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is the concentration very far from the plane where ( ) 0 and z z for
negative ions
The principle of charge neutrality far away from the surface n n
(4.5.2) ( )
( ) ze x kT
n x n e
4
The mobile ions not only feel the field they contribute to it
For total charge density ( ) x
(4.5.3)
( ) ( ) ( ) ( )
i i
i
x zen x ze n x n x
+
1
]
Where
i
z is the valence of the species i with concentration ( )
i
n x
Using Poisson equation:
2
0
D
1
]
Using hyperbolic sine function: ( ) sinh
2
x x
e e
x
(4.5.5)
( )
2
0
2
sinh
ze x zen
D kT
_
,
This is a nonlinear second order differential equation need and n
Where
2 2
2
0
2z e n
D kT
and
1
Since
2
4 1
0
1.386 10 J m mol
4
AV
e N
( ) ( )
3
2 4 1 1
3
23 1
20 2
-1 1
10 L
2 4 1.386 10 J m mol 0.1 mol L
m
6.022 10 mol
0.01078 10 m
78.54 8.314J K mol 298K
10
1
9.62 10 m 9.62
The equation can also be used for asymmetrical electrolyte solution z z
+
If ionic species i has valency
i
z and molar concentration
i
m we may replace
2
z with
ionic strength =
2
1
2
i i
i
I m z
Example 4.5.2: Potential near uniformly charged plane in salt solution
Using the Poisson-Boltzmann equation in 1D
(4.5.8)
2
2
2
d
dx
Whith solution
(4.5.9) ( )
1 2
x x
x Ae Ae
+
Two boundary conditions:
1. ( ) 0 for
1
0 x A
2. At 0 x ,
0
the potential at the surface
2 0
A
(4.5.10) ( )
0
x
x e
Approaches zero exponentially at x
In absence of charge would only decrease linearly effect of shielding
6
To complete the solution we need
0
The surface charge must be compensated by net charge in the solution
(4.5.11) ( )
2
0 2
0 0
d
x dx D dx
dx
Which comes from the Poisson equation
(4.5.12)
2
0 2
0
0 0
d d d d
dx
dx dx dx dx
(4.5.13)
2
0 0 0 0 2
0
0
d
D dx D
dx D
And the solution:
(4.5.14) ( )
0
0
x x
x e e
D
The range of the electrostatic potential shortens as increases
At
1
x
,
Since c where c n
Solution = monovalent with Debye length
1
Radial symmetry ( ) 0 r
and
2
2
0
(4.5.15)
2 2
2 2 2
2 2
1 d r d r
r
r dr dr
Solution:
(4.5.16)
1 2
r r
r Ae A e
+ or
1 2
r r
e e
A A
r r
+
Boundary conditions:
1. ( )
1
0 0 A
2. At
2 2
a
a
a a
e
r a A A a e
a
(4.5.17)
( ) r a
a
a
e
r
for r a >
To find
a
from Qtake the derivative of at r a
(4.5.18)
2
1 1
a r r
a a
r a r a
d a
a e e e
dr r r a
+ 1
+
1
]
On the other hand, since ( )
d
E E r
dr
r r
and
Q
Da
C
for r a
( )
2
r a
r a
d Q
E r
dr Da
C
Therefore we have for the potential
2
1
a
r a
d Q a
dr Da a
+
C
(4.5.19)
( ) 1
a
Q
Da a
+
C
8
When there are no salt 0 and
a
Q
Da
C
the effect of shielding comes from the
factor
( )
1
1 a +
(4.5.20) ( )
( )
( )
1
r a
Q
r e
Dr a
+
C
In the absence of salt 0 and ( )
1
r
r
The PoissonBoltzmann equation
describes spatial variations over microscopic length scales
holds for large spherical particles having uniform charges
also for small ions (Sodium or Chloride) which have single charge
The linearized PoissonBoltzmann equation
general property of linear differential equations solution = sum of solutions
For two point charges in uniform salt solution with
1
q at
1
r and
2
q at
2
r , the
Debye-Hckel potential
(4.5.21) ( )
1 2
1 2
1 2
1 2
,
r r
P
Cq Cq e e
r r
D r D r
+
Summing the potential may be easiest way for arbitrary constellation of charges
Strength of electrolytes
Strong or weak depending on whether they are fully dissociated
Salts, acid and base = electrolytes
In aqueous solutions dissolve and dissociate into ions
Strong dissociation is complete
Weak dissociation is partial
Level of dissociation = equilibrium dissociation constant K
(4.5.22)
K
MX M X
+
+ where
[ ]
M X
K
MX
+
1 1
] ]
Strong electrolytes 0.1 K >
Using the definition
10
log p
1 pK < strong electrolytes
Otherwise = Weak electrolyte
9
Two types of experiments about ion dissociation
1. measurements of colligative properties
Freezing point depression
f
T increases with the concentration of solute species
mas
f f
T K m where
f
K is a constant independent of the concentration
For NaCl , should concentration be that of NaCl or twice this value?
If mis the concentration of the neutral species then the value of i in the
colligative expression
f f
T iK m gives a measure of degree of
dissociation - 2 i full dissociation
2. ion conductivities
Found by dissolving salts in water and applying electric field which causes the ions to
flow resulting in measurable electrical current
Conductivity = current flow number of ions per unit of time divided by applied
voltage
Increasing concentration of electrolytes increases the number of carriers and thus
conductivity
At low concentration KCl fully dissociates into K
+
and Cl
twice the
concentration gives the number of ions that carry the current
Strong electrolytes defined by two observations
1. value of i measured by colligative properties
equals the number of ion types expected from complete dissociation
2 NaCl i ;
2 4
3 Na SO i
2. Kohlrauschs law (F. Kohlrausch 1840-1910)
Doubling electrolyte concentration = doubling conductivity of the solution
Each ion acts as independent carriers of electrical current
2 4
, , and NaCl HCl KCl K SO strong electrolytes at low concentration
10
Electrolytes dissociation can deviate in two different ways from ideal behavior
1. weak electrolyte (acetic acid + ammonia) do not fully dissociate at any
concentration conductivities and colligative i smaller than expected
2. even strong electrolytes may become nonideal at higher concentrations due to
effects of shielding
At low concentration, nonidealities depend only on valence and electrolyte
concentration each ion partly shielded by neighboring ions
Debye-Hckel theory for nonidealities of strong electrolytes
1923 Hckel 1936 Debye P. (Nobel Prize in chemistry)
Adaptation of the Poisson-Boltzmann theory explaining nonidealities of dilute solution
of strong electrolytes
To visualize Na
+
surrounded by Cl
ln kT = the electrostatic free energy that accounts for ion- induced distribution of
neighboring ions
To compute
dist
charging the central ion 2 kinds of work
1. Born energy for central ion in pure solvent (even without salt) process not
dependent on concentration of salt included in
0
term
2. Redistribution of surrounding ions counterions nearer than co- ions
dist
= electrostatic potential for nonidealities is the difference between total
potential
b
for charging the central ion and
nosalt
for charging up the central ion
in pure solvent 0
12
Inside b the total charge is ze and
(4.5.25)
( ) ( ) 1 1
dist b nosalt
ze ze ze
Db b Db D b
+ +
C C C
At any intermediate phase of charging
(4.5.26)
( ) 1
dist
ze
D b
+
C
Substituting and integrating:
Debye-Hckel equation
(4.5.27)
( )
( )
( )
( )
( )
2
1 1
0 0
2
ln
1 1
2 1
ze
ze
kT zed d
D b D b
ze
D b
1
1
+ +
]
+
C
C
C
If Na
+
is the central ion
+
Because b is the shortest distance between ionic center then the result for Cl
is
Now because the only property that can be measured for the solution is
electroneutral we use
2
+
The equation predicts that at low salt concentration 1 b = , ln c
13
For 0 b - limiting law because the ionic solutions are predicted to obey the relation at
the limit of sufficiently low concentration
With reasonable values for b excellent agreement up to 0.1M c for monovalent salts at
25
C
Debye-Hckel model useful to explain how rates of chemical reactions depend on salt
concentrations
Example 4.5.4: effect of salts on reaction rates
Consider the reaction ( )
A B AB P +
In absence of salts
0
k is the rate of reaction
(4.5.28)
( ) [ ][ ]
0
0
constant k AB A B
1
]
Adding salt
s
k depends on electrostatic nonideality
(4.5.29)
( ) [ ][ ]
( )
constant
A B
s
s
AB
k AB A B
1
]
Dividing by
0
k
(4.5.30)
( )
0
ln ln
s A B
AB
k
k
_
_
,
,
If total charge is conserved during the chemical reaction
( )
A B
AB
z z z +
14
Substituting in the Debye-Hckel equation
(4.5.31)
( )
( )
( )
2 2
2
2 2
0
0
ln 2
2 1 1
s A B
A B A B A B
k e z z e
z z z z A z z I
k D b D b
_
1
+ +
]
+ +
,
;
C C
Where
2
1
2
i i
i
I m z
is the ionic strength and
0
A is a constant (assuming 1 b = )
Limitations of the Debye-Hckel model
1. When salts dissociate into ions distribution not uniform clumpy because of
nonideality
2. Using Poisson-Boltzmann theory implicitly averaging eliminating discreteness
; Kjellander, R. 1996, Ber Bunsen Ges Phys Chem 100, 894
3. Model work best for low ion concentration + monovalent mobile ions because
clumpyness greater for multivalent better approach = Mote-Carlo simulations
taking into account all the charge interactions; Vlachy, V. 1999, Annu Rev Phy
Chem 50, 145
15
Section 6: Intermolecular interactions
Even uncharged atoms or molecules attract each other
Form noncovalent or covalent bonds
Condense into liquids and solids at low temperature
Noncovalent interactions between uncharged particles relatively weak and shortrange
But fundamental driving force in chemistry and biology
Intermolecular interactions measurements of pressure of nonideal gases
Even when atoms have no net charge charge distribution and polarizability can produce
weak attractions
Properties of intermolecular interactions:
Repel at short range and attract at long range
The bond between two particles is describe by pair potential energy ( ) u r as function of
separation
Bonding force = derivative of potential
(4.6.1) ( )
( ) du r
f r
dr
Pair potential has four main features:
1. Particles do not interact if they are far apart 0 u and 0 f as r
2. If charges close enough attract each other 0 f <
A positive force acts along r to bring the particles together
3. Particles repel each other at small distance 0 f >
A positive force acts along the r + to separate the particles
4. At At * r the attraction balances the repulsion
Pair potential has minimum 0 f
* r is the average length of the intermolecular bond
Two classes of intermolecular forces long range and short range
16
Common model = power law
(4.6.2) ( )
p
u r Ar
Where A is a constant and p a positive integer
Short range 3 p > and long range 3 p
Coulombic interaction ( )
1
u r
r
t is long range
Typical intermolecular interactions ( )
6
1
u r
r
t short range
Paulis principle electrons in same state cannot occupied the same space atoms
repel at short range
QM short range repulsion 9,12 p or 14
17
Short range attractions
Can be explained as electrostatic interactions
Coulomb law ( )
1 2
q q
u r
r
C
is long range
There are three different ways how long range forces can produce short range interactions
between neutral molecules
1. Molecules could be multipoles charge density varies throughout the molecule
Interactions between multipoles have shorter range than for monopoles
2. Dipolar molecules are free to orient
Orientation averaging reduces range of interaction
3. Atoms and molecules are polarizable can induce charge distribution by electric
field from nearby atoms or molecules or other external source
Interaction between polarizable molecules shorter range than interactions
between molecules with fixed dipoles
18
Multipole expansion
Any distribution of charges ( ) ( ) , , x y z r
r
can be described by a multipole expansion
First term of series = monopole
Second term = dipole
Third term = quadrupole
Fourth term = octupole
Etc.
Various terms = moments of the distribution of charges
Monopole = 0 moment = total charge distribution
( )
r dr
r r
Dipole = first moment
( )
r r dr
r r r
o Describes asymmetric arrangement of equal amounts of positive and
negative charges separated by distance r
r
o Dipole = lowest order distribution for a molecule that has no net charge
Quadrupole = second moment
( )
2
r r dr
r r r
o Next lowest order distribution for a molecule that has no net charge or no
dipole
Note that there are no tripole, pentupole etc. because can be expressed as linear
combination of some amount of net charges + dipole moments + quadrupole + etc.
Multiple expansion = sum of moments
Net charge + dipole = 0 + 1 moments
19
Dipoles
Dipoles could be:
permanents = separation of charges always
present
induced = appears in presence of applied field
Molecules can have both
For a permanent dipole ql
r
r
With units = Debye (D):
18 1 30
1D 1 10 esu cm 3.33564 10 C m
When one positive charge (proton) is separated from
one negative charge (electron) by 1:
19 10
30
1.6022 10 C 10 m
4.8033D
3.33564 10 C m
ql
Dipoles can arise from molecular asymmetry
20
Water, which has no net charge, has dipole moment of 1.85D, due to the partial negative
charge on the oxygen and the partial positive charge on the two hydrogen atoms
21
Attraction due to charge asymmetries
Interaction becomes shorter range and weaker as multiple moments involved
Monopole- monopole interaction ( )
1
u r
r
Monopole interacting with dipole ( )
2
1
u r
r
Dipole-dipole interaction ( )
3
1
u r
r
Such interactions can be attractive or repulsive depending on the orientation of the
molecules
Tables 24.2 and 24.3 compare energies between covalent and noncovalent interactions
22
Orientation averaging
Shortens the range of the interaction
Compare
1. A charge interacting with a dipole having fixed orientation
2. A charge interacting with a dipole having variable orientations
Case 1: when a charge Qis separated by a distance r from a dipole with moment
ql constrained to an angle , the pair energy:
(4.6.3) ( )
0
, cos u r u where
0 2
Q
u
Dr
C
Case 2: if the dipole is free to rotate then the average interaction energy:
(4.6.4) ( )
( )
( )
( )
,
0
,
0
, sin
sin
u r kT
u r kT
u r e d
u r
e d
Where more probable value is
2
(4.6.5) ( )
0
0
0
0
0
cos
cos 1 sin
cos
1 sin
u
u d
kT
u r
u
d
kT
1
]
1
]
There are two terms in the numerator and denominator
23
Fist term of denominator is simple
0
0
sin cos 2 d
For the other terms use cos sin x dx d
The first term of the numerator and second term of the denominator:
1
0 1
cos sin 0 d xdx
The last term in the numerator is:
(4.6.6)
1
2 2 2 2 2 3
1
2 2 2 0 0 0 0 0
0 0 1
1
2
cos sin cos cos
3 3
u u u u u x
d d x dx
kT kT kT kT kT
So the averaged energy of interaction is
(4.6.7)
( )
2
2
0
4
1 1
3 3
u Q
u r
kT kT D r
_
,
C
It has shorter range than for case 1
Generalizing: we expect two dipoles with fixed orientation to have interaction energy
( )
3
1
u r
r
and two dipoles with variable orientation to have average energy ( )
6
1
u r
r
The interaction energy between 2 permanent dipoles with moment
A
and
B
at
separation r and which are free to rotate
(4.6.8) ( )
2
6
0
2 1
3 4
A B
u r
kT D r
_
,
24
Example 4.6.1: dipole-dipole interaction of ethanol molecules
10 r in gas phase
From table 24.1 we find
30
C m
5.70 10
molecule
( )
( )
2
2
6
0
2
2
30 6
23 1
23 1 12 2 1 1 9
2 1
3 4
5.70 10 C m
2 1 1
6.02 10 mol
31.38 10 J K 300K 4 8.85 10 C J m 10 m
J
8.27
mol
u r
kT D r
_
,
1
_
1
1
,
]
At 5 r the energy would be
6
2 64 times stronger
J
529
mol
London dispersion forces
Attractive interactions are universal
Molecules need no net charge or asymmetry or orientation
Even spherical uncharged inert gas atoms condense into liquids at very low
energy
London forces = dispersion forces - Described by F. London (1900-1957) in 1937
Two molecules can induce attraction because they are polarizable
Polarizable atom or medium
responds to applied electric field
by redistributing its internal charge
Simple case = dipole pointing in
opposite direction as field applied
25
(4.6.9)
ind
E
r
r
Where is the polarizability of the medium
If the field is large
2 3
1 2 3
E E E + + +L
Polarizability = induced dipole moment per unit of applied electric field
Table 24.1 shows that typical polarizability in units of volume ~ a few cubic
Polarizability of neutral atom
When a neutral atom is exposed to an electric field produced by a charge it is attracted to
it
Model: positive charge Qat distance r from the center of a neutral atom
This induces a redistribution of the charge (induced dipole) in the neutral atom
separated by r :
ind
q r
Since more negative charges near the positive charge net attractive force on
neutral atom f qE
This is equal to the sum of the force
( )
2
r
q E r
_
,
of Qon nearby charge q ,
plus the force
2
r
qE r
_
+
,
of Q on the more distant q charges
(4.6.10)
2 2
ind
r r dE dE dE
f q E r E r q r E
dr dr dr
1 _ _
+
1
, ,
]
26
The field produced by a charge Q at distance r is
2 3
2
Q dE Q
E
Dr dr Dr
C C
(4.6.11)
2
5
1
2
Q
f
D r
_
,
C
The intermolecular potential
(4.6.12)
( ) ( )
2
4
1
2
Q
r f r dr f
D r
_
,
C
The minus sign indicates that the interaction is attractive irrespective of Qsign
The interaction is short range ( 3 p > ) and increases with the polarizability
When two neutral atoms interact the induce dipole in each atom produce a potential of
interaction ( )
6
1
u r
r
also increasing with polarizability
All short ranges attractions with a power la form = van der Walls forces
Lennard-Jones potential
(4.6.13) ( )
12 6
a b
u r
r r
Where a and b are parameters that depend on the type of interacting atoms
REF: Burkert, U. & Allinger, N. L. 1982, Molecular Mechanics, ACS Monograph 177, American
Chemical Society; Rigby, M. et al. 1986, The forces between Molecules, Oxford University Press
The positive sing in first term repulsion
Negative sign in second term attraction
The first term
12
r originally chosen because it can be calculated rapidly by computers
using square of
6
r
Virtue of the model: captures universal features of a short range attraction and shorter
range repulsion and parameters a and b give enough flexibility for the model to predict
experimental data
27
Hydrogen bonds
Weak interaction a few
1
kcal mol
Occur when hydrogen situated between two other atoms
Ex. - = N H O C L where the - N H group is the hydrogen donor and the = O Cgroup the
hydrogen bond acceptor
To a first interpretation, hydrogen bond = electrostatic interaction align - N H and
= O Cstretching - N H bond
Requires QM treatment
Empirical energy function
Popular approach to modeling interaction and conformation of large molecules
particularly in solution = assume energy U is the sum of four terms
1. Coulombic interactions between charged atoms
2. Spring forces that stretch + bend bonds
3. Periodic potential for torsional + rotations around bonds
4. Lenneard-Jones potential for non bonded interactions
Ref: McCammon, J.A. & Harvey, S.C. 1987, Dynamics of proteins and nucleic acids, Cambridge
University press; Cornell, W.D., Howard, A.E. & Kollman, P. 1991, Curr Opin Struct Biol, 1, 201; Brooks,
C.L., Karpus, M. & Pettitt, B.M. 1988 Advances in chemical physics, Vol. LXXI Proteins: A theoretical
perspective of dynamics, structures s, and thermodynamics, Wiley
(4.6.14)
( ) ( )
( )
2 2
0 0
12 6
2 2
1 cos
b
bondl engt hsb bondangles
ij ij i j
dihedral angles nonbondedpairsi j
ij ij ij
K K
U b b
a b q q
K n
r r Dr
<
+ +
_
+ + + + 1
]
,
C
Where
b
K is the spring constant for stretching bonds and
0
b is equilibrium bond length
K
)
28
Van der Walls gas model
Much of what is known about intermolecular interactions comes from measuring the
pressure of non ideal gases
Simplest model = van der Walls
Real gas more complex than ideal gas due to intermolecular interactions
Ideal gas
N p
V kT
independently of type of gas or atomic structures of gas molecules
Only applies at low densities
At higher density pressure affected by intermolecular interactions
I deal gas model do not predict that gas condense into liquids
Van der Walls equation ( ) , , p T V N
(4.6.15)
2
2
2
1
NkT aN RT
p a
V Nb V b
Where a and b are free parameters
Develop in 1873, as Ph. D. thesis of J. D. van der Walls (1837-1923) Nobel Prize 1910
Many ways to deduce equation one is to start from expression giving the pressure as a
sum of energy + entropy component
(4.6.16)
, , , T N T N T N
F U S
p T
V V V
_ _ _
+
, , ,
Energetic component
Need a model for the energy as a function of the volume ( ) U V
Total energy of the gas is the sum of all the inter-particle interactions
Ignore internal partition function - they are independent of the volume
And translational partition function will be part of entropy component
29
Use test particle divide space around the particle into spherical shells
shell at radius r from test particle
U = interaction energy between test particle and all other particles in the system
o To compute U multiply the number of the particles in the shell at radius
r by the energy interaction per particle ( ) u r and integrate on all the shells
o For a gas with density
N
V
and uniform distribution
(4.6.17) ( )
2
0
4
2 2
N N
U U u r r dr
This equation assume energy is pair wise additive and influence of third particle is
insignificant
For ( ) u r assume hard core sphere + attraction over short range :
(4.6.18) ( )
6
0
for *
*
for *
r r
u r
r
r r
r
<
'
_
,
Substituting
(4.6.19) ( )
( )
6 6 2
0 2
0
4
0 0
2 * * 1
4
2
N r N r N
U r dr dr
r V V r
_
,
In principle the upper limit should be equal to some dimension of gas container
but sum converges to final value for as few as 10-20 shells r is ok
Since there are no particles between 0 r and * r lower limit can be 0 r
30
Then
( )
3 4 3
0
*
1 1 1 1 1
3 3
* r
dr
r r
r
and
(4.6.20)
2
N
U a
V
where
( )
3
0
2 *
3
r
a u
The minus sign attractive interactions reduce the energy relative to an ideal gas
Entropic component
Use lattice model
Entropy S of distributing N particles onto M sites
(4.6.21)
( ) ln ln
S N M N
N M N
k M M
_
,
If total volume is V , then
0
V
b
M
is the volume per lattice and
(4.6.22)
0 0
0
ln ln 1
Nb Nb S V
N N
k V b V
_
_
,
,
Using the relation: F U TS
(4.6.23)
2
0
2
, , , 0
ln 1
T N T N T N
Nb F U S aN kT
p T
V V V V b V
_ _ _ _
+
, , , ,
For low densities ( )
2
ln 1
2
x
x x L putting
0
Nb
x
V
(4.6.24)
0 0
0
1
ln 1 1
2
Nb Nb kT NkT
b V V V
_ 1
+ +
1
, ]
L
The first term yields the ideal gas law
For denser gas, keep second term, and since
1
1
2
1
2
x
x
+
(4.6.25)
2
2
1
NkT aN
p
Nb V
V
V
_
,
Where
0
2
b
b is half volume of particle
31
In practice a and b are adjustable parameters
The van der Walls model is simplest model describing phase transition between gas and
liquid (boiling)
Another model for phase transition is:
Redlich-Kwog equation
(4.6.26)
( )
1
1 2
1 1
a kT
p
V b T V V b
+
Radial distribution function
Van der Walls model assume gas molecules are distributed uniformly
But at higher densities this assumption is not correct: molecules are clumpy due to
intermolecular attraction
True density is ( ) g r , where ( ) g r is the radial distribution function (or pair
correlation function)
The ratio of actual density at r and average density :
( ) ( ) ( )
g r r r
( ) 1 g r for homogeneous distribution and peak for more than average density
32
Gas: zero for * r r < because particle cannot be closer than * r , then randomly
distributed this is van der Walls assumption
Liquid: depression for small r (no overlap of particles) excess for first
neighbor shell followed by second slight depression before peaking again in
second shell third, fourth and so on shells few correlation ( ) 1 g r
Solid: long-ranged order in crystalline solids
Pair correlation functions can be found from experiments, using scattering
electromagnetic radiation
From this function one can get other useful quantities:
Average number of nearest neighbors of any molecule
o In first shell: ( )
2
4 g r r dr
o Total number of nearest neighbors: ( )
2
0
4
B
g r r dr
o Integrating over all shells ( )
2
0
4 1 g r r dr n n
the number of
particles (minus the particle test)
This modifies U the interaction energy between test particle and all other particles in the
system:
(4.6.27) ( ) ( )
2
0
4 U u r g r r dr
33
Lattice model
In lattice model w approximates intermolecular interactions
( ) * w u r the pair potential evaluated at equilibrium bond separation * r r
In lattice model, the sum over all pairs is treated as the sum over nearest neighbors
(4.6.28)
( ) ( ) ( )
2
0
4 *
2 2 2
r
N N Nwz
U u r g r r u r z
Justification = nearest neighbors have dominant contribution for dense phase (clumpy
distribution) with short-ranged interactions
For London interaction ( )
6
u r r
range
Contribution of second and more distant shells: numbered 1,2,3,
(4.6.29)
4
4
2
4
4
1
1
1
90
0.076
1
90
r
r
r
r
or 7.6% contribution
This is also the size of the error we do using such approximation
True of any short-ranged attractions van der Walls like same contribution to
pressure ( ) p V
34
Example 4.6.2: like attract like
Consequence of induced dipole interaction
For two uncharged molecules having permanent dipoles
A
and
B
interacting energy
A B
For molecules having induced dipoles:
A B
u the product of the polarizability
Imply pair interactions:
2
AA A
w c ,
2
BB B
w c and
AB A B
w c
Where 0 c > is a constant approximately the same for atoms and molecules similar in
size
The exchange parameter ( ) ( )
2 2
2
0
2
A B
AB A B A B
z cz
c
kT kT
_ +
>
,
Which is always positive the basis to understand why like dissolve like