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MAE 4262: ROCKETS AND MISSION ANALYSIS


Combustion Overview for Rocket Applications


November 2, 2010

Mechanical and Aerospace Engineering Department
Florida Institute of Technology

D. R. Kirk
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CONTENTS
Overview
Review of thrust chamber governing equations
Why operate H
2
-O
2
fuel rich?

Thermochemistry review

How to perform simple calculations

How to perform detailed H
2
-O
2
calculations using STANJAN

Nozzle Flow of Reacting Gases
2 Limiting Cases
Physical Understanding of these 2 Cases
Calculations
3
OVERVIEW
In our development of model for Thermal Rocket Thrust Chambers, we considered
two primary components:
1. Combustion (or Heating) Chamber
2. Nozzle

Developed a 1-D model that allowed us to predict important parameters
U
e
, Isp, Thrust (and associated derived characterization coefficients: C
F
, C*)
Model simplified with many assumptions

Next step was to examine nozzle
Types of nozzles, performance, impact of altitude, etc.
Connect performance to shape and design of optimum and realistic shapes

Now examine Combustion Chamber but must know something about
Combustion first
4
SUMMARY OF KEY EXIT VELOCITY EQUATIONS









Key Assumptions
Quantity of heat added at constant pressure
Constant specific heats
For high U
e
(for all thermal rockets), desire:
Propellants with low molecular weight, M
Propellant mixtures with large Q
R
/M (not at T
max
)
High combustion chamber pressure, P
02
( )
( )
( )
( )
(
(

|
|
.
|

\
|
~
(
(

|
|
.
|

\
|

=
(
(

|
|
.
|

\
|
=


1
02
1
02
2
1
02
2
1 2
1
1
2
1 2
p
p
M
Q
U
p
p
T
M
R
p
p
T C U
e R
e
e
o
e
o p e
How does this quantity help to
dictate whether to operate rocket
fuel rich or lean?
See Section 12.3 in H&P
(answer on next slide)
5
WHY DO LH
2
-LOX ROCKETS RUN FUEL RICH?
Desire high heating value, Q
R
, and low molecular weight, M
Running rocket fuel rich (or lean) will reduce Q
R
However, if fuel is lighter in molecular weight than oxidizer, fuel rich will
reduce average molecular weight
The overall ratio Q
R
/M is increased
In many cases fuel-rich mixtures are burned, as it is found that the
resultant reduction in M more than offsets the accompanying reduction in
Q
R
H&P, Section 11.2
Also note that when dissociation is present, O/F ratio, much less than
stoichiometric for maximum specific impulse

Explains why SSME run fuel-rich (H
2
-O
2
) fuel has lower molecular weight

Also explains why rockets use oxidizer-rich case when oxidizer has lower
molecular weight (V-2 rocket for example, alcohol-oxygen rocket)
6
OVERVIEW: GENERAL COMMENTS
Recall: Rocket performance strongly dependent on T/W and Isp

Design of combustion chamber is critical to both of these metrics
Isp depends strongly on composition and T of combustion products
Intensity of combustion (energy transferred per unit time per unit volume)
determines size (mass) of combustion chamber

Combustion products of a well designed combustion chamber are very nearly in
thermodynamic equilibrium

Q: What does thermodynamic equilibrium mean?

A: At combustion chamber T & P, time required for mixing of fuel and oxidizer
and for chemical reactions to take place is small compared to average
residence time in combustion chamber
7
OVERVIEW: GENERAL COMMENTS
Time-scale ratios are so important: Non-dimensional number
Known as Damkhler Number
Ratio of flow to chemical time scales

If Da >> 1
Flow change time is much longer than chemical time
There are many units of time for reactions to take place during flow traverse
System is in chemical equilibrium in combustion chamber
If Da << 1
Flow time is much shorter than chemical time
Flow changing at rate much faster than which chemical reactions may occur
May occur in rocket nozzles (frozen flow)

Typical numbers for rocket (and gas turbine engines) combustors
Flow time 1 ms, chemical time scale 1 s
Da ~ O(10
-3
/10
-6
) ~ O(1000)
chem
flow
Da
t
t
=
8
OVERVIEW: GENERAL COMMENTS
Combustion chamber properties are calculated using method of equilibrium
combustion thermochemistry
See H&P 2.3-2.4 for review of equilibrium combustion thermodynamics and
chemical reactions
Goal is to understand basic concepts and set up governing equations
Perform simplified calculations (examples to come)
Detailed description and realistic results need computer solver (STANJAN)

Rocket combustion chamber temperatures are so high that typically
substantial portion of combustion products are dissociated

During expansion in nozzle, T falls so rapidly there may be insufficient time for
dissociated products to recombine
Gas composition at each stage of expansion may not be in equilibrium (Da << 1)
When gas expands in such a manner it is called frozen flow
9
OVERVIEW: GENERAL COMMENTS
Q: What does stoichiometric ratio mean and how is it calculated?

A: Stoichiometric ratio of oxidizer to fuel for a balanced equation where all fuel and
all oxidizer is consumed. Consider again:



Stoichiometric ratio for this reaction (relevant to liquid rocket propulsion) given by:





If r < 8, there is more fuel than oxidizer
izer (relative to stoichiometric ratio) and mixture is called fuel-rich
If r > 8, there is more oxidizer than fuel (relative to stoichiometric ratio) and mixture
is called oxidizer-rich or fuel-lean
O H O H
2 2 2
2
1
+
( )
8
2
16
1 2
16 2
2
1
2
1
2
2
= =

= =
H
O
r
10
COMBUSTION THERMOCHEMISTRY
GOAL: Represent what happens in combustor, to convert liquid propellants to hot
gases at Tc and Pc.

Qualitatively:
Difference between chemical energies of reactants (chemicals injected into
combustion chamber) and that of reaction products (hot gases we seek to
describe) shows up as thermal energy of products

Think of it as sequence of 2 steady flow process:
1. Formation by chemical reactions of products from reactants at standard T & P
Such a process cannot happen in practice
Think of it as a process in which the reactions occur at standard T & P while heat
is added in the amount necessary to keep T constant
Heat added in such an ideal process is defined as the Standard Heat of Formation
AH
0
f
of the products if the reactants are elements in their standard states (H&P
textbook notation: H
RPf
)

2. Use heat added in step 1 to change T of products
T change is given by Steady-Flow Energy Equation
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COMBUSTION THERMOCHEMISTRY
Every chemical substance has a Standard Heat of Formation defined this way.
For example for water:




Cumbersome notation necessary to indicate reaction product is liquid water
Heat of formation of liquid water would differ from this by the heat of
vaporization

NOTE: Heat of formation of water is negative
Heat is released in its formation
Heat of formation is negative for all exothermic reactions
System must give off heat to maintain (or return to) reference temperature
( )
( )
KJ/mol 827 . 241
2
1
0
,
2 2 2
2
= A
+
gas
O H f
gas
H
O H O H
12
HEATS OF FORMATIONS
13
COMBUSTION THERMOCHEMISTRY
NOTE 1
Heat of formation may be negative, positive or zero (KJ/mole)
Heat is released in its formation
Heat of formation is negative for all exothermic reactions
This is because the system must give off heat to maintain (or return to)
reference temperature
Convention that head added is positive is purely arbitrary

NOTE 2
Heat of formation for the elements in their standard states is ZERO

NOTE 3
Substances that are stable at normal room T & P have negative heats of
formation
Substances that are unstable (explosives) have positive heats of formation
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EXAMPLE: APPLICATION TO ROCKETS
Consider a monopropellant rocket engine using Hydrazine fuel, N
2
H
4
Substance has physical properties much like those of water
However has a positive Standard Heat of Formation of 50.2 kJ/mole
Assume it decomposes to produce only N
2
and H
2


Catalyst Bed Tc, Pc
N
2
H
4
N
2
, H
2
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EXAMPLE: APPLICATION TO ROCKETS
Enthalpy of each product can be approximated by C
p
T
Chamber temperature is given by:









Specific heats are per mole if heat of formation is per mole
Constant pressure process
Cp = Cp(T)
Assumed products of combustion are nitrogen and hydrogen
In general there might be some ammonia (NH
3
) and perhaps other compounds in
the decomposition products of hydrazine
| |( )
0
, 0 , ,
4 2 2 2
2
H N f c H p N p
H T T C C A = +
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TEMPERATURE DEPENDENCE OF SPECIFIC HEATS
Example:
Enthalpy often approximated as
h(T)=C
p
T
In combustion chemistry, enthalpy
must take into account variable
specific heats, h(T)=C
p
(T)T
If C
p
(T) can be fit with quadratic,
solution for flame temperature for
certain classes of problems | < 1
and T < 1250 K leads to closed
form solutions
For higher order fits or | > 1
and/or T > 1250 K, iterative
closure schemes are required for
solution of flame temperature

Also will discuss a definition of
enthalpy that accounts for chemical
bonds
1
st
law concepts defining heat of
reaction, heating values, etc.
17
DISSOCIATION: GENERAL COMMENTS
Q: What does combustion products are dissociated mean?

A: Consider burning (combustion) of a hydrogen and oxygen mixture

In complete combustion we have:


All reactants go into forming products
In this case hydrogen and oxygen form water
At high enough temperature products may further breakdown
Reaction may proceed in reverse, H
2
O breaking down into H
2
and O
2



O H O H
2 2 2
2
1
+
O O H OH H O H O H q c v o | o + + + + + +
2 2 2 2 2
2
1
18
DISSOCIATION: GENERAL COMMENTS
Think about terms |, o, v, c, q as a wasted energy opportunity

Instead of liberating all chemical energy of reaction into just water, some of it is
subsequently wasted by using high T energy to form other products

Highest U
e
and I
sp
will always be achieved with no dissociation
Never occurs at operating T of actual rockets
Must deal with dissociation of products

Also note, left side of equation still has stoichiometric ratio of O/F
Ratio is not best one to use when dissociation occurs (lower side)
O O H OH H O H O H q c v o | o + + + + + +
2 2 2 2 2
2
1
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IN-CLASS EXAMPLE: SUMMARY
q c o o
v o | o
+ + + =
+ + + =
2 2
2 2 2
m
O O
OH O H
H H
O H O H
2
2
2
2
1
2
2 2
2
2 2 2

+
( )
( )
( )
( )
( )
( )
( )
( )
( )
2
2 2
2
2 2
2
2
2
,
2
,
2
,
2
1 ,
O
O
O P
O H
OH
OH P
H
H
H P
O H
O H
O H P
P
P
T K
P P
P
T K
P
P
T K
P P
P
T K
=
=
=
=
( )
( )
( )
( )
q c v o | o o
oc
q
|c
o
o|
v
c
o
|
o
+ + + + + =
=
=
=
|
|
.
|

\
|
=
c
O P
OH P
c
H P
c
O H P
P
T K
T K
P
T K
P
T K
2
,
2
,
2
,
2
1
,
2
O O H OH H O H mO H q c v o | o + + + + + +
2 2 2 2 2
Governing equation: 7 unknowns (T
c
, o, |, o, v, c, q), m and P
c
set
2 equations from H and O atom balance
4 linearly independent relations
from equilibrium approximation
Equilibrium constant expressions
written in terms of partial pressures
Equilibrium constant expressions
Written in terms of unknowns
6

e
q
u
a
t
i
o
n
s
,

7

u
n
k
n
o
w
n
s


T
c

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REAL CALCULATIONS: STANJAN INSTRUCTIONS
STANJAN is an easy to use DOS executable to solve adiabatic combustion equilibrium calculations. You can
download it directly from the course website and run it on your own computer.
Calculation of adiabatic flame temperature and product composition of H
2
-O
2
as example to illustrate use of
STANJAN for chemical rocket combustion.

Program dialog is shown below

Do you want to be instructed? n
Species file? Use comb.sud for this problem
Correct file? y, assuming you typed it right and got species list
reactants or products? r, First you must specify what you start with
Enter species in phase 1, e.g., H
2
,O
2
I typically start with gaseous species, use all CAPS, if you
make a typing error, will have to retype the whole line.
Species can be separated with spaces or commas.
Enter species in phase 2 < RET > Enter condensed phases here, there are none, so <RET>
Check atoms in molecules? y
Change Setup? Probably not, assuming you got summary that you expected
P (atm) ? e.g. 30 Enter press (atm) of reactants
T (K) ? e.g. 300 Enter T (K) of reactants
Sound speed? Probably not
Save output? You might need to save reactant output; it's going to be a summary of
the thermodynamic properties of the mixture you specified.
Monitor run: Probably not--there aren't any iterations for reactants
See JANNAF data? <RET>
Start printer if desired ? <RET>
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STANJAN INSTRUCTIONS
Change SETUP y
Now you have to specify product species you will allow to be present at equilibrium. The more you specify, the longer the calculations
will take to converge (although for our purposes it won't be very noticeable) and the more output you will get. More importantly, you
have to choose species that are appropriate to the problem, if you forget a major species, STANJAN will still calculate equilibrium for
composition you specify, but this wouldn't match what would occur in practice.

Change option: 2
Reactants or Products: p
Enter product species in phase 1
For H2-O2, select the following products: H2O,H2,H,O2,O,HO
These are all possible combinations
No products in any other phases
Check atoms: Probably not
Change Setup? Only if you made a mistake.
Run options
Choose the option that corresponds to the thermodynamic process which occurs between reactants at state 1 and products at state 2.
Adiabatic flame temperature calculations for constant pressure corresponds to p,H same as reactants, or option 11.
Estimate T: This is used to start iteration
3,000 is a good guess for all cases
Sound Speed? Y, if you're curious won't take much time.
Save run to file? <RET>

Do you want to do another calc?
If you want to change amount of reactants, go back and re-specify reactants and # of moles, don't change atom populations.
If you change reactants, it will do a frozen composition calculation to get initial mixture properties again.
If you then chose not to change Setup, it gives you prompt "mix reactants?" This is one that doesn't do anything.

22
EXAMPLE STANJAN CALCULATION: H
2
-O
2
COMBUSTION
Chamber Pressure = 30 atm, Inlet Temperature for H2, O2 = 300 K
0
1000
2000
3000
4000
5000
6000
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
m (Moles of O2)
T
e
m
p
e
r
a
t
u
r
e
,

K
No Dissociation
With Dissociation
Fuel Rich Fuel Lean
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EXAMPLE STANJAN CALCULATION: H
2
-O
2
COMBUSTION
m T Product Mole Fraction Mass Fraction m T Product Mole Fraction Mass Fraction
0.1 1772.31 H2O 0.2 0.6908 0.1 1772.02 H2O 0.1999 0.6108
H2 0.8 0.3092 H2 0.79996 0.30919
O2 0 0 O2 3.53E-12 2.17E-11
0.2 2840.63 H2O 0.4 0.85627 0.2 2772.76 H2O 0.39558 0.85209
H2 0.6 0.14373 H2 0.59206 0.14271
O2 0 0 O2 5.74E-06 2.20E-05
0.3 3689.95 H2O 0.6 0.93058 0.3 3307.6 H2O 0.54965 0.88438
H2 0.4 0.069421 H2 0.38081 6.86E-02
O2 0 0 O2 9.47E-04 2.71E-03
0.4 4395.34 H2O 0.8 0.97279 0.4 3520.31 H2O 0.63081 0.83643
H2 0.2 0.02721 H2 0.22414 3.33E-02
O2 0 0 O2 1.10E-02 2.59E-02
0.5 4999.19 H2O 1 1 0.5 3559.4 H2O 0.65403 0.75804
H2 0 0 H2 0.13308 1.73E-02
O2 0 0 O2 4.06E-02 8.36E-02
0.6 4713.77 H2O 0.90909 0.84918 0.6 3526.13 H2O 0.6479 0.68055
H2 0 0 H2 8.33E-02 9.79E-03
O2 0.090909 0.15082 O2 8.63E-02 1.61E-01
0.7 4462.78 H2O 0.83333 0.73788 0.7 3465.91 H2O 0.62974 0.61333
H2 0 0 H2 5.49E-02 5.99E-03
O2 0.16667 0.26212 O2 1.39E-01 2.40E-01
0.8 4240.2 H2O 0.76923 0.65238 0.8 3396.99 H2O 0.6072 0.5569
H2 0 0 H2 3.76E-02 3.86E-03
O2 0.23077 0.3476 O2 1.92E-01 3.13E-01
0.9 4041.34 H2O 0.71429 0.58464 0.9 3325.8 H2O 0.58363 0.50961
H2 0 0 H2 2.65E-02 2.59E-03
O2 0.28571 0.41536 O2 2.43E-01 3.77E-01
1 3862.53 H2O 0.6667 0.52964 1 3254.78 H2O 0.56036 0.46971
H2 0 0 H2 1.91E-02 1.79E-03
O2 0.3333 0.47036 O2 2.91E-01 4.33E-01
Chamber Pressure = 30 atm., Inlet Temperature H
2
, O
2
= 300 K
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STANJAN PRACTICE PROBLEMS
Determine impact of chamber pressure
Repeat calculation for Pc = 10 atm.
No dissociation, m = 0.2, 0.5, 0.7
With dissociation, m = 0.2, 0.5, 0.7
Repeat calculation for Pc = 80 atm.
No dissociation, m = 0.2, 0.5, 0.7
With dissociation, m = 0.2, 0.5, 0.7

Discuss how you would use STANJAN for perform
Frozen flow nozzle calculation
Equilibrium flow nozzle calculation
25
SUMMARY
Make sure you can
correct Equations
12.1a and 12.1b to
exhibit the trends
shown in Figure 12.1

Note location of
maximum Isp when
dissociation included

What are trade-offs?
Thrust
Carry more H
2
,
how is tank size
affected?
26
CHEMICAL REACTIONS OCCURING
WITHIN ROCKET NOZZLES
27
NOZZLE FLOW OF REACTING GASES
Suppose that we have determined composition of gases in combustion chamber
Now compute flow through nozzle taking into account chemical reactions

3 major deviations from simple model based on ideal gas behavior

1. Composition of gas is not necessarily constant in flow
Properties that are composition dependent must be treated as variables
along flow direction
Specific heats, gas constant and ratio of specific heats
2. Sum of thermal energy and kinetic energy is no longer constant
Exchange of chemical energy and thermal energy
3. Non-isentropic
We can neglect this entropy change for 2 special cases

28
NOZZLE FLOW OF REACTING GASES
To deal with the flow, we first note that energy conservation for the gas flow is:




This replaced the ideal gas energy equation:




Need statement about variation of entropy
Transfer from chemical to thermal energy takes place at finite rate, therefore
entropy increase
There are 2 limiting cases for which entropy change is very small
1. Chemical Equilibrium
2. Frozen Flow
2
) , (
2
u
P T H H
c
+ =
2
2
u
T C T C
p c p
+ =
29
NOZZLE FLOW OF REACTING GASES
Chemical Equilibrium
Approached if the reactions occur fast enough to keep up with T & P change
caused by expansion
Flow time >> Reaction time
Chemical energy is transferred through an infinitesimal AT



x
i
determined by equilibrium at local T & P

Frozen Flow
Reactions occur slowly, x
i
are fixed at their chamber values
Flow time << reaction time
No chemical energy release

( ) ( )
c i i
S T P S T P x S = =

, ,
( ) ( )
c i c c i
S T P S T P x S = =

, ,
30
NOZZLE FLOW OF REACTING GASES
Chemical Equilibrium and Frozen Flow are 2 limiting cases
Provide an upper and lower limit for the velocity at a given pressure

Chemical Equilibrium gives maximum thermal energy availability for
conversion for kinetic energy
Frozen Flow gives minimum

Phenomenological explanation of why this is so:
Gases leaving combustion chamber are so hot products of combustion are highly
dissociated
Dissociated compounds will tend to recombine because of large drop in T during
nozzle expansion process
Recombination is exothermic and acts as heat source in flow (changes in C
p
and )

However, Isp always lower with dissociation than with no dissociation at all

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