5/6/2023

MCE 419 – APPLIED

THERMODYNAMICS II
MCE 419 - Applied Thermodynamics

PROFESSOR ADEKOJO WAHEED

MCE 419: APPLIED THERMODYNAMICS (2 UNITS)

COURSE SYNOPSIS
• Gaseous mixture, Combustion, availability. Other methods of energy
conversion, e.g. fuel cells, thermo-electric generators, magneto
hydrodynamics, introduction to plasma state, laser beams. Elements of
compressible flows.

1
 5/6/2023

COURSE OUTLINE
Properties of a mixture of ideal gases
• Properties of a mixture of an ideal gas and a condensable vapour
• Psychrometry
Combustion
• Application of first and second laws of thermodynamics to combustion
Availability (Exergy)
Energy conversion
• Fuel cells
• Thermo-electric generator
• Magneto hydrodynamics
• Introduction to plasma state
• Laser beams
Elements of compressible flow

RESOURCES FOR OUR LEARNING

Textbook:
• Moran, MJ and Shapiro, HN (2006) Fundamentals of Engineering Thermodynamics,
Seventh Edition, .
1. Moran, Michael J., Shapiro, Howard N., Munson, Bruce R. and DeWitt, David P. (2003),
Introduction to Thermal Systems Engineering: Thermodynamics, Fluid Mechanics, and Heat
Transfer, John Wiley & Sons, Inc., USA.
2. Cengel, YA, Boles, MA, and Kanoglu, M (2019). Thermodynamics: An Engineering Approach,
9th Edition, McGraw-Hill Education.
3. U. S. DOE (1992),Thermodynamics, Heat Transfer, and Fluid Flow-Department of Energy
Fundamentals Handbook, Washington, D.C.
4. Rajput, RK (2006). Thermal Engineering, Laxmi Publications (P) Ltd., New Delhi.
5. Rajput, RK (2006). Engineering Thermodynamics, 3rd Edition,Laxmi Publications (P) Ltd.,
New Delhi.
6. Roger, GFC and Mayhew, YR (1992). Engineering Thermodynamics: Work and Heat
Transfer, Longman Group Limited, 4th Edition, UK.
• Ryan O’hayre, Suk-won Cha, Whitney G. Colella, Fritz B. Prinz (2016) Fuel Cell
Fundamentals, 3rd Edition, Published By John Wiley & Sons, Inc., Hoboken, New Jersey. 4

2
 5/6/2023

RESOURCES FOR OUR LEARNING

Textbook:
1. Moran, Michael J., Shapiro, Howard N., Munson, Bruce R. and DeWitt, David P. (2003),
Introduction to Thermal Systems Engineering: Thermodynamics, Fluid Mechanics, and Heat
Transfer, John Wiley & Sons, Inc., USA.
2. Cengel, Y. A. and Boles, M. A. (2006). Thermodynamics: An Engineering Approach, 5th
Edition, McGraw Hill.
3. U. S. DOE (1992),Thermodynamics, Heat Transfer, and Fluid Flow-Department of Energy
Fundamentals Handbook, Washington, D.C.
4. Rajput, R. K. (2006). Thermal Engineering, Laxmi Publications (P) Ltd., New Delhi.
5. Roger, G. F. C. and Mayhew, Y. R. (1992). Engineering Thermodynamics: Work and Heat
Transfer, Longman Group Limited, 4th Edition, UK.
Others
• Read assigned sections before coming to class.
• Class participation - welcome and essential.
• Other Instructors, i. e., Classmates, Organized Learning Groups very useful
• Homework: Submission, grading, and return policies will be announced in the class.
5

Lecture I
GAS MIXTURES
Properties of a mixture of ideal gases: Properties of a mixture of an ideal gas and a condensable
vapour, Psychrometry

3
 5/6/2023

Objectives
• Develop rules for determining nonreacting gas mixture properties from
knowledge of mixture composition and the properties of the individual
components.
• Define the quantities used to describe the composition of a mixture, such as
mass fraction, mole fraction, and volume fraction.
• Apply the rules for determining mixture properties to ideal-gas mixtures and
real-gas mixtures.
• Predict the P-v-T behavior of gas mixtures based on Dalton’s law of additive
pressures and Amagat’s law of additive volumes.
• Perform energy and exergy analysis of mixing processes.

PURE SUBSTANCE

A pure substance is a system which is

(i) homogeneous in composition,
(ii) homogeneous in chemical aggregation, and
(iii) invariable in chemical aggregation.

— “Homogeneous in composition” means that the composition of each part of

the system is the same as the composition of every other part. “Composition
means the relative proportions of the chemical elements into which the sample
can be analysed. It does not matter how these elements are combined.

4
 5/6/2023

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:
Molar analysis: specifying the
number of moles of each
component
Gravimetric analysis: specifying
the mass of each component
The mass of a mixture is equal to the
sum of the masses of its components.

Mass fraction

The number of moles of a nonreacting mixture is equal to Mole fraction

the sum of the number of moles of its components.

Apparent (or average) molar mass The sum of the mass and mole
fractions of a mixture is equal to 1.

Gas constant

The molar mass of a mixture

Mass and mole fractions of a mixture

are related by The sum of the mole fractions
of a mixture is equal to 1.

10

5
 5/6/2023

P-v-T BEHAVIOR OF GAS MIXTURES: IDEAL AND REAL GASES

• 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.
• Real gases approximate this behavior closely when they are at a low pressure or high
temperature relative to their critical-point values
• 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.
• A nonreacting mixture of ideal gases also behaves as an ideal gas because the behavior
of a molecule normally is not influenced by the presence of other similar or dissimilar
molecules.
• Air, for example, is conveniently treated as an ideal gas in the range where nitrogen and
oxygen behave as ideal gases.
• When a gas mixture consists of real (nonideal) gases, however, the prediction of the P-v-T
behavior of the mixture becomes rather involved
11

P-v-T BEHAVIOR OF GAS MIXTURES: The prediction of the P-v-T

IDEAL AND REAL GASES behavior of gas mixtures is usually
based on two models:
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
Dalton’s law of additive pressures for a mixture of two ideal gases. 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.

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

12

6
 5/6/2023

Pi component pressure Vi component volume

Pi /Pm pressure fraction Vi /Vm volume fraction
For ideal gases, Dalton’s and Amagat’s laws are identical and
give identical results.

The volume a component would occupy if it existed alone at the mixture T and P is called
the component volume (for ideal gases, it is equal to the partial volume yiVm).
13

Ideal-Gas Mixtures

This equation is only valid for ideal-gas mixtures as 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),
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.
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)
14

7
 5/6/2023

PROPERTIES OF GAS MIXTURES: IDEAL AND

REAL GASES
Extensive properties of a gas mixture
The extensive
properties of a
mixture are
determined by simply
adding the properties
of the components.

Changes in properties of a gas mixture

15

Intensive properties of a gas mixture

Properties per unit mass involve mass fractions (mfi)

and properties per unit mole involve mole fractions (yi). The intensive
The relations are exact for ideal-gas mixtures, properties of a
and approximate for real-gas mixtures. mixture are
determined by
weighted averaging.
16

8
 5/6/2023

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.

17

These relations are applicable to both ideal- and real-gas mixtures. The properties or property changes of individual
components can be determined by using ideal-gas or real-gas relations developed in earlier chapters.

Ratio of specific heats k is given as

C p ,m C p ,m
km  
C v ,m C v ,m
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. We employ the Gibbs-Dalton law that says each gas behaves as if it alone occupies the volume of
the system at the mixture temperature. That is, the pressure of each component is the partial pressure.

For constant specific heats, the entropy change of any component is

18

9
 5/6/2023

The entropy change of the mixture per mass of mixture is

The entropy change of the mixture per mole of mixture is

19

In these last two equations, recall that

Pi , 1  y i , 1 Pm , 1
Pi , 2  y i , 2 Pm , 2
Example 13-1

An ideal-gas mixture has the following volumetric analysis

Component % by Volume
N2 60
CO2 40

(a)Find the analysis on a mass basis.

For ideal-gas mixtures, the percent by volume is the volume fraction. Recall

yi  vf i
20

10
 5/6/2023

Comp. yi Mi yiMi mfi = yiMi /Mm

kg/kmol kg/kmol kgi/kgm
N2 0.60 28 16.8 0.488
CO2 0.40 44 17.6 0.512
Mm = yiMi = 34.4

(b) What is the mass of 1 m3 of this gas when P = 1.5 MPa and T = 30oC?
Ru
Rm  ( kJ / kg  K )
Mm
kJ
8 .3 1 4
 k m o l  K  0 .2 4 2 k J
kg kg  K
3 4 .4
km ol
Pm V m
mm 
R m Tm
1.5 M P a ( 1 m 3 ) 10 3 kJ

( 0 .2 4 2 k J / ( k g  K ) ) ( 3 0  2 7 3 ) K m 3 M P a
 2 0 .4 5 k g 21

(c) Find the specific heats at 300 K.

Using Table A-2, Cp N2 = 1.039 kJ/kgK and Cp CO2 = 0.846 kJ/kgK

2
C p ,m   1
m f i C p , i  ( 0 .4 8 8 ) ( 1.0 3 9 )  ( 0 .5 1 2 ) ( 0 .8 4 6 )

kJ
 0 .9 4 0
kg m  K
kJ
C v , m  C p , m  R m  ( 0 .9 4 0  0 . 2 4 2 )
kg m  K
kJ
 0 .6 9 8
kg m  K

22

11
 5/6/2023

(d) This gas is heated in a steady-flow process such that the temperature is increased by 120oC.
Find the required heat transfer. The conservation of mass and energy for steady-flow are

m& 1  m& 2  m&

m& 1 h 1  Q& i n  m& 2 h 2
Q& i n  m& ( h 2  h 1 )
 m& C p , m ( T 2  T1 )
The heat transfer per unit mass flow is
Q& in
q in   C p , m ( T 2  T1 )
m&
kJ
 0 .9 4 0 (1 2 0 K )
kg m  K
kJ
 1 1 2 .8
kg m 23

(e) This mixture undergoes an isentropic process from 0.1 MPa, 30oC, to 0.2 MPa. Find T2.

The ratio of specific heats for the mixture is

C p ,m 0 .9 4 0
k    1. 3 4 7
C v ,m 0 .6 9 8
Assuming constant properties for the isentropic process

(f) Find Sm per kg of mixture when the mixture is compressed isothermally from 0.1 MPa to 0.2 MPa.

24

12
 5/6/2023

But, the compression process is isothermal, T2 = T1. The partial pressures are given by
Pi  y i Pm
The entropy change becomes

For this problem the components are already mixed before the compression process. So,
y i , 2  y i ,1
Then,

25

2
 sm  
i1
m f i  si

kg N 2 kJ k g CO2 kJ
 ( 0 .4 8 8 )(  0 .2 0 6 )  ( 0 .5 1 2 )(  0 .1 3 1 )
kg m kg N2  K kg m k g CO2  K
kJ
  0 .1 6 7
kg m  K
Why is sm negative for this problem? Find the entropy change using the average specific heats of the
mixture. Is your result the same as that above? Should it be?

(g) Both the N2 and CO2 are supplied in separate lines at 0.2 MPa and 300 K to a mixing chamber
and are mixed adiabatically. The resulting mixture has the composition as given in part (a).
Determine the entropy change due to the mixing process per unit mass of mixture.

26

13
 5/6/2023

Take the time to apply the steady-flow conservation of energy and mass to show that the temperature
of the mixture at state 3 is 300 K.

But the mixing process is isothermal, T3 = T2 = T1. The partial pressures are given by

Pi  y i Pm
The entropy change becomes

27

But here the components are not mixed initially. So,

y N 2 ,1  1
y CO2 ,2  1
and in the mixture state 3,
y N 2 , 3  0 .6
y C O 2 , 3  0 .4
Then,

28

14
 5/6/2023

2
Then,  s m  
i1
m f i  si

kg N 2 kJ kg CO2 kJ
 ( 0 .4 8 8 ) ( 0 .1 5 2 )  ( 0 .5 1 2 ) ( 0 .1 7 3 )
kg m kg N 2  K kg m k g C O2  K
kJ
 0 .1 6 3
kg m  K
If the process is adiabatic, why did the entropy increase?

Extra Assignment
Nitrogen and carbon dioxide are to be mixed and allowed to flow through a convergent nozzle. The
exit velocity to the nozzle is to be the speed of sound for the mixture and have a value of 500 m/s when
the nozzle exit temperature of the mixture is 500°C. Determine the required mole fractions of the
nitrogen and carbon dioxide to produce this mixture. From Chapter 17, the speed of sound is given by

NOZZLE C = 500 m/s

C  kR T Mixture T = 500oC
N2 and CO2

Answer: yN2 = 0.589, yCO2 = 0.411 29

Gas-Vapor Mixtures and Air-

Conditioning
Description

30

15
 5/6/2023

PSYCHROMETRY
This is the study of properties of moist atmospheric air (i.e. a mixture of dry air and water vapor).

Knowledge of psychrometry is important for instance, in paper and textile industry, where close
control of the vapour content of atmosphere as well as temperature is required.

Psychrometry is also referred to as hygrometry. Hygrometry uses certain technical term which
arises either for need to specify the composition of mixture or from the method of measuring the
composition.
We will be concerned with the mixture of dry air and water vapor. This mixture is often called
atmospheric air.

The temperature of the atmospheric air in air-conditioning applications ranges from about –10 to
about 50oC. Under these conditions, we treat air as an ideal gas with constant specific heats.
Taking Cpa = 1.005 kJ/kgK, the enthalpy of the dry air is given by (assuming the reference state to
be 0oC where the reference enthalpy is taken to be 0 kJ/kga)

31

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. See Figure A-9 for the actual T-s diagram.

32

16
 5/6/2023

The enthalpy of the saturated vapor 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.

Pv  Ps a t @ T m ix

When the mixture pressure is increased while keeping the mixture temperature constant, the vapor
partial pressure increases up to the vapor saturation pressure at the mixture temperature and
condensation begins. Therefore, the partial pressure of the water vapor can never be greater than its
saturation pressure corresponding to the temperature of the mixture.

33

Relative humidity 
The relative humidity,  is the ratio of the actual mass (or partial
pressure pv) of the vapor to the mass (or partial pressure pg) of the
vapor when it is saturated at the same temperature.

Mass of vapor in air m

   v
Mass of vapor in air when saturated m g
or
Pressure of vapor in air p
   v
Pressure of vapor in air when saturated pg

34

17
 5/6/2023

Pv and Pg are shown on the following T-s diagram for the water-vapor alone.
Ste am
125

75
T[C]

Tm 25 Pg = 3.169 kPa o Vapor State

Tdp Pv = 1.491 kPa

-25
0 2 4 6 8 10 12

s [kJ/kg-K]

Pv 1. 4 9 1 k P a
Since P g  Pv ,   1 o r 1 0 0 % ,  
Pg

3 .1 6 9 k P a
 0 .4 7

35

Absolute humidity or specific humidity (sometimes called

humidity ratio), 
Absolute humidity (or moisture content) is the ratio of the mass of water vapor mv
to the mass of dry air ma in any given volume V of mixture
mass of water vap our in air m v
  
mass of dry air ma
PvV RvT P R
  v v
PaV RaT Pa Ra
Pv P
 0.622  0.622 v
Pa P - Pv
Using the definition of the specific humidity, the relative humidity may be expressed as

P 0 .6 2 2  P g
  and  
( 0 .6 2 2   ) P g P   Pg
36

18
 5/6/2023

Percentage Saturation
This is defined as the ratio of the specific humidity of a mixture to the specific
humidity of the mixture when saturated at the same temperature; it is expressed
as a percentage, i.e. percentage saturated,
Specific humidity 
  
Specific humidity w hen saturated  g

Percentage saturation can also be expressed as

  
P - P 
g

P - Pv 
In air-conditioning practice the percentage difference between  and  is in
the range 0.5 – 2%, approximately.

37

Dew Point, Tdp

The dew point is the temperature to which unsaturated air must

be cooled at constant pressure for it to be saturated (or for
condensation to begin)

Consider cooling an air-water vapor mixture while the mixture total

pressure is held constant. When the mixture is cooled to a
temperature equal to the saturation temperature for the water-vapor
partial pressure, condensation begins.
Steam
375

When an atmospheric air-vapor mixture is 325

275
cooled at constant pressure such that the 225

partial pressure of the water vapor is 1.491

T[C]

175

125 1.491 kPa

kPa, then the dew point temperature of that 75

mixture is 12.95oC. TDP

25

-25
0 2 4 6 8 10 12

s [kJ/kg-K]

38

19
 5/6/2023

Degree of Superheat
When a dry saturated vapour is heated at constant pressure its
temperature
rises and it becomes superheated. The difference between the actual
temperature of the superheated vapour and the saturation temperature at
the pressure of the vapour is called the degree of superheat.

Volume of mixture per mass of dry air, v

V m m R m T m / Pm
v  
ma ma
After several steps, we can show (you should try this)
V R a Tm
v   va 
ma Pa
So the volume of the mixture per unit mass of dry air is the specific volume
of the dry air calculated at the mixture temperature and the partial pressure
of the dry air

39

Mass of mixture
mv
m  m a  m v  m a (1  )  m a (1   )
ma

Mass flow rate of dry air, m& a

Based on the volume flow rate of mixture at a given state, the
mass flow rate of dry air is
V& m3 / s kg a
m& a  
v m 3 / kg a s

Enthalpy of mixture per mass dry air, h

Hm Ha  Hv m a ha  m v hv
h   
ma ma ma
 ha   hv

40

20
 5/6/2023

Example 1
Atmospheric air at 30oC, 100 kPa, has a dew point of 21.3oC. Find the
relative humidity, humidity ratio, and h of the mixture per mass of dry air.

Pv 2 .5 4 8 k P a
    0 .6 o r 6 0 %
Pg 4 .2 4 7 k P a

2 .5 4 8 k P a kgv
  0 .6 2 2  0 .0 1 6 2 6
( 1 0 0  2 .5 4 8 ) k P a kga
h  ha   hv
 C p , a T   ( 2 5 0 1 .3  1 .8 2 T )
kJ kgv kJ
 1. 0 0 5 ( 3 0 o C )  0 .0 1 6 2 6 ( 2 5 0 1 .3  1 .8 2 ( 3 0 o C ) )
k g a o C kg a kg v
kJ
 7 1 .7 1
kg a 41

Example 2
If the atmospheric air in the last example is conditioned to 20oC, 40 percent relative
humidity, what mass of water is added or removed per unit mass of dry air?
Solution
At 20oC, Pg = 2.339 kPa.
Pv   P g  0 .4 ( 2 .3 3 9 k P a )  0 .9 3 6 k P a
Pv 0 .9 3 6 k P a
w  0 .6 2 2  0 .6 2 2
P  Pv ( 1 0 0  0 .9 3 6 ) k P a
kgv
 0 .0 0 5 8 8
kg a
The change in mass of water per mass of dry air is
m v , 2  m v ,1
  2  1
ma
m v , 2  m v ,1 kgv
 ( 0 .0 0 5 8 8  0 .0 1 6 2 6 )
ma kga
This implies that as the mixture changes from
kg v
  0 .0 1 0 3 8 state 1 to state 2, 0.01038 kg of water
kga vapor is condensed for each kg of dry air. 42

21
 5/6/2023

Example 3
Atmospheric air is at 25oC, 0.1 MPa, 50 percent relative humidity. If the
mixture is cooled at constant pressure to 10oC, find the amount of water
removed per mass of dry air.

Sketch the water-vapor states relative to the saturation

lines on the following T-s diagram.

At 25oC, Psat = 3.170 kPa, and with  1 = 50%

Pv ,1  1 Pg ,1  0.5(3.170 kPa )  1.585 kPa
s
Tdp ,1  Tsat @ Pv  13.8o C

43

Pv ,1 15845
. kPa
w1  0.622  0.622
P  Pv ,1 (100  15845
. ) kPa
kgv
 0.01001
kga
Therefore, when the mixture gets cooled to T2 = 10oC < Tdp,1, the mixture is

saturated, and 2= 100%. Then Pv,2 = Pg,2 = 1.228 kPa.
Pv ,2 1.228 kPa
w2  0.622  0.622
P  Pv , 2 (100  1.228) kPa
kg v
 0.00773
kg a
The change in mass of water per mass of dry air is
mv , 2  mv ,1
  2  1
ma
Or as the mixture changes from
kgv state 1 to state 2, 0.00228 kg of
 (0.00773  0.01001)
kga water vapor is condensed for each
kgv kg of dry air.
 0.00228
kga 44

22