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Assignment 01: Polymers

1. Polyethylene of molecular weight 2800 is dissolved in ethylene at 10 C. Assume that


there is no enthalpic interaction between these species because of the similarity of ethylene
to polyethylene, develop epressions for the ecess !ibbs energy and activity coefficients
of ethylene and polyethylene as a function of composition. "ou may try to schematically
plot #e.g. using $atlab%.
Solution:
&he $w of polyethylene is 2800 and of ethylene is 28' the chain length of polyethylene is r (
2800)28 ( 100 #assuming polyethylene monomer has the same volume as that of ethylene%.
Assuming there is no enthalpic interaction between the two species,
0

, we have
mi
1 1 2 2 t 1 2 1 1 2 2
!
#* ln * ln % * * ln * ln
+&

+ + +
,or 1 mole of miture,
mi
1 1 2 2
!
ln ln
*+&

+
,or ideal miture,
-$
mi
1 1 2 2
!
ln ln
*+&

+
&he ecess !ibbs energy is then.

e
mi 1 2
1 2
1 2
!
ln ln
*+&

+
/ince
1
1
1 2

r

+
and
2
2
1 2
r
r

+
,
/o
e
mi
1 1
1 1 1 1
! 1 r
ln #1 % ln
*+& r#1 % r#1 %

+
+ +
#1%
&he activity coefficients.
1 1
1 2
1 1 1 1 1
1 1 1 r#1 %
ln ln 1 ln 1
r r#1 % r r#1 %

_ _
+ +

+ +
, ,
#2%
( ) ( )
2 1
2 1
2 1 1 1 1
r
ln ln 1 r ln 1 r
r#1 % r#1 %

+ +
+ +
#0%
,rom e1uations #120%, given
1
#the mole fraction of ethylene%, we can evaluate
e
mi
!
*+&

,
1

and
2
. &he following figure shows
1
and
2
as a function of
1
.
C*3000 Advanced Chemical 4ngineering &hermodynamics 1
2. Polymer2polymer and polymer2solvent systems are important in chemical industry, and
typically the ,lory25uggins theory is used to describe the activity in such systems.
Assuming the vapor phase is ideal and the vapour pressure of the polymer is negligible.
#a% 6evelop e1uations that can be solved for the bubble2point pressure as a function of
temperature for polymer2solvent mitures.
#b% 6evelop e1uations that can be solved for the polymer2polymer li1uid2li1uid immiscibility
as a function of temperature.
7hat data would you need to do numerical calculations for phase behaviour with the
e1uations you have developed above8
Solution:
#a% ,or vapor2li1uid e1uilibrium, the vapor phase is ideal, then

sat
i i i i
y P P
&he vapour pressure of the polymer is negligible, then
sat
1 1 1 1
P y P P #for solvent%
&he activity coefficient for solvent is
1 2
1 2 2
1
1
ln ln 1
r

+ +

,

&herefore
1 sat 2 sat 2 sat
1 1 1 1 2 2 1 1 2 2 1
1
1 1
P P ep ln 1 P ep 1 P
r r
1 1
_ _

+ + +

1 1
, , ] ]
6ata needed are polymer chain length, ,lory parameter and vapor pressure of solvent.
#b% ,or li1uid2li1uid e1uilibrium, in two #- and --% phases,

- - -- --
i i i i

&he activity coefficients for solvent and polymer are
1 1 2
1
2 1 2
1 2
r
ln ln 1 r
r
_

+ +

,
and
2 2 2
2
1 2 1
2 1
r
ln ln 1 r
r
_

+ +

,

&herefore
( ) ( )
2 2
1 1 - - - -- -- --
1 2 1 2 1 2 1 2
2 2
r r
ep 1 r ep 1 r
r r
1 1
_ _

+ +
1 1
, ,
] ]
( ) ( )
2 2
2 2 - - - -- -- --
2 1 2 1 2 1 2 1
1 1
r r
ep 1 r ep 1 r
r r
1 1
_ _

+ +
1 1
, ,
] ]
6ata needed are polymer chain length r
1
and r
2
, and ,lory parameter .
C*3000 Advanced Chemical 4ngineering &hermodynamics 2
3. -n a chemical plant, rubber is treated by a solvent #cymene% at 23 C. &he rubber and
cymene have density of 1.2 and 0.89 g)cm
0
, and molecular weight of 93000 and 10:,
respectively. &he vapor pressure of pure cymene is 10 ;Pa. &he ,lory25uggins parameter
between rubber and cymene is 0.00. Assume the chain length of rubber is 1000 and that of
solvent is 1.
#a% 4stimate the vapor pressure of solvent with 30 wt< rubber dissolved.
#b% 5ow will the vapor pressure change if the chain length of rubber increases.
#c% 5ow will the vapor pressure change if the ,lory25uggins parameter increases to 0.3.
Solution:
#a%
For solvent: MWs 10: : Rhos 0.89 :
For polymer: MWp 93000 : Rhop 1.2 :
Given
WTp 30% : WTs 1 WTp : WTs 0.3 T 2=8 : Psat 10 : kPa
The Flory parameter is: r 1000 :
0.00 :
The mole fraction and volume fraction of solvent are:
Xs
WTs
MWs
WTs
MWs
WTp
MWp
+

,
: Xs 0.==8 s
WTs
Rhos
WTs
Rhos
WTp
Rhop
+

,
: s 0.380
lns ln
s
Xs

,
1
1
r

,
1 s ( ) + 1 s ( )
2
+ :
lns 0.09: s e
lns
0.=08 :
Ps Psat Xs s : Ps =.090
#b% -f r increases, s becomes larger, so does Ps.
#c% -f increases positively, s becomes larger, so does Ps.

N 4. -n polymer devolatili>ation, it is important to predict the partial pressure of a solvent
above solvent2polymer miture. ?sing the ,lory25uggins theory to calculate the partial
pressure of ben>ene in ben>ene @ polyisobutylene #P-A% miture at 10 C and the mass
ratio of 0.33:0 for ben>ene to P-A. Assume that P-A has a negligible vapor pressure.
Data.
C*3000 Advanced Chemical 4ngineering &hermodynamics 0
A en>ene. solubility parameter
A
is 18.8, molecular weight $7
A
is B8, molar volume
C
A
is 88.29 cm
0
)mol, and saturation vapor pressure is 0.0909 bar at 10 C.
P-A. solubility parameter is 19.:, molecular weight $7
P-A
is :0000, the weight of a
monomeric unit $7
P-A,m
is 10:, and the monomeric volume C
P-A,m
is 101.= cm
0
)mol.
#a% 4stimate the activity coefficient of ben>ene.
#b% 4stimate the partial pressure of ben>ene in the vapor.
#c% Dnowing the eperimentally measured partial pressure of ben>ene e1ual to 0.038 bar, is
your estimation close to this eperimental value8 -f not, why8
Solution:
#a%

#c% &he estimated Ps ( 0.0:0 bar is lower than the eperimental 0.038 bar. &he primary
reason is the way to estimate the ,lory parameter is not accurate.
C*3000 Advanced Chemical 4ngineering &hermodynamics
#b% Ps Psat Xs s : Ps 0.0:0 ar ! "
:

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