Ideal Gas vs.

Real Gas: Gas

Compressibility Factor (z) and
The Principle of
Corresponding States
Discussion of Results
BY RAYMOND P. BALDELOVAR, BSPE 2A

1. Describe the behavior of z-factor as a function of pressure in an

isothermal process. Explain this behavior by comparing real gas and

ideal gas, using the kinetic molecular theory.

Figure 10.4 (Sheet 10) shows the isothermal (fixed temperature) zfactor

versus pressure relationship (obtained using the Virtual SOPE PVT Cell and Standing

and Katz Generalized compressibility chart, respectively) for the three different

gases, namely, CH4, C2H6, and C3H8. The plot shows that there is a significant

deviation from the ideal gas behavior which is particularly noticeable in the

intermediate pressure range at about 175 bar. At this pressure, use of the ideal gas

equation, (eq. 2), would produce an error of almost 15% in calculated gas volumes.

Furthermore, note that an isothermal increase of pressure in the methane, e.g. at

-44.28oC, results in a decrease of the compressibility factor after an initial normal

behavior. The trend reverses over a limited pressure range, prior to behaving

normally again. The ratio increases very gradually over the whole tested

temperature range, without any peculiarity.

 The determination of the zfactor as a function of pressure and temperature

facilitates the use of the simple equation,

PV = znRT

(eq. 1)

to fully define the state of the real gases as well as to observe the behavior of z-

factor as a function of pressure in an isothermal process. This equation is a PVT

relationship and in petroleum engineering, in general, the main use of such

functions is to relate surface to reservoir volumes of hydrocarbons.

Lets further discuss why there is a significant deviation from the ideal gas

behavior occurring using the Kinetic Molecular Theory. In case of ideal gases, no

intermolecular forces are acting. At any isothermal change of state, the decrease in

volume is directly proportional to the increase in pressure. It has been observed that

in many cases - e.g. in case of natural gases - the volume becomes less than half if

the pressure is doubled. This behavior of a gas in called a real one.

Below the BOYLE temperature (the temperature at which a non-ideal gas

behaves most like an ideal gas), the real gases are more compressible than an ideal

one, because of intermolecular forces of attraction and repulsion. If the pressure is

low (the forces of attraction can be neglected because of the great distance of

molecules) or in case of high temperatures (dominance of the kinetic energy of the

molecules), real gases behave similarly to perfect gases.

In case of real gases, the change in state as well as the behavior of z-factor

as a function of pressure in an isothermal process can be well described by the

equations of state (eq. 1). In the petroleum industry, the basic relation of the

equation of state is generally used because its easy applicability.

2. Describe the behavior of z-factor with different temperatures (fixed

pressure). What are the effects of temperature? Explain this behavior in

intermolecular level. (You can also describe it using the kinetic

molecular theory)

In an isobaric (fixed pressure) zfactor versus temperature relationship

(obtained using the Virtual SOPE PVT Cell and Standing and Katz Generalized

compressibility chart, respectively) for the three different gases, namely, CH 4, C2H6,

and C3H8, we can observe a similar phenomenon to the previous one presented

above, that is, when the temperature is changed by an isobaric process where the

constant pressure is higher than pc but lower than the cricondenbar of the system.

Note that an isobaric increase of temperature in the methane, e.g. at 175

bar, results in a decrease of the compressibility factor after an initial normal

behavior. The trend reverses over a limited temperature range, prior to behaving

normally again. The ratio increases very gradually over the whole tested

temperature range, without any peculiarity.

The explanation to this phenomenon is similar to the one presented above

using the Kinetic Molecular Theory. In case of ideal gases, no intermolecular forces

are acting. At any isobaric change of state, the increase in volume is directly

proportional to the increase in temperature. It has been observed that in many

cases - e.g. in case of natural gases - the volume becomes more than half if the

temperature is doubled. This behavior of a gas in called a real one.

 Below the BOYLE temperature, the temperature at which a non-ideal gas

behaves most like an ideal gas, the real gases are more compressible than an ideal

one, because of intermolecular forces of attraction and repulsion. If the pressure is

low (the forces of attraction can be neglected because of the great distance of

molecules) or in case of high temperatures (dominance of the kinetic energy of the

molecules), real gases behave similarly to perfect gases.

In case of real gases, the change in state as well as the behavior of z-factor

as a function of pressure in an isothermal process can be well described by the

equations of state (eq. 1). In the petroleum industry, the basic relation of the

equation of state is generally used because its easy applicability.

3. In line with the discussion above, discuss the pressure problem and

volume problem at lower and higher pressures with different

temperatures.

The behavior of real gases usually agrees with the predictions of the ideal gas

equation to within 1% at normal temperatures and pressures. At low temperatures

or high pressures, real gases deviate significantly from ideal gas behavior. The

question now is: why is there a significant deviation from the ideal gas?

We can further explain this deviation using the Kinetic Molecular Theory. The

postulates of the Kinetic Molecular Theory of gases ignore both the volume occupied

by the molecules of a gas and all interactions between molecules, whether

attractive or repulsive. In reality, however, all gases have no-zero molecular

volumes. Furthermore, the molecules of real gases interact with one another in

ways that depend on the structure of the molecules and therefore differ for each

gaseous substance. This was what the Dutch physicist Johannes van der Waals
realized in 1873 while searching for a way to link the behavior of liquids and gases.

Consequently, he developed an explanation for these deviations and an equation

that was able to fit the behavior of real gases over a much wider range of pressures.

This equation is known to be the van der Waals Equation.

Van der Waals modified the ideal gas law to describe the behavior of real

gases by explicitly including the effects of molecular size and intermolecular forces.

The explanations for the deviations are:

1. Under high pressures, a gas is compressed so the volume of the

molecules themselves becomes a significant fraction of the total volume

occupied by a gas. (available volume is less than the measure volume).

To account for this, van der Waals suggested that we must subtract a

correction factor, nb. (Corrects for the volume occupied by the molecules

themselves); and
2. At low temperatures (low kinetic energy) the molecules move so slowly

that you must take into account small attractive forces. The attraction to

the neighboring molecules causes the collisions with the walls of the

container to be less energetic, thus lowering the pressure (Pressure

results from the molecular collisions with the walls of the container).
To account for this, van der Waals suggested that we must subtract a

correction factor, n2a/V2.

Thus, he came up with the general equation:

4. Describe the differences between the calculated z-factor from the

laboratory experiment and the z-factor from the SK chart. Explain how

close the estimated value from the laboratory value (accuracy).

Compressibility factors (z) were determined experimentally (using the Virtual

SOPE PVT Cell) for the three different gases, namely, CH 4, C2H6, and C3H8. From the

data gathered, it can be seen that there is a poor comparision between the

computed and experimental compressibility factors. The deviation between them

was maximum in the low pressure zone of 101 bar to 61 bar, and at higher

temperatures. The percentage deviation of experimental values as compared to

computed values of compressibility factor varied from a maximum of 7% to -5%

The experimentally-determined compressibility factor (from the Virtual SOPE

PVT Cell) of the three different gases, namely, CH 4, C2H6, and C3H8, have an

altogether different trend than the estimated compressibility factor (from the

Standing and Katz Generalized compressibility chart). This is evident from the Figure

10.4 (Sheet 10). The deviation between the computed and experimental

compressibility factor is found to be maximum in the pressure range of 101 bar to

61 bar.

5. Discuss the validity of the principle of corresponding states. Can we

recreate the SK chart in the laboratory? Describe the difference

between SK chart and your new generalized compressibility chart.

All gases behave ideally when the pressure approaches zero. The pressure

volume relation for an ideal gas is,

PV = nRT

(eq. 2)
where v is the molar volume, P is (absolute) pressure, T is (absolute) temperature,

and R is the universal gas constant (Universal Gas Constant for Various Units table).

Hence one mole of any ideal gas occupies the same volume at a given pressure and

temperature.

Due to intermolecular forces, real gases do not behave ideally, particularly at

elevated pressures. Eq. (1) is extended to real systems by including a

compressibility factor, Z, as,

PV = znRT

(eq. 1)

The above approach is based on a very important concept, known as the

principle of corresponding states, which states that substances behave similarly

when they are at the same relative proximity to their critical points. This implies

that all substances behave similarly at their critical points, hence, should have

equal critical compressibility factor, Zc.

The real value of critical compressibility factor, however, is not the same for

all compounds (from the Standing and Katz Generalized compressibility chart). The

compressibility chart, however, provides reliable estimates particularly for

supercritical gases and at low pressure conditions. Charts relating the

compressibility factor to the reduced pressure and temperature, similar to Figure

10.4 (Sheet 10), but specific to compounds such as methane (CH 4), ethane (C2H6),

and propane (C3H8), have been produced to improve the accuracy of predicted

values.

As stated in the previous answer, the experimentally-determined

compressibility factor (from the Virtual SOPE PVT Cell) of the three different gases,
namely, CH4, C2H6 and C3H8, have an altogether different trend than the estimated

compressibility factor (from the SK Chart). This is evident from the Figure 10.4

(Sheet 10). The deviation between the computed and experimental compressibility

factor is found to be maximum in the pressure range of 101 bar to 61 bar. The

percentage deviation of experimental values as compared to computed values of

compressibility factor varied from a maximum of 7% to -5%.

It is, therefore, advisable to use experimentally-determined compressibility

factor for the three different gases, namely, CH 4, C2H6 and C3H8, to avoid serious

errors in petroleum engineering calculations, gas transmission and similar problems.

However, this is not to imply that the compressibility factors from the Standing and

Katz Generalized compressibility chart is incorrect but that it is to obtain more

accurate factors to be used in different calculation involving the three different

gases.

Conclusion
BY RAYMOND P. BALDELOVAR, BSPE 2A

It is known that considerable theoretical and experimental work is available

on the compressibility factor (z) of the three different gases methane (CH 4), ethane

(C2H6), and propane (C3H8), however, determining it for ourselves experimentally

using the Virtual SOPE PVT Cell and observing it firsthand gave us the opportunity to

investigate it more thoroughly. By doing so, we defined the validity of the Standing

and Katz Generalized Compressibility Chart (SK Chart) in determining z-factor by

comparing it the experimentally-determined compressibility factor (from the Virtual

SOPE PVT Cell). Based on the data obtained from the experiment, we can conclude

that the SK Chart is valid although small deviations were observed but tolerable.

These deviations do not imply that the compressibility factors from the

Standing and Katz Generalized compressibility chart is incorrect but that it is we can

obtain more accurate factors by experiment to be used in different calculation

involving the three different gases. We can further conclude that it is advisable to

use experimentally-determined compressibility factor for the three different gases,

to avoid serious errors in petroleum engineering calculations, gas transmission and

similar problems.

Furthermore, we were able to discuss thoroughly how different Real gas to

Ideal gas is using the Kinetic Molecular Theory. Likewise, we proved that Real Gas

does not obey The Kinetic Molecular Theory. We also proved the validity of the Law

of Corresponding States, as discussed extensively in the previous part of this paper.

To cope up with the deviation and to account for some correction factors between

the Real gas and Ideal gas, we can use the van der Waals Equation which was also

discussed extensively in the previous part of this paper.