CHEMICAL BONDING

4.1 Lewis Structure

Gilbert Newton Lewis

(1875–1946). American chemist.
Lewis made many important
contributions in the areas of
chemical bonding,
thermodynamics, acids and
bases, and spectroscopy.

Copyright ® aludinmohdserah
 KEYWORDS

Lewis dot symbol octet rule

Lewis structure

stability of electron configuration

covalent bond ionic bond

bond length formal charges

resonance structure
 5.1-05
TYPES OF CHEMICAL BONDING

Metal with non–metal:

Electron transfer and ionic bonding

Metal atom (low IE) loses it valence electrons,

non–metal (high negative EA) gains electrons
 5.1-06

Non–metal with non–metal:

Electron sharing and covalent bonding

A shared electron pair is considered to be

localized between the two atoms
 5.1-07

Metal with metal:

Electron pooling and metallic bonding

Electron–sea model
e- e- e- e- e-

e- e-
e- e- e-

e- e- e- e-
e-
e- e-
e- e- e- e-
e-
e- e-
 5.1-08

Fig. 9.2
 EXAMPLE – 01 5.1

State the type of bonding – ionic, covalent, or

metallic – you would expect in:
a) CsF(s)
b) N2(g)
c) Na(s)
d) ICl3(g)
e) N2O(g)
f) LiCl(s)
 5.1-09
LEWIS ELECTRON–DOT SYMBOLS

Element symbol represent nucleus and inner

electron and the surrounding dots represent
valence electrons

Valence electron: involved in chemical bonding

EXAMPLE:

•• ••
• Na •N • • Cl •
• • ••

Gilbert Newton Lewis (1875 – 1946). American chemist.

 5.1-10
GILBERT NEWTON LEWIS
 5.1-11

RELATIONSHIP BETWEEN
GROUP AND VALENCE ELECTRON
valence e-
Group configuration No. of valence e-
1 ns1 1
2 ns2 2
13 ns2 np1 3
14 ns2 np2 4
15 ns2 np3 5
16 ns2 np4 6
17 ns2 np5 7
5.1-12
 5.1-13
HOW TO WRITE LEWIS SYMBOLS

EXAMPLE:
valence electrons
N (Z = 7 )
Electron configuration: 1s2 2s2 2p3

Identify the number of valence electrons

Place one dot at a time on the four side

(top, right, bottom, left) of the element ••
symbol •N •
Pair up the dots until all are used •
 5.1-15

Lewis symbols do not show the electron configuration

of the valence electrons!

valence electrons
Example:
C (Z = 6 )

1s 2s 2p
Electron configuration: 1s2 2s2 2p2

•• •
•C • •C • correct

•
C has four unpaired dots because it form four bonds
 5.1-16
INFORMATION FROM LEWIS SYMBOLS

Element in the same group

 similar outer electron configuration
 similar Lewis dot symbol
 5.1-18

EXAMPLE:

•Na
Na loses one electron to form Na+ (+1 charge)

••
•N•
•
N gains three electrons to form N3– (–3 charge)
N can form three covalent bonds

••
••Cl•
••
Cl gains one electron to form Cl– (–1 charge).
Cl can form one covalent bond
 5.1-19
OCTET RULE

An atom other than H tends to form bonds

(by losing or gaining or sharing electrons)
until it is surrounded by eight valence electrons
The rule works mainly for elements in Period 2
 5.1-23
ELECTRON CONFIGURATION OF IONS

Stable configuration:
Noble gas configuration
Example: 1s2 2s2 2p6

Pseudonoble gas configuration

Example: [Kr]4d10

Half–filled orbitals
Example: 3d5
 5.1-24
NOBLE GAS CONFIGURATION
Atoms may lose or gain enough electrons
so as to forms stable ion with octet (or duplet)
configuration  ns2 np6
EXAMPLE:
Na• Na+ + e–
1s2 2s2 2p6 3s1 1s2 2s2 2p6 = [Ne]

••
••Cl •••–
••Cl
• + e–
•• •••
1s2 2s2 2p6 3s2 3p5 1s2 2s2 2p6 3s2 3p6
= [Ar]
 5.1-26
PSEUDO–NOBLE GAS CONFIGURATION

The (n–1)d10 configuration of a p–block metal

atom that empties its outer level

EXAMPLE:
•
• Sn • Sn4+ + 4e–
•
[Kr]4d10 5s2 5p2 [Kr]4d10
 5.1-27
HALF–FILLED ORBITALS

Some transition metal atoms form cations that

have electron configuration associated with
half–filled d orbital (d5)

EXAMPLE: Mn → Mn2+ + 2e–

3d 4s
[Ar] 3d5 4s2

3d 4s
[Ar] 3d5
 EXAMPLE – 07 5.1

What type of stability of the electron configuration of

ion Fe3+. Note: Fe (Z = 26)
Fe (Z = 26)
Electron configuration:
Is2 2s2 2p6 3s2 3p6 4s2 3d6
or Is2 2s2 2p6 3s2 3p6 3d6 4s2 = [Ar]3d6 4s2

Fe3+

Electron configuration:
Is2 2s2 2p6 3s2 3p6 3d5 = [Ar]3d5

 Type of stability = half–filled d orbital

 5.1-28
IONIC BOND
➢ Is an electrostatic force attraction between positive & negative ions of an
ionic compound.

Sometimes called electrovalent bond

 5.1-29
FORMATION OF IONIC BONDS
a bond in which involve the transfer of electron(s)
EXAMPLE:

Li Li+ + e
-
1s22s1 1s2
-
e + F F –

1s22s22p5 1s22s22p6

Li+ + F – Li+ F –

Total number of electrons lost by metal atoms

= Total number of electrons gained by the
nonmetal atoms
 5.1-32
Lewis electron–dot symbol
EXAMPLE:

+  -
●●


●F ● F


Li ● + Li
●● ●


Formation of CaO

 2+
 2-



 Ca + O Ca O



 

Formation of Al2O3




O


Al 

3+  2-

 2 Al 3 O



+


O


 

Al  


O


 
 5.1-35
COVALENT BOND
Bond in which two electrons are shared by
two atoms
EXAMPLE:

covalent bond

H—H

●● ●●
● F—F ●
● ●
●● ●●

covalent bond
 5.1-36
BONDING PAIR
The two electrons that form covalent bond

Shared electron pair

EXAMPLE:
bonding pair
H—H or H●
● H

●● ●●
● F—F ●
● ●
●● ●●

bonding pair
 5.1-37
LONE PAIR
Pairs of valence electrons that not involved
in bonding

Unshared electron pair

EXAMPLE:

lone pair

●● ●●
● F—F ●
● ●
●● ●●
 5.1-38
SINGLE BOND
One bonding pair of electrons
EXAMPLE:

single bond

H—H or H ●
H
●

●● ●● or ●● ●●
● F—F ● ●F ● F ●
● ● ● ● ●
●● ●● ●● ●●

●●
H—O—H
●●
 5.1-39
DOUBLE BOND
Two bonding pairs of electrons
2 atoms share 4 electrons

EXAMPLE:

double bond

●● ●● ●● ●●
O C O or O ●● C ●● O
●● ●●
●● ●● ●● ●●

H H H H
C C C ●● C
or ●●
H H H H
 5.1-40
TRIPLE BOND
Three bonding pairs of electrons.

2 atoms share 6 electrons.

EXAMPLE:

triple bond

● N● ● ●● N●
●N ● or
● ●●
N ●● ●
 5.1-41
BOND LENGTH
Distance between nuclei of two covalently
bonded atoms in a molecule
 5.1-42

For a given pair of atoms,

Bond length: single > double > triple

EXAMPLE:

Average bond length:

C—C > C═C > C≡C

(154 pm) (134 pm) (121 pm)
 5.1-43
RELATION OF BOND ORDER, BOND LENGTH,
AND BOND ENERGY

bond order increase

shorter bond

stronger bond
 EXAMPLE – 10 5.1

Rank the bonds in each set in order of

decreasing bond length:
a) C═O, C–O, C≡O
b) N═N, N–N, N≡N
 5.1-44
COORDINATE COVALENT BOND

Formed when one of the atoms donates both

electrons
Also called covalent dative bond

EXAMPLE:

H
H
+
• N H
H+ • H N H

H H

ammonium ion (NH4+)

 DATIVE BOND or COORDINATE BOND
• A covalent bond in which the
shared pair of bonding electrons
is provided by only one of the
bonding atoms.

B O N D
A + B A B
• The donor atom must have at
Covalent bond
least a lone pair of electrons,
while the acceptor atom must
Unpaired

C O V A L E N T
have an empty orbital to
e-A + B
accommodate the two electrons A B
Dative bond
• There is no different between a
dative bond and a normal
covalent bond. The differ only
lone empty Arrow pointing from donor
in the way in which it formed.
pair orbital atom to acceptor atom
 example
The coordinate
1 Hydroxonium ion, H3O+ bond is usually
represented by an
H2O + H+ → H3O+ → pointing from
the donor to the
the H+ ion has acceptor
an empty 1s
H orbital +

O H + H+ H O H



H

the oxygen atom in the two lone pair

the H2O molecule electrons from
has two lone pairs of oxygen atom are
electrons. shared for bonding.
41
 2 Ammonium ion 3 BF3NH3 molecule
,NH4+

NH3 + H+ → NH4+ BF3 + NH3 → BF3NH3

F
H +
•• F -B - F
•• H -N - H + F -B - F
H -N - H + H+ H -N - H H –N -H
H F
H H H
 EXAMPLE – 11 5.1

Boron trifluoride (BF3) accepts an electron pair

from ammonia (NH3) to form adduct BF3NH3.
Show which of the bond is the coordinate
covalent bond?

F H
F H
B + •N
• H B N H
F F
F N CH3
F
 Drawing Lewis Structure
1.count the total number of valence electron (v.e) present
anion – add the number of ‘- ’ cation – subtract the number of ‘ + ’
charge charge

2.draw the skeletal structure of the molecule or polyatomic ions.

the least electronegative atom
the more electronegative atom
occupies the central position, except
occupies the terminal position
the hydrogen atom.

3. draw a single covalent bond. Subtract 2 v.e for each bond. Complete
the octets of the terminal atoms.
one single bond represent 2 valence place any remaining valence electron
electrons (if any ) on the central atom
 Subtract the number of electrons used in this point from the total used at this
point from the total number of valence electrons.

If the octet rule is not satisfied for the central atom, try adding multiple bond
Use one or more of lone pairs of electrons of the terminal atoms to form double
or triple bond.
[ = bond - C,O,N,S,Se,P ] [ ≡ bond - C & N ]

Remember!!!!
In nearly all their compounds:
• H atoms form 1 bond
•C atoms form 4 bonds
•N atoms form 3 bonds
• O atoms form 2 bonds
•Halogens form 1 bond when they are terminal atoms; F is
always terminal atom
 5.1-54

When drawing Lewis structure, you had better to remember

the number of valence electrons of certain atoms:

EXAMPLE:

B , Al  Group 13  3 valence e

C  Group 14  4 valence e

N , P  Group 15  5 valence e

O , S  Group 16  6 valence e

halogens  Group 17  7 valence e

Xe  Group 18  8 valence e
 EXAMPLE – 14 5.1

Write a Lewis structure for:

a) ICl
b) Br2
c) H2O
d) NI3
e) SF2
 EXAMPLE – 15 5.1

Draw the Lewis structure of CO2.

 EXAMPLE – 16 5.1

Draw the Lewis structure of the carbonate ion;

CO32–.
EXCEPTION OF OCTET RULES ➢In octet configuration , atom should have
electronic configuration of noble gas

EXCEPTION Description Example Lewis Structure

OF OCTET
RULES

Incomplete • Central atom have less than 8 eletrons BeCl2,

Cl Be Cl
Octet • Elements in groups 2 & 13 , period 2 . AlCl3
Cl Al Cl
✓ Less metallic character
✓ Do not donate electron but share electron Cl

Expanded • Central atoms having 10 or even 12 valence electron PCl5 , ClF3,

Octet ✓ A central atom can accommodate additional pairs of by using SeF4,
Cl
empty d-orbitals in addition to occupied s and p orbitals.
✓ Therefore, this only occur in elements from period 3 or above Cl
where d-orbitals are available Cl P
Period 3: 3 subshells available ( 3s, 3p and 3d) Cl
Cl

ODD number • The electrons in a Lewis structure that satisfies the octet rule must ClO2,
electrons occur in pairs : bonding pairs or lone pairs. NO2
• A molecule with an odd number of electrons cannot satisfy the
octet rule on all of its atom.
• Most stable molecules have an even N O
• number of electrons, but few have an odd number of electrons.
 Formal Charge and Selecting the Best Lewis Structure
Formal Charge Selecting the Best Lewis Structure
✓Formal Charges are apparent charge When several Lewis structure are possible, the
assigned to bonded atom in a Lewis most stable and preferred Lewis structure is the
structure one which:
✓Is the difference between the valence
➢ FC approaching zero/ equal to zero
e- in an isolated atom and the
➢ Lewis structure with large FC are less
number of electrons assigned to that
plausible than those with small formal
atom in a Lewis structure.
charges
➢ -ve FC appears on the most electronegative
✓used to determine the most atoms
plausible Lewis structure.
➢ Positive FC appear on the least
electronegative atoms
Formal ➢ Adjacent atoms in a structure should not
Charge of total no
no of 1 no of carry the FC of the same sign.
an atom in of -
= valenc non- + bonding
Lewis bonding 2 ➢ Total FC for the atoms in a Lewis structure
ee e
Structure e must be a zero for a neutral molecule and
must equal the net charge for a polyatomic
ion
 Draw the right Lewis structure of COCl2.

2
Cl 1 Cl
O C Cl O C Cl
structure A structure B
Formal charges : Formal charges :
C = 4-[0+½(8)] = 0
C = 4-[0+½(8)] = 0
Cl1 = 7-[4+½(4)] = +1
Cl = 7-[6+½(2)] = 0
Cl2 = 7-[6+½(2)] = 0
O = 6-[4+½(4)] = 0
O = 6-[6+½(2)] = -1

the most plausible structure is structure B

Because it has lowest formal charge in each atom
53
Draw the right Lewis structure of NCO-
- -
O C N O C N

structure
A
Formal charges :
C = 4-[0+½(8)] = 0
N = 5-[4+½(4)] = -1
O = 6-[4+½(4)] = 0
structure B
Formal charges :
C = 4-[0+½(8)] = 0
N = 5-[2+½(6)] = 0
O = 6-[6+½(4)] = -1

the most plausible structure is structure B.

The -1 formal charge resides on the more electronegative
atom, O

54
 RESONANCE STRUCTURE
• For certain molecules or molecular ions,
two or more equivalent Lewis structures
Example : O3
can be drawn on the same skeleton. ●● ●● ●● ●● ●● ●●
• Resonance occurs when more than one
●● – O =●●
O = O – ●●

●●

●●
●●
O O O
valid Lewis structure can be written for a
particular molecule. NOTE THAT :
• This situation is usually represented by ▪ In all these resonance structures the
double-headed arrows. arrangement of the nuclei is the same (Same
skeletal structure)
Resonance structure: Lewis structure ▪ Only the placement of the electron differs.
having the same arrangement of atoms ▪ The arrow show the actual structure is an
but differ from one another in the
▪ average of the two resonance structures
position of their electrons.

Resonance hybrid: a single structure

which represents the actual contribution
of resonance structure. 55
 E X AM P L E
Draw resonance forms for :

CO32-

56
Example : CO32- ●●
●●
O (-1) 2-

●●
●●
(0) O 2- 2-

●●
●●
(-1) O

●●
●●
(0) C
(0) C C (0)
O
●●

●●

●●
O

●●
O O
●●

●●
O O

●●

●●
●●
●●
●●
(0)
●● ●●
(-1) (-1)
(-1) (-1) (0)

●●
O 2-

●●
C Resonance Hybrid
O
●●

●●
O
●●
 EXAMPLE : NCO- has 3 possible resonance forms

- - 0 -
●● 0 +1 ●● 0 ●● 0 0
2 1 ●●
N C O N=C= O N C O
1

●●

●●

●●
●●
●●
●● ●● ●●
A B C
➢ Structure A is not plausible because it has larger formal
charges than the others and +ve charge on O

➢ Structure B and C are significant contributors to the

resonance hybrid of cyanate ion because they have negative
formal charges on N and O;
➢ since Structure C has a negative charge (-1) resides on O which
is more electronegative than N.

➢  C is the most plausible Lewis structure. 58

 -1 0
(a) ●● ●●
O O

●●
●●

●●
●●
0 +1 0 0
●● ●●0 ●● ●●0
0H – O – P – O – H0 0H – O – P – O – H0
●● ●● ●● ●●

O – H0 O – H0

●●
0 0

●●
●● ●●

more stable
(b) BFCl2 will have only 1 Lewis structure.

F
B
Cl Cl

59