CHAPTER 7:

ACID-BASE REACTIONS
 LEARNING OUTCOME

 Definitions of acid & base Arrhenius, Bronsted-lowry &

Lewis
 Weak/strong versus concentrated/dilute acids, bases
 Standard solution, dilution process
 Volumetric analysis, titration & indicator
 pH, pOH Kw, pKw
 Ka, Kb, pKa, pKb
 Degree and percentage ionization
 Buffer
What is an acid?

What is a base?
 ACIDS & BASES

Acids and bases form a large group chemicals with

characteristic properties

Acids Bases
Taste sour Taste bitter
Change colour of wet litmus paper Change colour of wet litmus paper
to red (pH < 7) to blue (pH > 7)
React with metals Do not react with metals
 ACIDS

• Exhibit acidic properties in the presence of water –

form H3O+ ions (hydronium ion)
• React with base - form salt and water
HCl + NaOH → NaCl + H2O
• React with metals, - produce H2 gas
2 HCl + Na → 2 NaCl + H2
• React with carbonates – liberate CO2 gas
HCl + Na2CO3 → 2 NaCl + H2O + CO2
 COMMON ACIDS

NAME OF ACID FORMULA USES

Sulfuric Acid H2SO4 Battery acid

Fertilizers and
Nitric Acid HNO3
explosives
Phosphoric Acid H3PO4 Rust remover

Brick and ceramic tile

Hydrochloric acid HCl
cleaner

Flavoring,”
Acetic Acid CH3COOH
preservative
Carbonic Acid H2CO3 Carbonated water
 BASES

• Bases exhibit their basic properties only in

the presence of water due to the OH- ions

• React with an acid to form a salt and water

2 NaOH + H2SO4 → Na2SO4 + 2 H2O
 COMMON BASES

NAME OF BASES FORMULA USES

Oven and drain

Sodium hydroxide NaOH
cleaners

Potassium hydroxide KOH liquid soap

“MOM” Milk of
Magnesium hydroxide Mg(OH)2
magnesia

Barium hydroxide Ba(OH) 2 stabilizer for plastics

Ammonia NH3 Household cleaner

THEORY OF ACID AND BASE

Bronsted-
Arrhenius
Lowry

Lewis
 THE ARRHENIUS THEORY
Svante Augustus Arrhenius first presented this theory of
acids and bases in 1884.
Acids Bases
- substances that contain -substances that contain the
hydrogen hydroxyl group
and produces H+ in aqueous and produce OH- in
solutions aqueous solutions
Example: Example:
HCl, HNO3 and H2SO4 NaOH and Ca(OH)2

By the Arrhenius definition: Acids release a proton, or H+, in

water. Bases release a hydroxide ion, OH-, in water
acids

HCl (g) + H2O → H3O+ + Cl-

H2O
HNO3 H+ + NO3-

H2O
H2SO4 2 H+ + SO42-
 bases

H2O
NaOH Na+ + OH-
H2O
Ca(OH)2 Ca2+ + 2 OH-
• Arrhenius theory for acids and bases are
limited to:
➢ Compounds containing H and OH
respectively
➢ Only applicable to aqueous solutions
 THE BRONSTED-LOWRY THEORY

Proposed by Johannes Bronsted and Thomas

M.Lowry in 1923.

ACIDS BASES

Proton (H+) donor Proton (H+) acceptor

It states that any compound that can transfer a proton to any other
compound is an acid, and the compound that accepts the proton is a base.
• In connection with the Bronsted-Lowry
model, there are some terms that are used
frequently:-

I. Conjugate base

II. Conjugate acid

 CONJUGATE BASE CONJUGATE ACID

The species formed when a The species formed when a

proton is removed from an proton is added to a base
acid
An acid become its conjugate Accepts a proton
base when it donates proton

Conjugate acid-base pairs are chemical species

whose formulae differ only by one proton, H +
• Example of Bronsted-Lowry acid in water
solvent
• Hence, water acts as Bronsted-Lowry base

Conjugate
Acid
base

HA + H2 O  H3O+ + A-

Conjugate
Base
acid
• Example of Bronsted-Lowry base such as ammonia
accepts a proton from the solvent (water), acts as
Bronsted Lowry acid

Conjugate
Base
acid

NH3 + H2O  OH- + NH4+

Conjugate
Acid
base
The Conjugate Pairs in Some Acid-Base Reactions
Conjugate Pair

Acid + Base Base + Acid

Conjugate Pair

Reaction 1 HF + H 2O F- + H 3 O+

Reaction 2 HCOOH + CN- HCOO- + HCN

Reaction 3 NH4+ + CO32- NH3 + HCO3-

Reaction 4 H2PO4- + OH- HPO42- + H 2O

Reaction 5 H2SO4 + N2H5+ HSO4- + N2H62

+

Reaction 6 HPO42- + SO32- PO43- + HSO3-

 Exercise 1

Identify acid-conjugate base pairs in the reaction:

H3O+ (aq) + Cl- (aq) → HCl (g) + H2O(l)

Acid Base Conjugate Conjugate
acid base
Exercise 2

• Write a reaction that shows that HCO3- is a Brønsted

acid when reacted with OH-

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

• Write a reaction that shows that HCO3- is a Brønsted

base when reacted with H3O+(aq)

HCO3-(aq) + H3O+(aq) ↔ H2CO3(aq) + H2O(l)

 LEWIS THEORY

• A wider definition of acids and bases was stated by

G.N.Lewis in 1938

• Highlights the role of the electron pair

ACIDS BASES

Acids are defined as Bases are defined as

electron pair acceptors electron pair donors
 Example of Lewis acid-base:
ionization of ammonia

electron transfer

Lewis base Lewis acid Ion NH4+

Exercise 3

Identify the Lewis acids and Lewis bases in the following

reactions:
donor
(a)H+ + OH- H2O H+ - acid; OH- - base
acceptor
donor
(b) Cl- + BCl3 BCl4- BCl3 - acid; Cl- - base
acceptor

donor
(c) K+ + 6H2O K(H2O)6+ K+ - acid; 6H2O - base
acceptor
• Monoprotic acids:
➢ Each acid produces only a single proton
per molecule of the acid on dissociation.
➢ Also known as monobasic acid because they
form only one conjugate base each.

Monoprotic acid Conjugate base

HF F-
HCl Cl-
CH3COOH CH3COO-

25
• Polyprotic acids:

➢ An acid which can produce more than

one proton on dissociation.

Diprotic acid Conjugate base

H2SO4 HSO4- and SO42-
H2CO3 HCO3- and CO32- -

H2C2O4 HC2O4- and C2O42-

26
STRENGTH OF ACID AND BASE

The strength of an acid or base

depends on the degree of
dissociation of the acid or base in
water
 STRONG ACID WEAK ACID

dissociates completely dissociates partially

produce high conc. of H+ produce low conc. of H+

ions ions

Example:
Example:
HCl, HBr, HI, HNO3,
HF, H3PO4, CH3COOH
H2SO4, HClO4
 Complete dissociation of strong acid

Strong acid: HA(g or l) + H2O(l) H3O+(aq) + A-(aq)

 Incomplete dissociation of weak acid

Weak acid: HA(aq) + H2O(l) H3O+(aq) + A-(aq)

• The strength of an acids depends on its
ability to donate protons
➢ The stronger of the acid, the greater its
tendency to donate a proton to the base
➢ The stronger the acid, the weaker its
conjugate base
➢ The weaker the acid, the stronger its
conjugate base

31
32
 STRONG BASE WEAK BASE

dissociates completely dissociates partially

produce high conc. of OH-

produce low conc. of OH- ions
ions

Example:
NaOH, KOH, Ca(OH)2,
Sr(OH)2, Ba(OH)2 Example:
NH3, CH3NH2, C2H5NH2
(hydroxides of the Group I
and Group II metals)
• Strong bases dissociate completely to form
OH- ions in aqueous solutions.
H2O
NaOH (s) Na+ (aq) + OH- (aq)

H2O
KOH (s) K+ (aq) + OH- (aq)

• Weak bases do not dissociate completely to

form OH- ions in aqueous solutions.

F- (aq) + H2O (l) OH- (aq) + HF (aq)

NO2- (aq) + H2O (l) OH- (aq) + HNO2 (aq)

CONCENTRATED/DILUTED ACID & BASE

• Amount of solute you have dissolved in the

solution
• Examples: concentrated H2SO4 5 M
diluted H2SO4 0.5 M
• It depends on value of Molarity of the solution

moles of solute
Molarity (M) =
liters of solution
PREPARATION OF STANDARD
SOLUTION AND DILUTION
PROCESS
 STANDARD SOLUTION

• A standard solution is a solution whose

concentration is accurately known.

• This done by weighing out a sample of

solute, transferring it completely to a
volumetric flask, and adding enough solvent
to bring the volume up to the mark on the
neck of the flask.
Process of Making a Standard Solution from Solids
Using a standard flask to prepare a solution with a specified
concentration
Process of Making a Standard Solution from Liquids
n = number of moles M = Molarity
m = mass n = number of moles
MM = molar mass V = volume
m n
n= M=
MM V
m n
MM = V =
n M
m = n  MM n= MV
Exercise 4
What mass of K2CrO4 is needed to prepare exactly 0.2500 L
of a 0.250 M K2CrO4 solution in water?
Solution:

n K2CrO4 = 0.2500 L x 0.250 M = 0.0625 mol

m K2CrO4 = 0.0625 mol x molar mass K2CrO4

= 0.0625 mol x 194 g/mol

= 12.1 g
 DILUTION OF SOLUTION

• Dilution is the procedure for preparing a less

concentrated solution from a more concentrated
one.

Remains constant

M = moles of solute

Decreases volume (L)

Increases (water added)

Example:
We want to prepare 500 mL of 1.00 M acetic acid,
CH3COOH, from a 17.5 M stock solution of acetic acid. What
volume of the stock solution is required?

Because the moles of solute remain the same before and

after dilution, we can write

Mi  Vi = Mf  Vf
Volume after
dilution
Molarity before Volume before Molarity after
dilution dilution dilution
Exercise 5

What volume of 16 M sulfuric acid must be used to

prepare 1.5 L of a 0.10 M H2SO4 solution?
Solution:
Mi = 16 molL-1 Mf = 0.10 molL-1
Vi = ? Vf = 1.5 L

M f  Vf (0.10molL−1 )(1.5L )
Vi = Vi =
Mi 16molL−1
= 9.4  10-3 L
= 9.4 mL
 VOLUMETRIC ANALYSIS,
TITRATION CURVES & INDICATOR
CHOICE
 TITRANT & ANALYTE

• Principles of Volumetric Analysis is to

determine the volume of a reagent needed to
react with analyte.

• In a titration increments of a reagent solution

called the titrant are added to the analyte
until they have completely reacted. The titrant
usually added from a buret so we can
determine its exact volume.
In a titration, the titrant in the
buret is added to the solution in
the Enlenmeyer flask until the
indicator changes color to
show that the reaction is complete.
 Equivalence and End Point

• Two terms in determining when the reaction is

complete:
1. Equivalence point
This is the point at which you have added titrant
that is exactly equivalent to the analyte
two solutions exactly neutralize each other, where
equal amounts (in moles) of H+ and OH-.
2. End point
This is the point that you observe some change in
solution.
Alternative Method of Equivalence Point Detection

monitor pH
Ma and Va = molarity and volume of acid
Mb and Vb = molarity and volume of base
a and b = stoichiometric reaction coefficients

51
 TITRATION CURVE

• A graph of pH versus volume of titrant added (the

solution in the burette) is called titration curve

Equivalence
Titration pH change
point
Strong acid-strong base pH 7 3.5 - 9.5
Strong acid-weak base pH < 7 3.0 – 7.0
Weak acid-strong base pH > 7 6.5 – 10.5
Weak acid-weak base Not obvious Not obvious
STRONG ACID-STRONG BASE TITRATIONS

Example:

NaOH (aq) + HCl (aq) H2O (l) + NaCl (aq)

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

 The pH value for 0.1 mol dm -3 HCl is 1.0
The pH value for 0.1 mol dm-3 NaOH is 13
STRONG ACID-WEAK BASE TITRATIONS

Example:
HCl (aq) + NH3 (aq) NH4Cl (aq)

H+ (aq) + NH3 (aq) NH4Cl (aq)

At equivalence point (pH < 7):

NH4+ (aq) + H2O (l) NH3 (aq) + H+ (aq)

The pH value for 0.1 mol dm-3 HCl is 1.0
The pH value for 0.1 mol dm-3 NH3 is 9
WEAK ACID-STRONG BASE TITRATIONS

Example:

CH3COOH (aq) + NaOH (aq) CH3COONa (aq) + H2O (l)

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

At equivalence point (pH > 7):

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

The pH value for 0.1 mol dm-3 CH3COOH is 2.87
The pH value for 0.1 mol dm-3 NaOH is 12
58
 INDICATOR

 Indicators are dyes that can be added that will

change color in the presence of an acid or base
 Some indicators only work in a specific range
of pH
 Choice of Acid-Base Indicators

Type of Acid-Base
Suitable Indicators
Titration
Methyl orange,
Strong Acid-Strong Base
Phenolphthalein

Strong Acid-Weak Base Methyl orange

Weak Acid-Strong Base Phenolphthalein

→
Graphs A, B and C shown below represent 3 different titration curves.

pH pH pH

8.7
5.5 7.0

V Base V Acid V Base

Graph A Graph B Graph C

a) Choose the graph to represent the titration of the following pairs of

acid-base.
i) HCI + NaOH → NaCI + H2O Graph B
ii) HNO3 + NH4OH → NH4NO3 + H2O Graph A
iii) CH3COOH + KOH → CH3COOK + H2O Graph C
b) From the following list of indicators, choose the most suitable
indicator for
(i) titration B bromothymol blue

(i) titration C phenolphthalein

Indicator pH range

methyl orange red ( 3.2 – 4.4 ) yellow

phenolphthalein colourless ( 8.2 – 10.0 ) red

bromothymol blue yellow ( 6.0 – 7.6 ) blue

pH, pOH, Kw, pKw
Ka, Kb, pKa, pKb
 pH

• pH is a measure of the concentration of H+ or

H3O+ ions in a solution

pH = -log [H+] or pH = -log [H3O+]

• The unit is molarity, M (mol dm-3)

• The molarities of H3O+ ions are high for strong

acids (low pH), and low for weak acids (high
pH)
 pOH

• pOH is measure of the concentration of OH -

ions in a solution
pOH = -log [OH-]

• Unit of [OH-] is molarity, M (mol dm-3)

• The molarities of OH- ions are high for strong

bases and low for weak bases
pH scale
 Kw

• Water is an extremely weak electrolyte

• Water dissociates into ions very slightly in an

equilibrium process known as autoionization

• Autoionization of water is describe by:

• Because the concentration of H2O is constant,
therefore ion-product constant for water,
Kw

• The ionic product of water increases rapidly

with increasing temperature.
• Therefore:
pH + pOH = 14
Exercise 6

11.67 4.677x10-3

12.11 7.762x10-13
Exercise 7

3.09x10-12 11.51
4.37x10-10 4.64
6.61x10-13 12.18
3.89x10-9 5.59
Exercise 8

[H3O+] = 0.0063 M
pH = 2.20
pOH = 14 – pH
= 11.8
[OH-] = 1.58 x 10-12 M
Exercise 9

pOH = -log [OH-]

= 6.60
pH = 14 – pOH
= 7.4
In a neutral solution
[H+] = [OH-]

In an acidic solution
[H+] > [OH-]

In a basic solution
[H+] < [OH-]
Exercise 10

pH = -log [H3O+]
= 3.52
pOH = 14 – pH
= 10.48
[OH-] = 3.33 x 10-11M
The solution is acidic
Methods for measuring the pH of an aqueous solution

pH (indicator) pH
paper meter
pH VALUES OF STRONG ACIDS AND BASES

• Strong acids and strong bases dissociate

completely in water
• The concentration of H3O+ or OH- ions can be
obtained directly from their molarities
• pH can be calculated from the concentration of
H3O+ produced by the strong acid
• pOH can be calculated from the [OH-]
produced by strong base
Example:

What is the pH of 0.1M HCl

HCl(aq) → H+(aq) + Cl-(aq)

I 0.1 0 0
E 0 0.1 0.1

pH = -log(0.1) = 1
pH VALUES OF WEAK ACIDS AND BASES

• Weak acids and bases undergo partial

dissociation

• To calculate the [H+] or [OH-] ions, we need to

know the values of:

➢ Dissociation constant of a weak acid (Ka)

➢ Dissociation constant of a weak base (Kb)

➢ Degree of dissociation (α)

DEGREE AND PERCENTAGE
IONIZATION
DISSOCIATION CONSTANT OF A WEAK ACID (Ka)

• Chemical equation when a weak acid dissolves

in water:

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

• Equilibrium constant, Kc :

[H3O+][A-]
Kc =
[H2O][HA]

NOTE: concentration of water is virtually constant

 [H3O+][A-]
Kc [H2O] = Ka =
[HA]

Ka is dissociation constant of weak acid

• The values of Ka:

➢ Influenced only by the changes in
temperature. Usually stated at a 25 °C
➢ The stronger the acid, the greater the extent
of dissociation and larger the value of Ka
• The values of Ka are very small, it is more
convenient to use the values of pKa to
compare the strength of acids:
➢ The larger the value of pKa, the smaller the
value of Ka and the weaker the acid.

pKa = -log Ka
 RELATIONSHIP BETWEEN Ka AND pKa

Acid Name (Formula) Ka at 250C

Hydrogen sulfate ion (HSO4-) 1.02x10-2 1.991

7.1x10-4 3.15

acid strength
Nitrous acid (HNO2)
Acetic acid (CH3COOH) 1.8x10-5 4.74

Hypobromous acid (HBrO) 2.3x10-9 8.64

Phenol (C6H5OH) 1.0x10-10 10.00

DISSOCIATION CONSTANT OF A WEAK BASE (Kb)

• Examples of a weak base: Ammonia

NH3 (aq) + H2O (l) NH4+ (aq) + OH- (aq)

[NH4+][OH-]
Kb =
[NH3]

Kb is dissociation constant of weak base

• The larger the value of Kb , the stronger is the

base.
Base Strength
• The strength of a base can also be measured
in terms of pKb.
➢ The smaller the value of pKb, the stronger
is the base.

pKb = -log Kb
 DEGREE OF DISSOCIATION ()

• It is the percentage of weak acid or weak base

molecules which dissociate in water

• It is affected by the concentration of the weak

acid and weak base

• As the concentration of the weak acid or base

decreases, the degree of dissociation increases
(Ostwald dilution law)
• For weak acid
Ka = cα2
α = √(Ka /c)

• For weak base

Kb = cα2
α = √(Kb /c)
Exercise:

Hydrogen cyanide (HCN) solution of 0.001M has acid dissociation constant of

7.9 x 10-10. The degree of dissociation of HCN will be ______________

92
 PERCENTAGE OF DISSOCIATION

• Percentage dissociation for hydrolysis weak acid:

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

[HA]dissociated
% dissociation = x 100%
[HA]initial
[HA]dissociated = [H3O+]
• Percentage dissociation for hydrolysis weak
basic:
NH3 (aq) + H2O (l) NH4+ (aq) + OH- (aq)

[NH3]dissociated
% dissociation = x 100%
[NH3]initial
[NH3]dissociated = [OH-]
Example:
What is the pH of a 0.5 M HF solution (at 250C)
and percentage of dissociation of HF?

Solution:
[H+][F-]
Ka = = 7.1 x 10-4
[HF]
HF (aq) H+ (aq) + F- (aq)

I 0.50 0.00 0.00

C -x +x +x
E 0.50 - x x x
 x2 Approximate:
Ka = = 7.1 x 10-4
0.50 - x
Ka << 1
Ka  x2 0.50 – x  0.50
= 7.1 x 10-4
0.50 x2 = 3.55 x 10-4
x = 0.019

[H+] = [F-] = 0.019 M

[HF] = 0.50 – x = 0.48 M
pH = -log [H+] = 1.72
 [HF]dissociated
% dissociation = x 100%
[HF]initial

[H+]
= x 100%
[HF]initial

= 0.019 M x 100%
0.50 M
= 3.8%
BUFFER SOLUTION
• A buffer solution is a solution of:
1. A weak acid or a weak base and
2. The salt of the weak acid or weak
base

BOTH MUST BE PRESENT!

 BUFFER CAPACITY

• Buffer capacity is the ability to resist pH

change

• The more concentrated the components of a

buffer, the greater the buffer capacity

• The pH of a buffer is distinct from its buffer

capacity
 TYPE OF BUFFER

1. Acidic buffer (keep the pH below 7)

➢ It consists of a weak acid and a salt of the

weak acid (the conjugate base of the weak

acid)
2. Basic buffer (keep the pH above 7)
➢ It consists of a weak base and a salt of the

weak base (the conjugate acid of the weak

base)
 BUFFER ACTION

Acidic buffer solutions of CH3COOH & CH3COONa

pH = 5
CH3COONa (aq) CH3COO- (aq) + Na+ (aq)

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

Add strong acid

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

Add strong base

OH- (aq) + H+ (aq) H2O (l)
 Buffer with equal
concentrations
Buffer after addition of of conjugate base and Buffer after addition of
H3O+ acid OH-

CH3COOH H+ + CH3COO- CH3COOH + OH- CH3COO- + H2O

 HCl H+ + Cl-
H+ + CH3COO- CH3COOH + Cl-
HENDERSON-HASSELBALCH EQUATION & pH
OF BUFFERS

• pH of acidic buffer:

pH = pKa + log [conjugate base]

[acid]

• pH of alkaline buffer:

pOH = pKb + log [conjugate acid]

[base]
Example:

Calculate the pH of the 0.30 M NH3/0.36 M NH4Cl buffer

system. What is the pH after the addition of 20.0 mL of 0.050
M NaOH to 80.0 mL of the buffer solution?
(pKa= 9.25)
Solution:

NH4+ (aq) H+ (aq) + NH3 (aq)

[NH3]
pH = pKa + log
[NH4+]

[0.30]
pH = 9.25 + log = 9.17
[0.36]
 NH4+(aq) + OH-(aq) H2O(l) + NH3(aq)

start (moles) 0.029 0.001 0.024

end (moles) 0.028 0.0 0.025

final volume = 80.0 mL + 20.0 mL = 100 mL

0.028 mol 0.025

[NH4 +] = = 0.28 M [NH3] = = 0.25 M
0.10 L 0.10

[0.25]
pH = 9.25 + log = 9.20
[0.28]
 [NH3]
pH = pKa + log
[NH4+]

Kb = 1.74 x 10-5 [1]

pH = 9.24 + log
pKb = 4.76 [10]
pKa = 14 – pKb
= 9.24 pH = 8.24
[1]
ii) pH = 8.10 pH = 9.24 + log
[2]
PROBLEM:

Consider 1.0 L of a solution which is 0.8 M HF and 0.2 M NaF (Ka for HF =
7.2 x 10-4).

1. Calculate the pH of this solution.

2. Calculate the pH after 0.10 mol of HCl has been added to the original
solution. Assume no volume change on addition of HCl.

3. Calculate the pH after 0.20 mol of NaOH has been added to the original
buffer solution. Assume no volume change on addition of NaOH.
1. [NaF] Ka = 7.2 x 10-4
pH = pKa + log
[HF] pKa = 3.14
[0.2]
pH = 3.14 + log
[0.8]
pH = 2.54

2. Addition of 0.10 mole of HCl will produce 0.10 mole of

HF and reduce the moles of F- by 0.10 mole

[HF] = 0.8 M + 0.1 M = 0.9 M

[F-] = 0.2 M - 0.1 M = 0.1 M
[0.1]
pH = 3.14+ log
[0.9]
pH = 2.19
3. Addition of 0.20 mole of NaOH will produce 0.20 mole
of NaF and reduce the moles of HF by 0.20 mole

[HF] = 0.8 M - 0.2 M = 0.6 M

[F-] = 0.2 M + 0.2 M = 0.4 M

[0.4]
pH = 3.14+ log
[0.6]
pH = 2.96