Valence Bond Theory

Chapter 2
CHM361
Course outline

 Lewis structure
 Valence Shell Electron Pair Repulsion (VSEPR) Theory
 Valence bond Theory
 Orbital hybridization : sp, sp2, sp3, dsp2, sp3d2
Molecular geometry

 Molecular geometry is the 3D arrangement of atoms in a

molecule.
 Geometry affects physical and chemical properties
 Eg: melting point, boiling point, density, and the types of reactions
it undergoes

 In general, bond length and bond angles must be

determined by experiment
 However, we can predict the considerable success the
overall geometry of a molecule or ion if we know the
number of electrons surrounding a central atom in its
Lewis structure.
 The basis of this approach is the assumption that
electron pairs in the valence shell of an atom repel one
another.
 Valence shell – outermost electron-occupied shell of an
atom, it holds the electrons that are usually involved in
bonding.
Lewis structure

 Lewis structure is the simplest way to represent

electrons around an atom
 The electrons can be represented by cross or a dot
 The Lewis structure for an elements is given below, for
elements in period 2
 DRAWING LEWIS STRUCTURE
1) Count the total no of VE of the molecule.

2) Draw the skeletal structure of the molecule.

3) Complete the duplet (H) and octet for all terminal atom.

3) Calculate number of electrons in the molecule. Each bond is

counted as two
electrons.

4) Excess VE are placed on the central atom.

5) If central metal atom do not achieved octet, make double/triple

bond with terminal atom.

6) Calculate Formal charge.

 Example BF3
Valence-shell electron-pair
repulsion (VSEPR) Theory
 The study of molecular geometry is called the VSEPR.
 This is because it accounts for the geometric
arrangements of electron pairs around a central atom in
terms of the electrostatic repulsion between electron
pairs
General rules of the VSEPR

1. As far as electron-pair repulsion is concerned, double

bonds and triple bonds can be treated like single bonds.
This approximation is good for qualitative purposes.(but in
reality not)
2. If a molecule has two or more resonance structures, we
can apply the VSEPR model to any one of them. Formal
charges are usually not shown.
 With this model, we can predict the geometry of
molecules (and ions) in a systematic way.
Molecules in which the central
atom has no lone pairs

 For simplicity, we consider two elements, A (central

atom) and B with general formula Abx, where =2, 3,....
  Predicting the shape depends on the
electron domain.

  The electron domain geometry of an atom is

dictated by the
 number of electron domain attached to it directly.

  Electron domain:
 Single bond
 Lone pair
TABLE 1
ELECTRON 3D- STRUCTURE ELECTRON PAIR ANGLE
DOMAIN GEOMETRY

2 Linear 180°

3 Trigonal Planar 120°

4 Tetrahedral 109.5°

5 Trigonal- 120° & 90°

bipyramidal

6 Octahedral 90° & 180°

AB2 : Berryllium Chloride (BeCl2)
 The lewis structure of BeCl2 (g)

 The bonding pairs repel each other, they must be at

opposite ends of a straight line in order for them to be
as far as possible.
 The angle is predicted to be 180°, and the molecule is
linear.
 The ball and stick model
 AB3: Boron Trifluoride (BF3)
 Contains 3 covalent bonds, The BF bonds point to the
corners of an equilateral triangle with B in the centre of
the triangle
 The geometry of BF3 is trigonal planar with the FBF
angles is 120° and all four lie in the same plane.

Lewis structure of BF3

 AB4 : Methane (CH4)
 4 bonding pairs, the geometry is tetrahedral (has 4
sides/faces which are equilateral triangles.
 The central atom (C) is located at the center of the
tetrahedron and the other four atoms are at the
corners.
 The bond angles are all 109.5°
AB5 : Phosphorus Pentachloride (PCl5)
 The only way to minimize the repulsive forces among
the five bonding pairs is to arrange the bond in the form
of a trigonal bipyramid
 The central atom (P) is at the center of the common
triangle with the surrounding atoms positioned at the
five corners of the trigonal bipyramid.
 The atoms that are above and below the triangular
plane are said to occupy axial positions, and those that
are in the triangular planar are said to occupy
equatorial positions.
 The angle between any two equatorial bonds is 120°;
that between an axial bond and an equatorial bond is
90°, and that between the two axial bond is 180°
AB6: Sulfur Hexafluoride (SF6)
 The most stable arrangement of the 6 SF bonding pairs
is in the shape of an octahedron.
 Octahedron has 8 sides and can be generated by joining
2 square pyramids on a common base.
 The central atom (S) is the center of the square base
and the surrounding atoms are at the six corners.
 All bond angles are 90° except the one made by the
bonds between the central atom and the pairs of atoms
that are diametrically opposite each other (180°)
 We cannot use the terms axial and equatorial because
the six bonds are equivalents
Molecules in which the central
atom has one or more lone pairs

 More complicated if the central has both bonding pairs and

lone pairs
 3 types of repulsive forces are involved
 Between bonding pairs (weakest repulsive forces)
 Between lone pairs (strongest repulsive forces)
 Between bonding pair and lone pair
 Lone pairs experience greater repulsion from neighboring
lone pairs and bonding pair because lone pairs electron
occupy more space.
 For simplicity, we designate molecules with lone pairs as
ABxEy (A is center atom, B is surrounding atom and E is lone
pair on A. x and y are integers x = 2, 3, 4…..and y = 1, 2….
AB2E: Sulfur dioxide (SO2)
 Because VSEPR treats double bond as single bond, the
SO2 can be viewed as consisting of three electron pairs
on the central S atom. 2 bonding pairs and 1 lone pair
 Because of the lone pai, which has greater repulsion
than the bonding pair, the geometry of SO2 is „bent‟
shape.
 The 2 S-O bonds are pushed together slightly and the
OSO angle is less than 120°
AB3E: Ammonia (NH3)
 The ammonia contain 3 bonding pairs and 1 lone pair
 The geometry is trigonal pyramidal because lone pair
repels the bonding pairs more strongly, the 3 NH
bonding pairs are pushed closer together
 The bond angle is smaller than the ideal tetrahedral
AB2E2: Water (H2O)
 H2O contains 2 bonding pairs and 2 lone pairs
 2 OH bonding pairs are pushed toward each other, and
will have greater deviation from the tetrahedral angle
in NH3
 AB4E: Sulfur tetrafluoride (SF4)
 the central sulfur atom has 5 electron pairs, 4 bonding
pairs and 1 lone pair
 The repulsive is smaller for (B) and indeed (B) is the
structure observed experimentally
 The geometry is distorted tetrahedron or seesaw

(A) (B)
TABLE 2
ELECTRON BONDING LONE PAIR MOLECULAR EXAMPLE
DOMAIN GEOMETRY

2 2 0 linear

3 3 0 Trigonal
planar

2 1 bent
ELECTRON BONDING LONE PAIR MOLECULAR EXAMPLE
DOMAIN GEOMETRY

4 4 0 tetrahedral

3 1 Trigonal
pyramidal

2 2 bent
ELECTRON BONDING LONE PAIR MOLECULAR GEOMETRY EXAMPLE
DOMAIN

5 5 0 trigonal PCl5
bipyramidal

4 1 seesaw CF4

3 2 T-shaped ClF3

2 3 linear XeF2
ELECTRON BONDING LONE PAIR MOLECULAR GEOMETRY EXAMPLE
DOMAIN

6 6 0 octahedral SF6

5 1 square BrF5
pyramidal

4 2 square XeF4
planar
Geometry of molecules with
more than one central atom
 The geometry of molecules with more than one central
atom is difficult to define in most cases.
 We only describe the shape around each of the central
atoms.
 Eg: Methanol CH3OH
 The two central atoms in methanol is C and O. The CH
and CO bonding pairs are tetrahedrally arranged about
the C atom.
 The O atom is like the one in H2O in that it has 2 lone
pairs and 2 bonding pairs., therefore, HOC portion of
the molecule is bent, and the angle is approximately
105°
Guidelines for applying the
VSEPR model
1. Write the Lewis structure of the molecule, considering only
the electron pairs around the central atom
2. Count the number of electron pairs domain around are
central atom (bonding pairs and lone pairs). Treat double
and triple bond as though they were single bonds.
3. Use Table 1 and Table 2 to predict the geometry of the
electron pair and the molecule
4. In predicting bond angles, note that a lone pair repels
another lone pair or a bonding pair more strongly than a
bonding pair repels another bonding pair. Remember that in
general there is no easy way to predict bond angles
accurately when the central atom possessess one or more
lone pairs.
Valence Bond Theory

 To rationalize how the shape of atomic orbitals are

transformed into the orbitals occupied in covalently
bonded species, we need Valence Bond Theory
Valence bond theory

 Valence bond theory assumes that the electrons in a molecule

occupy orbitals of individual atoms
 A covalent bond is formed when two neighboring atomic orbitals
overlap. The overlapping orbitals may only contain two electrons of
opposite spin
 A bond forms between two atoms when these conditions are met:-
 An orbital of an atom come to occupy the same region of space as
an orbital of the other atom. The two orbitals are said to overlap
 The total number of electrons in the overlapping orbitals is no
more than two
 Strength of bonding depends on the amount of overlap- the greater
the overlap, the stronger the bond
 A stable molecules forms when the potential energy has decreased
to a minimum
Eg: H2
Orbitals
 The best overlap occurs when two orbitals are allowed
to meet “head on” in a straight line.
 When this occurs, the atomic orbitals merge to form a
single bonding orbital and a “single bond” is formed,
called a sigma (σ) bond.
 There are two types of
orbital overlap
 Sigma, s, overlap occurs
when there is one
bonding interaction that
results from the overlap
of two orbitals
 Pi, p, overlap occurs
when two bonding
interaction result from
the overlap of orbitals.
Formation of sigma bond

Formation of pi bond
 Single bond - 1σ bond C-C
 Double bond - 1σ bond 1 π bond C=C
 Triple bond - 1σ bond 2 π bond C=C
Hybridization of Atomic Orbitals
 sp Hybridization

 The combination of an s
orbital and a p orbital
produces 2 new orbitals.
 These new orbitals are called
hybrid orbitals
 The process is called
hybridization
 Both the s and one p orbital
are involved in bonding to the
connecting atoms
Eg:

 BeF2- predicted geometry by VSEPR is linear

 The orbital diagram for the valence electron in Be is

 Sp2 hybridization

http://wps.prenhall.com/wps/media/objects/3311/3391094/blb0905.html
Eg:

 BF3- The geometry predicted by VSEPR is trigonal planar

geometry.
 The orbital diagram of B is
Sp3 Hybridization
Eg:

 CH4 – the predicted geometry by VSEPR is tetrahedral

 The orbital diagram of C is
Hybridization of s, p, and d orbitals
Sp3d Hybridization
Eg:

 PF5 – The geometry predicted by VSEPR is trigonal

bypyramidal
 The orbital diagram of P is
Sp3d2 Hybridization
Eg:

 SF6 – The geometry predicted by VSEPR is octahedral

 The orbital diagram of S is
Hybridization in Molecules
Containing Lone Pairs
 H2O- The geometry predicted by VSEPR is bent.
 The orbital diagram of O is
Hybridization in Molecules
Containing Double and Triple Bonds

 Double bond
 Eg: C2H4
C2H4

E
Unhybridized
N
E
R      
G
Y 2p 2p    2p
 
excitation hybridization
three
2s 2s
  sp2
hybrid
1s 1s
orbitals
Hybridization in Molecules
Containing Double and Triple Bonds

 Triple bond
 Eg: C2H2
C2H2

E Unhybridized
N
E
R       
G
Y 2p 2p   2p
 
excitation hybridization two
2s 2s
  sp
1s 1s hybrid
orbitals
Summary of hybridization

We note that
 The concept of hybridization is not applied to isolated atom. It is
theoretical model used only to explain covalent bonding
 Hybridiazation is the mixing of at least two nonequivalent atomic
orbitals.
 Hybrid orbitals and pure atomic orbitals have very different shapes.
 The number of hybrid orbitals generated is equal to the number of
pure atomic orbitals that participate in the hybridization process
 Covalent bonds in polyatomic molecules and ions are formed by the
overlap of hybrid orbitals, or of hybrid orbitals with unhybridized
ones. Therefore, the hybridization bonding scheme is still within
the framework of valence bond theory, electron in a molecule are
assume to occupy hybrid orbitals of the individual atoms.
Procedure for hybridizing
atomic orbitals
1. Draw the Lewis structure of the molecule
2. Predict the overall arrangement of the electron pairs
(both bonding pairs and lone pairs) using the VSEPR
model
3. Deduce the hybridization of the central atom by
matching the arrangement of the electron pairs with
those of the hybrid orbitals shown in Table 10.4.
Thank you