Calculating [H

+
] and [OH

]
Just as we used K
sp
values to help us calculate ion concentrations in the last unit, we will use
K
a
and K
b
to calculate the concentrations of ions in acids and bases. This will be crucial to
determining pH later in this unit, so be sure to follow along carefully.
This is one of the most important sections of this unit mathematically, so be sure you
understand every step.
How you calculate ion concentrations
depends on whether you have a strong
acid (or base) or a weak acid (or base).

Calculating Ion Concentrations for Strong Acids & Bases
For strong acids and bases, the concentration of the ions can be readily calculated from the
balanced equation. Consider these examples carefully.
1. Calculate the hydrogen ion concentration in a 0.050 M solution of
hydrochloric acid.
Solution:We know that HCl is a strong acid that ionizes completely in
water (you should memorize the list of strong acids). Begin by writing
the balanced reaction: HCl
(aq)
H
+
(aq)
+ Cl
-
(aq)

From the balanced equation we see that 1 mole of HCl produces
1 mole of H
+
(a 1:1 ratio), therefore the concentration of H
+
will
equal that of HCl. Answer: [H
+
] = 0.050 M



Also [Cl
-
]
= 0.050 M


2. Calculate the hydroxide ion concentration in a 0.010 M solution of barium
hydroxide, Ba(OH)
2
. Barium hydroxide is a strong base.
Solution: Always begin by writing a balanced equation:
Ba(OH)
2 (aq)
Ba
2+
(aq)
+ 2 OH
-
(aq)

Since 2 moles of OH
-
are produced for every 1 mole of Ba(OH)
2
, the
concentration of OH
-
will be twice the concentration of Ba(OH)
2
.
Answer:
[OH
-
] = 2 0.010 = 0.020 M
Also [Ba
2+
] = 0.010 M

Calculating Ion Concentrations for Weak Acids & Bases
Weak acids and bases require a much different approach to finding ion concentrations. Once
you know you have a weak acid or base, follow these steps in finding ion concentrations:
1. Write a balanced equation for the reaction
2. You will need to know the value of K
a
or K
b
- if it is not given in the question,
look it up in a Table of Acid and Base Strengths.
3. Set up the equilibrium constant expression. You will know the value of K
a
(or
K
b
) and the concentration of the acid; you will be solving the equation for the
concentration of the ions.
1
.
Calculate the hydrogen ion concentration in a 0.10 M acetic acid
solution, HC
2
H
3
O
2
.
K
a
for acetic acid, a weak acid, is 1.8 10
-5
.
Solution:
Begin by writing the balanced reaction:
HC
2
H
3
O
2 (aq)
H
+
(aq)
+ C
2
H
3
O
2
-
(aq)

The question gives us the concentration of the acid, HC
2
H
3
O
2

(0.10 M).
We need to find the concentration of H
+
, which will also equal
the concentration of C
2
H
3
O
2
-
(why?)
Because ionization is NOT complete because this is a weak acid , [H
+
] will NOT
equal [HC
2
H
3
O
2
]. Instead we must calculate it using the equilibrium constant
expression.
Set up the
K
a
equation:
K
a
=
[H
+
] [ C
2
H
3
O
2
-
]

[HC
2
H
3
O
2
]



Substitute values into the equation.
Let x equal the unknowns
1.8 10
-5
=
(x) (x)

0.10

Rearrange the equation x
2
= (1.8 10
-5
)(0.10)
x
2
= 1.8 10
-6

Take the square root x = 1.310
-3

ANSWER [H
+
] = 1.310
-3

also [C
2
H
3
O
2
-
] = 1.310
-3

An important note - in our K
a
equation we used a value of 0.10M for [HC
2
H
3
O
2
]. This
isn't quite correct. At equilibrium, the concentration of HC
2
H
3
O
2
will actually be less:
initial [HC
2
H
3
O
2
] = 0.100
subtract the lost [H
+
]

- 0.013



equilibrium [HC
2
H
3
O
2
] = 0.087
Using this equilibrium concentration of [HC
2
H
3
O
2
] in our calculations above (instead of
0.10 M), however, does not change our answer significantly. Therefore for our
calculations we can safely ignore the negligible change in concentration of the acid.

2. Calculate the hydroxide ion concentration, [OH
-
], in a 0.025 M solution of
analine, C
6
H
5
NH
2
, a weak base with K
b
= 4.310
-10

Solution:
This question will test some of your skills. Begin by writing a balanced
equation. Since analine is a base that doesn't contain the hydroxide ion,
include H
2
O as a reactant. Also remember that a base is a hydrogen
acceptor and will gain an additional H
+
:
C
6
H
5
NH
2 (aq)
+ H
2
O
(l)
C
6
H
5
NH
3
+
(aq)
+ OH
-
(aq)

As we did in the previous example, we now set up the K
b
expression and
solve for ion concentrations. We see from the balanced equation that the
ions have a 1:1 ratio, therefore [OH
-
] will equal the [C
6
H
5
NH
3
+
].
Set up the K
b
equation, omitting
liquid water:
K
b
=
[C
6
H
5
NH
3
+
] [OH
-
]

[C
6
H
5
NH
2
]



Substitute values into the equation.
Let x equal the unknowns
4.310
-10
=
(x) (x)

0.025



Rearrange the equation x
2
= (4.310
-10
)(0.25)
x
2
= 1.110
-11

Take the square root x = 3.310
-6

ANSWER [OH
-
] = 1.310
-3
M
also [C
6
H
5
NH
3
+
] = 1.310
-3
M

Finding [OH
-
] in Acids and [H
+
] in Bases
Remember K
w
from the previous section? Now we learn why it is important.
When we need to determine ion concentrations of an acid, you should immediately realize you
will be finding the concentration of hydrogen ion (H
+
) and some anion (Cl
-
and C
2
H
3
O
2
-
in our
acid examples above). The concentration of the anion normally doesn't concern us much.
When finding ion concentrations of bases, we determine the concentration of hydroxide ions, OH
-
, and some cation (Ba
2+
and C
6
H
5
NH
3
+
in our base examples above). Again, we aren't too
concerned with the cation concentrations.
Remember water?
H
2
O
(l)
H
+
(aq)
+ OH
-
(aq)

K
w
= [H
+
] [OH
-
]
= 1.0 10
-14

When we make an acid solution, the hydrogen ion concentration will increase because we are
adding more H
+
ions to those already present in water.
Consider our strong acid example from above, in which [H
+
] = 0.05 M. If we add this to the
hydrogen ion concentration of pure water, 1.010
-7
(see last section), we get a total hydrogen ion
concentration of 0.0500001M. Clearly, the water adds little to the total and we can essentially
ignore its contribution.

[H
+
] from water: 1.010
-7

=
0.000 000 1
[H
+
] from HCl
+
0.05


Total [H
+
] 0.050 001
Next, remember that equilibrium constants are A CONSTANT (as long as temperature does
not change). Thus the value of K
w
will still have a value of 1.0 10
-14
even though [H
+
] has
increased due to the presence of the acid. We can use this information to calculate the
concentration of hydroxide ions present in the aqueous solution:

K
w
= [H
+
] [OH
-
]
Rearrange the equation [OH
-
] =
K
w


[H
+
]
Substitute known values and solve for [OH
-
]
[OH
-
] =
1.0 10
-14


0.05
[OH
-
] = 2.0 10
-13

Le Chtalier's Principle
Remember Le Chtalier's Principle? When we disrupt an equilibrium system by increasing the
concentration of a reaction participant, equilibrium will shift to minimize the stress. When we
increase the H
+
ion concentration in the water equilibrium system, the reaction will shift to the
left to "use up" the additional H
+
. This will cause the concentration of OH
-
to decrease. Indeed,
we see that [OH
-
] does decrease, from an original concentration of 1.010
-7
in pure water to 2.0
10
-13
in our acid solution.
We can apply the same calculations to determine hydrogen ion concentration in any basic
solution. Let's return to our weak base, analine, example from above.
We determined that in a 0.025 M solution of analine, C
6
H
5
NH
2
, the [OH
-
] was 1.3 10
-3
M. Our
new question - what is the H
+
ion concentration in this basic solution?
To solve, we again refer to our pure water equilibrium and its equilibrium constant expression.
This time, however, we have determined [OH
-
] and need to find [ H
+
].
Again it should be apparent that the contribution to [OH
-
] from the water, 1.010
-7
M, will have
no significant effect on the OH
-
concentration so we can ignore it from our calculations:

[OH
-
] from water: 1.010
-7

=
0.000 000 1
[OH
-
] from C
6
H
5
NH
2
1.3 10
-3

= +
0.001 3


Total [OH
-
] 0.001 3001

Use water's equilibrium constant to determine [H
+
]:

K
w
= [H
+
] [OH
-
]
Rearrange the equation [H
+
] =
K
w


[OH
-
]

Substitute in known values and calculate [H
+
]
[H
+
] =
1.0 10
-14


1.3 10
-3

[H
+
] = 7.7 10
-12


For any acid or base
you can calculate
both [H
+
] and [OH
-
]
Acids
First determine [H
+
]
then use K
w
to calculate [OH
-
]
Bases
First determine [OH
-
]
then use K
w
to calculate [H
+
]


Some things to think about:
In water, which is neutral (neither acidic nor basic), [H
+
] = 1.010
-7
M and [OH
-
]
= 1.010
-7
M
Acids increase [H
+
], so [H
+
] will be greater than 1.010
-7
and [OH
-
] will be less
than 1.010
-7
M
Bases increase [OH
-
], so [OH
-
] will be greater than 1.010
-7
, and [H
+
] will be less
than 1.010
-7
M