UNIVERSITY OF NAIROBI

DEPARTMENT OF CHEMISTRY
SCH 103; PHYSICAL CHEMISTRY 1 LECTURE NOTES

By:

Dr. John N. Wabomba

(Email: [email protected], Tel: 0721418428)

CHEMICAL EQUILIBRIUM
There are several examples of physical processes such as evaporation or vaporization and
dissolving that reach dynamic equilibrium, the state in which the forward and reverse
processes are continuing at equal rates. The same concepts apply to chemical reactions.
Chemical reactions also approach a state of dynamic equilibrium in which the forward and
reverse reactions continue at matching rates. By making use of the responses of the
equilibrium composition to changes in the pressure and temperature, we can influence the
formation of a product and hence increase its yield.

Description of Dynamic Equilibrium.

Let us consider a general reaction;
aA + bB cC + dD (1)
Where A, B, C and D represents reactants and products a, b, c and d are coefficients in the
balanced chemical equation. Reactants A and B reacts to form products C and D. however,
the reverse reaction, the decomposition of C and D, also occurs. At equilibrium the forward
and reverse reactions take place at the same rate.

1
 A
Concentration B
C

Time

Figure 1: Concentration Vs Time Valuation: (Note how the amounts of

substances become constant at equilibrium)

Figure 1 shows how the concentration of A, B, C and D change with time. At the start of
experiment the concentrations of C and D, which are, zero increases steadily and reaches a
constant value. On the other hand, the concentration of A and B decreases up to a certain
value when the concentration of reactants and products no longer change. The final
composition of the reaction mixture corresponds to a dynamic equilibrium in which the
products decompose as just as they are formed.

We show this dynamic character by writing the chemical equation of a reaction at

equilibrium with a double headed arrow ( ). This signifies that the forward reaction
and its reverse are continuing with equal rates.

Law of Mass Action

In chemistry, the law of mass action is the proposition that the rate of the chemical reaction is
directly proportional to the product of the activities or concentrations of the reactants. It
explains and predicts behaviors of solutions in dynamic equilibrium.

The Law of mass action evolved from the work of a French chemist Claude Louis Berthollet
(1748–1822) who considered the driving force behind chemical reactions and established the
relation between the mass of a substance and the rate at which it undergoes a chemical
reaction in 1801.

2
The law of mass action was however first formulated by Cato Maximilian Guldberg (a
Norwegian mathematician and chemist) and Peter Waage (Norwegian professor of
chemistry) in 1864 and later clarified by the Dutch chemist Jacobus van‘t Hoff in 1877. This
law has profoundly influenced our qualitative and quantitative understanding of a number of
physiological and pharmacological phenomena.

According to the Law of Mass Action, the velocity of a chemical reaction depends on the
concentrations of the reactants. At equilibrium the concentrations of the chemicals involved
bear a constant relation to each other, described by the equilibrium constant, K.

Using the reaction given in equation 1, the equilibrium constant Kc can be expressed as:

[C ]c [ D ]d
Kc= a b
[ A ] [ B] (2)

Where Kc is a constant.

Notice that the products C and D occur in the numerator and the reactants A and B in the
denominator. Each concentration is raised to a power equal to the stoichiometric coefficient

in the balanced equation. The molar concentrations and so on in the definition of

are the concentrations at equilibrium. The units of depend on the stoichiometry of

the reaction.

The law of mass action is a relation that states that he values of the equilibrium constant
are constant for a particular reaction at a given temperature, whatever equilibrium
concentrated are substituted. As the following example illustrate, the equilibrium constant
expression is defined in terms of the balanced chemical equation. If the equation is rewritten
with different coefficients, then the equilibrium expression will be changed.

Example 1

Write the equilibrium – constant expression for

i. CO(g) + 3H2 (g) CH4 (g) + H2O (g)
ii. CH4 (g) + H2O (g) CO(g) + 3H2 (g)
iii. N2 (g) + 3H2 (g) 2NH3 (g)

3
 iv. ½ N2 (g) + 3/2H2 (g) NH3 (g)

Solution
i.

ii.

iii.

iv.

Note: When the equation is written in reverse order, the expression is written in for

is inverted.
When the coefficients in the equation in iii are multiplied by ½ to give;
½N2 + 3/2H2 NH3 the equilibrium constant expression is square root of the previous
one.

That is;
K c =√ K c

Exercise

1. Write equilibrium constant expressions for each of the following reactions.

(a)
i. N (g) + Br (g) 2HBr (g)
ii. 4HCl (g) + O2 (g) 2H2O (g) + 2Cl2 (g)
iii. CO (g) + 2H2 (g) 3CH3OH (g)
iv. 3CH3OH (g) CO (g) + 2H2 (g)

(b) The equilibrium constant for the equation 2HI (g) H2 (g) + I2 (g) at 450oC is

1.84. What is the value of for the following equation? H2 (g) + I2 (g) 2HI (g).
(c) If you double or triple a chemical equation throughout, what happens to the original
value of the equilibrium constant?

4
Different Ways of Expressing Equilibrium Constants
since reacting species are not always in the same phase, there may be more than one way to
express the equilibrium constant for the same reaction. To begin with let's consider reactions
in which the reactants and products are in the same phase (homogeneous Equilibria).

Homogeneous Equilibria
The term homogeneous equilibrium applies to reactions in which all reacting species are in
the same phase. An example of homogeneous gas-phase equilibrium is the synthesis of
hydrogen iodide, which reaches the equilibrium.
H2 (g) + I2 (g) 2HI (g).

The equilibrium constant denotes that in this form of reaction, the concentration of the
species are expressed in moles per litre (M/L).The concentrations of reactants and gaseous
reactions can also be expressed in terms of their partial pressures. (PA).

From the ideal gas law equation, PV = nRT, we see that at constant temperature the pressure
P of a gas is directly related to the concentration in Mol/L of the gas;
that is;

P= ( Vn ) RT
Thus, for the equilibrium of hydrogen iodide manufacture we can write;
P 1HI
K p=
PH . PI
2 2

P P
Where P HI ; H2 and I2 are the equilibrium pressures (in atm) of HI, H2 and I2 respectively.
The subscript is Kp tells us that the equilibrium concentrations are expressed in terms of
pressure.

In general, is not equal to Kp, since the partial pressures of reactants and products are not
equal to their concentrations expressed in moles per litre. A simple relationship between Kp

and can be derived as follows. Let us consider the following equilibrium in the gas phase.

aA(g) bB(g)

5
where a and b are stoichiometric coefficients. The equilibrium constant is given by;

[ B ]b
Kc=
[ A ]a

PbB
K p=
and the expression for is; paA

where PA and PB are the partial pressures of A and B respectively.

Assuming ideal gas behaviour,
P A V=n A RT
n A RT
PA=
V
where; V is the volume of the container in litres.
Also;
P B V=nB RT

nB RT
P B=
V

Substituting these relations into the expression for , we obtain;

( ) ( )(
b b
nB RT nB
V V b−a
K p= = RT )

( ) ( )
a a
n A RT nA
V V
Now both nA/V and nB/V have the units of mol/L and can be replaced by [A] and [B], so that;

[ B ]b
K p = a ( RT ) Δn
[A]
=K c ( RT ) Δn (3)
where; ∆n = b - a = moles of gaseous products – moles of gaseous reactants.

Since pressures are usually expressed in atm, the gas constant R is given as;
0.0821L.atm/K.mol, and we can write the relationship between Kp and Kc as;

6
 K p =Kc ( 0 . 0821T ) Δn (4)

In general; Kp ≠ Kc except in the special cases when Δn = 0. In that case equation (4) can be
written as;

K p =Kc ( 0 . 0821T )0 =K c
Consider the reaction for the manufacture of hydrogen iodide; in which 2 moles of gaseous
products (2HI) are obtained from 2 moles of gaseous reactants (H2 + I2). Δn = 2 – 2 = 0.
H2(g) + I2(g) 2HI(g)
in this case, equation 4 can be written as;

K p =Kc ( 0 . 0821T )0 =K c
Another example of homogeneous equilibrium is illustrated by the ionization of acetic acid
(CH3COOH) in water;
CH3COOH(aq) + H2O(l) CH3COO -(aq) +H3O+(aq)
The equilibrium constant is;

K 'c =
[ CH3 COO −][ H 3 O+ ]
[CH 3 COOH ][ H 2 O ]
However, when the acid concentration is low (≤ 1M) and/or the equilibrium constant is small
(≤ 1) as it is in this case, the amount of water consumed in this process is negligible
compared with the total amount present. Thus we may treat [H 2O] as a constant and rewrite
the equilibrium constant as;

Kc =
[ CH3 COO− ][ H 3 O+ ]
[ CH3 COOH ]
Where; K c =K 'c [ H 2 O ]

This practice will be extended to acid-base Equilibria and to solubility Equilibria to be

discussed later.

The following examples illustrate the procedure for writing equilibrium constant expression
and calculating equilibrium constants and equilibrium concentrations.

Example 2
Write expressions for Kp and Kc where applicable, for the following reversible reactions at
equilibrium:
7
 a) HF (aq) + H2O (l) H3O+ (aq) + F-(aq)
b) 2NO(g) + O2 (g) 2NO2 (g)
c) 2H2S(g) + 3O2(g) H2O(g)+ 2SO2(g)
d) CH3COOH (aq) + C2H5OH(aq) CH3COOC2H5 + H2O(l)

Solution
'
a). Since there are no gases present, Kp does not apply and we have only K c

K 'c =
[ H 3 O+ ] [ F − ]
[ HF ] [ H 2 O ]
HF is a weak acid, so the amount of water consumed in acid ionization is negligible
compared to the total amount of water present as solvent. Thus we can rewrite the
equilibrium constant as;

Kc =
[ H 3 O+ ] [ F − ]
[ HF ]
b).
2
NO
[ NO2 ]2 P 2

Kc= 2
K p= 2
[ NO ] [ O2 ] P PO NO

c).
2 2 2 2

Kc=
[ H 2 O ] [ SO 2 ] K p=
P H 2 O P SO2
2 3 2 3
[ H 2 S ] [ O2 ] PH S PO
2 2

'
d). The equilibrium constant K c is given by;

K 'c =
[ CH3 COOC2 H 5 ] [ H 2 O ]
[ CH3 COOH ] [ C2 H 5 OH ]
Because the water produced in the reaction is negligible compared to the water in the
solvent, the concentration of water does not change. Thus we can write the new
equilibrium constant as;

Kc=
[ CH 3 COOC2 H 5 ]
[ CH3 COOH ] [ C2 H 5 OH ]

Example 3
The following equilibrium process has been studied at 230oC.
2NO(g) + O2(g) 2NO2 (g)

8
In one experiment the concentrations of the reacting species at equilibrium are found to be
[NO] = 0.0542 M, [O2] = 0.127 M, and [NO2] = 15.5 M. Calculate the equilibrium constant

( K c ) of the reaction at this temperature.

Solution
The equilibrium constant is given by;
2

Kc=
[ NO2 ]
[ NO ] 2 [ O 2 ]

Substituting the concentrations, we find that

(15 . 5 )2
Kc= 2
=6 . 44 × 105
( 0. 0542 ) ( 0. 127 )

Note: is given without units.

Heterogeneous Equilibria
A reversible reaction involving reactants and products that are in different phases leads to a
heterogeneous equilibrium. For example, when calcium carbonate is heated in a closed
vessel, the following equilibrium is attained:
CaCO3(s) CaO(s) + CO2 (g)
The two solids and one gas constitute three separate phases. At equilibrium, we might expect
the equilibrium constant to be;
[ CaO ] [ CO 2 ]
K 'c =
[ CaCO3 ] (5)
But how do we express the concentration of a solid substance? Given that both CaCO 3 and
CaO are pure solids, their “concentrations” do not change as the reaction proceeds. This
follows from the fact that the molar concentration of a pure solid (or a pure liquid) is a
constant at a given temperature; it does not depend on the quantity of the substance present.
For example, the molar concentration at 20 0C of copper (density: 8.96 g/cm3) is the same,
whether we have 1 gram or 1 ton of the metal:
8 . 96 g 1mol
× =0 . 141 mol/cm3 =141 mol/L
cm 3 63 . 55g

9
From the above discussion we can express the equilibrium constant for the decomposition of
CaCO3 in a different way. Rearranging Equation 5 above, we obtain;
[ CaCO3 ] K ' = CO
[ CaO ] c [ 2 ] (6)

'
Since both [CaCO3] and [CaO] are constants and K c is an equilibrium constant, all the terms
on the left-hand side of the equation are constants. We can simplify the equation by writing

[ CaCO3 ] K ' =K
[ CaO ] c c [ CO 2 ]
where , the “new” equilibrium constant, is now conveniently expressed in terms of a
single concentration, (i.e. that of CO2).

Note: The value of does not depend on how much CaCO 3 and CaO are present, as long
as some of each is present at equilibrium.

Alternatively, we can express the equilibrium constant as;

K p =PCO
2 (7)
The equilibrium constant in this case is numerically equal to the pressure of the CO 2 gas, an
easily measurable quantity.

The treatment given to pure solids can also be applied to liquids. Thus if a pure liquid is a
reactant or a product in a reaction, we can treat its concentration as constant and omit it from
the equilibrium constant expression.

Example 4

Write the equilibrium constant expression , and where applicable, for each of the
following heterogeneous systems:
a) (NH4)2Se (s) 2NH3(g)+ H2Se(g)
b) AgCl(s) Ag+(aq) + Cl-1(aq)
c) P4(s) + 6Cl2(g) 4PCl(l)
Solution
(a) The equilibrium constant is given by;

10
 K 'c =
[ NH 3 ]2 [ H 2 Se ]
[ ( NH3 )2 Se ]
However, since (NH4)2 Se is a solid, we write the new equilibrium constant as;

K c =[ NH 3 ]2 [ H 2 Se ]

Alternatively, the equilibrium constant can be expressed in terms of the partial

pressures of NH3 and H2Se whereby:
2
NH 3
K p= P PH Se
2

(b)

[ Ag+ ][ Cl− ]
K 'c =
[ ( AgCl ) ]
K c =[ Ag+ ] [ Cl− ]

Again, [AgCl] is not incorporated into because AgCl is a solid.

(c)

K 'c =
[ PCl 3 ]4
6
[ P 4 ][ Cl 2 ]
Since pure solids and liquids do not appear in the equilibrium constant expression,
we write;
1
Kc=
[ Cl 2 ]6
Alternatively, the equilibrium constant can be expressed in terms of the pressure of
Cl2;
1
K p= 6
Cl2
P

Example 5
Consider the following heterogeneous equilibrium;
CaCO3(s) CaO(s) + CO2(g)

At 800oC, the pressure of CO2 is 0.236 atm. Calculate: (a) and (b) for the reaction at
this temperature.
11
Solution
K p =PCO =0. 236
Using Equation (7), we write 2

From Equation (4), we know that

T = 800 + 273 = 1073K and ∆n = 1, so we substitute these in the equation and obtain;
0 . 236=K c ( 0. 0821×1073 )1
K c =2 .68×10−3

Exercise
Consider the following equilibrium at 395 K:
NH4HS(S) NH3(g) + H2S(g)
The partial pressure of each gas is0.256 atm. calculate Kp and Kc for the reaction.

Multiple Equilibria
The reactions considered so far are relatively simple. Now consider a more complicated
situation in which the product molecules in one equilibrium system are involved in a second
equilibrium process:
A+B C+D
C+D E+F
The products formed in the first reaction, C and D, react further to form products E and F. At
equilibrium we can write two separate equilibrium constants:
[C ] [ D ]
K 'c =
[ A ][ B ]
and

K}c ={ {left[Eright]left[Fright]} over {left[Cright]left[Dright]} }{¿ ¿

The overall reaction is given by the sum of the two reaction
A+B C+D K'c
C+D E+F K''c
Overall reaction: A+B E+F Kc

and the equilibrium constant for the overall reaction is;

[ E ][ F ]
Kc=
[ A ][ B ]
' } } } { ¿¿
We obtain this same expression if we take the product of the expressions for K c and K c ¿

12
 K'cK}c ={ {left[Cright]left[Dright]} over {left[Aright]left[Bright]} times { {left[Eright]left[Fright]} over {left[Cright]left[Dright]} ={ {left[Eright]left[Fright]} over {left[Aright]left[Bright]} }{¿ ¿
' } } } {¿ ¿
Therefore we arrive at; K c =K c K c ¿ (8)

Note: If a reaction can be expressed as the sum of two or more reactions, the equilibrium
constant for the overall reaction is given by the product of the equilibrium constants
of the individual reactions.

Among the many known examples of multiple Equilibria are the ionization of diprotic acids
in aqueous solution. The following equilibrium constants have been determined for carbonic
acid (H2CO3) at 25oC:

+
[ H + ] [ HCO−3 ]
H 2 CO3 ( aq ) ⇔ H ( aq ) +HCO−
3 ( aq ) ; K'c= =4 . 2×10−7
[ H 2 CO 3]

HCO−3 (aq)⇔ H+(aq)+CO23-(aq); K}c ={ {left[HrSup{size8{+{} } right]left [ bold CO rSub{size8{3} rSup{size 8{ bold 2−} right]} over {left[HrSub{size8{2}} ital CO rSub{size8{3} rSup{size8{-{} } right ]} } =4 . 8times 10 rSup{size8{ - 1 } } {¿ ¿

Note: The symbol "⇔ " is used to represent " " in the equations.

The overall reaction is the sum of these two reactions given as;
H 2 CO3 ( aq ) ⇔2 H + ( aq ) +CO 2-
3 ( aq )

and the corresponding equilibrium constant is given by;

[ H + ]2 [ CO 2-3 ]
Kc =
[ H 2 CO 3 ]
Using Equation (8) we arrive at;

Kc=K'cK}c }{}# bold=left(4. bold2timesbold10rSup{size8{bold−7} right) left(4. bold8timesbold10rSup{size8{bold−1} right){}#bold=2. bold0timesbold10rSup{size8{- bold17} {} }{¿ ¿¿
¿

13
Using Equilibrium Constant to Predict the Direction of Spontaneous Reaction

By looking at the magnitude of , one can tell whether a particular equilibrium favours
products or reactants. Consider the following three cases that can help in predicting whether
reactants or products are favoured in a given reaction.

For a general reaction shown below, taking place at ToC;

aA + bB cC + dD

The reaction constant, is given as;

Case I

If is large compared to 1, this means that the numerator (product concentration) is larger
than the denominator (reactants concentrations). This means that at this temperature the
reaction favours the formation of products (i.e. the forward reaction is favoured).
Case II

If is small compared to 1, then the reactants are favoured at equilibrium (i.e.

reverse/backward reaction is favoured).
Case III

If is neither large nor small between 0.1 and 1, neither reactants nor products are favoured
at equilibrium.

Exercise

The equilibrium constant for the reaction; N2 (g) + O2 (g) 2NO(g) equals 4.6 × 10-31 at
25oC. Does the equilibrium mixture contain mostly reactants or products?
If [N2] = [O2] = 0.4M at equilibrium, what is the equilibrium concentration of NO?

Predicting the Direction of a Reaction

The equilibrium constant for the reaction CO (g) + H2O (g) H2 (g) + CO2(g) is 5.1 at
850oC. Suppose that in a certain experiment we initially placed certain amounts of the
reactants and products. Would the reaction go towards the right or towards the left? That is,
would the mixture form more H2 (g) and CO2 in moving towards equilibrium or would it form
more CO and H2O?

14
To answer this question, we substitute the initial concentrations in the equilibrium constant
expression. This can be written as;

[ H 2 ]o [ CO 2 ] o
=Qc
[ CO ] o [ H 2 O ]o (9)

where; subscript o indicates initial concentrations.

This new constant is called reaction quotient (Qc). The reaction quotient, Qc, is an
expression that has the same form as the equilibrium constant expression, but whose
concentration values are not necessarily those at equilibrium.

To determine in which direction a reaction will proceed to achieve equilibrium, we compare

the values of Qc and Kc. The three possible cases are as follows:-

Qc > Kc; The ratio of initial concentrations of product to reactant is too large. To reach
equilibrium, the value of Qc must decrease to equal Kc. Thus, products must be
converted to reactants. The system proceeds from right to left (consuming
products, forming reactants) to reach equilibrium.
Qc = Kc; The initial concentration of reactants and products are equal to equilibrium
concentrations. The system is at equilibrium.
Qc < Kc; The ratio of initial concentrations of products to reactants is too small. in
order to reach equilibrium the value of Qc must increase to equal Kc.
Reactants must be converted into products. The system proceeds from left to
right.

Example 6
At the start of a reaction, there 1.50 mol N 2, 3.50 mol H2 and 0.55 mol NH3 in 60.0 L reaction
vessel at 350oC. If the reaction equilibrium constant (Kc) for the reaction;
N2 (g) + 3H2 (g) 2NH3(g)
is 0.510 at 350oC, determine whether the reaction is at equilibrium and if not, predict the
direction of reaction.

15
Solution
The composition of the gas has been in given terms of moles. We convert these to molar
concentrations by dividing by the volume (60.0L).

That is;
1 . 50 mol
[ N 2 ]o = 60 . 0 L
=0 . 025 M

3 . 50 mol
[ H 2 ]o = 60. 0 L
=0 . 0583 M

0 .55 mol
[ NH3 ]o= 60 .0 L
=0 .00917 M

Substituting these concentrations into the reaction quotient gives;

[ NH 3 ]20 ( 9. 17×10−3 )
2
Q= 3
= 3
=17 . 239=Q c
[ 2 ]o [ 2 ]o
N H ( 0 . 025 ) ( 0 . 058 )

Since Qc (17.239) is greater than Kc (0.510), the reaction will go to the left in order to reach
equilibrium. Therefore ammonia will dissociate back into H2 and N2.

Example 7
At the start of a reaction, there are 0.249 moles N 2, 3.21 × 10-2 moles H2 and 6.42 × 10-4
moles NH3 in a 3.50-L reaction vessel at 200oC. If the equilibrium constant (Kc) for the
reaction
N2 (g) + 3H2 (g) 2NH3(g)
is 0.65 at this temperature, decide whether the system is at equilibrium. If it is not, predict
which way the net reaction will proceed.
Solution
The initial concentrations of the reacting species are:

0. 249 mol
[ N 2 ]o = 3 .50 L
=0. 0711 M

3 . 21 × 10-2 mol
[ H 2 ]o = 3 . 50 L
=9 . 17 × 10− 3 M

6 . 42 × 10-4 mol
[ NH3 ]o= 3 . 50 L
=1. 83 × 10− 4 M

The reaction quotient can thus be determined as follows;

16
 [ NH3 ]20 ( 1 . 83 x 10− 4 )
2
Qc = = =0 . 611
[ N 2 ]o [ H 2 ]3o ( 0 .0711 ) ( 9 .17 x 10−3 )3

Since Qc is smaller than Kc = 0.65, the system is not at equilibrium. The net result will be an
increase in the concentration of NH3 and a decrease in the concentrations of N 2 and H2. That
is, the net reaction will proceed from left to right until equilibrium is reached.

Exercise
The equilibrium constant (Kc) for the formation of nitrosyl chloride, an orange yellow
compound, from nitric oxide and molecular chlorine
2NO(g) + Cl2(g) 2NOCl(g)
is 6.5 × 104 at 35oC. In a certain experiment, 2.0 × 10-2 mole of NO, 8.3 × 10-3 mole of Cl2 and
6.8 moles of NOCl are mixed in a 2.00L flask. In which direction will the system proceed to
reach equilibrium?

Calculating Equilibrium Concentrations

If we know the equilibrium constant for a particular reaction, we can calculate the
concentrations in the equilibrium mixture from the initial concentrations. Depending on the
information given, the calculation may be straightforward or complex. In the most common
situation, only the initial reactant concentrations are given. Let us consider the following
system, which has an equilibrium constant (Kc) of 24.0 at a certain temperature:
A B
Suppose that A is initially present at a concentration of 0.850 mol/L. How do we calculate
the concentrations of A and B at equilibrium? From the stoichiometry of the reaction we see
that for every mole of A converted, 1 mole of B is formed. Let x be the equilibrium
concentration of B in mol/L; therefore, the equilibrium concentration of A must be (0.850 – x)
mol/L. It is useful to summarize the changes in concentration as follows:
A B
Initial: 0.850 M 0M
Change: -x M +xM
Equilibrium: (0.850 - x) M xM

17
A positive (+) change represents an increase and a negative (-) change indicates a decrease in
concentration at equilibrium. Next we set up the equilibrium constant expression.
[ B] x
Kc= ; ⇒ 24 . 0= ∴ x=0. 816
[A] 0 . 850−x

Having solved for x, we calculate the equilibrium concentrations A and B as follows:

[A] = (0.850 – 0.816) M = 0.034 M
[B] = 0.816 M

The approach to solving equilibrium constant problems can be summarized as follows:-

1. Express the equilibrium concentrations of all species in terms of the initial
concentrations and a single unknown x, which represents the change in concentration.
2. Write the equilibrium constant expression in terms of the equilibrium concentrations.
3. Knowing the value of the equilibrium constant, solve for x.
4. Having solved for x, calculate the equilibrium concentrations of all species.

Example 8
A mixture of 0.500 moles H2 and 0.500 moles I2 was placed in a 1.00-L stainless-steel flask at
430oC. Calculate the concentrations of H 2, I2 and HI at equilibrium. The equilibrium
constant Kc for the reaction H2 (g) + I2 (g) 2HI (g) is 54.3 at this temperature.

Solution
Step 1: The stoichiometry of the reaction is 1 mol H2 reacting with 1 mol I2 to yield
2 mol HI. Let x be the depletion in concentration (mol/L) of either H 2 or I2 at
equilibrium. It follows that the equilibrium concentration of HI must be 2x.
The changes in concentrations can be summarized as follows:

H2 + I2 2HI
Initial: 0.500 M 0.500 M 0.000 M
Change: -x M -xM + 2x M
Equilibrium: (0.500 - x) M (0.500 - x) M + 2x M

Step 2: The equilibrium constant is given by;

18
 [ HI ] 2
Kc=
[ H 2] [ I 2 ]
Substituting in values we get;

[ 2x ]2
54 . 3=
( 0 . 500−x ) ( 0. 500−x )
Taking the square roots of both sides, we get;
2x
7 . 37=
0 .500−x
x=0 . 393
Step 3: At equilibrium, the concentrations are
[H2] = (0.500 - 0.393) M = 0.107 M
[I2] = (0.500 - 0.393) M = 0.107 M
[HI] = 2 × 0.393 M = 0.786 M

Example 9
For the same reaction and temperature as in the above example, suppose that the initial
concentrations of H2, I2, and HI are 0.00623 M, 0.00414 M, and 0.0224 M, respectively.
Calculate the concentrations of these species at equilibrium.

Solution
Step 1: Let x be the depletion in concentration (mol/L) for H 2 and I2 at equilibrium.
From the stoichiometry of the reaction if follows that the increase in
concentration for HI must be 2x. Next we write;

H2 + I2 2HI
Initial: 0.00623 M 0.00414 M 0.0224 M
Change: -x M -xM + 2x M
Equilibrium: (0.00623 - x) M (0.00414 - x) M (0.0224+2x) M

Step 2: The equilibrium constant expression is;

Substituting in the values we get;

19
 ( 0 . 0224+2 x )2
54 . 3=
( 0 . 00623 -x )( 0 . 00414−x )
Note: It is not possible to solve this equation by the square root shortcut, as the
starting concentrations [H2] and [I2] are unequal. Instead, we must first carry
out the multiplications. That is;
54.3 (2.58 ×10-5 – 0.0104x + x2) = 5.02 ×10-4 + 0.0896 + 4x2

Putting like terms together, we get

50.3x2 – 0.654x + 8.98x 10-4 = 0
This is a quadratic equation of the form ax2 + bx + c = 0. The solution for a quadratic
equation is given by;

−b±√ b2 −4 ac 2 x
x=
2a
Here we have; a = 50.3, b = -0.654, and c = 8.98 x 10-4, such that;

0 .654± √(−0 . 654 ) −4 ( 50 .3 ) ( 8. 98 x 10−4 )

2
x=
2×50 . 3
x = 0.0114 M or: x = 0.00156 M
The first solution is physically impossible since the amounts of H 2 and I2 reacted
would be more than those originally present. The second solution gives the correct
answer. Note that in solving equations of this type, one answer is always physically
impossible, so the choice of which value to use for x is easy to make.

Step 3: At equilibrium, the concentrations are

[H2] = (0.00623 - 0.00156) M = 0.00467 M
[I2] = (0.00623 - 0.00156) M = 0.00258 M
[HI] = (0.0224 + 2 × 0.00156) M = 0.0255 M

In some cases simplifications are possible that greatly reduce the mathematical difficulties in
equilibrium constant calculations. The following example shows the conditions under which
valid approximations can be made.

Example 10
The equilibrium constant (Kp) for the following reaction is found to be 4.31 × 10-4 at 200oC.
20
 N2 (g) + 3H2 (g) 2NH3(g)
In a certain experiment a student starts with 0.862 atm of N 2 and 0.373 atm of H2 in a
constant volume vessel at 200oC. Calculate the pressures of all species when equilibrium is
reached.

Solution
Step 1:
Since initially there is no NH3 present, we conclude that the reaction must proceed from left
to right to establish equilibrium. The ideal gas equation shows that the pressure of a gas is
directly proportional to the number of moles per litre of volume.

Thus we can represent the change needed to establish equilibrium in terms of pressures. The
changes in pressure can be summarized as follows:

N2 + 3H2 2NH3
Initial: 0.862 atm 0.373 atm 0 atm
Change: -x atm - 3x atm + 2x atm
Equilibrium: (0.862 - x) atm (0.373 - 3x) atm 2x atm

Step 2:
The equilibrium constant is given by;

Substituting in values, we get ;

( 2 x )2
4 .31×10−4 =
( 0 . 862 - x )( 0 . 373−3 x )3
Multiplying and collecting like terms together would give an equation with terms containing
x4, x3, x2, and x, which would be very difficult to solve. Fortunately, we can greatly simplify
the above equation by realizing that, because Kp is a small number, the amount of NH3
formed at equilibrium must also be very small. Thus we make the following approximations:
0.862 – x  0.862 and 0.373 – 3x  0.373. The equilibrium constant expression can now be
written as;

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 (2 x )2
4 .31×10−4 =
( 0 . 862 )( 0 . 373 )3

Solving for x gives x = 2.20 x 10-3 atm

Step 3:
At equilibrium pressures are;

= (0.862 – 2.20 × 10-3) atm = 0.860 atm

= (0.373 – 3 × 2.20 × 10-3) atm = 0.366 atm

= 2(2.20 × 10-3) atm = 4.40 × 10-3 atm

Finally we note that as a rule of thumb, the approximation is considered valid if the quantity
ignored is equal to or less than 5 percent of the quantity from which it is subtracted (or to
which it is added). To check our approximations we write

2 .20×10−3
100 %=0. 255 %
0 . 862

3×2. 20×10−3
100 %=1 .77 %
0 . 373

Thus our approximations are valid.

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Changing The Reaction Conditions
Getting the maximum amount of product from a reaction depends on the proper selection of
reaction conditions. By changing these conditions, we can increase or decrease the yield of
product. There are several ways in which one can alter the equilibrium composition of a
gaseous reaction mixture and possibly increase the yield of product(s).
They include;
1. Adding a catalyst
2. Removing products or adding reactants
3. Changes in volume and pressure
4. Changing temperature

1. Adding a Catalyst
A catalyst is a substance that increases the rate of a chemical reaction but is not itself
consumed by the reaction. The significance of a catalyst can be seen in the reaction of sulfur
dioxide with oxygen to give sulfur trioxide.

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

The equilibrium constant , for this reaction is 1.7 × 10 26, which indicates that for all
practical purposes the reaction should go almost completely to products. Yet, when sulfur is
burned in air or oxygen, it forms predominantly SO 2 and very little SO3. Oxidation of SO2 to
SO3 is simply too slow to give a significant amount of product. However, the rate of the
reaction is appreciable in the presence of a platinum or di-vanadium pentoxide catalyst. The
oxidation of SO2 in the presence of a catalyst is the main step in the contact process for the
industrial production of sulfuric acid, H2SO4. The acid is prepared by reacting SO 3 with
water.

It is important to understand that a catalyst has no effect on the equilibrium composition of a

reaction mixture. A catalyst merely speeds up the attainment of equilibrium.

23
2. Removing Products or Adding Reactants
One way to increase the yield of a desired product is to change concentrations in a reaction
mixture by removing a product or adding a reactant. Consider the methanation reaction shown
below;
CO(g) + 3H2(g) CH4(g) + H2O(g)

If we place 1.000 mol CO and 3.000 mol H 2 in a 10.00-L reaction vessel, the equilibrium
composition at 1200 K is 0.613 mol CO, 1.839 mol H 2, 0.387 mol CH4, and 0.387 mol H2O. is it
possible to alter this composition by removing or adding one of the substances to improve the
yield of methane? To answer this question, we can apply LeChatelier's principle.

LeChatelier's principle states that:

“If a system in chemical equilibrium is altered by change of some condition, the
chemical reaction tends to shift the equilibrium composition in a way so as to reduce
the effect of that change”.

Suppose we remove a substance from or add one to the equilibrium mixture in order to alter the
concentration of the substance. Chemical reaction then occurs to partially restore the initial
concentration of the removed or added substance. (However, if the concentration of substance
cannot be changed, as in the case of a pure solid or liquid reactant or product, changes in amount
will have no effect on the equilibrium.)

For example, suppose that water vapor is removed from the reaction vessel containing the
equilibrium mixture for methanation. LeChatelier's principle predicts the net chemical change
will occur to partially reinstate the original concentration of water vapor. This means that the
methanation reaction momentarily goes in the forward direction,
CO(g) + 3H2(g) CH4(g) + H2O(g)
until equilibrium is re-established. Going in the forward direction, the concentrations of both
water vapor and methane increase.

24
It is often useful to add an excess of a cheap reactant in order to force the reaction toward more
products. In this way, the more expensive reactant is made to react to a greater extent than it
would otherwise.

Consider the ammonia synthesis

N2 (g) + 3H2 (g) 2NH3(g)
If we wished to convert as much hydrogen to ammonia as possible, we might increase the
concentration of nitrogen. To understand the effect of this, first suppose that a mixture of
nitrogen, hydrogen, and ammonia is at equilibrium. If nitrogen is now added to this mixture, the
equilibrium is disturbed. According to LeChatelier's principle, the reaction will now go in the
direction that will use up some of the added nitrogen. Consequently, adding more nitrogen has
the effect of converting a greater quantity of hydrogen to ammonia.

Exercise
Consider each of the following Equilibria that are disturbed in the manner indicated. Predict the
direction of reaction.
(a) The equilibrium: CaCO3(s) CaO(s) + CO2(g) ,is disturbed by increasing the
pressure (that is, concentration) of carbon dioxide.
(b) The equilibrium: 2Fe(s) + 3H2O(g) Fe2O3(s) + 3H2(g) , is disturbed by increasing
the concentration of hydrogen.

Note: A reaction whose equilibrium constant is extremely small remains almost completely as
reactants and cannot be shifted to products by adding an excess of one reactant. For
example, the reaction;
CO2(g) + 2H2O(g) CH4(g) + 2O2(g)

has an equilibrium constant equal to 1×10-140 . This value is so small that the
equilibrium mixture practically consists only of carbon dioxide and water. Adding more
carbon dioxide to the reaction vessel has no appreciable effect. The reaction is
essentially irreversible.

25
3. Effect of Pressure and Volume Change
A pressure change obtained by changing the volume can affect the yield of product in a gaseous
reaction if the reaction involves a change in total moles of gas. The methanation reaction is an
example of a change in moles of gas.

The optimum conditions for catalytic methanation involve moderately elevated temperatures and
normal to moderately high pressures.

When the reaction goes in the forward direction, four moles of reactant gas (CO + 3H 2) become
two moles of product gas (CH4 + H2O). To see the effect of such a pressure change, consider
what happens when an equilibrium mixture from the methanation reaction is compressed to one-
half of its original volume at a fixed temperature. The total pressure is doubled ( PV = constant at
a fixed temperature, according to Boyle's law, so halving V requires that P double). Because the
partial pressures and therefore the concentrations of reactants and products have changed, the
mixture is no longer at equilibrium.

The direction in which the reaction goes to again attain equilibrium can be predicted by applying
LeChatelier's principle. Reaction should go in the forward direction, because then the moles of
gas decrease, and the pressure (which is proportional to moles of gas) decreases. In this way,
the, initial pressure increase is partially reduced.

In order to decide the direction of reaction when the pressure of the reaction mixture is increased
(say, by decreasing the volume), we ignore liquids and solids. These are not much affected by
pressure changes because they are nearly incompressible. It is however important to note that an
increase or a decrease in pressure of a gaseous reaction must result in changes of partial
pressures of substances in the chemical equation if it is to have an effect on the equilibrium
composition. Only changes in partial pressures, or concentrations, of these substances can affect
the reaction quotient.
Consider the effect of increasing the pressure in the methanation reaction by adding helium gas.
Although the total pressure increases, the partial pressures of CO, H 2, CH4, and H2O do not
26
change. Thus the equilibrium composition is not affected. But on the other hand, changing the
pressure by changing the volume of this system changes the partial pressures of all gases, so the
equilibrium composition is affected.

Note: If the pressure is increased by decreasing the volume of a reaction mixture, the reaction
shifts in the direction of fewer moles of gas.

Example 11
Look at each of the following equations and decide whether an increase of pressure obtained by
decreasing the volume will increase, decrease, or have no effect on the amounts of products.
(a) CO(g) + Cl2(g) COCl2(g)
(b) 2H2S(g) 2H2(g) + S2(g)
(c) C(graphite) + 2O2(g) 2CO2(g)

Solution
(a) Reaction decreases the number of molecules of gas (from two to one). According to Le
Chatelier's principle, an increase of pressure increases the amount of product.
(b) Reaction increases the number of molecules of gas (from two to three); hence, an
increase of pressure decreases the amounts of products.
(c) Reaction does not change the number of molecules of gas. (We ignore the change in
volume due to consumption of solid carbon (graphite) because the change in volume of a
solid is insignificant. Look only at gas volumes when deciding the effect of pressure
change on equilibrium composition. Pressure change has no effect.

Exercise
Can you increase the amount of product in each of the following equations by increasing the
pressure? Explain.
(a) CO2(g) + H2(g) CO(g) + H2O(g)
(b) 4CuO(s) 2Cu2O(s) + O2(g)
(c) 2SO2(g) + O2(g) 2SO3(g)

27
4. Effect of Temperature Change
Temperature has a profound effect on most reactions. In the first place, reaction rates usually
increase with an increase in temperature, meaning that equilibrium is reached sooner. Many
gaseous reactions are sluggish or have imperceptible rates at room temperature but speed up
enough at higher temperature to become commercially feasible processes.

Equilibrium constants vary with temperature. Table 1 gives values of for methanation at
various temperatures.
Table 1: Equilibrium Constants for Methanation at
Different Temperatures.
Temperature (K) Kc
298 4.9 x 1027
800 1.38 x 105
1000 2.54 x 102
1200 3.92

Note: equals 4.9 × 1027 at 298 K. Thus an equilibrium mixture at room temperature
is mostly methane and water.

Whether one should raise or lower the temperature of a reaction mixture to increase the
equilibrium amount of product can be shown by Le Chatelier's principle. Consider the
methanation reaction,
CO(g) + 3H2(g) CH4(g) + H2O(g); Ho = -206.2kJ

The value of Ho shows this reaction to be quite exothermic. Thus, as products are formed,
considerable heat is released. According to Le Chatelier's principle, as the temperature is raised,
the reaction shifts to form more reactants, thereby absorbing heat and attempting to counter the
increase in temperature. That is;

28
Thus, we can predict the equilibrium constant to be larger for lower temperatures, being in
agreement with the values of Kc, given in Table 1.

For an endothermic reaction (H positive), the amounts of products are increased at equilibrium

by an increase in temperature ( is larger at higher T). For an exothermic reaction (H

negative), the amounts of products are increased at equilibrium by a decrease in temperature (

is larger at lower T).

Example 12
Carbon monoxide is formed when carbon dioxide reacts with solid carbon (graphite) according
to the equation;
C(graphite) + 2CO2(g) 2CO(g) ; Ho = 172.5kJ
Is a high or low temperature more favourable to the formation of carbon monoxide?
Solution
The reaction absorbs heat in the forward direction.
Heat + CO2(g) + C(graphite)  2CO(g)
As the temperature is raised, reaction occurs in the forward direction, using heat and thereby
tending to lower the temperature. Thus high temperature is more favourable to the formation of
carbon monoxide. This is why combustions of carbon and organic materials can produce
significant amounts of carbon monoxide.

Exercise
Consider the equilibrium between molecular oxygen and ozone
3O2(g) 2O3(g); Ho = 284kJ/mol
What would be the effect of;
a) Increasing the pressure on the system by decreasing the volume,
b) Adding O2 to the system at constant volume
c) Decreasing the temperature and
d) Adding a catalyst?

29
Choosing Optimum Conditions for Reaction
Gaseous reactions are often very slow at room temperature. In practice, the methanation reaction
is run at moderately elevated temperatures (230-450oC) in the presence of a nickel catalyst,
where the rate of reaction is sufficiently fast but the equilibrium constant is not too small. Given
that the methanation reaction involves a decrease in moles of gas, the yield of methane should
increase as the pressure increases. However, the equilibrium constant is large at the usual
operating temperatures, so very high pressures are not needed to obtain economical yields of
methane. Pressures of 1 - 100atm are normally used for this reaction. As another example,
consider the Haber process for the synthesis of ammonia.
Fe catalyst
N 2 +3 H 2 ( g ) ⇔ 2NH 3 ; ΔH o =−91 . 8 kJ ,−206 .2 kJ
( g) (g)

Since the reaction is exothermic, the equilibrium constant is larger for lower temperatures. But
the reaction proceeds too slowly at room temperature to be practical, even in the presence of the
best available catalysts. The optimum choice of temperature, found experimentally to be about
450oC, is a compromise between an increased rate of reaction at higher temperature and an
increased yield of ammonia at lower temperature. Because the formation of ammonia decreases
the moles of gases, the yield of product is improved by high pressures. The equilibrium constant
Kc, is only 0.159 at 450oC, so higher pressures (up to 1000 atm) are required for an economical
yield of ammonia.

Exercise
Consider the reaction
CO2(g) 2CO(g) + O2(g); Ho = 566kJ/mol
Discuss the temperature and pressure conditions that would give the best yield of carbon
monoxide.

30