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Interatomic Bonding
ISSUES TO ADDRESS...
What promotes bonding?
What types of bonds are there?
What properties are inferred from bonding?
Chapter 2 - 1
12.011
1.008 etc.
Chapter 2 - 2
Atomic Structure
Valence electrons determine all of the
following properties
1)
2)
3)
4)
Chemical
Electrical
Thermal
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
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
N-shell n = 4
3d
4s
Energy
3p
3s
M-shell n = 3
Adapted from Fig. 2.4,
Callister & Rethwisch 8e.
2p
2s
L-shell n = 2
1s
K-shell n = 1
Chapter 2 - 5
Chapter 2 - 6
Chapter 2 - 7
SURVEY OF ELEMENTS
Most elements: Electron configuration not stable.
Atomic #
Element
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
...
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 - 9
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
3s
M-shell n = 3
Adapted from Fig. 2.4,
Callister & Rethwisch 8e.
2p
2s
L-shell n = 2
1s
K-shell n = 1
Chapter 2 - 10
He
Li Be
F Ne
Na Mg
Cl Ar
K Ca Sc
Rb Sr
Cs Ba
Se Br Kr
Te
Adapted from
Fig. 2.6,
Callister &
Rethwisch 8e.
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 - 11
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 - 12
Chapter 2 - 13
Chapter 2 - 14
donates
electrons
nonmetal
accepts
electrons
Dissimilar electronegativities
ex: MgO
Mg
Ionic Bonding
Cl (nonmetal)
unstable
electron
Na (cation)
stable
+
Coulombic
Attraction
Cl (anion)
stable
Chapter 2 - 16
Ionic Bonding
Energy minimum energy most stable
Energy balance of attractive and repulsive terms
EN = EA + ER =
A
r
B
rn
Repulsive energy ER
Interatomic separation r
Net energy EN
Adapted from Fig. 2.8(b),
Callister & Rethwisch 8e.
Attractive energy EA
Chapter 2 - 17
Chapter 2 - 18
Chapter 2 - 19
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 - 20
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
H: has 1 valence e-,
needs 1 more
Electronegativities
are comparable.
CH 4
H
shared electrons
from carbon atom
H
shared electrons
from hydrogen
atoms
Chapter 2 - 21
Chapter 2 - 22
Chapter 2 - 23
Primary Bonding
Metallic Bond -- delocalized as electron cloud
Ionic-Covalent Mixed Bonding
% ionic character =
(X A X B )2
4
1
e
x (100%)
XMg = 1.2
XO = 3.5
( 3.5 1.2 )2
4
% ionic character 1 e
Chapter 2 - 24
Chapter 2 - 25
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
H Cl
secondary
bonding
secondary
bonding
H Cl
secondary bonding
Chapter 2 - 26
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 - 27
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 - 28
unheated, T1
L
= (T2 -T1)
Lo
heated, T 2
~ symmetric at ro
Energy
unstretched length
ro
E
o
E
o
is larger if Eo is smaller.
larger
smaller
Chapter 2 - 29
Metals
(Metallic bonding):
Polymers
(Covalent & Secondary):
Directional Properties
Secondary bonding dominates
small Tm
small E
large
Chapter 2 - 30
Chapter 2 - 31
Chapter 2 - 32