Acids and Bases part 4

Titrations and pH Curves

A quick titration summary

In this topic, the titrations are the addition of an acid to a base or vice versa and observing a colour
change (the end point) when neutralisation occurs.

You record how much acid or base you added (the titre) to get the colour change and then usually carry
out a calculation.

The colour changes are seen by using a suitable indicator that changes colour within a specific pH range,
therefore you have to be careful that you use an appropriate indicator.

pH/titration curves are created by plotting pH (y-axis) against the volume of acid or base added during
the titration (x-axis).

Curve shapes

The curves come in various combinations of adding either an acid to an alkali (base) or vice-versa. So for
example when adding acid to alkali the various combinations you can have are:

strong acid added to a strong alkali (or vice-versa)

strong acid added to a weak alkali (or vice-versa)

weak acid added to a strong alkali (or vice-versa)

weak acid added to a weak alkali (or vice-versa)

Below are 4 examples of pH curves:

Drawing the curves

1. Where to start

Sometimes in previous parts to the question you will have calculated a pH, which is often the starting pH
for the curve.

If this is not the case then you need to estimate it: strong acid ~ 1, strong base ~ 13, weak acid ~ 3 and
weak base ~ 9.

be careful with the wording in the question. It is important to get the curve shape the correct way
round! Look for the phrase added to as this is where you start i.e. HC was added to NaOH means
start at a strong acid pH.

2. The first past of the curve

It increases slightly if adding base to acid. This area is the buffer region (see later for more on buffers).

3.The equivalence point

The steep/vertical part of the curve indicates the end point, which is known as the equivalence point.
This is where neutralisation and the colour change occurs.

At the equivalence point you need to draw a vertical lone down to the x-axis and read the volume. In the
example below it is about 25 cm3:
The length of the vertical section is also estimated. It should be between 3-5 pH units high. Note that the
curve gradually goes into the vertical section, it shouldnt be a 90 degree corner!

the middle of the vertical section is not always at pH 7 (see salt formation below).

4.The final part of the curve

Again you need to estimate this unless you have calculated the pH in another part of the question. Just be
sensible. If you are adding strong base then finish ~ 12-14, strong acid ~ 1, weak acid ~ 3 and weak base ~
9.

in Edexcel June 2016 Unit 4, they asked for the curve of a diprotic acid. This caused problems! It just
means there are two dissociations i.e. two equivalence points. Therefore the overall curve looks like
two curves, one after the other. The second equivalence point is double the volume of the first.

Salt Formation

As we are adding acid to base or vice-versa, all these reactions are simply:

Acid + Base Salt + Water

As mentioned above, the middle of the vertical section is not always at pH 7. If strong acid is added to
strong base or vice-versa then the mid-section will be at pH 7.

But if we use weak acid and strong base or vice-versa, then the mid-section pH will not be 7 due to the
salt formed.

1.Weak acid added to strong base

For example, ethanoic acid added to sodium hydroxide:

CH3COOH + NaOH CH3COONa + H2O

The salt formed will react with water:

CH3COO- + H2O CH3COOH + OH-

The important point here is that OH- ions are formed, therefore the solution is alkaline and the mid-
section will be > 7.
2.Weak base added to strong acid

For example, ammonia added to hydrochloric aid:

NH3 + HCl NH4Cl

The salt formed will react with water:

NH4+ + H2O NH3 + H3O+

This time H3O+ ions are formed, therefore the solution is acidic and the mid-section will be < 7.

Indicators

As the steep part of different curves cover different pH ranges, you have to select an indicator that
changes colour within that steep section of the curve.

A couple of common examples are Methyl Orange for the pH range of 3-4 or Phenolphthalein for pH in
the range 8-10.

In exam questions they often give you different indicators you have never heard of, but its the same
principle, just pick one where the colour change comes within the vertical section of the curve.

Half-equivalence point

An exam question that appears from time to time is working out the pK a or pH of a weak acid from a
titration curve.

These questions are very easy as long as you recognise the type of question quickly. We mentioned the
equivalence point above, and there is also another point called the half-equivalence point.

This is the point where half of the volume required for neutralisation has been added.
From the earlier curve we said that the equivalence point was where 25cm3 of alkali was required for
neutralisation.

Therefore, 12.5cm3 must be the half-equivalence point as shown above i.e. half of 25 (shown above).

If we then write out the usual Ka expression:

the vital information: at the half-equivalence point [HA]= [A-]

Therefore, we can cancel the [HA] and [A-] from the above expression to leave us with:

Ka = [H+]

and therefore:
pKa = pH

Example

When half of an ethanoic acid solution has been neutralised, the remaining ethanoic acid concentration is
equal to that of the sodium ethanoate that had formed. What is the pH at this point? The K a = 1.75 x 10-3
moldm-3.

The key to this question is to recognise that it as a half-equivalence question and therefore we can
immediately say that Ka=[H+].

We know it is a half-equivalence question as they have told us that the ethanoic acid (HA) concentration
= the sodium ethanoate concentration (A-). And they also said when half of an ethanoic acid solution has
been neutralised, so there should be no excuse for missing the point in this question!

We can then say that the [H+] is 1.75 x 10-3moldm-3 and using pH = -log10[H+], we get a pH of 2.75.