VALANCE SHELL

ELECTRON PAIR
REPULTION THEORY
.
 VSEPR-THEORY
VSEPR theory is used in chemistry to predict the geometry
of individual molecules from the number of electron pairs
surrounding their central atoms. It is also called the
Gillespie-Nyholm theory The VSEPR" is an
acronym. Pronounced either "ves-pur"or "vuh-seh-per"
Postulates of this theory for prediction of shape of
the molecules are

◦ 1-Valance electron pairs are arranged around the central atom to remain at maximum distance
apart as possible in order to minimize repulsion.
◦ 2-Lone pairs of electron occupies more space than bonding pair & decreasing order of
repulsion is Lone pair- lone pair > lone pair – bond pair > bond pair – bond pair.
◦ 3-The number of electron pairs in the valence shell of a central atom is determined after
drawing the Lewis structure of the molecule, and expanding it to show all bonding groups and
lone pairs of electrons. The sum of the number of atoms bonded to a central atom and the
number of lone pairs formed by its nonbonding valence electrons is known as the central
atom's steric number.
Postulates of this theory for prediction of shape of
the molecules are
◦ 4-Repulsive forces decree se sharply as with increase the interpair angle. They are
strong at 90o angle much weaker at 1200 angle and very weak at 1800 angle so order
will be 90o > 120o > 180o

◦ 5-The influence of bonding electron pair decrease with increase in the

electronegativity of the atoms in the molecules. In VSEPR, a double bond or
triple bond are treated as a single bonding group.
◦ 6-Electron pairs participate in the determination of the geometry of the molecules and
steric number calculation is critical in the determination of electronic geometry of
molecule.
◦ Steric No. = No. of bond pair (bp) + No. of lone pair(lp)
 Types of geometries of the molecules on
the base type of electron pair
1-Electronic Geometry: Electronic Geometry.
◦ That type of geometry arises due
to the arrangement of total
electron pair (lone + bond) in the
space.
..
Lone pair is represented in space N
via drawing a lobe H
H
◦
H
 Types of geometries of the molecules on
the base type of electron pair
2-Molecular Geometry: ◦ Molecular Geometry
◦ That type of geometry arises due
to the arrangement of only and
only total bond pair in the space.
N
The Lone pair in this cases not
represented in space via drawing a H
lobe but it is only written on
central metal atom.
H
◦ H
 Types of geometries of the molecules on
the base type of Bonded atom
3-Regular Geometry:
That type of geometry arises due
to the arrangement of total bond
in the space.
There is no lone pair in the
molecule only bond pair are
present. Only one type bonded
atom present.
◦
 Types of geometries of the molecules on
the base type of Bonded atom
4-Irregular Geometry: Irrigular geometry
That type of geometry arises due
to the arrangement of total bond
and lone in the space.
N
There is no lone pair in the
molecule only bond pair are H
present. Only one type or different
bonded atom present.
H
◦ H
Causes of deviation from idealized regular
geometries
◦ There are two type of inorganic molecules that show distortion . Transition
complex–compounds exhibit distortion due to John teller distortion.

Inorganic Main group-Inorganic

Transition Metal
compound Compounds Compounds
Causes of deviation from idealized regular
geometries Main group element
◦ 1-Lone pair effect on geometries of molecules. When the central metal atom
is surrounded by both bonding pair and the lone pairs of the electron and same
type of bounded atom attached than compound does not show regular
geometry. Lone pair is the cause of alternation.
◦ 2-Nature of the central metal Atom. As the n- value of the central metal atom
increases than the repulsive forces increases and the bond angle decreases.e.g.
H2O (105.50)>>>H2S (92.20)
Causes of deviation from idealized regular
geometries Main group element
◦ 3-Nature of bounded atoms. Bent's rule: An electron pair of a more
electropositive ligand constitutes greater repulsion. This explains why the Cl in
PClF4 prefers the equatorial position. A higher bond order constitutes greater
repulsion. This explains why in phosgene, the oxygen–chlorine bond angle
(124.1°) is larger than the chlorine–chlorine bond angle (111.8°) even though
chlorine is more electropositive than oxygen. The bond angle is decreased ae
the electronegativity of the bounded atom decreased because the repulsion
between the central atom electrons and the bounded atom is decreased. E.g.,
PI3(102o) > PBr3 (101.5) > PCl3( 100)
Classification of Molecules According To VSEPR:

◦ The "AXE method" of electron counting is universally applied in order to

categorize type of molecules according to the VSEPR theory. The A represents
the central atom and always has an implied subscript one. The X represents
each of ligands (atoms bonded to A). The E represents the number of lone
electron pairs surrounding the central atom. The sum of X and E is known as
the steric number.
 Classification of Molecules According To VSEPR:
Class S.# bps lps# Electronic Geometry Molecular geometry
#

AX 1 1 0
Linear linear

2 0 0
AX2
 Classification of Molecules According To VSEPR:
Class S.# bps lps# Electronic Geometry Molecular geometry
#

AX3 3 3 0

TT
Trigonal planer Trigonal planer

AX2E 3 2 1 X

A
Bent
X
 Classification of Molecules According To VSEPR:
Class S.# bps lps# Electronic Geometry Molecular geometry
#

AXE2 3 1 2

A X A X
Linear

AX4 4 4 0
 Classification of Molecules According To VSEPR:
Class S.# bps lps# Electronic Geometry Molecular geometry
#

AX3E 4 3 1

Tetrahedral

AX2E2 4 2 2

X
X
 Classification of Molecules According To VSEPR:
Class S.# bps lps# Electronic Geometry Molecular geometry
#

AXE3 4 1 3
Linear ( ClO1-)
X A
..
AX5 5 5 0

Trigonal bipyramidal
Trigonal bipyramidal
 Classification of Molecules According To VSEPR:
Class S.# bps lps# Electronic Geometry Molecular geometry
#

AX4E 5 5 1

AX3E2 5 3 2
 Classification of Molecules According To VSEPR:
Class S.# bps lps# Electronic Geometry Molecular geometry
#

AX2E3 5 2 3

AX6 6 6 0
 Classification of Molecules According To VSEPR:
Class S.# bps lps# Electronic Geometry Molecular geometry
#

AX5E 6 5 1

AX4E2 6 4 2
 Classification of Molecules According To VSEPR:
Class S.# bps lps# Electronic Geometry Molecular geometry
#

AX3E3 6 3 3 Distorted octahedral Liner

AX7 7 7 0 Pentagonal pyrimidal Pentagonal pyrimidal

AX6E1 7 6 1 pentagonal pyramidal pentagonal pyramidal

AX8 8 8 0 Square antipirismatic don’t need It’s example is TaF83-

to draw this geometry
Application of VSEPR Theory:
Procedure for...predicting molecular geometries.

Step-1
Draw the Lewis structure for the molecules: It consist of the following steps.
Firstly predict the central metal atom or ion in the given molecules and write its
Valence shell Bohar’s electronic configuration. On the base of the Boar’s
configuration of the central metal atom and predict the Lewis system for
drawing the reliable structure of the molecules that will satisfy the octate rule,
18 electron rule , 14 electron rule etc. in order to draw the stable structure of the
compound. For this purpose one must know that how these condition will
satisfied?
Application of VSEPR Theory:
Procedure for...predicting molecular geometries.

Saturated System: This is valid for those non- transition molecules that’s
valance shell electrons are sufficient to satisfy octate by forming single bond in
order to gain stability. Unsaturated system same as above but octate is satisfied
by forming multiple bonds.
Valance Shell Expansion System. There are some molecules which do not
obey the octate rule and the central atom expand the shell through the excitation
of electron from lower to higher energy and form multiple bonds in order to get
stability the follow either 14 or 18 electron count and got stability. e.g. IF 7,
PCl5, XeF4, etc.
Application of VSEPR Theory:
Procedure for...predicting molecular geometries.

Step -2 Determination the total number of electrons around the central metal
atom. Lone pairs, single bonds, double bonds, triple bonds each count as a one
group according to postulate and calculate steric number. .
Step -3 Refer to the table 1.1 to determine the electronic as well as the
molecular geometry of the molecules. And draw the geometry of molecules.
Step-4 Satisfy your structure by used hybridization concept but keep in mind the
VSEPR postulate never violate them.
 Q.Pridict electronic and molecular geometry of tiriodide ion using VSEPR
theory ??

Number of lone pair =03

Central atom is iodide ion. Bohar
Number of bond pair =02
confirmation = k=2,L=8, M=18,
Steric no.lp + bp = 3+2 =5
N=18, O = 08. Bonded atom is
iodine Bohar configuration = K=2, I
L=8. M=18, N=18,xx O=07

I
1-
xx 1-
I
Ixxx I xxx
Lewis structure of triiodide ion :
1- I
I I I Electronic Geometry

Moleculat geometry =Linear

Limitation of VSEPR- Theory:
There are groups of compounds where VSEPR fails to predict the correct
geometry.
1-Some AX2E0 molecule eg CaF2, 145°; SrF2, 120°; BaF2, 108°; SrCl2, 130°;
BaCl2, 115°; BaBr2, 115°; BaI2, 105°) linear according to it but actual these are
bent..
2-Some AX2E2 molecules One example of the AX2E2 geometry is molecular
lithium oxide, Li2O, a linear rather than bent structure, which is ascribed to its
bonds being essentially ionic and the strong lithium-lithium repulsion that
results.
Limitation of VSEPR- Theory:
3-Some AX6E1 and AX8E1 molecules
Some AX6E1 molecules, e.g. xenon hexafluoride (XeF6) and
the Te(IV) andBi(III)anions, TeCl2−6, TeBr2−6, BiCl3−6, BiBr3−6 and BiI3−6,
are octahedral, rather than pentagonal pyramids, and the lone pair does not
affect the geometry to the degree predicted by VSEPR.
4-Odd-electron molecules: For example, the decrease in the bond angle in
theseries NO+2 (180°), NO2 (134°), NO−2 (115°) not satisfied.