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Lecture03f - Van Der Waals
Lecture03f - Van Der Waals
Lecture03f - Van Der Waals
(Bonding) Continued
More on Van der Waals
& Hydrogen Bonding
Van Der Waals Bonding
This WEAK dipole interaction is the origin of the van der
Waals bond, which is therefore characterized by a LOW
cohesive energy, and so LOW melting temperatures
+ - + -
SPONTANEOUS DIPOLE FORMATION IN ONE ATOM
MAY INDUCE AN EQUAL AND OPPOSITE DIPOLE IN
ANOTHER ATOM NEARBY SO CAUSING ATTRACTION
THIS IS THE VAN DER WAALS BOND
Another type of van der Waals bonding is observed for
certain POLAR molecules, that have a PERMANENT
dipole moment
Van Der Waals Bonding
Although IONIZED atoms are electrically NEUTRAL, electrons
within them are in a CONSTANT state of motion, and so may
MOMENTARILY form small charge DIPOLES
DIPOLE
+e -e
FORMS
+ -
A CHARGE DIPOLE MAY SPONTANEOUSLY
A DIPOLE CONSISTS OF EQUAL AND
FORM IN A NEUTRAL ATOM DUE TO THE MOTION
OPPOSITE CHARGES SEPARATED BY
OF ELECTRONS AROUND THE NUCLEUS
SOME DISTANCE
dE nA mB
0 n 1 m 1
dr r ro r r
nA mB mn mB
r
r n 1 r m 1 nA
1
nA nm B m
ro & E (ro ) m
1
mB ro n
Intermolecular Forces
The origin of intermolecular forces
The classification of intermolecular forces
Van der Waals force
Hydrogen bonding
Explore an example in depth to show the
significance of existence of intermolecular forces.
The Origin of Intermolecular Forces
It is weak electrostatic force of attraction
that exist an area of negative charge on one
molecule
and an area of positive charge on a second
molecule.
What causes intermolecular forces?
Molecules are made up of charged
particles: nuclei and electrons. When one
molecule approaches another, there is a
multitude of interactions between the
particles in the two molecules. Each
electron in one molecule is subject to
forces from all the electrons and the nuclei
in the other molecule.
Intermolecular force is weak compared to covalent
bond. It is relatively weak interactions that occur
between molecules.
There are 2 types of intermolecular forces (both of
them are electrostatic attraction between dipoles
formed by uncharged molecules.)
1. Van der Waals' force
2. Hydrogen bonding
Van der waals force is formed by dipoles. There
are 3 types of dipoles:
1. Permanent dipoles
2. Instantaneous dipoles
3. Induced dipoles
Permanent Dipole
These molecules have a permanent separation of positive and negative
charge.
+ -
The pair of electrons in the covalent bond between hydroge and chlorine is
unequally shared due to the difference in electronegativity between hydrogen and
chlorine. Chlorine has a greater electronegativity compared to hydrogen and hence
Chlorine tends to attract the bonded electron pair to itself. chlorine becomes slightly
negatively charged (-), hydroge atom has a partial positive charged (+) .The
unsymmetrical distributed charge on the HCl molecule produces a permanent
dipole.
Instantaneous Dipole
Instantaneous dipole is due to the fluctuation of
electron clouds on non-polar molecules, positive and
negative charges exist temporarily.
Induced Dipole
Induced dipole exists when a permanent dipole or
instantaneous dipole comes close to a non-polar
molecule, the non-polar molecule will be induced to
form a dipole temporarily.
Classification diagram of intermolecular forces
Dipole-Dipole Interactions
Dipole-dipole interactions exist between molecules which are permanent
dipole. They tend to orientate themselves that the attractive forces between
molecules are maximized while repulsive forces are minimized.
In the illustration :
the H end of HCl is permanently slightly positive charge. The Cl end of
HCl has a permanent slight negative charge, the "H" in one molecule is
attracted to the "Cl" in a neighbor.
Instantaneous Dipole-Induced Dipole Interactions
Also known as London forces or Dispersion Forces
Instantaneous dipole-induced dipole Interactions exist in non-polar
molecules. These forces result from temporary charge imbalances. The
temporary charges exist because the electrons in a molecule or ion move
randomly in the structure. The nucleus of one atom attracts electrons form
the neighboring atom. At the same time, the electrons in one particle repel
the electrons in the neighbor and create a short lived charge imbalance.
These temporary charges in one molecule or atom attract opposite charges
in nearby molecules or atoms. A local slight positive charge + in one
molecule will be attracted to a temporary slight - negative charge in a
neighboring molecule.
Note: dispersion forces operate in all molecules whether they are polar or non-polar.
Dipole-Induced Dipole Interactions
Also known as induction force.
When a polar molecule approaches a nonpolar molecule, the
permanent dipole on the polar molecule can distort the electron
cloud of the nonpolar molecule, forming an induced dipole.
Van der Waals Radius & Covalent Radius
Van der Waals radius is one half
of the distance between the
nuclei of two atoms in adjacent
molecules.
Covalent radius is one half of
the distance between two atoms
in the same molecules.
Van der Waals radius of a non-
metal is always larger than the
corresponding covalent radius
because the covalent radius
because covalent bond is much
stronger than van der Waals
forces.
4) Van der Waals Bonds
Weakest bond
Usually between neutral molecules (even large
ones like graphite sheets)
Aided by polar or partial polar covalent bonds.
Even stable A-A bonds like O2 or Cl2 will get slightly
polar at low T & condense to liquid & ordered solid
as vibration slows & polarity
Weakness of the bond is apparent in graphite cleavage
Van der Waals Bonding
12
6
U LJ 4
r r
Lennard Jones potentials
The Lennard-Jones potential
12
6
u r 4
LJ
r r
He 2.2 1 10 -22
H2 2.7 4
Ar 3.2 15
N2 3.7 13
CO2 4.5 40
The Lennard-Jones Potential
12
6
u r 4
r r
Contributions:
u(r)/
Dipole-dipole (including H-bonding)
Induced dipole
London dispersion attraction
r/
0 1 2 3
Example Lennard-Jones (LJ) clusters E
21/6
12
6
E 4
Two atoms: R R R
R
a
assume pairwise E 4
i j R ij
R
1 2 3 ij
additive:
b Isomers
1 3 2 different minima on potential energy surface
number of isomers grows exponentially
with # of atoms
c a and b permutation-inversion isomers
Ea = Eb Ec
Intermolecular Potentials
Dense Gases, Liquids and Solids
Gases
Electric dipole ~ r -3
No long range interactions
2 dipoles
Interact via elastic collisions ~ r -6
Carey, V.P., Statistical Thermodynamics and Microscale Thermophysics, New York: Cambridge University Press, 1999.