CHAPTER 2:

Atomic Structure and Interatomic

Bonding

ISSUES TO ADDRESS...
What promotes bonding?

What types of bonds are there?

What properties are inferred from bonding?

 BOHR ATOM
orbital electrons:
n = principal
quantum number 1
n=3 2 Adapted from Fig. 2.1,
Callister 6e.

Nucleus: Z = # protons
= 1 for hydrogen to 94 for plutonium
N = # neutrons
Atomic mass A Z + N
 ELECTRON ENERGY
Electrons...
STATES
have discrete energy states
tend to occupy lowest available energy state.
 STABLE ELECTRON
CONFIGURATIONS
Stable electron configurations...
have complete s and p subshells
tend to be unreactive.
 SURVEY OF ELEMENTS
Most elements: Electron configuration not stable.
Electron configuration
1s1
1s2 (stable)
1s22s1
1s22s2
1s22s22p1
1s22s22p2
...
1s22s22p6 (stable)
1s22s22p63s1
1s22s22p63s2
1s22s22p63s23p1
...
1s22s22p63s23p6 (stable)
...
1s22s22p63s23p63d10 4s246 (stable)

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

 THE PERIODIC TABLE
Columns: Similar Valence Structure

Electropositive elements: Electronegative elements:

Readily give up electrons Readily acquire electrons
to become + ions. to become - ions.
 ELECTRONEGATIVITY
Ranges from 0.7 to 4.0,
Large values: tendency to acquire electrons.

Smaller electronegativity Larger electronegativity

 IONIC BONDING
Occurs between + and - ions.
Requires electron transfer.
Large difference in electronegativity required.
Example: NaCl
 EXAMPLES: IONIC BONDING
Predominant bonding in Ceramics
NaCl
MgO
H He
2.1 CaF2 -
Li Be O F Ne
1.0 1.5 CsCl 3.5 4.0 -
Na Mg Cl Ar
0.9 1.2 3.0 -
K Ca Ti Cr Fe Ni Zn As Br Kr
0.8 1.0 1.5 1.6 1.8 1.8 1.8 2.0 2.8 -
Rb Sr I Xe
0.8 1.0 2.5 -
Cs Ba At Rn
0.7 0.9 2.2 -
Fr Ra
0.7 0.9

Give up electrons Acquire electrons

 COVALENT BONDING
Requires shared electrons

Example: CH4
C: has 4 valence e,
needs 4 more
H: has 1 valence e,
needs 1 more
Electronegativities
are comparable.
 Calculating the degree of ionic
character
% ionic character = [1-e(-.25xDen^2)]x 100

Example: en(Mg) = 1.2

en(O) = 3.5
%ionic character = {1-e[-.25*(3.5-1.2)^2]} x 100
= 73.3%
 EXAMPLES: COVALENT BONDING
H2O

column IVA
H2 F2
C(diamond)
H He
2.1
SiC - Cl2
Li Be C O F Ne
1.0 1.5 2.5 2.0 4.0 -
Na Mg Si Cl Ar
0.9 1.2 1.8 3.0 -
K Ca Ti Cr Fe Ni Zn Ga Ge As Br Kr
0.8 1.0 1.5 1.6 1.8 1.8 1.8 1.6 1.8 2.0 2.8 -
Rb Sr Sn I Xe
0.8 1.0 1.8 2.5 -
Cs Ba Pb At Rn
0.7 0.9 1.8 2.2 -
Fr Ra
0.7 0.9 GaAs

Molecules with nonmetals

Molecules with metals and nonmetals
Elemental solids (RHS of Periodic Table)
Compound solids (about column IVA)
 METALLIC BONDING
Arises from a sea of donated valence electrons
(1, 2, or 3 from each atom).

Primary bond for metals and their alloys

 SECONDARY BONDING
Arises from interaction between dipoles
Fluctuating dipoles

Adapted from Fig. 2.13, Callister 6e.

Permanent dipoles-molecule induced

Adapted from Fig. 2.14,
-general case: Callister 6e.

Adapted from Fig. 2.14,

-ex: liquid HCl Callister 6e.

-ex: polymer
 SUMMARY: BONDING
Type Bond Energy Comments
Ionic Large! Nondirectional (ceramics)

Variable Directional
Covalent large-Diamond semiconductors, ceramics
small-Bismuth polymer chains)

Variable
Metallic large-Tungsten Nondirectional (metals)
small-Mercury
Directional
Secondary smallest inter-chain (polymer)
inter-molecular
 PROPERTIES FROM
BONDING: TM
Bond length, r Melting Temperature, Tm
F
F

Bond energy, Eo

Tm is larger if Eo is larger.
 PROPERTIES FROM BONDING: E
Elastic modulus, E
Elastic modulus
F DL
=E
Ao Lo

E ~ curvature at ro
Energy

unstretched length
ro E is larger if Eo is larger.
r
smaller Elastic Modulus

larger Elastic Modulus

 PROPERTIES FROM BONDING: a
Coefficient of thermal expansion, a
coeff. thermal expansion

DL
= a(T2-T1)
Lo

a ~ symmetry at ro

a is larger if Eo is smaller.
 Properties of common Metals
Material Melting Temp (oC) Elastic Modulus Thermal Expansion Coefficient
(GPa) a, (10-6 m/m/oC)

Tungsten, W 3410 410 4.5

Iron, Fe 1538 200 12

Aluminum, Al 660 69 23

Magnesium, Mg 649 45 14.4

 SUMMARY: PRIMARY BONDS
Ceramics Large bond energy
(Ionic & covalent bonding): large Tm
large E
small a

Metals Variable bond energy

(Metallic bonding): moderate Tm
moderate E
moderate a

Polymers Directional Properties

(Covalent & Secondary): Secondary bonding dominates
small T
small E
large a