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CN5030 14/15

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Part II. Intermolecular Forces




















The most fundamental equation of state, having the most sound
theoretical importance, is the virial equation of state. The virial equation
of state expresses the compressibility factor as polynomial in

v
1
:
+ + + = =
2
) ( ) (
1
v
T C
v
T B
RT
Pv
Z













Intermolecular forces are those forces maintaining liquid and solid states of
substances. The intermolecular forces are the root cause of the potential
energy among molecules of a substance. When the average kinetic energy of
molecules in a liquid/solid is greater than the intermolecular potential energy
then the substance will undergo vaporization or sublimization.

Three types of intermolecular forces:
^ Those due to permanent dipole or induced dipole interactions polar
interactions;
^ Those due to transient and random redistributions of charges over the
molecule dispersion forces (also known as London Dispersion
Forces), which exist to the exclusion of all others;
^ Those due to interactions of ions (charged molecules or atoms) ionic
interactions, or Coulomb interaction;
^ Those due to special forces, e.g. hydrogen bonding, electron
donor/acceptor complexation, t-interaction, and hydrophobic
interactions.

CN5030 14/15

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The contribution of the first few terms in the virial expansion of Z
for Ar at 25
o
C

P/bar
RT
Pv
Z =


+ + +
2
) ( ) (
1
v
T C
v
T B
remaining terms
1
) 00000 . 0 ( 00000 . 0 00064 . 0 1 + + +

10
) 00007 . 0 ( 00020 . 0 00648 . 0 1 + +

100
) 00036 . 0 ( 02127 . 0 06754 . 0 1 + +

1000
) 37232 . 0 ( 08788 . 0 38404 . 0 1 + + +


The
) (T B
is the most important virial coefficient because it reflects the
first deviation from ideality as the pressure of the gas is increased.















| | dr r e N T B
kT r
A
}

I
=
0
2 / ) (
1
~
2 ) ( t

) (r I
Potential energy

Non-covalent binding forces as it is independent of
direction (| and u).

A plot of Z versus P at low
pressures for NH
3
(g) at 0
o
C,
100
o
C, and 200
o
C. The slope
of the lines are equal to
RT T B / ) ( according to volume-
explicit virial equation. The
respective slopes give
1 3
345 . 0 ) 0 (

= mol dm C B
o
;
1 3
142 . 0 ) 100 (

= mol dm C B
o

1 3
075 . 0 ) 200 (

= mol dm C B
o


CN5030 14/15

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) Ion paring interactions (> 100Kcal /mol);
) Electrostatic interactions involving dipoles;
) Hydrogen bonding;
) t Effects;
) The hydrophobic effect;


Deviation from ideal (gas, or solution) behavior Attractive
forces between molecules


^ Electric properties of molecules

(1) The permanent dipole moment

ed =

The dipole moment of a pair of charges +e and e (1.6 10
-19
C) separated by
100 pm (0.1 nm) is 1.6 10
-29
Cm
1D = 3.335 64 10
-30
Cm

Polar molecules permanent dipole moment difference in
electronegativity
_ A ~ D /














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For polyatomic molecules configuration of molecule







































Cl
Cl
Cl
Cl
Cl

Cl
Cl






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CN5030 14/15

- 6 -


















The induced dipole moment

o =
i
, is the field strength orientation of the molecule
relative to the field.

where o is the polarizability (C
2
m
2
/J) of the molecule
electron cloud ease of being distorted the HOMO-LUMO
gaps (AE).

E
R e
A
=
3
2
2 2
o
(R, the radius of molecule)

o is often expressed as a polarizability volume, o (
3
)

0
4
'
tc
o
o =
where
) 1 (
0 0 e r
_ c c c c + = =


Polar or non-polar molecule depends on: functional group and
molecular geometric structure.
CN5030 14/15

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2 1 2 12
0
10 85419 . 8

= m N C c
(vacuum permittivity)



For electric field strength:




^ The interaction energy falls off more rapidly the higher the
order of the multipole. For the interaction of an n-pole with an
m-pole, the potential energy varies with distance as:

I 1
1
+m n
r


Multipole interaction potential energies

Interaction type Distance
dependence
Typical
energy/(kJ/mol)
Comment
Ion-ion 1/r 250

A-H

B



20

H-bond
Ion-dipole 1/r
2
15

Dipole-dipole


1/r
3

2

Between
stationary polar
molecules
1/r
6
0.6 Between rotating
polar molecules
London
(dispersion)

1/r
6
2 Between all types
of molecules



(1)
2
0
4 r
q
tc
= generated by a
point charge

(2)
3
0
4 r tc

= generated by a
dipole


a
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The dipole-dipole interactions

In a fluid of freely rotating molecules, the like partial charges of two
freely rotating molecules are close together as much as the two
opposite charges, and the repulsion of the former is cancelled by the
attraction of the latter random motions the situation at high
temperatures.


The mutual potential energy between two dipoles depends on their
relative orientation, and the molecules do not in fact rotate completely
freely, even in gas.


)] cos( sin sin
cos cos 2 [
4
3
0
j i j i
j i
j i
ij
r
| | u u
u u
tc

= I



0
2
6 2
0
2
2
2
1
) 4 (
f
r kT
ij
tc

= I
, where
3
2
0
2
= f

The importance in this equation is:
- the negative sign the average interaction is attractive
- inverse dependence on the distance
6
and temperature
- holding the assumption: d r >>

Example: At 25
o
C the average interaction energy for pairs of molecules with =1
D is ~-0.07kJ/mol when the separation is 0.5 nm. The level is less than the
average molar kinetic energy mol kJ RT / 7 . 3
3
2
= .
However, for small molecules with large dipole moments, the intermolecular
potential becomes significant.






Electric field effect and temperature effect
CN5030 14/15

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The dipole-induced-dople interactions

When a nonpolar molecule i is situated in an electric field created by
the presence of a nearby permanent dipole j, the resultant force
between the permanent dipole and the induced dipole is always
attractive.

3
0
*
4 r
j i
ij
tc

= I

o
i i
=
*

3
0
3
0
3
0
4 4 4 r r r
j i j j i
ij
tc

tc
o
tc
o
= = I



6
0
' 2
6 2
0
2
) 4 ( ) 4 ( r r
i j i j
tc
o
tc
o
= =



Example: For a molecule with =1D (such
as HCl) near a molecule of polarizability volume
o=1010
-30
m
3
(such as benzene), the
average interaction energy is about -
0.8kJ/mol when separation is 0.3 nm.


The induced-dople interactions

Nonpolar molecules (including closed-shell atoms, such as Ar) attract
one another even though neither has a permanent dipole moment.
The interaction between nonpolar molecules arises from the transient
dipoles that all molecules possess as a result of fluctuations in the
instantaneous positions of electrons. To appreciate the origin of the
interaction, suppose that the electrons in one molecule flicker into an
arrangement that gives the molecule an instantaneous dipole
moment
*
1
. This dipole generates an electric field that polarizes the
other molecule, and induces in that molecule an instantaneous dipole
moment
*
2
.

The two instantaneous dipoles
are correlated in direction.


CN5030 14/15

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The strength of the dispersion interaction depends on the polarizability
of the two molecules because of the instantaneous dipole moments
depend on the looseness of the control that the nuclear charge
exercises over the outer electrons.

(
(

+
= I
j i
j i j i
ij
I I
I I
r
6 2
0
) 4 ( 2
3
tc
o o


Example: For two CH
4
molecules o=2.610
-30
m
3
and I ~ 700 kJ/mol to obtain I
= -2kJ/mol for r = 0.3nm. A very rough check on this figure is the enthalpy of
vaporization of methane, which is 8.2 kJ/mol. However this comparison is
insecure, partly because the enthalpy of vaporization is a many-molecule
interaction result and partly because the long-distance assumption breaks down.



Polar molecules also interact by a dispersion interaction. Such
molecules therefore interact both through their permanent dipoles and
through the correlated, instantaneous fluctuations in these dipoles.

To show the relative magnitude of permanent dipole, induced dipole,
and dispersion forces in some representative cases, London has
presented calculated potential energies for a few simple molecules.

6
r
B
ii
= I
where 2
0
2
) 4 ( 4
3
tc
o
i i
I
B =













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Relative magnitudes of intermolecular forces between two identical
molecules at 0
o
C.

Molecule

(D)
B10
79
(J m
6
)
Dipole Induction Dispersion
CH
4
0 0 0 102
CCl
4
0 0 0 1460
c-C
6
H
12
0 0 0 1560
CO 0.10 0.0018 0.0390 64.3
HI 0.42 0.550 1.92 380
HBr 0.80 7.24 4.62 188
HCl 1.08 24.1 6.14 107
NH
3
1.47 82.6 9.77 70.5
H
2
O 1.84 203 10.8 38.1
(CH
3
)
2
CO 2.87 1200 104 486

The attractive potential between two dissimilar molecules is
approximately given by the geometric mean of the potentials between
the like molecules at the same separation.
( )
2 / 1
jj ii ij
I I = I
















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Relative magnitudes of intermolecular forces between two different
molecules at 0
o
C

Molecules Dipole moment
(debye)
B10
79
(Jm
6
)
(1) (2) (1) (2) Dipole Induction Dispersion
CCl
4
c-C
6
H
12
0 0 0 0 1510
CCl
4
NH
3
0 1.47 0 22.7 320
(CH
3
)
2
CO c-C
6
H
12
2.87 0 0 89.5 870
CO HCl 0.10 1.08 0.206 2.30 82.7
H
2
O HCl 1.84 1.08 69.8 10.8 63.7
(CH
3
)
2
CO NH
3
2.87 1.47 315 32.3 185
(CH
3
)
2
CO H
2
O 2.87 1.84 493 34.5 135


The ion-pairing interaction Coulomb force

Oppositely charged ions: e.g., Li
+
--- Cl
-
; R
4
N
+
--- C
6
H
5
-SO
3
-


Ion-pair ion solvation
c t 4
2
e Z Z
j i
j i

= I c plays an important role:
Org O H
c c >
2



Ion-dipole interactions salvation: dissolving ionic compounds
in polar aprotonic solvents, e.g., DMF, NMP,
DMSO,.Polyether









CN5030 14/15

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^ Repulsive and total interactions

When molecules are squeezed together, the nuclear and electronic repulsions
and the rising electronic kinetic energy begin to dominate the attractive forces.


Mies potential:

















m
m
n
n
r
B
r
B
= I

n > m





Constants c, o, n are obtained from gas-phase volumetric properties
as expressed by second virial coefficients.



( )
( )
(
(

|
.
|

\
|

|
.
|

\
|

= I
m n m n
m n
r r m n
m n o o c
/ 1
/

CN5030 14/15

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The Lennard-Jones potential:

A special case of the Mie potential with n = 12 and m = 6


(
(

|
.
|

\
|
|
.
|

\
|
= I
6
0
12
0
4
r
r
r
r
c




(
(

|
.
|

\
|

|
|
.
|

\
|

6
0
0
exp 4
r
r
r
r
c




























CN5030 14/15

- 15 -
^ Structure Effects

Mies potential applies to two non-polar, spherically symmetric molecules
that are completely isolated. Intermolecular forces of non-spherical
molecules depend not only on
the center-to-center distance
but also on the relative
orientation of the molecules.

(1) Molecular size and shape
effects

Alkanes (do not contain organic
functional groups)

Saturated hydrocarbon
molecules, for the same
number of carbons, branched
isomers have lower boiling
points, and with increasing
branching extent spherical
shape, the lower will be the
boiling point intermolecular contact.










0 ) (
1 1
> h H and 0 ) (
2 2
> h H because repulsive nature between 1 and 2.

) (
) (
2 2 2
1 1 1
h H x
h H x h
m
+
= A
and
) (
) (
'
2
'
2 2
1
'
1 1
'
h H x
h H x h
m
+
= A

'
m m
h h A > A because
'
2 2
h h <


) (
) (
2 2 2
1 1 1
h H x
h H x h
mix
+
= A

c-C
6
H
12
c-C
6
H
12


n-C
10
H
22
n-C
10
H
22


i-C
10
H
22
i-C
10
H
22


c-C
6
H
12
n-C
10
H
22
or i-C
10
H
22


1
H

2
H

'
2
H

0
'
2
< h

0
2
< h

0
1
< h

CN5030 14/15

- 16 -
F
C F
F
CH
2
OH H
3
C
C
CH
3
O
V: +
-5.7 (-3.2)
-4.75 (-2.0)
-6.79
(-2.29)
-8.7
(-4.1)
-5.05
(-1.18)
In CCl
4
F
C F
F
CH
2
OH H
3
C
C
CH
3
O
+
F
C F
F
CH
2
O
H
CH
3
C
CH
3
O
F
C F
F
CH
2
O
H
CH
3
C
CH
3
O
(2) Specific (Chemical) Forces

Broad definition of Lewis Acid-Base interactions:

Hydrogen bonding: O-H; N-H; F-H
others: acidic hydrogen on carbon: RCCH; X
3
CH; (RCO)
3
CH
(polarization assists hydrogen bonding)




























0 0.2 0.4 0.6 0.8 1.0
Mole fraction of acetone
CCl
4
+ CH
3
COCH
3

HCCl
3
+ CH
3
COCH
3

A
H
m
i
x

(
k
J
/
m
o
l
)





2


1


0

-1

-2

-3
) (
1 0
A mol kJ g
0
u A
The dimerization of N-
methylacetamide occurs in
CCl
4
, but is nearly
nonexistent in the solvent
Dioxane, which has the
same dielectic constant,
because dioxane can
accept hydrogen bonds.
CN5030 14/15

- 17 -
O
2
N

NO
2
NO
2

e
Values of AH
o
for some selected hydrogen bonds

Hydrogen bond Compounds involved Medium Strength (kcal/mol)
O-HO=C
Formic acid / formic acid Gas phase - 7.4
O-HO-H
Methanol / methanol Gas phase -7.6
O-HOR
2

Phenol / dioxane CCl
4
-5.0
O-HSR
2

Phenol / n-butyl sulfide CCl
4
-4.2
O-HSeR
2

Phenol / n-butyl selenide CCl
4
-3.7
O-Hsp
2
N
Phenol / pyridine CCl
4
-6.5
O-Hsp
3
N
Phenol / triethylamine CCl
4
-8.4
N-HSR2
Thiocyanic acid / n-butyl
sulfide
CCl
4
-3.6
*Jeffery, G. A. (1998). An introduction to hydrogen Bonding (Topics in Physical
Organic Chemistry), Oxford Univ. press.


Electron donor-electron acceptor:

Example 1.





















AH = -11.39kJ/mol
NO
2
NO
2
O
2
N
CH
3
CH
3
H
3
C
CH
3
CH
3
H
3
C CH
3
CH
3
CH
3
CH
3
H
3
C
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
AH = -6.15kJ/mol
AH = -9.63kJ/mol
AH = -14.86kJ/mol
AH = -18.30kJ/mol
Example 2:

CN5030 14/15

- 18 -
Cl
Cl Cl
CH
3
CH
3
CH
3
H
3
C CH
3
CH
3
Electron Acceptor

The coordination complex: Atoms with lone-electron pair
+ transition metals (with empty d-orbitals)

OC
.
> Fe(II)










The molecular complex















The other example:








E
l
e
l
c
t
r
o
n

D
o
n
o
r

) (
) (
2 2 2
1 1 1
v V x
v V x v
mix
+
= A

Heme Fe(II) can bind bind many other small
molecules with structures similar to O
2
including:
CO, NO, H
2
S

Self-assembled
monolayers of
alkylthiols
formed on to a
Au surface.
CN5030 14/15

- 19 -
t -effect:

Anther non-covalent binding force that is comparable in strength to a hydrogen bond
is the cation-t interaction.


A






B



C












1. The cation - t interaction
2. the polar - t interaction
3. t donor acceptor interaction
face +
edge
M
+
-AG
0
(kcal/mol)
Li+ 38
Na
+
27
K
+
19
Rb
+
16
A. The basic nature of the
interaction and binding energies
for simple cations to benzene.
B. The relationship between
dipoles and quadrupoles, and an
illustration of six bond dipoles
giving rise to a molecular
quadrupole.
C. Substitute effects on the cation-
t interaction. These are
calculated values.


CN5030 14/15

- 20 -
R
2
R
3
R
4
R
6
R
6
R
1
Aromatic Donor
Organic Polar Molecules
C R (R= R', OR')
O
N
C N
NO
2
P
O
Weak
Association
Alkenes
Form
Complex
x
Saturated
Hydrocarbons

Polar-t Interactions





Structure-based selectivity:



























The binding energy between benzene and
water is 1.9 kcal/mol in the gas phase, and
that of ammonia with benzene is 1.4
kcal/mol.

In a nonpolar solvent such as cyclohexane,
the binding between the NH
2
group of
aniline and the face of benzene is
1.6kcal/mol.
CN5030 14/15

- 21 -

Qualitative nature of molecular complex theory


Isolated molecular model that is applicable to low pressure gas phase







Hydrophobic Interactions

Amphiphilic molecules Dual nature Unique orientation in aq.
Micelle







Emulsion systems:
Hydrophobic
interaction








Specific
Intermolecular
force
Thermodynamic
properties
Poor Link
AH ~ 1-2kJ/mol;

AS ~ 140JK
-1
mol
-1

(at 25
o
C)
CN5030 14/15

- 22 -
H
O
H
H
O
H
H
2
C
H
O
H
H
O
H
H
2
C
Hydrophobic interactions are synonymous to dispersive interactions which are those
resulting from London,s dispersion forces. Hydrocarbons, which are strongly
dispersive in character and are in no way polar, do not mix with water because the
dispersive interactive forces between hydrocarbon molecules themselves and the
polar forces between water molecules themselves are very much greater than the
dispersive forces between a water molecule and a hydrocarbon molecule. Water
does not repel hydrocarbons, in fact, molecules can not repel one another (unless
they are inside each others Van Der Waals radii).

Solubilization of hydrocarbon molecules in water




















The thermodynamics of transfer of a nonpolar hydrocarbon solute from
a nonpolar solvent to water: 0 > A
transfer
G at TP It is a large decrease in
the entropy of the system ( 0 < A
transfer
S ) that accounts for the positive Gibbs
energy of transfer.

For example: CH
4
(in CCl
4
) CH
4
(aq) has mol kJ G
transfer
/ 12 + = A
mol kJ H
transfer
/ 10 = A , and mol K kJ S
transfer
= A / 75 at 298K

When a hydrocarbon molecule is
surrounded by water, the H
2
O
molecules form a clathrate cage. As a
result of this acquisition of structure, the
entropy of the water decreases, so the
dispersal of the hydrocarbon into the
water is entropy-opposed; its
coalescence is entropy-favoured.
AH > 0
Endothermic
AS < 0
Entropic Phenomenon
CN5030 14/15

- 23 -
Substances characterized by a positive Gibbs energy of transfer from a
nonpolar to a polar solvent are called hydrophobic.

An empirical constant: hydrophobicity constant,
0
log
S
S
=
is defined for
a small molecular group R, where S is the ratio of molecular solubility of
the compound R-A in n-octanol to that in water, and S
0
is the ratio of the
molar solubility of the compound H-A in n-octanol to that in water.
Therefore, positive values of indicate hydrophobicity and negative
values of indicate hydrophilicity.

It is observed experimentally that the values of most groups do not
depend on the nature of A.

R CH
3
CH
2
CH
3
(CH
2
)
2
CH
3
(CH
2
)
3
CH
3
(CH
2
)
4
CH
3


0.5 1.0 1.5 2.0 2.5











Hydrocarbon AG
0
(kJ/mol) AH
0
(kJ/mol) TAS
0
(kJ/mol)
Ethane 16.3 -10.5 -26.8
Propane 20.5 -7.1 -27.6
n-Butane 24.7 -3.3 -28.0
n-Hexane 32.4 0 -32.4
Benzene 19.2 2.1 -17.1
Toluene 22.6 1.7 -20.9





At the molecular level, formation of a solvent cage around a hydrophobic molecule
involves the formation of new hydrogen bonds among solvent molecules. This is an
exothermic process and accounts for the negative value of transfer enthalpy.

However, large cages (due to clustering together of solute molecules or large solute
molecules) will require less bound solvent molecules, namely a decrease in the
organization of the solvent molecules, and therefore a net increase in entropy of the
system.
CN5030 14/15

- 24 -
Summary:

The intermolecular interaction energy determines the thermodynamic
behavior of real gases and liquids.

For asymmetric polar molecules they have dipoles that is determined
by type of organic functional groups and geometry of molecule.

For symmetric (center) non-polar rigid molecules they have
multipoles, polarizabilities.

For non-polar soft molecules, London dispersion force is the main
intermolecular force. It depends upon the average distance between
molecules and orientation of molecules. The geometry and size of
molecule affect the interactions.

Special intermolecular interactions often support endothermic mixing.

Physical entanglement for large-sized and soft molecules enhances
intermolecular interactions.