A2 acid-base equilibria

Arrhenius theory

Acids are ionised by the action of water to release H+ ions in to solution. It is the H+ ion
that is responsible for acid properties.

e.g. HCl (g) + water  H+ (aq) + Cl—(aq)

Properties of bases

Bases neutralise acids to form salts and water.

Bases that are soluble in water are classified as alkalis eg. sodium carbonate (Na 2CO3)

Typical strong alkalis are group I hydroxides (eg. NaOH) and group II (e.g. Ba(OH) 2)

 Alkalis turn litmus blue

Arrhenius proposed that :

Alkali are ionised by the action of water to release hydroxide OH —(aq) ions in to solution
e.g. the hydrogen carbonate ion

NaHCO3 (s) + H2 O  Na+ (aq) + H2CO3(aq) + OH—(aq)

3.1.12.1 Brønsted–Lowry acid–base equilibria in aqueous solution

An acid is a proton donor.
A base is a proton acceptor.
Acid–base equilibria involve the transfer of protons.

An acid is defined a s a proton donor, a base is defined as a proton acceptor. Hence acid-
base reactions are defined as proton transfers:

HA + B-  HB + A-

A base is a particle with a lone pair of electrons able to form a dative covalent bond with
the proton. It may or may not have a negative charge.
 A2 acid-base equilibria
In aqueous solution water plays the role of the base, forming the hydronium ion H 3O+
(aq)

e.g. HCl (aq) + H2O (l) H3O+(aq) + Cl- (aq)

In the absence of a proton acceptor such as water, HCl cannot donate a proton and does
not exhibit acidic properties.

However water may also act as a proton donor:

e.g. H2O (l) + NH3 (aq) OH-(aq) + NH4+ (aq)

Hence water is classified as amphoteric – able to act as both an acid and a base.

Problems sheet on BL neutralisations

1. Label the acid-base conjugate pairs in the following acid-base reaction

a) HCl (l) + H2O (l) H3O+ (aq) + Cl- (aq)

b) HNO3 (l) + H2SO4 (l) HSO4- (aq) + H2NO3+(aq)

c) CH3COOH (l) + H2O (l) CH3COO -(aq) + H3O+ (aq)

d) NH3 (aq) + HCl (aq) NH4+(aq) + Cl-(aq)

e) H3O+(aq) + HSO4- (aq) H2O (l) + H2SO4 (aq)

f) HSO4- (aq) + OH-(aq) SO42- (aq) + H2O (l)

g) CO32- (aq) + H2O(l) HCO3- (aq) +OH- (aq)

 A2 acid-base equilibria
3.1.12.2 Definition and determination of pH

The pH scales is a measure of the acidity of a solution.

pH is defined as the negative log to the base 10 of the concentration of the hydrogen
ion.

pH = - log10 H+ (aq) 

Therefore a ten fold decrease in H+ in concentration produces an increase of 1 pH unit.

It is a logarithmic scale – producing convenient numbers to work with.

 pH numbers below 7 indicate an acidic solution

 pH number 7 indicates a neutral solution

 pH numbers above 7 indicate an alkaline solution.

Strong acids and bases are assumed to be fully ionised in aqueous solution : therefore
the concentration of the H+ or OH- ions produced can be predicted from the balanced
equation of the ionisation.

eg HCl (g) + water  H+ (aq) + Cl- (aq)

1 mole of monoprotic acid produces one mole of ions on dissolving

BUT
H2SO4 (l) + water  2H+ (aq) + SO42- (aq)

1 mole of diprotic acid produces 2 moles of hydrogen ions on dissolving

eg NaOH (s) + water  Na+ (aq) + OH- (aq)

1 mole of sodium hydroxide produces 1 mole ion hydroxide ions on dissolving

 A2 acid-base equilibria
To calculate the pH of a strong acid

Firstly, deduce the concentration of hydrogen ions formed based on the original acid
concentration and then apply the pH definition.

eg: Calculate the pH of 0.1 mol.dm-3 HCl

eg Calculate the pH of of 0.1 mol.dm-3 H2SO4

TASK : text p317 summary qns 1,4,

2. Calculate the pH of the following solutions ( Kw = 1 x 10-14 mol2dm-6)

Strong electrolytes can be assumed to be completely ionised

(a) 1.0 moldm-3 HCL (b) 0.1 moldm-3 HNO3 (c ) 2.0 moldm-3 HBr
(d) 0.22 moldm-3 H2SO4
 A2 acid-base equilibria

To calculate [H+] from a given pH re-arrange the pH definition.

Eg calculate the [H+] in a solution of pH 4.

pH = - log10 H+ (aq) 

4 = - log10 H+ (aq) 

- 4 = log10 H+ (aq) 

0.0001 mol dm-3 = [H+] = 1 x 10-4 mol dm-3

Task: text p317 summary qn 2

3. Calculate the hydrogen ion concentration in solutions of the following pH

(a) 0 (b) 1.0 (c ) 7.0 (d) 9.0

(e) 14.0 (f) 3.2 (g) 6.4 (h) 10.8

 A2 acid-base equilibria
3.1.12.3 The ionic product of water, KW

Water undergoes an endothermic ionization to a very small extent (at 298K):

H2O (l) H+ (aq) + OH- (aq)

The equilibrium constant expression is:

K= [H+(aq)] [OH- (aq)]

[H2O(l)]

which due to the virtually constant concentration of water simplifies to

Kw = [H+ (aq)] [OH- (aq)]

Kw is called the ionic product of water

Task – calculate the value and units of Kw at 298K given that water has a pH of 7

It follows from Eqn 1 above that:

The Ionic product of water and has a value of 1 x 10-14 mol2 dm-6at 298K.

Task - Predict the effect on Kw of a temperature increase ( hint- use Le Chatelier)

 A2 acid-base equilibria
To calculate the pH of the solution of a strong alkali

This is achieved via the value of Kw

e.g Calculate the pH of a 0.1 mol dm-3 solution of NaOH

Tasks: text p317 summary Qns 5 and 3

4. Calculate the pH of the following solutions ( Kw = 1 x 10-14 mol2dm-6)

Strong electrolytes can be assumed to be completely ionised

(a) 1.0 moldm-3 NaOH(b) 0.1 moldm-3 LiOH (c) 0.1 moldm-3 Ba(OH)2

(d) 0.05 moldm-3 Ca(OH)2 (e) 0.75 moldm-3 KOH

5. What is the pH of the solution resulting from adding 25 cm3 of 0.1 M NaOH to
24.5 cm3 of 0.1 M HCl?
 A2 acid-base equilibria
3.1.12.4 Weak acids and bases, Ka for weak acids

Weak acids and alkalis are ……………………………………………………………………………………………….

– an equilibrium between ions and molecules results. They are classified as weak.

Examples of weak acids are carbonic acid and ethanoic acid

i.e. H2CO3 (aq) HCO3— (aq) + H+ (aq)

Examples of weak alkalis are ammonia and ethylamine

i.e. NH3 (aq) + H2 O NH4+(aq) + OH—(aq)

This partial ionisation means that a solution of a weak acid is less acidic than a solution
of a strong acid :
i.e. comparing a weak acid solution to that of a strong acid of identical
concentration:

 the weak acid will be ……………………………………………………………………,

 the weak acid will react ……………………………………………………………………,

 the weak acid will have ……………………………………………………………………,

However, weak and strong acids react in the ………………………………………………………………,

as each other with a strong alkali, as the OH- ion acts on the acid to strip all the available
H+ ions from it.

The equilibrium constant expression

For any weak acid HA :

HA(aq) + H2O (l) A-(aq) + H3O+ (aq)

Applying the equilibrium law gives:

K =

and as the concentration of water is effectively a constant

K x [H20 (l)] = Ka =

where Ka is the equilibrium constant of the weak acid

 A2 acid-base equilibria
TASK
Calculate the pH of a solution of a weak acid based on data for concentration
and Ka, and discuss the assumptions made in the calculation

pH can be calculated from Ka and concentration data assuming that:

1. the initial concentration of the acid is effectively the same as the concentration
at equilibrium

2. the concentration of H+ ions is the same as the concentration of anion

e.g. What is the pH of 0.01 moldm-3 benzoic acid, given Ka as 6.4 x 10 -5 mol dm-1

C6H5COOH(aq) C6H5COO- (aq) + H+(aq)

Ka =

Assume that [H+ (aq)] = [C6H5COO- (aq)]

Square root both sides

Apply the definition of pH

 A2 acid-base equilibria
TASK

If the concentration of a weak acid solution and its pH is known then K a can be
calculated.

e.g. The pH of 0.01 moldm-3 ethanoic acid is 3.40 at 25 oC

CH3COOH (aq) + H2O (l) CH3COO- (aq) + H+ (aq)

Ka = [H+ (aq)] [CH3COO- (aq)]

[CH3COOH (aq)]
 A2 acid-base equilibria
pKa - very often data about Ka is presented in the more convenient form

Just as pH = - log10 H+ (aq) 

pKa = - log Ka

Task – convert Ka to pKa values and vice versa

The relative strength of an acid can be found by inspection of Ka or pKa values

 The more positive the value of pKa the ………………………………………………………….

 The smaller the value of Ka the ………………………………………………………………………..

Some example values are:

Acid pKa Ka

Increasing HCl -7 1 x 107

acidic
strength CH3COOH 4.8 1.6 x 10-5

HCN 9.3 5 x 10-10

 A2 acid-base equilibria
4.7 Measure the pH change during titrations and draw titration curves using
different combinations of strong and weak monobasic acids and bases

Using indicators such as:

 methyl orange (……………………………………………………………………………………………………)

 phenolphthalein (…………………………………………………………………………………………….…)
an accurate end point can be determined.

Using a pH meter the pH changes during a titration can be followed.

A graph of pH for a strong acid/ strong base titration has a typical shape

Take hydrochloric acid and sodium hydroxide as a typical strong acid and strong base.

Adding acid to the alkali

There is a rapid increase
in pH around the
equivalence point.

The pH only falls a very small amount until quite near the equivalence point. Then there
is a rapid change in pH.
 A2 acid-base equilibria
TASK –

25cm3 of 0.1mol.dm3 HCl was titrated with 0.1mol.dm3 NaOH.

a) Calculate the pH values when the following values of sodium hydroxide solution have
been added.

(i) (ii) (iii) (iv) (v) (vi) (vii) (viii)

Volume NaOH 0 5.0 10.0 20.0 24.0 25.0 26.0 30.0

added (cm3)

pH

b) Plot a graph of pH against volume of NaOH added.

 A2 acid-base equilibria

c) Thymol blue indicator has a pH range of 1.2 – 2.8.

If this indicator were used in this titration what volume of NaOH would have been
added when the indicator :

(i) started to change colour ?

(ii) completed its colour change ?

Would thymol blue be a suitable indicator for this titration?

 A2 acid-base equilibria

Titration curves for weak acid v weak base

For example; 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.

Running acid into the alkali

Notice that there isn't any vertical part to this graph. Instead, there is only a "point of
inflexion".
 A2 acid-base equilibria

Titration curves for strong acid v weak base

Required Practical 9

For example, hydrochloric acid as the strong acid and ammonia solution as a weak base

Adding acid to the alkali

At the start 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 acidic ( a bit less than pH 5), because pure
ammonium chloride isn't neutral. However, the equivalence point still falls on the
vertical part of the curve.

This is due to Salt Hydrolysis

This refers to the interaction between a salt in solution and water.

For any salt Na+A-

A- + H2 O  HA + OH-

Hence an anion such as the ethanoate ion, CH3COO- , forms an alkaline solution.

Hence weak acids (small Ka values) react to form salt solutions that are alkaline, where
as strong acids (Ka is very large) react to form generally neutral salt solutions.
 A2 acid-base equilibria

Titration curves for weak acid v strong base

For example; ethanoic acid and sodium hydroxide

Running acid into the alkali

For the first part of the graph, you have an excess of sodium hydroxide.

Past the equivalence point you have a buffer solution containing sodium ethanoate and
ethanoic acid.
 A2 acid-base equilibria

TASK -
Identify the type of acid base titration being carried out.
AND
and choose appropriate indicators for each titration type

(refer to Text p325 )

 A2 acid-base equilibria
3.1.12.6 Buffer action

Buffer solutions have the property of resisting changes in pH on addition of small

amounts of strong acid or alkali. Blood is an example, maintaining a pH of close to 7.4.

Buffers are a mixture of solutions of either:

 ………………………………………………………. ( eg. ethanoic acid and sodium ethanoate)

 ACIDIC BUFFER

Or:

 ………………………………………………………. (eg. ammonia and ammonium chloride)

 BASIC BUFFER

Buffers rely on the equilibrium involving weak acids

HA(aq) H+(aq) + A–(aq)

There are two assumptions underlying this expression:

1. The equilibrium concentration of the acid IS the same as the initial concentration
of the acid.

2. The concentration of the anion A- IS equal to the concentration of the acid salt,
because acid salts are ionic and completely dissociate.
Na+A- (aq)  Na+ (aq) + A- (aq)

HOW DO BUFFERS WORK:

Add acid (H+)

Add alkali (OH-)

In order for a buffer solution to act as a buffer there must be plenty of HA and A-!
Calculations with buffers
 A2 acid-base equilibria

The pH of a buffer solution is simple to calculate from the acid ionization constant and
concentration data.

Consider any weak acid mixed with a solution of its salt:

HA(aq) A-(aq) + H+ (aq)

Which gives Ka :

pH of the buffer solution is not affected by water (dilution).

Example:

Calculate the pH of a solution which contains 0.05 mol dm-3 CH3COOH and 0.20 mol
dm-3 CH3COO-Na+

(Ka = 2 x 10 -5 mol dm-3)

Explain the importance of buffer solutions in biological environments, eg buffers in

cells and in blood and in foods to prevent deterioration due to pH change (caused by
bacterial or fungal activity).
 A2 acid-base equilibria

Not specified in AQA specification but listed as PS exercise

 A2 acid-base equilibria
Use titration curves to show the buffer action and to determine Ka, from the pH at
the point where half the acid is neutralized

Consider the weak acid HA and its reaction with hydroxide ions:

HA + OH-  H2O + A-

Ka = [ A-][ H+]
[ HA ]

At the halfway point in the reaction

[ HA ] = [ A-]

Therefore
Ka = [ H+]

And
pKa = pH

Henderson-Hasselbalch equation:

pH = pKa - log ( [HA] / [A-])

Calculating pH change in buffer solutions:

 A2 acid-base equilibria
3 -3
1.00 dm of buffer solution containing ethanoic acid at 0.1 moldm concentration and
sodium ethanoate at 0.1 moldm-3 was made. Ka was 1.7 x10-5 and pH was 4.77.

10.0 cm3 of 1.00 moldm-3 HCl was added. Calculate the final pH.