CHAPTER 9

IONIC EQUILIBRIUM

9.1 Theories of Acids & Bases

9.2 Acid-Base Equilibria
9.3 Hydrolysis of Salt
9.4 The Common Ion Effect: Buffer Solutions
9.5 Acid-Base Titrations
9.6 Solubility Equilibria

9.1 Theories of Acids & Bases

9.1.1 Arrhenius Definition
Acids and bases are electrolytes (form ions when dissolved in water).
Svante Arrhenius, came up with the concept or idea that:
+
 acids dissociated in water to give H and
+ −
HCl(aq)  H (aq) + Cl (aq)
 bases dissociated in water to give hydroxide ions.
+ −
NaOH(aq)  Na (aq) + OH (aq)
Acids and bases neutralize one another because the hydrogen ion and
the hydroxide ion combine with one another to form water.
+ −
H (aq) + OH (aq)  H2O(l)
In general, this reaction will also produce a salt as a by-product. The
full equation would be a salt
HCl(aq) + NaOH(aq)  H2O(l) + NaCl(aq)

1
9.1.2 Brønsted-Lowry Definition
+
With the Brønsted-Lowry concept, we usually refer to a H as
a proton. That is because a proton is all that is left when…
+ −
HH +e
ACID
 An acid donates a proton to another substance.
 When an acid reacts, the proton is transferred from one substance
to another.
+ −
HCl(aq) + H2O(l)  H3O (aq) + Cl (aq)
Brønsted Acid
(donate proton)

 When an acid dissolves and dissociates in water it gives a proton to

the water.
+
 The following equation shows HCl giving a proton (H ) to
−
a hydroxide ion (OH ).
− −
HCl(aq) + OH (aq)  H2O(l) + Cl (aq)
Brønsted Acid
(donate proton)

BASE
 Bases are the opposite of acids. Bases accept protons.
−
 OH , for example can accept a proton to form water.
+ −
H (aq) + OH (aq)  H2O(l)
−
 Brønsted and Lowry realized that not all bases had to have OH .
 As long as something can accept a proton it is a base.
+ −
H2O(l) + HCl(aq)  H3O (aq) + Cl (aq)
Brønsted Base
(accept proton)
+ −
NH3(aq) + H2O(aq)  NH4 (aq) + OH (aq)
Brønsted Base
(accept proton)

2
Let’s take a closer look at the acid-base equation again…

Notice that H2O is a proton acceptor. Therefore, it is a base.

 Likewise, HCl is an acid because it is a proton donour.
+
 Because H3O is directly derived from water, it is its
+
conjugate pair. Since H3O is also capable of donating a
proton, it is a conjugate acid.
−
 Likewise, Cl is the directly derived from HCl, it is its
−
conjugate pair. Since Cl is also capable of accepting a proton,
it is a conjugate base.
+
 Therefore, H2O is a base and H3O is it’s conjugate acid.
−
 And, HCl is an acid and Cl it it’s a conjugate base.

NOTICE THAT…

 A weak base gives a strong conjugate acid.

 A strong acid gives a weak conjugate base.

3
And likewise…
 A strong base gives a weak conjugate acid.
 A weak acid gives a strong conjugate base.

Exercise 1:
Identify the two conjugate acid-base pair for the reactions below:
− 3− 2− 2−
a) HSO4 (aq) + PO4 (aq) SO4 (aq) + HPO4 (aq)
− − 2−
b) HCO3 (aq) + H2PO4 (aq) H2CO3(aq) + HPO4 (aq)
+
c) N2H4(aq) + H2O(l) N2H5 (aq) + OH−(aq)

4
9.1.3 Lewis Definition
Lewis Acid-base definition is based on the electron pair-transfer
concept. Lewis focused on what happens when a base accepts a
proton.
So, Lewis' definition of acid and base is…

A BASE is an electron pair donour

An ACID is an electron pair acceptor

For example,
+
When a hydroxide ion accepts a proton, H , it attaches itself to a
pair of electrons from the oxygen.

+
H O + H H O H
Lewis Base Lewis Acid
(electron pair (electron pair
donour) acceptor)

+
Likewise, when an ammonia molecule accepts a proton, H ,
it attaches itself to a pair of electrons from the nitrogen.

H H +
+
H N + H H N H

H H
Lewis Base Lewis Acid
(electron pair (electron pair
donour) acceptor)

What happens in each case is that the base donates a pair of electrons
+
to the H in order to allow it to form a coordinate covalent bond.

5
Neutralization, the reaction between acid and base is defined as:
the formation of a coordinate covalent bond between the
electron pair donour (base) and the electron pair acceptor (acid)

+
H O + H H O H
Lewis Base Lewis Acid (formation of dative bond)

Exercise 1:
Identify the Lewis acids and bases for the reactions below:
− 3− 3−
a) OH + HCO  CO + H2O
− 3− 2− 2−
b) HSO4 + PO4  SO4 + HPO4
c) 2AlCl3  Al2Cl6
2+ 2+
d) Cu + 4H2O  Cu(H2O)4

6
COMPARING THE CONCEPTS
a) The Arrhenius view:
+ −
HCl dissociates to form H and Cl .
+ −
HCl(aq)  H (aq) + Cl (aq)
This concept is only limited to acid-base reactions in aqueous
+ −
conditions involving H and OH .

b) The Brønsted-Lowry view:

shows a closer approximation to what is really going on. The
+
HCl doesn't just dissociate, but reacts with water to H3O .
− −
HCl(aq) + OH (aq)  H2O(l) + Cl (aq)
The idea here is that a proton is transferred from one chemical to
another in an acid-base reaction.
c) The Lewis view:
+
A H from HCl combines with a water molecule to
+
form H3O .
+
-
Cl H + O H Cl + H O H
H H

The reaction occurs because H2O provides an electron pair for

the hydrogen ion to accept. The electron dots emphasize the
Lewis point of view.
+ -
H O H + O H H O + H O H
H H
+
Likewise, when a hydroxide ion accepts a proton, H , it
attaches itself to a pair of electrons from the oxygen.

We use different acid-base theories to explain different reactions. This

is because each of the acid-base theory has its limitations…

7
Normally if the acid-base reaction is between strong mineral acids and
bases in aqueous solutions, the Arrhenius theory is adequate:
+ −
HCl(aq)  H (aq) + Cl (aq)
+ −
But in a acid-base reaction that does not involve H or/and OH
ions, the Brønsted-Lowry Definition is required.
+ −
NH3(aq) + H2O(aq) NH4 (aq) + OH (aq)
This theory is also useful to describe reactions of weak acids or bases
that do not completely ionize.

When we are dealing with acid-base reactions in a non- aqueous

environment, whereby ionization may not occur, we use the Lewis
acid-base theory.
H Cl H Cl
H N + B Cl H N B Cl

H Cl H Cl

9.2 Acid-Base Equilibria

9.2.1 The Auto-ionization of Water
Water, the most common solvent for acids & bases is a very weak
acid. Although water is a molecule, its high polarity enables it to
dissociate and form ions.
One water molecule will donate a proton to another to form a
hydronium ion and a hydroxide ion.
+ −
H2O(l) + H2O(l) H3O (aq) + OH (aq)

-14 o
= 1.0 x 10 (at 25 C)
The water equilibrium constant for this reaction is better known as the
auto-ionization constant of water, Kw.

8
The auto-ionization constant of water, Kw, is also known as the
ion-product constant for water.
+ −
In pure water, the concentration of H3O and OH produced by
the auto-ionization are equal.
Therefore…
+ −
Kw = [H3O (aq)] [OH (aq)]
+ +
= [H3O ] [H3O ]
-14 + 2
1.0 x 10 = [H3O ]
+ -7
[H3O ] = 1.0 10 14 = 1.0 x 10 M
+ −
Molar concentrations of H3O and OH in many solutions;
weak acids, bases and salts will always be very small.
To simplify analysis and discussions, a scale based on the negative
logarithm of molar concentrations is used.
This is known as the pH scale
+
pH = − log [ H3O ]
+
Or more simply… pH = − log [ H ]
From this relationship, we can determine the concentration of
+ +
H3O . [ H ] = antilog (− pH)
o
Therefore the pH of water (at 25 C) is…
pH of water =

Another example: calculate the pH of 0.1M of HCl.

Since HCl ionizes completely in water,
+ −
HCl(aq)  H (aq) + Cl (aq)

9
9.2.2 The pH Scale
Definitions of acidic,
basic and neutral
according to pH.
 pH is normally
measured using…
 pH meter (most
accurate)
 litmus paper (least
precise)
 pH paper
 Acid-base indicators

9.2.2 The pH Scale

The concept of pOH.
−
pOH = − log [OH ]
−
Because the auto-ionization of water produces OH as well as
+
H3O , the pOH of water is…
-7
[ OH− ]water = 1.0 x 10 M
pOH of water =
Just the same…
pKw = − log Kw
Therefore… pKw =

10
Notice that…
+ −
Kw = [H3O ] [OH ]
-14
= 1.0 x 10

+ −
−log Kw = −log ([H3O ] [OH ])

Exercise 2:
+ −
Calculate the [H3O ], [OH ], pH & pOH of:
a) 2.0 M HNO3
b) 0.45 M NaOH
c) 0.002 M H2SO4

11
9.2.3 Acid & Base Ionization Constants
Based on the Bønsted-Lowry Acid-Base theory, reactions between
acids & bases are seen as reversible.
− 2−
H2PO4 (aq) + NH3(aq) NH4+(aq) + HPO4 (aq)
As such, the net direction of the reaction is based on the relative
strengths of the acids & bases involved.

Strong Acids ionizes completely (stronger tendency to donate proton)

+ −
HCl(aq) + H2O(l)  H3O (aq) + Cl (aq)

Weak Acids ionizes partially (weaker tendency to donate proton)

+ −
H2S(aq) + H2O(l) H3O (aq) + HS (aq)

General guide on predicting strength of acidity:

 Mineral acids are generally stronger than organic acids.
 The higher difference in electronegativity between H and the
other atom, more acidic.
 The larger the size of the anion, more acidic.
 The more “O” atom in the acid, more acidic.
 Strengths of binary acids increase from top to bottom in a group
of the periodic table & from left to right.

12
General guide on predicting strength of acidity:
 Mineral bases are generally stronger than organic bases.
 Bases decreases in strength across the period from left to right
(Group 1 being strongest, followed by group 2).
 The larger the (metal) cation, the stronger the base.

B) Weak Acids
Since a weak acid do not ionize completely,
+ −
HA(aq) + H2O(l) H3O (aq) + A (aq)
[H 3O + ][A - ]
K =

But since [H2O] is a constant,

[H 3O + ][A - ]
K =
a [HA]
(Ka : acid dissociation constant)
Strength of an acid is BEST judged from it’s Ka value (NOT pH!)

13
Exercise 3:
-4
HNO2 is a weak acid with a Ka value of 7.1 x 10 . Write a chemical
equation to show its dissociation, and then calculate the pH of 0.010
M HNO2

Simplified calculations…

14
Exercise 4:
Acetic acid, CH3COOH, is a very weak acid with a Ka value of 1.8
-5
x 10 . Calculate the pH of 0.010 M acetic acid.

Simplified calculations…

15
When to use “simplified method”?
 When difference between Ka and concentration is more than
-3
1 x 10
-5
(e.g. when: [HA]0 = 0.0100M, and Ka = 1.00 x 10  safe
-5
[HA]0 = 0.0010M, and Ka = 1.00 x 10  not safe!
 For these equilibrium calculations to work properly, the acid
must not dissociate more than 5% in water.
+
 Double check by dividing the final (ionized) [H ] with the
initial (unionized) [HA].
Using the last example…
Acetic acid, CH3COOH, is a very weak acid with a Ka value of 1.8 x 10-5.
Calculate the pH of 0.010 M acetic acid.

Ostwald Dilution Law

If conditions are right, calculations for weak acids can be summarized
as follows…
+ −
HA(aq) H (aq) + A (aq)
[H + ][A - ]
+ −
Ka = [HA] but at equilibrium [H ] = [A ]
[H + ]2
+
= [HA] and [HA] = [HA]0 − [H ]
+
But in weak acids, Ka value is very small. Thus, [H ] << [HA]0
As such, [HA]0 − x ≈ [HA]0
[H + ]2
Therefore, Ka = [HA]
0

Giving us…
+
[H ] = Ka [HA]o

This is called the Ostwald Dilution Law.

16
 +
That means, the pH (or [H ]) of weak acids, can be determined if
we know: the Ka & the initial concentration.
Sometimes strength of acids (or bases) is given in the form: percent
ionization or percent dissociasion, α.

α= [H ]
100%
[HA]0

A high α indicates a strong acid or a base.

Acid HCl CH3COOH HSO4 − HNO2
α 99.99% 1.3% 29.0% 6.5%

Exercise 5:
Calculate the pH of an unknown acid, HX, if it 0.50 M of this acid
dissociates 9.5% when dissolved in water.

17
B) Weak Bases
Since a weak acid do not ionize completely,
+ −
B(aq) + H2O(l) BH (aq) + OH (aq)
[BH + ][OH - ]
Kc =
[B][H 2O]
But since [H2O] is a constant,

[BH + ][OH - ]
K =
b [B]
(Kb: base dissociation constant)
Strength of a weak base is BEST judged from it’s Kb value (NOT
pH!)
Exercise 6:
-5
NH3 is a weak base with a Kb value of 1.8 x 10 . Calculate the pH
of 0.010 M NH3.

18
If conditions are right, similar to weak acids, simplified calculations
for weak bases can be summarized as follows…
+ −
B(aq) + H2O(l) BH (aq) + OH (aq)
[BH + ][OH - ]
+ −
Kb = [B] but at equilibrium [BH ] = [OH ]
[OH - ]2
−
= [HA] and [B] = [B]0 − [OH ]
+
But in weak bases, Kb value is very small. Thus, [BH ] << [B]0
As such, [B]0 − x ≈ [B]0
[OH - ]2
Therefore, K =
b [B]0
Giving us…
−
[OH ] = Kb [B]o

This is called the Ostwald Dilution Law.

−
That means, the pOH (or [OH ]) of weak bases, can be determined if
we know: the Kb & the initial concentration.
Exercise 7:
Calculate the pH, pOH and percent ionization of the following
solutions:
-4
a) 0.03 M HF (Ka = 9.8 x 10 )
-6
b) 0.05 M N2H4 (Kb = 1.7 x 10 )
-8
c) 0.25 M HOCl (Ka = 3.0 x 10 )

19
Exercise 8:
0.100 M of an unknown monoprotic weak acid is found to have a
o
pH of 2.38 at 25 C. Determine its pKa at this temperature.

C) Relationship between Ka & Kb

According to the Brønsted-Lowry definition…

The conjugate base can react with water…

20
Since both equations are closely related (they have same species of
anions & molecules)…
Notice that when…

Ka x Kb =

Exercise 9:
-5
CH3COOH, a weak acid, has a Ka value of 1.8 x 10 . Determine the
strength of its conjugate base in pKb.

21
Acid Dissociation for Polyprotic Acids
+
A polyprotic acid is an acid that can donate more than one H ion per
acid molecule.
Dissociation of polyprotic acids differs at different levels, regardless
if the polyprotic acid is strong or weak.
Examples:
− + K
H2SO4: H2SO4 HSO4 + H a1 = very large
K -2
HSO4 − HSO4 2− +H + a2 = 1.3 x 10 M
K -2
H2SO3: H2SO3 HSO3 − +H + a1 = 1.40 x 10 M
K -8
HSO3 − HSO3 2− +H + a2 = 6.50 x 10 M
K -3
H3PO4: H3PO4 H2PO4 − +H + a1 = 7.90 x 10 M
K -8
H2PO4− HPO4 2− + H+ a2 = 6.31 x 10 M

K -13
HPO4 2− PO4 3− + H+ a3 = 3.98 x 10 M
Overall Ka is determined by multiplying the dissociation constants
for all levels of dissociation.
Example:
Ka for H2SO4 = very large (due to very large Ka1)

Ka for H3PO4 = Ka1 x Ka2 x Ka3

-3 -8 -13
= (7.90 x 10 ) x (6.31 x 10 ) x (3.98 x 10 )
=
Exercise 10
Ascorbic acid (H2C6H6O6; H2Asc for this problem), known as vitamin
-5 -12
C, is a diprotic acid (Ka1 = 1.0 x 10 and Ka2 = 5 x 10 ) found in
− 2-
citrus fruit. Calculate [H2Asc], [HAsc ], [Asc ], and the pH
of 0.050M H2Asc.

22
9.3 Hydrolysis of Salt
Weak acids & weak bases are not limited to molecular substances.
SALTS (ionic compounds) can also function as a Brønsted acid or
base.
This is especially evident in salts of:
STRONG ACID – WEAK BASE  (ACIDIC SALTS)
WEAK ACID – STRONG BASE  (BASIC SALTS)
Salts ionize completely in water, for example…
+ −
NH4Cl  NH4 (aq) + Cl (aq)
Its ions, however, can function as either as a Brønsted acid or base
when reacting with water…
+ +
NH4 (aq) + H2O(l) NH3(aq) + H3O (aq)
− −
Cl (aq) + H2O(l) HCl(aq) + OH (aq)

a) Acidic Salts
Acidic salts are produced when a strong acid reacts with a weak base.

Once the Kh (or Ka) of the salt is known, it’s pH can be determined.

23
For example, the pH of 0.50 M of NH4Cl…
+ −
NH4Cl  NH4 (aq) + Cl (aq)
+ +
NH4 (aq) + H2O(l)  NH3(aq) + H3O (aq)
Acidic salts are extremely weak acids, and have very small
-10
dissociation (e.g. Kh NH4Cl = 5.56 x 10 )

b) Basic Salts
Basic salts are produced when a weak acid reacts with a strong base.

The salt that is formed ionizes completely (as with all

ionic compounds)…
− +
CH3COONa  CH3COO (aq) + Na (aq)
Its ions, however, can function as either as a Brønsted acid or base
when reacting with water…
− −
CH3COO (aq) + H2O(l) CH3COOH(aq) + OH (aq)
+ +
Na (aq) + H2O(l) NaOH(aq) + H (aq)

24
For example, the pH of 0.50 M of CH3COONa…
+ −
CH3COONa  Na (aq) + CH3COO (aq)
− −
CH3COO (aq) + H2O(l) CH3COOH(aq) + OH (aq)
Basic salts are extremely weak bases, and have very small
-10
dissociation (e.g. Kh CH3COONa = 5.56 x 10 )

25
Summary
Remember that salts ionize 100%.
Salts can be either acidic or basic.
Acidity or basicity of salts are due to one of their ions.
Acidity or basicity of salts are very weak (even weaker than
weak acids or bases).
The hydrolysis constant for salts are very small, therefore it is
normally safe to assume that:
[ salt ion ]0 = [ salt ion ]eq
Therefore, short cut method is usually safe to use…

Exercise 11
Calculate the pH of the following solutions:
-5
a) 0.3 M sodium benzoate (Ka benzoic acid = 9.5 x 10 )
-7
b) 1.5 M N2H5Cl (Kb N2H4 = 1.7 x 10 )

26
9.4 The Common Ion Effect: Buffer Solution
What happens when we mix a weak acid with its salt? The
molecules of the weak acid would ionize partially…
+ −
CH3COOH H (aq) + CH3COO (aq)

+ −
CH3COONa  Na (aq) + CH3COO (aq)
Based on equilibrium concepts, we know that the addition of the
weak acid’s salt would cause a change in the ionic equilibrium.
Therefore, it is reasonable to say that the acidity of the weak acid
would have been effected.
We call the change the common ion effect.

Let’s look at the equations again…

+ −
CH3COONa  Na (aq) + CH3COO (aq)
+ −
CH3COOH H (aq) + CH3COO (aq)
Since the salt ionizes completely, equilibrium law does not apply for
that equation.
As for the weak acid…
[H + ]soln [CH 3 COO - ]soln
Ka = [CH 3 COOH]soln
Let’s analyze a few facts…
at equilibrium; [CH3COO−]soln = [CH3COO−]acid + [CH3COO−]salt
 But since salt ionizes 100%, and acid ionizes < 5%;
− −
[CH3COO ]acid << [CH3COO ]salt
 and [CH3COOH]0 ≈ [CH3COOH]soln due very little ionisation
of acid molecules.

So we can safely assume that…

− − −
[CH3COO ]salt ≈ [CH3COO ]soln (value of [CH3COO ]acid is negligible)

27
But remember, the salt is a weak acid, so…
− +
[CH3COO ]soln = [H ]acid

Applying these statements onto the ionic equilibrium equation…

[H + ]soln [CH 3 COO - ]salt
Ka = [CH 3 COOH]0
Rearranging the equation would give…

Likewise for base…

− +
BHY  Y (aq) + BH (aq)
− +
B(aq) + H2O(l) OH (aq) + BH (aq)

28
Exercise 12
Calculate the pH of the following solutions:
a) 50 mL 0.3 M sodium formate is mixed with 50 mL 0.1 M
-4
formic acid, HCOOH (Ka HCOOH = 1.7 x 10 )
b) 100 mL 0.2 M NH3 is mixed with 200 mL 0.1 M NH4Cl
-5
(Kb NH3 = 1.8 x 10 )

Buffer solution is…

 a solution of a weak acid and its salt.
 a solution of a weak base and its salt.

Example of an Acidic Buffer:

Mixture of acetic acid & sodium acetate (its salt)
+ −
CH3COONa  Na (aq) + CH3COO (aq)
+ −
CH3COOH H (aq) + CH3COO (aq)

29
Example of a Basic Buffer:
Mixture of ammonia & ammonium chloride (its salt)
− +
NH4Cl(aq)  Cl (aq) + NH4 (aq)
− +
NH3(aq) + H2O(l) OH (aq) + NH4 (aq)
Buffer solution resists changes in pH of small amounts in acids or
bases.
Let’s compare what happens when 1.0 mL 0.1 M HCl is added to a
100 mL pure water compared to 100 mL buffer solution.

In the buffer solution…

+
When H is added to an acidic buffer, it reacts with the conjugate base
in the buffer solution.
− +
HCOO (aq) + H (aq)  HCOOH(aq)
−
Therefore, the quantity of [HCOO ] is reduced.
and the quantity of [HCOOH] is increased.

30
n
HCOOH
n
HCOO−
 + +
Before + H H+ After + H
0.01 mol + 0.0001 mol 0.0101 mol
0.01 mol − 0.0001 mol 0.0099 mol
Using the Henderson-Hasselbalch Equation

-4
If Ka HCOOH = 1.7 x 10

31
Exercise 13
Using the same sample buffer solution: 100 mL 0.1M HCOOH, 0.1M
HCOONa, determine what is the pH change when 1.0 mL 1.0 M
NaOH is added.

Exercise 14
A buffer solution is prepared by mixing 300 mL of 2.0 M ammonium
chloride, NH4Cl, solution 200 mL to 0.5 M aqueous ammonia.
a) Calculate the pH of the buffer
b) Determine the pH of the buffer after addition of
i. 5.0 mL 0.5 M HNO3
ii. 10.0 mL 0.2 M KOH
-5
(Kb NH3 = 1.8 x 10 )

32
Exercise 15
Calculate the mole ratio between NaF and HF if a 3.00 pH buffer
solution is needed to be prepared.
-4
(Ka HF = 7.1 x 10 )

33
9.5 Titration
Acid-base titration normally gives an “S” curve when a pH vs.
volume of titrant is plot.

a) Strong Acid vs Strong Base

For example, titration between 25.00 mL 0.10 M HCl and 0.10 M
NaOH

EQUIVALENCE POINT is the point at which equimolar amounts of

acid and base have reacted. At this point, all acids have completely
reacted with all bases. Thus, the solution is 100% salt.
pH of Equivalence point is the pH of the salt.
Before Eq. point, pH of the solution is the pH of the solution in the
conical flask. (in this case, the pH of HCl that have not been
neutralized yet)
Near equivalence point, pH rises steeply.
After Eq. point, pH of the solution is the pH of the excess solution
added into the conical flask. (in this case, the pH of excess NaOH)

34
b) Strong Acid vs Weak Base
For example, titration between 25.00 mL 0.10 M HCl and 0.10 M
NH3

35
c) Weak Base vs Strong Acid
For example, titration between 0.10 M NH3 and 25.00 mL 0.10
M HCl.

36
c) Strong Base vs Weak Acid
For example, titration between 25.00 mL 0.10 M CH3COOH and
0.10 M NaOH

37
Summary of Shape of Titration Curves:
Strong Acid vs Strong Base Strong Base vs Strong Acid

Strong Acid vs Weak Base Weak Base vs Strong Acid

Weak Acid vs Strong Base Strong Base vs Weak Acid

Weak Acid vs Weak Base Weak Base vs Weak Acid

38
Exercise 16
Calculate the pH for the following steps within the titration of 20.00
mL 0.50 M KOH with 0.60 M benzoic acid, C6H5COOH;
a) Before titration begins
b) After addition of 10.00 mL benzoic acid
c) At equivalence point
d) After addition of 30.00 mL benzoic acid
e) Sketch the pH vs. volume of titrant graph for this
-5
titration. (Ka benzoic acid = 9.5 x 10 )

39
Indicators
During an acid-base titration process, the equivalence point is
determined using acid-base indicators.
This is usually done by dropping a few drops of indicators before the
titration process.
The end point occurs when the indicator changes colour. Not
all indicators change colour at the same pH or pH range,

40
Therefore, a good & precise titration can only be achieved if a
suitable indicator is used. That is one with its end point overlapping
the equivalence point of the titration.
Let’s look at the use of three indicators for the titration of a strong
acid vs. strong base.
For example, the titration between 25.00 mL 0.10 M HCl and 0.10 M
NaOH (titrant).

41
Although phenolphthalein may be suitable when the titrant is NaOH,
it may not be the case for the same titration in which HCl is the
titrant!

42
Let’s look at the use of three indicators for the titration of a
strong acid vs. weak base.
For example, titration between 25.00 mL 0.10 M HCl and 0.10 M
NH3 (titrant).

43
Exercise 17
For the titration between 20.00 mL 0.5 M CH3COOH and 0.5 M
NaOH, determine the pH of the solution in the conical flask…
a) before titration begins
b) after addition of 10.00 mL NaOH
c) after addition of 19.00 mL NaOH
d) at equivalence point
e) after addition of 21.00 mL NaOH
Sketch the pH vs. volume of titrant graph for this titration. Following
this, determine if phenolphthalein (pH range: 8.3 – 10.0) or methyl
orange (pH range: 3.1 – 4.4) is more suitable as the indicator for this
titration. Explain.
-5
(Ka CH3COOH = 1.8 x 10 )

44
9.6 Solubility Equilibria
When salt, an ionic compound, is added to water, it will dissolve.
When dissolved, the salt ionizes completely…
2+ −
CuCl2(s)  Cu (aq) + 2Cl (aq)
Salt will continue to dissolve until a point whereby the solution is
SATURATED.
When this happens, addition of more salt will not cause to dissolve.
At this point, an equilibrium exist in the system.
The quantity of undissolved (solid) salt that ionizes equals the amount
of salt ions that precipitates.
This equilibrium is called the solubility equilibrium.
2+ −
CuCl2(s) Cu (aq) + 2Cl (aq)
As in all equilibria systems, the equilibrium law can be written as...

Since CuCl2(s) is a constant…

2+ − 2
Ksp = [Cu (aq)] [Cl (aq)]
Ksp is the solubility product for CuCl2

Exercise 17
Write the solubility product expressions for the following compounds:
a) Silver chloride, AgCl
b) Sliver carbonate, Ag2CO3
c) Magnesium phosphate, Mg3(PO4)2
d) Iron(III) hydroxide, Fe(OH)3

45
Exercise 18
If the solubility product, Ksp, of a compound is known, its
solubility can be determined (and vice versa).
For example, the solubility product, Ksp, of silver chloride, AgCl,
−10
is 1.6 x 10 . Determine its solubility.

+ −
Ksp = [Ag (aq)] [Cl (aq)]

46
Exercise 19
Write the solubility product expression for lead(II) fluoride and
−8
determine its molar solubility. Ksp PbF2 = 4.1 x 10 .

Exercise 20
Determine the solubility product, Ksp, for copper(II) hydroxide if
−7 -1
its molar solubility is 1.8 x 10 mol L .

47
Based on the solubility product, Ksp, we can predict…
 Whether addition of certain quantity of salt would yield a
dissolved solution, a saturated solution or a super-saturated
solution.
 A mixture of two aqueous solution would cause a
precipitation to occur.
Similar to the concepts in chemical equilibrium, we can compare
the solubility product quotient, Qsp, with Ksp.
2+ −
CuCl2(s) Cu (aq) + 2Cl (aq)
Note that…
2+ − 2
Ksp = [Cu (aq)]equilibrium [Cl (aq)] equilibrium
Wheas…
2+ − 2
Qsp = [Cu ]0 [Cl ]0

Example
What happens when 1.00 g of PbI2 is mixed with 200 mL of water?
Will the compound dissolve completely? Explain.
−9
(Ksp, of PbI2, is 7.9 x 10 )

48
Exercise 21
Predict if a precipitate occur when 10.0 mL 0.15 M of calcium nitrate,
Ca(NO3)2, is added to 100.0 mL of 0.50 M sodium sulphate,
−5
Na2SO4, solution. (Ksp, of CaSO4, is 2.4 x 10 )

Exercise 22
o
At 25 C, the molar solubility of CoCO3 in a 0.10 M Na2CO3
−9 −1 sp
solution is 1.0 x 10 mol L . What is the K for CoCO3?

49
Exercise 23
Would a precipitate of silver acetate, CH3COOAg, form if 22.0 mL of
0.100 M AgNO3 were added to 45.0 mL of 0.0260 M CH3COONa?
−3
Ksp for CH3COOAg is 4.0 x 10 .

50
EXERCISE
1. Identify Lewis acid and Lewis base in each of the following reactions:
(a) SnCl4(s) + 2Cl-(aq) SnCl62-(aq)
(b) Hg2+(aq) + 4CN-(aq) Hg(CN)42-(aq)

2. Classify each of the following species as a Bronsted acid, base or both:

- + + - 2-
H2O, OH , H3O , NH3, NH4 , NH2 , CO3 , HBr, HCN

3. Identify the acid-base conjugate pairs in each of the following reactions:

- -
(a) CH3COO + HCN CH3COOH + CN
- - 2-
(b) HCO3 + HCO3 H2CO3 + CO3
- 2- +
(c) H2PO4 + NH3 HPO4 + NH4
+ -
(d) HClO + CH3NH2 CH3NH3 + ClO

4. The concentration of OH- in a certain household ammonia cleaning solution is 0.0025

+
M. Calculate the concentration of H ions.

5. Indicate whether the following solutions are acidic, basic or neutral:

(a) 0.62 M NaOH
-3
(b) 1.4 x 10 M HCl
(c) 2.5 x 10-11 M H+
-10 -
(d) 3.3 x 10 M OH

6. The concentration of H+ ions in a bottle of vinegar was 3.2 x 10-4 M right after the cork
was removed. Only half of the vinegar was consumed. The other half, after it had been
open in the air for a month, was found to have a hydrogen ion concentration of 1.0 x 10-
3
M. Calculate the pH of the vinegar on these two occasions.

-1 0 -5
7. Calculate the pH of a 0.027 mol L solution of propionic acid at 25 C. (Ka = 1.3 x 10 )

8. How much NaOH (in grams) is needed to prepare 500 mL of solution with a pH of
10.00?

9. Calculate the concentration of H+ ions if the pOH of the solution is 9.40.

10. The pH of a 0.100 M solution of a weak acid HA is 2.85. What is the Ka of the acid?

51
11. Calculate the percentage of ionization for 0.60 M hydroflouric acid solution? (Ka HF
-4
= 7.1 x 10 )

12. What is the pH of a 0.40 M ammonia solution? (Kb NH3 = 1.8 x 10-5)

13. Calculate the pH and percentage of hydrolysis

(a) 0.15 M solution sodium acetate
-10
(b) 0.10 M NH4Cl solution ( Kh = 5.6 x 10 )

14. Calculate the pH of a solution containing 0.20 M CH 3COOH and 0.30 M

CH3COONa. What would be the pH of the 0.20 M CH3COOH solution if there was
-5
no salt present? ( Ka CH3COOH = 1.8 x 10 )

15. Calculate the pH of the 0.30 M NH3/0.36 M NH4Cl buffer system. What would the pH
be after the addition of 20.00 mL of 0.050 M NaOH to 80 mL of the buffer solution?

16. In the titration of 25.0 mL of 0.100 M acetic acid with sodium hydroxide, calculate the
pH after the addition of: (Ka = 1.8 x 10-5)
(a) 10.00 mL of 0.100 M NaOH
(b) 25.00 mL of 0.100 M NaOH
(c) 35.00 mL of 0.100 M NaOH
(d) to the acid solution. ( Kh = 5.6 x 10-10 )

17. In the titration of 25.0 mL of 0.100 M HCl with ammonia, calculate the pH after adding:
(a) 10.0 mL of 0.100 M NH3
(b) 25.0 mL of 0.100 M NH3
(c) 35.0 mL of 0.100 M NH3
-10
to the acid solution. ( Kh = 5.6 x 10 )

-2
18. The solubility of silver sulphate is 1.5 x 10 mol/L. Calculate the solubility product of
the salt.

19. It was found experimentally that the solubility of calcium sulphate is 0.67 g/L. Calculate
the Ksp for calcium sulphate.

20. Will precipitate form if 200 mL of 0.0040 M BaCl2 are added to 600 mL of 0.0080 M
K2SO4? ( Ksp BaSO4 = 1.1 x 10-10 )

52
STPM Past Year Questions
Q6-P2-2003
a) Ethanoic acid is an example of a weak acid.
i) Describe the properties of ethanoic acid as a Bronsted-Lowry
acid
ii) Describe the use of ethanoic acid in the preparation of a
buffer solution.
b) Phenolphthalein, HPh, is an acid-base indicator with a pH range
between 8.2 and 9.8. The equilibrium equation of
phenolphthalein in aqueous state is as follows:
+ −
HPh(aq) + H2O(l) H3O (aq) + Ph (aq)
Explain how phenolphthalein acts in acid-base titration.
3 -3
c) A solution is prepared by mixing 250.0 cm 0.05 mol dm
3 -3
nitric acid with 250.0 cm 0.05 mol dm calcium hydroxide
solution. Calculate the pH of the solution.

Q5-P2-2002
a) Boric acid, B(OH)3, is an antiseptic found in some eyewash.
In aqueous state, boric acid acts as a Lewis acid.
i) Define Lewis acid.
ii) Explain the acidic property of aqueous boric acid.
b) Phenol, C6H5OH, is a weak organic acid. A solution containing
3 o
0.385 g of phenol in 2.00 dm of water has a pH of 6.29 at 25 C.
i) Explain why phenol is a weak organic acid.
ii) Calculate the acid dissociation constant, Ka, of phenol
o
at 25 C.

53