THERMODYNAMICS II

CHAPTER 1
IDEAL GASES AND THEIR MIXTURES
By: Abubeker N.
INTRODUCTION
 An ‘ideal gas’ is defined as a gas having no forces of intermolecular attraction.
 The gases which follow the gas laws at all ranges of pressures and temperatures are
considered as “ideal gases”.
 However, ‘real gases’ follow these laws at low pressures or high temperatures or
both.
 This is because the forces of attraction between molecules tend to be very small at
reduced pressures and elevated temperatures.
 The relation between the independent properties, such as pressure, specific volume
and temperature for a pure substance is known as the ‘equation of state’.

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COMPOSITION OF A GAS MIXTURE:
MASS AND MOLE FRACTIONS
 To determine the properties of a mixture, we need to know the composition of the
mixture as well as the properties of the individual components.
 There are two ways to describe the composition of a mixture:
 by specifying the number of moles of each component, called molar analysis
 by specifying the mass of each component, called gravimetric analysis.

 Consider a gas mixture composed of k components. The mass of the mixture mm is the
sum of the masses of the individual components, and the mole number of the mixture
Nm is the sum of the mole numbers of the individual components.
FIGURE 1–1 The mass of a mixture is equal to the sum of
the masses of its components.

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FIGURE 1–2 The number of moles of a non reacting mixture is
equal to the sum of the number of moles of its components.
CONT…
 That is,

 The ratio of the mass of a component to the mass of the mixture is called the
mass fraction mf, and the ratio of the mole number of a component to the
mole number of the mixture is called the mole fraction y:

 Dividing above Eq. above by mm and by Nm respectively, we can easily show

that the sum of the mass fractions or mole fractions for a mixture is equal to 1

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CONT…
 The mass of a substance can be expressed in terms of the mole number N and molar
mass M of the substance as
 m = NM.

 Then the apparent (or average) molar mass and the gas constant of a mixture
can be expressed as

 The molar mass of a mixture can also be expressed as

 Mass and mole fractions of a mixture are related by

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EXAMPLES
1. Consider a gas mixture that consists of 3 kg of O2, 5 kg of N2, and 12 kg of
CH4, as shown in Fig.. Determine (a) the mass fraction of each component, (b)
the mole fraction of each component, and (c) the average molar mass and gas
constant of the mixture.

FIGURE 1.3
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 P-V-T BEHAVIOR OF GAS MIXTURES:
IDEAL AND REAL GASES
 The P-v-T behavior of an ideal gas is expressed by the simple relation Pv =RT, which
is called the ideal-gas equation of state.
 The P-v-T behavior of real gases is expressed by more complex equations of state or
by Pv = ZRT, where Z is the compressibility factor.
 When two or more ideal gases are mixed, the behavior of a molecule normally is not
influenced by the presence of other similar or dissimilar molecules, and therefore a non
reacting mixture of ideal gases also behaves as an ideal gas.
 Air, for example, is conveniently treated as an ideal gas in the range where nitrogen
and oxygen behave as ideal gases.

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 CONT…
 The prediction of the P-v-T behavior of gas mixtures is usually
based on two models:
 Dalton’s law of additive pressures and
 Amagat’s law of additive volumes. FIGURE 1-4 Dalton’s law of
additive pressures for a
 Dalton’s law of additive pressures: The pressure of a gas mixture mixture of two ideal gases.
is equal to the sum of the pressures each gas would exert if it
existed alone at the mixture temperature and volume .
 Amagat’s law of additive volumes: The volume of a gas mixture
is equal to the sum of the volumes each gas would occupy if it FIGURE 1–5 Amagat’s
existed alone at the mixture temperature and pressure law of additive volumes for
a mixture of two ideal
gases. 8
 CONT…
 Dalton’s and Amagat’s laws hold exactly for ideal-gas mixtures,
but only approximately for real-gas mixtures.
 This is due to intermolecular forces that may be significant for
real gases at high densities.
FIGURE 1–6 The volume a
 Dalton’s and Amagat’s laws can be expressed as follows:
component would occupy if it
existed alone at the mixture T
and P is called the component
volume (for ideal gases, it is
equal to the partial volume
 In these relations, Pi is called the component pressure and Vi is yiVm).
called the component volume.
 The ratio Pi /Pm is called the pressure fraction and the ratio
Vi /Vm is called the volume fraction of component i. 9
IDEAL-GAS MIXTURES
 For ideal gases, Pi and Vi can be related to yi by using the ideal-gas relation for both the components
and the gas mixture:

 Therefore, strictly valid for ideal-gas mixtures since it is derived by

assuming ideal-gas behavior for the gas mixture and each of its
components.

 The quantity yiPm is called the partial pressure (identical to the component pressure for ideal gases),
and the quantity yiVm is called the partial volume (identical to the component volume for ideal
gases).
 Note that for an ideal-gas mixture, the mole fraction, the pressure fraction, and the
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volume fraction of a component are identical .
REAL-GAS MIXTURES
 Dalton’s law of additive pressures and Amagat’s law of additive
volumes can also be used for real gases, often with reasonable accuracy.

 The compressibility factor of the mixture Zm can be expressed in terms

of the compressibility factors of the individual gases Zi
 We obtain,

 whereZi is determined either at Tm and Vm (Dalton’s law) or at Tm and FIGURE 1–7 One way of
Pm (Amagat’s law) for each individual gas. predicting the P-v-T behavior
of a real-gas mixture is to use
 The compressibility-factor approach, in general, gives more accurate compressibility factor.
results when the Zi’s are evaluated by using Amagat’s law instead of
Dalton’s law. 11
CONT…

Fig. Compressibility factors, Z for oxygen Fig. Compressibility factors, Z for Carbon dioxide
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 CONT…
 Dalton’s law is more appropriate for gas mixtures at low
pressures.
 Amagat’s law is more appropriate at high pressures.

 When we use compressibility factors for the components of a gas

mixture, we account for
 the influence of like molecules on each other;
 the influence of dissimilar molecules remains largely unaccounted for.
 Another approach for predicting the P-v-T behavior of a gas FIGURE 1–8 Another way of
predicting the P-v-T behavior of a
mixture is to treat the gas mixture as a pseudopure substance. real-gas mixture is to treat it as a
pseudopure substance with critical
properties Pcr and Tcr.
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 CONT…
 The method is proposed by W. B. Kay in 1936 and called Kay’s rule, involves the
use of a pseudocritical pressure P’cr,m and pseudocritical temperature T’cr,m for the
mixture, defined in terms of the critical pressures and temperatures of the mixture
components as

• The compressibility factor of the mixture Zm is then easily determined by

using these pseudocritical properties.

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CONT…

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Figure 1.9 Generalized compressibility chart, pR ≤10.0.

EXAMPLES
1. A rigid tank contains 2 kmol of N2 and 6 kmol of CO2 gases at 300 K and 15
MPa. Estimate the volume of the tank on the basis of (a) the ideal-gas
equation of state, (b) Kay’s rule, and (c) compressibility factors and Amagat’s
law

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PROPERTIES OF GAS MIXTURES:
IDEAL AND REAL GASES
 The total internal energy, enthalpy, and entropy of a gas mixture can be
expressed, respectively, as

 By following a similar logic, the changes in internal energy, enthalpy, and

entropy of a gas mixture during a process can be expressed, respectively, as

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 CONT…
 The internal energy, enthalpy, and entropy of a mixture per unit mass or per unit
mole of the mixture can be determined by dividing the equations above by the mass
or the mole number of the mixture (mm or Nm).
 We obtain

 Similarly, the specific heats of a gas mixture can be expressed as

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Notice that properties per unit mass involve mass fractions (mfi) and properties
per unit mole involve mole fractions (yi).
 CONT…
Ideal-Gas Mixtures
 the h, u, cv, and cp of an ideal gas depend on temperature only and are independent of

the pressure or the volume of the ideal-gas mixture.

 The partial pressure of a component in an ideal-gas mixture is simply Pi = yiPm, where

Pm is the mixture pressure.

 The entropy change of individual gases in an ideal-gas mixture during a process can be
determined from

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where Pi,2 = yi,2Pm,2 and Pi,1 = yi,1Pm,1.
EXAMPLES
1. An insulated rigid tank is divided into two compartments by a partition, as shown
in Fig.. One compartment contains 7 kg of oxygen gas at 40°C and 100 kPa, and
the other compartment contains 4 kg of nitrogen gas at 20°C and 150 kPa. Now
the partition is removed, and the two gases are allowed to mix. Determine (a) the
mixture temperature and (b) the mixture pressure after equilibrium has been
established.

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 CONT…
Real-Gas Mixtures
 When the components of a gas mixture do not behave as ideal gases, the analysis
becomes more complex because the properties of real (non ideal) gases such as u, h, cv ,
and cp depend on the pressure (or specific volume) as well as on the temperature.
 When real-gas mixtures are involved, it may be necessary to account for the effect of
non ideal behavior on the mixture properties such as enthalpy and entropy.
 Consider the following T ds relation for a gas mixture:

 It can also be expressed as

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which yields
EXAMPLES
1. Air is a mixture of N2, O2, and small amounts of other gases, and it can be
approximated as 79 percent N2 and 21 percent O2 on mole basis. During a
steady-flow process, air is cooled from 220 to 160 K at a constant pressure of
10 Mpa. Determine the heat transfer during this process per kmol of air, using
(a) the ideal-gas approximation, (b) Kay’s rule, and (c) Amagat’s law.

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 Questions
What you understand?
and
Suggestions?

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