Lecture 4: Secondary bonds , Materials Physics
2nd class/polymer Dep.
Secondary Bonds
Electric Dipoles
To understand these forces the idea of dipoles is needed. An electric
dipole is basically a pair of equal positive and negative charges separated
by a small distance.
These dipoles will arise, for example, in a molecule, where atoms share
an electron, but the electron spends more time with one atom, because
it is bigger, and less time with the smaller atom.
The effective charge separation may be only a fraction (perhaps a
tenth) of the electron's charge.
Bonding between dipoles happens when the positive end of one dipole
is attracted to the negative end of another.
1
Lecture 4: Secondary bonds , Materials Physics
2nd class/polymer Dep.
Since the effective charges are small compared with those involved in
primary bonding, secondary bonding is about one tenth of primary bond
strengths.
Van Der Waals Bonding
2
Lecture 4: Secondary bonds , Materials Physics
2nd class/polymer Dep.
Secondary bonds are weak in comparison to primary
bonds.
They are found in most materials, but their effects are often
overshadowed by the strength of the primary bonding.
Secondary bonds are not bonds with a valence electron
being shared or donated. They are usually formed when an
uneven charge distribution occurs, creating what is known
as a dipole (the total charge is zero, but there is slightly
more positive or negative charge on one end of the atom
than on the other).
These dipoles can be produced by a random fluctuation of the electrons
around what is normally an electrically symmetric field in the atom.
Once a random dipole is formed in one atom, an induced dipole is
formed in the adjacent atom.
This is the type of bonding present in N2 molecules, and is known as
Van Der Waals Bonding.
Secondary bonding may also exist when there is a permanent dipole in
a molecule due to an asymmetrical arrangement of positive and
negative regions.
3
Lecture 4: Secondary bonds , Materials Physics
2nd class/polymer Dep.
Molecules with a permanent dipole can either induce a dipole in
adjacent electrically symmetric molecules, and thus form a weak bond,
or they can form bonds with other permanent dipole molecules.
Secondary Bonds 2
Hydrogen Bonding
Hydrogen bonding is the strongest form of secondary
bonding and is formed from the polar nature of molecules
containing hydrogen.
The hydrogen side of the molecule is more positive than the
atom it is bonded to, allowing an attraction to form with the
negative end of another molecule.
In hydrogen bonding, the hydrogen is attached directly to
an element which is electronegative. This causes the
hydrogen to acquire a significant positive charge.
4
Lecture 4: Secondary bonds , Materials Physics
2nd class/polymer Dep.
The melting and boiling points of materials containing hydrogen
bonding, are abnormally high, for their atomic weights, due to hydrogen
bonding.
Bonds in periodic table:
The Periodic Table with Electron Configurations
For a background on the periodic table,
Atoms have their electrons confined in potential energy wells around them, but not at
any energy, there are only a few discrete energy levels allowed. These levels are like
steps on a ladder where your feet cannot be supported at any height, but only on the
rungs.
The electrons then cannot be at intermediate energies, they will fall down to the next
"rung" on the energy ladder, grouping in three dimensional "shells".
The periodic table arises because only certain numbers of electrons are allowed in
each shell, as also illustrated in the diagram. Electrons are held at upper levels
5
Lecture 4: Secondary bonds , Materials Physics
2nd class/polymer Dep.
because they cannot all fall down to the bottom.
The valence electrons are in the outer (highest) energy levels and are the main
determiners of chemical activity and bonding. "Valence" comes from a Latin word
meaning "power" and used for the "combining power" of an atom,
As the outer shells determine most of the chemical properties, the
Periodic Table below shows only the electron numbers in the two outer
shells, the colours indicate how shells are filled.
IA IIA IIIB IVB
VB
VIB
VII
B
{-
VIII
B
-}
IB
IIB
IIIA IVA
VA
VIA
VII
A
H
1
0
He
2
1
Li Be
2.1 2.2
B
2.3
C
2.4
N
2.5
O
2.6
F
2.7
Ne
2.8
2
Na Mg
.8. .8.
2
3 1
Al
Si
P
S
Cl
Ar
.8.3 .8.4 .8.5 .8.6 .8.7 .8.8
K Ca Sc Ti
V
Cr Mn Fe Co Ni
Cu Zn Ga Ge As Se Br Kr
.8. .8. .9.2 .10. .11. .13. .13. .14. .15. .16. .18. .18. .18. .18. .18. .18. .18. .18.
2
2
2
1
2
2
2
2
1
2
3
4
5
6
7
8
4 1
Rb Sr
.8. .8.
2
5 1
Y
Zr
Nb Mo Tc Ru Rh Pd
.9.2 .10. .12. .13. .14. .15. .16. .18
2
1
1
1
1
1
Cs Ba La* Hf
Ta W
Re Os Ir
.8. .8. .9.2 .10. .11. .12. .13. .14. .17
2
2
2
2
2
2
6 1
Fr
Ra Ac* Rf
Ha
Sg
Ns
Hs
Mt
Ag Cd In
Sn Sb Te I
Xe
.18. .18. .18. .18. .18. .18. .18. .18.
1
2
3
4
5
6
7
8
Pt
Au Hg Tl
Pb Bi
Po At
Rn
.17. .18. .18. .18. .18. .18. .18. .18. .18.
1
1
2
3
4
5
6
7
8
Uu
Uu
Uu
Uut Uu
Uu
Uu
Uus Uu
6
Lecture 4: Secondary bonds , Materials Physics
.8. .8.
2
7 1
*
.9.2
2nd class/polymer Dep.
n
u
b
q
p
h
o
Ce* Pr
Nd Pm Sm Eu Gd Tb Dy Ho Er
Tm Yb Lu
.8.2 .8.2 .8.2 .8.2 .8.2 .8.2 .9.2 .8.2 .8.2 .8.2 .8.2 .8.2 .8.2 .9.2
Th* Pa U
Np Pu Am Cm Bk
*
.9.2 .9.2 .9.2 .9.2 .9.2 .9.2
.10.
2
Cf
Es
Fm
Md
No
Lr
The inert gases of Group 0, namely Helium, Neon, Argon, Krypton,
Xenon, and Radon, each have 8 valence electrons and form few
chemical compounds. (Helium is an exception with only 2 outer
electrons). This suggests that 8 valence electrons form a stable
electronic structure where an atom tends not to share electrons with
other atoms.
An element will be chemically reactive if it can get to the stable
electronic
configuration
of
an
inert
gas,
either
• by losing one or two electrons to another atom, or
• by gaining one or two electrons from another atom (at most three),or
• by sharing three or more electrons.
Summarising:
*The Periodic Table gives an indication of how electrons will be shared.
*Ionic bonds tend to form between elements at the edges.
*Covalent bonds tend to form between elements in the middle.
*Metallic bonds have overlapping potentials releasing some electrons to
form
a
"glue".
*Secondary bonds are the result of electric dipole interaction.
*Hydrogen
bonds
form
with
permament
dipoles.
*Van der Waals bonds generally form from fluctuating dipoles.
Ionic
Strong
n=1, m=9
non-directional
long range
charge stacking
requirements
Covalent
Strong
n=6, m=12
Directional
short range
no charge
stacking
requirements
Metallic
strong
non-directional
long range
no charge
stacking
requirements
Van der Waals
weak
n=6, m=12
non-directional
short range
dipole orientation
Hydrogen
weak
n=2
non-directional
short range
dipole orientation
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Lecture 4: Secondary bonds , Materials Physics
2nd class/polymer Dep.
*Ionic crystals tend to be brittle because of the charge restriction.
*Covalent crystals tend to be brittle because of the directional
restriction.
*Metals tend to be plastic because there are no directional or charge
restrictions.
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