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+ Chapter 7
Reg. Solution Theory
Flory Huggins
Osmotic Pressure
Phase Behavior
(chi)
Excluded Volume
Gm = H m T Sm
We are interested to know whether or not these two substances will
(1) spontaneously mix (Gm < 0)
(2) form more than one phase
It is the second point that is often misunderstood. Gm < 0 is the criteria for spontaneous
mixing, but does not ensure a single phase. A system can (and often does) form more than
one phase in its mixed state, as a means of further lowering its free energy.
CBE 514
+ Chapter 7
Reg. Solution Theory
Flory Huggins
Osmotic Pressure
Phase Behavior
(chi)
Excluded Volume
Sm = Sm (S1 + S2 )
The configurational entropy is given by the Boltzmann equation:
S = k ln
where:
Sm
whole
system
m!
m!
m !
= k ln
k ln 1 + k ln 2
m !m2 !
m1 !
m2 !
1
S1 + S2 = ( ln1 + ln1) = 0
Sm
ln N ! = N ln N N
where:
xi =
Sm
whole
system
= k ( m1 ln x1 + m2 ln x2 )
mi
mole (number) fraction of species i
m
CBE 514
+ Chapter 7
Reg. Solution Theory
Flory Huggins
Osmotic Pressure
Phase Behavior
(chi)
Excluded Volume
Sm
whole
system
= k ( m1 ln x1 + m2 ln x2 )
(1) this model assumes the arrangement of molecules in the mixture is random and there is
no energetic benefit from being in one configuration over an another. If there were, we would
have weighted each configuration by an appropriate Boltzmann factor (e-(E/RT)).
(2) the configurational entropy of mixing is always greater than zero. As such it always favors
spontaneous mixing.
0 x 1 ln x < 0 S
>0
1
m whole
system
(3) the symmetry comes from the assumption of equal sizes (hardly true in real systems).
(4) Other useful forms:
Sm
Sm
Sm
whole
system
= R ( n1 ln x1 + n2 ln x2 )
lattice site
(molecule)
= k ( x1 ln x1 + x2 ln x2 )
= R ( x1 ln x1 + x2 ln x2 )
where:
xi =
( multiply by
NA NA )
( divide by m )
( multiply by
NA m)
mi mi N A ni
=
= mole fraction of species i
m
m NA
n
CBE 514
+ Chapter 7
Reg. Solution Theory
Flory Huggins
Osmotic Pressure
Phase Behavior
(chi)
Excluded Volume
H m = U m + ( PV )m
6) our system only involves weak dispersion forces (no H-bonding, ionic, dipole-dipole
interactions, etc.).
As with entropy of mixing, we must be able to define the relative enthalpies of the mixed and
pure components:
H m = H m (H 1 + H 2 )
The enthalpy of mixing will depend on the energy associated with the interaction of the
molecules in our system. Let's define each type of interaction energy:
Note that dispersion forces are always attractive, thus interaction energies are negative!
CBE 514
+ Chapter 7
Reg. Solution Theory
Flory Huggins
Osmotic Pressure
Phase Behavior
(chi)
Excluded Volume
H1 =
1
m1 z w11
2
H2 =
1
m2 z w22
2
Since each molecule interacts with z other molecules, some will be species 1 and some will
be species 2. We'll assume that the fraction of these z interactions that are with type 1 is
identical to the mole fraction of species 1 in the mixture (perfect mixing).
Hm =
1
1
m1 x1zw11 + m1 (1 x1 ) zw12 + m2 x1zw12 + m2 (1 x1 ) zw22
2
2
species 1 interactions
species 2 interactions
Now we can combine these to give us the enthalpy of mixing (after some algebra):
H m =
m1m2
m
w
w
z w12 11 22
2
2
H m =
m1m2
zw
m
CBE 514
+ Chapter 7
Reg. Solution Theory
Flory Huggins
Osmotic Pressure
Phase Behavior
(chi)
Excluded Volume
m1m2
zw
m
One important property of Hm, when only dispersion interactions are involved, is that self
interactions are more attractive (more negative) than cross interactions. As a result:
w 0
H m 0
and the enthalpy of mixing opposes mixing! We also should recognize that:
= w per molecule
exchanged
zw11
zw22
zw12
zw12
1
( 2zw12 zw11 zw22 )
2
2 molecules exchanged
CBE 514
+ Chapter 7
Reg. Solution Theory
Flory Huggins
Osmotic Pressure
Phase Behavior
(chi)
Excluded Volume
H m
whole
system
m1m2
kT = x1m2 kT = x2 m1 kT
m
Gm = H m T Sm
Gm
whole
system
= [ x1m2 kT ] T k ( m1 ln x1 + m2 ln x2 )
H m
Sm
Several more convenient forms follow, differing largely by how they are normalized.
Gm
kT
Gm
RT
Gm
kT
Gm
RT
whole
system
per kT
whole
system
per RT
= m1 ln x1 + m2 ln x2 + x1m2
= n1 ln x1 + n2 ln x2 + x1n2
lattice site
(molecule)
per kT
= x1 ln x1 + x2 ln x2 + x1 x2
mole of
lattice sites
(mol of molecules )
per RT
= x1 ln x1 + x2 ln x2 + x1 x2
CBE 514
+ Chapter 7
Reg. Solution Theory
Flory Huggins
Osmotic Pressure
Phase Behavior
(chi)
Excluded Volume
1 =
A repeat unit is now defined not by a
monomer, but by a segment of the
polymer occupying the same volume as
a solvent molecule.
m1
m1 + Nm2
and
2 = 1 1 =
Nm2
m1 + Nm2
CBE 514
+ Chapter 7
Reg. Solution Theory
Flory Huggins
Osmotic Pressure
Phase Behavior
(chi)
Excluded Volume
Sm = Sm (S1 + S2 ) = k ln m k ln 1 k ln 2
Derivation of Sm=k ln m:
1. Assume i polymer chains have been added to the lattice (i < m2).
2. Find the number of configurations possible when adding the (i +1)th chain.
a. Open sites left:
open sites = m iN
b. Probability a site is open after i polymer chains have been laid down:
fi =
c.
m iN
m
Segment
1st
Choices
m - iN
Notes
segment can be placed anywhere that is open
2nd
zfi
3rd - Nth
(z-1)fi
CBE 514
+ Chapter 7
Reg. Solution Theory
Flory Huggins
Osmotic Pressure
Phase Behavior
(chi)
Excluded Volume
10
m iN
m iN
m iN
N 1 m iN
i +1 = ( m iN ) z
1
...
z
1
=
m
iN
z
1
(
)
(
)
(
)
(
)
m
m
m
m
1st segment
2nd segment
3rd segment
N 1
Nth segment
Now, to lay down m2 polymer chains in succession, we just take the product of all the i+1s:
total
1 m2 1
1 m2 1
m iN
=
i +1 =
( m iN ) ( z 1)N 1
m2 ! i = 0
m2 ! i = 0
m
N 1
This can be simplified using several clever tricks, discussed in detail in your text. The result
is:
ln total = ln m = ( m1 + m2 ) ln ( m1 + Nm2 ) m1 ln m1 m2 ln m2 m2 ( N 1) (1 ln ( z 1))
This last relationship is nice because it applies to any mixture of m1 solvent and m2 polymer
molecules. To find S1 and S2, we just have to set m2 and m1 equal to zero, respectively:
ln 1 = 0
what we would
expect for pure
solvent!
ln 2 = m2 ln ( Nm2 ) m2 ln m2 m2 ( N 1) (1 ln ( z 1))
Many unique
ways to lay down
m2 chains on the
lattice!
CBE 514
+ Chapter 7
Reg. Solution Theory
Flory Huggins
Osmotic Pressure
Phase Behavior
(chi)
Excluded Volume
11
Sm = Sm (S1 + S2 ) = k ln m k ln 1 k ln 2
Sm
whole
system
Nm2
m1
= k m1 ln
+
m
ln
2
m + Nm
m1 + Nm2
1
2
This form can be reduced to several more convenient forms, just as before:
Sm
Sm
Sm
Sm
whole
system
whole
system
= k ( m1 ln 1 + m2 ln 2 )
= R ( n1 ln 1 + n2 ln 2 )
lattice site
= k 1 ln 1 + 2 ln 2
= R 1 ln 1 + 2 ln 2
( multiply by
NA NA )
( divide by m )
( multiply by
NA m)
In regular solution theory, we noted in parentheses that this was also equivalent to "per molecule" and
"per mole of molecules", respectively. Note that this relationship no longer holds since the polymer
molecules occupy multiple lattice sites. One way you can interpret this is to recognize this is the free
energy "per solvent molecule volume" or "per mole of solvent molecule volumes", respectively.
CBE 514
+ Chapter 7
Reg. Solution Theory
Flory Huggins
Osmotic Pressure
Phase Behavior
(chi)
Excluded Volume
12
H m = H m (H 1 + H 2 )
w11 interaction energy between two molecules of type 1
H1 =
1
m1 z w11
2
1
( N m2 ) z w22
2
1
1
m11zw11 + m1 (1 1 ) zw12 + Nm21zw12 + Nm2 (1 1 ) zw22
2
2
species 1 interactions
species 2 interactions
Substituting these modified definitions into the overall expression above, and simplifying:
H m
H m
whole
system
lattice site
= 12 kT
H m
per mole of
lattice sites
= 12 RT
CBE 514
+ Chapter 7
Reg. Solution Theory
Flory Huggins
Osmotic Pressure
Phase Behavior
(chi)
Excluded Volume
13
Gm = H m T Sm
Gm
whole
system
= [1 Nm2 kT ] T k ( m1 ln 1 + m2 ln 2 )
H m
Sm
Several more convenient forms follow, differing largely by how they are normalized.
Gm
kT
Gm
RT
Gm
kT
Gm
RT
whole
system
per kT
whole
system
per RT
= m1 ln 1 + m2 ln 2 + 1 Nm2
= n1 ln 1 + n2 ln 2 + 1 Nn2
lattice site
per kT
mole of
lattice sites
per RT
= 1 ln 1 +
2
ln 2 + 12
N
2
ln 2 + 12
N
= 1 ln 1 +
CBE 514
+ Chapter 7
Reg. Solution Theory
Flory Huggins
Osmotic Pressure
Phase Behavior
(chi)
Excluded Volume
14
Gm
kT
lattice site
(molecule)
per kT
= 1 ln 1 + 2 ln 2 +
1 2
N
H m
Sm
k
kT
CBE 514
+ Chapter 7
15
Below is a nice comparison of the phase behavior predicted for regular solution theory and
Flory-Huggins Theory. Notice the asymmetry in the polymer-solvent system at even N = 20!
Regular Solution Theory (N = 1)
metastable
one phase
one phase
critical point
binodal
unstable
metastable
unstable
two phase
Gm < 0
spinodal
two phase
Gm > 0
Gm < 0
Gm > 0
0
0.1
0.2
0.3
0.4
0.5
x2 = 2
0.6
0.7
0.8
0.9
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Binodal line that separates the one phase region from the two phase region. The intersection of the
binodal with any isotherm (line of constant T) will give the compositions of the two phases in coexistence.
Spinodal anything under the binodal will be at its lowest free energy when phase separated, however, in
some cases it is possible to get a one phase mixture to exist under the binodal. If this is the case, the one
phase mixture will be metastable above the spinodal (below the binodal). It will be unstable below the
spinodal, and any fluctuation will induce separation.
16
0.7
Low T
0.35
0.5
0.3
0.15
High T
0.1
0.1
0.3
0.5
0.7
Gm > 0
free energy as
a single phase
0.25
0.2
0.4
0.6
0.8
Gm k T
H m kT
+ Chapter 7
Sm k
CBE 514
Low T
0.05
0.05
0.15
free energy as
two phases
0.25
High T
Gm < 0
0.35
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
17
0.35
0.15
species 2: 2
(2 )
(2 )
0.05
0.15
0.35
0
0.1
0.2
0.3
0.4
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
0.5
0.6
0.7
0.8
0.9
1.0
250
= 2
0.05
0.25
species 1: 1 ( ) = 1 ( )
2
T=120 K
T=170 K
T=210 K
T=242 K
0.25
Gm k T
+ Chapter 7
200
T (K )
CBE 514
150
100
50
CBE 514
+ Chapter 7
Reg. Solution Theory
Flory Huggins
Osmotic Pressure
Phase Behavior
(chi)
Excluded Volume
18
Gm
per mole
of molecules
= x1 ( 1 ) + (1 x1 ) ( 2
0
1
0
2
Flory-Huggins
1 ( x1 )
1 ( x1)
= 2 + x1 ( 1 2 )
For example, the free energy of points x1 and x1
Gm
Gm
per mole
of molecules
per mole
of molecules
= 2 ( x1 ) + x1 ( 1 ( x1 ) 2 ( x1 ))
= 2 ( x1) + x1( 1 ( x1) 2 ( x1))
1 ( x1 ) = 1 ( x1)
2 ( x1 ) = 2 ( x1)
2 ( x1 )
2 ( x1)
x1
x1
Inspection of the these criteria with the above two expressions shows that the ONLY way to meet the
phase equilibrium criteria is of the free energy expressions have the same slope and intercept that is
they are a common tangent to the free energy expression for the mixture.
19
2 Gm
x 2
i
=0
Gm
x 2
divides
out
2
T,p
T=120 K
T=170 K
T=210 K
T=242 K
0.25
0.15
0.05
0.05
0.15
0.25
T,p
0.35
Gm k T
+ Chapter 7
Gm
= i
=0
2
xi T , p i T , p
0.35
0
0.1
0.2
0.3
0.4
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
0.5
0.6
0.7
0.8
0.9
1.0
250
200
T (K )
CBE 514
150
100
50
CBE 514
+ Chapter 7
Reg. Solution Theory
Flory Huggins
Osmotic Pressure
Phase Behavior
(chi)
Excluded Volume
20
Gm
lattice site
Gm
2
T,p
2 Gm
2
2
= kT (1 2 ) ln (1 2 ) + 2 ln 2 + (1 2 )2
N
ln 2 1
= kT ln (1 2 ) 1 +
+ + (1 2 ) 2
N
N
T,p
1
1
= kT
+
2 = 0
(1 2 ) 2 N
1
1
+
2 = 0
1 2 N
spinodal
It is possible to solve for 2 explicity using the quadratic equation. Note that each
temperature gives a new , which gives two new composition values:
1 1 1
1
1
1
1
1
2 = +
1
1 1 + +
1
N 42
N
2 4 N
CBE 514
+ Chapter 7
Reg. Solution Theory
Flory Huggins
Osmotic Pressure
Phase Behavior
(chi)
Excluded Volume
21
3 Gm
3
i
3 Gm
3
2
T,p
=0
1
1
+
2 = 0
1 2 N
and
T,p
1
1
= kT
=0
2
2
N
2
(
2)
22 +
2
1
2
=0
( N 1)
( N 1)
2 =
( N 1)
N
( N 1)
positive
root only
2, c =
spinodal
N 1
1
=
( N 1) N + 1
1 1
2
c = +
+ 1
2 N
N
+ Chapter 7
Reg. Solution Theory
Flory Huggins
Osmotic Pressure
Phase Behavior
(chi)
Excluded Volume
22
2, c =
1
N +1
1 1
2
c = +
+ 1
2 N
N
1 1 1
1
1
1
1
1
2 = +
1 1 + +
1
1
2
N
4
N
2 4 N
450
400
2, c
, Tc
(-)
300
N = 20
N=3
N = 1 (RST)
350
T (K )
CBE 514
(+)
250
200
150
100
50
0
c, =
1
2
2, c, = 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
CBE 514
+ Chapter 7
Reg. Solution Theory
Flory Huggins
Osmotic Pressure
Phase Behavior
(chi)
Excluded Volume
23
V1
=
(1 2 )2
RT
where:
V1
= 0.34 +
(1 2 )2
RT
V1
when
(1 2 )2 < 0.3
RT
CBE 514
+ Chapter 7
Reg. Solution Theory
Flory Huggins
Osmotic Pressure
Phase Behavior
(chi)
Excluded Volume
24
eff =
+ = H + S
and allows for contributions not taken into account in the original Flory-Huggins model, such
as hydrogen bonding between the polymer and solvent. (in that case, can be negative). The
temperature independent term, , is typically associated with excess entropy of mixing
perhaps a product of preferred packing orientation on the lattice, for example.
0
0.1
0.2
0.3
one phase
UCST
0.4
0.5
0.6
0.7
0.8
0.9
two phase
T
two phase
LCST
one phase
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
CBE 514
+ Chapter 7
Reg. Solution Theory
Flory Huggins
Osmotic Pressure
Phase Behavior
(chi)
Excluded Volume
25
Osmotic Pressure
Our final topic in this chapter is to correlate the osmotic pressure of a polymer solution to
Gm and more importantly, . Why? Well it is easy to measure osmotic pressure, and
therefore it also becomes a way of measuring directly. It also turns out that we can also
measure Mn of a polymer simply by measuring osmotic pressure as well and that of
course is of great value.
Consider the following apparatus:
o
1 T,p
0
= 1 T , p
= 1 T , p +
0
p0 +
p0
1
p dp
T
V1
V1 RT ln x1
1
x
ln (1 x2 ) 2
RT V1
V1
While we just simplified this expression for the osmotic pressure by using a dilute solution
condition, we now want to modify it to deal with concentrated solutions as well. We can do
that by creating a virial expansion to take into account deviations from the dilute condition.
CBE 514
+ Chapter 7
Reg. Solution Theory
Flory Huggins
Osmotic Pressure
Phase Behavior
(chi)
Excluded Volume
26
Osmotic Pressure
A virial expansion in mole fraction of polymer gives:
x
= 2 + 2 x22 + 3 x23 + ...
RT V1
The mole fraction of polymer can be re-expressed in terms of concentration:`
x2 =
n2
cV M n
Vc
=
1
n1 + n2 (V V1 ) + cV M n M n
small
c V12 2
=
+ 2
c + ...
RT M n M n2
c
=
+ Bc 2 + B3c 3 + ...
RT M n
c
=
RT M n
The Mn in the denominator has the effect of converting the mass concentration to a molar
concentration. That is, the osmotic pressure depends exclusively on the number of
molecules added per unit volume, not their chemical makeup or size, etc. This is the
definition of a colligative property, like freezing point depression, or boiling point elevation!
CBE 514
+ Chapter 7
Reg. Solution Theory
Flory Huggins
Osmotic Pressure
Phase Behavior
(chi)
Excluded Volume
27
c
=
+ Bc 2 + B3c 3 + ...
RT M n
1
=
+ Bc + B3c 2 + ...
cRT M n
1
Mn
What does B represent? It accounts for two-body interactions when concentrations are
moderate. When the polymer is in a good solvent, the polymer prefers to be surrounded by
solvent relative to itself. Coil interactions are repulsive and solvent is driven to dilute the
polymer solution even more. As a result, B > 0 (greater ). If the solvent is poor, polymer
coils are attracted to each other in an attempt to exclude solvent molecules, and less
solvent flows across the membrane: B < 0 (smaller ). Notice the intercept of the right plot
is Mn-1.
When B = 0, the polymer is indifferent to whether solvent or polymer is in contact with it,
which is called the theta condition, and the solvent (and temperature) for which this is true
is called a theta solvent.
CBE 514
+ Chapter 7
Reg. Solution Theory
Flory Huggins
Osmotic Pressure
Phase Behavior
(chi)
Excluded Volume
28
Gm
V1 = 1 10 = 1 =
=
RT
n
ln
+
n
ln
+
n
(
)
(
)
1
1
2
2
1 2
n
n1 p,T ,n2
1
p,T ,n2
n n
V1 = RT ln 1 + 1 1 + 2 2 + 2 + n1 2
1 n1 2 n1
n1
1
n1
Nn2
2
22
=
=
= 1 2
=
2 =
n1 n1 n1 + Nn2 ( n1 + Nn2 )
( n1 + Nn2 ) Nn2 n1
2
Nn2
Nn2
2
22
=
=
= 1 2
=
2 =
n1 n1 n1 + Nn2
n1
( n1 + Nn2 ) Nn2
( n1 + Nn2 )
Substituting and in terms of polymer volume fraction now:
V1 = RT ln (1 2 ) + 2 1 + 22
CBE 514
+ Chapter 7
Reg. Solution Theory
Flory Huggins
Osmotic Pressure
Phase Behavior
(chi)
Excluded Volume
22
ln (1 2 ) = 2
...
2
Substituting into our previous expression:
1
22
1
1
= 2
... + 2 2 + 22 = 2 22 ...
RT
V1
2
N
2
V1 N V1
A final step is to convert from polymer volume fraction to polymer concentration:
2 =
V2 c NV1c
=
Mn
Mn
and
V2 = NV1
c
1 V22 1 2
c
=
+
2 c + ... =
+ Bc 2 + ...
RT M n
2 V1 M n
Mn
Our final important result:
1 V22 1
B=
2
2 V1 M n
29