Activity Coefficients

Activity Coefficient
Estimation Methods
Bharat Chandramouli
February 5, 2002
The activity coefficient is a measure

of the non-ideality of mixing
Gs RT lnx w RT ln w

Gmix ideal Gsenonideal
Two components, Enthalpic and

Entropic
Estimation/Measurement
Activity coefficients in single

component/simple mixtures easy to
measure
1
sat
x sat
Activity coefficients in water or

octanol can be calculated from
solubility given sufficiently sensitive
methods
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 iom
calculation from solubility parameters

UNIFAC calculation
UNIFAC the UNIversal

Functional group Activity
Coefficient
model is
The activity coefficient
calculated from two components
i
ln ln
ln
Combinational
Residual (interactions)
(V, SA)
(Experiment Fit)
UNIFAC
The group contribution components consist of
volume contributor -Rk

surface area contribution -Qk
interaction parameter between functional groups
Amk
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 CH3-CH2-OH
Main
Group.
Subgroup Rk (vol)
Qk (SA)
CH3
CH3
CH3 (1)
0.9011 0.848
0, 0
CH2
CH2
CH2 (2)
0.6744 0.540
0, 0
OH
OH
OH (2)
1.000
986.5,
156.4
1.200
Amk
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

i
ln om( V / RT)
i ,om
i ,om
Cohesive energy density

Molar Volume
Size effect term
Enthalpy
Entropy
The Size Effect Term

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
Fori ,an
dilute solution
om infinitely
i
i
i,om
d ln( V / V ) 1 V / V
Cohesive Energy (Ecoh)
Closely linked to the heat of evaporation

It is a measure of a the ability of a liquid
molecule to stay together
i
i
i
Ecoh Ed(ispersive
) E p(olar
) Eh( ydrogen
)
Theory of cohesive energy developed by

Hildebrand for dispersive systems and
extended by Hansen for polar and
hydrogen bonding
Solubility parameter
Solubility parameters are

measures of cohesive energy
(ecoh)1/ 2 (Ecoh/ i V )1/ 2

solubility parameter
coh. energy density
cohesive energy
Calculating solubility
parameters
Hansen and others compiled molar

attraction constants for functional
groups, which are additive
contributions to the solubility
parameter
i
d Fd ,k / iV
p ( Fp2,k )1/ 2 / iV
h ( Eh ,k / iV )1/ 2
Attraction Constants (F)
The product of V was found to vary

linearly across homologous series
Additivity of structural sub-groups
F = V values compiled for dispersion
and polar components of
Hansen later compiled additive
contributions to Eh
Multi-component Mixtures
How are om parameters

calculated?
Parameters weighted using
component mole fraction and
molar om
volume ito get average om
d ( x Fd,k )/ V om
p [ (i x Fp2,k )]1/ 2 / V om
om
h [ (i x Eh,k )/ V om]1/ 2
om
Cohesive Energy Density

i,om
om
A can be derived as
2 i
om
2 i
om
( d d ) b( p p ) b( h h )
b is a weighting factor based on

dispersive forces, has been
tabulated for a variety of compounds
ib corrects for the fact that polar and
H bonding forces are localized
Putting the two components

together ln i =
om
V [(om d i d )2 i b(om p i p )2 i b(om h i h )2 ]/ RT

+
i
ln( V /
om
V ) 1 V /
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
ib not widely available for many
compounds, so estimation may be difficult
Where do you use this?

1.
Water solubility estimation

sat
xw
2.
1
sat
w
Solvent-Water partitioning (Kow)

1
1 1
Ksw sat
Cw (1, L ) s V s
Gas/Particle Partitioning
gas
Thermodynamic Equilibrium?
Kp
Cgas particle C part

Temperature
Humidity
particle
Compound
Particle type
What happens when a semivolatile organic

(SOC) encounters a particle??
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
7.501
RTfom
Kp 9
10 MWomi ompL0
fom- fraction extractable organic matter
om - activity coefficient of SOC in om
MWom - molecular weight of om

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Activity Coefficient

The activity coefficient is a measure

Gmix ideal Gsenonideal

Two components, Enthalpic and

Activity coefficients in single

Activity coefficients in water or

Need for estimation

What about complex mixtures?

Group contribution methods are

calculation from solubility parameters

UNIFAC the UNIversal

The group contribution components consist of

volume contributor -Rk

To calculate interactions, similar sub-groups

Interaction parameters are fit from

This method calculates activity

Hansen Activity Coefficient

The activity coefficient is given by

Cohesive energy density

The Size Effect Term

Cohesive Energy (Ecoh)

Closely linked to the heat of evaporation

Theory of cohesive energy developed by

Solubility parameters are

(ecoh)1/ 2 (Ecoh/ i V )1/ 2

coh. energy density

Hansen and others compiled molar

Attraction Constants (F)

The product of V was found to vary

How are om parameters

Cohesive Energy Density

b is a weighting factor based on

Putting the two components

V [(om d i d )2 i b(om p i p )2 i b(om h i h )2 ]/ RT

First, calculate group contributions

UNIFAC more powerful interaction

Where do you use this?

Water solubility estimation

Solvent-Water partitioning (Kow)

Cgas particle C part

What happens when a semivolatile organic

Mode of SOC-particle interaction depends

Adsorption Solid particle, no organic liquid

SOCs such as PAHs, and alkanes primarily

Pankow (1994) for absorptive

om - activity coefficient of SOC in om

MWom - molecular weight of om

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