CH 17 3-15 Acid-Base Calculations

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
K
H Y
HY
+ -
a
+ -
=
Since the weak acid is 5.0% ionized, it is also 95%
unionized.
Calculate the concentrations of all species in
solution.
| | | |
| | M M
M
M M
114 . 0 ) 12 . 0 ( 95 . 0
10 0 . 6
0060 . 0 ) 12 . 0 ( 05 . 0
3
= =
=
= = =
HY
Y H
+
Substitute into the ionization constant expression
to get the value of K
a

| || |
| |
( ) ( )
( )
4
3 3
10 2 . 3
114 . 0
10 0 . 6 10 0 . 6

+
=

=
=

HY
Y H
K
a
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
3
+
=
=
10
11 10
2 97
3
.
. M
Use the [H
3
O
+
] and the ionization reaction to
determine concentrations of all species.
( )
| || |
| |
( )( )
( )
5
a
3 - 3 -
a
3 - 3 - 3 -
- +
10 2 . 1 K
0.10
10 1.1 10 1.1
HA
A H
K
0.10
10 1.1 10 1.1 10 1.1 - 0.10 s ]' [ Equil.
A H HA
+
=

= =
~

+
Calculate the concentrations of the various species in a
0.15 M acetic acid, CH
3
COOH, solution.
It is always a good idea to write down the ionization
reaction and the ionization constant expression.
| || |
| |
5
3
-
3 3
a
-
3 3 2 3
10 8 . 1
COOH CH
COO CH O H
K
COO CH O H O H COOH CH
+
+
= =
+
+
Calculate the concentrations of the various species in a
0.15 M acetic acid, CH
3
COOH, solution.
Next we combine the basic chemical concepts with some
algebra to solve the problem
xM xM x)M - (0.15 ] [ m Equilibriu
xM xM xM - Change
M 0 0M 0.15M ] [ Initial
COO CH O H O H COOH CH
-
3 3 2 3
+ +
+ +
+
+
+
Substitute these algebraic quantities into the
ionization expression.
| || |
| |
( )( )
( )
5
3
3 3
a
10 8 . 1
15 . 0
COOH CH
COO CH O H
K
+
=
=
=
x
x x
Solve the algebraic equation, using a simplifying assumption or
using the quadratic.
( )
5 2
5
2
10 8 . 1 15 . 0
10 8 . 1
15 . 0
=
=
x x
x
x
2a
4ac b b
c b a
0 10 7 . 2 10 8 . 1
2
6 5 2

=
= +

x
x x
( ) ( ) ( )( )
( )
3 - 3
6
2
5 5
10 1.6 - and 10 6 . 1
1 2
10 7 . 2 1 4 10 8 . 1 10 8 . 1
=

=

x
x
Pick the algebraic answer that makes chemical sense.
[H
3
O
+
] = x = 1.6 x 10
-3

Solve the algebraic equation, using simplifying
assumption. x may be small enough to ignore . . .
Sometimes called the 5% rule . .

( ) ( )
5 2 5 2
5
2
10 8 . 1 15 . 0 10 8 . 1 15 . 0
% 5 % 1 100
15 . 0
0016 . 0
1484 . 0 0016 . 0 15 . 0
10 8 . 1
15 . 0

~ =
< = =
=
x x x
x
x
x
Complete the algebra and solve for concentrations.
| | | |
| | ( ) M M
M x
x
x
15 . 0 10 6 . 1 15 . 0 COOH CH
COO CH O H 10 6 . 1
10 7 . 2
10 8 . 1 15 . 0
3
3
3 3
3
6
5 2
~ =
= = =
~
~

Calculate the percent ionization for the 0.15 M
acetic acid.
| |
| |
%
.
.
.
ionization =
CH COOH
CH COOH
3
ionized
3
original

=

=
100%
16 10
015
100% 11%
3
M
M
Calculate the concentrations of the species in
0.15 M hydrocyanic acid, HCN, solution.
K
a
= 4.0 x 10
-10
for HCN

You do it!
| |
( )
| || |
| |
( )( )
| | | |
| | ( ) M M x
M x
x
x
x x
xM xM M x
xM xM xM
M
15 . 0 15 . 0
10 7 . 7
10 0 . 6
10 0 . 4
15 . 0
6
11 2
10
~ =
= = =
=
=
= =
+
+
+
+
+
HCN
CN H
HCN
CN H
K
- 0.15 m Equilibriu
+ + - Change
0.15 Initial
CN O H O H HCN
a
-
3 2
The percent ionization of 0.15 M HCN solution is
calculated as in the previous example.
| |
| |
%
.
.
.
ionization =
HCN
HCN
ionized
original

=

=
100%
7 7 10
015
100% 0 0051%
6
M
M
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
-5
b
-
4 2 3
10 1.8 K OH NH O H NH = + +
+
Determining pH from K
b
and Initial [B]I
Problem: Ammonia is commonly used cleaning agent in households and
is a weak base, with a K
b
of 1.8 x 10
-5
. What is the pH of a 1.5 M NH
3
Solution and percent ionization?
Plan: Ammonia reacts with water to form [OH
-
] , calculate [H
3
O
+
] and
the pH. The balanced equation and K
b
expression are:
NH
3 (aq)
+ H
2
O
(l)
NH
4
+
(aq)
+ OH
-
(aq)
K
b
=
[NH
4
+
] [OH
-
]
[NH
3
]
Concentration (M) NH
3
H
2
O NH
4
+
OH
-
Initial 1.5 ---- 0 0
Change -x ---- +x +x
Equilibrium 1.5 - x ---- x x
making the assumption: since K
b
is small: 1.5 M - x = 1.5 M
Determining pH from K
b
and Initial [B]II
Substituting into the K
b
expression and solving for x:
K
b
= = = 1.8 x 10
-5
[NH
4
+
] [OH
-
]
[NH
3
]
(x)(x)
1.5
x
2
= 2.7 x 10
-5
= 27 x 10
-6
x = 5.20 x 10
-3
= [OH
-
] = [NH
4
+
]
Calculating pH:
[H
3
O
+
] = = = 1.92 x 10
-12
K
w
[OH
-
]
1.0 x 10
-14
5.20 x 10
-3
pH = -log[H
3
O
+
] = - log (1.92 x 10
-12
) = 12.000 - 0.283
pH = 11.72
Calculate the percent ionization for weak bases
exactly as we did for weak acids.
| |
| |
% 35 . 0
% 100
5 . 1
10 2 . 5
% 100
NH
NH
ionization %
3
original
3
ionized
3
=
M
M
| |
| |
11.72 2.28 - 4 1 pH
pOH pH pK
28 . 2 10 5.2 -log pOH
10 5.2 OH
w
3 -
-3 -
= =
+ =
= =
= M
The pH of an aqueous ammonia solution is
11.37. Calculate the molarity (original
concentration) of the aqueous ammonia
solution.
You do it!
| |
| | M
M
3
4
3 63 . 2 pH -
4 2 3
10 3 . 2 NH
10 3 . 2 10 10 OH
2.63 = pOH
14.00 = pOH + pH 11.37; = pH
OH NH O H NH
+

=
= = =

+ +
Use the ionization equation and some algebra to
get the equilibrium concentration.
( )
3 - 3 - 3 -
3 - 3 - 3 -
-
4 2 3
10 2.3 + 10 2.3 + 10 2.3 - ] m[ Equilibriu
10 2.3 + 10 2.3 + 10 2.3 - Change
] Initial[
OH NH O H NH

+
+
+
M x
xM
Substitute into the ionization constant expression.
| || |
| |
( )( )
( )
3
3 3
5
5
3
4
b
10 3 . 2
10 3 . 2 10 3 . 2
10 8 . 1
10 8 . 1
NH
OH NH
K
+

=
= =
x
Examination of the equation suggests that
(x-2.3x10
-3
)~x. Making this assumption
simplifies the calculation and gives
( )
3
5
2
3
NH 30 . 0
10 8 . 1
10 3 . 2
M x
x
=
=

The Relation Between K
a
and K
b
of a Conjugate
Acid-Base Pair
Acid HA + H
2
O H
3
O
+
+ A
-
Base A
-
+ H
2
O HA + OH
-
2 H
2
O H
3
O
+
+ OH
-
[H
3
O
+
] [OH
-
] = x
[H
3
O
+
] [A
-
]
[HA]
[HA] [OH
-
]
[A
-
]
K
w
= K
a
x K
b
For HNO
2
K
a
= 4.5 x 10
-4
K
b
= 2.2 x 10
-11
K
a
x K
b
= (4.5 x 10
-4
)(2.2 x 10
-11
) = 9.9 x 10
-15
or ~ 10 x 10
-15
= 1 x 10
-14
= K
w
Calculate the K
b
for the anions of a weak acids.
F
-
, fluoride ion, the anion of hydrofluoric acid, HF.
For HF, K
a
=7.2 x 10
-4
.
| |
| |
| |
F H O HF OH
K
HF OH
F
K
K
K
2
b
w
a for HF
b

+

+
= =
=

=
10 10
7 2 10
14 10
14
4
11
.
.
.
The Relation Between K
a
and K
b
of a
Conjugate Acid-Base Pair
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.
H
3
PO
4 (aq)
+ H
2
O
(l)
H
2
PO
4
-
(aq)
+ H
3
O
+
(aq)
H
2
PO
4
-
(aq)
+ H
2
O
(l)
HPO
4
2-
(aq)
+ H
3
O
+
(aq)
HPO
4
2-
(aq)
+ H
2
O
(l)
PO
4
3-
(aq)
+ H
3
O
+
(aq)
H
3
PO
4 (aq)
+ 3 H
2
O
(l)
PO
4
3-
(aq)
+ 3 H
3
O
+
(aq)
Polyprotic Acids
Many weak acids contain two or more acidic hydrogens.
polyprotic acids ionize stepwise
ionization constant for each step
Consider arsenic acid, H
3
AsO
4
, which has three ionization
constants
1 K
a1
=2.510
-4
2 K
a2
=5.610
-8

3 K
a3
=3.010
-13
The first ionization step is
| || |
| |
4
10 5 . 2

+
+
= =
+
4 3
4 2
a1
4 2 4 3
AsO H
AsO H H
K
AsO H H AsO H
Polyprotic Acids
Arsenic Acid
The second ionization step is
| || |
| |
8
- 2
4 2
2
4
a2
2
4
-
4 2
10 6 . 5
AsO H
HAsO H
K
HAsO H AsO H
+
+
= =
+
Polyprotic Acids
The third ionization step is
| || |
| |
13
- 2
4
3
4
a3
3
4
- 2
4
10 0 . 3
HAsO
AsO H
K
AsO H HAsO
+
+
= =
+
Polyprotic Acids
Notice that the ionization constants vary in the following
fashion:

This is a general relationship.
a3 a2 a1
K K K > >
Polyprotic Acids
Calculate the concentration of all species in 0.100 M
arsenic acid, H
3
AsO
4
, solution.
1 Write the first ionization ionization step and represent
the concentrations.
( ) xM xM M x 100 . 0
AsO H H AsO H
4 2 4 3
+
Polyprotic Acids
2 Substitute into the expression for K
1
.
| || |
| |
( ) ( )
( )
apply not does assumption g simplifyin
0 10 5 . 2 10 5 . 2
10 5 . 2
10 . 0

K
10 5 . 2
AsO H
AsO H H
K
5 4 2
4
a1
4
4 3
4 2
a1
= +
=
=
= =

+
x x
x
x x
Polyprotic Acids
Use the quadratic equation to solve for x, and
obtain two values
( ) ( )( )
( )
| | | |
| | ( ) M M x
M xM
M x M x
x
095 . 0 100 . 0 AsO H
10 9 . 4 AsO H H
10 9 . 4 and 10 1 . 5
1 2
10 5 . 2 1 4 10 5 . 2 10 5 . 2
4 3
3
4 2
3 3
5
2
4 4
= =
= = =
= =

=
+

Polyprotic Acids
4 Now we write the equation for the second step
ionization and represent the concentrations.
yM M y M y
yM yM yM
M
10 (4.9 ) - 10 (4.9 m equilibriu
change
M 10 4.9 10 4.9 step 1st from
HAsO + H AsO H
3 - 3 -
3 - 3 -
- 2
4
+ -
4 2
) +
+ +

Polyprotic Acids
A comparison of the various species in 0.100 M
H
3
AsO
4
solution follows.
Species Concentration
H
3
AsO
4
0.095 M
H
+
0.0049 M
H
2
AsO
4
-
0.0049 M
HAsO
4
2-
5.6 x 10
-8
M
AsO
4
3-
3.4 x 10
-18
M
OH
-
2.0 x 10
-12
M

Polyprotic Acids
Hydrolysis
Hydrolysis refers to the reaction of a
substance with water or its ions.

solution the of basicity the Note
OH HA O H A
? next do A does what
A Na NaA
2

+
+ +
+
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 O H O Cl
2 3
+ +
+
~100%
Hydrolysis
-
3 2
F O H O H HF + +
+
+
+ A Na NaA
The conjugate base of HCl, the Cl
-
ion, is a very weak base.

True of all strong acids and their anions.
Cl H O No rxn. in dilute aqueous solutions
3
+
+
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 H
3
O
+
ions to form nonionized HF.
HF + H O H O F
only slightly
F + H O HF + H O
nearly completely
2 3
+ -
-
3
+
2

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
Hydrolysis
Salts of Strong Bases and Strong Acids
Salts made from strong acids and strong bases
form neutral aqueous solutions.
An example is potassium nitrate, KNO
3
, made
from nitric acid and potassium hydroxide.
neutral OH or O H produce not does n dissolutio
O H + OH O H O H
NO K KNO
-
3
+
3
-
2 2
3
+ O H in % 100 ~
) (
3
2
+
+
+
s
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.
+
3
-
2 2
- O H in % 100 ~
) (
O H + OH O H + O H
ClO Na NaClO
2
+
+
s
Salts of Strong Bases and Weak Acids
O H HClO O H ClO
2 3
-
+ +
+
O H HClO O H ClO
O H + OH O H + O H
ClO Na NaClO
2 3
-
+
3
-
2 2
- O H in % 100 ~
) (
2
+ +

+
+
+
s
Combine these equations into one single equation
that represents the reaction:
+ + OH HClO O H ClO
2
-
Calculate [OH
-
], pH and percent hydrolysis for the
hypochlorite ion in 0.10 M sodium hypochlorite,
NaClO, solution.
Na ClO Na ClO
0.10 0.10 0.10
~100%inH O
2
+ +
+
M M M
Set up the equation for the hydrolysis and the algebraic
representations of the equilibrium concentrations.
( )
ClO + H O HClO+ OH
Initial: 0.10
Change: - + +
At equil: 0.10-
-
2
-
M M M
xM xM xM
x M xM xM
0 0
Substitute the algebraic expressions into the
hydrolysis constant expression.
| || |
| |
7
b
10 9 . 2
ClO
OH HClO
K

= =
( )( )
( )
K
b
=
=

x x
x 010
2 9 10
7
.
.
( )( )
( )
| | | |
10.23 pH 3.77; pOH
OH HClO
K
b
= =
= = = =
=
M x x
x
x x
4 8 2
7
10 7 . 1 ; 10 9 . 2
10 9 . 2
10 . 0
The percent hydrolysis for the hypochlorite ion
may be represented as:
| |
| |
%
% .
hydrolysis =
ClO
ClO
hydrolysis =
1.7 10
0.10
-
hydrolyzed
-
original
-4
=
100%
100% 017%
M
M
Salts made from weak bases and strong acids form
acidic aqueous solutions.
An example is ammonium bromide, NH
4
Br, made
from ammonia and hydrobromic acid.
( )
acidic is solution O H excess generates
O H NH OH NH
O H OH O H O H
Br NH Br NH
3
2 3
-
4
3
-
2 2
-
4
100% ~ O H
s
-
4
2
+
+
+
+
+
+
+
+ +
Salts of Weak Bases and Strong Acids
The reaction may be more simply represented as:
+
+
+ +
O H NH O H NH
3 3 2 4
+
+ +
H NH NH
3 4
Salts of Weak Bases and Strong Acids
Or even more simply as:
If Parent K
base
> K
acid
make basic solutions
An example is ammonium hypochlorite, NH
4
ClO, made
from aqueous ammonia, NH
3
,and hypochlorous acid,
HClO.
K
b
for NH
3
= 1.8x10
-5

K
a
for HClO = 3.5x10
-8

Salts of Weak Bases and Weak Acids
63
Because the K
b
for ClO
-
ions is three orders
of magnitude larger than the K
a
for NH
4
+

ions, OH
-
ions are produced in excess
solution is basic
If Parent K
base
< K
acid
make acidic solutions
An example is trimethylammonium
fluoride,(CH
3
)
3
NHF, made from trimethylamine,
(CH
3
)
3
N,and hydrofluoric acid acid, HF.
K
b
for (CH
3
)
3
N = 7.4x10
-5

K
a
for HF = 7.2x10
-4
Because the K
a
for (CH
3
)
3
NH
+
ions is one
order of magnitude larger than the K
b
for F
-

ions, H
+
ions are produced in excess.
solution is acidic

CH 17 3-15 Acid-Base Calculations

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CH 17 3-15 Acid-Base Calculations

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Calculation of Ionization Constants

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

Calculation of Ionization Constants

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