IONIC EQUILIBRIUM

ACID-BASE EQUILIBRIUM
SALT HYDROLYSIS
BUFFER SYSTEM
CONTENTS

Ionic equilibrium (monoprotic acid and monobase)

• Definition of acid and base by Arrhenius, Bronsted- Lowry and
Lewis.
• Types of acids and bases and conjugate pair
• pH, pOH, Kw and pKw
• Ka, Kb, pKa and pKb
• Degree and percentage ionisation
• Hydrolysis reaction. Hydrolysis constant. Derivation of Kb = Kw/Ka
▫ Acidic, basic and neutral salt solution
▫ Salt hydrolysis. Calculation of its pH values
• Buffer
▫ Definition
▫ Example of buffer action of weak acids and bases and their salts
▫ Simple calculation of pH of buffer solution
ACID- PROPERTIES
• Acids have sour taste.
• Acids change the colour of litmus blue to red.
• Acids react with electropositive metals to
liberate hydrogen gas.
• Acids react with carbonate or bicarbonate to
liberate carbon dioxide gas.
• Acids react with bases form salt and water only.
BASE-PROPERTIES
• Bases are slippery to the touch.
• Bases change colour of red litmus to blue.
• Bases react with ammonium salt to produce
ammonia gas.
• Bases react with acid to form salt and water only.
DEFINITION OF ACIDS AND BASES
THREE MAIN DEFINITIONS

• Arrhenius’s Definition
• Bronsted-Lowry’s Definition
• Lewis Definition
 Arrhenius Acid & Base
• Acids are substances that ionised in aqueous
solution to form hydrogen ions, thereby,
increasing the concentration of H+ (aq) ions

• Acid: produces H+ in aqueous solution

• Base: produces OH- in aqueous solution

HCl (aq) + H2O (l)  H3O+ (aq) + Cl- (aq)

Brønsted-Lowry Acids and Bases
• An acid is a chemical substance which donates proton to
another substance Acid: proton donor
• A base is a chemical substance which takes proton from
another substances. Base: proton acceptor

• The H+ consists of 1 proton and 0 electron

HCN(aq) + NH3(aq)  NH4+(aq) + CN-(aq)

acid base

• The H+ is transferred from HCN to NH3

• HCN is a proton donor therefore it is an acid
• NH3 is a proton acceptor therefore it is a base
Examples

1. CH3NH2 (aq) + H2O (l)  CH3NH3+ (aq) + OH- (aq)

2. CO32- (aq) + H2O (l) HCO3- (aq) + OH- (aq)
3. C2H5O- (aq) + H2O (l)  C2H5OH (aq) + OH- (aq)
4. NH3 (g) + HCl (g)  NH4Cl (s)
5. NH3 (l) + HCl (l)  NH4Cl (l)

In reaction 4 and 5 above, the ammonia molecule receives a

proton from hydrogen chloride molecule. Hence,
ammonia is a base (proton acceptor) while hydrogen
chloride is an acid (proton donor).
Conjugate Acid-Base Pair

Consider the reaction of ethanoic acid and water.

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

Acid Base Conjugate base conjugate acid
• The relationship of conjugate acid-base pair
can be represent by the equation

Acid 1 + Base 2 Conjugate + Conjugate

Base 1 Acid 2

HA + B A- + HB+

A conjugate base is produce when an acid

losses a proton.
• A conjugate acid is produce when a base
accepts a proton.
Arrhenius vs Brønsted-Lowry
• Arrhenius definition restricted to water as a
solvent
• However Brønsted-Lowry theory includes non-
aqueous solvents
• Brønsted-Lowry includes acid/base in the
absence of solvent
• Protons can be transferred in the gas phase:
HCl(g) + NH3(g)  NH4Cl(s)
 Lewis Acids & Bases
• A Lewis base donates a lone pair of electrons
• A Lewis acid accepts a lone pair of electrons

• Lewis acids/bases are a broader definition than the

Brønsted-Lowry definition

• H+ is an electron pair acceptor; a Lewis acid

Soluble metal oxides are strong bases
SUMMARY

ACID
• Arrhenius : produces H+ ion (aq)
• Bronsted-Lowry : H+ donor
• Lewis : e- pair acceptor

BASE
• Arrhenius : produces OH- ion (aq)
• Bronsted-Lowry : H+ acceptor
• Lewis : e- pair donor
Amphoteric / amphiprotic

• any compound that can act both as an acid and a

base
• ex) H2O, HSO4-, H2PO4-, HPO42-

• HCl + H2O H3O+ + Cl-…………………… Eq 1

(acid) (base)

• RNH2 + H2O RNH3+ + OH-…………………… Eq2

(acid) (base)
 Acid Strength
• The strength of an acid is defined by the equilibrium position
of its dissociation (ionization) reaction:
HA(aq) + H2O(l) H3O+(aq) + A-(aq)

Strong Acid:
• Acids that fully dissociate (100%) in water
• Its equilibrium position lies far to the right. (HNO3)
• Common strong acids are H2SO4, HCl, HNO3, HClO4

Weak Acid:
• Acids that dissociate only partially in water
• Its equilibrium lies far to the left. (CH3COOH)
• Common weak acids are H3PO4, HNO2, HOCl, organic acids (-
COOH).
Strong Acid (a) and a Weak Acid (b) in Water
 Ionization and Percent ionization
• Acid ionization (or acid dissociation) is the reaction of
an acid with water to produce hydronium ion (hydrogen
ion) and the conjugate base anion.
• The strength of acid and base is depends on the
percentage of ionization and degree of dissociation for
each substances in water
• Degree of dissociation, α

For acid [H ]
HA  H+ + A- 
[HA]
For base 
XOH  OH- + X+ [OH ]

[XOH]
• Percent ionization is used to specify the amount of weak
acid that has dissociated in achieving equilibrium in an
aqueous solution. The percent dissociation is defined as
follows:
amount dissociated ( M )
% dissociation   100%
initial concentration( M )

• Percent of Ionization
For acid
HA  H+ + A- [H  ]
% ionisation  100%
[HA]
For base
XOH  OH- + X+ [OH ]
% ionisation  100%
[XOH]
Acid-Ionization Equilibria
• For a weak acid, the equilibrium concentrations of ions
in solution are determined by the acid-ionization
constant (also called the acid-dissociation constant) -
Ka

Consider the generic monoprotic acid, HA.

 
HA (aq )  H 2O( l ) H 3O (aq )  A (aq )
 
[ H 3O ][ A ]
Kc 
[ HA ][H 2O]
acid-ionization constant, Ka
Since the concentration of water remains
relatively constant, we rearrange the equation
to get:
 
[H 3O ][A ]
K a  [H 2O]K c 
[HA]

 
[H 3O ][A ]
Ka 
[HA]
base-ionization constant, Kb
B + H2O <--> BH+ + OH-

BOH <--> B+ + OH-


[OH ][B ]
Kb 
[BOH]
Ka and Kb
• Ka and Kb is inversely related
• Ka x Kb = Kw = 10-14
• pKa + pKb = pKw = 14
 Water as an Acid and a Base
• A substance is said to be amphoteric if it can behave either as
an acid or as a base. Water is amphoteric (it can behave either
as an acid or a base).
H2O + H2O  H3O+ + OH
acid 1 base 2 conj acid 2 conj base 1
Writing the equilibrium constant :
[H 3O  ][OH- ]
K
[H 2 O]
K[H 2 O]  [H 3O  ][OH- ]
K[H 2 O]  K w
K w  [H 3O  ][OH- ]  [H  ][OH- ]  110 14 at 25o C
Where, Kw is the ion-product constant or dissociation constant
for water.
[H+] = [OH-] = 1.0 x 10-7 M at 25oC in pure water.
The pH Scale
• The pH scale provides a convenient way to
represent solution acidity. The pH is a log scale
based on 10.
pH  log[H+]
• pH in water ranges from 0 to 14. The pH
decreases as [H+] increases.
Kw = 1.00  1014 = [H+] [OH]
pKw = -log Kw = 14.00 = pH + pOH

As pH rises, pOH falls (sum = 14.00).

• pOH = -log [OH-]
Salt Hydrolysis
• Hydrolysis is the reaction of a dissociated salt with water
to form an acidic or a basic solution.

Hydrolysis: The Process

• A salt in solution dissociates into positive and negative
ions.

• If the ion’s parent acid or base is weak, that ion will tend to
hydrolyze with water, combining with H+ or OH- from
water molecules, leaving the unreacted H+ or OH- as
excess.
Hydrolysis: The Process
• Reaction of anions of a weak acid combine with H+:
A- + H2O →HA + OH-
• Solution is basic – excess OH-

• Reaction of cations of a weak base combine with OH-:

B+ + H2O → BOH + H+
• Solution is acidic – excess H+
Hydrolysis constant, Kh
• The equilibrium constant, Kh, for
hydrolysis is just a Ka or Kb, depending
on the type of hydrolysis.

NH4+ + H2O  NH3 + H3O+

Kh = Ka of NH4+ = Kw/Kb of NH3

F- + H2O  HF + OH-
Kh = Kb of F- = Kw/Ka of HF
 Hydrolysis: The Process cont’d
• Strong acid and base parents tend to dissociate
completely and thus do not tie up H+ or OH-.
• Depending on the combination of parents, the resulting
solution will be acidic, basic or neutral.

Example of Hydrolysis
NH4Cl (aq)  NH 4+ (aq) + Cl- (aq)
• The parent acid is HCl, a strong acid (does not hydrolyze).
• The parent base is NH3, a weak base (hydrolyzes):

NH 4+ (aq) + H2O (l)  NH3 (aq) + H3O+(aq)

• The H3O+ concentration is increased, so the solution is
acidic.
Salts of
Strong Acids and Strong Bases
• Produce a neutral solution (pH=7)

Example: NaCl + H2O

• HCl NaOH
Strong Acid Strong Base
• Neither parent hydrolyzes so the result is a neutral solution.
Solutions of Salts of Strong Acids and Weak Bases
• Produce an acidic solution (pH<7)
Example: ZnCl2 + H2O
• HCl Zn(OH)2
Strong Acid Weak Base
• The weak base hydrolyzes resulting in a acidic
solution.

Solutions of Salts of Weak Acids and Strong Bases

• Produce a basic solution (pH>7)
Example:
K2C O3 + H2O
• Parents:
H2C O3 KOH
Weak Acid Strong Base
Result: Basic Solution
Solutions of Salts of Weak Acids and Weak Bases

• The pH of their salt’s solution depends on their

relative strength.
Summary

Parents
Strong Acid + Strong Base  Neutral
Solution
Strong Acid + Weak Base Acidic
Solution
Weak Acid + Strong Base Basic
Solution
Guidelines for determining acidity
of a salt solution
• Salts from a strong acid and strong base: pH = 7
• Salts from a strong base and weak acid: pH > 7
• Salts from a weak base and strong acid: pH < 7
• Salts from a weak base and weak acid: pH
depends on the Ka and Kb of the acid and base
 41

Example 1
 42

• Example 2: finding Kb from pH

QUESTIONS
• The acid ionization constant, Ka for benzoic acid
(C6H5COOH) is 6.6 x 10-5 at 25 °C. The ion
product of water, Kw at 25 °C is 1.0 x 10-14.
Calculate at 25°C the pH of 0.5 M benzoic acid.
 BUFFER
WHAT IS A BUFFER SOLUTION?
A buffer solution is solution that can resist drastic
changes in pH upon the addition of small amount of
strong acid or strong base.

 Sometimes it is important in chemical and biological

systems that pH remains nearly constant

This can be achieved by using BUFFERS –

solutions that resist drastic changes in pH
 Two types of buffer solutions:

Acidic buffer
A mixture of a weak acid + soluble ionic salt of the weak
acid.
Example: A mixture of CH3CO2H/NaCH3CO2

Basic buffer
A mixture of a weak base + soluble ionic salt of the weak
base
Example: NH3/NH4Cl
Which of the following are buffer systems? (a) KF/HF
(b) KCl/HCl, (c) Na2CO3/H2 CO3

(a) KF is a weak acid and HF is its salt that contain

conjugate base F- -buffer solution

(b) HCl is a strong acid -not a buffer solution

(c) H2CO32- is a weak acid and Na2CO3- is its salt that contains
conjugate base CO32- -buffer solution

16.3
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!

A buffer solution has the ability to resist changes in pH

upon the addition of small amounts of either acid or base.

Consider an equal molar mixture of CH3COOH and CH3COONa

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

Adding more acid creates a shift left IF

enough acetate ions are present
 48

Common ion effect

A common ion is an ion that is the same as an ion
that is present in a chemical system at
equilibrium.

For Example:
CH3CO2H(aq) + H2O(l) == H3O+(aq) + CH3CO2-
(aq)

A common ion is the acetate ion, (CH3CO2-),

which maybe obtained from NaCH3CO2.
The common ion effect is the shift in equilibrium caused by
the addition of a compound having an ion in common with the
dissolved substance.

Consider mixture of CH3COONa (strong electrolyte) and

CH3COOH (weak acid).

CH3COONa (s) Na+ (aq) + CH3COO- (aq)

common
CH3COOH (aq) H+ (aq) + CH3COO- (aq) ion
pH of a buffer solution
• Use the Henderson-Hasselbach
equation

pH = pKa + log [conjugate base]

[acid]

[salt]
pH = pKa + log
[acid]
 OR…… Use the Henderson-Hasselbach equation
Consider mixture of salt NaA and weak acid HA.
NaA (s) Na+ (aq) + A- (aq) [H+][A-] pK = -log K
Ka = a a
HA (aq) H+ (aq) + A- (aq) [HA]

Ka [HA]
[H+] =
[A-] Henderson-Hasselbach
[HA] equation
-log [H+] = -log Ka - log -
[A ] [conjugate base]
pH = pKa + log
[A-] [acid]
-log [H+] = -log Ka + log
[HA]
[A-]
pH = pKa + log
[HA]
 What is the pH of a solution containing 0.30 M HCOOH
and 0.52 M HCOOK?

Mixture of weak acid and conjugate base!

HCOOH (aq) H+ (aq) + HCOO- (aq)

Initial (M) 0.30 0.00 0.52
Change (M) -x +x +x
Equilibrium (M) 0.30 - x x 0.52 + x
[HCOO-]
Common ion effect pH = pKa + log
[HCOOH]
0.30 – x  0.30
[0.52]
0.52 + x  0.52 pH = 3.77 + log = 4.01
[0.30]
HCOOH pKa = 3.77
 HCl H+ + Cl-

HCl + CH3COO- CH3COOH + Cl-

16.3
 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?
NH4+ (aq) H+ (aq) + NH3 (aq)

[NH3] [0.30]
pH = pKa + log pKa = 9.25 pH = 9.25 + log = 9.17
[NH4 ]
+ [0.36]
final volume = 80.0 mL + 20.0 mL = 100 mL

start (M) 0.29 0.01 0.24

NH4+ (aq) + OH- (aq) H2O (l) + NH3 (aq)
end (M) 0.28 0.0 0.25

[0.25]
pH = 9.25 + log = 9.20
[0.28]
 Exactly 100 mL of 0.10 M HNO2 are titrated with 100 mL of a 0.10 M NaOH
solution. What is the pH at the equivalence point ?
start (moles) 0.01 0.01
HNO2 (aq) + OH- (aq) NO2- (aq) + H2O (l)
end (moles) 0.0 0.0 0.01
0.01
Final volume = 200 mL = 0.05 M
[NO2-] = 0.200
NO2- (aq) + H2O (l) OH- (aq) + HNO2 (aq)

Initial (M) 0.05 0.00 0.00

Change (M) -x +x +x

Equilibrium (M) 0.05 - x x x

[OH-][HNO2] x2
Kb = = = 2.2 x 10-11 pOH = 5.98
[NO2-] 0.05-x

0.05 – x  0.05 x  1.05 x 10-6 = [OH-] pH = 14 – pOH = 8.02