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Biochemical and

Chemical Engineering

PC-SAFT: Theory and Application

Markus C. Arndt, Gabriele Sadowski


Laboratory of Thermodynamics

Workshop on Hydrogel Modelling


24 November 2011, Stuttgart

Outline
Idea of PC-SAFT
Its contributions:
hard sphere
hard chain
dispersion
association
dipoles
electrostatic energy
elastic forces

Conclusion

exemplary modelling results


Laboratory of Thermodynamics
Prof. Dr. G. Sadowski

Basic idea of PC-SAFT




PC-SAFT: Perturbed-Chain Statistical Associating Fluid Theory


Developed by Joachim Gro and Gabriele Sadowski
Molecular model from statistical mechanics
Molecules are built of spherical segments
- may compose chains
- with repulsive and attractive interactions

polymer

solvent

schematic Flory-Huggins
Lattice Chain Model for a
polymer solution

Theory for chain molecules


structure of chain fluid?
 intermolecular radial distribution function
interaction between chain fluid?
 interaction potential

Gross, Sadowski, Fluid Phase Equilib. (168) 2000


Gross, Sadowski, Ind. Eng. Chem. Res. (40) 2001

Laboratory of Thermodynamics
Prof. Dr. G. Sadowski

Radial distribution function g(r)




gives the relative probability of finding


other molecules surrounding a center
molecule in the distance of r

2
g(r) 1

product of ( g(r)) gives the local density


in the distance of r from the center of
a molecule

0
0

r/

is a function of density, molecule size and shape,


as well as of interaction potential
dr

calculated from molecular simulations or


integral calculations (statistical mechanics)

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

Modified square-well fluid:


soft 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


Problems for real systems:


Analytical function of radial distribution is not available
Interaction potentials for real systems are unknown

Solution: perturbation theory


reference system: hard-sphere fluid
1st perturbation: chain formation
 hard-chain fluid
reference system: hard-chain fluid
2nd perturbation: attraction (dispersive interaction)
 hard-chain fluid with attractive interactions

Contributions to Helmholtz energy: a residual = a hard sphere + a chain formation

+ a dispersion

a hard chain
Laboratory of Thermodynamics
Prof. Dr. G. Sadowski

PC-SAFT parameters


Pure-component parameters for molecules (non-polar, non-associating, uncharged):


segment diameter
segment number

dispersion energy

Mixtures: One-fluid theory


mean segment number

m = ximi
i

Berthelot-Lorenz combining rules between components i and j:

ij =

1
i + j )
(
2

ij = i j (1 kij )

kij = binary parameter

Laboratory of Thermodynamics
Prof. Dr. G. Sadowski

PC-SAFT hard chain contribution




ahc
ahs
= m
xi (mi 1) ln giihs (dii )
kT
kT
i

Hard-chain term
with m = ximi

mean segment number

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


Perturbation theory of Barker and Henderson


ij 3 hard chain 2
a disp
= 2 x i x j mi m j
ij g
r dr + ...
kT
kT
i
j
1

u(r)

= I1 ( 3 , m )
for square-well potential

ls

I1 ( 3 , m )

- power function in 3 (reduced density)


- simple dependence of coefficients ai upon m (segment number)
- fitted to simulation data of square-well fluids

Laboratory of Thermodynamics
Prof. Dr. G. Sadowski

PC-SAFT equation of state




Contributions to Helmholtz energy

a residual =

a hard sphere

+ a chain formation

+ a dispersion

a hard chain

but what about other molecular interactions?

Laboratory of Thermodynamics
Prof. Dr. G. Sadowski

10

Further contributions to PC-SAFT




ProtonDonator

Association  hydrogen bonding


association between two (hard-sphere) molecules
with association sites (proton donator and acceptor)
reference system: hard-sphere fluid
perturbation: square-well attraction

Additional pure-component parameters for associating molecules:


association energy AiBi
association volume AiBi

Mixtures: One-fluid theory


Wohlbach-Sandler combining rules:

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

no additional binary parameter


Laboratory of Thermodynamics
Prof. Dr. G. Sadowski

11

PC-SAFT association contribution

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

Further contributions to PC-SAFT




a polar =

Dipole and Quadrupole

a2
1 a3 a2

reference system: two-center Lennard-Jones fluid


perturbation: dipole (Stockmayer potential) or quadrupole

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

ii jj kk ii3 3jj kk3


xi x j xk
n ,i n , j n ,k i2 j 2 k2J 3DD
,ijk
3
(kT ) ij ik jk

= an,ij + bn,ij ij 3n
kT
n =0
4

DD
2,ij

DD
3,ijk

= c n,ijk 3n
n =0

applicable for polar components (ketones, esters, ethers, aldehydes, etc.)


no additional pure-component parameters required
direct use of the dipole moment from experiments or quantum mechanics
Laboratory of Thermodynamics
Prof. Dr. G. Sadowski

13

Further contributions to PC-SAFT




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

no additional pure-component parameters required


ion-specific, not salt-specific parameters
direct use of the molecules electric charge
Laboratory of Thermodynamics
Prof. Dr. G. Sadowski

14

Further contributions to PC-SAFT




Elastic energy of a network


reference system:
hard-chain fluid
perturbation: elastic force due to deformation
2

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

one new parameter to be adjusted: network functionality n


use of experimental setup
Laboratory of Thermodynamics
Prof. Dr. G. Sadowski

15

Adjustable parameter is inevitable






Assumption: tetrahedrally oriented monodisperse chains


Reality: Networks are not homogenously built
Imperfections and network errors may
cause greater stiffness
give greater mesh size
be elastically ineffective
Experimental procedure?

varying chain length

 Accounted for with adjustable parameter n

entanglement

dangling ends
chain loops

unoccupied binding
sites of cross-linker

Laboratory of Thermodynamics
Prof. Dr. G. Sadowski

16

Contributions and parameters of PC-SAFT

mseg

aresidual = ahard-chain +

(+kij)

hb

hb

adispersion
(+ aassociation)

(+ adipole) (+ aelectrostatic) (+ aelastic)

2 up to 6 (+1) adjustable pure component parameters to obtain the


Helmholtz energy in arbitrary mixtures
Parameter fitted to experimental data of pure components or a mixture
such as liquid density, vapor pressure, activity coefficient, solubility, ..

Laboratory of Thermodynamics
Prof. Dr. G. Sadowski

17

Why Helmholtz energy A?




PC-SAFT  Helmholtz Energy A may be used for

pressure p and compressibility factor Z


density by iteration
chemical potential
fugacity coefficient
Entropy S
internal energy U
enthalpy H
Gibbs energy G

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

 complete thermodynamic description of a system

Laboratory of Thermodynamics
Prof. Dr. G. Sadowski

18

Modelling approach of phase equilibria


vapour phase

liquid phase

Modelling the thermodynamic equilibrium


Condition: isofugacity criterion
Using the concept
with the fugacity coefficient from PC-SAFT:

i = i
fi = fi
xii p = xii p

Laboratory of Thermodynamics
Prof. Dr. G. Sadowski

19

Vapour Liquid Equilibria (VLE)




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

Albers, unpublished 2011

Laboratory of Thermodynamics
Prof. Dr. G. Sadowski

20

Liquid Liquid Equilibria (LLE)




Miscibility gap water ethylacetate narrows with increasing temperature


and with the solubiliser methanol (at 20 C)

LL

Exp: Sorensen; Liquid-liquid Equilibrium Data Collection 1980

Laboratory of Thermodynamics
Prof. Dr. G. Sadowski

21

Solid Liquid Equilibria (solubility)




Amino acids in water (binary and ternary systems)


25 C

30 C
L-alanine

glycine

SL

L-valine

L
L-leucine

Held et al., Ind. Eng. Chem. Res (50) 2011

Laboratory of Thermodynamics
Prof. Dr. G. Sadowski

22

Solid Liquid Equilibria (solubility)




Ternary sugar solubility in water

35 C

SL
25 C

Held, unpublished
Exp: Ferreira et al., Ind. Eng. Chem. Res (42) 2003

Laboratory of Thermodynamics
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



Binary mixture of PNIPAAm-solvent (cross-linked to hydrogel)


Considering elastic force: xii p = xiip
xii p = xii(p-pelast)
p =| p
elastic pressure
y = 0.005

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

Hydrogels: other mixtures






Poly(acrylic acid) PAA water


Loose chains: no LLE
 Cross-linked gel: high swelling
without transition




PNIPAAm water/2-propanol (20 C)


Pronounced co-nonsolvency

1.5
T [K]
1

0.5

m/m0 [-]
Exp: Shin et al., Eur Polym J, 34 (2), 1998

Exp: Miki et al., Mater. Res. Soc. of Japan, 32 (889), 2007

Laboratory of Thermodynamics
Prof. Dr. G. Sadowski

26

Ternary swelling: PNIPAAm in water/ethanol

Ternary System: Swelling depends on


Temperature
Concentration of
Water/EtOH

PNIPAAm in water
PNIPAAm in ethanol
Ternary mixture (25 C)

Laboratory of Thermodynamics
Prof. Dr. G. Sadowski

27

Conclusion (I)


Advantages of PC-SAFT compared to other EOS and activity-coefficient models


physically-based model
 accounts for size and shape of molecules
 suitable also for complex and large molecules
equations of state account for the density (pressure) dependence
reliable for extrapolation
 to other conditions (T, p, concentration)
 to multi-component systems (binary  ternary, )
results confirmed the wide applicability of PC-SAFT
all thermodynamic properties can be derived from Helmholtz energy function
Laboratory of Thermodynamics
Prof. Dr. G. Sadowski

28

Conclusion (II)


Hydrogel networks can be modelled with PC-SAFT


by considering a new elastic contribution:
aelast in the Helmholtz energy
Pelast in the isofugacity equation

Gel swelling and the gel concentrations depend on


chain length
temperature
concentration of solutes/cosolvents

T [K]

Further research with focus on more complex


systems, polyelectrolytes and diffusion
m/m0 [-]

Laboratory of Thermodynamics
Prof. Dr. G. Sadowski

29

PC-SAFT: Theory and Application

Thank you for your attention!


Questions?

Laboratory of Thermodynamics
Prof. Dr. G. Sadowski

30

Deduction and explanation of PC-SAFT


Gross, J.; Sadowski, G. Application of perturbation theory to a hard-chain
reference fluid: An equation of state for squarewell chains. Fluid Phase
Equilib. 2000, 168, 183.
Gross, J.; Sadowski, G. Perturbed-Chain SAFT: An Equation of State Based on a
Perturbation Theory for Chain Molecules. Ind. Eng. Chem. Res. 2001, 40, 1244.

Laboratory of Thermodynamics
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

PC-SAFT polar contibutions




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

ii jj kk ii3 3jj kk3


2 2 2 DD
xi x j x k
n
n
n

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

ii jj kk ii5 5jj kk5

(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

J 2,ij = a n,ij + bn ,ij


kT
n =0

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

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