BICOL UNIVERSITY

COLLEGE OF ENGINEERING

Chem 14: Physical Chemistry for Engineers I (Laboratory)

SY 2019-2020, 2nd semester

Van der Waals Isotherms

Ericka Mae F. Gonzales, Felmar Joyce T. Lleva, Kirby F. Mendioro

I. Introduction

The van der Waals equation is a thermodynamic equation of state based on

the theory that fluids are composed of particles with non-zero volumes, and subject to a inter-
particle attractive force. It was based on work in theoretical physical chemistry performed in the
late 19th century by Johannes Diderik van der Waals, who did related work on the
attractive force that also bears his name. The equation is known to be based on a traditional set of
derivations deriving from van der Waals' and related efforts, as well as a set of derivation based
in statistical thermodynamics.

It is an equation of state that generalizes the ideal gas law based on plausible reasons that

real gases do not act ideally. The ideal gas law treats gas molecules as point particles that interact
with their containers but not each other, meaning they neither take up space nor change kinetic
energy during collisions. The ideal gas law states that volume (V) occupied by n moles of any
gas has a pressure (P) at temperature (T) in kelvins given by the following relationship,
where R is the gas constant:

PV =nRT

At a fixed temperature, the Van der Waals equation describes the dependence p(V). In
the pV-plane, this dependence is represented as a family of isotherms, each of which corresponds
to a certain temperature. To investigate this dependency in more detail, we transform the Van der
Waals equation to the following form:
( p+aV 2 ) ( V −b )=RT V 2
( p V 2+ a)(V −b)=RT V 2
p V 3+ aV − pb V 2−ab−RT V 2=0
p V 3−( pb+ RT ) V 2 +aV −ab=0∨: p
V 3− ( b+ RTp ) V 2 +apV −abp=0.
 For a fixed value of p, the resulting equation is a third-degree equation with respect to the
variable V. It is known that a cubic equation can have 1 or 3 real roots. With lowering the
temperature, an undulating region appears on the isotherm. The transition between the two types
of isotherms occurs at a certain temperature TK, which is called the critical temperature.

The van der Waals equation can therefore be recast in the form of a universal reduced
equation of state

3
( Pr +
)
V 2r
( 3 V r −1 )=8 T r

in terms of reduced variables

P V
Pr = V = T =T /T r
Pc r V r r
Isotherms where Tr is constant can be plotted on the Vr versus Pr diagram for different values
of Tr between 0.80 and 1.20. The critical isotherm is when Tr =1.

II. Materials and Methods

The following resources were used to complete this activity:
Laptop/desktop computer
Calculator
Pen and paper

Methods
1. The reduced volume (Vr) and reduced temperature (Tr) were pre-assigned for uniformity.

2. The reduced pressure for each value of reduced volume at a specific reduced temperature
were calculated with appropriate formulas. Since the values are given, the formula that
corresponds to the reduced pressure is derived from universal reduced equation of state:
8 Tr 3
Pr = − 2
3 V r −1 V r
3. The initial values of reduced volume and temperature were entered in Microsoft Excel to
compute the reduced pressure.

4. The computed values of reduced pressure (Pr) versus reduced volume (Vr) under specific
reduced temperature (Tr) were plotted to investigate the behavior of the graph as the
reduced volume and temperature is increasing infinitesimally.
III. Results and Discussion

Figure 1. Computed reduced pressure (Pr) at different reduced temperature (Tr) and volume (Vr) using Excel

This figure shows the Van der Waals equation of state for one mole of an imperfect fluid
a a
( V )
reads P+ 2 (V −b )=RT  . The critical constants are predicted to be Pc =
27 b2
 ,V c =3 b
8a
, T C = . The Van der Waals equation can be recast in the form of a universal reduced
27 Rb
3
( )
equation of state p+ 2 ( 3 v−1 )=8 t   in terms of reduced variables  p=P /P c, v=V /V c ,t=T /T c  .
v
Isotherms where t is constant is plotted on the v versus p diagram. 
 Figure 2. Van der Waals Isotherms at several reduced temperature (Tr)

Figure 2 shows the relationship between volume and pressure at constant temperature.
According to the Ideal Gas Equation, PV =nRT , pressure and volume should have an inverse
relationship. Notice that the higher isotherms on the graph, which represent the gas’ state at
higher temperature, show the typical, concave decreasing curve of an inverse relationship. As
temperature decreases, however, the isotherms on the lower portion of the graph significantly
deviate from this ideal inverse relationship between P and V.

Guide Questions:

1. What is the importance of the Van der Waals equation?

J.D. van der Waals in 1873. Introduced the approximate equation of state to have a
broader view of all gases. This equation is an excellent example of an expression that can be
obtained by thinking scientifically about a mathematically complicated but physically simple
problem, that is, it is a good example of ‘model building’. The advantage of the van der
Waals equation, however, is that it is analytical and allows us to draw some general
conclusions about real gases.

2. What does the constants a and b in the Van der Waals equation represent?

The constants a and b have positive values and are characteristic of the individual gas.
They are characteristic of each gas but independent of the temperature. The constant a
provides a correction for the intermolecular forces. Constant b is a correction for finite
molecular size and its value is the volume of one mole of the atoms or molecules. Since the
constant b is an indication of molecular volume, it could be used to estimate the radius of an
atom or molecule, modeled as a sphere.

3. What are the critical constants, reduced constants, and what is their importance?

The temperature, pressure, and molar volume at the critical point are called the
critical temperature, Tc, critical pressure, pc, and critical molar volume, Vc, of the substance.
Collectively, pc, Vc, and Tc are the critical constants of a substance. The critical point is the
point at which the volumes at each end of the horizontal part of the isotherm have merged to
a single point. The critical constants pc, Vc, and Tc are the pressure, molar volume, and
temperature, respectively, at the critical point.
A reduced variable is the actual variable divided by the corresponding critical constant. It can
be used to easily calculate the values of the pressure, volume and temperature. Reduced
properties are used to define corresponding states. Reduced properties provide a measure of
the “departure” of the conditions of the substance from its own critical conditions.

4. What is the principle of corresponding states?

 According to the principle of corresponding states, real gases at the same reduced
volume and reduced temperature exert the same reduced pressure. As long as two gases are at
corresponding states (same reduced conditions), it does not matter what components you are
talking about, or what is the nature of the substances you are talking about; they will behave
alike.

5. Describe the plotted isotherms. What do you notice? Give an explanation of your
observations.

The figure shows the plotted van der waals isotherms showing P r on the y-coordinate
vs Vr on the x-coordinate for the different values of reduced temperature (T r). It can be
observed that the plotted isotherms resemble the curves from van der waals’ experimental
isotherms. The behavior of the gas and its change in phases can also be deduced in the figure
wherein as the reduced volume (Vr) of the gas increases, the reduced pressure (Pr) decreases
at different values of reduced temperature. At high temperature and large volume, the van der
Waals isotherms resemble experimental isotherms of the gas. At low temperature and small
volume (below the critical temperature and volume), the van der Waals isotherms resemble
experimental isotherms of the liquid. Below the critical temperature the van der Waals
isotherms oscillate.

6. Notice that when you were requested to plot the isotherms, identifying for what gas the
isotherm is for is not necessary. Deduce why.

Because real gases at the same reduced temperature and volume exert the same
reduced pressure. The dependence of the compression factor on the reduced pressure for a
variety of gases at various reduced temperature gives similar result.

IV. Conclusion

The van der Waals equation is a state equation for real gases that modifies the ideal gas
equation (PV = nRT) in order to consider intermolecular interactions. These interactions result
from molecules attracting each other when they are approaching and repelling each other when
they are colliding.

Experimental isotherms do not exhibit smooth transition from saturated liquid to saturated
vapor; rather, they contain a horizontal segment within the two-phase region where saturated
liquid and vapor coexist in varying proportions at the saturation or vapor pressure. The Van der
Waals isotherm is a schematic PV diagram showing isotherms. Superimposed is the “dome”
representing states of saturated liquid and saturated vapor.

Experimental observation shows that compressibility factor Z for different fluids exhibits
similar behavior when correlated as a function of reduced temperature T r and reduced pressure
Pr. These thermodynamic coordinates provide the basis for the simplest form of the theorem of
corresponding states that all fluids, when compared at the same reduced temperature and reduced
pressure, have approximately the same compressibility factor, and all deviates from ideal-gas
behavior to about the same degree.
V. References

Bett, K. E., Rowlinson, J. S. and Saville, G. (1975) Thermodynamics for Chemical Engineers,
Athlone Press, London.

Reid, R. C, Prausnitz, J. M. and Sherwood, T. K. (1977) The Properties of Gases and Liquids,
McGraw-Hill, New York.

Smith, J. M., Van Ness, H.C. and Abbott, M.M. (2000) Introduction to Chemical Engineering
Thermodynamics Seventh Edition, McGraw-Hill, New York.

Atkins, P. and de Paula, J. (2014) Physical Chemistry: Thermodynamics, Structure, and Change,
Tenth Edition, W.H Freeman and Company, New York