DEFENCE ENGINEERING COLLEGE

APPLIED THERMODYNAMICS
MV2012
Gas Mixtures
Introduction
 A pure substance is defined as a substance having a constant
and uniform chemical composition, and this definition
includes a homogeneous mixture of gases when there is no
chemical reaction taking place.
 The thermodynamics properties of a mixture of gases can be
determined in the same way as for a single gas.
 The most common example of this is dry air, which is a
mixture of nitrogen, oxygen and a small percentage of other
gases.
 The properties of air has been determined and it is considered
as a single substance.
 An ideal gas is one in which the equation of state is given by
PV  mRT or PV  NRu T
3
Empirical law of mixture of gases
Dalton’s law of partial pressure
 Consider a closed vessel of volume V at temperature T which
contains a mixture of a perfect gases at known pressure.
 If some of the mixture were removed then the pressure
would be less than the initial value.
 If the mixture removed were the full amount of the one of the
gas constituting the mixture then the reduction in pressure
would be equal to the contribution of that gas to the initial total
pressure.
 Each gases constituting the mixture contributes to the total
pressure by an amount known as partial pressure of that gas.
 The relationship between the partial pressures of the
constituting gases is expressed by Dalton’s law .

4
Dalton’s law states as
 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.

5
Amagat’s law of partial volumes
It states that,
 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.

6
 COMPOSITION OF A GAS MIXTURE
 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, or by specifying the mass of each
component, called gravimetric analysis.

7
 Consider a gas mixture composed of k components.
 Then 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.

 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.

8
 Note that the sum of the mass fractions or mole fractions for
a mixture is equal to 1.

 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

9
 The mass and mole fractions of a mixture are related by

 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

10
 The quantity yi Pm is called the partial pressure and the
quantity yiVm is called the partial volume.
 Note that for an ideal-gas mixture, the mole fraction, the
pressure fraction and the volume fraction of a component are
identical.
PROPERTIES OF GAS MIXTURES
 For the extensive properties of a non-reacting ideal or real-
gas mixture , Just add the contributions of each component of
the mixture.

11
 Similarly the changes in internal energy, enthalpy, and entropy
of a gas mixture during a process can be expressed as,

 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).

12
 Similarly, the specific heats of a gas mixture can be expressed
as

 Ratio of specific heats k is given as C p ,m C p ,m

km  
Cv ,m Cv ,m
13
 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.
 The entropy of a mixture of ideal gases is equal to the sum of
the entropies of the component gases as they exist in the
mixture.

14
 The entropy change of the mixture per mole of mixture is

 Where

15
Vapor- Air mixture
 Air is a mixture of nitrogen, oxygen, and small amounts of
some other gases.
 Air in the atmosphere normally contains some water vapor
(moisture) and is referred to as atmospheric air. By contrast, air
that contains no water vapor is called dry air.
 It is often convenient to treat air as a mixture of water vapor
and dry air since the composition of dry air remains relatively
constant, but the amount of water vapor changes as a result of
condensation and evaporation from oceans, lakes, rivers and
other water bodies.
 Although the amount of water vapor in the air is small, it plays
a major role in human comfort. Therefore, it is an important
consideration in air-conditioning applications.

16
 dry air can be treated as an ideal gas with a constant cp value
of 1.005 kJ/kg · K and the enthalpy and enthalpy change of dry
air can be determined from where T is the air temperature in
°C and ΔT is the change in temperature.

 It certainly would be very convenient to also treat the water

vapor in the air as an ideal gas and you would probably be
willing to sacrifice some accuracy for such convenience.
 Then the atmospheric air can be treated as an ideal-gas
mixture whose pressure is the sum of the partial pressure of
dry air Pa and that of water vapor Pv:
 The partial pressure of water vapor is usually referred to as the
vapor pressure.

17
The assumption that the water vapor is an ideal gas is valid when the
mixture temperature is below 50oC. This means that the saturation
pressure of the water vapor in the air-vapor mixture is below 12.3 kPa.
For these conditions, the enthalpy of the water vapor is approximated by
hv(T) = hg at mixture temperature T. The following T-s diagram for
water illustrates the ideal-gas behavior at low vapor pressures.
The saturated vapor value of the enthalpy is a function of temperature
and can be expressed as

Note: For the dry air-water vapor mixture,

the partial pressure of the water vapor in
the mixture is less that its saturation
pressure at the temperature.

18