pH (TITRATION) CURVES

The equivalence point of a titration

When you carry out a simple acid-base titration, you use an
indicator to tell you when you have the acid and alkali mixed in
exactly the right proportions to "neutralise" each other. When the
indicator changes colour, this is often described as the end point
of the titration.
In an ideal world, the colour change would happen when you mix
the two solutions together in exactly equation proportions. That
particular mixture is known as the equivalence point.
For example, if you were titrating sodium hydroxide solution with
hydrochloric acid, both with a concentration of 1 mol dm -3, 25 cm3 of
sodium hydroxide solution would need exactly the same volume of
the acid - because they react 1 : 1 according to the equation.

In this particular instance, this would also be the neutral point of

the titration, because sodium chloride solution has a pH of 7.
For example, if you titrate ammonia solution with hydrochloric acid,
you would get ammonium chloride formed. The ammonium ion is
slightly acidic, and so pure ammonium chloride has a slightly acidic
pH.
That means that at the equivalence point (where you had mixed the
solutions in the correct proportions according to the equation), the
solution wouldn't actually be neutral. To use the term "neutral point"
in this context would be misleading.
Similarly, if you titrate sodium hydroxide solution with ethanoic acid,
at the equivalence point the pure sodium ethanoate formed has a
slightly alkaline pH because the ethanoate ion is slightly basic.

Simple pH curves
Titration curves for strong acid v strong base
We'll take hydrochloric acid and sodium hydroxide as typical of a
strong acid and a strong base.

Running acid into the alkali

You can see that the pH only falls a very small amount until quite
near the equivalence point. Then there is a really steep plunge. If
you calculate the values, the pH falls all the way from 11.3 when
you have added 24.9 cm3 to 2.7 when you have added 25.1 cm3.

Running alkali into the acid

This is very similar to the previous curve except, of course, that the
pH starts off low and increases as you add more sodium hydroxide
solution.

Again, the pH doesn't change very much until you get close to the
equivalence point. Then it surges upwards very steeply.
Titration curves for strong acid v weak base
This time we are going to use hydrochloric acid as the strong acid
and ammonia solution as the weak base.

Running acid into the alkali

Because you have got a weak base, the beginning of the curve is
obviously going to be different. However, once you have got an
excess of acid, the curve is essentially the same as before.
At the very beginning of the curve, the pH starts by falling quite
quickly as the acid is added, but the curve very soon gets less
steep. This is because a buffer solution is being set up - composed
of the excess ammonia and the ammonium chloride being formed.

Notice that the equivalence point is now somewhat acidic ( a bit

less than pH 5), because pure ammonium chloride isn't neutral.
However, the equivalence point still falls on the steepest bit of the
curve. That will turn out to be important in choosing a suitable
indicator for the titration.
Running alkali into the acid
At the beginning of this titration, you have an excess of hydrochloric
acid. The shape of the curve will be the same as when you had an
excess of acid at the start of a titration running sodium hydroxide
solution into the acid.

It is only after the equivalence point that things become different.

A buffer solution is formed containing excess ammonia and
ammonium chloride. This resists any large increase in pH - not that
you would expect a very large increase anyway, because ammonia
is only a weak base.

Titration curves for weak acid v strong base

We'll take ethanoic acid and sodium hydroxide as typical of a weak
acid and a strong base.

Running acid into the alkali

For the first part of the graph, you have an excess of sodium
hydroxide. The curve will be exactly the same as when you add
hydrochloric acid to sodium hydroxide. Once the acid is in excess,
there will be a difference.

Past the equivalence point you have a buffer solution containing

sodium ethanoate and ethanoic acid. This resists any large fall in
pH.
Running alkali into the acid

The start of the graph shows a relatively rapid rise in pH but this
slows down as a buffer solution containing ethanoic acid and
sodium ethanoate is produced. Beyond the equivalence point
(when the sodium hydroxide is in excess) the curve is just the same
as that end of the HCl - NaOH graph.

Titration curves for weak acid v weak base

The common example of this would be ethanoic acid and ammonia.

It so happens that these two are both about equally weak - in that
case, the equivalence point is approximately pH 7.

Acid - Base Titration:

Reaction of NaOH with

In aqueous solutions, addition of bases to water leads to an increase in the pH of the

solution, while the addition of acids leads to a decrease in the pH. The changes in the
pH can be followed using either specific dyes, called indicators, or a pH electrode. Acids
and bases neutralize, or reverse, the action of one another. By adding a known amount
6 Acid - Base Titration: Reaction of NaOH with HCl

of acid to a basic solution, until it completely reacts with it, the amount of the base can
be determined. This procedure is called: Acid - Base Titration. During neutralization,
acids and bases react with each other to produce ionic substances, called salts.
In this experiment, changes in pH and temperature, occurring while an acid (hydrochloric
acid) is added to a base (sodium hydroxide) solution, are followed using a pH electrode
and a Temperature sensor.

Equipment

Nova5000
A pH electrode
A Temperature sensor (-25 C to 110 C)
A polystyrene coffee cup
50 ml buret pipette
A glass funnel
2 g NaOH
100 ml NHCl solution
Magnetic stirrer

ACID-BASE INDICATORS
Indicators as weak acids
Litmus
Litmus is a weak acid. It has a seriously complicated molecule
which we will simplify to HLit. The "H" is the proton which can be
given away to something else. The "Lit" is the rest of the weak acid
molecule.
There will be an equilibrium established when this acid dissolves in
water. Taking the simplified version of this equilibrium:

The un-ionised litmus is red, whereas the ion is blue.

Now use Le Chatelier's Principle to work out what would happen if

you added hydroxide ions or some more hydrogen ions to this
equilibrium.

Adding hydroxide ions:

Adding hydrogen ions:

If the concentrations of HLit and Lit - are equal:

At some point during the movement of the position of equilibrium,
the concentrations of the two colours will become equal. The colour
you see will be a mixture of the two.

The reason for the inverted commas around "neutral" is that there
is no reason why the two concentrations should become equal at

pH 7. For litmus, it so happens that the 50 / 50 colour does occur at

close to pH 7 - that's why litmus is commonly used to test for acids
and alkalis. As you will see below, that isn't true for other indicators.
Methyl orange
Methyl orange is one of the indicators commonly used in titrations.
In an alkaline solution, methyl orange is yellow and the structure is:

Now, you might think that when you add an acid, the hydrogen ion
would be picked up by the negatively charged oxygen. That's the
obvious place for it to go. Not so!
In fact, the hydrogen ion attaches to one of the nitrogens in the
nitrogen-nitrogen double bond to give a structure which might be
drawn like this:

You have the same sort of equilibrium between the two forms of
methyl orange as in the litmus case - but the colours are different.

You should be able to work out for yourself why the colour changes
when you add an acid or an alkali. The explanation is identical to
the litmus case - all that differs are the colours.

In the methyl orange case, the half-way stage where the mixture of
red and yellow produces an orange colour happens at pH 3.7 nowhere near neutral. This will be explored further down this page.
Phenolphthalein
Phenolphthalein is another commonly used indicator for titrations,
and is another weak acid.
In this case, the weak acid is colourless and its ion is bright pink.
Adding extra hydrogen ions shifts the position of equilibrium to the
left, and turns the indicator colourless. Adding hydroxide ions
removes the hydrogen ions from the equilibrium which tips to the
right to replace them - turning the indicator pink.
The half-way stage happens at pH 9.3. Since a mixture of pink and
colourless is simply a paler pink, this is difficult to detect with any
accuracy!

The pH range of indicators

The importance of pKind
Think about a general indicator, HInd - where "Ind" is all the rest of
the indicator apart from the hydrogen ion which is given away:

Because this is just like any other weak acid, you can write an
expression for Ka for it. We will call it Kind to stress that we are

talking about the indicator.

Think of what happens half-way through the colour change. At this

point the concentrations of the acid and its ion are equal. In that
case, they will cancel out of the Kind expression.

You can use this to work out what the pH is at this half-way point. If
you re-arrange the last equation so that the hydrogen ion
concentration is on the left-hand side, and then convert to pH and
pKind, you get:

That means that the end point for the indicator depends entirely on
what its pKind value is. For the indicators we've looked at above,
these are:
indicator

pKind

litmus

6.5

methyl orange

3.7

phenolphthalein

9.3

The pH range of indicators

Indicators don't change colour sharply at one particular pH (given
by their pKind). Instead, they change over a narrow range of pH.
Assume the equilibrium is firmly to one side, but now you add
something to start to shift it. As the equilibrium shifts, you will start
to get more and more of the second colour formed, and at some
point the eye will start to detect it.
For example, suppose you had methyl orange in an alkaline
solution so that the dominant colour was yellow. Now start to add
acid so that the equilibrium begins to shift.
At some point there will be enough of the red form of the methyl
orange present that the solution will begin to take on an orange tint.
As you go on adding more acid, the red will eventually become so
dominant that you can no longe see any yellow.
There is a gradual smooth change from one colour to the other,
taking place over a range of pH. As a rough "rule of thumb", the
visible change takes place about 1 pH unit either side of the pK ind
value.
The exact values for the three indicators we've looked at are:
indicator

pKind

pH range

litmus

6.5

5-8

methyl orange

3.7

3.1 - 4.4

phenolphthalein

9.3

8.3 - 10.0

The litmus colour change happens over an unusually wide range,

but it is useful for detecting acids and alkalis in the lab because it
changes colour around pH 7. Methyl orange or phenolphthalein

would be less useful.

This is more easily seen diagramatically.

For example, methyl orange would be yellow in any solution with a

pH greater than 4.4. It couldn't distinguish between a weak acid
with a pH of 5 or a strong alkali with a pH of 14.

Choosing indicators for titrations

Remember that the equivalence point of a titration is where you
have mixed the two substances in exactly equation proportions.
You obviously need to choose an indicator which changes colour
as close as possible to that equivalence point. That varies from
titration to titration.
Strong acid v strong base
The next diagram shows the pH curve for adding a strong acid to a
strong base. Superimposed on it are the pH ranges for methyl
orange and phenolphthalein.

You can see that neither indicator changes colour at the

equivalence point.
However, the graph is so steep at that point that there will be
virtually no difference in the volume of acid added whichever
indicator you choose. However, it would make sense to titrate to the
best possible colour with each indicator.
If you use phenolphthalein, you would titrate until it just becomes
colourless (at pH 8.3) because that is as close as you can get to
the equivalence point.
On the other hand, using methyl orange, you would titrate until
there is the very first trace of orange in the solution. If the solution
becomes red, you are getting further from the equivalence point.
Strong acid v weak base

This time it is obvious that phenolphthalein would be completely

useless. However, methyl orange starts to change from yellow
towards orange very close to the equivalence point.
You have to choose an indicator which changes colour on the steep
bit of the curve.
Weak acid v strong base

This time, the methyl orange is hopeless! However, the

phenolphthalein changes colour exactly where you want it to.
Weak acid v weak base

The curve is for a case where the acid and base are both equally
weak - for example, ethanoic acid and ammonia solution. In other
cases, the equivalence point will be at some other pH.

You can see that neither indicator is any use. Phenolphthalein will
have finished changing well before the equivalence point, and
methyl orange falls off the graph altogether.
It may be possible to find an indicator which starts to change or
finishes changing at the equivalence point, but because the pH of
the equivalence point will be different from case to case, you can't
generalise.
On the whole, you would never titrate a weak acid and a weak base
in the presence of an indicator.
Sodium carbonate solution and dilute hydrochloric acid
This is an interesting special case. If you use phenolphthalein or
methyl orange, both will give a valid titration result - but the value
with phenolphthalein will be exactly half the methyl orange one.

It so happens that the phenolphthalein has finished its colour

change at exactly the pH of the equivalence point of the first half of
the reaction in which sodium hydrogencarbonate is produced.

The methyl orange changes colour at exactly the pH of the

equivalence point of the second stage of the reaction.