University of Gondar

School of Technology
Department of Mechanical

Thermodynamics II

COMPILED BY: ALTASEB K.

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CHAPTER-ONE
1. Ideal gases & their mixtures
1.1 Composition of a gas mixture: mass and mole fractions

1. What is mixture? And d/t b/n mixture and solution?

2. How can analysis the composition of mixture?
3. What are the properties of mixture? And how can
determine them?
4. What is the d/t b/n mixture and pure substance?
5. What is the d/t b/n real gas and ideal gases? And there
properties?

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 To specify the properties of a mixture requires the composition and the values of two independent intensive
properties such as temperature and pressure.
 There are two ways to describe the composition of a mixture:
 Molar analysis (volumetric analysis ): listing of the mole fractions of the components of a mixture
 Gravimetric analysis: listing of the mass fractions of the components of a mixture
 Consider a closed system consisting of a gaseous mixture of two or more components.
 Mass of the mixture (𝒎𝒎) = is the sum of the masses of the individual components
𝒌

𝒎𝒎 = 𝒎𝟏 + 𝒎 𝟐 + ⋯ 𝒎𝒌 = 𝒎𝒊 (𝟏. 𝟏)
𝒊=𝟏
Example:

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 Mole number of the mixture 𝑵𝒎 = is the sum of the mole numbers of the individual components
𝒌
𝑵𝒎 = 𝑵𝟏 + 𝑵𝟐 + ⋯ 𝑵𝒌 = 𝒊=𝟏 𝑵𝒊 (𝟏. 𝟐)

Example:

 Mass fraction (𝒎𝒇 ): the ratio of mass of a component to the mass of the mixture. It indicates the relative
amounts of the components present in the mixture
𝒎𝒊
𝒎𝒇 = (𝟏. 𝟑)
𝒎𝒎
 The sum of the mass fractions of all the components in a mixture is equal to unity.
𝒌
𝒊=𝟏 𝒎𝒇𝒊 =𝟏 (𝟏. 𝟒)
 Mole Fraction (y): the ratio of mole number of a component to the mole number of the mixture. It indicates the
relative amounts of the components present in the mixture in terms of mole.

𝑵𝒊
𝒚= 𝟏. 𝟓
𝑵𝒎 4
 The sum of the mole fractions of all the components in a mixture is equal to unity.
𝒌

𝒚𝒊 = 𝟏 𝟏. 𝟔
𝒊=𝟏
 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, N
𝒎𝒎 𝑚1 :𝑚2 :⋯:𝑚𝑘
𝑀𝑚 = = ; since 𝑚𝑖 = 𝑁𝑖 𝑀𝑖
𝑁 𝑁
𝑘
𝑁1 𝑀1 + 𝑁2 𝑀2 + ⋯ + 𝑁𝑘 𝑀𝑘
𝑀𝑚 = = 𝑦𝑖 𝑀𝑖 1.7
𝑁
𝑖=1
 The apparent (average) molar mass (M) and the gas constant of a mixture (𝑅𝑚 ) can be expressed as:
Ru
Rm = (1.8)
Mm
KJ
R u = 8.314 KMol. K
 The molar mass of a mixture can also be expressed as:

mm mm 1 1
Mm = = mi = mi = mf (1.9)
𝐍𝐦 5
Mi (mm Mi ) Mi
 Mass and mole fractions of a mixture are related by:
𝑚𝑖 𝑁𝑖 𝑀𝑖 𝑀𝑖
𝑚𝑓 = = = 𝒚𝒊
𝒎𝒎 𝑁𝑚 𝑀𝑚 𝑀𝑚
Examples:
1. Consider a gas mixture that consists of 3 kg of O2, 5 kg of N2, and 12 kg of CH4. 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.
Solution:
a) The total mass of the mixture (𝒎𝒎 ) can be determined as:
𝑚𝑚 = 𝑚O2 +𝑚N2 +𝑚CH4 = 3𝑘𝑔 + 5𝑘𝑔 + 12𝑘𝑔 = 20𝑘𝑔
Then the mass fraction of each component becomes
𝑚
𝑚O2 = O2 =
3𝑘𝑔
20𝑘𝑔 = 0.15
𝒎𝒎
𝑚N2 5𝑘𝑔
𝑚N2 = = 20𝑘𝑔 = 0.25
𝒎𝒎
𝑚CH4 12𝑘𝑔
𝑚CH4 = = 20𝑘𝑔 = 0.60
𝒎𝒎 6
b) To find the mole fractions, we need to determine the mole numbers of each component first:
𝑚O2 3𝑘𝑔
𝑁O2 = 𝑀O2 = 32𝐾𝑔/𝐾𝑚𝑜𝑙 = 0.094𝑘𝑚𝑜𝑙

𝑚N2 5𝑘𝑔
𝑁N2 = 𝑀N2 = 28 𝑘𝑔/𝑘𝑚𝑜𝑙 = 0.179𝑘𝑚𝑜𝑙

𝑚𝑚 12𝑘𝑔
𝑁CH4 = 𝑀CH4 = 𝑘𝑔 = 0.75𝑘𝑚𝑜𝑙
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𝑘𝑚𝑜𝑙
𝑁𝑚 = 𝑁O2 + 𝑁N2 + 𝑁CH4 = 0.094𝑘𝑚𝑜𝑙 + 0.179𝑘𝑚𝑜𝑙 + 0.750𝑘𝑚𝑜𝑙 = 1.023𝑘𝑚𝑜𝑙
N
yO2 = O2 =
0.094kmol
= 0.092
Nm 1.023kmol

NN2 0.179kmol
yN2 = = = 0.175
Nm 1.023kmol

NCH4 0.75kmol
yCH4 = = = 0.733
Nm 1.023kmol

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c) The average molar mass and gas constant of the mixture are determined from their definitions,

mm 20kg
Mm = = = 19.6kg/kmol
Nm 1.023kmol
𝑘
(or) Mm = 𝑖=1 𝑦𝑖 𝑀𝑖 = 0.092 ∗ 32 + 0.175 ∗ 28 + 0.733 ∗ 16 = 19.6𝑘𝑔/𝑘𝑚𝑜𝑙
8.314𝐾𝐽 𝐾𝑀𝑜𝑙.𝐾 𝐾𝐽
𝑅𝑚 = = 0.424
19.6𝑘𝑔/𝑘𝑚𝑜𝑙 𝑘𝑔.𝑘

2. The molar analysis of the gaseous products of combustion of a certain hydrocarbon fuel is CO2, 0.08; H2O, 0.11;
O2, 0.07; N2, 0.74. (a) Determine the apparent molecular weight of the mixture. (b) Determine the composition
in terms of mass fractions (gravimetric analysis).
Solution:
a) Mm = 0.08 ∗ 44 + 0.11 ∗ 18 + 0.07 ∗ 32 + 0.74 ∗ 28 = 28.46𝑘𝑔/𝑘𝑚𝑜𝑙
b) Component Ni M𝑖 m𝑖 = Ni ∗ M𝑖 m𝑓 = m𝑖 m𝑚 (%)
CO2 0.08 44 3.52 12.37
H2O 0.11 18 1.98 6.96
O2 0.07 32 2.24 7.87
N2 0.74 28 20.72 72.80
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Ni =1 m𝑚 = m𝑖 =28.46 m𝑓 =100
Assignment1:
1. Consider a mixture of two gases A and B. Show that when the mass
fractions mfA and mfB are known, the mole fractions can be
determined from.
2. A gas mixture consists of 20 percent O2, 30 percent N2, and 50
percent CO2 on mass basis. Determine the volumetric analysis of the
mixture and the apparent gas constant.

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1.2 P-v-T BEHAVIOR OF GAS MIXTURES: IDEAL AND REAL GASES
 Consider a system consisting of a number of gases contained within a closed vessel of volume 𝑽𝒎 . The
temperature of the gas mixture is 𝐓𝒎 and the pressure is 𝑷𝒎 . The 𝑷𝒎 , 𝑽𝒎 , 𝐓𝒎 , and the total number of moles of
mixture 𝐍𝐦 are related by:
Nm Ru 𝐓𝒎 mm Rm 𝐓𝒎
 𝑷𝒎 = = , for ideal-gas equation of state.
𝑽𝒎 𝑽𝒎

 For real gases is expressed by more complex equations of state or by 𝑷𝒎 𝑽𝒎 = ZNm R u 𝐓𝒎 = Zmm R 𝑚 𝐓𝒎 , where Z
is the compressibility factor.
 The prediction of the P-v-T behavior of gas mixtures is usually based on two models:
i. Dalton’s law of additive pressures
ii. Amagat’s law of additive volumes
I. Dalton’s law of additive pressures: The pressure of a gas mixture is equal to the sum of the partial pressure
each gas would exert if it existed alone at the mixture temperature and volume. This expression is exact for ideal
gases and approximate for real gases.
𝒌
𝑷𝒎 = 𝒊=𝟏 𝑷𝒊 ; (𝑽𝒎 & 𝐓𝒎 ) 10
Ni Ru Tm
Pi = Limitations of Dalton’s law of additive presser:
Vm
Ni Ru Tm

Pressure fraction =
Pi
=
Vm N
= N i = yi
 Assumes individual component are not
Pm Nm Ru Tm
m
Vm
influenced by the pressure of other components
Pressure fraction 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝑝𝑟𝑒𝑠𝑢𝑟𝑒 = Pi = yi Pm
k k
of the mixture.
i=1 Pi = Pm i=1 yi
k
 Valid for ideal gase mixture, but for real gase
Pm = i=1 Pi
some errors. This is due to intermolecular
E.g air pressure = 𝑷𝑵𝟐 + 𝑷𝑶𝟐 + 𝑷𝑨𝒓 + ⋯
Forces in the real gase at ↑ pressure & ↓
temperature

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ii. Amagat’s law of additive volumes: The volume of a gas mixture is equal to the sum of the Partial volume of
each gas would occupy if it existed alone at the mixture temperature and pressure. This expression is exact for
ideal gases and approximate for real gases.
𝒌
𝑽𝒎 = 𝒊=𝟏 𝑽𝒊 ; 𝑷𝒎 & 𝐓𝒎 ;
NR T
Vi = i u m
Pm
Ni R u Tm
Vi Pm Ni
Volume fraction = = Nm R u Tm = = yi
Vm Nm
Pm
Vi = yi Vm
k k
i=1 Vi = Vm i=1 yi
k
Vm = i=1 Vi
E.g air volume = 𝑽𝑵𝟐 + 𝑽𝑶𝟐 + 𝑽𝑨𝒓 + ⋯

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1.2.1 Ideal-Gas Mixtures
For the ideal gases:
 The compressibility factor Z=1.
 The mole fraction, the pressure fraction, and the volume fraction of a component are identical.
P V 𝐍
(i.e. i = i = 𝐢 = yi )
Pm Vm 𝐍𝐦
1.2.2 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 component pressures or component volumes should be evaluated from relations that take into
account the deviation of each component from ideal-gas behavior.
 The way to measure the deviation from ideal behavior can be define by the following two ways:
 Use more exact equations of state (van der Waals, Beattie–Bridgeman, Benedict–Webb–Rubin,
etc.) instead of the ideal-gas equation of state.
 Compressibility factor Z
 Kay’s rule
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Example: for Van der Waals equation:

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 By using compressibility factor Z we can analysis the deviation as:
𝑷𝑽 = Z𝑁𝑅𝑇
𝑘
𝑍𝑚 = 𝑖=1 𝑦𝑖 𝑧𝑖

Zi is determined either at Tm and Vm

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

 Amagat’s law involves the use of mixture pressure

Pm, which accounts for the influence of intermolecular forces between the molecules of
different gases.
 Dalton’s law disregards the influence of dissimilar molecules in a mixture
on each other. As a result, it tends to under predict the pressure of a gas
mixture for a given Vm and Tm.

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 Dalton’s law is more appropriate for gas mixtures at low pressures.
 Amagat’s law is more appropriate at high pressures.

Kay’s rule
 Another approach for predicting the P-v-T behavior
of a gas mixture is to treat the gas mixture as
a pseudopure substance with critical properties 𝑃𝑐𝑟 ′
𝑎𝑛𝑑 𝑇𝑐𝑟 ′
 Zm is determined by using these pseudo critical
properties.
 The result by Kay’s rule is accurate to within about 10% over a wide range of
temperatures and pressures.

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Assignment 2:
1. A rigid tank that contains 1 kg of N2 at 25°C and 300 kPa is
connected to another rigid tank that contains 3 kg of O2 at 25°C
and 500 kPa. The valve connecting the two tanks is opened, and
the two gases are allowed to mix. If the final mixture temperature
is 25°C, determine the volume of each tank and the final mixture
pressure.

2. A volume of 0.3 m3 of O 2 at 200 K and 8 MPa is mixed with 0.5

m3 of N2 at the same temperature and pressure, forming a
mixture at 200 K and 8 MPa. Determine the volume of the mixture,
using (a) the ideal-gas equation of state, (b) Kay’s rule, and (c)
the compressibility chart and Amagat’s law.
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