Lecture W01

Dr. Ammar Tariq

GAS MIXTURES

Chapter 13
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
▪ The properties of the individual components
There are TWO ways to describe the composition of a mixture:
1. Mass (or Gravimetric) analysis: specifying the mass of each component
The mass of a mixture is equal to the sum of the masses of its components.

Hence:

… (13–1 a)

Mass fraction Note … (13–2 a)

Composition of a gas mixture: Mass and Mole
fractions
2. Molar Analysis: specifying the number of moles of each component
The number of moles of a mixture is equal to the sum of the number of
moles of its components.

Hence: … (13–1 b)

Similar to the mass

Mole fraction … (13–2 b) analysis

Also Molar mass [kg/kmol]

Mass [kg] No of moles [kmol]

Composition of a gas mixture: Mass and Mole
fractions
 Apparent (or average) molar mass of a mixture

 Gas constant of a mixture

 The molar mass of a mixture

 Mass and mole fractions of a mixture are related by

5
P-v-T behavior of gas mixtures: Ideal and
Real gases
 When two or more ideal gases are mixed, the
behavior of a molecule normally is not influenced by
the presence of other similar or dissimilar molecules
 Therefore, a non-reacting mixture of ideal gases also
behaves as an ideal gas
 The prediction of the P-v-T behavior of gas mixtures
is usually based on two models
 Dalton’s law of additive pressures
 Amagat’s law of additive volumes
P-v-T behavior of gas mixtures: Ideal and Real gases

Dalton’s law of additive Amagat’s law of additive

pressures: volumes:
The pressure of a gas mixture is The volume of a gas mixture is
equal to the sum of the pressures equal to the sum of the volumes
each gas would exert if it existed each gas would occupy if it
alone at the mixture temperature existed alone at the mixture
and volume. temperature and pressure..

Fig. 13–5: Dalton’s law of additive Fig. 13–6: Amagat’s law of additive
pressures for a mixture of two ideal gases. volumes for a mixture of two ideal gases.
P-v-T behavior of gas mixtures: Ideal and Real
gases
 Dalton’s and Amagat’s laws can be expressed as follows:
exact for ideal gases
and approximate for
real gases (Why?)
“intermolecular forces”

For ideal gases,

 In these relations: however, these two
laws are identical and
 Pi is component pressure
give identical results.
 Vi is component volume
 Also note that:
 Pi / Pm is pressure fraction of the ith component
 Vi / Vm is volume fraction of the ith component
P-v-T behavior of gas mixtures: Ideal and Real
gases

 The volume a component would occupy if it

existed alone at the mixture Tm and Pm is called
the component volume (Vi).
 For ideal gases, the component volume is equal
to the partial volume yiVm(details to follow).
P-v-T behavior of gas mixtures: Ideal and Real
gases
 For ideal gases, Pi and Vi can be related to yi by
using the ideal-gas relation (PV=NRuT) for both the
components and the gas mixture:

 Also:

… (13.8)

Pressure Volume Mole

fraction fraction fraction

 This equation is only valid for ideal-gas mixtures

P-v-T behavior of gas mixtures: Ideal and Real
gases
 Note that:
 The quantity yiPm is called the partial pressure
(identical to the component pressure for ideal gases)
 The quantity yiVm 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
 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)
P-v-T behavior of gas mixtures: Ideal and Real
gases

Real-Gas Mixtures
 Dalton’s law of additive pressures and Amagat’s law
of additive volumes can also be used for real gases.
 However, while applying these laws the component
pressures or component volumes should be
evaluated from relations that take into account the
deviation of each component from ideal-gas
behavior.
P-v-T behavior of gas mixtures: Ideal and Real
gases

 We use the compressibility factor such that:

… (13.9)

 The compressibility factor of the mixture Zm can

be expressed in terms of the compressibility
factors of the individual gases Zi such that:

… (13.10)

 Note that Zi is determined either at Tm and Vm

(Dalton’s law) or at Tm and Pm (Amagat’s law) for
each individual gas.
P-v-T behavior of gas mixtures: Ideal and Real
gases

 The relation (13-10) gives more accurate

results when the Zi’s are evaluated by using
Amagat’s law
 Reason: Amagat’s law involves the use of mixture
pressure Pm, which accounts for the influence of
intermolecular forces between different gases.
 As a rule of thumb:
 Dalton’s law is more appropriate for gas mixtures at low
pressures.
 Amagat’s law is more appropriate at high pressures.
P-v-T behavior of gas mixtures: Ideal and Real
gases
 The P-v-T behavior of a gas mixture can also be
predicted by using Kay’s rule where:
 Gas mixture is treated as a pseudo-pure substance
 The pseudo-critical pressure P’cr,m and pseudo-critical
temperature T’cr,m are used in terms of the critical pressures and
temperatures of the mixture components, defined as:

… (13.11, a, b)

 The compressibility factor of the mixture Zm is then easily

determined by using these pseudo-critical properties.
 The result thus obtained is accurate to within 10% over a wide
range of temperatures and pressures
EXAMPLE 13–2 P-v-T Behavior of Nonideal Gas Mixtures
A rigid tank contains 2 kmol of N2 and 6 kmol of CO2 gases at 300 K
and 15 MPa (Fig. 13–10). 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.
Properties of Gas Mixtures: Ideal and Real Gases
Temperature:
For any uniform mixture, the temperature is same for
each constituent and for the mixture such that:
𝑻𝒎 = 𝑻𝑨 = 𝑻𝑩

Mass, Number of Moles, and Apparent Molar Mass:

𝑚 𝑚 = 𝑚𝐴 + 𝑚 𝑩 + 𝑚𝐶 Holds valid for all

mixtures and not
𝑁 𝑚 = 𝑁𝐴 + 𝑁 𝑩 + 𝑁 𝐶 just for ideal
𝑀𝑚 = 𝑦𝐴 𝑀𝑨 + 𝑦𝐵 𝑀𝑩 + 𝑦𝐶 𝑀𝐶 gases
Properties of Gas Mixtures: Ideal and Real
Gases
Pressure:
Mixture pressure equals the sum of partial pressure of its
constituents (A, B & C), such that:
𝑃𝑚 = = 𝑃𝐴 𝑇𝑚, 𝑉𝑚 + 𝑃𝐵 𝑇𝑚, 𝑉𝑚 + 𝑃𝐶 𝑇𝑚, 𝑉𝑚
where, 𝑃𝐴(𝑇𝑚 , 𝑉𝑚) = 𝑦𝐴 𝑃𝑚

Volume:
Mixture volume equals the sum of partial volumes of its
constituents, such that:
𝑉𝑚 = 𝑉𝐴(𝑇𝑚, 𝑃𝑚) + 𝑉𝐵(𝑇𝑚, 𝑃𝑚) + 𝑉𝐶(𝑇𝑚, 𝑃𝑚)
where, 𝑉𝐴(𝑇𝑚, 𝑃𝑚) = 𝑦𝐴
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.
 Properties of Gas Mixtures: Ideal and Real
Gases
Intensive properties of a gas mixture

The intensive
properties of a
mixture are
Properties per unit mass involve mass fractions (mfi) and determined by
properties per unit mole involve mole fractions (yi). weighted
averaging.
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.
The Gibbs (Tds) Equations and Entropy Change
of Ideal Gases
 First Gibbs equation, or (First Tds relationship)
Tds = du + Pdv
 Second Gibbs equation, or (Second Tds relationship)
Tds = dh − vdP
 Using the two Gibbs equations, we reach to the following
relations for ideal gases :
T  P   T2   v2 
s = c p ,avg ln  2  − R ln  2  s = cv ,avg ln   + R ln  
 T1   P1   T1   v1 
 Only true for ideal gases, assuming constant heat capacities
and valid for both reversible & irreversible processes!
Real-Gas Mixtures
T ds relation for a gas mixture

This equation suggests that the generalized property

relations and charts for real gases developed in Chap.
12 can also be used for the components of real-gas
mixtures. But (reduced)TR and PR for each component
should be evaluated using Tm and Pm.
If the Vm and Tm are specified instead of Pm and Tm,
evaluate Pm using Dalton’s law of additive pressures.
Another way is to treat the mixture as a pseudopure It is difficult to predict the
substance having pseudocritical properties, determined behavior of nonideal-gas
in terms of the critical properties of the component
mixtures because of the
gases by using Kay’s rule.
influence of dissimilar
Kay’s rule molecules on each other.