Covalent Bonding

Chapter 3

“Read in the name your God who created “ )I( Inorganic Chemistry 3 )I( Miftahul Khair, M.Sc (miftah@fmipa.unp.ac.id)
1

http://kimia.unp.ac.id
 2

Jurusan Kimia
Chemistry Department
 1. Models of Covalent Bonding

• The properties of atoms  atomic orbitals, so

the properties of covalent compounds  molecular orbitals.

• An electron in a molecular orbital is the property of the whole

molecule, not of an individual atom.

• Molecular orbital energy levels :

- aspects of chemical bonding that are difficult to comprehend in
terms of the simple Lewis electron-dot representations.

Jurusan Kimia
Chemistry Department
 O2 molecule

• Michael Faraday: oxygen gas is attracted into a magnetic

field  paramagnetic  unpaired electrons .
• Bond strength studies : O2 molecule has a double
bond.

electron-dot diagrams
the ground-state molecular orbital
diagram

4
Jurusan Kimia
Chemistry Department
 2. Introduction to Molecular Orbitals
• When two atoms approach, their atomic orbitals overlap.
• The electrons now belong the molecule as a whole.
• To represent this process, we can combine the two atomic wave
functions to give two molecular orbitals.
• This realistic representation involves the linear combination of atomic
orbitals (LCAO method).

Jurusan Kimia
Chemistry Department
Jurusan Kimia
Chemistry Department
 • Another way to picture the two types of molecular orbitals is to
consider them as wave combinations.
• The overlap of electron wave functions of the constituent atoms in
constructive interference corresponds to a bonding orbital.
Destructive interference, however, corresponds to an antibonding
orbital.

Jurusan Kimia
Chemistry Department
Statements about molecular orbitals:

1. For orbitals to overlap, the signs on the overlapping lobes must be the same.
2. Whenever two atomic orbitals mix, two molecular orbitals are formed : bonding and
antibonding.
3. For significant mixing to occur, the atomic orbitals must be of similar energy.
4. Each molecular orbital can hold a maximum of two electrons, one with spin +1/2 ,
the other -1/2
5. The electron configuration of a molecule can be constructed by using the Aufbau
principle by filling the lowest energy molecular orbitals in sequence.
6. When electrons are placed in different molecular orbitals of equal energy, the parallel
arrangement (Hund’s rule) will have the lowest energy.
7. The bond order in a diatomic molecule is defined as the number of bonding electron
pairs minus the number of antibonding pairs.

8
Jurusan Kimia
Chemistry Department
 3. Molecular Orbitals for Period 1
Diatomic Molecules
Start with the simplest diatomic species H2+

H + H+  H2+ molecular ion.

electron configuration: (σ1s)1

Simultaneous attraction of the electron to two

H nuclei  Energy of the electron σ1s < 1s
Total Bond bond bond strength
e- order length (pm) (kJ/mol) •net reduction in total electron energy is the
1 1/2 106 255 driving force in covalent bond formation.
9

Jurusan Kimia
Chemistry Department
 Hydrogen molecule, H2

H + H  H2

electron configuration: (σ1s)2

Total Bond bond length bond strength The greater the bond order,
e- order (pm) (kJ/mol)
the greater the strength of the bond
2 1 74 436 and the shorter the bond length

Match!

10
Jurusan Kimia
Chemistry Department
 He2+ molecular ion.

He + He+  He2+ molecular ion.

Total Bond bond bond strength

e- order length (pm) (kJ/mol)
1-1/2=
3 108 251
1/2 Weaker bond is confirmed by the bond length
and bond energy, the same as those of the
dihydrogen ion.
electron configuration: (σ1s)2 (σ*1s)1

11

Jurusan Kimia
Chemistry Department
He2 molecule

He + He  He2 molecule.

2 e- decrease in energy while, 2e-increase in energy

by the same quantity.  no net decrease in energy
Total Bond bond bond strength
e- order length (pm) (kJ/mol)
4 1-1= 0 or
net bond order = 0

electron configuration: (σ1s)2 (σ*1s)2

So, no covalent bonding !
12

Jurusan Kimia
Chemistry Department
 4. Molecular Orbitals for Period 2
Diatomic Molecules
• At a new period, the inner (core) e- become irrelevant to the bonding
process.

• Li (2s1) and Be (2s2)

 only construct a molecular orbital energy diagram corresponding to the 2s
atomic orbitals.

• The outermost occupied orbitals /the frontier orbitals  crucial orbitals for
bonding.

• HOMO/highest occupied molecular orbitals  crucial for bonding

• LUMO/ lowest unoccupied molecular orbitals  crucial for reaction.

13

Jurusan Kimia
Chemistry Department
Li2 (g) molecule

Li + Li  Li2 molecule.

Total Bond bond bond strength

e- order length (pm) (kJ/mol)
2 1 OK OK
Occupancy of frontier(valence) molecular orbital : (σ2s)2

14

Jurusan Kimia
Chemistry Department
 Problem : Try Be2 molecule ! Possible ?

15

Jurusan Kimia
Chemistry Department
Heavier Period 2 elements

Formation of molecular orbitals from 2p atomic orbitals, by mixing in two

ways : end to end and side to side :
1.end to end  a pair of bonding and antibonding orbitals σ2p and σ*2p

• σ bond = bond formed by atomic orbital overlap along the axis joining the
two nuclear centers.
• orbitals can only overlap if the signs of the lobes are the same—in this case,
we show positive to positive.
16

Jurusan Kimia
Chemistry Department
 2. Side to side.  the bonding and antibonding molecular orbitals , for
both px and py

every atom has three 2p atomic orbitals 3 bonding and 3

antibonding molecular orbitals.

Jurusan Kimia
Chemistry Department
 Bonding models  explain experimental observations.

the shorter the bond length and the higher the bond energy, the
stronger the bond.

Bond energy (kJ/mol) Bond order

200–300 single bonds,
500–600 double bonds
900–1000 triple bonds

18
Jurusan Kimia
Chemistry Department
The three diatomic molecules N2, O2, and F2

• The bonding and antibonding orbitals formed from both 1s and 2s

atomic orbitals are filled. So,
• No net bonding contribution from these orbitals.
• Only consider the filling of the molecular orbitals derived from the 2p
atomic orbitals.

19

Jurusan Kimia
Chemistry Department
 N2
• At the beginning of the period, the
levels differ in energy by only about
0.2 MJ/mol.
• In these circumstances, the wave
functions for the 2s and 2p orbitals
become mixed.

increase in energy of the σ2p

molecular orbital to the point
where it has greater energy than
the π2p orbital.
electron configuration: (π2p)4
(σ2p)2
This ordering of orbitals applies
to dinitrogen and the preceding
elements in Period 2, the σ- π
crossover occurring between N2
and O2
20
Jurusan Kimia
Chemistry Department
The Period 2 elements beyond N2
Hund’s rule must works,

• two unpaired e-
• bond order

• bond order

21
Jurusan Kimia
Chemistry Department
 3.5 Molecular Orbitals for Heteronuclear
Diatomic Molecules
the same period : Z >, Zeff >  orbital energies <

• the molecular orbitals derived

primarily from the 2s atomic
orbitals of one element overlap
significantly in energy with those
derived from the 2p atomic
orbitals of the other element.

• σNB (nonbonding molecular orbitals) two

molecular orbitals whose energies are
between those of the contributing atomic
orbitals.

22

Jurusan Kimia
Chemistry Department
 23

Jurusan Kimia
Chemistry Department
 Molecular orbital diagrams can also be constructed to
develop bonding schemes for molecules containing more
than two atoms.

But, its better to predict of the shapes of

molecules than orbital energy levels.

24
Jurusan Kimia
Chemistry Department
 A Brief Review of Lewis Structures
Lewis; atoms combine by sharing electron pairs

Molecular orbital  bond length and bond energy in covalent molecules.

Lewis  molecular shape of complex molecules.

Lewis (electron-dot) :
the driving force of bond formation as being the attainment by each
atom in the molecule of an octet of electrons in its outer (valence)
energy level (except hydrogen) , completion of the octet is
accomplished by a sharing of electron pairs between bonded atoms.

25

Jurusan Kimia
Chemistry Department
 Constructing Electron-Dot Diagrams
1. Identify the central atom, (lower electronegativity).
Write the symbol of the central atom and place the symbols of the
other atoms around the central atom.
2. Count the total number of valence electrons.

3. Place an electron pair (single covalent bond) between the

central atom
and each of the surrounding atoms. Add lone pairs to the
surrounding atoms. Then any excess electrons are added to the
central atom.
4. If the number of electrons on the central atom is less than
eight and there are “leftover” electrons, add lone pairs to the
central atom. If the number of electrons on the central atom is
less than eight and there are no more electrons, construct
double and triple bonds using lone pairs from surrounding
atoms.

26

Jurusan Kimia
Chemistry Department
 Exceeding the Octet

< 8 e- or > 8 e- in central atom

the use of d orbitals was invoked to make possible a

theoretical maximum of 18 bonding e-

27

Jurusan Kimia
Chemistry Department
 Partial Bond Order
In some cases, the only structure that can be drawn does not correlate with our
measured bond information

Ex: NO3-

N-O = 122 pm.

N-Otheoritical = 144 pm.

resonance.

average bond order =1 1/3

.

fractional bond order

28

Jurusan Kimia
Chemistry Department
 Formal Charge
In some cases, we can draw more than one feasible electron-dot diagram, one
such example being dinitrogen oxide. Try !

Ex: N2O

asymmetric linear
with a central N atom.

which possibilities are unrealistic formal charge

formal charge :
•divide the bonding e- equally among the
constituent atoms and
•Compare number of assigned electrons for each
atom with its original number of valence e-.
•Any difference  charge sign

29

Jurusan Kimia
Chemistry Department
 the lowest energy structure
will be the one with the smallest formal charges on the atoms

(c) is eliminated
optimum representation= resonance mixture of a and b.

30

Jurusan Kimia
Chemistry Department
 Valence-Shell Electron-Pair Repulsion
Rules
also called the electron domain (ED) model.
repulsions between electron pairs in the
outermost occupied energy levels on a central atom cause those
electron pairs to be located as far from each other as is geometrically
possible

•Electron-dot diagrams can be used to derive the probable molecular

shape.
•use a very simplistic set of rules that tells us nothing about the bonding :
ignore the differences between the energies of
the s, p, and d orbitals and simply regard them as degenerate

•effective at predicting molecular shapes

31

Jurusan Kimia
Chemistry Department
 32

Jurusan Kimia
Chemistry Department
Steps for using VSEPR:

1. Draw a Lewis Dot Structure.

2. Predict the geometry around the central atom.
3. Predict the molecular shape.

… also, we can try and predict the angles between atoms.

Jurusan Kimia
Chemistry Department
All e- pairs push each other as far apart
as possible.
• Shared (bonding) pairs are “stretched” between two atoms
that want them.
• “Longer & Thinner”

• Unshared (non-bonding) pairs are not “stretched.”

• “Shorter & Thicker”

Jurusan Kimia
Chemistry Department
 2 domains on central atom

LINEAR

• 2 domains
• both are bonding pairs

• They push each other to

opposite sides of center
(180 apart).

Jurusan Kimia
Chemistry Department
BeCl2
 3 domains on central atom

TRIGONAL PLANAR

• 3 domains
• all are bonding pairs

• They push each other

apart equally at 120
degrees.

Jurusan Kimia
Chemistry Department
GaF3
 3 domains on central atom

BENT

• 3 domains:
• 2 are bonding pairs
• 1 is a lone pair

• The 2 bonding pairs are

pushed apart by 3rd pair
(not seen)
Jurusan Kimia
Chemistry Department
SnF2
 NOTE:

• The geometry around the

central atom is trigonal
planar.

• The molecular shape is

bent.

Jurusan Kimia
Chemistry Department
SnF2
 4 domains on central atom

TETRAHEDRAL

• 4 domains

• Each repels the other

equally - 109.5 - not the
expected 90.
• Think in 3D.

Jurusan Kimia
Chemistry Department
CH4
 4 e- pairs on central atom

TRIGONAL
PYRAMIDAL

• 4 domains
• 3 bonding pairs
• 1 lone pair

• The thicker, lone pair

forces the others a little bit
closer together (~107.3)
Jurusan Kimia
Chemistry Department
NH3
 Tetrahedral vs. Trigonal pyramidal

Tetrahedral geometry Tetrahedral geometry

around the central atom around the central atom
Tetrahedral Molecular Shape Trigonal Pyramidal Molecular Shape

Jurusan Kimia
Chemistry Department
 Tetrahedral vs. Trigonal pyramidal

On the right, the 4th lone pair, is not seen as part of

the actual molecule, yet affects shape.
If another one of the bonding pairs on “trigonal
pyramidal”
Jurusan Kimia were a lone pair, what is the result?
Chemistry Department
 4 domains on central atom, con’t

BENT

• 4 domains
• 2 bonding pairs
• 2 lone pairs

• The bonds are forced

together still closer
(104.5) by the 2 thick
unshared pairs.
Jurusan Kimia
Chemistry Department
H2O
 Comparing the 2 “bents”…

Both bent molecules are affected by unshared pairs –

Jurusan Kimia 1 pair on the left, 2 on the right.
Chemistry Department
 Other Molecular Geometry

Just for fun, let’s look at some

others that we will not study in
detail in this course…

Note that if there are more than five domains around the
central atom, it must be an exception to the octet rule!

http://kimia.unp.ac.id
 5 e- pairs on central atom

TRIGONAL BIPYRAMIDAL

• 5 shared pairs

• Three pairs are found in

one plane (“equator”) 120
apart; the other two pairs
are at the “poles,” 180
apart, 90 from the
“equator.”
Jurusan Kimia
Chemistry Department
PCl5
 5 e- pairs on central atom

SEE-SAW

• 4 shared pairs & 1

unshared pair

• One of the equator pairs is

unshared & pushes the
other 2 together.
• The 2 poles are pushed
slightly together.
Jurusan Kimia
Chemistry Department
SF4
 5 e- pairs on central atom

T-SHAPED

• 3 shared & 2 unshared

pairs

• 2 of the 3 equator pairs

are unshared.
• All 3 remaining pairs are
pushed together.

Jurusan Kimia
Chemistry Department
ClF3
 5 e- pairs on central atom

LINEAR

• 2 shared & 3 unshared

pairs

• All 3 equator pairs are

unshared. The 2
remaining pairs are forced
to the poles.

Jurusan Kimia
Chemistry Department
XeF2
 5 e- pairs on central atom

5 shared, 0 unshared 4 shared, 1 unshared

Jurusan Kimia
3 shared, 2 unshared
Chemistry Department 2 shared, 3 unshared
 6 e- pairs on central atom

OCTAHEDRAL

• 6 shared pairs

• Each pair repels the others

equally.
• All angles = 90

Now, if one of these

pairs was unshared …
Jurusan Kimia
Chemistry Department
SF6
 6 e- pairs on central atom

SQUARE PYRAMIDAL

• 5 shared pairs & 1

unshared pair

• 4 shared pairs in one

plane; the 5th pair at the
pyramid’s top.

If the pair at the top was

unshared
Jurusan Kimia …
Chemistry Department
IF5
 6 e- pairs on central atom

SQUARE PLANAR

• 4 shared & 2 unshared

pairs

• The 4 shared pairs are in

the same plane; the 2
unshared pairs are 90
from them.

Jurusan Kimia
Chemistry Department
XeF4
 6 e- pairs on central atom

6 shared, 0 unshared 5 shared, 1 unshared

Jurusan Kimia
Chemistry Department 4 shared, 2 unshared
 End of part 1 of 2

55

Jurusan Kimia
Chemistry Department