Basic Chemistry I (CHEM 101)

Group B
ORGANIC CHEMISTRY

Unit 1
Structure and Properties
(Part-1)

B.Sc. First Year

Syllabus (4 Hrs.)
• Atomic orbitals, molecular orbitals, hybrid orbitals,
• polarity of bonds,
• melting point,
• acids and bases,
• dipole-dipole interaction, hydrogen bonding,
• inductive effect, electromeric effect,
• resonance, mesomeric effect or conjugative effect,
• hyperconjugation effect,
• steric effect,
• IUPAC nomenclature.

Mark on red are include in this presentation

Syllabus
Text Books: for theoretical course CHEM 101
1. R. T. Morrison & R. N. Boyd, Organic Chemistry, 6th and 7th
Edition, Prentice- Hall of India Pvt., Ltd., 2008.
2. I. L. Finar, Organic Chemistry, Vol. I and Vol. II, Prentice Hall,
London, 1955, (available recent edition).
3. Streitweiser & Heathcock, Introductory Organic Chemistry,
Wiley and Sons, New York, 1981
4. J. March, Advanced Organic Chemistry, 4th Edition, Wiley
Eastern Ltd., India, 2005.
5. N. D. Cheronis and J.B. Entrikin, Identification of Organic
Compounds, A Student’s Text using Semi-micro Techniques,
John Wiley& Sons, Inc. (Latest edition).
6. L. Shriner, R.C Fusion and D.Y Cartin, The Systematic
Identification of Organic Compounds, A Hand Manual, John
Wiley and Sons, Inc. New York (Latest).
Syllabus
Reference Books: for theoretical course CHEM 101
1. S. D. Gautam, M. K. Prasad & D. P. Bhattarai, Fundamental
Chemistry, 1st Edition, Heritage Publishers and Distributors
Pvt. Ltd., Nepal, 2013
2. M. L. Sharma & P. N. Chaudhary, A Textbook of B. Sc.
Chemistry (Vol. I & II), 2nd Edition, Ekta Books Nepal, 2007

Other Books: for theoretical course CHEM 101

1. S. K. Chapagain & B. Mishra, A Textbook of B. Sc. Chemistry
(Vol. I), Sukunda Pustak Bhawan
Atomic orbitals
• A volume of space about the nucleus of an atom where
there is a high probability of finding an electron is known
as orbital.
• The orbital of an electron in free atom is described as an
atomic orbital.
• An atomic orbital can be described mathematically by its
wave function.
• Atomic orbitals have characteristic quantum numbers.
• The principal quantum number (n)
• The azimuthal quantum number (l )
• The magnetic quantum number (m)
• The spin quantum number (s)
Atomic orbitals
• An orbital represents that an electron can move
around nucleus along three dimensional space (x, y
and z-axes).
• An orbital is the three dimensional region within which
there is higher probability that an electron having a
certain energy will be found.
• It is the most probable space in which the electron
spends most of its time (90 - 95%) while in constant
motion.
• It is the spatial description of the motion of an electron
corresponding to a particular energy level.
Atomic orbitals
• The energy of electron in an atomic orbital is always
the same.
• Each energy level corresponds to a three dimensional
electron wave which envelopes the nucleus.
• This wave possesses a definite size, shape and
orientation and thus can be represented pictorially.
• Only one electron of hydrogen atom revolves around
its nucleus with a high velocity that in one second it
completes about 1.31 x 1024 revolutions in the Bohr's
first orbit.
• Each sub-shell consists of orbitals.
• An orbital can accommodate a maximum of two
electrons, which possess the same energy but
opposite spins.
Atomic orbitals
• Different sub shells and their orbitals

Sub shell Orbitals Total no. of orbitals

s s 1
p px , py , pz 3
d dxy , dyz , dxz , dz2 , dx2-dy2 5
f fxyz , fx3 , fy3 , fz3 , fx(y2-z2) , 7
fy(x2-z2) , fz(x2-y2)

• The shape, size and orientation of different energy

orbitals are different.
• Equal energy orbitals have the same size and shape.
Atomic orbitals
s - orbital
• s – orbitals are spherically symmetrical.
• The s-sub shell is made up of only one orbital which is
in the form of a spherical cloud.
• The nucleus is at the center and
the probability of finding electron
is same in all directions.
• The electron can be found
anywhere in space, but it is found
with the greatest probability close
to the nucleus at a distance of 0.53
x 10-8 cm for 1s orbital.
• The orbital at the lowest energy level is called the 1s
orbital.
• The higher s-orbitals (2s, 3s etc.) are also non
directional and spherically symmetrical.
Atomic orbitals
s - orbital
• The size of the orbital depends upon the value of the
principal quantum number (n).

• 2s-orbital consists of inner and outer spheres.

• There is a region between these spheres where the
electron density is zero.
• This region is called node or nodal plane or nodal
surface.
Atomic orbitals
s - orbital
• The number of nodal planes in an orbital of any energy
level (n) = n – 1.
• The energy of various s-orbitals follow the order:
1s < 2s < 3s …….
p - orbital
• p-orbital are dumb bell shape.
• The probability of finding the p-
electrons is maximum in two lobes
on the opposite sides of the nucleus.
• p-orbitals have three orientations and
they are named as px, py and pz and
subscript x, y and z referring to the
co-ordinate axes along which their
lobes of maximum electron density
lie.
p - orbital
• The three axes are at right angles to each other and
three orbitals are also perpendicular to each other.

• Each of the three p-orbitals has two lobes touching

each other at the origin and these lobes are
symmetrical about the one of the three axes.
• The nucleus remains at the center between two lobes
and there is no probability of finding electrons in the
nucleus.
• This point is a place of zero electron density and is
known as the nodal plane.
Molecular orbital
• Covalent bond of molecular orbital is formed according
to the molecular orbital theory put forward by Hund and
Mullikan (1932).
• Two atomic orbitals combine linearly to form molecular
orbitals (MOs) in between two nuclei.
• One is the bonding MO which is formed by same phase
overlap and other is antibonding MO formed by
opposite phase overlap.
• A MO unlike an atomic orbital is a polycentric orbital.
• Head to head overlap of atomic orbitals can form
σ bonding and σ* antibonding MOs and side on overlap
forms π bonding and π* antibonding MOs.
• The electron cloud density concentrates in between two
nuclei of bonding MO whereas in antibonding MO it is
concentrated away from the nuclei.
Molecular orbital
• The potential energy of bonding MOs are lower and
antibonding MOs are higher than overlapping atomic
orbitals.
Formation of molecular orbitals by the combination of s-
atomic orbitals
• The head to head combination of two ‘1s’ atomic
orbitals will produce σ1s and σ *1s molecular orbitals.

+ - subtraction overlap

Antibonding MO (σ*1s)

+ Addition overlap

Bonding MO (σ1s)
Molecular orbital
Formation of molecular orbitals by the combination of p-
orbitals along the inter nuclear axis (head to head)
• The 2px atomic orbitals overlap end to end to form
two molecular orbitals and they are designated σ2px
(bonding) and σ *2px (antibonding).

Atomic orbitals

- + + - +

2px 2px

Bonding MO (σ2px)

- + - + - +

2px 2px
Antibonding MO (σ*2px)
Molecular orbital
Formation of molecular orbitals by the combination of p-
orbitals due to sideways overlap
• two 2py atomic orbitals overlap side wise π2py and
π*2py MOs are formed.
Atomic orbitals

+ - + -
subtraction
overlap
- + - +

Antibonding MO (π*2py)

+ + +
Addition
overlap
- - -

Bonding MO (π2py)
Molecular orbital
Hydrogen molecule
• In hydrogen molecule, each hydrogen atom has 1s orbital.
• Two 1s orbitals overlap to form molecular orbitals, their
energies are in the order : σ1s < σ *1s
• Both electrons are in σ1s bonding orbital and the
antibonding orbital will be remain vacant.
• These two electrons in the bonding orbital have opposite
spin.
• The electronic configuration of molecule is σ1s2.
Molecular orbital
Hydrogen molecule
• The molecular orbital energy level diagram for hydrogen
molecule is as