CBE 514
+ Chapter 7
Reg. Solution Theory
Flory Huggins
Osmotic Pressure
Phase Behavior
(chi)
Excluded Volume
Thermodynamics of Polymer Solutions
Regular Solution Theory
To understand the thermodynamics of polymer solutions (polymer dissolved in a solvent), it
is instructive to start by exploring the simpler case of mixing two small molecules. The
important thermodynamic quantity is the free energy of mixing:
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.
Lattice Model (Lattice is 3-D!!!!)
m1 = number of molecules of species 1
m2 = number of molecules of species 2
m = m1 + m2 = total number of sites
Assumptions
1) each solvent molecule occupies the same volume
2) cell size is chosen equal to this volume
3) lattice has a coordination number of z.
4) there are no empty sites.
CBE 514
+ Chapter 7
Reg. Solution Theory
Flory Huggins
Osmotic Pressure
Phase Behavior
(chi)
Excluded Volume
Thermodynamics of Polymer Solutions
Regular Solution Theory: Entropy of Mixing
We can use our lattice model to help us calculate the entropy of mixing:
Sm = Sm (S1 + S2 )
The configurational entropy is given by the Boltzmann equation:
S = k ln
where:
k Boltzmann Constant (1.3806503 10-23 m2 kg s-2 K-1)
total number of unique configurations possible
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
Using Stirling's Approximation as we did in Chapter 6, we can simplify this expression:
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
Thermodynamics of Polymer Solutions
Regular Solution Theory: Entropy of Mixing
It is useful to make some important comments about this expression:
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 )
mol of lattice sites
(mol of molecules )
= 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
Thermodynamics of Polymer Solutions
Regular Solution Theory: Enthalpy of Mixing
We'll start our derivation of the enthalpy of mixing by recognizing two additional assumptions
of the lattice model:
Assumptions
5) there is no volume change upon mixing (the number of lattice sites is constant)
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:
w11 interaction energy between two molecules of type 1
w22 interaction energy between two molecules of type 2
w12 interaction energy between one molecule of type 1
and one molecule of type 2
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
Thermodynamics of Polymer Solutions
Regular Solution Theory: Enthalpy of Mixing
We can define the pure component enthalpies quite easily using these interaction energies:
H1 =
1
m1 z w11
2
H2 =
1
m2 z w22
2
z is simply the number of molecules
that another molecule "sees" in any
single instant in time. It is called the
coordination number.
this factor of corrects for
the double counting, since
w11 involves two molecules.
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
Thermodynamics of Polymer Solutions
Regular Solution Theory: Flory-Huggins Interaction Parameter
H m =
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:
zw is the exchange energy per molecule
In fact, we typically define a new term, called the Flory-Huggins Interaction Parameter which
is based on this exchange energy:
fraction of kT (thermal energy) required to take 1 molecule
zw
=
of type 1 out of its beaker, 1 molecule of type 2 from its
kT
beaker, and exchange them (per molecule)
= 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
Thermodynamics of Polymer Solutions
Regular Solution Theory: Free Energy of Mixing
We can now write a final expression for the enthalpy of mixing using .
H m
whole
system
m1m2
kT = x1m2 kT = x2 m1 kT
m
Our free energy of mixing follows directly.
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
(multiply both sides by 1 N A )
(divide both sides by m)
(divide both sides by nN A = m)
CBE 514
+ Chapter 7
Reg. Solution Theory
Flory Huggins
Osmotic Pressure
Phase Behavior
(chi)
Excluded Volume
Thermodynamics of Polymer Solutions
Flory-Huggins Theory for Polymer Solutions: Lattice
The regular solution theory we just developed applies to small molecule binary mixtures.
Although we used a lattice to develop the theory, notice that no part of the lattice exists in the
final result. This is the sign of a good model.
We can now extend these ideas to situations in which the molecules are not the same size,
and in particular the case in which one is very large (polymer) and the other is very small
(solvent). We simply need to modify our lattice model a little bit.
F-H Lattice Model (Lattice is 3-D!!!!)
A. m1 = number of solvent molecules
m2 = number of polymer (solute) molecules
B. Each lattice site has a volume of one solvent molecule
Each polymer molecule occupies N lattice sites
m = m1 + Nm2 = total number of sites
C. Switch to volume fractions
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 =
D. Lattice has a coordination number of z.
E. There are no empty sites.
Nm2
m1 + Nm2
CBE 514
+ Chapter 7
Reg. Solution Theory
Flory Huggins
Osmotic Pressure
Phase Behavior
(chi)
Excluded Volume
Thermodynamics of Polymer Solutions
Flory-Huggins Theory for Polymer Solutions: Entropy of Mixing
As before we must calculate the values of the three configurational entropy terms
contributing to the entropy of mixing:
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
Lay down the (i +1)th chain, segment by segment:
Segment
1st
Choices
m - iN
Notes
segment can be placed anywhere that is open
2nd
zfi
segment must be placed in one of z nearest
neighbor sites, and only a fraction may be free
3rd - Nth
(z-1)fi
one of the nearest neighbors must be occupied
by the chain being laid down.
CBE 514
+ Chapter 7
Reg. Solution Theory
Flory Huggins
Osmotic Pressure
Phase Behavior
(chi)
Excluded Volume
Thermodynamics of Polymer Solutions
10
Flory-Huggins Theory for Polymer Solutions: Entropy of Mixing
The number of possible configurations for the (i +1)th chain, is just the product of each of the
terms in the second column. Here, we neglect the difference between z and z-1.
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
Thermodynamics of Polymer Solutions
11
Flory-Huggins Theory for Polymer Solutions: Entropy of Mixing
Finally we can combine each of these terms to get our Flory-Huggins entropy of mixing:
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
mol of lattice sites
= 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
Thermodynamics of Polymer Solutions
12
Flory-Huggins Theory for Polymer Solutions: Enthalpy of Mixing
The calculation of the enthalpy in the Flory-Huggins model is almost directly analogous to
that of Regular Solution Theory, except we must incorporate the size of the polymer chain
and the fact we are now using volume fractions.
H m = H m (H 1 + H 2 )
w11 interaction energy between two molecules of type 1
H1 =
1
m1 z w11
2
w22 interaction energy between two segments of type 2
H2 =
1
( N m2 ) z w22
2
w12 interaction energy between one molecule of type 1
and one segment of type 2
Hm =
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
= 1 Nm2 kT = m12 kT = 1 Nn2 RT = n12 RT
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
Thermodynamics of Polymer Solutions
13
Flory-Huggins Theory for Polymer Solutions: Free Energy of Mixing
It is now just a matter of combining these expressions for the entropy and enthalpy of mixing
into our expression for the free energy of mixing:
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 +
(multiply both sides by 1 N A )
2
ln 2 + 12
N
(divide both sides by m)
2
ln 2 + 12
N
(divide both sides by nN A = m)
= 1 ln 1 +
CBE 514
+ Chapter 7
Reg. Solution Theory
Flory Huggins
Osmotic Pressure
Phase Behavior
(chi)
Excluded Volume
Thermodynamics of Polymer Solutions
14
Flory-Huggins: Phase-Behavior of Mixed Polymer Solutions
So now we have a convenient model for for calculating the free energy of a polymer solution
relative to its pure component solutions.
Gm
kT
lattice site
(molecule)
per kT
= 1 ln 1 + 2 ln 2 +
1 2
N
H m
entropic term, which will always favor mixing!
Note that as N increases (polymers get larger),
the ability of these terms to favor mixing
decreases! The entropic gain associated with
mixing is diminished as the molecules get larger.
Super High MW polymers do not dissolve!
Sm
k
kT
enthalpic term, which will always oppose mixing if
> 0 (true if interactions are dispersive only)
Assumptions of Model (re-stated):
1. No volume change upon mixing (Vm=0)
2. Sm originates entirely from the ideal combinatorial entropy of
mixing.
3. Hm only contains the internal energy of mixing
4. Random mixing is assumed (energetics of clustering not
considered)
5. All interactions are short-range (z), isotropic, and additive.
6. Local concentration is always given by the bulk concentration.
(mean-field assumption or model) This fails in the dilute
polymer solution limit! (See figure at right)
CBE 514
+ Chapter 7
Thermodynamics of Polymer Solutions
15
Phase-Behavior in Polymer-Solvent Systems
Reg. Solution Theory
Flory Huggins
Osmotic Pressure
Phase Behavior
(chi)
Excluded Volume
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
Flory-Huggins Theory (N = 20)
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.
Thermodynamics of Polymer Solutions
16
Phase Separation: Driving Force
To understand where the binodal comes from, we need to look at the plot of free energy
versus composition:
The compositions at which the
Gm
H m Sm
two phases form must have a
=
+
kT per lattice site
kT
k
common tangent! The common
per kT
tangent ensures equal chemical
potentials for both species!
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
Reg. Solution Theory
Flory Huggins
Osmotic Pressure
Phase Behavior
(chi)
Excluded Volume
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
phase 1: single prime
0.4
0.5
0.6
0.7
0.8
0.9
phase 2: double prime
Reg. Solution Theory
Flory Huggins
Osmotic Pressure
Phase Behavior
(chi)
Excluded Volume
Thermodynamics of Polymer Solutions
17
Finding the Binodal: Common Tangent Construction
At each temperature in the two-phase
region, it is possible to find two points
along the free energy curve which share
a common tangent (slope and intercept!).
For reasons we will see later, the sharing
of a common tangent between
compositions ensures a species has the
same chemical potential in both phases
the criteria for chemical equilibrium in a
multiphase system!
0.35
0.15
species 2: 2
(2 )
(2 )
By drawing a common tangent at each
temperature, the compositions of the two
phases can be obtained for all
temperatures. These can then be replotted to give the binodal curve for the
system.
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
Thermodynamics of Polymer Solutions
18
The Origin of the Common Tangent Construction
What we are going to find is that the binodal corresponds to the two points on the free
energy curve which have a common tangent. In a symmetric system this turns out to be the
local minima. However, in a polymer solvent mixture where the molecules are of dramatically
different sizes, the double tangent does not pass through the minima (only close to them).
The free energy of any point on a curve can be expressed
as the mole-weighted average of the chemical potentials of
the two species in the mixture
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))
However, the criteria for phase equilibrium is:
1 ( x1 ) = 1 ( x1)
2 ( 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.
Reg. Solution Theory
Flory Huggins
Osmotic Pressure
Phase Behavior
(chi)
Excluded Volume
Thermodynamics of Polymer Solutions
19
Flory-Huggins: Locating the Spinodal (Graphically)
The spinodal determines the boundary
inside the two-phase region and
represents the dividing line for regions in
which one phase mixtures are
metastable and unstable. The
thermodynamic criteria for the spinodal is
given by:
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
Graphically, the spinodal corresponds to
the inflection points in the free energy
versus composition curve. Like the
binodal, it can be constructed graphically
as shown on the right, but is much more
accurately (and easily) obtained
analytically. Note the following equality
which makes working in terms of volume
fraction easy:
2
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
Thermodynamics of Polymer Solutions
20
Flory-Huggins: Locating the Spinodal (Analytically)
To solve the analytical solution to the spinodal for a Flory-Huggins polymer mixture, we
must set the second derivative of the free energy with respect to the volume fraction of
polymer equal to zero. The result will be a quadratic expression, that will give two
compositions per temperature.
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
Thermodynamics of Polymer Solutions
21
Flory-Huggins: Locating the Critical Point (Analytically)
The critical point occurs at the maximum of the spinodal, which occurs at the temperature in
which the spinodal gives only a single solution. One way to locate it is to solve the previous
expression for 2 for the value of that makes the term under the square root equal to zero.
The other, more rigorous method is to solve for the point along the spinodal at which the
slope = 0. More specifically:
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)
It is possible to solve for 2 explicity using the quadratic equation.
2 =
( N 1)
N
( N 1)
positive
root only
2, c =
spinodal
N 1
1
=
( N 1) N + 1
Substituting 2,c back into the spinodal expression gives c :
1 1
2
c = +
+ 1
2 N
N
+ Chapter 7
Reg. Solution Theory
Flory Huggins
Osmotic Pressure
Phase Behavior
(chi)
Excluded Volume
Thermodynamics of Polymer Solutions
22
Flory-Huggins: Effect of Polymer Size
We can now go back and look at the phase behavior for various degrees of N.
For any particular system, as N
b e c o m e s l a r g e r, p h a s e
separation is preferred at higher
and higher temperatures. Even at
very low values of N, one phase
is almost exclusively solvent
except near the critical point.
One interesting case to look at is
what happens as the size of the
polymer gets infinitely large!
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
Thermodynamics of Polymer Solutions
23
Flory-Huggins: Calculating (Measuring)
One of the traditional ways of predicting for small molecule systems is through the
following relationship,
V1
=
(1 2 )2
RT
where:
V1 molar volume of the solvent
i solubility parameter (related to the energy lost when a mole of species i is
removed from solution
This is very convenient, since
solubility parameters have
been tabulated for many
solvents and polymers!
The problem is, it doesn't work
very well for polymer solvent
mixtures. In fact, there is not
even a trend, such as it always
overestimates, etc. Even so,
some empirical studies using
these values have found that a
small shift does improve
accuracy for many systems.
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
Thermodynamics of Polymer Solutions
24
Flory-Huggins: Calculating (Measuring)
One of the ways to overcome the lack of accuracy in this predictive method is to simply
measure for your specific system. For example, one could measure Gm or a more
appropriate thermodynamic property (such as osmotic pressure) and use as a fitting
parameter to match the data. Typically is represented as a linear function for these
purposes:
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
Both terms can be either
positive or negative. Notably, FH Theory, as developed, can
only describe UCST (upper
critical solution temperature)
behavior. By allowing and to
take on positive or negative
values, it is possible to describe
LCST (lower critical solution
temperature) behavior as well.
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
Thermodynamics of Polymer Solutions
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:
At equilibrium the chemical potential of each
species must be equal. Here we express that
equality for the solvent:
o
1 T,p
0
= 1 T , p
= 1 T , p +
0
p0 +
p0
1
p dp
T
V1
Rearranging, and assuming very dilute conditions
such that the activity coefficient is one:
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
Thermodynamics of Polymer Solutions
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
Third Virial Coefficient: accounts
for three-body interactions which
are only relevant at significant
concentrations.
Combining these two expressions gives:
c V12 2
=
+ 2
c + ...
RT M n M n2
c
=
+ Bc 2 + B3c 3 + ...
RT M n
In the very dilute limit when the higher
terms in the virial expansion are negligible,
c
=
RT M n
Second Virial Coefficient (no subscript,
historically): accounts for two-body
interactions, relevant at moderate to
high concentrations
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
Thermodynamics of Polymer Solutions
27
The Second Virial Coefficient and the Theta Condition
There are a couple typical representations of the osmotic pressure expression:
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
Thermodynamics of Polymer Solutions
28
Osmotic Pressure using Flory Huggin's Theory
The previous relationship was completely model independent. It is possible, if we return to
the original definition of osmotic pressure based on chemical potential, to incorporate the
Flory-Huggins free energy into our expression:
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
Thermodynamics of Polymer Solutions
Osmotic Pressure using Flory Huggin's Theory
We can now use the fact that for dilute polymer volume fractions,
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
Recall that in a theta solvent, B = 0! That means in the Flory
Theory for polymer solutions, = is also indicative of the theta
condition. We also saw that for large N, c= ! This reinforces
the idea that at the theta condition, the solvent is "just" becoming
a poor solvent
- beyond that, we get a transition from a
homogeneous 1-phase system to a 2-phase system!
29
