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Subtopic 18.3
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pH curves
18.3.0 The big picture ()
18.3 ()
18.3.1 pH curves and indicators ()
18.3.0 () 18.3.2 Salt hydrolysis and buffer solutions ()
18.3.3 Checklist ()
18.3.1 ()
18.3.2 ()
18.3.3 ()
The big picture
Essential idea: pH curves can be investigated experimentally but are
mathematically determined by the dissociation constants of the acid and base.
An indicator with an appropriate end point can be used to determine the
equivalence point of the reaction.
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Understanding the nature of acidity and alkalinity, and their measurement in terms of
pH value, is central to many aspects of modern chemistry and various phenomena in
our world. The following animations and links are presented here to give you chance
to explore different aspects of these ideas.
The final link is to a downloadable spreadsheet and database facility that enables you
to plot the titration curves for different combinations of strong and weak acids and
bases and evaluate why the curves are the shape they are. It can be found here
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(http://www2.iq.usp.br/docente/gutz/Curtipot_.html).
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The features of a titration curve for a strong acid and strong alkali.
Figure 2. The features of a titration curve for a strong acid and strong alkali.
Important
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Titration curve for a weak acid (ethanoic acid) and a strong alkali (NaOH).
Figure 3. Titration curve for a weak acid (ethanoic acid) and a strong alkali (KOH).
The half-equivalence point can be found on the x-axis at the point which is half the
volume added at the equivalence point. On the pH curve in Figure 3, this corresponds
to the 25 cm3 point. At the half-equivalence point, exactly half the acid has reacted
with base and been neutralised, with the other half remaining unreacted. The
properties of the solution at this point make it an ideal buffer solution, which
explains why the pH remains fairly constant when a small amount of base is added to
the acid.
At the half-equivalence point, the pH is equal to the pKa of the acid. The pH at the
half-equivalence point can be read directly from the graph, and the pKa of the acid
can be deduced. At this point the Ka = [H+], therefore the pKa = pH.
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Exam tip
When presented with a pH curve, make sure that you are able to find the
pH at the equivalence point.
Of the four possible pH curves of strong and weak acids and bases, only two have
been considered here. The other two possibilities we will look at below in the context
of the use of indicators. You will find it helpful to view the four possible pH curves as
made up of two regions – an acidic region (strong or weak) and a basic region (strong
or weak) – and then any curve can be assembled by combining the appropriate
regions together.
Be aware
It is possible to carry out these titrations the other way round – with the
alkali in the flask, and adding the acid from the burette. You should
realise that the curves obtained in this case are simply reflections of
those we have considered here (see the strong acid–strong base curves
below; Figures 5 and 7).
Acid–base indicators
In section 8.3.2 (https://app.kognity.com/study/app/chemistry-hl-2016/acids-bases/ph-
scale/acid-base-indicators/), we saw that an indicator changes colour depending on
the pH of the solution. Indicators are weak acids or bases with the dissociated and
undissociated forms having different colours. Like all weak acids and weak bases,
they exist in an equilibrium between the two forms which are represented as HIn (the
undissociated form) and In− (the dissociated form).
Colour A Colour B
Increasing [H+] by adding acid shifts the equilibrium to the left and colour A
will be seen.
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Decreasing [H+] by adding OH− ions shifts the equilibrium to the right and
colour B will be seen.
To summarise, the addition of an acid shifts the position of equilibrium to the side of
the undissociated form (HIn) and the addition of a base shifts the equilibrium to the
side of the dissociated form (In−).
Table 1 has a list of indicators, their pH ranges and pKa values. This information can
be found in section 22 of the IB Chemistry data booklet.
You will notice from the table that indicators do not necessarily change colour around
pH 7. Most indicators are weak acids with their own value of pKa and change colour
over a pH range that centres on that value. The change in colour of bromothymol
blue, known as its end-point, happens in the range pH 6.0–7.6, which is within the
approximate range of the pKa ± 1.0.
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Figure 4 illustrates 'what the eye sees' during the colour change of bromothymol blue.
The human eye is able to differentiate between the two colours when the
concentration of one form to another has a ratio of 10:1. Note that this is in the range
of 2 pH units, which explains why the end-point of an indicator is given as its pKa ± 1
pH unit.
Figure 5 shows how the colour change of bromothymol blue is capable of detecting
the equivalence point in the titration of a strong alkali with a strong acid. The key
factor here is that the colour change takes place over a small addition of acid,
coinciding with the vertical inflection in the pH curve which means that there is a
sharp end point.
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Important
Take care not to confuse the equivalence point and the end-point. The
end-point is the pH when the indicator changes colour and the
equivalence point is when acid and base have reacted in
stochiometrically equivalent amounts. A good indicator for a titration is
one for whom these two points coincide and the indicator changes
colour near to the equivalence point.
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Figure 7 shows the relationship between the pH range over which phenolphthalein
changes colour and the pH curve for a strong alkali/strong acid titration. This
shows that even though phenolphthalein changes colour around pH 9.6, it still gives a
sharp end-point for this titration as the range over which the colour changes falls in
the vertical region of the curve.
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Figures 5 and 7 show that both phenolphthalein and bromothymol blue would be
appropriate indicators for titrations between a strong acid and an alkali. In fact the
size of pH change around the equivalence point in such titrations is sufficiently great
that several different indicators could be used here. Figure 8 emphasises that methyl
orange would also be appropriate even though it changes colour over a very different
range to phenophthalein.
Figure 8. The titration curve for a strong acid / strong alkali titration showing that a
range of different indicators can be used for this experiment.
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Figure 9. The titration curve for a strong acid / weak alkali titration showing why
phenolphthalein is not an appropriate indicator for this experiment.
Table 2 summarises the usual choices of indicator for the different possible
combinations of acid–base titrations.
The titration of a weak acid with a weak base does not give a clearly defined
equivalence point as there is no significant jump in pH to identify. Consequently,
there is no suitable indicator for this case. This will be discussed in more detail in the
next section.
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Figure 10. The titration of phosphoric acid with sodium hydroxide, showing the three
equivalence points involved.
The example shown in Figure 11 is a particular case where the conductivity reaches
zero at the end point because the salt formed is insoluble – the reaction is between
barium hydroxide and sulfuric acid:
Checkpoint questions
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Table 1. pH of different salt solutions in relation to their parent acids and bases.
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Neutralisat Hydrolysis
ion Acid and Salt by ions Type of salt pH of
reaction base formed present solution solution
Some salts, however, dissolve in water to produce either acidic or alkaline solutions.
This occurs because one of the constituent ions of the salt reacts with water to release
an excess of either hydroxide or hydrogen ions. This phenomenon is referred to
as salt hydrolysis and it occurs with salts that are formed from either weak acids or
weak bases. The pH of an aqueous salt is dependent on the strength of the conjugate
acid and bases formed and their ability to hydrolyse water, producing H+ or OH− ions.
An example of hydrolysis by the salt formed from a weak acid and strong base is that
of sodium ethanoate. The ethanoate ion (CH3COO−) is the conjugate base of a weak
acid and is therefore strong enough to hydrolyse a water molecule.
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Buffer solutions
A buffer solution resists a change in pH when small amounts of acid or base are
added. Figure 2 shows the significant change in pH produced by simply adding a
very small volume of acid or alkali to unbuffered water.
Buffer solutions have many uses in chemistry – they are utilised whenever it
is necessary to have a controlled pH. Buffers are necessary in electrophoresis, for
example, and are used to calibrate pH meters. They are also an important ingredient
in shampoos and dyes. In addition, the pH of blood is buffered to a slightly basic
value of pH 7.4, as the action of enzymes is heavily pH dependent.
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When a small amount of base is added, the OH– ions will combine with the
undissociated ethanoic acid molecules, therefore removing the hydroxide ions from
the solution and resisting a change in pH:
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equation (note that like the equilibrium lies to the left as NH3 is a weak base):
The salt, ammonium chloride, fully dissociates into ammonium ions and chloride
ions:
The mixture contains relatively high concentrations of both NH3 and NH4+, that is the
base and its conjugate acid, which react with added H+ or OH− ions in the buffer
solution.
When a small amount of acid is added, the H+ ions will combine with the NH3 to
form NH4+, removing most of the added H+ ions and resisting a change in pH:
When a small amount of base is added, the OH– ions will combine with NH4+ to form
NH3 and H2O, therefore removing most of the added OH– and resisting a change of
pH:
Generally, buffer solutions can be made by mixing a weak acid or weak base with an
equimolar solution of a salt containing its conjugate. An alternative approach, which
results in an acidic buffer solution, is to start with a weak acid and add half as many
moles of strong base. Similarly, a basic buffer can be prepared by starting with a weak
base and adding half as many moles of strong acid.
For example, if 1.0 mol of ethanoic acid is reacted with 0.5 mol of sodium hydroxide,
the resulting solution would contain 0.5 mol of ethanoic acid and 0.5 mol of sodium
ethanoate. Alternatively, if 1.0 mol of ammonia is reacted with 0.5 mol of
hydrochloric acid, the resulting solution would contain 0.5 mol of ammonia and 0.5
mol of ammonium chloride. In both of these examples, the final solutions contain
equal amounts of a weak acid (or base) and its conjugate base (or acid), therefore
acting as buffer solutions.
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The key point in any of the above methods is that the initial solution must be a weak
acid or base, otherwise the starting acid or base would already be 100% dissociated
into ions. Both components of a conjugate acid–base pair have to be present in the
solution for it to be able to neutralise any added acid or base.
A buffer solution is prepared by using a weak acid or base with a pKa or pKb value
that is as close to the required pH or pOH of the buffer as possible. Regardless of the
method of buffer preparation, the nature of an acid–base buffer remains the same – a
constant pH is sustained following any addition of small amounts of acid or base.
Checkpoint questions
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Checklist
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