient, Q
N2O4(g) 2NO2(g)
 9.2 The equilibrium constant, K,
and the reaction quotient, Q

• For a given OVERALL system composition

equilibrium concentrations are independent
of direction of approach
9.2 The equilibrium constant, K, and
the reaction quotient, Q
aA + bB cC + dD
• The following holds when equilibrium is
established:
 C e    D e 
c d
     
K c   c a  c b
  A e    B e 
     
• Equilibriumconstant
 c expression
  c 

• Kc – equilibrium constant
• Kc dependent on temperature, always specify
temperature when Kc reported
9.2 The equilibrium constant, K, and
the reaction quotient, Q
aA + bB cC + dD
• The following holds when equilibrium is
established:

C c  D d
Kc 
 A a B b
• Equilibrium constant expression
• Kc – equilibrium constant
• Kc dependent on temperature, always specify
temperature when Kc reported
9.2 The equilibrium constant, K, and
the reaction quotient, Q
aA + bB cC + dD
C c  D d
Qc 
 A a B b
• Qc – reaction quotient
• Expression for systems not necessarily at
equilibrium
• Kc can have only one positive value at a
specific temperature
• Qc can have any positive value
9.2 The equilibrium constant, K, and
the reaction quotient, Q
• Qc = Kc at equilibrium
• Qc > Kc system reacts to use up
products and generate more reactants
• Qc < Kc system reacts to use up
reactants and generate more products
c d
 pC   p D 
   
p  p 
Kp  a b
 p A   pB 
   
p  p 
9.2 The equilibrium constant, K, and
the reaction quotient, Q
• The relationship between Kp and Kc
n
 RT  g

K p  K c   

p 
Δng = (number of moles of gaseous products) –
(number of moles of gaseous reactants)
– Important to use correct units in this
equation
• Equilibrium concentrations in mol m-3

   
• Equilibrium pressures in Pa
K c mol m 3  1000 n  K c mol L1
g
9.2 The equilibrium constant, K, and
the reaction quotient, Q
• Manipulating equilibrium constant
expressions
– When the direction of an equation is
reversed, the new equilibrium constant is
the reciprocal of the original
Kc 
 PCl 5 
PCl3 + Cl2 PCl5 PCl 3  Cl2 

Kc '

 P Cl3   Cl2 
PCl5 PCl3 + Cl2
 P Cl5 
' 1
Kc 
Kc
9.2 The equilibrium constant, K, and
the reaction quotient, Q
• Manipulating equilibrium constant
expressions
– When the coefficients in an equation are
multiplied by a factor, the equilibrium
constant is raised to a power equal to
that factor.
K 
PCl 5 
PCl3 + Cl2 PCl5 c
PCl 3  Cl2 
2
Kc " 
 P Cl5 
2PCl3 + 2Cl2 2PCl5
 P Cl3  2  Cl2  2
K c ''  K c 2
9.2 The equilibrium constant, K, and
the reaction quotient, Q
• Manipulating equilibrium constant
expressions
– When chemical equilibria are added,
their equilibrium constants are multiplied.
Kc1 
 N2 O  2
2N2 + O2 2N2O
 N2  2  O 2 
 NO 2  4
2N2O + 3O2 4NO2 Kc 2 
 N2 O  2  O 2  3
 NO 2  4
2N2 + 4O2 4NO2 Kc 3 
 N2  2  O 2  4
 N2 O  2  NO 2  4 
 NO 2  4
Kc1 Kc 2  Kc 3
 N2  2  O 2   N2 O  2  O 2  3  N2  2  O 2  4
9.2 The equilibrium constant, K, and
the reaction quotient, Q
• The magnitude of the equilibrium
constant
– Product concentrations are in the
numerator of Kc
– The size of Kc gives a measure of how
far the reaction proceeds towards
completion when equilibrium is reached
 9.2 The equilibrium constant, K,
and the reaction quotient, Q
• The magnitude of the equilibrium
constant
reactant product
9.2 The equilibrium constant, K, and
the reaction quotient, Q
• Equilibrium constant expressions for
heterogeneous systems
– Homogeneous reaction, all reactants and
products are in the same phase
– Heterogeneous reaction, more than one
phase exists in reaction mixture
2NaHCO3(s) Na2CO3(s) + H2O(g) + CO2(g)
Kc = [H2O(g)][CO2(g)]
– Do not include the concentrations of pure
solids or pure liquids
 9.2 The equilibrium constant, K,
and the reaction quotient, Q
• Equilibrium constant
expressions for
heterogeneous systems
– For any pure liquid or solid at
constant temperature, the
ratio of amount of substance
to volume of substance is
constant
 9.3 Equilibrium and Gibbs
free energy
• Free energy diagrams
– Phase changes
 9.3 Equilibrium and Gibbs
free energy
• Free energy diagrams
– Chemical reactions

3
4

4
1
2
9.3 Equilibrium and Gibbs free
energy
• The relationship between ΔGθ and K
G  G   RT lnQ
– R is the gas constant, 8.3141 J K–1 mol–1
– T is the temperature in kelvin
– lnQ is the natural logarithm of the reaction
quotient
• Gaseous reactions: Q is calculated using partial
pressures expressed in Pa
• Reactions in solution: Q is calculated from
molar concentrations
9.3 Equilibrium and Gibbs free
energy
• The relationship between ΔGθ and K
G  G   RT lnQ
The reaction 2NO2(g) N2O4(g) has ΔGθ = –5.40 kJ
mol-1 at 298 K. In a reaction mixture, the partial
pressures of NO2 and N2O4 are 0.25 × 105 Pa and
0.60 x 105 Pa, respectively. In which direction must
this reaction proceed to reach equilibrium?
pN O  p 
2 4
 N O 

2 4

p   
Qp   p
2 G  G  R T ln  2
 p NO 
    p NO  
 p 
2

 p  
2

    
9.3 Equilibrium and Gibbs free
energy
G   5 . 40 kJ mol 1  5 .40  10 3 J mol 1 T  298 K
1
R  8 . 314 J K mol 1 p   1  10 5 Pa
p N O  0 . 60  10 5 Pa
2 4
p NO  0 . 25  10 5 Pa
2

 5 
 0.60  10 
 
 
5
3 -1 1 -1
G  5.40  10 J mol  8.314 J K mol  298 K  ln  1  10
5 2
  0.25  10  
 5  
  1  10  
G  2 . 0  10 2 J mol 1

ΔG is positive, forward reaction is nonspontaneous

so the reverse reaction occurs
9.3 Equilibrium and Gibbs free
energy
• The relationship between ΔGθ and K

G  G  RT lnQ

– If the system is at equilibrium

• ΔG = 0
• Q=K

0  G  R T ln K

G  R T ln K
9.3 Equilibrium and Gibbs free
energy
• The relationship between ΔGθ and K
G   R T ln K
2SO2(g) + O2(g) 2SO3(g)
ΔGθ = -1.40 x 102 kJ mol-1 for this reaction at 25 °C.
What is the value of Kp at this temperature?
 G  K p  e 56 .5
ln K p 
RT
K p  3  10 24
ln K p 

 1.40  10 5 J mol1 
 
8.314 J K-1 mol1  298 K 
ln K p  56.5
9.3 Equilibrium and Gibbs free
energy
• The relationship between ΔGθ and K
– Thermodynamic data collected at 25 °C
may be used to calculate the values of
equilibrium constants at temperatures
other than 25 °C
– Values of ΔHθ and ΔSθ do not change
much with temperature
9.4 How systems at equilibrium
respond to change
• Le Châtelier’s principle
– If an outside influence upsets an equilibrium,
the system undergoes a change in a direction
that counteracts
the disturbing influence and, if possible, returns
the system to equilibrium
– Better to compare equilibrium constant, K, and
reaction quotient, Q, when examining the effect
of perturbation to a chemical process at
equilibrium
9.4 How systems at equilibrium
respond to change
• Adding or removing a product or
reactant
– When not a pure solid or liquid removal
or addition of a reactant or product
instantaneously alters the concentration
of that species in the reaction mixture
– The value of Q changes so that Q ≠ K,
the system is no longer at equilibrium
9.4 How systems at equilibrium
respond to change
• Adding or removing a product or
reactant
– Q = K equilibrium
– Q < K shift towards products
– Q > K shift towards reactants
[Cu(H2O)4]2+(aq) + 4Cl-(aq) [CuCl4]2-(aq) + 4H2O(l)

CuCl4 2  
Q   
4
Cu  OH2  2   Cl 
 4   
9.4 How systems at equilibrium
respond to change
• Changing the pressure in gaseous
reactions
– Two ways of changing the total pressure
• Changing the volume of the system
• Adding an inert gas
– Consider the equilibrium
N2(g) + 3H2(g) 2NH3(g)
2
 p NH 
 
 p 
3

Qp   
3
 p N  p H 
  
 p   p  
2 2

  
9.4 How systems at equilibrium
respond to change
• Changing the pressure in gaseous
reactions
– Changing the volume of the system
 n NH 
2 2
 p NH 
 
 p 
3
3

Qp    Qc  V2 c 
n
 nH 
3 3 V
 p N  p H  nN
   
 p   p  
2 2
2 2

   V V3
 
2 2
Qc 
 NH3 
Qc 
n NH 3
V 2
 N2   H2  3  
3
nN  nH 2 2
9.4 How systems at equilibrium
respond to change
• Changing the pressure in gaseous
reactions
– Adding an inert gas
• Increases total pressure of system
• Does not alter the position of equilibrium
• Add helium to N2/H2/NH3 equilibrium mixture
• Does not react with products or reactants
2
• Qp is not changed  p 
 NH 
 p 
3

Qp   
3
 p N  p H 
  
 p   p  
2 2

  
9.4 How systems at equilibrium
respond to change
• Changing the temperature of a reaction
mixture
– Value of the equilibrium constant, K, can
only be changed by altering the temperature
– The van’t Hoff equation states:

d ln K H 
– The slope of thedTplotof lnK
2 versus T has the
RT
same sign as ΔH θ
 9.4 How systems at equilibrium
respond to change
• Changing the temperature of a reaction
mixture

ΔHθ is positive ΔHθ is negative

Endothermic Exothermic
Q<K Q>K
Products are favoured Reactants are favoured
9.4 How systems at equilibrium
respond to change
• Changing the temperature of a
reaction mixture
H   1 1 
ln KT  ln KT    
2 1
R T1 T 2 

– Can use the van’t Hoff equation to

calculate the K at a specified
temperature if the value of K at
another temperature is known
9.4 How systems at equilibrium
respond to change
• Addition of a catalyst
– Catalysts affect the rates of chemical
reactions without being used up
– Addition of a catalyst may help bring a
system to chemical equilibrium more
rapidly
– Addition of a catalyst does not affect the
position of equilibrium
9.5 Equilibrium calculations

• Calculating Kc from equilibrium

concentrations
– Measure the concentrations of reactants
and products after equilibrium reached
– Substitute these equilibrium values into
the equilibrium constant expression to
calculate Kc
9.5 Equilibrium calculations
At a certain temperature, a mixture of H2 and I2 was
prepared by placing 0.020 mol of H2 and 0.020 mol I2
into a 2.00 litre flask. After a period of time, the
equilibrium:
H2(g) + I2(g) 2HI(g)
was established. The purple colour of the
I2 vapour was used to monitor the reaction, and it
was determined that, at equilibrium, the
I2 concentration had dropped to 0.020 mol L–1.

What is the value of Kc for this reaction at this

temperature?
9.5 Equilibrium calculations

 HI 2
Kc 
 H2 I2 
equilibrium initial change in
= +
concentration concentration concentration

H2(g) + I2(g) 2HI(g)

Initial concentration (mol L-1) 0.100 0.100 0.000
Change in concentration (mol L-1) -0.080 -0.080 +2(0.080)
Equilibrium concentration (mol L-1) 0.020 0.020 0.160
 0.160  2
Kc 
 0.020   0.020 
K c  64
9.5 Equilibrium calculations

• The concentration table — a summary

1. Only equilibrium concentrations can be
substituted into the equilibrium constant
expression
2. Initial concentrations should be in mol L–1. The
initial concentrations are those present in the
reaction mixture when it is prepared
3. Changes in concentrations always occur in the
same ratio as the coefficients in the balanced
equation
9.5 Equilibrium calculations

• The concentration table — a summary

4. In constructing the ‘Change in
concentration’ row reactant concentrations
should all change in the same direction
and have the same sign.
Row product concentrations should all
change in the opposite direction and have
the opposite sign.
9.5 Equilibrium calculations

• Calculating equilibrium concentrations

from initial concentrations
– Involves the use of initial concentrations
and Kc to calculate equilibrium
concentrations
– Require a little applied algebra

– Concentration tables can be very helpful

9.5 Equilibrium calculations

The water-gas shift reaction:

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

has Kc = 4.06 at 500 °C.

If 0.100 mol of CO and 0.100 mol of H2O(g)

are placed in a 1.00-litre reaction vessel at
this temperature, what are the concentrations
of the reactants and products when the
system reaches equilibrium?
 9.5 Equilibrium calculations

Kc 
 CO 2  H2   4 .06
 CO  H2 O 
CO(g) + H2O(g) CO2(g) + H2(g)
Initial concentration (mol L-1) 0.100 0.100 0.0 0.0
Change in concentration (mol L-1) -x -x +x +x
Equilibrium concentration (mol L-1) 0.100-x 0.100-x x x

 x  x  x  2 .01 0 .100  x 
Kc   4 . 06
 0 .100  x  0 .100  x  x  0 .201  2 .01x
x2
 4 . 06
 0 .100  x  2
x  2 . 01x  0 .201
x 3 . 01x  0 .201
 4 .06  2 .01 x  0 . 0668
 0 .100  x 
9.5 Equilibrium calculations

 CO   0 .100  x  0 .100  0 .0668  0 .033 M

 H2 O   0.100  x  0.100  0.0668  0.033 M
 CO 2   x  0 .0668 M
 H2   x  0.0668 M

Qc 
 CO 2   H2 
 CO   H2 O 
 0.0668  2
Qc  2
 4.1
 0.033 

Rounding Kc to 2 significant figures gives 4.1, so the

calculated concentrations are correct.