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ME2121

Thermodynamics

Lecture 7
Gaseous Mixtures (Non-Reacting)
Sections 13.1 to 13.3 (Cengel & Boles)

Definitions & Basics

A non-reacting gaseous mixture is a multi-component system in


which the constituents do not react with one another.
No chemical reaction!

Mass fraction
The total mass of a mixture is the sum of the constituents:

m mi
i

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The ratio mi/m is called the mass fraction


of the component in the mixture.

L7: Gaseous Mixtures (Non-reacting)

Definitions & Basics

Mole
The mole is the amount of substance of a system containing as many
elementary entities as there are atoms in 0.012 kg of C.

must be specified and may be atoms, molecules, ions,


electrons or other particles or groups.

Example of a mole
One mole of O2 is a mass of 0.032 kg since O has a molar mass of 32.
(compared to 12 for Carbon-12)

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L7: Gaseous Mixtures (Non-reacting)

Definitions & Basics (contd.)

Avogrado's hypothesis

Equal volumes of all gases contain the same number of


molecules when the volumes are measured under the same
conditions of temperature and pressure.
For any gas, 1 mole contains 6.022 x 1023 elementary entities
1 kmole contains 6.022 x 1026 elementary entities

Elementary entities could be atoms e.g. for He & Ar, or


molecules e.g. for O2, N2 & H2.

The kilomole (kmol) is the amount of substance numerically equal


to its molar mass in kg
E.g. 1 kmole of O2 has a mass of 32 kg.

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L7: Gaseous Mixtures (Non-reacting)

Definitions & Basics (contd.)

Mole fraction
The total number of moles, n for a mixture is the sum of the moles
of the constituents.
The ratio, ni/n is termed the mole fraction, xi.
xi 1 for a mixture
i

N.B.: The number of atoms or molecules is directly related to the


volume of the gas!
i.e. the mole fraction is also a measure of the volume fraction!

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L7: Gaseous Mixtures (Non-reacting)

Definitions & Basics (contd.)

Molar mass of gaseous mixture,

Mass of ith component,


mi ni M i where M i molar mass of the ith component

1
ni M i i xi M i
n i

where overscore denotes per mole or kmole (as appropriate)

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L7: Gaseous Mixtures (Non-reacting)

Definitions & Basics (contd.)

Daltons law of partial pressures


The pressure of a mixture of gases is equal to the sum of the
pressures of the individual constituents when each occupies a volume
equal to that of the mixture at the same temperature.
The mixture and constituents are assumed to behave as ideal gases!
This is proven by considering a specified volume V and temperature T,

n n1 n2 ...... ni ni

PV nRT where R = universal gas constant

PV PV
PV
PV
PV

1 2 ...... i i
RT RT RT
RT
i RT
P P1 P2 ...... Pi Pi
i

Also x i

ni PV
RT Pi
i

n PV RT P

partial pressure of the ith component


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L7: Gaseous Mixtures (Non-reacting)

Definitions & Basics (contd.)

Amagats law of partial volumes (also known as Leducs Law)


The volume of a mixture of gases is equal to the sum of the volumes
of the individual constituents when each exists alone at the pressure
and temperature of the mixture.
Ideal gas behaviour is assumed for the mixture and constituents!
Considering a specified pressure P and temperature T,

n n1 n2 ...... ni ni

PV nRT where R = universal gas constant

PV
PV
PV PV1 PV2

...... i i
RT RT RT
RT
i RT
V V1 V2 ......Vi Vi

Also x i

ni PVi RT Vi

n
PV RT V

partial volume of the ith component


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L7: Gaseous Mixtures (Non-reacting)

Pi
P
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Total Mixture Properties

Internal energy
For a constituent,

U i ni ui where ui is the internal energy per mole


of the ith constituent at the mixture temperature.
Total mixture internal energy:

U U 1 U 2 ......U i U i
i

The internal energy per mole of mixture may be calculated:

U
U
n

U
i

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n u

i i

xi ui
i

L7: Gaseous Mixtures (Non-reacting)

Total Mixture Properties (contd.)

Enthalpy
Total mixture enthalpy:
H U PV
The enthalpy per mole of mixture may be calculated:

H U

V Pi 1
1
U i PiV ni ui PiV
n
n i
n i

i.e. H xi hi
i

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Total Mixture Properties (contd.)

Specific heats
For ideal gases, the specific heat quantities per mole:

CV

dU
xi CV , i
dT
i

CP

dH
xi C P , i
dT
i

The relation with universal gas constant:

R C P CV xi R
i

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Total Mixture Properties (contd.)

Entropy
Total mixture entropy:

S S i ni S i
i

Entropy per mole of mixture:

1
S i xi S i
n i
i

Question: How are specific properties of a mixture related with


those of its constituents?
e.g. show that

s mf i si
i

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Entropy of Mixing

For each component (ideal gas behaviour assumed),


Tds dh vdP and Pv RT
C dT R
ds P
dP
T
P
dS i

C P dTi R
dPi where Ti temperature of component
Ti
Pi

Therefore for the mixture,

dT
dP
dS xi C P i xi Ri i
Ti i
Pi
i

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Entropy of Mixing (contd.)

But dS Mds and xi

ni mi

n Mi

m
M

ds

mi Ri dPi
dS 1 mi C P i dTi

M m i M i Ti i M i Pi

ds

dPi
dTi
1
mi C P i
mi Ri

Pi
Ti i
m i

The entropy change resulting from mixing may be calculated from the
temperature and partial pressure changes and constituent masses!

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L7: Gaseous Mixtures (Non-reacting)

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Example 1
The percentage volumetric composition of air is as follows: nitrogen (N ) 78.09,
oxygen (O ) 20.95, argon (Ar) 0.96. Given that the molar masses of the
constitutients are 28, 32 and 40, respectively, calculate the % gravimetric
composition. If the mixture is maintained at 150 kPa and 25C, determine the
partial pressure of the oxygen.

Solution:
The mass per kmole of mixture for each constituent, and hence the %
gravimetric composition may be calculated as shown in the following table:

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Example 1 (contd)

Constituent

Volume
fraction

Molar
mass

Mass per
kmole

% grav comp.

(a)

(b)

(c)

(d)=(b)x(c)

(e)=(d)/(d)

N2

0.7809

28

21.87

75.55

O2

0.2095

32

6.70

23.14

Ar

0.0096

40

0.38

1.31

TOTAL

28.95

100.0

Partial pressure of O2
= vol fraction of O2 x total pressure
= 0.2095 x 150 = 31.44 kPa
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Example 2
Two containers, each of volume 0.7 m3, are isolated from each other by a
partition. One contains O2, the other N2, each at 7 bar and 90C. The partition
is removed and mixing occurs. Calculate the end state of the mixture and the
entropy change.

Solution:
Assuming adiabatic conditions, there will be no changes of pressure, P and
temperature, T of the mixture.
Considering Avogrado's Law,
no. of moles of O2, nO2 = no. of moles of N2 , nN2
Therefore mole fraction of both O2 and N2 ,
x O2 = x N2 = 0.5 after removal of partition

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Example 2 (contd.)

Partial pressures of O2 and N2 after removal of the partition,

PO2 PN 2 0.5 P where P is the pressure of the mixture


Therefore change of entropy in the mixing process may be calculated:

Tds dh vdP and Pv RT


ds

C P dT R
dP
T
P
PV nR T
dT = 0

P
S nO2 R ln
PO2

P
n N 2 R ln

PN 2

=1.87 kJ/K

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Assignment 5
Please attempt:
Problem Set 3:
Q 1 (problem-solving class)
Q 2 (Imparo online tutorial)
(Please attempt problems before referring to the Outline Solutions
for maximum benefit in learning)
Enjoy!!

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L7: Gaseous Mixtures (Non-reacting)

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