‫بسم هللا الرحمن الرحيم‬

Assignment: 01
Course: physical chemistry
Submitted To: Respected Prof. Khizar Qureshi
Submitted By: amsal shahbaz
ID:19002067-008
Semester: 4th Batch-002
Department of Chemistry, Sialkot
Topic: applications of van der Waals equation

The main reason for the importance of the van der Waals equation is that it was the first and the
simplest equation that was able to explain liquefaction. It is also in a scaling form in terms of the
reduced variables, not just near the critical form. It is not meant to be qualitatively good
otherwise for data fitting.
* The Vander Waal's equation holds good for real gases up to moderately high pressures.
* It explains the isotherms of PV/RT vs P for various gases.
* From this equation it is possible to obtain expressions for Boyle's temperature, critical
constants and inversion temperature in terms of the Vander Waal's constants 'a' and 'b'.

Application of the van der Waals equation of state to polymers .4.

Correlation and prediction of lower critical solution temperatures
for polymer solutions
The van der Waals equation of state is used for the correlation and the prediction of the lower
critical solution behavior or mixtures including a solvent and a polymer. The equation of state
parameters for the polymer are estimated from experimental volumetric data at low pressures.
The equation of state parameters for the solvent are estimated via the classical Soave method,
i.e., using the critical properties and a generalized equation for the energy parameter. When
extended to mixtures, the van der Waals one-fluid mixing rules along with the Berthelot
combining rule for the molecular cross energy parameter are used. The arithmetic mean
combining rule is used for the cross-co-volume parameter. The deviations from the Berthelot
combining rule are taken into account via a simple expression which has been previously
obtained from vapor-liquid equilibrium data of a thermal polymer solutions and has been
successfully used for the prediction of upper critical solution temperatures for various binary
polymer solutions. In this work, we demonstrate and explain some of the problems which cubic
equations of state exhibit in describing the lower critical solution behavior for polymer solutions.
These problems are overcome by using a temperature-dependent interaction parameter, even for
small temperature ranges, leading to excellent results. Despite the problems, we have developed
an empirical methodology in using the van der Waals equation of state with a single interaction
parameter for predicting the lower critical solution behavior of polymer/solvent solutions. The
results are satisfactory. typically, the difference between the predicted and the experimental
lower critical solution temperatures is between 10- and 35-degrees C.

Application to Compressible Fluids

The equation is also usable as a PVT equation for compressible fluids (e.g., polymers). In this
case specific volume changes are small and it can be written in a simplified form:
(p+A) (V-B) =CT
where p is the pressure, V is specific volume, T is the temperature and A, B, C are parameters.

Liquefaction of Gases
The isotherms plotted between P vs V at different temperatures for one mole of CO 2 gas are
shown below. 
Following conclusions can be drawn from these graphs: 
* At higher temperatures, say 50 oC, the isotherms show ideal behaviour. 
* As the temperature is lowered, the isotherms show deviation from ideal behaviour. 
* At 30.98 oC, carbon dioxide remains as gas up to 73 atm. But liquid appears for the first
time at 73 atm (represented by point ‘O’). Hence 30.98 oC is called critical temperature for
CO2. 
And above 73 atm, there is a steep rise in the pressure. This steep portion of the curve represents
the isotherm of liquid state for which small decrease in volume results in steep rise in the
pressure. 
* At even lower temperature, 20 oC, the liquid appears at point ‘A’. Further compression
does not change the pressure up to point ‘B’. After point, B the curve again becomes steep
representing the isotherm for liquid CO2.

Merits of Van der Waals Equation of State

1. Able to predict the behaviour of gases better than the ideal gas equation,
2. Applicable not only to gases but for all fluids.
3. The arrangement of the equation in a cubic equation in volume. The cubic equation gives
three volumes that are useful for calculating the volume at and below critical
temperatures.
4. Able to calculate the critical conditions of liquefaction and derive an expression of the
Principle of Corresponding States.

REFERENCES
 Van der Waals equation - Wikipedia
 REAL GASES | DEVIATION FROM IDEAL GAS BEHAVIOUR | VAN DER WAALS EQUATION
(adichemistry.com)
 Van der Waals Equation - Derivation, Relation Between Ideal Gas Law, Application (byjus.com)
 Does the Van der Waals equation have any industrial, or practical application?
(researchgate.net)