Calculation of Ionization Constants

In a 0.12 M solution, a weak monoprotic acid, HY,

is 5.0% ionized. Calculate the ionization constant
for the weak acid.

HY H + Y
+ -

Ka =
[ H ][Y ]+ -

[H Y ]
Calculation of Ionization Constants
Since the weak acid is 5.0% ionized, it is also 95%
unionized.
Calculate the concentrations of all species in
solution.

[H ] = [Y ] = 0.05(0.12M ) = 0.0060M
+

3
= 6.0 10 M
[HY ] = 0.95(0.12M ) = 0.114M
Calculation of Ionization Constants
Substitute into the ionization constant expression
to get the value of Ka

Ka =
[H ][Y ]
+

[HY ]
=
(6.0 10 )(6.0 10 )
3 3

(0.114)
4
= 3.2 10
Calculation of Ionization Constants
The pH of a 0.10 M solution of a weak monoprotic
acid, HA, is found to be 2.97. What is the value
for its ionization constant?
pH = 2.97 so [H+]= 10-pH

[ H O ] = 10
3
+ 2.97

3
= 11
. 10 M
Calculation of Ionization Constants
Use the [H3O+] and the ionization reaction to
determine concentrations of all species.
HA H +
+ A -

(
Equil. [ ]' s 0.10 - 1.1 10 -3
) 1.110 -3
1.110 -3

0.10

Ka =
[H ][A ] (1.110 )(1.1 10 )
+
=
-3 -3

[HA] (0.10)
5
K a = 1.2 10
 Calculation of Ionization Constants
Calculate the concentrations of the various species in a
0.15 M acetic acid, CH3COOH, solution.
It is always a good idea to write down the ionization
reaction and the ionization constant expression.
+
CH 3COOH + H 2 O H 3O + CH 3COO -

Ka =
[H O ][CH COO ]
3
+
= 1.8 10
3
-
5

[CH 3COOH]
 Calculation of Ionization Constants
Calculate the concentrations of the various species in a
0.15 M acetic acid, CH3COOH, solution.
Next we combine the basic chemical concepts with some
algebra to solve the problem

CH 3 COOH + H 2 O
H 3 O + + CH 3 COO -
Initial [ ] 0.15M 0M 0M
Change - xM + xM + xM
Equilibriu m [ ] (0.15 - x)M + xM + xM
Calculation of Ionization Constants

Substitute these algebraic quantities into the

ionization expression.

Ka =
[H O ][CH COO ]
3
+
3

[CH 3COOH ]
=
( x )( x )
= 1.8 10 5

(0.15 x )
Calculation of Ionization Constants
Solve the algebraic equation, using a simplifying assumption or
using the quadratic.
2
x 5
= 1.8 10
0.15 x
x = (0.15 x)1.8 10
2 5

5 6
x + 1 . 8 10
2
x 2 . 7 10 =0
a b c
b b 4ac
2
x=
2a
Calculation of Ionization Constants

x=
(
1.8 10 5
) (1.8 10 )
5 2
(
4(1) 2.7 10 6
)
2(1)
3
x = 1.6 10 and - 1.6 10 -3

Pick the algebraic answer that makes chemical sense.

[H3O+] = x = 1.6 x 10-3
Calculation of Ionization Constants
Solve the algebraic equation, using simplifying
assumption. x may be small enough to ignore . . .
Sometimes called the 5% rule . .
2
x
= 1 . 8 10 5
0 . 15 x

0 . 0016
0 . 15 0 . 0016 = 0 . 1484 x100 = 1 % < 5 %
0 . 15

x = (0 . 15 x )1 . 8 10
2 5
x (0 . 15 )1 . 8 10
2 5
 Calculation of Ionization Constants
Complete the algebra and solve for concentrations.
5
x 0.15 1.8 10
2

6
x 2.7 10
3
[ +
x = 1.6 10 M = H 3O = CH 3COO ] [
]
[CH 3COOH ] = (0.15 1.6 10 )M 0.15M
3
Calculation of Ionization Constants
Calculate the percent ionization for the 0.15 M
acetic acid.

% ionization =
[ CH3COOH]ionized
100%
[CH3COOH]original
3
. 10 M
16
= 100% = 11%
.
. M
015
Calculation of Ionization Constants

Calculate the concentrations of the species in

0.15 M hydrocyanic acid, HCN, solution.
Ka = 4.0 x 10-10 for HCN

You do it!
Calculation of Ionization Constants
HCN + H2 O
H3 O + + CN-
Initial[ ] 0.15 M
Change - xM + xM + xM
Equilibrium (0.15 - x )M xM xM

Ka =
[H ][CN ]
+
=

(x )(x ) = 4.0 10 10
[HCN] 0.15 x
x 2 = 6.0 10 11
[ ] [
x = 7.7 10 6 M = H + = CN ]
[HCN] = (0.15 x )M 0.15M
Calculation of Ionization Constants
The percent ionization of 0.15 M HCN solution is
calculated as in the previous example.

% ionization =
[ HCN]ionized 100%
[ HCN]original
6
. 10 M
77
= 100% = 00051%
.
015
. M
Calculation of Ionization Constants
All of the calculations and understanding we have at present can be
applied to weak acids and weak bases!
One example of a weak base ionization is ammonia ionizing in water.
Calculate the % Ionization and the pH

+
NH3 + H2O NH + OH 4
-
K b = 1.8 10 -5
 Determining pH from Kb and Initial [B]I
Problem: Ammonia is commonly used cleaning agent in households and
is a weak base, with a Kb of 1.8 x 10-5. What is the pH of a 1.5 M NH3
Solution and percent ionization?
Plan: Ammonia reacts with water to form [OH-] , calculate [H3O+] and
the pH. The balanced equation and Kb expression are:
NH3 (aq) + H2O(l) NH4+(aq) + OH-(aq)
[NH4+] [OH-]
Kb =
[NH3]
Concentration (M) NH3 H2O NH4+ OH-
Initial 1.5 ---- 0 0
Change -x ---- +x +x
Equilibrium 1.5 - x ---- x x
making the assumption: since Kb is small: 1.5 M - x = 1.5 M
 Determining pH from Kb and Initial [B]II
Substituting into the Kb expression and solving for x:

[NH4+] [OH-] (x)(x)

Kb = = = 1.8 x 10-5
[NH3] 1.5
x2 = 2.7 x 10-5 = 27 x 10-6
x = 5.20 x 10-3 = [OH-] = [NH4+]
Calculating pH:
Kw 1.0 x 10-14
[H3O+] = = = 1.92 x 10-12
[OH-] 5.20 x 10-3

pH = -log[H3O+] = - log (1.92 x 10-12) = 12.000 - 0.283

pH = 11.72
 Calculation of Ionization Constants
Calculate the percent ionization for weak bases
exactly as we did for weak acids.

% ionization =
[OH ] = 5.2 10 M
- -3
[NH 3 ]ionized 100%
pOH = -log [5.2 10 ] = 2.28
-3
[NH 3 ]original
pK w = pH + pOH 3
5.2 10 M
= 100%
pH =14 - 2.28 = 11.72 1.5 M
= 0.35%
Calculation of Ionization Constants
The pH of an aqueous ammonia solution is
11.37. Calculate the molarity (original
concentration) of the aqueous ammonia
solution.
You do it!
Calculation of Ionization Constants
+
NH 3 + H 2 O NH 4 + OH

pH = 11.37; pH + pOH = 14.00

pOH = 2.63
[OH ] = 10 = 10 = 2.3 10
- pH 2.63 3
M
[NH ] = 2.3 10 M
+
4
3
Calculation of Ionization Constants
Use the ionization equation and some algebra to
get the equilibrium concentration.
NH + + OH -
NH 3 + H 2 O 4

Initial[ ] xM
Change - 2.3 10 -3 + 2.3 10-3 + 2.3 10-3
( )
Equilibrium[ ] x - 2.3 10-3 M + 2.3 10-3 + 2.3 10-3
Calculation of Ionization Constants
Substitute into the ionization constant expression.

Kb =
[NH ][OH ]+
4

= 1.8 10 5

[NH3 ]
1.8 10 5
=
(2.310 )(2.310 )
3 3

(x 2.310 ) 3
Calculation of Ionization Constants
Examination of the equation suggests that
(x-2.3x10-3)x. Making this assumption
simplifies the calculation and gives

(2.3 10 ) 3 2
= 1.8 10 5

x
x = 0.30 M NH 3
 The Relation Between Ka and Kb of a Conjugate
Acid-Base Pair

Acid HA + H2O H 3 O+ + A-

Base A- + H2O HA + OH-

2 H2 O H3O+ + OH-

[H3O+] [A-] [HA] [OH-]

[H3O+] [OH-] = x
[HA] [A-]

Kw = Ka x Kb

Ka = 4.5 x 10-4
For HNO2 Ka x Kb = (4.5 x 10-4)(2.2 x 10-11) = 9.9 x 10-15
Kb = 2.2 x 10-11 or ~ 10 x 10-15 = 1 x 10 -14 = Kw
 The Relation Between Ka and Kb of a
Conjugate Acid-Base Pair

Calculate the Kb for the anions of a weak acids.

F-, fluoride ion, the anion of hydrofluoric acid, HF.
For HF, Ka=7.2 x 10-4.
F + H 2 O
HF + OH
[ HF][OH
]= Kw
Kb =
[F ]

Ka for HF
. 1014
10 11
Kb = 4 = 14
. 10
7.2 10
 The Stepwise Dissociation of Phosphoric Acid
Phosphoric acid is a weak acid, and normally only looses one proton
in solution, but it will loose all three when reacted with a strong base
with heat. The ionization constants are given for comparison.

H3PO4 (aq) + H2O(l) H2PO4-(aq) + H3O+(aq)

H2PO4-(aq) + H2O(l) HPO42-(aq) + H3O+(aq)

HPO42-(aq) + H2O(l) PO43-(aq) + H3O+(aq)

H3PO4 (aq) + 3 H2O(l) PO43-(aq) + 3 H3O+(aq)

 Polyprotic Acids
Many weak acids contain two or more acidic hydrogens.
polyprotic acids ionize stepwise

ionization constant for each step

Consider arsenic acid, H3AsO4, which has three ionization

constants
1 Ka1=2.510-4

2 Ka2=5.610-8

3 Ka3=3.010-13
 Polyprotic Acids
Arsenic Acid
The first ionization step is

+
H3 AsO 4 H + H2 AsO 4

K a1 =
[H ][H AsO ]
+
2

= 2.5 10
4 4

[H3 AsO 4 ]
 Polyprotic Acids
The second ionization step is

+ 2
H 2 AsO H + HAsO
-
4 4

=
[H ][HAsO ]
+
= 5.6 10
2
8

[H AsO ]
4
K a2 2-
2 4
 Polyprotic Acids

The third ionization step is

+ 3
HAsO H + AsO
2-
4 4

=
[H ][AsO ]
+
= 3.0 10
3
13

[HAsO ]
4
K a3 2-
4
 Polyprotic Acids

Notice that the ionization constants vary in the following

fashion:

K a1 > K a2 > K a3
This is a general relationship.
 Polyprotic Acids
Calculate the concentration of all species in 0.100 M
arsenic acid, H3AsO4, solution.
1 Write the first ionization ionization step and represent
the concentrations.

+
H 3 AsO 4 H + H 2 AsO 4
(0.100 x )M xM xM
 Polyprotic Acids
2 Substitute into the expression for K1.

K a1 =
[H ][H AsO ]
+
2

= 2.5 10
4 4

[H 3AsO4 ]
K a1 =
( x )( x )
= 2.5 10 4
(0.10 x )
x 2 + 2.5 10 4 x 2.5 10 5 = 0
simplifying assumption does not apply
 Polyprotic Acids

Use the quadratic equation to solve for x, and

obtain two values

x=
4
2.5 10 (2.5 10 )
4 2
(
4(1) 2.5 10 5 )
2(1)
x = 5.110 3 M and x = 4.9 10 3 M
[H ] = [H AsO ] = xM = 4.9 10
+
2

4
3
M
[H 3AsO4 ] = (0.100 x )M = 0.095M
 Polyprotic Acids
4 Now we write the equation for the second step
ionization and represent the concentrations.

H 2 AsO -4 H+ + HAsO 24-

from 1st step 4.9 10 -3 M 4.9 10 -3 M
change yM + yM + yM
equilibriu m (4.9 10 -3 - y ) M (4.9 10 -3 + y ) M yM
 Polyprotic Acids
5 Substitute into the second step ionization
expression.

[H O ][HAsO ]
+ 2

[H AsO ]
8
K a2 = 3

= 5.6 10
4

( 4.9 10 + y )( y )
2 4
-3
K a2 =
(4.9 10 y )
-3

apply assumption
 Polyprotic Acids

(4.9 10 )( y )
-3
= 5.6 10 8
K =
a2
(4.9 10 ) -3

y = 5.6 10 M = [H ] = [HAsO ]
8 +
2nd
2
4

note [H ] >> [H ]
+
1st
+
2nd
 Polyprotic Acids
6 Now we repeat the procedure for the third
ionization step.

HAsO 24 H+ + AsO 34
(
1st and 2nd ionizations 5.6 10 -8 M ) (4.9 10 -3
+ 5.6 10 -8 M )
change zM + zM + zM
equilibrium (5.6 10 8 z ) M (4.9 10 3 + 5.6 10 8 + z ) M zM
 Polyprotic Acids
7 Substitute into the third ionization expression.

[H O ][AsO ]
+ 3
= 3.0 10 13

[HAsO ]
3 4
K a3 = 2
4

(4.9 10 + 5.6 10 + z )( z )
3 8
K a3 =
(5.6 10 z ) 8

apply assumption
 Polyprotic Acids

(4.9 10 )(z ) = 3.0 10

3
13

(5.6 10 )
8

[z ] = 3.4 10 M = [H ]
18 +
3rd [
= AsO 3
4 ]
 Polyprotic Acids
Use Kw to calculate the [OH-] in the 0.100 M
H3AsO4 solution.

[H ][OH ] = 10. 10
+ 14

14 14
. 10 . 10
[OH ] = [ H ] = 4.9 10
10 10
+ 3

[OH ] = 2.0 10
12
M
 Polyprotic Acids
A comparison of the various species in 0.100 M
H3AsO4 solution follows.

Species Concentration
H3AsO4 0.095 M
H+ 0.0049 M
H2AsO4- 0.0049 M
2- -8
HAsO4 5.6 x 10 M
3- -18
AsO4 3.4 x 10 M
- -12
OH 2.0 x 10 M
 Hydrolysis
Hydrolysis refers to the reaction of a
substance with water or its ions.

+
NaA Na + A

what does A do next ?

A + H 2 O HA + OH
Note the basicity of the solution
 Hydrolysis
The conjugate base of a strong acid is a very weak base.
The conjugate base of a weak acid is a stronger base.
Hydrochloric acid, a typical strong acid, is essentially
completely ionized in dilute aqueous solutions.

+
HCl + H 2 O H 3O + Cl ~100%

+
HF + H 2 O H 3O + F -

+
NaA Na + A
 Hydrolysis

The conjugate base of HCl, the Cl- ion, is a very weak base.

True of all strong acids and their anions.

Cl + H 3O + No rxn. in dilute aqueous solutions

 Hydrolysis
HF, a weak acid, is only slightly ionized in dilute aqueous solutions.
Its conjugate base, the F- ion, is a much stronger base than the Cl- ion.
F- ions combine with H3O+ ions to form nonionized HF.

HF + H 2 O
H 3O + + F-
only slightly
F- + H 3O +

HF + H 2 O
nearly completely
 Hydrolysis

Dilute aqueous solutions of salts that contain

no free acid or base come in four types:
1 Salts of strong acids and strong bases
2 Salts of weak acids and strong bases
3 Salts of strong acids and weak bases
4 Salts of weak acids and weak bases
Salts of Strong Bases and Strong Acids
Salts made from strong acids and strong bases
form neutral aqueous solutions.
An example is potassium nitrate, KNO3, made
from nitric acid and potassium hydroxide.

KNO3 ( s ) ~ K + + NO 3
100% in H 2 O

H 2 O + H 2 O OH - + H 3O +
+
dissolution does not produce H 3O or OH neutral
-
Salts of Strong Bases and Weak Acids
Salts made from strong bases and weak acids hydrolyze to
form basic solutions.
Anions of weak acids (strong conjugate bases) react with

water to form hydroxide ions

An example is sodium hypochlorite, NaClO, made from
sodium hydroxide and hypochlorous acid.

+
NaClO( s )
Na + ClO
~100% in H 2 O -

H 2O + H 2O OH + H 3O- +

+
ClO + H 3 O HClO + H 2 O
-
Salts of Strong Bases and Weak Acids

NaClO( s ) ~ Na + + ClO -
100% in H 2 O

H 2O + H 2O OH - + H 3O +
ClO - + H 3O + HClO + H 2 O

Combine these equations into one single equation

that represents the reaction:

ClO + H 2 O HClO + OH
-
Salts of Strong Bases and Weak Acids
Calculate [OH-], pH and percent hydrolysis for the
hypochlorite ion in 0.10 M sodium hypochlorite,
NaClO, solution.

+ +
Na ClO
Na ~100%inH 2 O
+ ClO
0.10 M 0.10 M 0.10 M
Salts of Strong Bases and Weak Acids
Set up the equation for the hydrolysis and the algebraic
representations of the equilibrium concentrations.

-
ClO + H2O HClO + OH-

Initial: 0.10 M 0M 0M
Change: - xM + xM + xM
At equil: (0.10- x) M xM xM
Salts of Strong Bases and Weak Acids
Substitute the algebraic expressions into the
hydrolysis constant expression.

[HClO] [OH
] = 2.9 10 7
=
Kb
[ClO ]
Salts of Strong Bases and Weak Acids

Substitute the algebraic expressions into the

hydrolysis constant expression.

Kb =
( x )( x )
= 2.9 10 7
(010
. x)
Salts of Strong Bases and Weak Acids

Substitute the algebraic expressions into the

hydrolysis constant expression.

Kb =
(x )(x ) = 2 .9 10 7

(0.10 x )
8
x = 2 .9 10 ; x = 1 .7 10 M
2 4
= [HClO ] = [OH ]

pOH = 3.77; pH = 10.23

Salts of Strong Bases and Weak Acids

The percent hydrolysis for the hypochlorite ion

may be represented as:

[ ClO- ]hydrolyzed
100%
[ClO ]
% hydrolysis = -
original

1.7 10-4 M
% hydrolysis = 100% = 017%
.
0.10 M
Salts of Weak Bases and Strong Acids
Salts made from weak bases and strong acids form
acidic aqueous solutions.
An example is ammonium bromide, NH4Br, made
from ammonia and hydrobromic acid.

+ +
NH Br
4
-
(s )
H 2 O ~100%
NH 4 + Br -

H 2O + H 2O
OH - + H 3O +
+ -
NH 4 + OH NH 3 + H 2 O
+
generates excess H 3O solution is acidic
Salts of Weak Bases and Strong Acids
The reaction may be more simply represented as:

+
NH + H 2 O
NH 3 + H 3O +
4

Or even more simply as:

NH
+
NH 3 + H +
4
Salts of Weak Bases and Weak Acids
If Parent Kbase > Kacid
make basic solutions

An example is ammonium hypochlorite, NH4ClO, made

from aqueous ammonia, NH3,and hypochlorous acid,
HClO.
Kb for NH3 = 1.8x10-5
Ka for HClO = 3.5x10-8
Salts of Weak Bases and Weak Acids

Because the Kb for ClO- ions is three orders

of magnitude larger than the Ka for NH4+
ions, OH- ions are produced in excess
solution is basic

63
Salts of Weak Bases and Weak Acids
If Parent Kbase < Kacid
make acidic solutions

An example is trimethylammonium
fluoride,(CH3)3NHF, made from trimethylamine,
(CH3)3N,and hydrofluoric acid acid, HF.
Kb for (CH3)3N = 7.4x10-5
Ka for HF = 7.2x10-4
Salts of Weak Bases and Weak Acids

Because the Ka for (CH3)3NH+ ions is one

order of magnitude larger than the Kb for F-
ions, H+ ions are produced in excess.
solution is acidic
 End-of-Chapter Exercises
5, 8, 9, 14, 17, 21, 24, 31, 33, 45, 52, 57, 59, 60, 67, 68