Activity Coefficient

Estimation Methods
Bharat Chandramouli
February 5, 2002

Activity Coefficient

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

Activity Coefficient

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