Chapter One

Mixture of Ideal
Gases
Engineering Thermodynamics II
[MEng 3131 ]
1
Outline
• Composition of Gas mixtures
• P-v-T behavior of Gas Mixtures
• Properties of Gas Mixtures
• Adiabatic Mixing of Perfect Gases
• Mixing of Ideal Gases initially at different
Pressure and Temperature

2
 Composition of Gas Mixtures
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: By specifying the
number of moles of each component,
gravimetric analysis: By specifying
the mass of each component, 3
 Composition of Gas Mixtures [Continued]
Consider a gas mixture composed of k components.
The mass of the mixture mm is the sum of the masses of the individual
components,
The mole number of the mixture Nm is the sum of the mole numbers of the
individual components.
k k
mm  m
i 1
i and N m  N
i 1
i

The ratio of the mass of a component to the mass of the mixture is

called the mass fraction (mf),
The ratio of the mole number of a component to the mole number of the
mixture is called the mole fraction y:
mi Ni
mf i  and yi 
mm Nm 4
 Composition of Gas Mixtures [Continued]
Dividing the 1st equation by mm and Nm, the sum of the mass fraction or
mole fraction
k k

 mf
i 1
i
1 and y
i 1
i
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
The apparent (or average) molar mass of a mixture can be expressed as
m
Mm  m 
m i

 NM
i i
k

  yi M i (kg/kmol)
Nm Nm Nm i 1
5
Composition of Gas Mixtures [Continued]

• The average (or apparent) gas constant of the mixture can be

determined from

Ru
Rm  [kJ/(kg.K) ]
Mm

6
 Example 1.1.
Consider a gas mixture that consists of 3 kg of O 2, 5 kg of N2 and
12 kg of CH4, as shown. Determine the
(a) mass fraction of each component,
(b)mole fraction of each component,
(c) average molar mass and gas constant of the mixture

7
Examples
Example 1.2.
The composition of moist air is given on a molar basis to be 78 percent
N2 , 20 percent O2 , and 2 percent water vapor. Determine the mass
fractions of the constituents of air.

Example 1.3.
A gas mixture consists of 8 kmol of H 2 and 2 kmol of N2. Determine the
mass of each gas and the apparent gas constant of the mixture.

8
Examples
Example 1.4.
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.

Example 1.5.
A gas mixture has the following composition on a mole basis: 60
percent N2 and 40 percent CO2. Determine the gravimetric analysis of
the mixture, its molar mass, and gas constant.
9
 P-v-T Behavior of Gas Mixtures
An ideal gas – whose molecules are spaced far apart so that the behavior of a
molecule is not influenced by the presence of other molecules-a situation
encountered at low densities.
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
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,
A non-reacting mixture of ideal gases also behaves as an ideal gas.
e.g. Air
10
P-v-T Behavior of Gas Mixtures
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.
Dalton’ 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.

11
P-v-T Behavior of Gas Mixtures

Dalton’s and Amagat’s laws hold

exactly for ideal-gas mixtures, but
only approximately for real-gas
mixtures.
This is due to intermolecular forces
that may be significant for real gases
at high densities.
For ideal gases, these two laws are
identical and give identical results.
12
 Dalton’s and Amagat’s Law

Pm   Pi (Tm , Vm )
k

Dalton ' s law :

i 1

k 
Amagat' s law : Vm   Vi (Tm , Pm ) 
i 1

exact for ideal gases, approximat e for real gases

 In these relations, Pi is called the component pressure and Vi is

called the component volume.
 Note that Vi is the volume a component would occupy if it existed
alone at Tm and Pm, not actual volume occupied by the component
in the mixture. 13
 Ideal-Gas Mixtures
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:
Pi (Tm , Vm ) N i RuTm / Vm Ni
   yi
Pm N m RmTm / Vm N m
Vi (Tm , Pm ) N i RuTm / Pm Ni
   yi
Vm N m RuTm / Pm N m
Therefore,
Pi Vi N
  i  yi (*)
Pm Vm N m
Note that for an ideal gas mixture, the mole fraction , the pressure
fraction, and the volume fraction of a component are identical.
14
 Ideal-Gas Mixtures
The above equation is strictly
valid for ideal-gas mixtures since
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),
The quantity yiVm is called the
partial volume (identical to the
component volume for ideal
gases).
N.B.
The composition of an ideal-gas mixture (such
as the exhaust gases leaving a combustion
chamber) is frequently determined by a
volumetric analysis (Orsat gas analyzer) and Eq.
(*).
A sample gas at a known volume, pressure, and
temperature is passed into a vessel containing
reagents that absorb one of the gases.
The volume of the remaining gas is then
measured at the original pressure and
temperature.
The ratio of the reduction in volume to the
original volume (volume fraction) represents the
mole fraction of that particular gas.
15
Examples
Example 1.6.
A rigid tank contains 8 kmol of O2 and 10 kmol of CO2 gases
at 290 K and 150 kPa. Estimate the volume of the tank.

Example 1.7.
A gas mixture at 350 K and 300 kPa has the following
volumetric analysis: 65 % N2, 20 % O2, and 15% CO2.
Determine the mass fraction and partial pressure of each gas.
16
Example 1.8
A rigid tank that contains 1kg of N 2 at 25oC and 300 kPa is
connected to another rigid tank that contains 3kg of O 2 at 25oC
and 500kPa. The valve connecting the two tanks is opened,
and the two gases are allowed to mix. If the final mixture
temperature is 25oC, determine the volume of each tank and
the final mixture pressure.

17
 Properties of Gas Mixtures
Consider a gas mixture that consists of 2 kg of
N2 and 3 kg of CO2.
 The mass (an extensive property) of this mixture is 5 kg.
Extensive properties of a non-reacting ideal- or
real-gas mixture:
Just add the contributions of each component of the
mixture.

18
Properties of Gas Mixtures

19
 Properties of Gas Mixtures
• The total internal energy, enthalpy, and entropy of a gas mixture
can be expressed, respectively, as
k k k
U m   U i   mi ui   N i ui
i 1 i 1 i 1
k k k
H m   H i   mi hi   N i hi
i 1 i 1 i 1
k k k
S m   Si   mi si   N i si
i 1 i 1 i 1
20
 Properties of Gas Mixtures
• By following a similar logic, the changes in internal energy,
enthalpy, and entropy of a gas mixture during a process can be
expressed, respectively, as
k k k
U m   U i   mi ui   N i ui
i 1 i 1 i 1
k k k
H m   H i   mi hi   N i  hi
i 1 i 1 i 1
k k k
S m   Si   mi si   N i  si
21
i 1 i 1 i 1
 Properties of Gas Mixtures
The internal energy, enthalpy, and entropy of a gas 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).
The relations given above are generally valid and are applicable to both ideal- and
real-gas mixtures.
The only major difficulty associated with these relations is the determination of
properties for each individual gas in the mixture.
The analysis can be simplified greatly, by treating the individual gases as an ideal
gas. k k

u m   mf i ui and u m   yi u i
k 1 k 1

Cv ,m   mf i Cv ,i C v ,m   yi C v ,i
k k

hm   mf i hi and hm   yi hi and
k 1 k 1

C p ,m   mf i C p ,i C p ,m   yi C p ,i
k k

sm   mf i si and s m   y i si and
22
k 1 k 1
 Ideal-Gas Mixtures
The gases that comprise a mixture are often at a high
temperature and low pressure relative to the critical-point
values of individual gases.
In such cases, the gas mixture and its components can be
treated as ideal gases with negligible error.
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 T m, and mixture
volume Vm. This principle is known as the Gibbs-Dalton law.
23
 Ideal-Gas Mixtures
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.
The partial pressure of a component in an ideal-gas mixture is simply
Pi  yi Pm ,
Evaluation of change in u and h of the components of an ideal-gas
mixture during a process is relatively easy since it requires only a
knowledge of the initial and final temperatures.
In evaluating the changes in s of the components since the entropy of
an ideal gas depends on the pressure or volume of the component as
well as on its temperature.
24
 Ideal-Gas Mixtures
The entropy change of individual gases in an ideal-gas mixture during a
process can be determined from

Pi , 2 Ti , 2 Pi , 2
si  si , 2  si ,1  Ri ln
 
 C p ,i ln  Ri ln
Pi ,1 Ti ,1 Pi ,1
  Pi , 2 Ti , 2 Pi , 2
or  s i  s i , 2  s i ,1  Ri ln  C p ,i ln  Ri ln
Pi ,1 Ti ,1 Pi ,1
where Pi , 2  yi , 2 Pm , 2 and Pi ,1  yi ,1 Pm ,1

25
 Example 1.9.
A 0.90m3 rigid tank is divided into two equal compartments by a partition. One
compartment contains Ne at 20oC and 100 kPa, and the other compartment contains
Ar at 50oC 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
N.B. Ru= 8.314 kPa.m3/kmol.K;
MAr= 39.95 kg/kmol;
MNe = 20.18 kg/kmol;
Cv,Ar= 0.3122 kJ/kg.K and
Cv,Ne= 0.6179 kJ/kg.K @ Room Temperature, 300 K.
26
 Adiabatic Mixing of Perfect Gases
Figure shows two gases A and B separated from each other in a closed
vessel by a thin diaphragm.
If the diaphragm is removed or punctured then the gases mix and each then
occupies the total volume, having as if the other gas were not present.
This process is equivalent to a free expansion of each gas, and is
irreversible.
The process can be simplified by the assumption that it is adiabatic : this
means that the vessel is perfectly thermally insulated and there will
therefore be an increase in entropy of the system.

27
 Adiabatic Mixing of Perfect Gases
In a free expansion process, the internal energy initially is equal to
the internal energy finally.

U 1  N ACv , ATA  N B Cv ,BTB

U 2  ( N ACv , A  N B Cv ,B )T
where C v is in kJ/kmole.K
28
 Adiabatic Mixing of Perfect Gases
• If the result is extended to any number of gases, we have
k k
U1   N i Cv ,iTi and U 2  T  N i Cv ,i
i 1 i 1

Since U1  U 2 , it follows that :

k k

N C
i 1
i T  T  N i C v ,i
v ,i i
i 1
k

N C i T
v ,i i
T i 1
k

N C
i 1
i v ,i

29
When two streams of fluid meet to form a common stream in steady flow, they give
another form of mixing

Applying steady-flow energy equation to the mixing section (neglecting

changes in kinetic and potential energy ), we get

   
m A hA1  m B hB1  Q  m A hA 2  m B hB 2  W 30
In case of adiabatic flow : Q  0, and W  0

   
m A hA1  m B hB1  m A hA 2  m B hB 2
Also h  c pT , hence, c p in [kJ / kgK ]
 

m A c p ATA  mB c p BTB  m A c p AT  mB c p BT
k  k 

m c T Tm c
i 1
i
pi i
i 1
i
pi

k 

m c T i
pi i

T i 1
k 

m c
i 1
i
pi
31
 Also , C p  Mc p and M  m / N
 NC p  mcp
k

NC T i pi i

Hence, T i 1
k

NC
i 1
i pi

 The above equations represent one condition which must be satisfied in

an adiabatic mixing process of perfect gas in steady flow.
 In a particular problem some other information must be known (e.g., sp.
Volume or the final pressure).
32
Example 1.10
A vessel of 2 m3 capacity contains O2 at 500 kPa and 50 oC. The vessel
is connected to another vessel of 1.5 m3 capacity containing CO at 100
kPa and 20oC. The connecting valve is opened and the gases mixed
adiabatically. Determine the final temperature and pressure of the
mixture.

Take : Cv = 21.1 kJ/kmol K for O2

Cv = 20.9 kJ/kmol K for CO

33
 Mixing of Ideal Gases initially at different
Pressure and Temperature
 Consider three ideal gases A,B and C initially at different pressures
and temperatures and separated by partitions.
 Let the gases be mixed by removing the partitions.
 The total volume occupied by the mixture and the mass of the
mixture are given by :

V  VA  VB  VC
and
m  m A  mB  mC
34
 Mixing of Ideal Gases initially at different
Pressure and Temperature
In terms of the mixing masses, the internal energy of the gases after mixing can
be related to the internal energy of the gases before mixing by the expression:

mu  m Au A  mB u B  mC uC
Since u for a perfect gas is equal to cv T, this relation may be re-written as;

mcvT  mA cv , ATA  mB cv ,BTB  mC cv ,CTC

with mcv equal to m A cv , A  mB cv ,B  mC cv ,C
mA cv , ATA  mB cv ,BTB  mC cv ,CTC m A cv , ATA  mB cv ,BTB  mC cv ,CTC
T T
mcv m A cv , A  mB cv ,B  mC cv ,C
35
 Multiplyin g each term in the numerator and
Applying the perfect gas law
denominato r by the respective molecular weights :
PAVAcv , A PBVB cv , B PCVC cv ,C
   M A PAV A cv , A M B PBVB cv , B M C PCVC cv ,C 
RA RA RA    
T  M A RA M B RB M C RC 
PAVAcv , A PBVB cv , B PCVC cv ,C T  
   M A PAV A cv , A  M B PBVB cv , B  M C PCVC cv ,C 
TA R A TB RB TC RC

 M A R ATA M B RBTB M C RC TC 


The product Mcv is the same for ideal gases

and the product MR  R u is a constant for
all ideal gases.
PAV A  PBVB  PCVC
T 
PAV A PV P V
 B B  C C
TA TB TC 36
• If the pressure are all equal before mixing, the resulting mixing
temperature will be obtained from:
VA  VB  VC
T
VA VB VC
 
TA TB TC
• For equal volumes before mixing

PA  PB  PC
T
PA PB PC
 
TA TB TC
37