CHAPTER 2:

BONDING AND PROPERTIES

Properties depend on
- arrangement of atoms
- interactions between atoms
Study Bonding:
What promotes bonding?
What types of bonds are there?
What properties are inferred from bonding?

Chapter 2 - 1

Atomic Structure (Freshman Chem.)

atom

electrons 9.11 x 10-31 kg

protons
1.67 x 10-27 kg
neutrons

nucleus of atom: size of a point on a page -!

atomic number

= No. of protons in nucleus of atom

= No. of electrons of neutral species
A [=] atomic mass unit = amu = 1/12 mass of 12C
Atomic wt = wt of 6.023 x 1023 molecules or atoms
1 amu/atom = 1g/mol

Unit

C
H

12.011
1.008 etc.

Chapter 2 - 2

Atomic Structure
Valence electrons: in the outer-shell
determine all of the following properties
1)
2)
3)
4)

Chemical: reactivity
Electrical: conductivity
Thermal: conductivity
Optical: transmittance

Chapter 2 - 3

Electronic Structure - Review

Electrons have wavelike and particulate properties.
This means that electrons are in orbitals defined by a
probability.
Each orbital at discrete energy level determined by
quantum numbers.
Quantum #

Designation

n = principal (energy level-shell)

l = subsidiary (orbitals)
ml = magnetic (direction in space)

K, L, M, N, O (1, 2, 3, etc.)
s, p, d, f (0, 1, 2, 3,, n -1)
1, 3, 5, 7 (-l to +l)

ms = spin

, -

Chapter 2 - 4

Electron Energy States

Electrons...

have discrete energy states

tend to occupy lowest available energy state.
4d
4p

N-shell n = 4

3d
4s
Energy

3p
3s

M-shell n = 3

2p
2s

L-shell n = 2

1s

K-shell n = 1
Chapter 2 - 5

SURVEY OF ELEMENTS - Review

Most elements: Electron configuration not stable.
Element
Atomic #
Hydrogen
1
Helium
2
Lithium
3
Beryllium
4
Boron
5
Carbon
6
...
Neon
10
Sodium
11
Magnesium
12
Aluminum
13
...

Electron configuration
1s 1
1s 2
(stable)
1s 2 2s 1
1s 2 2s 2
1s 2 2s 2 2p 1
1s 2 2s 2 2p 2
...

Argon
...
Krypton

1s 2 2s 2 2p 6 3s 2 3p 6
(stable)
...
1s 2 2s 2 2p 6 3s 2 3p 6 3d 10 4s 2 4p 6 (stable)

18
...
36

1s 2 2s 2 2p 6
(stable)
1s 2 2s 2 2p 6 3s 1
1s 2 2s 2 2p 6 3s 2
1s 2 2s 2 2p 6 3s 2 3p 1
...

Why? Valence (outer) shell usually not filled completely.

Chapter 2 - 6

Electron Configurations
Valence electrons those in unfilled shells
Filled shells more stable
Valence electrons are most available for bonding and
tend to control the chemical properties
Primary Bonding: Ionic, Covalent and Metallic

example: C (atomic number = 6)

1s2 2s2 2p2
valence electrons

Chapter 2 - 7

Electronic Configurations
ex: Fe - atomic # = 26 1s2 2s2 2p6 3s2 3p6
4d
4p

3d 6 4s2

N-shell n = 4 valence
electrons

3d
4s
Energy

3p
3s

M-shell n = 3

2p
2s

L-shell n = 2

1s

K-shell n = 1
Chapter 2 - 8

give up 1e
give up 2e
give up 3e

Columns: Similar Valence Structure

accept 2e
accept 1e
inert gases

The Periodic Table

He

Li Be

F Ne

Na Mg

Cl Ar

K Ca Sc
Rb Sr

Cs Ba

Se Br Kr
Te

Xe

Po At Rn

Fr Ra

Electropositive elements:
Readily give up electrons
to become + ions.

Electronegative elements:
Readily acquire electrons
to become - ions.
Chapter 2 - 9

Electronegativity
Ranges from 0.7 to 4.0,
Large values: tendency to acquire electrons.

Smaller electronegativity

Larger electronegativity
Chapter 2 - 10

Ionic bond metal

nonmetal

donates
electrons

accepts
electrons

Dissimilar electronegativities
Neon

ex: MgO

10

1s 2 2s 2 2p 6

Mg

1s2 2s2 2p6 3s2

[Ne] 3s2

Mg2+ 1s2 2s2 2p6

[Ne]

(stable)

1s2 2s2 2p4

O2- 1s2 2s2 2p6

[Ne]
Chapter 2 - 11

Ionic Bonding

Occurs between + and - ions.

Requires electron transfer.
Large difference in electronegativity required.
Example: NaCl
Na (metal)
unstable

Cl (nonmetal)
unstable
electron

Na (cation)
stable

Coulombic
Attraction

Cl (anion)
stable

Chapter 2 - 12

Examples: Ionic Bonding

Predominant bonding in Ceramics

NaCl
MgO
CaF 2
CsCl

Give up electrons

Acquire electrons
Chapter 2 - 13

Covalent Bonding
similar electronegativity share electrons
bonds determined by valence s & p orbitals
dominate bonding
Example: CH4
C: has 4 valence e -,
needs 4 more

CH 4

H: has 1 valence e -,
needs 1 more

Electronegativities
are comparable.

shared electrons
from carbon atom

H
shared electrons
from hydrogen
atoms

Chapter 2 - 14

Primary Bonding
Metallic Bond -- delocalized as electron cloud
Ionic-Covalent Mixed Bonding

(X A X B )2

% ionic character =
4
1
e

where XA & XB are Pauling electronegativities

Ex: MgO

x (100%)

XMg = 1.3
XO = 3.5

% ionic character

(3.5 1.3 )2

4
1 e

x (100%) 70.2% ionic

Chapter 2 - 15

SECONDARY BONDING
Arises from interaction between dipoles
Fluctuating dipoles
asymmetric electron
clouds

secondary
bonding

ex: liquid H 2
H2
H2

H H

H H
secondary
bonding

Permanent dipoles-molecule induced

-general case:
-ex: liquid HCl
-ex: polymer

H Cl

secondary
bonding

secondary
bonding

H Cl

secon
dary
bond
ing

Adapted from Fig. 2.14,

Callister 7e.

secondary bonding
Chapter 2 - 16

Summary: Bonding
Comments

Type

Bond Energy

Ionic

Large!

Nondirectional (ceramics)

Covalent

Variable
large-Diamond
small-Bismuth

Directional
(semiconductors, ceramics
polymer chains)

Metallic

Variable
large-Tungsten
small-Mercury

Nondirectional (metals)

Secondary

smallest

Directional
inter-chain (polymer)
inter-molecular
Chapter 2 - 17

Interactions Between Atoms

Far Atoms: Attraction

Close Atoms: Repulsion

Atomic Radius (R)

+
+
r

Spacing (r)
Dynamic Equilibrium

Equilibrium spacing = ro
ro = 2 R

Chapter 2 - 18

Chapter 2 - 19

Bonding Curve

Chapter 2 - 20

Bonding Curve
Energy minimum energy most stable
Energy balance of attractive and repulsive terms
ro

EN = EA + ER =

A
r

B
rn

Repulsive energy ER

Interatomic separation r
Net energy EN

Attractive energy EA
Chapter 2 - 21

Bonding - Estimations
Estimation of Bonding Energy (Eo) and Equilibrium Spacing (ro)
Given:

E = certain f(r) e.g. E =

Bonding occurs at energy minimum

At minimum: Derivative dE/dr = g(r) = 0

Solve g(r) = 0 for r ro
Substitute r=ro in the Energy Eqn:
Get Eo = E (r=ro)
Atomic radius R = ro/2

A
r

B
r n

Energy
ro

r
Eo =
bond energy

For many atoms, ro is approximately 0.3 nm.

Chapter 2 - 22

Properties From Bonding: Tm

Bond length, r

Melting Temperature, Tm
Energy

r
Bond energy, Eo

ro

Energy

r
smaller Tm

unstretched length
ro

Eo =
bond energy

larger Tm
Tm is larger if Eo is larger.

Chapter 2 - 23

Properties From Bonding :

Coefficient of thermal expansion,
Coefficient of thermal expansion

length, L o

unheated, T1

L
=(T2 -T1)
Lo

heated, T2

~ symmetry at ro
Energy
unstretched length
ro

Eo
Eo

is larger if Eo is smaller.

Larger
Smaller
Chapter 2 - 24

Summary: Primary Bonds

Ceramics
(Ionic & covalent bonding):

Metals

Large bond energy

large Tm
large E
small

Variable bond energy

(Metallic bonding):

Polymers

Directional Properties

(Covalent & Secondary):

secon
da

moderate Tm
moderate E
moderate

r y bo
n di n g

Secondary bonding dominates

small Tm
small E
large

Bonding in Solids > Liquids > Gases

Chapter 2 - 25

ANNOUNCEMENTS
Reading: Focus on Atomic Bonding in Solids
Core Problems:
2.7, 2.8, 2.12, 2.13,
2.17, 2.19, 2.21 (Callister 3rd Addition)
Quiz: Next Class

Chapter 2 - 26

Quiz
Rank materials A, B and C according to
1.
2.
3.
4.

Increasing melting temperature

Decreasing bonding energy
Increasing Atomic Radius
Increasing coefficient of thermal expansion

>
>
>
>

>
>
>
>

Energy

B Atomic Spacing r
c

Chapter 2 - 27

Quiz
Rank materials A, B and C according to
1.
2.
3.
4.

Increasing melting temperature

Decreasing bonding energy
Increasing Atomic Radius
Increasing coefficient of thermal expansion

>
>
>
>

>
>
>
>

Energy
A
B

Atomic Spacing r

c
Chapter 2 - 28