CHAPTER 2:

BONDING AND PROPERTIES

ISSUES TO ADDRESS...
• What promotes bonding?

• What types of bonds are there?

• What properties are inferred from bonding?

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 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

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 ELECTRON ENERGY STATES

Electrons...
• have discrete energy states
• tend to occupy lowest available energy state.
Increasing energy

4p
n=4 3d
4s
n=3 3p
3s
n=2 2p
2s
n=1 1s Adapted from Fig. 2.5,
Callister 6e.

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 STABLE ELECTRON CONFIGURATIONS

Stable electron configurations...

• have complete s and p subshells
• tend to be unreactive.

Z Element Configuration
2 He 1s2 Adapted from Table 2.2,
10 Ne 1s22s 22p6 Callister 6e.

18 Ar 1s2 2s22p63s23p6
36 Kr 1s2 2s22p63s23p63d10 4s24p6

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 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 22s 1
Beryllium 4 1s 22s 2
Boron 5 1s 22s 22p 1 Adapted from Table 2.2,
1s 22s 22p 2 Callister 6e.
Carbon 6
... ...
Neon 10 1s 22s 22p 6 (stable)
Sodium 11 1s 22s 22p 63s 1
Magnesium 12 1s 22s 22p 63s 2
Aluminum 13 1s 22s 22p 63s 23p 1
... ...
Argon 18 1s 22s 22p 63s 23p 6 (stable)
... ... ...
Krypton 36 1s 22s 22p 63s 23p 63d 10 4s 24 6 (stable)

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

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 THE PERIODIC TABLE
• Columns: Similar Valence Structure

inert gases
give up 1e
give up 2e

accept 2e
accept 1e
give up 3e
Metal

Nonmetal
H He
Li Be Intermediate Ne
O F
Na Mg Adapted
S Cl Ar
from Fig. 2.6,
K Ca Sc Se Br Kr Callister 6e.

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.
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 ELECTRONEGATIVITY
• Ranges from 0.7 to 4.0,
• Large values: tendency to acquire electrons.
H He
2.1 -
Li Be F Ne
1.0 1.5 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

Smaller electronegativity Larger electronegativity

Adapted from Fig. 2.7, Callister 6e. (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.
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 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

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 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

Adapted from Fig. 2.7, Callister 6e. (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.
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 COVALENT BONDING

• Requires shared electrons

• Example: CH4 shared electrons
H
C: has 4 valence e, from carbon atom
CH4
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 6e.

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 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
Adapted from Fig. 2.7, Callister 6e. (Fig. 2.7 is GaAs
adapted from Linus Pauling, The Nature of the Chemical Bond, 3rd edition, Copyright
1939 and 1940, 3rd edition. Copyright 1960 by Cornell University.

• Molecules with nonmetals

• Molecules with metals and nonmetals
• Elemental solids (RHS of Periodic Table)
• Compound solids (about column IVA) 11
 METALLIC BONDING

• Arises from a sea of donated valence electrons

(1, 2, or 3 from each atom).

+ + +

+ + +

+ + + Adapted from Fig. 2.11, Callister 6e.

• Primary bond for metals and their alloys

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 SECONDARY BONDING
Arises from interaction between dipoles
• Fluctuating dipoles
asymmetric electron ex: liquid H2
clouds H2 H2

+ - secondary + - H H H H
secondary
bonding Adapted from Fig. 2.13, Callister 6e. bonding

• Permanent dipoles-molecule induced

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

secondary Adapted from Fig. 2.14,

-ex: liquid HCl H Cl bonding H Cl Callister 6e.

secon
-ex: polymer d a ry b
ondin
g
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 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

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 PROPERTIES FROM BONDING: TM
• Bond length, r • Melting Temperature, Tm
F
F Energy (r)
r

• Bond energy, Eo ro
r
Energy (r)
smaller Tm
unstretched length
ro larger Tm
r
Eo= Tm is larger if Eo is larger.
“bond energy”

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 PROPERTIES FROM BONDING: E
• Elastic modulus, E cross
sectional
length, Lo
area Ao
Elastic modulus
undeformed F ∆L
∆L =E
Ao Lo
deformed F

• E ~ curvature at ro
Energy

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

larger Elastic Modulus 16

 PROPERTIES FROM BONDING: α
• Coefficient of thermal expansion, α
length, Lo coeff. thermal expansion
unheated, T1
∆L ∆L
= α (T2-T1)
heated, T2 Lo

• α ~ symmetry at ro
Energy

ro
r α is larger if Eo is smaller.
larger α

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

Metals Variable bond energy

(Metallic bonding): moderate Tm
moderate E
moderate α

Polymers Directional Properties

(Covalent & Secondary): Secondary bonding dominates
small T
secon
d a ry b
ondin
small E
g large α

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