3/15/2012

1
Atomic Structure and Interatomic
Bonding:
Callister Chapter 2
What promotes bonding?
What types of bonds are there?
What properties are conditional from bonding?
consider carbon: graphite and diamond
graphite soft, "greasy"
diamond hardest material known
How are atoms arranged?
atomic structure
2
Atomic Structure
atom electrons 9.11 x 10
-31
kg
protons
neutrons

atomic number = # of protons in nucleus of atom
= # of electrons of neutral species

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

Atomic wt = wt of 6.023 x 10
23
molecules or atoms

1 amu/atom = 1g/mol

C
H
12.011
1.008 etc.
Bohr model of
atomic structure
Electron
Cloud
Nucleus
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3
3
Atomic Structure
Valence electrons determine all of the
following properties
1) Chemical
2) Electrical
3) Thermal
4) Optical
4
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 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)
m
l
= magnetic 1, 3, 5, 7 (-l to +l)
m
s
= spin , -
Bohr & Schrodinger
5
Electron Energy States
1s
2s
2p
K-shell n = 1
L-shell n = 2
3s
3p
M-shell n = 3
3d
4s
4p
4d
Energy
N-shell n = 4
have discrete energy states
tend to occupy lowest available energy state.
Electrons...
Adapted from Fig. 2.4,
Callister 7e.
I
n
c
r
e
a
s
i
n
g

e
n
e
r
g
y

l
e
v
e
l
s

The number of available electron in some of the
electron shell and sub shells
7
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)

1s
2
2s
2
2p
2

valence electrons
8
Electronic Configurations
ex: Fe - atomic # =
26
Adapted from Fig. 2.4,
Callister 7e.
1s
2s
2p
K-shell n = 1
L-shell n = 2
3s
3p
M-shell n = 3
3d
4s
4p
4d
Energy
N-shell n = 4
1s
2
2s
2
2p
6
3s
2
3p
6
3d
6
4s
2
Valence
electrons
I
n
c
r
e
a
s
i
n
g

e
n
e
r
g
y

l
e
v
e
l
s

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The Periodic Table
Columns: Similar Valence Structure
Adapted from
Fig. 2.6,
Callister 7e.
g
i
v
e

u
p

1
e

g
i
v
e

u
p

2
e

g
i
v
e

u
p

3
e

i
n
e
r
t

g
a
s
e
s

a
c
c
e
p
t

1
e

a
c
c
e
p
t

2
e

O
Se
Te
Po At
I
Br
He
Ne
Ar
Kr
Xe
Rn
F
Cl S
Li Be
H
Na Mg
Ba Cs
Ra Fr
Ca K Sc
Sr Rb Y
Elements of Group IA have one valence electron.
Elements in Group 4A have four valence electrons, etc
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Smaller electronegativity Larger electronegativity
Adapted from Fig. 2.7, Callister 7e. (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.
Electronegativity
Electronegativity is the ability of an atom to
attract electrons to itself.
Interactions between atoms
Electrons in the outermost levels interact first.
When the outer shells are unfilled, atoms
gain, lose, or borrow electrons which is the
basis of bonding.
Eg NaCl
13
BondingProperties
13
Ionic bond metal + nonmetal

donates accepts
electrons electrons

Dissimilar electronegativities

ex: MgO Mg 1s
2
2s
2
2p
6
3s
2
O 1s
2
2s
2
2p
4

[Ne] 3s
2


Mg
2+
1s
2
2s
2
2p
6
O
2-
1s
2
2s
2
2p
6

[Ne] [Ne]
14
Occurs between + and - ions.
Requires electron transfer.
Large difference in electronegativity required.
Example: NaCl
Ionic Bonding
Na (metal)
unstable
Cl (nonmetal)
unstable
electron
+
-
Coulombic
Attraction
Na (cation)
stable
Cl (anion)
stable
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15
Ionic Bonding
Energy minimum energy most stable
Energy balance of attractive and repulsive terms
Attractive energy E
A

Net energy E
N

Repulsive energy E
R

Interatomic separation r
r
A
n
r
B
E
N
= E
A
+ E
R
=
+
Adapted from Fig. 2.8(b),
Callister & Rethwisch 8e.
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Predominant bonding in Ceramics
Adapted from Fig. 2.7, Callister 7e. (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.
Examples: Ionic Bonding
Give up electrons Acquire electrons
NaCl
MgO
CaF
2
CsCl
Chapter 2 -
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C: has 4 valence e
-
,
needs 4 more
H: has 1 valence e
-
,
needs 1 more
Methane gas .
Adapted from Fig. 2.10, Callister 7e.
Covalent Bonding
similar electronegativity share electrons
bonds determined by valence s & p orbitals
dominate bonding
Example: CH
4
shared electrons
from carbon atom
shared electrons
from hydrogen
atoms
H
H
H
H
C
CH
4
Electronegativities
are comparable.
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NonMetallic Elemental
Molecules; e.g. F
2
Hydrogen Compounds;
e.g., HF, HNO
3
Elemental Solids; e.g.,
C, Si, Ge
Near Group-IVA Solid
Compounds; e.g. GaAs

Covalent bonding
Covalent bonds are formed by sharing of the valence electrons
Covalent bonds are very directional
Covalent bond model: an atom can have at most 8-N covalent
bonds, where N = number of valence electrons
Covalent bonds can be very strong, eg diamond, SiC, Si, etc,
also can be very weak, eg Bismuth

Polymeric materials exhibit covalent type bonding.
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Electrons Shared By All Atoms
sea of electrons around ion cores
Ion Cores
Atom Gives Up e
-
to the sea, leaving remaining
Atom with a Positive Ionic Charge
The Ion contains the Large & Heavy Nucleus
and is thus FIXED in Space
Generally Apply to Electro-Positive Elements
e.g.; Transition Metals such as Ti, Ni, Zn

Metallic bonding
A metallic bond is non-directional
(bonds form in any direction)
atoms pack closely high density.
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http://207.10.97.102/chemzone/lessons/03bonding/mleebonding/metallicblue.gif
Metallic bonds may be weak or strong.
Bonding energies: range from 68 kJ/mol (0.7 eV/atom) for
Hg to 850 kJ/mol (8.8 eV/atom) for W.
Melting temperatures: -39 C for Hg and 3410 C for W.

Metallic bonding
Metals can be reshaped
high melting points
hardness
electrical conductivity
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Mixed Ionic+Covalent Bonding
Many Compounds Exhibit
Ionic-Covalent Mixed Bonding
semiconducting compounds such as GaAs, ZnSe
( )
2
4
100%
%Ionic 1
1
A B
X X
e

| |
|
=
|
\ .
where X
A
& X
B
are Pauling ElectroNegativities
Example MgO: X
Mg
= 1.2, X
O
= 3.5
ionic 73.4% (100%) x e 1 character ionic %
4
) 2 . 1 5 . 3 (

2
=
|
|
|
.
|

\
|
=

22
Determine how ionic the bonds between the
following atoms would be
Sodium and
chlorine
Na E
0
0.9
Cl E
0
3.0
=2.1
68% ionic
Carbon and
nitrogen
C E
0
2.5
N E
0
3.0
=0.5
10% ionic
90%covalent
Potassium and
suphur
K E
0
0.8
S E
0
2.5
=2.1
50% ionic
( )
2
4
100%
%Ionic 1
1
A B
X X
e

| |
|
=
|
\ .
X
A
X
B
% Ionic
electronegativity
charges
from
periodic table
Covalent vs Ionic Bonding
The polarity of a covalent
bond is the partial ionic
character
Real bonds lie
somewhere between ionic
and covalent
The difference in
electronegativity
corresponds directly to the
percent ionic character of
the bond
Very few materials have pure ionic or covalent bonding;
electronegativity inpart defines how much time electrons
spend between ion cores
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Type Substance Energy
(eV/atom)
Melt. Temp
(C)
Ionic
NaCl 3.3 801
MgO 5.2 2800
Covalent
Si 4.7 1410
C 7.4 >3550
Metallic
Hg 0.7 -39
Al 3.4 660
Fe 4.2 1538
W 8.8 3410
Bonding Energies and Melting
Temperatures
Dipole Forces
Electrostatic interactions
between adjacent
molecules are called
Dipole Forces
The most extreme form of
dipole forces result from
the interaction of a
hydrogen atom with a
highly electronegative
atom resulting in
hydrogen bonding.
Secondary bonding Dipole Forces
Dispersion Forces (or Van der Waals
forces)
Interactions resulting from
momentary concentration
variations in the electron
clouds of adjacent atoms
The interactions are brief
and weak, but large
molecules (such as
polymers) have
opportunities for many
simultaneous interactions
27
Hydrogen Bonding
Hydrogen bonding in HF
solid ice
liquid water
Special type of secondary
bonding, exists between some
molecules that have hydrogen
as one of constituents
The increase in volume of ice is about
9%. This increase causes enough
force to break most rigid containers.
This is the same force, repeated on a daily basis, that creates "pot holes" in the roads in
the winter time.
http://www.elmhurst.edu/~chm/vchembook/122Adensityice.html
28
Adapted from Fig. 2.14,
Callister 6e.
The dipole moment of water provides a "handle" for
interaction with microwave electric fields in a microwave
oven.

Microwaves can add energy to the water molecules, they
vibrate and heat the compounds.
Secondary Bonding, Polar
29
C Bonding-Type Properties
Diamond:
covalent (directional) bonds
Graphite:
covalent bonds within layers
van der Waals b/w layers
layers slide
soft, greasy (lubricant)
hardest known material
Bond energy, Eo
Bond length, r
F
F
r
Melting Temperature, Tm
if bonding energy Eo is large
melting temperature Tm
is large.
Properties from Bonding: T
M

AL F
A
o

= E
L
o

Elastic modulus
r
larger Elastic Modulus
smaller Elastic Modulus
Energy
r
o

unstretched length
Properties from Bonding: E
Elastic modulus, E
E ~ curvature at ro
if slope r=r
o
is steep
Modulus is high
Coefficient of thermal expansion, o

= o (T
2
-T
1
)
AL
L
o

coeff. thermal expansion
Properties from Bonding: o
o ~ symmetry at ro
Eg. Thermostats for central
heating
o is larger if E
o
is smaller.
Bonding Energies and Melting
Temperatures for Various Substances
34
Summary: Primary Bonds
Ceramics
(Ionic & covalent bonding):
Metals
(Metallic bonding):
Polymers
(Covalent & Secondary):
Large bond energy
large Tm
large E
small o
Variable bond energy
moderate Tm
moderate E
moderate o
Directional Properties
Secondary bonding dominates
small T
m
small E
large o
Reading:

The structure of crystalline solids Part I:
Callister Chapter 3.
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