Activity Coefficient Estimation

Methods
Bharat Chandramouli
February 5, 2002
Activity Coefficient
The activity coefficient is a measure of
the non-ideality of mixing



Two components, Enthalpic and
Entropic


ideal non
ideal
ln ln

+ =
e
s
mix G
w
G
w s
RT x RT G
A
A
A
Estimation/Measurement
Activity coefficients in single
component/simple mixtures easy to
measure


Activity coefficients in water or octanol
can be calculated from solubility given
sufficiently sensitive methods

sat
sat
x
1
=
Need for estimation
What about complex mixtures?
What about dynamic systems with
changing compositions?
It becomes more practical to use
estimation methods to approximate in
these cases
Estimation Methods
Group contribution methods are most
common because they have predictive
ability
There are two group contribution
methods commonly used for
i
om
calculation from solubility parameters
UNIFAC calculation
UNIFAC the UNIversal Functional
group Activity Coefficient model
The activity coefficient is calculated
from two components





R i C i i
ln ln ln + =
Combinational
(V, SA)
Residual (interactions)
(Experiment Fit)
UNIFAC
The group contribution components consist of
volume contributor -R
k

surface area contribution -Q
k

interaction parameter between functional groups
A
mk

To calculate interactions, similar sub-groups
are assigned to groups and interactions are
between these groups
Calculate activity coefficients by summing all
contributions and interactions

UNIFAC-Simple example
Ethanol CH
3
-CH
2
-OH






Main Group. Subgroup R
k (
vol)

Q
k
(SA)

A
mk
CH
3
CH
3
CH
3
(1) 0.9011 0.848 0, 0
CH
2
CH
2
CH
2
(2) 0.6744 0.540 0, 0
OH OH OH (2) 1.000 1.200 986.5, 156.4
UNIFAC Methods
Interaction parameters are fit from
experimental data
This work is still ongoing and many
parameters still not available
Hansen Solubility Parameter
This method calculates activity
coefficients from the solubility
parameter
Theory of cohesive energy developed
by Hildebrand for dispersive systems
and extended by Hansen for polar and
hydrogen bonding
Hansen Activity Coefficient
The activity coefficient is given by





d A RT V
om i om i i
om
i , ,
) / ( ln + =
Molar Volume
Cohesive energy density
Size effect term
Enthalpy Entropy
The Size Effect Term

i,om
d is a measure of the effect of
differing sizes of i and om on their
entropy of mixing
This was derived by Flory and Huggins
using statistical thermodynamics
For an infinitely dilute solution

V V V V d
i i om i
/ 1 ) / ln(
,
+ =
Cohesive Energy (E
coh
)
Closely linked to the heat of evaporation
It is a measure of a the ability of a liquid
molecule to stay together


Theory of cohesive energy developed by
Hildebrand for dispersive systems and
extended by Hansen for polar and hydrogen
bonding
) ( ) ( ) ( ydrogen h
i
olar p
i
ispersive d
i
coh
i
E E E E + + =
Solubility parameters are measures of
cohesive energy




2 / 1 2 / 1
) / ( ) ( V E e
i
coh coh
= = o
solubility parameter
coh. energy density
cohesive energy
Solubility parameter
Calculating solubility
parameters
Hansen and others compiled molar
attraction constants for functional
groups, which are additive contributions
to the solubility parameter
2 / 1
,
2 / 1 2
,
,
) / (
/ ) (
/

=
=
=
V E
V F
V F
i
k h h
i
i
k p p
i
i
k d d
i
o
o
o
Attraction Constants (F)
The product of oV was found to vary
linearly across homologous series
Additivity of structural sub-groups
F = oV values compiled for dispersion
and polar components of o
Hansen later compiled additive
contributions to E
h

Multi-component Mixtures
How are om parameters calculated?
Parameters weighted using component
mole fraction and molar volume to get
average om




=
=
=
2 / 1
,
2 / 1 2
,
,
] / ) ( [
/ )] ( [
/ ) (
om k h
i
h
om
om k p
i
p
om
om k d
i
d
om
V E x
V F x
V F x
o
o
o
Cohesive Energy Density

i,om
A can be derived as

i
b is a weighting factor based on
dispersive forces, has been tabulated
for a variety of compounds

i
b corrects for the fact that polar and H
bonding forces are localized




2 2 2
) ( ) ( ) (
h
i
h
om i
p
i
p
om i
d
i
d
om
b b o o o o o o + +
Activity Coefficient
Putting the two components together


RT b b V
h
i
h
om i
p
i
p
om i
d
i
d
om i
/ ] ) ( ) ( ) [(
2 2 2
o o o o o o + +
V V V V
om i om i
/ 1 ) / ln( +
+
ln
i

om

=
Calculation
First, calculate group contributions for
each component in the mixture
Calculate om parameters by weighting
with mole fraction and molar volume
Calculate parameters for compound of
interest
Calculate activity coefficient
Hansen or UNIFAC?
UNIFAC more powerful interaction
UNIFAC not universalmissing parameters
Hansen has certain inconsistencies as certain
parameters have to be culled from different
sources. Very sensitive to parameter choice

i
b not widely available for many compounds,
so estimation may be difficult

Where do you use this?
1. Water solubility estimation


2. Solvent-Water partitioning (K
ow
)


sat
w
sat
w
x

1
=
s s
sat
w
sw
V
L C
K
1 1
) , 1 (
1

=
Gas/Particle Partitioning








What happens when a semivolatile organic
(SOC) encounters a particle??
particle
gas
Particle type
Compound Temperature
Humidity
Thermodynamic Equilibrium?

part
K
gas
C particle C
p
+
Partitioning Modes
Mode of SOC-particle interaction depends on
the particle
Adsorption Solid particle, no organic liquid layer
(dust, inorganic salts)
Absorption Particle either liquid, or has substantial
liquid layer (combustion particles, secondary
organic aerosol)
SOCs such as PAHs, and alkanes primarily
partition to organic or carbonaceous aerosols
rather than to mineral-based aerosols

Predictive Partitioning models
Pankow (1994) for absorptive
partitioning

0 9
10
501 . 7
L om
i
om
om
p
p MW
RTf
K

=
f
om
- fraction extractable organic matter
i

om
- activity coefficient of SOC in om
MW
om
-

molecular weight of om