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Thermody
Thermody
heat, work and properties of system which are in equilibrium. It describes state
proof. Like
I-1)Thermodynamic systems:
space.
boundary of the system. The boundary may be fixed or it may move, as and when
2020/2021 Page 1
Master: gas engineering/Compressible fluids thermodynamics (Amar
Thelidji university /Laghouat). By:Abdelmouiz .Ahmed
or imaginary.
I-1-2) Open System : An open system is one in which matter flows into or out
of the system.
I-1-3) Isolated System:
An isolated system is that system which exchanges neither energy nor matter
a) Homogeneous System :
b) Heterogeneous System :
system.
I-4) Pure substance:
A pure substance is one that has a homogeneous and invariable chemical
composition even though there is a change of phase. In other words, it is a
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Master: gas engineering/Compressible fluids thermodynamics (Amar
Thelidji university /Laghouat). By:Abdelmouiz .Ahmed
state, but not upon how the state is reached. There are two sorts of property :
system.
Examples : Temperature and pressure.
2. Extensive properties: These properties depend on the mass of the system.
system of mass m is V, then the specific volume of matter within the system is
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Master: gas engineering/Compressible fluids thermodynamics (Amar
Thelidji university /Laghouat). By:Abdelmouiz .Ahmed
3. All collisions of molecules are perfectly elastic, that is, there is no loss of
An ideal gas obeys the law PV = RT. In reality there is no ideal or perfect gas.
At a very low pressure and at a very high temperature, real gases like hydrogen,
oxygen, nitrogen, helium etc. behave nearly the same way as perfect gases.
temperature is constant.
Charles led to the discovery that the volume of an ideal gas is directly
maintained constant.
c) Avogadro's Law : Avogadro's law states that, under the same conditions
of temperature and pressure, equal volumes of all ideal gases contain the
same number of molecules. There are 6.023 X 1023 molecules per mole of
ideal gas .
To derive the equation of state for a perfect gas let us consider a unit mass of a
perfect gas to change its state in the following two successive processes.
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Master: gas engineering/Compressible fluids thermodynamics (Amar
Thelidji university /Laghouat). By:Abdelmouiz .Ahmed
The magnitude of this constant depends upon the particular gas and it is
denoted by R, where R is called the ideal gas constant.
II-2) Density of an ideal gas:
Since density is defined as the mass of gas per unit volume, an equation of state
can be used to calculate the densities of a gas at various temperatures and
pressures. The equation for the density of an ideal gas is :
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Master: gas engineering/Compressible fluids thermodynamics (Amar
Thelidji university /Laghouat). By:Abdelmouiz .Ahmed
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Master: gas engineering/Compressible fluids thermodynamics (Amar
Thelidji university /Laghouat). By:Abdelmouiz .Ahmed
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Master: gas engineering/Compressible fluids thermodynamics (Amar
Thelidji university /Laghouat). By:Abdelmouiz .Ahmed
Where the correction factor, Z, is known as the compressibility factor and the
equation is known as the compressibility equation of state. Compressibility
factor is also known as gas deviation factor, super-compressibility, or z-factor.
Sometimes the reciprocal of compressibility factor is called super-
compressibility.
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Master: gas engineering/Compressible fluids thermodynamics (Amar
Thelidji university /Laghouat). By:Abdelmouiz .Ahmed
The Law of Corresponding States says that all pure gases have the same z-
factor at the same values of reduced pressure and reduced temperature.
II-6) Compressibility Equation of State for Gas Mixtures: The Law of
Corresponding States has been extended to cover mixtures of gases which are
closely related. As was brought out before, obtaining the critical point for multi-
component mixtures is somewhat difficult; therefore, pseudo-critical
temperature and pseudo-critical pressure have been invented. These quantities
are defined as (Kay's mixture rules) :
Where T'Pc and P'Pc are used to calculate Tpr, and PPr for acid gases. The
pseudo-critical temperature adjustment factor, є, is obtained from Figure. The
symbol YH2S represents the mole fraction of hydrogen sulfide in the gas.
2020/2021 Page 9
Master: gas engineering/Compressible fluids thermodynamics (Amar
Thelidji university /Laghouat). By:Abdelmouiz .Ahmed
This equation differs from the ideal gas equation by the addition of the term (a
/VM2) to pressure and the subtraction of the constant b from molar volume. The
term (a /VM2) represents an attempt to correct pressure for the forces of
attraction between the molecules. The actual pressure exerted on the walls of
the vessel by real gas is less, by the amount (a /VM2), than the pressure exerted
by an ideal gas. The constant b is regarded as the correction to the molar volume
due to the volume occupied by the molecules. Constants a and b are
characteristic of the particular gas, whereas R is the universal gas constant. The
van der Waals equation is an improvement over the ideal gas equation. However,
it has limited use since it is accurate only at low pressures. Equations like the
van der Waals equation often are called two constant equations of state,
although there are actually three constants: a, b, and R. These equations also are
called cubic equations of state. The Vander Waals equation in cubic form is:
The addition of the fourth constant, c, enables better agreement with data.
However, mathematical manipulations required in thermodynamic calculations are
more diffcult. So Berthelot (1899) removed the constant c, resulting in :
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Master: gas engineering/Compressible fluids thermodynamics (Amar
Thelidji university /Laghouat). By:Abdelmouiz .Ahmed
The constants a, b, and c in the equations above have different values for
different substances. Also, note that the constants have different values for
each of the equations.
III-3) Equations of State at the Critical Point:
The critical temperature isotherm on a pressure-volume diagram for a pure
substance has a horizontal point of inflection as it passes through the critical
pressure. For a pure substance at the critical point
Where B, C, ... are not constants but are functions of temperature and are called
the second, third, ... virial coefficients.
Each of the equations of state previously presented can be expressed in virial
form. The van der Waals equation can be approximated as:
Thus the second virial coefficient, according to van der Waals, is:
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Master: gas engineering/Compressible fluids thermodynamics (Amar
Thelidji university /Laghouat). By:Abdelmouiz .Ahmed
Further, Beattie and Bridgeman postulated that "when two slowly moving
molecules encounter one another, there is a tendency for them to move under
the influence of each other for an appreciable length of time due to the
intermolecular forces between them." In effect, molecules moving together
decreases the number of aggregates in the system.
This aggregation of molecules is more likely to occur at low kinetic energies and
at high densities of molecules. Thus, the value of R is affected by the
reciprocals of temperature and molar volume. Beattie and Bridgeman proposed
replacement of R by
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Master: gas engineering/Compressible fluids thermodynamics (Amar
Thelidji university /Laghouat). By:Abdelmouiz .Ahmed
The constants are the same as for the Beattie-Bridgeman equation and the same
numerical values may be used. The equation is less accurate than the Beattie-
Bridgeman equation. The constants for these equations have been derived
experimentally from data for pure gases. However, the equation can be used for
gas mixtures by combining the constants using the following mixture rules.
The advantage over the Clausius equation is that a third empirical constant is
not included. Soave suggested that a/T1/2 be replaced with a temperature
dependent term, aT.
The fact that aT varies with temperature is not inconvenient since most
applications of this equation are at constant temperature. The equation for aT is:
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Master: gas engineering/Compressible fluids thermodynamics (Amar
Thelidji university /Laghouat). By:Abdelmouiz .Ahmed
&-Mixing Rules :
The following mixture rules are recommended for use with both the Soave-
Redlich-Kwong and the Peng-Robinson equations of state.
The terms δij are binary interaction coefficients, which are assumed to be
independent of pressure and temperature. Values of !he binary interaction
coefficients must be obtained by fitting the equation of state to gas-liquid
equilibria data for each binary mixture. 19 The binary interaction coefficients
have different values for each binary pair and also take on different values for
each equation of state.
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Master: gas engineering/Compressible fluids thermodynamics (Amar
Thelidji university /Laghouat). By:Abdelmouiz .Ahmed
n represents the total number of moles in the mixture, and nL represents the
total number of moles in the liquid, ng represents the total number of moles in
the gas; Zj represents the mole fraction of the jth component in the total
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Master: gas engineering/Compressible fluids thermodynamics (Amar
Thelidji university /Laghouat). By:Abdelmouiz .Ahmed
mixture including both liquid and gas phases, Xj represents the mole fraction of
the jth component in the liquid, Yj represents the mole fraction of the jth
component in the gas;
Zjn represents the moles of the jth component in the total mixture,
XjnL represents the moles of the jth component in the liquid, and
Yjng represents the moles of the jth component in the gas.
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Master: gas engineering/Compressible fluids thermodynamics (Amar
Thelidji university /Laghouat). By:Abdelmouiz .Ahmed
Series of exercises
Exercise 01: Calculate the mass of methane gas contained at 1000 psia and 68°F
in a cylinder with volume of 3.20 cuft. Assume that methane is an ideal gas.
Solution :
Exercise03:
Calculate the partial pressure exerted by methane in the following gas when the
gas is at a pressure of 750 psia. Assume that the gas is a mixture of ideal gases.
Solution:
Exercise 04: Dry air is a gas mixture consisting essentially of nitrogen, oxygen,
and small amounts of other gases. Compute the apparent molecular weight of air
given its approximate composition.
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Master: gas engineering/Compressible fluids thermodynamics (Amar
Thelidji university /Laghouat). By:Abdelmouiz .Ahmed
Solution :
Exercise 05: Calculate the specific gravity of a gas of the following composition.
Solution:
Exercise 06: Calculate the mass of methane gas contained at 1,000 psia and
68°F in a cylinder with volume of 3.20 cu ft. Do not assume that methane is an
ideal gas.
Solution:
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Master: gas engineering/Compressible fluids thermodynamics (Amar
Thelidji university /Laghouat). By:Abdelmouiz .Ahmed
Exercise 07: Determine the specific volume of ethane at 918 psia and 117'F.
Use Figure below to determine the compressibility factor.(TC=549.9 °R,
PC=706.5°C).
Solution:
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Master: gas engineering/Compressible fluids thermodynamics (Amar
Thelidji university /Laghouat). By:Abdelmouiz .Ahmed
Solution:
Exercise 09:
Determine a value of z-factor for the dry gas given below for use at 3810 psia
and 194°F.
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Master: gas engineering/Compressible fluids thermodynamics (Amar
Thelidji university /Laghouat). By:Abdelmouiz .Ahmed
Solution:
Exercise 10: Calculate the molar volume of the gas given below at 100°F and
250 psia. Use the Beattie modification of the Beattie-Bridgeman equation.
Solution:
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Master: gas engineering/Compressible fluids thermodynamics (Amar
Thelidji university /Laghouat). By:Abdelmouiz .Ahmed
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Master: gas engineering/Compressible fluids thermodynamics (Amar
Thelidji university /Laghouat). By:Abdelmouiz .Ahmed
Exercise 11: A laboratory cell with volume of 0.008829 cuft (250.0cc) contains
0.007357 lb mole (79.28 g) of gas. The composition of the gas is given below.
The temperature is to be raised to 709.6°R (250°F). Use the SRK equation of
state to calculate the pressure to be expected.
Use values of 0.02 for binary interaction coefficient between methane and n-
butane, 0.01 between ethane and n-butane, and 0.0 between methane and ethane.
Solution:
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Master: gas engineering/Compressible fluids thermodynamics (Amar
Thelidji university /Laghouat). By:Abdelmouiz .Ahmed
Exercise 12: Calculate the compositions and quantities of the gas and liquid
when 1.0 lb mole of the following mixture is brought to equilibrium at 150°F and
200 psia.
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Master: gas engineering/Compressible fluids thermodynamics (Amar
Thelidji university /Laghouat). By:Abdelmouiz .Ahmed
The summation equals one for a value of n L = 0.547. Thus, there are 0.547
moles of liquid for every mole of total mixture, and the compositions of the
liquid and gas phases are:
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Master: gas engineering/Compressible fluids thermodynamics (Amar
Thelidji university /Laghouat). By:Abdelmouiz .Ahmed
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Master: gas engineering/Compressible fluids thermodynamics (Amar
Thelidji university /Laghouat). By:Abdelmouiz .Ahmed
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Master: gas engineering/Compressible fluids thermodynamics (Amar
Thelidji university /Laghouat). By:Abdelmouiz .Ahmed
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