CHEMICAL BONDING II

Alvan F. Shalas, M.Farm., Apt

 INTRODUCTION
• Two theories go hand in hand in a discussion of covalent bonding.
• The valence shell electron pair repulsion (VSEPR) theory helps us to
predict the spatial arrangement of atoms in a polyatomic molecule or
ion.
• VSEPR does not, however, explain how bonding occurs, just where it
occurs and where lone (unshared) pairs of valence shell electrons are
directed.
• The valence bond (VB) theory describes how the bonding takes place,
in terms of overlapping atomic orbitals.
 Valence Shell Electron Pair Repulsion Theory
(VSEPR)
The basic ideas :
• Each region of high electron density in the valence shell of a central
atom is significant. Such a region is referred to as an electron group.
• The groups of valence shell electrons on the central atom repel one
another.
• They are arranged about the central atom so that the repulsions
among them are as small as possible.
• This results in maximum separation of the electron groups about the
central atom.
 Valence Shell Electron Pair Repulsion Theory
(VSEPR)
1. Each bonded atom is counted
as one electron group for VSEPR,
regardless of whether the
bonding is single, double, or
triple.
2. Each lone pair of valence
electrons on the central atom is
counted as one electron group
for VSEPR.
Valence Shell Electron Pair Repulsion Theory
(VSEPR)

According to VSEPR theory

“The molecule or ion is most stable when the electron groups on the
central atom are as far apart as possible”

• The arrangement of these electron groups around the central atom is

referred to as the electronic geometry of the central atom.
• The arrangement of atoms around the central atom, which is based on
electronic geometry, is called the molecular geometry
 Valence Shell Electron Pair Repulsion Theory
(VSEPR)
The electronic geometry
 Valence Shell Electron Pair Repulsion Theory
(VSEPR)
The electronic geometry
 Polar Molecules:
The Influence of Molecular Geometry
• Molecular shapes play a crucial
role in determining molecular
dipole moments
• We can view each bond dipole
as an electronic vector, with a
magnitude and a direction
 Polar Molecules:
The Influence of Molecular Geometry
 Valence Bond Theory
• The basic idea :

• Covalent bonding s described as electron pair sharing that results from the overlap of
orbitals from two atoms.

• Valence bond (VB) theory describes how bonding occurs.

• The VSEPR theory is used to describe the orientations of the electron groups.
• The VB theory is used to describe the atomic orbitals that overlap to produce the
bonding with that geometry.
• We also assume that each lone pair occupies a separate orbital.
• Thus, the two theories work together to give a fuller description of the bonding.
 Molecular Shapes and Bonding
1. AB2 Species (No Lone Pairs on A)
(BeCl2, BeBr2, and BeI2 ,CdX2 ,HgX2, CO2)

A. Experimental Facts and Lewis Formulas

• These compounds are known to be linear (bond angle5180˚), nonpolar, covalent compounds
• Experimentally the Be-Cl bonds are identical in bond length and strength
 Molecular Shapes and Bonding
B. VSEPR Theory
• VSEPR theory places the two electron pairs on Be
180° apart  linear electronic geometry.
• Both electron pairs are bonding pairs, so VSEPR
also predicts a linear atomic arrangement, or
linear molecular geometry, for BeCl2.
• If we examine the bond dipoles, we see that the
electronegativity difference is large (1.5 units)
and each bond is quite polar
• The two bond dipoles are equal in magnitude and
opposite in direction. They therefore cancel to
give a nonpolar molecule
 Molecular Shapes and Bonding
C. Valence Bond Theory

How will a Be atom bond to two Cl atoms?

• The Be atom must somehow make available one orbital for each
bonding Cl electron (the unpaired p electrons)
• The Be 2s and 2p orbitals could not overlap a Cl 3p orbital with
equal effectiveness
 Molecular Shapes and Bonding
C. Valence Bond Theory

• They must hybridize to give two new

orbitals that reflect the equal
contribution of the s and p orbitals.
These are called sp hybrid orbitals
• An atom can combine its valence shell
orbitals to form a new set of orbitals
that is at a lower total energy in the
presence of the other atoms than the
pure atomic orbitals would be.
• This process is called hybridization, and
the new orbitals that are formed are
called hybrid orbitals
 Molecular Shapes and Bonding
C. Valence Bond Theory
• There is one electron in each of these
hybrid orbitals on the Be atom.
• Recall that each Cl atom has a half-
filled 3p orbital that can overlap with
a half-filled sp hybrid of Be.
 Molecular Shapes and Bonding
2. Trigonal Planar Electronic Geometry: AB3 Species (No Lone Pairs on A)
(BF3, BCl3,, BBr3, BI3, H2C=O (formaldehyde)

A. Experimental Facts and Lewis

Formulas
• Boron is a Group 3A element that forms
many covalent compounds by bonding Formaldehyde BF3 (boron trifluoride)
to three other atoms
 Molecular Shapes and Bonding
B. VSEPR Theory
• Boron, the central atom, has three electron groups
(three bonded atoms, no lone pairs on B).
• The VSEPR theory predicts trigonal planar electronic
geometry for molecules such as BF3 because this
structure gives maximum separation among the three
electron groups.
• There are no lone pairs of electrons associated with
the boron atom, so a fluorine atom is at each corner
of the equilateral triangle, and the molecular
geometry is also trigonal planar.
• All four atoms are in the same plane
• The three bond dipoles are symmetrically distributed,
so they cancel to give a nonpolar molecule
BF3 (boron trifluoride)
 Molecular Shapes and Bonding
B. VSEPR Theory

Formalde
hyde
 Molecular Shapes and Bonding

C. Valence Bond Theory

• The 2s orbital and two of the 2p
orbitals of B hybridize to form a set of
three equivalent sp2 hybrid orbitals
 Molecular Shapes and Bonding
C. Valence Bond Theory
• The B atom supplies one electron in each of these
hybrid orbitals.
• Each of the three F atoms has a 2p orbital with
one unpaired electron.
• The 2p orbitals can overlap the three sp2 hybrid
orbitals on B
 Molecular Shapes and Bonding
3. Tetrahedral Electronic Geometry: AB4 Species (No Lone Pairs on A)
CH4, CF4,CCl4, SiH4, and SiF4

A. Experimental Facts and Lewis Formulas

• All are tetrahedral, nonpolar molecules (bond angles
= 109.5°).
• In each, the Group 4A atom is located in the center
of a regular tetrahedron.
• The other four atoms are located at the four corners
of the tetrahedron.
• The Group 4A atom contributes four electrons to the
bonding in a tetrahedral AB4 molecule, and the other
four atoms contribute one electron each.
 Molecular Shapes and Bonding
B. VSEPR Theory
• VSEPR theory predicts tetrahedral
electronic geometry for an AB4 molecule
that has no unshared electrons on A.
• There are no lone pairs of electrons on the
central atom, so another atom is at each
corner of the tetrahedron.
• VSEPR theory predicts a tetrahedral
molecular geometry for each of these
molecules
 Molecular Shapes and Bonding
B. VSEPR Theory
• Examination of bond dipoles shows that in CH 4
the individual bonds are only slightly polar,
whereas in CF4 the bonds are quite polar.
• In CH4 the bond dipoles are directed toward
carbon, but in CF4 they are directed away from
carbon.
• Both molecules are very symmetrical, so the
bond dipoles cancel, and both molecules are
nonpolar.
• This is true for all AB4 molecules in which
there are no unshared electron pairs on the
central element and all four B atoms are
identical.
 Molecular Shapes and Bonding
C. Valence Bond Theory
• According to VB theory, each Group
4A atom (ex: C) must make four
equivalent orbitals available for
bonding.
• To do this, C forms four sp3 hybrid
orbitals by mixing the s and all three
p orbitals in its outer (n = 2) shell
 Molecular Shapes and Bonding
C. Valence Bond Theory
• Each of the four atoms that bond to C has a
half-filled atomic orbital; these can overlap
the half-filled sp3 hybrid orbitals on C
Molecular Shapes and Bonding
Molecular Shapes and Bonding
Molecular Shapes and Bonding
 Molecular Shapes and Bonding
Compounds Containing Double Bonds

• Each atom has three electron groups.

The VSEPR theory tells us that each C
atom is at the center of a trigonal plane.
• Valence bond theory describes each
doubly bonded carbon atom as sp2
hybridized, with one electron in each
sp2 hybrid orbital and one electron in
the unhybridized 2p orbital
 Molecular Shapes and Bonding
Compounds Containing Double Bonds
• The two C atoms interact by head-on (end-to-
end) overlap of sp2 hybrids pointing toward
each other to form a sigma (σ) bond and by
side-on overlap of the unhybridized 2p orbitals
to form a pi (π) bond.
• A sigma bond is a bond resulting from head-on
overlap of atomic orbitals. The region of
electron sharing is along and cylindrically
around an imaginary line connecting the
bonded atoms
• A pi bond is a bond resulting from side-on
overlap of atomic orbitals. The regions of
electron sharing are on opposite sides of an
imaginary line connecting the bonded atoms
and parallel to this line.
 Molecular Shapes and Bonding
Compounds Containing Double Bonds

“A double bond consists of one sigma bond

and one pi bond”
 Molecular Shapes and Bonding
Compounds Containing Triple Bonds

“A triple bond consists of one sigma bond

and two pi bonds”
 Molecular Orbital Theory
• Valence bond and molecular orbital theories are alternative
descriptions of chemical bonding. They have strengths and
weaknesses, so they are complementary.
• Valence bond theory is descriptively attractive, and it lends itself well
to visualization.
• Molecular orbital theory gives better descriptions of electron cloud
distributions, bond energies, and magnetic properties, but its results
are not as easy to visualize.
 Molecular Orbital Theory
Molecular Orbital Theory :

“The combination of atomic orbitals on different atoms forms

molecular orbitals (MOs), so that electrons in them belong to the
molecule as a whole”
 Molecular Orbital Theory
Each solution to the Schrödinger equation, called a wave
function, represents an atomic orbital.

Y = A sin (2t+ )
A = Amplitude
f = phase angle
w = angular frequency = 2pn

MATHEMATICAL DESCRIPTION OF A WAVE

 Molecular Orbital Theory

• When waves are combined, they may

interact either constructively or destructively.
• Likewise, when two atomic orbitals overlap,
they can be in phase or out of phase
 Molecular Orbital Theory
• The overlap of two atomic orbitals always produces
two MOs: one bonding and one antibonding.
• When they overlap in phase, constructive
interaction occurs in the region between the
nuclei, and a bonding molecular orbital is
produced. The energy of the bonding orbital is
always lower (more stable) than the energies of the
combining orbitals.
• When the orbitals overlap out of phase, destructive
interaction reduces the probability of finding
electrons in the region between the nuclei, and an
antibonding molecular orbital is produced. This is
higher in energy (less stable) than the original
atomic orbitals, leading to a repulsion between the
two atoms.
 Molecular Orbital Theory
• In a bonding molecular orbital,
the electron density is high
between the two atoms, where
it stabilizes the arrangement by
attracting both nuclei.
• By contrast, an antibonding
orbital has a node (a region of
zero electron density) between
the nuclei; this allows the nuclei
to repel one another more
strongly, which makes the
arrangement less stable.
Molecular Orbital Theory
 Delocalization and the Shapes
of Molecular Orbitals
Alternative representations of the bonding in
the carbonate ion, CO3 2- :
(a) Lewis formulas of the three valence bond
resonance structures.
(b) Representation of the p orbital overlap in
the valence bond resonance structures. In
each resonance form, the p orbitals on two
atoms would overlap to form the p
components of the hypothetical double
bonds. Each O atom has two additional sp2
orbitals (not shown) in the plane of the
nuclei. Each of these additional sp2 orbitals
contains an oxygen unshared pair.
 Delocalization and the Shapes
of Molecular Orbitals
(c) In the MO description, the
electrons in the p-bonded region
are spread out, or delocalized, over
all four atoms of the CO 2- ion. This
3

MO description is more consistent

with the experimental observation
of equal bond lengths and energies
than are the valence bond pictures
in parts (a) and (b).
TERIMA KASIH