A group contribution method is a technique to estimate and predict thermodynamic and other

properties from molecular structures. Process designers need to know some basic chemical
properties of the components and their mixtures. Experimental measurement is often too
expensive..
Using group or atom properties group contribution method predicts properties of pure
components and mixtures. This reduces the number of needed data dramatically. Instead of
needing to know the properties of thousands or millions of compounds, only data for a few
dozens or hundreds of groups have to be known.
Additive group contribution method
The simplest form of a group contribution method is the determination of a component property
by summing up the group contribution.

This simple form assumes that the property (normal boiling point in the example) is strictly
linear dependent from the number of groups and additionally no interaction between groups and
molecules are assumed. This simple approach is used in

Joback method

Wilson and Jasperson method

Constantinou and Gani method

Marrero and Pardillo

Additive group contributions and correlations

This technique uses the pure additive group contributions to correlate the wanted property with
an easy accessible property. This is often done for the critical temperature.
This approach often gives better results than pure additive equations because the relation with a
known property introduces some knowledge about the molecule. Commonly used additional
properties are the molecular weight, the number of atoms, chain length, and ring sizes and
counts.
Group interactions

For the prediction of mixture properties it is in most cases not sufficient to use a purely additive
method. Instead the property is determined from group interaction parameters.
(

Where P stands for property and Gij for group interaction value.
A typical group contribution method using group interaction values is the UNIFAC method,
which estimates activity coefficients.
UNIFAC:

In the UNIFAC method, the activity co-efficient is estimated through group contributions.

The liquid is treated as a solution of different structural groups from which the molecules are formed,
rather than a solution of molecules themselves. This method is based on the UNIQUAC model where the
activity co-efficient is divided into two parts the molecular size contribution and the interaction
contributions.

Group contributions of higher orders

Some newer methods introduce second-order groups. The second-order order groups can be
super-groups containing several first-order (standard) groups. This allows the introduction of
new parameters for the position of groups. Another possibility is to modify first-order group
contributions if specific other groups are also present.

Assignment 1 b4

Q5) Distinguish between partial molar volume and molar volume. Does the partial molar
volume of substance vary with conc of substance with solution.

the partial molar volume of 1.

a The molar volume, symbol Vm, is
substance X in a mixture is the the volume occupied by one mole of a
change in volume per mole of X substance (chemical element or chemical
added to the mixture

compound) at a given temperature and

It is denoted by

pressure. It is equal to the molar mass

The partial molar volume can be (M) divided by the mass density ().
written as

It is denoted by Vm

The molar volume of a substance

can be found by measuring its

The partial molar volume of a

molar mass and density then

substance

applying the relation

is

an

intensive

property.

Partial molar volume can be

positive as well as negative

The molar volume is extensive

property

Molar volume is always positive

The partial molar volumes of the components of a mixture vary with the composition of the
mixture, because the environment of the molecules in the mixture changes with the composition.
It is the changing molecular environment (and the consequent alteration of the interactions
between molecules) that results in the thermodynamic properties of a mixture changing as its
composition is altered

As the partaial molar volume varies with the composition and volume, it also varies with the
concentration of the substance in the solution