Acid Base Equilibria and Buffer Solutions

Chemistry For STPM
Chapter 10:
Acid Base Equilibria and
Buffer Solutions
10.1 Theories of Acid and Bases
Arhenius Theory Lewis Theory
Bronsted-Lowry Acid: Electron pair

Acid + Water  H+
acceptor[short of e,
Base + Water  OH- cation]
Acid: Proton
donor Base: Electron pair donor
HCl + H2O  [extra e, anion]
Base: Proton
Cl- + H3O+
acceptor
NH3 + BF3 NH3BF3
RNH2 + H2O 
RNH3 + OH- HCl + NH3  Cl- + NH4+
Acid Base Conjugate base,
conjugate
Water can acts as acid andacid
base:Amphoteric Solvent
10.2 Electrolyte
Chemical Compound
Electrolyte Non-electrolyte
Strong: Fully dissociate into ions in

aqueous solution, high degree of
dissociation, good electrical conductor
Weak: Partially dissociate into ions in

aqueous solution, low degree of
dissociation, poor electrical conductor
10.3 The Strength of Acid and Base
Strong Acid and Weak Acid

Able to donate proton hardly donate proton ;
easily; completely dissociate partially dissociate
HCl + H2O  Cl- + H3O+

Acid Base Conj. Base
conj. acid
•The stronger the acid, the weaker its conjugate
• HCl is strong acid, easier to donate H+, equilibrium
lies to the right.
• Conjugate base Cl- hardly receive H+.
Ostwald Dilution Law
CH3COOH CH3COO- + H+
t= 0 s (mol) c 0 0
t =equilibrium c (1-α) cα cα
Ka = Cα2 /(1-α)
Dissociation Constant of Acid(Ka)
For weak acid, dissociation constant α is small,
(1-α)
(1- = 1, thus Ka = Cα2 .
[H+] = Cα = c √ Ka/c = √ Ka x c
NH3 + H2O NH4+ + OH-
t= 0 s (mol) c 0 0
t =equilibrium c (1-α) cα cα
Kb = Cα2 /(1-α)
Dissociation Constant of Base(Kb)
For weak base, dissociation constant α I

small,
(1-α)
(1- = 1, thus Kb = Cα2 .
[OH-] = Cα = c √ K b/c = √ Kb xc
pKa = -log10 Ka
•The higher Ka, the stronger the acid.
•The higher pKa, the weaker the acid.
•The higher Kb, the stronger the base
• The higher pKb, the weaker the base
Various Value of Ka
Acid Equilibrium pKa
H3PO4 H3PO4 H2PO4- + H+ pk1 = 2.1
H2PO4- H2PO4- HPO42- + H+ pk2 = 7.2
HPO42- HPO42- PO43- + H+ Pk3 = 12.4
The degree of second dissociation is less than first

dissociation.
Second proton is hardly to be released due to strong
attraction of proton by negatively charged ion.
10.4 Factor Affecting Acid and Base Strength
1. Which is behave as acid? Why?

Na(OH) @ SO2(OH)2
2. Arrange the strength acid in decreasing order.
Give reasons for the arrangement.
CH3COOH, ClCH2COOH, Cl2CHCOOH
1. When an electronegative element is attached to OH, the

O-H bond is weakened and proton tend to be released.
Since Na is electropositive element, H unlikely to be lost.
Thus, Na(OH) is a base whereas SO2(OH)2 is acid.
2. Carboxylic Acid, R(Akyl group) is attached electron

withdrawing group, electron from O – H will be pulled
away by Cl, thus H is easier to be given off.
Cl2CHCOOH , ClCH2COOH, CH3COOH
Dissociation of Water
Consider
H2O H+ + OH-
Kc = [H+][OH-]/ [H2O]
Given: Kw = [H+][OH-]
Then : Kw = Kc [H2O]
Kw = Ka x Kb = 10-14 ………Explain!
pKw = pKa + pKb = 14
In pure water: [H+]=[OH-] = 10-7 mol dm-3
The Kw affected by the temperature
Practice 1
1. When 0.1 mol of etanoic acid is dissolved in
water and the volume made up to 1 dm3 ,
the concentration of H+ is 1.34 x 10-3
mol/dm3 .
2. Which is the stronger acid, HClO or HBrO?
Explain your answer.
10.6 pH Scale
pH = -log10 [H+]
Type of solution:
Neutral: [H+] = 10-7
Acidic : [H+] >10-7
Basic : [H+] <10-7
pKw = pKa + pKb = 14 From [10.5]
Thus : pH = 14 + lg [OH] =14 – pOH
Note:
For Strong Acid, [H+] can be obtained directly
from the molarities.
For Weak Acid, to find [H+], we need to know Ka.
PRACTICE 2
1. Calculate the pH of 0.02 mol/dm3 sulphuric acid.
2. Calculate the pH of a solution prepared by mixing 25.0
cm3 of 0.1 mol/dm3 hydrochloric acid with 15.0 cm3 of
0.1 mol/dm3 sodium hydroxide solution.
3. Calculate the pH for 0.01 mol/dm3 of Ba(OH)2.
4. Calculate the pH of a solution prepared by mixing 25.0
cm3 of 0.1 mol/dm3 hydrochloric acid with 25.0 cm3 of
0.2 mol/dm3 sodium hydroxide solution.
5. The pH of 0.15 mol/dm3 butyl amine solution is 12.0 at
198 K. Calculate the dissociation constant of the base
and the degree of dissociation.
10.7 Acid- Base Indicators
1. The indicators can change color because their
ions have colors that are different from the un-
dissociated molecule.
2. Litmus is a weak acid:
Hln + H2O H3O+ + ln-
Red Blue
Why litmus paper show red in acidic solution?
In acidic solution, the [H3O+] is high. Thus, the
equilibrium shift to the left.
Indicator Dissociation Constant
KHln = [H3O+] [ln-]
[Hln]
Rearrange
[H3O+] = KHln [Hln]
[ln-]
Or pH = p KHln
lg [Hln]
-
[ln-]
When [Hln] = [ln-]; pH = p KHln
The colour changes for indicators
Indicators pKHln pH range Acid color Alkali color
Methyl Orange 3.7 3.2-4.2 Red Yellow

Methyl Red 5.1 4.2-6.3 Red Yellow
Bromothymol 7.1 6.0-7.6 Yellow Blue
Blue
Phenolphthalein 9.3 8.2-10.0 Colorless Red
Choosing Indicators For an Acid Base titration
1. An acid-base titration is a method used to

determine the concentration of either an acid or
base.
2. The end-point is the point at which the indicator
change colour
3. Type of acid base titration:
a) strong acid and strong base
b) weak acid and strong base
c) strong acid and weak base
d) weak acid and weak base
Strong acid and strong base
pH HCl + NaOH  NaCl + H2O
12 The pH changes sharply from 3.5 to 10.5
phenolphthelein
8
7
Bromothymo blue
Methyl orange
2
0 10 20 25 30 cm3 NaOH
Weak acid and strong base
CH3COOH + NaOH  NaCl + H2O
pH
The pH changes sharply from 6.5 to 10.5
12
9 Phenolphthalein
8
Ka = 1.8 x 10-5 mol/dm3

2 c = 0.1 mol/dm3
0 10 20 25 30 cm3 NaOH
Strong acid and Weak base
pH HCl + NH3  NH4Cl
12
6
5
Methyl orange
2
0 10 20 25 30 cm3 NaOH
Weak acid and Weak base
pH CH3COOH + NH3  CH3COONH4
There is no sharp increase of pH at the endpoint
0 10 20 25 30 cm3 NaOH
Titration of Weak Polyprotic Acid
pH H3PO4 + NaOH 
12
10 Formation of Na2HPO4
Phenolphthalein
8
4 Formation of NaH2PO4
Methyl orange
2
0 25 50 cm3 NaOH
Titration of Weak Polyprotic Acid
1. A weak polyprotic acid shows a titration curve with

separate equivalence point for each acidic hydrogen
displaced.
H3PO4 + NaOH NaH2PO4 + H2O …First equivalent point [3.6]

NaH2PO4 + NaOH Na2HPO4 + H2O . Second equivalent point [9.0]
Na2HPO4 + NaOH Na3PO4 + H2O …Third equivalent point [13.0]
PRACTICE 3
Sketch the graph to show the changes in pH during
the titration of 25 cm3 of 0.1 mol/dm3 sodium
hydroxide solution with 0.1 mol/dm3 sulphuric acid.
Ask yourself: Next what u need to know?
Correct
?
or
?
Salt Hydrolysis
Type of Salt Example Nature of salt
Strong acid + Strong Neutral
base
Strong acid + Weak base Acidic
Weak acid + Strong base Alkaline
Weak acid + Weak base Depends Ka
For Strong Acid and Base: Na+ + Cl- + H2O  No reaction
For Strong acid and weak base: NH4Cl  NH+ + Cl-

Cl- + H2O  No reaction NH4+ + H2O  NH3 + H3O+
For Weak acid + Strong base: CH3COONa  CH3COO- + Na+

Na+ + H2O  No reaction
CH3COO- + H2O  CH3COOH + OH-
10.8 Buffer solution
Acidic Buffer solution Alkaline Buffer solution
Mixture of weak acid Mixture of weak base

and its salt whose pH and its salt whose pH
value changes very value changes very
slightly when a small slightly when a small
amount of an acid or amount of an acid or
alkali is added alkali is added
The action of buffer solution
CH3COOH CH3COO- + H+ NH3 + H2O NH4+ + OH-

CH3COONa  CH3COO- + Na+ NH4Cl  NH4+ + Cl-
Calculating the pH of Acidic and Alkaline Buffer
Let’s: HA  H+ + A – @ NH4 +  H+ + NH3
Ka = [H+][A-]/[HA] Ka = [H+][NH3]/[NH4]
How To Get How To Get
pH = pKa + lg [Salt]/[Acid] pOH = pKb + lg [Salt]/[Base]

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Chemistry For STPM

Arhenius Theory Lewis Theory

Bronsted-Lowry Acid: Electron pair

Strong: Fully dissociate into ions in

Weak: Partially dissociate into ions in

Strong Acid and Weak Acid

HCl + H2O  Cl- + H3O+

For weak base, dissociation constant α I

HPO42- HPO42- PO43- + H+ Pk3 = 12.4

The degree of second dissociation is less than first

1. Which is behave as acid? Why?

1. When an electronegative element is attached to OH, the

2. Carboxylic Acid, R(Akyl group) is attached electron

Indicators pKHln pH range Acid color Alkali color

Methyl Orange 3.7 3.2-4.2 Red Yellow

1. An acid-base titration is a method used to

12 The pH changes sharply from 3.5 to 10.5

Ka = 1.8 x 10-5 mol/dm3

There is no sharp increase of pH at the endpoint

1. A weak polyprotic acid shows a titration curve with

H3PO4 + NaOH NaH2PO4 + H2O …First equivalent point [3.6]

For Strong acid and weak base: NH4Cl  NH+ + Cl-

For Weak acid + Strong base: CH3COONa  CH3COO- + Na+

Acidic Buffer solution Alkaline Buffer solution

Mixture of weak acid Mixture of weak base

Let’s: HA  H+ + A – @ NH4 +  H+ + NH3

How To Get How To Get

pH = pKa + lg [Salt]/[Acid] pOH = pKb + lg [Salt]/[Base]

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