CHAPTER SEVEN

EQUILIBRIUM
CONCEPTS
AND
ACID-BASE
By: Medhanie G.
1
Objectives of the Chapter:

Explain the dynamic nature of a chemical equilibrium

Predict the response of a stressed equilibrium using Le
Châtelier’s principle
Identify acids, bases based on the three acid-base
concepts
Calculate the pH and pOH of a given solution
Describe the composition and function of acid-base
buffer
Calculate the pH of the buffer before and after the
addition of added acid or base
2
 7.1. Introduction
The convention for writing chemical equations involves
placing reactant formulas on the left side of a reaction
arrow and product formulas on the right side.

By this convention, and the definitions of “reactant” and

“product,” a chemical equation represents the reaction in
question as proceeding from left to right.

Reversible reactions, however, may proceed in both

forward (left to right) and reverse (right to left) directions.

3
When the rates of the forward and reverse reactions are
equal, the concentrations of the reactant and product
species remain constant over time and the system is at
equilibrium.

The relative concentrations of reactants and products in

equilibrium systems vary greatly; some systems contain
mostly products at equilibrium, some contain mostly
reactants, and some contain appreciable amounts of both.

4
Figure 7.1: Illustrates fundamental equilibrium concepts
using the reversible decomposition of colorless dinitrogen
tetroxide to yield brown nitrogen dioxide, an elementary
reaction described by the equation:
N2O4 (g) => 2NO2(g)
(b) Changes in
concentration over
time as the
decomposition
reaction achieves
equilibrium.

(c) At equilibrium,
the forward and 5
It’s important to emphasize that chemical equilibria are
dynamic; a reaction at equilibrium has not “stopped,”
but is proceeding in the forward and reverse directions
at the same rate.

Physical changes, such as phase transitions, are also

reversible and may establish equilibria. As one example,
consider the vaporization of bromine:

Br2(l) ⇌ Br2(g)

6
 7.2. Chemical Equilibrium
The status of a reversible reaction is conveniently
assessed by evaluating its reaction quotient (Q). For a
reversible reaction described by:
mA + nB ⇌ xC + yD
The reaction quotient is derived directly from the
stoichiometry of the balanced equation as:
[C ] x [ D ] y
Qc 
[ A]m [ B ]n
• Where: The subscript c denotes the use of molar
concentrations in the expression. 7
 If the reactants and products are x
PC PD y
gaseous, a reaction quotient may Qp  m n
be similarly derived using partial PA PB
pressures:
Example 7.1: Write the concentration-based reaction
quotient expression for each of the following reactions:
[O3 ]2
A.3O2(g) ⇌ 2O3(g) Qc 
[O2 ]3
[ NH 3 ]2
B. N2(g) +3H2(g) ⇌ 2NH3(g) Qc 
[ N 2 ][ H 2 ]3

[ NO2 ]4 [ H 2O]6
Qc 
C. 4NH3(g) +7O2(g) ⇌ 4NO2(g) + 6H2O(g) [ NH 3 ]4 [O2 ]7
8
The numerical value of Q varies as a reaction proceeds
towards equilibrium; therefore, it can serve as a useful
indicator of the reaction’s status.

The constant value of Q exhibited by a system at

equilibrium is called the equilibrium constant, K:
K = Q at equilibrium

[C ] x [ D ] y
K c  Qc 
[ A]m [ B ]n

9
Example 7.2: Evaluating a Reaction Quotient

 Gaseous nitrogen dioxide forms dinitrogen tetroxide

according to this equation:
2NO2(g) => N2O4 (g)

 When 0.10 mol NO2 is added to a 1.0-L flask at 25°C, the

concentration changes so that at equilibrium, [NO 2] =
0.016 M and [N2O4] = 0.042 M.

a. What is the value of the reaction quotient before any

reaction occurs?
b. What is the value of the equilibrium constant for 10the
Solution
a. Before any reaction started or before any product
is formed the concentrations of:
0.1 mol
[ NO2 ]   0 .1 M [ N 2O4 ]  0
1 .0 L
[ N 2O4 ] 0
Thus, K c  Qc  2
 2
0
[ NO2 ] (0.1 M )

b. At equilibrium: The Equilibrium Constant is

1.6x102
[ N 2O4 ] (0.042 M )
K c  Qc    1.6 x10 2

[ NO2 ]2 (0.016 M ) 2

11
7.2.1. Homogeneous Equilibria

A homogeneous equilibrium is one in which all reactants

and products are present in the same phase.

By this definition, homogeneous equilibria take place

in solutions.
These solutions are most commonly either liquid or
gaseous phases, as shown by the examples below:
[C2 H 2 Br2 ]
A. C2H2(aq) +2Br2(aq) ⇌ C2H2Br2(aq) Kc 
[C2 H 2 ][ Br2 ]2

B. HF(aq) +H2O(l) ⇌ H3O+(aq) + F-(aq) [ H 3O  ][ F  ]

Kc 
[ HF ]
12
These examples all involve aqueous solutions, those in
which water functions as the solvent.

In the examples, water also functions as a reactant, but its

concentration is not included in the reaction quotient.

The reason for this omission is related to the more

rigorous form of the Q (or K) expression in which
relative concentrations for liquids and solids are equal to
1 and needn’t be included.

Consequently, reaction quotients include concentration or

pressure terms only for gaseous and solute species.
13
 The equilibria below all involve gas-phase
solutions: [C2 H 4 ][ H 2 ]
A. C2H6(g) ⇌ C2H4(g) + H2(g) Kc 
[C2 H 6 ]
[ NH 3 ]2
B. N2(g) + 3H2(g) ⇌ 2NH3(g) Kc 
[ N 2 ][ H 2 ]3
For gas-phase solutions, the equilibrium constant may be
expressed in terms of either the molar concentrations (Kc)
or partial pressures (Kp) of the reactants and products.
A relation between these two K values may be simply
derived from the ideal gas equation and the definition of
molarity:
n
PV  nRT P    RT  MRT
V  14
For the gas-phase reaction:

mA + nB ⇌ xC + yD

( PC ) x ( PD ) y
Kp 
( PA ) m ( PB ) n
([C ] xRT ) x ([ D ] xRT ) y
Kp 
([ A] xRT ) m ([ B ] xRT ) n
x y x y
[C ] [ D ] ( RT ) ( x  y ) ( m  n )
Kp  m n
x m n
 K C ( RT )
[ A] [ B ] ( RT )
n
K p  K C ( RT )
15
Example 7.3: Write the equations relating Kc to Kp for
each of the following reactions:
n  2  1  1
A. C2H6(g) ⇌ C2H4(g) + H2(g)
K p  K C ( RT ) n  K C ( RT )
n  2  2  0
B. CO(g) + H2O(g) ⇌ CO2(g) + H2(g)
K p  K C ( RT ) n  K C ( RT ) 0  K C
n  2  (1  3)  2
C. N2(g) + 3H2(g) ⇌ 2NH3(g) KC
K p  K C ( RT ) n  K C ( RT )  2 
( RT ) 2

D. Kc is equal to 0.28 for the following reaction at 900 °C: What is

KP at this temperature? CS2(g) + 4H2(g) ⇌ CH4(g) + 2H2S(g)
n  (2  1)  (1  4)  2 K P  0.28 x(0.0821x1173) 2
K p  K C ( RT ) n  K C ( RT )  2 K P  3.02 x10 5
16
 7.2.2. Heterogeneous Equilibria

A heterogeneous equilibrium involves reactants and

products in two or more different phases, as illustrated
by the following examples:
2
A. PbCl2(s) ⇌ Pb2+(aq) + 2Cl- (aq) K C  [ Pb ][Cl ]  2

1 1
B. CaO(s) + CO2(g) ⇌ CaCO3(s) KC  
[CO2 ] PCO2
[CS 2 ] PCS 2
C. C(s) + 2S(g) ⇌ CS2(g) KC  2

[S ] ( PS ) 2

D. Br2(l) ⇌ Br2(g) K C  [ Br2 ]

17
7.3. Le Chatelier’s Principle
A system at equilibrium is in a state of dynamic balance,
with forward and reverse reactions taking place at equal
rates.

If an equilibrium system is subjected to a change in

conditions that affects these reaction rates differently (a
stress), then the rates are no longer equal and the system is
not at equilibrium.

The system will subsequently experience a net reaction in

the direction of greater rate (a shift) that will re-establish
the equilibrium.
18
This phenomenon is summarized by LeChâtelier’s
principle: if an equilibrium system is stressed, the system
will experience a shift in response to the stress that re-
establishes equilibrium.

Reaction rates are affected primarily by concentrations,

as described by the reaction’s rate law, and temperature,
as described by the Arrhenius equation.

Consequently, changes in concentration and temperature

are the two stresses that can shift an equilibrium.

19
 7.3.1. Effect of a Change in
Concentration

If an equilibrium system is subjected to a change in the

concentration of a reactant or product species, the rate of
either the forward or the reverse reaction will change.

As an example, consider the equilibrium reaction:

H2(g) + I2(g) ⇌ 2HI (g) KC= 50 @ 4000c

[ HI ]2
QC   KC
[ H 2 ][ I 2 ]
20
When this system is at equilibrium, the forward and reverse
reaction rates are equal.
Ratef=Rater
If the system is stressed by adding reactant, either H2 or I2, the
resulting increase in concentration causes the rate of the
forward reaction to increase, exceeding that of the reverse
reaction:
Ratef>Rater

This same shift will result if some product HI is removed from

the system, which decreases the rate of the reverse reaction,
again resulting in the same imbalance in rates.

21
 7.3.2. Effect of a Change in
Temperature

When an equilibrium shifts in response to a temperature

change, it is re-established with a different relative
composition that exhibits a different value for the
equilibrium constant.

Predicting the shift an equilibrium will experience in

response to a change in temperature is most conveniently
accomplished by considering the enthalpy change of the
reaction.
22
For example, the decomposition of dinitrogen tetroxide is
an endothermic (heat consuming) process:
N2O4 (g) => 2NO2(g) ∆H=+57.20 KJ

For purposes of applying Le Chatelier’s principle, heat

(q) may be viewed as a reactant:
Heat + N2O4 (g) => 2NO2(g)

Raising the temperature of the system is causing to

increasing the amount of a product, and so the
equilibrium will shift to the right.
Lowering the system temperature will likewise
cause the equilibrium to shift left.
23
 [Link] of Change in
Pressure
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.
24
For a general reaction, mA + nB ⇌ xC + yD
The effect of pressure is decided by ∆n. ∆n = (x+y)-(m+n)

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.
25
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.

26
 7.4. Equilibrium Calculations
A. Calculation of an Equilibrium Constant
Example 7.4: Iodine molecules react reversibly with iodine
ions to produce triiodide ions. [ I 3 ]
I2(aq) + I-(g) ⇌ I-3(aq) KC 
[ I ][ I  ]
2

If a solution with the concentrations of I2 and I- both equal to 1x10-3M

before reaction gives an equilibrium concentration of 6.61x10-4M,
what is the equilibrium constant for the reaction?
Solution:
I2(aq) + I-(g) ⇌ I-3(aq)
Initial (M) 1x10-3M 1x10-3M 0
Change (M) –x –x +x
Equilibrium (M) 1x10-3M – x 1x10-3M – x +x 27
 At equilibrium the concentration of I 2 is 6.61x10-4
M so that 1x10 3  x  6.61x10 4 M
x  3.39 x10 4 M

I2(aq) + I-(g) ⇌
I-3(aq)
Initial (M) 1x10-3M 1x10-3M 0
Change (M) –3.39x10-4M –3.39x10-4M 3.39x10-4M
Equilibrium (M) 6.61x10-4M 6.61x10-4M 3.39x10-4M
[ I 3 ] 3.39 x10 4 M
KC  KC 
[ I 2 ][ I  ] 6.61x10  4 M x 6.61x10  4 M

K C  776
28
B. Calculation of a Missing Equilibrium
Concentration

Example: At 2000 0c, the value of the Kc for the reaction,

N2(g) + O2(g) ⇌ 2NO(g), is 4.1x10-4. Calculate the
equilibrium concentration of NO(g) in air at 1 atm pressure.
The equilibrium concentrations of N2 and O2 at this
pressure and temperature
[ NO]2
are 0.036 M and 0.0089 M
respectively. K C  [ NO ] 2
 K C [ N 2 ][O2 ]
[ N 2 ][O2 ]
Solution:
[ NO ]  ( 4.1x10 4 )(0.036)(0.0089)

4
[ NO ]  3.6 x10 M
29
 C. Calculation of Equilibrium Concentrations
from Initial Concentrations
Example 7.6: Under certain conditions, the equilibrium constant Kc
for the decomposition of PCl5(g) in to PCl3 (g) and Cl2 (g) is 0.0211.
What are the equilibrium concentrations of PCl5, PCl3 and Cl2 in a
mixture that initially contained only PCl5 at a concentration of 1 M?

Solution:
PCl5(g) ⇌ PCl3(g) +
Cl2(g)
Initial (M) 1M 0 0
Change (M) –x +x +x
[ PCl3 (M)
Equilibrium ][Cl2 ] 1 M – x X ( x)( x) X
KC   0.0211 KC   0.0211
[ PCl5 ] (1  x) 30
 2
x
0.0211  0.0211(1  x)  x 2

(1  x)
x  0.0211x  0.0211  0
2

• The quadratic equation ax2+bx+c=0 form can be rearranged

to solve
 b for
 bx:2  4ac  0.0211  (0.0211) 2  4(1)(0.0211)
x x
2a 2(1)
x  0.135 M
The equilibrium concentrations are:
[PCl5] = 1.0-0.135= 0.87 M
[PCl3] = 0.135 M
[Cl2] = 0.135 M
31
Example 7.7: What are the concentrations at equilibrium of
a 0.15 M solution of HCN?
HCN(g) ⇌ H+ (aq) + CN-(aq) Kc = 4.9x10-10
Solution:
[ H  ][CN  ] x2
KC  KC   4.9 x10 10
[ HCN ] 0.15  x

x  0.15, then (0.15  x)  0.15

x2
4.9 x10 10  x  7.4 x10
2 11
0.15

6
x  8.6 x10 M
32
 7.5. Concepts of Acid-Base
7.5.1. Arrhenius Concept
An Arrhenius acid dissociates in water to form hydrogen
ions (H+), while an Arrhenius base dissociates in water to
form hydroxide ions (OH-).

Limitation:
The Arrhenius definitions of acidity and alkalinity
are restricted to aqueous solutions.
Thus, the Arrhenius definition can only describe
acids and bases in an aqueous environment.
33
 7.5.2. Br∅nsted-Lowery Concept
An acid is a proton donor, any species that donates an
H+ ion.
An acid must contain H in its formula; HNO3 and H2PO4- are
two examples, all Arrhenius acids are Brønsted-Lowry acids.

A base is a proton acceptor, any species that accepts an

H+ ion.
A base must contain a lone pair of electrons to bind the H + ion;
a few examples are NH3, CO32-, F -, as well as OH -.
Brønsted-Lowry bases are not Arrhenius bases, but all
Arrhenius bases contain the Brønsted-Lowry base OH-.

34
The concept of conjugate pairs is useful in describing
Br∅nsted-Lowry acid base reactions (and other reversible
reactions, as well).
When an acid donates H+, the species that remains is called the
conjugate base of the acid because it reacts as a proton acceptor
in the reverse reaction.
Likewise, when a base accepts H+, it is converted to its
conjugate acid.

35
 7.5.3. Lewis concept
A Lewis acid is defined as an electron pair acceptor,
and a Lewis base as an electron pair donor.

Examples of Lewis Acids: H+, K+, Mg2+, Fe3+, BF3,

, AlCl3, Br2.
Examples of Lewis Bases: OH-, F-, H2O, NH3,
SO42-, H-, CO, C6H6.

36
Lewis Acid: a species that accepts an electron pair (i.e., an
electrophile) and will have vacant orbitals, or the ability to
form a vacant orbital.
Lewis Base: a species that donates an electron pair (i.e., a
nucleophile) and will have lonepair electrons.
In a Lewis Acid-Base reaction a bond is formed where both
electrons come from the Lewis base, and this is called a
Coordinate Covalent bond (or dative covalent bond).

Lewis Acids: There are three general types of Lewis

Acids, that is, chemical species that can accept electrons.
A. Molecules with an incomplete octet
B. Molecules with double bonds
C. Metal ions with vacant d-orbitals.
37
A. Incomplete Octets

Boron Trifluoride is an exception to the octet rule and

has an incomplete octet, and can thus accept electrons to
form a bond.

In the process it goes from sp2 hybrid to sp3 hybrid.

38
B. Double Bonds

A double bond has 4 electrons shared between 2 atoms in a PI

and sigma orbital.

If you break the pi bond and move the two electrons to a non-
bonding orbital on one atom, the other atom develops an
incomplete octet and can function as a Lewis acid.

This is shown next figure where the pi electrons move onto the
oxygen, allowing the sulfur to receive electrons from a Lewis
base.

39
C. Metal Cations

Many metals have vacant d-orbitals that can accept electrons

and thus behave as Lewis Acids.

In fact, most metals react with water when they dissolve in

water to form what is called a complex ion.

For example, aluminum(III) is not a free ion, but a complex

with 6 water molecules.

40
 7.6. pH and pOH
pH/pOH is a measure of acidity or basicity of a
solution.

pH is defined as the negative logarithm of the

hydronium ion [H3O+] molar concentration in mol/L.

pH = -log[H+] = -log [H3O+]

The hydronium ion molarity yields the equivalent

expression:
[H3O+] = 10-pH
41
pOH of a solution is defined as the negative logarithm of
the hydroxide ion molar concentration in mol/L.
pOH = -log[OH-]
The hydroxide ion molarity yields the equivalent
expression:
[HO-] = 10-pOH

From the definitions of pH and pOH and the ion- product

of water,
pH + pOH = 14

The pH and pOH of a solution is dimensionless.

42
 7.6.1. Dissociation of Water
Ion-product of water:
H2O + H2O ⇌ H3O+ + OH-

The dissociation constant for the above reaction is:

Kw = [H3O+][OH-]
 log K w   log([ H 3O  ][OH  ])
 
 log K w  ( log[ H 3O ])  ( log[OH ])
pK w  pH  pOH

Where Kw is ion product of water, which is temperature

dependent at 250C, Kw is 1 10-14.
43
In pure water, or in a neutral solution of salts in water,
the concentration of the H3O+ and OH- ions is equal.

[H3O+] = [OH-] = √ Kw = 1 10-7 M, at 25oC

In acidic solutions, the concentration of the hydronium

ions is greater than that of the hydroxyl ions, or:
[H3O+] > 1.0 x 10-7 M and
[OH-] < 1.0 x 10-7 M.

In basic or alkaline solutions:

[OH-]>[H3O+], or
[OH-] > 1.0 x 10-7M.
44
Example 7.8: What is th pH of stomach acid, a
solution of HCl with a hydronium ion concentration
of 1.2x10-3 M? 3

pH   log[ H 3O ] pH   log(1 . 2 x10 M)
Solution:
pH  3  log 1.2 pH  2.92
Example 7.9: Calculate the hydronium ion
concentration of blood, the pH of which is 7.3.


Solution:pH   log[ H 3O ] 7.3   log[ H 3O ]

[ H 3O ]  10  pH [ H 3O  ]  10 7.3  anti log of  7.3
 8
[ H 3O ]  5 x10 M 45
 7.7. Relative Strength of Acids and Bases
The relative strength of an acid or base is the extent to which it
ionizes when dissolved in water.
If the ionization reaction is essentially complete, the acid or
base is termed strong; if relatively little ionization occurs, the
acid or base is weak.
Strong Acids Strong Bases
Perchloric Acid, Lithium Hydroxide,
HClO4 LiOH
Hydrochloric Acid, Sodium Hydroxide,
HCl NaOH
Hydrobromic Acid, Potassium Hydroxide,
HBr KOH
Calcium Hydroxide, 46
The relative strengths of acids or bases may be quantified by
measuring their equilibrium constants in aqueous solutions.

In solutions of the same concentration, stronger acids ionize to

a greater extent, and so yield higher concentrations of
hydronium ions than do weaker acids.

The equilibrium constant for an weak acid is called the acid-

ionization constant, Ka. For the reaction of an acid HA:

HA(aq) + H2O(l) ⇌ H3O+(aq) + A-(aq)

 
[ H 3O ][ A ]
Ka 
[ HA]
47
The equilibrium constant for an weak Base is called
the Base-ionization constant, Kb. For the reaction of
an acid B:

B(aq) + H2O(l) ⇌ BH+(aq) + OH-(aq)

 
[ BH ][OH ]
Kb 
[ B]

48
Another measure of the strength of an acid or base is its
percent ionization.

The percent or degree of ionization of a acid or base is

defined in terms of the composition of an equilibrium
mixture:

[ H 3O ]
% ionization    x100
[ HA]

[OH ]
% ionization    x100
[ B]
49
Example 7.10: Calculate the [H+] in a 0.1 M HCNO
solution. What is the degree of ionization of cyanic acid in
this same solution? (K1=210-4)
Solution: - HCNO(aq) + H2O(aq) H3O+(aq) + CNO-(aq)
Initial 0.1m 0M 0M
Change -x +x +x
[ ]eq. 0.1 – x x x
 
[ H 3O ][CNO ] x2 x2
Ka  Ka    2 x10  4
[ HCNO ] 0.1  x 0.1

x  [ H  ]  [CNO  ]  0.0045M
[ H 3O  ] 0.0045M
 x100  x100  4.5%
[ HCNO ]
0.1M
50
Example 7.11: Calculate the OH- ion conc. in 0.4 M NH3
solution. What is the degree of ionization of NH 3 solution
in this same solution? (Kb= 1.810-5)

Solution: - NH3 (aq)+H2O(aq) NH4+ (aq)+OH-(aq)

Initial 0.4 M 0M 0M
Change -x +x +x
[ ]Eq (0.4 – x) M xM xM
x2 x2

[ NH 4 ][OH  ] Kb    1.8 x10 5
Kb  0.4  x 0.4
[ NH 3 ]

x  [OH  ]  2.7 x10 3 M


[OH ] 3
 x100   2.7 x10 M x100  0.675%
[ NH 3 ] 0.4 M 51
 7.7.1. p-Functions
The p- value is the negative base (-10) logarithm of the
molar concentration of a certain species:
pX = -log [X] = log 1/[X]

We can also express equilibrium constants for the

strength of acids and bases in a log form:

pKa = - log(Ka)
pKb = - log (Kb)
Kw = Ka * Kb

52
7.7.2. Strength of Acids and Bases

53
Strength of Acids and Bases

54
 7.7.3. The Common Ion Effect
In acid-base ionization of a single electrolyte there is
formation of one anion and one cation of the solute
material.
What happens when a solution contains two different
dissolved compounds?
Example 7.12: - Both CH3COONa and CH3COOH are in solution and
they dissociate and ionize to produce CH3COO- ions:
CH3COONa (s) H2O CH3 COO - (aq) + Na+(aq)
CH3COOH (aq) CH3 COO - (aq) + H+(aq)

CH3COONa is a strong electrolyte, so it dissociates

completely in solution, but CH3COOH, a weak acid, ionizes
partially. 55
According to Le Chatelier’s principle, the addition of CH3COO-
ions from CH3COONa to a solution of CH3COOH will suppress the
ionization of CH3COOH, that is, shifts the equilibrium to the left
there by decreasing the H+ ion concentration.
Thus, a solution containing both CH3COOH and CH3COONa will be
less acidic than a solution containing only CH3COOH at the same
concentration.
The shift in equilibrium of the CH3COOH ionization is caused by
the additional acetate, CH3COO -, ions which comes from the salt.

The shift in equilibrium caused by the addition of a compound

having an ion in common with the dissolved substances is called the
Common ion effect. It is a special case of Le Chatelier’s principle.

56
 7.8. Buffer solutions
It is a solution that has the ability to resist change in pH
up on the addition of small amounts of either acid or
base.

Buffer solution is a solution of a weak acid/weak

base and its salt.
A buffer solution must contain an acid to react with OH -
ions that may be added to it and a base to react with any
added H+ ions.
Furthermore, the acid and the base components of the buffer
must not consume each other in a neutralization reaction.
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 Buffer solution

Types of buffer solution

a. Acidic buffer: CH3COOH and CH3COONa

b. Basic buffer: NH4OH and NH4Cl

c. Salt or neutral buffer: CH3COONH4

58
 Now, to find the pH, Let us consider
CH3COOH(aq) + H2O(l) ⇌ H3O+(aq) + CH3COO-(aq)
 
Since CH3COOH is parially
[ H 3O ][CH 3COO ]
Ka  ionized, so most of CH3COO–
[CH 3COOH ] will come from the salt.

 [CH 3COOH ] Hence, [CH3COO–] = [Salt]

[ H 3O ]  K a
[CH 3COO  ] Taking log of both sides
[ Acid ]
 log[ H 3O  ]   log K a  log Similarly, for Basic Buffer
[ Salt ]

[ Salt ] [ Salt ]
pH  pK a  log pOH  pK b  log
[ Acid ] [ Base]
59
Example 7.13: Calculate the pH of a buffer solution containing 0.1
M each of acetic acid and sodium acetate. (Ka=1.8×10–5)
• What will be the change in pH on adding
(a) 0.01 moles of HCl to 1.0 L of solution?
(b) 0.01 moles of NaOH to 1.0 L of solution?
• Assume that no change in volume occurs on the addition of HCl
or NaOH.
Solution: [ Salt ]
pH  pK a  log
[ Acid ]
5 0.1 pH  4.745  0
pH   log(1.8 x10 )  log
0.1
pH  4.745 60
a) 0.01 moles of HCl give 0.01 moles of H+ which reacts
with 0.01 moles of CH3COO– to form CH3COOH.
Therefore,
[CH 3COO  ]  0.1  0.01  0.09M
[CH 3COOH ]  0.1  0.01  0.11M
0.09
pH  4.745  log pH  4.745  0.087
0.11
pH  4.658
Change in pH = 4.745 – 4.658 = 0.087 units.
Hence, pH will decrease!
61
(b) On adding 0.01 moles of NaOH to a litre of solution,
0.01 moles of OH– will react with 0.01 moles of
CH3COOH. Therefore,
[CH 3COO  ]  0.1  0.01  0.11M
[CH 3COOH ]  0.1  0.01  0.09 M
0.11
pH  4.745  log pH  4.745  0.086
0.09
pH  4.831
Change in pH = 4.831 – 4.745 = 0.086 units.
Hence, pH will increase!
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