Chapter 6: Chemical Equilibrium

6-1 Equilibrium

6-2 Chemical equilibrium

6-3 Equilibrium position

6-4 Le Châtelier’s principle

 6-1 Equilibrium
A. Equilibrium
a. Equilibrium is a state in which there are no observable changes as time goes by.
b. There are two types of equilibrium: Physical and Chemical

Physical Equilibrium Chemical Equilibrium

H20 (l) ↔ H20 (g) N2O4 (g) ↔ 2NO2 (g)
 6-2 Chemical Equilibrium
A. Chemical equilibrium
a. Definition: When a reaction takes place in a closed system, it reaches a condition where
the concentrations of all reactants and products remain constant over time.
b. Characteristics:
1. Equilibrium is not static but is a highly dynamic situation.
2. At equilibrium, forward reaction rate = reverse reaction rate.
3. At equilibrium, the concentrations of the reactants and the products remain constant
4. The equilibrium position of a reaction is determined by many factors, including:
 Initial concentrations
 Relative energies of reactants and products
 The relative “organization” of the reactants and products
 6-2 Chemical Equilibrium
A. Chemical equilibrium
c. For a reaction with no apparent changes in the concentration over time in a closed vessel,
two possible reasons:
1. The system is at equilibrium.
2. The forward and reverse reactions are too slow
that the system moves toward equilibrium at a
rate that cannot be detected.

B. The law of mass action (質量作用定律)

a. It is proposed based on experimental observation.
b. It describes a reversible reaction with equilibrium constant.

c. The equilibrium constants are customarily given without units.

The reason involves corrections for the non-ideal behavior of the substances in the
reaction. When these corrections are made, the units cancel out and the corrected K
has no units.
 6-2 Chemical Equilibrium
C. The equilibrium constant
a. The magnitude of equilibrium constant (K) tells us if the equilibrium reaction
favors the reactants or products
 If K » 1……..favors products
 If K « 1……..favors reactants
 6-2 Chemical Equilibrium
C. The equilibrium constant
a. The magnitude of equilibrium constant (K) tells us if the equilibrium reaction
favors the reactants or products
 If K » 1……..favors products
 If K « 1……..favors reactants
 6-2 Chemical Equilibrium
C. The equilibrium constant
b. The equilibrium expression for a reaction is the reciprocal of that for the reaction
written in reverse.
2NH 3 ( g ) N 2 ( g ) + 3H 2 ( g ) N 2 ( g ) + 3H 2 ( g ) 2NH 3 ( g )

K=
[N 2 ][H 2 ]
3
K' =
[NH 3 ]
2
=
1
[NH 3 ]2 [N 2 ][H 2 ]3 K
c. When the balanced equation for a reaction is multiplied by a factor n, the
equilibrium expression for the new reaction is the original expression raised to
the nth power. 1/ 2 3/ 2
[N 2 ] [H 2 ]
3 1/ 2
 [N ][H ]
=  2 22


NH 3 ( g ) 1
N 2 ( g ) + 32 H 2 ( g ) K" = = K1/2
2
[NH 3 ]  [NH 3 ]


 General form
 6-2 Chemical Equilibrium
C. The equilibrium constant
c. The equilibrium constant can also be expressed in terms of pressures for gas
reactants and products.

⇒ P∝C (Ideal gas equation)

C = n / V = The number of mole n of gas per unit volume V = molar concentration of gas

jA + kB lC + mD Q P = CRT

K=
(C )(C l m
)=K
(C )(C )
C D
j k c
A B

K =
(P )(P l m
) = (C C × RT ) (C D × RT )
l m
=
( )( )
CC C D
l m
×
(RT ) l +m

(P )(P ) (C ( )( )
C D
p
A
j
B
k
A × RT ) j
(C B × RT )k
C A
j
C B
k
( RT ) j+k

= K c (RT ) = K c (RT )
(l + m )−( j + k ) ∆n

K p = K c (RT ) ∆n = (l + m ) − ( j + k )
∆n
 6-2 Chemical Equilibrium
D. The Concept of Activity
a. In terms of thermodynamics, the most accurate definition of equilibrium does
not simply involve the observed equilibrium pressure or concentration but
involves the ratio of the equilibrium pressure of concentration to a reference
pressure (1 atm) or concentration ( 1 mol/L).
Pi Ci
Activity (ith component) = ai = or
Preference Creference
Pi = partial presure of the ith gaseous component Preference = 1 atm (exactly)
Ci = concentration of the ith gaseous component Creference = 1 mol/L (exactly)
b. Equilibrium expression

jA(g) + kB(g) lC(g) + mD(g)

l m
 PC   PD  l m
    PC (atm)   PD (atm) 
P  P    
K=
(aC ) (aD )
l m
=
ref  ref  = 1 atm  1 atm
l m
 = C D = K (unitless)
P P
(aA ) j (aB )k  PA
j
  PB 
k j
 PA (atm)   PB (atm) 
k j
PA PB
k p

       
P  P   1 atm   1 atm 
 ref   ref 
 6-2 Chemical Equilibrium
D. The Concept of Activity
b. Equilibrium expression
jA(g) + kB(g) lC(g) + mD(g)

l m
 CC   CD  l m
    C (mol/L )   C (mol/L ) 
C  C   C  D 
K=
(aC ) (aD )
l m
=
ref  ref
l
 =  1 mol/L   1 mol/L  = CC C D = K (unitless)
m

(aA ) j (aB )k  CA
j
  CB 
k j
 C A (mol/L )   C B (mol/L ) 
k
C
j
C
k C

       
A B

C  C   1 mol/L   1 mol/L 
 ref   ref 

 Because the reference states of Kp and Kc are different, in general Kc _____

Kp, unless the sum of the powers in the numerator and the denominator are
___________.
 6-2 Chemical Equilibrium
E. Heterogeneous Equilibria
a. Equilibria with reactants and products in the same phase: homogeneous equilibria.
e.g. N 2 ( g ) + 3H 2 ( g ) 2NH 3 ( g )
b. Equilibria with reactants and products in different phases: heterogeneous equilibria.

According to experimental results, the position of a

heterogeneous equilibrium does not depend on the
amount of pure solids or liquids present.
Let C1 = [CaO], C2 = [CaCO3 ]
Concentrations of pure solid or liquids
  are not included in the equilibrium
expression for the reaction.
Exercise: Determine the equilibrium expression of the following two reactions.
 6-3 Equilibrium Position
A. Equilibrium position
Definition: A set of reactant and product concentrations that satisfies the equilibrium constant
expression.
a. Equilibrium constant depends on the ratio of the concentrations.
b. There is only one value of equilibrium constant (K) for a given system at a given
temperature.
c. There are infinite number of equilibrium positions at a given temperature depending on
the initial concentrations.
K=
[NH3 ]
2

N 2 ( g ) + 3H 2 ( g ) 2NH 3 ( g )
[N2 ][H2 ]3
 6-3 Equilibrium Position
B. Application of the equilibrium constant
With the equilibrium constant, we are able to predict the following features of a reaction:
1. The extent (inherent tendency) of a reaction to occur.
2. Whether a given set of concentrations reach an equilibrium.
3. The equilibrium position that will be achieved by a set of initial concentration.
1. Determine the extent of a reaction with the equilibrium constant

a. K >1, the reaction system consists of mostly products

at equilibrium  The equilibrium lies to the right
b. K <1, the reaction system consists of mostly reactants
at equilibrium  The equilibrium lies to the left

c. The size of K and the time required to reach equilibrium are not directly related.
 The time required to achieve equilibrium depends on the reaction rate, which is
determined by the size of the activation energy (Ea).
 The size of K is determined by the energy difference between products and reactants
(∆E, thermodynamic factors)
 6-3 Equilibrium Position
2. Determine if the system has reached equilibrium
Reaction quotient: determined by applying the law of mass action using initial
concentrations instead of equilibrium concentrations.

N 2 ( g ) + 3H 2 ( g ) 2NH 3 ( g )

1. Q = K, the system is at equilibrium

 no shift occurs
2. Q > K, the initial concentrations of
products are large than that of reactants
 The system shits to the left to
consume products to reach equilibrium.
3. Q < K, the initial concentrations of
reactants are large than that of products
 The system shits to the right to form
products to reach equilibrium.
 6-3 Equilibrium Position
3. Determine equilibrium position
a. Calculate equilibrium pressure
Example 1:

At equilibrium, the pressure of N2O4 was found to be 2.71 atm.

Calculate the equilibrium pressure of NO2(g).
 6-3 Equilibrium Position
3. Determine equilibrium position
a. Calculate equilibrium pressure
Example 2: At a certain temperature a 1.00-L flask initially contained 0.298 mol PCl3(g) and
8.7010-3 mol PCl5(g). After the system had reached equilibrium, 2.0010-3 mol Cl2(g) was
found in the flask. Gaseous PCl5 decomposes according to the reaction:

Calculate the equilibrium concentrations of all species and the equilibrium constant, K

At equilibrium,
 6-3 Equilibrium Position
3. Determine equilibrium position
b. Calculate equilibrium concentration
Example 1:

In a particular experiment, 3.000 mole of each component was added to a 1.500 L

flask. Calculate the equilibrium concentrations of all species.

Because Q<K, reaction shifts to right to reach equilibrium


 6-3 Equilibrium Position
3. Determine equilibrium position
b. Calculate equilibrium concentration
Example 2:

Because Q<K, reaction shifts to right to reach equilibrium

If x = 2.14, [H2] = 1-x < 0 (不合理)  x = 0.968

[H2] = 1-x = 0.032 M, [F2] = 2-x = 1.032 M, [HF] = 2x = 1.936 M
 6-3 Equilibrium Position
3. Determine equilibrium position
c. Consider systems with small equilibrium constants
Example:

Initial concentrations:

Because K is small, we can expect that x will be a small value as well.

∴ 

Supplement:
Gibbs Free Energy and Equilibrium constant

Courtesy of Prof. Jie-Ren Li , Dept. of Chem., NCKU

Courtesy of Prof. Jie-Ren Li , Dept. of Chem., NCKU
Courtesy of Prof. Jie-Ren Li , Dept. of Chem., NCKU
 6-4 Le Châtelier’s principle
A. Le Châtelier’s principle
If a change is imposed on a system at equilibrium, the position of the equilibrium will shift in a
direction that tends to reduce that change.
a. The effect of a change in concentration
N 2 ( g ) + 3H 2 ( g ) 2NH 3 ( g )
 6-4 Le Châtelier’s principle
A. Le Châtelier’s principle
If a change is imposed on a system at equilibrium, the position of the equilibrium will shift in a
direction that tends to reduce that change.
a. The effect of a change in concentration
N 2 ( g ) + 3H 2 ( g ) 2NH 3 ( g )

Q<K, reaction shifts to right to reach equilibrium

If a component (reactant or product) is added to a reaction system at equilibrium (at constant

T and P or constant T and V), the equilibrium position will shift in the direction that lowers the
concentration of that component. If a component is removed, the opposite effect occurs.
 6-4 Le Châtelier’s principle
A. Le Châtelier’s principle
a. The effect of a change in concentration
Exercise: Arsenic can be extracted from its ores by first reacting the ore with
oxygen (called roasting) to form solid As4O6, which is then reduced using
carbon:

Predict the direction of the shift of the equilibrium position in response to each of
the following changes in conditions.
1) Addition of carbon monoxide
2) Addition or removal of carbon or tetraarsenic hexoxide (As4O6)
3) Removal of gaseous arsenic (As4)
 6-4 Le Châtelier’s principle
A. Le Châtelier’s principle
b. The effect of a change in pressure
Three ways can be done to change the pressure of a reaction system:
 Add or remove a gaseous reactant or product = change concentration
 Add an inert gas ( inert gas is not involved in the reaction)
1. The addition of an inert gas has no effect on the equilibrium position.
2. The addition of an inert gas increases the total pressure but has no effect on the
concentration or partial pressures of the reactants or products.
 The system remains at the original equilibrium position.
 Change the volume of the container
1. When the volume of the container is changed, the concentrations of both reactants
and products are changed.
2. According to the ideal gas principle, at constant temperature and pressure, the volume
of a gas is directly proportional to the number of gas present.


3. When the volume of the container holding a gaseous system is reduced, the system
responds by reducing its own volume.  This equilibrium position shifts to decrease
the total number of gaseous molecules in the system.
 6-4 Le Châtelier’s principle
A. Le Châtelier’s principle
b. The effect of a change in pressure
 Change the volume of the container
When the volume of the container holding a gaseous system is reduced, the system
responds by reducing its own volume.  This equilibrium position shifts to decrease the
total number of gaseous molecules in the system.

According to the ideal gas principle,



The reaction system can reduce its volume by reducing the number of molecules.
 When the volume of the container is reduced, the above reaction will shift right,
because the reactant side has four molecules while the product side has two
molecules .
 Although the equilibrium constant dose not change, the new equilibrium position moves
toward the right side which involves the smaller number of gas molecules.
Exercise:
 6-4 Le Châtelier’s principle
A. Le Châtelier’s principle
c. The effect of a change in temperature
Note: 1. Both changes in concentration and pressure do not alter the equilibrium
constant of a reaction; however, changes in temperature do affect the
equilibrium constant.
2. The value of equilibrium constant, K, changes with temperature.
Co(H2O)62+(aq) + 4 Cl-(aq) CoCl4 2- (aq) + 6 H2O (l)
 4-4 Le Châtelier’s principle
A. Le Châtelier’s principle
c. The effect of a change in temperature
 For exothermic reaction (放熱反應): treat heat (energy) as the product

∆Ho = H(products) – H(reactants) = -92 kJ < 0

If additional energy is added in the above system, according to Le Châtelier’s

principle, the system will move toward the direction to consume the added
energy.
 The above reaction will shift left if addition energy (heat) is added into the
system.
 For endothermic reaction (吸熱反應): treat heat (energy) as the reactant

∆Ho = H(products) – H(reactants) = 556 kJ > 0

Since the above reaction is an endothermic reaction, when additional energy is

added to the system, the reaction shifts right to consume the added energy.
4-4 Le Châtelier’s principle

Courtesy of Prof. Jie-Ren Li , Dept. of Chem., NCKU

 6-4 Le Châtelier’s principle
• Rudolf Julius Emanuel Clausius • Benoît Paul Émile Clapeyron
(魯道夫·克勞修斯) (埃米爾·克拉佩龍)

 Physicist and mathematician of Germany  Physicist and engineer of France

 Significant contribution:  Significant contribution:
1. Originator of the concept of entropy 1. Calusius-Clapeyron equation
2. Restated the two laws of 2. Ideal gas equation (PV=nRT)
thermodynamics
 6-4 Le Châtelier’s principle
A. Le Châtelier’s principle
d. The effect of catalysts
1. Catalysts increase the rate of both the forward and reverse reactions.
2. Equilibrium is achieved faster, but the equilibrium composition remains
unaltered.
 6-4 Le Châtelier’s principle
A. Le Châtelier’s principle
d. Review question
 ∆Ho > 0, Endothermic reaction
 6-4 Le Châtelier’s principle
B. Equilibria involving real gases
a. The value of K calculated form the law of mass action is the true value of the
equilibrium constant only if the observed pressures (concentrations) are
corrected for any non-ideal behavior.
b. Precisely speaking, the equilibrium constant without corrected for non-ideal
behavior (Kpobs) is defined as follow:

K pobs =
(P ) obs 2
NH 3

(P )(P )
obs
N2
obs 3
H2

c. For a real gas at pressure above 1 atm, Pobs < Pideal , and the discrepancy
between Pobs and Pideal increases with increasing total pressure.
For this case, Kpobs ___________ with the increasing total pressure.

d. How the find the limiting value (the “true” value) of Kp?
1. Experimental method: 2. Theoretical method: correct the
observed equilibrium pressure for any
non-ideal behavior.
γ i Pi obs
Kp =
(γ obs
PNH )
2

ai =
NH 3 3

Pref (γ N2 PNobs
2
)(
γ H 2 PHobs2 )
3