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Real Gas Behavior: Gravimetric Determination of the Second Virial

Coefficient of CO2

Objectives
 To learn how to experimentally examine the relation between the pressure and the
number of moles of a gas under isochoric and isothermal conditions.
 To observe deviations of the behavior of CO2 from that of an ideal gas in the pressure
range up to 11 bar.
 To understand the reasons for CO2 gas to behave in a non-ideal manner.
 To determine the second virial coefficient for CO2 using the relationship between
compressibility and the inverse of Vm.

Introduction
An equation of state is a mathematical expression that links the state properties of a gas.
The ideal gas equation is derived from three individual gas laws: Boyle’s law, Charles’ law, and
Avogadro’s principle and is shown in Eq. (1)[1].

PV=nRT (1)

A gas which abides by Eq. 1 under all conditions is defined as

ideal. A real gas closely resembles an ideal gas if it is monatomic, at low
pressures, high temperatures, or large molar volumes. The compression
factor, Z is used to assess deviations from gas ideality; it is defined as:
Z= Vm/ Vm° (2)
where Vm is the measured molar volume and Vm° is the molar volume of
Figure 1. Potential energy a perfect gas. When the gas is moderately compressed, Vm is less than
of intermolecular
interactions[1]. Vm°, and attractive forces dominate (Z<1). On the other hand, under
very high pressure conditions, Vm is greater than Vm° because repulsive forces are dominant
(Z>1). Figure 1 is a potential energy curve that illustrates how the attractive and repulsive forces
that affect Z depend on intermolecular distance. Since the Vm° of an ideal gas is equal to RT/P,
an equivalent expression for the compression factor can be derived as Eq. (3). 1
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Z = PVm / RT (3)

A variety of expressions have been adapted to account for deviations from ideal gas
behavior. One of these is the viral equation of state as shown in Eq. (4), where the first virial
coefficient, 1, defines the contribution of ideal gas behavior to real gas behavior[1].

PVm = RT[1+(B/Vm)+(C/V2m)+ …] (4)

The series in brackets is analogous to the compression factor Z (refer to Eq. (3)). The constant B
is the second virial coefficient and correlates to interaction between two molecules (C is
consistent with three, etc.). B is a function of temperature and is large and negative at low
temperatures and small and positive at high temperatures[2]. The purpose of this lab is to
determine the value for the second virial coefficient of carbon dioxide. The first virial
coefficient is equal to 1 and B/ Vm >> C/Vm, with respect to molar volumes, making B most
significant in deviations from ideality. The Boyle temperature, TB, corresponds to the
temperature at which the second virial coefficient is zero; at this temperature real gases behave
as ideal gases over relatively large pressure ranges. Here Z
approaches 1 with slope equal to zero, Eq. (5). Under ideal gas
conditions, the slope for Z is always zero.
dZ/d(1/ Vm)  B as Vm  ∞ and p  0 (5)
Figure 2 shows the relationship between the compression factor and
pressure at several temperatures. “The compression factor Z
approaches 1 at low temperatures but does so with different slopes.
For a perfect gas, the slope is zero, but real gases may have either
positive or negative slopes, and the slope may vary with temperature.
Figure 2. Compression factor, Z,
versus pressure[1] At the Boyle temperature, the slope is zero and the gas behaves
perfectly over a wider range of conditions than at other temperatures”[1].
Other equations which aim to describe the behavior of real gases are the van der Waals
(shown below), Berthelot, and Dieterici equations (refer to Atkins page 19 for more detail).

(6)
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If the van der Waals equation accurately describes the behavior of an ideal gas, the Boyle
temperature can be determined if B is set equal to a portion of the Van der Waals equation, Eq.
(7), where a depends on attractive forces and b is related to the size of the molecule.

B= b − (a/RT) (7)
Table 1 lists second virial coefficient values of four different gases with their corresponding
Boyle temperatures.

Table 1. Second Virial Coefficients, (cm3/mol) for four gases and Boyle temperatures[1].
Virial Coefficient, B
at 273K at 600K TB (K)
Ar -21.7 11.9 411.5
CO2 -149.7 -12.4 714.8
N2 -10.5 21.7 327.2
Xe -153.7 -19.6 768.0

Modern day methods for predicting the second virial coefficient include those used by
Iglasias-Silva and coworkers[3]. The third virial coefficient for carbon dioxide has also been
predicted at high temperatures[4]. Modern research involves determining third and fourth virial
coefficients for hard prolate spherocylinders[5].

Experimental Procedure
Part 1: Balance Calibration
1. Tare the balance. While wearing the provided gloves, carefully place the vessel on the
balance and record its mass.
2. Using the tweezers with plastic tips (using regular metal tweezers will damage the
standard weights), add a one gram weight standard to the balance, and record the
combined mass of the weight and vessel.
3. Repeat step 2, each time adding the next combination of weights (two grams, three
grams, four grams, etc.) and recording the new mass, until you reach 12 grams.
4. Repeat steps 2 and 3 three times to ensure good statistics.
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5. Be sure to record the predicted masses of the weights. You will need these for your
calculations.

Part 2: Evacuation of Vessel (typically the vessel will be evacuated prior to class)
6. Using the provided gloves, attach the vessel to vacuum line C. Clamp it so it does not
fall.
7. Fill a cold trap dewar with liquid nitrogen and place it such that the vacuum trap is in the
dewar. At this point, you can turn the vacuum pump on.
8. Open valve C (while the vessel is still screwed shut) in order to evacuate the vacuum line.
Continue to evacuate until the pressure is 0.02 Torr (verify with manometer). This
should take approximately 10 minutes.
9. While the line is being evacuated, measure atmospheric pressure using the barometer
located in the room with the CO2 tank.
10. Once the line is evacuated, open the valve on the vessel. Evacuate the vessel to a
pressure of 0.02 Torr for approximately 10 minutes.
11. Close the valve on the vessel, close valve C, and detach the vessel from the line.
12. Record the mass of the evacuated vessel.

Part 3: Data Collection

Figure 3. Experimental apparatus schematic.

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13. Study figure 3 and identify the corresponding parts in the lab setup. Identify the gas
regulator (annotated by the arrow), which will be used to control CO2 loading into in the
vessel. The inlet gauge (right) shows tank pressure; the outlet gauge (left) shows the
pressure at which the regulator will cease delivering gas from the tank.
14. Ensure the small round black valve (labeled C) is shut for this step: Open the tank valve
(D) and set the regulator to load the correct pressure for CO2 by turning the regulator
knob. Verify that the loading pressure has been set to 9 bar by reading the outlet gauge on
the pressure regulator.
15. First attach the vessel to the yellow CO2 tubing and then place it in the stainless steel
sleeve. Do not allow the vessel to touch water!
16. While the vessel is still closed, fill the line with CO2 until it reaches approximately 9 bar
(valves C and D). Next, purge the line until the pressure is just above 0 bar (valve B). Do
not purge the line completely or air will enter the line. Repeat.
17. Open valve A on the vessel
18. Allow the pressure to equilibrate for 5 minutes.
19. Next, record the pressure and the thermocouple temperature.

* The pressure gauge used is NIST calibrated within 0.05%. Thermocouple

temperature readings have uncertainties of ± 0.1 oC.

20. Close valve A on the vessel.

21. Open valve B below the pressure gauge to release remaining CO2 from the line.
22. First take the vessel out of the sleeve and then unhook the vessel from the CO2 tubing,
and record the mass of the vessel.
23. Readjust the regulator valve for the next data point by turning the knob counterclockwise.
(Note that a positive pressure must be maintained within the regulator for the outlet gauge
to correctly display the pressure at which it is set to stop delivering gas.)
24. First reattach the vessel to the CO2 tubing and then place it in the stainless steel sleeve.
25. Open valve A on the vessel. The pressure should drop to approximately 8 bar (∆P = 1
bar). If ∆P < 1 bar, open valve B below the pressure gauge to release extra CO2 from the
line until the desired pressure is reached.
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26. Using the same procedure, obtain temperature and mass readings for six additional CO2
pressures (7, 6, 5, 4 and 3). Remember, these are only approximate pressure values and
they indicate gauge pressures.
27. Remember to obtain the atmospheric pressure from the barometer in the room.
4. Data Analysis
1. To assure balance accuracy with the added mass of the vessel, plot measured mass values
against the standard mass values (from Part 1). An R2 value close to one indicates
acceptable measurements were obtained. Include this plot, regression line, and R2 value
in your report.
2. Convert the pressure data obtained in lab (Part 3) to absolute pressure. Keep in mind that
gauge pressures were recorded (in bar).
3. Determine the amount of carbon dioxide in the vessel in each trial by subtracting the
evacuated cylinder’s mass from the trial’s mass (cylinder plus gas) and converting to
moles.
4. Calculate the molar volume of each trial. (Vessel Volume = 0.5612 L)
Vm = Vvessel/moles of CO2
5. Create a table including pressure (step 1), temperature (in K), moles of CO2 (step 2) and
molar volume (step 3).
6. Make a plot of Pressure versus moles. Indicate a line which represents ideal behavior.
Include this graph in your report.
7. Calculate the compression factor Z for each trial.

8. Plot Z - 1 versus 1/Vm. Use linear regression and force the regression to go through the
origin of your plot. Include the R2 value in your report.
9. Report the experimental second virial coefficient of carbon dioxide, B. Calculate the
error associated with this measurement using linear regression output data.
10. Report the uncertainty associated with the calculation of Z.
11. Report the y-intercept calculated in step 6 and its associated uncertainty. Indicate its
ideal value. Explain any deviation from this ideal value.
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Report Questions
1. Why is it important to account for the atmospheric pressure when completing your data
analysis?
2. Compare your value for the second virial coefficient to the literature value. Don’t forget
to take temperature dependence into account. Consider possible sources of error for this
experiment and the influence they could have on your results.
3. What is the reason for CO2 to deviate from ideal gas behavior in the pressure range
applied?

References
1. Atkins, P.; De Paula, J. Atkins' Physical Chemistry 8th ed. W.H. Freeman and Company:
New York. 2006, 14-16, 19.
2. Diamond, J.H.; Smith E.B. The Virial Coefficients of Gases: A Critical Compilation
Oxford University Press. 1969. vii-xii.
3. Iglesias-Silva, G.A.; Hall, K. R. Ing. Eng. Chem. Res. 2001, 40 (8), 1968.
4. Colina, C.M.; Olivera-Fuentes, C. Ind. Eng. Chem. Res. 2002, 41(5), 1064.
5. Boublik, T. J. Phys. Chem. B. 2004, 108 (22), 7424.