Chapter 6

Chemical Equilibrium

Reversible and Irreversible Reactions

A reversible reaction is a chemical reaction that results in an equilibrium mixture of
reactants and products; for example, formation of ammonia is a reversible reaction.
N2(g) + 3H2(g) 2NH3(g)
Another example of reversible reaction is the formation of hydrogen iodide from
hydrogen gas and iodine vapours.
H2(g) + I2(g) 2HI(g)

Chemical reactions which proceed in only one direction are known as irreversible
reactions. When the equation for irreversible reaction is written, a single arrow () is
used indicating that the reaction can proceed in only one direction.
While writing reversible reaction, double arrow ( ) is used indicating that
the reaction can go from reactant to product side and also from the product to the
reactant side. The reaction from the reactant side to the product side is known as
forward reaction and reaction from product to the reactants is known as reverse or
backward reaction.

Exercise 6 . 1
Answer the following questions:
1. Define the terms reversible reaction and irreversible reaction.
2. Give examples of reversible and irreversible reactions.
3. Which symbol or sign is used to represent the reversibility and irreversibility of
the reaction?
 Characteristics of Chemical
Equilibrium
Equilibrium
The equilibrium is dynamic in nature which means that although at the macroscopic
level the properties do not change with time, however, at the molecular level the two
processes are still taking place. So the equilibrium is attained when the rate of two
opposing processes become equal.
Ice and water present together in a thermos flask at 0°C is another example of
dynamic equilibrium. The equilibrium is attained when the rates of melting and freezing
become equal.

The saturated solution is also an example of dynamic equilibrium. Saturated solution is

a solution in which undissolved solute is in equilibrium with the solute dissolved in the
solution. The molecules from undissolved solute go into the solution and equal number
of solute molecules get precipitated from the solution. Therefore, the concentration of
the solution remains constant.

Chemical Equilibrium
An equilibrium involving a chemical reaction is known as chemical equilibrium. When a
chemical reaction takes place, the reactants are consumed and the products are
formed. As a result the concentrations of reactants decrease with time and that of
products increase. If the reaction is reversible in nature and it takes place in a closed
vessel then the products decompose to give back reactants. After some time the
concentrations of the reactants and products become constant, that is they do not
change with time. This state is known as chemical equilibrium.
Chemical equilibrium is the state of the reaction when the macroscopic
properties like temperature, pressure, volume and concentration of the reaction
do not change with time.

Conditions for Attainment of Chemical Equilibrium

In a reversible reaction, reactant molecules react to give products and at the same
time some product molecules give back reactants. The rate of reaction depends upon
the concentration of reactants. The rate of forward reaction depends upon the
concentration of reactants while the rate of reverse reaction depends upon the
concentration of products as shown in Figure 6.1. Initially only the reactants are
present, therefore, the rate of forward reaction is fast. The reaction in the reverse
direction does not take place as no product is present. As the reaction progresses,
due to the decrease in the concentration of reactants, the rate of forward reaction
decreases. At the same time, due to the increase in the concentration of products, the
rate of reverse reaction increases. As the reaction further progresses a stage is
reached when the rate of forward reaction becomes equal to the rate of reverse
reaction. When this stage is attained, the concentrations of reactants and products do
not change. The reaction has attained chemical equilibrium.

Forward reaction

Equilibrium

Backward reaction

Time

Fig 6 . 1 Change in the rate of reaction with time for the forward and reverse reactions.

For example, as seen earlier, formation of ammonia from nitrogen and hydrogen is a
reversible process. At the start of the reaction only nitrogen and hydrogen are present.
They combine to form ammonia. The rate of formation of ammonia is large. With the
progress of reaction, the concentrations of nitrogen and hydrogen decrease so the rate
of formation of ammonia decreases. As more and more ammonia molecules are
formed, some of the molecules start decomposing to give back nitrogen and
hydrogen. With the progress of reaction, the number of ammonia molecules increases,
so the rate of decomposition of ammonia also increases. As the reaction proceeds, the
rate of formation of ammonia decreases while the rate of decomposition of ammonia
increases. A stage is reached when the two rates become equal and equilibrium is
attained.

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

The chemical equilibrium is also dynamic in nature since the reaction does not stop at
equilibrium. The macroscopic properties remain constant because the rate of forward
reaction becomes equal to the rate of reverse reaction and hence no net reaction
takes place.
Another example is the decomposition of dinitrogen tetraoxide to form nitrogen
dioxide.
N2O4(g) 2NO2(g)
colourless reddish brown

When colourless N2O4 is taken in a closed vessel, after some time its colour changes
to brown indicating that NO2 has been formed. Similarly, if NO2 is taken in a
closed vessel, initially the colour is reddish brown but the colour starts fading and
after some time it becomes brown. This colour change takes place because some
NO2 molecules dimerize to form N2O4. In both the cases, the final colour is same
indicating that at equilibrium both N2O4 andNO2 are present.
From these observations it can be concluded that the chemical equilibrium is attained
whether the reaction is started with reactants or with products. That is, chemical
equilibrium can be obtained from forward direction as well as reverse direction.
It should be noted that the concentrations of products and reactants are not
necessarily equal at equilibrium, only the rate of forward and reverse reactions are
equal.
In summery Chemical Equilibrium has the following Characteristics

 The reaction is reversible in nature.

 The reaction takes place in a closed vessel, that is, during the
reaction;reactants and products are neither added nor removed from the
reaction vessel.
 The rate of forward reaction is equal to the rate of reverse reaction.
 All the reactants and products are present at equilibrium.
 The macroscopic properties like temperature, pressure, volume and
concentration do not change with time.
 The equilibrium is dynamic in nature.
 The state of equilibrium can be obtained from either side.
 The concentrations of reactants and products are generally not equal.
 The free energy change of the reaction is zero at equilibrium.

Exercise 6 . 2
Answers the following questions:
1. When a mixture of SO2 and O2 is introduced into a reaction vessel at a
temperature of 700 K, a reaction that produces SO3 occurs as:
2SO2(g) + O2(g)  2SO3(g)
a When do we say that the system has reached chemical equilibrium? Explain
your answer.
b Why is the equilibrium state referred to as dynamic?
c Write the equation that shows the presence of the three species in
equilibrium.
2. Label a, b and c for the figure below. Explain trends of the rate of the forward
reaction and the rate of the reverse reaction.

(a)

(c)

(b)

Time
 3. Label a, b and c for the figure shown below. Explain what happens to the
concentration of the reactants and the concentration of the products.

Concentration (a)

(c)

(b)

Time

4. What are the conditions that remain constant at equilibrium?

Equilibrium Expression and Equilibrium Constant

Law of Mass Action
Two Norwegian scientists C.M. Guldberg and Peter Waage studied reversible
chemical reactions and gave a law characterizing the dynamic chemical equilibrium.
This law is known as law of mass action. According to this law:
• The combining power of two reactants A and B depends upon their nature as
well as their active concentrations.
• The rate at which A and B combine is directly proportional to the product of
their concentration terms each raised to the power of its respective coefficient in
the balanced chemical reaction.
The general equation that represents a reversible reaction is:
aA + bB mM + nN
For the forward reaction A and B are reactants and M and N are products.
It is assumed that the reaction is homogeneous in nature, that is all the reactants and
the products are present in the same state.
The rate of forward reaction (rf ) depends upon the concentrations of A and B and is
given by the expression
rf  [A]a [B]b or rf = kf [A]a [B]b
where [A] and [B] are the concentrations of A and B respectively. The rate of reverse
reaction is given by the expression
rb  [M]m [N]n or rb = kb [M]m [N]n
where [M] and [N] are the concentrations of M and N respectively. kf and kb are
rate constants for forward and reverse reactions, respectively.
At equilibrium, the rate of forward reaction is equal to the rate of reverse reaction.
Therefore,
rf = rb
or kf [A]a [B]b = kb [M]m [N]n
kf and kb are constant. Therefore, the ratio of kf to kb is also a constant.

kf [M]m [N]n
  Keq
kb [A]a[B]b
The ratio of kf and kb is represented by Keq. Since this constant represents the
reaction at equilibrium it is known as equilibrium constant. [M], [N], [A] and [B] are
concentrations at equilibrium. When the concentrations are expressed in
molarities, the equilibrium constant is represented by Kc. When the reactants and
the products are in the gaseous state, their concentrations can be expressed in terms
of partial pressures. In such cases, the equilibrium constant isdenoted by Kp.
Rules for Writing the Equilibrium Constant Expression for
Homogeneous Reactions
Homogeneous reaction is a reaction in which all the reactants and the products are
present in the same physical state.
For a homogeneous reaction, rules followed while writing the expression for
equilibrium constant are:
• The concentrations of all the substances formed as products are written in the
numerator.
• The concentrations of all the reactants are written in the denominator.
 • Each concentration term is raised to the power by its respective coefficient as
written in the balanced chemical reaction.
For a general reaction at equilibrium
aA + bB mM + nN
the expression for Kc is:

[M]m [N]n
Kc =
[A]a[B]b

When all the reactants and the products are in the gaseous state, their concentrations
can be written in terms of partial pressures. In such cases the equilibrium constant is
denoted by Kp. The expression for Kp is

For the formation of ammonia,

N2(g) + 3H2(g) 2NH3(g)
the expression of equilibrium constant in terms of molarities is:

Exercise 6. 3
Write the equilibrium constant expression for the following reactions:
1. NH3(g) + CH3COOH(aq) NH+ (aq) + CH COO–
4 3

2. (aq)
HF(aq) H+(aq) + F–(aq)
3. 2NO(g) + Br2(g) 2NOBr(g)
4. 2HF(g) H2(g) + F2(g)
Units of Kc
The unit of Kc of a reaction depends upon the number of moles of the reactants and
products involved in the reaction. Therefore, for a general reaction;
aA + bB mM + nN
The unit of Kc will be

Example
1. For the reaction:

NH3(g) + CH3COOH(aq) NH+4(aq) + CH3COO–(aq)

Kc =
 NH +4   CH 3 COO – 
    =
mol L-1  mol L -1
 1
 NH3 CH3 COOH mol L-1  mol L
-1

2. For the reaction:

2HF(g) H2(g) + F2(g)

H+  F– 
    =
 
mol L-1 mol L-1 
 mol L-1
 
Kc =
HF mol L-1

Unit of Kp
The unit of Kp is decided by the unit of pressure. If the partial pressure is expressed
in atm, then the unit of Kp, will be:
If the partial pressure is measured in kPa, then the unit of Kp will be (kPa)(m+n)–(a+b)

NH3 atm2 1
1. N (g) + 3H (g) = 
atm2
N2 H2

 2
atm2
2HI(g) Kp = 
P 2
P 2


NO 2
K =  atm
2 4
PN O2 4
 atm 

Equilibrium Constant for Heterogeneous Reactions

In heterogeneous reactions, the reactants and products are present in more than one
physical state. For example, thermal decomposition of calcium carbonate is an
example of heterogeneous reaction.

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

Some other examples of heterogeneous reactions are

NH4Cl(s) NH3(g) + HCl(g)

CO2(g) + H2O(l) H+(aq) + HCO – (aq)

3

Rules for Writing the Expression for Equilibrium Constant for

Heterogeneous Reaction
• The concentration terms of products are written in the numerator and the
concentration terms of reactants are written in the denominator raised to the
power of their respective coefficient in the balanced chemical equation.

• While writing the expression for Kc, the molarities of gaseous reactants and
 products and species present in the solution are written.

• Concentration terms of solids and pure liquids do not appear in the

expression, as they are taken to be unity.

• While writing the expression for Kp, partial pressures of only the gaseous
reactants and products are written in the expression for equilibrium constant.

Example
The equilibrium constant expression for some heterogeneous reactions areshown
below:
a CaCO3(s): CaO(s) + CO2(g) Kp = pCO
2
b NH4Cl(s) : NH3(g) + HCl(g) Kp = (pNH )(pHCl )
3

H  HCO– 
+ –    3 
c CO 2(g) + H 2O(l) : H (aq) + HCO (aq) Kc =
3
CO2 
1
d Fe3+(aq) + 3OH–(aq) : Fe(OH)3(s) Kc = 3
Fe3  OH– 
  
 Exercise 6. 4
Answer the following questions:
1. 5.0 mole of ammonia were introduced into a 5.0 L reaction chamber in which
it is partially decomposed at high temperatures.

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

At equilibrium at a particular temperature, 80.0% of the ammonia had reacted.
Calculate Kc for the reaction.
2. 1.25 mol NOCl was placed in a 2.50 L reaction chamber at 427°C. After
equilibrium was reached, 1.10 moles NOCl remained. Calculate the
equilibrium constant for the reaction.
2NOCl(g) 2NO(g) + Cl2(g)
3. A sample of nitrosyl bromide was heated to 100°C in a 10.0 L container in
order to partially decompose it.
2NOBr(g) 2NO(g) + Br2(g)
At equilibrium the container was found to contain 0.0585 mol of NOBr, 0.105
mol of NO, and 0.0524 mol of Br2. Calculate the value of Kc.
4. The brown gas NO2 and the colourless gas N2O4 exist in equilibrium.
N2O4(g) 2NO2(g)
0.625 mol of N2O4 was introduced into a 5.00 L vessel and was allowed to
decompose until it reached equilibrium with NO2. The concentration of N2O4
at equilibrium was 0.0750 M. Calculate Kp for the reaction.

Relation between Kc and Kp

For the general reaction

a A(g) + bB(g) mM(g) + nN(g)
 It is assumed that all the gaseous species behave like an ideal gas. According to
the ideal gas equation, the partial pressure (p) is given by
p = nRT / V and n/V = C
where n = amount of the gaseous species in moles. R = Gas constant
T = Temperature in kelvin
V = Volume of the reaction mixture
C = Molarity
Thus, pA = nA RT / V = CART
pB = nB RT / V = CBRT
pM = nM RT / V = CMRT
pN = nN RT / V = CNRT

here n = (m + n) – (a + b) for gaseous species

Kp = Kc(RT )n
When the number of gaseous reactants and products are equal then,
a + b=m+n
Therefore, n = 0 and hence Kp = Kc
 Example
1. The equilibrium constant for the reaction:
2SO3(g) 2SO2 (g) + O2(g)
is 1.8 × 10–3 kPa at 427°C. Calculate Kc for the reaction at the same
temperature.
Solution:
Given: Kp = 1.8 × 10–3 kPa = 1.8 Nm–2 T = 427°C = 700 K.
R = 8.314 N m K–1 mol–1
We know that
Kp = Kc(RT)n
For the given reaction, n = (2+1) – 2 = 1
Therefore, Kc = Kp/(RT)
 1.8 Nm2
=  3.09 mol m3
700 K  8.314 N m K1mol1

2. What are the values of Kp and Kc at 1000°C for the reaction

CaCO3(s) CaO(s) + CO2(g)
if the pressure of CO2 in equilibrium with CaCO3 and CaO is 3.87 atm?

Enough information is given to find Kp first. Writing the Kp expression for

this heterogeneous reaction:
Kp = pCO = 3.87
2
Then to get Kc, rearrange the equation,
Kp = Kc(RT ) n
where n, the change in the number of moles of gas in the reaction is +1.
Calculation:

Kp
Kc =
(RT )n

3.87
Kc =  0.0370
(0.0821)(1273)
3. At 400 °C, Kc = 64 for the reaction
H2(g) + I2(g) 2HI(g)
a What is the value of Kp for this reaction?
b If at equilibrium, the partial pressures of H2 and I2 in a container are
0.20 atm and 0.50 atm, respectively, what is the partial pressure of HI
in the mixture?
Solution:
a The equation relating Kp to Kc is
Kp = Kc(RT)n
Here the change in the number of moles of gas n is:
 n = 2 mol HI – 1 mol H2 – 1 mol I2 = 0
Since, n = 0, Kp and Kc are the same.
Kp = Kc(RT)0 = Kc
Kp = Kc = 64
b Writing the equilibrium constant expression

2
p HI
Kp =  64
pH pI
2 2

and substituting the given pressures

p2
HI
= 64
(0.20)(0.50)

the partial pressure of HI is

pHI = (0.20)(0.50)(64)

pHI = 2.53 atm

Exercise 6. 5
Answers the following questions:
1. The following equilibrium constants were determined at 1123 K:
C(s) + CO2(g) 2CO(g) Kc = 1.4 × 1012
CO(g) + Cl2(g) COCl2(g) Kc = 5.5 × 10–1
COCl2(g)
Write the equilibrium constant expression Kc and calculate the equilibrium
constant at 1123 K for the following reaction:
C(s) + CO2(g) + 2Cl2(g) 2COCl2(g)
2. For the decomposition of ammonium chloride,
NH4Cl(s) NH3(g) + HCl(g) at 427°C, Kp = 4.8.
Calculate Kc for this reaction.
 3. Write the equilibrium constant expression for the following equations:
a 2HgO(s) 2Hg(l) + O2(g)
b Ni(s) + 4CO(g) Ni(CO)4(g)
c 2NO(g) + Br2(g) 2NOBr(g)
4. For the reaction:
H2(g) + Br2(g) 2HBr(g)
Kp = 7.1 × 104 at 700 K. What is the value of Kp for the following reactions
at the same temperature?
a 2HBr(g) H2(g) + Br2(g)
b ½ H2(g) + ½ Br2(g) HBr(g)
5. The reversible reaction:
N2O4(g) 2NO2(g)
has a value of Kp = 0.113 at 25°C. Determine the numerical value of Kc at
25°C for the reaction,
½N2O4(g) NO2(g)
Is it greater than, equal to, or less than 0.113? Explain.

The value of equilibrium constant predicts the extent of reaction at equilibrium. It also
tells about the relative concentrations of products and reactants present at equilibrium,
that is, the position of equilibrium.
Position of equilibrium: Kc can have three types of values.

Case 1: When Kc >1

This indicates that the value of numerator is greater than the denominator. So the
formation of products is favoured at equilibrium.

Case 2: When Kc <1

This indicates that the value of numerator is less than the denominator. So the
formation of products is not favoured at equilibrium.

Case 3: When Kc =1
 This indicates that the rate of forward reaction is equal to the rate of backward
reaction.

Extent of reaction: Kc value also predicts the extent of the reaction at equilibrium.
Very large values of Kc indicates that the extent of the reaction is very large at
equilibrium. So most of the reactants have been consumed at equilibrium. A very small
value of Kc indicates that the extent of reaction is very small at equilibrium. Most of
the reactants will be in the unreacted state.
Reaction Quotient (Q)
Reaction quotient is the ratio of concentrations of products to the concentrations of
reactants raised to the power of their respective coefficients at any stage after the start
of the reaction. For the general reaction,
aA + bB mM +
nNthe expression for the reaction quotient is
[M]m[N]n
Q=
[A]a[B]b

[A] , [B], [M] and [N] are concentrations at any stage during the reaction. At the
initial stages of the reaction, the amount of product formed is low, therefore, the value
of Q is small. With the progress of the reaction, since the concentration of products
increases, the value of Q also increases. When the reaction attains equilibrium, Q
becomes equal to the equilibrium constant.
Reaction Quotient in Terms of Molarities
When the concentrations are expressed in molarities, the reaction quotient is Qc.
[M]m[N]n
Qc =
[A]a[B]b
At equilibrium,
[M]m [N]n 
Qc =   = Kc

a b
 [A] [B] eq

Reaction Quotient in Terms of Partial Pressure

When the concentrations are taken in partial pressures, the reaction quotient is Qp
and is given by the expression
Application of Reaction Quotient
Reaction quotient predicts the direction of the reaction at any stage, that is for the
given concentration of reactants and products. It also decides whether the reaction
has attained equilibrium or not.
When Q is less than K, then the reaction will proceed in the forward direction and
more products will be formed till the equilibrium is reached.
When Q is greater than K, then the reaction will proceed in the reverse direction and
more reactants will be formed till the equilibrium is reached.
When Q is equal to K, then the reaction has attained equilibrium.

Example
At a certain temperature the reaction:

CO(g) + Cl2(g) COCl2(g)

has an equilibrium constant Kc = 13.8. Is the following mixture an equilibrium

mixture? If not, in which direction (forward or backward) will the reaction
proceed to reach equilibrium? [CO]0 = 2.5 mol L–1; [Cl2]0 = 1.2 mol L–1; and
[COCl2]0 = 5.0 mol L–1.
Solution: Recall that for the system to be at equilibrium Qc = Kc. Substitute the given
concentrations into the reaction quotient for the reaction, and determine Qc.

Since Qc < Kc the reaction mixture is not an equilibrium mixture, and a net
forward reaction will bring the system to equilibrium.

Calculating the Equilibrium Concentrations
Not only can we estimate the extent of reaction from the Kc value, but also the
expected concentrations at equilibrium can be calculated from knowledge of the initial
concentrations and the Kc value. In these types of problem it will be very helpful to
use the following approach.
1. Express the equilibrium concentrations of all the species in terms of the initial
concentrations and an unknown x, which represents the change in concentration.
Substitute the equilibrium concentrations derived in part 1 into the equilibrium
constant expression, and solve for x. The equilibrium concentration is given by:
equilibrium concentration = initial concentration ± the change due to the reaction
where the + sign is used for a product, and the – sign for a reactant.Use x to
calculate the equilibrium concentration of all the species.
 Example
Let us consider the reactioin between hydrogen and iodine in which 1 mole of H2
and 2 moles of I2 were added in 500 mL flask. First we need expressions for the
equilibrium concentrations of H2, I2, and HI. Tabulating the initial concentrations
as:

Concentration H2 + I2 2HI

Initial 1.00 mol/0.50 L 2.00 mol/0.50 L 0

Change – – –
Equilibrium – – –
Since the answer involves three unknowns, we will relate the concentrations to
each other by introducing the variable x. Recall, that the equilibrium concentration
= initial concentration ± change in concentration. Let x = the change in
concentration of H2. That is, let x = the number of moles of H2 reacting per liter.
From the coefficients of the balanced equation we can tell that if the change in H2
is –x, then the change in I2 must also be –x, and the change in HI must be +2x.

Concentration H2 + I2 2HI
Initial (M) 2.0 4.0 0
–x –x
Change (M)
(2.0 – x) (4.0 – x)
Equilibrium (M) +2x
 Now substitute the equilibrium concentrations from the table into the Kc
expression,

 2x 
2

Kc =
 2.0– x  4.0– x

and solve for x.
 2x 
2

Kc = = 64
x2 – 6.0x  8.0

Rearranging, we get:

4x2 = 64x2 – 384x + 512

and grouping yields

60x2 – 384x + 512 = 0

We will use the general method of solving a quadratic equation of the form

ax2 + bx + c = 0
The root x is given by

–b  b2 – 4ac
x=
2a

In this case, a = 60, b = –384, and c = 512. Therefore,

–  –384  (–384)2 – 4  60  512 

x=
2  60 

384  2.5104
x=
120

384 158
x= = 1.9 and 4.5 mol/L
120
 Recall that x = the number of moles of H2 (or I2) reacting per liter. Of the two
answers (roots), only 1.9 is reasonable, because the value 4.5 M would mean that
more H2 (or I2) reacted than was present at the start. This would result in a
negative equilibrium concentration, which is physically meaningless. We therefore
use the root x = 1.9 M to calculate the equilibrium concentrations:

[H2] = 2.0 – x = 2.0 M – 1.9 M = 0.1 M

[I2] = 4.0 – x = 4.0 M – 1.9 M = 2.1 M

[HI] = 2x = 2(1.9 M) = 3.8 M. The results can be checked

by inserting these concentrations back into the Kc expression
to see if Kc = 64.

 HI  3.8 
2 2

Kc = = = 68
 H 2  I2   0.1 2.1


Thus the concentrations we have calculated are correct. The difference between
64 and 68 results from rounding off which is to maintain the correct number of
significant figures. Therefore, our result is correct only to the number of significant
figures given in the problem.
1. For the equilibrium:
2NO2(g) Kc = 0.36 at 100°C
a sample of 0.25 mol N2O4 is allowed to dissociate and come to equilibrium in a
1.5 L flask at 100°C. What are the equilibrium concentrations of NO2 and
N2O4?
2. The decomposition of NOBr is represented by the equation:

At equilibrium the concentrations of NO and Br2 are 1.05×10–2 M and

5.24×10–3 M, respectively. What is the concentration of NOBr?

3. The reaction:
PCl5(g) PCl3(g) + Cl2(g)
has the equilibrium constant value Kc = 0.24 at 300 °C.
a Is the following reaction mixture at equilibrium?
[PCl5] = 5.0 mol/L, [PCl3] = 2.5 mol/L, [Cl2] = 1.9 mol/L
b Predict the direction in which the system will react to reach equilibrium

4. At 400°C, the equilibrium constant for the reaction:

H2(g) + I2(g) 2HI(g)
is 64. A mixture of 0.250 mol H2 and 0.250 mol I2 was introduced into an
empty 0.75 L reaction vessel at 400°C, find the equilibrium concentrations of
all components

5. At 700 K, the reaction:

2SO2(g) + O2(g) 2SO3(g)
has an equilibrium constant Kc = 4.3 × 106.
a Is a mixture with the following concentrations at equilibrium?
[SO2] = 0.10 M; [SO3] 10 M; [O2] = 0.10 M.
b If not at equilibrium, predict the direction in which a net reaction will occur
to reach a new equilibrium.
 Changing Equilibrium Conditions–Le Chatelier’s
Principle

Factors Affecting the Equilibrium Constant

The equilibrium constant depends upon the following factors:

1. Temperature at which the experiment is performed.

2. The form of equations which describe the equilibrium.

For example, for the reaction

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

If the reaction is multiplied by 2,

2N2(g) + 6H2(g) 4NH3(g)

the expression for Kc becomes

[NH3 ]4
Kc  =
[N2 ]2[H2 ]6
Kc = (Kc)2

If the reaction is reversed, 2NH3(g) : N2(g) + 3H2(g)

the Kc becomes
[N2 ][H2 ]3
Kc =
[NH3 ]2
Kc = 1/Kc

The equilibrium constant does not depend upon the initial concentrations of the
reactants. Kc and Kp are independent of pressure.
 Le Chatelier’s Principle
When the reaction has attained equilibrium then the temperature, pressure, volume and
concentrations remain constant. These four properties are known as reaction
parameters. Le Chatelier’s principle describe the changes that will take place when
any one of the reaction parameters are changed at equilibrium.
Statement: If any one or more of the reaction parameters is changed at equilibrium
then the reaction will proceed in that direction so as to undo the change in the
parameter and the equilibrium is again attained. Le Chatelier’s principle describes
the effect of the change in parameters on the position of equilibrium. That is, it
predicts whether the changes in reaction parameters will favour the formation of
reactants or products.

Effect of Change in Temperature on the Position of Equilibrium

According to Le Chatelier’s principle, if the temperature of the reaction at equilibriumis
increased then the reaction will proceed in that direction where heat is absorbed so as
to undo the effect of heating. Similarly if the temperature of the reaction at
equilibrium is lowered then the reaction will proceed in that direction where the heat is
produced so that the equilibrium is again attained.

For an exothermic reaction, when the temperature is lowered, the reaction will
proceed in the forward direction, since the heat produced during forward reaction will
undo the effect of lowering of temperature. When the temperature is increased, then
the reaction will proceed in the reverse direction where the heat is absorbed.

For an endothermic reaction, when the temperature is lowered, the reaction will
proceed in the reverse direction where heat is produced so as to undo the effect of
lowering of temperature. When the temperature is increased, the reaction proceeds in
the forward direction. Effect of temperature in terms of amount of reactants and
products formed can be summarized as:

When the equilibrium shifts in the forward direction, then the concentration of
products increases and that of reactants decreases.

So for exothermic reactions when the temperature is lowered, more products are
formed. That is, the decrease in temperature favours exothermic reactions.

For endothermic reactions, when the temperature is increased, more products are
 formed, That is, increase in temperature favours endothermic reactions.

For example, formation of ammonia is an exothermic process.

N2(g) + 3H2(g) 2NH3(g) H = – 92 kJ mol–1

If the temperature is lowered at equilibrium, the reaction will proceed in the forward
direction till the new equilibrium is established. So the concentration of ammonia will
increase. If the temperature is increased at equilibrium, then the reaction will proceed
in reverse direction which is endothermic in nature. So the concentration of ammonia
will decrease.

Dissociation of dinitrogen tetroxide is endothermic in nature.

N2O4(g) 2NO2(g)

Therefore, according to Le Chatelier’s principle, the formation of NO2 is favoured by

increase in the temperature at equilibrium..2

Effect of Change in Pressure on the Position of Equilibrium

According to Le Chatelier’s principle, if the pressure at equilibrium is increased then
the reaction will proceed in that direction where the pressure is reduced. Since the
pressure depends upon the number of moles, on increasing the pressure the reaction
will proceed in that direction where the number of moles are reduced.
If the pressure at equilibrium is decreased then the reaction will proceed in that
direction where the number of moles is more.
For a general reaction,
aA + bB mM + nN
the effect of pressure is decided by n.
n = (m + n) – (a + b)
If n > 0, that means the total moles of products is greater than the total moles of
reactants. Lowering of pressure will favour the reaction in forward direction. That is,
more products will be formed at equilibrium if the pressure is lowered.
If n < 0, that means the total moles of products is less than the total moles of
reactants. Increasing the pressure will favour the reaction in forward direction. That is,
more products will be formed at equilibrium if the pressure is increased.
If n = 0, then the change in pressure has no effect on the position of equilibrium.
For example, in the formation of ammonia,
N2(g) + 3H2(g) 2NH3(g)
n = 2–(1+3) = –2
Therefore, an increase in pressure at equilibrium will favour the forward reaction.
For the dissociation of dinitrogen tetroxide, N2O4(g) 2NO2(g)
n = 2 – 1= 1
The decrease in pressure at equilibrium, favours the forward reaction.

Effect of Change in the Concentration on the Position of Equilibrium

At equilibrium, on increasing the amount of a substance, the reaction proceeds in that

direction where the substance is consumed. When the amount of the reactants is
increased the reaction proceeds in the forward direction and when the amount of
products is increased, the reaction proceeds in the backward direction. The
forward reaction is favoured if the products formed are removed from the vessel.

Effect of Catalyst on the Position of Equilibrium

Catalyst is a substance that alters the rate of a reaction without being consumed
during the reaction. The catalyst does not effect the position of equilibrium. It alters
the time in which the equilibrium is attained. This is due to the fact that the catalyst
changes the rate of the forward reaction and the reverse reaction by the same extent
so the equilibrium is not effected.

Effect of Addition of Inert Gases on the Position of Equilibrium

When a non reactive gas is added to a reaction at equilibrium, the effect depends on
various factors.
Case 1. When the non-reactive gas is added at constant volume there is no change
on the position of equilibrium.
Case 2. When the non-reactive gas is added and the volume of the system changes
then the effect of position is decided by the stoichiometry of the reaction.
For a general reaction,
 aA + bB mM + nN
n = (m + n) – (a + b)

If n < 0, then the addition of inert gas favours the formation of the reactants.
If n > 0, then the addition of inert gas favours the formation of products.
If n = 0, then the addition of inert gas has no effect on the position of equilibrium.

Example
For the reaction at equilibrium:

2NaHCO3(s) Na2CO3(s) + H2O(g) + CO2(g) H°rxn = 128 kJ

state the effects (increase, decrease, no change) of the following stresses on
the number of moles of sodium carbonate, Na2CO3, at equilibrium in a closed
container. Note that Na2CO3 is a solid (this is a heterogeneous equation); its
concentration will remain constant, but its amount can change.

a Removing CO2(g) c Raising the temperature

b Adding H2O(g) d Adding NaHCO3(s).

Solution:

a If the CO2 concentration is lowered, the system will react in such a way as
to offset the change. That is, a shift to the right will replace some of the
missing CO2. The number of moles of Na2CO3 increases.

b Addition of H2O(g) exerts a stress on the equilibrium that is partially offset

by a shift in the equilibrium to the left (net reverse reaction). This consumes
Na2CO3 as well as some of the extra H2O. The number of moles of
Na2CO3 decreases.

c An increase in temperature will increase the Kc value of an endothermic

reaction. There is a shift to the right, and more Na2CO3 is formed.

d The position of a heterogeneous equilibrium does not depend on the

amount of pure solids or liquids present. The same equilibrium is reached
whether the system contains 1 g of NaHCO3(s) or 10 g of NaHCO3. No
 shift in the equilibrium occurs. No change in the amount of Na2CO3 occurs.

Optimum Conditions
The conditions that give maximum yield of the products are known as optimum
conditions. These conditions are decided by the enthalpy of reaction and its
stoichiometry applying Le Chatelier’s principle.

1. For exothermic reactions the yield of products is increased by performing the

reaction at lower temperatures.

2. For endothermic reactions the yield of products is increased by performing the

reaction at higher temperatures.

3. When n > 0, the decrease in pressure favours the formation of products.

4. When n < 0, the increase in pressure favours the formation of products.
5. Removing the products from the reaction vessel shifts the equilibrium reaction in
the forward direction.

Chemical Equilibrium and Industry

Industrial processes are designed to give maximum possible yield of the products. The
conditions for carrying out the reactions are based on Le Chatelier’s principle. The
following processes illustrate the application of Le Chatelier’s principle in the industry.

Haber Process for the Manufacture of Ammonia and Contact Process for the
Manufacture of Sulphuric acid are some application of Chemical Equilibrium
and Industry.

Exercise 6 . 7
Answers the following questions:
1. Which compound is manufactured by Haber process?
2. What are the raw materials used in Haber process?
3. What is the role of iron in Haber process?
4. How are the reactions made to run faster in the Haber process?
5. Draw a flow chart to show what happens in the three stages of Haber process.
6. What is a mixture of H2SO4 and free SO3?
7. What are the raw materials for making SO2 in the contact process?
8. Why is SO3 not directly added to make sulphuric acid?
REVIEW EXERCISE

Part I: Multiple Choice Questions

1. Which of the following is correct about a reaction at equilibrium?

a The concentrations of reactants and products are equal.

b The system is static in nature.

c The forward and backward rates are equal.

d None.

2. For a reaction to shift towards the product direction, which of the following
condition holds true?

a Qc = Kc = 0 c Qc > Kc

b Qc < Kc d Qc = Kc

3. Given the equation 2C(s) + O2(g) : 2CO(g), the expression for Kc is:

a 2[CO] / 2[C][O2] c [CO]2 / [O2]

b [CO]2 / [C]2[O2] d 2[CO] / [O2]

4. In which of the following cases does the reaction go farthest towards
completion:
a K = 103 c K = 10
b K = 10–2 d K=1
5. For the reaction C(s) + CO2(g) 2CO(g), the partial pressures of
CO2 and CO are 2.0 atm and 4.0 atm, respectively, at equilibrium. What is
the value ofKp for this reaction?
a 0.5 atm c 8.0 atm
b 4.0 atm d 32.0 atm
6. The equilibrium partial pressures of SO2, O2 and SO3 are 0.1 atm, 0.25 atm
and 0.5 atm respectively. The equilibrium constant for the reaction SO3(g) :
SO2(g) + ½O2(g) is:
 a 0.1 c 0.05
b 10 d 20
7. Which of the following is likely to happen when pressure is applied to the
following system at equilibrium:
H2O(s) H2O(l)
a More water will be formed
b More ice will be formed
c Water will evaporate
d No change occurs
8. The equilibrium constant for the reaction N2(g) + 3H2(g) 2NH3(g)
is K1 and for the reaction 2NH3(g) N2(g) + 3H2(g) is K2. The
relation betweenK1 and K2 is:
a K1 = K2 c K1 = – K2
b K1 = 1/ K2 d K1 = (K2)0.5
9. What will happen when CaO is added to the following reaction at equilibrium?
CaCO3(s) CaO(s) + CO2(g)
a No change occurs.
b Reaction shifts in the forward direction.
c More CaCO3 is formed.
d Total pressure increases.
10. Under what conditions are Kp and Kc equal?
a n = 1 c n = –1
b n = 0 d They are never equal

Part II: Answer the following questions

11. For the reaction at equilibrium,
2SO2(g) + O2(g) 2SO3(g); H = – 196 kJ mol–1
Predict the direction of the change on:
 a Removal of SO2.
b Addition of noble gas (argon) at constant pressure.
c Decreasing volume of the system.
d Increasing temperature of the system.
e Addition of a catalyst.
12. Balance the following equations and write the equilibrium constant expressions,
in terms of Kc and Kp.
a NH3(g) + O2(g) N2(g) + H2O(g)
b N2(g) + H2(g) NH3(g)
c CaCO3(s) CaO(s) + CO2(g)
13. For the reaction at 200°C
2A(g) + B(g) 3C(g)
the equilibrium constant is 3.0. Given the following information,

Species Concentration

[A] 2.0 M

[B] 3.0 M

[C] 2.0 M

Predict the direction in which the reaction should proceed to reach equilibrium.
14. Given the reaction
2CO2(g) 2CO(g) + O2(g)
what is the concentration of CO in equilibrium at 25°C in a sample of gas
originally containing 1.00 mol L–1 of CO2? For the dissociation of CO2 at
25°C, Kc = 2.96 × 10–92.
Ionic Equilibria
Ionic equilibrium of acid and base

Ionization of Water
How do you calculate the concentration of H3O+ ions if the concentrations of
OH– ions and Kw, at 25°C are given?
Recall that water is amphiprotic. So, to a slight extent, water molecules can transfer protons
among themselves. In the self-ionization of water, the proton lost by one water molecule is
gained by the other.

The self-ionization of water can be represented by the following equation:

Since this reaction is reversible, we can apply the law of mass action to write the equilibrium
constant expression.
[H O+ ] [OH– ]
Kc = 3
[H 2O]2

where, Kc is the equilibrium constant, in terms of concentration.

Because only very small fractions of water molecules are ionized, the concentration of
water, [H2O], remains unchanged. This equilibrium expression can be simplified by including
the constant [H2O]2 term with the value of Kc to obtain a new equilibrium constant, the
ion-product for water, Kw.
Kc [H2O]2 = KW = [H3O+] [OH–]
 Note that Kw is the product of the molar concentrations of H3O+ and OH– ions at a
particular temperature.

Since we use H+(aq) and H3O+(aq) interchangeably to represent the hydrated proton, the
equilibrium constant can also be expressed as
Kw = [H+][OH–]
In pure water at 25°C, the concentrations of H+ and OH– ions are equal and found to be
[H+] = 1.0 × 10–7 M and [OH–] = 1.0 × 10–7 M at 25°C
Kw = [H+][OH–] = (1.0 × 10–7) (1.0 ×10–7) = 1.0 × 10–14
As you have learned in your studies of chemical equilibrium in Grade 11, the value of Kc,
in this case Kw, changes as temperature changes. In any aqueous solution at 25°C, no
matter what it contains, the product of [H+] and [OH–] must always equal 1.0 × 10–14.
There are three possible situations.
a A neutral solution, where [H+] = [OH–].
b An acidic solution, where [H+] > [OH–].
c A basic solution, where [OH–] > [H+]

Exercise 6.8

1. Calculate [H+] or [OH–], as required, for each of the following solutions at 25°C,and
state whether the solution is neutral, acidic, or basic.
a [OH–] = 1.0 ×10–4 M c [H+] = 1.0 × 10–7 Mb
[OH–] = 1.0 × 10–8 M
2. Calculate the concentration of OH– in a solution in whicha
[H3O+] = 2.0 × 10–5 M
b [H3O+] = [OH–]
c [H3O+] = 102 × [OH–]
3. Calculate [H3O+] in a solution that is at 25°C and has [OH–] = 6.7 × 10–2 M. Isthe
solution neutral, acidic, or basic?
4. At 40°C, the value of Kw is 2.92 × 10–14. Calculate the [H+] and [OH–] of pure
water at 40°C. Why water is a weak electrolyte

The pH scale

The concentration of H+ in aqueous solution is usually very small and inconvenient

to express and to draw as graphs. Sören Sörensen, in 1909, developed the pH scale to
solve this problem. The pH of a solution is defined as the negative logarithm of the
 hydrogen ion concentration (in mol/L):

pH = –log [H3O+] or pH = –log [H+]

Note that the negative logarithm gives us positive numbers for pH. What is the pH
value of a neutral, basic and acidic solution?

A pH-meter is used to measure the pH of a solution. pH decreases as the

concentration of H+ ions increases; in other words, the more acidic the solution, the
lower its pH; the more basic the solution, the higher its pH. The pH notation has been
extended to other exponential quantities. For example, hydroxide concentrations can
be expressed in terms of pOH, where pOH =–log [OH–]. Similarly, pKw can be
expressed as –log Kw .

Exercise 6. 8
1. A solution formed by dissolving an antacid tablet has a pH of 9.18 at 25°C. Calculate
[H+], [OH–] and pOH.
2. A solution is prepared by diluting concentrated HNO3 to 2.0 M, 0.30 M and
0.0063 M HNO3 at 25°C. Calculate [H3O+], [OH–], pH and pOH of the three
solutions.

Measures of the Strengths of Acids and Bases in Aqueous

Solution

The strength of acids and bases can be described in many ways. Some of the ways are
the concentration of hydrogen and hydroxide ions, pH and pOH, percent dissociation,
Ka and Kb.
Concentration of hydrogen and hydroxide ions

Acid strength refers to the ability of an acid to release protons. A strong acid gives up
protons more easily than a weak acid. For two acids of equal concentrations, the strongest
acid produces the greater quantity of hydrogen ions. Base strength refers to the ability of a
base to accept protons. A strong base accepts more protons readily than a weak base. A
solution of a stronger base will contain a larger concentration of hydroxide ions than a
solution of a weaker base if both solutions are of equal concentration.
The pH scale

The concentration of H+ in aqueous solution is usually very small and inconvenient

to express and to draw as graphs. Sören Sörensen, in 1909, developed the pH scale to
solve this problem. The pH of a solution is defined as the negative logarithm of the
hydrogen ion concentration (in mol/L):

pH = –log [H3O+] or pH = –log [H+]

Note that the negative logarithm gives us positive numbers for pH. What is the pH
value of a neutral, basic and acidic solution?

A pH-meter is used to measure the pH of a solution. pH decreases as the

concentration of H+ ions increases; in other words, the more acidic the solution, the
lower its pH; the more basic the solution, the higher its pH. The pH notation has been
extended to other exponential quantities. For example, hydroxide concentrations can
be expressed in terms of pOH, where pOH =–log [OH–]. Similarly, pKw can be
expressed as –log Kw .

Exercise 6. 8
3. A solution formed by dissolving an antacid tablet has a pH of 9.18 at 25°C. Calculate
[H+], [OH–] and pOH.
4. A solution is prepared by diluting concentrated HNO3 to 2.0 M, 0.30 M and
0.0063 M HNO3 at 25°C. Calculate [H3O+], [OH–], pH and pOH of the three
solutions.

Measures of the Strengths of Acids and Bases in Aqueous

Solution

The strength of acids and bases can be described in many ways. Some of the ways are
the concentration of hydrogen and hydroxide ions, pH and pOH, percent dissociation,
Ka and Kb.
Concentration of hydrogen and hydroxide ions
Acid strength refers to the ability of an acid to release protons. A strong acid gives up
protons more easily than a weak acid. For two acids of equal concentrations, the strongest
acid produces the greater quantity of hydrogen ions. Base strength refers to the ability of a
base to accept protons. A strong base accepts more protons readily than a weak base. A
solution of a stronger base will contain a larger concentration of hydroxide ions than a
solution of a weaker base if both solutions are of equal concentration.
 pH and pOH
If the pOH of a solution at 25°C is 12, is it acidic, neutral or basic?
It is possible to predict the strength of acids from their pH values. The smaller the pH
value, the stronger the acid. The concentration of hydroxide ions in a solution can be
expressed in terms of the pOH of the solution. Hence, the strength of bases can also be
determined from their pOH values. The smaller the pOH value, the stronger the base.

Percent Ionization
How do you determine the percent ionization of an acid or a base?
The extent to which an acid or base ionizes is called percent ionization. Mathematically,

Ionized acid or base concentration at equilibrium

Percent ionization = × 100
Initial concentration of ionized acid or base

The strength of an acid depends on the percentage of the acid molecules that dissociate in
water solution. If a higher percentage of the original acid molecules dissociate, then the
acid is a strong acid. Strong acids and strong bases ionize nearly completely in water.
However, weak acids and weak bases dissociate partially in water, and their percent of
ionization is small.

Dissociation (Ionization) Constants

Acid Dissociation Constant, Ka
What is the relationship between strength of acids with their acid-dissociation
constant values?
The acid-dissociation constant is a quantitative measure of the strength of the acid in a
given solvent. For the dissociation of the acid, HA;
HA(aq) + H2O(l) : H3O+(aq) + A–(aq)
the dissociation-constant expression can be written as:
H O+  A– 
K =    
3


 H 2 O  HA 
Since the concentration of water is nearly constant, we can write;

The product of the two constants, K and [H2O], is itself a constant. It is designated as Ka,
which is the acid-dissociation constant or the acid-ionization constant. Hence for a weak
acid, HA:
 H O+   A – 
  
Ka = 
3

HA
The Ka value for a strong acid is very large, because [HA] in the
denominator is very small since the acid dissociates essentially
completely. Similarly, the Ka value for a weak acid is relatively small, since
[H3O+] and [A–] are very small, and [HA] in the denominator is large. The
ionization-constants of some weak monoprotic acids are tabulated in Table
2.2.

Name of the Acid Formula Ka

Acetic acid CH3COOH 1.8 × 10–5
Ascorbic acid C6H8O6 8.0 × 10–5
Benzoic Acid C6H5COOH 6.5 × 10–5
Formic acid HCOOH 1.7 × 10–4
Hydrocyanic acid HCN 4.9 × 10–10
Hydrofluoric acid HF 6.8 × 10–4
Hypobromous acid HOBr 2.5 × 10–9
Hypochlorous acid HOCl 3.0 × 10–8
Nitrous acid HNO2 4.5 × 10–4
How do you calculate the pH of weak acids?
Generally, we can calculate the hydrogen-ion concentration or pH of an acid solution at
equilibrium, given the initial concentration of the acid and its Ka value. Alternatively, if we
know the pH of a weak acid solution and its initial concentration, we can determine its Ka.
The following may help you to solve weak-acid dissociation problems.
1. identify the major species that can affect the pH of the solution. In most cases we
can ignore the dissociation of water. Why?
2. write balanced equations for the reactions producing H3O+.
3. list the initial concentration of the species participating in the equilibrium.
4. define the change needed to achieve equilibrium. That is, define x.
5. write the equilibrium concentration, in terms of x.
6. write the acid dissociation constant, Ka, in terms of equilibrium concentration.


7. first solve for x by the approximation method. If the approximation is not valid, use
the quadratic equation.
8. having solved for x, calculate the equilibrium concentrations of all species and/or the
pH of the solution.
 Exercise 6 . 9
For a 0.036 M HNO2 solution.
a Write a chemical equation that shows the ionization of nitrous acid in water.
b Calculate the equilibrium concentration of hydrogen ions and nitrous acid at 25°C,
using the approximation method. Then check whether the approximation is valid or
not.
c If the approximation is invalid, use the quadratic formula to calculate the
concentration of hydrogen ions.
d Calculate the pH of the solution.

Base dissociation constant, Kb

In the same way as for acids, the dissociation of a base in water can be written as
B(aq) + H2O(l) BH+(aq) + OH–(aq)

which gives the equilibrium expression of the form:

where Kb is the base dissociation constant. Kb values for strong bases are large, while Kb values
for weak bases are small. Table 2.3 shows the Kb values of some common weak bases at 25°C.

Base Formula Kb
Ammonia NH3 1.8 × 10–5
Aniline C6H5NH2 4.0 × 10–10
Ethylamine C2H5NH2 4.7 × 10–4
Hydrazine N2H4 1.7 × 10–6
Hydroxylamine NH2OH 1.1 × 10–6
Methylamine CH3NH2 4.4 × 10–4
Pyridine C5H5N 1.7 × 10–9
 Exercise 6. 10
For a 0.040 M ammonia solution:
a Write a chemical equation that shows the ionization of ammonia in water.
b Calculate the equilibrium concentration of ammonia, ammonium ions and hydroxide
ions, using the approximation method. Check whether the approximation is valid
or not.
c If the approximation is invalid, use the quadratic formula to calculate the
concentration of ammonia, ammonium ions and hydroxide ions.
d Calculate the pOH and pH of the solution.

COMMON ION EFFECT AND BUFFER SOLUTION

The Common ion Effect

Th The Common ion Effect

The common-ion effect is caused by the addition of a compound having an ion in common
with the dissolved substance that shift the equilibrium.
The presence of the common ion suppresses the ionization of a weak acid or a weak base.
For example, if sodium acetate and acetic acid are dissolved in the same solution, they
both dissociate and ionize to produce CH3COO– ions.

Sodium acetate, CH3COONa, is a strong electrolyte, so it dissociates completely in

solution, but acetic acid, CH3COOH, is a weak acid and ionizes partially. According
to Le Chatelier’s principle, the addition of CH3COO– ions from CH3COONa to a
solution of CH3COOH will suppress the ionization of CH3COOH and decrease the
concentration of hydrogen ions.
Therefore, a solution containing both CH3COOH and CH3COONa will be less
acidic than a solution containing only CH3COOH of the same concentration. The
shift in equilibrium of the acetic acid ionization is caused by the acetate ions from
the sodium acetate. CH3COO– is the common ion because it is supplied by both
CH3COOH and CH3COONa.
Buffer Solutions
How does a buffer solution resist a pH change?
A buffer solution is a solution that resists changes in pH from the addition of a limited
amount of an acid or a base. Table 2.4 shows how the pH of unbuffered and buffered
solutions change when a small amount of acid or base is added.
Table 2.4 Comparison of buffered and unbuffered solutions.

Initial pH of pH after addition of pH after addition of

1.0 L sample 0.010 mol NaOH 0.010 mol HCl
Unbuffered solution: 4.8 12.0 2.0
1.28 × 10–5 M HCl
Buffered solution: 4.8 4.8 4.7
0.099 M CH3COOH
0.097 M CH3COONa

Buffers contain either a weak acid and its conjugate base or a weak base and its
conjugate acid.

A buffer solution must contain a relatively large concentration of acid to react with any
OH– ions that are added to it. Similarly, it must contain a relatively large concentration of
base to react with any H+ ions. To understand the action of buffer, consider a buffer that
contains approximately equal molar amounts of a weak acid, HA, and its conjugate base,
A–. When a strong acid is added to the buffer, it supplies hydrogen ions that react with the
base A–.

On the other hand, when a strong base is added to the buffer, it supplies hydroxide ions
that react with the acid, HA.

Thus, a buffer solution resists changes in pH through its ability to combine with the H+ and
OH– ions.

Buffers are very important to chemical and biological systems. The pH in the human body
varies greatly from one fluid to another. For example; the pH of blood is about 7.4, whereas
the gastric juice in our stomach has a pH of about 1.5. The pH values, which are crucial for
proper enzyme function and the balance of osmotic pressure, are maintained by buffers in
most cases.
 Exercise 6. 11
Calculate the pH:
a of a buffer solution containing 0.1 M acetic acid and a 0.1 M solution of sodium
acetate.
b when 1.0 mL of 0.10 M HCl is added to 100 mL of the buffer in (a);
c when 1.0 mL of 0.10 M NaOH is added to 100 mL of the buffer in (a);
d of an unbuffered solution containing 1.8 × 10–5 HCl;
e change of the an unbuffered solution in (d) after adding
i) 1.0 mL of 0.1 M NaOH to 100 mL of the solution,
ii) 1.0 mL of 0.10 M HCl to 100 mL of the solution.

HYDROLYSIS OF SALTS
What does salt hydrolysis mean?
The word “hydrolysis’ is derived from the Greek words hydro, meaning “water”, and lyses,
meaning “to split apart”. Solutions of salts contain two types of ions, namely cations and anions.
The term salt hydrolysis describes the reaction of an anion or a cation of a salt, or both, with water.
Depending on the strengths of the parent acids and bases, the cation of a salt can serve as an acid,
base or neutral.

Hydrolysis of Salts of Strong Acids and Strong Bases

The anions derived from strong acids are weak conjugate bases and do not undergo hydrolysis. The
strong bases are the ionic hydroxides of Group IA and IIA metals. The cations of these metals also
do not hydrolyze. For example, sodium chloride, NaCl, is a salt of a strong acid, HCl, and a strong
base, NaOH. Since chloride ions, Cl–, and sodium ions, Na+, do not hydrolyze, the solution of the
salt will be neutral. Can you give more examples?
Hydrolysis of Salts of Weak Acids and Strong Bases
Solutions of these salts are basic because the anion of the weak acid is a moderately strong base and
can be hydrolyzed as follows.

Hydrolysis of Salts of Strong Acids and Weak Bases

A cation (the conjugate acid of a weak base) hydrolyzes as an acid. As in the first case,
anions of a strong acid are weak conjugate bases and do not hydrolyze.
Consider the hydrolysis of NH4Cl. Ammonium ion, NH +, is acidic and reacts with water
to produce ammonia and hydronium ions.
Hydrolysis of Salts of Weak Acids and Weak Bases

The solution of these salts contain both a strong acid (the cation of the weak base) and a
strong base (the anion of the weak acid). Whether the solution of such a salt is acidic, basic
or neutral depends on the relative strengths of the acidic cation and the basic anion. If the
acid is stronger than the base, the solution is acidic and if the base is stronger than the acid,
the solution is basic. If they are of equal strengths, the solution is neutral.

Summery
• The strength of acids and bases in aqueous solution depends on several factors
such as the percent of dissociation, the dissociation constant, the
concentration of hydrogen ions and hydroxide ions, pH and pOH.
• The extent to which a weak acid ionizes can be expressed by using the
equilibrium constant for the ionization reaction.
• Generally, we can calculate the hydrogen-ion concentration or pH of an acid
solution at equilibrium, given the initial concentration of the acid and its Ka
value.
• The common-ion effect tends to suppress the ionization of a weak acid or a
weak base. This action can be explained by Le Chatelier’s principle.
• A buffer solution is a combination of either a weak acid and its conjugate
base or a weak base and its conjugate acid. The solution reacts in such a way
that the pH of the solution remains nearly constant. Buffer systems play a vital
role in maintaining the pH of body fluids.

REVIEW EXERCISE
Part I: Multiple-Choice Questions
1. A Brønsted-Lowry base is defined as a substance that:
a acts as a proton donor
b increases [H+] when placed in water
c decreases [H+] when placed in water
d acts as a proton acceptor
2. Given the reaction
HC O– (aq) + H O (l) H O+ (aq) + C O2– (aq)
2 4 2 3 2 4
 which of the following is a conjugate acid-base pair?
a HC O– and H O c H O and C O 2–
2 4 2 2 2 4
b HC O – and H O+ d HC O – and C O 2–
2 4 3 2 4 2 4
3. In the reaction
 a Salt c Lewis acid
b Lewis base d Brønsted base
4. Which of the following is the conjugate base of HCO– ?
a OH– c CO 2–
b H2CO3 d HCO+
5. What is the pH of an aqueous solution at 25°C in which [OH–] is 0.00250 M?
a 2.60 c 11.4
b 3.60 d 12.4
6. A substance that is capable of acting as both an acid and a base is:
a amphiprotic c diprotic
b conjugated d binary acid-base
7. The magnitude of Kw indicates that:
a water autoionizes very slowly
b water autoionizes very quickly
c water autoionizes only to a very small extent
d water autoionizes completely

8. When sodium acetate is added to an aqueous solution of acetic acid its pH:
a increases c remains constant
b decreases d may increase or decrease
9. pKa values of three acids A, B and C, are 4.5, 3.5 and 6.5, respectively. Which of
the following represents the correct order of acid strength?
a A>B>C c C >A> B
b B >A> C d C>B>A
10. An acid buffer can be prepared by mixing solutions of:
a sodium chloride and hydrochloric acid
b sodium borate and boric acid
c sodium sulfate and sulfuric acid
d sodium hydroxide and hydrochloric acid
11. Which of the following is not true about strong acid-strong base titration?
a the pH is low at the beginning of the titration
b at the equivalence point, the pH is 7.00
 c any indicator whose color changes in the pH range from about 4 to 10 can be used
d none of the above
12. Which of the following salts will yield a basic solution on dissolution in water?
a a salt of weak acid and weak base
b a salt of strong acid and strong base
c a salt of weak acid and strong base
d a salt of strong acid and weak base
13. A more generalized acid-base concept is that of:
a Brønsted and Lowry c Lewis
b Arrhenius d none of these
14. Which of the following anions is the weakest base?
a NO – c CH COO–
2 3
b NO – d PO 3–
3 4
15. Which of the following buffer solutions has a pH greater than 7?
a CH3COOH/CH3COONa
b HCOOH/HCOOK
 c CH3COOH/CH3COONH4
d NH4OH/NH4Cl

Part II: Short Answer Questions

16. Define acid and base according to:
a Arrhenius concept
b Brønsted-Lowry concept
c Lewis concept
17. Given the following species, identify the acids and bases according to the Brønsted-
Lowry concept.
a HNO3 b OCl– c NH–
d NH+ e CH NH+
4 3 3
18. Write the conjugate acids of the following bases.
a OH– b Cl– c OCl– d CN–
e HCO– f HPO2– g HS–
19. What are the conjugate bases of the following acids?
a H2S b HCOOH c HSO– d HSO–
e HS– f HNO2 g HCN
20. Write the equation for the reaction of sulphuric acid and water, and identify the
acid, the base, the conjugate acid and the conjugate base.
21. Identify the conjugate acid-base pairs in the following reactions using notation such
as acid (1) and base (1)

a H2S(aq) + HS–(aq) + NH+(aq)

b CN–(aq) + HCN(aq) + OH–(aq)
c H2C2O4(aq) + HC2O–4 (aq) + H3O+(aq)
d HCO 3–(aq) + CO3–
2 (aq) + H2O(l)
22. a What is meant by amphiprotic substance?
b Write an equation for the autoionization of water that demonstrates that water is
amphiprotic.
23. Which of the following are amphiprotic?
a OH– b NH3 c H2O d H2S
e NO – f HCO – g CH COO– h HNO
3 3 3 3
24. Rank the base in each of the following groups in order of increasing base strength,
and explain the reason for the order you assign.
a H2O, OH–, H–, Cl–
b ClO– , ClO–, ClO–, ClO–
4 2 3
c NH–, HS–, HTe–, PH–
2 2
d BrO– , ClO– , lO–
2 2 2
25. Which of the following acids are classified as Lewis acids but not as BrØnsted-
Lowry acids?
a HBrO3 b SbCl3
c HSO –
d AlF3
26. Calculate [OH–] for each of the following solutions:
a [H+] = 0.005 M
b [H+] = 1.3 × 10–9 M
c A solution in which [OH–] is 100 times greater than [H+].
27. Calculate the pH of each of the following:
a [H+] = 3.6 × 10–3 M b [H+] = 0.047 M
c pOH = 5.33 d [OH–] = 6.7 × 10–2 M
28. What is the pOH of each of the following solutions?
a 1.0 × 10–2 M NaOH b 0.00520 M Ba(OH)2
c 0.0068 M LiOH d 3.51 × 10–4 M HCl
29. Hydrogen cyanide, HCN, is a weak acid with a dissociation constant of 4.8 × 10–10.
Calculate the percent dissociation, the pH, and the OH– concentration of a 0.15 M
solution of HCN in water.
30. Calculate the [OH–] in a 1.0 × 10–3 M solution of the weak base methylamine
(CH3NH2), whose Kb = 4.4 × 10–4. What percentage of the base has dissociated?
31. A 0.01 M butanoic acid solution is 3.9% dissociated at 298 K. Calculate the Ka
value for butanoic acid.
32. a What is meant by the common-ion effect?
b Give an example of a salt that can decrease the ionization of HCl in solution.
c Explain why the ionization of a weak acid is suppressed by the presence of its
conjugate base.
33. Describe the effect on pH (increase, decrease or no change) that results from each
of the following additions.
a Sodium formate, NaCOOH, to a solution of formic acid, HCOOH.
b Ammonium perchlorate, NH4ClO4, to a solution of ammonia, NH3.
c Potassium bromide, KBr, to a solution of potassium nitrite, KNO2.
d Hydrochloric acid, HCl, to a solution of sodium acetate, NaCOOCH3.
34. Explain why a mixture of HCl and KCl does not function as a buffer, whereas a
mixture of HC2H3O2 and NaC2H3O2 does.
35. Calculate the pH of the buffer system made up of 0.15 M NH3/0.35 M NH4Cl.
36. The pH of a sodium acetate/acetic acid buffer is 4.5. Calculate the ratio of
[CH3COOH]/[CH3COO–].
37. A buffer is prepared by adding 20.0 g of acetic acid, CH3COOH, and 20.0 g of
sodium acetate; CH3COONa, to enough water to form 2.00 L of solution.
a Determine the pH of the buffer.
b Write the complete ionic equation for the reaction that occurs when a few drops
of hydrochloric acid are added to the buffer.
c Write the complete ionic equation for the reaction that occurs when a few drops
of potassium hydroxide solution are added to the buffer.
38. A buffer is prepared by adding 1.00 g of acetic acid, CH3COOH, and 1.50 g of
sodium acetate, CH3COONa, to enough water to form a 0.10 L solution.
a What is the pH of this buffer?
b What is the pH after the addition of 1.00 mL of a 1.00 M HCl solution?
c What is the pH after the addition of 1.00 mL of 1.00 M KOH solution?