Acid-Base

Equilibria
 ICEBREAKER:
ACID OR BASE?
SYSTEMATIC NAME
COMMON NAME
2
𝐻𝐶𝑙

3
𝑁𝑎𝑂𝐻

4
𝑁𝑎2 𝐶𝑂3

5
𝐶𝐻3 𝐶𝑂𝑂𝐻

6
𝐻2 𝑂

7
ACID-BASE EQUILIBRIA
Solutes in aqueous solutions may be classified according to
their ability to conduct electricity into:

Nonelectrolyte
An aqueous solution of this solute
does not conduct electricity
because its particles are in
molecular form.
Electrolyte
An aqueous solution of this solute
conducts electricity due to the
presence of ions.

8
Electrolytes
Electrolytes can be further classified into strong electrolytes
and weak electrolytes

Strong electrolytes are solutes Weak electrolytes are solutes that

that are completely or almost are partially ionized in solution
completely ionized in solution resulting to a mixture of molecules
which accounts for its ability to and ions. The solution contains
strongly conduct electricity. lower number of ions compared
Dissolved salts, strong acids, and with the same quantity of a strong
strong bases are strong electrolyte and is a weak conductor
electrolytes. of electricity. Weak acids and weak
bases are weak electrolytes.

9
Brønsted – Lowry
Acids and Bases
The Brønsted – Lowry concept, introduced
independently in 1923 by Danish chemist Johannes Nicolaus
Brønsted and English chemist Thomas Martin Lowry, is
based on the behavior of a substance during proton (H+)
transfer. This concept is not limited to aqueous solutions.

10
Brønsted – Lowry
Acids and Bases
According to the Brønsted – Lowry concept, an acid is
a substance which is capable of donating a proton while a
base is a substance which is capable of accepting a proton. A
pair of substances which are related through the loss or gain
of a proton is called a conjugate acid-base pair.

11
Consider the following examples of reactions that show
proton transfer:
(1) HClO4 + H2O → H3O+ + ClO4-
(2) HF + H2O ↔ H3O+ + F-
(3) NH3 + H2O ↔ NH4+ + OH-

In example 1, ClO4- is obtained from HClO4 by the loss of a proton. We can

therefore say ClO4- is the conjugate base of the acid HClO4. In the same
reaction, H3O+ is the conjugate acid of the base H2O because H3O+ is formed
after the H2O molecule has gained a proton. We say therefore that there are
two conjugate acid-base pairs: H3O+ and H2O is one pair, HClO4 and ClO4- is the
other. In example 2 HF and F- form a conjugate acid-base pair. In example 3,
NH3 acts as a base because it accepts a proton from H2O. In this reaction NH4+
is the conjugate acid of NH3 while OH- is the conjugate base of the acid H2O.

12
The Acid-Base Properties
of Water
The reactions given in the previous example illustrate the
acid-base properties of water. H2O acts as an acid when it donates
a proton as shown in its reaction with NH3 forming the conjugate
base, OH-. On the other hand, in its reaction with HClO4 and HF, it
acts as a base because it accepts a proton to form the H3O+ ion.
Hence, H2O is called an amphoteric substance because it has the
ability to act both as an acid and as a base.

13
This property can be observed during the ionization of water.
Water undergoes autoprotolysis as shown by the equation:
H2O + H2O ↔ H3O+ + OH-
And the equilibrium constant may be written as:
𝐻3 𝑂+ 𝑂𝐻 −
𝐾𝑐 =
𝐻2 𝑂 2
But since ionization of water occurs only to a very slight extent,H2O
is essentially pure and [H2O] = constant. We therefore get:
𝐾𝑐 × 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 = 𝐻3 𝑂+ 𝑂𝐻−

14
In very dilute solutions, the equation may be rewritten as:
𝐾𝑐 = 𝐾𝑤 = 𝐻3 𝑂+ 𝑂𝐻 −
In pure water at 25 degrees C, 𝐻3 𝑂 + = 𝑂𝐻 − = 1.0 × 10−7 𝑀 and 𝐾𝑤 in the
above equation has a value of 1.0 x 10-14. It is called the water
autoionization constant or the ion-product constant for water. This mean
that whether we have pure water or a solution, the relationship,
𝐾𝑤 = 𝐻3 𝑂+ × 𝑂𝐻 − = 1.0 × 10−14
Is always true at 25 degrees C as long as water is present.
A solution is acidic when the [H3O+] is greater than [OH-]. This means that at
25 degrees C, [H3O+] is greater than 1.0 x 10-7 M and the [OH-] is less that 1.0
x 10-7. In a basic solution, [OH-] is greater than [H3O+] and therefore, [H3O+] is
lower than 1.0 x 10-7 M while [OH-] is greater than 1.0 x 10-7 M. When the
solution is neutral, [H3O+] = [OH-] and at 25 degrees C, both the values of
[H3O+] and [OH-] are 1.0 x 10-7 M.

15
pH: A Measure of Acidity
Since concentrations of H3O+ and OH- ions in dilute
solutions are usually very low, acidity and basicity of solutions can
be better expressed by using the p-scale (or negative logarithm
scale) in expressing the concentrations of the said ions. By
definition:
𝑝 − 𝑆𝑜𝑙𝑢𝑡𝑒 = − log[𝑆𝑜𝑙𝑢𝑡𝑒]
This means that the p- value for any solute is obtained by taking
the negative logarithm of its molar concentration. Among the p
values commonly used are pH, which is defined as the negative
logarithm of the hydronium ion concentration and pOH, the
negative logarithm of the hydroxide ion concentration.

16
In any aqueous solution, [H+] = [H3O+] and we can write:
𝑝𝐻 = − log 𝐻+ = − log[𝐻3 𝑂+ ]
Similarly, pOH can be written as:
𝑝𝑂𝐻 = − log[𝑂𝐻 − ]
From the ionization of water, we have seen that:
𝐾𝑤 = 𝐻3 𝑂+ 𝑂𝐻−
Expressing the relationship logarithmically, we get:
− log 𝐾𝑤 = − log 𝐻3 𝑂+ − log 𝑂𝐻 −
And:
𝑝𝐾𝑤 = 14.0 = 𝑝𝐻 + 𝑝𝑂𝐻

17
We can then identify solutions by their pH and pOH values using
the following criteria:
For acidic solutions at 25 degrees C, since:
𝐻3 𝑂+ > 1.0 × 10−7 𝑀 𝑎𝑛𝑑 𝑂𝐻 − < 1.0 × 10−7
Therefore, pH < 7.0 and pOH > 7.0
For basic solutions at 25 degrees C, since:
𝐻3 𝑂+ < 1.0 × 10−7 𝑀 𝑎𝑛𝑑 𝑂𝐻 − > 1.0 × 10−7
Therefore, pH > 7.0 and pOH < 7.0
For neutral solutions at 25 degrees C, since:
𝐻3 𝑂+ = 𝑂𝐻 − = 1.0 × 10−7
Therefore, pH = pOH = 7.0

18
 1

The Ionization of
Weak Acids and Bases
The Ionization of Weak Acids
Ionic equilibrium results when a weak acid is dissolved in water.
Consider the equilibrium which results when HCN is dissolved in
water:
𝐻𝐶𝑁 + 𝐻2 𝑂 ↔ 𝐻3 𝑂+ + 𝐶𝑁 −
For the ionic reaction, the equilibrium constant may be written as:
𝐻3 𝑂+ 𝐶𝑁 −
𝐾𝑐 = 𝐾𝑎 =
𝐻𝐶𝑁
Where Ka is the acid ionization constant.
The ionization of weak acids is never complete and all species, the
unionized acid, the hydronium ion, H3O+, and the anion of the acid are all
present in equilibrium with the unionized species predominating in the
solution.
20
The following guide rules may help in solving problems on ionization
constants:
1. Express the equilibrium concentrations of all species in terms of the
initial concentration and an unknown, for example, i, which represents
the change in concentration due to ionization
2. Express the acid ionization constant in terms of the equilibrium
concentrations
Values of Ka that are available from tables were determined at 25 degrees
C. Unless stated otherwise, assume that the temperature is 25 degrees C.
The value of Ka is a measure of the tendency of the molecule to ionize in
solution and donate its acidic proton. The greater the equilibrium lies
more toward the direction of the ionization reaction, the greater is the
value of Ka. The higher the value of Ka, the stronger is the acid.

21
Sample Problem: A weak monoprotic acid, HA, is found to be 3.0%
ionized in 0.010 M solution. Calculate the value of Ka for HA.
Solution:
Since the acid is 3.0% ionized, the change in concentration of HA
due to ionization is 3.0% of 0.010 M or 0.00030 M.
The reaction table for the ionization is described by:

𝐻𝐴 + 𝐻2 𝑂 ↔ 𝐻3 𝑂+ + 𝐴−
Initial concentration 0.010 0 0
Change in Concentration -0.00030 +0.00030 +0.00030
Equilibrium Concentration 0.010- 0.00030 0.00030
0.00030

𝐻3 𝑂+ 𝐴− (0.00030 × 0.00030)
𝐾𝑎 = = = 9.3 × 10−6
𝐻𝐴 (0.010 − 0.00030)
22
Sample Problem: Calculate the % ionization of benzoic acid,
C6H5COOH, in a 0.010 M aqueous solution.
𝐾𝑎 = 6.5 × 10−5
Solution:
If we let a = concentration of ionized benzoic acid, then the reaction
table will be given by:
𝐶6 𝐻5 𝐻𝑂𝑂𝐻 + 𝐻2 𝑂 ↔ 𝐻3 𝑂+ + 𝐶6 𝐻5 𝐶𝑂𝑂−
Initial concentration 0.010 0 0
Change in Concentration -a +a +a
Equilibrium Concentration 0.010-a a a

𝐻3 𝑂+ 𝐶6 𝐻5 𝐶𝑂𝑂− 𝑎)(𝑎
𝐾𝑎 = = = 6.5 × 10−5
𝐶6 𝐻5 𝐻𝑂𝑂𝐻 0.010 − 𝑎

23
Since benzoic acid is a weak acid, the concentration of the ionized
acid is very small compared with the initial concentration and the
quantity (0.010-a) can be rounded off to 0.010. We now get
𝑎 2
6.5 × 10−5 =
0.010
2
𝑎 = 6.5 × 10 −5 0.010 = 6.5 × 10−7
𝑎 = 8.1 × 10−4
𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑖𝑜𝑛𝑖𝑧𝑒𝑑 𝑎𝑐𝑖𝑑 𝑎𝑡 𝑒𝑞𝑢𝑙𝑖𝑏𝑟𝑖𝑢𝑚
% 𝑖𝑜𝑛𝑖𝑧𝑎𝑡𝑖𝑜𝑛 = × 100
𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑎𝑐𝑖𝑑
8.1 × 10−4
= = 8.1%
0.010 𝑀

24
The Ionization of Weak Bases
If instead of a weak acid, we have a weak base such as NH3, the
ionization reaction is:
𝑁𝐻3 + 𝐻2 𝑂 ↔ 𝑁𝐻4 + + 𝑂𝐻 −

And the equilibrium constant expression may be written as:

𝑁𝐻4 + 𝑂𝐻−
𝐾𝑏 =
𝑁𝐻3

25
 Just like weak acids, the value of the base ionization
constant, Kb, is a measure of the strength of the weak base. The
basic property of the base is a measure of its tendency to accept a
proton during a Brønsted – Lowry acid-base reaction. The greater
the value of Kb, the greater is the tendency of the base to abstract a
proton from water or any other proton donor, and the stronger the
base.
Solutions of weak bases are like solutions of weak acids
where most of the molecules of the unionized base predominate
over the ions formed by the reaction of the base with water. Hence,
the values of the ionization constants are very much lower than 1.0.

26
Sample Problem: Calculate the hydronium ion and hydroxide ion
concentrations of a 0.15M aqueous solution of pyridine.
Solution:
Kb of pyridine (C5H5N) = 1.8 x 10-9

𝐶5 𝐻5 𝑁 + 𝐻2 𝑂 ↔ 𝐶5 𝐻5 𝑁𝐻 + + 𝑂𝐻 −
Initial concentration 0.15 0 0

Change in Concentration -b b b

Equilibrium Concentration 0.15-b b b

27
Since pyridine is a very weak base (Kb << 1.0), the value of b would
be very small compared to 0.15 and the quantity (0.15M-b) is
approximately equal to 0.15 M.
This gives 𝑏 = 1.7 × 10−5 𝑀

Since [OH-] is now known, we can solve for [H3O+]

𝐻3 𝑂+ 𝑂𝐻− = 𝐾𝑏

𝐾𝑏 1.0 × 10−14
𝐻3 𝑂+ = − = −5 = 5.9 × 10−10 𝑀
𝑂𝐻 1.7 × 10

28
 2

The pH Solutions of
Weak Acids and Bases
 The pH of acidic solutions at 25°C are always less than
7.0 while for basic solutions, pH is always greater than 7.0.
This is because the hydronium ion concentration is greater
than 1.0 x 10-7 M in acids while it is less than 1.0 x 10-7 in bases.
On the other hand, the pOH of acidic solutions is always
greater than 7.0, while for basic solutions pOH is always less
than 7.0. This is because the hydroxide ion concentration in
acids is always less than 1.0 x 10-7 M while it is always greater
than 1.0 x 10-7 M in bases.

30
Sample Problem: Calculate the [H3O+], [OH-], and pH of a
0.0010 M aqueous solution of HCl.
Solution:
Since HCl is a strong acid, it is completely ionized in
water.
HCl + H2O → H3O+ + Cl-
Therefore,
[H3O+] = [HCl] = 0.0010 M

31
Since,
[H3O+] x [OH-] = 1.0 x 10-14
𝐾𝑤 1.0×10−14
[OH-] = = = 1.0 x 10-11
𝐻3 𝑂+ 0.0010
pH = -log[H3O+]
= -log(0.001 M)
= 3.0

32
Sample Problem: Calculate the ionization constant of a
hypothetical weak acid, HX, if the pH of a 0.020M aqueous
solution is 5.82
Solution:
Let: a = [H3O+] in solution
HX(aq) + H2O ↔ H3O+(aq) + X-(aq)
0.020 - a a a
Equilibrium concentration (M):
pH = -log[H3O+]
5.82 = -log[H3O+]
a = [H3O+] = 1.5 x 10-6 M
𝐻3 𝑂+ [𝑥 − ] (1.5×10−6 )(1.5𝑥10−6 )
Ka = = = 1.1 x 10-10
𝐻𝑋 0.020−(1.5𝑥10−6 )

34
 3

The Ionization of Electrolytes

And the Common-Ion Effect
Consider the ionization in water of the weak acid HF described by
the equation:
HF + H2O ↔ H3O+ + F-
If we add NaF(aq) to the solution, it ionizes completely, NaF(aq)
→ Na+(aq) + F-(aq). This causes an increase in the concentrations of F-
ions which in turn causes the equilibrium to shift toward the
direction of the backward reaction. The F- ions from the dissolved
salt react to decrease. Similarly, if the H3O+ concentration is
increased, the additional H3O+ will react with the F- ions in the
solution and cause the degree of ionization to decrease. The
presence of a common ion in a solution of a weak electrolyte
suppresses the ionization of the solute. This is called the common-
ion effect.

36
Sample Problem: Compare the % ionization of NH3 in a 0.50 M
solution with that in a solution that is 0.50 M with both NH3 and NH4.
Kb of NH3 = 1.76 x 10-5
Solution:
In the solution of 0.50 M NH3, the equilibrium involved is
NH3 + H2O ↔ NH4+ + OH-
0.50 - a a a

Where a = concentration ionized in 0.50 M NH3 solution

𝑁𝐻4 + [𝑂𝐻 − ]
Kb =
𝑁𝐻3

37
 𝑎 (𝑎) 𝑎2
1.76 x 10-5 = =
0.50 −𝑎 0.50
a2 = (1.76 x 10-5) (0.50)
a2 = 8.8 x 10-6
a = 3.0 x 10-3
𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑖𝑜𝑛𝑖𝑧𝑒𝑑
Therefore, % 𝑖𝑜𝑛𝑖𝑧𝑎𝑡𝑖𝑜𝑛 = 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 x 100
3.0 𝑥 10−3 𝑀
= 0.50𝑀
𝑥 100 = 0.60%
The same equilibrium exists in the solution that contains both NH3 and
NH4Cl

Where b = concentration of NH3 ionized in the solution that is 0.50 M with

NH3 and 0.50 M with NH4Cl
38
Note that the concentration of NH4+ ions in the solution is the sum of the
concentrations of NH4+ ions from the partial ionization of NH3 and the
complete ionization of the salt NH4Cl
𝑁𝐻4 + [𝑂𝐻 − ]
Kb = 𝑁𝐻3
0.50 𝑀 + 𝑏 (𝑏) 0.50 𝑀 𝑥 𝑏
1.76 x 10-5 = =
0.50 −𝑏 0.50
Since 0.50 >> b, (0.50 M + b) ≈ 0.50 M and (0.50 – b) ≈ 0.50M, and the
equation reduces to

𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑖𝑜𝑛𝑖𝑧𝑒𝑑
Therefore, % 𝑖𝑜𝑛𝑖𝑧𝑎𝑡𝑖𝑜𝑛 = 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 x 100
1.76 𝑥 10−5 𝑀
= x 100 = 0.0035%
0.50 𝑀

39
 4

The Henderson-Hasselbach
Equation
When two solutes that contain the same ion (common ion) are
dissolved in the same solution, both solutes ionize to form CN- ions:
HCN + H2O(l) ↔ H3O+(aq) + CN-(aq)
NaCN(aq) → Na+(aq) + CN-(aq)
The presence of CN- ion produced from the complete ionization of
NaCN causes the HCN equilibrium to shift to the left. This
suppresses the ionization of HCN and decreases the concentration
of H3O+ ions in solution. Hence, a solution which contains both NaCN
and HCN is less acidic than one which contains HCN only.
The shift in equilibrium caused by the addition of a
compound having an ion common with the dissolved substance is
called common-ion effect.

41
Consider the pH of a solution that contains both HCN and NaCN. For
the HCN equilibrium, ionization is given by:
HCN(aq) + H2O(l) ↔ H3O+(aq) + CN-(aq)
For which:
𝐻2 𝑂+ [𝐶𝑁− ]
Ka = 𝐻𝐶𝑁
Rearranging the equation to solve for [H3O+], results in:
[𝐻𝐶𝑁]
[H3O+] = Kax
𝐶𝑁−
[𝐻𝐶𝑁]
-log[H3O+] = -logKa + log 𝐶𝑁−1
[𝐶𝑁−1 ]
pH = pKa +log
𝐻𝐶𝑁

42
The equation, which is called the Henderson-Hasselbach equation, can
be expressed in the more general form:
pH = pKa + log([conjugate base]/[acid])
In the equation, conjugate base refers to the salt of the acid.
In calculations involving common-ion effect, when the starting
concentrations of the acid and the conjugate base (salt) are quite high
(0.10 M) the ionization of the acid and the hydrolysis of the salt can be
neglected and the starting concentrations of the acid and the salt can
be used in the computation.
If the solution consists of a weak base and its salt, the Henderson-
Hasselbach equation takes the form
pOH = pKb + log ([conjugate acid]/[base])
In the equation, conjugate acid refers to the salt of the base.
43
Sample Problem:
(A) Calculate the pH of a 0.25 M aqueous solution of CH3COOH
(B) What would be the pH of the solution if it is also 0.20 M with
CH3COONa?
Solution:
(A) Let a = [H3o+] at equilibrium

𝐶3 COO𝐻 + 𝐻2 𝑂 ↔ 𝐻3 𝑂+ + 𝐶3 C𝑂OH −
Initial concentration 0.25 0 0

Equilibrium concentration 0.25 - a a a

44
 𝐻3 𝑂+ [𝐶𝐻3 𝐶𝑂𝑂] 𝑎 (𝑎)
Ka =
𝐶𝐻3 𝐶𝑂𝑂𝐻
=
0.25 −𝑎
= 1.8 x 10-5
Since CH3COOH is a weak acid, the concentration of the ionized
acid is very small compared with the initial concentration and the
quantity (0.25 – a) can e rounded off to 0.25
𝑎2
1.8 x 10-5 =
0.25
a2 = 1.8 x 10-5 x 0.25 = 4.5 x 10-6
a = 2.1 x 10-3 M
pH = -log[H3O+] = -log(2.1 x 10-3) = 2.68

45
(B) For this solution which contains both the weak acid and its salt,
the Henderson-Hasselbach equation can be used.
[acid] = [CH3COOH] = 0.25M
[conjugate base] = [CH3COONa] = 0.20M
pKa = -logKa = -log(1.8x) = -(-4.74) = 4.74
Substituting in the Henderson – Hasselbach equation, we get
[𝑐𝑜𝑛𝑗𝑢𝑔𝑎𝑡𝑒 𝑏𝑎𝑠𝑒]
pH = pKa + log [𝑎𝑐𝑖𝑑]
0.20 𝑀
= -4.74 + log = 4.64
0.25 𝑀

46
Buffer Solutions
A solution of a weak acid of a weak base and its salt which
has the ability to resist changes in pH upon the addition of small
amounts of acid or base is called a buffer solution. For the buffer
solution to function effectively, it must contain over a limited pH
range. This pH range, called the buffer capacity, is the pH range
over which a buffer is effective is defined by the equation
pH range = pHbuffer ± ∆𝑝𝐻
∆pH refers to the change in pH observed after the addition
of 1 millimole of strong acid ostrong base to 1 liter of buffer solution.
The pH range is usually 1 pH unit higher or lower than the pKa of the
weak acid or the pOH is 1 unit higher or lower than the pKb of the
weak base.
47
Buffer Action
Buffers have the ability to resist changes in pH upon addition
of small amounts of acids and bases because they contain both
acidic and basic species. This condition is satisfied by the presence
of a conjugate acid-base pair in the system. In the case of a buffer
solution of HCN and NaCN, HCN is the acidic species while CN- ion
from NaCN is the basic species. The acidic species neutralizes the
OH- ions from the added base while the basic species neutralizes
the H3O+ ions from the added acid.

48
If an acid is added to the buffer solution of HCn and NaCN, the basic
component of the buffer which in this case is CN-, the conjugate
base of the acid that comes from the salt, reacts with the added
base to form unionized HCN by the reaction:
H3O+(aq) + CN-(aq) ↔ HCN(aq) + H2O(l)

The pH of the solution does not increase because the OH-

ions from the added base react with HCN.

49
Sample Problem:
It is desired to prepare a buffer solution of pH 4.90 using 0.10
M acetic acid, CH3COOH, and crystals of sodium acetate,
CH3COONa. If 200mL of the acetic acid solution is used, how many
grams of crystals of sodium acetate will be added? Assume no
volume change results from the addition of the solid to the solution.
Ka of CH3COOH = 1.8 x 10-5

50
Solution:
We use the Henderson-Hasselbach equation to
calculate the desired concentration of the salt.
pKa = -logKa= -log(1.8 x 10-5) = 4.74
𝑠𝑎𝑙𝑡
pH = pKa + log 𝑎𝑐𝑖𝑑
𝑠𝑎𝑙𝑡
4.90 = 4.74 + log 0.10 𝑀
[salt] = 0.14 M
Masssalt = 0.14 mol/L x 0.200 L x 82 g/mol = 2.30g

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