Lecture-11

Polymer Solution Thermodynamics

1
Entropy of mixing of two different small
molecules  n n 
S mix   k n1 ln 1  n2 ln 2 
 n0 n0 
n1  n2  n0
S mix  n1 n2 
  k  ln x1  ln x 2 ,
n0  n0 n0 
n1
 x1
n0
n 0!
S mix  k ln
n1!n 2 !
  n1 ln x1  n 2 ln x 2 
Gmix  kT  n1 ln x1  n2 ln x 2   H mix 2
 Flory Huggins Theory

• Athermal Solution
DHmix=0

• Entropy of Mixing
J-1 st molecule can be arranged in

3
Continued..

   p / n2 ! As all chains are identical

 Continued..
ln
Continued..

Entropy of pure polymer

Entropy of Solvent
Continued..
Entropy Change on Mixing

 n mn 
S mix  k n1 ln 1  n2 ln 2 
 n0 n0 
S mix  k  n1 ln 1  n2 ln  2  , n0  n1  mn2
 Flory Huggins Theory
• Athermal Solution
DHmix=0

• Entropy of Mixing

 n mn2 
S mix  k n1 ln 1  n2 ln 
 n 0 n 0 

S mix  k  n1 ln 1  n2 ln  2 , n0  n1  mn2

8
 Enthalpy Change upon mixing
For polymer
• DH>0,
• DVmix=0, DH=DU

9
Energy of Interaction of Polymer segment
only with surroundings

10
Energy of Interaction of Polymer segment
only with surroundings

z2 e22  z1e12

n02
Ep   z2e22  z1e12 
2 11
Energy of Interaction of solvent only with
surroundings

z2 e12  z1e11

n01
Es   z2e21  z1e11 
2

12
Energy of Interaction of Polymer segment
in amorphous state

n02
E p0   ze22 
2
Energy of Interaction of solvent in pure
state
n01
Es 0   ze11 
2
13
Total change in internal energy on mixing

U  E p  E s  E p0  E s0 
n 0 2 n 01
  z 2 e 22  z1e12    z 2 e 21  z1e11 
2 2
n  n 
 0 2  ze 22   0 1 ze11
2 2
zn 0
  21 2 e12  1 2 e11  1 2 e 22 
2
zn 0
 1 2  2e12  e11  e 22 
2
 zn 01 2 e
 ze 
 kT n1 2
 kT 

HM  kTn1 2 14
Total Free Energy Change and chemical
potential of components
Gmix  kTn1 ln 1  n2 ln  2  n1 2 

n1 mn2
1  ; 2 
n1  mn2 n1  mn2
1 2

n1 n1  mn2
1 m1

n2 n1  mn2

15
Chemical potential of polymer and solvent

1 1 Gmix

kT kT n1
 1
 ln 1   2 1     22
 m
 2 1 Gmix

kT kT n2
 ln  2  1 1  m   m12
 Phase Equilibrium
Liquid-Liquid equilibrium
What are the free energy plot for two components which
completely (a)Immiscible (b)Miscible (c) miscible at a certain
concentration?

Gmix  0;
 2 Gmix
Gmix  0, 0 Miscibility condition
x 2
2

 2 Gmix
0
x 2
2 Spinodal Point
Liquid Liquid Equilibrium Mixture of Ethanol and
Dodecane
 Binodal Curve or Coexistence Curve

Binodal Curve: defining the region of composition and

temperature in a phase diagram for a binary mixture
across which a transition occurs from miscibility of the
components to conditions where single-phase mixtures
are metastable or unstable.

Binodal compositions: are defined by pairs of points on the

curve of Gibbs energy of mixing vs composition that have
common tangents, corresponding to compositions of equal
chemical potentials of each of the two components in two
phases.
 Spinodal Curve:
A curve that separates a metastable region from an unstable
region in the coexistence region of a binary mixture.
Above the spinodal curve the process of moving towards
equilibrium occurs by droplet nucleation, while below the
spinodal curve there are periodic modulations of the order
parameter,
which have a small amplitude at first (i.e., spinodal
decomposition).
 Phase Equilibria
What are the free energy plot for two components
which completely (a)Immiscible (b)Miscible ?

Gmix  0;
 2 Gmix
Gmix  0, 0 Miscibility condition
x 2
2

 2 Gmix
0
x 2
2 Spinodal Point
Free-energy change of mixing per mole of a binary
mixture as a function of mixture composition.
Temperature–composition diagram

UCST
Phase Behavior of Solution of
Monodisperse Polymer

24
Chemical potential of polymer and solvent

1 1 Gmix

kT kT n1
 1
 ln 1   2 1     22
 m
 2 1 Gmix

kT kT n2
 ln  2  1 1  m   m12
Chemical potential of Solvent at m=1000
1.5

1 c=0.5
5

c=0.532
1 0

0.5
T X

c=0.54
Dm1/k

0
0 0.01 0.02 0.03 0.04 0.05
-0.5 c=0.55
c=0.6
-1
f2
Volume fraction and F-H interaction parameter for
phase separation

1
 2c 
1 m
1 1 1
c   
2 m 2m
Polyisobutylene in diisobutyl ketone

J.Am. Chem. Soc. 74,4760,1952

Dependence of c on Volume fraction
PDMS(3850) in benzene
PS in MEK

c
Rubber in benzene

PS in Toluene
Dependence of c on temperature
DHM is dependent on temperature
1  
    1  
2  T

1 1 1
c    1
2 m 2m Intercept 
1 1 1 1 1  Slope 1 1
 1     
Tc     m 2m 
 Explanation of c
1   1  
    1       
2  T 2  T
  s  H
UCST Data for Solutions of PS in DOP

Determine the temperature dependence of the interaction parameter.

1
Intercept 
1 1
Slope 
Dependence of c on Chain length
const
  0 
M
For polystyrene/cyclohexane (PS/CH) solutions
Sun et al. , Macromol. Theory Simul. 2001, 10, 692.
 Polymers Blends
G mix  n1v1 n 2v2 zen 0 
 kT  ln 1  ln  2   21 
 v1 v2 

Gmix  n1v1 n2 v 2 zen0 

 kT  ln 1  ln 2  21 
V  v1V v2V V 

1 2 ze 
 kT  ln 1  ln 2  21 
 v1 v2 vs 
 H M
See section 9.6 of the “Fundamentals of polymer engineering ” 34
Strengths and Weaknesses of the F-H
Model
•Successful in explaining the observations
concerning the phase behavior of polymer-solvent
system
•Applicable for flexible polymer
•Not applicable at very dilute solution
•c is function of chain length
•DVmix=0

See section 9.3.7 of the “Fundamentals of polymer engineering ” 35

Mixing rule of interaction energy
zn0
U   212e12  12e11  12e22 
2
 z e 
 zn012 e  kT  n12  kTn12
 kT 
2
e11 e22 1
e  e12   e11  
2 2 r116
1 2 1  2
e12   6   3 3 ; if r11  r12  r22
r12 r11 r22

37
Interaction energy Parameter
1 2 1  2
e12   6   3 3 ; if r11  r12  r22
r12 r11 r22
e11 e 22
  e11 e22 e  e12  
2 2
1 2 1 2
ze z

kT 2
 e11  e22  2
e12  
6
r12

3
r11 3
r22

; if r11  r12  r22

38
 Solubility Parameter
zeii
U i ,vap   N av
2
Cohesive energy density the amount of energy needed to
completely remove unit volume of
U i ,vap zeii molecules from their neighbours to
CED    N av  i2
infinite separation 
Vi 2Vi
 ze 
   12 
V1
1   2   2

 kT  RT

39
Calculation of Solubility Parameter of Polymers

• By swelling
• Group molar attraction constant
• Hansen’s Three dimensional solubility
parameter
Solubility values for common
polymers and solvents

Polymer d Solvent d
(cal/cm3)1/2
PEO 9.9 Water 23.4
PVC 9.7 CCl4 8.6
PDMS 7.4 Toluene 8.9
PE 7.9 Carbon 10
disulfide
PS 9.1 THF 9.1
PMMA 9.2 Hexane 7.3

41
Determination of mol. Wt & c
• End group analysis
• Osmotic Pressure
• Vapour Pressure Osmometer
• Intrinsic Viscosity
• Gel Permeation Chromatography
• Light Scattering
Osmotic pressure

 A (T , P )
  A (T , P   , x A )

f A (T, P )
 f̂ A (T, P   , x A ) 43
 Condition of Equilibrium
f A (T , P)  fˆA (T , P   , x A )
fˆA (T , P   , x A )  x A f A (T , P   ) Lewis Randall rule

f A (T, P  ) 1 f A (T , P)
 ln  ln x A
f A (T, P ) xA f A (T , P   )

  ln  f A (T , P )  v
  T  A For Pure material
 P  RT
f (T , P   ) v A
ln A 
f A (T , P ) RT
f (T , P   ) v A x2 x3
ln A    ln x A  x 2 ln 1  x   x   
f A (T , P ) RT 2 3
RTx2
 x2 x3
vA 1  x  n
 1  nx  n (n  1)  n (n  1)( n  2)
2! 3!
 Osmotic Pressure
vA
  ln x A   ln(1  x 2 ) x2 x3
RT ln 1  x   x   
 1 c 2 3
 ln x A   Bc 2  B 3 c 3  .....
RT vA M

x2 
 w 2 / M2 V / V
 w 2 / M 2    w 1 / M1 
V
 c / M2 
 w 2 / M 2    w 1 / M1 
 c / M2 vA
 Maxwell Relation
dG  SdT  VdP  dn
  G    G 
   
P  n  n  P 
    A ( T , P, x 1 )     V (T , P, x 1 )  
  T, n    T, P
 P   n 
 vA
 Condition of Equilibrium
 A (T , P )   A (T , P   , x A )
   A (T , P, x1 ) 
  T  v A
 P 
 A (T , P   , x1 )   A (T , P, x1 )  v A
 A (T , P )   A (T , P, x1 )  v A
 1
 ln 1   2 1     22  v A / RT
 m
 22  1 M n 2
  2    2 1     22  v A / RT c
2  m mv A
1 1  Mn c
 2   22      v A / RT m 2 
m 2  2
2vA
1 c 1 
 / RTc    
mv A  2 v A  2 2 2 
 1 
1 c 1   / c  RT   Bc  B 2 c 2 
     Mn 
M n vA22 2 
 Theta condition

1 1 
 2   22      v A / RT
m 2 
 1 
1 c 1   / c  RT   Bc  B 2 c 2 
 / RTc    
mv A  2 v A  2 2  2   Mn 

1 c 1 
   
Mn v  2 2 
A 2
The following data are available for polymers A and B in the
same solvent at 27OC:

Conc A Osmotic Conc. of B Osmotic

g/dl pressure g/dl pressure
cm of solvent cm of solvent
.32 .7 .4 1.6
.66 1.82 .9 4.44
1 3.1 1.4 8.95
1.4 5.44 1.8 13.01
1.9 9.3
Solvent density and polymer density are 0.88 and
1.15 gm/cc respectively. Estimate average
molecular weight (Mn), second Virial coefficient
and c parameter for the two polymers. Molecular
weight of solvent is 78.
 Elevation of boiling point
Pure solvent Vapour in equilibrium with a polymer Solution

Pure Vapour A
T, P v
f A (T , P ) 
f̂ A L (T, P, x A )
Liquid A+ Polymer

See section 8.3 of the “Fundamentals of polymer engineering ” 50

 Condition of Equilibrium
v L
fA (T, P)  f̂ A (T, P, x A )
L L
Lewis and Randall rule f̂ A (T, P, x A )  x A f A (T, P)
v L
fA (TB , P)  f A (TB , P) For pure component
Eq. condition at boiling point

f A v (TB , P) f A L (TB , P)

v
f A (T , P ) x A f A L (T , P )
f A v (TB , P) f A L (TB , P)
ln  ln  ln x A
v L
f A (T , P ) f A (T, P )
 Condition of Equilibrium
Clausius-Clapeyron Equation for pure material
d ln f h 0  h

dT RT 2
f (TB , P ) h0  h  1 1
ln    
f (T , P ) R  TB T 

v L
f A (TB , P) f A (TB , P)
ln v
 ln L
 ln x A
f A (T , P) f A (T , P )

h0  hv h0  h L
 2
TB   2
TB  ln x A
RTB RTB
 Elevation of boiling point
 h0  h L h0  hv 
 2
 2 
TB   ln x A
 RTB RTB 
ln x A  ln 1  x 2    x 2
x2 
 w 2 / M2 V / V
 w 2 / M 2    w 1 / M1 
T B RTB2 v A  c / M2 
V
 v  w 2 / M 2    w 1 / M1 
c h  hLM n
 c / M2 vA
Vapour Pressure Osmometer

Minimum measurable
Solvent Vapour temperature

DT=10-5C

55
Ubbelhode Viscometer

56
 Analysis of the viscosity
Hagen Poiseuille Equation
p 32v

L D2
t
t 

t s s
Einstein relation
r  1  2.5
n2 v per

V 57
 Various terminologies of viscosity
• Relative Viscosity
• Specific Viscosity
• Reduced Viscosity
• Intrinsic Viscosity
• Inherent viscosity
 Reduced viscosity of infinitely dilute
solution
 sp 2 .5 v p N A

C M Independent of Concentration

Correlation of viscosity of polymer solution

Huggins Equation Kraemer equation
 sp ln  r
    k   C ;     k   C
2 2

C C
For many polymers in good solvent k=0.4+-0.1, k’=0.05+-0.05,
r  2

59
 Intrinsic Viscosity
Unit: ml/gm
3
Rg
   1/ 2
n 1/ 2
M
M

Mark Houwink equation

   KM a

60
Viscosity average molecular weight
niMi
 sp   Kc i M i ; c   ci  
a

i i i NAV

  niMi1 a  1 / a
 
Mv   
  niMi 
 

61
 Example
If the Mark– Houwink exponent for nylon 66
dissolved in 90% formic acid is 0.72, calculate
Mn; Mw, and Mv for a sample that contains
50% by weight of a fraction having molecular
weight 10,000 and rest molecular weight
20,000.
 Example
Viscosity of polystyrene in toluene was measured using Ubbelohde viscometers.
Following data were obtained.
 
Concentration time (s)
g/dL
0 65.8
0.54 101.2
1.08 144.3
1.62 194.6
2.16 257.0
 
Find out the Molecular weight of PS using Mark Houwink parameters of a=0.725
and K=1.110-4 dLg-1. Comment on the molecular weight one can determine
using the method.
 Example
• Following two equations can describe the variation of
osmotic pressure and relative viscosity with concentration of
narrow molecular weight PMMA in acetone at 300C (density
0.780 g/cm3).

 0.586c  1.519;  r  1  0.154c 2  0.57c
c
• where, p is in cm of solvent, c is in g of polymer/100 ml
solution. Estimate intrinsic viscosity, Huggins constant (k),
Number average molecular weight, Flory Huggins interaction
parameter.
 Gel Permeation Chromatography

Solvent Constant Detector

Temp.
Column
Effluent
Dia-1cm
Packing :
Length- Organic solvent: Cross linked PS
30-50cm Water: Cross linked PMMA
Size: 0.1 to 10mm
Injection Valve
1mL of .1 to 1% Solution
See section 8.7 of the “Fundamentals of polymer engineering ” 65
 Size-exclusion chromatography – principle
1. Column separation technique
2. Based on enthalpy-free partitioning of analyzed solutes, most often the polymer
chains, of different molecular weight / length (size) between mobile and stationary
phases

Ve  V0  K d (Vt  V0 )
Kd - partition coefficient 0  Kd  1

solute exluded
solute permeated

Ve - elution volume for given size

Velution

V0 - interstitial volume (between particles

of column packing)

Vt - total available volume of column

(interstitial and pore volumes)
 Size-exclusion chromatography – setup
Injection of polymer
of unknown molecular
weight characteristics Commercial columns of defined
Detector signal = f(elution volume)
characteristics for column
packing:
Pump diameter, exclusion calibration curve
eluent limit, pore-size with standards:
distribution elution volume = f(MW)

molecular weight
characteristics
(MWD, Mw, Mn) of polymer

detector calibration curve molecular weight distribution

exclusion
sign al

log M

signal
separation

permeation
elution volume elution volume log M

GPC signal  w(log M )  ln(10) M f w ( M )  ln(10) M 2 f n ( M )

A Typical GPC Chromatogram

Mass Concentration

Vm+Vs
Vm

Time or elution volume

Elution Volume: Volume of solvent emerging from the column

from the instant of sample injection

68
 GPC
• Polymer Sample has been fractionated
• We do not know the molecular weight
corresponding to a particular elution volume
• Calibration curve is needed

69
 GPC: Calibration curve
Same polymer in
different solvent
and temperature
has different radius
Log M

of gyration

Elution Volume
Universal
calibration curve is
needed
70
 Universal calibration curve

3
Rg
  
M
  M  R g 3
Log   M 

PS, PB,PMMA,PS-PMMA in
Tetra hydrofuran at Room Temp.

Elution Volume
71
 LIGHT SCATTERING

the energy of radiation exactly equals the energy gap

Absorption between, say, the electronic or vibrational energy
levels of the molecules making up the liquid medium

infrared and nuclear magnetic resonance spectroscopy

 LIGH T SCATTERING
Due to the presence of induced instantaneous
Scattering dipole moments

Energy of the incident beam = Energies of the

transmitted beam + all of the scattered beams

Elastic Scattered light has the same frequency

as the incident light: Rayleigh and Mie
Inelastic Scattered light has a different
frequency: Raman scattering
 Elastic Scattering

Polymer in solution

Rayleigh ratio Optical constant