Anda di halaman 1dari 21

THE VAN DER WAALS EQUATION OF STATE, THE

LAW OF CORRESPONDING STATES, AND THE


COMPRESSION FACTOR
Experiment No. 1

Trixie Babes Magrare Capio


BS Chemistry III

Lab Partners
Rammela Ann Camelote
Joanues Ignacio

Chemistry 116 Section 1

September 8, 2016

I.

Abstract
The experiment focuses on determining and comparing the behavior of the
real gases (experimental and van der Waals equation of state) to ideal gas by the use
of isotherms graphs. Studying the law of corresponding states, reduced variables,
Maxwell construction and the compression factor of the gases were also presented.
The experiment was carried out using a computer with MS Excel programmed to
calculate and generate data and set of instruction and questions as guide. The results
that were generated and presented in graphical way have successfully supported and
agreed with all the concepts that were covered.

II.

Introduction
Behavior of gases have been described by the equation PV = nRT for a long
time since most gases behave ideally in regular working temperature and pressure.
This ideal gas follows the kinetic molecular theory which includes the ideas such as 1)
that gas do not interacts and 2) the volume occupied by gas molecules is negligible.
Van der Waals equation is trying to correct these two points in kinetic molecular
theory because gases deviate from ideality in low temperature or high pressure.
Corrections in the volume occupied by the molecules (b) and inter molecular forces
(a) in ideal gas law were added to predict the behavior of real gases.

)(

Van der Waals equation however is not a perfect equation of state to describe
real gases. Below critical temperature the graph of van der waals form loops which is
|P age1

unrealistic. These were fixed by Maxwell by replacing loops by horizontal lines


placed where the areas above and below the loop equates to each other to resemble
the experimental data.
Van der Waals equation can also be expressed in reduced forms of the
variables temperature, pressure and volume:

and

where

and

These variables were plugged in to the van der waals equation forming an
equation that is unit less and independent of the identity of the gas. This independence
on the identity of gas made them behave similarly. This equation is called the Law of
corresponding states.

The ideality of the gas can be calculated using the compression factor Z. The
forces of attraction dominating the gases could also be predicted by this equation.

The closer the value is to 1 the more it behaves as an ideal gas; a value less
than 1 will favor attraction while greater than 1 values will favor repulsion.
These theories will all be tested in this experiment. The gases that will be
looked through are Helium gas and Ethene gas. Data will be generated through a MS
Excel program will be gathered a plotted to test the presented theories and compare

|P age2

the ideal gas to real gas (by van der waals equation of state) and the generated
(theoretical data) to experimental data.
This experiment aimed to illustrate the relationship of gases and their behavior
based on the van der waals equation of state.

III.

Materials and Methods


The experiment was carried out using MS Excel that was programed to
calculate the pressure values using the Van der Waals equation of state. Helium gas
and ethane gas were chosen to be studied in this experiment.
First, critical points (temperature, volume and pressure) of the chosen gas
were input to the pvt calc worksheet. Four graphs, comparing van der waals gas and
ideal gas, were generated by varying the temperatures: 1) above critical temperature,
2) critical temperature, 3) slightly below critical temperature and 4) below critical
temperature. The graphs were saved in the word document.
Second, using the Maxwell worksheet, Maxwell construction was performed.
For five different temperatures, including the critical point, pressure values were
taken where the difference between area 1 and area 2 was less than 2%, preferably
0%. Pressure, molar volume (v1 & v3) and temperature values were collected and
tabulated in worksheet_Q3. P-v phase diagram was constructed using these data. In
the same worksheet the molar volume and pressure values from the pvT calc were
tabulated. The pressure values between the v1 and v3 were replaced by the pressure
value taken from Maxwell construction to illustrate the graph of an experimental real
gas. This was done to all the temperatures. After these, the data were used to construct
|P age3

a p V phase diagrams. In worksheet_Q4, a p T diagram was made using the


temperature and pressure from the worksheet_Q3 calculated from Maxwell equation.
Third, in worksheet_Q5, calculate a temperature for both of the chosen gases
so that the reduced temperature values would be equal. The temperatures were used to
generate the pressure and volumes that were used to calculate the reduced pressure
and volume. Pressure pr was graphed as a function of the reduced molar volume r. 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 was also plotted.
Then, the experimental values and van der waals equation of Argon and
Ethane were compared by plotting the plotting p as a function of 1/v. Using the same
technique used in worksheet_Q5 the plot pr as a function of 1/vr was generated to test
for the law of corresponding states.
Lastly, compression factor of Helium gas was calculated using another MS
Excel programmed file named Z-calc. Equations to solve TB and pressure were
encoded. Pressure values at the critical temperature were generated and copy and
pasted to the worksheet. The pressures in atm and z values were calculated. This was
repeated in two more temperature, one above and one below the critical temperature.
The data were plotted in one graph and compared.

|P age4

IV.

Results

T =7K > Tc

T = 5.3K = Tc

T = 5 K < Tc

T = 4.5 K << Tc

|P age5

Figure 1.Van der Waals vs Ideal Gas graph of Helium Gas at Different Temperatures

|P age6

Figure 3.p - V Diagram for Helium Gas (above) & Ethene Gas (below)

|P age7

Figure 4.Binodal Curve for Helium Gas (above) & Ethene Gas (below)

|P age8

Figure 5.p - T Diagram for Helium Gas (above) & Ethene Gas (below)

|P age9

Figure 6.Reduced Pressure as a function of the Reduced Molar Volume at the


same Reduced Temperature (1.64K)

| P a g e 10

Figure 7.Reduced Pressure as a function of the Reduced Molar Volume

| P a g e 11

Figure 8.Experimental Values vs Van der Waals Equation in same Reduced


Temperature

Figure 9.Argon vs Ethene in same Reduced Temperature

| P a g e 12

Figure 10.Z Values vs Pressure in Different Temperatures of Helium Gas

V.

Discussion
All the numerical data gathered were plotted in different manner based on
their relationship and the aim of the experiment.
In figures 1 and 2, graphs show the trend of van der Waals equation of state
compared to the ideal gas. Both of the isotherms behave in almost the same manner as
the ideal gas in temperature above the critical temperature. In the critical point, a point
where the graph slightly deviates from ideal gas can be observed. In temperatures
lower than critical point, loops can be seen which cannot be seen in experimental data.
The high temperature means that the kinetic energy of the molecules is high.
With the increase of kinetic energy the intermolecular forces of attraction between the
| P a g e 13

by Maxwell construction. The result of Maxwell construction can be interpreted using


the Binodal curve that was constructed using the same data.
Binodal curve can identify the area where the liquid and gas phase coexist.
Binodal curve can give enough information regarding this coexistence. The parts of
the binodial curve were shown in figure 11. Dew line, at the right side of the curve, is
the point where the gas starts to condense and form a liquid phase. Tie line is the
horizontal line that was constructed by the Maxwell construction. Straight line implies
that as the volume decreases as the pressure remains constant. This was due to the gas
molecule interaction forming the liquid phase. As the liquid phase forms it relieves
pressure to the whole system as volume decreases. As the volume decrease reached
the limit where molecules can no longer attract each other; the interaction becomes
repulsive allowing the liquid phase turn back to gas phase increasing the pressure.
Bubble line, at the left side of the curve, is the point where the liquid boils and goes
back at to its gas phase. When this happen the pressure increases tremendously.
Additional information like the molar volumes of the liquid phase and gas phase can
also be found by solving for the roots of the cubic equation. Roots of the cubic
equation signify the molar volumes of liquid phase and gas phase. The largest root is
the vapor molar volume; the smallest root is the value of the liquid molar volume
while the middle root does not represent any real behavior because of its instability.
Critical temperature isotherms only have one root, meaning the vapor molar volume
and the liquid molar volume were equal therefore there is no distinction between gas
phase and liquid phase. This is the critical point where liquid phase and phase cannot
be distinguished.
A phase diagram (pressure as a function of volume) was plotted using the
temperature and pressure data obtained in the Maxwell construction. Phase diagram is
| P a g e 14

a visual representation that shows at which point a specific phase is stable. The phase
diagram used in the experiment is a p T phase diagram with three possible phases
(solid, liquid and gas). These phases were separated by first order phase transition
lines, the continuous line on the graph, indicating the transition of one state to the
other and/or the instability of a phase. This line was also called co existing line as two
phases coexist at this point. These transition lines differ in each compound but follow
the same principle. Above critical point, there will be no distinction between gas and
liquid.
The graph in figure 5 was compared to the phase diagram of a real substance
shown in figure 12. Both of the generated graphs of helium and ethane resemble the
line CB. This lies between the gas phase and liquid phase. The line is a set of pressure
with corresponding temperature at which the liquid boils and gas condense at the
same rate. This agrees to the coexistence of gas phase and liquid phase that was stated
on the previous section.
Data for the law of corresponding states (shown in figure 7) was the next
generated and plotted to test if the two compounds would behave similarly despite
having different identity. At the same reduced temperature, helium gas and ethane gas
follow the same trend. Comparisons between different gases can be possible because
of the reduced variables. Gases in Corresponding states have the same reduced
variables values, even if they have different pressure, volume and temperature values.
This reduced form of van der waals equation of state allow calculations of the reduced
properties of a gas without any compound dependent variable. Because of this, gases
in corresponding states behave the same.

| P a g e 15

Another set of gases, argon and ethane, were studied to identify the difference
of the experimental data and the theoretical data generated by van der Waals equation
of state. Figure 8 shows that experimental isotherms of ethane and argon behaved
similarly when compared to its van der waals counterpart. As the volume 1/v
decreases the pressure increases however the 1/v value of the van der waals equation
of state was much more lower that the experimental value. This shows that equations
of state only approximate the behavior of a gas. Experimental values were also tested
for the law of corresponding states. Comparing the law of corresponding states result
of the equation of state to the experimental data, the experimental data correspond
more. Since, experimental data was a product of a thorough experiment it would be
more accurate.
Lastly, compression value of helium gas was calculated. Compression value
shows the ideality of the gas. In figure 10, the graph shows that the Z values were
mostly positive values. Since helium does have really weak attractive forces,
repulsion forces dominate.

VI.

Conclusions
Ideal gases equation is only applicable in low pressure and high temperature
that is why van der Waals equation of state was used to describe the behavior of real
gases. Through this experiment, the students were able to lean and understand the
behavior of real gases by the help of a preprogramed MS Excel. Beyond
understanding such concepts, this also helped the student learn how to operate the
program in order to graph and present the data successfully.

| P a g e 16

Furthermore, the results of the experiment have answered all the questions
from instructions. The graphs generated have satisfied and supplemented the theories
that were presented.
Minimal errors have been committed and corrected as the data was being
processed and interpreted.

VII. Contribution of Authors


The three authors have contributed towards the success of the experiment.
During the course of the experiment, Capio and Camelote worked with two gases
simultaneously while Ignacio instructed and interpreted the instructions and the data.

VIII. Literature Cited


[1] Adewumi, M. Principle of Corresponding States (PCS). Penn State College of
Earth and Mineral Science. [Online], 2014. https://www.e-education.psu.edu/
(accessed September 1, 2016).
[2] Ideal and Non-Ideal Gases. University of Bistol [Online]
http://www.bris.ac.uk/chemistry/ (accessed September 1, 2016).
[3] Van der Waals Equation of a Real Gas. Fayetteville State University [Online]
http://www.uncfsu.edu/ (accessed September 1, 2016)
[4] Van der Waals Equation of State. Brigham Young [Online] University
https://www.et.byu.edu/ (accessed September 4, 2016)
| P a g e 17

[5] Atkins, P.W., de Paula, J. Physical Chemistry, 9th edition, Oxford University
Press, 2010
[6] Mortimer R. Physical Chemistry 3rd edition, Elsevier Academic Press, 2008

IX.

Appendices

Figure 11. p - V Diagram with parts of Binodal Curves for Helium Gas

Figure 12. p T Phase Diagram of a real substance

| P a g e 18

Table 1.Critical Values of Helium and Ethene

Substance

p(cr)/[ 10^5 Pa]

T(cr)/[K]

v(cr)/[m3.mol-1]

Helium
Ethene
Argon
Benzene

2.28993596
51.168923
4863580.8
4924375.56

5.21
283.1
150.72
562.7

0.00005776
0.0001311
0.00007525
0.00026

Table 2.Pressure Values of Helium Gas where the % Area Difference is less than 2%.

T/K

psat/10^5 Pa

% Area Diff

5.21
5
4.8
4.6
4.4

2.28993596
1.938449
1.63608
1.36444
1.12256

0%
0%
0%
0%
0%

Table 3.Pressure Values of Ethene Gas where the % Area Difference is less than 2%.

T/K

psat/10^5 Pa

% Area Diff

239
245
261
271.7
283.1

25.0435
27.94355
36.6637
43.32199
51.168923

0%
0%
0%
0%
0%

Table 4.Experimental Data of Ethane gas and Argon gas at Reduced Temperature = 1.64
Ethane at T=500K

Argon at T=247K

/[m3.mol-1]

p/[Pa]

/[m3.mol-1]

p/[Pa]

8.31E-02
2.07E-02
4.11E-03
2.03E-03
9.90E-04
6.46E-04
4.75E-04
3.73E-04
3.07E-04
2.27E-04
1.82E-04
1.55E-04
1.30E-04
1.18E-04
1.09E-04
1.02E-04
9.68E-05

5.00E+04
2.00E+05
1.00E+06
2.00E+06
4.00E+06
6.00E+06
8.00E+06
1.00E+07
1.20E+07
1.60E+07
2.00E+07
2.40E+07
3.00E+07
3.50E+07
4.00E+07
4.50E+07
5.00E+07

4.05E-02
1.01E-02
2.00E-03
9.86E-04
4.80E-04
3.11E-04
2.28E-04
1.79E-04
1.46E-04
1.08E-04
8.63E-05
7.35E-05
6.21E-05
5.63E-05
5.22E-05
4.92E-05
4.69E-05

5.00E+04
2.00E+05
1.00E+06
2.00E+06
4.00E+06
6.00E+06
8.00E+06
1.00E+07
1.20E+07
1.60E+07
2.00E+07
2.40E+07
3.00E+07
3.50E+07
4.00E+07
4.50E+07
5.00E+07
| P a g e 19

8.94E-05
8.42E-05

6.00E+07
7.00E+07

4.35E-05
4.11E-05

6.00E+07
7.00E+07

Equation 1.Derivation of Reduced form of Van der Waals Equation of State.

))
(

))
(

)
[

(
(

)
]

))

Equation 2.Cubic form of Van der Waals Equation of State.


(

)(

| P a g e 20