Lecture 22

Polymer Solutions
The model
Ideal polymer solution
Bragg-Williams approximation

Lattice model polymer solution

N1 solvent molecules and N2 polymer molecules each consisting of n
units (monomers) all distributed on N sites

N1 + nN2 = N

Ideal solution
w = 2AB AA BB

Only entropy matters.

S = k ln

Where omega is number of ways of placing N1 polymers

on N sites.
Placing first segment of i+1 th chain can be done in

N in
ways.
Placing the second in

N ni
c
N
ways. And placing next in

N ni
(c 1)
N

ways since one site is occupied by previous segment

Ideal solution - entropy

Combining previous expressions placing i+1 molecule
n

N ni
n2
i+1 = c(c 1) N

Similarly placing i molecule

n

i = c(c 1)

n2

N n(i 1)
N

Placing all polymer molecules can be done in

ways

1 2 ...... N 2

N 2!

Ideal solution - entropy II

After some algebra

N
N2
N 2 (n2) nN 2 !
c (c 1)
n
n

N 2!N N 2 (n1)
N N !
2
n

And using Stirlings approximation

Ssol

nN 2
N1
= ln = N 2 ln
N1 ln + N 2 [lnc + (n 2)ln(c 1) + (1 n) + ln n ]
k
N
N

Ideal solution - entropy of mixing

Entropy of pure solvent is zero (one way of filling) and entropy
of pure polymer is
S poly
= N 2 [lnc + (n 2)ln(c 1) + (1 n) + ln n ]
k
Therefore the entropy of mixing

Smix = Ssol S poly

?
nN 2
N1 ?
= k?N 2 ln
+ N1 ln ?
?
N
N ?

Per mol of molecules

Smix = R[ X 2 ln 2 + X1 ln 1 ]

where

1 =

N1
N

and 2 =

nN 2
N

Non-ideal solution
w = 212 211 222

Using Bragg-Williams approximation

Fmix

cw

= E mix TSmix = N 1 2 + kT [ X 2 ln 2 + X1 ln 1 ]
2

And on the molar bases

Fmix

cw
n
nX 2
X1
= N Av X1 X 2
+ X1 ln
2 ln

2 + RT X
2
X1 + nX 2
X1 + nX 2

( X1 + nX 2 )

Polymer blends
Mixture of two polymers with degree of polymerization of n1
and n2. The molar entropy of mixing is
Fmix

cw
n1n 2
n1 X1
n 2 X 2
= N Av
X1 X 2
+ RTX 1 ln
+ X 2 ln

2
n1 X1 + n 2 X 2
n1 X1 + n 2 X 2
n1 X1 + n 2 X 2

Take for example n1 = n2 = n and X1 = X2 = 0.5

Fmix = N Av

cw
0.25n + RT [0.5ln0.5 + 0.5ln0.5]
2

Which differs from the expression for small molecules by n

factor
in energy, which implies that small energetic differences
for polymers will have large effects.