Chapter 2: Atomic Structure &

Interatomic Bonding

ISSUES TO ADDRESS...
• 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
}
neutrons 1.67 x 10-27 kg

• atomic number = # of protons in nucleus of atom

= # of electrons of neutral species

• A [=] atomic mass unit = amu = 1/12 mass of 12C

Atomic wt = wt of 6.022 x 1023 molecules or atoms

1 amu/atom = 1g/mol

C 12.011
H 1.008 etc.
Chapter 2 - 2
 Atomic Structure

• Valence electrons determine all of the

following properties
1) Chemical
2) Electrical
3) Thermal
4) Optical

Chapter 2 - 3
 Electronic Structure
• Electrons have wavelike and particulate
properties.
– This means that electrons are in orbitals defined by a
probability.
– Each orbital at discrete energy level is determined by
quantum numbers.

Quantum # Designation
n = principal (energy level-shell) K, L, M, N, O (1, 2, 3, etc.)
l = subsidiary (orbitals) s, p, d, f (0, 1, 2, 3,…, n -1)
ml = magnetic 1, 3, 5, 7 (-l to +l)
ms = spin ½, -½

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 M-shell n = 3
3s
Adapted from Fig. 2.4,
Callister & Rethwisch 8e.
2p L-shell n = 2
2s

1s K-shell n = 1
Chapter 2 - 5
 SURVEY OF ELEMENTS
• Most elements: Electron configuration not stable.
Element Atomic # Electron configuration
Hydrogen 1 1s 1
Helium 2 1s 2 (stable)
Lithium 3 1s 2 2s 1
Beryllium 4 1s 2 2s 2
Boron 5 1s 2 2s 2 2p 1 Adapted from Table 2.2,
Callister & Rethwisch 8e.
Carbon 6 1s 2 2s 2 2p 2
... ...
Neon 10 1s 2 2s 2 2p 6 (stable)
Sodium 11 1s 2 2s 2 2p 6 3s 1
Magnesium 12 1s 2 2s 2 2p 6 3s 2
Aluminum 13 1s 2 2s 2 2p 6 3s 2 3p 1
... ...
Argon 18 1s 2 2s 2 2p 6 3s 2 3p 6 (stable)
... ... ...
Krypton 36 1s 2 2s 2 2p 6 3s 2 3p 6 3d 10 4s 2 4p 6 (stable)

• 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

– example: C (atomic number = 6)

1s2 2s2 2p2

valence electrons

Chapter 2 - 7
 Electronic Configurations
ex: Fe - atomic # = 26 1s2 2s2 2p6 3s2 3p6 3d 6 4s2

4d
4p N-shell n = 4 valence
electrons
3d
4s

Energy 3p M-shell n = 3
3s
Adapted from Fig. 2.4,
Callister & Rethwisch 8e.
2p L-shell n = 2
2s

1s K-shell n = 1

Chapter 2 - 8
 The Periodic Table
• Columns: Similar Valence Structure

inert gases
give up 1e-
give up 2e-

accept 2e-
accept 1e-
give up 3e-

H He
Li Be O F Ne
Adapted from
Na Mg S Cl Ar Fig. 2.6,
Callister &
K Ca Sc Se Br Kr
Rethwisch 8e.
Rb Sr Y Te I Xe
Cs Ba Po At Rn
Fr Ra

Electropositive elements: Electronegative elements:

Readily give up electrons Readily acquire electrons
to become + ions. to become - ions.
Chapter 2 - 9
 Electronegativity
• Ranges from 0.7 to 4.0,
• Large values: tendency to acquire electrons.

Smaller electronegativity Larger electronegativity

Adapted from Fig. 2.7, Callister & Rethwisch 8e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the
Chemical Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell University.

Chapter 2 - 10
 Ionic bond – metal + nonmetal

donates accepts
electrons electrons

Dissimilar electronegativities

ex: MgO Mg 1s2 2s2 2p6 3s2 O 1s2 2s2 2p4

[Ne] 3s2

Mg2+ 1s2 2s2 2p6 O2- 1s2 2s2 2p6

[Ne] [Ne]

Chapter 2 - 11
 Ionic Bonding
• Occurs between + and - ions.
• Requires electron transfer.
• Large difference in electronegativity required.
• Example: NaCl

Na (metal) Cl (nonmetal)
unstable unstable
electron

Na (cation) + - Cl (anion)
stable Coulombic stable
Attraction

Chapter 2 - 12
Chapter 2 - 13
 Ionic Bonding
• Energy – minimum energy most stable
– Energy balance of attractive and repulsive terms
A B
EN = EA + ER =  
r rn
Repulsive energy ER

Interatomic separation r

Net energy EN
Adapted from Fig. 2.8(b),
Callister & Rethwisch 8e.

Attractive energy EA
Chapter 2 - 14
 Examples: Ionic Bonding
• Predominant bonding in Ceramics
NaCl
MgO
CaF 2
CsCl

Give up electrons Acquire electrons

Adapted from Fig. 2.7, Callister & Rethwisch 8e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the
Chemical Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell University.

Chapter 2 - 15
 Covalent Bonding
• similar electronegativity  share electrons
• bonds determined by valence – s & p orbitals dominate bonding
• Example: CH4

shared electrons
H
C: has 4 valence e-, from carbon atom
CH 4
needs 4 more
H: has 1 valence e-, H C H
needs 1 more
shared electrons
Electronegativities H from hydrogen
are comparable. atoms

Adapted from Fig. 2.10, Callister & Rethwisch 8e.

Chapter 2 - 16
 Primary Bonding
• Metallic Bond -- delocalized as electron cloud

• Ionic-Covalent Mixed Bonding

 (X A  X B )2 
% ionic character =   4

1
 e x (100%)
 
 
where X & X are Pauling electronegativities
A B

Ex: MgO XMg = 1.2


XO = 3.5

 
( 3.5  1.2 )2 
 
% ionic character  1  e 4
 x (100%) 73.4% ionic

 
Chapter 2 - 17
 SECONDARY BONDING
Arises from interaction between dipoles
• Fluctuating dipoles
asymmetric electron ex: liquid H 2
clouds H2 H2

+ - + - H H H H
secondary secondary
bonding Adapted from Fig. 2.13,
bonding
Callister & Rethwisch 8e.

• Permanent dipoles-molecule induced

secondary
-general case: + - bonding
+ -
Adapted from Fig. 2.15,
Callister & Rethwisch 8e.
secondary
-ex: liquid HCl H Cl bonding H Cl
secon
-ex: polymer dary
bondi secondary bonding
ng
Chapter 2 - 18
 Summary: Bonding
Type Bond Energy Comments
Ionic Large! Nondirectional (ceramics)

Covalent Variable Directional

large-Diamond (semiconductors, ceramics
small-Bismuth polymer chains)

Metallic Variable
large-Tungsten Nondirectional (metals)
small-Mercury
Secondary smallest Directional
inter-chain (polymer)
inter-molecular
Chapter 2 - 19
 Properties From Bonding: Tm
• Bond length, r • Melting Temperature, Tm
Energy
r

• Bond energy, Eo ro
r
Energy smaller Tm

unstretched length
ro larger Tm
r
Eo = Tm is larger if Eo is larger.
“bond energy”

Chapter 2 - 20
 Properties From Bonding : 
• Coefficient of thermal expansion, 
length, Lo coeff. thermal expansion
unheated, T1
L L
= (T2 -T1)
heated, T2 Lo

•  ~ symmetric at ro
Energy
unstretched length
ro
r  is larger if Eo is smaller.

Eo
larger 

Eo smaller 
Chapter 2 - 21
Chapter 2 - 22
 Summary: Primary Bonds
Ceramics Large bond energy
(Ionic & covalent bonding): large Tm
large E
small 

Metals Variable bond energy

(Metallic bonding): moderate Tm
moderate E
moderate 

Polymers Directional Properties

(Covalent & Secondary): Secondary bonding dominates
small Tm
secon
dary
bondi small E
ng
large 

Chapter 2 - 23
 ANNOUNCEMENTS
Reading:

Core Problems:

Self-help Problems:

Chapter 2 - 24