Principles of Chemical Equilibrium

Dynamic Equilibrium
Three simple physical phenomena:

1. Vaporization of liquid within a closed container

rate 1
Liquid vapor
rate 2

EQUILIBRIUM : rate 1 = rate 2  Pvap = constant

vapor pressure of a liquid is a property associated
with an equilibrium condition.
Dynamic Equilibrium

2. Solute dissolves in a solvent

dissolved
solute solution
(solid) (liquid)
precipitate

EQUILIBRIUM : rate dissolving = rate precipitating 

concentration remains constant
solubility of a solute is a property associated with an
equilibrium condition
 Dynamic Equilibrium
I2 + H2O CCl4
3. Extraction

rafinate : I2 left + H2O

extract : most of I2 +CCl4

I2 in H2O (1) I2 in CCl4 (2)

EQUILIBRIUM: C1 = constant; C2 = constant

C2  85 C1
C1/C2 = distribution coefficient
distribution coefficient of a solute between two
immiscible solvents is a property associated with an
equilibrium condition
The equilibrium constant expression

Methanol synthesis
in 10 L flask, T = 483 K

CO(g) + 2 H2 (g) CH3OH(g)

Three approaches to equilibrium in the reaction above are

shown in the next table
The equilibrium constant expression
CO(g) H2(g) CH3OH(g)
Experiment 1
initial amounts, mol 1.000 1.000 0.000
equilibrium amounts, mol 0.911 0.822 0.0892
eq. concentrations, mol/L 0.0911 0.0822 0.00892
Experiment 2
initial amounts, mol 0.000 0.000 1.000
equilibrium amounts, mol 0.753 1.506 0.247
eq. concentrations, mol/L 0.0753 0.1506 0.0247
Experiment 3
initial amounts, mol 1.000 1.000 1.000
equilibrium amounts, mol 1.380 1.760 0.620
eq. concentrations, mol/L 0.138 0.176 0.062
The equilibrium constant expression
Conclusion:
1. In no case is any reacting species
completely consumed
2. The equilibrium amounts of reactants &
products in these 3 cases appear to have
nothing in common

Attempts to find a constant ratio of equilibrium

concentrations in methanol synthesis
 The equilibrium constant expression

exp Trial 1: Trial 2: Trial 3:

[ CH3OH] [ CH3OH]__ [ CH3OH]
[CO] [H2] [CO] ( 2 [H2] ) [CO] [H2]2
1 0.00892 0.00892 0.00892
 1.19  0.596  14.5
0.0911 x 0.0822 0.0911 x 2 x 0.0822 0.0911 x 0.0822 2

2 0.0247 0.0247 0.0247

 2.17  1.09  14.4
0.0753 x 0.1506 0.0753 x 2 x 0.1506 0.0753 x 0.1506 2

3 0.062 0.062 0.062

 2.55  1.28  14.5
0.138 x 0.176 0.138 x 2 x 0.176 0.138 x 0.176 2
The equilibrium constant expression

[ CH 3OH]
Trial 3: constant value
[CO]. [H 2 ]2

Kc
 The Equilibrium Constant Expression

Example 16.1
These equilibrium concentrations are measured
in reaction (at 483 K)

CO(g) + 2 H2 (g) CH3OH(g) Kc= 14.5

[CO] = 1.03 M and [CH3OH] = 1.56 M. What

is the equilibrium concentration of H2?
General Expression for Kc

aA+bB+… gG+hH+…

g h
[G] [H] ...
Kc = a b
[A] [B] ...
Relationship Involving Equilibrium Constant

 Relationship of Kc to the balanced

Chemical Equation:
1. When we “ reverse” an equation, we
“invert” the value of Kc
example:
CO(g) + 2 H2 (g) CH3OH(g) Kc= 14.5

CH3OH(g) CO(g) + 2 H2(g) Kc’= ?

Relationship Involving Equilibrium Constant
2. When we “multiply” the coefficients in a
balanced equation, by a factor (2,3, …), we
“raise” the equilibrium constant to the
corresponding power (2,3,…)
example:
2 CO(g) + 4 H2 (g) 2 CH3OH(g) Kc”=?

3. When we “divide” the coefficients in a

balanced equation, by a factor (2,3, …), we
“take” the corresponding “root” of equilibrium
constant.
Relationship Involving Equilibrium Constant

Example 16.2
The following Kc value is given at 298 K for
the synthesis of NH3 from its elements:

N2(g) + 3 H2 (g) 2 NH3(g) Kc= 3.6.108

What is the value of Kc at 298 K for the

reaction:
NH3 (g) ½ N2 (g) + 3/2 H2 (g)
 Combining Kc

N2(g) + ½ O2 (g) N2O(g) Kc= 2.4.10-18

N2(g) + O2 (g) 2 NO(g) Kc= 4.1.10-31

N2O(g) + ½ O2 (g) 2NO(g) Kc= ?

Equilibria involving Gases

2 SO2(g) + O2 (g) 2 SO3(g)

2
[SO3 ] 2
Kc= 2
 2.8.10 (1000 K)
[SO 2 ] [O 2 ]

Kp = ?
Equilibria involving Gases

General Reaction:

aA+bB+… gG+hH+…

Kp = Kc (RT)ngas

 n gas = (g+h+…) – (a+b+…)

Equilibria Involving Pure Liquids &
Solids
Heterogeneous Reaction
C(s) + H2O (g) CO (g) + H2 (g)

[ CO] [H 2 ]
Kc =
[H 2 O]

CaCO3 (s) CaO (s) + CO2 (g)

Kc= [CO2]
Kp = Kc. RT = PCO2
Example 16.4
At equilibrium in the following reaction at
60 °C, the partial pressures of the gases
are found to be PHI = 3.65 x 10-3 atm and
PH2S 10-1 atm.
= 9.96x
What is the value of Kp for the reaction?

H2S (g) + I2 (s) 2 HI(g) + S(s)

Significance of Kc value
2 H2(g) + O2 (g) 2 H2O(l) Kp = 1.4 x 1083
(298 K)
1
Kp >>>  2
>>>
(PH2 ) .PO2

 nH2 or nO2  0
 H2 or O2 almost used up
reaction goes to completion
2 H2(g) + O2 (g) 2 H2O(l)
Significance of Kc value

CaCO3 (s) CaO (s) + CO2 (g) Kp = 1.9 x10-23

(298 K)
K p = PCO2   n CO 2  0
The reaction does not occur to any significant extent

CaCO3 (s) CaO (s) + CO2 (g)

EQUILIBRIUM :
10-10  Kc or Kp  1010
Reaction Quotient
 Direction of a net reaction is important:
- at times we do not need detailed equilibrium
calculations  may only need qualitative description
- as a first step in calculating equilibrium
 Initial concentration  RATIO

[G]g [ H ]h ...
Reaction Quotient = Qc =
[ A]a [ B]b ...
Reaction Quotient

 Equilibrium : Qc = Kc
 If Qc < Kc  a net reaction proceeds
from left to right (the forward
reaction)
 If Qc > Kc  a net reaction proceeds
from right to left (the reverse
direction)
 Reaction Quotient

Example 16.5: For the water-gas shift reaction:

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

Kc =1.00 at about 1100 K. The following amounts of

substances are brought together and allowed to react at
1100K : 1.00 mol CO, 1.00 mol H2O, 2.00 mol CO2 and
2.00 mol H2. Compared with their initial amounts, which of
the substances will be present in greater amount and which,
in a lesser amount, when equilibrium is established?
Altering Equilibrium Conditions

Le Chatelier’s principles:
When an equilibrium system is subjected to a
change in temperature, pressure or
concentration of a reacting species, the
system responds by attaining a new
equilibrium that partially offsets the impact of
the change
Effect of changing the amounts of reacting species

2 SO2(g) + O2 (g) 2 SO3(g)

Kc = 2.8 x 102 (1000 K)

SO3
1 mol SO3 1.46
mol
SO3
0.68
mol
SO2 0.54
SO2
0.32 10 L 10 L mol
mol
0.16 mol O2 0..27 mol
O2

(a) (b)
Effect of changes in pressure/ volume

 How to change the pressure?

1. Add a gaseous reactant/product to an
equilibrium mixture
2. Add inert gas to the constant-volume
reaction mixture  P total increase but P
partial of reacting species unchanged.
3. Change its volume  increasing P
Effect of changes in pressure/ volume

 Volume increase  equilibrium moves

to LARGER number of moles (total
coefficient)
 Volume decrease  equilibrium moves
to SMALLER number of moles
 Pressure >< Volume
Effect of temperature
 Raising the temperature of an equilibrium
mixture shifts the equilibrium condition in the
direction of the endothermic reaction
 Lowering the temperature causes a shift in
the direction of the exothermic reaction

Example:
2 SO2(g) + O2 (g) 2 SO3(g) H°= -180 kJ

SO3 >>  T ?
Effect of a catalyst

A catalyst in a reaction mixture speeds

up both the forward & reverse reactions.
Equilibrium is achieved more rapidly
BUT the equilibrium amounts are
UNCHANGED
 Equilibrium Calculations
 Example 16.9
Equilibrium is established in the reaction
N2O4(g)  NO2(g) at 25°C. The quantity of the two
gases present in a 3.00 L vessel are 7.64 g N2O4 and
1.56 g NO2. What is the value of Kc for this reaction?
 Example 16.10
When a 0.0200 mol sample of SO3 is introduced into
an evacuated 1.52 L vessel at 900 K, 0.0142 mol SO3
is found to be present at equilibrium. What is the
value of Kp for the dissociation of SO3 at 900 K?

2 SO3(g) 2 SO2(g) + O2 (g)

Equilibrium Calculations
 Example 16.11
A sample of NH4HS is introduced into an
evacuated flask at 25 °C. What is the total gas
pressure at equilibrium?
NH4HS (s) NH3(g) + H2S(g) Kp= 0.108

 Example 16.12
A 0.0240 mol sample of N2O4 is allowed to
come to equilibrium with NO2in a 0.372 L flask
at 25 °C. Calculate the amount of N2O4 present
at equilibrium.
N2O4 (g) 2 NO2(g) Kc= 4.61 x 10-3
Equilibrium Calculations
 Example 16.13
Solid silver is added to a solution with these
initial concentrations: [ Ag+] =0.200 M, [Fe2+] =
0.100M and [Fe3+] = 0.300M. The following
reversible reaction occurs:

Ag+(aq) + Fe2+(aq) Ag(s) + Fe3+(aq) Kc= 2.98

What are the ion concentrations when

equilibrium is established?