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TEACHER'S COPY

LECTURE 13 IONIC EQUILIBRIA: ACIDBASE EQUILIBRIA

LEARNING OUTCOMES
Candidates should be able to:
(a) show understanding of, and apply the BronstedLowry theory of acids and bases, including
the concept of conjugate acids and conjugate bases
(b) explain qualitatively the differences in behaviour between strong and weak acids and bases in
terms of the extent of dissociation
(c)
explain the terms pH; Ka; pKa; Kb; pKb; Kw and apply them in calculations, including the
relationship Kw = KaKb
(d) calculate [H+(aq)] and pH values for strong acids, weak monobasic (monoprotic) acids, strong
bases, and weak monoacidic bases
(e) explain the choice of suitable indicators for acidbase titrations, given appropriate data
(f)
describe the changes in pH during acidbase titrations and explain these changes in terms of
the strengths of the acids and bases
(g) (1) explain how buffer solutions control pH
(2) describe and explain their uses, including the role of H2CO3/HCO3 in controlling pH in
blood
(h) calculate the pH of buffer solutions, given appropriate data

CONTENT
1

Understanding Acids and Bases


BronstedLowry theory of acids and bases

Calculations Involving Acids and Bases


pH, pOH and the ionic product of water, Kw
Dissociation constants, Ka and Kb
Salt hydrolysis

Buffer Solutions
Buffer action
pH of buffer solutions
Blood as a buffer system

Acidbase Titrations
pH indicators
Titration curves

(Independent Learning Section 3.2 )


(Independent Learning Sections 3.5, 3.6)

(Independent Learning Sections 4.1, 4.2)

REFERENCES
1.
2.

Peter Cann & Peter Hughes (2002). Chemistry for Advanced Level. John Murray. Chapters 6 & 12.
Martin S. Silberberg (2006). Chemistry The Molecular Nature of Matter & Change,
4th Edition. McGraw Hill. Chapters 18 & 19.

__________________________________________________________________________________________________
Cheng ML/ Soh SK/ Tan CS/ Teo ME
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UNDERSTANDING ACIDS AND BASES

1.1

BronstedLowry Theory of Acids & Bases


An acid is defined as any species which donates a proton, H+.
An acid must thus contain H in its formula. E.g. HNO3 and H2PO4
A base is defined as any species which accepts a proton, H+.
A base must contain a lone pair of electrons to bind the H+ ion (via dative bond). E.g. NH3, CO32,
F and OH
A BronstedLowry acidbase reaction involves the transfer of a proton from an acid to a base.
Acidbase reactions do not only occur in aqueous solutions. They can also occur between gases, in
nonaqueous solutions and in heterogeneous mixtures.
EXERCISE 1
Identify the Bronsted acid and base in each of the following (forward) reactions:
(a)

HNO3 + NH3 NO3 + NH4+


acid
base

(b)

HNO3 + H2O H3O+ + NO3


acid
base

(c)

NH3 + H2O NH4+ + OH


base
acid

(d)

HNO3 + H2SO4 H2NO3+ + HSO4


base
acid

What can you say about the acidbase nature of water?


H2O is amphoteric (can act as an acid or a base, depending on the other substance present).
Note:
In aqueous solution, H+ (a bare proton) does not exist on its own. Instead, it forms a dative bond
with a water molecule to form H3O+, called hydronium, hydroxonium or oxonium ion. Chemists
often use H+(aq) and H3O+(aq) interchangeably to refer to the solvated H+ ion.
Other definitions of acids and bases:
Arrhenius acidbase
definition

An acid is a substance that dissociates in water to produce H+(aq).


A base is a substance that dissociates in water to produce OH(aq).

Lewis acidbase
definition

Acids are species that accept an electron pair, e.g. AlCl3


Bases are species that donate an electron pair e.g. NH3
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1.2

Conjugate AcidBase Pair


Consider the following acidbase reaction:
CH3CO2H
acid

CH3CO2
conjugate base

H2O
base

H3O+
conjugate acid

In the forward reaction:


CH3CO2H acts as a Bronsted acid, donating a proton to the Bronsted base, H2O.
In the reverse reaction:
CH3CO2 acts as a Bronsted base, accepting a proton from the Bronsted acid, H3O+.
CH3CO2H and CH3CO2 form a conjugate acidbase pair;
H2O and H3O+ form another conjugate acidbase pair.
In general,
conjugate acidbase pair
acid 1

base 2

base 1

acid 2

conjugate acidbase pair

An acid after donating a proton forms its conjugate base.


A base after accepting a proton forms its conjugate acid.
A conjugate acidbase pair constitutes two species which differ from each other by a proton.
In any acidbase reaction, there are two conjugate acidbase pairs.

EXERCISE 2
Identify the conjugate acidbase pairs in each of the following reactions:

(a)

HNO3 + NH3 NO3 + NH4+

HNO3 / NO3 and NH3 / NH4+

(b)

HNO3 + H2O H3O+ + NO3

HNO3 / NO3 and H2O / H3O+

(c)

NH3 + H2O NH4+ + OH

NH3 / NH4+ and H2O / OH

(d)

HNO3 + H2SO4 H2NO3+ + HSO4

HNO3 / H2NO3+ and H2SO4 / HSO4

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1.3

Strong and Weak Acids and Bases


A strong acid is one that dissociates completely in water to give H3O+. It gives up a proton more
readily compared to the H3O+ ion.
e.g.

HCl
strong acid

H2O

Cl
conjugate base

H3O+

The conjugate base of a strong acid has a very low tendency to accept a proton.
So the reverse reaction is negligible singleheaded arrow ().
Other examples of strong acids: HNO3, HBr, HI, HClO3, HClO4, H2SO4
A weak acid is one that dissociates partially in water to give H3O+. It gives up a proton less readily
compared to the H3O+ ion.
e.g.

CH3CO2H
weak acid

H2O

CH3CO2
conjugate base

H3O+

The conjugate base of a weak acid has a tendency to accept a proton.


So the reverse reaction occurs to some extent doubleheaded arrow ().
A mixture of undissociated CH3CO2H molecules and the ions exists in solution.
Other examples of weak acids: H2SO3, HNO2, H2CO3, H2S, HF, HCN, most organic acids

A strong base is one that dissociates completely in water to give OH.


e.g.

NaOH

Na+ + OH

Other examples of strong bases: KOH, Ba(OH)2


A weak base is one that dissociates partially in water to give OH.
e.g.

NH3 + H2O NH4+ + OH

Other examples of weak bases: hydrazine N2H4, amines such as CH3NH2, C6H5NH2

The strength of an acid (or base) is different from the concentration of the acid (or base).
Concentration of an acid (or base) = No. of moles of acid (or base) dissolved in 1 dm3 of solution.
EXERCISE 3
Match each acid on the left with the correct description on the right.
0.001 mol dm3 HNO3

concentrated but weak acid

4.0 mol dm3 CH3CO2H

dilute but strong acid

0.001 mol dm3 CH3CH2CO2H

dilute and weak acid


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CALCULATIONS INVOLVING ACIDS AND BASES

2.1

Concept of pH, pOH and the Ionic Product of Water

A)

pH and pOH
The concentration of H+ and OH in an aqueous solution is usually quite small. A convenient
indication of the concentration of H+(aq) is to express it in terms of its negative logarithm to base 10.

pH = lg [H+(aq)]

Hence,

[H+(aq)] = 10pH

E.g. for 0.01 mol dm3 HCl, [H+(aq)] = 102 mol dm3 and pH = 2.
Note:
pH is a measure of the (total) concentration of H+ in a solution. It is not a measure of the strength of
the acid unless the two acids being compared have the same initial concentration (see Section 2.6).
Similarly, a convenient indication of the concentration of OH(aq) is to express it in terms of its
negative logarithm to base 10.

pOH = lg [OH(aq)]

and

[OH(aq)] = 10pOH

E.g. for 0.01 mol dm3 NaOH, [OH(aq)] = 102 mol dm3 and pOH = 2.

B)

Ionic product of water, Kw


Pure water conducts electricity slightly. This indicates the presence of trace concentrations of ions
which arise from the very slight selfionisation or autoionisation of water.
H2O(l)

H3O+(aq)

H2O(l)

OH(aq)

A simpler way of representing the equilibrium is:


H2O(l)

H+(aq)

OH(aq)

The equilibrium constant, Kc, for the reaction is given by:


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Kc

[H+][OH]
[H2O]

Since the extent of ionisation is very small, [H2O] is almost constant (at 55.6 mol dm3).
Therefore,

Kc x [H2O] = [H+][OH]

Kw = [H+][OH]

or

where Kw is a constant known as the ionic product of water

Taking lg on both sides of equation:


lg Kw = (lg [H+]) + (lg [OH])
pKw = pH + pOH

* remember the symbol p means log10

The value of Kw depends only on temperature. It is always a constant at constant temperature.


Experimentally, at 25oC,

Kw = 1.0 x 1014 mol2 dm6

(value is given in the Data Booklet)

pKw = pH + pOH = 14

C)

Relationship between [H+(aq)], [OH(aq)] and pH


In pure water as well as any aqueous solution, the following equilibrium exists:
H+(aq)

H2O(l)

OH(aq)

Thus, an acidic solution contains a few hydroxide ions, and an alkaline solution contains a few
hydrogen ions.
The product of [H+] and [OH] always equals Kw since Kw is an equilibrium constant and its numerical
value is only affected by temperature.
When

[H+(aq)] = [OH(aq)] neutral solution


[H+(aq)] > [OH(aq)] acidic solution
[H+(aq)] < [OH(aq)] alkaline solution

At 25o C, since Kw = 1014 mol2 dm6


Type of solution
Neutral

[H+] / mol dm3


= 1.0 x 10

Acidic

> 1.0 x 10

Basic

< 1.0 x 10 7

[OH] / mol dm3

pH

pOH

= 1.0 x 10

= 7.00

= 7.00

< 1.0 x 10

< 7.00

> 7.00

> 7.00

< 7.00

> 1.0 x 10 7

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EXERCISE 4 [Ref: N96/4/8, N03/1/1, N95/4/33]


Like other equilibrium constants, the value of Kw depends only on temperature:
Temperature / oC

Kw / mol2 dm6

0
10
25
40
60

1.5 1015
3.0 1015
1.0 1014
3.0 1014
9.5 1014

[H+] = [OH] =

K w / mol dm3

3.9 108
5.5 108
1.0 107
1.7 107
3.1 107

State whether the following statements are true or false.


(i)

The ionic dissociation of water, H2O(l) H+(aq) + OH(aq), is an endothermic


process.

(ii)

The dissociation of water increases by a factor of 6 between 10 oC and 60 oC.

(iii)

The association of water molecules by hydrogen bonding increases as


temperature increases.

(iv)

When water is heated, the concentration of H+(aq) increases.

(v)

Water remains a neutral liquid at 60 oC.

(vi)

When water is heated, the concentration of OH(aq) increases.

(vii)

The pH of pure water at temperatures greater than 25 oC is greater than 7.

(viii)

In pure water, the concentration of H+(aq) is higher than that of OH(aq) at


60 oC.

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2.2

pH of Strong Acid/Strong Base Solutions


Strong acids and strong bases are fully dissociated, hence

Similarly,

[H+] = [strong monobasic acid]

and

[H+] = 2 x [strong dibasic acid]

[OH] = [strong monoacidic base]

and

[OH] = 2 x [strong diacidic base]

Note: If the concentration of the acid or base is 107 mol dm3 or lower, the contribution of H+ or OH
from autoionization of H2O becomes significant. We will need to include it in the calculation.
EXERCISE 5
(a)

An aqueous solution contains 1.0 105 mol dm3 of hydrogen iodide (a strong acid). Calculate
the concentration of H+ in mol dm3, and hence the pH of this solution at 25 oC.
Ans: [H+] = 1.00 105 mol dm3, pH = 5.00
+

HI(aq) H (aq) + I (aq)


[H+] = [HI] = 1.0 105 mol dm3
pH = lg [H+] = lg (1.0 105) = 5.00

(b)

An aqueous solution contains 0.10 mol dm3 of calcium hydroxide (a strong base). Calculate
the concentration OH in mol dm3, and hence the pH of this solution at 25 oC.
Ans: [OH] = 0.200 mol dm3, pH = 13.3
Ca(OH)2(aq) Ca2+(aq) + 2OH(aq)
[OH] = 2 [Ca(OH)2] = 0.200 mol dm3
pOH = lg [OH] = lg 0.2 = 0.699
pH = 14 pOH = 14 0.699 = 13.3

(c)

An aqueous solution contains 0.010 mol dm3 of Ba(OH)2 (a strong base) and 0.050 mol dm3
of KOH. Calculate the pH of this solution at 25 oC.
Ans: pH = 12.8
Ba(OH)2(aq) Ba2+(aq) + 2OH(aq)
KOH(aq) K+(aq) + OH(aq)
Total [OH] = 20.010 + 0.050 = 0.070 mol dm3
pH = 14 pOH = 14 + lg 0.070 = 12.8
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(d)

Solution X contains HCl, it has pH 2.2. Solution Y has the same volume as solution X, it contains
HNO3 and has pH 1.6. The two solutions are mixed. Calculate the pH of the acid mixture.
Ans: 1.80
2.2
10 1.6 = 0.0157 mol dm3
Total [H+] = 10

pH = lg 0.0157 = 1.80

(e)

An aqueous solution contains 1 x 108 mol dm3 of HNO3. Calculate the pH of this solution.
Ans: 6.96
+

HNO3 (aq) H (aq) + NO3 (aq)


H2O (l) H+ (aq) + OH (aq) (autoionization of water)
[H+] = 108 + 107 = 1.1 x 107 mol dm3

Hence,

pH = lg (1.1 x 107) = 6.96

2.3

Dissociation Constants

A)

Acid dissociation constant, Ka


A weak acid HA dissociates partially in water to give H3O+.
HA

H2O

H3O+

In dilute aqueous solution, [H2O] is almost constant (at 55.6 mol dm3). The equilibrium constant may
be written as:

Ka

and

[H+]eqm[A]eqm
[HA]eqm

mol dm3

pKa = lg Ka

For strong acids e.g. HCl, Ka is very large and not used.
Like other equilibrium constants, the value of Ka depends only on temperature.
The value of Ka indicates the extent to which the weak acid dissociates in water at the specified

temperature.
To compare the strength of two weak acids, compare their Ka values.
At the same temperature, larger Ka (smaller pKa) stronger acid.

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Some Weak Acids and their Ka values

B)

Equilibrium reaction

Ka /mol dm3

CH3CO2H + H2 O CH3CO2 + H3O+

1.8 X 105

HCO2H + H2 O HCO2 + H3O+

1.8 x 104

C6H5CO2H + H2 O C6H5CO2 + H3O+

6.5 x 105

HCN + H2 O CN + H3O+

4.9 x 1010

Base dissociation constant, Kb


A weak base dissociates partially in water to give OH.
B

BH+

H2O

OH

In dilute aqueous solution, [H2O] is almost constant (at 55.6 mol dm3). The equilibrium constant may
be written as:
Kb

and

[BH+]eqm[OH]eqm
[B]eqm

mol dm3

pKb = lg Kb

For strong bases e.g. NaOH, Kb is very large and not used.
The value of Kb depends only on temperature.
The value of Kb indicates the extent to which the weak base dissociates in water at the specified

temperature.
To compare the strength of two weak bases, compare their Kb values.
At the same temperature, larger Kb (smaller pKb) stronger base.

Some Weak Bases and their Kb values


Equilibrium reaction

Kb /mol dm3

NH3 + H2 O NH4+ + OH

1.8 X 105

CH3NH2 + H2 O CH3NH3+ + OH

4.4 x 104

HS + H2 O H2S + OH

1.8 x 104

CO32 + H2 O HCO3 + OH

1.8 x 104

In aqueous solution, the two large classes of weak bases are nitrogencontaining molecules such

as NH3 and the amines (e.g. CH3CH2NH2), and the anions or conjugate bases of weak acids (e.g.
ethanoate ion, CH3CO2).

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C)

Relationship between Ka, Kb and Kw


Consider the weak acid, CH3CO2H, and its conjugate base, CH3CO2.
CH3CO2H CH3CO2 + H+
Ka

[CH3CO2][H+]
[CH3CO2H]

(1)

CH3CO2 + H2O CH3CO2H + OH


Kb

[CH3CO2H][OH]
[CH3CO2]

(2)

Ka x Kb = [H+] [OH] = Kw

(1) X (2),

Therefore, for any conjugate acidbase pair,


Ka x Kb = Kw
Taking lg on both sides of equation:
(lg Ka) + (lg Kb) = lg Kw
pKa + pKb = pKw

* remember the symbol p means log10

Hence, we can determine the value of Ka, given the Kb value of its conjugate base and vice versa.
From Ka x Kb = Kw , we see that for a conjugate acidbase pair,
as the strength of the acid decreases (smaller Ka), the strength of its conjugate base increases (larger
Kb) and vice versa.
E.g. CH3CO2H is a weak acid (Ka of CH3CO2H = 1.80 x 105 mol dm3), its conjugate base CH3CO2 is a
stronger base than water. Hence CH3CO2 has a tendency to accept a proton from water.
However, CH3CO2 is still a weak base (Kb of CH3CO2 = 5.56 x 1010 mol dm3).
2.4

Degree of Dissociation
The fraction of molecules which is ionised into ions in water is called the degree of dissociation, .
For an acid,

In general,

amount ionised
initial amount

for a strong acid or strong base,


for a weak acid or weak base,

[acid]dissociated
[acid]initial
is close to 1
<< 1
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2.5

pH of Weak Acid/Weak Base Solutions


Since weak acids and weak bases dissociate partially in water, [H+] or [OH] in the solution will be
less than the concentration of the weak acid or weak base.
We use Ka or Kb to calculate the [H+] or [OH] in the solution at equilibrium.
EXERCISE 6
Find (a) the pH and (b) the degree of dissociation of a solution of ethanoic acid, CH3COOH, of
concentration 0.1 mol dm3. [Given: Ka of CH3COOH = 1.8 x 105 mol dm3]
Ans: 2.87; 1.34 102 or 1.34 %
(a)
Initial conc
Change
Eqm conc

Ka

x = [H+] =

H+

HA
0.1
x
0.1 x
[H+][A]

+x
x

[HA]

x2
0.1 x

+x
x
x2

(assume x << 0.1)

0.1

1.8 10 5 0.1 = 1.34 x 103 mol dm3

pH = lg (1.34 x 103) = 2.87

(b)

= 1.34 x 103/0.1 = 1.34 x 102 (1.34% dissociated)

Note:
The assumption (x << 0.1) is valid since a weak acid only dissociates partially.
Check: x = 1.3325 x 103 (by solving quadratic equation) << 0.1
Solving quadratic equations is not required at A Level.
Generally, for a weak monobasic acid,

Ka

[H+] =

[H+]eqm[A]eqm
[HA]eqm

[H+]eqm2
[HA]eqm

[H+]eqm2
[HA]initial

[HA]initial Ka
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EXERCISE 7
The pH of a weak acid, HA, of concentration 0.100 mol dm3 was found to be 3.0. Calculate the pKa of
the acid.
Ans: 5.00
HA(aq) H+(aq) + A (aq)
Since pH = 3.0,

Ka

[H+] = 103 mol dm3

[H+]eqm[A]eqm

(103) (103)

[HA]eqm

0.1 103
1.01 x 105

mol dm3

pKa = lg Ka = 5.00
Note:

If [H+]eqm is known, the assumption [H+] << [HA] is not required in the calculations.

EXERCISE 8
Caffeine, C8H10N4O2, a stimulant found in coffee and tea, is a weak base.
C8H10N4O2 + H2O (C8H11N4O2)+ + OH
At 25 oC, a 0.020 mol dm3 caffeine solution has a pH of 11.5.
(a)
(b)

(a)

Write the Kb expression of caffeine and calculate its value at 25 oC.


Calculate the degree of dissociation, for caffeine at 25 oC.
Ans: 5.94 104 mol dm3; 0.158 or 15.8 %

Kb = [C 8H11N4 O 2 ][OH ]

[C 8H10N4 O 2 ]

pOH = 14 pH = 14 11.5 = 2.5


[OH] = 102.5 = 3.162 103 mol dm3
Kb =

(b)

(3.162 10 3 )2
0.020 3.162 10 3

= 5.94 104 mol dm3

3
= 3.162 10
= 0.158

0.020

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2.6

Strength of Acids and Bases


The strength of an acid (or base):
is a measure of how readily the acid (or base) donates its proton (or accepts a proton).
depends on its structure [ref: Topics 15 & 17]
is indicated by its Ka (or Kb) value [ref: p. 9p.10]
is different from the concentration of the acid (or base) [ref: p. 4 Ex 3]
Are pH or degree of dissociation, , reliable indicators of the strength of an acid (or base)?
EXERCISE 9
In Exercise 6 (p.12), the pH and the degree of dissociation of a solution of ethanoic acid of
concentration 0.1 mol dm3 were found to be:
pH: .

degree of dissociation, : .

Now, find (a) the pH and (b) the degree of dissociation of ethanoic acid of concentration 0.001 mol
dm3. How have the pH and been affected by the dilution?

(a)

pH = 3.87 (using assumption) or pH = 3.90 (solving quadratic equation)

(b)

= 0.134 (13.4% dissociated) or = 0.125 (12.5% dissociated)


pH is higher (lower [H+] present) pH increases with dilution.
is higher increases with dilution.

Since pH and degree of dissociation of an acid (or base) will change with change in concentration,
they are not reliable indicators of acid (or base) strength.
Hence, the values of pH, and Ka for a weak acid at a constant temperature will vary with dilution
(i.e. volume of water increases) as follows:
pH

Ka

Volume of water
(pH 7 as dilution )

Ka

Volume of water

Volume of water

( 1 as dilution )

Ka does not vary with concentration. It is a constant at constant temperature. Therefore Ka is the
best indicator of the strength of a weak acid.
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EXERCISE 10 [Ref: J97/1/3(b)]


Each of the following reactions contains two Bronsted acids and two Bronsted bases. Suggest with
brief reasoning which is the stronger acid and which is the stronger base.
(a)

NH3(aq)
weaker base

H2O(l)
weaker acid

NH4+(aq)
stronger acid

OH(aq)
stronger base

Kc = 3.2 107

Kc is very small, this suggests that the position of equilibrium lies very much to the left.
So NH4+ is a better proton donor than H2O, OH is a better proton acceptor than NH3.

(b)

C6H5O
stronger base

CH3CO2H
stronger acid

C6H5OH
weaker acid

CH3CO2
weaker base

Kc = 1.3 106

Kc is very large, this suggests that the position of equilibrium lies very much to the right.
So CH3CO2H is a better proton donor than C6H5OH, C6H5O is a better proton acceptor than
CH3CO2.

Note:
In part (a), NH3 is a weak base (Kb = 1.80 x 105 mol dm3) so its conjugate acid NH4+ is a stronger acid
than water. Recall from Section 2.3C, Ka x Kb = Kw.
However, NH4+ is still a weak acid (Ka of NH4+ = 5.56 x 1010 mol dm3).
From part (b), we see that the stronger acid is able to protonate the conjugate base of the weaker
acid.
Strong acids (e.g. HCl) are often used to liberate the weak acids (e.g. CH3CO2H) from their salt (e.g.
CH3COONa+).
HCl(aq)
+ CH3CO2(aq) Cl(aq) + CH3COOH(aq)
stronger acid
salt
weaker acid

2.7

Salt Hydrolysis and pH of Salt Solutions


An ionic salt may be prepared from a reaction between an aqueous acid and an aqueous base.
E.g. KCl may be prepared from KOH(aq) and HCl(aq).
Salt hydrolysis is a reaction in which ions react with water to produce OH or H3O+ ions.
Salts derived from a strong acid and a strong base (e.g. NaCl, KNO3) do not undergo salt hydrolysis.
Hence the resulting solution is neutral pH = 7 at 25 oC.
However, ions in salts derived from weak acids/bases (in particular, the anions of weak acids, and
cations of weak bases), as well as metal cations with high charge density, could undergo hydrolysis
to result in solutions of pH greater/less than 7 (at 25 oC).
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A)

Salt derived from a strong acid and a weak base


E.g. NH4+Cl
NH4+Cl is derived from HCl and NH3.
NH3 is a weak base so its conjugate acid NH4+ is a stronger acid than water. NH4+ undergoes
hydrolysis forming H3O+ ions.
NH4+(aq)

H2O(l)

NH3(aq)

H3O+(aq)

The anion Cl does not hydrolyse.


pH of a solution of NH4Cl is < 7 since [H3O+] > [OH].
Note:
NH4+ is a stronger acid than water (see Ex 10(a)) so is able to donate a proton to water.
However, it is still a weak acid (Ka of NH4+ = 5.56 x 1010 mol dm3). Hence a reversible arrow is
used in the salt hydrolysis equation.
The anion Cl (derived from strong acid HCl) is a weaker base than water so does not hydrolyse.

B)

Salt derived from a weak acid and a strong base


E.g. CH3CO2Na+
CH3CO2Na+ is derived from CH3CO2H and NaOH.
CH3CO2H is a weak acid so its conjugate base CH3CO2 is a stronger base than water. CH3CO2
undergoes hydrolysis forming OH ions.
CH3CO2 (aq)

H2O(l)

CH3CO2H(aq)

OH(aq)

The cation Na+ does not hydrolyse.


pH of a solution of CH3CO2Na+ is > 7 since [H3O+] < [OH].

C)

Salt derived from a weak acid and a weak base


E.g. CH3CO2NH4+
Both cation and anion hydrolyse.
pH of the salt solution depends on Ka of the acid (cation) and Kb of the base (anion)
If

Ka(cation) > Kb(anion) salt solution is acidic


Ka(cation) = Kb(anion) salt solution is neutral
Ka(cation) < Kb(anion) salt solution is basic
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D)

Salt containing an aqueous metal cation with high charge density


E.g. Al3+, Fe3+, Cr3+
Consider the ionic compound, aluminium nitrate Al(NO3)3. When it dissolves in water, the Al3+ and
NO3 ions are separated and is hydrated by water molecules.
Al(NO3)3(s) + 6H2O(l) [Al(H2O)6]3+(aq) + 3NO3(aq)
Note:
The hydrated cations are coordinated to water molecules through dative (coordinate) bonds to
form complexes. E.g. [Al(H2O)6]3+, [Fe(H2O)6]3+, [Cr(H2O)6]3+
The Al3+ ion is small and highly charged, it has high charge density. It withdraws sufficient electron
density from the OH bonds of the coordinated H2O molecules, weakening the OH bonds. When
one OH bond breaks, a proton is released:
[Al(H2O)6]3+(aq) + H2O(l) [Al(H2O)5(OH)]2+(aq) + H3O+(aq)
We call this a hydrolysis reaction. Since [H3O+] > [OH], Al3+(aq) is acidic, pH < 7.

H
+

H
+

Figure shows [Al(H2O)6]3+ acting as an acid, donating a proton to another H2O molecule

The Ka values of hydrated metal cations are given in the table:


Free ion
Fe3+
Cr3+
Al3+

Hydrated ion
[Fe(H2O)6]3+(aq)
[Cr(H2O)6]3+(aq)
[Al(H2O)6]3+(aq)

Ka /mol dm3 (at 25 oC)


6 103
1 104
1 105

Note:
In the presence of a base stronger than water e.g. OH, further abstraction of protons can occur.
[Al(H2O)5(OH)]2+(aq) + H2O(l) [Al(H2O)4(OH)2]+(aq) + H3O+(aq)

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EXERCISE 11
State whether the following solutions are acidic, alkaline or neutral. Write an equation, including
state symbols, for any hydrolysis reaction.
(a)

KBr(aq)
neutral, no hydrolysis reaction

(b)

NaCN(aq)
alkaline
CN(aq) + H2O(l) HCN(aq) + OH(aq)

(c)

CH3NH3+Cl (aq)
acidic
CH3NH3+(aq) + H2O(l) CH3NH2(aq) + H3O+(aq)

(d)

Ka very small HCO3 is a


weak acid, so CO32 is a
stronger base than water, CO32
hydrolyses in water

Na2CO3(aq), given: Ka of HCO3 = 4.7 1011 mol dm3


alkaline
CO32(aq) + H2O(l) HCO3(aq) + OH(aq)

(e)

NH4HS(aq), given: Kb of NH3 = 1.8 105 mol dm3


Ka1 of H2S = 9 108 mol dm3

Both ions undergo hydrolysis:


NH4+(aq) + H2O(l) NH3(aq) + H3O+(aq)
HS(aq) + H2O(l) H2S(aq) + OH(aq)

H2S is a weak diprotic acid


Ka1 : H2S(aq) HS(aq) + H+(aq)
Ka2 : HS(aq) S2(aq) + H+(aq)

(1)
(2)

Ka of NH4+ = 5.6 1010 mol dm3


Kb of HS = 1.1 107 mol dm3
Since Kb of HS > Ka of NH4+, (2) occurs to a larger extent than (1).
Thus, resultant [OH] > [H3O+]. The salt solution is alkaline.

(f)

FeCl3(aq)
acidic
Fe(H2O)63+(aq) + H2O(l) Fe(OH)(H2O)52+(aq) + H3O+(aq)
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EXERCISE 12 (Calculating pH of salt solution)


Calculate the pH of a 0.10 mol dm3 CH3CO2 Na+(aq) at 25oC.
Ka value for ethanoic acid is 1.8 x 105 mol dm3.
Ans: 8.87

Initial conc
Eqm conc

Kb (CH3CO2)

CH3CO2
0.10
0.10 x

CH3CO2H
x
Kw

Ka (CH3CO2H)

5.56 x 1010

x2/(0.10 x)

x2/0.10

OH
x

(assuming 0.10 >> x)

[OH] = x = 7.45 x 106 mol dm3 pOH = 5.13


pH = 14pOH = 8.87

BUFFER SOLUTIONS

3.1

What are Buffer Solutions?


A buffer solution is one that is able to resist pH changes upon addition of a small amount of acid or
base.
Types of buffer solution:
acidic buffer: an aqueous solution of a weak acid and its salt (conjugate base)
alkaline buffer: an aqueous solution of a weak base and its salt (conjugate acid)
So a buffer (usually) consists of two solutes one provides a weak Bronsted acid and the other
provides a weak Bronsted base. Together, they form a conjugate acidbase pair.

EXERCISE 13 [Ref: N2003/I/33]


Which of the following could act as buffer solutions?
1.
2.
3.

NaHCO3 and Na2CO3


CH3CO2H and NaCl
HNO3 and NaNO3

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3.2

Principles of Buffer Action (independent learning subtopic)

A)

Acidic buffer
E.g. CH3CO2H and CH3CO2Na+
Ethanoic acid is a weak acid and dissociates partially.
CH3CO2H CH3CO2 + H+

(1)

Adding sodium ethanoate (completely soluble in water) to this solution adds a lot of extra ethanoate
ions.
CH3CO2Na+ CH3CO2 + Na+
According to Le Chatelier's Principle, the position of equilibrium (1) shifts further to the left (i.e. the
dissociation of ethanoic acid is suppressed).
Concept Check: What happens to the pH of the solution when sodium ethanoate is added to ethanoic
acid?
The solution now contains the following:
large reservoir of unionised ethanoic acid;
large reservoir of ethanoate ions from the sodium ethanoate;
and can act as an acidic buffer solution.
Action of Acidic Buffer
(i)

When a small amount of H+ is added to this buffer, the H+ ions react with the large reservoir of
the CH3CO2 (conjugate base):
CH3CO2 + H+ CH3CO2H
The added H+ ions are removed and pH remains almost constant.

(ii)

When a small amount of OH is added to this buffer, the OH ions react with the large
reservoir of the unionized CH3CO2H molecules:
CH3CO2H + OH CH3CO2 + H2O
The added OH ions are removed and pH remains almost constant.

Note:
Buffer action equations are written with single (nonreversible) arrows.
In (i), after the reaction, [CH3CO2H] increases slightly and [CH3CO2 ] decreases slightly.
In (ii), after the reaction, [CH3CO2H] decreases slightly and [CH3CO2 ] increases slightly.
As the original amounts of CH3CO2H and CH3CO2 are large compared to the amount of H+ or OH
ions added, the ratio [CH3CO2H] / [CH3CO2 ] remains almost constant,
and [H+] = Ka [CH3CO2H] / [CH3CO2 ] remains almost constant, so pH remains almost constant.
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B)

Alkaline buffer
E.g. aqueous NH3 and NH4+Cl
Ammonia is a weak base and dissociates partially.
NH3(aq) + H2O(l) NH4+(aq) + OH (aq)

(2)

Adding ammonium chloride (completely soluble) to this solution adds a lot of extra ammonium ions.
NH4+Cl NH4+ + Cl
According to Le Chatelier's Principle, the position of equilibrium (2) shifts further to the left (i.e. the
dissociation of NH3 is suppressed).
Concept Check: What happens to the pH of the solution when ammonium chloride is added to
ammonia?
The solution now contains the following:
large reservoir of unionised ammonia;
large reservoir of ammonium ions from the ammonium chloride;
and can act as an alkaline buffer solution.
Action of Alkaline Buffer
(i)

When a small amount of H+ is added to this buffer, the H+ ions react with the large reservoir of
the NH3 (weak base):
NH3 + H+ NH4+
The added H+ ions are removed and pH remains almost constant.

(ii)

When a small amount of OH is added to this buffer, the OH ions react with the large
reservoir of the NH4+ (conjugate acid) from the salt:
NH4+ + OH NH3 + H2O
The added OH ions are removed and pH remains almost constant.

Note:
As the original amounts of NH3 and NH4+ are large compared to the amount of H+ or OH ions added,
the ratio [NH3] / [NH4+ ] remains almost constant,
and [OH] = Kb [NH3] / [NH4+ ] remains almost constant, pOH and thus pH remains almost constant.

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3.3

pH of Buffer Solutions

A)

Acidic buffer
In a buffer consisting of HA and its salt A, the following equilibrium exists:
HA(aq) + H2O(l) H3O+(aq) + A (aq)
and

Ka

[H+]eqm[A]eqm
[HA]eqm

As the presence of excess A(aq) suppresses the dissociation of HA,


[HA]eqm [HA]initial
(since is very small)

+
[A ]eqm [Na A ]initial
(since [A] from HA is very small)
therefore

and

Ka

[H+]

[H+]eqm[A]initial
[HA]initial

Ka

[H+]eqm[salt]
[acid]

[acid]
[salt]

Hence pH can be found easily.


Note:
When the ratio [acid]/[salt] remain almost constant, [H+] and therefore pH will remain almost
constant (see Section 3.2A).
In a buffer,
[H+] [A ]

[H+] = (Ka x [acid])


cannot be used.
+

Recall
[H ] = [A ] if the solution contains only the weak acid HA.
Alternatively, to find pH of a buffer, take lg on both sides of boxed equation,

lg[H ] lgKa lg
pH pKa lg

[acid]
[salt]

[s alt]
[acid]

HendersonHasselbalch Equation

It is important to use the correct concentrations in the numerator and denominator of the last term
in the equation.
B)

Alkaline buffer
In a similar manner as above, the pOH and pH of an alkaline buffer can be found using:
and

[OH ]

Kb

[base]
[salt]
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EXERCISE 14 (Calculating pH of buffer solution)


What is the pH of a buffer solution made by adding 3.28 g of sodium ethanoate (M r = 82) to 2 dm3 of
0.010 mol dm3 ethanoic acid? (Ka of ethanoic acid = 1.8 x 105 mol dm3)
Ans: 5.35

Concentration of ethanoate ions, [CH3CO2 ]

Ka

1.8 x 10

= 0.02 mol dm3

[CH3CO2H]
[H+] (0.02)

[H+]
pH

3.28/82

[H+][CH3CO2 ]

0.010

= 9.0 x 106 mol dm3


= lg [H+]
=

5.05

EXERCISE 15
Calculate the change in pH when 1 cm3 of a 1.00 mol dm3 NaOH is added to 1 dm3 of
(a)
water;
(b)
the buffer in Exercise 14
Ans: +4 units; +0.05 units
(a)

[OH] =

pOH = 3

1
= 9.99 x 104 mol dm3
1.001

1
1000

pH = 11

Change in pH = 11 7 = +4 units

(b)

CH3CO2H + OH CH3CO2 + H2O


No. of moles of NaOH added = 1/1000 x 1 = 0.001
[CH3CO2] = (0.04 + 0.001) / V
[CH3CO2H] = (0.010 0.001) / V

After the reaction,

Ka

[H+]
pH

1.8 x 10

[H+] (0.04 + 0.001)


0.010 0.001

= 3.95 x 106 mol dm3


= lg [H+] =
5.40

Change in pH = 5.40 5.35 = +0.05 units


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3.4

Buffer Capacity and Buffer Range


The capacity of a buffer is the quantity of H3O+ or OH it can remove before its pH changes
drastically.
A buffer should have high [HA] and [A], or high [B] and [BH+], to provide a large reservoir of the
relevant components.
The more concentrated the components of a buffer, the greater the buffer capacity.
The more similar the concentrations of the buffer components, the greater the buffer capacity.

A)

Maximum Buffer Capacity


[salt]

It can be shown that the most effective buffer has

[acid]

or

[salt]
[base]

Using the boxed equations in Section 3.3, it can be shown that


pH = pKa

(for acidic buffer)

or

pOH = pKb

(for alkaline buffer)

This buffer is said to have the maximum buffer capacity and it can most effectively resist a change in
pH in either direction (i.e. when either acid or base is added).

B)

Effective Buffer Range


The further the buffercomponent concentration ratio is from 1, the less effective the buffering
action (i.e., lower buffer capacity).
In practice, a buffer is no longer effective when [salt]/[acid] or [salt]/[base] > 10/1 or < 1/10.
Since log10 (10/1) = +1 and log10 (1/10) = 1,

[a ci d]
[s a l t]

for an acidic buffer,

[H+] = Ka

for an alkaline buffer,

[OH] = Kb

[ba s e]
[s a l t]

effective buffer pH range = pKa 1

effective buffer pOH range = pKb 1

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EXERCISE 16
Which of the following acids would be the best choice to combine with its sodium salt to make a
solution buffered at pH 4.25?
For your choice, calculate the ratio of the salt (conjugate base) to the acid concentrations required to
attain the desired pH.
Acid
chlorous acid (HClO2)
nitrous acid (HNO2)
methanoic acid (HCO2H)
hypochlorous acid (HClO)

pKa
1.95
3.34
3.74
7.54

The best choice is methanoic acid because its pKa lies closest and within 1 unit of the desired pH.

Ka

10

3.5

3.74

=
[salt]
[acid]

[H+][salt]
[acid]
104.25 [salt]
[acid]
=

3.24

Check: Ratio is between 0.1 and 10 (effective range)

Buffer System in Human Blood (independent learning subtopic)


The pH of our blood must be kept constant at about 7.4 since enzymes operate only within a narrow
pH range.
The most important buffer system in blood plasma involves the weak acid H2CO3 (an aqueous
solution of CO2) and its conjugate base, HCO3 ions.
The following equilibria operate in the H2CO3/HCO3 buffer system:
H+(aq) + HCO3 (aq) H2CO3(aq) H2O(l) + CO2(g)
Read the article on the following page for an elaboration on this buffer system.
If blood pH rises above about 7.45, you can suffer from a condition called
alkalosis. This can arise from hyperventilation or oxygen deficiency at high
altitude. It can lead to over excitability of the central nervous system, muscle
spasms and death. One way to treat alkalosis is to breath into a paper bag.
The CO2 exhaled is recycled into the body. Can you explain how that helps?
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3.6

2013 H2 Chemistry AcidBase Equilibria

Importance of Buffer Solutions in Everyday Life (independent learning subtopic)


Injections and drips into a patients body must be carefully buffered so that the pH of body fluids
does not change much.
In bacteriological research, pH of culture medium is maintained to control the growth of bacteria.
In agriculture, the pH of soil is maintained to optimize plant growth.
The pH of many industrial processes must also be carefully controlled, e.g. electroplating and
manufacture of dyes and leather.
Baking soda, which is sodium hydrogencarbonate, NaHCO3, is sometimes added to swimming
pools to control the pH of the water.
Although most buffer systems consist of two separate species that react with H+ or OH, the
HCO3 ion is an example of a single ion that is able to serve both functions:
On addition of small amount of acid,

HCO3(aq) + H+(aq) H2CO3(aq)

On addition of small amount of alkali,

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

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ACIDBASE TITRATIONS

4.1

AcidBase Indicators (independent learning subtopic)


An indicator is a weak acid, whose acid form, HIn, is a different colour from its ionised form, In.

HIn(aq)
red
red
colourless

E.g. for litmus


for methyl orange
for phenolpthalein

H+(aq)

In(aq)
blue
yellow
pink

At different pH values, the proportion of HIn to In is different, giving rise to different colours.
For litmus:
In acidic solutions, [H+] is high. The position of equilibrium lies on the left. Predominant form of
litmus is HIn so the solution will appear red.
In alkaline solutions, [OH] is high so [H+] is low. The position of equilibrium lies on the right.
Predominant form of litmus is In hence the solution will appear blue.

4.2

Working pH Range of Indicators (independent learning subtopic)


For most indicators, the predominant form must be at least 10 times more concentrated than the
other form for its colour to be distinguished from the other coloured form.
Given that the dissociation constant of an indicator, termed KIn, is

KIn

[H+][ In]

[HIn]

Taking lg on both sides and rearranging,

pH

pKIn + lg

[ In]
[HIn]

For litmus:
If the ratio of [In]/[HIn] 10/1, i.e. pH pKIn + 1, the solution appears blue.
If the ratio of [In]/[HIn] 1/10, i.e. pH pKIn 1, the solution appears red.
Therefore, the litmus changes from red to blue over a pH range of
pH = pKIn 1

to

pH = pKIn + 1

That is, the working range of an indicator (i.e. pH range where a marked colour change occurs) is
approximately

pKIn 1

.
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Common indicators and colour changes

EXERCISE 17
At low pH, the colour of bromocresol green is yellow, and at high pH, the colour is blue. Calculate the
pH at which the colour of bromocresol green (KIn = 1.58 x 105) is green.
HIn(aq)
yellow

H+(aq)

In(aq)
blue

When [HIn] = [In],

bromocresol green appears green (yellow + blue)

4.3

pH = pKIn = 4.80

Choice of Indicators
During an acidbase titration, one solution is run into the other in the presence of an indicator.
Endpoint: the point in a titration at which the indicator changes colour when 1 drop of excess
titrant is added.
Equivalence point: the point in a titration at which the exact number of moles of acid and base
react completely.
The endpoint coincides with the equivalence point only when a suitable indicator is used.
The indicator must have a distinct colour change.
The working range of the indicator must coincide with the rapid pH change for the titration.
The rapid pH change for the titration depends on the strengths of acid and alkali used. Either the
acid or the alkali, or both, may be strong or weak, so that there are four possible combinations.
Type
strong acid strong alkali
strong acid weak alkali
weak acid strong alkali
weak acid weak alkali

suitable indicator
methyl orange or phenolphthalein
methyl orange
phenolphthalein
no suitable indicator
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4.4

AcidBase Titration Curves


A titration curve (a graph of pH against the volume of the titrant added) shows how the pH changes
during a titration. It can be obtained by measuring the pH of the solution using a pH meter.
Four types of acidbase titration curves are shown on the following pages. Note that in all of them,
the acid is in the conical flask while the base is added from the burette.

(A)

Strong Acid Strong Base Titration


E.g. addition of 0.10 mol dm3 NaOH to 25.0 cm3 of 0.10 mol dm3 HCl
Features of the curve:
3
At VNaOH = 0 cm
Initial pH = pH of HCl = lg 0.10 = 1
Low as HCl is a strong acid (fully dissociated
in water).
X

Equivalence
point, pH = 7

At 0 < VNaOH < 25 cm3


pH gradually rises as an increasing amount of
H+ is neutralized by the NaOH added.

At VNaOH = 25 cm3
Equivalence point is reached.
pH = 7 as the salt formed does not undergo
hydrolysis.

Volume of NaOH added / cm3


Suitable indicator:
methyl orange or phenolphthalein

Note for teachers:


Graph is not given in the students notes. Students will
sketch the titration curve during the lecture.

Note the sharp pH change near equivalence


point (see Homework 1, parts (c) and (e)).

At VNaOH > 25 cm3


There is excess NaOH present in the solution.
As NaOH is a strong base, [OH] is high, hence
pH is high (exact value depends on [NaOH]
that is in excess).

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Homework 1
Determine the pH of the solution in the conical flask at the point when each of the following
volumes of NaOH is added.
(a)

0.00 cm3

Ans: 1.00

(b)

12.50 cm3 (This is called the halfneutralisation or halfequivalence point.)

Ans: 1.48

(c)

24.90 cm3

Ans: 3.70

(d)

25.00 cm3

Ans: 7.00

(e)

25.10 cm3

Ans: 10.3

(f)

50.00 cm3

Ans: 12.5

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B)

Weak Acid Strong Base Titration


E.g. addition of 0.10 mol dm3 NaOH to 25.0 cm3 of 0.10 mol dm3 CH3CO2H

X
buffer region

Equivalence
point, pH > 7

Volume of NaOH added / cm3


Features of the curve:
3
At VNaOH = 0 cm
Initial pH = pH of CH3CO2H
pH is not equal to 1.0 as CH3CO2H is a weak acid (only ionises partially in water).
At 0 <VNaOH < 25 cm

1. Once the NaOH is added and some acid is neutralized, the solution contains a mixture of weak
acid and its salt a buffer solution forms.
2. The pH at the initial part of the titration curve and the part immediately before
complete neutralisation changes more sharply as these lie outside the effective buffer range
of the buffer.
3. The maximum buffer capacity occurs when half of the number of moles of acid is neutralized
at VNaOH = 12.50 cm3 (where [acid] = [salt]). At this point, pH = pKa of the weak acid.
At VNaOH = 25 cm

Equivalence point is reached. pH > 7 as the anion undergoes hydrolysis to produce OH:
CH3CO2(aq) + H2O(l) CH3CO2H(aq) + OH(aq)
Suitable indicator: phenolphthalein
The sharp change in pH in the curve near equivalence point occurs over a smaller pH range
compared to the previous strong acidstrong base titration.
At VNaOH > 25 cm

There is excess NaOH present in the solution. As NaOH is a strong base, [OH] is high and hence
pH is high (exact value depends on [NaOH] in excess).
Homework 2
Determine the pH of the solution in the conical flask at the point when each of the following
volumes of NaOH is added. (Ka of CH3CO2H = 1.8 105 mol dm3)
(a) 0.00 cm3
Ans: 2.87
3
(b) 12.50 cm (halfneutralisation point)
Ans: 4.74
3
(c)
25.00 cm (see Section 2.7, Exercise 12)
Ans: 8.72
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C)

Strong Acid Weak Base Titration


E.g. addition of 0.10 mol dm3 NH3 to 25.0 cm3 of 0.10 mol dm3 HCl

Equivalence
point, pH < 7

Volume of NH3 added / cm3


Features of the curve:
3
At Vweak base = 0 cm
Initial pH = pH of HCl = lg 0.10 = 1
Low as HCl is a strong acid (fully dissociated in water).
At 0 < Vweak base < 25 cm

pH gradually rises as increasing amount of H+ is neutralized by added weak base. However, no


buffer is formed as there is no weak base present in excess in the conical flask.
At Vweak base = 25 cm

Equivalence point is reached. pH < 7 as the cation undergoes hydrolysis to produce H3O+:
NH4+(aq) + H2O(l) NH3(aq) + H3O+(aq)
Suitable indicator: methyl orange
At Vweak base > 25 cm

There is excess weak base present. The solution contains a mixture of weak base and its salt a
buffer solution forms.
What is the Vweak base and pH at which the buffer with maximum capacity occurs?
Ans: 50 cm3, 9.26

Homework 3
Determine the pH of the solution in the conical flask at the equivalence point.
(Kb of NH3 = 1.8 105 mol dm3)

Ans: 5.28

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D)

Weak Acid Weak Base Titration


E.g. addition of 0.10 mol dm3 NH3 to 25.0 cm3 of 0.10 mol dm3 CH3CO2H

Volume of NH3 added / cm3


Features of the curve:
3
At Vweak base = 0 cm
Initial pH = pH of CH3CO2H
pH is not equal to 1.0 as CH3CO2H is a weak acid (only ionises partially in water).
At 0 < Vweak base < 25 cm

Once the weak base is added and some acid is neutralised, the solution contains a mixture of
weak acid and its salt a buffer solution forms.
At Vweak base = 25 cm

Equivalence point is reached. There is no sharp change in pH, hence no suitable indicator can be
used, a pH meter may be used to help detect the equivalence point.
Both the cation and anion undergo hydrolysis (see Section 2.7C).
At Vweak base > 25 cm

There is excess weak base present in the solution together with its salt another buffer region is
formed.

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4.5

2013 H2 Chemistry AcidBase Equilibria

Titration Curves with More than One Equivalence Point


Polyprotic acids have more than one ionisable proton. The successive Ka values may differ by several
orders of magnitude. This means the first H+ is lost more easily than subsequent ones.
E.g.

H2SO3(aq) + H2O(l) HSO3(aq) + H3O+(aq)


HSO3(aq) + H2O(l) SO32(aq) + H3O+(aq)

Ka1 = 1.4 x 102 mol dm3


Ka2 = 6.5 x 108 mol dm3

In a titration of H2SO3, we can assume that all the H2SO3 molecules will lose one H+ ion before any of
the HSO3 ions loses its H+.
OH
OH
H2SO3 > HSO3 > SO32

Volume of NaOH added /cm3


Note that the titration curve has two steep portions, which corresponds to two equivalence points.
A similar curve is also obtained for a titration involving a mixture of two acids with an appreciable
difference in Ka values (or a mixture of 2 bases with an appreciable difference in Kb values).
In practice, we can observe the two separate endpoints with the proper choice and use of two
different indicators. Consider the titration of sodium carbonate with dilute HCl.

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2013 H2 Chemistry AcidBase Equilibria

Hwa Chong Institution

There are 2 stages in the titration:


CO32(aq) + H+(aq) HCO3(aq)
HCO3(aq) + H+(aq) H2O(l) + CO2(g)

(1)
(2)

The first rapid change in pH for reaction (1) occurs at pH = 8.5. Therefore a suitable indicator for the
first equivalence point is phenolphthalein.
The second rapid change in pH for reaction (2) occurs at pH = 4. Therefore a suitable indicator for the
second equivalence point is methyl orange.
To observe the two endpoints separately, phenolphthalein is first added. Methyl orange is added
only after the equivalence point is reached.
If methyl orange is used at the start of the experiment, only one endpoint is observed and the titre
obtained is twice that obtained with phenolphthalein.
EXERCISE 18 (Double indicator titration)
A 25.0 cm3 portion of a solution containing sodium carbonate and sodium hydrogencarbonate
needed 22.50 cm3 of a solution of hydrochloric acid of concentration 0.100 mol dm3 to decolourise
phenolphthalein. On addition of methyl orange, a further 28.50 cm3 of the acid was needed to turn
this indicator orange. Calculate the concentration of sodium carbonate and sodium
hydrogencarbonate in the solution.
Ans: 0.0900 mol dm3; 0.0240 mol dm3
With phenolphthalein indicator:
Na2CO3(aq) + HCl(aq) NaHCO3(aq) + NaCl(aq) (1)
No of moles of HCl used = 0.100 x 0.0225 = 2.25 x 103
No of moles of Na2CO3 = 2.25 x 103
[Na2CO3] = 2.25 x 103/0.025 = 0.0900 mol dm3
With methyl orange indicator:
NaHCO3(aq) + HCl(aq) NaCl(aq) + H2O(l) + CO2(g)
(from original NaHCO3 and
the NaHCO3 formed in (1))

No of moles of HCl used = 0.100 x 0.0285 = 2.85 x 103


No of moles of HCl used for NaHCO3 formed from Na2CO3 = 2.25 x 103
No of moles of HCl used for original NaHCO3 = 2.85 x 103 2.25 x 103 = 0.60 x 103
[NaHCO3] in the original solution = 0.60 x 103/ 0.025 = 0.0240 mol dm3
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2013 H2 Chemistry AcidBase Equilibria

Hwa Chong Institution

Ionic Equilibria Summary


Concept

Application

An acid is a proton donor.


A base is a proton acceptor.
pX = log10X

X = 10

To identify if a molecule or ion is behaving as an acid or


base given an equation or vice versa
pX

To define quantities such as pH, pOH, pKw, pKa and pKb

Kw = [H ][OH] = 1 x 1014 (at 25C)

To calculate [H ] or [OH] given the value of the other.

Kw shows the relationship between [H ] and [OH] in any


aqueous solutions.

In pure water, [H ] = [OH] = 1 x 107 (at 25C)

pKw = pH + pOH = 14 (at 25C)

To calculate pH from pOH, or vice versa

For any conjugate acidbase pair,


Ka x Kb = Kw
o
pKa + pKb = pKw = 14 (at 25 C)

To calculate Ka from Kb, or vice versa.


You use this equation when you need one of these K
values but have the other.

H + A
+

HA
Ka =

[H ] eqm [A ] eqm
[HA] eqm

To calculate the pH of a
2
weak acid, Ka [H ] eqm
[HA] initial
buffer, Ka

[H ] eqm [ salt] initial


[acid] initial

To compare the strength of weak acids.


The larger the Ka value, the stronger the acid.
B + H2O
Kb =

BH + OH
+

[BH ] eqm [OH ] eqm


[B] eqm

To calculate the pH of a
[OH ] 2 eqm
weak base, Kb
[B] initial
buffer, Kb

[OH ] eqm [salt] initial


[base] initial

To compare the strength of weak bases.


The larger the Kb value, the stronger the base.
Salt hydrolysis a reaction in which ions react with
water to form acidic or alkaline solutions
+
+
e.g. NH4 + H2O
NH3 + H3O

CH3CO2 + H2O
CH3CO2H + OH

To explain why the pH of a salt derived from


strong acid and weak base (e.g. NH4Cl) is < 7
weak acid and strong base (e.g. CH3CO2Na) is > 7

Checklist for pH calculations


Do you know how to calculate the pH of a solution containing
a strong acid or strong base
a weak acid or weak base
a salt such as CH3CO2Na or NH4Cl
a buffer
Using the above, can you sketch a titration curve, and mark the various key points on the curve (initial pH, equivalence
point, buffer with maximum capacity)?
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