Assist. Prof. Dr.

Hamed Al-Falalahi Engineering Thermodynamics II

Lecture Ten
(Real Gases/Compressibility)

10.1 The Objective

10.2 Critical State and Critical Constant
10.3 Reduced Variables
10.4 Compressibility
10.5 Compressibility Charts
10.6 Calculating the Compressibility Factor Using the Pitzer Factors Z O and Z1
10.7 Real Gas Mixtures

10.1 The Objective

The Objectives in Studying this Lecture are:
• Explain what the law of corresponding states means.
• Define the critical state.
• Calculate the reduced temperature, reduced pressure, reduced ideal volume, and use any
two of these three parameters to obtain the compressibility factor, z, from the
compressibility charts.
• Use compressibility factors and appropriate charts to predict the p-V-T behavior of a gas,
or, given the required data, find a compressibility factor.
• Calculate the compressibility factor z using the Pitzer acentric factor.
• Use Kay's method of pseudocritical values to calculate the pseudo-reduced values, and
predict p, V, T, and n via the compressibility factor.

The lecture layout

In this lecture we explain how the critical properties of gases can be employed to facilitate the
calculation of a compressibility factor, a factor that transforms the ideal gas law into a
relation that can be used to solve for p, V, n, and T for single-and multi-component real gases.

10.2 Critical State and Critical Constant

The critical state for the gas-liquid transition is the set of physical conditions at which the
density and other properties of the liquid and vapor become identical.
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10.3 Reduced Variables

For H2 and He only;

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These are corrected, or normalized, conditions of temperature, pressure, or volume, normalized

(divided) by their respective critical conditions.
In theory, the law of corresponding states indicates that any compound should have the same
reduced volume at the same reduced temperature and reduced pressure so that a universal gas law
might be;
…………..……………………... (1)

Unfortunately, Equation (1) does not make accurate predictions universally. It can be check this
conclusion by selecting a compound such as water, applying Equa tion (1) at some low
temperature and high pressure to calculate V, and comparing the results with the value obtained
for V for the corresponding conditions from the steam tables that are in the folder in the back of
the Textbook, Let's see what is the difference between the two results.

10.4 Compressibility
How can the ideas presented above be used? One common way is to modify the ideal gas law
by inserting an adjustable coefficient z, the compressibility factor, a factor that compensates for
the nonideality of the gas, and can be looked at as a measure of nonideality. Thus, the ideal gas
law is turned into a real gas law, a generalized equation of state.

…………..……………………... (2)

…………..……………………... (3)

Figure.1 (a) Compressibility factor at 100°C for several gases as a function of pressure;
(b) compressibility factor for several gases as a function of reduced temperature and
reduce pressure.

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You will find graphs or tables of z to be convenient sources for values of z. If the compressibility
factor is plotted for a given temperature against the pressure for different gases, figures like Figure
1-a result. However, if the compressibility is plotted against the reduced pressure as a function of
the reduced temperature, then for most gases the compressibility values at the same reduced
temperature and reduced pressure fall at about the same point, as illustrated in Fig. 1-b.

10.5 Compressibility Charts

Because of the generalization feature shown in Figure 1-b., you can use what is called the
generalized compressibility factor z for your gas calculations. Figures 2-a and 2-b shows two
examples of the generalized compressibility factor charts, or z-factor charts, prepared by
Nelson and Obert.* These charts are based on data for 30 gases. Figure 2-a represents z for 26
gases (excluding H2 , He, NH3, and H2O) with a maximum deviation of 1%, and H2 and H2O
within a deviation of 1.5%. Figure 2-b is for nine gases and errors can be as high as 5%. Note
that the vertical axis is not z but zTr in Figure 2-b. To use the charts for H2 and He (only),
make corrections to the actual constants to get pseudocritical constants.

Tr
Vrc

Figure.2- a Generalized compressibility chart for lower pressures showing z as a function of pr Tr,
and

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Vri

Tr

Figure.2-b Generalized compressibility chart for higher values of pr

you can use Figure 2-a and Figure 2-b for these two gases using the pseudo-critical constants
as replacements for their true values. You will find these two charts and additional charts for
other ranges of pr and Tr in this book.
Instead of the reduced specific volume, a third parameter shown on the charts is the
dimensionless ideal reduced volume defined by

where is the ideal critical volume, and is calculated from

…………..……………………... (4)

Both and are easy to calculate since Tc and Pc are presumed known
or can be estimated for a compound.

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EXAMPLE -10.1 Use of the Compressibility Factor to Calculate a Specific Volume

In spreading liquid ammonia fertilizer, the charges for the amount of NH3 used are based on
the time involved plus the pounds of NH3 injected into the soil. After the liquid has been
spread, there is still some ammonia left in the source tank (volume = 120 ft3), but in the form
of a gas. Suppose that your weight tally, which is obtained by difference, shows a net weight
of 125 Ib of NH3 left in the tank at 292 psig. Because the tank is sitting in the sun, the
temperature in the tank is 125°F.
Your boss complains that his calculations show that the specific volume of the NH3 gas is
1.20 ft3/lb, and hence that there are only 100 Ib of NH3 in the tank. Could he be correct? See
Figure E-1

Figure.E-1

Solution:

Basis: 1 Ib of NH 3
You can apply pV = znRT to calculate n and check the amount of NH3 in the tank.
Apparently, your boss used the ideal gas law in getting his figure of 1.20 ft3/lb of NH3
gas:

However, he should have included the compressibility f a c t o r in the gas law because
NH3 does not behave as an ideal gas under the observed conditions of temperature and
pressure. Let us again compute the mass of gas in the tank, this time using

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You know all of the values of the variables in the equation except z, the additional
information needed (taken from Appendix D or the CD) is

Then since z is a function of Tr and pr

From the Nelson and Obert chart, Figure 1 4 . 4 , you can read z ≈ 0.855. (The value
maybe somewhat in error because ammonia was not one of the gases included in the
preparation o f the figure.) Now V can be calculated f r o m the ratio of
P Vrea1 = zreal nRT to P Videa I = Zideal nRT, the net result of which is
On the basis of 1 lb NH3

On the basis of 120 ft3 in the tank

Certainly, 1 1 7 Ib i s a more realistic figure than 100 Ib, and it is easily possible to be in
error by 8 lb if the residual weight of NH3 in the tank is determined b y difference. As a
matter of interest, as an alternative t o making the calculations, you could look up the
specific volume of NH3 at the conditions i n the tank in a hand-
Book. You would find that V = 0.973 ft3/1b, and hence the compressibility factor
calculation yielded a specific volume with an error of about 5.9% versus an error of
23% using the ideal gas law.

EXAMPLE -10-2 Use of the Compressibility Factor to Calculate a Pressure

Liquid oxygen is used in the steel industry, in the chemical industry, in hospitals, as a rocket
fuel oxidant, and for wastewater treatment as well as many other applications. A hospital
tank of 0.0284 m3 volume is filled with 3.500 kg of liquid O2 that will vaporize at -25°C. Will
the pressure in the tank exceed the safety limit of the tank specified as 104 kPa?

Solution:

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10.6 Calculating the Compressibility Factor Using the Pitzer Factors Z O and Z1
Several methods have appeared in the literature and in computer codes to cal culate z via an
equation in order to obtain more accurate values of z than can be obtained from charts. Equation (5)
employs the Pitzer acentric factor, ω. Table (1) is an abbreviated table of the acentric factors from
Pitzer
…………..……………………... (5)

The acentric factor ω indicates the degree of acentricity or nonsphericity of a molecule. For
helium and argon, ω is equal to zero. For higher molecular weight hydrocarbons and for molecules
with increased polarity, the value of ω increases. Table (2) lists the value of z obtained for ethylene
(C2 H4 ) at two conditions by three different methods: (a) by Equation (5), (b) from the gener alized
compressibility charts, and (c) from the ideal gas law. The three values are compared with the
experimental value (from Perry's Handbook, 7th edition).
TABLE.1 Values of the Pitzer* Acentric Factor

where z° and z1 are listed in tables in Appendix C as a function of Tr and p r, and ω is unique for each
compound.
TABLE.1 A Comparison of Values of the Compressibility Factor z for Ethylene

Method of analysis

(5)

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10.7 Real Gas Mixtures

Then,

……………...(6)

……………...(7)

………………………...(8)

………………………...(9)

………..…………………...(10)

………….………………...(11)
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EXAMPLE -10.3 Calculation of p-V-T Properties for a Real Gas Mixture

A gaseous mixture has the following composition (in mole percent):
Methane, CH4 20
Ethylene, C2H4 30
Nitrogen, N2 50
at 90 atm pressure and 100°C. Compare the volume per mole as computed by the methods
of: (a) the ideal gas law and (b) the pseudoreduced technique (Kay's method).

Solution:

-2b

(5)

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In instances in which the temperature or pressure of a gas mixture is unknown, to avoid a trial-
and-error solution using the generalized compressibility charts, you can compute the
pseudocritical ideal volume and a pseudo reduced ideal volume V r I , thus;

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