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26 views

Ch- 1

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Temesgen Erena
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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ENGINEERING THERMODYNAMICS

-II
chapter one.
IDEAL GASES AND THEIR
MIXTURES

1. IDEAL GASES AND THEIR MIXTURES 1


Objectives
• Develop rules for determining non-reacting 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.
• Predict the P-v-T behavior of gas mixtures based on
Dalton’s law of additive pressures and Amagat’s law of
additive volumes.
• Apply the rules for determining mixture properties to
ideal-gas mixtures and real-gas mixtures.
1.1 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
The mass of a mixture is equal to the
sum of the masses of its components.

Mass
fraction
The number of moles of a nonreacting
mixture is equal to the sum of the number Mole
of moles of its components. fraction
 Apparent (or average) molar mass M  The sum of the mass and
mole fractions of a mixture
is equal to 1.

 Gas constant

 The molar mass of a mixture

 Mass and mole fractions of a


mixture are related by
The sum of the mole
fractions of a mixture is
equal to 1.
EXAMPLE -1.1
Consider a gas mixture that consists of 3kg of o2, 5kg of N2 and
12kg 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
1.2. P-v-T BEHAVIOR OF GAS MIXTURES: IDEAL
AND REAL GASES
 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.

 The real gases approximate this behavior closely when they are at a
low pressure or high temperature relative to their critical-point values.

 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.
P-v-T BEHAVIOR OF GAS MIXTURES: IDEAL AND
REAL 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
Dalton’s law of additive pressures for a mixture is equal to the sum of the
mixture of two ideal gases. 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
Amagat’s law of additive volumes it existed alone at the mixture
for a mixture of two ideal gases. temperature and pressure.
Pi component pressure Vi component volume
Pi /Pm pressure fraction Vi /Vm volume fraction

The volume a 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 yiVm).
Ideal-Gas Mixtures
For ideal gases, Dalton’s and Amagat’s laws are identical and give identical results.

 Note that for an ideal-gas


mixture, the mole fraction, the
pressure fraction, and the
volume fraction of a
component are identical.
 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 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).
Real-Gas Mixtures
Compressibility factor

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 One way of predicting the P-v-T
for the influence of intermolecular behavior of a real-gas mixture is
forces between the molecules of to use compressibility factor.
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.

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

Amagat’s law is more appropriate at high pressures.


Real-Gas Mixtures
Kay’s rule

Zm is determined by using these


pseudocritical properties.

The result by Kay’s rule is accurate to


within about 10% over a wide range of
temperatures and pressures.
EXAMPLE-1.2
A rigid tank contains 2kmol of N2 and 6kmol of CO2 gases at 300 K and15MPa.
Estimate the volume of the tank on the basis of
(a) the ideal-gas equation of state,
(b) Kay’s rule,
(c) compressibility factors and Amagat’s law, and
(d ) compressibility factors and Dalton’s law. Exercise
Solution (a) the ideal-gas equation of state,
Analysis (a) When the mixture is assumed to behave as an ideal gas, the
volume of the mixture is easily determined from the ideal-gas relation for the
mixture:
• (b) Kay’s rule,
By using the critical-point properties of N2 and CO2 from Table A–1 and Fig. A-15b, we
can easily the critical properties of mixtures
(c) compressibility factors and Amagat’s law
First determine the Z of each component on the basis
of Amagat’s law:
Assignment: 1.1
• 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.
1.3. PROPERTIES OF GAS MIXTURES:
IDEAL AND REAL GASES
Extensive properties of a gas mixture

Changes in properties of a gas mixture The extensive


properties of a
mixture are
determined by
simply adding the
properties of the
components.
Intensive properties of a gas mixture

The intensive
properties of a
mixture are
determined by
weighted
averaging.

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.
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 cp of an ideal gas
depend on temperature only and are
independent of the pressure or the volume of
the ideal-gas mixture.
Partial pressures (not
the mixture pressure)
are used in the
evaluation of entropy
changes of ideal-gas
mixtures.
Example 1.3
A 0.9-m3 rigid tank is divided into two equal compartments by a partition. One
compartment contains Ne at 20°C and 100 kPa, and the other compartment
contains Ar at 50°C and 200 kPa. Now the partition is removed, and the
two gases are allowed to mix. Heat is lost to the surrounding air during this
process in the amount of 15 kJ. Determine (a) the final mixture temperature
and (b) the final mixture pressure.
Example 1.4
• A mixture that is 20 percent carbon dioxide, 10 percent oxygen, and 70 percent nitrogen by
volume undergoes a process from 300 K and 100 kPa to 500 K and 400 kPa. Determine the
makeup of the mixture on a mass basis and the enthalpy change per unit mass of mixture.
Assignment 1.2
Air, which may be considered as a mixture of 79 percent N2 and 21
percent O2 by mole numbers, is compressed isothermally at 200 K
from 4 to 8MPa in a steady-flow device. The compression process
is internally reversible, and the mass flow rate of air is 2.9 kg/s.
Determine the power input to the compressor and the rate of heat
rejection by treating the mixture (a) as an ideal gas and (b) as a
non-ideal gas and using Amagat’s law.
Assignment 1.3
An ideal-gas mixture has the following volumetric analysis
Component % by Volume
N2 60
CO2 40
a) Find the analysis on a mass basis.
b) What is the mass of 1 m3 of this gas when P = 1.5MPa and T = 30oC?
c) Find the specific heats at 300 K.
d) This gas is heated in a steady-flow process such that the temperature is
increased by 120oC. Find the required heat transfer.
e) This mixture undergoes an isentropic process from 0.1MPa, 30oC, to 0.2MPa.
Find T2.
f) Find ∆Sm per kg of mixture when the mixture is compressed isothermally
from 0.1MPa to 0.2MPa.
g) Both the N2 and CO2 are supplied in separate lines at 0.2MPa and 300 K to a
mixing chamber and are mixed adiabatically. The resulting mixture has the
composition as given in part (a). Determine the entropy change due to the
mixing process per unit mass of mixture.
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