Acid-base equilibria

Introduction:
It is essential that you can write
the expression for K
a
of a weak
acid.
Make sure that you know how to
use your calculator to evaluate
logarithms, and how to turn p
H
and
pK
a
values into [H
+
] and K
a
values.

Acid-base equilibria

Buffer solutions do not have a
constant p
H
. They resist changes
in p
H
.
You may use H
+
, H
+
(aq) or H
3
O
+

as the formula of hydrogen ion.

Things to learn
Arrhenius acid is a substance that
produce H
+
ions when they dissolve in
water:
HA(aq) H
+
(aq) + A
-
(aq)
Arrhenius base is a substance that produce
the hydroxide (OH-) ion in solution:
B(aq) + H
2
O(aq) BH
+
(aq) + OH
-
(aq)
It is suggested that the H
+
ion exists in association with a
water molecule as the H
3
O
+
ion, called the oxonium ion.

Things to learn
Things to learn
Things to learn
p
OH
= - log[OH
-
(aq)]
p
H
+ p
OH
= 14 at 25
o
C.
A strong acid is totally ionized in
aqueous solution, and a weak acid is
only partially ionized in aqueous
solution.
K
a
, for a weak acid, HA = [H
+
][A
-
] / [HA].
p
K
a = - log K
a


Conjugate acid/base pairs
Conjugate acid/base pairs
P
H
p
H
Scale
p
H
Scale
p
H
of strong acids and bases
So at neutral solution is one where
[H
+
] = [OH
-
], and the p
H
= 7

An acid solution is one where [H
+
] >
[OH
-
], and the p
H
< 7.

An alkaline solution is one where [H
+
]
< [OH
-
], and the p
H
> 7.



p
H
of strong acids and bases
For a strong monobasic acid:
p
H
= - log [acid]
Therefore the p
H
of a 0.321 mol dm
-3

solution of HCl = - log (0.0321) = 0.49
For a strong alkali with one OH
-
ion in
the formula:
p
OH
= - log[alkali] and
p
H
= 14 p
OH




p
H
of strong acids and bases
Therefore the p
H
of a 0.109 mol dm
-3

solution of NaOH is calculated:
p
OH
= -log(0.109) = 0.96
Therefore p
H
= 14 0.96 = 13.04



p
H
of strong acids and bases
Therefore the p
H
of a 0.109 mol dm
-3

solution of NaOH is calculated:
p
OH
= -log(0.109) = 0.96
Therefore p
H
= 14 0.96 = 13.04



p
H
of weak acids
Weak acids are partially ionized. A
general equation for this is:
HA(aq) = H
+
(aq) + A
-
(aq)

The acid produces equal amounts of H+
and A-, so that:
[H
+
(aq) = [A
-
(aq)]




Worked example
Indicators
For use in a titration, an indicator must
change colour within the pH of the vertical
part of the titration curve.

Vertical range of pH Suitable indicator
Strong acid and base

Weak acid/strong base
Strong acid/weak base
3.5 to 10.5

7 to 10.5
3.5 to 7
Methyl orange or
phenolphthalein
Phenolphthalein
Methyl orange
Buffer solutions
Buffer solutions
The weak acid is partially ionized:

CH
3
COOH(aq) H
+
(aq) + CH
3
COO
-
(aq)

The CH
3
COO
-
ions from the salt suppress
most of the ionization of the acid, and so
both [CH
3
COOH(aq)] and [CH
3
COO
-
(aq)]
are large.
Buffer solutions
Calculation of the pH of a buffer solution
Calculation of the pH of a buffer solution
Worked example
Enthalpy of neutralization
Checklist
For attempting the questions on this topic, check
that you:
Can identify acid/base conjugate pairs.
Can define pH and K
w
.
Can define K
a
and pK
a
for weak acids.
Understand what is meant by the terms strong
and weak as applied to acids and bases.
Can calculate the pH of solutions of strong
acids, strong bases and weak acids.
Checklist
Can recall the titration curves for the
neutralization of strong and weak acids.
Can use the curves to calculate the value
of K
a
for a weak acid.
Understand the reasons for the choice of
indicator in an acid/base titrations.
Can define a buffer solution, explain its
mode of action and calculate its p
H
.
Test your knowledge and understanding
For the following questions, cover the
margin, write your answer, then check to
see if you are correct.
Identify the acid/base conjugate pairs in
the reaction:
H
2
SO
4
+ CH
3
COOH CH
3
COOH
2
+
+
HSO
4
-

Test your knowledge and understanding
Calculate the p
H
of :
0.11 mol dm
-3
HCl
0.11 mol dm
-3
LiOH
0.11 mol dm
-3
Ba(OH)
2

Calculate the p
H
of 0.22 mol dm
-3

C
2
H
5
COOH which has pK
a
= 4.87.