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Lecture 02/unit II (Chemical Bonding) VSEPR Theory

The VSEPR (Valence Shell Electron Pair Repulsion) theory predicts molecular geometry based on electron pair repulsion around a central atom. It postulates that electron pairs arrange themselves to minimize repulsion, determining a molecule's shape. The theory was developed in 1940 and further refined in 1957. It accurately predicts the geometry of many molecules based on the number of electron pairs, but has limitations, such as failing to explain isoelectronic species that differ in shape.

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146 views4 pages

Lecture 02/unit II (Chemical Bonding) VSEPR Theory

The VSEPR (Valence Shell Electron Pair Repulsion) theory predicts molecular geometry based on electron pair repulsion around a central atom. It postulates that electron pairs arrange themselves to minimize repulsion, determining a molecule's shape. The theory was developed in 1940 and further refined in 1957. It accurately predicts the geometry of many molecules based on the number of electron pairs, but has limitations, such as failing to explain isoelectronic species that differ in shape.

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Lecture 02/Unit II(Chemical Bonding)

VSEPR Theory :

The theory was first presented by Sidgwick and Powell in 1940. VSEPR Theory is used to
predict the shape of the molecules from the electron pairs that surround the central atoms of the
molecule.

The Valence Shell Electron Pair Repulsion Theory abbreviated as VSEPR theory. According to
this theory the electron pairs arrange themselves around the central metal atom in such a way that
there is minimum repulsion between them so that the molecule has minimum energy and
maximum stability. This arrangement of the atom determines the geometry of the resulting
molecule.

However this theory was further developed by Ronald Nyholm and Ronald Gillespie in 1957 to
predict and explain molecular shapes and bond angles more exactly.

Postulates of VSEPR Theory:

The postulates of the VSEPR theory are listed below

 The central metal atom is bonded to the other atoms through electron pairs by single
covalent bonds.

 The electron pairs around the central metal atom are so arranged in space so as to
minimize the coulombic repulsions between them, leading to stable arrangement.

 The geometry of the molecule is determined by the total number of electrons pairs, bond
pairs as well as lone pairs, surrounding the central metal atom.
 When the central atom in a molecule is surrounded by bond pairs only, the molecule will
have regular shape or the geometry as given in the following table:

No. Of Shape of the Molecule Bond Angle Example


Electron
pairs
2 Linear 180o BeF2
3 Trigonal Planar 120o BF3
4 Tetrahedral 109o 28’ CH4
5 Trigonal Bipyramidal 120o and 90o PCl5
6 Octahedral 90o SF6
7 Pentagonal Bipyramidal 72o and 90o IF7

 When the central atom in a molecule is surrounded by bond pair as well as lone pair the
geometry is distorted or irregular. This is because a lone pair of electrons take up more
space around the central atom than a bond pair as lone pair is attracted to one nucleus
whereas bond pair is under influence of two nuclei. Consequently, the presence of lone
pairs will alter the bond angle to a small extent which does not pertain to any geometry.

 As the number of lone pair of electron pair in the valence shell of central atom increases
the bond angle decreases if all the molecules are formed by similar type of hybridization.

Name of Molecule Hybdidization No. Of Lone pair Bond Angle


CH4 Sp3 0 109o 28’
NH3 Sp3 1 107.3o
H2O Sp3 2 104.5o

 It is found that the repulsion between the lone pair electrons is greater than repulsion
between bond pair electrons. The order of decreasing repulsion being:
Lone pair-Lone pair Lone pair-bond pair Bond pair-bond pair

 As the electronegativity of central atom decreases, the bond angle also decreses if the
molecules are formed by similar type of hybridization. As electronegativity decreases the
distance of valence shell electrons from the nucleus increases.

Name of Molecule Electronegtavity of central Bond Angle


atom
H2O 3.5 104.5o
H2S 2.5 92.5o
H2Se 2.4 91.5o

 If the central atoms remains the same but the surrounding atom varies, then with the
decrease in the electronegativity value of the surrounding atoms, the bond angle
increases.

Name of Molecule Electronegativity of central Bond Angle


atom
PCl3 3.0 100o
PBr3 2.8 101.5o
PI3 2.5 102o

 Repulsive forces are stronger at 90o weaker at 120o and weakest at 180o .

The different geometries that molecules can assume keeping with VSEPR theory can be seen in
the illustration provided below
Limitations of VSEPR Theory:

Some significant limitations of the VSEPR theory include:

 This theory fails to explain isoelectronic species (i.e. elements having the same number
of electrons). The species may vary in shapes despite having the same number of
electrons.

 Another limitation of VSEPR theory is that it predicts that halides of group 2 elements
will have a linear structure, whereas their actual structure is a bent one.

 This theory fails to explain the shapes of certain compounds of transition elements. For
example, complexes of transition of metals having d8 configuration are often square
planar and not tetrahedral as predicted by Nyholm and Gillespie theory.

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