Chapter 1 -Introduction to Organic chemistry
1. INTRODUCTION
1.1 What is organic chemistry? Why should you study it?
Every living organism is made of organic chemicals
The proteins that make up your hair, skin and muscles; the DNA that
control your genetic heritage, the food that nourish you; the medicine
that heal you are all organic chemicals.
If you want to be part of the many exciting developments now
happening in medicine and the biological sciences, must first
understand organic chemistry.
So, organic chemistry is the study of carbon compounds.
Examples: hydrocarbons, amine, aromatic compounds and their
derivatives, carbonyl compounds, biological molecules (carbohydrate,
proteins, fat & lipids, nucleic acid) …etc
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Organic compounds those derived from living things (plants and
animals).
Organic compounds have carbon and hydrogen
while inorganic compounds those that came from mineral
constituents of the earth or were found with non-living things.
In 1807, Jöns Jakob B. gave names to the two kinds of materials.
Organic compounds and
Inorganic compounds
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What was the basis of this classification?
Early chemists believed that organic compounds differed from
inorganic compounds because living things had a special ‘life
force’(Vitalism ) within them, which was invisible and hard to detect.
Compounds derived from minerals—those lacking that vital force—
were “inorganic.”
According to the theory of ‘life force’:
The only source of organic compounds was nature itself (plants and
animals).
It is impossible to synthesize organic compounds in the laboratory.
The studied compounds are extracted from living organisms
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Failure of Vitalism Theory
In 1816, Michel Chevreul synthesized soap from animal fat by the
reaction of animal fat (organic) with alkali.
Conversion of fat (organic) into soap and soap into fatty acid without
the intervention of outside vital force was the first demonstration
that organic compounds could be inter-converted into each other in
the laboratory.
This is the first experiment that indicated the vital force theory was
with drawbacks.
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In 1828 Friedrich Wöhler, prepared urea as the first organic compounds in
laboratory and broke vital force theory.
Friedrich Wöhler produced urea, [(NH2)2CO] a compound known to be excreted
by mammals by heating ammonium cyanate, an inorganic mineral.
The ‘life force’ theory continued until Friedrich Wöhler synthesized urea in the
laboratory.
Organic chemistry is the branch of chemistry that studies C-H bond
containing compounds derived from plants and animals.
Except:
The oxides of carbon
Carbonates synthesized in laboratories
Hydrogen carbonates
Cyanides and cyanates
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Cont..
Most of the compounds found in nature—those we rely on for
Food Clothing (cotton, wool, silk), and
Medicine Energy (natural gas, petroleum) are organic as well
Important organic compounds are not, however, limited to the ones
we find in nature.
Chemists have learned to synthesize millions of organic compounds
never found in nature, including
synthetic fabrics glue
plastics medicines
synthetic rubber photographic film and Super
The main reason for the presence of millions of carbon compounds is the
unique property of carbon called catenation.
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Atomic Structure of Carbon
There are four different kinds of orbitals, denoted s, p, d,
and f. Shapes of atomic orbitals
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Energy levels
The atomic orbitals described above are not equal in
energy
degenerate
Electronic configuration
1. Aufbau principle(building up)
Electrons which will fill up lower energy atomic orbitals before entering
higher energy orbitals.
The orbitals of lowest energy are filled first, according to the order
1s<2s <2p< 3s< 3p< 4s< 3d< 4p< 5s< 4d< 5p< 6s< 4f< 5d< 6p< 7s< 5f
6C 1s2 2s2 2p2 (2px1, 2py1 and 2pz) based on Afubau principle first fill up 1s
before 2s and 2s before 2p because 1s<2s<2p in energy.
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2. Pauli exclusion principle
states that
a) no more than two electrons can occupy each atomic orbital
b) the two electrons must be of opposite spin(up ↑ and down ↓ )
3. Hund’s rule
Hund’s rule states that when there are degenerate orbitals—two or more
Electronic configuration for carbon
orbitals with the same energy—an electron will occupy an empty orbital
before it will pair up with another electron.
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CHEMICAL BONDING
types chemical - Ionic bonding
complete transfer of electrons between two atoms of widely different
electronegativities.
results from the attraction between the positive cation and negative anion.
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Covalent Bonds
• sharing electrons
Polar
Equal sharing => Non-polar eg. H2 Unequal sharing => Polar eg. HF
O2
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Covalent bonds are more accurately explained using modern bonding theories:
Valence bond theory (VBT) and
Molecular orbital theory (MOT).
Valence shell electron pair repulsion (VSEPR)
Valence bond theory
VBT states that covalent bond is formed by the overlap of the two orbitals in the
atoms.
That means the two orbitals share a common region in space.
for example, the H-H bond results from the overlap of two singly occupied
hydrogen 1s orbitals.
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Quantum mechanical description of valence electrons to form
bond:
Consider formation of H2 molecule:
+
An overlapping of
waves causes an increase
in electron density in the
region of overlap.
VBT is based on
hybridization
The Central Themes of VB Theory
Basic Principle
The two wave functions are in phase so the amplitude increases
between the nuclei.
Wave function of orbitals:
quantum mechanical description
e-
+
Repulsive forces increase
faster than attractive forces at distances closer than 74 pm rise because
increased electron-electron and nuclear-nuclear repulsions
HH (too close)
weak net attraction at
long distances
74 pm
H H (too far)
Potential H• + H•
energy H H
H H Attractive forces increase
H H faster than repulsive forces
-436 kJ/mol as atoms approach each
H2 other
Internuclear distance
Maximum net attraction (minimum potential energy) at
74 pm internuclear distance. Stable molecule formed
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There is an optimum distance between nuclei that leads to maximum stability
Called the bond length. the bond length for H2 molecule is 74pm
Hybridization
The mixing of two or more orbitals that have comparable
energies, followed by their splitting in to an equal number
of degenerate orbitals.
The new orbitals are called hybrid orbitals which are
lower in energy than parent orbitals.
+
s p sp sp
parent orbitals hybrid orbitals
Formation of hybrid orbitals
The geometry of the molecule is determined by the
number and type of the hybrid orbitals around the
central atom.
Two Types of Covalent Bonds
s (sigma) bond “head-to-head” overlap along the bond axis
(pi) bond “side-to-side” overlap of p orbitals:
2p
2p p bond
Single bond -- always a δ bond
Double bond -- combination of one δ bond and one p bond
Triple bond -- combination of one δ bond and two p bonds
s (sigma) bonds
“head-to-head” overlap along the bond axis
p (pi) bonds
“side-to-side” overlap of p orbitals:
Hybrid Orbitals
Key Points
The number of hybrid orbitals obtained equals the number of atomic
orbitals mixed.
The type of hybrid orbitals obtained varies with the types of atomic orbitals
mixed.
Types of Hybrid Orbitals
sp sp2 sp3 sp3d sp3d2
Relative bond strength increases.
Write the characteristics of each hybrid orbital.
Geometry of hybrid orbital
Question:
Construct the geometry of
the following hybrid orbitals:
sp3d
sp3d2
1. What is the hybridization of each of the carbon atoms in
the following compound and describe the sigma and pi
bond?
1. How many sigma and pi bonds are in the acetic acid
(vinegar) molecule CH3COOH?
H
O
Sigma bonds =7
H C C O H
pi bonds = 1
H
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Example
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Cont…
Note:
Length => Single bond ( ) > Double bond (=) > Tirple bond ( ≡)
Strength => Double bond (s + π) > single bond ( s), but it is not twice as
strong.
Therefore, that a π bond is weaker than a s bond.
C-H s bond is shorter and stronger than a C-C s bond. This is because the
s orbital of hydrogen is closer to the nucleus than is the sp3 orbital of
carbon.
The nuclei are closer together in a bond formed by sp3-s overlap than
they are in a bond formed by sp3-sp3 overlap.
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MOT
VBT- explains formation of covalent bonds as a result
of sharing of electrons in overlapping orbitals of
different atoms.
MOT- predicts that the atomic orbitals on different
atoms combine to form a set of new orbitals (MOs).
The electrons contained in the molecular orbitals
belongs to the molecule as a whole.
Since orbitals are wave functions, they can combine
either constructively (forming a bonding molecular
orbital), or destructively (forming an antibonding
molecular orbital).
Comparison of VB and MO Theory
Valence Bond Theory (“simple” but somewhat limited)
e– pair bonds between two atoms using overlap of atomic
orbitals on two atoms
Molecular Orbital Theory (more general but “complex”)
All e–’s in molecule fill up a set of molecular orbitals that are
made up of linear combinations of atomic orbitals on two or
more atoms
MO’s can be:
“localized” -- combination of AO’s on two atoms, as in the
diatomic molecules
“delocalized” -- combination of AO’s on three or more atoms
as in benzene (C6H6)
What type of combinations are there?
1. Constructive 2. Destructive
In-phase overlap Out-of-phase overlap
Addition overlap Subtraction overlap
The electron density of The electron density of
Aos lies b/n the two in the region b/n the
nuclei. nuclei gets substantially
Results a low energy reduced.
bonding molecular Results a high energy
orbital. antibonding molecular
orbital.
Types of MOs
1. Bonding molecular orbital (Mo)
Formed by addition overlap
lower in energy than the atomic orbitals from which it is
composed.
Lobes of same sign atomic orbitas overlap
An electron in bonding MO contributes towards the attraction
between the two atoms
2. Antibonding (*Mo):
Formed by subtraction overlap
higher in energy (unstable) than the atomic orbitals from
which it is composed.
An electron in antibonding MO contributes towards the
repulsion between the two atoms.
28 Lobes of opposite sign atomic orbitas overlap
Molecular Orbital (MO) Theory
s-s combination
ANTBONDING
These two new orbitals have different
energies.
BONDING
The one that is lower in energy is called the bonding orbital,
The one higher in energy is called an antibonding orbital.
MOs from 2p atomic orbitals
s
p-p
combination
1) One sigma bond through overlap of orbitals along the internuclear
axis.
2) Two pi bonds through overlap of orbitals above and below (or to the
sides) of the internuclear axis.
Molecular electroconfiguration
Molecule having electrons <14
Cont…
Bond order is the number of covalent bonds present between
two bonded atoms in a molecule.
BO= Nb-Na where Nb= number of electrons in bonding
2 molecular orbitals.
Na= number of electrons in antibonding
molecular orbitals.
s1s
1s 1s
Bond Order = 1/2[(# of bonding e–
’s) - (# of antibonding e–’s)]
s1s
For H2 = 1/2 [2-0] = 1 (a
H H2 H single bond)
Relative MO energy levels for homonuclear diatomic molecules
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