LECTURE NOTES ON

GAS TURBINES AND PROPULSION

Joseph M. Powers

Department of Aerospace and Mechanical Engineering

University of Notre Dame
Notre Dame, Indiana 46556-5637
USA

updated
19 January 2025, 10:21am
2

CC BY-NC-ND. 19 January 2025, J. M. Powers.

Contents

Preface 7

1 Thermodynamics review 9
1.1 Definitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.2 Canonical equations of state . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
1.3 Isentropic relations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

2 Compressible flow review 21

2.1 Generalized one-dimensional equations . . . . . . . . . . . . . . . . . . . . . 21
2.1.1 Mass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.1.2 Momentum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.1.3 Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2.1.4 Influence coefficients . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
2.2 Flow with area change . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
2.2.1 Isentropic Mach number relations . . . . . . . . . . . . . . . . . . . . 33
2.2.2 Sonic properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
2.2.3 Effect of area change . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
2.2.4 Choking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
2.3 Normal shock waves . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
2.3.1 Governing equations . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
2.3.2 Rayleigh line . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
2.3.3 Hugoniot curve . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
2.3.4 Solution procedure for general equations of state . . . . . . . . . . . 49
2.3.5 Calorically perfect ideal gas solutions . . . . . . . . . . . . . . . . . . 50
2.3.6 Acoustic limit . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
2.3.7 Non-ideal gas solutions . . . . . . . . . . . . . . . . . . . . . . . . . . 61
2.4 Flow with area change and normal shocks . . . . . . . . . . . . . . . . . . . 64
2.4.1 Converging nozzle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
2.4.2 Converging-diverging nozzle . . . . . . . . . . . . . . . . . . . . . . . 66
2.5 Flow with friction–Fanno flow . . . . . . . . . . . . . . . . . . . . . . . . . . 68
2.6 Flow with heat transfer–Rayleigh flow . . . . . . . . . . . . . . . . . . . . . 74
2.7 Two-dimensional equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77

3
4 CONTENTS

2.7.1 Conservative form . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78

2.7.2 Non-conservative form . . . . . . . . . . . . . . . . . . . . . . . . . . 78
2.8 Mach waves . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
2.9 Oblique shock waves . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
2.10 Small disturbance theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
2.11 Centered Prandtl-Meyer rarefaction . . . . . . . . . . . . . . . . . . . . . . . 92
2.12 Wave interactions and reflections . . . . . . . . . . . . . . . . . . . . . . . . 97
2.12.1 Oblique shock reflected from a wall . . . . . . . . . . . . . . . . . . . 97
2.12.2 Oblique shock intersection . . . . . . . . . . . . . . . . . . . . . . . . 98
2.12.3 Shock strengthening . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
2.12.4 Shock weakening . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
2.13 Supersonic flow over airfoils . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
2.13.1 Flat plate at angle of attack . . . . . . . . . . . . . . . . . . . . . . . 99
2.13.2 Diamond-shaped airfoil . . . . . . . . . . . . . . . . . . . . . . . . . . 104
2.13.3 General curved airfoil . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
2.13.4 Transonic transition . . . . . . . . . . . . . . . . . . . . . . . . . . . 105

3 Thrust and performance parameters 107

4 Cycle analysis 111

4.1 Carnot . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
4.1.1 Analysis for a calorically perfect ideal gas . . . . . . . . . . . . . . . 111
4.2 Brayton air standard cycle . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
4.2.1 Classical . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
4.2.2 Regeneration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
4.2.3 Turbojet propulsion . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
4.2.4 Turbojet with afterburners . . . . . . . . . . . . . . . . . . . . . . . . 131
4.2.5 Ramjet propulsion . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134
4.2.6 Turbofan propulsion . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
4.3 Reciprocating engine power cycles . . . . . . . . . . . . . . . . . . . . . . . . 141
4.3.1 Otto . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
4.3.2 Diesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146

5 Simple chemistry for propulsion 153

5.1 Aerospace propulsion motivation . . . . . . . . . . . . . . . . . . . . . . . . 153
5.2 Time-dependent simple reaction, without flow . . . . . . . . . . . . . . . . . 155
5.3 Steady nozzle flow with simple reaction . . . . . . . . . . . . . . . . . . . . . 159

6 Chemical kinetics 167

6.1 Isothermal, isochoric kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
6.1.1 O − O2 dissociation and recombination . . . . . . . . . . . . . . . . . 171
[Link] Pair of irreversible reactions . . . . . . . . . . . . . . . . . . 171
[Link].1 Mathematical model . . . . . . . . . . . . . . . . . 171

CC BY-NC-ND. 19 January 2025, J. M. Powers.

CONTENTS 5

[Link].2 Example calculation . . . . . . . . . . . . . . . . . 177

[Link].2.1 Species concentration versus time . . . . . . 178
[Link].2.2 Pressure versus time . . . . . . . . . . . . . 179
[Link].2.3 First law analysis . . . . . . . . . . . . . . . 180
[Link].2.4 Dynamical system form . . . . . . . . . . . . 181
[Link].3 Effect of temperature . . . . . . . . . . . . . . . . . 185
[Link] Single reversible reaction . . . . . . . . . . . . . . . . . . . . 186
[Link].1 Mathematical model . . . . . . . . . . . . . . . . . 186
[Link].1.1 Kinetics . . . . . . . . . . . . . . . . . . . . 186
[Link].1.2 Thermodynamics . . . . . . . . . . . . . . . 188
[Link].2 Example calculation . . . . . . . . . . . . . . . . . 189
6.1.2 Zel’dovich mechanism of NO production . . . . . . . . . . . . . . . . 192
[Link] Mathematical model . . . . . . . . . . . . . . . . . . . . . . 192
[Link].1 Standard model form . . . . . . . . . . . . . . . . . 192
[Link].2 Reduced form . . . . . . . . . . . . . . . . . . . . . 193
[Link].3 Example calculation . . . . . . . . . . . . . . . . . 197
[Link] Stiffness, time scales, and numerics . . . . . . . . . . . . . . 202
[Link].1 Effect of temperature . . . . . . . . . . . . . . . . . 202
[Link].2 Effect of initial pressure . . . . . . . . . . . . . . . 204
[Link].3 Stiffness and numerics . . . . . . . . . . . . . . . . 206
6.2 Adiabatic, isochoric kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . 208
6.2.1 Thermal explosion theory . . . . . . . . . . . . . . . . . . . . . . . . 208
[Link] One-step reversible kinetics . . . . . . . . . . . . . . . . . . 209
[Link] First law of thermodynamics . . . . . . . . . . . . . . . . . 210
[Link] Dimensionless form . . . . . . . . . . . . . . . . . . . . . . . 213
[Link] Example calculation . . . . . . . . . . . . . . . . . . . . . . 214
[Link] High activation energy asymptotics . . . . . . . . . . . . . . 216
6.2.2 Detailed H2 − O2 − N2 kinetics . . . . . . . . . . . . . . . . . . . . . 219

7 Aerothermochemistry 223
7.1 Molecular mass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
7.2 Stoichiometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
7.2.1 General development . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
7.2.2 Fuel-air mixtures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
7.3 First law analysis of reacting systems . . . . . . . . . . . . . . . . . . . . . . 235
7.3.1 Enthalpy of formation . . . . . . . . . . . . . . . . . . . . . . . . . . 235
7.3.2 Enthalpy and internal energy of combustion . . . . . . . . . . . . . . 237
7.3.3 Adiabatic flame temperature in isochoric stoichiometric systems . . . 238
[Link] Undiluted, cold mixture . . . . . . . . . . . . . . . . . . . . 238
[Link] Dilute, cold mixture . . . . . . . . . . . . . . . . . . . . . . 239
[Link] Dilute, preheated mixture . . . . . . . . . . . . . . . . . . . 241
[Link] Dilute, preheated mixture with minor species . . . . . . . . 242

CC BY-NC-ND. 19 January 2025, J. M. Powers.

6 CONTENTS

7.4 Chemical equilibrium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243

7.5 Chemical kinetics of a single isothermal reaction . . . . . . . . . . . . . . . . 249
7.5.1 Isochoric systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
7.5.2 Isobaric systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
7.6 Some conservation and evolution equations . . . . . . . . . . . . . . . . . . . 262
7.6.1 Total mass conservation: isochoric reaction . . . . . . . . . . . . . . . 263
7.6.2 Element mass conservation: isochoric reaction . . . . . . . . . . . . . 263
7.6.3 Energy conservation: adiabatic, isochoric reaction . . . . . . . . . . . 265
7.6.4 Energy conservation: adiabatic, isobaric reaction . . . . . . . . . . . . 266
7.6.5 Entropy evolution: Clausius-Duhem relation . . . . . . . . . . . . . . 269
7.7 Multiple reaction extensions . . . . . . . . . . . . . . . . . . . . . . . . . . . 271
7.8 Equilibrium conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 278
7.8.1 Minimization of G via Lagrange multipliers . . . . . . . . . . . . . . 278
7.8.2 Equilibration of all reactions . . . . . . . . . . . . . . . . . . . . . . . 284
7.9 Concise reaction rate law formulations . . . . . . . . . . . . . . . . . . . . . 286
7.9.1 Reaction dominant: J ≥ (N − L) . . . . . . . . . . . . . . . . . . . . 287
7.9.2 Species dominant: J < (N − L) . . . . . . . . . . . . . . . . . . . . . 288
7.10 Adiabatic, isochoric kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . 288
7.11 Steady rocket nozzle flow with detailed kinetics . . . . . . . . . . . . . . . . 290

CC BY-NC-ND. 19 January 2025, J. M. Powers.

Preface

These are lecture notes for AME 40431 Gas Turbines and Propulsion, a required course for
Aerospace Engineering majors in the Department of Aerospace and Mechanical Engineering
at the University of Notre Dame. Most of the students in this course are seniors majoring in
aerospace engineering. The objective of the course is to survey both practical and theoretical
problems in aerospace propulsion.
The notes draw on the author’s course notes for other classes, AME 50531 Intermediate
Thermodynamics and AME 30332 Compressible Aerodynamics. One of the most challenging
aspects of gas turbine, reciprocating engine, and rocket propulsion is the combustion process
in which chemical energy is converted first to thermal and then to kinetic energy. While most
courses and books treat this descriptively at best, these notes dive deeper into quantitative
prediction of equilibrium thermochemistry and finite rate chemical kinetics.
These notes emphasize both problem-solving as well as some rigorous undergraduate-level
development of the underlying classical theory. It should also be remembered that practice is
essential to the learning process; the student would do well to apply the techniques presented
here by working as many problems as possible.
The notes, along with information on the course, can be found on the world wide web at
[Link] At this stage, anyone is free to make copies
for their own use. I would be happy to hear from you about suggestions for improvement.
Joseph M. Powers
powers@[Link]
[Link]
Notre Dame, Indiana; USA
CC BY: $ = 19 January 2025
\

The content of this book is licensed under Creative Commons Attribution-Noncommercial-No Derivative
Works 3.0.

7
8 CONTENTS

CC BY-NC-ND. 19 January 2025, J. M. Powers.

Chapter 1

Thermodynamics review

Borgnakke and Sonntag, Chapters 1-7,1

Farokhi, Chapter 2.1-2.3.2

Here is a brief review of some standard concepts from a first course in thermodynamics.

1.1 Definitions
• property: characterizes the thermodynamics state of the system

– extensive: proportional to system’s extent, upper case variables

∗ V : total volume, SI-based units are m3 ,
∗ E: total internal energy, SI-based units are kJ,
∗ H: total enthalpy, SI-based units are kJ,
∗ S: total entropy, SI-based units are kJ/K.
– intensive: independent of system’s extent, lower case variables (exceptions are
temperature T and pressure P , which are intensive). Intensive properties can be
on a mass basis or a molar basis:
∗ v: specific volume, SI-based units are m3 /kg,
∗ e: specific internal energy, SI-based units are kJ/kg,
∗ h: specific enthalpy, SI-based units are kJ/kg,
∗ s: specific entropy, SI-based units are kJ/kg/K.
∗ v: molar specific volume, SI-based units are m3 /kmole,
∗ e: molar specific internal energy, SI-based units are kJ/kmole,
∗ h: molar specific enthalpy, SI-based units are kJ/kmole,
∗ s: molar specific entropy, SI-based units are kJ/kmole/K.
1
Borgnakke, C. and Sonntag, R. E, 2017, Fundamentals of Thermodynamics, 9th edition, Wiley.
2
Farokhi, S., 2022, Aircraft Propulsion: Cleaner, Leaner, and Greener, Wiley.

9
10 CHAPTER 1. THERMODYNAMICS REVIEW

• density: ρ = 1/v, mass per unit volume, SI-based units are kg/m3 .

• equations of state: relate properties

– Calorically Perfect Ideal Gas (CPIG) has P v = RT and e − eo = cv (T −

To ).
– Calorically Imperfect Ideal Gas (CIIG) has P v = RT and e − eo =
RT
c (T̂ ) dT̂ .
To v
– Non-ideal state equations have P = P (T, v), e = e(T, v).

• Any intensive thermodynamic property can be expressed as a function of at most two

other intensive thermodynamic properties (for simple compressible systems).

– P = RT /v: thermal equation of state for ideal gas, SI-based units are kPa.
√
– c = γP v: sound speed for CPIG, SI-based units are m/s; γ = cP /cv , the ratio
of specific heats.

• energy: Etot = E + (1/2)m(u · u) + mgz, total energy = internal+kinetic+potential.

We will mainly consider velocity vector u = ui + 0j + 0k.

• first law: dEtot = δQ − δW ; if kinetic and potential are ignored, dE = δQ − δW ;

with δQ = T dS and δW = P dV , we get the Gibbs equation dE = T dS − P dV .

• second law: dS ≥ δQ/T .

• process: moving from one state to another, in general with accompanying heat trans-
fer and work.

• cycle: process which returns to initial state.

R2
• specific reversible work: 1 w2 = 1 P dv; δw = P dv.
R2
• specific reversible heat transfer: 1 q2 = 1 T ds; δq = T ds.

Figure 1.1 gives an example of an isothermal thermodynamic process going from state 1
to state 2 in various thermodynamic planes for an ideal gas. Figure 1.2 gives a sketch of a
thermodynamic cycle.

Example 1.1
Consider an ideal gas in the T − s plane. Compare the slope of an isochore to that of an isobar at
a given point.

Recall the Gibbs equation for a simple compressible substance:

T ds = de + P dv. (1.1)

CC BY-NC-ND. 19 January 2025, J. M. Powers.

1.1. DEFINITIONS 11

P T
v1

1 v2
P1
1
2
T1=T2 2
P2 T1=T2

v1 v2 s1 s2 s
v

P v
v1
P2
P1 v2
1
2
v2
1
P1
P2 2 v1
1

T1=T2 T1 = T2 T
T

Figure 1.1: Sketch of isothermal thermodynamic process for an ideal gas.

We have for the ideal gas

de = cv dT, if ideal gas. (1.2)

This holds for all ideal gases, be they calorically perfect or imperfect. Thus, the Gibbs equation can be
rewritten as

T ds = cv dT +P dv. (1.3)
| {z }
=de

On an isochore, v is constant, so dv = 0. So on an isochore, we have

T ds = cv dT, on an isochore. (1.4)

or, using the partial derivative notation,

∂T T
= . (1.5)
∂s v cv

Next recall the definition of enthalpy, h:

h = e + P v. (1.6)

CC BY-NC-ND. 19 January 2025, J. M. Powers.

12 CHAPTER 1. THERMODYNAMICS REVIEW

P T

v s

qcycle = wcycle

Figure 1.2: Sketch of thermodynamic cycle.

We can differentiate Eq. (1.6) to get

dh = de + P dv + v dP. (1.7)

Substitute Eq. (1.7) into the Gibbs equation, (1.1), to eliminate de in favor of dh to get

T ds = dh − P dv − v dP +P dv = dh − v dP. (1.8)
| {z }
=de

For an ideal gas, dh = cP dT , where cP is at most a function of T , so

T ds = cP dT −v dP. (1.9)
| {z }
=dh

Now for the isobar, dP = 0. Thus on an isobar, we have

T ds = cP dT, on an isobar. (1.10)

And so the slope on an isobar in the T − s plane is

∂T T
= . (1.11)
∂s P cP

Because cP > cv , (recall for an ideal gas that cP (T ) − cv (T ) = R > 0), we can say that the slope of the
isochore is steeper than the isobar in the T − s plane.

Example 1.2
Consider the following isobaric process for air, modeled as a CPIG, from state 1 to state 2. P1 =
100 kPa, T1 = 300 K, T2 = 400 K. Show the second law is satisfied.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

1.1. DEFINITIONS 13

Because the process is isobaric, P = 100 kPa describes a straight line in the P − v and P − T planes
and P2 = P1 = 100 kPa. Because we have an ideal gas, we have for the v − T plane:
 
R
v= T, straight lines! (1.12)
P
 
RT1 0.287 kgkJK (300 K) m3
v1 = = = 0.861 , (1.13)
P1 100 kPa kg
 
RT2 0.287 kgkJK (400 K) m3
v2 = = = 1.148 . (1.14)
P2 100 kPa kg
Because the gas is ideal:
de = cv dT. (1.15)
Because our ideal gas is also calorically perfect, cv is a constant, and we get
Z e2 Z T2
de = cv dT , (1.16)
e1 T1
e2 − e1 = cv (T2 − T1 ), (1.17)
 
kJ kJ
= 0.7175 (400 K − 300 K) = 71.750 . (1.18)
kg K kg
Also we have
T ds = de + P dv, (1.19)
= cv dT + P dv, (1.20)
RT R RT
from ideal gas : v = : dv = dT − 2 dP, (1.21)
P P P
RT
T ds = cv dT + R dT − dP, (1.22)
P
dT dP
ds = (cv + R) −R , (1.23)
T P
dT dP
= (cv + cP − cv ) −R , (1.24)
T P
dT dP
= cP −R , (1.25)
T P
Z s2 Z T2 Z P2
dT dP
ds = cP −R , (1.26)
s1 T1 T P1 P
   
T2 P2
s2 − s1 = cP ln − R ln . (1.27)
T1 P1
(1.28)
Now because P is a constant,
     
T2 kJ 400 K kJ
s2 − s1 = cP ln = 1.0045 ln = 0.2890 . (1.29)
T1 kg K 300 K kg K
Then one finds
Z v2 Z v2
1 w2 = P dv = P dv = P (v2 − v1 ) , (1.30)
v1 v1
 
m3 m3 kJ
= (100 kPa) 1.148 − 0.861 = 28.700 . (1.31)
kg kg kg

CC BY-NC-ND. 19 January 2025, J. M. Powers.

14 CHAPTER 1. THERMODYNAMICS REVIEW

Now

de = δq − δw, (1.32)
δq = de + δw, (1.33)
Z 2 Z 2 Z 2
δq = de + δw, (1.34)
1 1 1
1 q2 = (e2 − e1 ) + 1 w2 , (1.35)
kJ kJ kJ
= 71.750 + 28.700 = 100.450 . (1.36)
kg kg kg
Now in this process the gas is heated from 300 K to 400 K. One would expect at a minimum that the
surroundings were at 400 K. Check for second law satisfaction.
1 q2
s2 − s1 ≥ ? (1.37)
Tsurr
kJ
kJ 100.450 kg
0.2890 ≥ ? (1.38)
kg K 400 K

kJ kJ
0.2890 ≥ 0.2511 , yes. (1.39)
kg K kg K

1.2 Canonical equations of state

If we have a single equation of state in a special canonical form, we can form both thermal
and caloric equations. Because

de = T ds − P dv, dh = T ds + v dP, (1.40)

it is suggested that the form

e = e(s, v), h = h(s, P ), (1.41)

is useful.

Example 1.3
Canonical Form

If  
s
h(s, P ) = KcP P R/cP exp + (ho − cP To ) , (1.42)
cP
derive both thermal and caloric state equations P (v, T ) and e(v, T ).

CC BY-NC-ND. 19 January 2025, J. M. Powers.

1.2. CANONICAL EQUATIONS OF STATE 15

P T
T1 = 300 K v1
T2 = 400 K

1 2 P =P =100 kPa v2
1 2 T2
2
1
T1

v1 v2 s1 s2 s
v

P v
v1

v2 P1=P2 =100 kPa

1 2
P1=P2 =100 kPa v2 2

v1 1

T1 T2 T1 T2 T
T

Figure 1.3: Sketch for isobaric example problem.

Now for our material

   
∂h R/cP s ∂h R/cP −1 s
= KP exp , = KRP exp . (1.43)
∂s P cP ∂P s cP
Now because
∂h ∂h
= T, = v, (1.44)
∂s P ∂P s

we have
   
R/cP s R/cP −1 s
T = KP exp , v = KRP exp . (1.45)
cP cP
Dividing one by the other gives
T P RT
= , so P = . (1.46)
v R v
Substituting our expression for T into our canonical equation for h we also get
h = cP T + (ho − cP To ) = cP (T − To ) + ho . (1.47)
which is useful in itself. Substituting in for T and To
 
P v Po vo
h = cP − + ho . (1.48)
R R

CC BY-NC-ND. 19 January 2025, J. M. Powers.

16 CHAPTER 1. THERMODYNAMICS REVIEW

Using h ≡ e + P v, we get
 
Pv Po vo
e + P v = cP − + eo + Po vo , (1.49)
R R
so
c  c 
P P
e = − 1 Pv − − 1 Po vo + eo , (1.50)
 cR  R
P
= − 1 (P v − Po vo ) + eo , (1.51)
 cR 
P
= − 1 (RT − RTo ) + eo , (1.52)
R
= (cP − R) (T − To ) + eo , (1.53)
= (cP − (cP − cv )) (T − To ) + eo , (1.54)
= cv (T − To ) + eo . (1.55)

So one canonical equation gives us all the information we need! Oftentimes, it is difficult to do a single
experiment to get the canonical form.

1.3 Isentropic relations

Of particular importance in thermodynamics in general and compressible flow in particular
are relations that describe an isentropic process, s = constant. Recall the second law:
δq
ds ≥ . (1.56)
T
If the process is reversible, we get
δq
ds = . (1.57)
T
If the process is adiabatic, we get

δq ≡ 0, so ds = 0. (1.58)

So an isentropic process is both adiabatic and reversible. In this case the Gibbs relation and
the first law reduce to the same expression:

de = −P dv. (1.59)

That is, the energy change is all due to reversible pressure volume work.

We would like to develop an expression between two variables for an isentropic process.

With knowledge of P (T, v)

CC BY-NC-ND. 19 January 2025, J. M. Powers.

1.3. ISENTROPIC RELATIONS 17

• form e(T, v),

• eliminate T to form e(P, v),

• take a derivative and substitute into Gibbs/first law.

∂e ∂e
dP + dv = −P dv, (1.60)
∂P v ∂v P
 
∂e ∂e
dP + +P dv = 0. (1.61)
∂P v ∂v P

Integration of this equation gives a relationship between P and v.

Example 1.4
Calorically Perfect Ideal Gas

Find the relationship for a calorically perfect ideal gas which undergoes an isentropic process.

Ideal Gas:
P v = RT. (1.62)
Calorically Perfect:
e = cv T + e o . (1.63)
Thus,
Pv cv 1
e = cv + eo = P v + eo = P v + eo . (1.64)
R cP − cv γ−1
The necessary derivatives are

∂e 1 ∂e 1
= v, = P. (1.65)
∂P v γ−1 ∂v P γ−1

So substituting into our developed relationship gives

 
1 1
v dP + P + P dv = 0, (1.66)
γ−1 γ−1
v dP + γP dv = 0, (1.67)
dP dv
= −γ , (1.68)
P v
P v
ln = −γ ln , (1.69)
Po v
 v oγ
o
= ln , (1.70)
v
P  v γ
o
= , (1.71)
Po v
P vγ = Po voγ = constant. (1.72)

CC BY-NC-ND. 19 January 2025, J. M. Powers.

18 CHAPTER 1. THERMODYNAMICS REVIEW

Also using the thermal state equation, we find

P RT
T vo  v γ
v o
= RTo
= = , (1.73)
Po vo
To v v

T  v γ−1  P  γ−1γ
o
= = . (1.74)
To v Po

Find the work in a process from v1 to v2

Z 2
1 w2 = P dv, (1.75)
1
Z v2
dv
= Po voγ γ
, (1.76)
v1 v
 1−γ  v2
γ v
= Po vo , (1.77)
1 − γ v1
Po voγ  1−γ 
= v2 − v11−γ , (1.78)
1−γ
P2 v2 − P1 v1
= . (1.79)
1−γ

Also
P2 v2 − P1 v1
de = δq − δw = 0 − δw, so e2 − e1 = . (1.80)
γ−1

Figure 1.4 gives a sketch for the calorically perfect ideal gas undergoing an isentropic
expansion in various planes.

Example 1.5
Virial Gas

Find the relationship between P and v for a virial gas with constant cv which undergoes an isentropic
process.

Virial Gas:
RT
P = . (1.81)
v−b
This is van der Waals with a = 0 and cv constant so:

e = cv T + e o . (1.82)

Thus,
P (v − b)
e = cv + eo . (1.83)
R

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1.3. ISENTROPIC RELATIONS 19

P T
v1

P1
v2
T1
T1 T2
P2 T2

v1 v2 s1=s2 s
v

P v
P2
v1

v2
P1

v1 P1
v2
P2

T2 T1 T1 T
T

Figure 1.4: Sketch of isentropic expansion process

Thus the necessary derivatives are

∂e cv ∂e cv
= (v − b) , = P. (1.84)
∂P v R ∂v P R
So substituting into our developed relationship gives
cv c 
v
(v − b) dP + P + P dv = 0, (1.85)
R R 
R
(v − b) dP + 1 + P dv = 0. (1.86)
cv
Now with γ̂ ≡ 1 + R/cv , we get
dP γ̂
+ P = 0, (1.87)
dv v−b
 Z   Z 
γ̂ dP γ̂ γ̂
exp dv + exp dv P = 0, (1.88)
v−b dv v−b v−b
   dP    γ̂
exp ln (v − b)γ̂ + exp ln (v − b)γ̂ P = 0, (1.89)
dv v−b
γ̂ dP γ̂ γ̂
(v − b) + (v − b) P = 0, (1.90)
dv v−b
d  γ̂

(v − b) P = 0, (1.91)
dv
(v − b)γ̂ P = (vo − b)γ̂ Po , (1.92)
 γ̂
P vo − b
= . (1.93)
Po v−b

CC BY-NC-ND. 19 January 2025, J. M. Powers.

20 CHAPTER 1. THERMODYNAMICS REVIEW

CC BY-NC-ND. 19 January 2025, J. M. Powers.

Chapter 2

Compressible flow review

Farokhi, Chapter 2.4-2.20,

White, Chapter 9: pp. 511-5591,
Liepmann and Roshko, Chapter 2: pp. 39-652 ,
Shapiro, Vol. 1, Chapters 4-8: pp. 73-262. 3

This chapter will review one- and two-dimensional flow of a compressible fluid.

2.1 Generalized one-dimensional equations

For this section:
• the flow is uni-directional in the x− direction with u 6= 0 and with the y− and z−
components of the velocity vector both zero: v ≡ 0, w ≡ 0,
• spatial gradients are admitted in x, but not in y or z: ∂/∂x 6= 0, ∂/∂y ≡ 0, ∂/∂z ≡ 0.
Friction and heat transfer will not be modeled rigorously. Instead, they will be modeled in
a fashion which captures the relevant physics and retains analytic tractability. Flow with
area change is illustrated by the following sketch of a control volume. See Figure 2.1. For
this problem adopt the following conventions:
• surface 1 and 2 are open and allow fluxes of mass, momentum, and energy,

• surface w is a closed wall; no mass flux through the wall,

• external heat flux qw (energy/area/time: W/m2 ) through the wall allowed-qw known
function,

• diffusive, longitudinal heat transfer ignored, qx = 0,

1
White, F. M., 1986, Fluid Mechanics, McGraw-Hill.
2
Liepmann, H. W, and Roshko, A., 2002, Elements of Gasdynamics, Dover.
3
Shapiro, A. H., 1953, The Dynamics and Thermodynamics of Compressible Fluid Flow, Wiley.

21
22 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

circumferential perimeter length =

Figure 2.1: Control volume sketch.

• wall shear τw (force/area: N/m2 ) allowed–τw known function,

• diffusive viscous stress not allowed τxx = 0,
• cross-sectional area a known fixed function: A(x).

2.1.1 Mass
Take the overbar notation to indicate a volume averaged quantity. The amount of mass in a
control volume after a time increment ∆t is equal to the original amount of mass plus that
which came in minus that which left:
ρ̄Ā∆x t+∆t
= ρ̄Ā∆x t + ρ1 A1 (u1 ∆t) − ρ2 A2 (u2 ∆t) . (2.1)
Rearrange and divide by ∆x∆t:
ρ̄Ā t+∆t
− ρ̄Ā
ρ2 A2 u2 − ρ1 A1 u1
t
+ = 0. (2.2)
∆t ∆x
Taking the limit as ∆t → 0, ∆x → 0, we get
∂ ∂
(ρA) + (ρAu) = 0. (2.3)
∂t ∂x
If steady, we take ∂/∂t = 0 and get
d
(ρAu) = 0, (2.4)
dx
dρ dA du
Au + ρu + ρA = 0, (2.5)
dx dx dx
1 dρ 1 dA 1 du
+ + = 0. (2.6)
ρ dx A dx u dx

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2.1. GENERALIZED ONE-DIMENSIONAL EQUATIONS 23

Integrate from x1 to x2 :
Z x2 Z x2
d
(ρAu) dx = 0 dx, (2.7)
x1 dx x1
Z 2
d (ρAu) = 0, (2.8)
1
ρ2 u2 A2 − ρ1 u1 A1 = 0, (2.9)
ρ2 u2 A2 = ρ1 u1 A1 ≡ ṁ = C1 . (2.10)

2.1.2 Momentum
Newton’s Second Law says the time rate of change of linear momentum of a body equals the
sum of the forces acting on the body. In the x direction this is roughly as follows:

d
(mu) = Fx . (2.11)
dt

In discrete form, this becomes

mu|t+∆t − mu|t
= Fx , (2.12)
∆t
mu|t+∆t = mu|t + Fx ∆t. (2.13)
R
Here Fx ∆t is a small increment of impulse. In the physics literature impulse is Fx dt and
has units N s. So the new momentum is the old momentum plus the impulse imparted. In the
propulsion literature, impulse sometimes has a different interpretation. Some texts, including
ours, define impulse as a type of force with units of N. The student should recognize the
variability in these definitions. For a control volume containing fluid, one must also account
for the momentum which enters and leaves the control volume. The amount of momentum
in a control volume after a time increment ∆t is equal to the original amount of momentum
plus that which came in minus that which left plus that introduced by the forces acting on
the control volume. Note that

• the pressure force at surface 1 pushes the fluid,

• the pressure force at surface 2 restrains the fluid,

• the force due to the reaction of the wall to the pressure force pushes the fluid if the
area change is positive,

• the force due to the reaction of the wall to the shear force restrains the fluid.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

24 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

So the momentum equation becomes

ρ̄Ā∆x ū t+∆t
= ρ̄Ā∆x ū t
+ (ρ1 A1 (u1 ∆t)) u1
− (ρ2 A2 (u2 ∆t)) u2
+ (P1 A1 ) ∆t − (P2 A2 ) ∆t


+ P̄ (A2 − A1 ) ∆t


− τw L̄∆x ∆t.

Rearrange and divide by ∆x∆t:

ρ̄Āū t+∆t
− ρ̄Āū t ρ2 A2 u22 − ρ1 A1 u21
+
∆t ∆x
P2 A2 − P1 A1 A2 − A1
=− + P̄ − τw L̄.
∆x ∆x

In the limit ∆x → 0, ∆t → 0, one gets

∂ ∂
∂ ∂A
(ρAu) + ρAu2 = − (P A) + P − τw L. (2.14)
∂t ∂x ∂x ∂x

In steady state:

d
d dA
ρAu2 = − (P A) + P − τw L, (2.15)
dx dx dx
du d dA dP dA
ρAu + u (ρAu) = −P −A +P − τw L, (2.16)
dx dx dx dx dx
du dP L
ρu = − − τw , (2.17)
dx dx A
L
ρu du + dP = −τw dx, (2.18)
A
1 L
du + dP = −τw dx, (2.19)
ρu ṁ
 2
u L
ρd + dP = −τw dx. (2.20)
2 A

Wall shear lowers the combination of pressure and dynamic head. If there is no wall shear,
then
 
u2
dP = −ρ d . (2.21)
2

CC BY-NC-ND. 19 January 2025, J. M. Powers.

2.1. GENERALIZED ONE-DIMENSIONAL EQUATIONS 25

An increase in velocity magnitude decreases the pressure. If there is no area change, dA = 0,

and no friction τw ≡ 0, we get

du dP
ρu + = 0, (2.22)
dx dx
d
add u mass u (ρu) = 0, (2.23)
dx
d

ρu2 + P = 0, (2.24)
dx
ρu2 + P = ρo u2o + Po = C2 . (2.25)

2.1.3 Energy
The first law of thermodynamics states that the change of total energy of a body equals the
heat transferred to the body minus the work done by the body:

E2 − E1 = Q − W, (2.26)
E2 = E1 + Q − W. (2.27)

So for the control volume this becomes the following when one also accounts for the energy
flux in and out of the control volume in addition to the work and heat transfer:
   

ū2
ū2
ρ̄Ā∆x ē + = ρ̄Ā∆x ē +
2 t+∆t 2 t
   
u21 u22
+ρ1 A1 (u1 ∆t) e1 + − ρ2 A2 (u2 ∆t) e2 +
2 2


+qw L̄∆x ∆t + (P1 A1 ) (u1 ∆t) − (P2 A2 ) (u2 ∆t) .

Note:

• the mean pressure times the area difference does no work because it is acting on a
stationary boundary,
4
• the work done by the shear force is not included.
4
In neglecting work done by the wall shear force, I have taken an approach which is nearly universal, but
fundamentally difficult to defend. At this stage of the development of these notes, I am not ready to enter
into a grand battle with all established authors and probably confuse the student; consequently, results for
flow with friction will be consistent with those of other sources. The argument typically used to justify this
is that the real fluid satisfies no-slip at the boundary; thus, the wall shear actually does no work. However,
one can easily argue that within the context of the one-dimensional model which has been posed that the
shear force behaves as an external force which reduces the fluid’s mechanical energy. Moreover, it is possible
to show that neglect of this term results in the loss of frame invariance,


a serious defect indeed. To model
the work of the wall shear, one would include the term τw L̄∆x (ū∆t) in the energy equation.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

26 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

Rearrange and divide by ∆t∆x:

   
ū2 ū2
ρ̄Ā ē + 2
− ρ̄Ā ē + 2
t+∆t t
(2.28)
∆t    
u22 P2 u21 P1
ρ2 A2 u2 e2 + 2
+ ρ2
− ρ1 A1 u1 e1 + 2
+ ρ1
+ = qw L̄. (2.29)
∆x
In differential form as ∆x → 0, ∆t → 0, we get
     
∂ u2 ∂ u2 P
ρA e + + ρAu e + + = qw L. (2.30)
∂t 2 ∂x 2 ρ

In steady state, we get

  
d u2 P
ρAu e + + = qw L, (2.31)
dx 2 ρ
 2
  2

d u P u P d
ρAu e+ + + e+ + (ρAu) = qw L, (2.32)
dx 2 ρ 2 ρ dx
 
d u2 P qw L
ρu e+ + = , (2.33)
dx 2 ρ A
 
de du 1 dP P dρ qw L
ρu +u + − 2 = . (2.34)
dx dx ρ dx ρ dx A

Subtract the product of momentum and velocity:

du dP τw Lu
ρu2 +u = − , (2.35)
dx dx A
de P u dρ qw L τw Lu
ρu − = + , (2.36)
dx ρ dx A A
de P dρ (qw + τw u) L
− 2 = . (2.37)
dx ρ dx ṁ

Because e = e(P, ρ), we have the total differential from the calculus of many variables as

∂e ∂e
de = dρ + dP. (2.38)
∂ρ P ∂P ρ

Then we can scale by dx to get

de ∂e dρ ∂e dP
= + , (2.39)
dx ∂ρ P dx ∂P ρ dx

CC BY-NC-ND. 19 January 2025, J. M. Powers.

2.1. GENERALIZED ONE-DIMENSIONAL EQUATIONS 27

so the first law of thermodynamics becomes

∂e dρ ∂e dP P dρ (qw + τw u) L
+ − 2 = , (2.40)
∂ρ P dx ∂P ρ dx ρ dx ṁ
 
∂e P
−
dP  ∂ρ P ρ  dρ2
(qw + τw u) L
+ ∂e
= ∂e
. (2.41)
dx ∂P ρ
dx ṁ ∂P ρ

Now it can be shown that

 
∂e P
∂P ∂ρ
− ρ2
c2 = = − P
∂e
, (2.42)
∂ρ s ∂P ρ

so
dP dρ (qw + τw u) L
− c2 = ∂e
, (2.43)
dx dx ṁ ∂P ρ
dP dρ (qw + τw u) L
− c2 = ∂e
. (2.44)
dx dx ρuA ∂P ρ

In the special case of flow with no heat transfer qw ≡ 0, but with area change and wall
friction allowed, we get
 
d u2 P
ρu e+ + = 0, (2.45)
dx 2 ρ
u2 P u 2 Po
e+ + = eo + o + = C3 , (2.46)
2 ρ 2 ρo
u2 u2
h+ = ho + o = C3 . (2.47)
2 2

Example 2.1
Adiabatic flow of argon 5
Given: Argon, γ = 5/3, flows adiabatically through a duct. At section 1, P1 = 200 psia, T1 =
500 ◦ F, u1 = 250 ft/s. At section 2 P2 = 40 psia, u2 = 1100 ft/s.

◦
Find: T2 in F and s2 − s1 in Btu/lbm/◦ R.

Assume: Ar is a calorically perfect ideal gas, tables give R = 38.68 ft lbf/lbm/◦ R, cP = 0.1253 Btu/lbm/◦ R.

5
adopted from White’s 9.1, p. 583.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

28 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

Analysis: First get the units into shape:

T1 = 500 + 460 = 960 ◦ R, (2.48)

   
Btu ft lbf lbm ft ft2
cP = 0.1253 779 32.17 = 3140 2 ◦ , (2.49)
lbm ◦ R Btu lbf s2 s R
  
ft lbf lbm ft ft2
R = 38.68 32.17 = 1244 2 ◦ , (2.50)
lbm ◦ R lbf s2 s R
  
ft lbf 1 Btu Btu
R = 38.68 = 0.04965 . (2.51)
lbm ◦ R 779 ft lbf lbm ◦ R
Now consider an energy balance:

u22 u21
h2 + = h1 + , (2.52)
2 2
u22 u21
cP T 2 + h o + = cP T 1 + h o + , (2.53)
2 2
1

T2 = T1 + u2 − u22 , (2.54)
2cP 1
 2   !2
1 1 ft ft
T2 = 960 ◦ R + 250 − 1100 = 777 ◦ R, (2.55)
2 3140 s2ft◦2R s s
T2 = 777 − 460 = 317 ◦ F. (2.56)

The flow sped up; temperature went down. Thermal energy was converted into kinetic energy.
Calculate the entropy change. For the calorically perfect ideal gas:
   
T2 P2
s2 − s1 = cP ln − R ln , (2.57)
T1 P1
   
Btu 777 ◦ R Btu 40 psia
= 0.1253 ln − 0.04965 ln , (2.58)
lbm ◦ R 960 ◦ R lbm ◦ R 200 psia
Btu
= −0.0265 − (−.0799) = 0.0534 . (2.59)
lbm ◦ R
The entropy change is positive. Because the flow is adiabatic, there must have been irreversible friction
which gave rise to this.

Example 2.2
6
Adiabatic flow of steam

Same problem now with steam Given: Steam flows adiabatically through a duct. At section 1,
P1 = 200 psia, T1 = 500 ◦ F, u1 = 250 ft/s. At section 2 P2 = 40 psia, u2 = 1100 ft/s.
◦
Find: T2 in F and s2 − s1 in Btu/lbm/◦ R.

Analysis:
6
adopted from White’s 9.2, p. 583.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

2.1. GENERALIZED ONE-DIMENSIONAL EQUATIONS 29

Use steam tables for property values.

Energy balance:
u22 u21
h2 + = h1 + , (2.60)
2 2
1 2

h2 = h1 + u − u22 , (2.61)
2 1
    2  2 !
Btu 1 1 Btu 1 lbf s2 ft ft
h2 = 1269 + 250 − 1100 , (2.62)
lbm 2 779 ft lbf 32.17 lbm ft s s
Btu
h2 = 1246 . (2.63)
lbm
Interpolate the steam tables at P2 = 40 psia, h2 = 1246 Btu/lbm and find
Btu
T2 = 420 ◦ F, s2 = 1.7720 . (2.64)
lbm ◦ R
The tables give s1 = 1.6239 Btu/lbm/◦ R, so the entropy change is
Btu
s2 − s1 = 1.7720 − 1.6239 = 0.148 . (2.65)
lbm ◦ R

Example 2.3
Flow of air with heat addition

Given: Air initially at P1 = 100 kPa, T1 = 300 K, u1 = 10 m/s flows in a duct of length 100 m.
The duct has a constant circular cross sectional area of A = 0.02 m2 and is isobarically heated with
a constant heat flux qw along the entire surface of the duct. At the end of the duct the flow has
P2 = 100 kPa, T2 = 500 K.

Find: the mass flow rate ṁ, the wall heat flux qw and the entropy change s2 − s1 ; check for
satisfaction of the second law.

Assume: Calorically perfect ideal gas, R = 0.287 kJ/kg/K, cP = 1.0035 kJ/kg/K

First consider the geometry:

A = πr2 , (2.66)
r
A
r = , (2.67)
π
√ p
L = 2πr = 2 πA = 2 π (0.02 m2 ) = 0.501 m. (2.68)

Get the mass flux.

P1 = ρ1 RT1 , (2.69)
P1 100 kPa kg
ρ1 = =   = 1.161 3 . (2.70)
RT1 0.287 kJ m
kg K (300 K)

CC BY-NC-ND. 19 January 2025, J. M. Powers.

30 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

So
 
kg  m 
kg
ṁ = ρ1 u1 A1 = 1.161 3 10 0.02 m2 = 0.2322 . (2.71)
m s s

Get the flow variables at state 2:

P2 100 kPa
ρ2 = =   , (2.72)
RT2 0.287 kgkJK (500 K)
kg
= 0.6969 , (2.73)
m3
ρ2 u2 A2 = ρ1 u1 A1 , (2.74)
ρ1 u1 A1 ρ1 u 1
u2 = = (2.75)
ρ A ρ2 ,
  2 2

kg
1.161 m 3 10 ms m
= kg
= 16.67 . (2.76)
0.6969 m3
s

Now consider the energy equation:

 
d u2 P qw L
ρu e+ + = , (2.77)
dx 2 ρ A
 
d u2 qw L
h+ = , (2.78)
dx 2 ṁ
Z L   Z L
d u2 qw L
h+ dx = dx, (2.79)
0 dx 2 0 ṁ
u2 u2 qw LL
h2 + 2 − h1 − 1 = , (2.80)
2 2 ṁ
u22 u21 qw LL
cP (T2 − T1 ) + − = , (2.81)
2 2  ṁ   
ṁ u2 u2
qw = cP (T2 − T1 ) + 2 − 1 . (2.82)
LL 2 2

Substituting the numbers, one finds,

!

!
m 2 m 2
0.2322 kg
s J 16.67 s 10 s
qw = 1003.5 (500 K − 300 K) + − , (2.83)
(100 m) (0.501 m) kg K 2 2
 2

kg J m
= 0.004635 2 200700 − 88.9 2 , (2.84)
m s kg s
 
kg J J
= 0.004635 2 200700 − 88.9 , (2.85)
m s kg kg
W
= 930 2 . (2.86)
m

Heat flux is positive, so thermal energy was transmitted into the air.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

2.1. GENERALIZED ONE-DIMENSIONAL EQUATIONS 31

Now find the entropy change.

   
T2 P2
s2 − s1 = cP ln − R ln , (2.87)
T1 P1
       
J 500 K J 100 kPa
= 1003.5 ln − 287 ln , (2.88)
kg K 300 K kg K 100 kPa
J
= 512.6 − 0 = 512.6 . (2.89)
kg K
Is the second law satisfied? Assume the heat transfer takes place from a reservoir held at 500 K. The
reservoir would have to be at least at 500 K in order to bring the fluid to its final state of 500 K. It
could be greater than 500 K and still satisfy the second law.
Q12
S2 − S1 ≥ , (2.90)
T
Q̇12
Ṡ2 − Ṡ1 ≥ , (2.91)
T
Q̇12
ṁ (s2 − s1 ) ≥ , (2.92)
T
qw Atot
≥ , (2.93)
T
qw LL
≥ , (2.94)
T
qw LL
s2 − s1 ≥ , (2.95)
ṁT

J 930 s Jm2 (100 m) (0.501 m)
512.6 ≥   , (2.96)
kg K 0.2322 kg (500 K)
s
J J
512.6 ≥ 401.3 . (2.97)
kg K kg K

2.1.4 Influence coefficients

Now, uncouple these equations. First, summarize:
dρ du ρu dA
u +ρ = − , (2.98)
dx dx A dx
du dP τw L
ρu + = − , (2.99)
dx dx A
dP dρ (qw + τw u) L
− c2 = ∂e
. (2.100)
dx dx ρuA ∂P ρ

In matrix form, this is

   dρ   − ρu dA 
u ρ 0 dx
A dx
 0 ρu 1  du  = 
τw L 
−
 (qw +τA . (2.101)
dx w u)L
2 dP
−c 0 1 dx ρuA ∂e
| ∂P ρ

CC BY-NC-ND. 19 January 2025, J. M. Powers.

32 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

Use Cramer’s rule to solve for the derivatives. First calculate the determinant of the coeffi-
cient matrix:



u ((ρu)(1) − (1)(0)) − ρ (0)(1) − (−c2 )(1) = ρ u2 − c2 . (2.102)

Implementing Cramer’s rule, we get

 


(qw +τw u)L
ρu − ρu dA
−ρ − τwAL +ρ
dρ A dx
ρ
∂e
ρuA ∂P |
= , (2.103)
dx ρ (u2 − c2 )
 
2 ρu dA

τw L

(qw +τw u)L
−c − A dx + u − A − u ρuA ∂e
du ∂P |ρ
= 2 2
, (2.104)
dx ρ (u − c )
 
2 ρu dA

2 τw L

2 (qw +τw u)L
ρuc − A dx − ρc − A + ρu
dP ∂e
ρuA ∂P |ρ
= . (2.105)
dx ρ (u2 − c2 )

Simplify
(qw +τw u)L
−ρu2 dA + τw L +
dρ 1 dx ∂e
ρu ∂P | ρ
= , (2.106)
dx A (u2 − c2 )
(qw +τw u)L
c2 ρu dA − uτw L −
du 1 dx ∂e
ρ ∂P | ρ
= , (2.107)
dx A ρ (u2 − c2 )
(qw +τw u)Lu
−c2 ρu2 dA + c2 τw L +
dP 1 dx ∂e
ρ ∂P | ρ
= . (2.108)
dx A (u2 − c2 )

Note that we have

• a system of coupled non-linear ordinary differential equations,

• in standard form for dynamic system analysis: du/dx = f(u) with u = (ρ, u, P )T ,

• valid for general equations of state,

• singular when velocity sonic u = c.

2.2 Flow with area change

This section will consider flow with area change with an emphasis on isentropic flow. Some
problems will involve non-isentropic flow but a detailed discussion of such flows will be
delayed.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

2.2. FLOW WITH AREA CHANGE 33

2.2.1 Isentropic Mach number relations

Take special case of

• τw = 0,

• qw = 0,

• calorically perfect ideal gas (CPIG).

Then
d
(ρuA) = 0, (2.109)
dx
d

ρu2 + P = 0, (2.110)
 dx 2 
d u P
e+ + = 0. (2.111)
dx 2 ρ

Integrate the energy equation with h = e + P/ρ to get

u2 u2o
h+ = ho + . (2.112)
2 2
If one defines the “o” condition to be a condition of rest, then uo ≡ 0. This is a stagnation
condition. So

u2
h+ = ho , (2.113)
2
u2
(h − ho ) + = 0. (2.114)
2
Because we have a CPIG, we get

u2
cP (T − To ) + = 0, (2.115)
2
u2
T − To + = 0, (2.116)
2cP
To u2
1− + = 0. (2.117)
T 2cP T

Now note that

cP − cv cP cP − cv γR
cP = cP = cP = , (2.118)
cP − cv cv c v − 1 γ−1

CC BY-NC-ND. 19 January 2025, J. M. Powers.

34 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

so
To γ − 1 u2
1− + = 0, (2.119)
T 2 γRT
To γ − 1 u2
= 1+ . (2.120)
T 2 γRT
Recall the sound speed and Mach number for a CPIG:
 u 2
c2 = γRT if P = ρRT, e = cv T + eo , M2 ≡ , (2.121)
c
thus,
To γ −1 2
= 1+ M , (2.122)
T 2
 −1
T γ−1 2
= 1+ M . (2.123)
To 2
Now if the flow is isentropic one has
 γ−1   γ−1
T ρ P γ
= = . (2.124)
To ρo Po
Thus,
 − 1
ρ γ − 1 2 γ−1
= 1+ M , (2.125)
ρo 2
 − γ
P γ − 1 2 γ−1
= 1+ M . (2.126)
Po 2
For air γ = 7/5, so
 −1
T 1
= 1 + M2 , (2.127)
To 5
 − 52
ρ 1
= 1 + M2 , (2.128)
ρo 5
 − 72
P 1
= 1 + M2 . (2.129)
Po 5
Figures 2.2, 2.3 2.4 show the variation of T , ρ and P with M 2 for isentropic flow. Other
thermodynamic properties can be determined from these, e.g. the sound speed:
s r  −1/2
c γRT T γ−1 2
= = = 1+ M . (2.130)
co γRTo To 2

CC BY-NC-ND. 19 January 2025, J. M. Powers.

2.2. FLOW WITH AREA CHANGE 35

T (K)
300

250

200

150

100

50

2
0 2 4 6 8 10 M

Figure 2.2: Static temperature versus M 2 . Calorically perfect ideal gas, R = 0.287 kJ/kg/K,
γ = 7/5, To = 300 K.

P (bar)
1.0

0.8

0.6

0.4

0.2

2
0 2 4 6 8 10 M

Figure 2.3: Static pressure versus M 2 . Calorically perfect ideal gas, R = 0.287 kJ/kg/K,
γ = 7/5, Po = 1 bar.

Example 2.4
Airplane problem

Given: An airplane is flying into still air at u = 200 m/s. The ambient air is at 288 K and 101.3 kPa.
Find: Temperature, pressure, and density at nose of airplane
Assume: Steady isentropic flow of CPIG.

Analysis: In the steady wave frame, the ambient conditions are static while the nose conditions are
stagnation.

u u 200 ms
M= = √ = r   = 0.588. (2.131)
c γRT 7 J
5 287 kg K 288 K

CC BY-NC-ND. 19 January 2025, J. M. Powers.

36 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

1.2

1.0

0.8

0.6

0.4

0.2

2
0 2 4 6 8 10 M

Figure 2.4: Static density versus M 2 . Calorically perfect ideal gas, R = 0.287 kJ/kg/K,
γ = 7/5, ρo = 1.16 kg/m3 .

so
 
1
To = T 1 + M2 , (2.132)
5
 
1
= (288 K) 1 + 0.5882 = 307.9 K, (2.133)
5
  52
1
ρo = ρ 1 + M2 , (2.134)
5
  25
101.3 kPa 1 2 kg
=   1 + 0.588 = 1.45 3 , (2.135)
0.287 kgkJK 288 K 5 m
 7
1 2 2
Po = P 1+ M , (2.136)
5
  72
1 2
= (101.3 kPa) 1 + 0.588 = 128 kPa. (2.137)
5

Note the temperature, pressure, and density all rise in the isentropic process. In this wave frame, the
kinetic energy of the flow is being converted isentropically to thermal energy.

Example 2.5
7
Pressure measurement in compressible flows

Given: Air at u = 750 ft/s, Mercury manometer which reads a change in height of 8 in. See
Figure 2.5.

Find: Static pressure of air in psia

7
adopted from White, 9.26, p. 584.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

2.2. FLOW WITH AREA CHANGE 37

air at
100 F
z g
static
state, 1

stagnation 8 inches
state, o
mercury

Figure 2.5: Compressible Pitot tube sketch.

Assume: Ideal gas behavior for air

First consider the manometer which is governed by fluid statics. In fluid statics, there is no motion,
thus there are no viscous forces or fluid inertia; one thus has a balance between surface and body forces.
Consider the linear momentum equation:

dv
ρ = −∇P + ρHg g + ∇ · τ , (2.138)
dt
0 = −∇P + ρHg g, (2.139)
dP
= ρHg gz , (2.140)
dz
P1 − Po = ρHg gz (z1 − zo ) , (2.141)
     
lbm 1 lbf s2 ft 1 ft
= 845.9 3 −32.2 2 (0 in − (−8 in)) , (2.142)
ft 32.2 ft lbm s 12 in
lbf
= −563.9 2 , (2.143)
ft
lbf
Po − P1 = 563.9 2 , (2.144)
ft
lbf
Po = P1 + 563.9 2 . (2.145)
ft

Now calculate the local Mach number

T1 = 100 + 460 = 560 ◦ R (2.146)

ft
u1 750 s
M1 = √ = q = 0.646. (2.147)
γRT1 2

(1.4) 1717 s2ft◦ R (560 ◦ R)

Isentropic flow relations relate stagnation to static properties, so for air

 3.5  3.5
1 1
Po = P1 1 + M12 = P1 1 + (0.646)2 = 1.324P1. (2.148)
5 5

CC BY-NC-ND. 19 January 2025, J. M. Powers.

38 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

Substituting from the measured pressure difference

lbf
P1 + 563.9 = 1.324P1, (2.149)
ft2
lbf
−0.324P1 = −563.9 , (2.150)
ft2
−563.9 lbf
ft2 lbf
P1 = = 1740 2 , (2.151)
−0.324 ft
 
lbf lbf
Po = (1.324) 1740 2 = 2304 2 , (2.152)
ft ft
  2
lbf 1 ft
P1 = 1740 2 = 12.1 psia, (2.153)
ft 12 in
  2
lbf 1 ft
Po = 2304 2 = 16.0 psia. (2.154)
ft 12 in

What might one estimate if one did not account for compressibility effects? Assume one had the same
static pressure and calculate what velocity one would predict.

First calculate the static density.

 
P1 1740 lbf 2 ft lbm lbm
ρ1 = = ft2

ft 32.2 = 0.05827 3 . (2.155)
RT1 1717 s2 ◦ R (560 ◦ R) lbf s2 ft

One would then use an incompressible Bernoulli equation:

2
ρ (0) ρ1 u21
Po + = P1 + , (2.156)
2 s 2
s
 
lbf
2 (Po − P1 ) 2 563.9 ft2 ft lbm ft
u1 = = lbm
32.2 = 789.4 . (2.157)
ρ1 0.05827 ft3
lbf s2 s

So the relative error in using the incompressible approximation would be

ft ft
789.4 s − 750 s
Error = ft
= 0.053. (2.158)
750 s

Example 2.6
8
Adiabatic duct flow

Given: Air flowing adiabatically through a duct. At section 1, u1 = 400 ft/s, T1 = 200 ◦ F, P1 =
35 psia. Downstream u2 = 1100 ft/s, P2 = 18 psia.

Find: M2 , umax , Po2 /Po1 .

8
adopted from White’s 9.30, p. 585.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

2.2. FLOW WITH AREA CHANGE 39

Assume: Calorically perfect ideal gas, steady, one-dimensional flow.

Some preliminaries:

T1 = 200 + 460 = 660 ◦ R, (2.159)

   
Btu ft lbf lbm ft ft2
cP = 0.240 779 32.17 2
= 6015 2 ◦ , (2.160)
lbm R
◦ Btu lbf s s R
  
ft lbf lbm ft ft2
R = 53.34 32.17 = 1716 . (2.161)
lbm ◦ R lbf s2 s2 ◦ R

Energy conservation gives stagnation conditions at state 1:

u21
h1 + = ho1 , (2.162)
2
u21
cP T 1 + = cP To1 , (2.163)
2


ft 2
u21 400 s
To1 = T1 + = 660 ◦ R + ft2

= 673 ◦ R. (2.164)
2cP 2 6015 s2 ◦ R

Note because in adiabatic flow ho is a constant, ho2 = ho1 and because ideal gas To2 = To1 . So

To2 = 673 ◦ R, (2.165)

ft 2
u22 1100 s
T2 = To2 − = 673 ◦ R − 2
= 572
◦
R. (2.166)
2cP 2 6015 s2ft◦ R

Calculate the Mach numbers:

p
c1 = γRT1 , (2.167)
s  
ft2 ft
c1 = 1.4 1716 (660 ◦ R) = 1259 , (2.168)
s2 ◦ R s
u1 400 fts
M1 = = = 0.318, (2.169)
c1 1259 fts
p
c2 = γRT2 , (2.170)
s  
ft2 ft
c2 = 1.4 1716 (572 ◦ R) = 1173 , (2.171)
s2 ◦ R s
ft
u2 1100 s
M2 = = ft
= 0.938. (2.172)
c2 1173 s

CC BY-NC-ND. 19 January 2025, J. M. Powers.

40 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

Because for CPIG air one has

 − 72
P 1
= 1 + M2 , (2.173)
Po 5
 7
1 2 2
Po = P 1+ M , (2.174)
5
  27
1 2
Po1 = (35 psia) 1 + 0.318 = 37.54 psia, (2.175)
5
  27
1 2
Po2 = (18 psia) 1 + 0.938 = 31.74 psia, (2.176)
5
Po2 31.74 psia
= = 0.845. (2.177)
Po1 37.54 psia
The stagnation pressure drop indicates that friction was present. If one computed an entropy change
one would see an increase in entropy.
The maximum velocity is found by converting all the thermal energy to kinetic energy. Taking
zero thermal energy to correspond to absolute zero (despite the fact that air would not be a gas at this
point) one could estimate

u2max
ho = (2.178)
2,
u2max
cP T o = , (2.179)
2 s 
p 
ft2 ft
umax = 2cP To = 2 6015 2
(673 ◦ R) = 2845 . (2.180)
s ◦R s

2.2.2 Sonic properties

Let “*” denote a property at the sonic state M 2 ≡ 1. Then
 −1  − 1   γ−1
1
T∗ γ−1 2 2 ρ∗ γ − 1 2 γ−1 2
= 1+ 1 = , = 1+ 1 = , (2.181)
To 2 γ+1 ρo 2 γ+1
 − γ   γ−1
γ  −1/2 r
P∗ γ − 1 2 γ−1 2 c∗ γ−1 2 2
= 1+ 1 = , = 1+ 1 = , (2.182)
Po 2 γ+1 co 2 γ+1
r
p 2γ
u∗ = c∗ = γRT∗ = RTo . (2.183)
γ+1
If we have air then γ = 7/5, and we get
T∗ ρ∗ P∗ c∗
= 0.8333, = 0.6339 = 0.5283, = 0.9123. (2.184)
To ρo Po co

CC BY-NC-ND. 19 January 2025, J. M. Powers.

2.2. FLOW WITH AREA CHANGE 41

2.2.3 Effect of area change

The influence of mass equation must be considered. In the isentropic limit the mass, mo-
mentum, and energy equation for a CPIG reduce to

dρ du dA
+ + = 0, (2.185)
ρ u A
ρu du + dP = 0, (2.186)
dP dρ
= γ . (2.187)
P ρ

Substitute energy then mass into momentum to get

P
ρu du + γ dρ = 0, (2.188)
ρ
P  ρ ρ 
ρu du + γ − du − dA = 0, (2.189)
ρ u A
 
P 1 1
du + γ − 2 du − dA = 0, (2.190)
ρ u uA
 
γP/ρ P dA
du 1 − = γ , (2.191)
u2 ρ uA
 
du γP/ρ γP/ρ dA
1− = , (2.192)
u u2 u2 A
 
du 1 1 dA
1− 2 = , (2.193)
u M M2 A
du
dA
M2 − 1 = , (2.194)
u A
du 1 dA
= 2
. (2.195)
u M −1 A

Figure 2.6 shows the performance of a fluid in a variable area duct. It is noted that

• equation singular when M 2 = 1,

• if M 2 = 1, one needs dA = 0,

• an area minimum necessary to transition from subsonic to supersonic flow!!,

• it can be shown area maximum not relevant.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

42 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

consider u > 0

subsonic subsonic
diffuser nozzle

dA >0, M 2 <1 so
du < 0, flow slows down dA <0, M 2 <1 so
dP >0 du > 0, flow speeds up
dP < 0

supersonic supersonic
nozzle diffuser

dA >0, M 2 >1 so dA < 0, M 2 > 1 so

du > 0, flow speeds up du < 0, flow slows down
dP < 0 dP >0

Figure 2.6: Behavior of fluid in sub- and supersonic nozzles and diffusers.

Consider A at a sonic state. From the mass equation:

ρuA = ρ∗ u∗ A∗ , (2.196)
ρuA = ρ∗ c∗ A∗ , (2.197)
A ρ∗ 1
= c∗ , (2.198)
A∗ ρ u
ρ∗ p 1
= γRT∗ , (2.199)
ρ u
√ √
ρ∗ γRT∗ γRT
= √ , (2.200)
ρ γRT u
r
ρ∗ T∗ 1
= , (2.201)
ρ T M
r
ρ∗ ρo T∗ To 1
= . (2.202)
ρo ρ To T M
Substitute from earlier-developed relations and get:
   21 γ−1
γ+1
A 1 2 γ−1 2
= 1+ M . (2.203)
A∗ M γ+1 2
Figure 2.7 shows the performance of A/A∗ versus M. Note:

CC BY-NC-ND. 19 January 2025, J. M. Powers.

2.2. FLOW WITH AREA CHANGE 43

0 1 2 3 M

Figure 2.7: Area scaled by A∗ versus M. Calorically perfect ideal gas, R = 0.287 kJ/kg/K,
γ = 7/5.

• A/A∗ has a minimum value of 1 at M = 1,

• For each A/A∗ > 1, there exist two values of M,

• A/A∗ → ∞ as M → 0 or M → ∞.

2.2.4 Choking
Consider mass flow rate variation with pressure difference:

• small pressure difference gives small velocity, small mass flow,

• as pressure difference grows, velocity and mass flow rate grow,

• velocity is limited to sonic at a particular duct location,

• this provides fundamental restriction on mass flow rate,

• it can be proven rigorously that sonic condition gives maximum mass flow rate.

We have

ṁmax = ρ∗ u∗ A∗ , (2.204)
  γ−11 r 
2 2γ
if ideal gas: = ρo RTo A∗ , (2.205)
γ+1 γ+1
  γ−11  1/2
2 2 p
= ρo γRTo A∗ , (2.206)
γ+1 γ+1
  21 γ+1
γ−1 p
2
= ρo γRTo A∗ . (2.207)
γ+1

CC BY-NC-ND. 19 January 2025, J. M. Powers.

44 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

A flow which has a maximum mass flow rate is known as choked flow. Flows will choke at
area minima in a duct.

Example 2.7
9
Isentropic area change problem with choking

Given: Air with stagnation conditions Po = 200 kPa To = 500 K flows through a throat to an exit
Mach number of 2.5. The desired mass flow is 3.0 kg/s.

Find: a) throat area, b) exit pressure, c) exit temperature, d) exit velocity, and e) exit area.

Assume: CPIG, isentropic flow, γ = 7/5.

Po 200 kPa kg
ρo = =  = 1.394 3 . (2.208)
RTo kJ
0.287 kg K (500 K) m

Because it necessarily flows through a sonic throat:

  12 γ−1
γ+1
2 p
ṁmax = ρo γRTo A∗ , (2.209)
γ+1
ṁmax
A∗ =   21 γ−1
γ+1 , (2.210)
2
√
ρo γ+1 γRTo
3 kg
=   r s
  = 0.008297 m2 . (2.211)
kg J
1.394 m 3 (0.5787) 1.4 287 kg K (500 K)

Because Me is known, use the isentropic relations to find other exit conditions.
 − γ−1
γ  −3.5
γ−1 2 1 2
Pe = Po 1 + Me = (200 kPa) 1 + 2.5 = 11.71 kPa, (2.212)
2 5
 −1  −1
γ−1 2 1
Te = To 1 + Me = (500 K) 1 + 2.52 = 222.2 K. (2.213)
2 5
Note
Pe 11.71 kPa kg
ρe = =  = 0.1834 3 . (2.214)
RTe kJ
0.287 kg K (222.2 K) m

Now the exit velocity is simply

s  
p J m
ue = Me ce = Me γRTe = 2.5 1.4 287 (222.2 K) = 747.0 . (2.215)
kg K s
Now determine the exit area:
   12 γ−1
γ+1   3
A∗ 2 γ−1 2 0.008297 m2 5 1 2
A= 1+ Me = 1 + 2.5 = 70.0219 m2 . (2.216)
Me γ + 1 2 2.5 6 5

9
adopted from White, Fluid Mechanics McGraw-Hill: New York, 1986, p. 529, Ex. 9.5.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

2.2. FLOW WITH AREA CHANGE 45

Example 2.8
10
Discharge problem

Given: Air in tank, Po = 700 kPa, To = 20 ◦ C, V = 1.5 m3 . Throat area in converging nozzle of
0.65 cm2 , exhausting to 1 atm environment.

Find: Time for pressure in tank to decrease to 500 kPa.

Assume: CPIG, stagnation temperature constant (so small heat transfer to tank in time of opera-
tion).

Analysis:
First, To = 20 + 273 = 293 K. Now check for choked flow. At the initial state
Patm 101.3 kPa
= = 0.145. (2.217)
Po 700 kPa
But for air P∗ /Po = 0.5283, so the flow must be choked at the exit and the mass flow is restricted.
(Further expansion takes place outside the nozzle).
For choked flow one has
  21 γ−1
γ+1
2 p
ṁe = ρo γRTo A∗ , (2.218)
γ+1
   12 γ−1
γ+1
Po 2 p
= γRTo A∗ , (2.219)
RTo γ+1
  s    2
P

= 
o
  0.5787 1.4 287 J (293 K) 0.65 cm2
1 m
, (2.220)
287 kgJ K (293 K) kg K 100 cm
 
kg
= 1.5348 × 10−7 Po . (2.221)
s Pa
Now mass conservation gives
d
mcv = −ṁe , (2.222)
dt
d
(ρo V ) = −ṁe , (2.223)
dt 
d Po
V = −ṁe , (2.224)
dt RTo
dPo RTo
= − ṁe , (2.225)
dt V 
287 kgJ K (293 K)  
−7 kg
= − 1.5348 × 10 Po , (2.226)
1.5 m3 s Pa
 
1
= − 0.008604 Po , (2.227)
s
   
1
Po = A exp − 0.008604 t . (2.228)
s
10
from White, 9.33,35.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

46 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

Use initial value of Po to fix the constant A so

Po = 700 exp (−0.008604t) . (2.229)

When does Po = 500 kPa?

   
1
500 kPa = (700 kPa) exp − 0.008604 t , (2.230)
s
 
500 kPa 1
ln = − 0.008604 t, (2.231)
700 kPa s
1 500 kPa
t=−

1 ln 700 kPa = 39.1 s. (2.232)
0.008604 s

2.3 Normal shock waves

This section will develop relations for normal shock waves in fluids with general equations of
state. It will be specialized to calorically perfect ideal gases to illustrate the general features
of the waves. Assumptions for this section are as follows
• one-dimensional flow,

• steady flow,

• no area change,

• viscous effects and wall friction do not have time to influence the flow,

• heat conduction and wall heat transfer do not have time to influence the flow.
The piston problem as sketched in Figure 2.8 will be considered.
Consider this physical problem:
• drive piston with a known velocity vp into fluid at rest (v1 = 0) with known properties,
P1 , ρ1 in the x∗ laboratory frame,

• determine the disturbance speed D,

• determine the disturbance properties v2 , P2 , ρ2 ,

• Recognize in this frame of reference that we have an unsteady problem.

Consider a transformed problem:
• use a Galilean transformation x = x∗ − Dt, u = v − D to transform to the frame in
which the wave is at rest, therefore rending the problem steady in this frame,

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2.3. NORMAL SHOCK WAVES 47

vp = v2
D u2 u = -D
v = v2 v=0 P2 P1
P2 P1

laboratory frame steady frame

x

Figure 2.8: Normal shock sketch.

• solve as though D is known to get downstream “2” conditions: u2 (D), P2(D), ...,

• invert to solve for D as function of u2 , the transformed piston velocity: D(u2),

• back transform to get all variables as function of v2 , the laboratory piston velocity:
D(v2 ), P2 (v2 ), ρ2 (v2 ), ....

2.3.1 Governing equations

Under these assumptions the conservation principles in conservative form and equation of
state are in the steady frame as follows:

d
(ρu) = 0, (2.233)
dx
d

ρu2 + P = 0, (2.234)
 dx
 
d u2
ρu h + = 0, (2.235)
dx 2
h = h(P, ρ). (2.236)

Upstream conditions are ρ = ρ1 , P = P1 , u = −D. With knowledge of the equation of state,

one gets h = h1 . Integrating the equations from upstream to state “2” gives:

ρ2 u2 = −ρ1 D, (2.237)
ρ2 u22 + P2 = ρ1 D 2 + P1 , (2.238)
u2 D2
h2 + 2 = h1 + , (2.239)
2 2
h2 = h(P2 , ρ2 ). (2.240)

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48 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

2.3.2 Rayleigh line

Manipulate the momentum equation:

P2 = P1 + ρ1 D 2 − ρ2 u22 , (2.241)
ρ2 D 2 ρ22 u22
P2 = P1 + 1 − . (2.242)
ρ1 ρ2

Because mass gives ρ22 u22 = ρ21 D 2 , one gets an equation for the Rayleigh Line, a line in (P, 1/ρ)
space:
 
1 1
P2 = P1 + ρ21 D 2 − . (2.243)
ρ1 ρ2

Note:

• the Rayleigh line passes through ambient state,

• the Rayleigh line has a negative slope,

• the magnitude of the slope is proportional to the square of the wave speed,

• it is independent of state and energy equations.

2.3.3 Hugoniot curve

Operate on the energy equation, using both mass and momentum to eliminate velocity. First
eliminate u2 via the mass equation:

u22 D2
h2 + = h1 + , (2.244)
2 2
 2
1 ρ1 D D2
h2 + = h1 + , (2.245)
2 ρ2 2
  !
2
D2 ρ1
h2 − h1 + −1 = 0, (2.246)
2 ρ2
 
D 2 ρ21 − ρ22
h2 − h1 + = 0, (2.247)
2 ρ22
 
D 2 (ρ1 − ρ2 ) (ρ1 + ρ2 )
h2 − h1 + = 0. (2.248)
2 ρ22

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2.3. NORMAL SHOCK WAVES 49

Now use the Rayleigh line to eliminate D 2 :

 
−1
2 1 1 1
D = (P2 − P1 ) − , (2.249)
ρ21
ρ1 ρ2
  −1
1 ρ2 − ρ1
= (P2 − P1 ) , (2.250)
ρ21 ρ1 ρ2
  
1 ρ1 ρ2
= (P2 − P1 ) , (2.251)
ρ21 ρ2 − ρ1

so the energy equation becomes

   
1 1 ρ1 ρ2 (ρ1 − ρ2 ) (ρ1 + ρ2 )
h2 − h1 + (P2 − P1 ) = 0, (2.252)
2 ρ21 ρ2 − ρ1 ρ22
  
1 1 ρ1 + ρ2
h2 − h1 − (P2 − P1 ) = 0, (2.253)
2 ρ1 ρ2
 
1 1 1
h2 − h1 − (P2 − P1 ) + = 0. (2.254)
2 ρ2 ρ1

Solving finally for the enthalpy difference, one finds

  
1 1 1
h2 − h1 = (P2 − P1 ) + . (2.255)
2 ρ2 ρ1

This equation is the Hugoniot equation. Its features include

• the enthalpy change equals pressure difference times mean volume,

• it is independent of wave speed D and velocity u2 ,

• it is independent of equation of state.

2.3.4 Solution procedure for general equations of state

The shocked state can be determined by the following procedure:

• specify an equation of state h(P, ρ),

• substitute the equation of state into the Hugoniot to get a second relation between P2
and ρ2 ,

• use the Rayleigh line to eliminate P2 in the Hugoniot so that the Hugoniot is a single
equation in ρ2 ,

• solve for ρ2 as functions of “1” and D,

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50 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

• back substitute to solve for P2 , u2 , h2 , T2 as functions of “1” and D,

• invert to find D as function of “1” state and u2 ,

• back transform to laboratory frame to get D as function of “1” state and piston velocity
v2 = vp .

2.3.5 Calorically perfect ideal gas solutions

Follow this procedure for the special case of a calorically perfect ideal gas.

h = cP (T − To ) + ho , P = ρRT, (2.256)

so
   
P Po cP P Po
h = cP − + ho = − + ho , (2.257)
Rρ Rρo R ρ ρo
   
cP P Po γ P Po
= − + ho = − + ho . (2.258)
cP − cv ρ ρo γ −1 ρ ρo
Evaluate at states 1 and 2 and substitute into the Hugoniot:
       
γ P2 Po γ P1 Po
− + ho − − + ho
γ − 1 ρ2 ρo γ − 1 ρ1 ρo
  
1 1 1
= (P2 − P1 ) + , (2.259)
2 ρ2 ρ1

    
γ P2 P1 1 1 1
− − (P2 − P1 ) + = 0, (2.260)
γ − 1 ρ2 ρ1 2 ρ2 ρ1
   
γ 1 1 1 γ 1 1 1
P2 − − − P1 − − = 0, (2.261)
γ − 1 ρ2 2ρ2 2ρ1 γ − 1 ρ1 2ρ2 2ρ1
   
γ+1 1 1 γ+1 1 1
P2 − − P1 − = 0, (2.262)
2 (γ − 1) ρ2 2ρ1 2 (γ − 1) ρ1 2ρ2
   
γ+1 1 1 γ+1 1 1
P2 − − P1 − = 0. (2.263)
γ − 1 ρ2 ρ1 γ − 1 ρ1 ρ2
So
γ+1 1 1
γ−1 ρ1
− ρ2
P2 = P1 γ+1 1 1
. (2.264)
γ−1 ρ2
− ρ1

We have
• a hyperbola in (P, 1/ρ) space,

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2.3. NORMAL SHOCK WAVES 51

P (kPa)
500
shocked state
P2

400
excluded zone
slope of Rayleigh line < 0
excluded
300
zone, Rayleigh line, slope
from mass and momentum

200
Hugoniot,
initial state from energy
100
P1
excluded zone, 2nd law violation

2 3 4 5 6 7

excluded zone, negative pressure

Figure 2.9: Rayleigh line and Hugoniot curve for γ = 7/5, P1 = 100 kPa, T1 = 300 K,
Mshock = 2.

1 γ−1 1
• ρ2
→ γ+1 ρ1
causes P2 → ∞, note, γ = 7/5, ρ2 → 6 for infinite pressure,

• as 1
ρ2
→ ∞, P2 → −P1 γ−1
γ+1
, note negative pressure, not physical here.

The Rayleigh line and Hugoniot curves are sketched in Figure 2.9. Note:

• intersections of the two curves are solutions to the equations,

• the ambient state “1” is one solution,

• the other solution “2” is known as the shock solution,

• shock solution has higher pressure and higher density,

• higher wave speed implies higher pressure and higher density,

• a minimum wave speed exists:

– occurs when Rayleigh line tangent to Hugoniot,

– occurs for very small pressure changes,
– corresponds to a sonic wave speed,
– disturbances are acoustic,

• if pressure increases, it can be shown that entropy increases,

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52 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

• if pressure decreases (wave speed less than sonic), entropy decreases; this is non-
physical.

Substitute the Rayleigh line into the Hugoniot to get a single equation for ρ2
  γ+1 1 1
1 1 γ−1 ρ1
− ρ2
P1 + ρ21 D 2 − = P1 γ+1 1 1
. (2.265)
ρ1 ρ2 γ−1 ρ2
− ρ1

This equation is quadratic in 1/ρ2 and factorizable. Use computer algebra to solve and get
two solutions, one ambient 1/ρ2 = 1/ρ1 and one shocked solution:
 
1 1 γ−1 2γ P1
= 1+ . (2.266)
ρ2 ρ1 γ + 1 (γ − 1) D 2 ρ1

The shocked density ρ2 is plotted against wave speed D for CPIG air in Figure 2.10. Note

• density solution allows allows all wave speeds 0 < D < ∞,

• the plot range, however, is c1 < D < ∞,

• the Rayleigh line and Hugoniot show D ≥ c1 ,

• solution for D = D(vp ), to be shown, rigorously shows D ≥ c1 ,

• strong shock limit: D 2 → ∞, ρ2 → (γ + 1)/(γ − 1),

• acoustic limit: D 2 → γP1 /ρ1 , ρ2 → ρ1 ,

• non-physical limit: D 2 → 0, ρ2 → 0.

Back substitute into Rayleigh line and mass conservation to solve for the shocked pressure
and the fluid velocity in the shocked wave frame:
 
2 2 γ−1 γ −1 2γ P1
P2 = ρ1 D − P1 , u2 = −D 1+ . (2.267)
γ+1 γ+1 γ+1 (γ − 1) D 2 ρ1

The shocked pressure P2 is plotted against wave speed D for CPIG air in Figure 2.11 including
both the exact solution and the solution in the strong shock limit. Note for these parameters,
the results are indistinguishable. The shocked wave frame fluid particle velocity u2 is plotted
against wave speed D for CPIG air in Figure 2.12. The shocked wave frame fluid particle
velocity M22 = ρ2 u22 /γ/P2 is plotted against wave speed D for CPIG air in Figure 2.13. Note
in the steady frame that

• the Mach number of the undisturbed flow is (and must be) > 1: supersonic,

• the Mach number of the shocked flow is (and must be) < 1: subsonic.

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2.3. NORMAL SHOCK WAVES 53

strong
shock
7 limit

6
5
4 exact
solution
3
2
1
D (m/s)
500 1000 1500 2000 2500 3000

Figure 2.10: Shock density versu shock wave speed for calorically perfect ideal air, γ = 7/5,
R = 287 J/kg/K.

Transform back to the laboratory frame u = v − D:

 
γ−1 2γ P1
v2 − D = −D 1+ , (2.268)
γ+1 (γ − 1) D 2 ρ1
 
γ−1 2γ P1
v2 = D − D 1+ . (2.269)
γ+1 (γ − 1) D 2 ρ1
Manipulate this equation and solve the resulting quadratic equation for D and get
s  2
γ+1 γP1 2 γ +1
D= v2 ± + v2 . (2.270)
4 ρ1 4

Now if v2 > 0, one expects D > 0 so take positive root, also set velocity equal piston velocity
v2 = vp to get
s  2
γ+1 γP1 γ + 1
D= vp + + vp2 . (2.271)
4 ρ1 4

Note:
• acoustic limit: as vp → 0, D → c1 ; the shock speed approaches the sound speed,

• strong shock limit: as vp → ∞, D → (γ + 1)vp /2.

The shock speed D is plotted against piston velocity vp for CPIG air in Figure 2.14. Both
the exact solution and strong shock limit are shown. If the Mach number of the shock is

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54 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

6
ambient =
4 0.1 MPa
exact solution
2 and strong
shock limit
500 1000 1500 2000 2500 3000 D (m/s)

Figure 2.11: Shock pressure versus shock wave speed for calorically perfect ideal air, γ = 7/5,
R = 287 J/kg/K.

defined as
D
Ms ≡ , (2.272)
c1
one gets
s  2
γ + 1 vp vp2 γ+1
Ms = √ + 1+ . (2.273)
4 γRT1 γRT1 4

The shock Mach number Ms is plotted against piston velocity vp for CPIG air in Figure 2.15.
Both the exact solution and strong shock limit are shown.

Example 2.9
11
Normal shock problem

Given: Air flowing through normal shock. Upstream u1 = 600 m/s, To1 = 500 K, Po1 = 700 kPa.

Find: Downstream conditions M2 , u2 , T2 , P2 , Po2 and s2 − s1 .

Assume: calorically perfect ideal gas

Analysis:
11
adopted from White’s 9.46, p. 586.

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2.3. NORMAL SHOCK WAVES 55

D (m/s)
500 1000 1500 2000 2500 3000
-100

-200
strong
shock
-300
limit
-400
exact
-500 solution

Figure 2.12: Shock wave frame fluid particle velocity versus shock wave speed for calorically
perfect ideal air, γ = 7/5, R = 287 J/kg/K.

First get all local unshocked conditions.

u21
To1 = T1 + , (2.274)
2cP

2
u21 600 ms
T1 = To1 − = 500 K −   = 320.81 K, (2.275)
2cP 2 1004.5 kgJ K
s  
p J m
c1 = γRT1 = 1.4 287 (320.81 K) = 359.0 , (2.276)
kg K s
u1 600 ms
M1 = = = 1.671, (2.277)
c1 359.0 ms
 −3.5  −3.5
1 2 1 2
P1 = Po1 1 + M1 = (700 kPa) 1 + (1.671) = 148.1 kPa, (2.278)
5 5
P1 148.1 kPa kg
ρ1 = =   = 1.609 3 , (2.279)
RT1 0.287 kJ
(320.81 K) m
kg K
   12 γ−1
γ+1    21 1.4−1
1.4+1
A1 1 2 γ−1 2 1 2 1.4 − 1
= 1+ M1 = 1+ 1.6712 ,(2.280)
A1∗ M1 γ + 1 2 1.671 1.4 + 1 2
= 1.311. (2.281)

Now in this case it is fortunate because the incoming velocity D = 600 m/s is known. Note that the
shock density only depends on D2 , so one can be a little sloppy here with sign. Solve for the shocked

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56 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

0.8 exact
solution
0.6
strong
shock 0.4
limit
0.2

D (m/s)
0 500 1000 1500 2000 2500 3000

Figure 2.13: Mach number squared of shocked fluid particle versus shock wave speed for
calorically perfect ideal air, γ = 7/5, R = 287 J/kg/K.
D (m/s)
exact
1200 solution

1000
800 strong
600 shock
acoustic limit
limit 400
200

200 400 600 800 1000

Figure 2.14: Shock speed versus piston velocity for calorically perfect ideal air, γ = 7/5,
R = 287 J/kg/K.

state:
 
1 1 γ−1 2γ P1
= 1+ 2
(2.282)
ρ2 ρ1 γ + 1 (γ − 1) D ρ1
!
1 1.4 − 1 2 (1.4)
148100 Pa m3
= 1+
= 0.2890 , (2.283)
1.609 kg 1.4 + 1 m 2 1.609 kg kg
m3 (1.4 − 1) 600 s m3
1 kg
ρ2 = m3
= 3.461 3 . (2.284)
0.2890 kg
m

Now a variety of equations can be used to determine the remaining state variables. Mass gives u2 :

ρ2 u 2 = ρ1 u 1 , (2.285)
 

kg m
ρ1 u 1 1.609 m3 600 s m
u2 = = kg
= 278.9 . (2.286)
ρ2 3.461 m3
s

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2.3. NORMAL SHOCK WAVES 57

exact
solution
3

2 strong
acoustic shock
limit limit
1

200 400 600 800 1000

Figure 2.15: Shock Mach number versus piston velocity for calorically perfect ideal air,
γ = 7/5, R = 287 J/kg/K.

Momentum gives P2

P2 + ρ2 u22 = P1 + ρ1 u21 , (2.287)

2 2
P2 = P1 + ρ1 u1 − ρ2 u2 , (2.288)
   
kg  m 2 kg  m 2
= 148100 Pa + 1.609 3 600 − 3.461 3 278.9 = 458125 Pa.
m s m s
(2.289)

Solving for the remaining assorted variables is straightforward:

P2 458125 Pa
T2 = =   = 461.2 K, (2.290)
ρ2 R kg
3.461 m 287 kgJ K
3
s  
p J m
c2 = γRT2 = 1.4 287 (461.2 K) = 430.5 , (2.291)
kg K s
u2 278.9 ms
M2 = = = 0.648, (2.292)
c2 430.5 ms
   
1 2 1 2
To2 = T2 1 + M2 = 461.2 K 1 + 0.648 = 500 K, unchanged as required, (2.293)
5 5
 3.5  3.5
1 1
Po2 = P2 1 + M22 = 458 kPa 1 + 0.6482 = 607.4 kPa, diminished, (2.294)
5 5
   
T2 P2
s2 − s1 = cP ln − R ln (2.295)
T1 P1
       
J 461.2 K J 458 kPa J
= 1004.5 ln − 287 ln = 40.6 , (2.296)
kg K 320.81 K kg K 148.1 kPa kg K
   21 γ−1
γ+1
A2 1 2 γ−1 2
= 1+ M2 , (2.297)
A2∗ M2 γ + 1 2
   21 1.4−1
1.4+1
1 2 1.4 − 1
= 1+ 0.6482 = 1.966. (2.298)
0.648 1.4 + 1 2

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58 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

Because A2 = A1 = A,
A
A2 A1∗ 1.311
= A
= = 0.667. (2.299)
A2∗ A2∗
1.966

Note the entropy increased despite not including any entropy-generating mechanisms in this model.
Why? First, the differential equations themselves required the assumption of continuous differentiable
functions. Our shock violates this. When one returns to the more fundamental control volume forms,
it can be shown that the entropy-generating mechanism returns. From a continuum point of view, one
can also show that the neglected terms, that momentum and energy diffusion, actually give rise to a
smeared shock. These mechanisms generate just enough entropy to satisfy the entropy jump which was
just calculated.

Example 2.10
Piston Problem

Given: A piston moving at vp = 1000 m/s is driven into helium which is at rest in the ambient
state at a pressure of P1 = 10 kPa, T1 = 50 K.

Find: The shock speed and post shock state.

Assume: helium is calorically perfect and ideal.

For helium,

 
J γR 1.667 2077 kgJ K J
γ = 1.667, R = 2077 , cP = = = 5192.5 . (2.300)
kg K γ −1 1.667 − 1 kg K
We also see
P1 10000 Pa kg
ρ1 = =   = 0.0963 3 , (2.301)
RT1 2077 kgJ K (50 K) m
s  
p J m
c1 = γRT1 = 1.667 2077 (50 K) = 416.0 . (2.302)
kg K s

Now the wave speed D one gets from

s  2
γ+1 γP1 2
γ+1
D = vp + + vp , (2.303)
4 ρ1 4
v
u  2
1.667 + 1  m u t 1.667 (10000 Pa)  m 2 1.667 + 1
= 1000 + kg
+ 1000 , (2.304)
4 s 0.0963 m 3
s 4
m
= 1452.5 . (2.305)
s

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2.3. NORMAL SHOCK WAVES 59

The strong shock limit is appropriate here as a quick check:

γ+1 1.667 + 1  m m
D∼ vp = 1000 = 1333.3 . (2.306)
2 2 s s

2 γ−1
P2 = ρ1 D 2 − P1 , (2.307)
γ+1 γ+1
 
2 kg  m 2 1.667 − 1
= 0.0963 3 1452.5 − (10000 Pa) , (2.308)
1.667 + 1 m s 1.667 + 1
= 149877 Pa = 150 kPa, (2.309)
ρ2 u 2 = ρ1 u 1 , (2.310)
ρ2 (v2 − D) = ρ1 (v1 − D) , (2.311)
ρ2 (vp − D) = ρ1 (0 − D) , (2.312)
−ρ1 D
ρ2 = (2.313)
vp − D
 

kg
− 0.0963 m 3 1452.5 ms kg
= m m = 0.309 3 , (2.314)
1000 s − 1452.5 s m
P2 149877 Pa
T2 = =    = 233.5 K. (2.315)
ρ2 R 0.309 kg 2077 J
m3 kg K

2.3.6 Acoustic limit

Consider that state 2 is a small perturbation of state 1 so that

ρ2 = ρ1 + ∆ρ, (2.316)
u2 = u1 + ∆u1 , (2.317)
P2 = P1 + ∆P. (2.318)

Substituting into the normal shock equations, one gets

(ρ1 + ∆ρ) (u1 + ∆u) = ρ1 u1 , (2.319)

(ρ1 + ∆ρ) (u1 + ∆u)2 + (P1 + ∆P ) = ρ1 u1 2 + P1 , (2.320)
γ P1 + ∆P 1 γ P1 1 2
+ (u1 + ∆u)2 = + u1 . (2.321)
γ − 1 ρ1 + ∆ρ 2 γ − 1 ρ1 2

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60 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

Expanding, one gets

ρ1 u1 + ũ1 (∆ρ) + ρ1 (∆u) + (∆ρ) (∆u) = ρ1 u1 , (2.322)


ρ1 u1 2
+ 2ρ1 u1 (∆u) + u1 (∆ρ) + ρ1 (∆u)2 + 2u1 (∆u) (∆ρ) + (∆ρ) (∆u)2
2
(2.323)
+ (P1 + ∆P ) = ρ1 u1 2 + P1 , (2.324)
 
γ P1 1 P1 1

+ ∆P − 2 ∆ρ + ... + u1 2 + 2u1 (∆u) + (∆u)2 (2.325)
γ − 1 ρ1 ρ1 ρ1 2
γ P1 1 2
= + u1 . (2.326)
γ − 1 ρ1 2
Subtracting the base state and eliminating products of small quantities yields
u1 (∆ρ) + ρ1 (∆u) = 0, (2.327)
2ρ u (∆u) + u1 2 (∆ρ) + ∆P = 0, (2.328)
 1 1 
γ 1 P1
∆P − 2 ∆ρ + u1 (∆u) = 0. (2.329)
γ − 1 ρ1 ρ1
In matrix form this is
    
u1 ρ1 0 ∆ρ 0
 u1 2 2ρ1 u1 1   ∆u  = 0 . (2.330)
γ P1 γ 1
− γ−1 ρ21
u1 γ−1 ρ1 ∆P 0
As the right hand side is zero, the determinant must be zero, and there must be a linear
dependency of the solution. First check the determinant:
   
2γ γ u1 2 γ P1
u1 u1 − u1 − ρ1 + = 0, (2.331)
γ −1 γ − 1 ρ1 γ − 1 ρ21
 
u1 2 1 2 P1
(2γ − (γ − 1)) − γ u1 + γ = 0 (2.332)
γ−1 γ−1 ρ1
 
2 2 P1
u1 (γ + 1) − γ u1 + γ = 0, (2.333)
ρ1
P1
u1 2 = γ = c21 . (2.334)
ρ1
So the velocity is necessarily sonic for a small disturbance! Take ∆u to be known and solve
a resulting 2 × 2 system:
    
u1 0 ∆ρ −ρ1 ∆u
γ P1 γ 1 = . (2.335)
− γ−1 ρ2 γ−1 ρ1 ∆P −u1 ∆u
1

Solving yields
s
ρ1 ∆u P1
∆ρ = − q , ∆P = −ρ1 γ ∆u. (2.336)
γ Pρ11 ρ1

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2.3. NORMAL SHOCK WAVES 61

2.3.7 Non-ideal gas solutions

Non-ideal effects are important

• near the critical point

• for strong shocks

Some other points:

• qualitative trends the same as for ideal gases

• analysis is much more algebraically complicated

• extraneous solutions often arise which must be discarded

Example 2.11
Shock in van der Waals gas

Given: Shock wave D = 500 m/s propagating into N2 at rest at T1 = 125 K, P1 = 2 MPa.

Find: Shocked state

Assume: van der Waals equation of state accurately models gas behavior, specific heat constant.

First, some data for N2 are needed. At P1 = 2 MPa, N2 has a boiling point of 115.5 K, so the
material is in the gas phase but very near the vapor dome. R = 296.8 J/kg/K, cv = 744.8 J/kg/K,
Tc = 126.2 K, Pc = 3390000 Pa.
Because the material is near the vapor dome, the van der Waals equation may give a good first
correction for non-ideal effects.
RT a RT ρRT
P = − = 1 − aρ2 = − aρ2 . (2.337)
v − b v2 ρ − b 1 − bρ

Now one must be careful to have a thermodynamically consistent caloric state equation. One can seek

e = e(T, v). (2.338)

Then, one has for the differential

∂e ∂e
de = dT + dv. (2.339)
∂T v ∂v T

Now from the Gibbs equation, one also has

de = T ds − P dv, (2.340)
de ds
= T − P, (2.341)
dv dv
∂e ∂s
= T − P. (2.342)
∂v T ∂v T

CC BY-NC-ND. 19 January 2025, J. M. Powers.

62 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

∂e
Use Eq. (2.342) to eliminate ∂v T in Eq. (2.339) to get
 
∂e ∂s
de = dT + T −P dv. (2.343)
∂T v ∂v T

∂s ∂P
Now taking the Maxwell equation, ∂v T = ∂T v , and substituting into Eq. (2.343), one gets
 
∂e ∂P
de = dT + T −P dv. (2.344)
∂T v ∂T v

∂e
Recalling that cv ≡ ∂T v , one then gets
 
∂P
de = cv dT + T −P dv. (2.345)
∂T v

Now for the van der Waals equation, one has

∂P R
= , (2.346)
∂T v v−b
so
  
RT RT a
de = cv dT + − − dv, (2.347)
v−b v − b v2
a
= cv dT + 2 dv. (2.348)
v
Assuming cv = cv (T ), one can integrate to obtain
Z T  
1 1
e(T, v) = eo + cv (T̂ ) dT̂ + a − . (2.349)
To vo v

Taking cv constant and exchanging v for ρ gives

e(T, ρ) = eo + cv (T − To ) + a (ρo − ρ) . (2.350)

Eliminating T in favor of P then gives

!
P + aρ2 (1 − bρ)
e(P, ρ) = eo + cv − To + a (ρo − ρ) , (2.351)
ρR

and in terms of h = e + P/ρ:

!
P + aρ2 (1 − bρ) P
h(P, ρ) = eo + cv − To + a (ρo − ρ) + . (2.352)
ρR ρ

Now h2 − h1 allows cancellation of the “o” state so that

!
P2 + aρ22 (1 − bρ2 ) P1 + aρ21 (1 − bρ1 ) P2 P1
h 2 − h 1 = cv − − a (ρ2 − ρ1 ) + − . (2.353)
ρ2 R ρ1 R ρ2 ρ1

The constants a and b are fixed so that an isotherm passing through the critical point, P = Pc , T = Tc ,
passes through with ∂P/∂v|T = 0 and ∂ 2 P/∂v 2 T = 0. A standard analysis from Borgnakke and

CC BY-NC-ND. 19 January 2025, J. M. Powers.

2.3. NORMAL SHOCK WAVES 63

Sonntag, p. 501, yields

 2
J 2
27 R2 Tc2 27 296.8 kg K (126.2 K) Pa m6
a = = = 174.6 (2.354)
64 Pc 64 3390000 Pa kg2
 
RTc 296.8 kgJ K (126.2 K) m3
b = = = 0.00138 . (2.355)
8Pc 8 (3390000 Pa) kg

Find the ambient density.

 
ρ1 296.8 kgJ K (125 K)  Pa m6

2000000 Pa =   − 174.6 2
ρ21 (2.356)
m3
1 − 0.00138 kg ρ1 kg

Three solutions from computer algebra can be obtained:

kg kg
ρ1 = 69.0926 , ρ1 = (327.773 ± 112.702 i) . (2.357)
m3 m3

The first is physical and other two non-physical. Tabular data from experiments gives ρ1 = 71.28 kg/m3 ,
error = (71.28 − 69.09)/71.28 = 0.03, so it seems the first root is the physical root. Note that the van
der Waals prediction is a significant improvement over the ideal gas law which gives ρ1 = P1 /R/T1 =
2000000/296.8/125 = 53.91 kg/m3 , error = (71.28 − 53.91)/71.28 = 0.214! Even with this improvement
there are much better (and more complicated!) equations of state for materials near the vapor dome.
Now use the Rayleigh line and Hugoniot equations to solve for the shocked density:
 
1 1
P2 = P1 + ρ21 D2 − , (2.358)
ρ1 ρ2


! !
P2 + aρ22 (1 − bρ2 ) P1 + aρ21 (1 − bρ1 ) P2 P1
cv − − a (ρ2 − ρ1 ) + −
ρ2 R ρ1 R ρ2 ρ1
   
1 1 1
− (P2 − P1 ) + = 0. (2.359)
2 ρ2 ρ1

Plugging in all the numbers into a computer algebra program yields the following solutions for ρ2 :

kg
ρ2 = 195.309 , shocked solution, (2.360)
m3
kg
= 69.0926 3 , inert solution, (2.361)
m
kg
= (85.74 + 657.9 i) , non-physical solution, (2.362)
m3
kg
= (85.74 − 657.9 i) 3 , non-physical solution. (2.363)
m

The Rayleigh line then gives the pressure:

 2  !
kg m 2 1 1
P2 = 2000000 Pa + 69.0926 3 500 kg
− kg
, (2.364)
m s 69.0926 m3 195.309 m3
= 13162593 Pa = 13.2 MPa. (2.365)

CC BY-NC-ND. 19 January 2025, J. M. Powers.

64 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

The state equation gives the temperature.

P2 + aρ22 (1 − bρ2 )
T2 = , (2.366)
ρ2 R
   2     
Pa m6 kg m3 kg
13162593 Pa + 174.6 kg2 195.3 m3 1 − 0.00138 kg 195.3 m3
=    , (2.367)
kg
195.3 m 3 296.8 kgJ K
= 249.8 K. (2.368)
Note the temperature is still quite low relative to standard atmospheric conditions; it is unlikely at
these low temperatures that any effects due to vibrational relaxation or dissociation will be important.
Our assumption of constant specific heat is probably pretty good.
The mass equation gives the shocked particle velocity:
ρ2 u 2 = ρ1 u 1 , (2.369)
 

kg m
ρ1 u 1 69.0926 m3 500 s m
u2 = = kg
= 176.89 . (2.370)
ρ2 195.3 m3
s

An ideal gas approximation (γN2 = 7/5) would have yielded

 
1 1 γ−1 2γ P1
= 1+ , (2.371)
ρ2 ρ1 γ + 1 (γ − 1) D2 ρ1
! !
1 7/5 − 1 2 (7/5) 2000000 Pa
= 1+
, (2.372)
kg
53.91 m3 7/5 + 1 m 2 53.91 kg
(7/5 − 1) 500 s m3
kg
ρ2 = 158.65 , ideal gas approximation, (2.373)
m3
kg kg
195.3 m3 − 158.65 m 3
relative error = kg
= 0.188. (2.374)
195.3 m 3

The Rayleigh line then gives the pressure:

 2  !
kg m 2 1 1
P2 = 2000000 Pa + 53.91 3 500 kg
− kg
, (2.375)
m s 53.91 m3 158.65 m3
= 10897783 Pa = 10.90 MPa, (2.376)
13.2 MPa − 10.9 MPa
relative error = = 0.174. (2.377)
13.2 MPa

2.4 Flow with area change and normal shocks

This section will consider flow from a reservoir with the fluid at stagnation conditions to a
constant pressure environment. The pressure of the environment is commonly known as the
back pressure: Pb . We have the generic problem, given A(x), stagnation conditions and Pb ,
find the pressure, temperature, density at all points in the duct and the mass flow rate.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

2.4. FLOW WITH AREA CHANGE AND NORMAL SHOCKS 65

2.4.1 Converging nozzle

A converging nozzle operating at several different values of Pb is sketched in Figure 2.16.

e d c
1

Pb
b

Po Pe

0 P*/Po 1 P /P
b o

P(x)/Po 1
a--subsonic exit

b--subsonic exit

P*/Po c--sonic exit

d--choked, external expansion
e--choked, external expansion

xe x

Figure 2.16: Converging nozzle sketch.

The flow through the duct can be solved using the following procedure
• check if Pb ≥ P∗ ,
• if so, set Pe = Pb ,
• determine Me from isentropic flow relations,
• determine A∗ from A/A∗ relation,
• at any point in the flow where A is known, compute A/A∗ and then invert A/A∗ relation
to find local M.
Note:
• these flows are subsonic throughout and correspond to points a and b in Figure 2.16,
• if Pb = P∗ , then the flow is sonic at the exit and just choked; this corresponds to point
c in Figure 2.16.
• if Pb < P∗ , then the flow chokes, is sonic at the exit, and continues to expand outside
of the nozzle; this corresponds to points d and e in Figure 2.16.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

66 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

2.4.2 Converging-diverging nozzle

A converging-diverging nozzle operating at several different values of Pb is sketched in Figure
2.17.

h g fed c
1
Pb
b
Po Pt Pe
possible a
normal
shock
0 P*/Po 1 Pb/Po
P(x)/Po
1 a--subsonic exit
b--subsonic exit
c--subsonic design

P*/Po
sonic
d--shock in duct
throat
e-shock at end of duct
f--external compression
g--supersonic design
h--external expansion
xt xe
x

Figure 2.17: Converging-diverging nozzle sketch.

The flow through the duct can be solved using the a very similar following procedure

• set At = A∗ ,

• with this assumption, calculate Ae /A∗ ,

• determine Mesub , Mesup , both supersonic and subsonic, from A/A∗ relation,

• determine Pesub , Pesup, from Mesub , Mesup ; these are the supersonic and subsonic design
pressures,

• if Pb > Pesub , the flow is subsonic throughout and the throat is not sonic. Use same
procedure as for converging duct: determine Me by setting Pe = Pb and using isentropic
relations,

• if Pesub > Pb > Pesup , the procedure is complicated:

– estimate the pressure with a normal shock at the end of the duct, Pesh ,
– If Pb ≥ Pesh , there is a normal shock inside the duct

CC BY-NC-ND. 19 January 2025, J. M. Powers.

2.4. FLOW WITH AREA CHANGE AND NORMAL SHOCKS 67

– If Pb < Pesh , the duct flow is shockless, and there may be compression outside the
duct,

• if Pesup = Pb , the flow is at supersonic design conditions, and the flow is shockless,

• if Pb < Pesup , the flow in the duct is isentropic, and there is expansion outside the duct.

Example 2.12
12
Nozzle problem

Given: Air at To = 600 K flowing through converging-diverging nozzle. At = 1 cm2 , Ae = 3 cm2 ,

ṁ = 148.5 kg/hr. Pitot tube at exit plane gives Poe = 200 kPa, Pe = 191.5 kPa.

Find: exit velocity, location of possible normal shock in duct, Mach number just upstream of normal
shock

Assume: Air is calorically perfect and ideal

kg hr kg
ṁ = 148.5 = 0.04125 . (2.378)
hr 3600 s s
Now if there is no shock, the stagnation pressure would be constant in the duct; one can use the choked
flow formula to compare to the actual mass flow rate:
  12 γ−1
γ+1
Po 2 p
ṁe = γRToA∗ , (2.379)
RTo γ + 1
  21 7/5−1
7/5+1 s    2
200000 Pa 2 J 2

1m
=   7/5 287 (600 K) 1 cm , (2.380)
287 kgJ K (600 K) 7/5 + 1 kg K 100 cm

kg
= 200000 × 165 × 10−9 = 0.033 . (2.381)
s
Now the actual mass flow is higher than this, so the stagnation pressure upstream must also be higher;
therefore, there must be a shock in the duct which lowers the stagnation pressure. Use this equation
to determine what the upstream stagnation pressure must be.
 
kg −9 kg 1
0.04125 = Po1 × 165 × 10 , (2.382)
s s Pa
Po1 = 250 kPa. (2.383)

So
Po2 200 kPa
= = 0.800. (2.384)
Po1 250 kPa
12
adopted from White’s 9.69, p. 588.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

68 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

The flow conditions could be deduced from this; one can also utilize the normal shock tables for air.
These are valid only for a calorically perfect ideal air. Interpolating this table yields
M1 ∼ 1.83, M2 ∼ 0.61. (2.385)
The area ratio is determined from the isentropic flow tables. Recall that A∗ changes through a shock,
so in this case one wants to use conditions upstream of the shock. From the tables at M1 = 1.83 one
finds A1 /A∗ = 1.4723 so,
A1 = 1.4723 × 1 cm2 = 1.4723 cm2 . (2.386)
Get the exit velocity. Even if there is a shock, the stagnation temperature is constant; thus, one has
from energy conservation:
u2e
he + = ho , (2.387)
2 p p
ue = 2 (ho − he ) = 2cP (To − Te ), (2.388)
s v !
  u u   γ−1
Te t Pe γ
= 2cP To 1 − = 2cP To 1 − , (2.389)
To Poe
v
u 
u    1.4−1 !
= t2 1004.5 J (600 K) 1 −
191.5 kPa 1.4 m
= 121.9 . (2.390)
kg K 200 kPa s

2.5 Flow with friction–Fanno flow

Wall friction is typically considered by modelling the wall shear as a constant. Wall friction
is usually correlated with what is known as the Darcy friction factor: f , where
8τw
f≡ . (2.391)
ρu2
Now in practice f is related to the local flow Reynolds number based on pipe diameter D:
ReD
ρuD
ReD ≡ , (2.392)
µ
and roughness of the duct ǫ/D, where ǫ is the average surface roughness.
 ǫ
f = f ReD , . (2.393)
D
For steady laminar duct flow, the friction factor is independent of ǫ. It turns out the Poiseuille
flow solution gives the friction factor, which turns out to be
64
f= . (2.394)
ReD

CC BY-NC-ND. 19 January 2025, J. M. Powers.

2.5. FLOW WITH FRICTION–FANNO FLOW 69

If the flow is steady and turbulent, the friction factor is described by the following empirical
formula known as the Colebrook equation:
 
1 ǫ/D 2.51
= −2.0 log10 + . (2.395)
f 1/2 3.7 ReD f 1/2
Often one needs to iterate to find f for turbulent flows. Alternatively, one can use the
Moody chart to estimate f . This is simply a graphical representation of the Colebrook
formula. Most fluid texts will contain a Moody chart. While in principle f varies with a
host of variables, in practice in a particular problem, it is often estimated as a constant.
To get a grasp on the effects of wall friction, consider a special case of generalized one-
dimensional flow:

• steady,
• one-dimensional,
• adiabatic,
• constant area duct,
• Darcy friction model,
• calorically perfect ideal gas.

Our equations from the section on influence coefficients

(qw +τw u)L
−ρu2 dA + τw L +
dρ 1 dx ∂e
ρu ∂P |
ρ
= , (2.396)
dx A (u2 − c2 )
(qw +τw u)L
c2 ρu dA − uτw L −
du 1 dx ∂e
ρ ∂P |
ρ
= , (2.397)
dx A ρ (u2 − c2 )
(qw +τw u)Lu
−c2 ρu2 dA + c2 τw L +
dP 1 dx ∂e
ρ ∂P | ρ
= , (2.398)
dx A (u2 − c2 )
reduce to
1 + ρ ∂e1
dρ τw L ∂P |ρ
= , (2.399)
dx A (u − c2 )
2

1 + ρ ∂e1
du uτw L ∂P |ρ
= − , (2.400)
dx A ρ (u − c2 )
2

u2
c2 +
dP τw L ρ
∂e
ρ ∂P |
= 2 2
. (2.401)
dx A (u − c )

CC BY-NC-ND. 19 January 2025, J. M. Powers.

70 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

Now for a circular duct

L 2πr 2 4
L = 2πr A = πr 2 , = 2 = = . (2.402)
A πr r D
For a calorically perfect ideal gas
1 P
e = , (2.403)
γ−1 ρ
∂e 1 1
= , (2.404)
∂P ρ γ −1ρ
∂e 1
ρ = , (2.405)
∂P ρ γ−1
1
∂e
= γ − 1, (2.406)
ρ ∂P ρ
1
1+ ∂e
= γ. (2.407)
ρ ∂P ρ

So making these substitutions yields

dρ 4τw γ
= , (2.408)
dx D (u − c2 )
2

du 4uτw γ
= − , (2.409)
dx D ρ (u − c2 )
2

dP 4τw c2 + u2 (γ − 1)
= . (2.410)
dx D (u2 − c2 )
Substituting for τw gives
dρ f ρu2 γ
= , (2.411)
dx 2D (u − c2 )
2

du f ρu2 u γ
= − , (2.412)
dx 2D ρ (u − c2 )
2

dP f ρu2 c2 + u2 (γ − 1)
= . (2.413)
dx 2D (u2 − c2 )
Rearranging to place in terms of M 2 gives
dρ f ρM 2 γ
= , (2.414)
dx 2D (M 2 − 1)
du f M 2u γ
= − 2
, (2.415)
dx 2D (M − 1)
dP f ρu2 1 + M 2 (γ − 1)
= . (2.416)
dx 2D (M 2 − 1)

CC BY-NC-ND. 19 January 2025, J. M. Powers.

2.5. FLOW WITH FRICTION–FANNO FLOW 71

Now with the definition of M 2 for the calorically perfect ideal gas, one gets

ρu2
M2 = , (2.417)
γP
dM 2 u2 dρ 2ρu du ρu2 dP
= + − , (2.418)
dx γP dx γP dx γP 2 dx
 
u2 f ρM 2 γ 2ρu f M 2u γ ρu2 f ρu2 1 + M 2 (γ − 1)
= + − − ,
γP 2D (M 2 − 1) γP 2D (M 2 − 1) γP 2 2D (M 2 − 1)
(2.419)
4 4 4 2
fM γ 2f M γ γf M 1 + M (γ − 1)
= − − , (2.420)
2D (M 2 − 1) 2D (M 2 − 1) 2D (M 2 − 1)
γf M 4 2


= 1 − 2 − 1 − M (γ − 1) , (2.421)
2D (M 2 − 1)
  
γf M 4 2 γ−1
= 1+M . (2.422)
D (1 − M 2 ) 2
So rearranging gives

(1 − M 2 ) dM 2 dx
2 γ−1


= f . (2.423)
2
γ (M ) 1 + M 2
2
D

Integrate this expression from x = 0 to x = L∗ where L∗ is defined as the length at which

the flow becomes sonic, so M 2 = 1 at x = L∗ .
 
Z 1 1 − M̂ 2 dM̂ 2 Z L∗
dx
 2 
= f . (2.424)
M 2 γ M̂ 2 2 γ−1 0 D
1 + M̂ 2

An analytic solution for this integral is

1 − M2 1 + γ (1 + γ) M 2 f L∗
2
+ ln 2
= . (2.425)
γM 2γ 2 + M (γ − 1) D

Example 2.13
13
Flow in a duct with friction

Given: Air flowing in pipe D = 1 in, L = 20 ft, P1 = 40 psia, u1 = 200 ft/s, T1 = 520 ◦ R.

Find: Exit pressure P2 , ṁ

Assume: calorically perfect ideal gas, Darcy friction factor models wall shear, constant viscosity

13
from White, 9.82, p. 589.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

72 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

First get the mass flow rate.

lbf

 2

P1 40 in2 144 in
ft2 lbm
ρ1 = = ft lbf

= 0.2077 3 , (2.426)
RT1 53.34 lbm ◦ R (520 R)
◦ ft
 2 !
D
ṁ = ρ1 u1 A1 = ρ1 u1 π , (2.427)
2
   2 !
lbm ft 1 in 1 ft lbm
= 0.2077 3 200 π = 0.2266 . (2.428)
ft s 2 12 in s

Now compute the friction factor. First for cast iron pipes, one has surface roughness ǫ = 0.00085 ft, so

ǫ 0.00085 ft 12 in
= = 0.0102. (2.429)
D 1 in 1 ft
The Reynolds number is needed, which involves the viscosity. For air at 520 ◦ R, µ ∼ 4.08×10−7 lbf s/ft2
so


1

ρ1 u 1 D 0.2077 lbm
ft3 200 fts 12 ft
ReD = = lbf s


= 263739. (2.430)
µ 4.08 × 10 −7
ft2 32.17 lbf sft
lbm
2

Because ReD >> 2300, the flow is turbulent and one needs to use the Colebrook formula to estimate
the Darcy friction factor:
 
1 ǫ/D 2.51
= −2.0 log10 + , (2.431)
f 1/2 3.7 ReD f 1/2
 
0.0102 2.51
= −2.0 log10 + . (2.432)
3.7 263739f 1/2

Now reading the Moody chart gives f = 0.04. A numerical trial and error solution of the Colebrook
equation gives

f = 0.0384. (2.433)

Now find M1 .

u1 200 fts
M1 = √ = q

= 0.1789. (2.434)
γRT1 1.4 53.34 ft lbf
32.17 lbm ft
(520 ◦ R)
lbm ◦ R lbf s2

Now
f L1∗ 1 − M12 1+γ (1 + γ) M12
= + ln (2.435)
D γM12 2γ 2 + M12 (γ − 1)
1 − 0.17892 1 + 1.4 (1 + 1.4) 0.17892
= 2 + 2 (1.4) ln 2 + 0.17892 (1.4 − 1) = 18.804, (2.436)
1.4 (0.1789)
1


18.804 12 ft
L1∗ = = 40.81 ft. (2.437)
0.0384
So at a distance 40.81 ft from station 1, the flow will go sonic. It is needed to find M2 at a station 20 ft
from station 1. So

CC BY-NC-ND. 19 January 2025, J. M. Powers.

2.5. FLOW WITH FRICTION–FANNO FLOW 73

L2∗ = 40.81 ft − 20 ft, = 20.81 ft, (2.438)

f L2∗ 0.0384 (20.81 ft)
= 1 = 9.589, (2.439)
D 12 ft
1 − M22 1 + 1.4 (1 + 1.4) M22
9.589 = + ln (2.440)
1.4M22 2 (1.4) 2 + M22 (1.4 − 1)
Iterative solution gives
M2 = 0.237925 (2.441)
Because energy conservation holds in this flow
u22 u21
h2 + = h1 + , (2.442)
2 2


ft 2
u2 u2 200
T2 + 2 = T1 + 1 = 520 ◦ R + s
ft2

, (2.443)
2cP 2cP 2 6015 s2 ◦ R
u22
T2 + = 523.33 ◦ R, (2.444)
2cP
M 2 γRT2
T2 + 2 = 523.33 ◦ R, (2.445)
2cP
 
(γ − 1) 2
T2 1 + M2 = 523.33 ◦ R, (2.446)
2
523.33 ◦ R 523.33 ◦ R
T2 = (γ−1)
= (1.4−1)
= 517.47 ◦ R. (2.447)
1+ 2 0.2379252
2 M2 1+ 2

Now get the velocity.

s  
p ft2 ft
u2 = M2 γRT2 = 0.237925 1.4 1715 2
(517.47 ◦ R) = 265.2 , (2.448)
s ◦R s
ρ2 u 2 = ρ1 u 1 , (2.449)
  !
u1 lbm 200 fts lbm
ρ2 = ρ1 = 0.2077 3 = 0.1566 , (2.450)
u2 ft 265.2 fts ft3
P2 = ρ2 RT2 , (2.451)
    
lbm ft lbf ◦ ft2
= 0.1566 3 53.34 (517.47 R) , (2.452)
ft lbm ◦ R 144 in2
= 30.02 psia, (2.453)
T2 P2
s2 − s1 = cP ln − R ln , (2.454)
T1 P1
   
ft2 517.47 ◦ R ft2 30.02 psia
= 6015 2 ◦ ln − 1715 2
ln , (2.455)
s R 520 R
◦ s R ◦ 40 psia
ft2
= 462.9 2 ◦ . (2.456)
s R

CC BY-NC-ND. 19 January 2025, J. M. Powers.

74 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

2.6 Flow with heat transfer–Rayleigh flow

Flow with heat transfer is commonly known as Rayleigh flow. To isolate the effect of heat
transfer, the following assumptions will be adopted:
• constant area duct,
• no wall friction,
• calorically perfect ideal gas.
Consequences of heat addition are as follows:
• stagnation temperature changes,
• heating drives both subsonic and supersonic flows towards sonic states,
• cooling drives both subsonic and supersonic flows away from the sonic state,
• heating increases To , decreases Po , both subsonic and supersonic,
• cooling decreases To , increases Po , both subsonic and supersonic.
The governing equations are

ρ2 u2 = ρ1 u1 , (2.457)
ρ2 u22
+ P2 = ρ1 D 2 + P1 , (2.458)
   
u22 u21
ρ2 u2 A h2 + = ρ1 u1 A h1 + + qw LL, (2.459)
2 2
 
γ P Po
h = − + ho . (2.460)
γ−1 ρ ρo
These are a more general case of the equations for a normal shock. One could get equivalents
of Rayleigh lines and Hugoniots. The Rayleigh line would be the same as the equations are
the same; the Hugoniot would be modified because of the heat transfer term.
If one defines the heat transfer per unit mass of flow q in terms of the wall heat flux qw :
qw LL
q≡ , (2.461)
ρ1 u1 A
the energy equation becomes
u22 u21
h2 + = h1 + + q, (2.462)
2 2
ho2 = ho1 + q, (2.463)
q = ho2 − ho1 , (2.464)
q
= To2 − To1 . (2.465)
cP

CC BY-NC-ND. 19 January 2025, J. M. Powers.

2.6. FLOW WITH HEAT TRANSFER–RAYLEIGH FLOW 75

With lots of effort very similar to that used for the normal shock equations, expressions can
be developed relating the “2” state to the “1” state. If one takes the final “2” state to be
sonic 2 → ∗ and the initial “1” state to be unsubscripted, it is found for the calorically
perfect ideal gas that

To (γ + 1) M 2 (2 + (γ − 1) M 2 )
= . (2.466)
To∗ (1 + γM 2 )2

Example 2.14
14
Heat addition problem

Given: Fuel air mixture enters combustion chamber at u1 = 250 ft/s, P1 = 20 psia, T1 = 70 ◦ F.
The mixture releases 400 Btu/lbm.

Find: Exit properties u2 , P2 , T2 , heat addition to cause flow to go sonic at the exit.

Assume: The fuel air mixture behaves just like calorically perfect ideal air.

Initial state

T1 = 70 + 460 = 530 ◦ R, (2.467)

s  
p ft2 ft
c1 = γRT1 = 1.4 1716 2 ◦ (530 ◦ R) = 1128.4 , (2.468)
s R s
u1 250 fts
M1 = = = 0.2216, (2.469)
c1 1128.4 fts
lbf

 lbm ft2

in2

P1 20 in 2 32.17 lbf s2 144 ft 2 lbm
ρ1 = = ft2

= 0.1019 3 , (2.470)
RT1 1716 s2 ◦ R (530 R) ◦ ft
   
1 1
To1 = T1 1 + M12 = (530 ◦ R) 1 + 0.22162 = 535.2 ◦ R, (2.471)
5 5
 3.5  3.5
1 1
Po1 = P1 1 + M12 = (20 psia) 1 + 0.22162 = 20.70 psia. (2.472)
5 5

Now calculate To∗ , the stagnation temperature corresponding to sonic flow

To1 (γ + 1) M12 2 + (γ − 1) M12 (1.4 + 1) 0.22162 2 + (1.4 − 1) 0.22162
= 2 = 2 , (2.473)
To∗ (1 + γM12 ) (1 + (1.4) (0.22162))
= 0.2084, (2.474)
To1 535.2 ◦ R
To∗ = = = 2568.3 ◦ R. (2.475)
0.2084 0.2084

14
adopted from White, pp. 557-558.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

76 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

Now calculate the effect of heat addition:

   
Btu ft lbf lbm ft ft2
q = 400 779 32.17 2
= 10.024 × 106 2 , (2.476)
lbm Btu lbf s s
2
q 10.024 × 106 fts2
To2 = To1 + = 535.2 + 2 = 2201.7 ◦ R, (2.477)
cP 6015 s2ft◦ R
To2 2201.7 ◦ R
= = 0.8573, (2.478)
To∗ 2563.3 ◦ R


To2 (γ + 1) M22 2 + (γ − 1) M22
= 2 , (2.479)
To∗ (1 + γM22 )


(1.4 + 1) M22 2 + (1.4 − 1) M22
0.8573 = 2 . (2.480)
(1 + 1.4M22 )

Computer algebra gives four solutions. For a continuous variation of M , choose the positive subsonic
branch. Other branches do have physical meaning.

relevant branch M2 = 0.6380, (2.481)

M2 = −0.6380, (2.482)
M2 = 1.710, (2.483)
M2 = −1.710. (2.484)

Calculate other variables at state 2:

 −1  
1 1
−1
T2 = To2 1 + M22 = (2201.7 ◦ R) 1 + 0.63802 = 2036 ◦ R, (2.485)
5 5
s  
p ft2 ft
c2 = γRT2 = 1.4 1716 2 ◦ (2036 ◦ R) = 2211.6 , (2.486)
s R s
 
ft ft
u2 = M2 c2 = (0.6380) 2211.6 = 1411 , (2.487)
s s
ρ2 u 2 = ρ1 u 1 (2.488)
  !
u1 lbm 250 fts lbm
ρ2 = ρ1 = 0.1019 3 ft
= 0.01806 3 , (2.489)
u2 ft 1411 s ft
  2
 
lbm ft 1 lbf s2 ft2
P2 = ρ2 RT2 = 0.01806 3 1716 2 ◦ (2036 ◦ R) , (2.490)
ft s R 32.17 lbm ft 144 in2
= 13.62 psia (2.491)

Is momentum satisfied?

P2 + ρ2 u22 = P1 + ρ1 u21 , (2.492)

     2  
lbf 144 in2 lbm ft 1 lbf s2
13.62 2 + 0.01806 1411
in ft2 ft3 s 32.17 lbm ft
     2  
lbf 144 in2 lbm ft 1 lbf s2
= 20 2 + 0.1019 250 , (2.493)
in ft2 ft3 s 32.17 lbm ft
lbf lbf
3078.97 2 = 3077.97 2 , close! (2.494)
ft ft

CC BY-NC-ND. 19 January 2025, J. M. Powers.

2.7. TWO-DIMENSIONAL EQUATIONS 77

Get the entropy change.

T2 P2
s2 − s1 = cP ln − R ln , (2.495)
T1 P1
       
ft2 2036 ◦ R ft2 13.62 psia
= 6015 2 ◦ ln − 1716 2 ◦ ln , (2.496)
s R 530 ◦ R s R 20 psia
ft2
= 8754.66 2 ◦ , (2.497)
 s R   
ft2 1 Btu 1 lbf s2 Btu
= 8754.66 2 ◦ = 0.3493 . (2.498)
s R 779 ft lbf 32.17 lbm ft lbm ◦ R

Check the second law:

q
s2 − s1 ≥ , (2.499)
T
Btu
Btu 400 lbm
0.3493 ≥ , (2.500)
lbm ◦ R 2036 ◦ R
Btu Btu
0.3493 ≥ 0.1965 , yes! (2.501)
lbm ◦ R lbm ◦ R
Find the maximum heat release:

qmax = cP (To∗ − To1 ) , (2.502)

    
ft2 ◦ ◦ 1 Btu 1 lbf s2
= 6015 2 ◦ (2568.3 R − 535.2 R) , (2.503)
s R 779 ft lbf 32.17 lbm ft
Btu
= 488 . (2.504)
lbm

2.7 Two-dimensional equations

Assume now:

• ∂/∂t ≡ 0; steady flow,

• w ≡ 0, ∂/∂z ≡ 0; two-dimensional flow,

• no viscous stress or heat conduction, so isentropic except through shocks,

• calorically perfect ideal gas.

With these assumptions, the following equations govern the flow away from shock disconti-
nuities.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

78 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

2.7.1 Conservative form

∂ ∂
(ρu) + (ρv) = 0, (2.505)
∂x ∂y
∂
∂
ρu2 + P + (ρuv) = 0, (2.506)
∂x ∂y
∂ ∂

(ρvu) + ρv 2 + P = 0, (2.507)
∂x ∂y
     
∂ 1 2 2

P ∂ 1 2 2

P
ρu e + u +v + + ρv e + u +v + = 0, (2.508)
∂x 2 ρ ∂y 2 ρ
1 P
e= + eo . (2.509)
γ−1 ρ

2.7.2 Non-conservative form

   
∂ρ ∂ρ ∂u ∂v
u +v +ρ + = 0, (2.510)
∂x ∂y ∂x ∂y
 
∂u ∂u ∂P
ρ u +v + = 0, (2.511)
∂x ∂y ∂x
 
∂v ∂v ∂P
ρ u +v + = 0, (2.512)
∂x ∂y ∂y
   
∂e ∂e ∂u ∂v
ρ u +v +P + = 0, (2.513)
∂x ∂y ∂x ∂y
1 P
e= + eo . (2.514)
γ−1 ρ

2.8 Mach waves

Mach waves are small acoustic disturbances in a flow field. Recall that small disturbances
propagate at the ambient sound speed. Let’s consider a small sphere moving at u1 through
a fluid with ambient sound speed co .
• u1 < co , subsonic flow, sphere does not catch acoustic waves,
• u1 = co , sonic flow, upstream flow always unaware of sphere,
• u1 > co , supersonic flow, larger region still unaware of sphere.
Consider that in time ∆t, the sphere will move u1 ∆t and the wave will propagate will be
felt by a circle with radius co ∆t, see Figure 2.18. From the geometry,
 
co ∆t co 1 1
sin β = = = , β = arcsin . (2.515)
u1 ∆t u1 M1 M1

CC BY-NC-ND. 19 January 2025, J. M. Powers.

2.9. OBLIQUE SHOCK WAVES 79

co Δ t co Δ t

u1 < co u1 = co

subsonic sonic
flow flow

u1 Δt

u1 Δt Mach wave

zone of silence

co Δt

u1 > co

supersonic
flow

u1 Δt

Figure 2.18: Acoustic disturbance sketch.

2.9 Oblique shock waves

An oblique shock is a shock which is not normal to the incoming flow field. It can be shown
that in the limiting case as the oblique shock strength goes to zero, the oblique shock wave
becomes a Mach wave, as described in the previous section. Oblique waves can be understood
by considering the following problem. Given:
• a straight wedge inclined at angle θ to the horizontal,

• a freestream flow parallel to the horizontal with known velocity u = u1 i + 0 j,

• known freestream pressure and density of P1 and ρ1 ,

• steady flow of a calorically perfect ideal gas (this can be relaxed and one can still find
oblique shocks).
Find:
• the angle of shock inclination β,

• downstream pressure and density P2 , ρ2 .

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80 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

Similar to the piston problem, the oblique shock problem is easiest analyzed if we instead
consider

• β as known,

• θ as unknown.

They are best modeled in a two-dimensional coordinate system with axes parallel and per-
pendicular to the shock, see Figure 2.19, so that

x = x̃ sin β + ỹ cos β, y = −x̃ cos β + ỹ sin β, (2.516)

u = ũ sin β + ṽ cos β, v = −ũ cos β + ṽ sin β. (2.517)

Consequently, in this coordinate system, the freestream is two-dimensional. It is easily shown

oblique shock wave

unshocked shocked
freestream flow
(supersonic)

y
wedge
x

Figure 2.19: Oblique shock schematic.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

2.9. OBLIQUE SHOCK WAVES 81

that the equations of motion are invariant under a rotation of axes, so that
∂ ∂
(ρũ) + (ρṽ) = 0, (2.518)
∂ x̃ ∂ ỹ
∂
∂
ρũ2 + P + (ρũṽ) = 0, (2.519)
∂ x̃ ∂ ỹ
∂ ∂

(ρṽ ũ) + ρṽ 2 + P = 0, (2.520)
∂ x̃ ∂ ỹ
     
∂ 1 2 2

P ∂ 1 2 2

P
ρũ e + ũ + ṽ + + ρṽ e + ũ + ṽ + = 0, (2.521)
∂ x̃ 2 ρ ∂ ỹ 2 ρ
1 P
e= + eo . (2.522)
γ−1 ρ
To analyze oblique shocks, we make one additional assumption

• ∂/∂ ỹ = 0

Note however that, contrary to one-dimensional flow we will not enforce ṽ = 0, so

• ṽ 6= 0.
Consequently, all variables are a function of x̃ at most and ∂/∂ x̃ = d/dx̃. The governing
equations reduce to
d
(ρũ) = 0, (2.523)
dx̃
d

ρũ2 + P = 0, (2.524)
dx̃
d
(ρṽ ũ) = 0, (2.525)
  dx̃ 
d 1 2
P
ρũ e + ũ + ṽ 2 + = 0, (2.526)
dx̃ 2 ρ
1 P
e= + eo . (2.527)
γ−1 ρ
Integrate and apply freestream conditions:

ρ2 ũ2 = ρ1 ũ1 , (2.528)

ρ2 ũ22
+ P2 = ρ1 ũ21 + P1 , (2.529)
ρ2 ṽ2 ũ2 = ρ1 ṽ1 ũ1 , (2.530)
   
1 2 2

P2 1 2 2

P1
ρ2 ũ2 e2 + ũ + ṽ2 + = ρ1 ũ1 e1 + ũ + ṽ1 + (2.531)
2 2 ρ2 2 1 ρ1
1 P
e= + eo . (2.532)
γ −1 ρ

CC BY-NC-ND. 19 January 2025, J. M. Powers.

82 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

Now using the mass equation, the ỹ momentum equation reduces to

ṽ2 = ṽ1 (2.533)

Using this result and the mass a state equations gives

ρ2 ũ2 = ρ1 ũ1 , (2.534)

ρ2 ũ22
+ P2 = ρ1 ũ21 + P1 , (2.535)
1 P2 1 2 P2 1 P1 1 2 P1
+ ũ2 + = + ũ1 + . (2.536)
γ − 1 ρ2 2 ρ2 γ − 1 ρ1 2 ρ1

These are exactly the equations which describe a normal shock jump. All our old results
apply in this coordinate system with the additional stipulation that the component of velocity
tangent to the shock is constant.
Recall our solution for one-dimensional shocks in a calorically perfect ideal gas:
 
1 1 γ−1 2γ P1
= 1+ . (2.537)
ρ2 ρ1 γ + 1 (γ − 1) D 2 ρ1

For this problem D = ũ1 , so

 
1 1 γ−1 2γ P1
= 1+ . (2.538)
ρ2 ρ1 γ + 1 (γ − 1) ũ21 ρ1

With the freestream Mach number normal to the wave defined as

2 ũ21
M1n ≡ , (2.539)
γ Pρ11

we get
 
ρ1 γ −1 2
= 1+ 2
, (2.540)
ρ2 γ+1 (γ − 1) M1n

and because from mass ρ1 /ρ2 = ũ2 /ũ1 , we get

 
ũ2 γ−1 2
= 1+ 2
. (2.541)
ũ1 γ+1 (γ − 1) M1n

Now for our geometry

ũ1
tan β = , (2.542)
ṽ1
ũ2 ũ2
tan (β − θ) = = , (2.543)
ṽ2 ṽ1

CC BY-NC-ND. 19 January 2025, J. M. Powers.

2.9. OBLIQUE SHOCK WAVES 83

So
ũ2 tan (β − θ)
= . (2.544)
ũ1 tan β
Thus,
 
tan (β − θ) γ −1 2
= 1+ 2
. (2.545)
tan β γ+1 (γ − 1) M1n
Now note that
2
M1n = M12 sin2 β, (2.546)

so
 
tan (β − θ) γ−1 2
= 1+ , (2.547)
tan β γ+1 (γ − 1) M12 sin2 β
 
γ − 1 (γ − 1) M12 sin2 β + 2
= , (2.548)
γ+1 (γ − 1) M12 sin2 β
(γ − 1) M12 sin2 β + 2
tan (β − θ) = tan β ≡ χ, (2.549)
(γ + 1) M12 sin2 β
tan β − tan θ = χ + χ tan θ tan β, (2.550)
tan β − χ = tan θ (1 + χ tan β) , (2.551)
tan β − χ
tan θ = . (2.552)
1 + χ tan β
With a little more algebra and trigonometry, this reduces to

M12 sin2 β − 1
tan θ = 2cotβ . (2.553)
M12 (γ + cos 2β) + 2
Given M1 , γ and β, this equation can be solved to find θ the wedge angle. It can be inverted
to form an equation cubic in sin β to solve explicitly for β. Figure 2.20 gives a plot of oblique
shock angle β versus wedge angle θ.
Note the following features:
• for a given θ < θmax , there exist two β’s,

– lower β is weak solution,

∗ limθ→0 β = arcsin (1/M), a Mach wave,
∗ relevant branch for most external flows, matches in far-field to acoustic wave,
can exist in internal flows,
∗ total Mach number primarily supersonic, M22 = (ũ2 + ṽ 2 )/c22 > 1 for nearly
all 0 < θ < θmax ,

CC BY-NC-ND. 19 January 2025, J. M. Powers.

84 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

expanded view of plane

strong branch
90 (post-shock, subsonic)
75

Μ1 = 2
2nd law 50
violation
60
maximum wedge Μ1= 3
25
angle for attached
oblique shock

-40 -20 20 40
Μ1 = 2
30 weak branch -25
(post-shock supersonic, primarily)
Μ1 = 3
2nd law
-50 violation

-75
0
0 10 20 30 40 50

Figure 2.20: Shock angle β versus wedge angle θ.

2
∗ normal Mach number subsonic, M2n = ũ2 /c22 < 1,
– higher β is the strong solution,
∗ limθ→0 β = π/2, a normal shock wave,
∗ relevant branch for some internal flows,
∗ total Mach number completely subsonic, M22 = (ũ2 + ṽ 2 )/c22 < 1 for all 0 <
θ < θmax ,
2
∗ normal Mach number subsonic, M2n = ũ2 /c22 < 1,
• for θ > θmax , no solution exists; shock becomes detached,
• Consider fixed θ, increasing freestream Mach number M1 , see Figure 2.21,
– 0 < M1 < 1, subsonic incoming flow, no shocks continuous pressure variation,
– 1 < M1 < M1a , supersonic incoming flow, detached curved oblique shock,
– M1a < M1 < ∞, supersonic incoming flow, attached straight oblique shock,
– as M1 → ∞, β → β∞ ,
• Consider fixed supersonic freestream Mach number M1 , increasing θ, see Figure 2.22,
– θ ∼ 0, Mach wave, negligible disturbance,

CC BY-NC-ND. 19 January 2025, J. M. Powers.

2.9. OBLIQUE SHOCK WAVES 85

– small θ, small β, small pressure, density rise,

– medium θ, medium β, moderate pressure and density rise,
– large θ, curved detached shock, large pressure and density rise.

continuous pressure shock approaching detached

variation wedge from infinity oblique shock

M1 < 1
1 < M1 < M1a
subsonic, shockless flow slightly supersonic flow moderately supersonic flow

attached attached
oblique shock oblique shock
at limiting wave
angle

Figure 2.21: Shock wave patterns as incoming Mach number varies.

Example 2.15
Oblique Shock Example

Given: Air flowing over a wedge, θ = 20◦ , P1 = 100 kPa, T1 = 300 K, M1 = 3.0.

Find: Shock angle β and downstream pressure and temperature P2 , T2 .

Assume: calorically perfect ideal gas.

First do some preliminaries:

s  
p J m
c1 = γRT1 = (1.4) 287 (300 K) = 347.2 , (2.554)
kg K s
 m m
u1 = M1 c1 = (3.0) 347.2 = 1041.6 , (2.555)
s s
P1 105 Pa kg
ρ1 = =   = 1.1614 3 . (2.556)
RT1 287 J (300 K) m
kg K

CC BY-NC-ND. 19 January 2025, J. M. Powers.

86 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

M1 fixed, supersonic, P1, fixed

M1 M1 M1 M1

Mach wave attached shocks detached shock

small disturbance moderate disturbances large disturbance

Figure 2.22: Shock wave patterns as wedge angle is varied.

Now find the wave angle:

M12 sin2 β − 1 3.02 sin2 β − 1

tan θ = 2cotβ , tan 20◦ = 2cotβ . (2.557)
M12(γ + cos 2β) + 2 3.02 (1.4+ cos 2β) + 2

There are three solutions:

• weak oblique shock; common, β = 37.76◦ ,

• strong oblique shock; which is rare, β = 82.15◦,

• second law violating “rarefaction” shock, β = −9.91◦.

1. Weak Oblique Shock

 m m
ũ1 = u1 sin β = 1041.6 sin 37.76◦ = 637.83 , (2.558)
 s s
m ◦ m
ṽ1 = u1 cos β = 1041.6 cos 37.76 = 823.47 , (2.559)
 s   s
ũ1 637.83 ms
M1n = = = 1.837, (2.560)
c1 347.2 ms

 
ρ1 γ−1 2
= 1+ 2 , (2.561)
ρ2 γ+1 (γ − 1) M1n
kg  
1.1614 m3 1.4 − 1 2
= 1+ 2
= 0.413594, (2.562)
ρ2 1.4 + 1 (1.4 − 1) 1.837

CC BY-NC-ND. 19 January 2025, J. M. Powers.

2.9. OBLIQUE SHOCK WAVES 87

kg
1.1614 m 3 kg
ρ2 = = 2.8081 3 , (2.563)
0.41359 m
ρ2 ũ2 = ρ1 ũ1 , (2.564)
 

kg m
ρ1 ũ1 1.1614 m3 637.83 s m
ũ2 = = kg
= 263.80 , (2.565)
ρ2 2.8081 m3 s
m
ṽ2 = ṽ1 = 823.47 , (2.566)
s
u2 = ũ2 sin β + ṽ2 cos β, (2.567)
v2 = −ũ2 cos β + ṽ2 sin β, (2.568)
 m  m m
◦
u2 = 263.80 sin 37.76 + 823.47 cos 37.76◦ = 812.56 , (2.569)
 s s s
m ◦
 m ◦ m
v2 = − 263.80 cos 37.76 + 823.47 sin 37.76 = 295.70 . (2.570)
s s s

Check on the wedge angle.

   m 
v2 295.70 s
θ = arctan = arctan m = 19.997◦, (2.571)
u2 812.56 s
P2 = P1 + ρ1 ũ21 − ρ2 ũ22 , (2.572)
    
kg m 2 kg m 2
P2 = 105 Pa + 1.1614 3 637.83 − 2.8081 3 263.80 = 377072 Pa, (2.573)
m s m s

Now get the temperature.

P2 377072 Pa
T2 = =   = 467.88 K, (2.574)
ρ2 R 2.8081 mkg
3 287 J
kg K
s  
p J m
c2 = γRT2 = (1.4) 287 (467.88 K) = 433.58 , (2.575)
kg K s
ũ2 263.8 ms
M2n =
= = 0.608, (2.576)
c2 433.58 ms
q
2
2
p
u22 + v22 812.56 ms + 295.7 ms
M2 = = = 1.994, (2.577)
c2 433.58 ms
T2 P2
s2 − s1 = cP ln − R ln , (2.578)
T1 P1
   
J 467.88 K J 377072 Pa J
= 1004.5 ln − 287 ln = 65.50 . (2.579)
kg K 300 K kg K 105 Pa kg K

2. Strong Oblique Shock

CC BY-NC-ND. 19 January 2025, J. M. Powers.

88 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

 m m
ũ1 = u1 sin β = 1041.6 sin 82.15◦ = 1031.84 , (2.580)
 s s
m ◦ m
ṽ1 = u1 cos β = 1041.6 cos 82.15 = 142.26 , (2.581)
 s   s
ũ1 1031.84 ms
M1n = = = 2.972, (2.582)
c1 347.2 ms
 
ρ1 γ−1 2
= 1+ 2 , (2.583)
ρ2 γ+1 (γ − 1) M1n
kg  
1.1614 m 3 1.4 − 1 2
= 1+ = 0.26102, (2.584)
ρ2 1.4 + 1 (1.4 − 1) 2.9722
kg
1.1614 m 3 kg
ρ2 = = 4.4495 3 , (2.585)
0.26102 m
ρ2 ũ2 = ρ1 ũ1 , (2.586)
 

kg
ρ1 ũ1 1.1614 m 3 1031.84 ms m
ũ2 = = kg
= 269.33 , (2.587)
ρ2 4.4495 m 3
s
m
ṽ2 = ṽ1 = 142.26 , (2.588)
s
u2 = ũ2 sin β + ṽ2 cos β, (2.589)
v2 = −ũ2 cos β + ṽ2 sin β, (2.590)
 m  m  m
u2 = 269.33 sin 82.15◦ + 142.26 cos 82.15◦ = 286.24 , (2.591)
 s s s
m ◦
 m ◦ m
v2 = − 269.33 cos 82.15 + 142.26 sin 82.15 = 104.14 . (2.592)
s s s

Check on the wedge angle.

 
v2
θ = arctan , (2.593)
u2
 
104.14 ms
= arctan = 19.99◦ , (2.594)
286.24 ms
P2 = P1 + ρ1 ũ21 − ρ2 ũ22 , (2.595)
    
5 kg m 2 kg  m 2
P2 = 10 Pa + 1.1614 3 1031.84 − 4.4495 3 269.33 , (2.596)
m s m s
P2 = 1013775 Pa (2.597)

P2 1013775 Pa
T2 = =    = 793.86 K, (2.598)
ρ2 R kg
4.4495 m 287 J
3 kg K

s  
p J m
c2 = γRT2 = (1.4) 287 (793.86 K) = 564.78 , (2.599)
kg K s
m
ũ2 269.33 s
M2n = = m = 0.477, (2.600)
c2 564.78 s

CC BY-NC-ND. 19 January 2025, J. M. Powers.

2.9. OBLIQUE SHOCK WAVES 89

q


p m 2 m 2
u22 + v22 286.24 s + 104.14 s
M2 = = m = 0.539, (2.601)
c2 564.78 s
T2 P2
s2 − s1 = cP ln − R ln , (2.602)
T1 P1
   
J 793.86 K J 1013775 Pa
= 1004.5 ln − 287 ln , (2.603)
kg K 300 K kg K 105 Pa
J
s2 − s1 = 312.86 . (2.604)
kg K
3. “Rarefaction Shock”

 m m
ũ1 = u1 sin β = 1041.6 sin (−9.91◦) = −179.26 , (2.605)
 s s
m ◦ m
ṽ1 = u1 cos β = 1041.6 cos (−9.91 ) = 1026.06 , (2.606)
 s   s
ũ1 −179.26 ms
M1n = = = −0.5163, (2.607)
c1 347.2 ms
 
ρ1 γ−1 2
= 1+ 2 , (2.608)
ρ2 γ+1 (γ − 1) M1n
!
kg
1.1614 m 3 1.4 − 1 2
= 1+ 2 = 3.2928, (2.609)
ρ2 1.4 + 1 (1.4 − 1) (−0.5163)

kg
1.1614 m 3 kg
ρ2 = = 0.3527 3 , (2.610)
3.2928 m
ρ2 ũ2 = ρ1 ũ1 , (2.611)
 

kg m
ρ1 ũ1 1.1614 m3 −179.26 s m
ũ2 = = kg
= −590.27 , (2.612)
ρ2 0.3527 m3 s
m
ṽ2 = ṽ1 = 1026.06 , (2.613)
s
u2 = ũ2 sin β + ṽ2 cos β. (2.614)
v2 = −ũ2 cos β + ṽ2 sin β, (2.615)
 m  m m
◦
u2 = −590.27 sin (−9.91 ) + 1026.06 cos (−9.91◦ ) = 1112.34 , (2.616)
s s s
 m  m m
v2 = − −590.27 cos (−9.91◦ ) + 1026.06 sin (−9.91◦) = 404.88 . (2.617)
s s s
Check on the wedge angle
 
v2
θ = arctan , (2.618)
u2
 
404.88 ms
= arctan = 20.00◦, (2.619)
1112.34 ms
P2 = P1 + ρ1 ũ21 − ρ2 ũ22 , (2.620)
    
5 kg m 2 kg  m 2
P2 = 10 Pa + 1.1614 3 −179.26 − 0.3527 3 −590.27 , (2.621)
m s m s
P2 = 14433 Pa, (2.622)

CC BY-NC-ND. 19 January 2025, J. M. Powers.

90 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

P2 14433 Pa
T2 = =    = 142.59 K, (2.623)
ρ2 R 0.3527 mkg
287 J
3 kg K
s  
p J m
c2 = γRT2 = (1.4) 287 (142.59 K) = 239.36 , (2.624)
kg K s
ũ2 −590.27 ms
M2n = = = −2.47, (2.625)
c2 239.36 ms
q
2
2
p
u22 + v22 1112.34 ms + 404.88 ms
M2 = = = 4.95, (2.626)
c2 239.36 ms
T2 P2
s2 − s1 = cP ln − R ln , (2.627)
T1 P1
   
J 142.59 K J 14433 Pa J
= 1004.5 ln − 287 ln = −191.5 . (2.628)
kg K 300 K kg K 105 Pa kg K

2.10 Small disturbance theory

By taking a Taylor series expansion of the relationship between β and θ about θ = 0, for
fixed M1 and γ, it can be shown that

1 γ+1 M14
tan β = p 2 + θ, θ << 1. (2.629)
M1 − 1 4 (M12 − 1)2

Note that if θ = 0 that

1
tan β = p , (2.630)
M12 − 1
1
tan2 β = 2 , (2.631)
M1 − 1
sin2 β sin2 β 1
2
= 2 = 2 , (2.632)
cos β 1 − sin β M1 − 1
1
sin2 β M12
2 = , (2.633)
1 − sin β 1 − M12
1
1
sin β = , (2.634)
M1
 
1
β = arcsin . (2.635)
M1

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2.10. SMALL DISTURBANCE THEORY 91

After a good deal of algebra and trigonometry, it can also be shown that the pressure change,
change in velocity magnitude, w, and change in entropy for flow over a thin wedge is

P2 − P1 γM 2
= p 21 θ, (2.636)
P1 M1 − 1
w2 − w1 θ
= −p 2 , (2.637)
w1 M1 − 1
s2 − s1
∼ θ3 . (2.638)
s1
In terms of changes,

∆P γM 2
= p 21 ∆θ, (2.639)
P1 M1 − 1
∆w ∆θ
= −p 2 , (2.640)
w1 M1 − 1
∆s
∼ ∆θ3 . (2.641)
s1
Note that a small positive ∆θ gives rise to

• an increase in pressure,

• a decrease in velocity magnitude,

• a very small change in entropy.

Figure 2.23 shows the pattern of waves that one obtains when subjecting a flow to a series
of small turns and the pattern that evolves as the turning radius is shrunk.

• compression waves converge,

• expansion waves diverge,

• convergence of compression waves leads to region of rapid entropy rise–shock formation,

• divergence of pressure waves leads to no shock formation in expansion.

This has an analog in one-dimensional unsteady flow. Consider a piston with an initial
velocity of zero accelerating into a tube

• lead compression wave travels at sound speed,

• lead wave increases temperature (and sound speed) of disturbed flow,

• each successive acoustic wave travels faster than lead wave,

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92 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

wave convergence
shock formation
breakdown of isentropic assumption

isentropic compression

isentropic expansion
wave divergence
no shock formation

oblique
shock

Prandtl-Meyer
expansion

Figure 2.23: Wave pattern and streamlines for flows undergoing a series of small turns and
for sudden turns.

• eventually acoustic waves catch and form a shock.

Consider a piston with zero initial velocity which decelerates

• lead expansion wave travels at sound speed,

• lead wave decreases temperature (and sound speed) of disturbed flow,

• each successive acoustic wave travels slow than lead wave,

• no shock formation.

A schematic for these one-dimensional unsteady flows is shown in Figure 2.24

2.11 Centered Prandtl-Meyer rarefaction

If we let ∆θ → 0, the entropy changes become negligibly small relative to pressure and
velocity changes, and the flow is isentropic. The relations can be replaced by differential

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2.11. CENTERED PRANDTL-MEYER RAREFACTION 93

t t
accelerating
piston shoc k
path

decelerating
slow, acoustic piston
lead wave path

x x

P1, P1,

t suddenly t
accelerated
piston path

shock
locus

suddenly
decelerated
piston
path Prandtl-Meyer
expansion fan

x x

Figure 2.24: Schematic of compression and expansion waves for one-dimensional unsteady
piston-driven flow.

relations:

dP γM 2
= √ dθ, (2.642)
P M2 − 1
dw dθ
= −√ , (2.643)
w M2 − 1
ds
∼ 0. (2.644)
s

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94 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

Recall now that for adiabatic flow

To γ−1 2
=1+ M , (2.645)
T 2
γRTo γ−1 2
=1+ M , (2.646)
γRT 2
c2o γ−1 2
= 1 + M , (2.647)
c2 2
 − 1
γ −1 2 2
c = co 1 + M , (2.648)
2
 − 3
co γ−1 2 2
dc = − 1+ M (γ − 1) M dM, (2.649)
2 2
γ−1
dc M dM
= − 2 γ−1 2 . (2.650)
c 1+ 2 M
Also
w = cM, so dw = c dM + M dc, (2.651)
dw dM dc
= + , (2.652)
w M c
γ−1
dw dM M dM
= − 2 γ−1 2 , (2.653)
w M 1+ 2 M
dw 1 dM
= γ−1 , (2.654)
w 1+ 2 M M 2

dθ 1 dM
− √ = γ−1 , (2.655)
M2 − 1 1 + 2 M2 M
√
M2 − 1 dM
−dθ = . (2.656)
M 1 + γ−1
2
M2
Now positive θ corresponds to compression and negative θ corresponds to expansion. Let us
define ν so that positive ν gives an expansion.
ν ≡ − θ + θo , (2.657)
dν = −dθ. (2.658)
Now integrate the expression
√
M2 − 1 dM
dν = . (2.659)
M 1 + γ−1
2
M2
Let ν = 0 correspond to M = 1. This effectively selects θo .
r r
γ+1 −1 γ−1 √
ν(M) = tan (M 2 − 1) − tan−1 M 2 − 1. (2.660)
γ−1 γ+1

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2.11. CENTERED PRANDTL-MEYER RAREFACTION 95

The function ν(M) is called the Prandtl-Meyer function. It is plotted in Figure 2.25. Many
texts tabulate the Prandtl-Meyer function. For a known turning angle, one can find the
Mach number. As the flow is entirely isentropic, all other flow variables can be obtained
through the isentropic relations. Note:

q 
γ+1
• as M → ∞, ν → (π/2) γ−1
− 1 , corresponds to vacuum conditions,

• given ν, one can calculate M,

• isentropic relations give P , ρ, T , etc.

• Prandtl-Meyer function tabulated in many texts.

120
100
80
60
40
20

10 20 30 40 M

Figure 2.25: Prandtl-Meyer function.

Example 2.16
Centered Expansion

Given: Calorically perfect, ideal air with P1 = 100 kPa, T1 = 300 K, u1 = 500 m/s, turned through
a 30◦ expansion corner.

Find: Fluid properties after the expansion.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

96 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

P1 100 kPa kg
ρ1 = =   = 1.1614 3 , (2.661)
RT1 J
0.287 kg K (300 K) m
s  
p J m
c1 = γRT1 = 1.4 287 (300 K) = 347.2 , (2.662)
kg K s
u1 500 ms
M1 = = = 1.4401, (2.663)
c1 347.2 ms
 
γ−1
To = T1 1 + M12 , (2.664)
2
 
1
To = 300 K 1 + 1.44012 = 424.43 K, (2.665)
5
  γ−1
γ
γ−1 2
Po = P1 1 + M1 , (2.666)
2
 3.5
1
Po = 100 kPa 1 + 1.44012 = 336.828 kPa. (2.667)
5

Now calculate the Prandtl-Meyer function for the freestream:

r r q
γ+1 γ−1
ν(M1 ) = tan−1 (M12 − 1) − tan−1 M12 − 1, (2.668)
γ−1 γ+1
r r
1.4 + 1 1.4 − 1 p
ν(M1 ) = tan−1 (1.44012 − 1) − tan−1 1.44012 − 1, (2.669)
1.4 − 1 1.4 + 1
ν(M1 ) = 0.177138 rad, (2.670)
180◦
ν(M1 ) = 0.177138 rad = 10.1493◦. (2.671)
π rad

The interpretation here is that an initially sonic flow would have had to had turned 10.1493◦ to achieve
a Mach number of M1 = 1.4401. Now add on the actual turning:

ν(M2 ) = ν(M1 ) + 30◦ , (2.672)

◦ ◦ ◦
ν(M2 ) = 10.1493 + 30 = 40.1493 , (2.673)
π rad
ν(M2 ) = 40.1493◦ = 0.700737 rad. (2.674)
180◦

CC BY-NC-ND. 19 January 2025, J. M. Powers.

2.12. WAVE INTERACTIONS AND REFLECTIONS 97

A trial and error solution gives the M2 which corresponds to ν(M2 ) = 0.700737 rad:
r r q
1.4 + 1 1.4 − 1
0.700737 rad = tan−1
(M22 − 1) − tan−1 M22 − 1, (2.675)
1.4 − 1 1.4 + 1
M2 = 2.54431, (2.676)
 −1
γ−1
T2 = To 1 + M22 , (2.677)
2
 −1
1 2
T2 = 424.43 K 1 + 2.54331 = 189.4 K, (2.678)
5
 − γ−1
γ
γ−1 2
P2 = Po 1 + M2 , (2.679)
2
 −3.5
1
P2 = 336.828 kPa 1 + 2.543312 = 18.43 kPa, (2.680)
5
P2 18.43 kPa kg
ρ2 = =  = 0.3390 3 , (2.681)
RT2 J
0.287 kg K (189.4 K) m
s  
p J m
c2 = γRT2 = 1.4 287 (189.4 K) = 275.87 , (2.682)
kg K s
 m  m
w2 = M2 c2 = 2.54431 275.87 = 701.89 . (2.683)
s s

2.12 Wave interactions and reflections

Shocks and rarefactions can intersect and reflect in a variety of ways.

2.12.1 Oblique shock reflected from a wall

An oblique shock which reflects from a wall is represented in Figure 2.26. Note:

• analysis just that of two oblique shocks,

• flow always turns to be parallel to wall,

• angle of incidence not equal angle of reflection due to non-linear effects,

• interior pressure profile has two steps,

• wall pressure profile has single step,

• P2 > 2P1 ; that is, the pressure is higher than that obtained in the acoustic limit.

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98 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

Μ1 Μ2 Μ3

P3
P2
interior streamline
P1 pressure field

P3

P1 wall pressure

Figure 2.26: Reflection of an oblique shock from a wall.

2.12.2 Oblique shock intersection

Two oblique shocks intersect as sketched in Figure 2.27. Note:

• the flow always turns to be parallel to the wall,

• when shocks intersect, the flow turns again to be parallel to itself.

2.12.3 Shock strengthening

A flow turned by a corner through an oblique shock can be strengthened by a second turn
as sketched in Figure 2.28 Note that three new waves generated:

• strengthened shock,

• slipstream in which pressures match, velocity directions match, but velocity magnitudes
differ,

• weak rarefaction wave.

2.12.4 Shock weakening

A flow turned by a corner through an oblique shock can be weakened by a second turn as
sketched in Figure 2.29.

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2.13. SUPERSONIC FLOW OVER AIRFOILS 99

Μ2

Μ1 Μ3

Μ2

Figure 2.27: Interaction of two oblique shocks.

2.13 Supersonic flow over airfoils

The standard problem in flow over an airfoil is to determine the lift and the drag. While in
actual design it is the magnitude of the lift force FL , and drag force FD , that is most crucial,
there exists dimensionless numbers the lift coefficient CL and the drag coefficient CD which
give good relative measures of airfoil performance.

FL FD
CL ≡ 1 , CD ≡ 1 . (2.684)
ρ u2 A
2 1 1
ρ u2 A
2 1 1

Though this is the traditional formula, it is probably not the best for interpreting how the
forces vary when flight speed is varied. This is because when u1 , flight speed is varied both
numerator and denominator change. To remedy this, we can instead scale by the ambient
sound speed to define a dimensionless lift force F∗L and dimensionless drag force F∗D :

FL FD
F∗L ≡ , F∗D ≡ . (2.685)
ρ1 c21 A ρ1 c21 A

2.13.1 Flat plate at angle of attack

The simplest problem is that of a flat plate at angle of attack αo . A schematic is illustrated
in Figure 2.30. Note:

• flow over the top is turned through an isentropic rarefaction to P2 ,

• flow over the bottom is turned through an oblique shock to P2′

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100 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

am
stre
slip

ra
re
fa
ct
io
n
Figure 2.28: Shock strengthening sketch.

Figure 2.29: Shock weakening sketch.

• Because P2′ > P2 , there is both lift and drag forces!

• both a shock and rarefaction are attached to the trailing edge to turn the flow to the
horizontal,

• the flow regions are separated by a slipstream in which pressure and velocity directions
match,

(P2′ −P2 ) cos αo

• FL = (P2′ − P2 ) A cos αo , CL = 1
ρ u2
,
2 1 1

(P2′ −P2 ) sin αo

• FD = (P2′ − P2 ) A sin αo , CD = 1
ρ u2
,
2 1 1

• the drag here is known as wave drag or induced drag,

• other components of drag, skin friction drag and thickness drag are zero due to inviscid
limit and zero thickness limit.

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2.13. SUPERSONIC FLOW OVER AIRFOILS 101

far
e
g edg field
din io n Mach
P1 lea efact wave
T1 rar
M1

P2

slipstream

le oc
ad k
sh

in
g
far
ed
ge
field
Mach
wave

Figure 2.30: Supersonic flow over a flat plate.

In the small disturbance limit

∆P γM12
= p ∆θ, (2.686)
P1 M12 − 1
γP1 M 2
P2′ = P1 + p 2 1 αo , (2.687)
M1 − 1
γP1 M 2
P2 = P1 + p 2 1 (−αo ) , (2.688)
M1 − 1
2γP1 M 2
P2′ − P2 = p 2 1 αo , (2.689)
M1 − 1
2γP1 u21
P2′ − P2 = p αo , (2.690)
M12 − 1 γP ρ1
1

2
P2′ − P2 = p 2 ρ1 u21 αo , (2.691)
M1 − 1
2
FL = p 2 ρ1 u21 αo A cos αo , (2.692)
M1 − 1
2
FL = p ρ1 u21 αo A(1), (2.693)
M12 − 1
4αo
CL = p 2 , (2.694)
M1 − 1

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102 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

2
FD = p 2 ρ1 u21 αo A sin αo , (2.695)
M1 − 1
2
FD = p 2 ρ1 u21 αo2 A, (2.696)
M1 − 1
4 α2
CD = p 2 o , (2.697)
M1 − 1
FL 2 M12 αo
F∗L = = p , (2.698)
ρ1 c21 A M12 − 1
FD 2 M12 αo2
F∗D == p , (2.699)
ρ1 c21 A M12 − 1
high Mach number limit: F∗L = 2M1 αo , (2.700)
high Mach number limit: F∗D = 2M1 αo2 . (2.701)

Dimensionless lift and drag are plotted versus Mach number in Figure 2.31.

2 0. 5
dimensionless lift force
flat plate at small angle of attack dimensionless drag force
0.4 flat plate at small angle of attack
1.5

0.3
1 invalid region

0.2
invalid region
0.5
0.1

0 2 4 6 8 10 M1 0 2 4 6 8 10 M 1

Figure 2.31: Dimensionless lift and drag versus incoming Mach number for flat plate at small
angle of attack.

Example 2.17
Lift and drag on an inclined flat plate

Given: Flat plate, of chord length 2 m, depth 10 m inclined at 20◦ to the horizontal in a freestream
of M1 = 3, P1 = 100 kPa, T1 = 300 K.

Find: Lift and drag forces on the plate.

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2.13. SUPERSONIC FLOW OVER AIRFOILS 103

First some preliminaries:

s  
p J m
c1 = γRT1 = (1.4) 287 (300 K) = 347.2 , (2.702)
kg K s
 m  m
u1 = M1 c1 = (3.0) 347.2 = 1041.6 , (2.703)
s s
P1 105 Pa kg
ρ1 = =   = 1.1614 3 (2.704)
RT1 287 kgJ K (300 K) m
  γ−1
γ
γ−1
Po = P1 1 + M12 , (2.705)
2
 3.5
1 2
Po = 100 kPa 1 + 3 = 367.327 kPa. (2.706)
5

In a previous example, we found the oblique shock state under identical conditions: P2′ = 377072 Pa.
Now consider the rarefaction.
r r q
γ+1 γ−1
ν(M1 ) = tan−1
(M12 − 1) − tan−1 M12 − 1, (2.707)
γ−1 γ+1
r r
1.4 + 1 1.4 − 1 2 p
ν(M1 ) = tan−1 (3 − 1) − tan−1 32 − 1 = 0.8691 rad = 49.7973◦, (2.708)
1.4 − 1 1.4 + 1
ν(M2 ) = ν(M1 ) + 20◦ , (2.709)
ν(M2 ) = 49.7973◦ + 20◦ = 69.7973◦, (2.710)
r r q
1.4 + 1 1.4 − 1
69.7973◦ = 1.218 rad = tan−1 (M22 − 1) − tan−1 M22 − 1, (2.711)
1.4 − 1 1.4 + 1
M2 = 4.3209, (2.712)
 − γ−1
γ
γ−1 2
P2 = Po 1 + M2 , (2.713)
2
 −3.5
1 2
P2 = 367.327 kPa 1 + 4.3209 = 1.591 kPa, (2.714)
5

FL = (P2′ − P2 ) A cos αo , (2.715)

FL = (377072 Pa − 1591 Pa) (10 m) (2 m) cos 20◦ , (2.716)
FL = 7142073 N, (2.717)
FL 7142073 N
CL = 1 2
=  
2 , (2.718)
2 ρ1 u 1 A
1 kg
2 1.1614 m 3 1041.6 ms (10 m) (2 m)
CL = 0.5668, (2.719)
FD = (P2′
− P2 ) A sin αo , (2.720)
FD = (377072 Pa − 1591 Pa) (10 m) (2 m) sin 20◦ , (2.721)
FD = 2320600 N, (2.722)
FD 2320600 N
CD = 1 2
=  
2 , (2.723)
2 ρ1 u 1 A
1 kg
2 1.1614 m 3 1041.6 ms (10 m) (2 m)
CD = 0.1842. (2.724)

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104 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

Compare with thin airfoil theory:

4αo
CL thin = p 2 , (2.725)
M1 − 1
4 (20◦ ) π180rad
◦
CL thin = √ = 0.4936, (2.726)
2
3 −1
4α2
CD thin = p 2o , (2.727)
M1 − 1
rad 2


4 (20◦ ) π180 ◦
CD thin = √ = 0.1723. (2.728)
32 − 1

2.13.2 Diamond-shaped airfoil

The simplest supersonic airfoil with camber for analysis purposes is the diamond shaped
airfoil as sketched in Figure 2.32. The sketch shows the airfoil at zero angle of attack. The
upper half of the wedge is inclined at angle ǫ to the horizontal In this case there will be no
lift but there will be drag. Note the following features:

far field
Mach waves

P1
T1
M1

lead oblique P2 P3
P4 trailing oblique
shock
shock

Prandtl-Meyer
rarefaction

Figure 2.32: Supersonic flow over a diamond-shaped airfoil.

• sudden turn through lead oblique shock,

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2.13. SUPERSONIC FLOW OVER AIRFOILS 105

• turn through isentropic Prandtl-Meyer rarefaction,

• final turn through oblique shock attached to trailing edge,

• far field limit: acoustic (Mach) waves,

• thin airfoil limit CL thin = √ 4ǫ2 , same as for flat plate!

M1 −1

2
• thin airfoil limit CD thin = √ 4ǫ2 , same as for flat plate!
M1 −1

2.13.3 General curved airfoil

A general airfoil with camber is sketched in Figure 2.33. The sketch shows the airfoil at zero
angle of attack. In this case there will be no lift but there will be drag. Note the following
features:

• lead oblique shock,

• lead shock weakened by series of non-centered rarefaction waves,

• shock at trailing edge, also weakened by non-centered rarefaction waves,

• far field: acoustic (Mach) waves.

Figure 2.33: Supersonic flow over a curved airfoil.

2.13.4 Transonic transition

Transonic flow exists whenever there is a continuous transition from subsonic to supersonic
flow. One example of a transonic flow is sketched in Figure 2.3415 that shows an accelerating
airfoil. Note:
15
adopted from Bryson, A. E., An experimental investigation of transonic flow past two-dimensional wedge
and circular-arc sections using a Mach-Zehnder interferometer, NACA Tech. Note 2560, 1951.

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106 CHAPTER 2. COMPRESSIBLE FLOW REVIEW

sonic locus sonic locus

shock shock

M<1 M>1 M<1 M<1 M>1 M<1

M1 = 0.852 M1 = 0.892

M>1 shock shock

shock

M>1
M<1 M>1 M>1
M<1
sonic locus M>1
M<1

M1 = 1.207 M1 = 1.315 M1 = 1.465

Figure 2.34: Transition from subsonic to transonic to supersonic flow.

• for high subsonic Mach number a bubble of supersonic flow appears,

• smooth transition from subsonic to supersonic,

• shock transition from supersonic to subsonic,

• as Mach number increases, supersonic bubble expands,

• for slightly supersonic Mach number, new shock approaches from far field,

• as supersonic Mach number increases, shock from far field approaches leading edge and
supersonic bubble disappears,

• challenging problems, not easily solved till 1960’s!

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Chapter 3

Thrust and performance parameters

Farokhi, Chapter 3.

In this brief chapter we will highlight some critical notions regarding thrust and performance
of aerospace propulsion devices.
The reader is referred to Farokhi’s text for some of the notation. For air-breathing jet
propulsion, we can take the mass flow rate of the air to be ṁ0 . Now the fuel is burned and
expelled with the air out the exhaust. Let us take the mass flow rate of the fuel to be ṁf .
Then, taking 0 to be the freestream state and 9 to be the nozzle exit, the momentum balance
gives us

F = (ṁ0 + ṁf )u9 − ṁ0 u0 + (P9 − P0 )A9 . (3.1)

The first two terms are obvious. The text provides a loose justification for the term involving
the pressure difference, though it must be said that the justification is a consequence of a
large number of assumptions.
For a rocket, there is no incoming air, and we have instead, following Farokhi

F = (ṁox + ṁf )u9 + (P9 − P0 )A9 . (3.2)

Here ṁox is the mass flow rate of the oxidizer and ṁf is the mass flow rate of the fuel.
The specific thrust is the thrust scaled by the mass flow rate. This departs from ther-
modynamics in that the thrust is scaled by a mass flow rate instead of a mass. For an
air-breathing jet, we adopt Farokhi’s definition
F
specific thrust = . (3.3)
ṁ0
It has units of velocity, m/s. Note one could have also scaled by the total mass flow rate,
ṁ0 + ṁf . For a dimensionless value, one can include the ambient sound speed in the scaling:

F
dimensionless specific thrust = . (3.4)
ṁ0 co

107
108 CHAPTER 3. THRUST AND PERFORMANCE PARAMETERS

This scaling is useful for comparing engines of different sizes.

Another performance parameter scales the mass flow rate of the fuel by the thrust force so
as to allow better comparison of fuel usage performance. The thrust specific fuel consumption
is
ṁf
thrust specific fuel consumption = TSFC = . (3.5)
F
It has units of inverse velocity, s/m. Note the text has an error in the units on p. 143.
For rockets, there is a traditional version of Eq. (3.3). Certainly, one could define a
rocket’s specific thrust at F/(ṁf + ṁox ). However, it is more traditional to scale additionally
by the gravitational acceleration at the surface of the earth, go = 9.81 m/s2 and define the
specific impulse, Isp as
F
Isp = , rocket engine. (3.6)
ṁp go
Here, we have taken

ṁp ≡ ṁox + ṁf . (3.7)

For a jet, we could define an equivalent specific impulse as

F
Isp = , air breathing engine. (3.8)
ṁf go
The units of Isp are time, s, as is easily seen
N N s3 kg m s3
[Isp ] = = = 2 = s. (3.9)
(kg/s)(m/s2 ) kg m s kg m
There are many measures of thermal efficiency. Let us consider one for an air-breathing
jet. Let us scale the net change in kinetic energy per unit time against the chemical energy
conversion rate of the fuel:
u29 u20 u2 u20
ṁ9 2
− ṁ0 2
(ṁ0 + ṁf ) 29 − ṁ0 2
ηth = = . (3.10)
ṁf qR ṁf qR
Let us next consider the so-called propulsive efficiency, ηp . We scale the propulsive power
F u0 by the net change in kinetic energy per unit time:
F u0
ηp = u29 u20
. (3.11)
(ṁ0 + ṁf ) 2
− ṁ0 2

Use Eq. (3.1) to eliminate F to get

((ṁ0 + ṁf )u9 − ṁ0 u0 + (P9 − P0 )A9 ) u0
ηp = u29 u20
. (3.12)
(ṁ0 + ṁf ) 2
− ṁ0 2

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 109

Now assume the jet is perfectly expanded so P9 = P0 and neglect ṁf as small relative to
ṁ0 , and we get
(u9 − u0 ) u0 2 (u9 − u0 ) u0 2 (u9 − u0 ) u0 2u0 2
ηp = = = = = (3.13)
u29
−
u20 2
u9 − u02
(u9 − u0 )(u9 + u0 ) u9 + u0 1 + uu09
2 2

Note if u0 = u9 , we get ηp = 1. However, there is no thrust force in this limit!

We define the overall efficiency, η0 , as the product of the thermal and propulsive efficien-
cies:
∆KE ˙ F u0 F u0
η0 = ηth ηp = = . (3.14)
˙
ṁf qR ∆KE ṁf qR
This represents the fraction of the chemical energy conversion rate that is converted to power
of the thrust force.
Let us estimate the range of an aircraft taking into account that it is losing mass as fuel
is consumed. Consider a steady flight speed at fixed altitude. Under these conditions, lift
force L balances the weight W and thrust F balances drag D:

L = W, F = D. (3.15)

We can also say that

F u0 = Du0. (3.16)

Use Eq. (3.14) to eliminate F u0:

η0 ṁf qR = Du0 . (3.17)

Now ṁf g0 represents the time rate of change of the weight of the vehicle, dW/dt. So
1 dW
η0 qR = Du0 . (3.18)
g0 dt
Now because L = W , divide the left side by W and the right side by L to get
1 dW D
η0 qR = u0 . (3.19)
g0 W dt L
Now, u0 = dR/dt, where R is a distance of flight. So
1 dW D dR
η0 qR = . (3.20)
g0 W dt L dt
Rearrange and “multiply” by dt to get
qR L dW
dR = η0 . (3.21)
g0 D W

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110 CHAPTER 3. THRUST AND PERFORMANCE PARAMETERS

Assume η0 and L/D are constant. Integrate and take R = 0 when fully fueled to get

qR L Wf
R = η0 ln . (3.22)
g0 D Wi
Here Wf is the final weight and Wi is the initial weight. This is known as the Breguet range
equation. Note η0 and L/D are dimensionless and qR /g0 has units (m2 /s2 )/(m/s2 ) = m. Jet
fuel has a thermal energy of qR ∼ 50 MJ/kg. This gives qR /g0 = (50×106 J/kg)/9.81 m/s2 =
5.1 × 106 m = 5100 km. This is comparable to the distance from South Bend to Dublin,
which is 5816 km. This range would be modulated by values of η0 , L/D and ln Wf /Wi .

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Chapter 4

Cycle analysis

Farokhi, Chapters 4, 5,
Borgnakke and Sonntag, Chapters 5, 8, 9, 10.

4.1 Carnot
The Carnot cycle is the most well-known thermodynamic cycle. It is a useful idealization,
but is difficult to realize in practice. Its real value lies in serving as a standard to which
other cycles can be compared. These are usually fully covered in introductory courses. The
cycle can be considered as follows
• 1 → 2: isentropic compression,
• 2 → 3: isothermal expansion,
• 3 → 4: isentropic expansion, and
• 4 → 1: isothermal compression.
This forms a rectangle in the T − s plane The P − v plane is more complicated. Both are
shown in Figure 4.1.

4.1.1 Analysis for a calorically perfect ideal gas

For this discussion, consider a calorically perfect ideal gas. The isotherms are then straight-
forward and are hyperbolas described by
1
P = RT . (4.1)
v
The slope of the isotherms in the P − v plane is found by differentiation:
∂P 1
= −RT , (4.2)
∂v T v2
P
= − . (4.3)
v

111
112 CHAPTER 4. CYCLE ANALYSIS

P T
2

isot
isotherm 3
her 2
m

isentrope
isentrope
isent
ro p

3
e

iso
th e

ise
1 rm ro 1 isotherm 4
nt
p e

v s

Figure 4.1: Sketch of P − v and T − s planes for a CPIG in a Carnot cycle.

The slope of the isentrope is found in the following way. Consider first the Gibbs equation,
Eq. (1.1):

T ds = de + P dv. (4.4)

Because the gas is calorically perfect, one has

de = cv dT, (4.5)

so the Gibbs equation, Eq. (4.4), becomes

T ds = cv dT + P dv. (4.6)

Now for the ideal gas, one has

P v = RT, (4.7)
P dv + v dP = RdT, (4.8)
P dv + v dP
= dT. (4.9)
R

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4.1. CARNOT 113

So then
 
P dv + v dP
T ds = cv +P dv, (4.10)
R
| {z }
=dT
c  cv
v
T ds = + 1 P dv + v dP, Take ds = 0, (4.11)
R R
c  cv ∂P
v
0 = +1 P + v , (4.12)
R R ∂v s
cv
∂P +1 P
= − R cv , (4.13)
∂v s R
v
cv
c −c
+1 P
= − P cvv , (4.14)
cP −cv
v
cv + cP − cv P
= − , (4.15)
cv v
cP P
= − , (4.16)
cv v
P
= −γ . (4.17)
v
Because γ > 1, the magnitude of the slope of the isentrope is greater than the magnitude of
the slope of the isotherm:
∂P ∂P
> . (4.18)
∂v s ∂v T

Example 4.1
(Adapted from Borgnakke and Sonntag, 7.94, p. 274) Consider an ideal gas Carnot cycle with air
in a piston cylinder with a high temperature of 1200 K and a heat rejection at 400 K. During the heat
addition, the volume triples. The gas is at 1.00 m3 /kg before the isentropic compression. Analyze.

Take state 1 to be the state before the compression. Then

m3
T1 = 400 K, v1 = 1.00 . (4.19)
kg

By the ideal gas law

 
kJ
RT1 0.287 kg K (400 K)
P1 = = m3
= 1.148 × 102 kPa. (4.20)
v1 1.00 kg

Now isentropically compress to state 2. By the standard relations for a CPIG, one finds
 γ−1   γ−1
T2 v1 P2 γ
= = . (4.21)
T1 v2 P1

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114 CHAPTER 4. CYCLE ANALYSIS

So
  γ−1
1    1
T1 m3 400 K 1.4−1 m3
v2 = v1 = 1.00 = 0.06415 . (4.22)
T2 kg 1200 K kg
Note that v2 < v1 as is typical in a compression. The isentropic relation between pressure and volume
can be rearranged to give the standard

P2 v2γ = P1 v1γ . (4.23)

Thus, one finds that

 γ m3
!1.4
v1 2
1.00 kg
P2 = P1 = (1.148 × 10 kPa) 3 = 5.36866 × 103 kPa. (4.24)
v2 0.06415 mkg

Note the pressure has increased in the isentropic compression. Check to see if the ideal gas law is
satisfied at state 2:
 
kJ
RT2 0.287 kg K (1200 K)
P2 = = 3 = 5.36866 × 103 kPa. (4.25)
v2 0.06415 m
kg

This matches. Now the expansion from state 2 to 3 is isothermal. This is the heat addition step in
which the volume triples. So one gets
 
m3 m3
v3 = 3v2 = 3 0.06415 = 0.19245 . (4.26)
kg kg

T3 = T2 = 1200 K. (4.27)
The ideal gas law then gives
 
RT3 0.287 kgkJK (1200 K)
P3 = = 3 = 1.78955 × 103 kPa. (4.28)
v3 0.19245 mkg

Process 3 to 4 is an isentropic expansion back to 400 K. Using the isentropic relations for the CPIG,
one gets
  γ−1 1    1
T3 m3 1200 K 1.4−1 m3
v4 = v3 = 0.19245 = 3.000 . (4.29)
T4 kg 400 K kg
 γ m3
!1.4
v3 0.19245 kg
P4 = P3 = (1.78955 × 103 kPa) m3
= 3.82667 × 101 kPa. (4.30)
v4 3.000 kg

Check:  
kJ
RT4 0.287 kg K (400 K)
P4 = = m3
= 3.82667 × 101 kPa. (4.31)
v4 3.000 kg

A summary of the states is given in Table 4.1.

Now calculate the work, heat transfer and efficiency. Take the adiabatic exponent for air to be
γ = 1.4. Now because
cP
γ= , cP − cv = R, (4.32)
cv

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4.1. CARNOT 115

3
T (K) P (kPa) v ( mkg )
1 400 1.148 × 102 1.000
2 1200 5.36886 × 103 0.06415
3 1200 1.78955 × 103 0.19245
4 400 3.82667 × 102 3.000

Table 4.1: State properties for Carnot cycle.

one gets

R + cv
γ = , (4.33)
cv
γcv = R + cv , (4.34)
cv (γ − 1) = R, (4.35)
R 0.287 kgkJK kJ
cv = = = 0.7175 . (4.36)
γ−1 1.4 − 1 kg K

Recall the first law:

e2 − e1 = 1 q2 − 1 w2 . (4.37)
Recall also the caloric equation of state for a CPIG:

e2 − e1 = cv (T2 − T1 ). (4.38)

Now process 1 → 2 is isentropic, so it is also adiabatic, hence 1 q2 = 0, so one has

e2 − e1 = 1 q2 −1 w2 , (4.39)
|{z}
=0
cv (T2 − T1 ) = −1 w2 , (4.40)
 
kJ
0.7175 (1200 K − 400 K) = −1 w2 , (4.41)
kg K
kJ
1 w2 = −5.7400 × 102 . (4.42)
kg

The work is negative as work is being done on the system in the compression process.
Process 2 → 3 is isothermal, so there is no internal energy change. The first law gives

e3 − e2 = 2 q3 − 2 w3 , (4.43)
cv (T3 − T2 ) = 2 q3 − 2 w3 , (4.44)
| {z }
=0
0 = 2 q3− 2 w3 , (4.45)
Z v3
2 q3 = w
2 3 = P dv, (4.46)
v2
Z v3 Z v3
RT dv v3
= dv = RT2 = RT2 ln , (4.47)
v2 v v2 v v2
  m3
kJ 0.19245 kg 2 kJ
= 0.287 (1200 K) ln 3 = 3.78362 × 10 . (4.48)
kg K 0.06415 m
kg
kg

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116 CHAPTER 4. CYCLE ANALYSIS

     
kJ kJ kJ
Process ∆e kg
q kg
w kg
1→2 5.74000 × 102 0 −5.74000 × 102
2→3 0 3.78362 × 102 3.78362 × 102
3 → 4 −5.74000 × 102 0 5.74000 × 102
4→1 0 −1.26121 × 102 −1.26121 × 102
Total 0 2.52241 × 102 2.52241 × 102

Table 4.2: First law parameters for Carnot cycle.

The work is positive, which is characteristic of the expansion process.

Process 3 → 4 is adiabatic so 3 q4 = 0. The first law analysis gives then

e4 − e3 = 3 q4 −3 w4 , (4.49)
|{z}
=0
cv (T4 − T3 ) = −3 w4 , (4.50)
 
kJ
0.7175 (400 K − 1200 K) = −3 w4 , (4.51)
kg K
kJ
3 w4 = 5.74000 × 102 . (4.52)
kg
Process 4 → 1 is isothermal. Similar to the other isothermal process, one finds

e1 − e4 = 4 q1 − 4 w1 , (4.53)
cv (T1 − T4 ) = 4 q1 − 4 w1 , (4.54)
| {z }
=0
0 = 4 q1
− 4 w1 , (4.55)
Z v1
4 q1 = 4 w1 = P dv, (4.56)
v4
Z v1   m3
RT v1 kJ 1.0000 kg
= dv = RT4 ln = 0.287 (400 K) ln m3
, (4.57)
v4 v v4 kg K 3.0000 kg
kJ
= −1.26121 × 102 . (4.58)
kg
Table 4.2 summarizes the first law considerations. The cycle work is found by adding the work of each
individual process:

wcycle = 1 w2 + 2 w3 + 3 w4 + 4 w1 , (4.59)
kJ
= (−5.74 + 3.78362 + 5.74 − 1.26121) × 102 = 2.52241 × 102 . (4.60)
kg
The cycle heat transfer is

qcycle = 1 q2 + 2 q3 + 3 q4 + 4 q1 , (4.61)
kJ
= (0 + 3.78362 + 0 − 1.26121) × 102 = 2.52241 × 102 . (4.62)
kg
Note that
wcycle = qcycle . (4.63)

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4.2. BRAYTON AIR STANDARD CYCLE 117

Check now for the cycle efficiency. Recall that the thermal efficiency is
what you want wcycle
η= = . (4.64)
what you pay for qin
Here this reduces to
kJ
wcycle 2.52241 × 102 kg
η= = kJ
= 0.6667. (4.65)
2 q3 3.78362 × 102 kg
Recall that the efficiency for any Carnot cycle should be
Tlow
η =1− . (4.66)
Thigh

So general Carnot theory holds that the efficiency should be

400 K 2
η =1− = ∼ 0.6667. (4.67)
1200 K 3
Recall further that for a Carnot cycle, one has
qlow Tlow
= . (4.68)
qhigh Thigh

For this problem then one has

−4 q1 Tlow
= , (4.69)
2 q3 Thigh
kJ
1.26121 × 102 kg 400 K
kJ
= , (4.70)
3.78362 × 102 kg 1200 K
1 1
= . (4.71)
3 3
Indeed, the appropriate relation holds.

4.2 Brayton air standard cycle

It is useful to model several real engineering devices by what is known as an air standard
cycle. This is based on the following assumptions:
• CPIG,
• no inlet or exhaust stages,
• combustion process replaced by heat transfer process,
• cycle completed by heat transfer to surroundings (not exhaust), and
• all process internally reversible.
In some cycles, it is common to model the working fluid as a fixed mass. In others, it is
common to model the system as a control volume.

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118 CHAPTER 4. CYCLE ANALYSIS

4.2.1 Classical
The Brayton cycle is the air standard model for gas turbine engines. It is most commonly
modeled on a control volume basis. It has the following components:

• 1 → 2: isentropic compression,

• 2 → 3: isobaric heat transfer to combustion chamber,

• 3 → 4: isentropic expansion through turbine, and

• 4 → 1: isobaric heat exchange with surroundings.

A schematic for the Brayton cycle is shown in Figure 4.2. Diagrams for P − v and T − s for

fuel

combustion
chamber 3
2

compressor turbine w

1 air products 4

environmental exhaust return

Figure 4.2: Schematic for Brayton cycle.

the Brayton cycle are shown in Figure 4.3.

The efficiency of the air standard Brayton cycle is found as
wnet
η= . (4.72)
qH

For the cycle, the first law holds that

wnet = qnet = qH − qL . (4.73)

One notes for an isobaric control volume combustor that

dEcv
= Q̇cv − Ẇcv +ṁhin − ṁhout . (4.74)
dt } |{z}
| {z =0
=0

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4.2. BRAYTON AIR STANDARD CYCLE 119

P T

2 3 3

isentrope
isobar

2
isentrope 4

4 1 isobar
1

v s

Figure 4.3: P − v and T − s diagrams for the Brayton cycle.

So

Q̇cv = ṁ(hout − hin ), (4.75)

Q̇cv
= hout − hin , (4.76)
ṁ
q = hout − hin = cP (Tout − Tin ). (4.77)

So the thermal efficiency is

 
T4
wnet qH − qL qL cP (T4 − T1 ) T1 T1
−1
η= = =1− =1− =1−  . (4.78)
qH qH qH cP (T3 − T2 ) T2 TT32 − 1

Now because of the definition of the process, one also has

P3 P2
= . (4.79)
P4 P1
And because 1 → 2 and 3 → 4 are isentropic, one has
 γ/(γ−1)  γ/(γ−1)
P2 T2 P3 T3
= = = . (4.80)
P1 T1 P4 T4

So one then has

T2 T3
= . (4.81)
T1 T4
Cross-multiplying, one finds
T3 T4
= . (4.82)
T2 T1

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120 CHAPTER 4. CYCLE ANALYSIS

Subtracting unity from both sides gives

T3 T4
−1= − 1. (4.83)
T2 T1
So the thermal efficiency takes the form
T1 1 1
η =1− = 1 − T2 = 1 −  (γ−1)/γ . (4.84)
T2 T1 P2
P1

Note that if a Carnot cycle were operating between the same temperature bounds that
ηCarnot = 1 − T1 /T3 would be greater than that for the Brayton cycle.
One must also account for deviations from ideality. These effects are summarized in
component efficiencies. The relevant efficiencies here, assuming a control volume approach,
are
h2s − h1 h3 − h4
ηc = , ηt = . (4.85)
h2 − h1 h3 − h4s
For a CPIG, one gets then
T2s − T1 T3 − T4
ηc = , ηt = . (4.86)
T2 − T1 T3 − T4s

Example 4.2
(adopted from Moran and Shapiro, Example 9.6) Air enters the compressor of an air-standard
Brayton cycle at 100 kPa, 300 K with a volumetric flow rate is 5 m3 /s. The pressure ratio in the
compressor is 10. The turbine inlet temperature is 1400 K. Find the thermal efficiency, the back work
ratio and the net power. Both the compressor and turbine have efficiencies of 0.8.

First calculate the state after the compressor if the compressor were isentropic.
 γ/(γ−1)
P2 T2s
= = 10, (4.87)
P1 T1
T2s = T1 (10)(γ−1)/γ = (300 K)(10)(1.4−1)/1.4 = 579.209 K. (4.88)
Now
T2s − T1
ηc = , (4.89)
T2 − T1
T2s − T1 (579.209 K) − (300 K)
T2 = T1 + = (300 K) + = 649.012 K. (4.90)
ηc 0.8
Now state three has T3 = 1400 K. Recall that 2 → 3 involves heat addition in a combustion chamber.
Now calculate T4s for the ideal turbine. Recall that the expansion is to the same pressure as the
compressor inlet so that P3 /P4 = 10. The isentropic relations give
 γ/(γ−1)
T4s P4
= , (4.91)
T3 P3
 (γ−1)/γ  (1.4−1)/1.4
P4 1
T4s = T3 = (1400 K) = 725.126 K. (4.92)
P3 10

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4.2. BRAYTON AIR STANDARD CYCLE 121

Now account for the actual behavior in the turbine:

T3 − T4
ηt = , (4.93)
T3 − T4s
T4 = T3 − ηt (T3 − T4s ) = (1400 K) − (0.8)((1400 K) − (725.126 K)) = 860.101 K. (4.94)
Now calculate the thermal efficiency of the actual cycle.
wnet qH − qL qL cP (T4 − T1 ) T4 − T1
η = = =1− =1− =1− , (4.95)
qH qH qH cP (T3 − T2 ) T3 − T2
860.101 K − 300 K
= 1− = 0.254181. (4.96)
1400 K − 649.012 K
If the cycle were ideal, one would have
wnet qH − qL qL cP (T4s − T1 ) T4s − T1
ηideal = = =1− =1− =1− , (4.97)
qH qH qH cP (T3 − T2s ) T3 − T2s
(725.126 K) − (300 K)
= 1− = 0.482053. (4.98)
(1400 K) − (579.209 K)
Note also that for the ideal cycle one also has
T1 300 K
ηideal = 1 − =1− = 0.482053. (4.99)
T2s 579.209 K
The back work ratio is
wcomp cP (T2 − T1 ) T2 − T1 (649.012 K) − (300 K)
bwr = = = ,= = 0.646439. (4.100)
wturb cP (T3 − T4 ) T3 − T4 (1400 K) − (860.101 K)
If the process were ideal, the back work ratio would have been
wcomp cP (T2s − T1 ) T2s − T1 (579.209 K) − (300 K)
bwrideal = = = = = 0.413721. (4.101)
wturb cP (T3 − T4s ) T3 − T4s (1400 K) − (725.126 K)
Now get the net work. First get the mass flow rate from the volume flow rate. This requires the specific
volume.  
kJ
RT1 0.287 kg K (300 K) m3
v1 = = = 0.861 . (4.102)
P1 100 kPa kg
Now 3
V̇ 5 ms kg
ṁ = ρ1 V̇ = = m3
= 5.8072 . (4.103)
v1 0.861 kg s
Recall cP = γcv = 1.4(717.5 J/kg/K) = 1004.5 J/kg/K = 1.0045 kJ/kg/K. Now
Ẇcycle = ṁcP ((T3 − T4 ) − (T2 − T1 ), (4.104)
  
kg kJ
= 5.8072 1.0045 ((1400 K) − (860.101 K) − (649.012 K) + (300 K)),(4.105)
s kg K
= 1113.51 kW. (4.106)
If the cycle were ideal, one would have
Ẇideal = ṁcP ((T3 − T4s ) − (T2s − T1 ), (4.107)
  
kg kJ
= 5.8072 1.0045 ((1400 K) − (725.126 K) − (579.209 K) + (300 K)),(4.108)
s kg K
= 2308.04 kW. (4.109)

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122 CHAPTER 4. CYCLE ANALYSIS

Note that the inefficiencies had a significant effect on both the back work ratio and the net work of the
engine.

Example 4.3
Consider a CPIG air standard Brayton cycle with fixed inlet conditions P1 and T1 . We also fix the
maximum temperature as the metallurgical limit of the turbine blades, Tmax . Find the temperature
ratio θ that maximizes the net work. Then find the temperature ratio that maximizes the thermal
efficiency.

We have
  γ−1   γ−1
P2 γ
P4 γ
T2 = T1 θ, T2 = T1 , T3 = Tmax , T4 = T3 . (4.110)
P1 P3

We also have P4 = P1 and P2 = P3 . So

  γ−1   1−γ
P1 k
P2 γ
Tmax
T4 = Tmax = Tmax = . (4.111)
P2 P1 θ

Now, the net work is

wnet = (h3 − h4 ) − (h2 − h1 ), (4.112)

= cP (T3 − T4 − T2 + T1 ), (4.113)
= cP (Tmax − Tmax θ−1 − T1 θ + T1 ), (4.114)
 
Tmax Tmax −1
= cP T 1 − θ −θ+1 . (4.115)
T1 T1

Note wnet = 0 when θ = 1 and when θ = Tmax /T1 .

To find the maximum wnet we take dwnet /dθ and set to zero:
 
dwnet Tmax −2
= cP T 1 θ −1 , (4.116)
dθ T1
 
Tmax −2
0 = cP T 1 θ −1 , (4.117)
T1
r
Tmax
θ = ± . (4.118)
T1
We take the positive root, because a negative temperature ratio does not make sense:
r
Tmax
θ= . (4.119)
T1

The second derivative tells us whether our critical point is a maximum or a minimum.

d2 wnet
= −2cP Tmax θ−3 . (4.120)
dθ2

CC BY-NC-ND. 19 January 2025, J. M. Powers.

4.2. BRAYTON AIR STANDARD CYCLE 123

When θ > 0, d2 wnet /dθ2 < 0, so we have found a maximum of wnet . The maximum value is
 −1/2  1/2 !
Tmax Tmax
wnet |max = cP Tmax − Tmax − T1 + T1 , (4.121)
T1 T1
 −1/2  1/2 !
Tmax Tmax Tmax Tmax
= cP T 1 − − +1 , (4.122)
T1 T1 T1 T1
 1/2 !
Tmax Tmax
= cP T 1 −2 +1 , (4.123)
T1 T1
 1/2 !2
Tmax
= cP T 1 −1 . (4.124)
T1

Now, at what value of θ is the thermal efficiency maximum? Consider

η = 1 − θ−1 , (4.125)
dη 1
= . (4.126)
dθ θ2
At a maximum, we must have dη/dθ = 0. So we must have θ → ∞ in order to have η reach a maximum.
But we are limited to θ ≤ Tmax /T1 . So the achievable θ that maximizes η is

Tmax
θ= . (4.127)
T1

So the efficiency at our highest allowable θ is

1 T1
η =1− Tmax
=1− . (4.128)
T1
Tmax

But at the value of peak efficiency, the net work is approaching zero! So while this is highly efficient,
it is not highly useful!
Lastly, what is the efficiency at the point where we maximize work?
r
T1
η =1− . (4.129)
Tmax
A plot of scaled net work, wnet /cP /T1 versus
√ temperature ratio is given for Tmax /T1 = 10 inpFig. 4.4.
Here, the θ that maximizes w√net is θ = 10 = 3.162. At that value of θ, we find η = 1 − 1/10 =
0.683772 and wnet /cP /T1 = ( 10 − 1)2 = 4.675.

4.2.2 Regeneration
One can improve cycle efficiency by regeneration. The hot gas in the turbine is used to
preheat the gas exiting the compressor before it enters the combustion chamber. In this
cycle, one takes
• 1 → 2: compression,

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124 CHAPTER 4. CYCLE ANALYSIS

wnet/(cPT1)
5
4.675
4

2 4 6 8 10
3.162 = T2/T1

Figure 4.4: Scaled net work versus temperature ratio for Brayton cycle with Tmax /T1 = 10.

• 2 → x: compression exit gas goes through regenerator (heat exchanger),

• x → 3: combustion chamber,

• 3 → 4: expansion in turbine, and

• 4 → y: turbine exit gas goes through regenerator (heat exchanger).

A schematic for the Brayton cycle is shown in Figure 4.5.

y regenerator

x 4
combustion
2 chamber 3

compressor turbine w

Figure 4.5: Schematic for Brayton cycle with regeneration.

For this to work, the gas at the turbine exit must have a higher temperature than the gas
at the compressor exit. If the compression ratio is high, the compressor exit temperature is
high, and there is little benefit to regeneration.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

4.2. BRAYTON AIR STANDARD CYCLE 125

Now consider the regenerator, which is really a heat exchanger. The first law holds that
dEcv
= Q̇cv − Ẇcv +ṁh2 − ṁhx + ṁh4 − ṁhy , (4.130)
dt
| {z } |{z} |{z}
=0 =0
=0
0 = h2 − hx + h4 − hy , (4.131)
= cP (T2 − Tx ) + cP (T4 − Ty ), (4.132)
= T2 − Tx + T4 − Ty . (4.133)

Now consider the inlet temperatures to be known. Then the first law constrains the outlet
temperatures such that
T2 + T4 = Tx + Ty . (4.134)
If the heat exchanger were an ideal co-flow heat exchanger, one might expect the outlet
temperatures to be the same, that is, Tx = Ty , and one would have Tx = Ty = (1/2)(T2 + T4 ).
But in fact one can do better. If a counter-flow heat exchanger is used, one could ideally
expect to find
Tx = T4 , Ty = T2 . (4.135)
The thermal efficiency is
wnet wt − wc
η = = , (4.136)
qH qH
cP (T3 − T4 ) − cP (T2 − T1 )
= , (4.137)
cP (T3 − Tx )
(T3 − T4 ) − (T2 − T1 ) (T3 − T4 ) − (T2 − T1 )
= = , (4.138)
T3 − Tx T3 − T4
 
T2
T2 − T1 T 1 T1
− 1
= 1− =1−  , (4.139)
T3 − T4 T3 1 − TT34
     
(γ−1)/γ (γ−1)/γ
P2 P2
T1 P1
−1 T1 P1
−1
= 1−   (γ−1)/γ  = 1 −   (γ−1)/γ  , (4.140)
P4
T3 1 − P3 T3 1 − PP21
 (γ−1)/γ
 (γ−1)/γ 1 − P1
T1 P2 P2
= 1−  (γ−1)/γ , (4.141)
T3 P1
1 − PP12
 (γ−1)/γ
T1 P2
= 1− . (4.142)
T3 P1

Note this is the Carnot efficiency moderated by the pressure ratio. As the pressure ratio
rises, the thermal efficiency declines.

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126 CHAPTER 4. CYCLE ANALYSIS

The regenerator itself will not be perfect. To achieve the performance postulated here
would require infinite time or an infinite area heat exchanger. As both increase, viscous
losses increase, and so there is a trade-off. One can summarize the behavior of an actual
regenerator by an efficiency defined as

hx − h2 actual
ηreg = ′
= . (4.143)
hx − h2 ideal
If we have a CPIG, then
Tx − T2
ηreg = . (4.144)
Tx′ − T2

Example 4.4
(extension for Moran and Shapiro, Example 9.6) How would the addition of a regenerator affect
the thermal efficiency of the isentropic version of the previous example problem?

One may take the rash step of trusting the analysis to give a prediction from Eq. (4.142) of
 (γ−1)/γ
T1 P2
η = 1− , (4.145)
T3 P1
 
300 K
= 1− (10)(1.4−1)/1.4 = 0.586279. (4.146)
1400 K

Without regeneration, the thermal efficiency of the ideal Brayton cycle had a value of 0.482053. Had
the engine used a Carnot cycle between the same temperature limits, the efficiency would have been
0.785714.

4.2.3 Turbojet propulsion

If one modifies the Brayton cycle so that the turbine work is just sufficient to drive the
compressor and the remaining enthalpy at the turbine exit is utilized in expansion in a
nozzle to generate thrust, one has the framework for jet propulsion. Here the control volume
approach is used. A schematic for a turbojet engine is shown in Figure 4.6. Diagrams for
P − v and T − s for the jet propulsion Brayton cycle are shown in Figure 4.7. An important
component of jet propulsion analysis is the kinetic energy of the flow. In the entrance region
of the engine, the flow is decelerated, inducing a ram compression effect. For high velocity
applications, this effect provides sufficient compression for the cycle and no compressor or
turbine are needed! However, such a device, known as a ramjet, is not self-starting, and so
is not practical for many applications.
One can outline the ideal jet propulsion cycle as follows:

• 1 → a: deceleration and ram compression in diffuser,

CC BY-NC-ND. 19 January 2025, J. M. Powers.

4.2. BRAYTON AIR STANDARD CYCLE 127

burner 3
2

1 a 4
diffuser compressor turbine nozzle

environmental exhaust return

Figure 4.6: Schematic for turbojet propulsion.

P T
3
2 3
4
isobar
isentrope
4 2

isentrope 5
a
a
1 isobar
1 5

v s

Figure 4.7: P − v and T − s diagrams for turbojet propulsion Brayton cycle.

• a → 2: isentropic compression in the compressor,

• 2 → 3: isobaric heating in the combustion chamber,
• 3 → 4: isentropic expansion in turbine,
• 4 → 5: isentropic conversion of thermal energy to kinetic energy in nozzle, and
• 5 → 1: isobaric heat transfer in surroundings.
The goal of the jet propulsion cycle is to produce a thrust force which is necessary to
balance a fluid-induced aerodynamic drag force. When such a balance exists, the system is
in steady state. One can analyze such a system in the reference frame in which the engine
is stationary. In such a frame, Newton’s second law gives
d
(mCV uCV ) = F
|{z} + P1 A1 i − P5 A5 i +ṁu1 − ṁu5 . (4.147)
| {z }
|dt {z } thrust force small
=0

Solving for the thrust force, neglecting the small differences in pressure, one gets,
F = ṁ (u5 − u1 ) . (4.148)

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128 CHAPTER 4. CYCLE ANALYSIS

The work done by the thrust force is the product of this force and the air speed, u1 = |u1 |.
This gives
|Ẇp | = |F · u1 | = |ṁ(u5 − u1 ) · u1 | . (4.149)
Now the efficiency of the cycle is a bit different. The net work of the turbine and compressor
is zero. Instead, the overall efficiency is defined as
Propulsive Power |Ẇp |
η0 = = , (4.150)
Energy Input Rate |Q̇H |
|ṁu1 · (u5 − u1 )|
= . (4.151)
ṁ|(h3 − h2 )|

The analysis presented here is common for simple Brayton cycles and differs slightly from
that used in deriving the roughly equivalent Eq. (3.14). The air standard analysis presented
here ignores the mass flow rate of the fuel, and treats the combustion process as a simple
heat addition.
Note the following unusual behavior for flight in an ideal inviscid atmosphere in which
the flow always remains attached. In such a flow D’Alembert’s paradox holds: there is
no aerodynamic drag. Consequently there is no need for thrust generation in steady state
operation. Thrust would only be needed to accelerate to a particular velocity. For such
an engine then the exit velocity would equal the entrance velocity: u5 = u1 and F = 0.
Moreover, the propulsive efficiency is ηp = 0.

Example 4.5
(adopted from Çengal and Boles, p. 485). A turbojet flies with a velocity of 850 ft/s at an altitude
where the air is at 5 psia and −40 ◦ F. The compressor has a pressure ratio of 10, and the temperature
at the turbine inlet is 2000 ◦ F. Air enters the compressor at a rate of ṁ = 100 lbm/s. Assuming an
air standard with CPIG air, find the
• temperature and pressure at the turbine exit,
• velocity of gas at nozzle exit, and
• overall efficiency.

For the English units of this problem, one recalls that

lbm ft Btu ft2
1 Btu = 777.5 ft lbf, gc = 32.2 , 1 = 25037 2 . (4.152)
lbf s2 lbm s
For air, one has
Btu ft lbf ft2 Btu
cP = 0.240 , R = 53.34 = 1717.5 2 ◦ = 0.0686 , γ = 1.4. (4.153)
lbm ◦ R lbm R◦ s R lbm ◦ R
First one must analyze the ram compression process. An energy balance gives
u21 u2
h1 + = ha + a . (4.154)
2 2
|{z}
small

CC BY-NC-ND. 19 January 2025, J. M. Powers.

4.2. BRAYTON AIR STANDARD CYCLE 129

It is usually sufficient to neglect the kinetic energy of the fluid inside the engine. While it still has
a non-zero velocity, it has been slowed enough so that enthalpy dominates kinetic energy inside the
engine. So one takes

u21
ha = h1 + , (4.155)
2
u21
0 = h1 − ha + , (4.156)
2
u21
0 = cP (T1 − Ta ) + , (4.157)
2
u21
Ta = T1 + . (4.158)
2cP

The ambient temperature is

T1 = −40 + 460 = 420 ◦ R. (4.159)
So after ram compression, the temperature at the inlet to the compressor is


ft 2 Btu
850 s 1 lbm
Ta = (420 R) + ◦
Btu

2 = 480.119 ◦ R. (4.160)
2 0.240 lbm ◦ R 25037 fts2

Now get the pressure at the compressor inlet via the isentropic relations:
 γ/(γ−1)  1.4/(1.4−1)
Ta 480 ◦ R
Pa = P1 = (5 psia) = 7.98582 psia. (4.161)
T1 420 ◦ R

Now consider the isentropic compressor.

P2 = 10Pa = 10(7.98582 psia) = 79.8582 psia. (4.162)

Now get the temperature after passage through the compressor.

 (γ−1)/γ
P2 (1.4−1)/1.4
T2 = Ta = (480 ◦ R) (10) = 926.965 ◦ R. (4.163)
Pa

The temperature at the entrance of the turbine is known to be 2000 ◦ F = 2460 ◦ R. Now the turbine
work is equal to the compressor work, so

wc = wt , (4.164)
h2 − ha = h3 − h4 , (4.165)
cP (T2 − Ta ) = cP (T3 − T4 ), (4.166)
T2 − Ta = T3 − T4 , (4.167)
T4 = T3 − T2 + Ta , (4.168)
= 2460 ◦ R − 926.965 ◦ R + 480 ◦ R, (4.169)
◦
= 2013.15 R. (4.170)

Use the isentropic relations to get P4 :

 γ/(γ−1)  1.4/(1.4−1)
T4 2013.15 ◦ R
P4 = P3 = (79.8582 psia) = 39.5928 psia. (4.171)
T3 2460 ◦ R

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130 CHAPTER 4. CYCLE ANALYSIS

Expansion through the nozzle completes the cycle. Assume an isentropic nozzle, therefore

 (γ−1)/γ
P5
T5 = T4 , (4.172)
P4
 (γ−1)/γ
P1
= T4 , (4.173)
P4
 (1.4−1)/1.4
◦ 5 psia
= = (2013.15 R) , (4.174)
39.5928 psia
= 1114.60 ◦ R. (4.175)

Now consider the energy balance in the nozzle:

u25 u24
h5 + = h4 + , (4.176)
2 2
|{z}
small
u25
0 = h5 − h4 + , (4.177)
2
u2
= cP (T5 − T4 ) + 5 , (4.178)
p 2
u5 = 2cP (T4 − T5 ), (4.179)
v !
u  
u Btu 25037
2
ft
= t 2 0.240 (2013.15 ◦ R − 1114.60 ◦ R) s2
, (4.180)
lbm ◦ R Btu
1 lbm

ft
= 3286.11 . (4.181)
s

Now find the thrust force magnitude

  
lbm ft ft ft lbm
|F| = ṁ(u5 − u1 ) = 100 3286.11 − 850 = 243611 , (4.182)
s s s s2
ft lbm
243611 s2
= lbm ft
, (4.183)
32.2 lbf s2
= 7565.57 lbf. (4.184)

The power is the product of the thrust force and the air speed, so

  
ft Btu
|ẆP | = |F · u1 | = (7565.57 lbf) 850 , (4.185)
s 777.5 ft lbf
Btu
= 8271.04 , (4.186)
s !
 
Btu 1.415 hp
= 8271.04 Btu
, (4.187)
s s
= 11703.5 hp. (4.188)

CC BY-NC-ND. 19 January 2025, J. M. Powers.

4.2. BRAYTON AIR STANDARD CYCLE 131

Now for the heat transfer in the combustion chamber

Q̇H = ṁ(h3 − h2 ), (4.189)

= ṁcP (T3 − T2 ), (4.190)
  
lbm Btu
= 100 0.240 (2460 ◦ R − 926.965 ◦ R), (4.191)
s lbm ◦ R
Btu
= 36792.8 . (4.192)
s
So the overall efficiency is
Btu
ẆP 8271.04 s
ηO = = Btu
= 0.2248. (4.193)
Q̇H 36792.8 s

The remainder of the energy is excess kinetic energy and excess thermal energy, both of which ultimately
dissipate so as to heat the atmosphere.

4.2.4 Turbojet with afterburners

If we combust additional fuel after the turbine, we can heat the fluid to a hotter temperature
because in the afterburner state, we do not have to be concerned with the turbine blade
temperature restriction.

Example 4.6
Consider the previous example problem with an afterburner. A turbojet flies with a velocity of
850 ft/s at an altitude where the air is at 5 psia and −40 ◦ F. The compressor has a pressure ratio of
10, and the temperature at the turbine inlet is 2000 ◦ F. After the turbine, additional heat is added to
bring the fluid to a temperature of 3000 ◦ F. Air enters the compressor at a rate of ṁ = 100 lbm/s.
Assuming an air standard with CPIG air, find the
• velocity of gas at nozzle exit, and
• overall efficiency.

For the English units of this problem, one recalls that

lbm ft Btu ft2
1 Btu = 777.5 ft lbf, gc = 32.2 , 1 = 25037 2 . (4.194)
lbf s2 lbm s
For air, one has
Btu ft lbf ft2 Btu
cP = 0.240 , R = 53.34 = 1717.5 2
= 0.0686 , γ = 1.4. (4.195)
lbm ◦ R lbm R◦ s R ◦ lbm ◦ R
First one must analyze the ram compression process. An energy balance gives
u21 u2
h1 + = ha + a . (4.196)
2 2
|{z}
small

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132 CHAPTER 4. CYCLE ANALYSIS

It is usually sufficient to neglect the kinetic energy of the fluid inside the engine. While it still has
a non-zero velocity, it has been slowed enough so that enthalpy dominates kinetic energy inside the
engine. So one takes
u21
ha = h1 + , (4.197)
2
u21
0 = h1 − ha + , (4.198)
2
u21
0 = cP (T1 − Ta ) + , (4.199)
2
u21
Ta = T1 + . (4.200)
2cP
The ambient temperature is
T1 = −40 + 460 = 420 ◦ R. (4.201)
So after ram compression, the temperature at the inlet to the compressor is

2
850 fts 1 Btu
lbm
◦
Ta = (420 R) + Btu

2 = 480.119
◦
R. (4.202)
2 0.240 lbm ◦R 25037 fts2
Now get the pressure at the compressor inlet via the isentropic relations:
 γ/(γ−1)  1.4/(1.4−1)
Ta 480 ◦ R
Pa = P1 = (5 psia) = 7.98582 psia. (4.203)
T1 420 ◦ R
Now consider the isentropic compressor.

P2 = 10Pa = 10(7.98582 psia) = 79.8582 psia. (4.204)

Now get the temperature after passage through the compressor.

 (γ−1)/γ
P2 (1.4−1)/1.4
T2 = Ta = (480 ◦ R) (10) = 926.965 ◦ R. (4.205)
Pa
The temperature at the entrance of the turbine is known to be 2000 ◦ F = 2460 ◦ R. Now the turbine
work is equal to the compressor work, so

wc = wt , (4.206)
h2 − ha = h3 − h4 , (4.207)
cP (T2 − Ta ) = cP (T3 − T4 ), (4.208)
T2 − Ta = T3 − T4 , (4.209)
T4 = T3 − T2 + Ta , (4.210)
= 2460 ◦ R − 926.965 ◦ R + 480 ◦ R, (4.211)
◦
= 2013.15 R. (4.212)

Use the isentropic relations to get P4 :

 γ/(γ−1)  1.4/(1.4−1)
T4 2013.15 ◦ R
P4 = P3 = (79.8582 psia) = 39.5928 psia. (4.213)
T3 2460 ◦ R
Now we kick in the afterburners. Burn isobarically so that P4a = P4 = 39.5298 psia, T4a = 3000+460 =
3460 ◦ R.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

4.2. BRAYTON AIR STANDARD CYCLE 133

Expansion through the nozzle completes the cycle. Assume an isentropic nozzle, therefore
 (γ−1)/γ
P5
T5 = T4a , (4.214)
P4a
 (γ−1)/γ
P1
= T4a , (4.215)
P4a
 (1.4−1)/1.4
5 psia
= = (3460 ◦ R) , (4.216)
39.5928 psia
= 1915.67 ◦ R. (4.217)

Now consider the energy balance in the nozzle:

u25 u24a
h5 + = h4a + , (4.218)
2 2
|{z}
small
u25
0 = h5 − h4a + , (4.219)
2
u2
= cP (T5 − T4a ) + 5 , (4.220)
p 2
u5 = 2cP (T4a − T5 ), (4.221)
v !
u  
u Btu 25037
2
ft
= t2 0.240 (3460 ◦ R − 1915.67 ◦ R) Btu
s2
, (4.222)
lbm ◦ R 1 lbm

ft
= 4308.07 . (4.223)
s

This is much greater than the 3286.11 ft/s without the afterburners. Now find the thrust force magni-
tude
  
lbm ft ft ft lbm
|F| = ṁ(u5 − u1 ) = 100 4308.07 − 850 = 345807 , (4.224)
s s s s2
ft lbm
345807 s2
= lbm ft
, (4.225)
32.2 lbf s2
= 10739.3 lbf. (4.226)

Compare to the value without the afterburners of 7565.57 lbf. The power is the product of the thrust
force and the air speed, so
  
ft Btu
|ẆP | = |F · u1 | = (10739.3 lbf) 850 , (4.227)
s 777.5 ft lbf
Btu
= 11740.7 , (4.228)
s !
 
Btu 1.415 hp
= 11740.7 Btu
, (4.229)
s s
= 16613.2 hp. (4.230)

Compare to the thrust power without the afterburners of 11703.5 hp. Now calculate the heat transfer

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134 CHAPTER 4. CYCLE ANALYSIS

in the combustion chamber and afterburner:

Q̇H = ṁ(h3 − h2 ) + ṁ(h4a − h4 ), (4.231)

= ṁcP (T3 − T2 + T4a − T4 ), (4.232)
  
lbm Btu
= 100 0.240 (2460 ◦ R − 926.965 ◦ R + 3460 ◦ R − 2013.15 ◦ R), (4.233)
s lbm ◦ R
Btu
= 71517.1 . (4.234)
s
So the overall efficiency is
Btu
ẆP 11740.7 s
ηO = = Btu
= 0.164167. (4.235)
Q̇H 71517.1 s

The overall efficiency dropped from its value without the afterburners of 0.2248.

4.2.5 Ramjet propulsion

A ramjet has no compressor, fan, or turbine. It relies purely on ram compression. Then
after the combustor, all the available enthalpy is converted into kinetic energy. It is a simple
device. It cannot take off under its own power however, and so needs assisted launch.

Example 4.7
Consider the previous example problem in a ramjet configuration. A ramjet flies with a velocity
of 850 ft/s at an altitude where the air is at 5 psia and −40 ◦ F. Heat is added to bring the fluid to a
temperature of 3000 ◦ F. Air enters the inlet at a rate of ṁ = 100 lbm/s. Assuming an air standard
with CPIG air, find the
• velocity of gas at nozzle exit, and
• overall efficiency.

Using the numbering system of the previous examples, our cycle is

1 → a → 4a → 5 → 1 → . . . (4.236)

For the English units of this problem, one recalls that

lbm ft Btu ft2

1 Btu = 777.5 ft lbf, gc = 32.2 , 1 = 25037 2 . (4.237)
lbf s2 lbm s
For air, one has

Btu ft lbf ft2 Btu

cP = 0.240 , R = 53.34 = 1717.5 2
= 0.0686 , γ = 1.4. (4.238)
lbm ◦ R lbm R◦ s R ◦ lbm ◦ R

CC BY-NC-ND. 19 January 2025, J. M. Powers.

4.2. BRAYTON AIR STANDARD CYCLE 135

First one must analyze the ram compression process. An energy balance gives

u21 u2
h1 + = ha + a . (4.239)
2 2
|{z}
small

It is usually sufficient to neglect the kinetic energy of the fluid inside the engine. While it still has
a non-zero velocity, it has been slowed enough so that enthalpy dominates kinetic energy inside the
engine. So one takes

u21
ha = h1 + , (4.240)
2
u21
0 = h1 − ha + , (4.241)
2
u21
0 = cP (T1 − Ta ) + , (4.242)
2
u21
Ta = T1 + . (4.243)
2cP

The ambient temperature is

T1 = −40 + 460 = 420 ◦ R. (4.244)

So after ram compression, the temperature at the inlet to the compressor is

ft 2 Btu
850 s 1 lbm
Ta = (420 R) + ◦
Btu

2 = 480.119 ◦ R. (4.245)
2 0.240 lbm ◦ R 25037 fts2

Now get the pressure after the ram compression via the isentropic relations:

 γ/(γ−1)  1.4/(1.4−1)
Ta 480 ◦ R
Pa = P1 = (5 psia) = 7.98582 psia. (4.246)
T1 420 ◦ R

Burn isobarically so that P4a = Pa = 7.98582 psia, T4a = 3000 + 460 = 3460 ◦ R.
Expansion through the nozzle completes the cycle. Assume an isentropic nozzle, therefore

 (γ−1)/γ
P5
T5 = T4a , (4.247)
P4a
 (γ−1)/γ
P1
= T4a , (4.248)
P4a
 (1.4−1)/1.4
◦ 5 psia
= = (3460 R) , (4.249)
7.98582 psia
= 3026.75 ◦ R. (4.250)

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136 CHAPTER 4. CYCLE ANALYSIS

Now consider the energy balance in the nozzle:

u25 u24a
h5 + = h4a + , (4.251)
2 2
|{z}
small
u25
0 = h5 − h4a + , (4.252)
2
u2
= cP (T5 − T4a ) + 5 , (4.253)
p 2
u5 = 2cP (T4a − T5 ), (4.254)
v !
u  
u Btu 25037 ft2
= t 2 0.240 (3460 ◦ R − 3026.75 ◦ R) s2
, (4.255)
lbm ◦ R Btu
1 lbm

ft
= 2281.83 . (4.256)
s
This is less than that achieved in the previous two configurations. Now find the thrust force magnitude
  
lbm ft ft ft lbm
|F| = ṁ(u5 − u1 ) = 100 2281.83 − 850 = 143183 , (4.257)
s s s s2
143183. ft slbm
2
= lbm ft
, (4.258)
32.2 lbf s2
= 4446.66 lbf. (4.259)
Again this is less than the previous two configurations. The power is the product of the thrust force
and the air speed, so
  
ft Btu
|ẆP | = |F · u1 | = (4446.66 lbf) 850 , (4.260)
s 777.5 ft lbf
Btu
= 4861.3 , (4.261)
s !
 
Btu 1.415 hp
= 4861.3 Btu
, (4.262)
s s
= 6878.74 hp. (4.263)
Now calculate the heat transfer in the combustion chamber :
Q̇H = ṁ(h4a − ha ), (4.264)
= ṁcP (T4a − Ta ), (4.265)
  
lbm Btu
= 100 0.240 (3460 ◦ R − 480.119 ◦ R), (4.266)
s lbm ◦ R
Btu
= 71517.1 . (4.267)
s
So the overall efficiency is
ẆP 4861.3 Btu
s
ηO = = = 0.067974. (4.268)
Q̇H 71517.1 Btu
s
The overall efficiency is not high.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

4.2. BRAYTON AIR STANDARD CYCLE 137

4.2.6 Turbofan propulsion

Let us consider the turbofan configuration. See Figure 4.8. The key feature is the presence of

bypass

burner

fan
diffuser 4
compressor turbine nozzle

bypass

Figure 4.8: Schematic for turbofan propulsion.

a large fan, driven by the turbine. The fan pulls air into the chamber. However a significant
fraction of the air bypasses the main engine core and exhausts through the nozzle, generating
thrust. It effectively lowers the speed of the exhaust jet. Thus less kinetic energy is expelled
into the wake, where it does not serve a useful purpose.
Recall from Eq. (3.1) that for a perfectly expanded jet and neglecting ṁf , we have the
thrust force as
F = ṁ0 (u9 − u0 ), (4.269)
where 9 is the exit state and 0 is the inlet state. So
F
u9 = u0 + . (4.270)
ṁ0
Use this in the expression for propulsive efficiency, Eq. (3.13), to get
2u0
ηp = , (4.271)
u0 + ṁF0 + u0
1
= . (4.272)
1 + 2ṁF0 u0

Recalling the expression for specific thrust, Eq. (3.3), which equals F/ṁ0 , we see for fixed
flight speed u0 that propulsive efficiency increases if specific thrust decreases. To bring down

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138 CHAPTER 4. CYCLE ANALYSIS

specific thrust, we must decrease u9 , the exhaust velocity. Instead of directing this energy
to the exhaust, we direct it to an additional set of turbine blades so as to extract additional
power from the turbine. We use this power to drive a fan, which acts as a propeller to
generate thrust. We take ṁ0 to represent the mass flow rate through the core. We then take
additional air and pass it through a fan. The air that passes through the fan is a fraction of
that passing through the core:

ṁf an = αṁ0 . (4.273)

Here α is the bypass ratio:

ṁf an
α= . (4.274)
ṁ0

The total mass passing through the configuration is

ṁair = (1 + α)ṁ0 . (4.275)

Example 4.8
Consider a variant on a previous example. A turbofan with bypass ratio α = 1.5 flies with a velocity
of 850 ft/s at an altitude where the air is at 5 psia and −40 ◦ F. The compressor has a pressure ratio
of 10, and the temperature at the turbine inlet is 2000 ◦ F. Air enters the compressor at a rate of
ṁ0 = 100 lbm/s. Assuming an air standard with CPIG air, find the
• temperature and pressure at the turbine exit,
• velocity of gas at nozzle exit, and
• overall efficiency.

For the English units of this problem, one recalls that

lbm ft Btu ft2

1 Btu = 777.5 ft lbf, gc = 32.2 , 1 = 25037 2 . (4.276)
lbf s2 lbm s
For air, one has

Btu ft lbf ft2 Btu

cP = 0.240 , R = 53.34 = 1717.5 = 0.0686 , γ = 1.4. (4.277)
lbm ◦ R lbm ◦ R s2 ◦ R lbm ◦ R
First one must analyze the ram compression process. An energy balance gives

u21 u2
h1 + = ha + a . (4.278)
2 2
|{z}
small

It is usually sufficient to neglect the kinetic energy of the fluid inside the engine. While it still has
a non-zero velocity, it has been slowed enough so that enthalpy dominates kinetic energy inside the

CC BY-NC-ND. 19 January 2025, J. M. Powers.

4.2. BRAYTON AIR STANDARD CYCLE 139

engine. So one takes

u21
ha = h1 + , (4.279)
2
u21
0 = h1 − ha + , (4.280)
2
u21
0 = cP (T1 − Ta ) + , (4.281)
2
u21
Ta = T1 + . (4.282)
2cP
The ambient temperature is
T1 = −40 + 460 = 420 ◦ R. (4.283)
So after ram compression, the temperature at the inlet to the compressor is

2
850 fts 1 Btu
lbm
◦
Ta = (420 R) + Btu

2 = 480.119
◦
R. (4.284)
2 0.240 lbm ◦R 25037 fts2

Now get the pressure at the compressor inlet via the isentropic relations:
 γ/(γ−1)  1.4/(1.4−1)
Ta 480 ◦ R
Pa = P1 = (5 psia) = 7.98582 psia. (4.285)
T1 420 ◦ R
Now consider the isentropic compressor.

P2 = 10Pa = 10(7.98582 psia) = 79.8582 psia. (4.286)

Now get the temperature after passage through the compressor.

 (γ−1)/γ
P2
T2 = Ta = (480 ◦ R) (10)(1.4−1)/1.4 = 926.965 ◦ R. (4.287)
Pa
The temperature at the entrance of the first turbine is known to be 2000 ◦ F = 2460 ◦ R. Now the first
turbine work is given by is equal to the compressor work, so

wc = wt , (4.288)
h2 − ha = h3 − h4 , (4.289)
cP (T2 − Ta ) = cP (T3 − T4 ), (4.290)
T2 − Ta = T3 − T4 , (4.291)
T4 = T3 − T2 + Ta , (4.292)
= 2460 ◦ R − 926.965 ◦ R + 480 ◦ R, (4.293)
◦
= 2013.15 R. (4.294)

Use the isentropic relations to get P4 :

 γ/(γ−1)  1.4/(1.4−1)
T4 2013.15 ◦ R
P4 = P3 = (79.8582 psia) = 39.5928 psia. (4.295)
T3 2460 ◦ R
Now consider the fan. Let us take the fan inlet to have Pf = Pa = 7.98582 psia and Tf = Ta =
480.119 ◦ R. Let us isentropically compress the fan air stream to the same state as the core so

T2f = 926.965 ◦ R, P2f = 79.8582 psia. (4.296)

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140 CHAPTER 4. CYCLE ANALYSIS

For the fan, we have

q
u5f = 2cP (T2f − T1 ), (4.297)
v !
u  
u Btu 25037
2
ft
= t2 0.240 (926.965 ◦ R − 420 ◦ R) Btu
s2
, (4.298)
lbm ◦ R 1 lbm

ft
= 2468.32 . (4.299)
s

Matching the fan work to that of a second turbine requires

ṁ0 cP (T4 − T4b ) = αṁ0 cP (T2f − Tf ), (4.300)

T4 − T4b = α(T2f − Tf ), (4.301)
T4b = T4 − α(T2f − Tf ), (4.302)
T4b = 2013.15 ◦ R − 1.5(926.965 ◦ R − 480.119 ◦ R), (4.303)
= 1342.89 ◦ R. (4.304)

Use the isentropic relations to get the pressure after the second turbine P4b :
 γ/(γ−1)  1.4/(1.4−1)
T4b 1342.89 ◦ R
P4b = P4 = (39.5928 psia) = 9.59804 psia. (4.305)
T4 2013.15 ◦ R

Expansion through the nozzle completes the cycle. Assume an isentropic nozzle, therefore
 (γ−1)/γ
P5
T5 = T4b , (4.306)
P4b
 (γ−1)/γ
P1
= T4b , (4.307)
P4b
 (1.4−1)/1.4
◦ 5 psia
= = (1342.89 R) , (4.308)
9.59804 psia
= 1114.60 ◦ R. (4.309)

Now consider the energy balance in the nozzle:

u25 u24b
h5 + = h4b + , (4.310)
2 2
|{z}
small
u25
0 = h5 − h4b + , (4.311)
2
u25
= cP (T5 − T4b ) + , (4.312)
p 2
u5 = 2cP (T4b − T5 ), (4.313)
v !
u  
u Btu 25037 fts2
2

= t2 0.240 (1342.89 ◦ R − 1114.60 ◦ R) Btu

, (4.314)
lbm ◦ R 1 lbm

ft
= 1656.33 . (4.315)
s

CC BY-NC-ND. 19 January 2025, J. M. Powers.

4.3. RECIPROCATING ENGINE POWER CYCLES 141

Now find the thrust force magnitude

|F| = ṁ0 (u5 − u1 ) + αṁ0 (u5f − u1 ), (4.316)

     
lbm ft ft lbm ft ft
= 100 1656.33 − 850 + 1.5 100 2468.32 − 850 , (4.317)
s s s s s s
ft lbm
= 323380 , (4.318)
s2
323380 ft slbm
2
= , (4.319)
32.2 lbm ft
lbf s2
= 10042.9 lbf. (4.320)

The power is the product of the thrust force and the air speed, so
  
ft Btu
|ẆP | = |F · u1 | = (10042.9 lbf) 850 , (4.321)
s 777.5 ft lbf
Btu
= 10979.3 , (4.322)
s !
 
Btu 1.415 hp
= 10979.3 Btu
, (4.323)
s s
= 15535.8 hp. (4.324)

Now for the heat transfer in the combustion chamber

Q̇H = ṁ0 (h3 − h2 ), (4.325)

= ṁ0 cP (T3 − T2 ), (4.326)
  
lbm Btu
= 100 0.240 (2460 ◦ R − 926.965 ◦ R), (4.327)
s lbm ◦ R
Btu
= 36792.8 . (4.328)
s
So the overall efficiency is
Btu
ẆP 10979.3 s
ηO = = Btu
= 0.29841. (4.329)
Q̇H 36792.8 s

The overall efficiency increased.

4.3 Reciprocating engine power cycles

Here are some common notions for engines that depend on pistons driving in cylinders. The
piston has a bore diameter B. The piston is connected to the crankshaft, and the stroke S
of the piston is twice the radius of the crank, Rcrank :

S = 2Rcrank . (4.330)

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142 CHAPTER 4. CYCLE ANALYSIS

2Rcrank

Figure 4.9: Piston-cylinder configurations illustrating geometric definitions.

See Figure 4.9 for an illustration of this geometry for a piston-cylinder arrangement in two
configurations. The total displacement for all the cylinders is

Vdispl = Ncyl (Vmax − Vmin ) = Ncyl Acyl S. (4.331)

Note that
B2
Acyl = π . (4.332)
4
The compression ratio is not the ratio of pressures; it is the ratio of volumes:
Vmax
rv = CR = . (4.333)
Vmin
For these engines the volumes are closed in expansion and compression, so the net work is
I
wnet = P dv = Pmef f (vmax − vmin ). (4.334)

Here one has defined a mean effective pressure: Pmef f . The net work per cylinder per cycle
is
Wnet = mwnet = Pmef f m(vmax − vmin ) = Pmef f (Vmax − Vmin ). (4.335)
Now consider the total power developed for all the cylinders. Assume the piston operates at
a frequency of ν cycles/s:

Ẇnet = Ncyl Pmef f (Vmax − Vmin )ν. (4.336)

CC BY-NC-ND. 19 January 2025, J. M. Powers.

4.3. RECIPROCATING ENGINE POWER CYCLES 143

It is more common to express ν in revolutions per minute: RPM = ν(60 s/min), so

RPM
Ẇnet = Pmef f Ncyl (Vmax − Vmin ) s , (4.337)
| {z } 60 min
=Vdispl

RPM
= Pmef f Vdispl s . (4.338)
60 min

This applies for a two-stroke engine. If the engine is a four stroke engine, the net power is
reduced by a factor of 1/2.

4.3.1 Otto
The air-standard Otto cycle approximates the gasoline engine. It employs a fixed mass
approach.
Diagrams for P − v and T − s for the Otto cycle are shown in Figure 4.10.

P T

3
3

isentrope isochore

2
4
2 isentrope 4
1 isochore
1

v s

Figure 4.10: P − v and T − s diagrams for the Otto cycle.

One can outline the Otto cycle as follows:

• 1 → 2: isentropic compression in the compression stroke,

• 2 → 3: isochoric heating in the combustion stroke during spark ignition,

• 3 → 4: isentropic expansion in power stroke, and

• 4 → 1: isochoric rejection of heat to the surroundings.

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144 CHAPTER 4. CYCLE ANALYSIS

Note for isochoric heating, such as 2 → 3, in a fixed mass environment, the first law gives
Z v3
e3 − e2 = 2 q3 − 2 w3 = 2 q3 − P dv, (4.339)
v2
Z v2
e3 − e2 = 2 q3 − P dv, (4.340)
v2
| {z }
=0
2 q3 = e3 − e2 = cv (T3 − T2 ), if CPIG. (4.341)

The thermal efficiency is found as follows:

wnet qH − qL qL cv (T4 − T1 )
η = = =1− =1− , (4.342)
qH qH qH cv (T3 − T2 )
 
T4
T4 − T1 T1 T1 − 1
= 1− =1−  . (4.343)
T3 − T2 T T3 − 1 2 T2

Now one also has the isentropic relations:

 γ−1  γ−1
T2 V1 T3 V4
= , = . (4.344)
T1 V2 T4 V3
But V4 = V1 and V2 = V3 , so  γ−1
T3 V1 T2
= = . (4.345)
T4 V2 T1
Cross multiplying the temperatures, one finds
T3 T4
= . (4.346)
T2 T1
Thus the thermal efficiency reduces to

T1
η =1− . (4.347)
T2

In terms of the compression ratio rv = V1 /V2 , one has

1
η = 1 − rv1−γ = 1 − . (4.348)
rvγ−1

Note if the compression ratio increases, the thermal efficiency increases. High compression
ratios introduce detonation in the fuel air mixture. This induces strong pressure waves in
the cylinder and subsequent engine knock. It can cause degradation of piston walls. Some
deviations of actual performance from that of the air-standard Otto cycle are as follows:

CC BY-NC-ND. 19 January 2025, J. M. Powers.

4.3. RECIPROCATING ENGINE POWER CYCLES 145

• specific heats actually vary with temperature,

• combustion may be incomplete (induces pollution and lowers fuel efficiency),

• work of inlet and exhaust ignored, and

• losses of heat transfer to engine walls ignored.

Example 4.9
(adopted from Moran and Shapiro, p. 363). The temperature at the beginning of the compression
process of an air-standard Otto cycle with a compression ratio of 8 is 540 ◦ R, the pressure is 1 atm,
and the cylinder volume is 0.02 ft3 . The maximum temperature is 3600 ◦ R. Find

• temperature and pressure at each stage of the process,

• thermal efficiency, and

• Pmef f in atm.

For the isentropic compression,

 γ−1
V1
T2 = T1 , (4.349)
V2
= (540 ◦ R)(8)1.4−1 , (4.350)
◦
= 1240.69 R. (4.351)

One can use the ideal gas law to get the pressure at state 2:

P2 V2 P1 V1
= , (4.352)
T2 T1
V1 T2
P2 = P1 , (4.353)
V2 T1
 
1240.69 ◦ R
= (1 atm)(8) , (4.354)
540 ◦ R
= 18.3792 atm. (4.355)

Now V3 = V2 because the combustion is isochoric. And the maximum temperature is T3 = 3600 ◦ R.
This allows use of the ideal gas law to get P3 :

P3 V3 P2 V2
= , (4.356)
T3 T2
 
V2 T3 3600 ◦ R
P3 = P2 = (18.3792 atm)(1) = 53.3333 atm. (4.357)
V3 T2 1240.59 ◦ R
|{z}
=1

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146 CHAPTER 4. CYCLE ANALYSIS

One uses the isentropic relations for state 4:

 γ−1
T3 V4
= , (4.358)
T4 V3
 γ−1
T4 V3
= , (4.359)
T3 V4
 γ−1  1−γ
V2 V1
T4 = T3 = T3 = (3600 ◦ R)(8)1−1.4 = 1566.99 ◦ R. (4.360)
V1 V2

For the pressure at state 4, use the ideal gas law:

P4 V4 P3 V3
= , (4.361)
T4 T3
 
V3 T4 V2 T4 1 1566.99 ◦ R
P4 = P3 = P3 = (53.3333 atm) = 2.90184 atm. (4.362)
V4 T3 V1 T3 8 3600 ◦ R

The thermal efficiency is

1 1
η =1− =1− = 0.564725. (4.363)
rvγ−1 81.4−1

Now get the mean effective pressure Pmef f .

Wnet = Pmef f (Vmax − Vmin ), (4.364)

Wnet m(e3 − e4 ) + m(e1 − e2 )
Pmef f = = , (4.365)
Vmax − Vmin V1 − V2
cv T 3 − T 4 + T 1 − T 2 P1 V1 cv T3 − T4 + T1 − T2
= m V2
= , (4.366)
V1 1 − V1 RT1 V1 1 − VV12
P1 cv T3 − T4 + T1 − T2 P1 1 T3 − T4 + T1 − T2
= V
= , (4.367)
T1 R 1− V 2 T1 γ − 1
1
1 − VV2 1

1 atm 1 3600 ◦ R − 1566.99 ◦ R + 540 ◦ R − 1240.59 ◦ R

= , (4.368)
540 ◦ R 1.4 − 1 1 − 81
= 7.04981 atm. (4.369)

4.3.2 Diesel
The air standard Diesel cycle approximates the behavior of a Diesel engine. It is modeled
as a fixed mass system. Here the compression is done before injection, so there is no danger
of premature ignition due to detonation. No spark plugs are used. Diagrams for P − v and
T − s for the Diesel cycle are shown in Figure 4.11. One can outline the Diesel cycle as
follows:

• 1 → 2: isentropic compression in the compression stroke,

CC BY-NC-ND. 19 January 2025, J. M. Powers.

4.3. RECIPROCATING ENGINE POWER CYCLES 147

P T

2 3
3
isobar
isentrope 2
4
isentrope
4 1 isochore

v s

Figure 4.11: P − v and T − s diagrams for the Diesel cycle.

• 2 → 3: isobaric heating in the combustion stroke,

• 3 → 4: isentropic expansion in power stroke, and

• 4 → 1: isochoric rejection of heat to the surroundings.

The thermal efficiency is found as follows:

wnet qH − qL qL
η = = =1− , (4.370)
qH qH qH
T4
e4 − e1 cv (T4 − T1 ) 1 T1 T1
−1
= 1− =1− = 1− T3
. (4.371)
h3 − h2 cP (T3 − T2 ) γ T2 T2
−1

All else being equal, the Otto cycle will have higher efficiency than the Diesel cycle.
However, the Diesel can operate at higher compression ratios because detonation is not as
serious a problem in the compression ignition engine as it is in the spark ignition.

Example 4.10
(adopted from Borgnakke and Sonntag, Ex. 12.8 pp. 501-502). An air standard Diesel cycle has a
compression ratio of 20, and the heat transferred to the working fluid has 1800 kJ/kg. Take air to be
an ideal gas with variable specific heat. At the beginning of the compression process, P1 = 0.1 MPa,
and T1 = 15 ◦ C. Find
• Pressure and temperature at each point in the process,
• Thermal efficiency,
• Pmef f , the mean effective pressure.

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148 CHAPTER 4. CYCLE ANALYSIS

The enthalpies and entropies at the reference pressure for variable specific heat air are tabulated
as functions of temperature in Table A7.1. Recall that
Z T
h(T ) = href + cP (T̂ ) dT̂ . (4.372)
Tref

Recall further that

T ds = dh − v dP, (4.373)
dh v
ds = − dP. (4.374)
T T
Now for an ideal gas it can be shown that dh = cP (T ) dT ; one also has v/T = R/P . Making these
substitutions into Eq. (4.374) gives
cP (T ) dT dP
ds = −R . (4.375)
T P
Integrating gives
Z T
cP (T̂ ) P
s(T, P ) = sref + dT̂ −R ln , (4.376)
Tref T̂ Pref
| {z }
=so
T

P
s(T, P ) = soT (T ) − R ln . (4.377)
Pref
Here the reference pressure is Pref = 0.1 MPa. Note that this happens to be the inlet state, which
is a coincidence; so at the inlet there is no correction to the entropy for pressure deviation from its
reference value. At the inlet, one has T1 = 15 + 273.15 = 288.15 K. One then gets from interpolating
Table A7.1 that
kJ kJ kJ
h1 = 288.422 , soT1 = s1 = 6.82816 , e1 = 205.756 . (4.378)
kg kg K kg
For the isentropic compression, one has
kJ 1
s2 = s1 = 6.82816 , V2 = V1 . (4.379)
kg K 20
Now from the ideal gas law, one has
P2 V2 P1 V1
= , (4.380)
T2 T1
P2 T2 V1
= , (4.381)
P1 T1 V2
P2 T2
= 20 . (4.382)
Pref 288 K
Now
P2
s2 (T2 , P2 ) = soT2 − R ln , (4.383)
Pref
     
kJ kJ T2
6.82816 = soT2 − 0.287 ln 20 , (4.384)
kg K kg K 288 K
     
kJ T2 kJ
0 = soT2 − 0.287 ln 20 − 6.82816 ≡ F (T2 ). (4.385)
kg K 288 K kg K

CC BY-NC-ND. 19 January 2025, J. M. Powers.

4.3. RECIPROCATING ENGINE POWER CYCLES 149

   
kJ kJ
T2 (K) soT2 kg K
F (T2 ) kg K
−4
900 8.01581 8.57198 × 10
1000 8.13493 8.97387 × 10−2
800 7.88514 −9.60091 × 10−2
850 7.95207 −4.64783 × 10−2
899.347 8.01237 −2.37449 × 10−3

Table 4.3: Iteration for T2 .

This then becomes a trial and error search in Table A7.1 for the T2 which satisfies the previous equa-
tion. If one guesses T2 ∼ 900 K, one gets soT2 = 8.01581 kJ/kg/K, and the right side evaluates to
0.000857198 kJ/kg/K. Performing a trial and error procedure, one finds the results summarized in
Table 4.3. Take T2 = 900 K as close enough!
Then
T2 V1 900 K
P2 = P1 = (0.1 MPa) (20) = 6.25 MPa. (4.386)
T1 V2 288 K
Now at state 2, T2 = 900 K, one finds that
kJ kJ
h2 = 933.15 , e2 = 674.82 . (4.387)
kg kg
The heat is added at constant pressure, so
qH = h3 − h2 , (4.388)
h3 = h2 + qH , (4.389)
   
kJ kJ kJ
= 933.15 + 1800 = 2733.15 . (4.390)
kg kg kg
One can then interpolate Table A7.1 to find T3 and soT3
   
kJ kJ
2733.15 kg − 2692.31 kg
T3 = (2350 K) +     ((2400 K) − (2350 K)), (4.391)
kJ
2755 kg − 2692.31 kJ
kg

= 2382.17 K, (4.392)
 
kJ
soT3 = 9.16913
kg K
   
kJ    
2733.15 kJ
kg − 2692.31 kg kJ kJ
+     9.19586 − 9.16913 , (4.393)
kJ
2755 kg − 2692.31 kJ kg K kg K
kg
kJ
= 9.18633 . (4.394)
kg K

One also has P3 = P2 = 6.25 MPa. Now get the actual entropy at state 3:
P3
s3 (T3 , P3 ) = soT3 − R ln , (4.395)
Pref
     
kJ kJ 6.25 MPa kJ
= 9.18633 − 0.287 ln = 7.99954 . (4.396)
kg K kg K 0.1 MPa kg K

CC BY-NC-ND. 19 January 2025, J. M. Powers.

150 CHAPTER 4. CYCLE ANALYSIS

   
kJ kJ
T4 (K) soT4 kg K
F (T4 ) kg K
−1
400 7.15926 −9.34561 × 10
800 7.88514 −4.07614 × 10−1
1400 8.52891 7.55464 × 10−2
1200 8.34596 −6.31624 × 10−2
1300 8.44046 8.36535 × 10−3
1250 8.39402 −2.68183 × 10−2
1288 8.42931 −1.23117 × 10−4

Table 4.4: Iteration for T4 .

Now 3 → 4 is an isentropic expansion to state 4, which has the same volume as state 1; V1 = V4 . So
the ideal gas law gives
P4 V4 P1 V1
= , (4.397)
T4 T1
P4 T4 V1
= , (4.398)
P1 T1 V4
P4 T4 V1
= . (4.399)
Pref T1 V4

Now consider the entropy at state 4, which must be the same as that at state 3:
P4
s4 (T4 , P4 ) = soT4 − R ln , (4.400)
Pref
 
 T4 V1 
= soT4 − R ln 
s3 
 T1 V4  , (4.401)
|{z}
=1
     
kJ o kJ T4
7.99954 = sT4 − 0.287 ln , (4.402)
kg K kg K 288 K
     
o kJ T4 kJ
0 = sT4 − 0.287 ln − 7.99954 = F (T4 ). (4.403)
kg K 288 K kg K

Using Table A7.1, this equation can be iterated until T4 is found. So T4 = 1288 K. At this temperature,
one has
kJ kJ
h4 = 1381.68 , e4 = 1011.98 . (4.404)
kg kg
Now one can calculate the cycle efficiency:
   
kJ kJ
e4 − e1 1011.98 kg − 205.756 kg
η =1− =1−     = 0.552098. (4.405)
h3 − h2 2733.15 kJ
− 933.15 kJ
kg kg

Now one has

   
kJ kJ kJ
qL = e1 − e4 = 205.756 − 1011.98 = −806.224 . (4.406)
kg kg kg

CC BY-NC-ND. 19 January 2025, J. M. Powers.

4.3. RECIPROCATING ENGINE POWER CYCLES 151

So,    
kJ kJ kJ
wnet = qH + qL = 1800 − 806.224 = 993.776 . (4.407)
kg kg kg
So
Wnet wnet wnet wnet
Pmef f = = = = RT1
, (4.408)
Vmax − Vmin vmax − vmin v1 − v2 P1 − RTP2
2

kJ
993.776 kg
=  
= 1265.58 kPa. (4.409)
kJ 288 K 900 K
0.287 kg K 100 kPa − 6250 kPa

CC BY-NC-ND. 19 January 2025, J. M. Powers.

152 CHAPTER 4. CYCLE ANALYSIS

CC BY-NC-ND. 19 January 2025, J. M. Powers.

Chapter 5

Simple chemistry for propulsion

Powers, Chapters 1, 12,1

Farokhi, Chapter 7.

Let us consider a reactive gas that undergoes a simple exothermic conversion of chemical en-
ergy to thermal energy that may undergo further conversion to kinetic energy in a propulsion
application. The model is useful for general understanding, but does not have the precision
required for engineering design. It does have the correct features that lead to qualitative
understanding of how exothermic reaction affects flow dynamics and can induce thrust in
a propulsion device. We will use a simple model that loosely mimics combustion of stoi-
chiometric mixtures of hydrogen and air, as described by Powers (2016). We first give a
motivation from problems in high speed propulsion. We then describe a simple model for
time-dependent reaction. The chapter closes by applying this reaction model to a problem
of steady reactive flow in a variable area duct such as an afterburner or rocket nozzle. In
later chapters, we will employ more detailed models that better capture real chemistry and
flow.

5.1 Aerospace propulsion motivation

In traditional jet propulsion, reaction is sufficiently fast that the conversion of chemical to
thermal to kinetic energy takes place inside the engine. For high speed propulsion devices,
the reaction time may approach the residence time of a fluid particle inside a device. If the
chemical energy is not released within the device, there will be an adverse effect on propulsion.
Often in high speed propulsion devices, the release of chemical energy is triggered by a shock
wave. The shock wave raises the temperature and can ignite an exothermic chemical reaction.
This is also the foundational physics that drives a detonation, defined as a shock-induced
combustion process. Kailasanath2 reviews many of the basic concepts that link detonation
1
Powers, J. M., 2016, Combustion Thermodynamics and Dynamics, Cambridge University Press.
2
Kailasanath, K., 2000, Review of propulsion applications of detonation waves, AIAA Journal, 38(9):
1698-1708.

153
154 CHAPTER 5. SIMPLE CHEMISTRY FOR PROPULSION

with propulsion. One can study the figures in this paper to understand this linkage. One
can consider the following hierarchy of relevant ideas for a detonation:

• A piston driving a wave into a tube generates a shock wave traveling faster than the
speed of sound.

• Increasing the piston velocity increases the shock speed.

• The post-shock temperature rises as the shock speed rises.

• High post-shock temperature can induce combustion in reactive mixtures.

• Post-shock exothermic reaction can serve to aid the pushing of a shock via acoustic
transmission of energy to the shock.

• If the supporting piston is withdrawn, the energy to drive the wave comes exclusively
from the exothermic reaction.

• A purely reaction-driven wave will travel at a moderately supersonic speed, and the
end of the reaction zone will correspond to a sonic state that is thermally choked.

• This state is known as the Chapman-Jouguet state.

• The thickness of the reaction wave is finite, and increases as density is lowered, which
is relevant to high-altitude conditions.

A simplistic view of several exotic high-speed air-breathing aerospace propulsion devices is

one the rides a reactive wave.

• A ram accelerator is propelled into a pre-mixed fuel air mixture, and may be boosted
to a high Mach number to a steady state where combustion-induced thrust balances
drag. See Grismer and Powers3 or Humphrey and Sobota.4

• A wave-rider engine requires injection of on-board fuel into an internal or external air
stream and mixing of fuel and air in flight.

Understanding of these devices is often attempted with traditional cycle analysis. However,
such analysis is unable to address real features such as

• the effects of finite rate exothermic chemistry that induces a competition between a
fluid particle’s residence time inside a combustor and reaction time required to release
its chemical energy,
3
Grismer, M. J., and Powers, J. M., 1995, Calculations for steady propagation of a generic ram accelera-
tor configuration, Journal of Propulsion and Power, 11(1): 105-111.
4
Humphrey, J. W., and Sobota, T. H., 1991, Beyond rockets: the scramaccelerator, Aerospace America,
29(6): 18-21.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

5.2. TIME-DEPENDENT SIMPLE REACTION, WITHOUT FLOW 155

• the effects of fluid mechanics, both one-dimensional acoustics and multidimensional

compressible flow features such as oblique shocks, Prandtl-Meyer rarefactions, etc.
One can find a compelling case for the importance of detailed chemistry in propulsion,
based on work that had its genesis in a discussion group that met in 1989 in 356 Fitzpatrick
to consider wavelet analysis5 , and was represented by the Ph.D. work of Notre Dame student,
Dr. Oleg Vasilyev6 and many co-workers7 , one can view a video of Lichtl and Jones.8

5.2 Time-dependent simple reaction, without flow

First consider a simple binary mixture of two gases labelled A and B. Let us consider A to
be the reactant and B to be the product. Both A and B share many of the same properties,
including the same molecular mass, the same specific heat, modeled as a constant, and are
both ideal gases. The chemical reaction is taken to be exothermic and irreversible:

A → B. (5.1)

Initially the mixture is completely composed of A, and at the completion of reaction it is

completely composed of B. We take the mass fraction of each component to be YA and YB .
By nature of the mass fraction, we require

YA + YB = 1. (5.2)

We take the specific heat at constant volume for each component to be identical, cvA =
cvB = cv so that the mixture specific heat is

cv = YA cvA + YB cvB = YA cv + YB cv = (YA + YB )cv = cv . (5.3)

We take the internal energy of A and B to be

eA = cv T, eB = cv T − q. (5.4)

We see that eA − eB = q. With q > 0, we recognize this models positive chemical energy
residing in A. The mixture internal energy is

e = YA eA + YB eB , (5.5)
= (1 − YB )cv T + YB (cv T − q), (5.6)
= cv T − YB q. (5.7)
5
Strang, G., 1989, Wavelets and dilation equations: a brief introduction, SIAM Review, 31(4): 614-627.
6
Vasilyev, O. V., Paolucci, S. and Sen, M., 1995, A multilevel wavelet collocation method for solving par-
tial differential equations in a finite domain, Journal of Computational Physics, 120: 33-47.
7
Singh, S., Rastigejev, Y., Paolucci, S., and Powers, J. M., 2001, Viscous detonation in H2 − O2 − Ar us-
ing intrinsic low dimensional manifolds and wavelet adaptive multilevel representation, Combustion Theory
and Modelling, 5: 163-184.
8
Lichtl, A., and Jones, S, 2015, GPUs to Mars: full scale simulation of SpaceX’s Mars rocket engine.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

156 CHAPTER 5. SIMPLE CHEMISTRY FOR PROPULSION

We note initially that YA = 1 and YB = 0. At reaction completion, we have YA = 0 and

YB = 1. Let us define a reaction progress variable λ:

λ = YB . (5.8)

This gives YA = 1 − λ. At the initial state, we have λ = 0. At the final state, we have λ = 1.
So our caloric state equation for the mixture internal energy is

e = cv T − λq. (5.9)

In contrast to an inert ideal gas which has e = e(T ), for a reactive ideal gas, we have

e = e(T, λ). (5.10)

That is the internal energy is a function of both temperature and composition. Consider
combustion of the mixture in a closed, isochoric, adiabatic box. For such a mixture, we have

dE = δQ − δW. (5.11)

Because it is isochoric, δW = 0. Because it is adiabatic, δQ = 0. So we must have

dE = 0. (5.12)

Because it is closed, the mass in the box, m, remains constant. So with E = mE, we have

d(me) = 0, m de = 0, de = 0. (5.13)

Thus,

e = eo . (5.14)

The internal energy must remain constant. At the initial state, we can expect T = To and
λ = 0. So

eo = cv To − 0q = cv To . (5.15)

At the final state, λ = 1, but e still must be eo . To achieve this T must change. In general,
we have

eo = cv To = cv T − λq, (5.16)
λq
T = To + . (5.17)
cv
So at the final state, we have
q
Tf = To + . (5.18)
cv

CC BY-NC-ND. 19 January 2025, J. M. Powers.

5.2. TIME-DEPENDENT SIMPLE REACTION, WITHOUT FLOW 157

Exothermic reaction does not change the energy, but does increase the temperature.
Now let us consider the dynamics of the reaction, also called the kinetics of the reaction.
Let us adopt a common model that asserts the following for one-step kinetics:

dρA −E
= −ρA ae RT , (5.19)
dt
dρB −E
= ρA ae RT . (5.20)
dt
The molar concentration of A goes down for the irreversible reaction A → B and that of B
goes up. We can relate the molar concentration of species i to the mass fraction of species
i, Yi :

molesi molesi total mass massi molesi total mass massi ρYi
ρi = = = = . (5.21)
volume volume total mass massi mass volume total mass Mi
| {z i} | {z } | {z }
1/Mi ρ Yi

Thus, our kinetics becomes

 
d ρYA ρYA −E
= − ae RT , (5.22)
dt MA MA
 
d ρYB ρYA −E
= ae RT . (5.23)
dt MB MA

The term ρYA /MA is the molar concentration of A, and ρYB /MB is the molar concentration
of B. Here E is the activation energy, a is the collision frequency factor and models the
collision of gas molecules. This can be shown to be a special case of the well-known model of
the law of mass action with Arrhenius kinetics. For our simple model, we take MA = MB .
And because our system is isochoric and closed, we have ρ to be a constant. So the system
simplifies to

dYA −E
= −YA ae RT , (5.24)
dt
dYB −E
= YA ae RT . (5.25)
dt
Note that YA decreases for YA ∈ [0, 1] and YB increases for YA ∈ [0, 1]. When the reaction is
complete, YA = 0, and the system is in equilibrium. We add the two equations and get

d
(YA + YB ) = 0. (5.26)
dt
So, applying the initial conditions, we get, as desired

YA + YB = 1. (5.27)

CC BY-NC-ND. 19 January 2025, J. M. Powers.

158 CHAPTER 5. SIMPLE CHEMISTRY FOR PROPULSION

lambda T K
1.0 3000

0.8
2500

0.6
2000
0.4

1500
0.2

10 9 9
t9 s t9 s
5. 10 1. 10 1.5 10 2. 10 10 9 9
5. 10 1. 10 1.5 10 2. 10

Figure 5.1: Plot of λ(t), T (t) for simple kinetics problem with E = 0.

Let us then focus on B and use YB = λ to get

dλ E
= a(1 − λ)e− RT . (5.28)
dt
Iff E = 0, there is a simple exact solution:

λ = 1 − e−at , if E = 0. (5.29)

In this case the time constant of reaction is τ = 1/a. We see that λ begins at zero, and after
a few time constants, approaches unity. Then in this limit, we get a simple expression for
the temperature evolution:
q
T (t) = To + λ(t), (5.30)
cv
q

= To + 1 − e−at , if E = 0. (5.31)
cv
Consider some parameters, some of which are appropriate for hydrogen-air combustion.
Take To = 1000 K, γ = 7/5, R = 397.58 J/kg/K, cv = R/(γ − 1) = 993.95 J/kg/K,
q = 1.89566 × 106 J/kg, a = 5 × 109 s−1 , E = 0 J/kg. We plot λ(t) and T (t) in Fig. 5.1. We
see that as t → ∞ that
q
λ → 1, T → To + = 2907.11 K. (5.32)
cv
For nonzero E, we get a single differential equation for which numerical solution is re-
quired:
 
dλ −E
= a(1 − λ) exp , λ(0) = 0. (5.33)
dt R (To + λq/cv )

We solve this with the same parameters as before, except we take E = 8.29352 × 106 J/kg.
We plot λ(t) and T (t) in Fig. 5.2. We see again that as t → ∞ that

CC BY-NC-ND. 19 January 2025, J. M. Powers.

5.3. STEADY NOZZLE FLOW WITH SIMPLE REACTION 159

T K
1.0 3000

0.8
adiabatic flame
2500 temperature
0.6
induction time
2000
0.4

0.2 1500

t s t s
0.002 0.004 0.006 0.008 0.010 0.002 0.004 0.006 0.008 0.010

Figure 5.2: Plot of λ(t), T (t) for simple kinetics problem with E = 8.29352 × 106 J/kg.

q
λ → 1, T → To + = 2907.11 K. (5.34)
cv
Importantly, and consistent with nature, we see that the reaction incubates for t ∈ [0, 0.006 s].
In this time frame, only small temperature rises are predicted with an associated small change
in λ. However near the induction time, t ∼ 0.006 s, the reaction becomes vigorous. It may be
said to have ignited. The temperature rises rapidly and the reactants are rapidly depleted.
Once λ ∼ 1, the reaction is over and the material has reached its adiabatic flame temperature.
Note the adiabatic flame temperature is not a thermodynamic property, but depends on the
initial state of the system.

5.3 Steady nozzle flow with simple reaction

To consider reactive flow with area change, let us first extend Eqs. (5.22, 5.23) to
   
∂ ρAYA ∂ ρuAYA ρYA −E
+ = −A ae RT , (5.35)
∂t MA ∂x MA MA
   
∂ ρAYB ∂ ρuAYB ρYA −E
+ = A ae RT . (5.36)
∂t MB ∂x MB MA
When we impose our simplifying assumption of MA = MB , and add the two equations, and
recognize YA + YB = 1, we recover global mass conservation, Eq. (2.3). Then Eq. (5.36)
simplifies, after taking λ = YB , to
∂ ∂ −E
(ρAλ) + (ρuAλ) = Aρ(1 − λ)ae RT . (5.37)
∂t ∂x
Using the product rule, this expands to
   
∂ ∂ ∂λ ∂λ −E
λ (ρA) + (ρuA) +ρA +u = Aρ(1 − λ)ae RT , (5.38)
∂t ∂x ∂t ∂x
| {z }
=0
∂λ ∂λ −E
+u = a(1 − λ)e RT . (5.39)
∂t ∂x

CC BY-NC-ND. 19 January 2025, J. M. Powers.

160 CHAPTER 5. SIMPLE CHEMISTRY FOR PROPULSION

This is the extension of Eq. (5.28). In the steady state limit, this becomes

dλ −E
u = a(1 − λ)e RT . (5.40)
dx
Let us now pose a system of coupled nonlinear first order ordinary differential equations that
represent the following physics that might be present in a turbojet afterburner or rocket
nozzle:

• steady,

• area change allowed,

• no friction.

• no wall heat transfer,

• calorically perfect mixture of two ideal gases with identical molecular masses,

• simple one-step irreversible exothermic chemistry.

With these assumptions, we get Eqs. (2.98, 2.99, 2.37, 5.40) and the thermodynamic state
equations to reduce to

dρ du ρu dA
u +ρ = − , (5.41)
dx dx A dx
du dP
ρu + = 0, (5.42)
dx dx
de P dρ
ρ − = 0, (5.43)
dx ρ dx
dλ −E
u = a(1 − λ)e RT , (5.44)
dx
e = cv T − λq, (5.45)
P = ρRT. (5.46)

Note that cv = R/(γ − 1). Focus on the state variables ρ, u, P , and λ. We get

P 1 P
T = , e= − λq. (5.47)
ρR γ −1 ρ

Then we see
de 1 1 dP 1 P dρ dλ
= − 2
−q . (5.48)
dx γ − 1 ρ dx γ − 1 ρ dx dx

CC BY-NC-ND. 19 January 2025, J. M. Powers.

5.3. STEADY NOZZLE FLOW WITH SIMPLE REACTION 161

The first law of thermodynamics, Eq. (2.37), then becomes

1 dP 1 P dρ dλ P dρ
− − ρq − = 0, (5.49)
γ − 1 dx γ − 1 ρ dx dx ρ dx
| {z }
ρ de/dx
dP P dρ dλ P dρ
− − (γ − 1)ρq − (γ − 1) = 0, (5.50)
dx ρ dx dx ρ dx
dP P dρ dλ
−γ = (γ − 1)ρq , (5.51)
dx ρ dx dx
−Eρ
e P
= (γ − 1)ρqa(1 − λ) . (5.52)
u
So our system is
dρ du ρu dA
u +ρ = − , (5.53)
dx dx A dx
du dP
ρu + = 0, (5.54)
dx dx
−Eρ
dP P dρ e P
−γ = (γ − 1)ρqa(1 − λ) , (5.55)
dx ρ dx u
dλ −Eρ
u = a(1 − λ)e P . (5.56)
dx
Noting that the square of the sound speed for the CPIG is c2 = γP/ρ, we can uncouple these
equations to write them in canonical form:

−Eρ
dρ u − ρu dA
A dx
+ (γ − 1) uρ qa(1 − λ)e P
= (5.57)
dx u 2 − c2

−Eρ
du −c2 − ρu dA
A dx
− (γ − 1)ρqa(1 − λ)e P
= (5.58)
dx ρ (u2 − c2 )

−Eρ
dP uc2 − ρu dA
A dx
+ (γ − 1)ρuqa(1 − λ)e P
= , (5.59)
dx u 2 − c2
−Eρ
dλ a(1 − λ)e P
= . (5.60)
dx u
As an aside, we could show the appropriate sound speed is better described as the frozen
sound speed as it is relevant for the limit in which species mass fraction does not change.
That is, it is said to be frozen. We would find then that for this simple reactive flow that
∂P
c2 = .
∂ρ s,λ

We could also say

ρ −Eρ
Q = (γ − 1) qa(1 − λ)e P . (5.61)
u

CC BY-NC-ND. 19 January 2025, J. M. Powers.

162 CHAPTER 5. SIMPLE CHEMISTRY FOR PROPULSION

With this, we then get

dρ u − ρu dA
A dx
+Q
= (5.62)
dx u 2 − c2

du −c − ρu
2 dA
A dx
− uQ
= (5.63)
dx ρ (u2 − c2 )


dP uc2 − ρu dA
A dx
+ u2 Q
= , (5.64)
dx u 2 − c2
−Eρ
dλ a(1 − λ)e P
= . (5.65)
dx u
Consider now an example of reacting flow in a duct. Take the area to be

A(x) = 1 + x − x2 /2. (5.66)

Here the area has units of m2 when x has the units of m. So

dA
= 1 − x. (5.67)
dx
Consider the parameters, some of which are appropriate for hydrogen-air combustion. Take
now T1 = 1676.81 K, ρ1 = 4.2 kg/m3 , u1 = 2500 m/s, γ = 7/5, R = 397.58 J/kg/K, cv =
R/(γ −1) = 993.95 J/kg/K, q = 1.89566×106 J/kg, a = 5×109 s−1 , E = 8.29352×106 J/kg.
These conditions are slightly different than the previous problem. The temperature and
density are elevated, and the flow velocity can be shown to be supersonic. Relevant plots are
given in Fig. 5.3. These results can be compared with the predictions of a detailed chemical
kinetics model of a mixture of calorically imperfect gases; see the upcoming Fig. 7.8 that
plots T (x) for the same geometry and inlet conditions for an H2 − O2 − N2 mixture. A
good check on the numerical solution is to see that mass flow rate, ṁ = ρ(x)u(x)A(x), and
stagnation enthalpy, ho = e(x) + P (x)/ρ(x) + u(x)2 /2, are constant. Relevant plots of their
relative errors are given in Fig. 5.4. The error is likely due to finite values of ∆x employed
in the numerical simulation as well as accumulated roundoff error. The error can be reduced
by using finer discretizations for ∆x and higher precision in representation of real numbers
in the numerical solution of the governing equations.
The partition of stagnation enthalpy into chemical, thermal, and kinetic components
evolves over distance in the duct. But the stagnation enthalpy remains constant. We must
have
1
ho = cP T (x) + u(x)2 − qλ(x). (5.68)
2
Relevant plots of their relative values, cP T (x)/ho , u(x)2 /2/ho , and −qλ(x)/ho , are given in
Fig. 5.5. Note that ho is not the sum of positive definite terms, as cP T > 0, u2 /2 > 0, −qλ <
0. Clearly the chemical energy drops as the fluid reacts. Initially this is transformed into
thermal energy. As the flow expands through the nozzle, the thermal energy is transformed

CC BY-NC-ND. 19 January 2025, J. M. Powers.

5.3. STEADY NOZZLE FLOW WITH SIMPLE REACTION 163

u ms

5.0 2500

2400
4.5

2300
4.0

2200
3.5

2100
3.0
x m x m
0.2 0.4 0.6 0.8 1.0 0.2 0.4 0.6 0.8 1.0
P Pa
8 106
1.0
6
7 10
0.8
6 106
0.6
5 106
0.4
4 106
0.2
x m
0.2 0.4 0.6 0.8 1.0 x m
0.2 0.4 0.6 0.8 1.0

T K M
2.6

3500 2.4

2.2
3000
2.0
2500
1.8

2000 1.6

x m x m
0.2 0.4 0.6 0.8 1.0 0.2 0.4 0.6 0.8 1.0

Figure 5.3: Plot of flow variables for exothermic reactive flow in a duct with simple kinetics,
a = 5 × 109 s−1 .
relative stagnation enthalpy error
relative mass flow rate error 8. 10 8

8
6. 10 8 6. 10

8 8
4. 10 4. 10

8
2. 10 2. 10 8

x m
0.2 0.4 0.6 0.8 1.0 x m
0.2 0.4 0.6 0.8 1.0

Figure 5.4: Relative error in mass flow rate ṁ = ρuA and stagnation enthalpy, ho = e +
P/ρ + u2 /2 for exothermic reactive flow in a duct with simple kinetics.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

164 CHAPTER 5. SIMPLE CHEMISTRY FOR PROPULSION

1.0 thermal

0.8

0.6
kinetic
0.4

0.2

0.01 0.1 1 x (m)

-0.2
chemical
- 0.4

Figure 5.5: Partition of stagnation enthalpy for reactive flow in a variable area duct as a
function of distance.
1.0

0.8
thermal

0.6

0.4
kinetic
0.2
chemical
0.0
0.01 0.1 1 x (m)

Figure 5.6: Improved partition of stagnation enthalpy for reactive flow in a variable area
duct as a function of distance.

into kinetic energy. The scaled thermal, kinetic, and chemical energies add to unity, thus
preserving ho . Let us rescale so that we can better ascertain the partition of chemical,
thermal, and kinetic energy. Recall YA = 1 − λ. So we must have
1
ho = cP T + u2 − q(1 − YA ), (5.69)
2
1
ho + q = cP T + u2 + qYA , (5.70)
2
cP T u2 qYA
1 = + + . (5.71)
ho + q 2(ho + q) ho + q
This improved partition consisting of positive definite components is given in Fig. 5.6.
If we slow the chemical reaction, perhaps by introducing a more stable fuel, the energy
release from reaction becomes more distributed through the nozzle. Let us conduct the same
simulation, except that we reduce the collision frequency factor by a factor of twenty to
a = 2.5 × 108 s−1 . Relevant plots of T (x) and λ(x) are given in Fig. 5.7.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

5.3. STEADY NOZZLE FLOW WITH SIMPLE REACTION 165

T K 1.0
3500
0.8
3000 0.6

2500 0.4

2000 0.2

x m x m
0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0

Figure 5.7: Temperature T (x) and reaction progress λ(x) for flow in a diverging nozzle with
slower reaction kinetics, a = 2.5 × 108 s−1 .

T K 0.10

1650 0.08
1600 0.06
1550
0.04
1500
0.02
1450
x m x (m)
0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0

Figure 5.8: Temperature T (x) and reaction progress λ(x) for flow in a diverging nozzle with
very slow reaction kinetics, a = 1 × 107 s−1 .

If we slow the chemical reaction even more, perhaps by introducing an even more stable
fuel, the energy release from reaction may not primarily occur in the nozzle. Let us conduct
the same simulation, except that we now reduce the collision frequency factor by a factor to
a = 1 × 107 s−1 . Relevant plots of T (x) and λ(x) are given in Fig. 5.8.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

166 CHAPTER 5. SIMPLE CHEMISTRY FOR PROPULSION

CC BY-NC-ND. 19 January 2025, J. M. Powers.

Chapter 6

Chemical kinetics

Powers, Chapter 1,
Farokhi, Chapter 7.

Let us consider the reaction of N molecular chemical species composed of L elements via J
chemical reactions. Let us assume the gas is an ideal mixture of ideal gases that satisfies
Dalton’s law of partial pressures. The reaction will be considered to be driven by molecular
collisions. We will not model individual collisions, but instead attempt to capture their
collective effect.
An example of a model of such a reaction is listed in Table 6.1. There we find a N = 9
species, J = 37 step irreversible reaction mechanism for an L = 3 hydrogen-oxygen-argon
mixture from Maas and Warnatz,1 with corrected fH2 from Maas and Pope.2 The model has
also been utilized by Fedkiw, et al.3 We need not worry yet about fH2 , which is known as
a collision efficiency factor. The one-sided arrows indicate that each individual reaction is
considered to be irreversible. Note that for nearly each reaction, a separate reverse reaction is
listed; thus, pairs of irreversible reactions can in some sense be considered to model reversible
reactions.
In this model a set of elementary reactions are hypothesized. For the j th reaction we have
the collision frequency factor aj , the temperature-dependency exponent βj and the activation
energy E j . These will be explained in short order. Other common forms exist. Often
reactions systems are described as being composed of reversible reactions. Such reactions are
usually notated by two sided arrows. One such system is reported by Powers and Paolucci4
reported here in Table 6.2. Both overall models are complicated.
1
Maas, U., and Warnatz, J., 1988, Ignition processes in hydrogen-oxygen mixtures, Combustion and
Flame, 74(1): 53-69.
2
Maas, U., and Pope, S. B., 1992, Simplifying chemical kinetics: intrinsic low-dimensional manifolds in
composition space, Combustion and Flame, 88(3-4): 239-264.
3
Fedkiw, R. P., Merriman, B., and Osher, S., 1997, High accuracy numerical methods for thermally per-
fect gas flows with chemistry, Journal of Computational Physics, 132(2): 175-190.
4
Powers, J. M., and Paolucci, S., 2005, Accurate spatial resolution estimates for reactive supersonic flow
with detailed chemistry, AIAA Journal, 43(5): 1088-1099.

167
168 CHAPTER 6. CHEMICAL KINETICS

 PN 
(mol/cm3 )(
′
1−νM,j − ′
i=1 νij ) kJ


j Reaction aj s Kβj
βj Ej mole

1 O2 + H → OH + O 2.00 × 1014 0.00 70.30

2 OH + O → O2 + H 1.46 × 1013 0.00 2.08
3 H2 + O → OH + H 5.06 × 104 2.67 26.30
4 OH + H → H2 + O 2.24 × 104 2.67 18.40
5 H2 + OH → H2 O + H 1.00 × 108 1.60 13.80
6 H2 O + H → H2 + OH 4.45 × 108 1.60 77.13
7 OH + OH → H2 O + O 1.50 × 109 1.14 0.42
8 H2 O + O → OH + OH 1.51 × 1010 1.14 71.64
9 H + H + M → H2 + M 1.80 × 1018 −1.00 0.00
10 H2 + M → H + H + M 6.99 × 1018 −1.00 436.08
11 H + OH + M → H2 O + M 2.20 × 1022 −2.00 0.00
12 H2 O + M → H + OH + M 3.80 × 1023 −2.00 499.41
13 O + O + M → O2 + M 2.90 × 1017 −1.00 0.00
14 O2 + M → O + O + M 6.81 × 1018 −1.00 496.41
15 H + O2 + M → HO2 + M 2.30 × 1018 −0.80 0.00
16 HO2 + M → H + O2 + M 3.26 × 1018 −0.80 195.88
17 HO2 + H → OH + OH 1.50 × 1014 0.00 4.20
18 OH + OH → HO2 + H 1.33 × 1013 0.00 168.30
19 HO2 + H → H2 + O2 2.50 × 1013 0.00 2.90
20 H2 + O2 → HO2 + H 6.84 × 1013 0.00 243.10
21 HO2 + H → H2 O + O 3.00 × 1013 0.00 7.20
22 H2 O + O → HO2 + H 2.67 × 1013 0.00 242.52
23 HO2 + O → OH + O2 1.80 × 1013 0.00 −1.70
24 OH + O2 → HO2 + O 2.18 × 1013 0.00 230.61
25 HO2 + OH → H2 O + O2 6.00 × 1013 0.00 0.00
26 H2 O + O2 → HO2 + OH 7.31 × 1014 0.00 303.53
27 HO2 + HO2 → H2 O2 + O2 2.50 × 1011 0.00 −5.20
28 OH + OH + M → H2 O2 + M 3.25 × 1022 −2.00 0.00
29 H2 O2 + M → OH + OH + M 2.10 × 1024 −2.00 206.80
30 H2 O2 + H → H2 + HO2 1.70 × 1012 0.00 15.70
31 H2 + HO2 → H2 O2 + H 1.15 × 1012 0.00 80.88
32 H2 O2 + H → H2 O + OH 1.00 × 1013 0.00 15.00
33 H2 O + OH → H2 O2 + H 2.67 × 1012 0.00 307.51
34 H2 O2 + O → OH + HO2 2.80 × 1013 0.00 26.80
35 OH + HO2 → H2 O2 + O 8.40 × 1012 0.00 84.09
36 H2 O2 + OH → H2 O + HO2 5.40 × 1012 0.00 4.20
37 H2 O + HO2 → H2 O2 + OH 1.63 × 1013 0.00 132.71

Table 6.1: Third body collision efficiencies with M are fH2 = 1.00, fO2 = 0.35, and
fH2 O = 6.5.
CC BY-NC-ND. 19 January 2025, J. M. Powers.
 169

 PN 
(mol/cm3 )(
′
1−νM,j − ′
i=1 νij ) cal


j Reaction aj s K βj βj Ej mole
13
1 H2 + O2 ⇋ OH + OH 1.70 × 10 0.00 47780
2 OH + H2 ⇋ H2 O + H 1.17 × 109 1.30 3626
3 H + O2 ⇋ OH + O 5.13 × 1016 −0.82 16507
4 O + H2 ⇋ OH + H 1.80 × 1010 1.00 8826
5 H + O2 + M ⇋ HO2 + M 2.10 × 1018 −1.00 0
6 H + O2 + O2 ⇋ HO2 + O2 6.70 × 1019 −1.42 0
7 H + O2 + N2 ⇋ HO2 + N2 6.70 × 1019 −1.42 0
8 OH + HO2 ⇋ H2 O + O2 5.00 × 1013 0.00 1000
9 H + HO2 ⇋ OH + OH 2.50 × 1014 0.00 1900
10 O + HO2 ⇋ O2 + OH 4.80 × 1013 0.00 1000
11 OH + OH ⇋ O + H2 O 6.00 × 108 1.30 0
12 H2 + M ⇋ H + H + M 2.23 × 1012 0.50 92600
13 O2 + M ⇋ O + O + M 1.85 × 1011 0.50 95560
14 H + OH + M ⇋ H2 O + M 7.50 × 1023 −2.60 0
15 H + HO2 ⇋ H2 + O2 2.50 × 1013 0.00 700
16 HO2 + HO2 ⇋ H2 O2 + O2 2.00 × 1012 0.00 0
17 H2 O2 + M ⇋ OH + OH + M 1.30 × 1017 0.00 45500
18 H2 O2 + H ⇋ HO2 + H2 1.60 × 1012 0.00 3800
19 H2 O2 + OH ⇋ H2 O + HO2 1.00 × 1013 0.00 1800

Table 6.2: Nine species, nineteen step reversible reaction mechanism for an H2 /O2 /N2 mix-
ture. Third body collision efficiencies with M are f5 (H2 O) = 21, f5 (H2 ) = 3.3, f12 (H2 O) = 6,
f12 (H) = 2, f12 (H2 ) = 3, f14 (H2 O) = 20.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

170 CHAPTER 6. CHEMICAL KINETICS

These kinetics models describe the relaxation to a state of chemical equilibrium. The
chemical equilibrium behavior of the components of air is clearly displayed in Fig. 6.1. Here

Figure 6.1: Equilibrium composition of air at low density and various temperatures. Figure
from W. E. Moeckel and K. C. Weston, 1958, Composition and thermodynamic properties
of air in chemical equilibrium, NACA Technical Note 4265.

we see at low temperatures, T < 1000 K, diatomic N2 and O2 are dominant in air. Both of
these major components begin to dissociate at higher temperatures. For T > 6000 K, we no
longer find diatomic N2 and O2 , but instead find their monatomic components N and O. At
higher temperatures still, the molecule loses electrons, and positive ions remain.

6.1 Isothermal, isochoric kinetics

For simplicity, we will first focus attention on cases in which the temperature T and vol-
ume V are both constant. Such assumptions are known as “isothermal” and “isochoric,”
respectively. A nice fundamental treatment of elementary reactions of this type is given by
Vincenti and Kruger in their detailed monograph.5
5
W. G. Vincenti and C. H. Kruger, 1965, Introduction to Physical Gas Dynamics, Wiley, New York.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

6.1. ISOTHERMAL, ISOCHORIC KINETICS 171

6.1.1 O − O2 dissociation and recombination

One of the simplest physical examples is provided by the dissociation of O2 into its atomic
component O and its potential recombination back to O2 .

[Link] Pair of irreversible reactions

To get started, let us focus for now only on reactions 13 and 14 from Table 6.1 in the limiting
case in which temperature T and volume V are constant.

[Link].1 Mathematical model The reactions describe oxygen dissociation and recom-
bination in a pair of irreversible reactions:

13 : O + O + M → O2 + M, (6.1)
14 : O2 + M → O + O + M, (6.2)

with
 −2
17 mole K kJ
a13 = 2.90 × 10 3
, β13 = −1.00, E 13 = 0 , (6.3)
cm s mole
 −1
18 mole K kJ
a14 = 6.81 × 10 3
, β14 = −1.00, E 14 = 496.41 . (6.4)
cm s mole

The irreversibility is indicated by the one-sided arrow. Though they participate in the overall
hydrogen oxidation problem, these two reactions are in fact self-contained. So let us just
consider that we have only oxygen in our box with N = 2 species, O2 and O, J = 2 reactions
(those being 13 and 14), and L = 1 element, that being O.
Recall that in the cgs system, common in thermochemistry, that 1 erg = 1 dyne cm =
10 J = 10−10 kJ. Recall also that the cgs unit of force is the dyne and that 1 dyne =
−7

1 g cm/s2 = 10−5 N. So for cgs we have

erg kJ  10 erg  erg

E 13 = 0 , E 14 = 496.41 10 = 4.96 × 1012 . (6.5)
mole mole kJ mole

The standard model for chemical reaction induces the following two ordinary differential
equations for the evolution of O and O2 molar concentrations:

CC BY-NC-ND. 19 January 2025, J. M. Powers.

172 CHAPTER 6. CHEMICAL KINETICS

   
dρO β13 −E 13 β14 −E 14
= −2 a13 T exp ρO ρO ρM +2 a14 T exp ρO2 ρM , (6.6)
dt RT RT
| {z } | {z }
=k13 (T ) =k14 (T )
| {z } | {z }
=r13 =r14
| {z }
=ω̇O
   
dρO2 β13 −E 13 β14 −E 14
= a13 T exp ρO ρO ρM − a14 T exp ρO2 ρM . (6.7)
dt RT RT
| {z } | {z }
=k13 (T ) =k14 (T )
| {z } | {z }
=r13 =r14
| {z }
=ω̇O2

Here we use the notation ρi as the molar concentration of species i. Also a common usage
for molar concentration is given by square brackets, e.g. ρO2 = [O2 ]. We can also relate the
molar concentration of species i to the mass fraction of species i, Yi :
molesi molesi total mass massi molesi total mass massi ρYi
ρi = = = = . (6.8)
volume volume total mass massi massi | volume
{z } total{zmass} Mi
|
| {z }
1/Mi ρ Yi

The symbol M represents an arbitrary third body which is an inert participant in the reaction.
We also use the common notation of a temperature-dependent portion of the reaction rate
for reaction j, kj (T ), where
 
βj −E j
kj (T ) = aj T exp . (6.9)
RT

The symbol R is the universal gas constant:

J  
7 erg erg
R = 8.31441 10 = 8.31441 × 107 . (6.10)
mole K J mole K
The reaction rates for reactions 13 and 14 are defined as

r13 = k13 ρO ρO ρM , r14 = k14 ρO2 ρM . (6.11)

We will give details of how to generalize this form later. The system Eq. (6.6-6.7) can be
written simply as
dρO
= −2r13 + 2r14 ≡ ω̇O , (6.12)
dt
dρO2
= r13 − r14 ≡ ω̇O2 . (6.13)
dt

CC BY-NC-ND. 19 January 2025, J. M. Powers.

6.1. ISOTHERMAL, ISOCHORIC KINETICS 173

Even more simply, in vector form, Eqs. (6.12-6.13) can be written as

dρ
= ω̇, with ω̇ ≡ ν · r. (6.14)
dt
Here we have taken
     
ρO −2 2 r
ρ= , ν= , r = 13 . (6.15)
ρO2 1 −1 r14
In general, we will have ρ be a column vector of dimension N × 1, ν will be a rectangular
matrix of dimension N × J of rank R, and r will be a column vector of length J × 1. So
Eqs. (6.12-6.13) take the form
    
d ρO −2 2 r13
= . (6.16)
dt ρO2 1 −1 r14
Note here that the rank R of ν is R = L = 1. Let us also define a stoichiometric matrix φ
of dimension L × N. The component of φ, φli represents the number of element l in species
i. Generally φ will be full rank, which will vary because we can have L < N, L = N, or
L > N. Here we have L < N and φ is of dimension 1 × 2:


φ= 1 2 . (6.17)
Element conservation is guaranteed by insisting that ν be constructed such that
φ · ν = 0. (6.18)
So we can say that each of the column vectors of ν lies in the right null space of φ. For our
example, we see that Eq. (6.18) holds:
 

−2 2

φ·ν = 1 2 = 0 0 . (6.19)
1 −1
Let us take as initial conditions
ρO (t = 0) = b
ρO , ρO2 (t = 0) = b
ρ O2 . (6.20)
Now M represents an arbitrary third body, so here
ρM = ρO2 + ρO . (6.21)
Thus, the ordinary differential equations of the reaction dynamics reduce to
 
dρO β13 −E 13

= −2a13 T exp ρO ρO ρO2 + ρO
dt RT
 
β14 −E 14

+2a14 T exp ρO2 ρO2 + ρO , (6.22)
RT
 
dρO2 β13 −E 13

= a13 T exp ρO ρO ρO2 + ρO
dt RT
 
β14 −E 14

−a14 T exp ρO2 ρO2 + ρO . (6.23)
RT

CC BY-NC-ND. 19 January 2025, J. M. Powers.

174 CHAPTER 6. CHEMICAL KINETICS

Equations (6.22-6.23) with Eqs. (6.20) represent two non-linear ordinary differential equa-
tions with initial conditions in two unknowns ρO and ρO2 . We seek the behavior of these two
species concentrations as a function of time.
Systems of non-linear equations are generally difficult to integrate analytically and gen-
erally require numerical solution. Before embarking on a numerical solution, we simplify as
much as we can. Note that
dρO dρ
+ 2 O2 = 0, (6.24)
dt dt
d

ρO + 2ρO2 = 0. (6.25)
dt
We can integrate and apply the initial conditions (6.20) to get
ρO + 2ρO2 = b
ρO + 2b
ρO2 = constant. (6.26)
The fact that this algebraic constraint exists for all time is a consequence of the conservation
of mass of each O element. It can also be thought of as the conservation of number of
O atoms. Such notions always hold for chemical reactions. They do not hold for nuclear
reactions.
Standard linear algebra provides a robust way to find the constraint of Eq. (6.26). We
can use elementary row operations to cast Eq. (6.15) into a row-echelon form. Here our goal
is to get a linear combination which on the right side has an upper triangular form. To
achieve this add twice the second equation with the first to form a new equation to replace
the second equation. This gives
    
d ρO −2 2 r13
= . (6.27)
dt ρO + 2ρO2 0 0 r14
Obviously the second equation is one we obtained earlier, d/dt(ρO + 2ρO2 ) = 0, and this
induces our algebraic constraint. We also note the system can be recast as
      
1 0 d ρO −2 2 r13
= . (6.28)
1 2 dt ρO2 0 0 r14
This is of the matrix form
dρ
L−1 · P · = U · r. (6.29)
dt
Here L and L−1 are N × N lower triangular matrices of full rank N, and thus invertible.
The matrix U is upper triangular of dimension N × J and with the same rank as ν, R ≥ L.
The matrix P is a permutation matrix of dimension N × N. It is never singular and thus
always invertible. It is used to effect possible row exchanges to achieve the desired form;
often row exchanges are not necessary, in which case P = I, the N × N identity matrix.
Equation (6.29) can be manipulated to form the original equation via
dρ −1
=P
| · L · U} ·r.
{z (6.30)
dt
=ν

CC BY-NC-ND. 19 January 2025, J. M. Powers.

6.1. ISOTHERMAL, ISOCHORIC KINETICS 175

What we have done is the standard linear algebra decomposition of ν = P−1 · L · U.

We can also decompose the algebraic constraint, Eq. (6.26), in a non-obvious way that
is more readily useful for larger systems. We can write
1 
ρ O2 = b
ρ O2 − ρO − b
ρO . (6.31)
2
Defining now ξ O = ρO − b
ρO , we can say
     
ρO b
ρ 1

= bO + 1 ξO . (6.32)
ρO2 ρO2 − | {z}
| {z } | {z } | {z2 }
=ρ b =D =ξ
=ρ

This gives the dependent variables in terms of a smaller number of transformed dependent
variables in a way which satisfies the linear constraints. In vector form, the equation becomes
b + D · ξ.
ρ=ρ (6.33)

Here D is a full rank matrix which spans the same column space as does ν. Note that ν
may or may not be full rank. Because D spans the same column space as does ν, we must
also have in general

φ · D = 0. (6.34)

We see here this is true:

 

1
1 2 = (0). (6.35)
− 21

We also note that the term exp(−E j /RT ) is a modulating factor to the dynamics. Let
us see how this behaves for high and low temperatures. First for low temperature, we have
 
−E j
lim exp = 0. (6.36)
T →0 RT
At high temperature, we have
 
−E j
lim exp = 1. (6.37)
T →∞ RT
And lastly, at intermediate temperature, we have
   
−E j Ej
exp ∼ O(1) when T =O . (6.38)
RT R
A sketch of this modulating factor is given in Fig. 6.2. Note

CC BY-NC-ND. 19 January 2025, J. M. Powers.

176 CHAPTER 6. CHEMICAL KINETICS

Figure 6.2: Plot of exp(−E j /R/T ) versus T ; transition occurs at T ∼ E j /R.

• for small T , the modulation is extreme, and the reaction rate is very small,

• for T ∼ E j /R, the reaction rate is extremely sensitive to temperature, and

• for T → ∞, the modulation is unity, and the reaction rate is limited only by molecular
collision frequency.

Now ρO and ρO2 represent molar concentrations which have standard units of mole/cm3 .
So reaction rates, dρO /dt and dρO2 /dt, have units of mole/cm3 /s. Note that after conversion
of E j from kJ/mole to erg/mole we find the units of the argument of the exponential to be
dimensionless. That is
 
Ej erg mole K 1
= ⇒ dimensionless. (6.39)
RT mole erg K

Here the brackets denote the units of a quantity, and not molar concentration. Let us get
units for the collision frequency factor of reaction 13, a13 . We know the units of the rate
(mole/cm3 /s). Reaction 13 involves three molar species. Because β13 = −1, it also has an
extra temperature dependency. The exponential of a dimensionless number is dimensionless,
so we need not worry about that. For units to match, we must have
     
mole mole mole mole
= [a13 ] K−1 . (6.40)
cm3 s cm3 cm3 cm3

So the units of a13 are

 −2
mole K
[a13 ] = . (6.41)
cm3 s

CC BY-NC-ND. 19 January 2025, J. M. Powers.

6.1. ISOTHERMAL, ISOCHORIC KINETICS 177

For a14 we find a different set of units! Following the same procedure, we get
    
mole mole mole
3
= [a14 ] 3 3
K−1 . (6.42)
cm s cm cm

So the units of a14 are

 −1
mole K
[a14 ] = . (6.43)
cm3 s

This discrepancy in the units of aj the molecular collision frequency factor is a burden of tra-
ditional chemical kinetics, and causes many difficulties when classical non-dimensionalization
is performed. With much effort, a cleaner theory could be formulated; however, this would
require significant work to re-cast the now-standard aj values for literally thousands of re-
actions which are well established in the literature.

[Link].2 Example calculation Let us consider an example problem. Let us take T =

5000 K, and initial conditions b ρO = 0.001 mole/cm3 and b ρO2 = 0.001 mole/cm3 . The
initial temperature is very hot, and is near the temperature of the surface of the sun. This
is also realizable in laboratory conditions, but uncommon in most combustion engineering
environments.
We can solve these in a variety of ways. Let us choose to solve both Eqs. (6.22-6.23)
without the reduction provided by Eq. (6.26). However, we can check after numerical solution
to see if Eq. (6.26) is actually satisfied. Substituting numerical values for all the constants
to get
   −2 !
−E 13 mole K
β13
−2a13 T exp = −2 2.9 × 10 17
3
(5000 K)−1 exp(0),
RT cm s
 −2
mole 1
= −1.16 × 1014 3
, (6.44)
cm s
   −1 !
−E 14 mole K
2a14 T β14 exp = 2 6.81 × 1018 3
(5000 K)−1
RT cm s
 erg 
−4.96 × 1012 mole
× exp erg ,
8.31441 × 107 mole K
(5000 K)
 −1
10 mole 1
= 1.77548 × 10 , (6.45)
cm3 s
   −2
β13 −E 13 13 mole 1
k13 = a13 T exp = 5.80 × 10 3
, (6.46)
RT cm s
   −1
β14 −E 14 9 mole 1
k14 = a14 T exp = 8.8774 × 10 3
. (6.47)
RT cm s

CC BY-NC-ND. 19 January 2025, J. M. Powers.

178 CHAPTER 6. CHEMICAL KINETICS

0.00150

O2
0.00100

0.00070

0.00050

10-11 10-10 10-9 10-8 10-7 10-6 t (s)

Figure 6.3: Molar concentrations versus time for oxygen dissociation/recombination problem.

Then the differential equation system becomes

dρO
= −(1.16 × 1014 )ρ2O (ρO + ρO2 ) + (1.77548 × 1010 )ρO2 (ρO + ρO2 ), (6.48)
dt
dρO2
= (5.80 × 1013 )ρ2O (ρO + ρO2 ) − (8.8774 × 109 )ρO2 (ρO + ρO2 ), (6.49)
dt
mole mole
ρO (0) = 0.001 3
, ρO2 (0) = 0.001 . (6.50)
cm cm3
These non-linear ordinary differential equations are in a standard form for a wide variety of
numerical software tools. Numerical solution methods for such equations are not the topic
of these notes.

[Link].2.1 Species concentration versus time A solution was obtained numeri-

cally, and a plot of ρO (t) and ρO2 (t) is given in Fig. 6.3. Note that significant reaction does
not commence until t ∼ 10−10 s. This can be shown to be very close to the time between
molecular collisions. For 10−9 s < t < 10−8 s, there is a vigorous reaction. For t > 10−7 s,
the reaction appears to be equilibrated. The calculation gives the equilibrium values ρeO and
ρeO2 , as
mole mole
lim ρO = ρeO = 0.0004424 3
, lim ρO2 = ρeO2 = 0.00127 . (6.51)
t→∞ cm t→∞ cm3
Note that at this high temperature, O2 is preferred over O, but there are definitely O
molecules present at equilibrium.
We can check how well the numerical solution satisfied the algebraic constraint of element
conservation by plotting the dimensionless residual error r
ρO + 2ρO2 − b
ρO − 2b
ρO2
r= , (6.52)
b
ρO + 2b
ρO 2

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6.1. ISOTHERMAL, ISOCHORIC KINETICS 179

r
1.5 x 10-16

1.0 x 10-16

5.0 x 10-17

t (s)
10-11 10-10 10-9 10-8 10-7 10-6

Figure 6.4: Dimensionless residual numerical error r in satisfying the element conservation
constraint in the oxygen dissociation example.

as a function of time. If the constraint is exactly satisfied, we will have r = 0. Any non-zero
r will be related to the numerical method we have chosen. It may contain roundoff error
and have a sporadic nature. A plot of r(t) is given in Fig. 6.4. Clearly the error is small,
and has the character of a roundoff error. In fact it is possible to drive r to be smaller by
controlling the error tolerance in the numerical method.

[Link].2.2 Pressure versus time We can use the ideal gas law to calculate the
pressure. Recall that the ideal gas law for molecular species i is
Pi V = ni RT. (6.53)
Here Pi is the partial pressure of molecular species i, and ni is the number of moles of
molecular species i. Note that we also have
ni
Pi = RT. (6.54)
V
Note that by our definition of molecular species concentration that
ni
ρi = . (6.55)
V
So we also have the ideal gas law as
Pi = ρi RT. (6.56)
Now in the Dalton mixture model, all species share the same T and V . So the mixture
temperature and volume are the same for each species Vi = V , Ti = T . But the mixture
pressure is taken to be the sum of the partial pressures:
N
X
P = Pi . (6.57)
i=1

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180 CHAPTER 6. CHEMICAL KINETICS

Substituting from Eq. (6.56) into Eq. (6.57), we get

N
X N
X
P = ρi RT = RT ρi . (6.58)
i=1 i=1

For our example, we only have two species, so

P = RT (ρO + ρO2 ). (6.59)
The pressure at the initial state t = 0 is
P (t = 0) = RT (b
ρO + b
ρO2 ), (6.60)
   
erg mole mole
= 8.31441 × 107 (5000 K) 0.001 + 0.001 , (6.61)
mole K cm3 cm3
dyne
= 8.31441 × 108 = 8.31441 × 102 bar. (6.62)
cm2
This pressure is over 800 atmospheres. It is actually a little too high for good experimental
correlation with the underlying data, but we will neglect that for this exercise.
At the equilibrium state we have more O2 and less O. And we have a different number
of molecules, so we expect the pressure to be different. At equilibrium, the pressure is
P (t → ∞) = lim RT (ρO + ρO2 ), (6.63)
t→∞
  
7 erg  mole mole
= 8.31441 × 10 (5000 K) 0.0004424 + 0.00127 ,
mole K cm3 cm3
(6.64)
dyne
= 7.15 × 108 = 7.15 × 102 bar. (6.65)
cm2
The pressure has dropped because much of the O has recombined to form O2 . Thus there
are fewer molecules at equilibrium. The temperature and volume have remained the same.
A plot of P (t) is given in Fig. 6.5.

[Link].2.3 First law analysis The first law of thermodynamics can tell us the heat
transfer required to maintain an isothermal condition. The first law is
E2 − E1 = 1Q2 − 1W2 . (6.66)
For the isochoric problem, we have 1W2 = 0. So, we have

1Q2 = E2 − E1 , (6.67)
= (nO eO + nO2 eO2 )|t→∞ − (nO eO + nO2 eO2 )|t=0 , (6.68)
1Q2


= ρO eO + ρO2 eO2 t→∞ − ρO eO + ρO2 eO2 t=0 , (6.69)
V

 
e e b b
= ρO eO + ρO2 eO2 − ρO eO + ρO2 eO2 . (6.70)

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6.1. ISOTHERMAL, ISOCHORIC KINETICS 181

8 x 108

7 x 108
10-11 10-10 10-9 10-8 10-7 10-6 t (s)

Figure 6.5: Pressure versus time for oxygen dissociation example.

Now for the ideal gas the internal energy is only a function of temperature. Because the
problem is isothermal, the internal energy of each component remains constant. So

1Q2
= eO (ρeO − b
ρO ) + eO2 (ρeO2 − b
ρO2 ). (6.71)
V
We find the internal energies at 5000 K from using the chemkin software. Substituting
numbers, we get
  
1Q2 12 erg mole mole
= 3.06812 × 10 0.0004424 − 0.001
V mole cm3 cm3
   
12 erg mole mole
+ 1.39179 × 10 0.00127 − 0.001 , (6.72)
mole cm3 cm3
erg
= −1.323 × 109 . (6.73)
cm3
Because 1Q2 < 0, the reaction is exothermic; thermal energy is released to the environment
to maintain the temperature. As the concentration of O2 increased, we see that this process
is a recombination process, which is typically exothermic. Conversely a reaction in which O
increased would be a dissociation reaction and would typically be endothermic.

[Link].2.4 Dynamical system form Now Eqs. (6.48-6.49) are of the standard form
for an autonomous dynamical system:
dy
= f(y). (6.74)
dt
Here y is the vector of state variables (ρO , ρO2 )T . And f is an algebraic function of the state
variables. For the isothermal system, the algebraic function is in fact a polynomial.

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182 CHAPTER 6. CHEMICAL KINETICS

The dynamical system is in equilibrium when

f(y) = 0. (6.75)
This non-linear set of algebraic equations can be difficult to solve for large systems. For
common chemical kinetics systems, such as the one we are dealing with, there is a guarantee
of a unique equilibrium for which all state variables are physical. There are certainly other
equilibria for which at least one of the state variables is non-physical. Such equilibria can
be quite mathematically complicated.
Solving Eq. (6.75) for our oxygen dissociation problem gives us symbolically from Eq. (6.6-
6.7)
   
−E 13 e e e β13 −E 14
−2a13 exp ρO ρO ρM T + 2a14 exp ρeO2 ρeM T β14 = 0, (6.76)
RT RT
   
β13 −E 13 e e e β14 −E 14
a13 T exp ρO ρO ρM − a14 T exp ρeO2 ρeM = 0. (6.77)
RT RT
We notice that ρeM cancels. This so-called third body will in fact never affect the equilib-
rium state. It will however influence the dynamics. Removing ρeM and slightly rearranging
Eqs. (6.76-6.77) gives
   
β13 −E 13 e e β14 −E 14
a13 T exp ρO ρO = a14 T exp ρeO2 , (6.78)
RT RT
   
β13 −E 13 e e β14 −E 14
a13 T exp ρO ρO = a14 T exp ρeO2 . (6.79)
RT RT
These are the same equations! So we really have two unknowns for the equilibrium state ρeO
and ρeO2 but seemingly only one equation. Note that rearranging either Eq. (6.78) or (6.79)
gives the result
 
β14 −E 14
ρeO ρeO a14 T exp RT
=   = K(T ). (6.80)
ρeO2 a T β13 exp −E 13
13 RT

That is, for the net reaction (excluding the inert third body), O2 → O+O, at equilibrium the
product of the concentrations of the products divided by the product of the concentrations
of the reactants is a function of temperature T . And for constant T , this is the so-called
equilibrium constant. This is a famous result from basic chemistry. It is actually not complete
yet, as we have not taken advantage of a connection with thermodynamics. But for now, it
will suffice.
We still have a problem: Eq. (6.80) is still one equation for two unknowns. We solve
this be recalling we have not yet taken advantage of our algebraic constraint of element
conservation, Eq. (6.26). Let us use the equation to eliminate ρeO2 in favor of ρeO :
1 b 
e
ρ O2 = ρ − ρO + b
e
ρO2 . (6.81)
2 O

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6.1. ISOTHERMAL, ISOCHORIC KINETICS 183

300 000

200 000

100 000

-0.004 -0.003 -0.002 -0.001 0.001

-100000

-200000

Figure 6.6: Equilibria for oxygen dissociation example.

So Eq. (6.78) reduces to

      
−E 13 −E 14 1 b
a13 T β13
exp ρeO ρeO = a14 T β14
exp ρ − ρO + b
e
ρO2 . (6.82)
RT RT 2 O
| {z }
=ρeO
2

Equation (6.82) is one algebraic equation in one unknown. Its solution gives the equilibrium
value ρeO . It is a quadratic equation for ρeO . Of its two roots, one will be physical. We note
that the equilibrium state will be a function of the initial conditions. Mathematically this
is because our system is really best posed as a system of differential-algebraic equations.
Systems which are purely differential equations will have equilibria which are independent
of their initial conditions. Most of the literature of mathematical physics focuses on such
systems of those. One of the foundational complications of chemical dynamics is that the
equilibria is a function of the initial conditions, and this renders many common mathematical
notions from traditional dynamic system theory to be invalid. Fortunately, after one accounts
for the linear constraints of element conservation, one can return to classical notions from
traditional dynamic systems theory.
Consider the dynamics of Eq. (6.22) for the evolution of ρO . Equilibrating the right
hand side of this equation, gives Eq. (6.76). Eliminating ρM and then ρO2 in Eq. (6.76) then
substituting in numerical parameters gives the cubic algebraic equation

33948.3 − (1.78439 × 1011 )(ρO )2 − (5.8 × 1013 )(ρO )3 = ω̇O (ρO ) = 0. (6.83)

This equation is cubic because we did not remove the effect of ρM . This will not affect the
equilibrium, but will affect the dynamics. We can get an idea of where the roots are by
plotting ω̇O (ρO ) as seen in Fig. 6.6. Zero crossings of ω̇O (ρO ) in Fig. 6.6 represent equilibria

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184 CHAPTER 6. CHEMICAL KINETICS

of the system, ρeO , ω̇O (ρeO ) = 0. The cubic equation has three roots
mole
ρeO = −0.003 , non-physical, (6.84)
cm3
mole
ρeO = −0.000518944 , non-physical, (6.85)
cm3
mole
ρeO = 0.000442414 , physical. (6.86)
cm3
Note the physical root found by our algebraic analysis is identical to that which was identified
by our numerical integration of the ordinary differential equations of reaction kinetics.
We can get a simple estimate of the stability of the equilibria by considering the slope of
ω̇O near ω̇O = 0. Our dynamic system is of the form
dρO
= ω̇O (ρO ). (6.87)
dt
• Near the first non-physical root at ρeO = −0.003 mole/cm3 , a positive perturbation
from equilibrium induces ω̇O < 0, which induces dρO /dt < 0, so ρO returns to its
equilibrium. Similarly, a negative perturbation from equilibrium induces dρO /dt > 0,
so the system returns to equilibrium. This non-physical equilibrium point is stable.
Note stability does not imply physicality!
• Perform the same exercise for the non-physical root at ρeO = −0.000518944 mole/cm3 .
We find this root is unstable.
• Perform the same exercise for the physical root at ρeO = 0.000442414 mole/cm3 . We
find this root is stable.
In general if ω̇O crosses zero with a positive slope, the equilibrium is unstable. Otherwise, it
is stable.
Consider a formal Taylor series expansion of Eq. (6.87) in the neighborhood of an equi-
librium point ρ3O :
d dω̇O
(ρO − ρeO ) = ω̇O (ρeO ) + (ρO − ρeO ) + . . . (6.88)
dt | {z } dρO ρO =ρeO
=0

We find df /dρO by differentiating Eq. (6.83) to get

dω̇O
= −(3.56877 × 1011 )ρO − (1.74 × 1014 )ρ2O . (6.89)
dρO
We evaluate dω̇O /dρO near the physical equilibrium point at ρO = 0.0004442414 to get
dω̇O
= −(3.56877 × 1011 )(0.0004442414) − (1.74 × 1014 )(0.0004442414)2,
dρO
1
= −1.91945 × 108 . (6.90)
s

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6.1. ISOTHERMAL, ISOCHORIC KINETICS 185

Thus the Taylor series expansion of Eq. (6.22) in the neighborhood of the physical equi-
librium gives the local kinetics to be driven by
d
(ρO − 0.000442414) = −(1.91945 × 108 ) (ρO − 0.0004442414) + . . . . (6.91)
dt
So in the neighborhood of the physical equilibrium we have


ρO = 0.0004442414 + A exp −1.91945 × 108 t . (6.92)
Here A is an arbitrary constant of integration. The local time constant which governs the
times scales of local evolution is τ where
1
τ= = 5.20983 × 10−9 s. (6.93)
1.91945 × 108 s−1
This nano-second time scale is very fast. It can be shown to be correlated with the mean
time between collisions of molecules.

[Link].3 Effect of temperature Let us perform four case studies to see the effect of
T on the system’s equilibria and it dynamics near equilibrium.
• T = 3000 K. Here we have significantly reduced the temperature, but it is still higher
than typically found in ordinary combustion engineering environments. Here we find
mole
ρeO = 8.9371 × 10−6 , τ = 1.92059 × 10−7 s. (6.94)
cm3
The equilibrium concentration of O dropped by two orders of magnitude relative to
T = 5000 K, and the time scale of the dynamics near equilibrium slowed by two orders
of magnitude.
• T = 1000 K. Here we reduce the temperature more. This temperature is common in
combustion engineering environments. We find
mole
ρeO = 2.0356 × 10−14 3
, τ = 2.82331 × 101 s. (6.95)
cm
The O concentration at equilibrium is greatly diminished to the point of being difficult
to detect by standard measurement techniques. And the time scale of combustion has
significantly slowed.
• T = 300 K. This is obviously near room temperature. We find
mole
ρeO = 1.14199 × 10−44 3
, τ = 1.50977 × 1031 s. (6.96)
cm
The O concentration is effectively zero at room temperature, and the relaxation time
is effectively infinite. As the oldest star in our galaxy has an age of 4.4 × 1017 s, we see
that at this temperature, our mathematical model cannot be experimentally validated,
so it loses its meaning. At such a low temperature, the theory becomes qualitatively
correct, but not quantitatively predictive.

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186 CHAPTER 6. CHEMICAL KINETICS

• T = 10000 K. Such a high temperature could be achieved in an atmospheric re-entry

environment. We find
mole
ρeO = 2.74807 × 10−3 , τ = 1.69119 × 10−10 s. (6.97)
cm3
At this high temperature, O become preferred over O2 , and the time scales of reaction
become extremely small, under a nanosecond.

[Link] Single reversible reaction

The two irreversible reactions studied in the previous section are of a class that is common
in combustion modeling. However, the model suffers a defect in that its link to classical
equilibrium thermodynamics is missing. A better way to model essentially the same physics
and guarantee consistency with classical equilibrium thermodynamics is to model the process
as a single reversible reaction, with a suitably modified reaction rate term.

[Link].1 Mathematical model

[Link].1.1 Kinetics For the reversible O −O2 reaction, let us only consider reaction
13 from Table 6.2 for which

13 : O2 + M ⇌ O + O + M. (6.98)

For this system, we have N = 2 molecular species in L = 1 elements reacting in J = 1

reaction. Here
 −1
11 mole −0.5 cal
a13 = 1.85 × 10 (K) , β13 = 0.5, E 13 = 95560 . (6.99)
cm3 mole
Units of cal are common in chemistry, but we need to convert to erg, which is achieved via
  
cal J  7 erg  erg
E 13 = 95560 4.186 10 = 4.00014 × 1012 . (6.100)
mole cal J mole
For this reversible reaction, we slightly modify the kinetics equations to
  
dρO β13 −E 13 1
= 2 a13 T exp ρ O2 ρ M − ρ ρ ρ = ω̇O , (6.101)
dt RT Kc,13 O O M
| {z }
=k13 (T )
| {z }
=r13
  
dρO2 β13 −E 13 1
= − a13 T exp ρO2 ρM − ρ ρ ρ = ω̇O2 . (6.102)
dt RT Kc,13 O O M
| {z }
=k13 (T )
| {z }
=r13

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6.1. ISOTHERMAL, ISOCHORIC KINETICS 187

Here we have used equivalent definitions for k13 (T ) and r13 , so that Eqs. (6.101-6.102) can
be written compactly as
dρO
= 2r13 , (6.103)
dt
dρO2
= −r13 . (6.104)
dt
In matrix form, we can simplify to
   
d ρO 2
= (r13 ). (6.105)
dt ρO2 −1
| {z }
=ν

Here the N × J or 2 × 1 matrix ν is

 
2
ν= . (6.106)
−1

Performing row operations, the matrix form reduces to

   
d ρO 2
= (r13 ), (6.107)
dt ρO + 2ρO2 0
or
     
1 0 d ρO 2
= (r13 ). (6.108)
1 2 dt ρO2 0

So here the N × N or 2 × 2 matrix L−1 is

 
−1 1 0
L = . (6.109)
1 2

The N × N or 2 × 2 permutation matrix P is the identity matrix. And the N × J or 2 × 1

upper triangular matrix U is  
2
U= . (6.110)
0
Note that ν = L · U or equivalently L−1 · ν = U:
    
1 0 2 2
= . (6.111)
1 2 −1 0
| {z } | {z } |{z}
=L−1 =ν =U

Once again the stoichiometric matrix φ is

φ= 1 2 . (6.112)

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188 CHAPTER 6. CHEMICAL KINETICS

And we see that φ · ν = 0 is satisfied:

 

2

1 2 = 0 . (6.113)
−1

As for the irreversible reactions, the reversible reaction rates are constructed to conserve
O atoms. We have
d

ρO + 2ρO2 = 0. (6.114)
dt
Thus, we once again find

ρO + 2b
ρO + 2ρO2 = b ρO2 = constant. (6.115)

As before, we can say

     
ρO b
ρ 1

= bO + 1 ξO . (6.116)
ρO2 ρO2 − | {z}
| {z } | {z } | {z2 }
=ρ b =D =ξ
=ρ

This gives the dependent variables in terms of a smaller number of transformed dependent
variables in a way which satisfies the linear constraints. In vector form, the equation becomes

b + D · ξ.
ρ=ρ (6.117)

Once again φ · D = 0.

[Link].1.2 Thermodynamics Equations (6.101-6.102) are supplemented by an ex-

pression for the thermodynamics-based equilibrium constant Kc,13 which is:
 
Po −∆Go13
Kc,13 = exp . (6.118)
RT RT

Here Po = 1.01326 × 106 dyne/cm2 = 1 atm is the reference pressure. The net change of
Gibbs free energy at the reference pressure for reaction 13, ∆Go13 is defined as

∆Go13 = 2g oO − g oO2 . (6.119)

We further recall that the Gibbs free energy for species i at the reference pressure is defined
in terms of the enthalpy and entropy as
o
g oi = hi − T soi . (6.120)
o
It is common to find hi and soi in thermodynamic tables tabulated as functions of T .

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6.1. ISOTHERMAL, ISOCHORIC KINETICS 189

We further note that both Eqs. (6.101) and (6.102) are in equilibrium when
1 e e e
ρeO2 ρeM = ρ ρ ρ . (6.121)
Kc,13 O O M

We rearrange Eq. (6.121) to find the familiar

Q
ρeO ρeO [products]
Kc,13 = e =Q . (6.122)
ρ O2 [reactants]

If Kc,13 > 1, the products are preferred. If Kc,13 < 1, the reactants are preferred.
Now, Kc,13 is a function of T only, so it is known. But Eq. (6.122) once again is one
equation in two unknowns. We can use the element conservation constraint, Eq. (6.115) to
reduce to one equation and one unknown, valid at equilibrium:
ρeO ρeO
Kc,13 = . (6.123)
b
ρO2 + 21 (b
ρO − ρeO )

Using the element constraint, Eq. (6.115), we can recast the dynamics of our system by
modifying Eq. (6.101) into one equation in one unknown:
 
dρO β13 −E 13
= 2a13 T exp
dt RT
 
 1 b 1 b 1 1 b 
×(bρ
 2 2
O + ( ρO − ρO )) (bρO + ( ρ O − ρO ) + ρO ) − ρO ρO (bρ O + ( ρO − ρ O ) + ρO ) ,

| {z }|
2
2 {z } K c,13 |
2
2 {z }
=ρO2 =ρM =ρM

(6.124)

[Link].2 Example calculation Let us consider the same example as the previous sec-
tion with T = 5000 K. We need numbers for all of the parameters of Eq. (6.124). For O, we
find at T = 5000 K that
o erg erg
hO = 3.48382 × 1012 , soO = 2.20458 × 109 . (6.125)
mole mole K
So
 erg   erg 
g oO = 3.48382 × 1012 − (5000 K) 2.20458 × 109 ,
mole mole K
erg
= −7.53908 × 1012 . (6.126)
mole
For O2 , we find at T = 5000 K that
o erg erg
hO2 = 1.80749 × 1012 , soO2 = 3.05406 × 109 . (6.127)
mole mole K

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190 CHAPTER 6. CHEMICAL KINETICS

As an aside, these numbers are consistent with those for eO and eO2 used in Eq. (6.73)
becuase eO = hO −RT = 3.06812×1012 erg/mole, eO2 = hO2 −RT = 1.39179×1012 erg/mole.
Returning to g oi , we have
 erg   erg 
g oO2 = 1.80749 × 1012 − (5000 K) 3.05406 × 109 , (6.128)
mole mole K
erg
= −1.34628 × 1013 . (6.129)
mole
Thus, by Eq. (6.119), we have
erg
∆Go13 = 2(−7.53908 × 1012 ) − (−1.34628 × 1013 ) = −1.61536 × 1012 . (6.130)
mole
Thus, by Eq. (6.118) we get for our system

1.01326 × 106 dyne2

Kc,13 = erg

cm
7
8.31441 × 10 mole K (5000 K)
!!
erg
−1.61536 × 1012 mole
× exp − erg

, (6.131)
8.31441 × 107 mole K
(5000 K)
mole
= 1.187 × 10−4 . (6.132)
cm3
Substitution of all numerical parameters into Eq. (6.124) and expansion yields the fol-
lowing

dρO
= 3899.47 − (2.23342 × 1010 )ρ2O − (7.3003 × 1012 )ρ3O = ω̇O (ρO ), ρO (0) = 0.001.(6.133)
dt
A plot of the time-dependent behavior of ρO and ρO2 from solution of Eq. (6.133) is
given in Fig. 6.7. The behavior is similar to the predictions given by the pair of irreversible
reactions in Fig. 6.2. Here direct calculation of the equilibrium from time integration reveals

mole
ρeO = 0.000393328 . (6.134)
cm3
Using Eq. (6.115) we find this corresponds to

mole
ρeO2 = 0.00130334 . (6.135)
cm3
We note the system begins significant reaction for t ∼ 10−9 s and is equilibrated for t ∼ 10−7 s.
The equilibrium is verified by solving the algebraic equation

ω̇O (ρO ) = 3899.47 − (2.23342 × 1010 )ρ2O − (7.3003 × 1012 )ρ3O = 0. (6.136)

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6.1. ISOTHERMAL, ISOCHORIC KINETICS 191

0.00150

O2
0.00100

0.00070

0.00050

O
0.00030

t (s)
10-11 10-9 10-7 10-5 10-3

Figure 6.7: Plot of ρO (t) and ρO2 (t) for oxygen dissociation with reversible reaction.

40 000

30 000

20 000

10 000

-0.004 -0.003 -0.002 -0.001 0.001

-10000

-20000

Figure 6.8: Plot of ω̇O (ρO ) versus ρO for oxygen dissociation with reversible reaction.

This yields three roots:

mole
ρeO = −0.003 , non-physical, (6.137)
cm3
mole
ρeO = −0.000452678 , non-physical, (6.138)
cm3
mole
ρeO = 0.000393328 , physical. (6.139)
cm3

A plot of ω̇O (ρO ) is given in Fig. 6.8. Linearizing Eq. (6.133) in the neighborhood of the
physical equilibrium yields the equation

d
(ρO − 0.000393328) = −(2.09575 × 107 ) (ρO − 0.000393328) + . . . (6.140)
dt

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192 CHAPTER 6. CHEMICAL KINETICS

This has solution

ρO = 0.000393328 + A exp −2.09575 × 107 t . (6.141)

Again, A is an arbitrary constant. Obviously the equilibrium is stable. Moreover the time
constant of relaxation to equilibrium is
1
τ= = 4.77156 × 10−8 s. (6.142)
2.09575 × 107 s−1
This is consistent with the time scale to equilibrium which comes from integrating the full
equation.

6.1.2 Zel’dovich mechanism of NO production

Let us consider next a more complicated reaction system: that of NO production known
as the Zel’dovich6 mechanism. This is an important model for the production of a major
pollutant from combustion processes. It is most important for high temperature applications.

[Link] Mathematical model

The model has several versions. One is

1: N + NO ⇌ N2 + O, (6.143)
2: N + O2 ⇌ NO + O. (6.144)

similar to our results for O2 dissociation, N2 and O2 are preferred at low temperature. As
the temperature rises N and O begin to appear, and it is possible when they are mixed for
NO to appear as a product.

[Link].1 Standard model form Here we have the reaction of N = 5 molecular species
with
 
ρNO
 ρN 
 
ρ= 
 ρ N2  . (6.145)
 ρO 
ρ O2

We have L = 2 with N and O as the 2 elements. The stoichiometric matrix φ of dimension

L × N = 2 × 5 is
 
1 1 2 0 0
φ= . (6.146)
1 0 0 1 2
6
Yakov Borisovich Zel’dovich, 1915-1987, prolific Soviet physicist and father of thermonuclear weapons.

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6.1. ISOTHERMAL, ISOCHORIC KINETICS 193

The first row of φ is for the N atom; the second row is for the O atom.
And we have J = 2 reactions. The reaction vector of length J = 2 is
   
  β1 Ta,1 1
r1 a 1 T exp − ρ ρ − ρ ρ
r = =  T   N NO Kc,1 N2 O  , (6.147)
r2 β2
a2 T exp − Ta,2
T
ρN ρO2 − K1c,2 ρNO ρO
  
1
k1 ρN ρNO − Kc,1 ρN2 ρO
=    . (6.148)
k2 ρN ρO2 − K1c,2 ρNO ρO

Here, we have
   
β1 Ta,1 β2 Ta,2
k1 = a1 T exp − , k2 = a2 T exp − . (6.149)
T T

In matrix form, the model can be written as

   
ρNO −1 1
 ρN  −1 −1  
d   
 ρN  =  1
 r1
 2  0
 r2 . (6.150)
dt   
ρO 1 1
ρ O2 0 −1
| {z }
=ν

Here the matrix ν has dimension N × J which is 5 × 2. The model is of our general form
dρ
= ν · r ≡ ω̇. (6.151)
dt
Note that our stoichiometric constraint on element conservation for each reaction φ · ν = 0
holds here:
 
−1 1
  −1 −1  
1 1 2 0 0  1
 0 0
φ·ν = 0= 0 0 . (6.152)
1 0 0 1 2  1 
1
0 −1

We get 4 zeros because there are 2 reactions each with 2 element constraints.

[Link].2 Reduced form Here we describe non-traditional, but useful reductions, using
standard techniques from linear algebra to bring the model equations into a reduced form in
which all of the linear constraints have been explicitly removed.
Let us perform a series of row operations to find all of the linear dependencies. Our aim
is to convert the ν matrix into an upper triangular form. The lower left corner of ν already

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194 CHAPTER 6. CHEMICAL KINETICS

has a zero, so there is no need to worry about it. Let us add the first and fourth equations
to eliminate the 1 in the 4, 1 slot. This gives
   
ρNO −1 1
 ρN  −1 −1  
d 
 ρN
 
= 1
 r1

0  r2 . (6.153)
dt  2  
ρNO + ρO   0 
2
ρ O2 0 −1
Next, add the first and third equations to get
   
ρNO −1 1
 ρN  −1 −1  
d   
ρNO + ρN  =  0
 r1

1  r . (6.154)
dt  2
 ρNO + ρO   0

2 2
ρ O2 0 −1
Now multiply the first equation by −1 and add it to the second to get
   
ρNO −1 1
−ρNO + ρN   0 −2  
d   
 ρNO + ρN  =  0
 r1
 2   1  r2 . (6.155)
dt   
ρNO + ρO 0 2
ρ O2 0 −1
Next multiply the fifth equation by −2 and add it to the second to get
   
ρNO −1 1
 −ρNO + ρN   0 −2  
d 
 
= 0
 r1

ρ + ρ 1  r . (6.156)
dt 

NO N 2  
 0
ρNO + ρO 2 2
−ρNO + ρN − 2ρO2 0 0
Next add the second and fourth equations to get
   
ρNO −1 1
 −ρNO + ρN   0 −2  
d 
 
 
 r1

ρ + ρ = 0 1  r2 . (6.157)
dt 

NO N2  
 
ρN + ρO 0 0
−ρNO + ρN − 2ρO2 0 0
Next multiply the third equation by 2 and add it to the second to get
   
ρNO −1 1
 −ρNO + ρN   0 −2  
d   
 ρNO + ρN + 2ρN  =  0
 r1
 2   0 r2 . (6.158)
dt   
ρN + ρO 0 0
−ρNO + ρN − 2ρO2 0 0

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6.1. ISOTHERMAL, ISOCHORIC KINETICS 195

Rewritten, this becomes

     
1 0 0 0 0 ρNO −1 1
−1 1 0 0 0     
  d  ρN   0 −2 r1
1 1 2 0 0    0
  dt  ρN2  =  0  r2 . (6.159)
0 1 0 1 0   ρO   0 0
−1 1 0 0 −2 ρ O2 0 0
| {z } | {z }
=L−1 =U

A way to think of this type of row echelon form is that it defines two free variables, those
associated with the non-zero pivots of U: ρNO and ρN . The remain three variables ρN2 , ρO
and ρO2 are bound variables which can be expressed in terms of the free variables.
The last three of the ordinary differential equations are homogeneous and can be inte-
grated to form

ρNO + ρN + 2ρN2 = C1 , (6.160)

ρN + ρO = C2 , (6.161)
−ρNO + ρN − 2ρO2 = C3 . (6.162)

The constants C1 , C2 and C3 are determined from the initial conditions on all five state
variables. In matrix form, we can say
 
  ρNO  
1 1 2 0 0   ρN 
 C1
 0 1 0 1 0   ρN  = C2  . (6.163)
 2
−1 1 0 0 −2  ρO  C3
ρO2
Considering the free variables, ρNO and ρN , to be known, we move them to the right side to
get
    
2 0 0 ρN2 C1 − ρNO − ρN
0 1 0   ρO  =  C2 − ρN  . (6.164)
0 0 −2 ρO2 C3 + ρNO − ρN
Solving, for the bound variables, we find
   1 1 1

ρ N2 2
C 1 − ρ
2 NO
− ρ
2 N
 ρO  =  C2 − ρN . (6.165)
1 1 1
ρ O2 − 2 C3 − 2 ρNO + 2 ρN
We can rewrite this as
   1   1 
ρ N2 C
2 1
− 2 − 12  
 ρO  =  C2  +  0 −1  ρNO . (6.166)
ρN
ρ O2 − 12 C3 − 21 12

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196 CHAPTER 6. CHEMICAL KINETICS

We can get a more elegant form by defining ξNO = ρNO and ξN = ρN . Thus we can say our
state variables have the form
     
ρNO 0 1 0
 ρN   0   0 1   
     
1  ξNO
 ρN  =  1 C1  + − 1 −2 . (6.167)
 2  2   2 ξN
 ρ O   C2   0 −1 
ρO2 − 21 C3 − 21 1
2

By translating via ξNO = ξ NO + b

ρNO and ξN = ξ N + b ρN and choosing the constants C1 , C2
and C3 appropriately, we can arrive at
  b   
ρNO ρNO 1 0
 ρN   ρN  
b   
      01 11  ξ NO
 ρN  =  b + − 2 − 2  . (6.168)
 2   ρN2     ξ
 ρO   b ρO   
0 −1 | {z } N

ρO2 b
ρO2 − 21 12 =ξ
| {z } | {z } | {z }
=ρ b =D
=ρ

This takes the form of

b + D · ξ.
ρ=ρ (6.169)

Here the matrix D is of dimension N × R, which here is 5 × 2. It spans the same column
space as does the N × J matrix ν which is of rank R. Here in fact R = J = 2, so D has the
same dimension as ν. In general it will not. If c1 and c2 are the column vectors of D, we
see that −c1 − c2 forms the first column vector of ν and c1 − c2 forms the second column
vector of ν. Note that φ · D = 0:
 
1 0
  0 1   
1 1 2 0 0  − −  =
1 1
 0 0
φ·D= . (6.170)
1 0 0 1 2  2
 0 −1 
2 0 0
− 21 12

Equations (6.160-6.162) can also be linearly combined in a way which has strong phys-
ical relevance. We rewrite the system as three equations in which the first is identical to
Eq. (6.160); the second is the difference of Eqs. (6.161) and (6.162); and the third is half of
Eq. (6.160) minus half of Eq. (6.162) plus Eq. (6.161):

ρNO + ρN + 2ρN2 = C1 , (6.171)

ρO + ρNO + 2ρO2 = C2 − C3 , (6.172)
1
ρNO + ρN + ρN2 + ρO + ρO2 = (C1 − C3 ) + C2 . (6.173)
2

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6.1. ISOTHERMAL, ISOCHORIC KINETICS 197

Equation (6.171) insists that the number of nitrogen elements be constant; Eq. (6.172)
demands the number of oxygen elements be constant; and Eq. (6.173) requires the number
of moles of molecular species be constant. For general reactions, including the earlier studied
oxygen dissociation problem, the number of moles of molecular species will not be constant.
Here because each reaction considered has two molecules reacting to form two molecules,
we are guaranteed the number of moles will be constant. Hence, we get an additional
linear constraint beyond the two for element conservation. Note that because our reaction
is isothermal, isochoric, and mole-preserving, it will also be isobaric.

[Link].3 Example calculation Let us consider an isothermal reaction at

T = 6000 K. (6.174)
The high temperature is useful in generating results which are easily visualized. It insures
that there will be significant concentrations of all molecular species. Let us also take as an
initial condition
b mole
ρNO = b ρN = bρ N2 = b
ρO = b ρO2 = 1 × 10−6 . (6.175)
cm3
For this temperature and concentrations, the pressure, which will remain constant through
the reaction, is P = 2.4942 × 106 dyne/cm2 . This is a little greater than atmospheric.
Kinetic data for this reaction is adopted from Baulch, et al.7 and requires unit conversion
from molecules to moles via Avogardo’s number. The data for reaction 1 is
 −1
13 mole 1
a1 = 2.107 × 10 , β1 = 0, Ta1 = 0 K. (6.176)
cm3 s
For reaction 2, we have
 −1
9 mole 1
a2 = 5.8394 × 10 , β2 = 1.01, Ta2 = 3120 K. (6.177)
cm3 K1.01 s
Here the so-called activation temperature Ta,j for reaction j is really the activation energy
scaled by the universal gas constant:
Ej
. Ta,j = (6.178)
R
Substituting numbers we obtain for the reaction rates
   −1
13 0 −0 13 mole 1
k1 = (2.107 × 10 )(6000) exp = 2.107 × 10 3
, (6.179)
6000 cm s
   −1
9 1.01 −3120 13 mole 1
k2 = (5.8394 × 10 )(6000) exp = 2.27231 × 10 3
.
6000 cm s
(6.180)
7
Baulch, et al., 2005, Evaluated kinetic data for combustion modeling: supplement II, Journal of Physical
and Chemical Reference Data, 34(3): 757-1397 (see pp. 785-786).

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198 CHAPTER 6. CHEMICAL KINETICS

We will also need thermodynamic data. The data here will be taken from the chemkin
database.8 Thermodynamic data for common materials are also found in most thermody-
namic texts. For our system at 6000 K, we find
erg
g oNO = −1.58757 × 1013 , (6.181)
mole
erg
g oN = −7.04286 × 1012 , (6.182)
mole
erg
g oN2 = −1.55206 × 1013 , (6.183)
mole
erg
g oO = −9.77148 × 1012 , (6.184)
mole
erg
g oO2 = −1.65653 × 1013 . (6.185)
mole
Thus for each reaction, we find ∆Goj :

∆Go1 = g oN2 + g oO − g oN − g oNO , (6.186)

13 12 12 13
= −1.55206 × 10 − 9.77148 × 10 + 7.04286 × 10 + 1.58757 × 10 ,(6.187)
erg
= −2.37351 × 1012 , (6.188)
mole
∆Go2 = g oNO + g oO − g oN − g oO2 , (6.189)
13 12 12 13
= −1.58757 × 10 − 9.77148 × 10 + 7.04286 × 10 + 1.65653 × 10 ,(6.190)
erg
= −2.03897 × 1012 . (6.191)
mole
At 6000 K, we find the equilibrium constants for the J = 2 reactions are
   
−∆Go1 2.37351 × 1012
Kc,1 = exp = exp = 116.52, (6.192)
RT (8.314 × 107 )(6000)
   
−∆Go2 2.03897 × 1012
Kc,2 = exp = exp = 59.5861. (6.193)
RT (8.314 × 107 )(6000)
Again, omitting details, we find the two differential equations governing the evolution of
the free variables are
dρNO
= 0.723 + 2.22 × 107 ρN + 1.15 × 1013 ρ2N − 9.44 × 105 ρNO − 3.20 × 1013 ρN ρNO ,
dt
(6.194)
dρN
= 0.723 − 2.33 × 107 ρN − 1.13 × 1013 ρ2N + 5.82 × 105 ρNO − 1.00 × 1013 ρN ρNO .
dt
(6.195)

Solving numerically, we obtain a solution shown in Fig. 6.9. The numerics show a relaxation
8
R. J. Kee, et al., 2000, The Chemkin thermodynamic data base, part of the Chemkin Collection Release
3.6, Reaction Design, San Diego, CA.

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6.1. ISOTHERMAL, ISOCHORIC KINETICS 199

10 -5

10 -6
NO

10 -7

t (s)
10 -10 10 -9 10 -8 10 -7 10 -6 10 -5

Figure 6.9: NO and N concentrations versus time for T = 6000 K, P = 2.4942 ×

6 2
10 dyne/cm Zel’dovich mechanism.

to final concentrations of
mole mole
lim ρNO = 7.336 × 10−7 , lim ρN = 3.708 × 10−8 . (6.196)
t→∞ cm3 t→∞ cm3
Equations (6.194-6.195) are of the form

dρNO dρN
= ω̇NO (ρNO , ρN ), = ω̇N (ρNO , ρN ). (6.197)
dt dt
At equilibrium, we must have

ω̇NO (ρNO , ρN ) = 0, ω̇N (ρNO , ρN ) = 0. (6.198)

We find three finite roots to this problem:

mole
1 : (ρNO , ρN ) = (−1.605 × 10−6 , −3.060 × 10−8 ) , non-physical, (6.199)
cm3
mole
2 : (ρNO , ρN ) = (−5.173 × 10−8 , −2.048 × 10−6 ) , non-physical, (6.200)
cm3
mole
3 : (ρNO , ρN ) = (7.336 × 10−7 , 3.708 × 10−8 ) , physical. (6.201)
cm3
Obviously, because of negative concentrations, roots 1 and 2 are non-physical. Root 3
however is physical; moreover, it agrees with the equilibrium we found by direct numerical
integration of the full non-linear equations.
We can use local linear analysis in the neighborhood of each equilibria to rigorously as-
certain the stability of each root. Taylor series expansion of Eqs. (6.197) in the neighborhood

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200 CHAPTER 6. CHEMICAL KINETICS

of an equilibrium point yields

d ∂ ω̇NO ∂ ω̇NO
(ρNO − ρeNO ) = ω̇NO |e + (ρNO − ρeNO ) + (ρN − ρeN ) + . . . ,
dt | {z } ∂ρNO e ∂ρN e
=0
(6.202)
d ∂ ω̇N ∂ ω̇N
(ρN − ρeN ) = ω̇N |e + (ρNO − ρeNO ) + (ρN − ρeN ) + . . . . (6.203)
dt |{z} ∂ρNO e ∂ρN e
=0

Evaluation of Eqs. (6.202-6.203) near the physical root, root 3, yields the system
    
d ρNO − 7.336 × 10−7 −2.129 × 106 −4.155 × 105 ρNO − 7.336 × 10−7
= .
dt ρN − 3.708 × 10−8 2.111 × 105 −3.144 × 107 ρN − 3.708 × 10−8
| {z }
=J= ∂ ω̇/∂ρ|e

(6.204)

This is of the form

d ∂ ω̇
(ρ − ρe ) = · (ρ − ρe ) = J · (ρ − ρe ) . (6.205)
dt ∂ρ e

It is the eigenvalues of the Jacobian9 matrix J that give the time scales of evolution of the
concentrations as well as determine the stability of the local equilibrium point. Recall that
we can usually decompose square matrices via the diagonalization

J = S · Λ · S−1 . (6.206)

Here, S is the matrix whose columns are composed of the right eigenvectors of J, and Λ is
the diagonal matrix whose diagonal is populated by the eigenvalues of J. For some matrices
(typically not those encountered after our removal of linear dependencies), diagonalization
is not possible, and one must resort to the so-called near-diagonal Jordan form. This will
not be relevant to our discussion, but could be easily handled if necessary. We also recall the
eigenvector matrix and eigenvalue matrix are defined by the standard eigenvalue problem

J · S = S · Λ. (6.207)

We also recall that the components λ of Λ are found by solving the characteristic polynomial
which arises from the equation

det (J − λI) = 0, (6.208)

where I is the identity matrix. Defining z such that

S · z ≡ ρ − ρe , (6.209)
9
after Carl Gustav Jacob Jacobi, 1804-1851, German mathematician.

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6.1. ISOTHERMAL, ISOCHORIC KINETICS 201

and using the decomposition Eq. (6.206), Eq. (6.205) can be rewritten to form
d
(S · z) = |S · Λ{z· S−1} · (S · z), (6.210)
dt | {z }
J
ρ−ρe
dz
S· = S · Λ · z, (6.211)
dt
dz
S−1 · S · = S−1 · S · Λ · z, (6.212)
dt
dz
= Λ · z. (6.213)
dt
Eq. (6.213) reduces to the diagonal form
dz
= Λ · z. (6.214)
dt
This has solution for each component of z of

z1 = C1 exp(λ1 t), (6.215)

z2 = C2 exp(λ2 t), (6.216)
..
. (6.217)

Here, our matrix J, see Eq. (6.204), has two real, negative eigenvalues in the neighborhood
of the physical root 3:
1 1
λ1 = −3.143 × 107 , λ2 = −2.132 × 106 . (6.218)
s s
Thus we can conclude that the physical equilibrium is linearly stable. The local time con-
stants near equilibrium are given by the reciprocal of the magnitude of the eigenvalues.
These are

τ1 = 1/|λ1| = 3.181 × 10−8 s, τ2 = 1/|λ2| = 4.691 × 10−7 s. (6.219)

Evolution on these two time scales is predicted in Fig. 6.9. This in fact a multiscale problem.
One of the major difficulties in the numerical simulation of combustion problems comes in
the effort to capture the effects at all relevant scales. The problem is made more difficult as
the breadth of the scales expands. In this problem, the breadth of scales is not particularly
challenging. Near equilibrium the ratio of the slowest to the fastest time scale, the stiffness
ratio κ, is
τ2 4.691 × 10−7 s
κ= = = 14.75. (6.220)
τ1 3.181 × 10−8 s
Many combustion problems can have stiffness ratios over 106 . This is more prevalent at
lower temperatures.

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202 CHAPTER 6. CHEMICAL KINETICS

We can do a similar linearization near the initial state, find the local eigenvalues, and
the local time scales. At the initial state here, we find those local time scales are

τ1 = 2.403 × 10−8 s, τ2 = 2.123 × 10−8 s. (6.221)

So initially the stiffness, κ = (2.403 × 10−8 s)/(2.123 × 10−8 s) = 1.13 is much less, but the
time scale itself is small. It is seen from Fig. 6.9 that this initial time scale of 10−8 s well
predicts where significant evolution of species concentrations commences. For t < 10−8 s, the
model predicts essentially no activity. This can be correlated with the mean time between
molecular collisions–the theory on which estimates of the collision frequency factors aj are
obtained.
We briefly consider the non-physical roots, 1 and 2. A similar eigenvalue analysis of root
1 reveals that the eigenvalues of its local Jacobian matrix are
1 1
λ1 = −1.193 × 107 , λ2 = 5.434 × 106 . (6.222)
s s
Thus root 1 is a saddle and is unstable.
For root 2, we find
1 1
λ1 = 4.397 × 107 + i7.997 × 106 , λ2 = 4.397 × 107 − i7.997 × 106 . (6.223)
s s
The eigenvalues are complex with a positive real part. This indicates the root is an unstable
spiral source.
A detailed phase portrait is shown in Fig. 6.10. Here we see all three roots. Their
local character of sink, saddle, or spiral source is clearly displayed. We see that trajectories
are attracted to a curve labeled SIM for “Slow Invariant Manifold.” A part of the SIM is
constructed by the trajectory which originates at root 1 and travels to root 3. The other
part is constructed by connecting an equilibrium point at infinity into root 3. Details are
omitted here.

[Link] Stiffness, time scales, and numerics

One of the key challenges in computational chemistry is accurately predicting species concen-
tration evolution with time. The problem is made difficult because of the common presence
of physical phenomena which evolve on a widely disparate set of time scales. Systems which
evolve on a wide range of scales are known as stiff, recognizing a motivating example in
mass-spring-damper systems with stiff springs. Here we will examine the effect of tempera-
ture and pressure on time scales and stiffness. We shall also look simplistically how different
numerical approximation methods respond to stiffness.

[Link].1 Effect of temperature Let us see how the same Zel’dovich mechanism be-
haves at lower temperature, T = 1500 K; all other parameters, including the initial species

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6.1. ISOTHERMAL, ISOCHORIC KINETICS 203

sad dle 3 sink

0 SIM
SIM 1

-5

-10

-15
spiral
-20 source
2

-4 -3 -2 -1 0 1 2

Figure 6.10: NO and N phase portraits for T = 6000 K, P = 2.4942 × 106 dyne/cm2
Zel’dovich mechanism.

10 -6
NO

10 -8

10 -10

10 -12
N

t (s)
10 -11 10 -9 10 -7 10 -5 0.001 0.1 10

Figure 6.11: ρNO and ρN versus time for Zel’dovich mechanism at T = 1500 K, P =
6.23550 × 105 dyne/cm2 .

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204 CHAPTER 6. CHEMICAL KINETICS

concentrations are the same as the previous high temperature example. The pressure how-
ever, lowers, and here is P = 6.23550×105 dyne/cm2 , which is close to atmospheric pressure.
For this case, a plot of species concentrations versus time is given in Fig. 6.11.
At T = 1500 K, we notice some dramatic differences relative to the earlier studied
T = 6000 K. First, we see the reaction commences in around the same time, t ∼ 10−8 s. For
t ∼ 10−6 s, there is a temporary cessation of significant reaction. We notice a long plateau
in which species concentrations do not change over several decades of time. This is actually
a pseudo-equilibrium. Significant reaction recommences for t ∼ 0.1 s. Only around t ∼ 1 s
does the system approach final equilibrium. We can perform an eigenvalue analysis both
at the initial state and at the equilibrium state to estimate the time scales of reaction. For
this dynamical system which is two ordinary differential equations in two unknowns, we will
always find two eigenvalues, and thus two time scales. Let us call them τ1 and τ2 . Both
these scales will evolve with t.
At the initial state, we find

τ1 = 2.37 × 10−8 s, τ2 = 4.25 × 10−7 s. (6.224)

The onset of significant reaction is consistent with the prediction given by τ1 at the initial
state. Moreover, initially, the reaction is not very stiff; the stiffness ratio is κ = 17.9.
At equilibrium, we find
mole mole
lim ρNO = 4.6 × 10−9 , lim ρN = 4.2 × 10−14 , (6.225)
t→∞ cm3 t→∞ cm3
and

τ1 = 7.86 × 10−7 s, τ2 = 3.02 × 10−1 s. (6.226)

The slowest time scale near equilibrium is an excellent indicator of how long the system
takes to relax to its final state. Note also that near equilibrium, the stiffness ratio is large,
κ = τ2 /τ1 ∼ 3.8 × 105 . This is known as the stiffness ratio. When it is large, the scales in
the problem are widely disparate and accurate numerical solution becomes challenging.
In summary, we find the effect of lowering temperature while leaving initial concentrations
constant
• lowers the pressure somewhat, slightly slowing down the collision time, and slightly
slowing the fastest time scales, and

• slows the slowest time scales many orders of magnitude, stiffening the system signifi-
cantly, because collisions may not induce reaction with their lower collision speed.

[Link].2 Effect of initial pressure Let us maintain the initial temperature at T =

1500 K, but drop the initial concentration of each species to

b mole
ρNO = b
ρN = b
ρN2 = b
ρO2 = b
ρO = 10−8 . (6.227)
cm3

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6.1. ISOTHERMAL, ISOCHORIC KINETICS 205

10- 8

NO
10 -10

10 -12

10 -14
N

10 -16

t (s)
10- 8 10 - 6 10- 4 0.01 1 100

Figure 6.12: ρNO and ρN versus time for Zel’dovich mechanism at T = 1500 K, P =
6.2355 × 103 dyne/cm2 .

With this decrease in number of moles, the pressure now is

dyne
P = 6.23550 × 103 . (6.228)
cm2
This pressure is two orders of magnitude lower than atmospheric. We solve for the species
concentration profiles and show the results of numerical prediction in Fig. 6.12. Relative to
the high pressure P = 6.2355 × 105 dyne/cm2 , T = 1500 K case, we notice some similarities
and dramatic differences. The overall shape of the time-profiles of concentration variation
is similar. But, we see the reaction commences at a much later time, t ∼ 10−6 s. For
t ∼ 10−4 s, there is a temporary cessation of significant reaction. We notice a long plateau
in which species concentrations do not change over several decades of time. This is again
actually a pseudo-equilibrium. Significant reaction recommences for t ∼ 10 s. Only around
t ∼ 100 s does the system approach final equilibrium. We can perform an eigenvalue analysis
both at the initial state and at the equilibrium state to estimate the time scales of reaction.
At the initial state, we find

τ1 = 2.37 × 10−6 s, τ2 = 4.25 × 10−5 s. (6.229)

The onset of significant reaction is consistent with the prediction given by τ1 at the initial
state. Moreover, initially, the reaction is not very stiff; the stiffness ratio is κ = 17.9.
Interestingly, by decreasing the initial pressure by a factor of 102 , we increased the initial
time scales by a complementary factor of 102 ; moreover, we did not alter the stiffness.
At equilibrium, we find
mole mole
lim ρNO = 4.6 × 10−11 , lim ρN = 4.2 × 10−16 , (6.230)
t→∞ cm3 t→∞ cm3

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206 CHAPTER 6. CHEMICAL KINETICS

and

τ1 = 7.86 × 10−5 s, τ2 = 3.02 × 101 s. (6.231)

By decreasing the initial pressure by a factor of 102 , we decreased the equilibrium concentra-
tions by a factor of 102 and increased the time scales by a factor of 102 , leaving the stiffness
ratio unchanged.
In summary, we find the effect of lowering the initial concentrations significantly while
leaving temperature constant
• lowers the pressure significantly, proportionally slowing down the collision time, as well
as the fastest and slowest time scales, and

• does not affect the stiffness of the system.

[Link].3 Stiffness and numerics The issue of how to simulate stiff systems of ordinary
differential equations, such as presented by our Zel’dovich mechanism, is challenging. Here a
brief summary of some of the issues will be presented. The interested reader should consult
the numerical literature for a full discussion. See for example the excellent text of Iserles.10
We have seen throughout this section that there are two time scales at work, and they are
often disparate. The species evolution is generally characterized by an initial fast transient,
followed by a long plateau, then a final relaxation to equilibrium. We noted from the phase
plane of Fig. 6.10 that the final relaxation to equilibrium (shown along the green line labeled
“SIM”) is an attracting manifold for a wide variety of initial conditions. The relaxation onto
the SIM is fast, and the motion on the SIM to equilibrium is relatively slow.
Use of common numerical techniques can often mask or obscure the actual dynamics.
Numerical methods to solve systems of ordinary differential equations can be broadly cat-
egorized as explicit or implicit. We give a brief synopsis of each class of method. We cast
each as a method to solve a system of the form
dρ
= ω̇(ρ). (6.232)
dt
• Explicit: The simplest of these, the forward Euler method, discretizes Eq. (6.232) as
follows:
ρn+1 − ρn
= ω̇(ρn ), (6.233)
∆t
so that

ρn+1 = ρn + ∆t ω̇(ρn ). (6.234)

Explicit methods are summarized as

10
A. Iserles, 2008, A First Course in the Numerical Analysis of Differential Equations, Cambridge Uni-
versity Press, Cambridge, UK.

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6.1. ISOTHERMAL, ISOCHORIC KINETICS 207

– easy to program, because Eq. (6.234) can be solved explicitly to predict the new
value ρn+1 in terms of the old values at step n.
– need to have ∆t < τf astest in order to remain numerically stable,
– able to capture all physics and all time scales at great computational expense for
stiff problems,
– requiring much computational effort for little payoff in the SIM region of the phase
plane, and thus
– inefficient for some portions of stiff calculations.

• Implicit: The simplest of these methods, the backward Euler method, discretizes
Eq. (6.232) as follows:
ρn+1 − ρn
= ω̇(ρn+1 ), (6.235)
∆t
so that

ρn+1 = ρn + ∆t ω̇(ρn+1 ). (6.236)

Implicit methods are summarized as

– more difficult to program because a non-linear set of algebraic equations, Eq. (6.236),
must be solved at every time step with no guarantee of solution,
– requiring potentially significant computational time to advance each time step,
– capable of using very large time steps and remaining numerically stable,
– suspect to missing physics that occur on small time scales τ < ∆t,
– in general better performers than explicit methods.

A wide variety of software tools exist to solve systems of ordinary differential equations.
Most of them use more sophisticated techniques than simple forward and backward Euler
methods. One of the most powerful techniques is the use of error control. Here the user
specifies how far in time to advance and the error that is able to be tolerated. The algorithm,
which is complicated, selects then internal time steps, for either explicit or implicit methods,
to achieve a solution within the error tolerance at the specified output time. A well known
public domain algorithm with error control is provided by dlsode.f, which can be found in
the netlib repository.11
Let us exercise the Zel’dovich mechanism under the conditions simulated in Fig. 6.12,
T = 1500 K, P = 6.2355 × 103 dyne/cm2 . Recall in this case the fastest time scale near
equilibrium is τ1 = 7.86 × 10−5 s ∼ 10−4 s at the initial state, and the slowest time scale is
11
Hindmarsh, A. C., 1983, ODEPACK, a systematized collection of ODE solvers, Scientific Comput-
ing, edited by R. S. Stepleman, et al., North-Holland, Amsterdam, pp. 55-64. Source code at
[Link]

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208 CHAPTER 6. CHEMICAL KINETICS

Explicit Explicit Implicit Implicit

∆t (s) Ninternal ∆tef f (s) Ninternal ∆tef f (s)
102 106 10−4 100 102
101 105 10−4 100 101
100 104 10−4 100 100
10−1 103 10−4 100 10−1
10−2 102 10−4 100 10−2
10−3 101 10−4 100 10−3
10−4 100 10−4 100 10−4
10−5 100 10−5 100 10−5
10−6 100 10−6 100 10−6

Table 6.3: Results from computing Zel’dovich NO production using implicit and explicit
methods with error control in dlsode.f.

τ = 3.02 × 101 s at the final state. Let us solve for these conditions using dlsode.f, which
uses internal time stepping for error control, in both an explicit and implicit mode. We
specify a variety of values of ∆t and report typical values of number of internal time steps
selected by dlsode.f, and the corresponding effective time step ∆tef f used for the problem,
for both explicit and implicit methods, as reported in Table 6.3.
Obviously if output is requested using ∆t > 10−4 s, the early time dynamics near t ∼
−4
10 s will be missed. For physically stable systems, codes such as dlsode.f will still provide
a correct solution at the later times. For physically unstable systems, such as might occur in
turbulent flames, it is not clear that one can use large time steps and expect to have fidelity
to the underlying equations. The reason is the physical instabilities may evolve on the same
time scale as the fine scales which are overlooked by large ∆t.

6.2 Adiabatic, isochoric kinetics

It is more practical to allow for temperature variation within a combustor. The best model
for this is adiabatic kinetics. Here we will restrict our attention to isochoric problems.

6.2.1 Thermal explosion theory

Consider a small extension to the theory presented first in Sec. 5.2. There is a simple
description known as thermal explosion theory which provides a good explanation for how
initially slow exothermic reaction induces a sudden temperature rise accompanied by a final
relaxation to equilibrium.
Let us consider a simple isomerization reaction in a closed volume

A ⇌ B. (6.237)

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6.2. ADIABATIC, ISOCHORIC KINETICS 209

Let us take A and B to both be calorically perfect ideal gases with identical molecular masses
MA = MB = M and identical specific heats, cvA = cvB = cv ; cP A = cP B = cP . We can
consider A and B to be isomers of an identical molecular species. So we have N = 2 species
reacting in J = 1 reactions. The number of elements L here is irrelevant.

[Link] One-step reversible kinetics

Let us insist our reaction process be isochoric and adiabatic, and commence with only A
present. The reaction kinetics with β = 0 are
  
dρA −E 1
= − a exp ρA − ρ , (6.238)
dt RT Kc B
| {z }
=k
| {z }
=r
  
dρB −E 1
= a exp ρA − ρ , (6.239)
dt RT Kc B
| {z }
=k
| {z }
=r

ρA (0) = b
ρA , ρB (0) = 0. (6.240)
For our alternate compact linear algebra based form, we note that
  
−E 1
r = a exp ρA − ρ , (6.241)
RT Kc B
and that
   
d ρA −1
= (r). (6.242)
dt ρB 1
Performing the decomposition yields
   
d ρA −1
= (r). (6.243)
dt ρA + ρB 0
Expanded, this is
     
1 0 d ρA −1
= (r). (6.244)
1 1 dt ρB 0
Combining Eqs. (6.238-6.239) and integrating yields
d
(ρ + ρB ) = 0, (6.245)
dt A
ρA + ρB = b
ρA , (6.246)
ρB = b
ρA − ρA . (6.247)

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210 CHAPTER 6. CHEMICAL KINETICS

Thus, Eq. (6.238) reduces to

  
dρA −E 1 b
= −a exp ρA − ρ − ρA . (6.248)
dt RT Kc A
Scaling, Eq. (6.248) can be rewritten as
     
d ρA E 1 ρA 1 ρA
= − exp − − 1− . (6.249)
d(at) bρA RTo T /To b
ρA Kc b
ρA

[Link] First law of thermodynamics

Recall the first law of thermodynamics and neglecting potential and kinetic energy changes:
dE
= Q̇ − Ẇ . (6.250)
dt
Here E is the total internal energy. Because we insist the problem is adiabatic Q̇ = 0.
Because we insist the problem is isochoric, there is no work done, so Ẇ = 0. Thus we have
dE
= 0. (6.251)
dt
Thus, we find
E = Eo . (6.252)
Recall the total internal energy for a mixture of two calorically perfect ideal gases is

E = nA eA + nB eB , (6.253)
n n 
A B
= V eA + eB , (6.254)
V V
= V (ρA eA + ρB eB ) , (6.255)
    
PA PB
= V ρA hA − + ρB hB − , (6.256)
ρA ρB




= V ρA hA − RT + ρB hB − RT , (6.257)
  o
  o

= V ρA cP (T − To ) + hTo ,A − RT + ρB cP (T − To ) + hTo ,B − RT ,(6.258)
 o o

= V (ρA + ρB )(cP (T − To ) − RT ) + ρA hTo ,A + ρB hTo ,B , (6.259)
 o o

= V (ρA + ρB )((cP − R)T − cP To ) + ρA hTo ,A + ρB hTo ,B , (6.260)
 o o

= V (ρA + ρB )((cP − R)T − (cP − R + R)To ) + ρA hTo ,A + ρB hTo ,B , (6.261)
 o o

= V (ρA + ρB )(cv T − (cv + R)To ) + ρA hTo ,A + ρB hTo ,B , (6.262)
 o o

= V (ρA + ρB )cv (T − To ) + ρA (hTo ,A − RTo ) + ρB (hTo ,B − RTo ) , (6.263)


= V (ρA + ρB )cv (T − To ) + ρA eoTo ,A + ρB eoTo ,B . (6.264)

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6.2. ADIABATIC, ISOCHORIC KINETICS 211

Now at the initial state, we have T = To , so

 
Eo = V b ρA eoTo ,A + b
ρB eoTo ,B . (6.265)

So, we can say our caloric equation of state is

 
E − Eo = V (ρA + ρB )cv (T − To ) + (ρA − b ρA )eoTo ,A + (ρB − b
ρB )eoTo ,B , (6.266)
 
= V (b ρA + b
ρB )cv (T − To ) + (ρA − b
ρA )eoTo ,A + (ρB − b
ρB )eoTo ,B . (6.267)

As an aside, on a molar basis, we scale Eq. (6.267) to get

e − eo = cv (T − To ) + (yA − yAo )eoTo ,A + (yB − yBo )eoTo ,B . (6.268)

And because we have assumed the molecular masses are the same, MA = MB , the mole
fractions are the mass fractions, and we can write on a mass basis

e − eo = cv (T − To ) + (YA − YAo )eoTo ,A + (YB − YBo )eoTo ,B . (6.269)

Returning to Eq. (6.267), our energy conservation relation, Eq. (6.252), becomes
 
b b b o b o
0 = V (ρA + ρB )cv (T − To ) + (ρA − ρA )eTo ,A + (ρB − ρB )eTo ,B . (6.270)

Now we solve for T

0 = (b
ρA + bρB )cv (T − To ) + (ρA − b ρA )eoTo ,A + (ρB − b
ρB )eoTo ,B , (6.271)
ρ −b ρA o ρ −b ρB o
0 = cv (T − To ) + A eTo ,A + B eT ,B , (6.272)
b
ρA + b
ρB b
ρA + b ρB o
b
ρ − ρA eoTo ,A b ρ − ρB eoTo ,B
T = To + A + B . (6.273)
b
ρA + bρB cv b
ρA + b ρB cv

ρB = 0, giving also ρB = b
Now we impose our assumption that b ρA − ρA ,

b
ρA − ρA eoTo ,A ρB eoTo ,B
T = To + − , (6.274)
b
ρA cv b
ρA cv
b
ρ − ρA eoTo ,A − eoTo ,B
= To + A . (6.275)
b
ρA cv
o o
In summary, realizing that hTo ,A − hTo ,B = eoTo ,A − eoTo ,B we can write T as a function of ρA :

(b
ρA − ρA ) o o
T = To + (hTo ,A − hTo ,B ). (6.276)
b
ρA cv

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212 CHAPTER 6. CHEMICAL KINETICS

o o
We see then that if hTo ,A > hTo ,B , that as ρA decreases from its initial value of b
ρA that T
will increase. We can scale Eq. (6.276) to form
    o o !
T ρA hTo ,A − hTo ,B
=1+ 1− . (6.277)
To b
ρA cv To

We also note that our caloric state equation, Eq. (6.268) can, for yAo = 1, yBo = 0 as

e − eo = cv (T − To ) + (yA − 1)eoTo ,A + yB eoTo ,B , (6.278)

= cv (T − To ) + ((1 − yB ) − 1)eoTo ,A + yB eoTo ,B , (6.279)
= cv (T − To ) − yB (eoTo ,A − eoTo ,B ). (6.280)

Similarly, on a mass basis, we can say,

e − eo = cv (T − To ) − YB (eoTo ,A − eoTo ,B ). (6.281)

For this problem, we also have

 
−∆Go
Kc = exp , (6.282)
RT

with

∆Go = g oB − g oA , (6.283)
o o
= hB − T soB − (hA − T soA ), (6.284)
o o
= (hB − hA ) − T (soB − soA ), (6.285)
o o
= (hTo ,B − hTo ,A ) − T (soTo ,B − soTo ,A ). (6.286)

So
o o !
hTo ,A − hTo ,B − T (soTo ,A − soTo ,B )
Kc = exp , (6.287)
RT
o o !!
cv To hTo ,A − hTo ,B − T (soTo ,A − soTo ,B )
= exp , (6.288)
RT cv To
o o !!
1 1 hTo ,A − hTo ,B T (soTo ,A − soTo ,B )
= exp − . (6.289)
γ − 1 TTo cv To To cv

Here we have used the definition of the ratio of specific heats, γ = cP /cv along with R =
cP − cv . So we can solve Eq. (6.248) by first using Eq. (6.289) to eliminate Kc and then
Eq. (6.276) to eliminate T .

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6.2. ADIABATIC, ISOCHORIC KINETICS 213

[Link] Dimensionless form

Let us try writing dimensionless variables so that our system can be written in a compact
dimensionless form. First lets take dimensionless time τ to be

τ = at. (6.290)

Let us take dimensionless species concentration to be z with

ρA
z= . (6.291)
b
ρA
Let us take dimensionless temperature to be θ with
T
θ= . (6.292)
To
Let us take dimensionless heat release to be q with
o o
hT ,A − hTo ,B
q= o . (6.293)
cv To
Let us take dimensionless activation energy to be Θ with
E
Θ= . (6.294)
RTo
And let us take the dimensionless entropy change to be σ with
(soTo ,A − soTo ,B )
σ= . (6.295)
cv
So our equations become
  
dz Θ 1
= − exp − z− (1 − z) , (6.296)
dτ θ Kc
θ = 1 + (1 − z)q, (6.297)
 
1 1
Kc = exp (q − θσ) . (6.298)
k−1θ
It is more common to consider the products. Let us define for general problems
ρB ρB
λ= = . (6.299)
ρA + ρB b
ρA + b
ρB

Thus λ is the mass fraction of product. For our problem, b

ρB = 0 so

ρB ρc − ρA
λ= = A . (6.300)
b
ρA b
ρA

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214 CHAPTER 6. CHEMICAL KINETICS

Thus,

λ = 1 − z. (6.301)

We can think of λ as a reaction progress variable as well. When λ = 0, we have τ = 0, and

the reaction has not begun. Thus, we get
  
dλ Θ 1
= exp − (1 − λ) − λ , (6.302)
dτ θ Kc
θ = 1 + qλ, (6.303)
 
1 1
Kc = exp (q − θσ) . (6.304)
k−1θ

[Link] Example calculation

Let us choose some values for the dimensionless parameters:
7
Θ = 20, σ = 0, q = 10, k= . (6.305)
5
With these choices, our kinetics equations reduce to
   
dλ −20 −25
= exp (1 − λ) − λ exp , λ(0) = 0. (6.306)
dτ 1 + 10λ 1 + 10λ

The right side of Eq. (6.306) is at equilibrium for values of λ which drive it to zero.
Numerical root finding methods show this to occur at λ ∼ 0.920539. Near this root, Taylor
series expansion shows the dynamics are approximated by
d
(λ − 0.920539) = −0.17993(λ − 0.920539) + . . . (6.307)
dτ
Thus the local behavior near equilibrium is given by

λ = 0.920539 + C exp (−0.17993 τ ) . (6.308)

Here C is some arbitrary constant. Clearly the equilibrium is stable, with a time constant
of 1/0.17993 = 5.55773.
Numerical solution shows the full behavior of the dimensionless species concentration
λ(τ ); see Fig. 6.13. Clearly the product concentration λ is small for some long period of
time. At a critical time near τ = 2.7 × 106 , there is a so-called thermal explosion with a
rapid increase in λ. Note that the estimate of the time constant near equilibrium is orders
of magnitude less than the explosion time, 5.55773 ≪ 2.7 × 106 . Thus, linear analysis
here is a poor tool to estimate an important physical quantity, the ignition time. Once the
ignition period is over, there is a rapid equilibration to the final state. The dimensionless
temperature plot is shown in Fig. 6.14. The temperature plot is similar in behavior to the

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6.2. ADIABATIC, ISOCHORIC KINETICS 215

1.0

0.8

0.6

0.4

0.2

0 6 6 6 6 6
1 x 10 2 x10 3 x 10 4 x10 5 x 10

Figure 6.13: Dimensionless plot of reaction product concentration λ versus time τ for adia-
batic isochoric combustion with simple reversible kinetics.

10

6 6 6 6 6
1 x 10 2 x10 3 x 10 4 x10 5 x 10

Figure 6.14: Dimensionless plot of temperature θ versus time τ for adiabatic, isochoric
combustion with simple reversible kinetics.

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216 CHAPTER 6. CHEMICAL KINETICS

species concentration plot. At early time, the temperature is cool. At a critical time, the
thermal explosion time, the temperature rapidly rises. This rapid rise, coupled with the
exponential sensitivity of reaction rate to temperature, accelerates the formation of product.
This process continues until the reverse reaction is activated to the extent it prevents further
creation of product.

[Link] High activation energy asymptotics

Let us see if we can get an analytic prediction of the thermal explosion time, τ ∼ 2.7 × 106 .
Such a prediction would be valuable to see how long a slowing reacting material might take
to ignite. Our analysis is similar to that given by Buckmaster and Ludford in their Chapter
1.12
For convenience let us restrict ourselves to σ = 0. In this limit, Eqs. (6.302-6.304) reduce
to
   
dλ Θ −q
= exp − (1 − λ) − λ exp , (6.309)
dτ 1 + qλ (k − 1)(1 + qλ)
with λ(0) = 0. The key trouble in getting an analytic solution to Eq. (6.309) is the presence
of λ in the denominator of an exponential term. We need to find a way to move it to the
numerator. Asymptotic methods provide one such way.
Now we recall for early time λ ≪ 1. Let us assume λ takes the form

λ = ǫλ1 + ǫ2 λ2 + ǫ3 λ3 + . . . (6.310)

Here we will assume 0 < ǫ ≪ 1 and that λ1 (τ ) ∼ O(1), λ2 (τ ) ∼ O(1), . . . , and will define ǫ
in terms of physical parameters shortly. Now with this assumption, we have
1 1
= . (6.311)
1 + qλ 1 + ǫqλ1 + ǫ qλ2 + ǫ3 qλ3 + . . .
2

Long division of the term on the right side yields the approximation
1
= = 1 − ǫqλ1 + ǫ2 (q 2 λ21 − qλ2 ) + . . . , (6.312)
1 + qλ
= 1 − ǫqλ1 + O(ǫ2 ). (6.313)

So
 
Θ

exp − ∼ exp −Θ(1 − ǫqλ1 + O(ǫ2 )) , (6.314)
1 + qλ


∼ e−Θ exp ǫqΘλ1 + O(ǫ2 ) , (6.315)

We have moved λ from the denominator to the numerator of the most important exponential
term.
12
J. D. Buckmaster and G. S. S. Ludford, 1983, Lectures on Mathematical Combustion, SIAM, Philadelphia.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

6.2. ADIABATIC, ISOCHORIC KINETICS 217

Now, let us take the limit of high activation energy by defining ǫ to be

1
ǫ≡ . (6.316)
Θ
Let us let the assume the remaining parameters, q and k are both O(1) constants. When Θ
is large, ǫ will be small. With this definition, Eq. (6.315) becomes
 
Θ

exp − ∼ e−1/ǫ exp qλ1 + O(ǫ2 ) . (6.317)
1 + qλ
With these assumptions and approximations, Eq. (6.309) can be written as
d

(ǫλ1 + . . . ) = e−1/ǫ exp qλ1 + O(ǫ2 )
dτ   
−q
× (1 − ǫλ1 − . . . ) − (ǫλ1 + . . . ) exp .
(k − 1)(1 + qǫλ1 + . . . )
(6.318)
Now let us rescale time via
1
τ∗ = e−1/ǫ τ. (6.319)
ǫ
With this transformation, the chain rule shows how derivatives transform:
d dτ∗ d 1 d
= = 1/ǫ . (6.320)
dτ dτ dτ∗ ǫe dτ∗
With this transformation, Eq. (6.318) becomes
1 d 1 2


(ǫλ 1 + . . . ) = exp qλ 1 + O(ǫ )
ǫe1/ǫ dτ∗ e1/ǫ
  
−q
× (1 − ǫλ1 − . . . ) − (ǫλ1 + . . . ) exp .
(k − 1)(1 + qǫλ1 + . . . )
(6.321)
This simplifies to
d

(λ1 + . . . ) = exp qλ1 + O(ǫ2 )
dτ∗
  
−q
× (1 − ǫλ1 − . . . ) − (ǫλ1 + . . . ) exp .
(k − 1)(1 + qǫλ1 + . . . )
(6.322)
Retaining only O(1) terms in Eq. (6.322), we get
dλ1
= exp (qλ1 ) . (6.323)
dτ∗

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218 CHAPTER 6. CHEMICAL KINETICS

1.2

0.8

0.4

0.00 0.02 0.04 0.06 0.08 0.10 0.12

Figure 6.15: λ1 versus τ∗ for ignition problem.

This is supplemented by the initial condition λ1 (0) = 0. Separating variables and solving,
we get

exp(−qλ1 )dλ1 = dτ∗ , (6.324)

1
− exp(−qλ1 ) = τ∗ + C. (6.325)
q
Applying the initial condition gives
1
− exp(−q(0)) = C, (6.326)
q
1
− = C. (6.327)
q
So
1 1
− exp(−qλ1 ) = τ∗ − , (6.328)
q q
exp(−qλ1 ) = −qτ∗ + 1, (6.329)
 
1
exp(−qλ1 ) = −q τ∗ − , (6.330)
q
  
1
−qλ1 = ln −q τ∗ − , (6.331)
q
  
1 1
λ1 = − ln −q τ∗ − . (6.332)
q q

For q = 10, a plot of λ1 (τ∗ ) is shown in Fig. 6.15. We note at a finite τ∗ that λ1 begins to
exhibit unbounded growth. In fact, it is obvious from Eq. (6.323) that as
1
τ∗ → ,
q

CC BY-NC-ND. 19 January 2025, J. M. Powers.

6.2. ADIABATIC, ISOCHORIC KINETICS 219

that
λ1 → ∞.
That is there exists a finite time for which λ1 violates the assumptions of our asymptotic
theory which assumes λ1 = O(1). We associate this time with the ignition time, τ∗i :

1
τ∗i = . (6.333)
q

Let us return this to more primitive variables:

 
1 −1 1
exp τi = , (6.334)
ǫ ǫ q
1


ǫ exp ǫ exp Θ
τi = = . (6.335)
q Θq

For our system with Θ = 20 and q = 10, we estimate the dimensionless ignition time as

exp 20
τi = = 2.42583 × 106 . (6.336)
(20)(10)

This is a surprisingly good estimate, given the complexity of the problem. Recall the nu-
merical solution showed ignition for τ ∼ 2.7 × 106 .
In terms of dimensional time, ignition time prediction becomes
  !  
exp Θ 1 RTo cv To E
ti = = o o exp . (6.337)
aΘq a E hTo ,A − hTo ,B RTo

Note the ignition is suppressed if the ignition time is lengthened, which happens when

• he activation energy E is increased, because the exponential sensitivity is stronger than

the algebraic sensitivity,
o o
• the energy of combustion (hTo ,A − hTo ,B ) is decreased because it takes longer to react
to drive the temperature to a critical value to induce ignition, and

• the collision frequency factor a is decreased, which suppresses reaction.

6.2.2 Detailed H2 − O2 − N2 kinetics

Here is an example which uses multiple reactions for an adiabatic isochoric system is given.
We will simply present results at this stage. The equation for temperature evolution for the
adiabatic mixture requires further development and will be given in Sec. 7.7. Consider the
full time-dependency of a problem similar to the thermal explosion problem just considered.

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220 CHAPTER 6. CHEMICAL KINETICS

0 H
10 O
H2
O2
OH
H2O
−5 H 2 O2
10 HO 2
N2
Yi

−10
10

−15
10
−10 −5 0
10 10 10
t (s)

Figure 6.16: Plot of YH2 (t), YH (t), YO (t), YO2 (t), YOH (t), YH2 O (t), YHO2 (t), YH2 O2 (t), YN2 (t),
for adiabatic, isochoric combustion of a mixture of 2H2 + O2 + 3.76N2 initially at To =
1542.7 K, Po = 2.8323 × 106 Pa.

A closed, fixed, adiabatic volume, V = 0.3061251 cm3 , contains at t = 0 s a stoichiometric

hydrogen-air mixture of 2 × 10−5 mole of H2 , 1 × 10−5 mole of O2 , and 3.76 × 10−5 mole of
N2 at Po = 2.83230 × 106 Pa and To = 1542.7 K.13 The initial molar concentrations are

mole −5 mole −4 mole

ρH2 = 6.533 × 10−5 , ρ O = 3.267 × 10 , ρN = 1.228 × 10 . (6.338)
cm3 2
cm3 2
cm3
The initial mass fractions are calculated with aid of Eq. (6.8), so Yi = Mi ρi /ρ. They are

YH2 = 0.0285, YO2 = 0.226, YN2 = 0.745. (6.339)

To avoid issues associated with numerical roundoff errors at very early time for species
with very small compositions, the minor species were initialized at a small non-zero value
near machine precision; each was assigned a value of 10−15 mole. The minor species all have
ρi = 1.803 × 10−16 mole/cm3 . They have correspondingly small initial mass fractions.
We seek the reaction dynamics as the system proceeds from its initial state to its final
state. We use the reversible detailed kinetics mechanism of Table 6.2. This problem requires
a detailed numerical solution. Such a solution was performed by solving the appropriate
equations for a mixture of nine interacting species: H2 , H, O, O2 , OH, H2 O, HO2 , H2 O2 ,
and N2 . The dynamics of the reaction process are reflected in Figs. 6.16-6.17.
At early time, t < 10−7 s, the pressure, temperature, and major reactant species con-
centrations (H2 , O2 , N2 ) are nearly constant. However, the minor species, e.g. OH, HO2 ,
and the major product, H2 O, are undergoing rapid growth, albeit with math fractions that
remain small. In this period, the material is in what is known as the induction period.
13
This temperature and pressure correspond to that of the same ambient mixture of H2 , O2 and N2 which
was shocked from 1.01325 × 105 Pa, 298 K, to a value associated with a freely propagating detonation.

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6.2. ADIABATIC, ISOCHORIC KINETICS 221

7
4000 10

3500

3000

2500

P (Pa)
T (K)

2000

1500

1000

500
6
0 −10 −5
10 −10 −5
10 10 10 10
t (s) t (s)

Figure 6.17: Plots of T (t), P (t) for adiabatic, isochoric combustion of a mixture of 2H2 +
O2 + 3.76N2 initially at To = 1542.7 K, Po = 2.8323 × 106 Pa.

After a certain critical mass of minor species has accumulated, exothermic recombination
of these minor species to form the major product H2 O induces the temperature to rise, which
accelerates further the reaction rates. This is manifested in a thermal explosion. A common
definition of the end of the induction period is the induction time, t = tind , the time when
dT /dt goes through a maximum. Here one finds

tind = 6.6 × 10−7 s. (6.340)

A close-up view of the species concentration profiles is given in Fig. 6.18.

At the end of the induction zone, there is a final relaxation to equilibrium. The equilib-
rium mass fractions of each species are

Y O2 = 1.85 × 10−2, (6.341)

YH = 5.41 × 10−4, (6.342)
YOH = 2.45 × 10−2, (6.343)
YO = 3.88 × 10−3, (6.344)
Y H2 = 3.75 × 10−3, (6.345)
Y H2 O = 2.04 × 10−1, (6.346)
YHO2 = 6.84 × 10−5, (6.347)
Y H 2 O2 = 1.04 × 10−5, (6.348)
Y N2 = 7.45 × 10−1. (6.349)

We note that because our model takes N2 to be inert that its value remains unchanged.
Other than N2 , the final products are dominated by H2 O. The equilibrium temperature is
3382.3 K and 5.53 × 106 Pa.

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222 CHAPTER 6. CHEMICAL KINETICS

0
10

H
O
−5 H2
Yi 10 O2
OH
H2O
H 2 O2
−10
10 HO 2
N2

2 4 6 8 10
t (s) −7
x 10

Figure 6.18: Plot near thermal explosion time of YH2 (t), YH (t), YO (t), YO2 (t), YOH (t), YH2 O (t),
YHO2 (t), YH2 O2 (t), YN2 (t), for adiabatic, isochoric combustion of a mixture of 2H2 +O2 +3.76N2
initially at at To = 1542.7 K, Po = 2.8323 × 106 Pa.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

Chapter 7

Aerothermochemistry

Borgnakke and Sonntag, Chapters 13, 14,

Powers, Chapters 4, 5,
Farokhi, Chapters 7, 12.

This chapter will further develop notions associated with the thermodynamics of chemi-
cal reactions and their incorporation into models of reactive fluid mechanics for aerospace
application. This combination of
• aerodynamics,
• thermodynamics, and
• chemistry,
was named aerothermochemistry by von Kármán.1 The focus here will first be on single
chemical reactions, and this will be followed by an extension to multiple reactions. The
chapter is closed by application of hydrogen-air combustion in a supersonic duct with variable
area, such as might be found in aerospace applications.

7.1 Molecular mass

The molecular mass of a molecule is a straightforward notion from chemistry. One simply
sums the product of the number of atoms and each atom’s atomic mass to form the molecular
mass. If one defines L as the number of elements present in species i, φli as the number of
moles of atomic element l in species i, and Ml as the atomic mass of element l, the molecular
mass Mi of species i
X L
Mi = Ml φli , i = 1, . . . , N. (7.1)
l=1

1
von Kármán, T., 1955, Fundamental equations in aerothermochemistry, Second AGARD Combustion
Colloquium, Liége.

223
224 CHAPTER 7. AEROTHERMOCHEMISTRY

In vector form, one would say

MT = MT · φ, or M = φT · M. (7.2)
Here M is the vector of length N containing the molecular masses, M is the vector of length
L containing the elemental masses, and φ is the matrix of dimension L × N containing the
number of moles of each element in each species. Generally, φ is full rank. If N > L, φ has
rank L. If N < L, φ has rank N. In any problem involving an actual chemical reaction, one
will find N ≥ L, and in most cases N > L. In isolated problems not involving a reaction,
one may have N < L. In any case, M lies in the column space of φT , which is the row space
of φ.

Example 7.1
Find the molecular mass of H2 O.

Here, one has two elements H and O, so L = 2, and one species, so N = 1; thus, in this isolated
problem, N < L. Take i = 1 for species H2 O. Take l = 1 for element H. Take l = 2 for element O.
From the periodic table, one gets M1 = 1 kg/kmole for H, M2 = 16 kg/kmole for O. For element 1,
there are 2 atoms, so φ11 = 2. For element 2, there is 1 atom so φ21 = 1. So the molecular mass of
species 1, H2 O is
     

φ11 kg kg
M1 = M1 M2 = M1 φ11 + M2 φ21 = 1 (2) + 16 (1), (7.3)
φ21 kmole kmole
kg
= 18 . (7.4)
kmole

Example 7.2
Find the molecular masses of the two species C8 H18 and CO2 . Here, for practice, the vector matrix
notation is exercised. In a certain sense this is overkill, but it is useful to be able to understand a
general notation.

One has N = 2 species, and takes i = 1 for C8 H18 and i = 2 for CO2 . One also has L = 3 elements
and takes l = 1 for C, l = 2 for H, and l = 3 for O. Now for each element, one has M1 = 12 kg/kmole,
M2 = 1 kg/kmole, M3 = 16 kg/kmole. The molecular masses are then given by
 


φ11 φ12
M1 M2 = M1 M2 M3 φ21 φ22  , (7.5)
φ31 φ32
 

8 1

= 12 1 16 18 0 = 114 44 . (7.6)
0 2
That is for C8 H18 , one has molecular mass M1 = 114 kg/kmole. For CO2 , one has molecular mass
M2 = 44 kg/kmole.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

7.2. STOICHIOMETRY 225

7.2 Stoichiometry
7.2.1 General development
Stoichiometry represents a mass balance on each element in a chemical reaction. For example,
in the simple global reaction
2H2 + O2 ⇌ 2H2 O, (7.7)
one has 4 H atoms in both the reactant and product sides and 2 O atoms in both the reactant
and product sides. In this section stoichiometry will be systematized.
Consider now a general reaction with N species. This reaction can be represented by
N
X N
X
νi′ χi ⇌ νi′′ χi . (7.8)
i=1 i=1

Here χi is the ith chemical species, νi′ is the forward stoichiometric coefficient of the ith
reaction, and νi′′ is the reverse stoichiometric coefficient of the ith reaction. Both νi′ and νi′′
are to be interpreted as pure dimensionless numbers.
In Equation (7.7), one has N = 3 species. One might take χ1 = H2 , χ2 = O2 , and
χ3 = H2 O. The reaction is written in more general form as
(2)χ1 + (1)χ2 + (0)χ3 ⇌ (0)χ1 + (0)χ2 + (2)χ3 , (7.9)
(2)H2 + (1)O2 + (0)H2 O ⇌ (0)H2 + (0)O2 + (2)H2 O. (7.10)
Here, one has
ν1′ = 2, ν1′′ = 0, (7.11)
ν2′ = 1, ν2′′ = 0, (7.12)
ν3′ = 0, ν3′′ = 2. (7.13)
It is common and useful to define another pure dimensionless number, the net stoichio-
metric coefficients for species i, νi . Here νi represents the net production of number if the
reaction goes forward. It is given by
νi = νi′′ − νi′ . (7.14)
For the reaction 2H2 + O2 ⇌ 2H2 O, one has
ν1 = ν1′′ − ν1′ = 0 − 2 = −2, (7.15)
ν2 = ν2′′ − ν2′ = 0 − 1 = −1, (7.16)
ν3 = ν3′′ − ν3′ = 2 − 0 = 2. (7.17)
With these definitions, it is possible to summarize a chemical reaction as
N
X
νi χi = 0. (7.18)
i=1

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226 CHAPTER 7. AEROTHERMOCHEMISTRY

In vector notation, one would say

ν T · χ = 0. (7.19)
For the reaction of this section, one might write the non-traditional form

−2H2 − O2 + 2H2 O = 0. (7.20)

It remains to enforce a stoichiometric balance. This is achieved if, for each element, l =
1, . . . , L, one has the following equality:
N
X
φli νi = 0, l = 1, . . . , L. (7.21)
i=1

That is to say, for each element, the sum of the product of the net species production and
the number of elements in the species must be zero. In vector notation, this becomes

φ · ν = 0. (7.22)

One may recall from linear algebra that this demands that ν lie in the right null space of φ.

Example 7.3
Show stoichiometric balance is achieved for −2H2 − O2 + 2H2 O = 0.

Here again, the number of elements L = 2, and one can take l = 1 for H and l = 2 for O. Also
the number of species N = 3, and one takes i = 1 for H2 , i = 2 for O2 , and i = 3 for H2 O. Then for
element 1, H, in species 1, H2 , one has

φ11 = 2, H in H2 . (7.23)

Similarly, one gets

φ12 = 0, H in O2 , (7.24)
φ13 = 2, H in H2 O, (7.25)
φ21 = 0, O in H2 , (7.26)
φ22 = 2, O in O2 , (7.27)
φ23 = 1, O in H2 O. (7.28)
PN
In matrix form then, i=1 φli νi = 0 gives
 
  ν  
2 0 2  1 0
ν2 = . (7.29)
0 2 1 0
ν3

This is two equations in three unknowns. Thus, it is formally under-constrained. Certainly the trivial
solution ν1 = ν2 = ν3 = 0 will satisfy, but one seeks non-trivial solutions. Assume ν3 has a known value
ν3 = ξ. Then, the system reduces to
    
2 0 ν1 −2ξ
= . (7.30)
0 2 ν2 −ξ

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7.2. STOICHIOMETRY 227

The inversion here is easy, and one finds ν1 = −ξ, ν2 = − 21 ξ. Or in vector form,
   
ν1 −ξ
 ν2  =  − 1 ξ  , (7.31)
2
ν3 ξ
 
−1
= ξ − 21  , ξ ∈ R1 . (7.32)
1

Again, this amounts to saying the solution vector (ν1 , ν2 , ν3 )T lies in the right null space of the coefficient
matrix φli .
Here ξ is any real scalar. If one takes ξ = 2, one gets
   
ν1 −2
ν2  = −1 , (7.33)
ν3 2

This simply corresponds to

−2H2 − O2 + 2H2 O = 0. (7.34)
If one takes ξ = −4, one still achieves stoichiometric balance, with
   
ν1 4
ν2  =  2  , (7.35)
ν3 −4

which corresponds to the equally valid

4H2 + 2O2 − 4H2 O = 0. (7.36)

In summary, the stoichiometric coefficients are non-unique but partially constrained by mass conserva-
tion. Which set is chosen is to some extent arbitrary, and often based on traditional conventions from
chemistry. But others are equally valid.

There is a small issue with units here, which will be seen to be difficult to reconcile.
In practice, it will have little to no importance. In the previous example, one might be
tempted to ascribe units of kmoles to νi . Later, it will be seen that in classical reaction
kinetics, νi is best interpreted as a pure dimensionless number, consistent with the definition
of this section. So in the context of the previous example, one would then take ξ to be
dimensionless as well, which is perfectly acceptable for the example. In later problems, it
will be more useful to give ξ the units of kmoles. Note that multiplication of ξ by any scalar,
e.g. kmole/(6.02 × 1026 ), still yields an acceptable result.

Example 7.4
Balance an equation for hypothesized ethane combustion

ν1′ C2 H6 + ν2′ O2 ⇌ ν3′′ CO2 + ν4′′ H2 O. (7.37)

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228 CHAPTER 7. AEROTHERMOCHEMISTRY

One could also say in terms of the net stoichiometric coefficients

ν1 C2 H6 + ν2 O2 + ν3 CO2 + ν4 H2 O = 0. (7.38)

Here one takes χ1 = C2 H6 , χ2 = O2 , χ3 = CO2 , and χ4 = H2 O. So there are N = 4 species. There

are also L = 3 elements: l = 1 : C, l = 2 : H, l = 3 : O. One then has

φ11 = 2, C in C2 H6 , (7.39)
φ12 = 0, C in O2 , (7.40)
φ13 = 1, C in CO2 , (7.41)
φ14 = 0, C in H2 O, (7.42)
φ21 = 6, H in C2 H6 , (7.43)
φ22 = 0, H in O2 , (7.44)
φ23 = 0, H in CO2 , (7.45)
φ24 = 2, H in H2 O, (7.46)
φ31 = 0, O in C2 H6 , (7.47)
φ32 = 2, O in O2 , (7.48)
φ33 = 2, O in CO2 , (7.49)
φ34 = 1, O in H2 O. (7.50)
PN
So the stoichiometry equation, i=1φli νi = 0, is given by
 
  ν  
2 0 1 0  1 0
 6 0 0 2   ν2  =  0  . (7.51)
 ν3 
0 2 2 1 0
ν4

Here, there are three equations in four unknowns, so the system is under-constrained. There are many
ways to address this problem. Here, choose the robust way of casting the system into row echelon form.
This is easily achieved by Gaussian elimination. Row echelon form seeks to have lots of zeros in the
lower left part of the matrix. The lower left corner has a zero already, so that is useful. Now, multiply
the top equation by 3 and subtract the result from the second to get
 
  ν  
2 0 1 0  1 0
0 0 −3 2 ν2  = 0 . (7.52)
 ν3 
0 2 2 1 0
ν4

Next switch the last two equations to get

 
 ν  
2 0 1 0  1 0
ν
0 2 2 1  2
 ν3  = 0 . (7.53)
0 0 −3 2 0
ν4

Now divide the first by 2, the second by 2 and the third by −3 to get unity in the diagonal:
 
  ν  
1 0 12 0  1 0
0 1 1 1   ν2  0 .
2  ν3  = (7.54)
0 0 1 − 32 0
ν4

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7.2. STOICHIOMETRY 229

So-called bound variables have non-zero coefficients on the diagonal, so one can take the bound variables
to be ν1 , ν2 , and ν3 . The remaining variables are free variables. Here one takes the free variable to be
ν4 . So, set ν4 = ξ, and rewrite the system as
 1
   
1 0 2 ν1 0
0 1 1  ν2  = − 12 ξ  . (7.55)
2
0 0 1 ν3 3ξ

Solving, one finds

   1   1
ν1 −3ξ −3
ν2  − 7 ξ  − 7 
  =  26  = ξ  26  , ξ ∈ R1 . (7.56)
 ν3   ξ   
3 3
ν4 ξ 1

Again, one finds a non-unique solution in the right null space of φ. If one chooses ξ = 6, then one gets
   
ν1 −2
ν2  −7
  =  , (7.57)
ν3   4 
ν4 6

which corresponds to the stoichiometrically balanced reaction

2C2 H6 + 7O2 ⇌ 4CO2 + 6H2 O. (7.58)

In this example, ξ is dimensionless.

Example 7.5
Consider stoichiometric balance for a propane oxidation reaction which may produce carbon monox-
ide and hydroxyl in addition to carbon dioxide and water.

The hypothesized reaction takes the form

ν1′ C3 H8 + ν2′ O2 ⇌ ν3′′ CO2 + ν4′′ CO + ν5′′ H2 O + ν6′′ OH. (7.59)

In terms of net stoichiometric coefficients, this becomes

ν1 C3 H8 + ν2 O2 + ν3 CO2 + ν4 CO + ν5 H2 O + ν6 OH = 0. (7.60)

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230 CHAPTER 7. AEROTHERMOCHEMISTRY

There are N = 6 species and L = 3 elements. One then has

φ11 = 3, C in C3 H8 , (7.61)
φ12 = 0, C in O2 , (7.62)
φ13 = 1, C in CO2 , (7.63)
φ14 = 1, C in CO, (7.64)
φ15 = 0, C in H2 O, (7.65)
φ16 = 0, C in OH, (7.66)
φ21 = 8, H in C3 H8 , (7.67)
φ22 = 0, H in O2 , (7.68)
φ23 = 0, H in CO2 , (7.69)
φ24 = 0, H in CO, (7.70)
φ25 = 2, H in H2 O, (7.71)
φ26 = 1, H in OH, (7.72)
φ31 = 0, O in C3 H8 , (7.73)
φ32 = 2, O in O2 , (7.74)
φ33 = 2, O in CO2 , (7.75)
φ34 = 1, O in CO, (7.76)
φ35 = 1, O in H2 O, (7.77)
φ36 = 1, O in OH. (7.78)

The equation φ · ν = 0, then becomes

 
ν1
  ν2   
3 0 1 1 0 0  
ν3  0
8 0 0 0 2 1   = 0 .
ν4  (7.79)
0 2 2 1 1 1  
ν5  0
ν6

Multiplying the first equation by −8/3 and adding it to the second gives
 
ν1
  ν2   
3 0 1 1 0 0  
ν3  0
0 0 − 83 − 38 2  
1    = 0 . (7.80)
ν4 
0 2 2 1 1 1 ν5  0
ν6

Trading the second and third rows gives

 
ν1
  ν2   
3 0 1 1 0 0  
ν3  0
0 2 2 1 1 1   = 0 .
ν4  (7.81)
0 0 − 83 − 38 2 1  
ν5  0
ν6

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7.2. STOICHIOMETRY 231

Dividing the first row by 3, the second by 2 and the third by −8/3 gives
 
ν1
   ν2   
1 0 3 31 1
0 0  
 0
0 1 1 1 1 1   ν3  0 .
2 2 2  ν4  = (7.82)
0 0 1 1 − 43 − 38  
 ν5  0
ν6

Take bound variables to be ν1 , ν2 , and ν3 and free variables to be ν4 , ν5 , and ν6 . So set ν4 = ξ1 ,

ν5 = ξ2 , and ν6 = ξ3 , and get
    
1 0 31 ν1 − ξ31
0 1 1  ν2  =  − ξ1 − ξ2 − ξ3  . (7.83)
2 2 2
0 0 1 ν3 −ξ1 + 34 ξ2 + 83 ξ3

Solving, one finds

   1

ν1 8 (−2ξ2 − ξ3 )
ν2  =  1 (4ξ1 − 10ξ2 − 7ξ3 )  . (7.84)
8
1
ν3 8 (−8ξ1 + 6ξ2 + 3ξ3 )

For all the coefficients, one then has

   1
      
ν1 8 (−2ξ2 − ξ3 ) 0 −2 −1
ν2   1 (4ξ1 − 10ξ2 − 7ξ3 )  4 −10 −7
   18       
ν3   (−8ξ1 + 6ξ2 + 3ξ3 ) ξ1 −8 ξ2  6  ξ3  3 
  = 8 =  +  +  . (7.85)
 ν4   ξ1  8   8   8  
    8  0  0
 ν5   ξ2  0  8  0
ν6 ξ3 0 0 8

Here, one finds three independent vectors in the right null space. To simplify the notation, take
ξˆ1 = ξ1 /8, ξ̂2 = ξ2 /8, and ξ̂3 = ξ3 /8. Then,
       
ν1 0 −2 −1
 ν2  4 −10 −7
       
 ν3       
  = ξˆ1 −8 + ξ̂2  6  + ξˆ3  3  . (7.86)
 ν4  8  0  0
       
 ν5  0  8  0
ν6 0 0 8

The most general reaction that can achieve a stoichiometric balance is given by

(−2ξˆ2 − ξ̂3 )C3 H8 + (4ξˆ1 − 10ξˆ2 − 7ξˆ3 )O2 + (−8ξˆ1 + 6ξˆ2 + 3ξˆ3 )CO2 + 8ξˆ1 CO + 8ξˆ2 H2 O + 8ξˆ3 OH = 0. (7.87)

Rearranging, one gets

(2ξˆ2 + ξ̂3 )C3 H8 + (−4ξˆ1 + 10ξˆ2 + 7ξˆ3 )O2 ⇌ (−8ξˆ1 + 6ξˆ2 + 3ξˆ3 )CO2 + 8ξˆ1 CO + 8ξˆ2 H2 O + 8ξˆ3 OH. (7.88)

This will be balanced for all ξ̂1 , ξ̂2 , and ξˆ3 . The values that are actually achieved in practice depend
on the thermodynamics of the problem. Stoichiometry only provides some limitations.
A slightly more familiar form is found by taking ξˆ2 = 1/2 and rearranging, giving

(1 + ξ̂3 )C3 H8 + (5 − 4ξˆ1 + 7ξˆ3 )O2 ⇌ (3 − 8ξˆ1 + 3ξˆ3 )CO2 + 4H2 O + 8ξˆ1 CO + 8ξˆ3 OH. (7.89)

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232 CHAPTER 7. AEROTHERMOCHEMISTRY

One notes that often the production of CO and OH will be small. If there is no production of CO or
OH, ξ̂1 = ξ̂3 = 0 and one recovers the familiar balance of

C3 H8 + 5O2 ⇌ 3CO2 + 4H2 O. (7.90)

One also notes that stoichiometry alone admits unusual solutions. For instance, if ξ̂1 = 100, ξ̂2 = 1/2,
and ξˆ3 = 1, one has

2C3 H8 + 794CO2 ⇌ 388O2 + 4H2 O + 800CO + 8OH. (7.91)

This reaction is certainly admitted by stoichiometry but is not observed in nature. To determine
precisely which of the P infinitely many possible final states are realized requires a consideration of the
N
equilibrium condition i=1 νi µi = 0.
Looked at in another way, we can think of three independent classes of reactions admitted by the
stoichiometry, one for each of the linearly independent null space vectors. Taking first ξ̂1 = 1/4, ξˆ2 = 0,
ξˆ3 = 0, one gets, after rearrangement

2CO + O2 ⇌ 2CO2 , (7.92)

as one class of reaction admitted by stoichiometry. Taking next ξˆ1 = 0, ξ̂2 = 1/2, ξˆ3 = 0, one gets

C3 H8 + 5O2 ⇌ 3CO2 + 4H2 O, (7.93)

as the second class admitted by stoichiometry. The third class is given by taking ξˆ1 = 0, ξ̂2 = 0, ξˆ3 = 1,
and is
C3 H8 + 7O2 ⇌ 3CO2 + 8OH. (7.94)
In this example, both ξ and ξˆ are dimensionless.

In general, one can expect to find the stoichiometric coefficients for N species composed
of L elements to be of the following form:

N
X −L
νi = Dik ξk , i = 1, . . . , N. (7.95)
k=1

Here Dik is a dimensionless component of a full rank matrix of dimension N × (N − L)

and rank N − L, and ξk is a dimensionless component of a vector of parameters of length
N − L. The matrix whose components are Dik are constructed by populating its columns
with vectors which lie in the right null space of φli . Note that multiplication of ξk by any
constant gives another set of νi , and mass conservation for each element is still satisfied.
For later use, we associate νi with the number of moles ni , and consider a differential
change in the number of moles dni from Eq. (7.95) and arrive at

N
X −L
dni = Dik dξk , i = 1, . . . , N. (7.96)
k=1

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7.2. STOICHIOMETRY 233

7.2.2 Fuel-air mixtures

In combustion with air, one often models air as a simple mixture of diatomic oxygen and
inert diatomic nitrogen:
(O2 + 3.76N2 ). (7.97)
The air-fuel ratio, A and its reciprocal, the fuel-air ratio, F , can be defined on a mass
and mole basis.
mair nair
Amass = , Amole = . (7.98)
mf uel nf uel

Via the molecular masses, one has

mair nair Mair Mair

Amass = = = Amole . (7.99)
mf uel nf uel Mf uel Mf uel

If there is not enough air to burn all the fuel, the mixture is said to be rich. If there is
excess air, the mixture is said to be lean. If there is just enough, the mixture is said to be
stoichiometric. The equivalence ratio, Φ, is defined as the actual fuel-air ratio scaled by the
stoichiometric fuel-air ratio:

Factual Astoichiometric
Φ≡ = . (7.100)
Fstoichiometric Aactual

The ratio Φ is the same whether F ’s are taken on a mass or mole basis, because the ratio of
molecular masses cancel.

Example 7.6
Calculate the stoichiometry of the combustion of methane with air with an equivalence ratio of
Φ = 0.5.

First calculate the coefficients for stoichiometric combustion:

ν1′ CH4 + ν2′ (O2 + 3.76N2 ) ⇌ ν3′′ CO2 + ν4′′ H2 O + ν5′′ N2 , (7.101)

or
ν1 CH4 + ν2 O2 + ν3 CO2 + ν4 H2 O + (ν5 + 3.76ν2)N2 = 0. (7.102)

Here one has N = 5 species and L = 4 elements. Adopting a slightly more intuitive procedure for
variety, one writes a conservation equation for each element to get

ν1 + ν3 = 0, C, (7.103)
4ν1 + 2ν4 = 0, H, (7.104)
2ν2 + 2ν3 + ν4 = 0, O, (7.105)
3.76ν2 + ν5 = 0, N. (7.106)

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234 CHAPTER 7. AEROTHERMOCHEMISTRY

In matrix form this becomes

 
  ν  
1 0 1 0 0  1 0
4 0 0 2 0 ν2  0
   ν3  =   . (7.107)
0 2 2 1 0   0
 ν4 
0 3.76 0 0 1 0
ν5

Now, one might expect to have one free variable, because one has five unknowns in four equations.
While casting the equation in row echelon form is guaranteed to yield a proper solution, one can often
use intuition to get a solution more rapidly. One certainly expects that CH4 will need to be present
for the reaction to take place. One might also expect to find an answer if there is one mole of CH4 . So
take ν1 = −1. Realize that one could also get a physically valid answer by assuming ν1 to be equal to
any scalar. With ν1 = −1, one gets
    
0 1 0 0 ν2 1
 0 0 2 0   ν3   4 
   =  . (7.108)
 2 2 1 0   ν4   0 
3.76 0 0 1 ν5 0

One easily finds the unique inverse does exist, and that the solution is
   
ν2 −2
 ν3   1 
 = 
 ν4   2  . (7.109)
ν5 7.52

If there had been more than one free variable, the four by four matrix would have been singular, and
no unique inverse would have existed.
In any case, the reaction under stoichiometric conditions is

−CH4 − 2O2 + CO2 + 2H2 O + (7.52 + (3.76)(−2))N2 = 0, (7.110)

CH4 + 2(O2 + 3.76N2 ) ⇌ CO2 + 2H2 O + 7.52N2 . (7.111)

For the stoichiometric reaction, the fuel-air ratio on a mole basis is

1
Fstoichiometric = = 0.1050. (7.112)
2 + 2(3.76)
Now Φ = 0.5, so

Factual = ΦFstoichiometric = (0.5)(0.1050) = 0.0525. (7.113)

By inspection, one can write the actual reaction equation as

CH4 + 4(O2 + 3.76N2 ) ⇌ CO2 + 2H2 O + 2O2 + 15.04N2 . (7.114)

Check:
1
Factual = = 0.0525. (7.115)
4 + 4(3.76)

CC BY-NC-ND. 19 January 2025, J. M. Powers.

7.3. FIRST LAW ANALYSIS OF REACTING SYSTEMS 235

7.3 First law analysis of reacting systems

One can easily use the first law to learn much about chemically reacting systems.

7.3.1 Enthalpy of formation

The enthalpy of formation is the enthalpy that is required to form a molecule from combining
its constituents at P = 0.1 MPa and T = 298 K. Consider the reaction (taken here to be
irreversible)
C + O2 → CO2 . (7.116)
In order to maintain the process at constant temperature, it is found that heat transfer to
the volume is necessary. For the steady constant pressure process, one has
Z 2
E2 − E1 = 1Q2 − 1W2 , = 1Q2 − P dV = 1Q2 − P (V2 − V1 ), (7.117)
1
1Q2 = E2 − E1 + P (V2 − V1 ) = H2 − H1 , (7.118)
= Hproducts − Hreactants . (7.119)

So
X X
1Q2 = ni hi − ni hi . (7.120)
products reactants

In this reaction, one measures that 1Q2 = −393522 kJ for the reaction of 1 kmole of C
and O2 . That is the reaction liberates such energy to the environment. So measuring the
heat transfer can give a measure of the enthalpy difference between reactants and products.
Assign a value of enthalpy zero to elements in their standard state at the reference state.
Thus, C and O2 both have enthalpies of 0 kJ/kmole at T = 298 K, P = 0.1 MPa. This
enthalpy is designated, for species i,
o o
hf,i = h298,i , (7.121)

and is called the enthalpy of formation. So the energy balance for the products and reactants,
here both at the standard state, becomes
o o o
1Q2= nCO2 hf,CO2 − nC hf,C − nO2 hf,O2 , (7.122)
   
o kJ kJ
−393522 kJ = (1 kmole)hf,CO2 − (1 kmole) 0 − (1 kmole) 0 .
kmole kmole
(7.123)
o
Thus, the enthalpy of formation of CO2 is hf,CO2 = −393522 kJ/kmole, because the reaction
involved creation of 1 kmole of CO2 .

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236 CHAPTER 7. AEROTHERMOCHEMISTRY

Often values of enthalpy are tabulated in the forms of enthalpy differences ∆hi . These
are defined such that
o o o
hi = hf,i + (hi − hf,i ) = hf,i + ∆hi . (7.124)
| {z }
=∆hi

Lastly, one notes for an ideal gas that the enthalpy is a function of temperature only, and so
does not depend on the reference pressure; hence
o o
hi = hi , ∆hi = ∆hi , if ideal gas. (7.125)

Example 7.7
(Borgnakke and Sonntag, Ex. 15.6 pp. 629-630). Consider the heat of reaction of the following
irreversible reaction in a steady state, steady flow process confined to the standard state of P = 0.1 MPa,
T = 298 K:
CH4 + 2O2 → CO2 + 2H2 O(ℓ). (7.126)

The first law holds that

X X
Qcv = ni hi − ni hi . (7.127)
products reactants

All components are at their reference states. Table A.10 gives properties, and one finds

Qcv = nCO2 hCO2 + nH2 O hH2 O − nCH4 hCH4 − nO2 hO2 , (7.128)
   
kJ kJ
= (1 kmole) −393522 + (2 kmole) −285830
kmole kmole
   
kJ kJ
−(1 kmole) −74873 − (2 kmole) 0 , (7.129)
kmole kmole
= −890309 kJ. (7.130)

A more detailed analysis is required in the likely case in which the system is not at the
reference state.

Example 7.8
(adopted from Moran and Shapiro, p. 619) A mixture of 1 kmole of gaseous methane and 2 kmole of
oxygen initially at 298 K and 101.325 kPa burns completely in a closed, rigid, container. Heat transfer
occurs until the final temperature is 900 K. Find the heat transfer and the final pressure.

The combustion is stoichiometric. Assume that no small concentration species are generated. The
global reaction is given by
CH4 + 2O2 → CO2 + 2H2 O. (7.131)

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7.3. FIRST LAW ANALYSIS OF REACTING SYSTEMS 237

The first law analysis for the closed system is slightly different:

E2 − E1 = 1Q2 − 1W2 . (7.132)

Because the process is isochoric, 1W2 = 0. So

1Q2 = E2 − E1 , (7.133)
= nCO2 eCO2 + nH2 O eH2 O − nCH4 eCH4 − nO2 eO2 , (7.134)
= nCO2 (hCO2 − RT2 ) + nH2 O (hH2 O − RT2 ) − nCH4 (hCH4 − RT1 ) − nO2 (hO2 − RT1 ), (7.135)
= hCO2 + 2hH2 O − hCH4 − 2hO2 − 3R(T2 − T1 ), (7.136)
o o o o
= (hCO2 ,f + ∆hCO2 ) + 2(hH2 O,f + ∆hH2 O ) − (hCH4 ,f + ∆hCH4 ) − 2(hO2 ,f + ∆hO2 )
−3R(T2 − T1 ), (7.137)
= (−393522 + 28030) + 2(−241826 + 21937) − (−74873 + 0) − 2(0 + 0)
−3(8.314)(900 − 298), (7.138)
= −745412 kJ. (7.139)

For the pressures, one has

P1 V1 = (nCH4 + nO2 )RT1 , (7.140)

(nCH4 + nO2 )RT1
V1 = , (7.141)
P1
 
kJ
(1 kmole + 2 kmole) 8.314 kg K (298 K)
= = 73.36 m3 . (7.142)
101.325 kPa
Now V2 = V1 , so

(nCO2 + nH2 O )RT2

P2 = , (7.143)
V2
 
kJ
(1 kmole + 2 kmole) 8.314 kg K (900 K)
= = 306.0 kPa. (7.144)
73.36 m3
The pressure increased in the reaction. This is entirely attributable to the temperature rise, as the
number of moles remained constant here.

7.3.2 Enthalpy and internal energy of combustion

The enthalpy of combustion is the difference between the enthalpy of products and reactants
when complete combustion occurs at a given pressure and temperature. It is also known
as the heating value or the heat of reaction. The internal energy of combustion is related
and is the difference between the internal energy of products and reactants when complete
combustion occurs at a given volume and temperature.
The term higher heating value refers to the energy of combustion when liquid water is in
the products. Lower heating value refers to the energy of combustion when water vapor is
in the product.

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238 CHAPTER 7. AEROTHERMOCHEMISTRY

7.3.3 Adiabatic flame temperature in isochoric stoichiometric sys-

tems
The adiabatic flame temperature refers to the temperature which is achieved when a fuel and
oxidizer are combined with no loss of work or heat energy. Thus, it must occur in a closed,
insulated, fixed volume. It is generally the highest temperature that one can expect to
achieve in a combustion process. It generally requires an iterative solution. Of all mixtures,
stoichiometric mixtures will yield the highest adiabatic flame temperatures because there is
no need to heat the excess fuel or oxidizer.
Here four examples will be presented to illustrate the following points.

• The adiabatic flame temperature can be well over 5000 K for seemingly ordinary mix-
tures.

• Dilution of the mixture with an inert diluent lowers the adiabatic flame temperature.
The same effect would happen in rich and lean mixtures.

• Preheating the mixture, such as one might find in the compression stroke of an engine,
increases the adiabatic flame temperature.

• Consideration of the presence of minor species lowers the adiabatic flame temperature.

[Link] Undiluted, cold mixture

Example 7.9
A closed, fixed, adiabatic volume contains a stoichiometric mixture of 2 kmole of H2 and 1 kmole
of O2 at 100 kPa and 298 K. Find the adiabatic flame temperature and final pressure assuming the
irreversible reaction
2H2 + O2 → 2H2 O. (7.145)

The volume is given by

(nH2 + nO2 )RT1

V = , (7.146)
P1
kJ


(2 kmole + 1 kmole) 8.314 (298 K)
= kmole K
= 74.33 m3 . (7.147)
100 kPa

CC BY-NC-ND. 19 January 2025, J. M. Powers.

7.3. FIRST LAW ANALYSIS OF REACTING SYSTEMS 239

The first law gives

E2 − E1 = 1Q2 − 1W2 , (7.148)

= 0, (7.149)
nH2 O eH2 O − nH2 eH2 − nO2 eO2 = 0, (7.150)
nH2 O (hH2 O − RT2 ) − nH2 (hH2 − RT1 ) − nO2 (hO2 − RT1 ) = 0, (7.151)
2hH2 O − 2 hH2 − hO2 +R(−2T2 + 3T1 ) = 0, (7.152)
|{z} |{z}
=0 =0
2hH2 O + (8.314) ((−2) T2 + (3) (298)) = 0, (7.153)
hH2 O − 8.314T2 + 3716.4 = 0, (7.154)
o
hf,H2 O + ∆hH2 O − 8.314T2 + 3716.4 = 0, (7.155)
−241826 + ∆hH2 O − 8.314T2 + 3716.4 = 0, (7.156)
−238110 + ∆hH2 O − 8.314T2 = 0. (7.157)

At this point, one begins an iteration process, guessing a value of T2 and an associated ∆hH2 O . When
T2 is guessed at 5600 K, the left side becomes −6507.04. When T2 is guessed at 6000 K, the left side
becomes 14301.4. Interpolate then to arrive at

T2 = 5725 K. (7.158)

This is an extremely high temperature. At such temperatures, in fact, one can expect other species to
co-exist in the equilibrium state in large quantities. These may include H, OH, O, HO2 , and H2 O2 ,
among others.
The final pressure is given by
kJ


nH2 O RT2 (2 kmole) 8.314 kmole K (5725 K)
P2 = = = 1280.71 kPa. (7.159)
V 74.33 m3
The final concentration of H2 O is
2 kmole kmole
ρ H2 O = = 2.69 × 10−2 . (7.160)
74.33 m3 m3

[Link] Dilute, cold mixture

Example 7.10
Consider a variant on the previous example in which the mixture is diluted with an inert, taken
here to be N2 . A closed, fixed, adiabatic volume contains a stoichiometric mixture of 2 kmole of H2 ,
1 kmole of O2 , and 8 kmole of N2 at 100 kPa and 298 K. Find the adiabatic flame temperature and
the final pressure, assuming the irreversible reaction

2H2 + O2 + 8N2 → 2H2 O + 8N2 . (7.161)

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240 CHAPTER 7. AEROTHERMOCHEMISTRY

The volume is given by

(nH2 + nO2 + nN2 )RT1

V = , (7.162)
P1
kJ


(2 kmole + 1 kmole + 8 kmole) 8.314 (298 K)
= kmole K
= 272.533 m3 . (7.163)
100 kPa
The first law gives

E2 − E1 = 1Q2 − 1W2 ,
= 0,
nH2 O eH2 O − nH2 eH2 − nO2 eO2 + nN2 (eN2 2 − eN2 1 ) = 0,
nH2 O (hH2 O − RT2 ) − nH2 (hH2 − RT1 ) − nO2 (hO2 − RT1 ) + nN2 ((hN2 2 − RT2 ) − (hN2 1 − RT1 )) = 0,
2hH2 O − 2 hH2 − hO2 +R(−10T2 + 11T1 ) + 8( hN2 2 − hN2 1 ) = 0,
|{z} |{z} | {z } | {z }
=0 =0 =∆hN2 =0

2hH2 O + (8.314) (−10T2 + (11)(298)) + 8∆hN2 2 = 0,

2hH2 O − 83.14T2 + 27253.3 + 8∆hN2 2 = 0,
o
2hf,H2 O + 2∆hH2 O − 83.14T2 + 27253.3 + 8∆hN2 2 = 0,
2(−241826) + 2∆hH2 O − 83.14T2 + 27253.3 + 8∆hN2 2 = 0,
−456399 + 2∆hH2 O − 83.14T2 + 8∆hN2 2 = 0.

At this point, one begins an iteration process, guessing a value of T2 and an associated ∆hH2 O . When
T2 is guessed at 2000 K, the left side becomes −28006.7. When T2 is guessed at 2200 K, the left side
becomes 33895.3. Interpolate then to arrive at

T2 = 2090.5 K. (7.164)

The inert diluent significantly lowers the adiabatic flame temperature. This is because the N2 serves as
a heat sink for the energy of reaction. If the mixture were at non-stoichiometric conditions, the excess
species would also serve as a heat sink, and the adiabatic flame temperature would be lower than that
of the stoichiometric mixture.
The final pressure is given by

(nH2 O + nN2 )RT2

P2 = , (7.165)
V

kJ
(2 kmole + 8 kmole) 8.314 kmole K (2090.5 K)
= = 637.74 kPa. (7.166)
272.533 m3

The final concentrations of H2 O and N2 are

2 kmole kmole 8 kmole kmole

ρ H2 O = = 7.34 × 10−3 , ρ N2 = = 2.94 × 10−2 . (7.167)
272.533 m3 m3 272.533 m3 m3

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7.3. FIRST LAW ANALYSIS OF REACTING SYSTEMS 241

[Link] Dilute, preheated mixture

Example 7.11
Consider a variant on the previous example in which the diluted mixture is preheated to 1000 K.
One can achieve this via an isentropic compression of the cold mixture, such as might occur in an engine.
To simplify the analysis here, the temperature of the mixture will be increased, while the pressure will
be maintained. A closed, fixed, adiabatic volume contains a stoichiometric mixture of 2 kmole of H2 ,
1 kmole of O2 , and 8 kmole of N2 at 100 kPa and 1000 K. Find the adiabatic flame temperature and
the final pressure, assuming the irreversible reaction
2H2 + O2 + 8N2 → 2H2 O + 8N2 . (7.168)

The volume is given by

(nH2 + nO2 + nN2 )RT1
V = , (7.169)
P1
kJ


(2 kmole + 1 kmole + 8 kmole) 8.314 (1000 K)
= kmole K
= 914.54 m3 . (7.170)
100 kPa
The first law gives
E2 − E1 = 1Q2 − 1W2 ,
E2 − E1 = 0,
nH2 O eH2 O − nH2 eH2 − nO2 eO2 + nN2 (eN2 2 − eN2 1 ) = 0,
nH2 O (hH2 O − RT2 ) − nH2 (hH2 − RT1 ) − nO2 (hO2 − RT1 ) + nN2 ((hN2 2 − RT2 ) − (hN2 1 − RT1 )) = 0,
2hH2 O − 2hH2 − hO2 + R(−10T2 + 11T1 ) + 8(hN2 2 − hN2 1 ) = 0,
2(−241826 + ∆hH2 O ) − 2(20663) − 22703 + (8.314) (−10T2 + (11)(1000)) + 8∆hN2 2 − 8(21463) = 0,
2∆hH2 O − 83.14T2 − 627931 + 8∆hN2 2 = 0.
At this point, one begins an iteration process, guessing a value of T2 and an associated ∆hH2 O . When
T2 is guessed at 2600 K, the left side becomes −11351. When T2 is guessed at 2800 K, the left side
becomes 52787. Interpolate then to arrive at
T2 = 2635.4 K. (7.171)
The preheating raised the adiabatic flame temperature. Note that the preheating was by (1000 K) −
(298 K) = 702 K. The new adiabatic flame temperature is only (2635.4 K) − (2090.5 K) = 544.9 K
greater.
The final pressure is given by
(nH2 O + nN2 )RT2
P2 = , (7.172)
V

kJ
(2 kmole + 8 kmole) 8.314 kmole K (2635.4 K)
= = 239.58 kPa. (7.173)
914.54 m3
The final concentrations of H2 O and N2 are
2 kmole kmole 8 kmole kmole
ρ H2 O = = 2.19 × 10−3 , ρ N2 = = 8.75 × 10−3 . (7.174)
914.54 m3 m3 914.54 m3 m3

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242 CHAPTER 7. AEROTHERMOCHEMISTRY

[Link] Dilute, preheated mixture with minor species

Example 7.12
Consider a variant on the previous example. Here allow for minor species to be present at equilib-
rium. A closed, fixed, adiabatic volume contains a stoichiometric mixture of 2 kmole of H2 , 1 kmole
of O2 , and 8 kmole of N2 at 100 kPa and 1000 K. Find the adiabatic flame temperature and the final
pressure, assuming reversible reactions.

Here, the details of the analysis are postponed, but the result is given which is the consequence of a
calculation involving detailed reactions rates. One can also solve an optimization problem to minimize
the Gibbs free energy of a wide variety of products to get the same answer. In this case, the equilibrium
temperature and pressure are found to be

T = 2484.8 K, P = 227.89 kPa. (7.175)

Equilibrium species concentrations are found to be

kmole
minor product ρ H2 = 1.3 × 10−4 , (7.176)
m3
kmole
minor product ρH = 1.9 × 10−5 , (7.177)
m3
kmole
minor product ρO = 5.7 × 10−6 , (7.178)
m3
kmole
minor product ρ O2 = 3.6 × 10−5 , (7.179)
m3
kmole
minor product ρOH = 5.9 × 10−5 , (7.180)
m3

kmole
major product ρ H2 O = 2.0 × 10−3 , (7.181)
m3
kmole
trace product ρHO2 = 1.1 × 10−8 , (7.182)
m3
kmole
trace product ρ H2 O 2 = 1.2 × 10−9 , (7.183)
m3

kmole
trace product ρN = 1.7 × 10−9 , (7.184)
m3
kmole
trace product ρNH = 3.7 × 10−10 , (7.185)
m3

kmole
trace product ρNH2 = 1.5 × 10−10 , (7.186)
m3
kmole
trace product ρNH3 = 3.1 × 10−10 , (7.187)
m3
kmole
trace product ρNNH = 1.0 × 10−10 , (7.188)
m3
kmole
minor product ρNO = 3.1 × 10−6 , (7.189)
m3

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7.4. CHEMICAL EQUILIBRIUM 243

kmole
trace product ρNO2 = 5.3 × 10−9 , (7.190)
m3
kmole
trace product ρ N2 O = 2.6 × 10−9 , (7.191)
m3

kmole
trace product ρHNO = 1.7 × 10−9 , (7.192)
m3
kmole
major product ρ N2 = 8.7 × 10−3 . (7.193)
m3
Note that the concentrations of the major products went down when the minor species were considered.
The adiabatic flame temperature also went down by a significant amount: 2635 − 2484.8 = 150.2 K.
Some thermal energy was necessary to break the bonds which induce the presence of minor species.

7.4 Chemical equilibrium

Often reactions are not simply unidirectional, as alluded to in the previous example. The
reverse reaction, especially at high temperature, can be important.
Consider the four species reaction

ν1′ χ1 + ν2′ χ2 ⇌ ν3′′ χ3 + ν4′′ χ4 . (7.194)

In terms of the net stoichiometric coefficients, this becomes

ν1 χ1 + ν2 χ2 + ν3 χ3 + ν4 χ4 = 0. (7.195)

One can define a variable ζ, the reaction progress. Take the dimension of ζ to be kmoles.
When t = 0, one takes ζ = 0. Now as the reaction goes forward, one takes dζ > 0. And a
forward reaction will decrease the number of moles of χ1 and χ2 while increasing the number
of moles of χ3 and χ4 . This will occur in ratios dictated by the stoichiometric coefficients of
the problem:

dn1 = −ν1′ dζ, dn2 = −ν2′ dζ, dn3 = +ν3′′ dζ, dn4 = +ν4′′ dζ. (7.196)

Note that if ni is taken to have units of kmoles, νi′ , and νi′′ are taken as dimensionless, then
ζ must have units of kmoles. In terms of the net stoichiometric coefficients, one has

dn1 = ν1 dζ, dn2 = ν2 dζ, dn3 = ν3 dζ, dn4 = ν4 dζ. (7.197)

Again, for argument’s sake, assume that at t = 0, one has

n1 |t=0 = n1o , n2 |t=0 = n2o , n3 |t=0 = n3o , n4 |t=0 = n4o . (7.198)

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244 CHAPTER 7. AEROTHERMOCHEMISTRY

Then after integrating, one finds

n1 = ν1 ζ + n1o , n2 = ν2 ζ + n2o , n3 = ν3 ζ + n3o , n4 = ν4 ζ + n4o . (7.199)

One can also eliminate the parameter ζ in a variety of fashions and parameterize the
reaction one of the species mole numbers. Choosing, for example, n1 as a parameter, one
gets
n1 − n1o
ζ= . (7.200)
ν1
Eliminating ζ then one finds all other mole numbers in terms of n1 :
n1 − n1o n1 − n1o n1 − n1o
n2 = ν2 + n2o , n3 = ν3 + n3o , n4 = ν4 + n4o . (7.201)
ν1 ν1 ν1
Written another way, one has
n1 − n1o n2 − n2o n3 − n3o n4 − n4o
= = = = ζ. (7.202)
ν1 ν2 ν3 ν4
P
For an N-species reaction, N i=1 νi χi = 0, one can generalize to say

dni = = νi dζ, (7.203)

ni = νi ζ + nio , (7.204)
ni − nio
= ζ. (7.205)
νi
Note that
dni
= νi . (7.206)
dζ
A detailed consideration of mixture theory gives the energy E = E(V, S, ni ), with properties
extensive. Then
XN
∂E ∂E ∂E
dE = dV + dS + dni . (7.207)
∂V S,ni ∂S V,ni i=1
∂ni S,V,nj

Defining the new thermodynamics property, the chemical potential µi , as

∂E
µi ≡ , (7.208)
∂ni S,V,nj

one has the important Gibbs equation for multicomponent systems:

N
X
dE = −P dV + T dS + µi dni . (7.209)
i=1

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7.4. CHEMICAL EQUILIBRIUM 245

Obviously, by its definition, µi is on a per mole basis, so it is given the appropriate overline
notation. We define the Gibbs free energy as

G = E + P V − T S. (7.210)

Then

dG = dE + P dV + V dP − T dS − S dT. (7.211)

Invoking the Gibbs law, Eq. (7.209), we have then

N
X
dG = T dS − P dV + µi dni + P dV + V dP − T dS − S dT, (7.212)
i=1
N
X
= µi dni + V dP − S dT, (7.213)
i=1
XN
dG|T,P = µi dni . (7.214)
i=1

Recall the second law of thermodynamics is dS ≥ δQ/T , and the first law says δQ =
dE + P dV if the work δW is reversible work, so the second law is
1
dS ≥ (dE + P dV ). (7.215)
T
Eliminating dE, we get the second law as
N
X
T dS ≥ −P dV + T dS + µi dni + P dV, (7.216)
i=1
N
X
0 ≥ µi dni , (7.217)
i=1
XN
dG|T,P = µi dni ≤ 0. (7.218)
i=1

Gibbs free energy changes for isothermal, isobaric reactions must be negative. When they are
zero, the system must be in equilibrium. Now, one can eliminate dni in Eq. (7.218) by use of
Eq. (7.203) to get
N
X
dG|T,P = µi νi dζ ≤ 0, (7.219)
i=1
XN
∂G
= µi νi ≤ 0. (7.220)
∂ζ T,P i=1

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246 CHAPTER 7. AEROTHERMOCHEMISTRY

One could also remember that the second law speaks to directionality in time and asks how
systems behave for dt > 0. We can scale Eq. (7.219) by dt to get

N
X N
∂G dζ dζ X
= µi νi = µ νi ≤ 0. (7.221)
∂t T,P i=1
dt dt i=1 i

Now one straightforward, albeit naı̈ve, way to guarantee positive semi-definiteness of the
irreversible entropy production and thus satisfaction of the second law is to construct the
chemical kinetic rate equation so that

X N
dζ
= −k µi νi k ≥ 0, provisional, naı̈ve assumption. (7.222)
dt i=1

This provisional assumption of convenience will be supplanted later by a form which agrees
well with experiment. Here k is a positive semi-definite scalar. In general, it is a function of
temperature, k = k(T ), so that reactions proceed rapidly at high temperature and slowly at
low temperature. Then certainly the reaction progress variable ζ will cease to change when
the equilibrium condition

N
X
µi νi = 0, (7.223)
i=1

is met. Now, while Eq. (7.223) is the most compact form of the equilibrium condition, it is
not the most commonly used form. One can perform the following analysis to obtain the
form in most common usage. Start by equating the chemical potential with the Gibbs free
energy per unit mole for each species i: µi = g i . Then employ the definition of Gibbs free
energy for an ideal gas, and carry out a set of operations:

N
X
g i νi = 0, at equilibrium, (7.224)
i=1
N
X
(hi − T si )νi = 0, at equilibrium. (7.225)
i=1

For the ideal gas, one can substitute for hi (T ) and si (T, P ) and write the equilibrium con-

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7.4. CHEMICAL EQUILIBRIUM 247

dition as

  
  
  
 Z  Z  
N 
X 
T  T
c ( T̂ ) y P 
o
h298,i + cP i (T̂ ) dT̂ −T s o
+
Pi
d T̂ −R ln
i  νi = 0.
  298,i T̂ P 

i=1  298  298 o 

| {z } | {z } 

o
 =soT,i 
} 
=∆h T,i
| {z } | {z
o
=hT,i =hT,i =sT,i
| {z }
=gi

(7.226)

Now writing the equilibrium condition in terms of the enthalpies and entropies referred to
the standard pressure, one gets

XN    
o o yi P
hT,i − T sT,i − R ln νi = 0, (7.227)
i=1
P o

XN   XN  
o o yi P
hT,i − T sT,i νi = − RT νi ln , (7.228)
i=1 | {z } i=1
P o
=goT,i =µoT,i
N
X N
X  νi
yi P
− g oT,i νi = RT ln , (7.229)
i=1 i=1
Po
| {z }
≡∆Go
X N  ν
∆Go yi P i
− = ln , (7.230)
RT i=1
Po
YN  ν !
yi P i
= ln , (7.231)
i=1
Po
  Y N  ν
∆Go yi P i
exp − = , (7.232)
RT P o
| {z } i=1
≡KP
N 
Y ν
yi P i
KP = , (7.233)
i=1
Po
 PNi=1 νi Y n
P
= yiνi . (7.234)
Po i=1

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248 CHAPTER 7. AEROTHERMOCHEMISTRY

So

N 
Y ν
Pi i
KP = , at equilibrium. (7.235)
i=1
Po

Here KP is what is known as the pressure-based equilibrium constant. It is dimensionless.

Despite its name, it is not a constant. It is defined in terms of thermodynamic properties,
and for the ideal gas is a function of T only:

 
∆Go
KP ≡ exp − , generally valid. (7.236)
RT

Only at equilibrium does the property KP also equal the product of the partial pressures
as in Eq. (7.235). The subscript P for pressure comes about because it is also related to
the product of the ratio of the partial pressure to the reference pressure raised to the net
stoichiometric coefficients. Also, the net change in Gibbs free energy of the reaction at the
reference pressure, ∆Go , which is a function of T only, has been defined as

N
X
o
∆G ≡ g oT,i νi . (7.237)
i=1

The term ∆Go has units of kJ/kmole; it traditionally does not get an overbar. If ∆Go > 0,
one has 0 < KP < 1, and reactants are favored over products. If ∆Go < 0, one gets KP > 1,
and products are favored over reactants. One can also deduce that higher pressures P push
the equilibrium in such a fashion that fewer moles are present, all else being equal. One can
also define ∆Go in terms of the chemical affinity, referred to the reference pressure, as

∆Go = −αo . (7.238)

One can also define another convenient thermodynamic property, which for an ideal gas
is a function of T alone, the equilibrium constant Kc :

 PNi=1 νi  
Po ∆Go
Kc ≡ exp − , generally valid. (7.239)
RT RT

This property is dimensional, and the

PN
units depend on the stoichiometry of the reaction.
The units of Kc will be (kmole/m3 ) i=1 νi .
The equilibrium condition, Eq. (7.235), is often written in terms of molar concentrations

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7.5. CHEMICAL KINETICS OF A SINGLE ISOTHERMAL REACTION 249

and Kc . This can be achieved by the operations, valid only at an equilibrium state:
YN  νi
ρi RT
KP = , (7.240)
i=1
Po
   PNi=1 νi YN
−∆Go RT
exp = ρi νi , (7.241)
RT Po i=1
 PNi=1 νi   YN
Po −∆Go
exp = ρi νi . (7.242)
RT RT
| {z } i=1
≡Kc

So
N
Y
Kc = ρi νi , at equilibrium. (7.243)
i=1

One must be careful to distinguish between the general definition of Kc as given in Eq. (7.239),
and the fact that at equilibrium it is driven to also have the value of product of molar species
concentrations, raised to the appropriate stoichiometric power, as given in Eq. (7.243).

7.5 Chemical kinetics of a single isothermal reaction

In the same fashion in ordinary mechanics that an understanding of statics enables an under-
standing of dynamics, an understanding of chemical equilibrium is necessary to understand
to more challenging topic of chemical kinetics. Chemical kinetics describes the time-evolution
of systems which may have an initial state far from equilibrium; it typically describes the
path of such systems to an equilibrium state. Here gas phase kinetics of ideal gas mixtures
that obey Dalton’s law will be studied. Important topics such as catalysis and solid or liquid
reactions will not be considered.
Further, this section will be restricted to strictly isothermal systems. This simplifies the
analysis greatly. It is straightforward to extend the analysis of this system to non-isothermal
systems. One must then make further appeal to the energy equation to get an equation for
temperature evolution.
The general form for evolution of species is taken to be
 
d ρi ω̇i
= . (7.244)
dt ρ ρ
Multiplying both sides of Eq. (7.244) by molecular mass Mi and using the definition of mass
fraction Yi then gives the alternate form
dYi ω̇i Mi
= . (7.245)
dt ρ

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250 CHAPTER 7. AEROTHERMOCHEMISTRY

7.5.1 Isochoric systems

Consider the evolution of species concentration in a system which is isothermal, isochoric
and spatially homogeneous. The system is undergoing a single chemical reaction involving
N species of the familiar form
N
X
νi χi = 0. (7.246)
i=1

Because the density is constant for the isochoric system, Eq. (7.244) reduces to
dρi
= ω̇i . (7.247)
dt
Then, experiment, as well as a more fundamental molecular collision theory, shows that the
evolution of species concentration i is given by
≡ω̇i
z }|  {
  Y !
dρi −E
N  1 Y νk 
N
β ν ′
 
= νi aT exp ρk k
1 − ρk , isochoric system. (7.248)
dt RT  Kc 
| {z } | k=1{z } | k=1 {z }
≡k(T ) forward reaction reverse reaction
| {z }
≡r

This relation actually holds for isochoric, non-isothermal systems as well, which will not be
considered in any detail here. Here some new variables are defined as follows:
• a: a kinetic rate constant called the collision frequency factor. Its units will depend
on the actual reaction and could involve various combinations of length, time, and
temperature. It is constructed Pso that dρi /dt has units of kmole/m3 /s; this requires it
N
to have units of (kmole/m3 )(1− k=1 νk ) /s/Kβ .
′

• β: a dimensionless parameter whose value is set by experiments, sometimes combined

with guiding theory, to account for weak temperature dependency of reaction rates.
• E: the activation energy. It has units of kJ/kmole, though others are often used, and is
fit by both experiment and fundamental theory to account for the strong temperature
dependency of reaction.
Note that in Eq. (7.248) that molar concentrations are raised to the νk′ and νk powers. As
it does not make sense to raise a physical quantity to a power with units, one traditionally
interprets the values of νk , νk′ , as well as νk′′ to be dimensionless pure numbers. They are
also interpreted in a standard fashion: the smallest integer values that actually correspond
to the underlying molecular collision which has been modeled. While stoichiometric balance
can be achieved by a variety of νk values, the kinetic rates are linked to one particular set
which is defined by the community.

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7.5. CHEMICAL KINETICS OF A SINGLE ISOTHERMAL REACTION 251

Equation (7.248) is written in such a way that the species concentration production rate
increases when

• The net number of moles generated in the reaction, measured by νi increases,

• The temperature increases; here, the sensitivity may be very high, as one observes in
nature,

• The species concentrations of species involved in the forward reaction increase; this
embodies the principle that the collision-based reaction rates are enhanced when there
are more molecules to collide,

• The species concentrations of species involved in the reverse reaction decrease.

Here, three intermediate variables which are in common usage have been defined. First one
takes the reaction rate to be
 
  Y !
−E
N  1 Y νk 
N
β ν′  
r ≡ aT exp ρk k 1 − ρk  , (7.249)
RT  K c 
| {z } | k=1{z } | k=1{z }
≡k(T ) forward reaction reverse reaction

or
 
 
1 Y νk′′ 
N
Y N
β −E  νk′ 
r = aT exp  ρk − ρk  . (7.250)
RT  K c 
| {z } k=1
| {z } | k=1 {z }
≡k(T ), Arrhenius rate
| forward reaction{z reverse reaction }
law of mass action

The reaction rate r has units of kmole/m3 /s.

The temperature-dependency of the reaction rate is embodied in k(T ) is defined by what
is known as an Arrhenius rate law:
 
β −E
k(T ) ≡ aT exp . (7.251)
RT

This equation was advocated by van’t Hoff in 1884; in 1889 Arrhenius gave a physical justifi-
cation. The units of k(T ) actually depend on the reaction. This is a weakness of P
the theory,
3 (1− N ′
k=1 νk ) /s.
and precludes a clean non-dimensionalization. The units must be (kmole/m )
In terms of reaction progress, one can also take
1 dζ
r= . (7.252)
V dt

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252 CHAPTER 7. AEROTHERMOCHEMISTRY

The factor of 1/V is necessary because r has units of molar concentration per time and ζ
has units of kmoles. The over-riding importance of the temperature sensitivity is illustrated
as part of the next example. The remainder of the expression involving the products of the
species concentrations is the defining characteristic of systems which obey the law of mass
action. Though the history is complex, most attribute the law of mass action to Waage and
Guldberg in 1864.2
Last, the overall molar production rate of species i, is often written as ω̇i , defined as

ω̇i ≡ νi r. (7.253)

As νi is considered to be dimensionless, the units of ω̇i must be kmole/m3 /s.

Example 7.13
Study a nitrogen dissociation problem in which at t = 0 s, 1 kmole of N2 exists at P = 100 kPa
and T = 6000 K. Take the reaction to be isothermal and isochoric. Consider the elementary nitrogen
dissociation-recombination reaction

N2 + N2 ⇌ 2N + N2 . (7.254)

This has kinetic rate parameters of

cm3 K1.6 cal

a = 7.0 × 1021 , β = −1.6, E = 224928.4 . (7.255)
mole s mole
In SI units, this becomes
 3 1.6
 3  
21 cm K 1m 1000 mole m3 K1.6
a = 7.0 × 10 = 7.0 × 1018 , (7.256)
mole s 100 cm kmole kmole s
    
cal J kJ 1000 mole kJ
E = 224928.4 4.186 = 941550 . (7.257)
mole cal 1000 J kmole kmole

At the initial state, the material is all N2 , so PN2 = P = 100 kPa. The ideal gas law then gives at t = 0

P |t=0 = PN2 |t=0 = ρN2 t=0

RT, (7.258)
P |t=0
ρ N2 t=0
= , (7.259)
RT
100 kPa kmole
= kJ

= 2.00465 × 10−3 . (7.260)
8.314 kmole K (6000 K) m3

Thus, the volume, constant for all time in the isochoric process, is

nN2 |t=0 1 kmole

V = = kmole
= 4.9884 × 102 m3 . (7.261)
ρN2 t=0 2.00465 × 10−3 m3

2
P. Waage and C. M. Guldberg, 1864, Studies concerning affinity, Forhandlinger: Videnskabs-Selskabet i
Christiania, 35. English translation: Journal of Chemical Education, 63(12): 1044-1047.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

7.5. CHEMICAL KINETICS OF A SINGLE ISOTHERMAL REACTION 253

Now the stoichiometry of the reaction is such that

1
−dnN2 = dnN , (7.262)
2
1
−(nN2 − nN2 |t=0 ) = (nN − nN |t=0 ), (7.263)
| {z } 2 | {z }
=1 kmole =0
nN = 2(1 kmole − nN2 ), (7.264)
 
nN 1 kmole nN2
= 2 − , (7.265)
V V V
 
1 kmole
ρN = 2 − ρ N2 , (7.266)
4.9884 × 102 m3
 
−3 kmole
= 2 2.00465 × 10 − ρ N2 . (7.267)
m3
Now the general equation for kinetics of a single reaction, Eq. (7.248), reduces for N2 molar con-
centration to
   
dρN2 −E ′ ′ 1
= νN2 aT β exp (ρN2 )νN2 (ρN )νN 1 − (ρN2 )νN2 (ρN )νN . (7.268)
dt RT Kc
′ ′
Realizing that νN 2
= 2, νN = 0, νN2 = −1, and νN = 2, one gets
   
dρN2 −E 1 ρ2N
= − aT β exp ρ2N2 1 − . (7.269)
dt RT K c ρ N2
| {z }
=k(T )

Examine the primary temperature dependency of the reaction

 
−E
k(T ) = aT β exp , (7.270)
RT
  !
3 1.6 kJ
18 m K −1.6 −941550 kmole
= 7.0 × 10 T exp kJ
, (7.271)
kmole s 8.314 kmole KT
 
7.0 × 1018 −1.1325 × 105
= exp . (7.272)
T 1.6 T
Figure 7.1 gives a plot of k(T ) which shows its very strong dependency on temperature. For this
problem, T = 6000 K, so
 
7.0 × 1018 −1.1325 × 105 m3
k(6000) = 1.6
exp = 40071.6 . (7.273)
6000 6000 kmole s
Now, the equilibrium constant Kc is needed. Recall
 PNi=1 νi
 
Po −∆Go
Kc = exp . (7.274)
RT RT
PN
For this system, because i=1 νi = 1, this reduces to
      o o !
Po −(2goN − goN2 ) Po −(2(hN − T soT,N ) − (hN2 − T soT,N2 ))
Kc = exp = exp ,(7.275)
RT RT RT RT
   
100 −(2(597270 − (6000)216.926) − (205848 − (6000)292.984))
= exp , (7.276)
(8.314)(6000) (8.314)(6000)
kmole
= 0.000112112 . (7.277)
m3

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254 CHAPTER 7. AEROTHERMOCHEMISTRY

10 4

-4
10

10 -12

10 -20

10 -28

10 -36 T (K)
1000 1500 2000 3000 5000 7000 10000

Figure 7.1: k(T ) for nitrogen dissociation example.

The differential equation for N2 evolution is then given by

  kmole


2 !
dρN2 m3 1 2 2.00465 × 10−3 − ρN2
= − 40071.6 ρ2N2 1− m3
,
dt kmole 0.000112112 kmole
m3
ρ N2
| {z }
≡ω̇N2 (ρN2 )

(7.278)
= ω̇N2 (ρN2 ). (7.279)

The system is at equilibrium when ω̇N2 (ρN2 ) = 0. This is an algebraic function of ρN2 only, and can be
plotted. Figure 7.2 gives a plot of ω̇N2 (ρN2 ) and shows that it has three potential equilibrium points.
It is seen there are three roots. Solving for the equilibria requires solving
  kmole


2 !
m3 1 2 2.00465 × 10−3 m3 − ρN2
0 = − 40071.6 ρ2N2 1− kmole
. (7.280)
kmole 0.000112112 m3
ρ N2

The three roots are

kmole kmole kmole
ρ N2 = 0 , 0.00178121 , 0.00225611 . (7.281)
m3 }
| {z | {z m3 } | {z m3 }
unstable stable unstable

By inspection of the topology of Fig. 7.2, the only stable root is 0.00178121 kmole/m3 . This root
agrees with the equilibrium value found in an earlier example for the same problem conditions. Small
perturbations from this equilibrium induce the forcing function to supply dynamics which restore the
system to its original equilibrium state. Small perturbations from the unstable equilibria induce non-
restoring dynamics. For this root, one can then determine that the stable equilibrium value of ρN =
0.000446882 kmole/m3 .
One can examine this stability more formally. Define an equilibrium concentration ρeqN2 such that

ω̇N2 (ρeq
N2 ) = 0. (7.282)

CC BY-NC-ND. 19 January 2025, J. M. Powers.

7.5. CHEMICAL KINETICS OF A SINGLE ISOTHERMAL REACTION 255

unstable
equilibrium
1

0.0005 0.001 0.0015 0.002 0.0025

-1
unstable stable,
equilibrium physical
equilibrium
-2

Figure 7.2: Forcing function, ω̇N2 (ρN2 ), which drives changes of ρN2 as a function of ρN2 in
isothermal, isochoric problem.

Now perform a Taylor series of ω̇N2 (ρN2 ) about ρN2 = ρeq

N2 :

dω̇N2 1 d2 ω̇N2
ω̇N2 (ρN2 ) ∼ ω̇N2 (ρeq
N2 ) + (ρN2 − ρeq
N2 ) + (ρ − ρeq 2
N2 ) + . . . (7.283)
| {z } dρN2 ρN2 =ρeq
2 dρ2N2 N2
N2
=0

Now the first term of the Taylor series is zero by construction. Next neglect all higher order terms as
small so that the approximation becomes
dω̇N2
ω̇N2 (ρN2 ) ∼ (ρN2 − ρeq
N2 ). (7.284)
dρN2 ρN2 =ρeq
N2

Thus, near equilibrium, one can write

dρN2 dω̇N2
∼ (ρN2 − ρeq
N2 ). (7.285)
dt dρN2 ρN2 =ρeq
N2

Because the derivative of a constant is zero, one can also write the equation as
d dω̇N2
(ρN2 − ρeq
N2 ) ∼ (ρN2 − ρeq
N2 ). (7.286)
dt dρN2 ρN2 =ρeq
N2

This has a solution, valid near the equilibrium point, of

 
d
 N2ω̇
(ρN2 − ρeq
N2 ) = C exp t , (7.287)
dρN2 ρ =ρeq
N2 N2
 
dω̇ N
ρN2 = ρeq N2 + C exp
 2
t . (7.288)
dρN2 ρ =ρeq
N2 N2

CC BY-NC-ND. 19 January 2025, J. M. Powers.

256 CHAPTER 7. AEROTHERMOCHEMISTRY

concentration (kmole/m3)
0.002

0.001

t (s)
0.001 0.002 0.003 0.004 0.005

Figure 7.3: ρN2 (t) and ρN (t) in isothermal, isochoric nitrogen dissociation problem, T =
6000 K.

Here C is some constant whose value is not important for this discussion. If the slope of ω̇N2 is positive,
that is,
dω̇N2
> 0, unstable, (7.289)
dρN2 ρ =ρeq
N2 N2

the equilibrium will be unstable. That is a perturbation will grow without bound as t → ∞. If the
slope is zero,
dω̇N2
= 0, neutrally stable, (7.290)
dρN2 ρ =ρeq
N2 N2

the solution is stable in that there is no unbounded growth, and moreover is known as neutrally stable.
If the slope is negative,
dω̇N2
< 0, asymptotically stable, (7.291)
dρN2 ρN2 =ρeq
N 2

the solution is stable in that there is no unbounded growth, and moreover is known as asymptotically
stable. A numerical solution via an explicit technique such as a Runge-Kutta integration is found for
Eq. (7.278). The solution for ρN2 , along with ρN is plotted in Fig. 7.3. Linearization of Eq. (7.278)
about the equilibrium state gives rise to the locally linearly valid
d

ρ − 0.00178121 = −1209.39(ρN2 − 0.00178121) + . . . (7.292)
dt N2
This has local asymptotically stable solution

ρN2 = 0.00178121 + C exp (−1209.39t) . (7.293)

Here C is some integration constant whose value is irrelevant for this analysis. The time scale of
relaxation τ is the time when the argument of the exponential is −1, which is
1
τ= = 8.27 × 10−4 s. (7.294)
1209.39 s−1
One usually finds this time scale to have high sensitivity to temperature, with high temperatures giving
fast time constants and thus fast reactions.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

7.5. CHEMICAL KINETICS OF A SINGLE ISOTHERMAL REACTION 257

7.5.2 Isobaric systems

The form of the previous section is the most important as it is easily extended to a Cartesian
grid with fixed volume elements in fluid flow problems. However, there is another important
spatially homogeneous problem in which the formulation needs slight modification: isobaric
reaction, with P equal to a constant. Again, in this section only isothermal conditions will
be considered.
In an isobaric problem, there can be volume change. Consider first the problem of isobaric
expansion of an inert mixture. In such a mixture, the total number of moles of each species
must be constant, so one gets

dni
= 0, inert, isobaric mixture. (7.295)
dt
Now carry out the sequence of operations, realizing the total mass m is also constant:

1 d
(ni ) = 0, (7.296)
m dt
d  ni 
= 0, (7.297)
dt m

d ni V
= 0, (7.298)
dt V m
 
d ρi
= 0, (7.299)
dt ρ
1 dρi ρ dρ
− 2i = 0, (7.300)
ρ dt ρ dt
dρi ρi dρ
= . (7.301)
dt ρ dt

So a global density decrease of the inert material due to volume increase of a fixed mass
system induces a concentration decrease of each species. Extended to a material with a
single reaction rate r, one could say either

dρi ρ dρ
= νi r + i , or (7.302)
dt ρ dt
 
d ρi 1
= νi r, generally valid, (7.303)
dt ρ ρ
ω̇i
= . (7.304)
ρ

Equation (7.303) is consistent with Eq. (7.244) and is actually valid for general systems with
variable density, temperature, and pressure.
However, in this section, it is required that pressure and temperature be constant. Now

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258 CHAPTER 7. AEROTHERMOCHEMISTRY

differentiate the isobaric, isothermal, ideal gas law to get the density derivative.

N
X
P = ρi RT, (7.305)
i=1
XN
dρi
0 = RT , (7.306)
i=1
dt
XN
dρi
0 = , (7.307)
i=1
dt
XN  
ρi dρ
0 = νi r + , (7.308)
i=1
ρ dt
N
X N
1 dρ X
0 = r νi + ρ, (7.309)
i=1
ρ dt i=1 i
P
dρ −r N νi
= PN i=1ρi . (7.310)
dt i=1 ρ
P
ρr N νi
= − PNi=1 , (7.311)
i=1 ρi
PN
ρr i=1 νi
= − P
, (7.312)
RT
PN
ρRT r i=1 νi
= − , (7.313)
P
PN
ρRT r k=1 νk
= − . (7.314)
P

PN
Note that if there is no net number change in the reaction, k=1 νk = 0, the isobaric,
isothermal reaction also guarantees there would be no density or volume change. It is
convenient to define the net number change in the elementary reaction as ∆n:

N
X
∆n ≡ νk . (7.315)
k=1

Here ∆n is taken to be a dimensionless pure number. It is associated with the number

change in the elementary reaction and not the actual mole change in a physical system; it
is, however, proportional to the actual mole change.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

7.5. CHEMICAL KINETICS OF A SINGLE ISOTHERMAL REACTION 259

Now use Eq. (7.314) to eliminate the density derivative in Eq. (7.302) to get
P
dρi ρi ρRT r N k=1 νk
= νi r − , (7.316)
dt ρ P
 
 N 

 ρi RT X 
= r νi − νk 
, (7.317)
|{z}
reaction effect P 
| {zk=1 }
expansion effect

or
 
dρi
= r νi − yi ∆n . (7.318)
dt |{z} | {z }
reaction effect expansion effect

There are two terms dictating the rate change of species molar concentration. The first, a
reaction effect, is precisely the same term that drove the isochoric reaction. The second is
due to the fact that the volume can change if the number of moles change, and this induces
an intrinsic change in concentration. Note that the term ρi RT /P = yi , the mole fraction.

Example 7.14
Study a nitrogen dissociation problem in which at t = 0 s, 1 kmole of N2 exists at P = 100 kPa
and T = 6000 K. In this case, take the reaction to be isothermal and isobaric. Consider the elementary
nitrogen dissociation-recombination reaction

N2 + N2 ⇌ 2N + N2 . (7.319)

This has kinetic rate parameters of

cm3 K1.6 cal
a = 7.0 × 1021 , β = −1.6, E = 224928.4 . (7.320)
mole s mole
In SI units, this becomes
 3 1.6
 3  
21 cm K 1m 1000 mole m3 K1.6
a = 7.0 × 10 = 7.0 × 1018 , (7.321)
mole s 100 cm kmole kmole s
    
cal J kJ 1000 mole kJ
E = 224928.4 4.186 = 941550 . (7.322)
mole cal 1000 J kmole kmole
At the initial state, the material is all N2 , so PN2 = P = 100 kPa. The ideal gas law then gives at t = 0

P = PN2 = ρN2 RT, (7.323)

P
ρ N2 t=0
= , (7.324)
RT
100 kPa kmole
= kJ

= 2.00465 × 10−3 . (7.325)
8.314 kmole K (6000 K) m3

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260 CHAPTER 7. AEROTHERMOCHEMISTRY

Thus, the initial volume is

nN2 |t=0 1 kmole

V |t=0 = = kmole
= 4.9884 × 102 m3 . (7.326)
ρN2 t=0 2.00465 × 10−3 m3

In this isobaric process, one always has P = 100 kPa. Now, in general

P = RT (ρN2 + ρN ); (7.327)

therefore, one can write ρN in terms of ρN2 :

P
ρN = − ρ N2 , (7.328)
RT
100 kPa
= kJ

− ρ N2 , (7.329)
8.314 kmole K (6000 K)
 
kmole
= 2.00465 × 10−3 − ρ N2 . (7.330)
m3

Then the equations for kinetics of a single isobaric isothermal reaction, Eq. (7.317) in conjunction
with Eq. (7.249), reduce for N2 molar concentration to
     !
dρN2 β −E ′
νN ν ′ 1 ν ν ρN2 RT
= aT exp (ρN2 ) 2 (ρN ) N 1 − (ρ ) 2 (ρN )
N N
ν N2 − (νN2 + νN ) .
dt RT K c N2 P
| {z }
=r
(7.331)
′ ′
Realizing that νN 2
= 2, νN = 0, νN2 = −1, and νN = 2, one gets
   !
dρN2 2  ρ RT
−E 1 ρ N
= aT β exp ρ2N2 1 − N
−1 − 2 . (7.332)
dt RT K c ρ N2 P
| {z }
=k(T )

The temperature dependency of the reaction is unchanged from the previous reaction:
 
−E
k(T ) = aT β exp , (7.333)
RT
  !
3 1.6 kJ
m K −941550
= 7.0 × 1018 T −1.6 exp kmole
kJ
, (7.334)
kmole s 8.314 kmole KT
 
7.0 × 1018 −1.1325 × 105
= exp . (7.335)
T 1.6 T

For this problem, T = 6000 K, so

 
7.0 × 1018 −1.1325 × 105 m3
k(6000) = exp = 40130.2 . (7.336)
60001.6 6000 kmole s

The equilibrium constant Kc is also unchanged from the previous example. Recall
 PN
i=1 νi
 
Po −∆Go
Kc = exp . (7.337)
RT RT

CC BY-NC-ND. 19 January 2025, J. M. Powers.

7.5. CHEMICAL KINETICS OF A SINGLE ISOTHERMAL REACTION 261

unstable 3 unstable
equilibrium equilibrium
2

-0.002 -0.001 0.001 0.002 0.003

-1
stable,
stable,
physical
non-physical
equilibrium
equilibrium

Figure 7.4: Forcing function, ω̇N2 (ρN2 ), which drives changes of ρN2 as a function of ρN2 in
isothermal, isobaric problem.

PN
For this system, because i=1 νi = ∆n = 1, this reduces to
      o o !
Po −(2goN − g oN2 ) Po −(2(hN − T soT,N ) − (hN2 − T soT,N2 ))
Kc = exp = exp ,(7.338)
RT RT RT RT
   
100 −(2(597270 − (6000)216.926) − (205848 − (6000)292.984))
= exp , (7.339)
(8.314)(6000) (8.314)(6000)
kmole
= 0.000112112 . (7.340)
m3
The differential equation for N2 evolution is then given by
  −3 kmole


2 !
dρN2 m3 1 2.00465 × 10 − ρ N2
ρ2N2 1 − m 3
= 40130.2
dt kmole 0.000112112 kmole
m 3 ρ N 2

!
kJ
ρ N2 8.314 kmole K (6000 K)
× −1 − ≡ ω̇N2 (ρN2 ). (7.341)
100 kPa

The system is at equilibrium when ω̇N2 (ρN2 ) = 0. This is an algebraic function of ρN2 only, and can be
plotted. Figure 7.4 gives a plot of ω̇N2 (ρN2 ) and shows that it has four potential equilibrium points. It
is seen there are four roots. Solving for the equilibria requires solving
  −3 kmole


2 !
m3 1 2.00465 × 10 3 − ρ N
0 = 40130.2 ρ2N2 1 − m 2

kmole 0.000112112 kmole

m3
ρ N2

!
kJ
ρN2 8.314 kmole K (6000 K)
× −1 − . (7.342)
100 kPa

The four roots are

kmole kmole kmole kmole
ρN2 = −0.002005 , 0 , 0.001583 , 0.00254 . (7.343)
| {z m3 } m3 }
| {z |
3
{z m } |
3
{z m }
stable, non−physical unstable stable, physical unstable

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262 CHAPTER 7. AEROTHERMOCHEMISTRY

0.002

concentration (kmole/m3)
0.0015

0.001

0.0005

t (s)
0.001 0.002 0.003 0.004 0.005

Figure 7.5: ρN2 (t) and ρN (t) in isobaric, isothermal nitrogen dissociation problem.

By inspection of the topology of Fig. 7.2, the only stable, physical root is 0.001583 kmole/m3 . Small
perturbations from this equilibrium induce the forcing function to supply dynamics which restore the
system to its original equilibrium state. Small perturbations from the unstable equilibria induce non-
restoring dynamics. For this root, one can then determine that the stable equilibrium value of ρN =
0.000421 kmole/m3 .
A numerical solution via an explicit technique such as a Runge-Kutta integration is found for
Eq. (7.342). The solution for ρN2 , along with ρN is plotted in Fig. 7.5. Linearization of Eq. (7.342)
about the equilibrium state gives rise to the locally linearly valid

d

ρN2 − 0.001583 = −967.073(ρN2 − 0.001583) + . . . (7.344)
dt
This has local solution
ρN2 = 0.001583 + C exp (−967.073t) . (7.345)
Again, C is an irrelevant integration constant. The time scale of relaxation τ is the time when the
argument of the exponential is −1, which is

1
τ= = 1.03 × 10−3 s. (7.346)
967.073 s−1
Note that the time constant for the isobaric combustion is about a factor 1.25 greater than for isochoric
combustion under the otherwise identical conditions.

7.6 Some conservation and evolution equations

Here a few useful global conservation and evolution equations are presented for some key
properties. Only some cases are considered, and one could develop more relations for other
scenarios.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

7.6. SOME CONSERVATION AND EVOLUTION EQUATIONS 263

7.6.1 Total mass conservation: isochoric reaction

One can easily show that the isochoric reaction rate model, Eq. (7.248), satisfies the principle
of mixture mass conservation. Begin with Eq. (7.248) in a compact form, using the definition
of the reaction rate r, Eq. (7.250) and perform the following operations:

dρi
= νi r, (7.347)
 dt
d ρYi
= νi r, (7.348)
dt Mi
X L X L
d
(ρYi ) = νi Mi r = νi Ml φli r = Ml φli νi r, (7.349)
dt
|l=1 {z } l=1

=Mi
N
X N X
X L
d
(ρYi ) = Ml φli νi r, (7.350)
i=1
dt i=1 l=1
 

d  
N L X N
 X  X
ρ Yi  = Ml φli νi r, (7.351)
dt  i=1  l=1 i=1
| {z }
=1
X L X N
dρ
= r Ml φli νi . (7.352)
dt l=1 i=1
| {z }
=0

Therefore, we get

dρ
= 0. (7.353)
dt

PN
Note the term i=1 φli νi = 0 because of stoichiometry, Eq. (7.21).

7.6.2 Element mass conservation: isochoric reaction

Through a similar series of operations, one can show that the mass of each element, l =
1, . . . , L, in conserved in this reaction, which is chemical, not nuclear. Once again, begin

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264 CHAPTER 7. AEROTHERMOCHEMISTRY

with Eq. (7.250) and perform a set of operations,

dρi
= νi r, (7.354)
dt
dρ
φli i = φli νi r, l = 1, . . . , L, (7.355)
dt
d
(φli ρi ) = rφli νi , l = 1, . . . , L, (7.356)
dt
XN XN
d
(φli ρi ) = rφli νi , l = 1, . . . , L, (7.357)
i=1
dt i=1
N
! N
d X X
φli ρi = r φli νi , l = 1, . . . , L, (7.358)
dt i=1 i=1
| {z }
=0
N
!
d X
φli ρi = 0, l = 1, . . . , L. (7.359)
dt i=1

P
The term N i=1 φli ρi represents the number of moles of element l per unit volume, by the
following analysis

N
X XN
moles element l moles species i moles element l
φli ρi = = ≡ ρl e . (7.360)
i=1 i=1
moles species i volume volume

Here the elemental mole density, ρl e , for element l has been defined. So the element concen-
tration for each element remains constant in a constant volume reaction process:

dρl e
= 0, l = 1, . . . , L. (7.361)
dt

One can also multiply by the elemental mass, Ml to get the elemental mass density, ρel :

ρel ≡ Ml ρl e , l = 1, . . . , L. (7.362)

Because Ml is a constant, one can incorporate this definition into Eq. (7.361) to get

dρel
= 0, l = 1, . . . , L. (7.363)
dt

The element mass density remains constant in the constant volume reaction. One could also
simply say because the elements’ density is constant, and the mixture is simply a sum of the
elements, that the mixture density is conserved as well.

CC BY-NC-ND. 19 January 2025, J. M. Powers.

7.6. SOME CONSERVATION AND EVOLUTION EQUATIONS 265

7.6.3 Energy conservation: adiabatic, isochoric reaction

Consider a simple application of the first law of thermodynamics to reaction kinetics: that
of a closed, adiabatic, isochoric combustion process in a mixture of ideal gases. One may
be interested in the rate of temperature change. First, because the system is closed, there
can be no mass change, and because the system is isochoric, the total volume is a non-zero
constant; hence,
dm d dρ dρ
= 0, (ρV ) = 0, V = 0, = 0. (7.364)
dt dt dt dt
For such a process, the first law of thermodynamics is
dE
= Q̇ − Ẇ . (7.365)
dt
But there is no heat transfer or work in the adiabatic isochoric process, so one gets
dE d de dm de
= 0, (me) = 0, m +e = 0, = 0. (7.366)
dt dt dt dt
|{z} dt
=0

Thus for the mixture of ideal gases, e(T, ρ1 , . . . , ρN ) = eo . One can see how reaction rates
affect temperature changes by expanding the derivative in Eq. (7.366)
N
! N
d X X d
Yi ei = 0, (Yi ei ) = 0, (7.367)
dt i=1 i=1
dt
XN  
dei dYi
Yi + ei = 0, (7.368)
i=1
dt dt
X  dei dT
N
dYi

Yi + ei = 0, (7.369)
i=1
dT dt dt
XN  
dT dYi
Yi cvi + ei = 0, (7.370)
i=1
dt dt
N N
dT X X dYi
Yi cvi = − ei , (7.371)
dt i=1 i=1
dt
| {z }
=cv
N
X  
dT d Mi ρi
cv = − ei , (7.372)
dt i=1
dt ρ
XN X X N N
dT dρi
ρcv = − ei Mi=− ei ω̇i = − ei νi r, (7.373)
dt i=1
dt i=1 i=1
PN PN
dT ei ω̇i r i=1 νi ei
= − i=1 =− . (7.374)
dt ρcv ρcv

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266 CHAPTER 7. AEROTHERMOCHEMISTRY

If one defines the net energy change of the reaction as

N
X
∆E ≡ νi ei , (7.375)
i=1

one then gets

dT r∆E
=− . (7.376)
dt ρcv

The rate of temperature change is dependent on the absolute energies, not the energy dif-
ferences. If the reaction is going forward, so r > 0, and that is a direction in which the net
molar energy change is negative, then the temperature will rise.

7.6.4 Energy conservation: adiabatic, isobaric reaction

Solving for the reaction dynamics in an adiabatic isobaric system requires some non-obvious
manipulations. First, the first law of thermodynamics says dE = dQ − dW . Because the
process is adiabatic, one has dQ = 0, so dE + P dV = 0. Because it is isobaric, one gets
d(E + P V ) = 0, or dH = 0. So the total enthalpy is constant. Then

d d dh
H = 0, (mh) = 0, = 0, (7.377)
dt ! dt dt
N
X XN
d d
Yi hi = 0, (Yi hi ) = 0, (7.378)
dt i=1 i=1
dt
N
X N
X
dhi dYi dhi dT dYi
Yi + hi = 0, Yi + hi = 0, (7.379)
i=1
dt dt i=1
dT dt dt

N
X N
dT X dYi
Y i cP i + hi = 0, (7.380)
i=1
dt i=1
dt
N N
dT X X dYi
Y i cP i + hi = 0, (7.381)
dt i=1 dt
| {z } i=1
=cP
N  
dT X d ρi Mi
cP + hi = 0, (7.382)
dt i=1
dt ρ
N  
dT X d ρi
cP + hi Mi = 0. (7.383)
dt i=1
dt ρ

CC BY-NC-ND. 19 January 2025, J. M. Powers.

7.6. SOME CONSERVATION AND EVOLUTION EQUATIONS 267

Now use Eq (7.303) to eliminate the term in Eq. (7.383) involving molar concentration
derivatives to get

N
dT X νi r
cP + hi = 0, (7.384)
dt i=1
ρ
PN
dT r i=1 hi νi
= − . (7.385)
dt ρcP

So the temperature derivative is known as an algebraic function. If one defines the net
enthalpy change as
XN
∆H ≡ hi νi , (7.386)
i=1

one gets
dT r∆H
=− . (7.387)
dt ρcP

Now differentiate the isobaric ideal gas law to get the density derivative.

N
X
P = ρi RT, (7.388)
i=1
XN N
dP dT X dρ
=0 = ρi R + RT i , (7.389)
dt i=1
dt i=1
dt
N N  
dT X X ρi dρ
= ρ + T νi r + , (7.390)
dt i=1 i i=1 ρ dt
N N N
1 dT X X 1 dρ X
= ρ +r νi + ρ. (7.391)
T dt i=1 i i=1
ρ dt i=1 i

Solving, we get
PN PN
dρ − 1 dT i=1 ρi − r i=1 νi
= T dt PN ρi . (7.392)
dt i=1 ρ

One takes dT /dt from Eq. (7.385) to get

1 r
PN
hi νi PN PN
i=1 ρi − r νi
i=1
dρ T ρcP i=1
= PN ρi . (7.393)
dt i=1 ρ

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268 CHAPTER 7. AEROTHERMOCHEMISTRY

Now recall that ρ = ρ/M and cP = cP M, so ρ cP = ρcP . Then Equation (7.393) can be
reduced slightly:

=1
z }| {
XN
PN
hi νi ρ i PN
i=1
cP T
− i=1 νi PN hi νi
PN
dρ i=1
ρ i=1 cP T − i=1 νi
= rρ PN = rρ PN , (7.394)
dt i=1 ρi i=1 ρi
PN  
hi  
i=1 νi −1 N
cP T ρRT X hi
= rρ P
=r νi −1 , (7.395)
RT
P i=1 cP T
N
X  
hi
= rM νi −1 , (7.396)
i=1
cP T

PN
where M is the mean molecular mass. Note for exothermic reaction i=1 νi hi < 0, so
exothermic reaction induces a density decrease as the increased temperature at constant
pressure causes the volume to increase.
Then using Eq. (7.396) to eliminate the density derivative in Eq. (7.302), and changing
the dummy index from i to k, one gets an explicit expression for concentration evolution:

X N  
dρi ρ hk
= νi r + i rM νk −1 , (7.397)
dt ρ k=1
cP T
 
XN   XN  !
 ρ h  h
= r −1 
i k k
νi + ρ M νk
c P T  = r νi + yi νk
c PT
−1 . (7.398)
| {z } k=1 k=1
=yi

PN
Defining the change of enthalpy of the reaction as ∆H ≡ k=1 νk hk , and the change of
P
number of the reaction as ∆n ≡ N k=1 νk , one can also say

  
dρi ∆H
= r νi + yi − ∆n . (7.399)
dt cP T

Exothermic reaction, ∆H < 0, and net number increases, ∆n > 0, both tend to decrease the
molar concentrations of the species in the isobaric reaction.
Lastly, the evolution of the adiabatic, isobaric system, can be described by the simul-
taneous, coupled ordinary differential equations: Eqs. (7.385, 7.393, 7.398). These require
numerical solution in general. Note also that one could also employ a more fundamental
P
treatment as a differential algebraic system involving H = H1 , P = P1 = RT N i=1 ρi and
Eq. (7.302).

CC BY-NC-ND. 19 January 2025, J. M. Powers.

7.6. SOME CONSERVATION AND EVOLUTION EQUATIONS 269

7.6.5 Entropy evolution: Clausius-Duhem relation

Now consider whether the kinetics law that has been posed actually satisfies the second law
of thermodynamics. Consider the second law. There is an algebraic relation on the right
side. If it can be shown that this algebraic relation is positive semi-definite, then the second
law is satisfied, and the algebraic relation is known as a Clausius-Duhem relation.

N
1X
dS|E,V = − µ dni ≥ 0, (7.400)
T i=1 i
| {z }
irreversible entropy production
N N N
dS V X dni 1 V X dρi V X
= − µ =− µ =− µ ω̇i ≥ 0, (7.401)
dt E,V T i=1 i dt V T i=1 i dt T i=1 i
 
  Y !
V X
N
−E
N  1 Y νk 
N
β νk′  
= − µi νi aT exp ρk 1 − ρk  ≥ 0,
T i=1 RT  Kc 
| {z } | k=1{z } | k=1 {z }
≡k(T ) forward reaction reverse reaction
| {z }
≡r
| {z }
≡ω̇i
(7.402)
N N
! N
!
V X Y 1 νk′
Y
= − µi νi k(T ) ρk ρkνk ≥ 0,
1− (7.403)
i=1
T k=1
K c
k=1
N
! N
! N !
V Y ν′ 1 Y ν X
= − k(T ) ρk k 1− ρk k µi νi ≥ 0. (7.404)
T K c
k=1 k=1
| i=1{z }
=−α

Now change the dummy index from k back to i.

N
! N
!
dS V Y ν′ 1 Y νi
= k(T ) ρi i 1− ρ α ≥ 0, (7.405)
dt E,V T i=1
Kc i=1 i
V α dζ
= rα = . (7.406)
T T dt

Consider now the affinity α term in Eq. (7.404) and expand it so that it has a more useful
form:
N
X N
X XN   
o Pi
α=− µi νi = − g i νi = − g T,i + RT ln νi , (7.407)
i=1 i=1 i=1
Po

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270 CHAPTER 7. AEROTHERMOCHEMISTRY

So
 
N
X N
X  νi N  νi
Pi  −∆Go X Pi 
α = − g oT,i νi −RT ln = RT 
 RT − ln ,
 (7.408)
Po | {z } i=1 Po
|i=1 {z } i=1
=ln KP
=∆Go
N 
Y  νi ! YN  ν !
Pi 1 Pi i
= RT ln KP − ln = −RT ln + ln , (7.409)
i=1
P o K P i=1
P o
! 
PN 
N   ν i N   νi
1 Y Pi Y ρ RT
ν i P o i=1

= −RT ln = −RT ln  RT i  , (7.410)

KP i=1 Po Kc i=1
P o

N
!
1 Y νi
= −RT ln ρ . (7.411)
Kc i=1 i

Equation (7.411) is the common definition of affinity. Another form can be found by em-
ploying the definition of Kc from Eq. (7.239) to get
 − PNi=1 νi   N !
Po ∆Go Y νi
α = −RT ln exp ρi , (7.412)
RT RT i=1
 − PNi=1 νi YN
!!
∆Go Po
= −RT + ln ρi νi , (7.413)
RT RT i=1
 − PNi=1 νi YN
!
P o
= −∆Go − RT ln ρi νi . (7.414)
RT i=1

To see clearly that the entropy production rate is positive semi-definite, substitute
Eq. (7.411) into Eq. (7.404) to get
N
! N
! N
!!
dS V Y ν ′ 1 Y 1 Y
= k(T ) ρi i 1− ρi νi −RT ln ρi νi ≥ 0,
dt E,V T i=1
K c i=1
K c i=1
(7.415)
N
! N
! N
!
Y νi′ 1 Y νi 1 Y νi
= −RV k(T ) ρi 1− ρ ln ρ ≥ 0. (7.416)
i=1
Kc i=1 i Kc i=1 i

Define forward and reverse reaction coefficients, R′ , and R′′ , respectively, as

N
Y ′
′
R ≡ k(T ) ρi νi , (7.417)
i=1
YN
k(T ) ′′
R′′ ≡ ρi νi . (7.418)
Kc i=1

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7.7. MULTIPLE REACTION EXTENSIONS 271

Both R′ and R′′ have units of kmole/m3 /s. It is easy to see that
r = R′ − R′′ . (7.419)
Note that because k(T ) > 0, Kc > 0, and ρi ≥ 0, that both R′ ≥ 0 and R′′ ≥ 0. Because
νi = νi′′ − νi′ , one finds that
N N
1 Y νi 1 k(T ) Y νi′′ −νi′ R′′
ρ = ρ = ′. (7.420)
Kc i=1 i Kc k(T ) i=1 i R

Then Eq. (7.416) reduces to

   ′′ 
dS R′′ ′ R
= −RV R 1 − ′ ln ≥ 0. (7.421)
dt E,V R R′
Finally, we get
 
dS ′ ′′ R′
= RV (R − R ) ln ≥ 0. (7.422)
dt E,V R′′

Obviously, if the forward rate is greater than the reverse rate R′ − R′′ > 0, ln(R′ /R′′ ) > 0,
and the entropy production is positive. If the forward rate is less than the reverse rate,
R′ − R′′ < 0, ln(R′ /R′′ ) < 0, and the entropy production is still positive. The production
rate is zero when R′ = R′′ .
Note that the affinity α can be written as
 ′
R
α = RT ln . (7.423)
R′′
And so when the forward reaction rate exceeds the reverse, the affinity is positive. It is zero
at equilibrium, when the forward reaction rate equals the reverse.

7.7 Multiple reaction extensions

Let us now extend notions associated with the thermodynamics of a single chemical reactions
to systems in which many reactions occur simultaneously. Consider now the reaction of N
species, composed of L elements, in J reactions. This section will focus on the most common
case in which J ≥ (N − L), which is usually the case in large chemical kinetic systems in use
in engineering models. While much of the analysis will only require J > 0, certain results
will depend on J ≥ (N − L). It is not difficult to study the complementary case where
0 < J < (N − L).
The molecular mass of species i is still given by Eq. (7.1):
L
X
Mi = Ml φli , i = 1, . . . , N. (7.424)
l=1

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272 CHAPTER 7. AEROTHERMOCHEMISTRY

However, each reaction has a stoichiometric coefficient. The j th reaction can be summarized
in the following ways:
N
X N
X
χi νij′ ⇌ χi νij′′ , j = 1, . . . , J, (7.425)
i=1 i=1
N
X
χi νij = 0, j = 1, . . . , J. (7.426)
i=1

Stoichiometry for the j th reaction and lth element is given by the extension of Eq. (7.21):

N
X
φli νij = 0, l = 1, . . . , L, j = 1, . . . , J. (7.427)
i=1

The net change in Gibbs free energy and equilibrium constants of the j th reaction are defined
by the extensions of Eqs. (7.237, 7.236, 7.239):

N
X
∆Goj ≡ g oT,i νij , j = 1, . . . , J, (7.428)
i=1
 
−∆Goj
KP,j ≡ exp , j = 1, . . . , J, (7.429)
RT
 PNi=1 νij  
Po −∆Goj
Kc,j ≡ exp , j = 1, . . . , J. (7.430)
RT RT

The equilibrium of the j th reaction is given by the extension of Eq. (7.223):

N
X
µi νij = 0, j = 1, . . . , J, (7.431)
i=1

or the extension of Eq. (7.224):

N
X
g i νij = 0, j = 1, . . . , J. (7.432)
i=1

The multi-reaction equation for affinity is

N
X
αj = − µi νij , j = 1, . . . , J. (7.433)
i=1

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7.7. MULTIPLE REACTION EXTENSIONS 273

In terms of the chemical affinity of each reaction, the equilibrium condition is simply
αj = 0, j = 1, . . . , J. (7.434)
At equilibrium, then the equilibrium constraints can be shown to reduce to the extension
of Eq. (7.235):
N 
Y ν
Pi ij
KP,j = , j = 1, . . . , J, (7.435)
i=1
Po

or the extension of Eq. (7.243):

N
Y νij
Kc,j = ρi , j = 1, . . . , J. (7.436)
i=1

For isochoric reaction, the evolution of species concentration i due to the combined effect
of J reactions is given by the extension of Eq. (7.248):
≡ω̇i
z }|  {
  Y !
dρi X
J
−E
N  1 Y νkj 
N
βj j ν ′
kj  
= νij aj T exp ρk 1 − ρk , i = 1, . . . , N.
dt RT  Kc,j 
j=1 | {z } | k=1{z } | k=1
{z }
≡kj (T ) forward reaction reverse reaction
| {z }
≡rj =(1/V )dζj /dt

(7.437)
The extension to isobaric reactions is straightforward, and follows the same analysis as for
a single reaction. Again, three intermediate variables which are in common usage have been
defined. First one takes the reaction rate of the j th reaction to be the extension of Eq. (7.249)
 
  Y !
−E
N  1 Y νkj 
N
βj j ν ′
kj  
rj ≡ aj T exp ρk 1 − ρk  , j = 1, . . . , J, (7.438)
RT  Kc,j k=1 
| {z }| k=1
{z } | {z }
≡kj (T ) forward reaction reverse reaction

or the extension of Eq. (7.250)

 
  Y
′′ 
N N
βj −E j
 ′
νkj 1 Y νkj 
rj = aj T exp  ρk − ρk , j = 1, . . . , J, (7.439)
RT  k=1 Kc,j k=1 
| {z } | {z } | {z }
≡kj (T ), Arrhenius rate
| forward reaction {z reverse reaction }
law of mass action

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274 CHAPTER 7. AEROTHERMOCHEMISTRY

1 dζj
rj = . (7.440)
V dt

Here ζj is the reaction progress variable for the j th reaction.

Each reaction has a temperature-dependent rate function kj (T ), which is an extension of
Eq. (7.251):
 
βj −E j
kj (T ) ≡ aj T exp , j = 1, . . . , J. (7.441)
RT
The evolution rate of each species is given by ω̇i , defined now as an extension of Eq. (7.253):

J
X
ω̇i ≡ νij rj , i = 1, . . . , N. (7.442)
j=1

The multi-reaction extension of Eq. (7.203) for mole change in terms of progress variables
is
J
X
dni = νij dζj , i = 1, . . . , N. (7.443)
j=1

One also has Eq. (7.218):

N
X
dG|T,P = µi dni , (7.444)
i=1
XN J
X
= µi νik dζk , (7.445)
i=1 k=1
N
X XJ
∂G ∂ζk
= µi νik , (7.446)
∂ζj ζp i=1 k=1
∂ζj
N
X J
X
= µi νik δkj , (7.447)
i=1 j=1
N
X
= µi νij , (7.448)
i=1
= −αj , j = 1, . . . , J. (7.449)

For a set of adiabatic, isochoric reactions, one can show the extension of Eq. (7.376) is
PJ PN
dT j=1 rj ∆Ej i=1 ei ω̇i
=− =− , (7.450)
dt ρcv ρcv

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7.7. MULTIPLE REACTION EXTENSIONS 275

where the energy change for a reaction ∆Ej is defined as the extension of Eq. (7.375):

N
X
∆Ej = ei νij , j = 1, . . . , J. (7.451)
i=1

Similarly for a set of adiabatic, isobaric reactions, one can show the extension of Eq. (7.387):

PJ PN
dT j=1 rj ∆Hj i=1 hi ω̇i
=− =− , (7.452)
dt ρcP ρcP

where the enthalpy change for a reaction ∆Hj is defined as the extension of Eq. (7.386):

N
X
∆Hj = hi νij , j = 1, . . . , J. (7.453)
i=1

Moreover, the density and species concentration derivatives for an adiabatic, isobaric set can
be shown to be extensions of Eqs. (7.396, 7.399):

XJ XN  
dρ hi
= M rj νij −1 , (7.454)
dt j=1 i=1
cP T
XJ   
dρi ∆Hj
= rj νij + yi − ∆nj , (7.455)
dt j=1
c P T

where

N
X
∆nj = νkj . (7.456)
k=1

In a similar fashion to that shown for a single reaction, one can further sum over all
reactions and prove that mixture mass is conserved, element mass and number are conserved.

Example 7.15
Show that element mass and number are conserved for the multi-reaction formulation.

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276 CHAPTER 7. AEROTHERMOCHEMISTRY

Start with Eq. (7.437) and expand as follows:

J
X
dρi
= νij rj , (7.457)
dt j=1
J
X
dρi
φli = φli νij rj , (7.458)
dt j=1

XJ
d
(φli ρi ) = φli νij rj , (7.459)
dt j=1

X N XN X J
d
(φli ρi ) = φli νij rj , (7.460)
i=1
dt i=1 j=1
N
! J X N
d X X
φli ρi = φli νij rj , (7.461)
dt i=1 j=1 i=1
| {z }
=ρl e
J
X N
X
dρl e
= rj φli νij , (7.462)
dt j=1 i=1
| {z }
=0
dρl e
= 0, l = 1, . . . , L, (7.463)
dt
d
(Ml ρl e ) = 0, l = 1, . . . , L, (7.464)
dt
dρl e
= 0, l = 1, . . . , L. (7.465)
dt
It is also straightforward to show that the mixture density is conserved for the multi-reaction, multi-
component mixture:
dρ
= 0. (7.466)
dt

The proof of the Clausius-Duhem relationship for the second law is an extension of the
single reaction result. Start with Eq. (7.400) and operate much as for a single reaction model.
N
1X
dS|E,V = − µ dni ≥ 0, (7.467)
T i=1 i
| {z }
irreversible entropy production
N
dS V X dni 1
= − µ ≥ 0, (7.468)
dt E,V T i=1 i dt V
N
V X dρi
= − µ ≥ 0, (7.469)
T i=1 i dt

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7.7. MULTIPLE REACTION EXTENSIONS 277

N J
V X X
= − µ νij rj ≥ 0, (7.470)
T i=1 i j=1
N J
V XX
= − µ νij rj ≥ 0, (7.471)
T i=1 j=1 i
J N
V X X
= − rj µ νij ≥ 0, (7.472)
T j=1 i=1 i
J N N
! N
V X Y νij′ 1 Y νij X
= − kj ρ 1− ρ µi νij ≥ 0, (7.473)
T j=1 i=1 i Kc,j i=1 i i=1
J N N
! N
!!
V X Y ν′ 1 Y ν 1 Y νij
= − kj ρi ij 1− ρi ij RT ln ρ ≥ 0,
T j=1 i=1
Kc,j i=1
Kc,j i=1 i
(7.474)
J N N
! N
!
X Y ν′ 1 Y νij 1 Y νij
= −RV kj ρi ij 1− ρ ln ρ ≥ 0. (7.475)
j=1 i=1
Kc,j i=1 i Kc,j i=1 i

Note that Eq. (7.472) can also be written in terms of the affinities (see Eq. (7.433)) and
reaction progress variables (see Eq. (7.440) as
J
dS 1 X dζj
= αj ≥ 0. (7.476)
dt E,V T j=1 dt

Similar to the argument for a single reaction, if one defines extensions of Eqs. (7.417,
7.418) as
N
Y N
′
νij kj Y νij′′
R′j = kj ρi , R′′j = ρ , (7.477)
i=1
Kc,j i=1 i

then it is easy to show that

rj = R′j − R′′j , (7.478)
and we get the equivalent of Eq. (7.422):

J
X  
dS
R′j
= RV R′j − R′′j ln ≥ 0. (7.479)
dt E,V j=1
R′′j

Because kj (T ) > 0, R > 0, and V ≥ 0, and each term in the summation combines to
be positive semi-definite, one sees that the Clausius-Duhem inequality is guaranteed to be
satisfied for multi-component reactions.

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278 CHAPTER 7. AEROTHERMOCHEMISTRY

7.8 Equilibrium conditions

For multicomponent mixtures undergoing multiple reactions, determining the equilibrium

condition is more difficult. There are two primary approaches, both of which are essentially
equivalent. The most straightforward method requires formal minimization of the Gibbs free
energy of the mixture. It can be shown that this actually finds the equilibrium associated
with all possible reactions.

7.8.1 Minimization of G via Lagrange multipliers

P
Recall that dG|T,P ≤ 0. Recall also that G = N ∂G
i=1 g i ni . Because µi = g i = ∂ni , one
P,T,nj
P PN
also has G = N i=1 µi ni . We also have dG|T,P = i=1 µi dni . Now one must also demand
for a system coming to equilibrium that the element numbers are conserved. This can be
achieved by requiring

N
X
φli (nio − ni ) = 0, l = 1, . . . , L. (7.480)
i=1

Here recall nio is the initial number of moles of species i in the mixture, and φli is the number
of moles of element l in species i. If one interprets nio − ni as −νij , the negative of the net
P
mole change, Eq. (7.480) becomes − N i=1 φli νij = 0, equivalent to Eq. (7.427).

One can now use the method of constrained optimization given by the method of Lagrange
multipliers to extremize G subject to the constraints of element conservation. The extremum
will be a minimum; this will not be proved, but it will be demonstrated. Define a set of L
Lagrange multipliers λl . Next define an augmented Gibbs free energy function G∗ , which is
simply G plus the product of the Lagrange multipliers and the constraints:

L
X N
X
G∗ = G + λl φlk (nko − nk ). (7.481)
l=1 k=1

Now when the constraints are satisfied, one has G∗ = G, so assuming the constraints can be
satisfied, extremizing G is equivalent to extremizing G∗ . To extremize G∗ , take its differential

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7.8. EQUILIBRIUM CONDITIONS 279

with respect to ni , with P , T and nj constant and set it to zero for each species:

L N
!
∂G∗ ∂G ∂ X X
= + λl φlk (nko − nk ) = 0, i = 1, . . . , N,
∂ni T,P,nj ∂ni T,P,n ∂ni T,P,nj l=1 k=1
| {z }j
=µi

(7.482)
L
X N
X ∂nk
= µi − λl φlk = 0, i = 1, . . . , N, (7.483)
l=1 k=1
∂ni T,P,nj
| {z }
δki
L
X N
X
= µi − λl φlk δki = 0, i = 1, . . . , N, (7.484)
l=1 k=1
XL
= µi − λl φli = 0, i = 1, . . . , N. (7.485)
l=1

Next, for an ideal gas, one can expand the chemical potential so as to get
  L
X
Pi
µoT,i + RT ln − λl φli = 0, i = 1, . . . , N, (7.486)
Po
| {z } l=1
=µi
 
 !  L
 n P 1 X
o 
µT,i + RT ln  PN
i  − λl φli = 0, i = 1, . . . , N. (7.487)
 k=1 nk
Po 
 l=1
| {z }
=Pi

PN
Recalling that k=1 nk = n, in summary then, one has N + L equations
  L
X
ni P
µoT,i + RT ln − λl φli = 0, i = 1, . . . , N, (7.488)
n Po l=1
N
X
φli (nio − ni ) = 0, l = 1, . . . , L. (7.489)
i=1

in N + L unknowns: ni , i = 1, . . . , N, λl , l = 1, . . . , L.

Example 7.16
Consider
N2 + N2 ⇌ 2N + N2 . (7.490)

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280 CHAPTER 7. AEROTHERMOCHEMISTRY

Take the reaction to be isothermal and isobaric with T = 6000 K and P = 100 kPa. Initially one has
1 kmole of N2 and 0 kmole of N. Use the extremization of Gibbs free energy to find the equilibrium
composition.

First find the chemical potentials at the reference pressure of each of the possible constituents.
o o o
µoT,i = goi = hi − T soi = h298,i + ∆hi − T soi . (7.491)

For each species, one then finds

kJ
µoN2 = 0 + 205848 − (6000)(292.984) = −1552056 , (7.492)
kmole
kJ
µoN = 472680 + 124590 − (6000)(216.926) = −704286 . (7.493)
kmole
To each of these one must add  
ni P
RT ln ,
nPo
to get the full chemical potential. Now P = Po = 100 kPa for this problem, so one only must consider
RT = 8.314(6000) = 49884 kJ/kmole. So, the chemical potentials are
 
n N2
µN2 = −1552056 + 49884 ln , (7.494)
n N + n N2
 
nN
µN = −704286 + 49884 ln . (7.495)
n N + n N2

Then one adds on the Lagrange multiplier and then considers element conservation to get the
following coupled set of nonlinear algebraic equations:
 
n N2
−1552056 + 49884 ln − 2λN = 0, (7.496)
n N + n N2
 
nN
−704286 + 49884 ln − λN = 0, (7.497)
n N + n N2
nN + 2nN2 = 2. (7.498)

These non-linear equations are solved numerically to get

kJ
nN2 = 0.88214 kmole, nN = 0.2357 kmole, λN = −781934 . (7.499)
kmole

Example 7.17
Consider a mixture of 2 kmole of H2 and 1 kmole of O2 at T = 3000 K and P = 100 kPa. Assuming
an isobaric and isothermal equilibration process with the products consisting of H2 , O2 , H2 O, OH, H,
and O, find the equilibrium concentrations. Consider the same mixture at T = 298 K and T = 1000 K.

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7.8. EQUILIBRIUM CONDITIONS 281

The first task is to find the chemical potentials of each species at the reference pressure and
T = 3000 K. Here one can use the standard tables along with the general equation

o o o
µoT,i = goi = hi − T soi = h298,i + ∆hi − T soi . (7.500)

For each species, one then finds

kJ
µoH2 = 0 + 88724 − 3000(202.989) = −520242 , (7.501)
kmole
kJ
µoO2 = 0 + 98013 − 3000(284.466) = −755385 , (7.502)
kmole
kJ
µoH2 O = −241826 + 126548 − 3000(286.504) = −974790 , (7.503)
kmole
kJ
µoOH = 38987 + 89585 − 3000(256.825) = −641903 , (7.504)
kmole
kJ
µoH = 217999 + 56161 − 3000(162.707) = −213961 , (7.505)
kmole
kJ
µoO = 249170 + 56574 − 3000(209.705) = −323371 . (7.506)
kmole

To each of these one must add

 
ni P
RT ln ,
nPo

to get the full chemical potential. Now P = Po = 100 kPa for this problem, so one must only consider
RT = 8.314(3000) = 24942 kJ/kmole. So, the chemical potentials are

 
n H2
µ H2 = −520243 + 24942 ln , (7.507)
n H2 + n O 2 + nH2 O + nOH + nH + nO
 
n O2
µO 2 = −755385 + 24942 ln , (7.508)
n H2 + n O 2 + nH2 O + nOH + nH + nO
 
n H2 O
µ H2 O = −974790 + 24942 ln , (7.509)
n H2 + n O 2 + nH2 O + nOH + nH + nO
 
nOH
µOH = −641903 + 24942 ln , (7.510)
n H2 + n O 2 + nH2 O + nOH + nH + nO
 
nH
µH = −213961 + 24942 ln , (7.511)
n H2 + n O 2 + nH2 O + nOH + nH + nO
 
nO
µO = −323371 + 24942 ln . (7.512)
n H2 + n O 2 + nH2 O + nOH + nH + nO

Then one adds on the Lagrange multipliers and then considers element conservation to get the following

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282 CHAPTER 7. AEROTHERMOCHEMISTRY

coupled set of nonlinear equations:

 
n H2
−520243 + 24942 ln − 2λH = 0, (7.513)
nH + nO2 + nH2 O + nOH + nH + nO
 2 
n O2
−755385 + 24942 ln − 2λO = 0, (7.514)
nH2 + nO2 + nH2 O + nOH + nH + nO
 
n H2 O
−974790 + 24942 ln − 2λH − λO = 0, (7.515)
nH + nO2 + nH2 O + nOH + nH + nO
 2 
nOH
−641903 + 24942 ln − λH − λO = 0, (7.516)
nH2 + nO2 + nH2 O + nOH + nH + nO
 
nH
−213961 + 24942 ln − λH = 0, (7.517)
nH + nO2 + nH2 O + nOH + nH + nO
 2 
nO
−323371 + 24942 ln − λO = 0, (7.518)
nH2 + nO2 + nH2 O + nOH + nH + nO
2nH2 + 2nH2 O + nOH + nH = 4, (7.519)
2nO2 + nH2 O + nOH + nO = 2. (7.520)

These non-linear algebraic equations can be solved numerically via a Newton-Raphson technique.
The equations are sensitive to the initial guess, and one can use ones intuition to help guide the
selection. For example, one might expect to have nH2 O somewhere near 2 kmole. Application of the
Newton-Raphson iteration yields

n H2 = 3.19 × 10−1 kmole, (7.521)

n O2 = 1.10 × 10−1 kmole, (7.522)
n H2 O = 1.50 × 100 kmole, (7.523)
−1
nOH = 2.20 × 10 kmole, (7.524)
nH = 1.36 × 10−1 kmole, (7.525)
nO = 5.74 × 10−2 kmole, (7.526)
kJ
λH = −2.85 × 105 , (7.527)
kmole
kJ
λO = −4.16 × 105 . (7.528)
kmole

At this relatively high value of temperature, all species considered have a relatively major presence.
That is, there are no truly minor species.

Unless a very good guess is provided, it may be difficult to find a solution for this set of non-
linear equations. Straightforward algebra allows the equations to be recast in a form which sometimes

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7.8. EQUILIBRIUM CONDITIONS 283

converges more rapidly:

   2
n H2 520243 λH
= exp exp , (7.529)
n H2 + n O 2 + nH2 O + nOH + nH + nO 24942 24942
   2
n O2 755385 λO
= exp exp , (7.530)
nH2 + nO2 + nH2 O + nOH + nH + nO 24942 24942
     2
n H2 O 974790 λO λH
= exp exp exp , (7.531)
n H2 + nO2 + nH2 O + nOH + nH + nO 24942 24942 24942
     
nOH 641903 λO λH
= exp exp exp , (7.532)
n H2 + nO2 + nH2 O + nOH + nH + nO 24942 24942 24942
   
nH 213961 λH
= exp exp , (7.533)
n H2 + nO2 + nH2 O + nOH + nH + nO 24942 24942
   
nO 323371 λO
= exp exp , (7.534)
n H2 + nO2 + nH2 O + nOH + nH + nO 24942 24942
2nH2 + 2nH2 O + nOH + nH = 4, (7.535)
2nO2 + nH2 O + nOH + nO = 2. (7.536)

Then solve these considering ni , exp (λO /24942), and exp (λH /24942) as unknowns. The same result is
recovered, but a broader range of initial guesses converge to the correct solution.
One can verify that this choice extremizes G by direct computation; moreover, this will show
that the extremum is actually a minimum. In so doing, one must exercise care to see that element
conservation is retained. As an example, perturb the equilibrium solution above for nH2 and nH such
that

nH2 = 3.19 × 10−1 + ξ, nH = 1.36 × 10−1 − 2ξ. (7.537)

Leave all other species mole numbers the same. In this way, when ξ = 0, one has the original equilibrium
solution. For ξ 6= 0, the solution
P moves off the equilibrium value in such a way that elements are
conserved. Then one has G = N i=1 µi ni = G(ξ). The difference G(ξ) − G(0) is plotted in Fig. 7.6.
When ξ = 0, there is no deviation from the value predicted by the Newton-Raphson iteration. Clearly
when ξ = 0, G(ξ) − G(0), takes on a minimum value, and so then does G(ξ). So the procedure works.
At the lower temperature, T = 298 K, application of the same procedure yields different results:

n H2 = 4.88 × 10−27 kmole, (7.538)

n O2 = 2.44 × 10−27 kmole, (7.539)
n H2 O = 2.00 × 100 kmole, (7.540)
nOH = 2.22 × 10−29 kmole, (7.541)
nH = 2.29 × 10−49 kmole, (7.542)
nO = 1.67 × 10−54 kmole, (7.543)
kJ
λH = −9.54 × 104 , (7.544)
kmole
kJ
λO = −1.07 × 105 . (7.545)
kmole

At the intermediate temperature, T = 1000 K, application of the same procedure shows the minor

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284 CHAPTER 7. AEROTHERMOCHEMISTRY

40

30

20

10

-0.01 -0.005 0.005 0.01

Figure 7.6: Gibbs free energy variation as mixture composition is varied maintaining element
conservation for mixture of H2 , O2 , H2 O, OH, H, and O at T = 3000 K, P = 100 kPa.

species become slightly more prominent:

n H2 = 4.99 × 10−7 kmole, (7.546)

−7
n O2 = 2.44 × 10 kmole, (7.547)
n H2 O = 2.00 × 100 kmole, (7.548)
nOH = 2.09 × 10−8 kmole, (7.549)
nH = 2.26 × 10−12 kmole, (7.550)
nO = 1.10 × 10−13 kmole, (7.551)
kJ
λH = −1.36 × 105 , (7.552)
kmole
kJ
λO = −1.77 × 105 . (7.553)
kmole

7.8.2 Equilibration of all reactions

In another equivalent method, if one commences with a multi-reaction model, one can require
each reaction to be in equilibrium. This leads to a set of algebraic equations for rj = 0, which

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7.8. EQUILIBRIUM CONDITIONS 285

from Eq. (7.439) leads to

 PNi=1 νij   N
Y
Po −∆Goj νkj
Kc,j = exp = ρk , j = 1, . . . , J. (7.554)
RT RT k=1

With some effort it can be shown that not all of the J equations are linearly independent.
Moreover, they do not possess a unique solution. However, for closed systems, only one of
the solutions is physical, as will be shown in the following section. The others typically
involve non-physical, negative concentrations.
Nevertheless, Eqs. (7.554) are entirely consistent with the predictions of the N + L equa-
tions which arise from extremization of Gibbs free energy while enforcing element number
constraints. This can be shown by beginning with Eq. (7.487), rewritten in terms of molar
concentrations, and performing the following sequence of operations:
! L
ni /V P X
µoT,i + RT ln PN − λl φli = 0, i = 1, . . . , N, (7.555)
k=1 nk /V
Po
l=1
! L
ρiP X
µoT,i + RT ln PN − λl φli = 0, i = 1, . . . , N, (7.556)
k=1 ρ k
P o
l=1
  X L
ρi P
µoT,i + RT ln − λl φli = 0, i = 1, . . . , N, (7.557)
ρ Po l=1
  X L
o RT
µT,i + RT ln ρi − λl φli = 0, i = 1, . . . , N, (7.558)
Po l=1
  XL
o RT
νij µT,i + νij RT ln ρi − νij λl φli = 0, i = 1, . . . , N,
Po l=1
j = 1, . . . , J, (7.559)
N
X N
X   X N XL
RT
νij µoT,i + νij RT ln ρi − νij λl φli = 0, j = 1, . . . , J, (7.560)
Po
|i=1 {z } i=1 i=1 l=1
=∆Goj
N
X   X L X N
RT
∆Goj + RT νij ln ρi − λl φli νij = 0, j = 1, . . . , J, (7.561)
i=1
Po l=1
|i=1 {z }
=0
N
X  
RT
∆Goj + RT νij ln ρi = 0, j = 1, . . . , J. (7.562)
i=1
Po

Here, the stoichiometry for each reaction has been employed to remove the Lagrange multi-

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286 CHAPTER 7. AEROTHERMOCHEMISTRY

pliers. Continue to find

N
X  νij
RT ∆Goj
ln ρi = − , j = 1, . . . , J, (7.563)
i=1
Po RT
X N  νij !  
RT ∆Goj
exp ln ρi = exp − , j = 1, . . . , J, (7.564)
i=1
Po RT
YN  νij  
RT ∆Goj
ρi = exp − , j = 1, . . . , J, (7.565)
i=1
Po RT
PN
  i=1 νij YN  
RT ∆Goj
ρi νij = exp − , j = 1, . . . , J, (7.566)
Po i=1
RT
N
Y  PNi=1 νij  
Po ∆Goj
ρi νij = exp − , j = 1, . . . , J, (7.567)
RT RT
i=1 | {z }
=Kc,j

In summary,

N
Y
ρi νij = Kc,j , j = 1, . . . , J, (7.568)
i=1

which is identical to Eq. (7.554), obtained by equilibrating each of the J reactions. Thus,
extremization of Gibbs free energy is consistent with equilibrating each of the J reactions.

7.9 Concise reaction rate law formulations

One can additional analysis to obtain a more efficient representation of the reaction rate law
for multiple reactions. There are two important cases: 1) J ≥ (N − L); this is most common
for large chemical kinetic systems, and 2) J < (N − L); this is common for simple chemistry
models.
The species production rate is given by Eq. (7.437), which reduces to
J
dρi 1 X dζj
= νij , i = 1, . . . , N. (7.569)
dt V j=1 dt

Now recalling Eq. (7.96), one has

N
X −L
dni = Dik dξk , i = 1, . . . , N. (7.570)
k=1

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7.9. CONCISE REACTION RATE LAW FORMULATIONS 287

Comparing then Eq. (7.570) to Eq. (7.443), one sees that

J
X N
X −L
νij dζj = Dik dξk , i = 1, . . . , N, (7.571)
j=1 k=1
J
X N
X −L
1 1
νij dζj = Dik dξk , i = 1, . . . , N. (7.572)
V j=1
V k=1

7.9.1 Reaction dominant: J ≥ (N − L)

Consider first the most common case in which J ≥ (N − L). One can say the species
production rate is given
N −L J
dρi 1 X dξk X
= Dik = νij rj , i = 1, . . . , N. (7.573)
dt V dt j=1
k=1

One would like to invert

PNand solve directly for
Pdξ k /dt. However, Dik is non-square and has no
N
inverse. But because i=1 φli Dip = 0, and i=1 φli νij = 0, L of the equations N equations
in Eq. (7.573) are redundant.
At this point, it is more convenient to go to a Gibbs vector notation, where there is an
obvious correspondence between the bold vectors and the indicial counterparts:
dρ 1 dξ
= D· = ν · r, (7.574)
dt V dt
dξ
DT · D · = V DT · ν · r, (7.575)
dt
dξ
= V (DT · D)−1 · DT · ν · r. (7.576)
dt
Because of the L linear dependencies, there is no loss of information in this matrix projection.
This system of N − L equations is the smallest number of differential equations that can be
solved for a general system in which J > (N − L).
Lastly, one recovers the original system when forming
dξ
D· = V D · (DT · D)−1 · DT ·ν · r. (7.577)
dt | {z }
=P

Here, the N × N projection matrix P is symmetric, has norm of unity, has rank of N − L,
has N − L eigenvalues of value unity, and L eigenvalues of value zero. And, while application
of a general projection matrix to ν · r filters some of the information in ν · r, because the
N × (N − L) matrix D spans the same column space as the N × J matrix ν, no information
is lost in Eq. (7.577) relative to the original Eq. (7.574). Mathematically, one can say

P · ν = ν. (7.578)

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288 CHAPTER 7. AEROTHERMOCHEMISTRY

7.9.2 Species dominant: J < (N − L)

Next consider the case in which J < (N −L). This often arises in models of simple chemistry,
for example one- or two-step kinetics.
The fundamental reaction dynamics are most concisely governed by the J equations
which form

1 dζ
= r. (7.579)
V dt

However, r is a function of the concentrations; one must therefore recover ρ as a function

of reaction progress ζ. In vector form, Eq. (7.569) is written as

dρ 1 dζ
= ν· . (7.580)
dt V dt
Take as an initial condition that the reaction progress is zero at t = 0 and that there are an
appropriate set of initial conditions on the species concentrations ρ:

ζ = 0, t = 0, (7.581)
ρ = ρo , t = 0. (7.582)

Then, because ν is a constant, Eq. (7.580) is easily integrated. After applying the initial
conditions, Eq. (7.582), one gets
1
ρ = ρo + ν · ζ. (7.583)
V
Last, if J = (N − L), either approach yields the same number of equations, and is equally
concise.

7.10 Adiabatic, isochoric kinetics

Here an example which uses multiple reactions for an adiabatic isochoric system is given.

Example 7.18
Consider the full time-dependency of a problem considered in a previous example in which the
equilibrium state was found; see Sec. [Link],. A closed, fixed, adiabatic volume contains at t = 0 s a
stoichiometric mixture of 2 kmole of H2 , 1 kmole of O2 , and 8 kmole of N2 at 100 kPa and 1000 K.
Find the reaction dynamics as the system proceeds from its initial state to its final state.

This problem requires a detailed numerical solution. Such a solution was performed by solving
Eq. (7.437) along with the associated calorically imperfect species state equations for a mixture of
eighteen interacting species: H2 , H, O, O2 , OH, H2 O, HO2 , H2 O2 , N, NH2 , NH3 , N2 H, NO, NO2 , N2 O,
HNO, and N2 . The equilibrium values were reported in a previous example.

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7.10. ADIABATIC, ISOCHORIC KINETICS 289

0
H2
HO
10
O2 2 N2
H2
−5
10 hydrogen- O2 NO
−10 NO2
oxygen-related OH
10 N N2O

species H
O
−10
10 evolution −20
HO2 10 nitrogen
H2O2
HO
2
NO and nitrogen
−15
10 10
−30 oxides species
evolution
H2O2 a) b)
−20 −40
10 10
−6 −4 −2 −6 −4 −2
10 10 10 10 10 10
t (s) t (s)

3000 250

2500
200
P (kPa)
T (K)

2000
150
1500 induction
time
c) d)
1000 100
−6 −4 −2 −6 −4 −2
10 10 10 10 10 10
t (s) t (s)

Figure 7.7: Plot of a) ρH2 (t), ρH (t), ρO (t), ρO2 (t), ρOH (t), ρH2 O (t), ρHO2 (t), ρH2 O2 (t), b) ρN (t),
ρNO (t), ρNO2 (t), ρN2 O (t), ρN2 (t), c) T (t), and d) P (t) for adiabatic, isochoric combustion of
a mixture of 2H2 + O2 + 8N2 initially at T = 1000 K, P = 100 kPa.

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290 CHAPTER 7. AEROTHERMOCHEMISTRY

The dynamics of the reaction process are reflected in Fig. 7.7. At early time, t < 4 × 10−4 s, the
pressure, temperature, and major reactant species concentrations (H2 , O2 , N2 ) are nearly constant.
However, the minor species, e.g. OH, NO, HO2 and the major product, H2 O, are undergoing very
rapid growth, albeit concentrations whose value remains small. In this period, the material is in what
is known as the induction period.
After a certain critical mass of minor species has accumulated, exothermic recombination of these
minor species to form the major product H2 O induces the temperature to rise, which accelerates further
the reaction rates. This is manifested in a thermal explosion. A common definition of the end of the
induction period is the induction time, t = tind , the time when dT /dt goes through a maximum. Here
one finds
tind = 4.53 × 10−4 s. (7.584)
At the end of the induction zone, there is a final relaxation to equilibrium.

7.11 Steady rocket nozzle flow with detailed kinetics

Let us consider the reactive extension of the one-dimensional compressible flow model first
considered in Sec. 2.1. We extend the kinetics models developed to a moving fluid. Let us
extend Eq. (2.3) and say
X J
∂ ∂
(ρYi A) + (ρYi Au) = AMi νij rj . (7.585)
∂t ∂x j=1

Species mass is not conserved. Each evolves in accordance with the set of J chemical reactions
dictated by rj . One adds all species and sees that mixture mass is conserved:
N 
X  XN X J
∂ ∂
(ρYi A) + (ρYi Au) = AMi νij rj , (7.586)
i=1
∂t ∂x i=1 j=1
N
! N
! J X N
∂ X ∂ X X
ρA Yi + ρuA Yi = A Mi νij rj . (7.587)
∂t i=1
∂x i=1 j=1 i=1
PN
Now we insist that i=1 Yi = 1. We use this along with further rearrangement to get

XJ XN
∂ ∂
(ρA) + (ρuA) = A rj Mi νij . (7.588)
∂t ∂x j=1 i=1

Now the molecular mass is composed of the sum of the atomic mass of element l, Ml and
the number of atoms of element l in species i, φli :
L
X
Mi = Ml φli , i = 1, . . . , N. (7.589)
l=1

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7.11. STEADY ROCKET NOZZLE FLOW WITH DETAILED KINETICS 291

Rearranging the sum, we get

J N L
! J L N
∂ ∂ X X X X X X
(ρA) + (ρuA) = A rj Ml φli νij = A rj Ml φli νij . (7.590)
∂t ∂x j=1 i=1 j=1
l=1 l=1
|i=1 {z }
=0
PN
By construction of stoichiometrically balanced chemical reactions, we must have i=1 φli νij =
0. Thus, we have mass conservation for the mixture:
∂ ∂
(ρA) + (ρuA) = 0. (7.591)
∂t ∂x
We can define the species production rate for species i, ω̇i as
J
X
ω̇i = νij rj , (7.592)
j=1

The units of ω̇i are kmole/m3 /s. When multiplied by molecular mass Mi , the units of Mi ω̇i
are kg/m3 /s. Thus, we have
∂ ∂
(ρYi A) + (ρYi Au) = AMi ω̇i . (7.593)
∂t ∂x
Let us expand via the product rule to get
 
∂ ∂ ∂Yi ∂Yi
Yi (ρA) + (ρuA) +ρA + ρuA = AMi ω̇i , (7.594)
∂t ∂x ∂t ∂x
| {z }
=0
∂Yi ∂Yi
ρ + ρu = Mi ω̇i . (7.595)
∂t ∂x
In the steady state limit, we get
dYi Mi ω̇i
= . (7.596)
dx ρu
Now consider the energy equation, Eq. (2.37), in the limit of qw = 0, τw = 0:
de P dρ
− 2 = 0. (7.597)
dx ρ dx
For the mixture of gases, we have the mixturePenergy e = e(ρ, P, Yi ), i = 1, . . . , N − 1. Note
only N − 1 mass fractions are independent as N i=1 Yi = 1. So the total differential of e must
be
N
X −1
∂e ∂e ∂e
de = dρ + dP + dYi , (7.598)
∂ρ P,Yi ∂P ρ,Yi i=1
∂Yi P,ρ
N
X −1
de ∂e dρ ∂e dP ∂e dYi
= + + . (7.599)
dx ∂ρ P,Yi dx ∂P ρ,Yi dx i=1
∂Yi P,ρ dx

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292 CHAPTER 7. AEROTHERMOCHEMISTRY

So the first law of thermodynamics, Eq. (7.597), becomes

N −1
∂e dρ ∂e dP X ∂e dYi P dρ
+ + − = 0, (7.600)
∂ρ P,Yi dx ∂P ρ,Yi dx i=1
∂Yi P,ρ dx ρ2 dx
| {z }
de/dx
! N −1
∂e P dρ ∂e dP X ∂e dYi
− 2 + + = 0, (7.601)
∂ρ P,Yi ρ dx ∂P ρ,Yi dx i=1
∂Yi P,ρ dx
 
∂e P PN −1 ∂e dYi
∂ρ
− ρ2
dP P,Yi dρ i=1 ∂Yi
P,ρ
dx
+ ∂e
= − ∂e
. (7.602)
dx ∂P ρ,Yi
dx ∂P ρ,Yi
| {z }
−c2

Extend Eq. (2.42) for the frozen sound speed (c2 = ∂P/∂ρ|s,Yi ), and use Eq. (7.596) to
eliminate dYi /dx. We get a compact version of the first law of thermodynamics to be
PN −1 ∂e
Mi ω̇i
dP dρ i=1 ∂Yi
P,ρ
− c2 =− ∂e
≡ Q. (7.603)
dx dx ρu ∂P ρ,Yi

Here Q is a heat release term that includes the effects of complicated chemical reactions.
Let us analyze Q in more detail. From mixture theory, we must have
N
X
e(T, Yi ) = = Yj ej (T (P, ρ, Yi )), (7.604)
j=1
N −1 N −1
!
X X
= Yj ej (T (P, ρ, Yi )) + 1− Yj eN (T (P, ρ, Yi )). (7.605)
j=1 j=1

We also have the ideal gas law

XN
Yi 1 P
P = ρRT , so T = PN . (7.606)
i=1
Mi R i=1 Yi /Mi
ρ

With effort, one can show

N N
!
∂e X
∂ej ∂T X ∂T
= ei − eN + Yj = ei − eN + Yj cvj , (7.607)
∂Yi P,ρ j=1
∂T ∂Yi P,ρ j=1
∂Yi P,ρ

∂T
= ei − eN + cv . (7.608)
∂Yi P,ρ

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7.11. STEADY ROCKET NOZZLE FLOW WITH DETAILED KINETICS 293

The next steps are not obvious, but can be verified with detailed calculation by computational
mathematical software.
 
∂e P 1 1 cv
= ei − eN − − P 2 , (7.609)
∂Yi P,ρ ρR Mi MN N
j=1 (Yj /Mj )
 
1 1 cv T
= ei − eN − − PN , (7.610)
Mi MN j=1 Y j /M j
 
1 1 yi
= ei − eN − cv T − , (7.611)
Mi MN Yi /Mi
 
Mi yi
= ei − eN − cv T 1 − . (7.612)
MN Yi
We also need
N
X N
X
∂e ∂ej ∂T ∂T ∂T cv T
= Yj = Yj cvj = cv = . (7.613)
∂P ρ,Yi j=1
∂T ∂P ρ,Yi j=1
∂P ρ,Yi ∂P ρ,Yi P

So
PN −1  ei −eN 
Mi

yi

P i=1 cv T
− 1− MN Yi
Mi ω̇i
Q=− . (7.614)
ρu
Consider the very special case of a calorically perfect ideal gas with N = 2, equal molecular
masses, M1 = M2 = M, and equal specific heats cv1 = cv2 = cv . Then
   
P e1cv−e
T
2
M ω̇ 1 (ρRT /M) e1 −e2
cv T
M ω̇1
Q = − =− , (7.615)
ρu ρu
−E
(γ − 1) (e1 − e2 ) M ω̇1 (γ − 1) (e1 − e2 ) ρY1 ae RT
= − = , (7.616)
u u
−E
(γ − 1)qρ(1 − Y2 )ae RT
= . (7.617)
u
This is equivalent to Eq. (5.61).
Let us now modify Eqs. (2.98-2.100) to account for finite rate chemistry. Here we set
qw = 0 as the effects of heat release are now embedded within the chemistry model:
dρ du ρu dA
u +ρ = − , (7.618)
dx dx A dx
du dP
ρu + = 0, (7.619)
dx dx
dP dρ
− c2 = Q, (7.620)
dx dx
dYi Mi ω̇i
= , i = 1, . . . , N − 1. (7.621)
dx ρu

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294 CHAPTER 7. AEROTHERMOCHEMISTRY

T (K) T (K)

3500
3500
3000
3000
2500 full kinetics, simple kinetics
calorically imperfect ideal gases 2500
calorically perfect ideal gases
2000 2000

1500 1500
0.001 0.01 0.1 1.0 x (m) 0.001 0.01 0.1 1.0 x (m)

Figure 7.8: Plot of temperature as function of distance for steady hydrogen-air combustion
in a variable area duct for detailed kinetics with calorically imperfect ideal gases and simple
kinetics with calorically perfect ideal gases, repeated from Fig. 5.3.

We only need N −1 species equations and the mixture mass equation to describe the evolution
of all N species. Uncoupling, we get the multi-reaction extension of Eqs. (5.62-5.65):

dρ u − ρu dA
A dx
+Q
= 2 2
, (7.622)
dx u −c

du −c2 − ρu A dx
dA
− uQ
= 2 2
, (7.623)
dx ρ (u − c )


dP uc2 − ρu A dx
dA
+ u2 Q
= , (7.624)
dx u 2 − c2
dYi Mi ω̇i
= , i = 1, . . . , N − 1. (7.625)
dx ρu

Now exercise this model for combustion of a stoichiometric hydrogen-air mixture under
similar conditions used to obtain Fig. 5.3. We use a N = 11 species model with the species
being H2 , H, O2 , O, OH, HO2 , H2 O2 , H2 O, N, N2 , and NO. These species react in a
23 step kinetic scheme that includes NO production. Inlet mass fractions are those for a
stoichiometric reaction with YH2 = 0.0285, YO2 = 0.226, YN2 = 0.7455, and all other initial
mass fractions set to a vanishingly small value of 10−14 . The inlet temperature, density,
and velocity are T (0) = 1676.81 K, ρ(0) = 4.2 kg/m3 , u(0) = 2500 m/s. Take the area
to be A(x) = 1 + x − x2 /2. Here the area has units of m2 when x has the units of m.
So dA/dx = 1 − x. Results for temperature are given in Fig. 7.8. Also shown are the
temperature predictions from the simple one-step kinetics model with a calorically perfect
ideal gas from Fig. 5.3. It is seen that the temperatures are of the same order of magnitude,
and the induction zone distance is smaller for the full kinetics model. At the end of the

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7.11. STEADY ROCKET NOZZLE FLOW WITH DETAILED KINETICS 295

mass fractions, Yi
-4
10

-8
10

0.001 0.01 0.1 1.0 x (m)

Figure 7.9: Plot of YH2 , YO2 , YH2 O , and YNO as functions of distance for steady hydrogen-air
combustion in a variable area duct for detailed kinetics with calorically imperfect ideal gases
and simple kinetics.

nozzle, we predict the following species mass fractions:

Y H2 = 0.36282 × 10−2 , (7.626)

YH = 0.43888 × 10−3 , (7.627)
Y O2 = 0.12804 × 10−1 , (7.628)
YO = 0.25165 × 10−2 , (7.629)
YOH = 0.18692 × 10−1 , (7.630)
YHO2 = 0.34517 × 10−4 , (7.631)
Y H 2 O2 = 0.52394 × 10−5 , (7.632)
Y H2 O = 0.20843 × 100 , (7.633)
YN = 0.38361 × 10−5 , (7.634)
Y N2 = 0.73854 × 100 , (7.635)
YNO = 0.14909 × 10−1 . (7.636)

We see the reaction may not be complete as there is some significant fuel and oxidizer
remaining. We also see at this elevated temperature that NO is a significant product. Note
from Fig. 6.1 that NO has a significant equilibrium presence for T ∈ [1500 K, 3000 K].
Results for selected species mass fractions, YH2 , YO2 , YH2 O , and YNO , are given in Fig. 7.9.
It is useful to verify that these calculations have properly conserved physical quantities.
Let us check two: mass flow rate and stagnation enthalpy. First consider the mass flow rate.
In the steady state limit, Eq. (7.591) reduces to
d
(ρuA) = 0. (7.637)
dx
So we must have ρuA = ρ1 u1 A1 , where the 1 state is the inlet state. Let us then define the

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296 CHAPTER 7. AEROTHERMOCHEMISTRY

relative error in mass flow rate as

ρuA − ρ1 u1 A1
ǫṁ = . (7.638)
ρ1 u1 A1
For the energy equation, we can rewrite the steady energy equation in the limit of qw = 0,
Eq. (2.31) as
  
d u2 P
ρAu e + + = 0. (7.639)
dx 2 ρ

Because mass flow rate ρuA is a constant, and because h = e + P/ρ, we have
 
d u2
h+ = 0. (7.640)
dx 2

This results in the stagnation enthalpy ho = h + u2 /2 being constant within the duct. The
local error in stagnation enthalpy is thus
 
2 u2
h + u2 − h1 + 21
ǫho = u2
. (7.641)
h1 + 21

Here we recognize that h is the mixture enthalpy:

N
X
h= Yi hi (T ). (7.642)
i=1

The relative errors ǫṁ and ǫho are plotted in Fig. 7.10. The relative errors are small. If
one decreases the error tolerance of the numerical method used to integrate the ordinary
differential equations, the error may be reduced further until a roundoff error limit is reached.
One could also compute errors of the number of elements, which are also conserved quantities.

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7.11. STEADY ROCKET NOZZLE FLOW WITH DETAILED KINETICS 297

10 -12

10 -13
error

10 -14

10 -15

10 -16
0.001 0.01 0.1 1.0 x (m)

Figure 7.10: Plot of relative numerical errors of mass flow rate and stagnation enthalpy for
steady hydrogen-air combustion in a variable area duct for detailed kinetics with calorically
imperfect ideal gases and simple kinetics.

CC BY-NC-ND. 19 January 2025, J. M. Powers.