Chapter One

Engineering Thermodynamics II

Ideal Gas And Their Mixtures

2nd year Regular Degree Program Department

of Mechanical Engineering
Aksum university

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 Chapter Outline
 Composition of a Gas Mixture

 Mass and Mole Fractions

 P-v-T Behavior of Gas Mixture

 Ideal and Real Gases

 Properties of Gas Mixtures

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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:

either by specifying the number of moles of each component,
called molar analysis (volumetric analysis), or by specifying the
mass of each component, called gravimetric analysis.

 The number of moles, and the molecular weight of a component i

𝒎𝒊
are related by 𝒏𝒊 = … … … … … … … … … … … … … … … … 𝟏. 𝟏
𝑴𝒊
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 Cont’d
 The total mass of the mixture, m, is the sum of the masses of its

components:

𝑗
𝑚 = 𝑚1 + 𝑚2 +𝑚3 +…+𝑚𝑗 = σ𝑖=1 𝑚𝑖 … … … … … … … … … … … .1.2

 The relative amounts of the components present in the mixture

can be specified in terms of mass fractions.

 The mass fraction 𝑚𝑓𝑖 of component i is defined as

𝑚𝑖
𝑚𝑓𝑖 = … … … … … … … … … … … … … … … … … … … … … … … .1.3
𝑚

 A listing of the mass fractions of the components of a mixture is

sometimes referred to as a gravimetric analysis. 4

 Cont’d
 The sum of the mass fractions of all the components in a mixture
𝑗
is equal to unity. 1 = σ𝑖=1 𝑚𝑓𝑖 … … … … … … … … … . . 1.4

 The total number of moles in a mixture, n, is the sum of the

number of moles of each of its components.

𝑛 = 𝑛1 + 𝑛2 +𝑛3 +…+𝑛𝑗 =

σ𝑗𝑖=1 𝑛𝑖 … … … … … ………………………………………1.5

 The relative amounts of the components present in the mixture

also can be described in terms of mole fractions.

 The mole fraction 𝑦𝑖 of component i is defined as

𝑛𝑖 5
𝑦𝑖 = … … … … … … … … … … … . . 1.6
 Cont’d
 A listing of the mole fractions of the components of a mixture
may be called a molar analysis, is also called a volumetric
analysis.

 The sum of the mole fractions of all the components in a

mixture is equal to unity. 1=

σ𝑗𝑖=1 𝑦𝑖 … … … … … … … … … … … … … … … … … … … … … 1.7

 The apparent (or average) molecular weight of the mixture,

M, is defined as the ratio of the total mass of the mixture, m, to
the total number of moles of mixture,
…………………………………… … … … … … … … … … … … … . . 1.8
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 Cont’d
 The gas constant R is different for each gas and is determined from
𝑅𝑈
R= ,…………………………………………………………..1.9
𝑀

 Where Ru is the universal gas constant and M is the molar mass

(also called molecular weight) of the gas. The constant Ru is the
same for all substances, and its value is 8.314 kJ /Kmol K.

 The average gas constant of a mixture can be expressed a

𝑅𝑈
𝑅𝑎𝑣𝑟 = ,…………………………………………………..2.0
𝑀𝑎𝑣𝑟

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 Example 1
1. Molar analysis of air indicates that it is composed primarily of
nitrogen (78%) and oxygen (22%).

Determine

( a ) the mole fractions

(b) the gravimetric analysis

( c ) its molecular weight

( d )its gas constant.

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 P-v-T Behavior of Gas Mixture:
Ideal and Real Gas
 An ideal gas is defined as a gas whose molecules are spaced far
apart so that the behavior of a molecule is not influenced by the
presence of other molecules—a situation encountered at low
densities.

 is defined as a gas having no forces of intermolecular attraction.

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 Conti..
 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 an real gas is expressed by more complex

equations of state or by relation 𝑷𝒗 = 𝒁𝑹𝑻, where Z is the

compressibility factor.

 The prediction of the P-v-T behavior of gas mixtures is usually

based on two models:

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 Cont’d
a. Dalton’s law of additive pressures : The pressure of a gas
mixture is equal to the sum of the pressures each gas would
exert if it existed alone at the mixture temperature and volume.

b. 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 existed alone at the mixture temperature and
pressure.

 Dalton’s and Amagat’s laws hold exactly for ideal-gas

mixtures, but only approximately for real-gas mixtures.

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 Cont’d
 This is due to intermolecular forces that may be significant for
real gases at high densities.

 Dalton’s and Amagat’s laws can be expressed as follows:

Dalton’s law: 𝑃𝑚 = σ𝑘𝑖=𝑖 𝑃𝑖 (𝑇𝑚 , 𝑣𝑚 )

 𝑘 ቋ
Amagat’s laws: 𝑣𝑚 = σ𝑖=𝑖 𝑣𝑖 (𝑇𝑚 , 𝑃𝑚 )

 𝑃𝑖 is called the component pressure and 𝑣𝑖 is 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.

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 Cont’d
 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:

𝑃𝑖 𝑇𝑚 , 𝑣𝑚 𝑛𝑖 𝑅𝑢 𝑇𝑚 Τ𝑣𝑚 𝑛𝑖
= = = 𝑦𝑖
𝑃𝑚 𝑛𝑚 𝑅𝑢 𝑇𝑚 Τ𝑣𝑚 𝑛𝑚

𝑣𝑖 𝑇𝑚 , 𝑃𝑚 𝑛𝑖 𝑅𝑢 𝑇𝑚 Τ𝑃𝑚 𝑛𝑖
= = = 𝑦𝑖
𝑣𝑚 𝑛𝑚 𝑅𝑢 𝑇𝑚 Τ𝑃𝑚 𝑛𝑚

𝑃𝑖 𝑣𝑖
∴ = =𝑦𝑖
𝑃𝑚 𝑣𝑚

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 Cont’d

 The quantity 𝒚𝒊 𝑷𝒊 is called the partial pressure (identical to the

component pressure for ideal gases), and

 the quantity 𝒚𝒊 𝒗𝒊 is called the partial volume (identical to the

component volume for ideal gases).

 For an ideal-gas mixture, the mole fraction, the pressure

fraction, and the volume fraction of a component are identical.

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 Cont’d
 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.

 One way of doing that is to use more exact equations of state

(van der Waals, Beattie–Bridgeman, Benedict–Webb–Rubin,
etc.) instead of the ideal-gas equation of state.

 One way of predicting the P-v-T behavior of a real-gas mixture

is to use compressibility factor.

𝑷𝒗 = 𝒁𝑵𝑹𝒖 𝑻
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 Cont’d
 The compressibility factor of the mixture 𝒁𝒎 can be expressed
in terms of the compressibility factors of the individual gases
𝑍𝑖

 𝑍𝑚 = σ𝑘𝑖=1 𝑦𝑖 𝑍𝑖

 where 𝑍𝑖 is determined either at 𝑇𝑚 and 𝑣𝑚 (Dalton’s law) or at

𝑇𝑚 and 𝑃𝑚 (Amagat’s law) for each individual gas.

 Another approach for predicting the P-v-T behavior of a gas

mixture is to treat the gas mixture as a pseudopure substance.

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 Cont’d
 One such method, 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

𝑃′ 𝑐𝑟,𝑚 =σ𝑘𝑖=1 𝑦𝑖 𝑃𝑐𝑟,𝑖 and 𝑇 ′ 𝑐𝑟,𝑚 =σ𝑘𝑖=1 𝑦𝑖 𝑇𝑐𝑟,𝑖

 The compressibility factor of the mixture 𝑍𝑚 is then easily

determined by using these pseudocritical properties.

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 Example-2
P-v-T Behavior of Gas Mixtures

1. A rigid tank contains 2 kg of N, and 4 kg of CO, at a temperature

of 25 oC and 2 MPa. Find the partial pressures of the two gases and
the gas constant of the mixture.

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 Properties of Gas Mixture
 The extensive properties of a mixture such as H , U, and S are
determined by simply adding the properties of the components.

 The total internal energy, enthalpy, and entropy of a gas mixture can
be expressed, respectively, as
k k k
U m  U i   mi ui   N i ui (kJ)
i 1 i 1 i 1
k k k
H m   H i   mi hi   N i hi (kJ)
i 1 i 1 i 1
k k k
Sm   Si   mi si   N i si (kJ/K)
i 1 i 1 i 1
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 Cont’d
 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
k k
um   mf i ui and um   yi ui (kJ / kg or kJ / kmol)
i 1 i 1
k k
hm   mf i hi and hm   yi hi (kJ / kg or kJ / kmol)
i 1 i 1
k k
sm   mf i si and sm   yi si (kJ / kg  K or kJ / kmol  K)
i 1 i 1

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

k k
Cv , m   mf i Cv , i and Cv , m   yi Cv , i
i 1 i 1
k k
C p , m   mf i C p , i and C p , m   yi C p , i
i 1 i 1
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 Cont’d
 Ratio of specific heats k is given as
C p ,m C p ,m
km  
Cv ,m Cv ,m
 Under the ideal-gas approximation, the properties of a gas are
not influenced by the presence of other gases, and each gas
component in the mixture behaves as if it exists alone at the
mixture temperature 𝑇𝑚 and mixture volume 𝑣𝑚 .
 This principle is known as the Gibbs–Dalton law, which is an
extension of Dalton’s law of additive pressures.
 That is, the pressure of each component is the partial
pressure.
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 Cont’d
 For constant specific heats, the entropy change of any
component is

 The entropy change of the mixture per mass of mixture is

 The entropy change of the mixture per mole of mixture is

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 Cont’d
 In these last two equations, recall that

Pi , 1  yi , 1 Pm, 1
Pi , 2  yi , 2 Pm, 2

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 Example-3
1. A mixture is composed of 2 mol CO, and 4 mol N,. It is compressed
adiabatically in a cylinder from 100 kPa and 20°C to 2 MPa.
Assuming constant specific heats, calculate
( a ) the final temperature
( b )the work required, and
( c ) the change in entropy.

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