Acids & Bases

ACIDS and BASES 1

 Types of acids and bases
 Conjugate acid-base pairs
 Amphiprotic (amphoteric) substances

Acids and bases fall under one or more of the following three categories:
- Arrhenius acids/bases
- Bronsted-Lowry acids/bases
- Lewis acids/bases

1. Arrhenius acids and bases (1884)

Acids are substances which produce hydrogen ions in aqueous solution.
Bases are substances which produce hydroxide ions in aqueous solution.

HCl (aq)  H+(aq) + Cl-(aq)

KOH(aq)  K+(aq) + OH-(aq)

2. BRONSTED-LOWRY acids and bases (1922)

ACIDS are defined as substances, molecules or ions that can give up a proton (H+) to
a base.

BASES are defined as substances, molecules or ions that can accept a proton from an
acid.

 ACID - proton donor

 BASE - proton acceptor

HCl (g) + NH3 (g)  NH4+Cl-(s)

3. Lewis acids and bases (1923)

A Lewis acid accepts an electron pair eg BH3, BF3, AlCl3

A Lewis base donates an electron pair eg NH3

Reaction:
BF3 + :NH3  H3N:BF3

Acid Base
Arrhenius H+ in H2O OH- in H2O
B-L H+ donor to base H+ acceptor from acid
Lewis e- pair acceptor e- pair donor

Note: In this topic we shall be mainly considering B-L acids and bases.

1 S. ROLÉ / JC / ADV CHEM

 Acids & Bases

4. CONJUGATE ACID-BASE PAIRS

- A substance functions as an acid in the presence of a base.

- In the process, the acid itself becomes a base - the conjugate base of the
original acid.
- In the process, the base becomes an acid - the conjugate acid of the original
base.

Let's consider:
Adding ethanoic acid to water; some of the acid molecules will ionise in solution.
Each molecule that ionises loses a proton to become its conjugate base - the
ethanoate ion

CH3COOH(aq) CH3COO-(aq) + H+ (1)

Acid conjugate base + proton

The proton is then accepted by the base water to form its conjugate acid, the
hydronium ion.

H2O(l) + H+ H3O+(aq) (2)

Base + proton conjugate acid
Adding both equations gives

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

Acid + Base conj Base conj Acid

Therefore, there are TWO conjugate acid-base pairs

ACID BASE
1. CH3COOH and CH3COO-
2. H3O+ and H2O

Note:
 an acid and its conjugate base differ by only one proton;
 the relation between an acid HA and its conjugate base A- is
HA  A- + H+
 note that above reaction takes place in the presence of a second acid-base pair.
 According to the B-L theory, an acid is only an acid in the presence of a base, and
a base is only a base in the presence of an acid.

Practice: Identifying conjugate pairs.

2 S. ROLÉ / JC / ADV CHEM

 Acids & Bases

5. AMPHIPROTIC substances:

Substances that can behave either as B-L acids or B-L bases according to
circumstances are termed amphiprotic (or amphoteric).

Such substances include: H2O, HCO3-, HS-, H2PO4-, HC2O4- .

__________________________________________________________

IONISATION OF WATER

1. Ionisation equilibrium in pure water.

2. Ionic product Kw.
3. Calculations of [H+] and [OH-]
4. Effect of temperature on Kw.

1. Ionisation equilibrium in pure water.

Water is a special case of an amphiprotic substance; it reacts with itself.

H2O(l) + H2O(l) H3O+(aq) + OH-(aq)

Or simply

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

Kc (ionisation of water at 25oC) = 1.8x10-16moldm-1.

 Note Kc is very small.

 Equilibrium lies very far to the left.
 Most water molecules are un-ionised.
(approximately 18 molecules out of 10,000,000,000 are ionised)

3 S. ROLÉ / JC / ADV CHEM

 Acids & Bases

2. Derivation for Kw: The ionic product of water.

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

Kc = [H+(aq)] [OH-(aq)]
[H2O(l)]

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

Note:
 Kw can be measured experimentally and is found to be 1x10-14 mol2dm-6 at 25oC.
 The value for Kw is temperature dependent .
 The product of the concentrations of hydrogen ions and hydroxide ions Kw is
always constant for any dilute solution at a given temperature.

3. Estimating [H+(aq)] and [OH-(aq)]

Consider what happens when the equilibrium in pure water is upset by

- the addition of H+ ions from an acid.
- the addition of OH- ions from an alkali

Therefore,

 In a neutral solution:

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

Since [H+(aq)] [OH-(aq)] = 1x10-14 mol2dm-6 at 25oC

[H+(aq)] = [OH-(aq)] = 1x10-7 mol2dm-6

 In an acidic solution:

[H+(aq)] > [OH-(aq)]

[H+(aq)] > 1x10-7 mol2dm-6

[OH-(aq)] < 1x10-7 mol2dm-6

 In a basic or alkaline solution:

[H+(aq)] < [OH-(aq)]

[H+(aq)] <1x10-7 mol2dm-6

[OH-(aq)] >1x10-7 mol2dm-6

Note: an acidic solution has some OH- ; an alkaline solution has some H+
In all three cases,

4 S. ROLÉ / JC / ADV CHEM

 Acids & Bases

Kw = [H+(aq)] [OH-(aq)] = 1x10-14 mol2dm-6 at 25oC

Kw is called the ionic product of water.

Ex 1: Consider the eqm:

H2O(l) H+(aq) + OH-(aq) Kw = 1x10-14 mol2 dm-6

1. Calc [H+] and [OH-] in pure water.

2. If acid is added, how does the equilibrium shift?
3. Would the concentration of hydroxide ions be less or greater than
1x10-7moldm-3?
4. If alkali is added, how does the equilibriumm shift?
5. Would the concentration of hydrogen ions be less or greater than 1x10-
7
moldm-3?

Ex 2: Discuss

4. The effect of temperature on Kw.

2H2O(l) H3O+(aq) + OH-(aq) Ho = +6.5 kJ mol-1.

 The self-ionisation of water is an endothermic process.

 The forward endothermic reaction is favoured with increase in temperature; the
system absorbs more energy to counteract the increase in temperature.
 More water molecules dissociate at a higher temperature.
 The concentrations of the hydrogen ions and the hydroxide ions in pure water
increase as temperature increases.
 The value of Kw increases with increasing temperature.

5 S. ROLÉ / JC / ADV CHEM

 Acids & Bases

Ex 3: Consider the above equilibrium and endothermic value of +6.5 kJmol-1; Is the
concentration of hydrogen ions in pure water at 40o C less than or greater than the
value of 25oC? Explain your answer.

________________________________________________________

pH: the hydrogen ion exponent

- definition of pH
- calculations of pH from values of [H+]
- calculation of pH from values of Kw, [OH-]
- calculate [H+] from pH

DEFINITION of pH

 The concentration of hydrogen ions in a solution is a measure of the acidity or

alkalinity of a solution

Sorensen (1909),

Solution [H+] moldm-3 pH

A 0.001 1x10-3 3
B 0.000 1 1x10-4 4
C 0.000 000 1 1x10-7 7
D 0.000 000 001 1x10-9 9

Therefore,
[H+(aq)] = 1x10-pH moldm-3

Definition:
The pH of a solution is the negative logarithm to base ten of the molar hydrogen
ion concentration or
pH= - log10 [H+(aq)]

- The negative sign produces pH values which are positive for almost all
solutions encountered in practice.
- The logarithmic scale reduces the wide variation in [H+(aq)] to a narrow range
of pH
- As the concentration of the hydrogen ion increases, the pH value decreases
and vice versa.
- pH ranges from 0 to 14 for most practical purposes

In general, pX = -log10[X]

Try pOH, pKw

The ionic product Kw gives another useful relationship:

6 S. ROLÉ / JC / ADV CHEM

 Acids & Bases

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

pKw = pH + pOH

Ex 4:
a. Calculate the pH and pOH of pure water if Kw = 1x10-14 moldm-3 at 25oC.

b.Practise calculations of
(1) pH from [H+] or [OH-] values of fully ionised acids and alkalis.
(2) [H+] or [OH-] from pH values

Relative strengths of acids

1. Strong and weak acids
2. Degree of dissociation and dissociation constants
3. Calculations of Ka from pH, [H+]

1. (a) Strong acids.

Strong acids dissociate almost completely,e.g

HCl, H2SO4, HNO3. The word 'strong' refers to the extent of dissociation and not to
the concentration.
HCl(aq)  H+(aq) + Cl-(aq)

A difference of one pH number means a tenfold difference in acidity; pH 2 is 10 times

as acidic as pH 3

Effect on pH when diluting a strong acid

[ACID (aq)] moldm-1 pH
0.1 1x10-1 1
0.01 1x10-2 2
0.001 1x10-3 3
0.0001 1x10-4 4

(b) Weak acids

Acids which are not fully dissociated in water are weak acids, e.g. ethanoic acid,
carbonic acid.

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

At eqm 996 4 4

In a 1mole dm-3 solution of CH3COOH, the degree of dissociation is 4/1000. Most

molecules (996/1000) remain dissolved as wholly covalently bonded molecules.

'Weak" refers to the degree of dissociation and not to the concentration; 5M

CH3COOH is still a weak acid; 10-4M HCl is still a strong acid.

7 S. ROLÉ / JC / ADV CHEM

 Acids & Bases

Comparing pH's of same concentrations of a weak and a strong acid

[ACID] moldm-1 Observed pH Calculated pH
CH3COOH(aq) HCl(aq)
-4
0.0001 10 4.2 4
-3
0.001 10 3.5 3
0.01 10-2 3 2
-1
0.1 10 2.7 1
Note:

 In each case, the HCl solution has a higher concentration of H+ ions than the
ethanoic acid of the same concentration.
 This shows that ethanoic acid solutions are incompletely dissociated.
 As the ethanoic acid is diluted, its pH becomes closer to the pH of the strong acid.
Therefore dilution increases the extent of dissociation of the weak acid.
The effect of dilution can be explained using Le Chatelier's principle.
CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+(aq)
increase

 pH of an acid varies with concentration of H+ ions. To compare strengths of

different acids, pH values at the same concentration are considered.
Acid [ ] in moldm-3 pH
HCl 0.01 2
Benzoic acid 0.01 2.8
Ethanoic acid 0.01 3.0
Boric acid 0.01 5.6

 Values of concentration and values of pH are not reliable measures of the strength
of a particular acid.

2. Determination of [H+] or pH of a weak acid

The amount of [H+] ions in a weak acid can be found either by knowing
a. the degree of dissociation (α) or
b. the dissociation constant Ka

(a) Degree of dissociation α

α indicates the extent of dissociation of an acid.

[H+] = α [HA]

1.Calculate the pH of a solution of propanoic acid of concentration 0.010 moldm-3,

given that the degree of dissociation ‘α’ is 0.116.
2.An aqueous solution contains the acid HX at a concentration of 0.100 mol dm-3. The
degree of ionisation of the acid is 0.03. Calculate the pH of the solution.

(b) The Dissociation constant Ka

This is a constant at all dilutions for the same (weak) acid.

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

8 S. ROLÉ / JC / ADV CHEM

 Acids & Bases

Kc = [CH3COO-(aq) ] [ H3O+(aq)]
______________________________

[CH3COOH(aq)] [H2O(l)]

Ka = [CH3COO-(aq) ] [ H3O+(aq)]
______________________________

[CH3COOH(aq)]

For any weak acid HA dissociating in water

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

Ka = [H+(aq)] [A-(aq]
_______________________

[HA (aq)]
 Ka values are unaffected by concentration changes.
 Ka values change with temperature.
 Ka values provide an accurate measure of the extent to which an acid dissociates,
ie the strength of that acid.
 the larger the Ka value, the higher the concentration of H+ ions in solution.
 the larger the Ka value, the stronger the acid.
 Ka is for weak acids only. It is large and variable for strong acids.
 All Ka values are small. It is convenient to record the strength of an acid as a pKa
value.
pKa = -log10 Ka .

 The SMALLER the value of pKa , the LARGER the value of Ka, and the
STRONGER the (weak) acid.

ACIDITY CONSTANTS FOR WEAK ACIDS at 298K

Acid Ka moldm-3 pKa
Phosphoric H3PO4 7.5x10-3 2.1
Methanoic HCOOH 1.8x10-4 3.8
Ethanoic CH3COOH 1.8x10-5 4.8
Phenol C6H5OH 1.3x10-10 9.9

Base dissociation constant : Kb

B(aq) + H2O(l)  BH+(aq) + OH-(aq)

Kb = [BH+(aq)] [OH-(aq)]
___________________

[B(aq)]

 Kb is the base dissociation constant.

 Kb is a measure of the strength of a base.
 For convenience, Kb is usually expressed as pKb.

9 S. ROLÉ / JC / ADV CHEM

 Acids & Bases

pKb = - log10 Kb

 The SMALLER the value of pKb, the LARGER is the value of Kb, and the
STRONGER is the base.

BASICITY CONSTANTS FOR WEAK BASES at 298K

Base Kb moldm-1 pKb
Ethylamine C2H5NH2 6.5x10-4 3.2
Ammonia NH3 1.8x10-5 4.8
phenylamine C6H5NH2 4.3x10-10 9.4

Calculations – Ka, Kb, H+, pH, Kw, pKw, α

Relating Kw to Ka and Kb

Consider the ionisation of the acid HA:

HA + H2O H3O+ + A-

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

Consider the ionisation of the conjugate base A- of HA

A- + H2O HA + OH-

Kb = [HA] [OH-]
[A-]

If we multiply, Ka by Kb, the product is the expression of Kw.

Ka.Kb = [H3O+][OH-] = Kw

Kw = Ka.Kb

pKw = pKa + pKb

_______________________________________

Stepwise dissociation in Polyprotic acid

Diprotic (dibasic) acids - sulfuric acid (H2SO4), carbonic acid (H2CO3)

Tripotic (tribasic) acid -phosphoric acid (H3PO4)

(a) H2SO4 is a strong acid

Ka for the loss of the first proton is much greater than 1.
H2SO4(aq) + H2O(l)   H3O+(aq) + HSO4-(aq) Ka1 = 1 x 103
We therefore assume that essentially all the H2SO4 molecules in an aqueous solution
lose the first proton to form the HSO4-, or hydrogen sulfate, ion.

10 S. ROLÉ / JC / ADV CHEM

 Acids & Bases

Ka for the loss of the second proton is 10-2 i.e., only 10% of the H2SO4 molecules in a
1 M solution lose a second proton.
HSO4-(aq) + H2O(l)  H3O+(aq) + SO42-(aq) Ka2 = 1.2 x 10-2
H2SO4 only loses all H+ ions when it reacts with a base, such as ammonia.
Note the large difference between the values of Ka for the sequential loss of protons
by a polyprotic acid. We can assume that these acids dissociate one step at a time
an assumption known as stepwise dissociation.

Acid-Dissociation Equilibrium Constants for Common Polyprotic Acids

Acid Ka1 Ka2
Sulphuric VI acid (H2SO4) 1.0 x 10 1.2 x 10-2
3

ethanedioic acid (H2C2O4) 5.4 x 10-2 5.4 x 10-5

(b) H2S is a weak acid:

Some of the H2S molecules lose a proton in the first step to form the HS-, or hydrogen
sulfide, ion.
First step: H2S(aq) + H2O(l)  H3O+(aq) + HS-(aq)
A small fraction of the HS- ions formed in this reaction then go on to lose another
H+ ion in a second step.
Second step: HS-(aq) + H2O(l)   H3O+(aq) + S2-(aq)
Question: Write the two equilibrium constant expressions for the weak acid H2S

11 S. ROLÉ / JC / ADV CHEM