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CHEMICAL BONDING

IONIC BONDS
COVALENT BONDS
HYDROGEN BONDS
METALLIC BONDS

IONIC BONDING

Ionic Bond
An IONIC BOND is an electrostatic interaction that holds together a
positively charged ion (cation) and a negatively charged ion
(anion). In an ionic bond, one atom loses an electron to another
atom, forming a cation and anion, respectively. And, as
everyone knows, opposites attract.

Formation of NaCl

Sodium chloride
results from ionic
bonding.

In table salt, for example, a valence electron from a sodium


atom is transferred to a chlorine atom, forming Na+ and Cl-.
Because the ions have opposite charges, they are attracted to
each other. The loss of a valence electron and the attraction to
the atom that took it happen simultaneously.

IONIC BONDING

When an atom of a nonmeta


akes one or more electrons
from an atom of a metal
so both atoms end up with
eight valence electrons

IONIC BONDING
IS THE COMPOUND
AN IONIC COMPOUND?
Mg N
METAL

NONMETAL

SUBSCRIPTS

IONIC BOND FORMATION


Non-Metal

Metal

Neutral atoms come near each other.


Electron(s) are transferred from the Metal atom
to the Non-metal atom. They stick together
because of electrostatic forces, like magnets.

IONIC BONDING
Metals will tend to lose electrons
and become

POSITIVE CATIONS
+

Na 11 p
11 e Normal sodium atom

1e -

loses one electron

Na 11 p
10 e to become sodium ion

IONIC BONDING
Nonmetals will tend to gain
electrons and become

NEGATIVE ANIONS
+

Cl 17 p
17 e Normal chlorine atom

1e -

gains an electron

Cl

17 p
18 e -

to become a chloride ion

IONIC BONDING
POLYATOMIC IONS--a group
of atoms that act like one ion

NH4 --ammonium ion


+1

CO3 --carbonate ion


-2

PO4 --phosphate ion


-3

IONIC BONDING
Na

SO
4

SODIUM SULFATE

Properties of Ionic Compounds


Crystalline structure.
A regular repeating
arrangement of ions in the
solid.
Ions are strongly bonded.
Structure is rigid.
High melting points- because of

Crystalline structure
The
POSITIVE
CATIONS
stick to the
NEGATIVE
ANIONS, like
a magnet.

+
+
- - +
+ + - + - +
- + - +

Do they Conduct?
Conducting electricity is allowing
charges to move.
In a solid, the ions are locked in place.
Ionic solids are insulators.
When melted, the ions can move
around.
Melted ionic compounds conduct.
First get them to 800C.
Dissolved in water they conduct.

Ionic solids are brittle

+
+
-

+
+

+
+
-

+
+

Ionic solids are brittle


Strong Repulsion breaks crystal apart.

+
+ - + - +
+ - + - + - +

COVALENT BONDING

Quantum theory of Covalent


Bonds: Valence Bond Theory
The first quantum mechanical model to explain the nature and stability of a
covalent bond was formulated by Heitler and London 1927. This theory
was then modified by Pauling and Slater in 1931. This theory is commonly
known as the Valence-bond theory.

The main postulates of the valence bond theory are:


i.
A covalent bond is formed due to the overlap of the outermost halffilled orbitals of the combining atoms. The strength of the bond is
determined by the extent of overlap.
ii.
The two half-filled orbitals involved in the covalent bond formation
should contain electrons with opposite spins. The two electrons
then move under the influence of both the nuclei.
iii.
The completely-filled orbitals (orbitals containing two paired
electrons) do not take part in the bond formation.

iv.

An s-orbital does not show any preference for direction. The nonspherical orbitals such as, p- and d-orbitals tend to form bonds in
the direction of the maximum overlap, i.e., along the orbital axis.
v.
Between the two orbitals of the same energy, the orbital which is
non-spherical (e.g., p- and d- orbitals forms stronger bonds than the
orbital which is spherically symmetrical, e.g., s-orbital.
vi.
The valence of an element is equal to the number of half-filled
orbitals present in it.
In the valence bond model, the stability of a molecule is explained in
terms of the following types of interactions.
a.
electron - nuclei attractive interactions, i.e., the electrons of one
atom are attracted by the nucleus of the other atom also.
b.
electron - electron repulsive interactions, i.e., electrons of one
atom are repelled by the electrons of the other atom.
c.
nucleus - nucleus repulsive interactions, i.e., nucleus of one atom
is repelled by the nucleus of the other atom.
Various interactions which act between the two atoms are shown in Fig.

The attractive and the repulsive interactions oppose each other. When
the attractive interactions are stronger than the repulsive
interactions, certain amount of energy is released. Due to the
lowering of energy the molecule becomes stable.
Valence Bond Description of Hydrogen Molecule

Chemical Bond and the Valence Bond Theory: The Orbital Overlap
In the beginning, atoms in a molecule were thought to be held by bonds. These
bonds are represented by drawing a small line () between the combining
atoms. Lewis described a chemical bond in terms of pair of electrons shared
by the combining atoms. So, the pair of electrons shared by the two nuclei
may be considered to be a chemical bond. Thus, the line drawn between the
two atoms to represent a chemical bond in the older concept, may be seen as a
shared pair of electrons in the Lewis concept.
Sharing of an electron pair is possible only when the atom are close enough to
overlap their orbitals. Thus, the orbital overlap is necessary for the sharing
of electrons and hence for the bond formation.
TYPES OF OVERLAPPING
Various types of atomic orbital overlap leading to the formation of covalent bond
are:
1. s s overlap .
In this type of overlap, half-filled
s -orbitals of the two combining atoms overlap each other. This is shown in
Fig.

2. s p overlap .
Here a half-filled s -orbital of one atom overlaps with one of the p
-orbitals having only one electron in it. This is shown in Fig

3. pp overlap along the orbital axis. This is called head on, end-on or
end-to-end linear overlap. Here, the overlap of the two half-filled p-orbitals
takes place along the line joining the two nuclei. This is shown in Fig.

4. pp sideways overlap. This is also called lateral overlap. In this types


of overlap, two p-orbitals overlap each other along a line
perpendicular to the internuclear axis, i.e., the two overlapping porbitals are parallel to each other. This is shown in Fig.

TYPES OF COVALENT BONDS: SIGMA () AND PI () BONDS


The overlapping of orbitals is possible in two ways.
(i) along their orbital axis so that the electron density along the axis is
maximum.
(ii) along a direction perpendicular to the bond axis due to sideways
overlap of the orbitals.
Depending upon the manner in which the two atomic orbitals overlap
with each other, two types of bonds are formed. These are called, sigma
() bond, and pi () bond.

A covalent bond formed due to the overlap of orbitals of the two atoms
along the line joining the two nuclei (orbital axis) is called sigma ( )
bond. For example, the bond formed due to s-s and s-p, and p-p
overlap along the orbital axis are sigma bonds, (by convention Z-axis
is taken as inter-nuclear axis.

A covalent bond formed between the two atoms due to the sideways
overlap of their p -orbitals is called a pi ( ) bond

COVALENT BONDING

When an atom of one


nonmetal
shares one or more
electrons
with an atom of
another
nonmetal so both
atoms

COVALENT BOND
FORMATION

When one nonmetal shares one or


more electrons with an atom of
another nonmetal so both atoms
end up with eight valence
electrons

COVALENT BONDING
IS THE COMPOUND
A COVALENT COMPOUND?
CO
NONMETAL

NONMETAL

2
YES since it is made of only nonmetal elements

Covalent bonding
Fluorine has seven valence electrons

Covalent bonding
Fluorine has seven valence electrons
A second atom also has seven

Covalent bonding
Fluorine has seven valence electrons
A second atom also has seven
By sharing electrons

Covalent bonding
Fluorine has seven valence electrons
A second atom also has seven
By sharing electrons

Covalent bonding
Fluorine has seven valence electrons
A second atom also has seven
By sharing electrons

F F

Covalent bonding
Fluorine has seven valence electrons
A second atom also has seven
By sharing electrons

F F

Covalent bonding
Fluorine has seven valence electrons
A second atom also has seven
By sharing electrons

F F

Covalent bonding
Fluorine has seven valence electrons
A second atom also has seven
By sharing electrons
Both end with full orbitals

F F

Covalent bonding
Fluorine has seven valence electrons
A second atom also has seven
By sharing electrons
Both end with full orbitals

F F

8 Valence
electrons

Covalent bonding
Fluorine has seven valence electrons
A second atom also has seven
By sharing electrons
Both end with full orbitals

8 Valence
electrons

F F

Single Covalent Bond


A sharing of two valence electrons.
Only nonmetals and Hydrogen.
Different from an ionic bond because they
actually form molecules.
Two specific atoms are joined.
In an ionic solid you cant tell which atom
the electrons moved from or to.

Water

H
O

Each hydrogen has 1 valence


electron
Each hydrogen wants 1 more
The oxygen has 6 valence
electrons
The oxygen wants 2 more
They share to make each other
happy

Water
Put the pieces together
The first hydrogen is happy
The oxygen still wants one more

HO

Water
The second hydrogen attaches
Every atom has full energy levels

HO
H

Hydrogen Bonding
If a hydrogen atom is bonded to a highly electronegative element such as
fluorine, oxygen, nitrogen, then the shared pair of electrons lies more
towards the electronegative element. This leads to a polarity in the
bond in such a way that a slight positive charge gets developed on Hatom, viz.,
H+ : O H+ : F H+ : N
This positive charge on hydrogen can exert electrostatic attraction on the
negatively charged electronegative atom of the same or the other
molecule forming a bridge-like structure such as
X H+ Y H+
where X and Y are the atoms of strongly electronegative elements.
The bond between the hydrogen atom of one molecule and a more
electronegative atom of the same or another molecule is called
hydrogen bond.

A hydrogen bond is shown by a dotted line (.....).


Hydrogen bond is not a covalent bond as the 1s orbital of hydrogen is
already completed, and the 2s level is high up in its energy.
Conditions Necessary For the Formation of Hydrogen Bond
Hydrogen bond is formed only when the following conditions are
satisfied. (i) Only the molecules in which hydrogen atoms is linked to
an atom of highly electro-negative element, are capable of forming
hydrogen bonds.
(ii) The atom of the highly electronegative element should be small.
These conditions are met by fluorine, oxygen and nitrogen atoms. As a
results, all compounds containing hydrogen atom linked to an
atom of either N, O, or F exhibit hydrogen bonding.
Some Typical Compounds Showing Hydrogen Bonding
Hydrogen fluoride (HF).

Water (H2O).

Ice (H2O(s)).
Each Oxygen is "linked" in by a combination of a covalent bond and a
hydrogen bond to 4 other Oxygens.

Notice that each Oxygen can be linked to Hydrogen in one of two ways.

Or

Types of Hydrogen Bonding


There are two types of hydrogen bonding, viz.,
(a) Intermolecular hydrogen bonding (b) Intermolecular hydrogen
bonding
When the hydrogen bonding is between the H-atom of one molecule
and an atom of the electronegative element of another molecule, it is
termed as intermolecular hydrogen bonding. For example, hydrogen
bonding in water, ammonia etc., is intermolecular hydrogen bonding.

The intramolecular hydrogen bonding is between the hydrogen of one


functional group, and the electronegative atom of the adjacent
functional group in the same molecule. For example, the molecule of
o-nitrophenol, shows intramolecular hydrogen bonding. The pnitrophenol shows intermolecular hydrogen bonding.

Carbon dioxide

C
O

CO2 - Carbon is central atom (


I have to tell you)
Carbon has 4 valence
electrons
Wants 4 more
Oxygen has 6 valence
electrons
Wants 2 more

Carbon dioxide
Attaching 1 oxygen leaves the oxygen 1
short and the carbon 3 short

CO

Carbon dioxide

Attaching the second oxygen leaves


both oxygen 1 short and the carbon 2
short

OC O

Carbon dioxide

The only solution is to share more

O CO

Carbon dioxide

The only solution is to share more

O CO

Carbon dioxide

The only solution is to share more

O CO

Carbon dioxide

The only solution is to share more

O C O

Carbon dioxide

The only solution is to share more

O C O

Carbon dioxide

The only solution is to share more

O C O

Carbon dioxide
The only solution is to share more
Requires two double bonds
Each atom gets to count all the atoms
in the bond

O C O

Carbon dioxide
The only solution is to share more
Requires two double bonds
Each atom gets to count all the atoms
in the bond
8 valence
electrons

O C O

Carbon dioxide
The only solution is to share more
Requires two double bonds
Each atom gets to count all the atoms
in the bond
8 valence
electrons

O C O

Carbon dioxide
The only solution is to share more
Requires two double bonds
Each atom gets to count all the atoms
in the bond
8 valence
electrons

O C O

How to draw them


Add up all the valence electrons.
Count up the total number of electrons to
make all atoms happy.
Subtract.
Divide by 2
Tells you how many bonds - draw them.
Fill in the rest of the valence electrons to fill
atoms up.

Examples

HCN C is central atom


N - has 5 valence electrons wants 8
C - has 4 valence electrons wants 8
H - has 1 valence electrons wants 2

HCN has 5+4+1 = 10


HCN wants 8+8+2 = 18
(18-10)/2= 4 bonds
3 atoms with 4 bonds -will require multiple bonds
- not to H

HCN
Put in single bonds
Need 2 more bonds
Must go between C and N

HC N

HCN
Put in single bonds
Need 2 more bonds
Must go between C and N
Uses 8 electrons - 2 more to add

HC N

HCN
Put in single bonds
Need 2 more bonds
Must go between C and N
Uses 8 electrons - 2 more to add
Must go on N to fill octet

HC N

Polar Bonds
When the atoms in a bond are the same, the
electrons are shared equally.
This is a nonpolar covalent bond.
When two different atoms are connected,
the atoms may not be shared equally.
This is a polar covalent bond.
How do we measure how strong the atoms
pull on electrons?

Electronegativity
A measure of how strongly the atoms attract
electrons in a bond.
The bigger the electronegativity difference
the more polar the bond.
0.0 - 0.3 Covalent nonpolar
0.3 - 1.67 Covalent polar
>1.67 Ionic

How to show a bond is polar

Isnt a whole charge just a partial charge


means a partially positive
means a partially negative

The Cl pulls harder on the electrons


H
Cl
The electrons spend more time near the Cl

Polar Molecules
Molecules with ends

Polar Molecules
Molecules with a positive and a negative end
Requires two things to be true
The molecule must contain polar bonds
This can be determined from differences in
electronegativity.
Symmetry can not cancel out the effects of the
polar bonds.
Must determine geometry first.

Is it polar?
HF
H2O
NH3
CCl4
CO

Intermolecular Forces
What holds molecules to each other

Intermolecular Forces
They are what make solid and liquid molecular
compounds possible.
The weakest are called van der Waals forces there are two kinds
Dispersion forces
Dipole Interactions
depend on the number of electrons
more electrons stronger forces
Bigger molecules

Dipole interactions
Depend on the number of electrons
More electrons stronger forces
Bigger molecules more electrons

Fluorine is a gas
Bromine is a liquid
Iodine is a solid

Dipole interactions
Occur when polar molecules are attracted to
each other.
Slightly stronger than dispersion forces.
Opposites attract but not completely hooked
like in ionic solids.

Dipole interactions
Occur when polar molecules are attracted to
each other.
Slightly stronger than dispersion forces.
Opposites attract but not completely hooked
like in ionic solids.


HF


HF

Dipole Interactions

Hydrogen bonding
Are the attractive force caused by hydrogen
bonded to F, O, or N.
F, O, and N are very electronegative so it is
a very strong dipole.
The hydrogen partially share with the lone
pair in the molecule next to it.
The strongest of the intermolecular forces.

Hydrogen Bonding

H
+

+ H O
H +

H
H

H O
H

H
H

H O
H
H O

O
H

Hydrogen bonding

MOLECULAR
SHAPES
OF
COVALENT
COMPOUNDS

VSepR tHEORY
ALENCE

VSEPR

HELL
LECTRON
AIR
EPULSION

What Vsepr
means

Since electrons do not like each


other, because of their negative
charges, they orient themselves
as far apart as possible, from
each other.
This leads to molecules having
specific shapes.

Things to
remember
Atoms bond to form an Octet
(8 outer electrons/full outer
energy level)
Bonded electrons take up less
space then unbonded/unshared pairs of

HERE ARE
THE
RESULTING
MOLECULAR
SHAPES

Linear
EXAMPLE:

BeF2
Number of Bonds = 2
Number of Shared Pairs of Electrons = 2
Bond Angle = 180

Trigonal Planar
EXAMPLE:

GaF3
Number of Bonds = 3
Number of Shared Pairs of Electrons = 3
Number of Unshared Pairs of Electrons = 0
Bond Angle = 120

Bent #1
EXAMPLE:

H2O
Number of Bonds = 2
Number of Shared Pairs of Electrons = 2
Number of Unshared Pairs of Electrons = 2
Bond Angle = < 120

Bent #2
EXAMPLE:

O3
Number of Bonds = 2
Number of Shared Pairs of Electrons = 2
Number of Unshared Pairs of Electrons = 1
Bond Angle = >120

Tetrahedral
EXAMPLE:

CH4
Number of Bonds = 4
Number of Shared Pairs of Electrons = 4
Number of Unshared Pairs of Electrons = 0
Bond Angle = 109.5

Trigonal Pyramidal
EXAMPLE:

NH3
Number of Bonds = 3
Number of Shared Pairs of Electrons = 4
Number of Unshared Pairs of Electrons = 1
Bond Angle = <109.5

Trigonal bIPyramidal
EXAMPLE:

NbF5
Number of Bonds = 5
Number of Shared Pairs of Electrons = 5
Number of Unshared Pairs of Electrons = 0
Bond Angle = <120

OCTAHEDRAL
EXAMPLE:

SF6
Number of Bonds = 6
Number of Shared Pairs of Electrons = 6
Number of Unshared Pairs of Electrons = 1
Bond Angle = 90

Metallic Bonds
How atoms are held together in
the solid.
Metals hold onto there valence
electrons very weakly.
Think of them as positive ions
floating in a sea of electrons.

Sea of Electrons
Electrons are free to move through the
solid.
Metals conduct electricity.

+ + +
+ + + +
+ + + +

Metals are Malleable

Hammered into shape


(bend).
Ductile - drawn into
wires.

Malleable

+ + +
+ + + +
+ + + +

Malleable
Electrons allow atoms to slide by.
+ + + +
+ + + +
+ + + +

Sub Topic 6:

Molecular Orbital Theory


Molecular orbital theory was put forward by R.S. Mulliken to explain the nature
of bonding in
the molecules of covalent compounds. Mulliken was awarded Nobel Prize for
Chemistry in 1966.
Major postulates of the theory are:
(i) The wavefunction of an electron in a molecule is called molecular orbital
(MO). The
molecular orbital surrounds all the nuclei in the molecule, i.e., MOs are
polycentric.
(ii) The atomic orbitals (AOs) of nearly equal energy, and appropriate symmetry
combine to
give equal number of MOs. The MOs are constructed by the linear combination
of the atomic
orbitals (LCAO method).
(iii) MO of lower energy is called bonding molecular orbital b ), while that of
higher energy
as antibonding molecular orbital a ),

(v) The electrons of the constituent atoms of a molecule are distributed over all the
available
MOs in accordance with the Aufbau principle, the Pauli's exclusion principle and
Hunds rule.
(vi) Like atomic orbitals (AOs), the molecular orbitals can also be arranged
according to their energies. The internuclear axis is taken to be in the z-direction.
For the molecule or molecular ions formed from Li, Be, B, C, and N, the energies
of 2s and 2p orbitals are quite close to each other. Because of the repulsion
between the electrons that occupy 2s and 2p orbitals, the energy of the 2p
molecular orbital gets raised. Relative to 2p orbitals.

Splitting patterns for the second row Diatomic

If we combine the splitting


schemes for the 2s and 2p orbitals, we
can predict bond order in all of the
diatomic molecules and ions
composed of elements in the first
complete row of the periodic table.
Remember that only the valence
orbitals of the atoms need be
considered.

One minor complication that you should be aware of is that


the relative energies of the and bonding molecular
orbitals are reversed in some of the second-row diatomics.

The presence of one or more unpaired electrons accounts for the paramagnetic
nature of the molecule. The electronic configuration in which all the
electrons are paired indicate the diamagnetic nature of the species.
The strength of a chemical bond is described in terms of a parameter called bond
order.
As per definition, the bond order is expressed as,
Bond order = (No. of electrons in BMO-No. of electrons in ABMO)/2=(Nb-Na)/2
where, N b is the total number of electrons in bonding MOs.
N a is the total number of electrons in antibonding MOs.
(a)
When, N b > N a : Bond order > 0 (+ ve). Then, a stable bond formation is
indicated.
(b)
When, N b N a : Bond order 0. Then, the bond is unstable. In fact. such a
bond is not formed.
Conditions For the Formation of MOs From the Atomic Orbitals
Formation of MOs by the combination of atomic orbitals takes place only if the
following conditions are satisfied:
(i) The combining atomic orbitals should have nearly equal energies. Only the
atomic orbitals of nearly the same energy combine to form MOs. For
example, 1s atomic orbitals of two atoms can combine to form one bonding
1s ) and one antibonding * 1s ) orbitals. The 1s atomic orbital of one
atom cannot combine with 2s or 2p atomic orbital of the other atom.

(ii) The combining atomic orbitals should have the same symmetry.
The atomic orbitals are oriented in space. Only those atomic orbitals
can combine to form molecular orbitals which have the same
symmetry about the molecular axis. For example, a p x orbital of an
atom can combine with a p x orbital of another atom. A p x orbital
cannot combine with a p z orbital.
(iii) The combining atomic orbitals should overlap effectively. MOs
are formed only if the combining atomic orbitals overlap to a
reasonable extent.
In-phase and out-of-phase wave combinations
Matter waves corresponding to the two separate hydrogen 1s orbitals
interact; both in-phase and out-of-phase combinations are possible,
and both occur. One of the resultants is the bonding orbital that we just
considered. The other, corresponding to out-of-phase combination of
the two orbitals, gives rise to a molecular orbital that has its greatest
electron probability in what is clearly the antibonding region of space.
This second orbital is therefore called an antibonding orbital.

Dicarbon

Dioxygen

Types of Hybridisation
Depending upon the nature of the orbitals involved in
hybridisation, different types of hybridisation
become possible. The type of hybridisation shown by
an atom depends upon the requirements of the
reaction.

sp3 (es pee three) hybridisation. In any atom,


corresponding to energy levels (or shells) for which n
2, there is one s orbital and three p orbitals. For
example, for n = 2, we have one 2s and three 2p
orbitals; for n = 3, we have one 3s, and three 3p
orbitals. These four orbitals undergo mixing to
provide four new hybrid orbitals.
s
+
(px + py + pz)

sp3
one s-orbital
three p-orbitals
four hybrid
orbitals

Hybridisation sp3 , geometry


tetrahedral, bond angle 109.5

sp2 (ess pee two) hybridisation. In certain reactions, one s and two p
(say px and py) orbitals of an atom undergo mixing to produce three
equivalent sp2 hybridised orbitals. The three sp2 hybrid orbitals are
oriented in a plane along the three corners of an equilateral triangle,
i.e., they are inclined to each other at an angle of 120. The third porbital (say pz here) remains unchanged. Each hybrid orbital has
33.3% s-character and 66.7% p-character. Formation of sp2-hybrid
orbitals from one s and two p-orbitals is shown in Fig. 6.43.
s + (px + py) sp2
one s-orbital two p-orbitals three hybrid orbitals

Boron trifluoride has a plane trigonal shape


in which all three bonds are identical.

Hybridisation sp2 , geometry trigonal planar, bond angle 120

sp (ess-pee) hybridisation. In this type of hybridisation, one s and one


p (say pz) orbitals belonging to the same main energy level hybridise to
give two sp hybrid orbitals. These sp hybrid orbitals are oriented at an
angle of 180 to each other. Each hybrid orbital has 50% s- and 50%
p- character. The other two p-orbitals (say 2px and 2py) remain
unhybridised and are oriented at right angles to each other and to the
internuclear axis.

Hybridisation sp , geometry Linear, bond angle 180

Formation of ethene molecule.

Formation of ethyne (acetylene) molecule.

THE
END