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CHM 102

INTRODUCTORY CHEMISTRY II

COURSE LECTURERS: Azeez Luqmon A., PhD.,

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COURSE SYNOPSIS
 Chemical Bonding: Dependence of properties of solids,
liquids and gases on type of chemical bonding.
Electrovalent bond between ions. Covalent bonds. The
shape of simple molecules including CO2 (linear), CH4
(tetrahedral), NH3 (pyramidal), H2O (non-linear), SO2

(trigonal), SF8 (octahedral). Metallic bonds.

Intermolecular bonds. Hydrogen bonding and its


influence on properties.
Introduction to aromatic compounds, introduction to

macro-molecular compounds and natural products. 2
Course Objectives
With this course, students will

 Understand comprehensively chemical bonding and its types

 Understand different theories of predicting shapes

 Understand dependence of solid, liquid and gas properties as


functions of bonding
 Understand aromaticity, be able to draw benzene structures and
its derivatives
 Understand macromolecules, types and uses.

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Course Schedule

Week 1: chemical bonding – ionic, covalent, intermolecular, hydrogen.

Week 2: prediction of shapes of compounds using valence shell electron pair


repulsion and valence bond theory

Week 3: introduction to aromatic chemistry

Week 4: macromolecules, types and uses contd.

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CHEMICAL BONDING
IONIC BONDING: involves transfer of electrons from metal (forming positive ion) to non-metal
(forming negative ion). Example

1s22s22p63s1 1s22s22p63s23
1s22s22p6 1s22s22p63s23
p5
p6
Na looses an electron while Cl gains an electron to attain octet configuration. Other examples: MgCl2, Li2O

COVALENT BONDING: involves sharing of electrons. Other examples: O2, H2, N2

Chlorine molecule (Cl2 )


Coordinate Covalent Bonding: the shared pair of electrons is donated by only one of the bonded atoms

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Metallic bonding: is the electrostatic attraction between the delocalized electron cloud and metal ions.
It holds metal ion tightly and confers high melting point.
Factors affecting metallic bonding
 Size of the metal ion: it increases with decrease in size of metal ion
 Number of valence electrons: it increases with increase in number of valence electrons

Intermolecular forces: two types – van der Waal’s forces and hydrogen bonding. Both describe
electrostatic attraction between dipoles i.e. the attraction between the positive end of one molecule and
negative end of another molecule

Types of Dipoles:
Permanent dipole: it exits in all polar molecules due to difference in electronegativity
Instantaneous dipole: it occurs as a result of fluctuations in the electron cloud
Temporary
Induced dipole: is created due to influence of a neighbouring dipole

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Van der Waal’s: includes dipole-dipole, dipole-induced dipole and instantaneous dipole-induced dipole
interactions

Dipole – dipole interactions: it occurs when polar molecules orientate themselves in order to maximise
attractive forces between molecules while repulsive forces are minimized

Dipole - induced dipole: when a non-polar molecule approaches a polar molecule, a dipole will be induced
in the non-polar molecule

Instantaneous dipole - induced dipole: it occurs from fluctuations of electron cloud and can induce dipole
moment in neighbouring atoms. The greater the number of electrons in a molecule, the easier it is for
instantaneous dipole to be set up
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Hydrogen bonding: it exists when hydrogen is bonded to highly electronegative atom. It is the
strong dipole-dipole interaction between hydrogen and electronegative atom. It is weaker than
covalent bond but stronger than van der Waal’s forces. For hydrogen bonding to occur

A hydrogen atom must be bonded to directly to highly electronegative atom

An unshared pair of electron on the electronegative atom

SHAPES OF MOLECULES
Valence Shell Electron Pair Repulsion Model (VSEPR): uses electron pair of valence shells to predict
shapes

Number of Electron pair Shape Angle


2 Linear 180 oC
3 Trigonal planar 120 oC
4 Tetrahedral, square planar, trigonal pyramidal and angular 109.5 oC, 107.5 oC
5 Trigonal bipyramidal Axial 90 oC, Equi. 120 oC
6 Octahedral 90 oC 8
VSEPR Rules:
Identify the central atom
Count its valence electrons
Add one electron for each bonding atom
Add or subtract electrons for charge
Divide the total of these by 2 to find the total number of electron pairs
Use this number to predict the shape
Examples
NH3 –
Examples
N- central atom – 2,5
CH4 –
Valence electrons – 5
C- central atom – 2,4
Number of bonding atoms – 3
Valence electrons – 4
Total – 8
Number of bonding atoms – 4
Electron pair = 8/2 = 4 – tetrahedral. But
Total – 8
only three atoms are bonded, thus, it has a
Electron pair = 8/2 = 4 – tetrahedral. 9
lone pair of electron. The real shape is
H2O –
O PCl5 –
O- central atom – 2,6
H H P- central atom – 2,8,5
Valence electrons – 6
Valence electrons – 5
Number of bonding atoms – 2
o Number of bonding atoms – 5
Total – 8 1 0 4 .5 C
Total – 10
Electron pair = 8/2 = 4 – tetrahedral. But
Electron pair = 10/2 = 5 – trigonal bipyramidal.
only three atoms are bonded, thus, it has
2 lone pairs of electron. The real shape is
angular SF6 –
BCl3 – Cl

P- central atom – 2,3 S- central atom – 2,8,6


B
Valence electrons – 3 Valence electrons – 6
Cl
Cl
Number of bonding atoms – 3 Number of bonding atoms – 6

Total – 6 Total – 12

Electron pair = 6/2 = 3 – trigonal planar Electron pair = 12/2 = 6 – Octahedral 10


Valence Bond Theory: it uses hybridization theory to predict shapes
Hybridization – mixing of atomic orbitals into new hybrid orbitals

SP – linear
SP – trigonal planar
2

SP – Tetrahedral
3

SP d – trigonal bipyramidal
3

SP d – octahedral
3 2

Example – CO 2

Orbitals involved are S and P, thus, it is SP and linear

Other examples (CH4, NH3, H2O) would be done in the class to illustrate the prediction using valence bond theory
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Types of dienes
Isolated diene: H C 2 C
H
C
H2
C
H
CH2

Conjugated diene:H 2C C
H
C
H
C
H
CH3

Cumulative diene:H 2C C C
H
C
H2
CH3

Aromatic Chemistry
Rules of Aromaticity
 Must be cyclic
 Must be planar
 Must have delocalized double bonds
 Double bonds must be conjugated
 Must obey Huckel’s rule: 4n+2 = π electrons. n must be a whole number e.g. 1, 2, 3 etc
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Examples: benzene has 3 double bonds (6 π electrons)
4n+2 = 6, n = 1
Naphthalene has 5 double bonds (10 π electrons)
4n+2 = 10, n = 2

Benzene structure and Resonance

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Nomenclature of Benzene and its derivatives

Substituents at positions 1 and 2 –


ortho
Substituents at positions 1 and 3 –
meta
Substituents at positions 1 and 4 - para

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Introduction to macromolecular chemistry
Macromolecules are very large molecules important to living organisms. Most macromolecules are built
by joining smaller molecule subunits, often called “monomers

Macromolecules are used interchangeably with polymers

Proteins and Polypeptides


Proteins are polymers of amino acids bound by peptide bond

Enzymes: proteins with catalytic activities 15


Types of protein
Simple proteins – function of solubility in water
1. Albumins—soluble in water and in dilute neutral salt solutions
2. Globins—soluble in water (e.g., hemoglobins)
3. Globulins—insoluble in water, but soluble in dilute neutral salt solutions (e.g., g-globulins)
4. Prolamines—soluble in 70 % ethyl alcohol, insoluble in water
5. Histones— soluble in water and strongly basic solutions

Conjugated proteins are described by the non-protein groups:


1. Nucleoproteins—a basic protein such as histones or prolamines combined with nucleic acid
2. Phosphoproteins—proteins linked to phosphoric acid (e.g., casein in milk and vitellin in egg yolk)
3. Glycoproteins—a protein and a carbohydrate [e.g., mucin in saliva, mucoids in tendon and cartilage)
4. Chromoproteins—a protein combined with a coloured compound (e.g., haemoglobin and cytochromes)
5. Lipoproteins—proteins combined with lipids (such as fatty acids, fat, and lecithin) 16
Carbohydrate
Polymers of monosaccharides bound together by glycosidic bond

Most common - Glucose and fructose (C6H12O6) is the most common monosaccharide

Classification of Monosaccharides

 By location of the carbonyl group as aldose (aldehyde) or ketose (ketone); glucose is an aldose sugar

while fructose is a ketose sugar

 The number of carbons in the carbon skeleton 3, 5, or 6 carbons as triose, pentose or hexose. Both

glucose and fructose are hexose sugars

 Reducing or non-reducing – glucose is reducing and sucrose is non-reducing

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M o no - o r d isacchar id e

B ar fo ed 's test

r ed p p t = 1 0 m in r ed p p t = 2 - 3 m in

d isacchar id e m o no sacchar id e

B ened ict's test

r ed p p t. no p p t. o ther co lo u r s blu e

no n r ed u cing r ed u cing hex o se p ento se


d isacchar id e d isacchar id e ( r ibo se
( su cr o se) ( lacto se S eliw ano ff test
x y lo se)
m alto se)
r ed o ther

k eto hex o se ald o hex o se


( fr u cto se) ( g lu co se, g alacto se)

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Haworth projection of α- β-glucose
glucose ring ring

Fischer projection form

Haworth projection of
Fructose
Fischer projection form 19
Disaccharides
Two monosaccharides bond together using a dehydration reaction to create a disaccharide. The bond between two
monosaccharides is called a glycosidic bond. Examples: Sucrose (Table sugar), Lactose (Sugar found in milk), Maltose
(Malt sugar)

Sucrose:

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Polysaccharides
Many monosaccharides linked together through glycosidic bonds. The structure and function of a polysaccharide are
determined by its sugar monomers and the positions of glycosidic bonds
Examples: starch, glycogen, and cellulose
Starch - mixture of two polymers: amylose (formed by α-1,4-glycosidic linkage) and amylopectin (a branched-chain
polysaccharide formed by α-1,4-glucosidic bonds together with some α-1,6-glycosidic linkage).
CH OH CH OH CH OH
CH 2
OH 2 2 2

H H H H H H
H H

H H H
H H 3C
CH3 H
H 1 4
OH H OH H OH
OH
O O
O O
O

OH OH OH
OH H H H
H

amylose

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Glycogen is animal starch, similar to amylopectin but more highly branched.
Cellulose is a fibrous carbohydrate composed of chains of D-glucose units joined by β-1,4-glycosidic linkages.

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Reading List:

 Abass A. Olajire.Fundamental University Organic and Inorganic Chemistry . Sina 2tees publication. 2008.

 Sachin Kr. Ghosh.Advanced General Organic Chemistry (A modern Approach) . New Central Book
Agency (P) Limited. 2007

 Wong Y.C., Wong C.T., Onyinruka S.O., Akpanisi L.E. University General Chemistry Inorganic and Physical.
Africana-FEP Publishers LTD

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