Thermodynamics II AAiT

Chapter One
Mixture of Ideal Gases
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: either by specifying the number of
moles of each component, called molar analysis, or by specifying the mass of each component,
called gravimetric analysis.

Consider a gas mixture composed of k components. The mass of the mixture mtot is the sum of
the masses of the individual components, and the mole number of the mixture Ntot is the sum of
the mole numbers of the individual components.
k k
mtot = m1 + m2 + ...... + mk = ∑ mi and ntot = n1 + n2 + ...... + nk = ∑ ni (1.1)
i =1 i =1

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:
mi ni
mfi = and y= (1.2)
mtot ntot
A listing of the mass fractions of the components of a mixture is sometimes referred to as a
gravimetric analysis. A listing of the mole fractions of the components of a mixture may be
called a molar analysis. An analysis of a mixture in terms of mole fractions is also called a
volumetric analysis.
The sum of the mass fractions or mole fractions for a mixture is equal to unity.
k k
i.e ∑y
i =1
i =1 and ∑ mf
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. Then the average molar mass a mixture can be expressed as

M=
mtot
=
∑=m ∑n M
= ∑yM
i i i
k
(1.3)
avr i i
ntot ntot n tot i =1

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The gas constant R is different for each gas and is determined from
Ru
R= (1.4)
M

Where Ru is the universal gas constant and M is the molar mass (also called molecular weight)
of the gas. The constant Ru is the same for all substances, and its value is 3.1447 kJ / Kmol.K .
The average gas constant of a mixture can be expressed as

Ru
Ravr =
M avr (1.5)
The molar mass of a mixture can also be expressed as

mm
Mm =
nm (1.6)
Mass and mole fractions of a mixture are related by

mi ni M i M
=
mf i = = yi i
mm nm M m Mm (1.6)

1.2 P-v-T Behavior of Ideal Gas Mixtures

Many thermodynamic applications involve mixtures of ideal gases. That is, each of the gases in
the mixture individually behaves as an ideal gas. 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 a situation encountered at low densities.

The P-v-T behavior of an ideal gas is expressed by the simple relation, which is called the ideal-
gas equation of state.
Pv = RT (1.7)

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.

The prediction of the P-v-T behavior of gas mixtures is usually based on two models: Dalton’s
law of additive pressures and Amagat’s law of additive volumes. Both models are described and
discussed below.

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Dalton’s 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.

Figure 1.1 Dalton’s law of additive pressures for a mixture of two ideal gases.
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.

Figure 1.2 Amagat’s law of additive volumes for a mixture of two ideal gases.

For ideal gases, these two laws are identical and give identical results. Dalton’s and Amagat’s
laws can be expressed as follows:
k
Dalton’s law: Pm = ∑ Pi (Tm ,Vm ) (1.8)
i =k

k
Amagat’s law: Vm = ∑ Vi (Tm ,Vm ) (1.9)
i =k

In these relations, Pi is called the component pressure and Vi is called the component volume.
The ratio Pi /Pm is called the pressure fraction and the ratio Vi /Vm is called the volume fraction
of component i.
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 ) ni RuTm / Vm ni

= = = yi (1.10)
Pm nm RuTm / Vm nm
Vi (Tm ,Vm ) ni RuTm / Pm ni
= = = yi (1.11)
Vm nm RuTm / Pm nm

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Therefore

Pi Vi ni
= = = yi (1.12)
Pm Vm nm

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). Note that for an ideal-gas mixture, the mole fraction, the pressure fraction, and the
volume fraction of a component are identical.

1.3 Properties of Gas Mixture

Dalton’s law was re-formulated by Gibbs to include a second statement on the properties of
mixtures. The combined statement is known as the Gibbs-Dalton law, and is as follows
• The internal energy, enthalpy, and entropy of a gaseous mixture are respectively equal to
the sums of the internal energies, enthalpies, and entropies, of the constituents.
• Each constituent has that internal energy, enthalpy and entropy, which it could have if it
occupied alone that volume occupied by the mixture at the temperature of the mixture.
This statement leads to the following equations :
k
(mu ) m = m1u1 + m2u2 + ....... + mk uk Or (mu ) m = ∑ mi ui (1.13)
i =1
k
u = ∑ mfi ui (1.14)
i =1
k
(mh) m = m1h1 + m2 h2 + ....... + mk hk Or (mh) m = ∑ mi hi (1.15)
i =1
k
h = ∑ mfi hi (1.16)
i =1
k
(ms ) m = m1s1 + m2 s2 + ....... + mk sk Or (ms ) m = ∑ mi si (1.17)
i =1
k
s = ∑ mfi si (1.18)
i =1

1.4 Adiabatic Mixing of Perfect Gases

Figure 1.3 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
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the total volume, behave 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.

Figure 1.3 Gases before and after mixture

In a free expansion process, the internal energy initially is equal to the internal energy finally.

=U1 nACvATA + nB CvBTB (1.19)

and =
U 2 (nACvA + nB CvB )T
If this result is extended to any number of gases, we have
k k
U1 = ∑ ni CviTi and U 2 = T ∑ ni Cvi
i =1 i =1

Then U1=U2
k k
U1 = ∑ ni CviTi = U 2 = T ∑ ni Cvi
i =1 i =1

∑nC T i vi i
T= i =1
k
(1.20)
∑nC
i =1
i vi

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

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Figure 1.4 Fluid mixture

Applying steady-flow energy equation to the mixing section (neglecting changes in kinetic and
potential energy), we get
   
mA hA1 + mB hB1 +=
Q mA hA 2 + mB hB 2 + W (1.21)
In case of adiabatic flow: Q = 0, and also W = 0 in this case
   
mA hA1 + mB hB1 = mA hA 2 + mB hB 2 (1.22)
Also h = cpT, hence,
   
mA c pATA1 + mB c pBTB1 =mA c pAT + mB c pBT (1.23)

For any number of gases this becomes

k  k 

=i 1 =i 1
∑ mi c piTi = T ∑ mi c pi
k 
∑m c i pi i T
T= i =1
k 
(1.24)
∑m c
i =1
i pi

Also, Cp = Mcp and M = m/n

nC p = mc p
k

∑n c T
i pi i
Hence, T= i =1
k
(1.25)
∑n c
i =1
i pi

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Eqns. (9.28) and (9.29) 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., specific volume or the final pressure) before a complete solution is possible.

1.5 Mixing of Ideal Gases initially at different Pressure and Temperature

Consider three ideal gases A, B and C initially at different pressure and temperature and
separated by partitions. Let the gases be mixed by removing the partitions.

The total volume and mass occupied by the mixture are given by

V = VA + VB + VC and m = mA + mB + mC (1.26)

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 expression:

mu = ma ua + mbub + mc uc (1.27)

Since u for a perfect gas is equal to cv T, this relation may be rewrite as:

mcvT = ma cvaTa + mb cvbTb + mc cvcTc (1.28)

ma cvaTa + mb cvbTb + mc cvcTc

T= (1.29)
mcv

ma cvaTa + mb cvbTb + mc cvcTc

T= (1.30)
ma cva + mb cvb + mc cvc

Appling the perfect gas law i.e, PV = mRT

PaVa cva PV c PV c
+ b b vb + c c vc
Ra Rb Rc
T= (1.31)
PaVa cva PV c PV c
+ b b vb + c c vc
Ta Ra Tb Rb Tc Rc

Multiplying each terms in the numerator and denominator of equation by the respective
molecular weights:

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M a PaVa cva M b PV
b b cvb M PV c
+ + c c c vc
M a Ra M b Rb M c Rc
T= (1.32)
M a PaVa cva M b PV c M PV c
+ b b vb
+ c c c vc
M aTa Ra M bTb Rb M cTc Rc
The product Mcv is the same for ideal gases and the product MR=Ru is a constant for all ideal
gases. Cancellation of these quantities from equation results in:
PaVa + PV
b b + PV
T= c c
(1.33)
PaVa PV PV
+ b b+ c c
Ta Tb Tc
Where : mR=PV/T
PaVa + PV
b b + PV
T= c c
(1.34)
mR
If the pressure are all equal before mixing then, then from equation, the resulting mixing
temperature will be obtained from:
Va + Vb + Vc
T= (1.35)
Va Vb Vc
+ +
Ta Tb Tc
If the volume are all equal before mixing then, then from equation, the resulting mixing
temperature will be obtained from:

Pa + Pb + Pc
T= (1.38)
Pa Pb Pc
+ +
Ta Tb Tc

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