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Acids and Bases part 5

Buffers

a buffer is a solution that resists changes in pH when small amounts of acid or base are added

The key phrase is small amounts of acid or base. If you add too much acid or base then buffer solution
wont work.

The pH does not remain exactly as it was, it will change a little.

Buffer solutions are usually acidic or alkaline, with a large emphasis on acidic buffers.

Acidic Buffers

1. Making a buffer

Acidic buffers are made from a weak acid and a salt of that acid

e.g. ethanoic acid and sodium ethanoate (the salt). The salt is just ethanoic acid with O-Na+ at the end
instead of OH and it is named after an ester.

Ethanoic acid only partially dissociates (as it is a weak acid), setting up the usual equilibrium:

So we have lots of CH3COOH i.e. the equilibrium lies to the left but not much H+ or CH3COO-.

Addition of the salt

We have two options:

1. the salt can be added directly as a solid i.e. weigh out the necessary amount and add it to the
weak acid solution.

2. react sodium hydroxide with the weak acid to make the salt. The weak acid must be in excess.

This difference is important to recognise as it affects how you do the calculations. Whichever method is
used, the salt will dissociates fully:
The result is that there are now lots of CH3COOH and CH3COO- and not much H+. Sometimes referred to
as a reservoir of acid and ions. This is essential to keep the pH constant (see below).

the [H+] does not equal [A-]. This is the big difference between normal weak acid calculations and
buffers. So for buffers you cannot write [H+]2.

2. How a buffer works

Acidic Buffers
Looking at the equilibrium equation below, we can use Le Chatelier's principle to explain how a buffer
works.

It is best to think of how a buffer resists changes in two parts:

1.the initial change: when the extra H+ (acid) is added to the buffer, initially, the [H+] will go up and the
pH will drop.

Or if we add extra base (OH-), the pH will rise as we are effectively removing H+ from the solution. The
OH- reacts with the H+ to form water.

2.the equilibrium shifting: by adding extra acid, the equilibrium then shifts to the left to remove the
excess of H+. The H+ ions react with the CH3COO- and the pH rises close to where it started.

Or if we add extra base (OH-), the equilibrium shifts to the right to make more H+ and the pH drops back
toward where it started.

Alkaline Buffers
These are based upon the same principle as for the acidic buffers above.

The exam questions tend to focus upon acidic buffers, but that doesn't mean they won't ask any
questions on alkaline buffers.

The only example the tend to use is the buffer formed from NH4Cl (the salt) and NH3 (the weak base), to
set up the equilibrium below:
Just apply the same logic as discussed for the acidic buffers to explain why the pH returns close to the
original value after the addition of acid or base.

3. The salt:acid ratio

The final part is talking about the salt to acid ratio. Looking at the Ka expression, the salt is the [A-] and the
acid is the [HA]:

if the salt to acid ratio remains constant then the pH remains constant

Looking back to the start of the tutorial we said that there was a reservoir of HA and A-. If a small amount
of acid or base is added to the buffer, the number of moles added will be very small in comparison to the
number of moles of HA and A- already present.

This means that the number of moles of HA and A- after the addition of acid or base will change very
slightly but not significantly, therefore the ratio will remain as close to constant as possible.

Example

Lets assume that an acidic buffer using ethanoic acid has been set up and there are 0.21 moles of the
acid and 0.15 moles of the salt. 0.01 moles of NaOH is then added.

Similarly to a Kc question it is easy to see what is going on if you set it up as follows:

CH3COOH + NaOH CH3COONa + H2O

Initial 0.21 0.01 0.15


Change -0.01 -0.01 +0.01
Equilibrium 0.20 0 0.16

You can see that the equilibrium moles of acid and salt after the addition of NaOH are very close to the
original values i.e. the salt:acid ratio hasnt changed much.

The NaOH neutralises some of the acid and also increases the number of salt moles. I havent bothered
about the H2O moles as it is not in the Ka expression. You can write out omethign similar for the addition
of acid. We will look at this again in the next part of the tutorial.
Conclusions
If in the exam they ask how does the buffer resist changes to pH for 3 or more marks, just mentioning
the equilibrium shifting is not enough. You need to talk about all of the above:

1. the phrase reservoir of acid and salt, which shows you know how a buffer is made.

2. the explanation about the equilibrium shifting.

3. the overall result is that the [A-]/[HA] ratio is almost constant.

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