Chemistry (PhB-1202)

lecture-1 level-1
Quantitative Analysis
12/2/2023
Dr. Mohamed A. Ali
[email protected]
Office : 237 Biotechnology
Office Hours: Wednesday 9 : 2
 Analytical Chemistry

I. Qualitative Analysis II. Quantitative Analysis

What? How much?

- Detection
- Amount
- Identification
- Concentration
- Impurities
Types of Quantitative Analysis

a) Volumetric analysis Titration 0

Measuring volume of standard
solution (titrant) used for
complete reaction with the 8
sample.

b) Gravimetric analysis
Isolating and weighing of
the final product with
known pure, stable and
definite form.
Volumetric analysis Titration
Reaction between standard solution (titrant) and sample
► Types of reactions used in volumetric analysis
I- Ionic combination reactions
Formation of weakly ionizable products
A- Neutralization reaction: Formation of water
H+ + OH- → H2O
B- Precipitation reaction: Formation of precipitate
Ag+ + Cl- → AgCl
C- Complexation reaction: Formation of complex
Ag+ + 2 CN- → [Ag(CN)2]-

II- Electron transfer reactions Redox Titration

Electron transfer from one reactant to another
Volumetric analysis Titration
Reaction between standard solution (titrant) and sample
► Types of reactions used in volumetric analysis
► Requirements for volumetric reactions
1 Simple reaction
2 Single reaction
3 Instantaneous reaction (Rapid)
4 Suitable standard must be available as titrant.
5 The end point of the reaction should be easily detected
• Suitable indicator which changes the solution
color at the end point.
•Change in physical or chemical properties of
the solution at the end point.
Volumetric analysis Titration
Reaction between standard solution (titrant) and sample
Standard solutions
Solutions of exactly known concentration
Expressions of standard concentration
1- Molar standard solution
1 liter of it contains 1 mole (Molecular weight) of the substance
Eg. HCl (Mwt = 36.5 g)
1M HCl = 36.5 g/L 2M HCl = 2x36.5 g/L 0.5M HCl = 36.5/2 g/L

Eg. H2SO4 (Mwt = 98)

1M H2SO4 = 98 g/L 0.5M H2SO4= 98/2 g/L 0.1M H2SO4 = 98/10 g/L
Volumetric analysis Titration
Reaction between standard solution (titrant) and sample
Standard solutions
Solutions of exactly known concentration
Expressions of standard concentration
1 Molar standard solution
1 liter of it contains 1 mole (Molecular weight) of the substance
2 Normal standard solution
1 liter of it contains 1 equivalent weight of the substance
Equivalent weight = Molecular weight /n
For Acids; Eq.wt = M.wt / number of replaceable H+
For Bases;Eq.wt = M.wt / number of replaceable OH-
For Salts; Eq.wt = M.wt / number of cations x its valence
Eq.wt = M.wt / number of anions x its valence
Volumetric analysis Titration
Reaction between standard solution (titrant) and sample
Standard solutions
Solutions of exactly known concentration
Expressions of standard concentration
1 Molar standard solution
1 liter of it contains 1 mole (Molecular weight) of the substance
2 Normal standard solution
1 liter of it contains 1 equivalent weight of the substance
Equivalent weight = Molecular weight /n
Eq.wt of HCl = M.wt./1 Eq.wt of NaOH = M.wt./1
Eq.wt of H2SO4 = M.wt./2 Eq.wt of Ba(OH)3 = M.wt./3

Eq.wt of Na2CO3 = M.wt./2x1 = M.wt./1x2

Volumetric analysis Titration
Reaction between standard solution (titrant) and sample
Standard solutions
Solutions of exactly known concentration
Expressions of standard concentration
1 Molar standard solution
1 liter of it contains 1 mole (Molecular weight) of the substance
2 Normal standard solution
1 liter of it contains 1 equivalent weight of the substance
How to prepare 0.1M H2SO4 and 0.1N H2SO4?
0.1M H2SO4 = M.wt/10 g/L 98 g/L
10
0.1N H2SO4 = Eq.wt/10 g/L Eq.wt = 98/2 98 g/L
2x10
Volumetric analysis Titration
Reaction between standard solution (titrant) and sample
Standard solutions
Solutions of exactly known concentration
Expressions of standard concentration
1 Molar standard solution
1 liter of it contains 1 mole (Molecular weight) of the substance
2 Normal standard solution
1 liter of it contains 1 equivalent weight of the substance
Standard solutions having the same normality
react by equal volumes
Eg. 10 mL of 1N NaOH neutralized with 10 mL of 1N HCl
Eg. 10 mL of 1N NaOH neutralized with 10 mL of 1N H2SO4
Volumetric analysis Titration
Reaction between standard solution (titrant) and sample
Standard solutions
Solutions of exactly known concentration
Expressions of standard concentration
1 Molar standard solution
1 liter of it contains 1 mole (Molecular weight) of the substance
2 Normal standard solution
1 liter of it contains 1 equivalent weight of the substance
3 Empirical standard solution
1 mL of it reacts with a definite quantity of the sample
No relation between different empirical solutions
Volumetric analysis Titration
Reaction between standard solution (titrant) and sample
Standard solutions
Solutions of exactly known concentration
Preparation of standard solutions
1 Direct method For Primary Standard substances
Characteristics of primary standard:-
1 Pure
2 Easily tested for impurities.
3Stable(not absorb H2O or CO2 from air or volatile)
4- React stoichiometrically (quantitatively)
5 Readily soluble.
6 Have high molecular weight to minimize weighing error.
Volumetric analysis Titration
Reaction between standard solution (titrant) and sample
Standard solutions
Solutions of exactly known concentration
Preparation of standard solutions
1- Direct method For Primary Standard substances
Examples of primary standards
► Potassium acid phthalate KHC8H4O4 ►Benzoic acid
► Constant boiling point HCl ► Anhydrous Na2CO3
► Potassium bicarbonate KHCO3 ► Mercuric Oxide HgO
Volumetric analysis Titration
Reaction between standard solution (titrant) and sample
Standard solutions
Solutions of exactly known concentration
Preparation of standard solutions
1 Direct method For Primary Standard substances
2 Indirect method When substance is Not primary standard
Any substance lose one property of primary standard is
considered as secondary standard.
Examples of secondary standards
► Sodium hydroxide NaOH ►Potassium permenganate KMnO4
Volumetric analysis Titration
Reaction between standard solution (titrant) and sample
Standard solutions
Solutions of exactly known concentration
Preparation of standard solutions
1 Direct method For Primary Standard substances
2 Indirect method When substance is Not primary standard
First, prepare solution of approximate concentration which
is then standardized against primary standard to calculate
the standardization factor (f).
Volumetric analysis Titration
Reaction between standard solution (titrant) and sample
Standard solutions
Solutions of exactly known concentration
Preparation of standard solutions
1 Direct method For Primary Standard substances
2 Indirect method When substance is Not primary standard
▪ Standardization factor (f)
Number which is multiplied by volume of approximate normality
(unknown) to obtain the volume of exact normality(Known)
f = volume of known normality (0.95 – 1.05)
volume of unkown normality
Volumetric analysis Titration
Reaction between standard solution (titrant) and sample
Standard solutions
Solutions of exactly known concentration
Preparation of standard solutions
1 Direct method For Primary Standard substances
2 Indirect method When substance is Not primary standard
▪ Standardization factor (f)
▪ Equivalent factor (F)
Number which represents how many grams of sample react with
1 ml of the primary standard (or corrected secondary standard)
Acid-Base Theories
1- Arrhenius Theory
Acid: Substances which ionize to give H+ Eg. HCl
Base: Substances which ionize to give OH Eg. NaOH
Acid-Base Theories
1- Arrhenius Theory
2- Bronsted-Lowry Theory
Acid: Substances which donate proton.
HCl + H2O → Cl- + H3O+
Acid Base Conjugate base Conjugate acid

Base: Substances which accept proton.

+
NH3 + H2O → NH4 + OH-
Base Acid Conjugate acid Conjugate base

Amphoteric electrolyte
H2O + H2O → H3O+ + OH-
Conjugate acid Conjugate base
Acid-Base Theories
1- Arrhenius Theory
2 Bronsted-Lowry Theory
Acid: Substances which donate proton.
Base: Substances which accept proton.
➢ Find which is the acid and which is the base in the following
conjugate acid-base pairs.
Acid Base
❖ NH3 ; NH + +
4 NH4 NH3
❖CH3COOH ; CH3COO- CH3COOH CH3COO-
❖HPO2-4 ; H2PO4- H2PO4
- 2-
HPO4
➢ What is the conjugate acid and conjugate base of HSO 4- ?
+H +
- -H+ 2-
H2SO4 HSO4 SO4
Conjugate acid Conjugate base
Acid-Base Theories
1- Arrhenius Theory
2 Bronsted-Lowry Theory
3 Lewis Theory
Acid: Substances which accept lone pair of electrons Eg. BF3, AlCl3
Base: Substances which donate lone pair of electrons Eg. NH3
H F H F
H N: + B F H N B F
H F H F
Lewis base Lewis acid
H H
H N: + H+ H N H+
H H
Lewis base Lewis acid
Acid-Base titration in aqueous medium
Electrolytic dissociation theory Molecule → Cation+ + Anion-
Electrolytes: Which dissociate (ionize) and conduct electricity.
Non electrolytes: Which doesn't ionize and doesn't conduct electricity.
Degree of dissociation (α)
α= Number of dissociated molecules
Total number of molecules before dissociation
➢ For strong electrolytes; α is near unity
HCl → H+ + Cl- α = 0.92 ≈ One
NaOH → Na+ + OH- α = 0.91 ≈ One
➢ For weak electrolytes; α is far from unity
Equilibrium CH3COOH H+ + CH3COO- α = 0.013
K = [Products] H3BO3 H+ + H2BO3- α = 0.001
[Reactants] + -
NH4OH NH4 + OH α = 0.013
Acid-Base titration in aqueous medium
Electrolytic dissociation theory
Acid -base equilibrium in water
Equilibrium always exists in solutions of weak electrolytes
“ weak acids & weak bases”
CH3COOH H + CH3COO
+ - NH 4OH NH + + OH-
4
Ka = [H+] [Ac-] / [HAc] Kb = [NH4+] [OH -] / [NH4OH]
Ka: dissociation constant of acid Kb: dissociation constant of base

Dissociation of water
H2O H+ + OH-
K = [H+] [OH-] / [H2O]
Kw = [H+] [OH-] = 10-14 at 25oc
Kw: ionic product of water
Acid-Base titration in aqueous medium
Dissociation of water Kw = [H+] [OH-] = 10-14 at 25oc
For any aqueous solution; Kw = [H+] [OH-] = 10-14

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

[H+] = 10-3 [H+] = 10-11
[OH-] = 10-11 [OH-] = 10-3
Acid-Base titration in aqueous medium
Dissociation of water Kw = [H+] [OH-] = 10-14 at 25oc
Hydrogen Ion Exponent pH
pH = -log [H+]
[H+] = 10-3
pH = -log [H+]
pH = -log 10-3
pH = -(-3) log 10
pH = 3
[H+] decreases → pH value increases
[H+] = 10-3 → pH = 3
[H+] = 10-5 → pH = 5
[H+] = 10-7 → pH = 7
[H+] = 10-9 → pH = 9
Acid-Base titration in aqueous medium
Dissociation of water Kw = [H+] [OH-] = 10-14 at 25oc
For any aqueous solution; pKw = pH + pOH = 14

[H+] = 10-3 pH = pOH =7 [H+] = 10-11

pH = 3 pH = 11
pOH = 11 pOH = 3
Acid-Base titration in aqueous medium
Buffer solutions
Solutions which resist changes in pH upon addition of small
amount of acid or base
They consist of weak acid and its salt (conjugate base)
or weak base and its salt (Conjugate acid)

Weak acid & its salt Weak base & its salt
CH3COOH CH3COO- Na+ NH4OH NH4+ Cl-
(conjugate base) (conjugate acid)
OH- H+ H+ OH-
+
CH3COO- CH3COOH NH4 NH4OH
+ H2O + H2O
 Acid-base titration in aqueous medium
Neutralization indicators
1- Color Indicators
2 Turbidity Indicators
3 Fluorescence Indicators
1- Color Indicators

Substances (Weak acids or bases) which change their color with change in pH

• Phenolphthalein (Ph.Ph.), Colorless-Pink(one color indicator)

• Methyl Orange (M.O.), Red-Yellow(Two color indicator)

28
 Acid-base titration in aqueous medium
Neutralization indicators
1- Color Indicators

2-Turbidity Indicators For colored solutions

• Indicators that form flocculent precipitate or turbidity at the end point.

3-Fluorescence Indicators For colored or turbid solutions

• Compounds emit visible radiation when exposed to UV light.

• This property may stop or intensify at end point.

• E.g. Umbelliferone

29
 Acid-base titration in aqueous medium
Neutralization indicators
Titration curves
1- Strong acid – strong base titration
2- Weak acid – strong base titration
3- Weak base – strong acid titration
4- Weak base – weak acid titration pH
12
11
10
9 PhenolPhthalein
8
7
6
5
4 Methyl Orange
3
2
1
0
Volume of Standard (mL)
30