Topic 12

ACIDS, BASES AND BUFFERS

Bronsted-Lowry theory
Acids and bases in water
Calculating pH
Buffer solutions
Acid-alkali titrations
Indicators
 BRONSTED-LOWRY ACIDS AND BASES

1. The Bronsted-Lowry definition

There are many definitions of acids and bases in existence, but the most useful one is the
Bronsted-Lowry definition:

An acid is a substance which can behave as a proton donor. A proton can be

represented as a hydrogen ion, H+.
Any substance which contains hydrogen bonded to a more electronegative element can
thus behave as an acid:

HCl == H+ + Cl-
H2SO4 == H+ + HSO4-
CH3COOH == H+ + CH3COO-

A base is a substance which can behave as a proton acceptor. Any species which has
a lone pair of electrons can thus behave as a base:

NH3 + H+ == NH4+
OH- + H+ == H2O
CO32- + H+ == HCO3-

2. Conjugate acid-base pairs

Since all the above reactions are reversible, the species formed when an acid gives up a
proton can accept a proton and thus behave as a base. The species formed when a base
accepts a proton can give up a proton and behave as an acid:

Cl- + H+ == HCl
HSO4- + H+ == H2SO4
CH3COO- + H+ == CH3COOH

NH4+ == NH3 + H+
H2O == H+ + OH-
HCO3- == H+ + CO32-

Acids and bases thus come in pairs; every acid can lose a proton to become a base and
every base can accept a proton to become an acid. Species related in this way are known
as conjugate acid-base pairs.
Eg Cl- is the conjugate base of HCl; HCl is the conjugate acid of Cl-
Eg NH3 is the conjugate base of NH4+; NH4+ is the conjugate acid of NH3
Not all acids are equally good proton donors; in fact some give up their protons very
reluctantly; conversely, some bases accept protons readily whereas others accept protons
very reluctantly.

The better an acid is at losing protons, the worse its conjugate base will be at accepting
them. The better a base is at accepting protons, the worse its conjugate acid will be at
losing them. In other words, the weaker the acid, the stronger its conjugate base and vice
versa.

Acids and bases can be ranked in order of decreasing strength; a list of common acids and
their conjugate bases ranked in such a way is shown below:

ACID BASE

H2NO3+ (NO2+ + H2O) == HNO3 + H+

H2SO4 == HSO4- + H+
HNO3 == NO3- + H+
HCl == Cl- + H+
H3O+ == H2O + H+
H2SO3 (SO2 + H2O) == HSO3- + H+
HSO4- == SO42- + H+
H3PO4 == H2PO4- + H+
HF == F- + H+
HNO2 == NO2- + H+
CH3COOH == CH3COO- + H+
H2PO4- == HPO42- + H+
H2CO3 (CO2 + H2O) == HCO3- + H+
HSO3- == SO32- + H+
NH4+ == NH3 + H+
HCN == CN- + H+
HCO3- == CO32- + H+
HPO42- == PO43- + H+
H2O == OH- + H+
OH- == O2- + H+

The strongest acids are at the top; these have the weakest conjugate bases.

The strongest bases are at the bottom; these have the weakest conjugate acids.

Note that some species (eg H2O, HSO3-, HCO3- amongst others) appear in both columns.
Such species can behave as either acids or bases and are said to be amphoteric.
3. Acid-base reactions

Protons are not given up by acids unless there is a base which can accept them; and bases
can only accept protons if there is an acid present to provide them. Reactions between
acids and bases thus involve proton transfer from acid to base.

In acid-base reactions, acids react with bases to give the conjugate base of the reactant
acid and the conjugate acid of the reactant base. The reactant acid is given the label "acid
1" and its conjugate base is given the label "base 1". The reactant base is given the label
"base 2" and its conjugate acid is given the label "acid 2".

A general acid-base reaction can thus be represented as follows:

Acid 1 + Base 2 == Base 1 + Acid 2

Eg HCl + H2O == H3 O+ + Cl-

Acid 1 Base 2 Acid 2 Base 1

Eg NH3 + H2O == NH4+ + OH-

Base 1 + Acid 2 Acid 1 Base 2

Eg O2- + H2O == OH- + OH-

Base 1 + Acid 2 Acid 1 + Base 2

Eg H3O+ + OH- == H2O + H2O

Acid 1 Base 2 Base 1 Acid 2

Amphoteric substances can undergo acid-base reactions with themselves:

Eg H2O + H2O == H3O+ + OH-

Base 1 + Acid 2 Acid 1 Base 2

Eg HCO3- + HCO3- == CO32- + CO2 + H2O

Acid 1 Base 2 Base 1 Acid 2

Any acid-base reaction which takes place in aqueous solution will reveal which of two
acids is the stronger:

Eg HCl(aq) + H2O(l)  H3O+(aq) +Cl-(aq) goes 95%

So HCl is a stronger acid than H3O+

CH3COOH(aq) + H2O(l)  CH3COO-(aq) + H3O+(aq) only goes 1%

So H3O+ is a stronger acid than CH2COOH

CO32-(aq) + SO2(aq) [+ H2O(l)]  CO2(aq) [+ H2O(l)] + SO32-(aq) goes 90%

So SO2 is a stronger acid than CO2
 ACIDS AND BASES IN WATER

Most common acid-base reactions take place in aqueous solution, and thus acids and
bases are generally defined by the way in which they react with water.

1. Auto-ionisation of water

Water can behave both as an acid and a base: in aqueous solution a small fraction of the
water molecules undergo acid-base reactions with each other to produce the equilibrium:
2H2O(l) == H3O+(aq) + OH-(aq)

This is known as the auto-ionisation of water. The equilibrium expression for this
reaction can be written:

Kc = [H3O+][OH-]
[H2O]2

The concentration of water under these conditions is not changed significantly, since the
proportion of water which dissociates into its ions is small. The water concentration can
thus be assumed to be constant and it can be incorporated into Kc:

Kc[H2O] = Kw = [H3O+][OH-] Kw = [H3O+][OH-]

The expression [H3O+][OH-] is known as the ionic product of water and has a value of
1.0 x 10-14 mol2dm-6 at 25oC. This value is a constant at a given temperature. The ionic
product of water is slightly higher at higher temperatures, suggesting that the dissociation
is endothermic.

In pure water, the [H3O+] and [OH-] concentrations are equal.

It follows that [H3O+][OH-] = [H3O+]2 = Kw.
So [H3O+] = [OH-] = √Kw = 1.0 x 10-7 moldm-3.

Any solution in which the concentrations of H3O+ and OH- are equal is said to be
neutral.

The H3O+ ion is usually written in aqueous solution as H+(aq). This is an accepted
shorthand. For example, the auto-ionisation of water is frequently written:
Kw = [H+][OH-]
2. Acidic and alkaline solutions

An acid can be regarded as a substance which reacts with water by forcing it to accept a
proton and behave as a base:

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

The resulting solution contains an excess of H3O+ (H+) ions. Any solution which contains
more H3O+ ions than OH- ions is said to be acidic. The measure of the acidity of the
solution is the H3O+ concentration. The greater the H3O+ concentration, the more acidic
the solution.

A base can be regarded as a substance which reacts with water by accepting a proton
from water, forcing it to behave as an acid:

B+(aq) + H2O(l) == BH+(aq) + OH-(aq)

The resulting solution contains an excess of OH- ions. Any solution which contains more
OH- ions than H3O+ ions is said to be alkaline. The measure of the alkalinity of the
solution is the OH- concentration. The greater the OH- concentration, the more alkaline
the solution.

The concentration of OH - ions can be deduced from the concentration of H3O+ ions and
vice versa. The following table shows some examples:

[H3O+] [OH-] Type of

solution
0.1 1 x 10-13 Acidic
1 x 10-3 1 x 10-11 Acidic
1 x 10-5 1 x 10-9 Acidic
1 x 10-7 1 x 10-7 Neutral
1 x 10-9 1 x 10-5 Alkaline
1 x 10-11 1 x 10-3 Alkaline
1 x 10-13 0.1 Alkaline
3. The pH scale

The acidity and alkalinity of a solution is often measured by its pH.

The pH of a solution is the negative logarithm to the base ten of the H 3O+ concentration.
pH = -log10[H3O+].

If [H3O+] = 1.0M, the pH of the solution is 0. pH = -log10[H3O+]

If [H3O+] = 0.1M, the pH of the solution is 1.
If [H3O+] = 0.01M, the pH of the solution is 2.

The purpose of the logarithmic scale is to represent conveniently a very large range of
H3O+ concentrations into a simpler numerical scale.

In alkaline solutions, the OH- concentration is known. The concentration of H3O+ can be
deduced from the ionic product of water:
[H3O+][OH-] = 1.0 x 10-14 mol2dm6. [H3O+] = Kw/[OH-].

If [OH-] = 1.0M, [H3O+] = 1 x 10-14 M and the pH of the solution is 14.

If [OH-] = 0.1M, [H3O+] = 1 x 10-13 M and the pH of the solution is 13.
If [OH-] = 0.01M, [H3O+] = 1 x 10-12 M and the pH of the solution is 12.

Note that an increase in pH of one unit is equivalent to a tenfold fall in the H 3O+
concentration, and a decrease in pH of one unit is equivalent to a tenfold increase in
the H3O+ concentration.

Calculating the pH of water:

In pure water, [H3O+] = [OH-] = 1 x 10-7 M and the pH = 7.

It follows that the pH of acidic solutions is less than 7 and the pH of alkaline solutions is
greater than 7.

At higher temperatures, the ionic product of water is greater and [H 3O+] is greater than 1
x 10-7 M. The pH of pure water is thus slightly less than 7 at higher temperatures. The
solution is still neutral, since the concentrations of H3O+ and OH- are still the same. The
pH of a neutral solution is just lower at higher temperatures.
 STRONG AND WEAK ACIDS

Acids can be classified as one of two types; strong acids and weak acids. Each must be
considered separately:

1. Strong acids

A strong acid is one which dissociates completely in water into H3O+ and A-. A
strong acid must therefore be a better proton donor than H 3O+. Examples of strong acids
are HCl, HNO3 and H2SO4.

Calculating the pH of strong acids:

Since strong acids dissociate fully, the concentration of H3O+ will be the same as the
concentration of the acid (ignoring the auto-ionisation of water).
A 1.0M solution of HCl will therefore be 1.0 moldm-3 with respect to both H3O+ and Cl-
ions if the H3O+ present due to the auto-ionisation of water (which will be small in
comparison) is ignored:
HCl(aq) + H2O(l)  H3O+(aq) + Cl-(aq)
1.0 moldm-3 1.0 moldm-3

If [H3O+] = 1.0 moldm-3, the pH of 1.0 moldm-3 HCl is thus 0.

The [H3O+] in a 0.10 moldm-3 solution of HCl is 0.10 moldm-3. The pH of 0.10 moldm-3
HCl is thus 1.
The [H3O+] in a 0.05 moldm-3 solution of HCl is 0.05 moldm-3. The pH of 0.05 moldm-3
HCl is thus 1.3.
The [H3O+] in a 2 moldm-3 solution of HCl is 2 moldm-3. The pH of 2 moldm-3 HCl is
thus -0.3.

In theory, there is no minimum pH as the molarity of the acid can increase indefinitely. In
practice, the pH rarely falls below -0.5 as even strong acids do not dissociate fully at very
high concentrations (there is not enough water). Strong acids can thus only be said to be
fully dissociated if the solution is reasonably dilute (ie less than 0.1 moldm-3).

Diluting the acid tenfold causes the pH to rise by one unit.

2. Weak acids

A weak acid is one which only dissociates partially in water. It reaches equilibrium as
follows:

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

C-x x x

A weak acid is one which is a worse proton donor than H3O+. Examples are CH3COOH
(ethanoic acid), NaHSO4 (sodium hydrogensulphate) and CO2 (carbon dioxide).

The equilibrium expression for the dissociation of a weak acid is as follows:

Kc = [H3O+][A-]
[HA][H2O]
The water is in large excess, so its concentration is not significantly affected by this
equilibrium and so can be assumed to remain constant. The equilibrium expression can
thus be re-written:

Kc[H2O] = Ka = [H3O+][A-] Ka = [H3O+][A-]

[HA] [HA]

Ka is known as the acid dissociation constant for the acid and has units of moldm-3.
It is often quoted as pKa = -log10Ka.
pKa = -log10Ka

Some Ka and pKa values for different acids are shown below:

ACID Ka/moldm-3 pKa

HSO4- 1.0 x 10-2 2.0
CH3COOH 1.7 x 10-5 4.8
CO2 + H2O 4.5 x 10-7 6.3
NH4+ 5.8 x 10-10 9.2
HCO3- 4.8 x 10-11 10.3

The larger the Ka, the greater the degree to which the acid dissociates into its ions and the
stronger the acid.
Calculating the pH of weak acids

The H3O+ concentration can be calculated by the following method:

HA(aq) + HO(l) == H3O+(aq) + A-(aq)

C-x x x

Ka = [H3O+][A-]
[HA]

Ignoring the H3O+ present due to the auto-ionisation of water, the H3O+ and A-
concentrations can be assumed to be the same. Therefore [H 3O+][A-] = [H3O+]2.

If the degree of dissociation of HA is assumed to be small, then the molarity of the HA

can be assumed to be the same as that of the solution (assume C-x is approximately equal
to C).

Ka = [H3O+]2 so [H3O+]2 = Ka[HA] and [H3O+] =√ Ka[HA]

[HA]

eg Calculate the pH of 0.1 moldm-3 ethanoic acid, Ka = 1.7 x 10-5 moldm-3

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

Ka = [H3O+][ CH3COO-]
[CH3COOH]
Ignoring auto-ionisation of water, [H3O+] = [CH3COO-] so
[H3O+][CH3COO-] = [H3O+]2.
Assuming degree of dissociation of CH3COOH is small, [CH3COOH] = 0.1 moldm-3.

[H3O+]2 = Ka x 0.1, so [H3O+] = √Ka x 0.1 = 1.304 x 10-3 moldm-3 and pH = 2.9
By the same method, the pH of 0.01 moldm-3 CH3 COOH can be shown to be 3.4, and the
pH of 0.001 moldm-3 CH3COOH can be shown to be 3.9.

Note that when a weak acid is diluted tenfold, the pH does not increase by one unit
as expected. In fact it increases only by 0.5 units. This suggests that the weak acid
compensates for the dilution by dissociating to a greater extent:
In 0.1 moldm-3 ethanoic acid, approximately 1.3% of the molecules are dissociated into
ions.
In 0.01 moldm-3 ethanoic acid, approximately 4.1% of the molecules are dissociated into
ions.
In 0.001 moldm-3 ethanoic acid, approximately 13% of the molecules are dissociated into
ions.

Thus the more dilute the solution, the greater the extent to which the acid dissociates into
its ions. This is in accordance with Le Chatelier's principle:

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

As the amount of water increases, the equilibrium is shifted to the right and the degree of
dissociation is greater. This is not the case with strong acids, since they are fully
dissociated even at relatively high concentrations and are thus unable to respond to
dilution in the same way.
3. Dilute and concentrated solutions

A dilute solution of an acid is a solution with a low molarity (eg 0.001 moldm-3 HCl). A
concentrated solution of an acid is a solution with a high molarity (eg 1 moldm-3
CH3COOH).

It is impotant to realise that the concentration of the solution is not necessarily a good
measure of the acidity of the solution, since concentrated solutions of weaker acids may
be less acidic than more dilute solutions of stronger acids:

Eg the pH of 0.1 moldm-3 CH3COOH (Ka = 1.7 x 10-5 moldm-3) is 2.88, but the pH of
0.05 moldm-3 HCOOH (Ka = 1.6 x 10-4 moldm-3) is 2.55.
Thus the solution of HCOOH is more acidic, even though it is more dilute. This is
because it is a stronger acid (ie it has a larger Ka) and so dissociates to a greater extent.

It is not, however, always true that the stronger acid will give the more acidic solution.
Often concentrated solutions of weaker acids are more acidic than more dilute solutions
of stronger acids:

Eg the pH of 0.1 moldm-3 CH3COOH (Ka = 1.7 x 10-5 moldm-3) is 2.88, but the pH of
0.001 moldm-3 HCl is 3.0. Thus the solution of CH 3COOH is more acidic, even though it
is a weaker acid. This is because the molar concentration of the acid is higher.

The acidity of a solution (ie the concentration of H3O+) therefore depends on both
the concentration of the solution and the strength of the acid.

4. Very dilute solutions

In all the calculations considered so far, the H3O+ present due to the auto-ionisation of
water has been ignored. This is normally a reasonable assumption, since water only
ionises very slightly ([H3O+]= 1 x 10-7 moldm-3 in pure water).

In very dilute solutions, however, the H3O+ present due to the auto-ionisation of water is
significant and cannot be ignored. This is generally the case if the concentration of the
solution is less than 1 x 10 -6 moldm-3.

The pH of 1 x 10-6 moldm-3 HCl = 6.00

The pH of 1 x 10-7 moldm-3 HCl is not, however, equal to 7, since the solution is very
slightly acidic, and the pH of 1 x 10-8 moldm-3 HCl is certainly not 8.

At such low concentrations the H3O+ present due to the auto-ionisation of water is
significant and must be taken into consideration.
From a more thorough consideration of the equilibrium mixture, it can be shown that the
pH of a 1 x 10-7 moldm-3 solution of HCl is 6.79 and the pH of a 1 x 10-8 moldm-3
solution of HCl is 6.98.
5. polybasic acids

Acids which are capable of losing more than one proton are said to be polybasic.
Examples of polybasic acids are H2SO4, H3PO4 and CO2 + H2O.
Acids which can lose two protons in solution are said to be dibasic, and acids which can
lose three protons in solution are said to be tribasic.

Polybasic acids dissociate more than once in aqueous solution:

Eg H2SO4(aq) + H2O(l) == H3O+(aq) + HSO4-(aq)

HSO4-(aq) + H2O(l) == H3O+(aq) + SO42-(aq)

Each H2SO4 therefore gives two moles of H3O+ ions

Polybasic acids such as H2SO4 thus form more than one salt; H2SO4, a dibasic acid, forms
two sodium salts, NaHSO4 and Na2SO4. H3PO4, a tribasic acid, forms three sodium salts,
NaH2PO4, Na2HPO4 and Na3PO4.

The number of protons which an acid loses can be determined from its reaction with
alkali:
HxA(aq) + xNaOH(aq)  NaxA(aq) + xH2O(l)
Monoprotic acids react with sodium hydroxide in a 1:1 ratio.
Diprotic acids react with sodium hydroxide in a 2:1 ratio.
Triprotic acids react with sodium hydroxide in a 3:1 ratio, etc.
 BASES

1. Strong bases

A strong base is one which fully dissociates into its ions in water:
B(aq) + H2O(l)  BH+(aq) + OH-(aq)
Eg O2-(aq) + H2O(l)  2OH-(aq)

A strong base in water must therefore be a stronger base than OH -.

Strong bases in water are, in fact, quite rare as water is a very weak acid and will not
readily give up protons to other species. The oxide ion is one of the only common
examples of a strong base.

The hydroxide ion is, however quite stable and there are many examples of ionic
substances containing OH- ions. If these substances are soluble, they will completely
dissociate in aqueous solution. Though they do not actually react with water, they are
regarded as strong bases since they completely dissociate to give OH - ions. Exmples of
these substances are NaOH, KOH and Ba(OH)2.

Substances which dissolve in water to produce an excess of OH- ions are said to be
alkaline.

Calculating the pH of strong bases:

The pH of strong bases can be calculated if the concentration of the solution is known:

Eg 0.1 moldm-3 NaOH: [OH-] = 0.1 moldm-3, so [H3O+] = Kw/[OH-] = Kw/0.1 = 1 x 10-13
M. Thus the pH of 0.1 moldm-3 NaOH is 13.0

Eg 0.1 moldm-3 Ba(OH)2: [OH-] = 0.2 moldm-3, so [H3O+] = 5 x 10-14 moldm-3.

Thus the pH of 0.1 moldm-3 Ba(OH)2 = 13.3

Note that in these calculations the OH - present due to the auto-ionisation of water has
been ignored.

Since these compounds are ionic, they are fully dissociated at all concentrations. The
alkalinity of the solution is thus limited only by the solubility of the hydroxide. The
maximum possible pH at room temperature is 14.5, corresponding to a solution of approx
3 moldm-3 NaOH.

2. Weak bases

Weak bases do not dissociate fully in water. They behave in a similar way to weak acids
but pH calculations involving weak bases are not required at A-level.
 BUFFER SOLUTIONS

A buffer solution is a solution which can resist changes in pH on addition of small

quantities of acid or alkali or on dilution.

1. How buffers work

A buffer solution is a mixture of an acid and an alkali. The acid neutralises the alkali
added and the alkali neutralises the acid added.

The mixture cannot be a mixture of a strong acid and a strong alkali, or the two will react
with each other (eg a mixture of NaOH and HCl would react with each other and thus not
behave as an effective buffer). If the acid and alkali in the buffer are too weak, however,
they will not react effectively with the acid or alkali that are added.
A suitable mixture is one which contains a mixture of acid and alkali strong enough to
react with H3O+ and OH-, but weak enough not to react with each other.

An ideal mixture for this purpose is a mixture of a weak acid and its conjugate base.
For example CH3COOH and CH3COONa, or NH4Cl and NH3. The acids and bases in
these mixtures will react with OH- and H3O+ respectively but not with each other.

a) Resisting pH change on addition of acid and alkali

These mixtures will react with acid and alkali as follows:

CH3COOH(aq) + OH-(aq)  CH3COO-(aq) + H2O(l)

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

NH4+(aq) + OH-(aq)  NH3(aq) + H2O(l)

NH3(aq) + H3O+(aq)  NH4+(aq) + H2O(l)

b) Resisting pH change on dilution

On dilution, both the weak acid and the weak base can dissociate more to compensate for
the dilution:

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

CH3COO-(aq) + H2O(l)  CH3COOH(aq) + OH-(aq)

NH4+(aq) + H2O(l)  NH3(aq) + H3O+(aq)

NH3(aq) + H2O(l)  NH4+(aq) + OH-(aq)
c) Other buffer solutions

A buffer does not have to a mixture of a weak acid and its conjugate base; any mixture of
a weak acid and a weak base will have the same effect.

Substances which can behave as both weak acids and weak bases can also behave as
buffers.

One important example is sodium hydrogencarbonate; the HCO3- ion can behave as either
an acid or a base:

HCO3-(aq) + H3O+(aq)  CO2(g) + 2H2O(l)

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

Amino acids can also behave as buffers:

Eg CH3CH(NH2)COOH - 2-aminopropanoic acid
CH3CH(NH2)COOH(aq) + OH-(aq)  CH3CH(NH2)COO-(aq) + H2O(l)
CH3CH(NH2)COOH(aq) + H3O+(aq)  CH3CH(NH3+)COOH(aq) + H2O(l)

2. Calculating the pH of buffer solutions

If a mixture of a weak acid and its conjugate base is used as a buffer, the pH of the buffer
can be calculated by the following method:

Consider the mixture CH3COOH/CH3COONa:

The Ka of the acid can be written: Ka = [CH3COO-][H3O+]

[CH3COOH]

so [H3O+] = Ka[CH3COOH]
[CH3COO-]

In general, [H3O+] can be calculated from the formula:

[H3O+] =Ka[acid]
[H3O+] = Ka[acid] [base]
[base]

For example, a mixture containing 0.2 moldm-3 CH3COOH (Ka = 1.7 x 10-5 moldm-3) and
0.1 moldm-3 CH3COONa has a [H3O+] concentration of 1.7 x 10-5 (0.2/0.1) = 3.4 x 10-5
moldm-3.Therefore the pH of the solution is 4.5.
To prepare a buffer solution of a given pH, it is necessary to have the acid and base
concentrations in a suitable ratio.

Eg to prepare an NH3/NH4Cl buffer of pH = 10

[H3O+] = [acid] so [NH4+] = 1 x 10-10 = 1/5.6
Ka [base] [NH3] 5.6 x 10-10

So 5.6 moles of NH3 are required for every 1 mole of NH4Cl

Given equimolar solutions of both, 100 cm3 of this buffer could be made by taking 10
cm3 of NH4Cl, adding 56 cm3 of ammonia and the total volume made up to 100 cm3.

It is possible to express the pH directly in terms of the concentrations of the reactants:

[H3O+] = Ka[acid]
[base]

so log10[H3O+] = log10Ka + log10([acid]/[base])

so -log10[H3O+] = -log10Ka + log10([base]/[acid])

so pH = pKa + log10([base]/[acid])

pH = pKa + log10([base]/[acid])

3. Showing how buffer solutions limit changes in pH.

It is possible to show quantitatively the ability of buffer solutions to limit changes in pH:

Eg a mixture of 0.6 moldm-3 HClO (Ka = 3.7 x 10-8 moldm-3) and 0.2 moldm-3 NaClO has
a pH of 7.0.

If 0.01 moles of HCl are added to 100 cm3 of the buffer:

ClO-(aq) + H3O+(aq)  HClO(aq) + H2O(l)
Initially: 0.02 0.01 0.06
Finally: 0.01 - 0.07

So the [base]/[acid] ratio is 0.01/0.07

pH = pKa + log10([base]/[acid]) = 6.58 (a change of 0.4 units)

If 0.01 moles of HCl were added to 100 cm3 of pure water, the pH of the resulting
solution would be 1.0 (a change of 6 units)
If 0.01 moles of NaOH are added to the buffer:
HClO(aq) + OH-(aq)  ClO-(aq) + H2O(l)
Initially: 0.06 0.01 0.02
Finally: 0.05 - 0.03

So the [base]/[acid] ratio is 0.03/0.05

pH = pKa + log10([base]/[acid]) = 7.21 (a change of 0.2 units)

If 0.01 moles of NaOH were added to 100 cm3 of pure water, the pH of the resulting
solution would be 13.0.

So buffer solutions do not change their pH much on adding small quantities of acid or
alkali.

NB it is possible to exceed the buffering capacity of a buffer solution by adding too much
acid or alkali; in such cases the buffer will be unable to maintain the pH and the pH will
change dramatically. This would be the case of more than 0.02 moles of HCl or more
than 0.06 moles of NaOH were added to the above mixture.

It can be shown that buffer solutions are most efficient at resisting changes in pH
when the concentrations of acid and alkali are the same.

If there is much more acid than base in a buffer solution, then it is not very able to resist
changes in pH on adding acid. Similarly if there is much more base than acid in a buffer
solution it is not very able to resist changes in pH on adding alkali.
4. Natural buffers

There are many biological systems which rely on a fairly constant pH, and which rely on
the use of buffer solutions to maintain this pH.

a) blood

The pH of blood must be maintained at around 7.4. Hydrogencarbonate ions are used for
this purpose:

HCO3-(aq) + H3O+(aq)  CO2(g) + 2H2O(l)

HCO3-(aq) + OH-(aq)  CO2(aq) + H2O(l)

b) tears

The pH of tears must also be maintained at around 7.4, in this case by the use of amino
acids:

H2NCH2COOH(aq) + H3O+(aq)  H3N+CH2COOH(aq) + H2O(l)

H2NCH2COOH(aq) + OH-(aq)  H2NCH2COO-(aq) + H2O(l)
 ACID-ALKALI TITRATIONS

A reaction between an acid and an alkali is known as a neutralisation.

The concentration of an acid can be determined by titrating it against a standard alkali

solution using a suitable indicator, and the concentration of an alkali can be determined
by titrating against a standard acid solution.

If solution A is titrated against solution B, it means that solution A is in the conical flask
and solution B is in the burette.

The behaviour of acid-alkali mixtures during titrations depends on whether the acids and
bases are strong or weak.

1. pH changes during strong acid - strong alkali titrations

If 0.1 moldm-3 NaOH is added dropwise to 20 cm3 of 0.1 moldm-3 HCl (2 x 10-3 moles),
the change in pH of the solution can be calculated by considering the reaction taking
place.

Before the addition of NaOH, the pH of the solution is 1.0.

After the addition of 10 cm 3 (1 x 10-3 moles) of 0.1 moldm-3 NaOH:

NaOH + HCl  NaCl + H2O
Before: 1 x 10-3 2 x 10-3 -
After: - 1 x 10-3 1 x 10-3 Total volume = 30 cm3.
[H3O+] = 1 x 10-3 = 0.033 moldm-3 pH = 1.5
0.03

After the addition of 19.95 cm3 (1.995 x 10-3 moles) of 0.1 moldm-3 NaOH:
(ie 1 drop before the equivalence point)
NaOH + HCl  NaCl + H2O
-3
Before: 1995 x 10 2 x 10-3 -
After: - 5 x 10-6 1.995 x 10-3 Total volume = 39.95 cm3.
+ -6 -4 -3
[H3O ] = 5 x 10 = 1.25 x 10 moldm pH = 3.9
0.03995

After the addition of 20.0 cm3 of 0.1 moldm-3 NaOH (ie at the equivalence point)
[H3O+] = [OH-] = 1 x 10-7 M so pH = 7.0
After the addition of 20.05 cm3 (2.005 x 10-3 moles) of 0.1 moldm-3 NaOH:
(ie 1 drop after the end-point)
NaOH + HCl  NaCl + H2O
-3
Before: 2.005 x 10 2 x 10-3 -
After: 5 x 10-6 - 2 x 10-3 Total volume = 40.05 cm3.
[OH ] = 5 x 10 = 1.25 x 10 moldm , so [H3O ] = 8.0 x 10-11 moldm-3
- -6 -4 -3 +
pH = 10.1
0.04005

The pH of the solution during a strong acid - strong alkali titration therefore
changes from around 4 to 10 over two drops at the equivalence point.

A titration curve for a strong acid - strong alkali titration can be sketched as follows:

Addition of a strong alkali to a strong acid

14

12

10

8
pH

0
0 5 10 15 20 25 30 35 40 45
Volume of alkali added

The equivalence point of the titration is the mid-point of the vertical section of the graph.

2. pH changes during weak acid - strong alkali titrations

If 0.1 moldm-3 NaOH is added dropwise to 20 cm3 of 0.1 moldm-3 CH3COOH (2 x 10-3
moles), the change in pH of the solution can be calculated by considering the reaction
taking place.

Before the addition of NaOH, the pH of the solution is 2.9.

After the addition of 10 cm3 (1 x 10-3 moles) of 0.1 moldm-3 NaOH:

NaOH + CH3COOH  CH3COONa + H2O
Before: 1 x 10-3 2 x 10-3 -
After: - 1 x 10-3 1 x 10-3 Total volume = 30 cm3.
The solution now contains a mixture of a weak acid (CH 3COOH) and its conjugate base
(CH3COO-). It thus behaves as a buffer solution. The pH of the mixture can thus be
calculated by considering the relative concentrations of the CH 3COOH and CH3COO.
Ka = [H3O+][CH3COO-] so [H3O+] = Ka[CH3COOH] = 1.7 x 10-5 moldm-3, pH = 4.8
[CH3COOH] [CH3COO-]

After the addition of 19.95 cm3 (1.995 x 10-3 moles) of 0.1 moldm-3 NaOH:
(ie 1 drop before the equivalence point)
NaOH + CH3COOH  CH3COONa + H2O
-3
Before: 1.995 x 10 2 x 10-3 -
After: - 5 x 10-6 1.995 x 10-3 Total volume = 39.95 cm3.

[H3O+] = Ka x (5 x 10-6/0.3995) pH = 7.4

(1.995 x 10-3/0.03995)

After the addition of 20.05 cm3 (2.005 x 10-3 moles) of 0.1 moldm-3 NaOH:
(ie 1 drop after the equivalence point)
NaOH + CH3COOH  CH3COONa + H2O
-3
Before: 2.005 x 10 2 x 10-3 -
-6
After: 5 x 10 - 2 x 10-3 Total volume = 40.05 cm3.

[OH-] = 5 x 10-6 = 1.25 x 10-4 moldm-3, so [H3O+] = 8.0 x 10-11 moldm-3 pH = 10.1
0.04005

The pH of the solution during a weak acid - strong alkali titration therefore changes
from around 7 to 10 over two drops at the equivalence point.
A titration curve for a weak acid - strong alkali titration can be sketched as follows:

Addition of a strong alkali to a weak acid

14

12

10

8
pH

0
0 5 10 15 20 25 30 35 40 45
Volume of alkali added

Note that the pH increases fairly fast at the beginning of the titration, until there is
enough of the salt formed for an effective buffer solution.

The equivalence point of the titration is the mid-point of the vertical section of the graph.

Note that in this titration the pH of the solution at the end-point is not 7. The ethanoate
ion is basic: CHCOO-(aq) + H2O(l) == CH3COOH(aq) + OH-(aq)
The pH of this solution at the equivalence point is between 8 and 9
4. Strong acid - weak alkali titrations

If 0.1 moldm-3 NH3 is added to 20 cm3 0.1 moldm-3 HCl, the mixture behaves in a similar
way to a strong acid - strong alkali titration until the equivalence point is reached.

After the equivalence point, the solution contains a mixture of NH4+ and NH3 and thus
behaves as a buffer solution.

The pH of the solution during a strong acid - weak alkali titration changes from
around 4 to 7 at the equivalence point.

A titration curve for a strong acid - weak alkali titration can be sketched as follows:

Addition of a weak alkali to a strong acid

14

12

10

8
pH

0
0 5 10 15 20 25 30 35 40 45
Volume of alkali added

The solution at the equivalence point contains 0.05 moldm-3 NH4Cl. It is not neutral,
since the NH4+ ion is acidic: NH4+(aq) + H2O(l)  NH3(aq) + H3O+(aq)

The pH at the equivalence point is between 5 and 6.

5. Weak acid - weak alkali titrations

Weak acid - weak alkali titrations behave as buffer solutions throughout the titration.
Unlike titrations involving strong acids or strong alkalis, there is no dramatic pH change
at the end-point. The pH of the end-point is usually around 7, but it depends on the
relative strengths of the acid and the alkali.

A titration curve for a weak acid - weak alkali titration can be sketched as follows:

Addition of a weak alkali to a weak acid

14

12

10

8
pH

0
0 5 10 15 20 25 30 35 40 45
Volume of alkali added
 SUMMARY OF ACID-ALKALI TITRATION CURVES

The titration curves for all the different possible titrations can be sketched on the same
graph as follows:

Acid - alkali titrations

14

12

10

8
pH

0
0 5 10 15 20 25 30 35 40 45
Volume of alkali added

Type of titration pH at equivalence point pH change at equivalence

point
Strong acid - strong alkali 7.0 4 to 10
Weak acid - strong alkali Approx 8.5 7 to 10
Strong acid - weak alkali Approx 5.5 4 to 7
Weak acid - weak alkali Approx 7 No sudden change
6. Half -neutralisation

A weak acid is half-neutralised when exactly half the volume of alkali required for
neutralisation has been added.

Eg HA + OH-(aq)  A-(aq) + H2O(l)

If 0.5 moles of OH- ions is added to 1 mole of HA, half of the acid will be converted into
its salt.

HA + OH-(aq)  A-(aq) + H2O(l)

Initially: 1 0.5
After reaction 0.5 - 0.5

At half-neutralisation the number of moles, and hence concentration, of the salt and acid
will be the same. [HA] = [A-]

Given that Ka = [H3O+][A-] [H3O+] = Ka[HA]

[HA] [A-]

If [HA] = [A-] then [H3O+] = Ka and therefore pH = pKa.

Therefore at half-neutralisation: [H3O+] = Ka and pH = pKa.

at half-neutralisation: pH = pK a

The Ka of an acid can be deduced from a graph of pH against volume of alkali

added.
The pH of the mixture after exactly half the required amount of alkali has been
added corresponds to the pK a of the acid.
You calculate the Ka of the acid as follows:

Addition of a strong alkali to a weak acid

14

12

10

8
pH

0
0 5 10 15 20 25 30 35 40 45
Volume of alkali added

The equivalence point of the titration is the centre of the steep vertical section of the
curve.

This occurs at 20 cm3 in this case.

Therefore half-neutralisation occurs at 10 cm3 in this case.

The pH at half-neutralisation is 4.7.

So the pKa of the acid is 4.7

So the Ka of the acid = 10-4.7 = 1.7 x 10-5 moldm-3.

 ACID-BASE INDICATORS

1. Theory of indicators

An acid-base indicator is a weak acid which dissociates to give an anion of a different

colour.
Consider a weak acid HIn: HIn(aq) + H2O(l) == H3O+(aq) + In-(aq)
Colour 1 Colour 2

HIn and its conjugate base In- are different colours. The colour of the solution depends on
the relative concentrations of the two species.

If the solution is strongly acidic, the above equilibrium will be shifted to the left and Hin
will dominate. Colour 1 will thus dominate. If the solution is strongly alkaline, the above
equilibrium will shift to the right and In- will dominate. Colour 2 will thus dominate.
The colour of the indicator thus depends on the pH of the solution.

The colour will not change suddenly at a certain pH, but will change gradually over a pH
range. The colour of the indicator depends on the ratio of [HIn] to [In-].

In general, if [HIn]/[In-] > 10, then colour 1 will dominate. If [In-]/[Hin] > 10, then colour
2 will dominate. The pH at which this transition occurs is known as the end-point of the
indicator and depends on the KIn of the indicator.
KIn = [H3O+][In-] so [H3O+] = KIn[HIn]
[HIn] [In-]

If [H3O+] > 10 x KIn, then [HIn]/[In-] > 10 and colour 1 dominates.

If [H3O] < 0.1 x KIn, then [Hin]/[In-] < 0.1 and colour 2 dominates.
At intermediate H3O+ concentrations, neither colour dominates.

KIn values are often expressed as pKIn values, where pKIn = -log10KIn.

The end-point of an indicator is the pH at which the concentration of HIn and In are
equal. This happens when pH = pKin

The pKIn values of some indicators is shown below:

Indicator Colour in acid Colour in alkali pKa pH range of

(end-point) colour change
Thymol blue Red Yellow 1.7 1.2 - 2.8
Methyl orange Red Yellow 3.7 3.2 - 4.4
Methyl red Red Yellow 5.1 4.2 - 6.3
Litmus Red Blue 6.3 5.0 - 8.0
Phenolphthalein Colourless Pink 9.3 8.2 - 10.0
2. Use of indicators

Indicators are used in acid - alkali titrations in order to find the equivalence point of the
titration.

If they are to determine the equivalence point accurately, they must undergo a complete
colour change at the equivalence point. This means that the pH range of the colour
change (ie the end-point of the indicator) must fall completely within the pH range of the
equivalence point. Not all indicators can therefore be used for all titrations, and indicators
must be chosen carefully so that the end-point of the indicator matches the pH range at
the equivalence point.

The titration curves of various different types of titration are shown below:

Acid - alkali titrations

14

12

10

8
pH

0
0 5 10 15 20 25 30 35 40 45
Volume of alkali added

 In strong acid - strong alkali titrations, the pH changes from 4 to 10 at the

equivalence point so a suitable indicator must change colour within this range.

Methyl red, litmus and phenolphthalein are suitable indicators for these titrations.
Methyl orange is not ideal but it shows a significant enough colour change at the
end point to be widely used.

 In weak acid - strong alkali titrations, the pH changes from 7 to 10 at the

equivalence point so a suitable indicator must change colour within this range.

Phenolphthalein is only suitable indicator for weak acid - strong alkali titrations
that is widely available.
  In strong acid - weak alkali titrations, the pH changes from 4 to 7 at the
equivalence point so a suitable indicator must change colour within this range.

Methyl red is the most suitable indicator for these titrations. However methyl
orange is often used since it shows a significant enough colour change at the
equivalence point and is more widely available than methyl red.

 In weak acid -weak alkali titrations, there is no sudden pH change at the

equivalence point and thus there are no suitable indicators for these titrations. The
equivalence points of these titrations cannot be easily determined.

When carrying out these titrations, only one or two drops of indicators should be used
since they are themselves acidic and will themselves influence the equivalence point if
too much is added.

An indicator is suitable for a titration if its end-point falls within the pH change at
the equivalence point of the titration.