MECE 5397/6397

Rocket Propulsion
Chemical Rocket Propellant
Performance Analysis
University of Houston
Mechanical Engineering Department
John W. Alred
john.w.alred@nasa.gov

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

Next step was to examine nozzle

Ve, Isp, Thrust (and associated derived characterization

coefficients: CF, C*)
Model simplified with many assumptions

Types of nozzles, performance, impact of altitude, etc.

Connect performance to shape and design of optimum and
realistic shapes

Now examine Liquid Propellants and Combustion Chamber

and consider something about Combustion

Specific Impulse Isp

I sp

Tc
M

Optimum mixture oxidizer/fuel high Tc

High heat of formation, Hf high Tc
High hydrogen content low M
CO2

44 g/mol

CO

28 g/mol

N2

28 g/mol

H2O

18 g/mol

H2

2 g/mol

Propellants: General Comments

Combustion temperature directly reflects chemical energy of
reaction
For example, using O2 and RP-1 produces higher temperature
than O2 and H2

This is because RP-1 contains more chemical energy than H2

However, H2 has much lower molecular weight
Result is that O2 and H2 produces highest exit velocity (except F2H2)

Additional H2 may be added, which actually raises exit velocity

Maximum exhaust velocity is shifted away from stoichiometric
value, in direction of lower molecular weight
Why use a propellant with high molecular weight?
Exhaust velocity is not only criterion
Also interested in high thrust
Heavy propellants giver higher mass flow rate
Velocity might be lower, but overall thrust might be increased

This is an application dependent design trade-off

Propellants: General Comments

RP-1 is an inexpensive fuel, but provides lower performance
(similar to kerosene)
Fluorine and LH2 produces highest temperature of any bipropellant system
Highly toxic and corrosive
Hydrogen peroxide (H2O2) deteriorates at about 1% a year, so
cannot be used for long term missions.
Hydrazine (N2H4), Florine (F2) and UDMH (unsymmetrical
dimethylhydrazine) are good propellants but highly toxic and
flammable. Very dangerous to handle

Nitrogen tetroxide (N2O4) is a very good oxidizer

Easy to store and transport, but also very toxic, hazardous to skin
contact and creates toxic cloud (BFRC) in when exposed to
atmosphere

Common liquid rocket propellants

Oxidizers

Liquid oxygen, O2
Dinitrogen tetroxide, N2O4
Nitric acid, HNO3
Hydrogen Peroxide, H2O2

Fuels

Liquid hydrogen, H2
Hydrazine, N2H4
Monomethylhydrazine
Methane
Unsymetrical dimethylhydrazine
Kerosene
Ethanol

Liquid Oxygen (LOX), O2

Non storable oxidizer

Nontoxic
Mp= -219oC, Bp = -183oC
Used in combination with H2, kerosene,
ethanol
Density = 1.14 g/cm3

Dinitrogen Tetroxide (NTO), N2O4

Widely used storable oxidizer
Different percentages (1-3%) of nitric oxide,
NO, added as stress corrosion inhibitor (MON1 and MON-3)
MON-1 and MON-3 are used more often than
pure NTO
Bp= 21C, Mp=-11C, dens=1.43 g/cm3

Dinitrogen Tetroxide (NTO), N2O4

Safety concerns
Concern about reactivity of MON with titanium
alloys, ignition by friction on freshly formed surfaces
(e.g., pyrovalves).
History of accidents
Toxicity of vapor clouds in case of launch mishaps
State governments impose restrictions on
transportation of NTO/MON
Space agencies have considered manufacturing NTO
(and other toxic fuels) at the launch site to alleviate
transportation restrictions

Liquid Hydrogen, H2
Non storable cryogenic fuel, Mp= -259oC, Bp =
-253oC
Used in combination with LOX
Density = 0.07 g/cm3 bulky fuel tank
Material problems brittle at low
temperature
Air / H2 explosive

Hydrazine, N2H4
Can be used as a bipropellant fuel and as a
monopropellant
Thermally unstable and cannot be used as a
regenerative coolant in bipropellant engines
As a fuel, it is hypergolic with many oxidizers
Positive enthalpy of formation (+50.434
kJ/mol =+12.05 kcal/mol, liquid at 298 K)
Bp= 114C, Mp=+2C, dens= 1.00 g/cm3

Hydrazine, N2H4

Hydrazine toxicity concerns

Acute toxicity: short-term exposure
Chronic toxicity: long-term exposure
Volatile
Carcinogen

Monomethylhydrazine (MMH),
H3C-NH-NH2
Frequently used storable, hypergolic
bipropellant fuel for satellites and upper
stages
Can be used as a regenerative coolant in
bipropellant engines
Low freezing point (-52C)
Density = 0.87
Concern about toxicity of vapors (more
volatile than hydrazine itself), Bp= +88C

Data for Common Propellants

Liquid Propellant
Combustion Chamber

Sizing of a Combustion Chamber

Sizing of a Combustion Chamber

Combustion
Most of the higher performance propulsion systems
that will be looked at in this course will be using
chemical combustion as the means for generating
heat energy, energy that will ultimately be converted
into the delivery of thrust via mechanical rotation
(propeller, fan) or exhausting a high-speed jet
Alternatives to the combustion approach exist, for
some flight applications (later in the course).

Combustion: Flame Structure

Heat released (and chemical combustion products produced)

when fuel molecules come together and react with oxidizer
molecules above a threshold (auto-ignition) temperature
Premixed laminar flame - first category; process of combustion
is driven predominantly by pressure
Turbulent diffusion flame - second category; process of
combustion is driven predominantly by mixing
Commonly in propulsion system combustors, flame is a
combination of the above two

Summary of Key Exit Velocity Equations

Pe

Ve 2C pTC 1
PC

QR Pe
Ve 2
1
M PC

k 1

k 1

Pe
2kR

TC 1
k 1M PC

k 1

How does this quantity help to

dictate whether to operate rocket
fuel rich or lean?

Key Assumptions
Quantity of heat added at constant pressure
Constant specific heats

For high Ve (for all thermal rockets), desire:

Propellants with low molecular weight, M

Propellant mixtures with large QR/M (not necessarily at Tmax)
High combustion chamber pressure, PC

Why Do Many Rockets Run Fuel Rich?

Desire high heating value, QR, and low molecular weight, M
Running rocket fuel rich (or lean) will reduce QR
However, if fuel is lighter in molecular weight than oxidizer, fuel
rich will reduce average molecular weight
The overall ratio QR/M is increased
In many cases fuel-rich mixtures are burned, as it is found that
resultant reduction in M more than offsets accompanying
reduction in QR
Also note that when dissociation is present, the oxidizer-fuel (O/F)
ratio may be much less than stoichiometric for maximum specific
impulse

Explains why the Orbiter SSMEs run fuel-rich {O/F ratio (by
mass) 6/1 - O2-H2} fuel has lower molecular weight
Also explains why rockets use oxidizer-rich case when oxidizer
has lower molecular weight (for example, V-2 rocket - an
alcohol-oxygen rocket)

Overview: General Comments

Rocket performance strongly dependent on T/W & Isp

Design of combustion chamber is critical to both of

these metrics
Isp depends strongly on composition and temperature 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

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
Da
chem

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 ms
Da ~ Order of (10-3/10-6) or 1000

Overview: General Comments

Combustion chamber properties are calculated using method of
equilibrium combustion thermochemistry
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
(like NASA Chemical Equilibrium Analyzer - CEA)

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

Overview: General Comments

What does stoichiometric ratio mean and how is it calculated?

Stoichiometric ratio of oxidizer to fuel for a balanced equation where

all fuel and all oxidizer is consumed. Consider again:

1
H 2 O2 H 2O
2

Stoichiometric ratio for this reaction (relevant to liquid rocket

propulsion) given by:

1
1
2 16 16
O2
r 2
2

8
H2
2 1
2
If r < 8, there is more fuel than oxidizer (relative to stoichiometric
ratio) and mixture is called fuel-rich (i.e., SSME with O/F = 6)
If r > 8, there is more oxidizer than fuel (relative to stoichiometric
ratio) and mixture is called oxidizer-rich (or fuel-lean)

Combustion Thermochemistry
Represents what happens in combustor, to convert liquid
propellants to hot gases at Tc and Pc.

Qualitatively, the 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 processes:

1. Formation by chemical reactions of products from reactants at STP
(standard temperature and pressure)
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 DH0f of the products if the reactants are
elements in their standard states

2. Use heat added in step 1 to change T of products

T change is given by Steady-Flow Energy Equation

Combustion Review
Reaction, ideal result:
1
H 2 O 2 H 2 O DQr
2

1
( 32 kg per mole)
mO m O 2
r

8:1
mF m F
1(2 kg per mole)

stoichiometric oxidizer-to-fuel ratio

Molecular mass of ideal stoichiometric product of
combustion (reaction):

M 2 16 18 amu, water vapor

+ heat energy

Combustion Thermochemistry
Every chemical substance has a Standard Heat of Formation
defined this way.
For example for water:

1
H 2 O2 H 2O gas
2
DH 0f , H 2O gas 241.827KJ/mol
Cumbersome notation necessary to indicate reaction product is water
in its gaseous form
Heat of formation of liquid water (-285.830 KJ/mol) would differ from
this by the heat of vaporization (40.68 KJ/mol) plus the energy
difference from water formed at 25C and steam formed at 25C (~3
KJ/mol).

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

Heats Of Formations

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 heat 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

Example: Application to Rockets

Consider a monopropellant rocket engine using Hydrazine fuel, N2H4
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 N2 and H2

N2, H2
N2H4
Catalyst Bed

Tc, Pc

Example: Application to Rockets

Enthalpy of each product can be approximated by CpT
Chamber temperature is given by:

p, N2

2C p , H 2 Tc T0 DH

0
f ,N2H 4

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 (NH3) and perhaps other
compounds in the decomposition products of hydrazine

Temperature Dependence of Specific Heats

Example:
Enthalpy often approximated as
h(T)=CpT
In combustion chemistry,
enthalpy must take into account
variable specific heats,
h(T)=Cp(T)T
If Cp(T) can be fit with quadratic,
solution for flame temperature
for certain classes of problems
(with T < 1250 K) leads to
closed form solutions
For higher order fits, or T >
1250 K, iterative closure
schemes are required for
solution of flame temperature
1st Law concepts defining heat
of reaction, heating values, etc.

Dissociation: General Comments

What does combustion products are dissociated mean?

Consider burning (combustion) of a hydrogen and oxygen

mixture
In complete combustion we have:

1
H 2 O2 H 2O
2
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, H2O breaking down into H2 and
O2 and other products.

1
H 2 O2 H 2O H 2 OH H O2 O
2

Dissociation: General Comments

Non-ideal chemical reaction:
aH 2 bO 2 nH2O H 2 O nH2 H 2 nO2 O 2 nO O nH H nOH OH DQr

Molecular mass of non-ideal product of combustion :

n jM j 18n H 2O 2n H 2 32nO2 16nO n H 17nOH

M

n H 2O n H 2 nO2 nO n H nOH
nj

Dissociation: General Comments

Resulting gas specific heat:

n jC p, j
Cp
nj

Resulting gas ratio of specific heats:

Cp
Cv

Cp
Cp R

Cp

R
Cp
M

Dissociation: General Comments

1
H 2 O2 H 2O H 2 OH H O2 O
2

Think about terms , , , , 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 Ve and Isp will always be achieved with no
dissociation
Never occurs at operating temperatures 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)

Example: Summary
Governing equation: 7 unknowns (Tc, , , , , , ), m and Pc set

H 2 mO2 H 2O H 2 OH H O2 O
2 2 2
2m 2

2 equations from H and O atom balance

1
H 2 O2 H 2O
2
H 2 2H
H 2 O2 2OH
O2 2O

Equilibrium constant expressions Equilibrium constant expressions

written in terms of partial pressures
Written in terms of unknowns
K P , H 2O T

PH 2O

PH 2 PO2

P 2
K P , H T H

K P , H O T

K P , H T

PH 2

K P ,OH T

POH

PO
K P ,O T

PO2

K P ,O T

2 Pc

K P ,OH T

PH 2 PO2

Pc

2 Pc

6 equations, 7 unknowns Tc

4 linearly independent relations

from equilibrium approximation

Example CEA Calculation: H2-o2 Combustion

Chamber Pressure = 30 atm, Inlet Temperature for H2, O2 = 300 K
6000
No Dissociation
With Dissociation

Temperature, K

5000

4000

3000

2000

Fuel Rich

1000

Fuel Lean

0
0

0.1

0.2

0.3

0.4
0.5
0.6
m (Moles of O2)

0.7

0.8

0.9

Example CEA Calculation: H2-o2 Combustion

Chamber Pressure = 30 atm., Inlet Temperature H2, O2 = 300 K
m
0.1

T
1772.31

Product
H2O
H2
O2

Mole Fraction
0.2
0.8
0

Mass Fraction
0.6908
0.3092
0

m
0.1

T
1772.02

Product
H2O
H2
O2

Mole Fraction
0.1999
0.79996
3.53E-12

Mass Fraction
0.6108
0.30919
2.17E-11

0.2

2840.63

H2O
H2
O2

0.4
0.6
0

0.85627
0.14373
0

0.2

2772.76

H2O
H2
O2

0.39558
0.59206
5.74E-06

0.85209
0.14271
2.20E-05

0.3

3689.95

H2O
H2
O2

0.6
0.4
0

0.93058
0.069421
0

0.3

3307.6

H2O
H2
O2

0.54965
0.38081
9.47E-04

0.88438
6.86E-02
2.71E-03

0.4

4395.34

H2O
H2
O2

0.8
0.2
0

0.97279
0.02721
0

0.4

3520.31

H2O
H2
O2

0.63081
0.22414
1.10E-02

0.83643
3.33E-02
2.59E-02

0.5

4999.19

H2O
H2
O2

1
0
0

1
0
0

0.5

3559.4

H2O
H2
O2

0.65403
0.13308
4.06E-02

0.75804
1.73E-02
8.36E-02

0.6

4713.77

H2O
H2
O2

0.90909
0
0.090909

0.84918
0
0.15082

0.6

3526.13

H2O
H2
O2

0.6479
8.33E-02
8.63E-02

0.68055
9.79E-03
1.61E-01

0.7

4462.78

H2O
H2
O2

0.83333
0
0.16667

0.73788
0
0.26212

0.7

3465.91

H2O
H2
O2

0.62974
5.49E-02
1.39E-01

0.61333
5.99E-03
2.40E-01

0.8

4240.2

H2O
H2
O2

0.76923
0
0.23077

0.65238
0
0.3476

0.8

3396.99

H2O
H2
O2

0.6072
3.76E-02
1.92E-01

0.5569
3.86E-03
3.13E-01

0.9

4041.34

H2O
H2
O2

0.71429
0
0.28571

0.58464
0
0.41536

0.9

3325.8

H2O
H2
O2

0.58363
2.65E-02
2.43E-01

0.50961
2.59E-03
3.77E-01

3862.53

H2O
H2
O2

0.6667
0
0.3333

0.52964
0
0.47036

3254.78

H2O
H2
O2

0.56036
1.91E-02
2.91E-01

0.46971
1.79E-03
4.33E-01

Summary
Note location of
maximum Isp when
dissociation
included
What are tradeoffs?
Thrust
Carry more H2,
how is tank size
affected?

Chemical Reactions
Occuring Within Rocket
Nozzles

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

Nozzle Flow of Reacting Gases

To deal with the flow, we first note that energy conservation for the
gas flow is:
2

u
H c H (T , P)
2

This replaced the ideal gas energy equation:

2

u
C pTc C pT
2

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

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 DT

S xi P, T Si P, T S Mix
xi determined by equilibrium at local T & P
Frozen Flow
Reactions occur slowly, xi are fixed at their chamber values
Flow time << reaction time
No chemical energy release

S xi Pc , Tc Si P, T Sc

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 Cp and k)
However, Isp always lower with dissociation than with no
dissociation at all