Ionic Equilibrium

Electrolytes
Substances which on dissolution, even at moderate
dilution, ionize almost completely

Strong electrolytes.
Example:- HCl,HNO3,NaOH,NaCl,CaCl2 etc
HCl H+ + ClSubstances which on dissolution in water, dissociate to
a little extent
Weak electrolytes
Example:CH3COOH, NH4OH, AgCl etc
CH3COOH + HOH H3O- + CH3COO-

Concepts of acids/bases
1. Arrhenius concept:
Acids- substance furnishes H+ ions in aqueous solution
Bases - produce OH ions in aqueous solution

Example: HCl, H2SO4 , Mg(OH)2 , KOH etc

Concepts of acids/bases
2. Bronsted-Lowry concept:
Acid - donates proton (H+) to other substance
Base - can accept proton from an acid.
For example,
NH3 H2 O

Base

Acid

NH4

conjugate
Acid

OH
conjugate
Base

The stronger an acid weaker will be its conjugate base

and vice versa.

Concepts of acids/bases
3. Lewis concept:
Acid - can accept at least a pair of electrons
(electron deficient)
Base - can donate at least one pair of electrons to
form a coordinate bond.

For example,
..

N H3 + BF3
H3N : BF3

Here, NH3 is a Lewis base and BF3 is a Lewis acid.

The pH scale

Strong Acid/Bases
STRONG ACIDS
HI
HBr
HClO4
HCl
HClO3
H2SO4
HNO3

STRONG BASES
NaOH
KOH
LiOH
RbOH
CsOH
Ca(OH)2
Ba(OH)2
Sr(OH)2

The pH scale
pH = log [H+]
and pOH = log[OH ]
For an acid solution [H+] > 107.

For a basic solution [H+] < 107.

Also pH + pOH = 14 at 25oC

Dissociation of water
Pure water is very weak electrolyte and dissociates
to a small extent as
H2O H+ + OH[H ] [OH ]
K
H2O

Since the degree of dissociation of

water () is very small.

Kw = [H+] . [OH- ] where Kw = ionic product of water.

Kw= 1 1014 mol2 L2 at 25 C

Since the dissociation of water is endothermic process, the value of Kw increases
with temperature.

Sample Problems
Find the pH of the following strong solutions.
1. 2 X 102 M H2SO4
Solution:
(1)

H 2 102 M

2. 2 X 104 M Ca(OH)2

pH = log [H+]
pH = log 2 102
= 1.69
(2)

OH 2 104 M

Kw = [H+] . [OH- ]

1014

H
2 104

= 5 1011

H2SO4 2H SO24

+]

pH = log(5 1011)
= 5 1011

= 11 log5
= 10.3

Ka - acid dissociation constant or acid ionization constant.

Example:
CH3COOH(aq) +HOH(l) H3O+ (aq)+ CH3COO-(aq)

Kb - base dissociation constant or base ionization constant.

Example:

NH3(aq) + H2O(l) NH4+(aq) + OH-(aq)

DEGREE OF DISSOCIATION AND PERCENT

DISSOCIATION (OR IONIZATION).

degree of dissociation() - the fraction of molecules

that react with water to give ions.

=
%dissociation( %) is also the degree of
dissociation express in percentage

x 100

The larger the Ka the greater the

degree of dissociation (the greater the
% dissociation). The stronger the acid
the greater the % ionization.
As the original concentration
decreases the percent dissociation
increases.

HOW CAN WE FIND Ka's?

The most common way to obtain a Ka is to measure
the pH of a solution prepared by dissolving a known
amount of weak acid to form a given volume of
solution.
example:

The pH of a 0.10 M solution of HOCl is 4.23. What is

the value of Ka?

Calculation of the Concentration of Species in a Weak Acid

Solution Using Ka - THE APPROXIMATE METHOD

Example:
What are the concentrations of all species in a
0.10 M of acetic acid (CH3COOH)? What is the pH
of the solution? Ka for acetic acid is 1.7 X 10-5.

You will need a balanced equation and a chart.

CH3COOH + H2O H3O+ + CH3COO-

Then we put the results of the chart into the equation for
Ka.

To avoid using the quadratic equation and focus more

attention on what is happening chemically, we THINK AS
FOLLOWS: Since Ka is so small, x can be ASSUMED to be
much less than 0.10. That makes 0.10 - x = 0.10. Then we
don't have to use the quadratic equation to obtain x.

The above expression for Ka becomes:

BUT YOU will have to check your assumption:

To check if the assumption is ok, we will use the 5%
rule as given in the text. How do we calculate the 5%?

Another check to see if the assumption is ok is to

check to see if the precision rule allows you drop the
x. In the above case: 0.10 - 0.0013 = 0.10 (The
answer can only be reported to hundredths.)

The answer to the question then includes the

following:
[CH3COOH] = 0.10 M

[H2O] = 55.5 M
[H3O+] = 1.3 X 10-3 M

[CH3COO-] = 1.3 X 10-3 M

And there is one more species in the solution. What is
it and what is its concentration?

To answer the question, we still have to

calculate the pH.
pH = - log 1.3 x 10-3 = 2.89

Calculate the [H3O+] in a 0.100 M solution of nitrous

acid, HNO2, for which the Ka is 4.5 X 10-4.
You will need an equation and a chart.

HNO2+ +H2O H3O+ + NO2-

Now we have to see if the assumption is ok!!

0.100 - 0.0067 gives an answer to three digits
(0.093) so that indicates the approximation is not
appropriate for this problem.

Also, IF YOU TAKE:

You cannot use the approximate method, you must

use the quadratic equation.
What answer do we obtain with the quadratic
equation?

Problem

1. The pH of 0.03M solution of benzoic acid(HC7H5O2) is. 2.96.

Compute the ionization constant and %dissociation.
HC7H5O2 H+ + C7H5O22. Calculate the pH and % ionization of 0.5M formic acid
HCHO2 H+ + CHO2-