EXPERIMENT 1

THE VAN DER WAALS EQUATION OF STATE, THE LAW OF CORRESPONDING

STATES, AND THE COMPRESSION FACTOR

ABSTRACT

The experiment was carried out to graphically assess the behavior of real gases at

changing conditions and the ability of selected gas equations of state to predict the pressure-

volume-temperature relationships of gases. The gas-liquid coexistence curve of water and

benzene were plotted and the behavior of the ideal gas equation and van der Waals equation

was compared. Maxwell construction was used to correct the deficiency of the pV graph of

the van der Waals equation. The law of corresponding states was investigated using the van

der Waals equation of state and was observed how this law functions for real gases. The

compressibility factor was also used to account for the real gas behavior.

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INTRODUCTION

The properties of gases pose a challenge for chemists who seek to understand their

pressure-volume-temperature-properties. The Ideal Gas Law,

PV = nRT (1)

Where p is the pressure, V is the volume, and n is the number of moles of the gas at a certain

T temperature in relation with the gas constant R (Equation of State: Real Gases: van der

Waals and Other Equations, n.d).

It is a convenient estimate for predicting the behavior of gases at high temperatures

and low pressures. This equation assumes that gas molecules interact with their neighbors

exclusively through perfectly ellastic collisions and that particles exert no intermolecular

forces on each other. It is also assumed that the atoms or molecules themselves have no

volume and that the gas may therefore be compressed completely to an infinitely small

volume. Deviations from the ideal gas law are often expressed in terms of the compressibility

factor

pV
z= (2)
nRT

and become most significant at high pressures and low temperatures. If z<1, then attractive

interactions dominate and the volume of the gas is less than that predicted by the ideal gas

equation. If, however, z>1, then repulsive interactions dominate and the gas occupies a large

volume than expected (Atkins and de Paula, 2010).

Real gases deviate significantly from the ideal gas behavior at low temperatures or

high pressures. In a real gas the molecular volume is not negligible. A modification of the

ideal gas law was proposed by Johannes D. van der Waals in 1873 to consider the molecular

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size and molecular interaction forces. The famous equation is referred to as the van der Waals

equation of state and takes the followIng form:

a
p v b RT
v2
(3)

Where a is related to the volume occupied by the gas constituents while b is related to

the radius of influence of the intra-molecular interaction (van der Waals Equation of State,

n.d).

This equation has played an important role in the development of theories describing

fluids; both liquids and gases. Van der Waals equation has merit in that it involves just two

constants, both characteristic of given chemical substance. The parameter a makes an

allowance for the drop in pressure caused by the attractive interactions between the atoms or

molecules. The parameter b, called the covolume, represents the physical space occupied by

the molecules. Differentiating the van der Waals equation and solving the resulting equations

gives values for the molar pressure, volume and temperature at the critical point in terms of

the van der Waals parameters a and b.

27 R 2Tc2 RT
a b c
64 pc 8 pc
, (4)

The Law of Corresponding States is an interesting concept, following an observation

by van der Waals in 1881. When considering the properties of single-phase systems, it is

common to make use of the reduced variables.

P V T
Pr = P c Vr = Vc Tr = Tc (5)

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 Reduced variables allow comparisons between different gases. Gases with the same

values for the reduced variables are said to be in corresponding states, even if the actual

values of the pressure, volume and temperature are very different. Mathematical manipulation

shows that for a gas whose behavior can be modelled using the van der Waals equation, the

reduced pressure, reduced volume and reduced temperature are related by

8 Tr 3
Pr = 3 V r 1 (6)

This expression is independent of the values of a and b and infers that the behavior of

gases is the same if they are in corresponding states. It also allows us to calculate the reduced

properties of a gas even if the values of a and b are unknown. This principle of corresponding

states works best for atoms and for spherical or non-polar molecules because their deviations

from ideality can be successfully modelled using a van der Waals function. However, this

principle doesnt work well for non-symmetric highly polar molecules with more significant

deviations from ideality (Ideal and Nonideal Gases, n.d).

This experiment generally aims to provide a better understanding of the properties of

gases and to apply the ideal gas law and van der Waals equation of state to relate and

calculate values for pressure, volume, and temperature.

MATERIALS AND METHODS

Materials

The materials used in this experiment iclude the laptop, Microsoft Office Excel, and

laboratory manual.

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Methods

The first part of the experiment was choosing two different substances provided for

the class. Throughout the spreadsheet theres a color code; the values in blue are input

varibles and values in red shows the results. The parameters of these substances were

calculated by inputing of their critical temperature Tc, critical pressure pc, and critical molar

volume vc in the Microsoft Excel sheet pvT-calc. The next step was to calculate using again

the sheet pvT-calc how the pressure depends on the molar volume based on different

temperatures. The Maxwell construction was then performed on the sheet Maxwell. To do

this, the pressure and the molar volumes at which the liquid phase is in equilibrium with the

gas phase were calculated for each of the two substances for four temperatures below the

critical temperature. The Maxwell construction is good enough when the difference between

areas 1 and 2 is less than 2%. The temperatures at which these calculations were performed,

critical temperature, critical pressure and critical volume were tabulated in worksheet_Q3.

Using the data in worksheet_Q3 a p-v phase diagram was constructed. P-V phase

diagrams for each of the five temperatures equal to the critical temperature and below the

critical temperature were also generated using the p-V data from the Maxwell construction

and the pvT-calc worksheet. The diagrams were superimposed in one graph. A liquid-gas

coexistence curve in a p-T diagram was derived using the data obtained in question 3 then

this curve was plotted in sheet worksheet_Q4 for one of the substances. In worksheet_Q5 the

reduced pressure pr as a function of the reduced molar volume vr at the same reduced

temperature Tr was plotted in a single graph for the two substances. The critical constants

were taken in the sheet pvT-calc. Also in worksheet_Q5 the reduced pressure pr as a function

of the reduced molar volume r for the pressures and volumes of the coexistence curve were

plotted refering to worksheet_Q4 for values of p and V.

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 So far we have considered the law of corresponding states just theoretically utilizing

the Van der Waals equation of state. We then investigate how this law functions for real gases.

This was done using the experimental data for argon and ethane. Their experimental critical

constants and their relationships between the pressure and the molar volume are given in

Tables 1 and 2 of the sheet tables. The experimental data with the predictions of the van der

Waals equations and sheet worksheet_Q8 were compared by plotting p as a function of 1/v.

The experimental data given in table 2 of the sheet tables were tested in sheet worksheet_Q8

whether they obey the law of corresponding states by plotiing pr as a function of 1/vr. Finally,

in the file Z-calc.xls, the van der Waals constants and the TB for the assigned gas were

calculated using the data from tables sheet. P and Z values were generated for the given

molar volumes and specified temperature (Tb). In sheet worksheet, pressure was expressed in

atm and a p-Z diagram was prepared. The same procedures were performed again for two

other temperatures: one below TB and the other higher than TB. The three plots were

represented in a single graph.

RESULTS

Figure 1. The gas-liquid coexistence curve of water at 697.4 K >> TC

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Figure 2. The gas-liquid coexistence curve of water at 650.0 K > TC

Figure 3. The gas-liquid coexistence curve of water at 647.4 K = TC

Figure 4. The gas-liquid coexistence curve of water at 640.0 K < TC

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 Figure 5. The gas-liquid coexistence curve of water at 597.4 K << TC

Figure 6. The gas-liquid coexistence curve of benzene at 612.7 K >> TC

Figure 7. The gas-liquid coexistence curve of benzene at 570 K > TC

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Figure 8. The gas-liquid coexistence curve of benzene at 562.7 K = TC

Figure 9. The gas-liquid coexistence curve of benzene at 550.0 < TC

Figure 10. The gas-liquid coexistence curve of benzene at 512.7 << TC

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Figure 11. The equilibrium curve for water and benzene at three temperatures lower than their
critical temperature

Figure 12. The binodal curve for water and benzene at three temperatures lower than their
critical temperature

Figure 13. The liquid-gas coexistence curve of water and benzene

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 Figure 14. The reduced pressure
pr, reduced molar volume r and reduced temperature Tr of water and benzene

Figure 15. The reduced pressure pr and reduced molar volume Vr for the pressures and
volumes of the coexistence curve of water and benzene

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 Figure 16. p vs. 1/V of argon and ethane using experimental data

Figure 17. p vs. 1/V of argon and ethane using van der Waals equation of state

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 Figure 18. Law of corresponding states

Figure 19. p-Z diagram of water at temperatures TB, T=TB, and T > TB

DISCUSSION

The assigned gas for the group were water and benzene. The van der Waals contants a

27 R 2Tc2 RTc
a b
64 pc 8 pc
and b for water and benzene were calculated using the formulas and .

(Derivation of the formula is shown in Appendix B.)

Substituting the values of molar pressure, volume and temperature to the equation for each of

the gas we have:

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For water:

27 R 2Tc2 27(8.31) 2 (647.4) 2

a a
64 pc 64( 22119160)
= = 5.52 x 10-1

RTc (8.31)(627.4)
b
8 pc 8(22119160)
3.04 x 10-5

For benzene:

27 R 2Tc2 27(8.31) 2 (562.7) 2

a a
64 pc 64(4924376)
= = 1.87

RTc (8.31)(562.7)
b
8 pc 8( 4924376)
1.19 x 10-4

Parameter a corrects for the force of attraction between gas particles. Compounds for

which the force of attraction between particles is strong have large values for a. Larger a

values reflect stronger attractions between molecules. Parameter b represents the effect of the

finite molecular size or the repulsive forces among molecules on the pressure. Larger "b"

values are associated with larger molecules.

According to the Ideal Gas equation, pressure and volume should have an inverse

relationship. This relationship is known as Boyles Law. If we construct the p-v diagram for

an ideal gas at a given temperature, we end up with the isotherm shown in Figure 19.

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Figure 19. The graph showing the inverse
relationship between pressure and volume in the
ideal gas equation of state

Based on the p-V diagrams (Figures 1-10), temperature change affects the appearance

of the graph. The graph exhibis a lesser hyperbolic line at higher temperature. According to

Atkins, this phenomenon is influenced by the intermolecular forces that are involved at the

certain instances in the graph. At low-volume, nolecules are too repulsive that they give rise

to high presures and high potential energies but less compressibility. However, at large

volumes these molecules usually become more prone to attraction as they are already far

apart from each other caused by the large volume. These molecules eventually become very

compressible as the forces aid the drive the molecules together.

The van der Waals equation does not succeed to reproduce the gas-phase properties in

the region of the phase diagram in which liquid and vapor coexist. The oscillations that are

predicted by the calculated isotherms are unphysical because they predict that the volume of

the system will decrease as the pressure decreases. Maxwell's construction corrects this by

replacing the oscillating segment of the isotherm by a horizontal line, which is interpreted as

belonging to a two-phase system, with liquid and vapor in equilibrium. The Maxwell

construction is derived by arranging the two shaded regions produced by intersection with the

Van der Waals isotherm to have equal areas.

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 The Maxwell construction of these two substances were generated via trial and error

assumption of the pressure at which the value would equalize the area of the two loops and to

determine the region where the pressure remains constant or the transition phase. In Figure

12, the values are in a trend such that at every pressure, two values of the molar volume can

be plotted on the graph. These molar volumes indicate the start and end of a transition phase

as a gas compresses and, or expands at a given temperature. The critical values however

indicate the region where the gas becomes isothermic. In Figure 13, the trend between the

pressure and temperature is increasing. This can be explained by the collision of molecules in

high temperature which causes the system to have high pressures, and the separation of

molecules in low temperature causing the system to have low pressures.

In Figures 14 and 15, the curves of water and benzene are nearly coninciding into one

curve without considering the outlined parts of the line. These values were obtained at a

certain reduced temperature value of 1.5. According to Atkins, the observation that real gases

under one reduced volume and reduced temperature exert the same pressure is called the

principle of corresponding states. The slight disagreement between the two curves in the

graph indicates an error in the approximation. In Figure 18, the super imposing of both set of

data reveals the relationship of a closely relative function of pressure and reduced volume.

However, a very small degree of deviation is observed between the gases as the reduced

variables were presented. This phenomenon is observed in both substances, Argon and

Ethane. This implies that the Van de Waals would fail at some occasions, to a minute degree,

since this equation is meant for approximation and presentation only. As Atkins suggested,

the Virial equation is used when the van der Waals equation fails.

In Figure 19, the given gases were observed at the temperatures that were relative to the

Boyles Temperature. The compression values of both substances follow an increasing trend.

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The low value of Z at low temperature and pressure indicates that the gas molecules tend to

be scattered and hence exerting more attractive forces. Whereas the high z-values at high

temperature and pressures indicates that the gas molecules move towards each other as they

produce repulsive forces. With this, it can be stated that real gases could not attain the ideal

gas characteristics at extreme pressures and temperatures in which intermolecular forces

(IMFs) could not be considered to be ignored.

CONCLUSION

There are a lot of ways in characterizing and describing gases according to their

thermodynamic properties and these show that real gases are very much different from ideal

gases. This experiment provided information that in order to attain the characteristics of an

ideal gas, certain conditions must be followed. Also, this experiment tackled on the

capabilities and limitations of the van der Waals equation in the presentation of the properties

of gases. Limitations opened the idea in using alternative equations that can substitute the Van

der Waals function.

REFERENCES

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[1] Atkins, P.W., de Paula, J. Physical Chemistry, 9th edition, Oxford University Press: Great

Britain, 2010; pp 23-37

[2] Clark, J. Real gases http://www.chemguide.co.uk/physical/kt/realgases.html (accessed

Sep 3, 2016).

Fitzpatrick, R. Phase Transformations in Van der Waals Fluid

https://farside.ph.utexas.edu/teaching/sm1/thermalhtml/node123.html (accessed Sep 3, 2016).

[3] Lower, S. Real Gases http://www.chem1.com/acad/webtext/gas/gas_6.html (accessed Sep

3, 2016).

[4] Adams, R. Thermal Properties and Ideal Gases

https://cnx.org/contents/rymblkby@2/thermal-properties-and-ideal-g (accessed Sep 3, 2016).

[5] Gaje, Arnold. Physical Chemistry Lab Manual; Chemistry Department: University of the
Philippines Visayas Miagao, Iloilo, 2016, Experiment 1.

APPENDICES

Appendix A Tables

Table 1. Critical temperature Tc, critical pressure pc and the critical molar volume vc of water
Numerical constants
gas constant 8.31 J/K
van der Waals a 5.52E-01 N/(m^4mol^2)
van der Waals b 3.04E-05 (m^3)/mol

Table 2. Critical temperature Tc, critical pressure pc and the critical molar volume vc of
benzene
Numerical constants
gas constant 8.31 J/K
van der Waals a 1.87E+00 N/(m^4mol^2)
van der Waals b 1.19E-04 (m^3)/mol

Table 3. Temperatures at which liquid phase is in equilibrium with the gas phase for water
T/K P/Pa % Difference
647.4 K
600 K 16201910 0.00%

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 595 K 15641920 0.00%
593 K 15421211 0.00%

Table 4. Temperatures at which liquid phase is in equilibrium with the gas phase for benzene
T/K P/Pa % Difference
562.7
500 3016120 0.00%
495 2887930 0.00%
493 2837610 0.00%

Table 5. The reduce temperature of argon and ethane

Pcr/[Pa] Tcr/[K] Vcr/[m3.mol-1] T(K) Tr (K)
Argon 4863581 150.72 7.53E-05 247 1.6388
Ethane 4883846 305.4 0.000148 500 1.637197

Appendix B Derivation

The Relationship between the van der Waals Parameters and the Critical
Constants

If

a
p v b RT
v2

then

RT a
p= 2
V b V

At the critical point,

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 and

So, differentiating our expression for pressure with respect to volume at constant temperature

so that

Differentiating again gives

so that

Dividing these two expressions gives

and so

Substitution of this result into the expression that we obtained by differentiating once

gives

which, when rearranged, gives

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Substitution of the expressions for the critical volume Vc and critical temperature Tc into the
van der Waals equation gives

and so

Given these expressions for the values of the critical constants

so that

Similarly

Hence

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