General Chemistry

Chem110

Chapter 9
Chemical Bonding I: Basic Concepts
Objectives
• Draw Lewis dot symbols.
• Distinguish between ionic, covalent, and polar covalent bonds.
• Draw Lewis structures for molecules and ions.
• find the formal charges.
• Draw the resonance structures for molecules and ions.
• Apply exceptions to the octet rule.
Outline
9.1 Lewis dot symbols

9.2 The Ionic Bond

9.4 The Covalent Bond

9.5 Electronegativity

9.6 Writing Lewis Structures

9.7 Formal Charge and Lewis Structures

9.8 The Concept of Resonance

9.9 Exceptions to Octet Rules

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9.1 Lewis Dot Symbols

Valence electrons are in the outer shell electrons of an atom and the electrons that
participate in the chemical bonding.

Group Electron configuration Number of valence electron

1A ns1 1
2A ns2 2
3A ns2np1 3
4A ns2np2 4
5A ns2np3 5
6A ns2np4 6
7A ns2np5 7

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9.1 Lewis Dot Symbols
The Octet Rule: in forming chemical bonds, atoms usually gain, lose or share
electrons until they have 8 in the outer shell to reach the same electronic
configuration of the noble gasses (ns2 np6) (except hydrogen, helium and lithium).

When atoms interact to form chemical bond, only their outer region are in
contact.

Lewis Dot Representation: In the representation of an atom, the valence electrons

of an atom (outer most shell electrons) are represented by dots.

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9.1 Lewis Dot Symbols
9.1 Lewis Dot Symbols

Group 1A 2A 3A 4A 5A 6A 7A 8A
Lewis dots 
x  .x 
. x  
.
x  


x 
 


x 

 x 
  

 x 

    

Bonding 1 2 3 4 3 2 1 0
electrons
Nonbonding 0 0 0 0 2e 4e 6e 8e
electrons
(Pair of 1 pair 2 pairs 3 pairs 4 pairs
nonbonding
electrons)

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Example
An atom in the ground state has atomic number Z=5. Choose the correct electron-dot structure which
represents this atom?

Answer: (c)
Electron configuration (Z =5) 1s2 2s2 2p1
Valence electrons are in 2s2 2p1
⸫ VE = 3 e- 8
9.2 The Ionic Bond

Types of Atoms Types of bonds Bond Characteristic

Electrons
Metals to nonmetals Ionic
transferred
Metalloids to nonmetals Electrons
Covalent
Nonmetals to nonmetals shared

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 9.2 The Ionic Bond
Ionic bond is the electrostatic force that holds ions together in an ionic
compound.
(metals are low EN and nonmetals are high EN)

Li Li+ + e-

e- + F F -

Li+ + F - Li+ F -

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Example 9.1
Use Lewis dot symbols to show the formation of Aluminium oxide (Al2O3)

2 Al + 3 O →

[Ne] 3s2 3p1 1s2 2s2 2p4

2 Al3+ 3 O 2-
(Al2O3)
[Ne] 1s2 2s2 2p6 [Ne]
Practice Exercise: Use Lewis dot symbols to represent the formation of barium hydride, CaO, Li 2O,
and Mg3N2 .
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9.4 The Covalent Bond
A covalent bond is a chemical bond in which two or more electrons are shared by
two atoms.
(nonmetal high Electronegativity & nonmetal high Electronegativity)

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9.4 The Covalent Bond
 Single bond two atoms share one pairs of electrons

 Double bond two atoms share two pairs of electrons

 Triple bond two atoms share three pairs of electrons

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9.4 The Covalent Bond

Two shared electrons → one (single) covalent bond

Four shared electrons → two (double) covalent bonds

Six shared electrons → three (triple) covalent bonds

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9.5 Electronegativity
Polar Covalent bond

Polar covalent bond or polar bond is a covalent bond with greater electron density
around one of the two atoms

H F

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 9.5 Electronegativity
Electronegativity is the ability of an atom to attract toward itself the electrons in a
chemical bond.

• High electronegativity →pick up electron easily

• Electronegativity increase from left to right in period.
• Electronegativity increase from bottom to up in group .
• Nonmetals have high electronegativity, metals have low electronegativity.
• Transition metals don’t follow these trend.

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 9.5 Electronegativity
Electron Affinity & Electronegativity

• Electron Affinity - measurable, Cl is highest

X (g) + e- ͢ X-(g)

• Electronegativity - relative, F is highest

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9.5 Electronegativity

Variation of Electronegativity with Atomic Number

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9.5 Electronegativity
The Electronegativity of Common Elements

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9.5 Electronegativity
Classification of bonds by difference in electronegativity (EN)

EN Difference (ΔEN) Bond Type

0 Covalent
0 < and <2 Polar Covalent
2 Ionic

Increasing difference in electronegativity

Covalent bond Polar covalent bond Ionic bond

Share electrons Partial transfer electrons Transfer electrons

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Summary of Chemical Bond

Chemical Bond

Covalent Bond Ionic Bond

Non-metal + Non-metal Metal + Non-metal
Metalloid + Non-metal

Polar Covalent Bond ΔEN ≥ 2

Non polar Covalent Bond
Same or different elements: Different element:
H2, F2, CS2 HF, HCl
ΔEN = 0 0 < ΔEN < 2
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Example 9.2
Classify the following bonds as ionic, polar covalent, or covalent

a) HCl = 3 - 2.1 = 0.9 Polar covalent

b) KF = 4 - 0.8 = 3.2 Ionic
c) C-C = 2.5 - 2.5 =0 covalent

Practice Exercise: Which of the following bonds is covalent, which is polar covalent, and
which is ionic?
(a) the bond in CsCl, (b) the bond in H2S, (c) the NN bond in H2NNH2.

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Electronegativity and Oxidation number

The oxidation number is the number of charge an atom would have if electrons were
transferred completely in to the more electronegative of the bonded atoms in a molecule.

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Comparing of the properties of covalent and ionic compounds

• Covalent compounds are usually gases, liquid and low melting solid.
• Ionic compounds are solids at room temperature and high melting
point.
• Many ionic compounds are soluble in water , and the resulting
aqueous solutions conduct electricity, because the compounds are
strong electrolytes.

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9.6 Writing Lewis Structures
1) Draw skeletal structure of compound showing what atoms are bonded to each
other. Put least electronegative element in the centre.
Note: H atom always goes on the outside
2) Count the total number of valence electrons (Valence electrons). Add 1 for
each negative charge. Subtract 1 for each positive charge.
3) Draw single covalent bond between the central atom and each of the
surrounding atom. (each single bond represents 2electrons from the total
number of Valence electrons)
4) Use the valence electrons in step 2 to complete an octet for all the surrounded
atoms except hydrogen. Count and Compare it with the total no. of Ve- in
step2. If they are identical stop, if it is less add the remaining electrons to the
central atom
5) If the central atom has no octet, use lone pair/s on the one of the surrounded
atom to form double or triple bond with the central atom. 25
Example 9.3:

Write the Lewis structure of nitrogen trifluoride (NF3) in which all three F atoms

are bonded to the N atom.

Step 1 - N is less electronegative than F, put N in the centre

Step 2 - Count valence electrons N - 5 (2s 22p3) and F - 7 (2s22p5)

5 + (3 x 7) = 26 valence electrons

Step 3 - Draw single bonds between N and F atoms

Step 4 - Complete an octets on F atoms using all the e in step 2

(put the remaining 2 e on N)

Step 5 - Check, if all the atoms has octet ,3 single bonds (3x2e) + 10 lone
pairs (10x2e) = 26 valence electrons
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Example 9.4:

Write the Lewis structure for nitric acid (HNO3) in which the three O atoms are bonded to
the central N

Step 1 – N is less electronegative than O, Put N in the centre ,surrounded by 3O atoms, H

bonded to one of the O.

Step 2 - Count the valence electrons 5 + (3 x 6) +1 = 24 valence e-

Step 3 - Draw single bonds between N and O atoms and O and H.

Step 4 - Complete octet on O atoms using all the valence e in step 2.

Step 5 - Check, all the atoms has octet, N has no octet? Use one of the lone pair on the O
atom to form double bond with the N atom.

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Example 9.5:

Write the Lewis structure of carbonate ion (CO 32-).

Step 1 - C is less electronegative than O, put C in the centre.

Step 2 - Count valence electrons C - 4 (2s22p2) and O - 6 (2s22p4) and ion has two
negative charges (-2e). Thus, 4 + (3 x 6) + 2 = 24 valence electrons

Step 3 - Draw single bonds between C and O atoms.

Step 4 - Complete an octet on O atoms using all the e in step 2.

Step 5 - Check, all the atoms has octet, C has no octet? Use one of the lone pair on the O
atom to form double bond with the C atom.

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Home work:
Write the Lewis structure for the following examples:
• (CS2 )

• (HCOOH)

• (NO2- )

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Confirmation Method for writing Lewis Structures
1) Determine the total number of electrons in the valence shells of all of the
atoms of the molecule (A) , add electrons ( if molecule have net –ve charge ,
subtract electrons if molecule have net +ve charge)
2) Complete an octet for all atoms except hydrogen (B)
3) Find the number of bonding electrons by C = B-A
4) Find the number of bonds by C/2 = B-A/2
5) Find the number of nonbonding electrons by D= A-C , lone pair of electrons =
D/2

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Example

Write the Lewis structure of Ammonia (NH 3); then confirm it.

Put N in the centre because H atom always goes on the outside, complete as usual then find:
A= 5X1+1X3 = 8 valance electrons
B= 8X1+2X3 =14 electrons
C=14-8 = 6/2=3 bonds
D= 8-6 = 2 nonbonding electrons or 1 pair of electrons
and compare with the structure:

Lewis structure of NH3 consist of 3 single bond , 2 nonbonding electrons or 1 pair of electrons

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Example

• Write the Lewis structure of ammonium ion (NH4+); then confirm it.
Put N in the center because H atom always goes on the outsidecomplete as usual
then find:
A= 5X1+1X4 -1 = 8 valance electrons
B = 8X1+2X4 =16 electron
C =16-8 =8/2=4 bonds
D= 8-8 =0 non-bonding electrons
and compare with the structure

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9.7 Formal Charge and Lewis Structure

 Formal charges show how the charge distributed in a molecule

Formal charge is the difference between the number of valence electrons in an

isolated atom and the number of electrons assigned to that atom in a Lewis
structure

formal charge on an atom in a Lewis structure =

(total number of valence electrons in the free atom ) – (total number of nonbonding
electrons ) – 1/2 (total number of bonding electrons)

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9.7 Formal Charge and Lewis Structure

The sum of the formal charges of the atoms in a molecule or ion must equal the
charge on the molecule or ion:
For molecules , the sum of the charges should be zero

 For anions , the sum of the charges should be -ve

 For cations, the sum of the charges should be +ve

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9.7 Formal Charge and Lewis Structure
Example
Write formal charge of Ozone molecule (O3)
The sum of the formal charges of the atoms in a molecule or ion must equal the
charge on the molecule or ion.
-1 +1 = 0

Formal charge =
6 – 6 –(½x2) =-1
Formal charge =
6 – 4 –(½x4) = 0
Formal charge =
6 – 2 –(½x6) =+1
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Example 9.6:
Write formal charge for the carbonate ion (CO32-)

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9.7 Formal Charge and Lewis Structure
If there is more than one possible structure for a molecule
Formal charges help to decide which structure is the correct one, by applying the
following:
• For neutral molecules, a Lewis structure with no formal charges is preferable.
• Lewis structures with large formal charges are less plausible than those with small
formal charges.
• Lewis structures having similar distributions of formal charges, the most plausible
structure is the one in which negative formal charges are placed on the more
electronegative atoms.

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 Example 9.7:

Draw the most likely Lewis structure for formaldehyde (CH2O).

The two possible Lewis structures are: a and b but b is the most likely because it has
no formal charges.

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Home work:
• Write formal charges for the nitrite ion (NO2-).

• Draw the most reasonable Lewis structure of a molecule that contains

a N atom, a C atom, and a H atom.

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 9.8 The Concept of Resonance

Resonance structure is one of two or more Lewis structures for a single molecule that
cannot be represented accurately by only one Lewis structure (after formal charge has
been determined ).
• Resonance structures of ozone O3 is:

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9.8 The Concept of Resonance
Examples:
the resonance structures for the carbonate ion

the resonance structures for benzene molecule

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Example

Draw three resonance structures for the molecule nitrous oxide, N 2O (the atomic arrangement
is NNO). Indicate formal charges. Rank the structuresDraw three resonance structures for the
molecule nitrous oxide, N2O (the atomic arrangement is NNO). Indicate formal charges. Rank
the structures.

• All structures show formal charges

• Structure (b) is the most important, because the –ve charge is on the more
electronegative oxygen atom
• Structure (c) is the least important one, because larger formal charge, also the +ve
charge is on the more electronegative oxygen atom.
• Arrangement of importance (b) > (a) > (c)
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Home Work

Draw three resonance structures for the thiocyanate ion, SCN -, Rank
the structures in decreasing order of importance.

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9.9 Exceptions to the Octet Rule

1. The Incomplete Octet

2. Odd-Electron Molecules

3. The Expanded Octet

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The Incomplete Octet

 In some compounds, the number of electrons surrounding the central atom in a

stable molecule is fewer than eight.

Examples

• 2A (Be); e.g BeH2

Be is ONLY surrounded by 4 e-

• 3A (B & Al); e.g BF3

B is ONLY surrounded by 6 e-

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Odd-Electron Molecules

Odd-electrons molecules = RADICALS

Radical: atom has one electron alone
Example : (NO) and (NO2)

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The Expanded Octet
 3rd period and beyond (4th, 5th, 6th, 7th ) may form molecules in which the central
atom is surrounded by more than 8 electrons (expanded octet)

The reason of this: is the presence of the d orbital that can be used in bonding.

Example : SF6

 Sulphur is surrounded by 12 electrons → Expanded Octet

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Summary of Exceptions to the Octet Rule

Incomplete octet: Be, B, and Al

Odd-electrons: when the valance electrons is odd number (e.g. NO,

NO2 )

Expanded octet: elements of 3rd, 4th, & so on, may form expanded
octet

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Example 9.9

Draw the Lewis structure for aluminium triiodide (AlI 3)

The Al atom is surrounded by ONLY 6 e → AlI3 is an example of incomplete octet

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Examples 9.10
Draw Lewis structure for phosphorus pentafluoride (PF5), in which all five F atoms
are bounded to the central P atom.

Valance electrons = 5 + (7 x 5 ) = 40 e
Total electrons in Lewis structure =
(15 x 2) = 30 lone pairs
(5 x 2) = 10 e single bonds
Total = 40 e
P has (5 x 2) = 10 e → expanded octet
Formal Charges of P and F are Zero

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