Acid-Base Equilibria

Chapter 16
 Revision

Acids and bases:

 change the colours of certain indicators.
 neutralize each other..
 react to form salts.
 Bronsted-Lowry Acids and Bases
These two chemists pointed out that acids and bases can be
seen as proton transfer reactions.
• Acid 
• Base 

Consider the reaction:

HCl (g) + NH3 (g) NH4+ + Cl NH4Cl (s)

We can view it as a proton transfer.

In any reversible acid-base reaction, both forward and reverse

reactions involve proton transfers.
Consider the reaction of NH3 with H2O:

NH3 (aq) + H2O (aq) NH4+ (aq) + OH  (aq)

A conjugate acid-base pair consists of two species in an acid-

base reaction (one acid and one base) that differ by the loss
or gain of a proton.
Conjugate acid-base pairs:

Example
Identify the acid and base species in the following equation:

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

An amphiprotic species is a species that can act as either an
acid or a base (it can lose or gain a proton), depending on the
other reactant.

Consider water:
H2O + CH3O- OH- + CH3OH

H2O + HBr H3O+ + Br-

In aqueous solutions H+
H+ + O–H → H–O–H +
interacts with H2O to for
H3O+ (hydronium ion) H H
Relative Strengths of Acids and Bases
Strong acids and bases
dissociated completely in
water.
Weak acids and bases
dissociate only partially in
water.

The strongest acids have the

weakest conjugate bases
and the strongest bases have
the weakest conjugate acids.

Substances with negligible

acidity do not dissociate in
water.
Autoprotolysis or Autoionisation of H2O
Water undergoes self-ionisation since H2O acts as an acid and
a base.
H2O + H2O H3O+ + OH-

The equilibrium constant expression for this reaction is:

Kc = [H3O+] [OH-] = Kw ion-product constant of water
= 1.0 x 10-14 at 25°C The extent of auto-
protolysis is very small.

Using Kw you can calculate concentrations of H3O+ and OH- in

pure water.
[H3O+] [OH-] = 1.0 x 10-14
In pure water

If you add an acid or a base to water the concentrations of

H3O+ and OH- will no longer be equal. But Kw will still hold.
 pH Scale
Because concentration values may be very small, it is often
more convenient to express acidity in terms of pH.

Definition of pH
pH is defined as the negative logarithm of the molar
hydronium-ion concentration.

pH = -log [H3O+] often written as: pH = -log [H+]

Example
For a solution with a hydronium-ion concentration of
1.0 x 10-3 M, the pH is:
Is the pH scale only from
0 to 14?
Example
Calculate the pH of typical adult blood, which has a
hydronium ion concentration of 4.0 x 10-8 M.

Example
The pH of natural rain is 5.60. Calculate its hydronium ion
concentration.
 Other “p” Scales - pOH
In the same way that we defined pH, we can also define pOH:
pOH = -log [OH-]

Also: Kw = [H3O+] . [OH-] = 1.0 x 10-14

-log ([H+] [OH-]) = -log (1x10-14)

-log [H+] + -log [OH-] = -log (1x10-14)
pH + pOH = 14
Example
Calculate the concentrations of hydronium ion and hydroxide
ion at 25°C in 0.10 M HCl.
Example
What is the pH of an aqueous solution containing 1.0  10-3 M
Mg(OH)2?
Example
What is the pH of an aqueous solution containing 1.0 x 10-8 M
KOH?
 Weak Acids
Most acids ionise only partially and thus an equilibrium is
established.
Eg. Acetic Acid:
CH3COOH + H2O H3O+ + CH3COO-

In general for a monoprotic acid, HA:

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

and the corresponding equilibrium constant expression:

[H3O+] [A-]
Ka =
[HA]
Acid dissociation constant

Also: pKa = -log Ka

 HA (aq) + H2O H3O+ (aq) + A- (aq)
The extent of ionisation depends on the acid dissociation
constant and the concentration of the acid.

Doubling [HA] of a weak

acid does not double [H3O+]

The higher the

concentration, the lower
the extent of ionisation.

This is due to increased interactions between ions (positive

and negative particles) as their concentrations increase.
The greater the value of Ka the stronger the acid.

If Ka >> 1, then the acid is completely ionized and the acid is a

strong acid.
Example
Sore-throat medications sometimes contain the weak acid
phenol, HC6H5O. A 0.10 M solution of phenol has a pH of
5.43 at 25°C. Calculate the acid-dissociation constant, Ka,
for this acid at 25°C?
Example
What is its degree of ionisation?

Degree of ionisation = fraction of acid that were ionised

HA + H2O H3O+ + A-
Equilibrium
Example
Para-hydroxybenzoic acid is used to make certain
dyes. What are the concentrations of the hydrogen ion
and para-hydroxybenzoate anion in a 0.200 M aqueous
solution at 25°C? The Ka of this acid is 2.6 x 10-5.

What is the pH of the solution and the degree of ionisation of

the acid?
 Polyprotic Acids
Some acids dissociate to give two or more protons
 polyprotic acids.

In general: Ka2 is much smaller than Ka1

For a triprotic acid: Ka3 is much smaller than Ka2
For a weak diprotic acid like carbonic acid, H2CO3,
there are two simultaneous equilibria to consider.
And each equilibrium has an associated acid
dissociation constant.

Loss of the 1st proton: Loss of the 2nd proton:

H2CO3 + H2O H3O+ + HCO3- HCO3- + H2O H3O+ + CO32-

[H3O+] [HCO3-] [H3O+] [CO32-]

Ka1 = Ka2 =
[H2CO3] [HCO3-]
= 4.3 x 10-7 = 4.8 x 10-11

pKa1 = 6.4 pKa2 = 10.3

What do the values of Ka or pKa tell us?
 Weak Bases
Equilibria involving weak bases are treated similarly to those
for weak acids.

In general for a weak base, B:

B (aq) + H2O HB+ (aq) + OH- (aq)

and the corresponding equilibrium constant expression:

[HB+] [OH-]
Kb =
[B]
Base association constant
The greater the value of Kb the stronger the acid.
Example
Aniline, C6H5NH2, is used in the manufacturing of some
perfumes. What is the pH of a 0.035 M solution of aniline
at 25°C? The Kb = 4.2 x 10-10 at 25°C.
 Relationship between Ka and Kb
Consider a conjugate acid-base pair:

Acid dissociation:
[H3O+] [A-]
HA (aq) + H2O H3O+ (aq) + A- (aq) Ka =
[HA]

Base association for the conjugate base:

[HA] [OH-]
A- (aq) + H2O HA (aq) + OH- (aq) Kb =
[A-]

Multiplying:
[H3O+] [A-] [HA] [OH-]
Ka .Kb = x
[HA] [A-]
= [H3O+] [OH-]
Example
Obtain the Kb for the F- ion, the ion added to public water
supplies to protect teeth. For HF, Ka = 6.8 x 10-4.