Thermodynamics II (ME3320/5320)

Chapter 14

Dr. Zifeng Yang

Department of Mechanical and Materials Engineering
Wright State University
Email: [Link]@[Link]
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 Chapter 14. Gas Mixtures

Objectives:
• Develop rules for determining nonreacting gas mixture
properties from knowledge of mixture composition and the
properties of the individual components.
• Define the quantities used to describe the composition of a
mixture, such as mass fraction, mole fraction, and volume
fraction.
• Apply the rules for determining mixture properties to ideal-
gas mixtures and real-gas mixtures.
• Predict the P-v-T behavior of gas mixtures based on
Dalton’s law of additive pressures and Amagat’s law of
additive volumes.

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 1. 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:
Molar analysis: specifying the number of moles of each component
Gravimetric analysis: specifying the mass of each component

b k
mm   mi and N m   N i
i 1 i 1

Mass fraction

mi Ni
mfi  and yi 
mm Nm

Mole fraction 3
 1. Composition of a Gas Mixture: Mass and Mole Fractions

The sum of the mass and mole fractions of a mixture is equal to 1.

k k

 mf
i 1
i  1 and y
i 1
i 1

mm  mi N M   y M k
Mm    i i
i i
Nm Nm N m i 1

m = NM Apparent (or average) molar mass

Ru
Rm  Gas constant
Mm
mm mm 1 1
Mm     The molar mass of a
Nm  mi / M i   mi M i  
k
mfi mixture
i 1 M i
mi Ni M i Mi Relation between mass and mole
mf i    yi fractions of a mixture
mm N m M m Mm 4
 2. P-v-T Behavior of Gas Mixtures: Ideal and Real Gases

Figure 14-5 Figure 14-6

Dalton’s law of additive pressures for a Amagat’s law of additive volumes for a
mixture of two ideal gases. mixture of two ideal gases.

The prediction of the P-v-T behavior of gas mixtures is usually based on two
models:
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.
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.

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 2. P-v-T Behavior of Gas Mixtures: Ideal and Real Gases

Dalton’s law 𝑃 = 𝑃 𝑇 ,𝑉 Exact fir ideal gases, approximate

for real gases.
Amagat’s law 𝑉 = 𝑉 𝑇 ,𝑃

Pi component pressure

Vi component volume
Pi / Pm pressure fraction

Vi / Vm volume fraction
Figure 14-7
For ideal gases, Dalton’s and The volume a component would occupy if it
Amagad’s laws are identical existed alone at the mixture T and P is called the
and give identical results. component volume (for ideal gases, it is equal to
the partial volume yiVm ).
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 2. P-v-T Behavior of Gas Mixtures: Ideal and Real Gases

Ideal-Gas Mixtures
Pi Tm ,Vm  N i RuTm / Vm N
  i  yi
Pm N m RuTm / Vm N m
Pi Vi N
  i  yi
Vi Tm , Pm  N i RuTm / Pm N Pm Vm N m
  i  yi
Vm N m RuTm / Pm N m

This equation is only valid for ideal-gas mixtures as it is derived by assuming

ideal-gas behavior for the gas mixture and each of its components.
The quantity yi Pm is called the partial pressure (identical to the component
pressure for ideal gases), and the quantity 𝑦 𝑉 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
volume fraction of a component are identical.
The composition of an ideal-gas mixture (such as the exhaust gases leaving a
combustion chamber) is frequently determined by a volumetric analysis (Orsat
Analysis).
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 2. P-v-T Behavior of Gas Mixtures: Ideal and Real Gases

Real-Gas Mixtures

PV  ZNRuT
k
Z m   yi Zi
i 1

Z: Compressibility factor

Z i is determined either at
Tm and Vm (Dalton’s law) or at
Tm and Pm (Amagat’s law) for
each individual gas. Figure 14–8
Using Dalton’s law gives more One way of predicting the P-v-T behavior of a
accurate results. real-gas mixture is to use the compressibility
factor.

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 2. P-v-T Behavior of Gas Mixtures: Ideal and Real Gases

Kay’s rule
Z m is determined by using these
pseudocritical properties.

, ,

, ,
Figure 14–9
The result by Kay’s rule is Another way of predicting the P-v-T
accurate to within about 10% over behavior of a real-gas mixture is to
a wide range of temperatures and treat it as a pseudopure substance with
pressures. critical properties Pcr' and Tcr'

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 3. Properties of Gas Mixtures: Ideal and Real Gases

Extensive properties of a gas mixture

k k k
U m  U i  mi ui   N iu1 ( k J )
i 1 i 1 i 1

k k k
H m   H i  mi hi   Ni h1 ( k J )
i 1 i 1 i 1

k k k
Sm   Si  mi si   Ni si  kJ / K 
i 1 i 1 i 1

Changes in properties of a gas mixture

k k k
U m   U i  mi ui   N i u1  kJ 
i 1 i 1 i 1
k k k
Figure 14–11
H m   H i  mi hi   N i h1  kJ  The extensive properties of a mixture
i 1 i 1 i 1
k k k
are determined by simply adding the
Sm   Si   mi si   N i si  kJ/K  properties of the components.
i 1 i 1 i 1

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 3. Properties of Gas Mixtures: Ideal and Real Gases

Intensive properties of a gas mixture

k k
U m   mf iui  kJ / Kg  and um   yiui (kJ/kmol)
i 1 i 1
k k
hm   mf i hi  kJ/Kg  and hm   yi hi (kJ/kmol)
i 1 i 1
k k
sm   mf i si  kJ / Kg.K  and sm   yi si ( kJ / kmol.K )
i 1 i 1
k k
cv ,m   mf i cvj  kJ/Kg.K  and cv ,m   yi cv ,i ( kJ / kmol.K)
i 1 i 1
k k
c p ,m   mfi c pj  kJ/Kg.K  and c p ,m   yi c p ,i ( kJ / kmol.K)
i 1 i 1

Properties per unit mass involve mass fractions  mfi  and properties per unit mole
involve mole fractions yi
The relations are exact for ideal-gas mixtures, and approximate for real-gas
mixtures.
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 3. Properties of Gas Mixtures: Ideal and Real Gases

Ideal-Gas Mixtures
Gibbs–Dalton law: 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 .

Also, the h, u, cv , and c p of an ideal gas depend on temperature only and are
independent of the pressure or the volume of the ideal-gas mixture.

Pi ,2 Ti ,2 Pi ,2
si  s  s  R,ln

i ,2

i ,1  c p ,i ln  Ri ln
Pi ,1 Ti ,1 Pi ,1
Pi ,2 Ti ,2 Pi ,2
si  si,2  si,1  Ru ln  c p ,i ln  Ru ln
Pi ,1 Ti ,1 Pi ,1
Pi ,2  yi ,2 Pm,2 and Pi ,1  yi ,1Pm,1

Partial pressures (not the mixture

pressure) are used in the evaluation of
entropy changes of ideal-gas mixtures. 12
 3. Properties of Gas Mixtures: Ideal and Real Gases

Real-Gas Mixtures

dhm  Tm dsm  vm dpm T ds relation for a gas mixture

d   mf i hi   Tm d   mf i si     mfi vi  dPm

 mf  dh  T ds  v dP   0
i i m i i m

dhi  Tm dsi  vi dPm

This equation suggests that the generalized property

relations and charts for real gases developed in Chap. 13
can also be used for the components of real-gas mixtures

If the 𝑉 and 𝑇 are specified instead of Pm and Tm

evaluate 𝑃 using Dalton’s law of additive pressures.
Another way is to treat the mixture as a pseudo pure
substance having pseudocritical properties, Figure 14–16
determined in terms of the critical properties of the It is difficult to predict the behavior of
component gases by using Kay’s rule. nonideal-gas mixtures because of
the influence of dissimilar molecules
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on each other.
 Summary

• Composition of a gas mixture: Mass and mole fractions.

• P-v-T behavior of gas mixtures: Ideal and Real Gases.
• Properties of gas mixtures: Ideal and Real Gases.

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