Example:

Assume that 20 mL sample (Na2CO3) consume 12 mL 0.1 N HCl.

1- How much (amount) of Na2CO3 is present in 20 mL sample.
2- Calculate the concentration of Na2CO3 sample in g/mL & g/L.
Knowing that: 1ml 0.1 N HCl = 0.0053 g Na2CO3

-The amount of Na2CO3 in 20 mL sample can be calculated by multiplying 12

x 0.0053 = 0.0636 g

- The Na2CO3 concentration in 20 mL sample can be calculated by dividing

0.0636 by 20 we obtain amount of Na2CO3 per one mL sample =
concentration g/mL 0.00318 g/mL sample Na2CO3

- Multiplying 0.00318 x 1000, we can find out the concentration of the

sample in g/L = 3.18 gm/L.
I-Volumetric (Titrimetric)
Methods of Analysis

I-1- Acid-Base Titrations

 ACID- BASE THEORIES
1-Electrolytic dissociation theory (Arrhenius theory)

 When an electrolyte dissolves in water, it will dissociate to a certain

extent to give cations and anions.
 The acid is the electrolyte dissociates to give (H+), while, the base is
the electrolyte dissociates to give OH-.
Acid : Is the substance which ionize to give H+ Base : Is the substance which ionize to give OH-
eg. HCl eg NaOH

+
H OH-
Cl Cl- + Na Na+ +

 acid-base reaction (neutralization reaction), is a combination between

hydrogen ions and hydroxyl ions to form water. (H+ + OH- = H2O).
Points of weakness in electrolytic dissociation
theory

1. HCl gas has no acidic properties on dry litmus

paper.
2. Ammonia and amines, which are known bases,
although they contain no hydroxyl groups.
3. The basic character of solution of sodium metal
(Nao) in ethanol is due to the formation of
sodium ethoxide.
4. H+ is very small in size, its electric charge is
very intense, therefore, it can’t exist
independently in solution
 2. Bronsted-Lowry Theory
 An acid is any substance that produces proton(s), while a base accepts
proton(s).
 Acid proton + conjugate base
 Base + proton conjugate acid

H +
H
H + O O +
Cl Cl-
H H H

Acid base Conjugate acid

HCl H2O H3O+ Cl- Conjugate base
 +
_ H

N H N
+ H
H
H O
H H O
H H H

NH3 H2O OH- NH4+

base acid Conjugate base Conjugate acid

Acid Base conj-Acid conj-Base

HCl + H2 O H 3 O+ + Cl-
H2O + NH3 NH4+ + OH-

The stronger the acid the weaker its conjugate base and vice versa
 3. Lewis Theory:
Acid : Is substance which accept lone pair of electrons eg. BF3, AlCl3

Base : Is substance which donate lone pair of electrons eg NH3, amines

 Compounds containing no OH- and yet reacts alkaline, e.g., ammonia:

 Compounds containing no H-atoms, yet they react as acids, e.g., boron

trichloride with triethylamine

B N
+ adduct
Cl Cl
Cl H H H

Lewis acid Lewis base

 Acid-base titration in aqueous medium
Cation Anion +
Electrolytes
+ve -ve
Dissociate and Dissociate
Solution conduct electricity

Non electrolytes
Doesn't ionize and doesn't conduct electricity

no. of molecules dissociated

α (degree of dissociation) =
total no. of molecules before dissociation

When α is near unity strong electrolyte

If α is far from unity weak electrolyte

1) HCl H+ + Cl- α = 0.92

2) CH3COOH H+ + CH3COO- α = 0.013

3) NaOH Na+ + OH- α = 0.91

4) NH4OH NH4+ + OH- α = 0.013

5) H2O H+ + OH- α = 10-14

 The velocity of a chemical reaction is
proportional to the product of the active
masses of the reacting substances
(f)
A+B C+D
(b)
At equilibrium
K "equilibrium constant“ = [C] [D] / [A] [B]
1) Weak acid
HAc H+ + Ac-
Applying the law of mass action

[H+] [Ac-]
Ka =
[HAc]

"K" is the ionization constant or dissociation constant of the acid, usually

written Ka.

h h h
i i i
g g ionization g acidity
Ka
h h h
For polybasic acid
H2A H+ + HA-
HA- H+ + A2-

K1 = [H+] [HA-]/[H2A]
K2 = [H+] [A2-]/[HA-]

K1 and K2 are the primary and secondary dissociation

constants, respectively. (always K1 > K2)
 2) Weak base
NH4OH NH4+ + OH-
Applying the law of mass action

[NH4+] [OH-]
Kb =
[NH4OH]

"K" is the ionization constant or dissociation constant of the base, usually

written Kb.

h h h
i i i
g g ionization g alkalinity
Kb
h h h
 Acid -base equilibrium in water

H2O H+ + OH-

[H+] [OH-]
Dissociation constant Kw =
[H2O]

Kw (ionic product of water) = [H+] [OH-] = 10 -14

At 25oc [H+] =[OH-] = 10-7 so neutral

Solution

[H+] > 10-7 [H+] = [OH-] [H+] < 10-7

acidic Neutral alkaline
pH = -log [H+] [H+] = 10-7 pH = - log 10-7 = 7

while pOH= - log [OH-]

As Kw = [H+] [OH-] = 10-14

- log Kw = - log [H+] - log [OH-] = - log10-14

pKw = pH + pOH = 14

pH less than 7 neutral solution pH more than 7

pH = p OH = 7
acidic side basic side

Lemon is acidic, while milk is alkaline

1-pH of strong acid • pH = pCa

• p OH = p Cb pH = p Kw – p OH
2- pH of strong bases
• i.e. pH = p Kw – p Cb

3- pH of weak • pH = 1/2 pCa + 1/2 pKa

acids

4- pH of weak
bases pH =pKw - 1/2 pCb - 1/2 pKb
 a- Salt of strong
acid and strong • Always neutral i.e. pH = 7
base eg. NaCl Study
laws
b- Salt of strong
hard it will
acid and weak • pH = 1/2 pKw - 1/2 pKb + 1/2pCs be in the
base eg.NH4Cl exam
c- Salt of weak
acid and strong • pH = 1/2 pKw + 1/2 pKa - 1/2pCs
base eg.
CH3COONa

D- Salt of weak
acid and weak base • pH= 1/2 pKw + ½pKa- ½pKb
eg. CH3COONH4
Calculate the pH of the following:

1) 0.1 M NH4OH solution Kb= 10-4.74

2) 0.1 M NH4Cl solution pKb= 4.74

3) 0.1 N CH3COOH solution pKa= 4.76

1) Weak base:
pH = pKw - 1/2 pCb - 1/2 pKb

as Kb= so pKb = 4.74

= 14 – 1/2 (0.1) – ½ (4.76)

2) Salt of weak base and strong acid:

pH = 1/2 pKw - 1/2 pKb + 1/2pCs
= ½ (14) – ½ (4.74) + ½ (0.1)

3) Weak acid:
pH = 1/2 pCa + 1/2 pKa
=1/2 (0.1) + ½ 4.74
 They are solution which resist changes in pH upon
addition of small amount of acid or base.
 They consist of weak acid and its salt e.g.:
CH3COOH/CH3COONa or weak base and its salt e.g:
ammonium hydroxide-ammonium chloride

The pH doesn’t change upon

 Addition of strong acid
H+ + Ac- HAc (weak acid)

 Addition of strong base

OH- + HAc H2O + Ac-(salt)
 • weak acid and its salt eg. HAc and CH3COONa
• pH = pKa + log salt / acid
Type 1

• weak base and its salt eg. NH4OH and NH4Cl

• pH = pKw - pKb - log salt/base
Type 2

• [Salt]/[Acid] is known as buffer ratio

• When [Salt] = [Acid], so, pH=pka.
• Buffers of different pH values are prepared by varying the buffer ratio.
However, this ratio should be10/1 or 1/10, i.e., pH = pKa + 1
1- Calculate the pH of a buffer solution containing 0.1 M
acetic acid and 0.1 M sodium acetate pKa =4.76

pH = pKa + log salt / acid

It is
so
pH = 4.76 + log 0.1 / 0.1 = 4.76 simple
 It is the magnitude of the resistance of a buffer to
change in the pH.

OR, it is the ratio of strong acid or base added, to

the small changes in the pH brought about:

Buffer capacity   =  B/pH

 The higher the buffer capacity, the more efficient is the
buffer.

High buffer capacity occurs when:

1. the concentration of the two components is high
2. the two components are present in equal concentration.
Calculate the pH of a solution of 50 mM HCl

1-What is the pH of 0.1 M sulfuric acid?

a: 1 b: -1 c:0 d: 0.7 e: -0.7

2-What is the pH of 0.01 N acid solution whose ionization constant is 1.7 x 10-5 ?
a: 1.4 b: 1.7 c: 2.0 d: 3.6

What is the pH of a solution by mixing 50 ml of 0.4M HCl and 50 ml 0.2 M NaOH?

Remember that:
Molar concentration = No. of moles / volume in L
No. of moles = weight / molecular weight