19: Ionic equilibria

Question/key idea
Brønsted-Lowry theory

The Brønsted-Lowry theory of acids and bases is the most generally useful. According to this theory an acid
is a proton donor, and a base is a proton acceptor. Acids and bases may be molecules or ions.
When HCl gas is added to water a reaction occurs:
HCl + H 2 O H 3 O+ + Cl –
In this process the HCl donates a proton to the water, so HCl is the acid and water is the base. The equilibrium
is far to the right (in fact sometimes not shown as an equilibrium at all) and the HCl is therefore described
as a strong acid. In other cases e.g. ethanoic acid, the equilibrium is significantly further to the left and the
acid is said to be weak.
In general:
A strong acid is fully dissociated in water; a weak acid is partially dissociated.
Using Brønsted-Lowry theory any acid–base reaction can be seen as involving two acid-base pairs. In the
above reaction, once the HCl has lost a proton, the resulting Cl– ion could, in principle, regain a proton and
is thus a base; it is said to be the conjugate base of HCl. Similarly when water gains a proton to become
H 3 O+, the H 3 O+ is now a potential proton donor and so is described as the conjugate acid of water.

HCl + H2O H 3 O+ + Cl –
acid 1 base 2 acid 2 base 1

Such relationships can be used to assess the strength of an acid or a base. In this case since HCl is a strong
acid, its conjugate base, Cl–, must be a very weak base. Similarly, as water is a weak base, its conjugate acid,
H 3 O+, must be a strong acid.

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 Question/key idea
Water itself ionises to a very limited extent (about one molecule in 500 million is split up at any instant):

2 H2O H 3 O+ + OH –
In this process water is acting both as an acid (proton donor) and as a base (proton acceptor) and is said to
be amphoteric. Other examples of amphoteric species include the hydrogensulfate ion, HSO 4 – (which can
accept H+ to form H 2 SO 4 , or lose H+ to give SO 4 2–) and ammonia, NH 3 (which can accept H+ to form NH 4 + ,
or lose H+ to give NH 2 –).
Any substance that increases the concentration of H 3 O+ ions (H+ (aq) ) in water is an acid.

Any substance that increases the concentration of OH– ions is a base, since it accepts a proton from water.
A strong base dissolves in water to form hydroxide ions. Besides the soluble hydroxides, including NaOH
and KOH, ions like ethoxide, C 2 H 5 O–, and amide, NH 2 –, are strong bases:
e.g. C 2 H 5 O– + H 2 O C 2 H 5 OH + OH – (equilibrium lies far to the right)
Weak acids react to a very limited extent with water to give H 3 O+ ions: for a 0.1 mol dm–3 solution of
ethanoic acid only about 2% of the molecules are dissociated:
CH 3 COOH + H 2 O H 3 O+ + CH 3 COO–

Reactions of Acids
See ‘1: Moles, Equations & Acids’

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 Question/key idea
Ionic Product for Water
As described in the previous section, a small proportion of water molecules at any instant have split up into
ions:
H 2 O(aq) H+(aq) + OH–(aq)

(NOTE: except when considering Brønsted-Lowry processes, H+(aq) is more convenient than H 3 O+)

The equilibrium constant for the process is given by the expression:

[H + (aq)] × [OH - (aq)]

Kc =
[H 2 O(l)]

In dilute solutions the concentration of water is so much higher than that of the acid or base that is can be
considered to be constant (55.6 mol dm–3) and so the numerator is also constant; therefore:
K w = [H+(aq)]×[OH–(aq)]
K w is known as the ionic product for water. Its value at 298 K is very close to 1×10–14 mol2 dm–6.
Since the dissociation of water into ions is an endothermic process*, the value of K w increases with
increasing temperature (from Le Chatelier):

0°C 1.14×10–15; 25°C 1.01×10–14; 100°C 5.13×10–13 all mol2 dm–6

i.e. 0.114 1.01 51.3 all ×10–14 mol2 dm–6
* the reverse reaction, H+ + OH– → H 2 O, is simply a neutralisation, and is exothermic.

A neutral solution at any temperature is one in which there are equal concentrations of H+ and OH– ions.
Thus pure water is always neutral, even though its pH may not always be 7 if the temperature is not 298K!

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 Question/key idea
pH and calculations
(a) Definition
pH values provide a simple numerical indication of the acidity of an aqueous solution in terms of the
concentration of hydrogen ions present.

pH is defined as –log 10 [H+(aq)], where [H+(aq)] is the concentration of H+ ions in mol dm–3.

The lower the value of pH, the more acidic the solution.
pH values are commonly reported to two decimal places, for consistency.
pH can be converted back to give a value for [H+] by using the expression [H+] = 10-pH.

(b) pH of water
For pure water at 298 K:

[H+] = [OH–] = 1.0×10–7 mol dm–3 (i.e. K w )

since –log (1 ×10–7 ) = 7.00, the pH is 7.00. [log implies log 10 from now on]

The pH value corresponding to neutrality is thus 7, as water is assumed to be neutral, but note that the pH
of water varies with temperature because its K w varies. At temperatures above 298 K water dissociates
more, and the pH is less than 7, although the water is still neutral, since [H+(aq)] still equals [OH–(aq)].

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 Question/key idea
(c) pH of strong acids
Since strong acids are fully ionised in aqueous solution, [H+(aq)] can be obtained directly from the
concentration of the acid. Note that a diprotic strong acid, such as sulfuric acid, will produce two moles of
H+ ions per mole of H 2 SO 4 , so the H+ concentration will be twice that of the acid.

e.g. a 0.10 mol dm–3 solution of hydrochloric, or any other strong monobasic acid, has [H+(aq)] = 0.10, and
so its pH = –log (0.1) = 1.00.
Since concentrated acids may have concentrations greater than 1 mol dm–3, negative pH values are possible.

(d) pH of alkalis
In alkaline solutions there is still a finite H+(aq) concentration, which can be calculated from the value of K w .
e.g. For NaOH(aq) of concentration 0.10 mol dm–3 at 298 K

[H+] [ OH–] = 1×10–14 mol2 dm–6

NaOH is a strong alkali, so [OH–] = 0.10
1× 10 −14
Hence [H+] = = 1×10–13 , and so the pH is 13.00.
0.10

Weak Acids
(a) pK a
A weak acid in aqueous solution donates protons to water molecules, but the process is not complete, and
some undissociated acid molecules will always be present in solution. A dynamic equilibrium is again
established, and an equilibrium constant expression can be written:

HA(aq) H+(aq) + A–(aq); Ka = [ H + (aq)] × [A - (aq)]

[ HA(aq)]

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 Question/key idea
K a is known as the dissociation constant for the acid, and provides a direct measure of the relative strength
of the acid: the weaker the acid, the smaller will be the value of K a . For the remainder of this section we will
omit the (aq) in equilibrium expressions.

Values of K a are usually less than 1, and so it is often convenient to present them in the logarithmic form,
pK a , where pK a = –log(K a ).
Note that a higher value of pK a represents a weaker acid.

You should be able to convert between pK a and K a values. (K a = 10-pKa)

(b) pH of Weak Acids

The pH of a solution of a weak acid can be calculated if its K a (or pK a ) and concentration are known.
e.g. the pK a for ethanoic acid is 4.76
hence: K a = 10–4.76 = 1.74 × 10–5 mol dm–3
[H + ] × [A - ]
and Ka = (1)
[HA]

by definition (where A– represents the ethanoate ion, CH 3 COO–).

Since every molecule of ethanoic acid gives one ethanoate ion and one H+(aq) ion, there must be equal
numbers of the two ions in any solution, and so [H+] is equal to [ A–];
[H + ]2
Thus Ka = (2)
[HA]

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 Question/key idea
Since very few acid molecules actually dissociate at this concentration, [HA] is essentially the same as the
original concentration of the acid. So for a 0.10 mol dm–3 solution, inserting values into (2) gives:
[ H + ]2
1.74 × 10–5 =
0.10

from which [H+(aq)] = 1.74 × 10 −6 = 1.32 × 10–3 mol dm–3 and the pH is 2.88.

Remember, the assumptions made are:

• [H+] = [A–], i.e. neglecting H+ from water
• [HA] = concentration of acid, i.e. assuming acid is only very slightly dissociated

pH Curves
The characteristic shapes of curves showing how the pH changes for various strong/weak acid/base
combinations are shown below, for 10 cm3 of 0.10 mol dm–3 acid against 0.10 mol dm–3 base.

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 Question/key idea
On the left, for HCl/NaOH, the pH starts at 1, and the curve is almost horizontal up to the endpoint. Then it
rises sharply (end-point = middle of vertical section = about 7) and quickly flattens out again, heading
towards pH=13. The steep vertical section of the curve is called the equivalence point – it is where equivalent
amounts of acid and base are present. A suitable indicator for that particular reaction must change colour
in that region – the end point of a titration is the volume at which equivalence is reached.
Of the two most common indicators, methyl orange changes colour from about 3.5-5.0 (vertical line to left)
and phenolphthalein from about 8.5-10: either is suitable as it changes completely over the vertical section
around 10 cm3.
On the right, for CH 3 COOH/NaOH, the curve starts higher at 2.9 since the acid is weak, then the pH rises
gradually over a fairly straight section called the buffer region (see below). The end point is around pH=8.5,
then the latter part of the curve is similar to the first one. Only phenolphthalein is suitable to detect the
endpoint: methyl orange would change very slowly over the buffer region.

The last two graphs show similar patterns. On the left, strong acid against weak base can be titrated using
methyl orange to detect the end point, while on the right the weak acid and base give no sharp endpoint
and there is no suitable indicator.

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 Question/key idea
Summary:
• using a weak base, like ammonia, phenolphthalein is unsuitable because it doesn’t start to change
until after the endpoint.
• using a weak acid, like ethanoic acid, methyl orange is unsuitable because it changes steadily, and
change is complete before the endpoint.

Colours:
• Phenolphthalein: colourless from 1 to 8.5, turns pink from 8.5 to 10, remains pink above 10.
• Methyl orange: red from 1 to 3.5, then changes from red through orange to yellow between 3.5 and
5.0; yellow from 5.0 to 14.

Buffer Solutions
(a) How Buffers Work
A buffer solution is a system that minimises changes in pH on addition of small amounts of acid or base.
You should be able to see on the pH curve above for CH 3 COOH/NaOH that on the flat section of the curve,
referred to as the buffer region, the pH is not changing by a large amount even though base is being added.
Starting from the middle of this region, at 5cm3, small amounts of base or acid could be added without
significantly changing the pH. Thus, the solution present after 5cm3 had been added is called a buffer
solution (an acidic buffer, in this case).
A buffer solution could be purposefully made in two different ways:
(i) mixing a weak acid with its sodium salt (or similar) e.g. ethanoic acid and sodium
ethanoate, giving high concentrations of CH 3 COOH molecules and CH 3 COO– ions; or
(ii) a weak base with one of its salts e.g. ammonia and ammonium chloride, giving high
concentrations of NH 3 molecules and NH 4 + ions.

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 Question/key idea
Considering the dissociation of ethanoic acid, in the buffer we have deliberately made the concentrations
of CH 3 COOH molecules and CH 3 COO– ions (the conjugate base) large, and this determines the concentration
of H+ ions, and so the pH.
CH 3 COOH H+ + CH 3 COO–

When a little additional strong acid is added, most of the H+ ions react with some of the ethanoate to form
ethanoic acid:
H+ + CH 3 COO– → CH 3 COOH
Therefore the concentration of H+ in the solution only rises slightly, and there is a very small drop in pH.

Conversely, if some alkali is added, most of the OH– ions react with CH 3 COOH molecules:
OH– + CH 3 COOH → H 2 O + CH 3 COO–
This time the H+ doesn’t fall by nearly as much as expected, and the pH rises slightly.
(b) Calculating the pH of a buffer
As with weak acids, there are two methods, and the more straightforward one is described first.
(i) What is the pH of a buffer solution containing 0.500 mol dm–3 sodium ethanoate and
0.800 mol dm-3 ethanoic acid (Ka = 1.74 × 10–5 mol dm–3)?

In a buffer made up from a mixture of HA and NaA, it is a very good approximation that all of the acid HA
will be undissociated, and all the A– will come from the salt:
[HA] = conc. of acid; [A–] = conc. of salt

[H + ] × [A - ]
[H + ] × 0.500
Then: Ka = = = 1.74 × 10–5 mol dm–3
[HA] 0.800
from which [H+] = 2.78 × 10–5 mol dm–3, and pH = 4.56

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 Question/key idea
(ii) What is the pH of a buffer solution in which the molar ratio of ethanoic acid to sodium ethanoate is 5: 1?
NB: Since the substances are in the same volume, the concentrations must also be is a 5:1 ratio).
[H + ] × [A - ] [𝐻𝐻𝐻𝐻]
If: Ka = then: [H+] = K a x
[HA] [𝐴𝐴− ]
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[H+] = 1.74 × 10–5 x 1 = 8.7 x 10-5 mol dm–3
pH = 4.06
In the alternative method, the Henderson-Hasselbach equation is derived as follows from the dissociation
constant expression for the weak acid used in the buffer (representing the acid as HA):
[H + ] × [A - ]
Ka =
[HA]

[A − ]
Taking logs gives log K a = log[H+] + log
[ HA]

and so –log K a = –log[H+] – log [A − ]

[ HA]

[A − ]
or pK a = pH – log
[ HA]

[A − ]
from which pH = pK a + log
[ HA]

Since the acid is weak it is present almost entirely in the form of molecules, and virtually all the A– comes
from the salt present; so, to a good approximation, [A–] is the same as the concentration of the salt and
[HA] is the same as the concentration of the acid, giving
[concentration of salt] Note that, when the acid is half-neutralised,
pH = pKa + log
[concentration of acid] or the concentrations of acid and salt are
equal, [HA] = [A–], and [H+] = Ka (or pH = pKa).

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 Question/key idea
Examples using pK a :

(ii) What is the pH of the solution obtained when 41g of sodium ethanoate is dissolved in 1dm3 of 0.800 mol
dm–3 ethanoic acid (pKa = 4.76)?

Molar mass of CH 3 COONa = 82 g mol–1

41 g
Amount of CH 3 COONa in 41g = -1 = 0.500 mol; [CH 3 COONa] = 0.500 mol dm
–3
82 g mol
[A − ]
pH = pK a + log
[ HA]

0.500
= 4.76 + log = 4.56
0.800

(ii) What is the pH of the buffer solution obtained when 100 cm3 of 0.100 mol dm–3 ethanoic acid is mixed
with 20cm3 of 0.300 mol dm3 sodium ethanoate solution?
100
Amount of ethanoic acid = × 0.100 = 0.0100 mol
1000
20
Amount of sodium ethanoate = × 0.300 = 0.0060 mol
1000

[A − ] 0.0060
pH = pKa + log = 4.76 + log = 4.54
[ HA] 0.0100

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 Question/key idea
(iii) What is the pH of a solution obtained by mixing 70 cm3 of 0.100 mol dm–3 ammonia with 30 cm3 of 0.100
mol dm–3 ammonium chloride? (pK a of ammonium ions = 9.25)
NH 4 + H+ + NH 3
so the form of the Henderson-Hasselbach equation is:
pH = 9.25 + log [NH 3 ]
[ NH +
4]

Since the solutions have the same concentrations, the ratio of ammonia to ammonium ions is simply the
ratio of the volumes added:
70
pH = 9.25 + log = 9.62
30

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 Question/key idea
Calculating the pH of a buffer solution formed during the neutralisation of a weak acid by a strong base.
e.g. Calculate the pH of the buffer solution formed when 15.5 cm3 of 0.1 mol dm-3 NaOH is added to 25cm3
of 0.1 mol dm-3 CH 3 COOH. (K a for ethanoic acid = 1.74 x 10-5 mol dm-3)
CH 3 COOH + NaOH  CH 3 COONa + H 2 O
Ka = 1.74 x 10-5 mol dm-3
Initial moles of CH 3 COOH = 25/1000 x 0.1 = 0.0025
Initial moles of NaOH = 15.5/1000 x 0.1 = 0.00155

After neutralisation: Total volume = 25 + 15.5 = 40.5 cm3 (0.0405 dm3) = (Total volume = V).
n (CH 3 COONa) formed = 0.00155 (all the NaOH has reacted)
n (CH 3 COOH) left over = 0.025 – 0.00155 = 0.00095
[CH 3 COONa] = [A-] = n/V = 0.00155/0.0405 = 0.0383 mol dm-3
[CH 3 COOH] = [HA] = n/V = 0.00095/0.0405 = 0.0235 mol dm-3

[H + ] × [A - ] [𝐻𝐻𝐻𝐻]
Ka = then: [H+] = K a x
[HA] [𝐴𝐴− ]

[𝐻𝐻𝐻𝐻]
[H+] = K a x = 1.74 x 10-5 x 0.0235/0.0383 = 1.068 x 10-5 mol dm-3
[𝐴𝐴− ]
pH = - log (1.068 x 10-5) = 4.97

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 Question/key idea
Buffers in blood
The pH of blood needs to be maintained between a pH of 7.0 and 7.9 if it is to carry oxygen efficiently (typical
value: 7.4). This is achieved by buffer solutions, especially one involving carbonic acid and
hydrogencarbonate ions:
CO 2 (aq) + H 2 O H 2 CO 3 (aq) H+(aq) + HCO 3 –(aq)
The amount of CO 2 dissolved in the blood is controlled by the lungs:
CO 2 (g) CO 2 (aq)
The amount of hydrogencarbonate ions is regulated by the kidneys or using the enzyme carbonic anhydrase
found in the blood in tissues (this enzyme can, indecently, catalyse both the conversion of HCO 3 - to H 2 CO 3
and CO 2 to H 2 CO 3 ).

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 Question/key idea
Enthalpy of neutralisation

The standard enthalpy change of neutralisation (ΔH neut ө) of a substance is the change in heat
energy content during the neutralisation of an aqueous acid by an aqueous base to form one mole of H 2 O
(l), under standard conditions

e.g. HCl + NaOH → NaCl + H 2 O ΔH neut ѳ = –57.1 kJ mol–1

Note that as the enthalpy of neutralisation is per mole of water formed, the enthalpy change will be related
to the number of moles of H+ released by an acid in solution:

e.g. Enthalpy changes for reactions of three acids with sodium hydroxide:

HCl (aq) + NaOH (aq)  NaCl (aq) + H 2 O (l) -57.1 kJ/mol

H 2 SO 4 (aq) + 2NaOH (aq)  Na 2 SO 4 (aq) + 2H 2 O (l) -114.2 kJ/mol

H 3 PO 4 (aq) + 3NaOH (aq)  Na 3 PO 4 (aq) + 3H 2 O (l) -171.3 kJ/mol

So the enthalpy change for the reaction of one mole of each of the acids with sodium hydroxide is
proportional to the number of H+ ions released by the acid. Sulphuric acid’s is twice that of hydrochloric acid
because it is a dibasic acid – it releases two moles of H+ ions per mole of H 2 SO 4 . Likewise, phosphoric acid
is tribasic and has thrice the enthalpy change. NB: The enthalpy of neutralisation, however, is still the same
for all of these strong acids, as this is taken as the enthalpy change per mole of water formed.

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 Question/key idea
Stretch and Challenge: Multibasic acids.
Some acids are able to release more than one H+ ion per molecule – for example, ethanedioic acid, (COOH) 2
can release two H+ ions per molecule and is described as dibasic. Citric acid is tribasic. These multibasic
weak acids will release their H+ ions sequentially, not all at once. Each dissociation will have its own
equilibrium and thus its own K a and pK a value.

HO O
O O O O

HO OH
HO OH
HO
ethanedioic acid citric acid

e.g. Citric acid – three dissociations:

C 3 H 4 OH(COOH) 3 ⇋ H+ + C 3 H 4 OH(COOH) 2 (COO-) pK a = 3.15

C 3 H 4 OH(COOH) 2 (COO-) ⇋ H+ + C 3 H 4 OH(COOH)(COO-) 2 pK a = 4.77
C 3 H 4 OH(COOH)(COO-) 2 ⇋ H+ + C 3 H 4 OH(COO-) 3 pK a = 6.40

Notice how it becomes more ‘difficult’ for successive protons to dissociate – they are having to leave a
negatively charged species to which they are attracted. This is typical for a multibasic acid.

NB: DO NOT FORGET: Endorsement practical – Finding Ka of a weak acid by 2 different methods!

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