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For acid-base equilibria, the pH measures the H + ion concentration and, indirectly,

the OH- ion concentration.

Recall that the pH = -log [H+],


so that as the concentration of
H+ increases the as the pH
decreases. Since the
concentrations of H+ and OH-
are inversely proportional, as
one goes up, the other goes
down.

So for an acid-base equilibrium, such as the one shown, decreasing the pH amounts
to increasing the H+ concentration, which would cause the equilibrium to shift to the
left.

The opposite occurs if the pH is


raised and the H+
concentration lowered by
adding a base. The H+ ions
arent really removed from
solution, but the OH- ions in the
base react with the H+ ions to
form water, which effectively
takes them out of the acid-base
equilibrium reaction and does,
in fact, lower the concentration
of the H+ ions.

In each square in the table to the right, think about whether imposing the change at
the left will increase the concentration of the species at the top or if imposing the
change will decrease the concentration.
For example, in the first box you should think about what will happen to the concentration of HA
when adding HCl. Remember Le Chateliers principle. The equilibrium will shift in the direction
that counteracts the change imposed. For each change imposed, figure out which direction the
equilibrium must shift in order to counteract it, and then decide what effect shifting in that
direction will have on the concentrations of the other species in the reaction.

Let's walk through one together. Adding HA will increase the concentration of a reactant. The
equilibrium will therefore shift to the right to reduce it. This will cause the concentrations of
H3O+ and A- to increase. Since the H3O+ ion concentration increases, the pH decreases. Although
the concentration of HA will also go down when the equilibrium shifts, if will not decrease all
the way back to what it was before the additional HA was introduced. So, adding HA does, in
fact, increase the concentration of HA, but, because of the resulting equilibrium shift, it does not
increase by as much as was added.

change [HA] [H3O+] [A-] pH

increase (equilibrium is increase (HCl is a


decrease (gets
Add HCl shifting left to use up strong acid; source of decrease
more acidic)
additional H3O+) H3O+)

decrease (equilibrium is
Add decrease (reacts with increase (gets
shifting right to make up for increase
NaOH the OH-) more basic)
less H3O+)

Add HA increase increase increase decrease


increase (equilibrium is
Add A- shifting left to use up decrease increase increase
additional A-)

decrease (equilbrium is
Remove
shifting right to make up for increase decrease decrease
A-
less A-)

Buffers
A buffer solution makes use of Le Chateliers principle to prevent its pH from
changing very much when acid or base is added

A buffered solution is one that contains relatively high concentrations of both a


weak acid and its conjugate base. A simplified version of the equilibrium that
buffers your blood is show here as an example.
This bicarbonate buffer system is what
keeps the pH of your blood constant. However, carbonic acid, H 2CO3, is unstable and
decomposes to form carbon dioxide and water. Some of the carbon dioxide stays
dissolved in the blood and some of it is released into the air in your lungs.

If some process releases acid [H+] into the


blood, this equilibrium responds by shifting to
the left as long as there is HCO3- present for
the H+ to react with, thus removing the excess
H+ ions.

Thus, to protect against added acid, the buffer


solution must have a relatively high
concentration base, HCO3- , in solution.

If a process releases base into the blood,


which would react with and lower the
concentration of the H+, the equilibrium shifts
to the right as long as there is H2CO3, thus
replacing the lost H+ ions.

Thus, to protect against added base, the buffer


solution must have a relatively high
concentration of the weak acid as well.

The equation on your screen describes the behavior of buffer systems in general.
The value of the acid dissociation constant, K a, depends on what acid HA represents.
This equation also correctly predicts Le
Chateliers Principle. Suppose, for
example, that the system is at equilibrium (the equation is satisfied) and then some
H+ is added. With the extra H+ ions, the value of [H+][A-]/[HA] is too high. To return it
to its correct value, [H+] and [A-] must decrease and [HA] must increase, that is, the
equilibrium must shift to the left, just as Le Chateliers principle predicts.
To maximize the buffering capacity against both added acid and base, the
concentrations of A- and HA must both be high and, in fact, approximately equal.

The exact values of [A-] and [HA] depend on


what pH the buffer is trying to maintain.
There is a range of about 2 pH units within
which each conjugate acid-base pair can
function effectively as a buffer. This means
that the two concentrations can usually be
no more than a factor of ten different from
one another.

But if the concentrations of A- and HA are equal,


they cancel from the equation, and the H+
concentration will therefore be the same as Ka, the
acid dissociation constant.

If [A-] and [HA] are not the same, it is a simple


matter to solve the equation for [H+] and plug in the
values of Ka, [A-], and [HA]. The pH is then just the
negative logarithm of this value.
Thus, knowing the value of the Ka for a weak acid allows you to calculate the [H +]
for a buffer made from that acid and its conjugate base. If the two concentrations
are the same, the calculation is especially easy.