CHAPTER 17

Chemical Equilibrium
Basic Concepts

• Reversible reactions do not go to completion.

– They can occur in either direction
– Symbolically, this is represented as:

a A g  
+ b B g   c C g  + d D g 

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Basic Concepts

• Chemical equilibrium exists when two

opposing reactions occur simultaneously
at the same rate.
– A chemical equilibrium is a reversible reaction
that the forward reaction rate is equal to the
reverse reaction rate.
• Chemical equilibria are dynamic equilibria.
– Molecules are continually reacting, even
though the overall composition of the reaction
mixture does not change.
3
Basic Concepts
• Graphically, this is a representation of the
rates for the forward and reverse reactions
for this general reaction.
 cC +dD
a A g  + b B g   g  g 

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Basic Concepts

• One of the fundamental ideas of chemical

equilibrium is that equilibrium can be
established from either the forward or
reverse direction.

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Basic Concepts

6
Basic Concepts

7
 The Equilibrium Constant

• For a simple one-step mechanism reversible

reaction such as:

A (g )  B (g ) 
 C (g )  D (g )
• The rates of the forward and reverse reactions
can be represented as:
Rate f  k f A B  which represents the forward rate.
Rate r  k r C D  which represents the reverse rate.

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The Equilibrium Constant

• When system is at equilibrium:

Ratef = Rater
Substitute for the rate relationsh ip to give :
k f A B  k r C D 
which rearranges to
k f C D 

k r A B
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The Equilibrium Constant

• Because the ratio of two constants is a

constant we can define a new constant as
follows :
kf
 Kc and
kr

Kc 
 C D
A  B 10
The Equilibrium Constant

• Similarly, for the general reaction:

a A (g ) 
 b B (g )  c C (g )  d D (g )
we can define a constant

Kc 
C  D 
c d
 products

A  B 
a b  reactants

This expression is valid for all reactions.

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The Equilibrium Constant

• Kc is the equilibrium constant .

• Kc is defined for a reversible reaction at a
given temperature as the product of the
equilibrium concentrations (in M) of the
products, each raised to a power equal to
its stoichiometric coefficient in the
balanced equation, divided by the product
of the equilibrium concentrations (in M) of
the reactants, each raised to a power
equal to its stoichiometric coefficient in the12
balanced equation.
The Equilibrium Constant

Example 17-1: Write equilibrium constant

expressions for the following reactions at 500oC.
All reactants and products are gases at 500oC.


P C l5  P C l3  C l 2

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The Equilibrium Constant


H 2 + I 2  2 HI
You do it!

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The Equilibrium Constant


4 N H 3 + 5 O 2  4 N O + 6 H 2O
You do it!

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The Equilibrium Constant

• Equilibrium constants are dimensionless

because they actually involve a
thermodynamic quantity called activity.
– Activities are directly related to molarity

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The Equilibrium Constant

Example 17-2: One liter of equilibrium mixture from

the following system at a high temperature was
found to contain 0.172 mole of phosphorus
trichloride, 0.086 mole of chlorine, and 0.028 mole
of phosphorus pentachloride. Calculate Kc for the
reaction.

P C l5  P C l3  C l2
Equil []’s 0.028 M 0.172 M 0.086 M
You do it!
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The Equilibrium Constant

Example 17-3: The decomposition of PCl5 was

studied at another temperature. One mole of PCl5
was introduced into an evacuated 1.00 liter
container. The system was allowed to reach
equilibrium at the new temperature. At equilibrium
0.60 mole of PCl3 was present in the container.
Calculate the equilibrium constant at this
temperature.

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The Equilibrium Constant

Example 17-4: At a given temperature 0.80 mole

of N2 and 0.90 mole of H2 were placed in an
evacuated 1.00-liter container. At equilibrium 0.20
mole of NH3 was present. Calculate Kc for the
reaction.
You do it!

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Variation of Kc with the
Form of the Balanced Equation
• The value of Kc depends upon how the balanced
equation is written.
• From example 17-2 we have this reaction:


P C l5  P C l3  C l2
• This reaction has a Kc=[PCl3][Cl2]/[PCl5]=0.53

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Variation of Kc with the
Form of the Balanced Equation
Example 17-5: Calculate the equilibrium constant
for the reverse reaction by two methods, i.e, the
equilibrium constant for this reaction.

P C l3  C l2  P C l5
Equil. []’s 0.172 M 0.086 M 0.028 M
The concentrations are from Example 17-2.

K 'c 
 PCl5 

 0.028
 1.9
 PCl 3 Cl2  0.1720.086
Kc  1 ' or K c 
' 1
K  1
0.53  1.9
Kc c 21
The Reaction Quotient

• The mass action expression or reaction quotient

has the symbol Q.
– Q has the same form as Kc
• The major difference between Q and Kc is that
the concentrations used in Q are not
necessarily equilibrium values.
For this general reaction :
aA + bB  cC + dD

Q
C  D 
c d

A  B
a b 22
The Reaction Quotient

• Why do we need another “equilibrium

constant” that does not use equilibrium
concentrations?
• Q will help us predict how the equilibrium
will respond to an applied stress.
• To make this prediction we compare Q
with Kc.

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The Reaction Quotient

When:
Q=K c The system is at equilibrium.
Q  K c The reaction occurs to the left to a greater extent.
Q  K c The reaction occurs to the right to a greater extent.
To help understand this think of Q and K c as fractions.

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The Reaction Quotient

Example 17-6: The equilibrium constant for the

following reaction is 49 at 450oC. If 0.22 mole of
I2, 0.22 mole of H2, and 0.66 mole of HI were put
into an evacuated 1.00-liter container, would the
system be at equilibrium? If not, what must occur
to establish equilibrium?

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Uses of the Equilibrium Constant,
Kc
Example 17-7: The equilibrium constant, Kc, is
3.00 for the following reaction at a given
temperature. If 1.00 mole of SO2 and 1.00 mole of
NO2 are put into an evacuated 2.00 L container
and allowed to reach equilibrium, what will be the
concentration of each compound at equilibrium?
S O 2 (g )  N O 2 (g ) 
 S O 3 (g )  N O (g )

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Uses of the Equilibrium Constant,
Kc
Example 17-8: The equilibrium constant is 49 for
the following reaction at 450oC. If 1.00 mole of HI
is put into an evacuated 1.00-liter container and
allowed to reach equilibrium, what will be the
equilibrium concentration of each substance?
H +I   2 HI
2(g) 2(g) (g)

You do it!

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Disturbing a System at Equilibrium:
Calculations
• To help with the calculations, we must determine
the direction that the equilibrium will shift by
comparing Q with Kc.
• Example 17-12: An equilibrium mixture from the
following reaction was found to contain 0.20
mol/L of A, 0.30 mol/L of B, and 0.30 mol/L of C.
What is the value of Kc for this reaction?

A g   B g   C g 
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Disturbing a System at Equilibrium:
Calculations

A g  
 B g   C g 
Equil. []' s 0.20 M 0.30 M 0.30 M

Kc 
B C  0.30 0.30 
  0.45
A  0.20 

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Disturbing a System at Equilibrium:
Calculations
• If the volume of the reaction vessel were
suddenly doubled while the temperature
remained constant, what would be the new
equilibrium concentrations?
1 Calculate Q, after the volume has been doubled

A g   B g   C g 
Equil. []' s 0.10 M 0.15 M 0.15 M

Q=
BC  0.15 0.15 
  0.22
A  0.10  30
Disturbing a System at Equilibrium:
Calculations
• Since Q<Kc the reaction will shift to the right to
re-establish the equilibrium.
2 Use algebra to represent the new
concentrations.
A g  
 B g  + C g 
N ew initial []' s 0.10 M 0.15 M 0.15 M

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Disturbing a System at Equilibrium:
Calculations
• Since Q<Kc the reaction will shift to the right to
re-establish the equilibrium.
2 Use algebra to represent the new
concentrations.
A g  
 B g  + C g 
New initial []' s 0.10 M 0.15 M 0.15 M
Change -x M +xM +xM

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Disturbing a System at Equilibrium:
Calculations
• Since Q<Kc the reaction will shift to the right to
re-establish the equilibrium.
2 Use algebra to represent the new
concentrations.
A 
 B + C
g  g  g 
New initial []' s 0.10 M 0.15 M 0.15 M
Change - xM + xM + xM
New Equil. []' s 0.10 - x M 0.15 + x M 0.15 + x M
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Disturbing a System at Equilibrium:
Calculations
• Since Q<Kc the reaction will shift to the right to
re-establish the equilibrium.
2 Use algebra to represent the new
concentrations.
A g  
 B g  + C g 
New initial []' s 0.10 M 0.15 M 0.15 M
Change - xM + xM + xM
New Equil. []' s 0.10 - x M 0.15 + x M 0.15 + x M
Kc =
BC 
 0.45 
 0.15  x 0.15  x 
A  0.10  x  34
 Disturbing a System at Equilibrium:
Calculations

Solve this quadratic equation

2
0.045 - 0.45 x = 0.0225 + 0.30 x + x
x  0 .75 x  0 .0225  0
2

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Disturbing a System at Equilibrium:
Calculations

- b  b  4ac
2
x
2a
 0.75  0.75
2
 41 0.0225
x
21
 0.75  0.81
x  0.78 and 0.03 M
2
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Disturbing a System at Equilibrium:
Calculations

Since 0 < x < 0.10, we can discard - 0.78 as an answer.

The only posible value is x  0.03 M.
A   (0.10  x) M  0.07 M
B  C  0.15  x  M  0.18 M
These are the new concentrat ions after
the equilibriu m has been disturbed.

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Partial Pressures and the
Equilibrium Constant
• For gas phase reactions the equilibrium
constants can be expressed in partial pressures
rather than concentrations.
• For gases, the pressure is proportional to the
concentration.
• We can see this by looking at the ideal gas law.
– PV = nRT
– P = nRT/V
– n/V = M
– P= MRT and M = P/RT

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Partial Pressures and the
Equilibrium Constant
• For convenience we PVmay nRT
express the amount of
a gas in terms of its partial pressure rather than

its concentration. P    RT
n
 V  we must solve the
• To derive this relationship,
n
ideal gas equation.
Because   has the units mol/L,
V
P = []RT
Thus at constant T, the partial pressure of a gas
is directly proportion al to its concentrat ion.
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Partial Pressures and the
Equilibrium Constant
• Consider this system at equilibrium at
5000C.
 4 HCl + O
2 Cl 2 g  + 2 H 2 O g   g  2 g 

HCl  O 2 
4
PHCl  PO 
4

Kc  and K p 
PCl  PH O 
2

Cl2  H 2 O 
2 2 2
2
2
2

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Partial Pressures and the
Equilibrium Constant

Kc 
   
PHCl 4 PO2
PHCl  PO 4
  
1 5

    P  P   
RT RT 2 RT
P 2 P 2 2 2 1 4
Cl2 H 2O
RT RT Cl 2 H 2O RT

K c  K p  RT1  so for this reaction

-1 1
K c = K p (RT) or K p = K c (RT)
L atm
Must use R  0.0821
mol K 41
 Relationship Between Kp and Kc

• From the previous slide we can see that

the relationship between Kp and Kc is:

K p  K c RT  or K c  K p RT 
n  n

 n = (# of moles of gaseous products) - (# of moles of gaseous reactants)

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Heterogeneous Equlibria

• Heterogeneous equilibria have more than one

phase present.
– For example, a gas and a solid or a liquid and a gas.
C aC O 3  s  
 C aO  s   C O 2  g  at 5 0 0 Co

• How does the equilibrium constant differ for heterogeneous

equilibria?
– Pure solids and liquids have activities of unity.
– Solvents in very dilute solutions have activities that are essentially
unity.
– The Kc and Kp for the reaction shown above are:

K c = [C O 2 ] K p = PCO 2 43
Heterogeneous Equlibria

For this reaction :

SO  H SO
 H O   (at 25 C) o
2g  2    2 3 aq

H O   is the solvent.
2 

What are the forms of K and K ? c p

You do it!

K =
H SO 2 3
K 
1
c
SO  2
P
p
SO 2 44
Heterogeneous Equlibria

• What are Kc and Kp for this reaction?

C aF2  s   2
 C a  aq   2 F aq 
1- o
( at 2 5 C )
You do it!

K c = Ca 2
 F 
 2
K p is undefined

45
Heterogeneous Equlibria

• What are Kc and Kp for this reaction?


3 Fe  4 H O  Fe O  4 H o
( at 5 0 0 C )
s  2 g  3 4 s  2 g 

 P 
4

Kc =
 H2 
4
Kp 
H2

 H 2O P 
4 4
H 2O

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