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Outline
Idea of PC-SAFT
Its contributions:
hard sphere
hard chain
dispersion
association
dipoles
electrostatic energy
elastic forces
Conclusion
polymer
solvent
schematic Flory-Huggins
Lattice Chain Model for a
polymer solution
Laboratory of Thermodynamics
Prof. Dr. G. Sadowski
2
g(r) 1
0
0
r/
Laboratory of Thermodynamics
Prof. Dr. G. Sadowski
g(r)
Interaction potentials
0.99
Hard-sphere fluid:
hard-sphere repulsion
no attraction
Square-well fluid:
hard spheres
with attraction well
Lennard-Jones fluid:
soft spheres
with soft attraction well
u(r)
-0.01
4 0
3
2
u/
1
0
-1
4 0
3
2
u/
1
0
-1
4 0
3
u/ 2
1
0
-1
0
Laboratory of Thermodynamics
Prof. Dr. G. Sadowski
r/
1
r/
1
r/
r/
Perturbation theory
+ a dispersion
a hard chain
Laboratory of Thermodynamics
Prof. Dr. G. Sadowski
PC-SAFT parameters
dispersion energy
m = ximi
i
ij =
1
i + j )
(
2
ij = i j (1 kij )
Laboratory of Thermodynamics
Prof. Dr. G. Sadowski
ahc
ahs
= m
xi (mi 1) ln giihs (dii )
kT
kT
i
Hard-chain term
with m = ximi
23
ahs 1 3 1 2
23
=
+
+
ln
(
1
0
3
kT 0 ( 1 3 ) 3 ( 1 3 )2 32
hard-sphere term
did j 3 2
did j 2 22
1
hs
gij (dij ) =
+
+
( 1 3 ) di + d j ( 1 3 )2 di + d j ( 1 3 )3
n =
ximi din
6
i
radial distribution
function
n = {0,1,2,3}
di = i 1 0.12 exp 3 i
kT
temperature-dependent
segment diameter
Laboratory of Thermodynamics
Prof. Dr. G. Sadowski
PC-SAFT dispersion
u(r)
= I1 ( 3 , m )
for square-well potential
ls
I1 ( 3 , m )
Laboratory of Thermodynamics
Prof. Dr. G. Sadowski
a residual =
a hard sphere
+ a chain formation
+ a dispersion
a hard chain
Laboratory of Thermodynamics
Prof. Dr. G. Sadowski
10
ProtonDonator
AB =
i j
1 Ai Bi
+ Aj B j
2
A B = A B A B
i j
i i
j j
ii jj
1 2 ( ii + jj )
ProtonAcceptor
11
aassoc
X Ai 1
Ai
= xi ln X
+
kT
2
2
i
Ai
Association
with
B
AB
Ai
X = 1 + xj X j i j
j
Bj
Ai B j
=g
hs
ij
( dij )
Ai B j
Ai Bj
ij exp
kT
fraction of molecules
which are not bonded
1
Laboratory of Thermodynamics
Prof. Dr. G. Sadowski
association strength
12
a polar =
a2
1 a3 a2
ii jj ii3 3jj
a2 = x i x j
n ,i n , j i2 j 2J 2DD
,ij
2
3
(kT ) ij
i
j
4 2 2
a3 =
3
= an,ij + bn,ij ij 3n
kT
n =0
4
DD
2,ij
DD
3,ijk
= c n,ijk 3n
n =0
13
Electrostatic interactions
reference system:
hard-sphere fluid
perturbation: Debye-Hckel charge forces
a elec
e2
2
=
x
z
i i i
el
kT
12 kT i
with
Ne2
= el
kT
2
z i2 x i
i =
3 3
1
2
+
ln(1
+
2(1
+
)
+
(1
+
)
i
i
i
( i )3 2
2
14
a
n 2 3 V 3 V
= xp
1 1
kT
n 2 V0
Vmax
elast
with
V=
Vmax
nP N 1
xp 6 3
x
i
3
i
V
ln
V0
mi
1 3 2 109.5o
= x c N 2 sin
o
8
2 180
m
d
p p
15
entanglement
dangling ends
chain loops
unoccupied binding
sites of cross-linker
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Prof. Dr. G. Sadowski
16
mseg
aresidual = ahard-chain +
(+kij)
hb
hb
adispersion
(+ aassociation)
Laboratory of Thermodynamics
Prof. Dr. G. Sadowski
17
A
p =
V T
A
i =
ni T,V,n
j i
A
S =
T V
U = A + TS
H = U + pV
G = H TS
Laboratory of Thermodynamics
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18
liquid phase
i = i
fi = fi
xii p = xii p
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19
T 375
[K]
370
n-heptane ethanol
temperature dependence of VLE
Acetone n-heptane
pressure dependence of VLE
p 1,5
kij=0,036
[bar]
kij=0,038
338,15 K
365
1,0
360
VL
355
0,5
1,0132 bar
350
313,15 K
345
L
0,0
0,2
0,4
0,6
x/yHeptan [-]
0,8
1,0
0,0
0,2
0,4
0,6
x/yAceton [-]
0,8
1,0
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20
LL
Laboratory of Thermodynamics
Prof. Dr. G. Sadowski
21
30 C
L-alanine
glycine
SL
L-valine
L
L-leucine
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22
35 C
SL
25 C
Held, unpublished
Exp: Ferreira et al., Ind. Eng. Chem. Res (42) 2003
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Prof. Dr. G. Sadowski
23
PNIPAAm in water
Binary mixture of PNIPAAm-water (without cross-linker)
LLE and density
*
HN
[kg/m]
T [K]
LL
5 C
20 C
25 C
wPNIPAAm [-]
wPNIPAAm [-]
Exp: Wohlfarth C, CRC Handbook of Liquid-Liquid Equilibrium Data of Polymer Solutions 2008
Laboratory of Thermodynamics
Prof. Dr. G. Sadowski
24
PNIPAAm in water
T [K]
p = pelast
y = 0.010
y = 0.015
m/m0 [-]
Exp: Poschlad, Diss., Berlin, 2011
Exp: Zhi, Chem. Eng. Sci. (65) 2010
Laboratory of Thermodynamics
Prof. Dr. G. Sadowski
25
1.5
T [K]
1
0.5
m/m0 [-]
Exp: Shin et al., Eur Polym J, 34 (2), 1998
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Prof. Dr. G. Sadowski
26
PNIPAAm in water
PNIPAAm in ethanol
Ternary mixture (25 C)
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Prof. Dr. G. Sadowski
27
Conclusion (I)
28
Conclusion (II)
T [K]
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Prof. Dr. G. Sadowski
29
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Prof. Dr. G. Sadowski
30
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Prof. Dr. G. Sadowski
31
PC-SAFT - dispersion
a disp
= 2 I1(, m) xi x j mi mj ij 3ij
kT
i
j
kT
Dispersion term
m C1 I 2 (, m) xi x j mi mj ij 3ij
i
j
kT
2
with
Z hc
hc
C1 = 1 + Z +
defined variable
8 22
20 272 + 123 24
= 1 + m
+ (1 m)
2
(1 ) 4
[(1 )(2 )]
I1 (, m ) = ai ( m )
i =0
I 2 (, m ) = bi ( m ) i
power functions
i =0
ai ( m ) = a0i +
m 1
m 1 m 2
a1i +
a2i
m
m
m
bi ( m ) = b0i +
m 1
m 1 m 2
b1i +
b2i
m
m
m
Laboratory of Thermodynamics
Prof. Dr. G. Sadowski
defined coefficients
32
Pad approximation
Dipolar term
4 2 2
a3 =
3
a polar =
a2
1 a3 a2
ii jj ii3 3jj
2 2 DD
a2 = xi x j
n
n
j J 2, ij
i
j
i
,
2
3
(kt ) ij
i
j
j k J 3,ijk
,
i
,
j
,
k
i
3
(kt ) ij ik jk
Quadrupolar term
9 2 2
a3 =
16
2
ii jj ii5 5jj
3
2 2
a 2 = xi x j
n
n
j J 2,ij
,
i
,
j
i
2
7
(kt ) ij
4
i
j
xi x j x k
(kt )
3
3
ij
3
ik
3
jk
n ,i n , j n ,k i2 j 2 k2 J 3,ijk
Laboratory of Thermodynamics
Prof. Dr. G. Sadowski
33
PC-SAFT equations
Dipolar term
ij n
= a n ,ij + bn ,ij
kT
n =0
a n ,ij = a 0 n +
bn,ij = b0 n +
c n ,ijk = c 0 n +
DD
3,ijk
ij n
Quadrupolar term
with
DD
2 ,ij
mij 1
mij
mij 1
mij
a1n +
b1n +
mijk 1
mijk
mij 1 mij 2
mij
mij
mij 1 mij 2
mij
c1n +
mij
n =0
J 3,ijk = c n ,ijk n
n =0
mij = (mi m j )
1
2
a2n
b2 n
mijk 1 mijk 2
mijk
= c n ,ijk n
mijk
c2n
Laboratory of Thermodynamics
Prof. Dr. G. Sadowski
mijk = (mi m j mk )
1
3
34