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S! !! total! > 0!
Remove Barrier !
Heat !
S = k ln "
to calculate the entropy. But where on earth do you even start on a problem like this, when you have the jumbled up, randomly arranged mess that is the liquid state ?
Lattice Model !
*This is equivalent to assuming that there is no free volume, or the fluid is incompressible.
How many ways are there of putting two molecules on the lattice?
Model -the polymer is a chain of connected segments, each equal in size to a solvent molecule. !
#p =
} !
Interaction energy
! A ! A ! A ! A ! A ! B ! B ! B ! B ! B ! B ! A ! A
Let the attractive interaction energy between a pair of small A molecules be +AA. If we assume that we can simply add the interactions between all pairs, then we can say that the interaction of a chosen A molecule with all its nearest neighbors is z+AA, where z is the number of nearest neighbors.
! A
! B ! B
! B
! A
! B
! A ! % AB 1 = % AB - [% AA + % BB ] 2
! A ! B
! Hm = nAB !% AB
Then
! Hm = nA # B [z!% AB ]
z!% AB &= kT
The heat of mixing is then simply
! Hm = kT [nA# B &]
! B
! A
! A
CA ! B! =!?!
0! .! 5! 0! .! 5! CA ! B! =!CA ! A! CB ! B! 0.! ! 5! 0.! ! 5! 2! E ! ~ ! ( ! 2 C ! ! C ! C ! ) ! ( ! C ! C ! !! -! AB!-! AA!-! BB! =! AA! -! BB! )!
Solubility Parameters
'!A! =! C! !
0. 5 AA
!! !
& -
Positive !
Phase Behaviour
Single Phase
(Miscible Mixture)
& = a+ b T
Temperature
Phase Behaviour
!G ! 0 ! B2 ! xB1 ! xB2 ! 0 !
Q ! B1 ! Q* !
xB !
!G1 !
!G2 !
Phase Behaviour
!G ! 0 ! B2 ! xB1 ! xB2 ! 0 !
Q ! B1 ! Q* !
xB !
B2 ! xB !
!G1 !
!G2 !
0 !
xB1 !
xB2 !
0 !
B1 ! B2 ! xB !
! = !
2 ! 1 = ! B B
Composition B1
2 ! 1 = ! A A
Composition B2
Composition B1
!G !
Phase Diagrams
B1 ! B2 ! xB !
2 ! 1 = ! s s
Temperature
UCST
Composition
xB1 !
! S1 ! C
xB2 ! S2 ! B2 ! xB !
0 !
B1 !
!G !
! 0 ! B1 ! S1
0 ! S2 !
B2 ! xB !
Temperature
UCST Binodal
( !G =0 3 (xB
Spinodal
Composition
Phase Separated
Composition
We can now summarize our conditions for forming a single phase or miscible mixture; a) The free energy change on mixing should be negative. b) The second derivative of the free energy of mixing should be positive (which means a point of inflection on the free energy curve has not been reached and it is concave upwards across the composition range).
,.
Temperature
[#p]c$
Composition
- Blends ,.
mA1 / 2 + mB1 / 2
2
The Critical Value of the Solubility Parameter Difference for Polymer Solutions
UCST Upper Critical Solution Temperature Temperature
&c ~ 1 / 2
2 & c = 0.34 + Vr [' p - ' s ]c = 0.5 RT
[' p - ' s ] - 1
Composition
T (0 C)
10 5 0 -5
!
-10 0.00
0.05
0.10
0.15
1.2!
1.0!
0.8!
0.6!
FLORY - HUGGINS
0.4! 0.0! 0.2! 0.4! 0.6! 0.8! 1.0!
Phase Separated
Temperature
Composition
Temperature (C)
190
4800 10,300
140 100
19,800
50 0 -50 0.1
10,300 4800
0.2 0.3
Temperature
LCST - Lower Critical Solution Temperature UCST - Upper Critical Solution Temperature
An aside is in order here. The fact that the lower critical solution temperature is at a higher temperature than the upper critical solution temperature can be a bit confusing. The word lower in LCST is chosen to mean at the bottom (lowest temperature) of a two phase region, while the word upper in UCST designates the top of a two phase region.
Phase Separated
Composition
Dilute Solutions
!There is an intermolecular excluded volume effect in a good solvent (meaning & << 0.5, the critical value).! ! !There is also an intramolecular excluded volume effect, again in a good solvent, such that the chain expands its dimensions! relative to the usual end-to-end distance found in concentrated solutions or the melt. ! ! !The chain expansion varies with &, hence temperature, and there is a temperature, the theta temperature, where the chain again becomes ideal, or can be described by Gaussian statistics. ! ! !
%1 ) ~m ' &2
5 0. 5
( #p &* + + - - - - - ) 3 ~m
0. 6
Temperature
2 0 .5
~)m
0 .5
At the * temperature
1 &+ 2 R
2 0 .5
~m
0 .5