Experiment #4 PVT Relationships for Real Gases

(Computational Lab)
Students doing this experiment are to check into the laboratory as usual with all the required data. Submit an outline of what you will be doing and write the quiz. Then you are free to leave.

This experiment should familiarize you with the accuracy of the van der Waals equation of state in calculating gas pressures as compared to the ideal gas equation. It also provides an estimate of the vapour pressure of the liquid ethyl acetate at 40 K below its critical temperature. Since an experimental value is available, this experiment will give a good indication as to whether the van der Waals equation can be used with confidence below the critical temperature in the region of a gasliquid equilibrium. No laboratory experimentation is required in the experiment, but calculations must be done via EXCEL [or other spreadsheet software]. Those who do not have access to their own EXCEL can use the computers in the departmental reading room or elsewhere on the campus. Both equations of state used here, the ideal gas law and the van der Waalsm equation are discussed in Chapter 1 in Atkins and in almost all physical chemistry texts. Vapour pressures and phase diagrams for one component systems are dealt with in experiment #2, where the pressure versus temperature behaviour was investigated. Isotherms (i.e. plots of pressure vs molar volume for constant temperature) are shown for an ideal gas, a real gas and a van der Waals gas at 3 different temperatures (Figure 1).

(a) (b) (c) Figure 1: Isotherms for different gas models, where a) is the ideal gas, b) is a real gas, and c) is a van der Waals gas. At T1, the real isotherm in (b) is at a temperature such that the vapourliquid transition takes place at a pressure equal to the vapour pressure of the liquid. At Tc, the isotherm is at the "critical temperature", the highest temperature at which a liquid can exist. At all T > Tc, e.g. T3 the "liquid" (if the model allows for liquid) and vapour have the same densities at all pressures.

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The van der Waals. equation is used to replicate real gas behaviour:
(p + a n2 V
2

)(V - nb) = nRT

p=

RT a - 2 Vm-b Vm

[1]

In [1], the van der Waals constants a and b are characteristic of a particular substance. It can be shown that the equation predicts the appearance of a critical point for this substance. At the critical point (Tc, pc), the isotherm is horizontal and has an inflection point such that the condition for a gas to undergo condensation is:
2 p p =0 = 2 V T V T

This condition makes it possible to calculate a and b from values of the critical constants pc, Vm,c, and Tc (and vice versa):
T c=

8a 27bR

V m,c =3b pc =

a 27 b2

Below the critical temperature, the van der Waals equation gives three different values of volume for each value of pressure (i.e. the equation is cubic in volume). This is interpreted as the appearance of two phases and is typical of real gas equations of state. Typically, these equations of state are unable to mathematically handle sharp breaks (discontinuous slopes) in pressure-volume isotherms that occur at the beginning and end of the two-phase region. The actual isotherm is approximated in the van der Waals isotherm by drawing a horizontal line across the loop such that area 1 = area 2 (Figure 2). This line is called a Maxwell construction. The volumes at the two breaks correspond to the molar volume of the liquid and gas respectively.

Figure 2: A Maxwell construction shown drawn across a typical van der Waals loop in a van der Waal isotherm.

A close examination of the van der Waal equation shows other inadequacies. For example when Vm = b the pressure is infinite while for Vm < b the pressure is negative. Even when Vm > b, the pressure can be negative if: RT a < 2 ( V m -b) V m 43

Deviation from ideal gas behaviour is given by the compressibility factor:

Z= pVm RT

[2]

Z may be calculated by using the pressure found from equation [1]. The objectives of this experiment are: 1. Calculate and plot ideal and van der Waal gas pressures of ethyl acetate as a function of molar volume at three constant temperatures: the critical temperature (Tc) and Tc 40 K 2. Calculate and plot the compression factor Z as a function of the pressure at the three constant temperatures EXCEL or any calculation software may be used. This is a true experiment if done properly in the sense that you must look at the values that are being calculated and then revise your calculations. EXCEL is an excellent calculation tool in an interactive sense because the values are calculated in an instant so that you can quickly analyse what the calculations mean and how you should change them to get exactly what you want. In this sense its much better than mindlessly taking some temperature readings in a hands on lab where often readings are taken without much thought as to whether they even make any sense and only used later on in calculations. Before beginning the EXCEL calculations you should plan what pressure calculations you will start. You should be concerned about the range of pressure and molar volume values that you want to examine. You should note very carefully that pressure changes as a function of molar volume are relatively small for pressures below 10 20 atm. The most dramatic changes occur near the phase change region and at high pressures when molar volume values span a range of about 1.5b to 10b. Note that the phase change region will be small compared to the overall isotherm, which extends from over 50 atm to about 1 atm. Thus, aside from obtaining data for the overall isotherm the phase change region must be examined in detail. This means that you must calculate pressure and compression factors over a large range of molar volumes (to give 1 200 atm) and over a very limited range (1.5b 10 b).This can be done quickly in EXCEL. After the initial calculations and graph you may see that you want to calculate pressure values for molar volume values that are not evenly spaced (e.g. from 1 to 40 L mol-1). In generating values of Vm you dont have to have all the values separated by the same increment. This is especially useful in the phase change region where there are very large changes at the smallest Vm values and then less dramatic changes as the value of Vm increases. Alternatively, you could maintain the low increment over the entire Vm range. This would necessitate the calculation of 100 to 200 Vm values. While this is very easy to do and takes insignificant additional calculation time, the resulting graph would have too many data points. In this instance you could use the filter option in EXCEL.

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Procedure 1. Obtain the van der Waals constants and the critical constants for ethyl acetate. These are available in HCP. 2. Use Row 1 to define column headings i.e. symbols for molar volume, ideal gas pressure at three temperatures, van der Waals pressure and compression factor Z for three temperatures.
Since molar volume is the x co-ordinate in many of the plots put this in the first column.

3. Define constants to be used in the ideal gas, van der Waals and Z equations i.e. ideal gas constant R, van der Waals constants a and b and the three temperatures to be used.
Constants can be defined in EXCEL using the commands Insert, Name, Define. Most letters can be used to name constants but note that R is reserved for something unrelated to gas law and cannot be used for the name of the gas constant.

4. To obtain the overall isotherm from high to low pressure you need to get an estimate of the molar volume range to give pressure values from > 150 atm to 1 atm for one of the three temperatures. You can use the ideal gas equation. 5. Generate Vm values in Column 1 starting with a value that will give a high pressure and ending with a value that will give about 1 atm. 6. In cell [2,2] (row 2,column 2) write the equation for the ideal gas pressure using the symbol for the predefined constants and molar volume. Once this is entered the cell will contain the value of the pressure for the molar volume value in cell [2,1]. 7. Copy the equation in cell [2,2] and paste it to the remaining cells in column 2. This will generate all the pressure values for all the molar volume values in column 1. 8. Graph the result.
This procedure can be repeated for all pressure and compression factor calculations.

9. You will see that with molar volume increments of 1 to 2 L mol-1 the graph shows no loops that indicate a phase change region. This means that you must regenerate a new series of Vm values to cover the range of about 1.5 b to 10 b in small increments. Thus you should use another sheet to do calculations over this small range.
Note: In the printout of values do not accept the default number of digits; se the correct number of significant figures appropriate for your values.

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Calculations 1. From the van der Waals isotherm at Tc, estimate the value for the critical pressure and the critical molar volume and compare them to the experimental values. The critical pressure can also be calculated from the equations given earlier. Be prepared to comment on what the magnitude of the critical molar volume should be. 2. From the van der Waals isotherm at Tc 40, make a Maxwell construction and compare with the value calculated from the vapour pressure equation in HCP (shown below for your convenience): log p =
0.2158 A +B T

where p is in torr A is the heat of vaporization in cal mol-1 B is a constant For ethyl acetate A = 8301 cal mol-1 and B = 8.001. You should also find the experimental vapour pressure at 483 K. It is available in HCP. Account for the difference in vapour pressure values between the experimental, that obtained from the Maxwell construction and that obtained from the HCP equation.
Calculations and plots of the compression factor, Z, vs pressure should show analogous behaviour to the isotherm plots for the van der Waals equation (i.e. if there is a van der Waals loop there should be an analogous loop in the plot of Z vs p).

3. Note also the significance of Z < 1 and > 1 with respect to the dominance of attractive and repulsive forces. These plots should give a good idea of the pressure range in which one or other intermolecular force dominates. 4. Estimate the pressure range for which the ideal gas equation is reasonably valid for 563.3 K i.e. within about 10% of the van der Waals value [this assumes that the van der Waals value is close to the experimental value when the temperature is above Tc.

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Interview Report

Sign up for an interview on the sheet next to the report submission box in the laboratory. For the interview you should know the basic theory and have a qualitative idea about what the various plots should look like as well as an appreciation of the pressure range when the ideal gas can be used and when it is inadequate. For your interview, bring an informal report that contains: 1. The printout of EXCEL calculations for pressure and compression factors for Vm values over a wide range and over the phase change region. Printouts must indicate the equations being used and have sufficient documentation and labels to explain what is being done. Think carefully about how to present the data: do not provide pages of numbers that require analysis. 2. Plots showing: a. Where the van der Waals and ideal gas equations begin to diverge by about 10%. b. Van der Waals isotherms and Z values in the phase change region for all temperatures. c. A close up of the van der Waals loop with the Maxwell construction (gridlines should be printed to facilitate equal area calculations). A sample graph is shown below. d. Try to put several plots on one graph (e.g. the three van der Waals isotherms). 3. Calculations as outlined above with a brief analysis of how good the van der Waals equation is for ethyl acetate. 4. Please bring your data files on a portable storage device (USB drive or CD) in case there is difficulty with the data.

van der Waals ISOTHERM ETHYL ACETATE 483.3 K

33

31

29

PRESSURE atm

27

25

23

21

19 0.00

0.20

0.40

0.60

0.80

1.00

1.20

1.40

1.60

MOLAR VOLUMES L/mol

Figure 3: An example of a gridline graph for making a Maxwell construction.

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