Models of Chemical Bonding: Dr. Nur Farhana Binti Jaafar

Chapter 9:
Models of Chemical Bonding

Dr. Nur Farhana Binti Jaafar
1
Chapter Outline
9.1 Atomic Properties and Chemical Bonding
9.2 The Ionic Bonding Model
9.3 The Covalent Bonding Model
9.4 Bond Energy and Chemical Change
9.5 Between the Extremes:

electronegativity and Bond Polarity
9.6 An Introduction to Metallic Bonding
2
3
Atomic Properties and Chemical Bonding
Why do we need to study bonds?
 There are molecules and ionic compounds
 Attractive forces hold atoms together in complex substances
 Changes in these bonding forces are the underlying basis of chemical reactivity
 During reaction:
 Break old bonds

 Form new bonds
4
Ionic Bonding Covalent Bonding Metallic Bonding
5
Lewis Electron-Dot Symbol
Note it’s a-group number (1A to 8A), which the number of valence-electron dots.
6
Lewis Electron-Dot Symbol
To draw the Lewis symbol for any main-group element:
 Place one dot at a time on each of the four sides (top, right, bottom, left)
of the element symbol.
 Keep adding dots, pairing them, until all are used up.
 The specific placement of dots is not important. As example, the Lewis

symbol for nitrogen (N) which in Group 5A and has 5 valence electrons
can also be written as:
•• • • •
•N• or • N• or • N or N•
••
••
• •• • •
7
Lewis Symbols and Bonding
For a metal, the total number of dots in the Lewis symbol is the
number of electrons the atom loses to form a cation.
For a nonmetal, the number of unpaired dots equals:

 the number of electrons the atom gains to form an anion
 or the number it shares to form covalent bonds.
The octet rule states that when atoms bond, they lose, gain, or share
electrons to attain a filled outer level of 8 electrons (or 2, for H and
Li).
8
Lewis Structure
Many nonmetals form more than 1 covalent bond
C N O
Needs 4 e-’s Needs 3 e-’s Needs 2 e-’s
Forms 4 bonds Forms 3 bonds Forms 2 bonds
H
H N H O H
H C H
H H
H H
H C H H N H O H
H H H
methane ammonia water
9
Octet Rule
10
Post Transition Metals
Example
Sn [Kr] 4d10 5s2 5p2
Sn2+ [Kr] 4d10 5s2 Has emptied 5p subshell
However Sn4+ more stable than Sn2+
Sn4+ [Kr] 4d10 – it has stability (why?)
 Inert pair effect – two outer s electrons are unwillingly to be involved in

bonding
 It also has empty n = 5 orbitals
11
Translation Metal
 1st e's lost from ns orbital of outer shell
 Lose e's from highest n first, then highest ℓ
Example
Fe [Ar] 3d6 4s2

Fe2+ [Ar] 3d6 loses 4s e's 1st
Fe3+ [Ar] 3d5 then loses 3d e
Fe3+ has extra stability compare with Fe2+ due to exactly half-filled d orbital.
12
Translation Metal
 Not easy to predict which ions form and which are stable
 But ions with exactly filled or half-filled d subshells are extra stable and tend to
form.
Example:
Mn2+ [Ar]3d5
Fe3+ [Ar]3d5
Zn2+ [Ar]3d10
13
The Ionic Bonding Model
An ionic bond is formed when a metal transfers electrons to a nonmetal to

form ions, which attract each other to give a solid compound.
The total number of electrons lost by the metal atom(s) equals the
total number of electrons gained by the nonmetal atom(s).
14
Three ways to depict electron transfer in the formation of Li+ and F–
Electron configurations
Li 1s22s1 + F 1s22s22p5 → Li+ 1s2 + F– 1s22s22p6
Orbital diagrams
Li ↑↓ ↑ Li+ ↑↓
+ 1s 2s 2p 1s 2s 2p
F ↑↓ ↑↓ ↑↓ ↑↓ ↑ F- ↑↓ ↑↓ ↑↓ ↑↓ ↑↓
1s 2s 2p 1s 2s 2p
Lewis electron-dot symbols
•• •• –
Li• •F Li+ + F
••
••
••
•• ••
15
Sample Problem: Depicting Ion Formation
PROBLEM: Use partial orbital diagrams and Lewis symbols to depict the
formation of Na+ and O2– ions from the atoms, and determine the
formula of the compound formed.
PLAN: Draw orbital diagrams and Lewis symbols for Na and O atoms. To attain
filled outer levels, Na loses one electron and O gains two. Two Na atoms
are needed for each O atom so that the number of electrons lost equals
the number of electrons gained.
SOLUTION:
Lewis electron-dot symbols
Na• •• •• 2-
•O + O
••
••
2Na+
••
• ••
Na•
16
Orbital diagrams
Na ↑
3s 3p + O ↑↓ ↑↓ ↑ ↑
Na ↑ 2s 2p
3s 3p
2Na+ + O2– ↑↓ ↑↓ ↑↓ ↑↓
2s 2p
The formula is Na2O
17
The Born-Haber cycle for lithium fluoride
 Series of step from elements to ionic
solid which all enthalpies (H) are known
except lattice energy (Hlattice)
 Hess’s law can be used to determine

Hlattice
 2 possible path to calculate Hlattice
 Direct path
 Stepwise path
 Born-Haber cycle :
 Energy required for element to form ions

is supplied by the attraction among the
ions in the solid.
 Ionic solids exist only because the

lattice energy far exceeds the total
energy needed to form ions.
18
Two Paths to Evaluate Energy
1. Direct path
Na(s) + ½Cl2(g)  NaCl(s) Hf° = – 411.1 kJ/mol
2. Stepwise path
Na(s)  Na(g) Hf°(Na, g) = 107.8 kJ/mol

½Cl2(g)  Cl(g) Hf°(Cl, g) = 121.3 kJ/mol
Na(g)  Na+(g) + e– IE(Na) = 495.4 kJ/mol
Cl(g) + e–  Cl–(g) EA(Cl) = – 348.8 kJ/mol
Na+(g) + Cl–(g)  NaCl(s) Hlattice = – 787.0 kJ/mol

Na(s) + ½Cl2 (g)  NaCl(s) Hf° = – 411.3 kJ/mol
• IE : ionization energy
• EA: electron affinity
19
Periodic Trends in Lattice Energy
Lattice energy is the energy required to separate 1 mol of an ionic solid into
gaseous ions.
20
Lattice energy is a measure of the strength of the ionic bond.
Coloumb’s Law
Electrostatic energy  charge A x charge B

distance
Electrostatic energy  cation charge x anion charge  DHolattice

cation radius + anion radius
21
22
Sample Problem: Predicting Relative Lattice Energies from Ionic
Properties
PROBLEM: Use ionic properties to choose the compound in each pair with the
larger lattice energy: (a) Rbl or NaBr; (b) KCI or CaS.
PLAN: To choose the compound with the larger lattice energy, we apply
Coulomb's law and periodic trends in ionic radius and charge (see Figure
2.12).We examine the ions in each compound: for ions of similar size, higher
charge leads to a larger lattice energy; for ions with the same charge, smaller
size leads to larger lattice energy because the ions can get closer together.
SOLUTION:
(a) NaBr. All the ions have single charges, so charge is not involved. Size
increases down a group, so Rb+ is larger than Na+, and I– is larger than Br–.
Therefore, NaBr has the larger lattice energy because it consists of smaller
ions.
23
Sample Problem: Predicting Relative Lattice Energies from Ionic
Properties
SOLUTION:
(b) CaS. Size decreases from left to right, so K+ is slightly larger than Ca2+, and S2–
is slightly larger than CI–. However, these small differences are not nearly as
important as the charges: Ca2+ and S2– have twice the charge of K+ and Cl–, so
CaS has the larger lattice energy.
CHECK: The actual values for lattice energy are (a) Rbl = 598 kJ/mol; NaBr = 719
kJ/mol; and (b) KCI = 676 kJ/mol; CaS = 3039 kJ/mol.
24
Properties of Ionic Compounds
Electrical conductivity
Solid ionic Molten ionic Ionic compound

compound compound dissolved in water
26
Properties of Ionic Compounds
Melting and boiling point
27
Covalent Compounds
 Form individual separate molecules

Atoms bound by sharing e–’s
 Do not conduct electricity
 Often low melting point
Covalent Bonds
 Shared pairs of e–’s between 2 atoms
 2 H atoms come together, Why?
28
The Covalent Bonding Model
Covalent Bonds
 Attraction of valence e– of 1 atom by nucleus of other atom
 Shifting of e– density
 As distance between nuclei ,  probability of finding either e– near either

nucleus 
 Pulls nuclei closer together

29
30
Bonding Pairs and Lone Pairs
Atoms share electrons to achieve a full outer level of electrons. The shared
electrons are called a shared pair or bonding pair
The shared pair is represented as a pair of dots or a line:
••
H H or H–H
An outer-level electron pair that is not involved in bonding is called a lone

pair, or unshared pair
•• •• •• ••
F F or F–F
••
••
••
••
••
•• •• •• ••
31
Properties of a Covalent Bond
The bond order is the number of electron pairs being shared by a given pair of
atoms.
The bond energy (BE) is the energy needed to overcome the attraction between
the nuclei and the shared electrons.
The bond length is the distance between the nuclei of the bonded atoms.
32
Bond length and covalent radius
Internuclear distance Covalent Internuclear distance Covalent
(bond length) radius (bond length) radius
72 pm 114 pm
Internuclear distance Covalent Internuclear distance Covalent

(bond length) radius (bond length) radius
100 pm 133 pm
33
The Relation of Bond Order, Bond Length, and Bond Energy
34
Sample Problem: Comparing Bond Length and Bond Strength
PROBLEM: Using the periodic table, but not Tables 9.2 (in text book) or 9.3,
rank (slide no 39) the bonds in each set in order of decreasing
bond length and decreasing bond strength:
(a) S–F, S–Br, S–Cl (b) C=O, C–O, CΞO
PLAN: (a) S is singly bonded to three different halogen atoms, so the bond
order is the same. Bond length increases and bond strength
decreases as the atomic radius of the halogen increases.
(b) The same two atoms are bonded in each case, but the bond
orders differ. Bond strength increases and bond length decreases
as bond order increases.
35
Sample Problem: Comparing Bond Length and Bond Strength
SOLUTION:
(a) Atomic size increases going down a group, so F < Cl < Br.
Bond length: S–Br > S–Cl > S–F
Bond strength: S–F > S–Cl > S–Br
(b) By ranking the bond orders, we get

Bond length: C–O > C=O > CΞO
Bond strength: CΞO > C=O > C–O
36
Bond Energies and Hºrxn
The heat released or absorbed during a chemical change is due to differences

between the bond energies of reactants and products.
Hºrxn = SHºreactant bonds broken+ SHºproduct bonds formed
Using bond energies to calculate Hºrxn for HF formation.
37
Bond Energy and Chemical Change
Sample Problem: Using Bond Energies to Calculate Hºrxn
PROBLEM: Calculate Hºrxn for the chlorination of methane to form

chloroform.
bonds broken bonds formed

SHº positive SHº negative
PLAN: All the reactant bonds break, and all the product bonds form. Find
the bond energies in Table (Table 9.2;pg 371) and substitute the
two sums, with correct signs, into equation
Hºrxn = SHºreactant bonds broken+ SHºproduct bonds formed
38
SOLUTION:
For bonds broken:
4 x C-H = (4 mol)(413 kJ/mol) = 1652 kJ
3 x Cl-Cl = (3 mol)(243 kJ/mol) = 729 kJ
SHºbonds broken = 2381 kJ
For bonds formed:

3 x C-Cl = (3 mol)(–339 kJ/mol) = –1017 kJ
1 x C-H = (1 mol)(–413 kJ/mol) = –413 kJ
3 x H-Cl = (3 mol)(–427 kJ/mol) = –1281 kJ
SHºbonds formed = –2711 kJ
Hºreaction = SHºbonds broken + SH bonds formed

= 2381 kJ + (–2711 kJ) = –330 kJ
39
Electronegativity ()
 Relative attraction of atom for es in bond
 Ability of bonded atom to attract es to itself
 Quantitative basis
 Difference in electronegativity = estimate of bond polarity

  = |1  2|
Polar covalent bonds are much

more common than either pure
ionic or pure covalent bonds.
40
Between the Extremes: Electronegativity and Bond Polarity
Electronegativity ()
These are just qualitative numbers based on some basic idea. It has no units
and is not related to energy!
 Must know for 2nd row and H.

 (H) ~ 2.0
H  (F) ~ 4.0
 2   by 0.5 for each element as you go to the left
Li Be B C N O F
 1 1.5 2 2.5 3 3.5 4
P S Cl
2 2.5 3.0
41
Trend in Electronegativity
The most electronegative element is fluorine.
In general electronegativity decreases down a group as atomic size increases.
In general electronegativity increases across a period as atomic size decreases.

Nonmetals tend to be more electronegative than metals.
42
Electronegativity and Oxidation Number
Electronegativities can be used to assign oxidation numbers:
 The more electronegative atom is assigned all the shared electrons.
 The less electronegative atom is assigned none of the shared electrons.
 Each atom in a bond is assigned all of its unshared electrons.
 O.N. = no of valence e– – (no of shared e– + no of unshared e–)
43
Example:
Cl is more electronegative than H, so for Cl:

valence e- = 7
shared e- =2
unshared e- = 6
O.N. = 7 – (2 + 6) = -1
H is less electronegative than Cl, so for H:

valence e- = 1
shared e- = 0 (all shared e- assigned to Cl)
unshared e- = 0
O.N. = 1 – (0 + 0) = +1
44
The importance of Electronegativity Difference (ΔEN)
 ΔEN is the different between the EN values of

bonded atoms.
 ΔEN also related to partial ionic character of

bond: a greater ΔEN results in larger partial
changes and higher partial ionic character.
ΔEN ranges for classifying the partial ionic character of bonds.
46
The importance of Electronegativity Difference (ΔEN)
A: ΔEN correlates with ionic character.
B: Even in highly ionic LiF (ΔEN = 3.0) some

electron sharing occurs between the ions in
the gaseous ion pair.
47
Sample Problem: Determining Bond Polarity from EN Values
PROBLEM: (a) Use a polar arrow to indicate the polarity of each bond: N–H, F–N, I–Cl.
(b) Rank the following bonds in order of increasing polarity: H–N, H–O, H–C.
PLAN: (a) We use Figure 9.21 to find the EN values for each element. The polar arrow
points toward the more electronegative element.
(b) The greater the EN between the atoms, the more polar the bond.
SOLUTION: (a) The EN values are:

N = 3.0, H = 2.1; F = 4.0; I = 2.5, Cl = 3.0
N–H F–N I–Cl
48
Sample Problem: Determining Bond Polarity from EN Values
(b) The EN values are:

N = 3.0, H = 2.1; O = 3.5; C = 2.5
EN for H–N = 3.0 – 2.1 = 0.9

EN for H–O = 3.5 – 2.1 = 1.4
EN for H–C = 2.5 – 2.1 = 0.4
In order of polarity:
H-C < H-N < H-O
49
The Gradation in Bonding Across a Period
Electron density distributions in bonds of the Period 3 chlorides. There is a steady increase in the
height of electron density between peaks (bonding region) indicated an increase in electron sharing
from left to right.
50
Metallic Bonding
The electron sea model of metallic bonding proposes that:
 All metal atoms in the sample contribute their valence electrons to form a
delocalized electron “sea”
 The metal “ions” (nuclei with core electrons) lie in an orderly array within
this mobile sea.
 All the atoms in the sample share the electrons.
 The metal is held together by the attraction between the metal “cations”
and the “sea” of valence electrons.
51
Metallic Bonding
Properties of Metals
 Metals are generally solids with moderate to high melting points and much higher
boiling points
Melting points decrease down a group and increase across a period
 Metals can be shaped without breaking

The electron sea allows the metal ions to slide past each other
 Metals are good conductors of electricity in both the solid and liquid states
The electron sea is mobile in both phases
 Metals are good conductors of heat
52
Metallic Bonding

Models of Chemical Bonding: Dr. Nur Farhana Binti Jaafar

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Chapter 9:

Models of Chemical Bonding

9.2 The Ionic Bonding Model

9.3 The Covalent Bonding Model

9.4 Bond Energy and Chemical Change

9.5 Between the Extremes:

9.6 An Introduction to Metallic Bonding

 There are molecules and ionic compounds

 Attractive forces hold atoms together in complex substances

 Break old bonds

To draw the Lewis symbol for any main-group element:

 The specific placement of dots is not important. As example, the Lewis

For a nonmetal, the number of unpaired dots equals:

Many nonmetals form more than 1 covalent bond

Sn [Kr] 4d10 5s2 5p2

Sn2+ [Kr] 4d10 5s2 Has emptied 5p subshell

However Sn4+ more stable than Sn2+

Sn4+ [Kr] 4d10 – it has stability (why?)

 Inert pair effect – two outer s electrons are unwillingly to be involved in

 1st e's lost from ns orbital of outer shell

 Lose e's from highest n first, then highest ℓ

Fe [Ar] 3d6 4s2

An ionic bond is formed when a metal transfers electrons to a nonmetal to

Lewis electron-dot symbols

The formula is Na2O

 Hess’s law can be used to determine

 2 possible path to calculate Hlattice

 Energy required for element to form ions

 Ionic solids exist only because the

Na(s) + ½Cl2(g)  NaCl(s) Hf° = – 411.1 kJ/mol

Na(s)  Na(g) Hf°(Na, g) = 107.8 kJ/mol

Lattice energy is a measure of the strength of the ionic bond.

Electrostatic energy  charge A x charge B

Electrostatic energy  cation charge x anion charge  DHolattice

Solid ionic Molten ionic Ionic compound

Melting and boiling point

 Form individual separate molecules

 Do not conduct electricity

 Often low melting point

 Shared pairs of e–’s between 2 atoms

 2 H atoms come together, Why?

 Attraction of valence e– of 1 atom by nucleus of other atom

 As distance between nuclei ,  probability of finding either e– near either

 Pulls nuclei closer together

The shared pair is represented as a pair of dots or a line:

An outer-level electron pair that is not involved in bonding is called a lone

Internuclear distance Covalent Internuclear distance Covalent

(b) By ranking the bond orders, we get

The heat released or absorbed during a chemical change is due to differences

Hºrxn = SHºreactant bonds broken+ SHºproduct bonds formed

Using bond energies to calculate Hºrxn for HF formation.

PROBLEM: Calculate Hºrxn for the chlorination of methane to form

bonds broken bonds formed

For bonds formed:

Hºreaction = SHºbonds broken + SH bonds formed

 Relative attraction of atom for es in bond

 Ability of bonded atom to attract es to itself

 Difference in electronegativity = estimate of bond polarity

Polar covalent bonds are much

 Must know for 2nd row and H.

 2   by 0.5 for each element as you go to the left

The most electronegative element is fluorine.

In general electronegativity decreases down a group as atomic size increases.