Part 2: Acid and Base Equilibria

Key Concepts

• Introduction to Ka, Kb, pKa and pKb (and introduction to logarithms)

• Autoprotolysis and Kw
• Definition of pH
Strengths of Acids and Bases - Review
Acid Formula Base Formula
perchloric acid HClO4 perchlorate ClO4–
sulfuric acid H2SO4 hydrogen sulfate HSO4–
nitric acid HNO3 nitrate NO3–
hydronium ion H3O+ water H2O
acetic acid CH3COOH acetate CH3COO–
ammonium ion NH4+ ammonia NH3
bicarbonate HCO3– carbonate CO32–
water H2O Hydroxide OH–
ammonia NH3 amide ion NH2–
hydroxide OH– oxide ion O2–

Can we quantify these strengths?

Acid and Base Equilibria
We can quantify the extent to which acid-base reactions occur by
looking at the values of their equilibrium constants
For an acid HA reacting with water:

HA(aq) + H2O(l) ⇋ A-(aq) + H3O+(aq)

𝐴− [𝐻3 𝑂+ ]
The equilibrium constant expression is: 𝐾=
[𝐻𝐴]

Remember: pure liquids and solids do NOT appear in equilibrium constant expressions
Definition of Ka
The equilibrium constant for the dissociation of an acid in aqueous
solution is called the acidity constant, Ka

𝐴− [𝐻3 𝑂+ ]
𝐾𝑎 =
[𝐻𝐴]
Definition of Ka
The value of Ka tells us the extent of dissociation of an acid – i.e. how
strong/weak an acid is
For a strong acid:
− +
𝐴 [𝐻3 𝑂 ] Large amounts of H3O+

𝐾𝑎 = Small amounts of HA
→ Ka is large

For a weak acid:

[𝐻𝐴]
Small amounts of H3O+
Large amounts of HA
→ Ka is small
Definition of Kb
The same is true for bases

For a base B reacting with water:

B(aq) + H2O(l) ⇋ BH+(aq) + OH-(aq)

The equilibrium constant expression is therefore:

𝐵𝐻 + [𝑂𝐻− ]
𝐾𝑏 =
[𝐵]
Definition of Kb
The equilibrium constant for the dissociation of a base in aqueous
solution is called the basicity constant, Kb

For a strong base:

+ −
𝐵𝐻 [𝑂𝐻 ] Large amounts of OH-
𝐾𝑏 = Small amounts of B
→ Kb is large

For a weak base:

[𝐵]
Small amounts of OH-
Large amounts of B
→ Kb is small
Activity 4.5
 Polyprotic Acids
For a polyprotic acid, protons are donated sequentially
• the first H+ is donated more readily than the second (as the second is
donated from a negative ion)
Ka1
H2CO3(aq) + H2O(l) HCO3-(aq) + H3O+(aq) Step 1

Ka2
HCO3- (aq) + H2O(l) CO32- (aq) + H3O+(aq) Step 2

Ka
H2CO3(aq) + 2 H2O(l) CO32-(aq) + 2 H3O+(aq) overall
Polyprotic Acids
Ka1 > Ka2 > Ka3 etc for any polyprotic acid

Ability to donate protons decreases as each proton is lost

H2CO3 HCO3– easier than HCO3– CO32–

H2CO3 is therefore a stronger acid than HCO3–

pKa and pKb
H3O+ or –OH concentrations depend on acid/ base strength
• strength can vary greatly
• hence, H3O+ or –OH can have huge variations in size
• leading to very large and very small Ka values

We typically use pKa and pKb values to compare acid/base strength.

pKa = -logKa and pKb = -logKb

Introduction to Logarithms
If you can write the number x in the form 10y then taking the log10 of x gives
you the exponent, y

For example, if x = 10y

then log10(x) = y

A change of 1 ‘p’ unit (e.g., pKa) corresponds to a 10-fold change in the

base unit (e.g., Ka)
For example, log10(10) = 1
log10(100) = 2
log10(1000) = 3
Activity 4.6
Strengths of Acids and Bases

pKa = -log(Ka) and Ka = 10-pKa

pKb = -log(Kb) and Kb = 10-pKb

As pKa (or pKb) increases, the Ka (Kb) decreases and therefore acid
strength (base strength) also decreases
Activity 4.7
Autoprotolysis of Water
Water can accept or donate protons
• Species that do this are known as amphiprotic

HCl(aq) + H2O(l) ⇋ Cl-(aq) + H3O+(aq) water acts as base

NH3(aq) + H2O(l) ⇋ OH-(aq) + NH4+(aq) water acts as acid

Autoprotolysis of Water

The process of two water molecules exchanging a proton is known as

autoprotolysis or autoionisation

H2O(l) + H2O(l) ⇋ OH-(aq) + H3O+(aq)

water acts as both an acid and base

Autoprotolysis of Water
This is an equilibrium reaction, and therefore has an equilibrium constant

H2O(l) + H2O(l) ⇋ OH-(aq) + H3O+(aq) K = [H3O+][OH-]

Question: Why does H2O not appear in the expression for K?

In pure water at 25°C this reaction occurs only to a very

small extent

➢ [H3O+] = [OH-] = 10-7 M

Definition of Kw

All samples of water contain some hydronium ions and some

hydroxide ions
➢ The product of these ions is called the autoprotolysis constant, Kw

Kw = [H3O+][OH-]

➢ In all aqueous solutions at 25°C, Kw = 10-14

Acidic and Basic Solutions
➢In a neutral solution [H3O+] = [-OH] = 10-7 M

➢In an acidic solution – more hydronium ions are created, so [-OH]

must decrease
[H3O+] > 10-7 M [-OH] < 10-7 M

➢In a basic solution – more hydroxide ions are created, so [H3O+] must
decrease
[H3O+] < 10-7 M [-OH] > 10-7 M
Acidic and Basic Solutions
Activity 4.8
pH – A Measure of Acidity
• Quantifying acidity is important in agriculture, medicine and industry

• The pH scale expresses the acidity or basicity of a solution using

numbers from 1-14
Definition of pH

pH = -log[H3O+]

[H3O+] = 10-pH

pH is a log scale
➢ A change of 1 pH unit means a tenfold change in [H3O+]
concentration
Definition of pH
pH = -log[H3O+]

[H3O+] = 10-pH
pH Values of Common Substances
Activity 4.9
Definition of pOH
The pOH scale is analagous to the pH scale, but defined with respect to
[-OH]

pOH = -log[-OH]

➢ pH and pOH at 25°C are related by Kw

pH + pOH = 14
Relationship Between pH and pKa
Why is the pH of a 1 M HCl solution less than a 1 M CH3COOH solution?

HCl(aq) + H2O(l) ⇋ Cl-(aq) + H3O+(aq)

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

HCl is a strong acid (larger Ka, smaller pKa)

➢ Gives a higher [H3O+] → lower pH

CH3COOH is a weak acid (smaller Ka, larger pKa)

➢ Gives a lower [H3O+] → higher pH
Calculating pH of a Weak Acid Solution
Example 1 – calculate the pH of a solution of 0.1 M ethanoic acid
(CH3COOH) given Ka = 1.8 x 10-5
• What information do we have, what information can we therefore
calculate, and what information are we trying to get?

➢ We know the initial concentration of the acid in solution

➢ We know the Ka of the acid 𝐴− [𝐻3 𝑂+ ]

𝐾𝑎 =
➢ We want to calculate the pH, [𝐻𝐴]
so we will need to use pH = -log[H3O+]

➢ We will need to find the equilibrium concentration of H3O+

Calculating pH of a Weak Acid Solution
Example 1 – calculate the pH of a solution of 0.1 M ethanoic acid
(CH3COOH) given Ka = 1.8 x 10-5

Step 1: write the balanced equation

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

Calculating pH of a Weak Acid Solution
Example 1 – calculate the pH of a solution of 0.1 M ethanoic acid
(CH3COOH) given Ka = 1.8 x 10-5
Step 2: write the expression for Ka

𝐶𝐻3 𝑂𝑂− [𝐻3 𝑂+ ]

𝐾𝑎 =
[𝐶𝐻3 𝐶𝑂𝑂𝐻]
Calculating pH of a Weak Acid Solution
Example 1 – calculate the pH of a solution of 0.1 M ethanoic acid
(CH3COOH) given Ka = 1.8 x 10-5
Step 3: create an ICE (algebra) table

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

CH3COOH CH3COO- H 3 O+
Initial concentration 0.1 0 0
Change in concentration -x +x +x
Equilibrium concentration 0.1-x 0+x (=x) 0+x (=x)
Calculating pH of a Weak Acid Solution
Example 1 – calculate the pH of a solution of 0.1 M ethanoic acid
(CH3COOH) given Ka = 1.8 x 10-5

Step 4: use the final row of your algebra table to substitute into the
equilibrium expression.
𝐶𝐻3 𝑂𝑂− [𝐻3 𝑂+ ]
𝐾𝑎 =
[𝐶𝐻3 𝐶𝑂𝑂𝐻]
➢ Remember, our goal is to determine pH from
pH = -log[H3O+]

➢ We need to first determine [H3O+] (= x) (𝑥)(𝑥)

1.8 × 10−5 =
(0.1 − 𝑥)
Calculating pH of a Weak Acid Solution
Example 1 – calculate the pH of a solution of 0.1 M ethanoic acid
(CH3COOH) given Ka = 1.8 x 10-5
−5
(𝑥)(𝑥)
1.8 × 10 =
(0.1 − 𝑥)

(Solving for x can be a lengthy, difficult process of rearranging into a quadratic equation)

➢ We know that CH3COOH is a weak acid.

➢ Therefore, x will be much smaller than [CH3COOH] (this is called the weak
acid assumption)
➢ So, we can simplify the expression above to say that (0.1 – x) ≈ 0.1
Calculating pH of a Weak Acid Solution
Example 1 – calculate the pH of a solution of 0.1 M ethanoic acid
(CH3COOH) given Ka = 1.8 x 10-5
(𝑥)(𝑥)
1.8 × 10−5 =
(0.1 − 𝑥)
𝑥2
The equation becomes: 1.8 × 10−5 =
0.1

Step 5: rearrange and solve the simplified equilibrium expression for x

Calculating pH of a Weak Acid Solution
Example 1 – calculate the pH of a solution of 0.1 M ethanoic acid
(CH3COOH) given Ka = 1.8 x 10-5
Step 5: rearrange and solve the simplified equilibrium expression for x
𝑥2
1.8 × 10−5 =
0.1
➢ Remember x = [H3O+] (at equilibrium)
𝑥 2 = (1.8 × 10−5 ) × 0.1

𝑥 2 = 1.8 × 10−6 Therefore, [H3O+] = 1.3 x 10-3 M

𝑥= (1.8 × 10−6 )

𝑥 = 1.3 × 10−3
Calculating pH of a Weak Acid Solution
Example 1 – calculate the pH of a solution of 0.1 M ethanoic acid
(CH3COOH) given Ka = 1.8 x 10-5
Step 6: calculate pH

[H3O+] = 1.3 x 10-3 M and pH = -log[H3O+]

Therefore, pH = -log(1.3 x 10-3)

pH = 2.89
Relationship Between pH and pKb
Why is the pH of a 1 M NaOH solution greater than a 1 M NH3 solution?

NaOH(aq) + H2O(l) ⇋ -OH (aq) + Na+(aq) + H2O(l)

NaOH is a strong base (larger Kb, smaller pKb)

➢ Gives a higher [-OH] → lower pOH and higher pH

NH3 is a weak base (smaller Kb, larger pKb)

➢ Gives a lower [-OH] → higher pOH and lower pH
Calculating Kb of a Weak Base
Example 2 – The pH of a 0.20 M solution of ammonia (NH3) is 11.15.
What is the Kb of NH3?

What information do we have, what information can we calculate, and

what information are we trying to determine?

➢ We know the initial concentration of the base in solution

➢ We know the pH of the solution

𝐵𝐻 + [𝑂𝐻 − ]
𝐾𝑏 =
[𝐵]
➢ We want to calculate the Kb

➢ We need to find the equilibrium concentrations of all species.

Calculating Kb of a Weak Base
Example 2 – the pH of a 0.20 M solution of ammonia (NH3) is 11.15.
What is the Kb of NH3?

Step 1: write the balanced equation

NH3(aq) + H2O(l) ⇋ NH4+(aq) + OH-(aq)

Step 2: write the expression for Kb

𝑁𝐻4+ [𝑂𝐻 − ]
𝐾𝑏 =
[𝑁𝐻3 ]
Calculating Kb of a Weak Base
Example 2 – the pH of a 0.20 M solution of ammonia (NH3) is 11.15.
What is the Kb of NH3?
Step 3: create an ICE (algebra) table
NH3(aq) + H2O(l) ⇋ NH4+(aq) + OH-(aq)

NH3 NH4+ HO-

Initial concentration 0.2 0 0
Change in concentration
Equilibrium concentration
Calculating Kb of a Weak Base
Example 2 – the pH of a 0.20 M solution of ammonia (NH3) is 11.15.
What is the Kb of NH3?
Step 4: Use pH to determine [OH-] and fill in ICE table
Remember pH + pOH = 14 and [OH-] = 10-pOH
Rearranging gives, pOH = 14 - pH
pOH = 14 – 11.15 = 2.85

Therefore, [OH-] = 10-2.85 = 1.41 x 10-3 M

➢ [OH-] is the equilibrium concentration, now we can fill in the ICE table
Calculating Kb of a Weak Base
Example 2 – the pH of a 0.20 M solution of ammonia (NH3) is 11.15.
What is the Kb of NH3?
Step 4: Use pH to determine [OH-] and fill in ICE table
NH3(aq) + H2O(l) ⇋ NH4+(aq) + OH-(aq)

NH3 NH4+ HO-

Initial concentration 0.2 0 0
Change in concentration -1.4 x 10-3 +1.4 x 10-3 +1.4 x 10-3

Equilibrium concentration 0.1986 1.4 x 10-3 1.4 x 10-3

Calculating Kb of a Base
Example 2 – the pH of a 0.20 M solution of ammonia (NH3) is 11.15.
What is the Kb of NH3?

Step 5: use your ICE table to substitute into the equilibrium

expression (Kb)
𝑁𝐻4+ [𝑂𝐻 − ]
𝐾𝑏 =
[𝑁𝐻3 ]

(1.41 × 10−3 )(1.41 × 10−3 )

𝐾𝑏 = = 1.0 × 10−6
(0.1986)