AMCP 706-282 Ballistic Missile Series Propulsion and Propellats PDF

AMCP 706-282
ORDNANCE CORPS PAMPHLET
ORDNANCE ENGINEERING DESIGN HANDBOOK

BALLISTIC MISSILE SERIES
PROPULSION AND PROPELLANTS
-
ORDNANCE CORPS MAY 1960
OFFICE O F THE CHIEF O F GRDNANCE
Washington 2 5 , D. C., 3 1 M a y 1960
ORDP 20-282, Propulsion and Propellants, forming part of the Ballis-

tic Missile Series of the Ordnance Engineering Design Handbook, is pub-
lished for the information and guidance of all concerned.
OFFICIAL : J. H. HINRICHS
R. E. PETERS Lieutenant General, USA
Colonel, Ord Corps Chief of Ordnance
Executive Officer
DISTRIBUTION : Special
LIST OF ILLUSTRATIONS
Figure Title page

2-1. Fin-St biliz d Rocket Motor _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _10_ _ _
2-2. Development of Thrust in a Rocket Motor- - - - - - - - - - - - - - - - 11
2-3. Principal Components of an Uncooled Liquid Propellant
Rocket Engine- _ _ - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - 12
2-4. Configurations of Fluid Jets Used in Liquid Bipropellant
Injectors- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - 17
2-5. Stored Inert Gas Pressurization System for a Liquid Bipro-
pellant Rocket Engine--- _ _ _ _ _ - - - - - _ _ _ _ _ _ _ - _ _ _ - _ _ _ - - _ _ 19
2-6. Schematic Diagram of a Turbopump Arrangement for
Pressurizing a Liquid Bipropellant Rocket Engine- - - - - - - - 21
2-7. Typical Solid-Propellant Grain Configurations- - - - - - - - - - - - 23
3-1. Thermodynamic Conditions for Liquid and Solid Propel -
lant Rockets- _ _ - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - 28
3-2. Application of the Momentum Theorem of Fluid Mechanics
to an Arbitrary Propulsion System . . . . . . . . . . . . . . . . . . . . . 30
3-3. Free Body Diagram for a Rocket Propelled Ballistic Missile-- 30
3-4. Specific Impulse as a Function of the Impulse-Weight Ratio
for Different Values of W p / WE_ _ _ _ - - - - - - - - - - - - - - - - - - - - 35
4-1. Area Ratio of Exhaust Nozzle as a Function of the Pressure
Ratio for Different Values of the Specific Heat Ratio- - - - - 45
5-1. Performance af Several Fuels with Fluorine and with Oxygen- 58
5-2. Enthalpy of Combustion in Btu/lb of Several Fuels with
O x y g e n - - - - - _ - - - - - - _ - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - 64
6-1. Burning Characteristics of Several Heterogeneous Pro-
pellants at 60°F--- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - 74
...
111
LIST OF TABLES
Table Title pase
1-1. Principal Abbreviations of Measurement Units- - - - - - - - - - - - - 2
1-2. 3
1-3. 4
2-1. 24
4-1. 42
51.
50
5-2.
54
53. 57
5-4. 61
55.
62
5-6.
63
5-7. 65
5-8. 66
6-1. 72
6-2. 73
Appendix Tables
1. Molar Specific Heats at Constant Pressure for C-H-N-0
Compounds- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - 81
2. Enthalpy of C-H-N-0 Compounds above to = 298.16"K-- - - - 82
3. Values of the Parameter Or = (pe/pc)('-"''_ _ _ _ _ _ - - - _ _ _ _83_ _ _
4. Values of the Parameter fias a Function of p c / p s -- - - - - - - 84
5. Functions of the Specific Heat Ratio k 85
6. Enthalpies of Formation of Fuels at 300'K - - - - - - - - - - - - - - - - 87
7. Enthalpies of Formation for Oxidizers a t 300°K_ _ _ _ _ _ _ _ _ _ _ _ 8,8
8. Enthalpies of Formation for Reaction Products at 300"K---- 88
9. Equilibrium Constants as Functions of Temperature for
C-H-N-0 Compounds- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - 90
iv
Preface
This Handbook has been prepared as one of a series on Ballistic

Missiles. It presents information on the fundamental operating prin-
ciples of propulsion systems as found in ballistic missiles, with discusions
of propellants which have been found practicable or which have theo-
retically attractive possibilities. Criteria are presented whereby the
performance of propulsion systems can be judged.
The handbook was prepared for the Office of Ordnance Research,

Ordnance Corps, U. S. Army. The text and illustrations were ,prepared
by Vitro Laboratories under contract with Duke University, with the
technical assistance of Army Ballistic Missile Agency and the Special
Projects Branch of Navy Bureau of Ordnance.
Comments on, and requests for copies of, this Handbook should be
addressed to Commanding Officer, Office of Ordnance Research, U. S.
Army, Box CM, Duke Station, Durham, N. C.
i
ORDP 20-282
CONTENTS
Subject
iii
iv
1
9
27
37
49
71
81
92
..
II
Chapter 1
INTRODUCTION *
1-1. DEFINITIONS AND SCOPE ballistic missiles, and therefore no discussion of

thermal jet engines will be presented in this
All known methods of propelling a body through
volume. For information on those engines the
the earth’s atmosphere are based on Newton’s
reader is referred to references 1 and 2 a t the end
principle, for every action there is an equa.1 and
of this chapter.
opposite reaction. In a dynamic system a mass is
The propulsion engines employed for propelling
accelerated in a given direction by producing a
ballistic missiles are chemical rocket engines.
reaction force acting in the opposite direction.
Chemicals consumed in creating the propulsivc
Hence, a jet propulsion engine derives its thrust
jet are termed propellants. There are two main
from the fluid accelerated through the engine to
classes of rocket engines:’
emerge as a high speed jet of propulsive power a t
the tail of the engine. The high speed fluid jet is 1. liquid propellant rocket engines, which burn
termed the propulsive jet, and the reaction force chemicals that are in a liquid state prior to
that propels the vehicle is termed thrust. The combustion
thrust acting in the direction of mobion of the 2. solid propellant rocket motors, which burn
propelled vehicle has a direction that is always chemicals which are in a solid state prior to
opposite to that of the high speed fluid jet. combustion.
For propelling either an aircraft or a missile Since World War I1 all military services in the
through the earth’s atmosphere the most suitable United States Department of Defense have been
fluid for forming the propulsive jet is a hot gas. actively engaged in applying rocket jet propulsion
Jet propulsion engines for propelling such vehicles to weapon systems. All have developed, or are
are basically devices for producing propulsive jets developing, rocket jet propelled ballistic missiles.
formed of hot gases and may be grouped into two This volume covers the fundamental principles
broad classes, depending upon the methods governing the operation and performance of
employed for producing the hot, gaseous, pro- chemical rocket engines for ballistic missiles.
pulsive jets: Introductory Chapter 1 presents a review of basic
1. thermal jet engines, which consume atmos- thermodynamic relationships with definitions of
pheric air in creating the propulsive jet principal terms. This is followed by a description
2. rocket engines: which create the propulsive of the essential features of rocket engines in
jet by reacting suitable chemicals and do Chapter 2 and a discussion of rocket engine per-
not consume any atmospheric air. formance criteria in Chapter 3. Chapter 4 deals
The principal types of thermal jet engines are with the application of thermodynamic relations
the turbojet engine, the ramjet engine, and the to rocket engines, and in Chapters 5 and 6 the
pulsejet engine. Currently, thermal jet engines are properties and characteristics of liquid propellants
not employed either for launching or propelling and solid propellants are examined.
* This volume was written by M. J. Zucrow, Director of cation of the Assistant Secretary of Defense (Supply and
Jet Propulsion Laboratory, Purdue University, and Logistics), liquid fuel units are designated as rocket
edited by C. D. Fitz, Vitro Laboratories. engines and solid fuel units as rocket motors.
1 I n this handbook the phrase rocket enyine is occasionally A propulsive jet can be formed in other ways than by
employed as the generic term covering all non-air- direct chemical reaction; for example, by heating a
i)reathing reaction propulsion devices. According to a working substance in a nuclear reactor. Discussions in
recent change in Cataloging Handbook H6-1,a publi- this handbook are limited to chemical rockets.
I
ORDP 20-282
1-2. BASIC UNITS OF MEASUREMENT 1-3.1. Equation of State for a Perfect Gas.
The basic units of measurement used in this Let p denote the absolute static pressure, t the
handbook, unless specifically st.at.ed to be other- absolute static temperature, Z the molecular
wise, are listed below weight of the gas, and v its specific volume. Then
Dimension Basic Unit

mass 1 slug
force 1 pound (lb) where R,, = the universal gas constant, and
length 1 foot (ft) R = 1545/E = the gas constant for the specific
time 1 second (sec) gas.3
Table 1-1 indicates the abbreviations used in
measurement units. If vz = Ev = the volume of one mole of a
Table 1-2 presents a list of conversion factors. perfect gas, then
Table 1-3 gives t,he principal not,atioiis used in p v;;; = R,, t (1-2)
t,his volume.
1-3.2. Dalton's Law. If pm denotes the total
TABLE 1-1. PRINCIPAL ABBREVIATIONS static pressure exerted by a mixture of gases
OF MEASUREMENT UNITS having the initial partial pressures p l , p2, . . . p,,
A bbreviotion Quantity then
Btu British thermal unit
"C degrees Cent.igrade
cc cubic centimeters
"F degrees Fahrenheit
g gram
"K degrees Kelvin where p i = partial pressure of i-th species.
kg kilograms The molecular weight of the mixture of gases
lb pounds Em,is given by
psi pounds per square inch
psia pounds per square inch absolute n
pcf pounds per cubic foot
"R degrees Rankine C ni f i :
Em= --
i=l
(1-4)
2 ni
i-1
1-3. REVIEW OF BASIC THERMODYNAMIC where n i is the number of moles of i-th species,
RELATIONSHIPS and Ei is its molecular weight.
The temperature of the combustion gas pro-
duced in the combustion chamber of a rocket Let nm = C ni
i=l
motor is well above the critical temperatures for
its individual gaseous species. Moreover, the
Then (1-5)
combustion pressures are generally moderate
compared to the critical pressures for the con-
stituent gases. It is customary, therefore, to where Vm and t,,, denote respectively the volume
assume that the combustion gas behaves in and absolute temperature of the gas mixture.
accordance with the laws for perfect gases.2 For Equation (1-5) shows that in a mixture of perfect
convenience of reference, the basic relationships gases the number of moles of the i-th species is
for perfect gases will be reviewed. proportional to its partial pressure p i .
* Numbers in parentheses in the text indicate referenres

listed a t the end of the chapter. the expansion process in the nozzle. (Reference 3, 4)
2 Modifications must be made in the case where the 8 R u = 1.9864 Btu/" R lb-mol= 1.9864cal/"K g-mol=
combustion gas contains solid particles or vaporized 1545 ft-lb/"R lb-mole (Principal Notations a r e pre-
solids; the latter may undergo a phase change during sented in Table 1-3).
L
INTRODUCTION ORDP 20-282
TABLE 1-2. CONVERSION FACTORS
Given Multiply by To obtain
FORCE FORCE
dynes 1.020 x 10-6 kilograms
kilograms 2.205 pounds
pounds 32.174 poundals
4.448 X 106 dynes
PRESSURE PRESSURE
atmospheres 14.70 pounds per sq in
1.0132 X 106 dynes per sq cm
29.92 inches of mercury
bars 10' dynes per sq cm
dynes per sq cm 2.953 X 1 0 - 6 inches of mercury
7.501 X millimeters of mercury
pounds per sq in 2.036 inches of mercury
5.1715 X 10 millimeters of mercury
MASS MASS
grams 2.205 X 10-3 pounds
pounds 4.535 x 103 grams
slugs 32.174 pounds
14.594 X 103 grams
LENGTH LENGTH
centimeters 0.0328 1 feet
feet 30.48 centimeters
inches 2.540 centimeters
microns 10-4 centimeters
angstroms 10-8 centimeters
VOLUME VOLUME
cubic feet 2.832 X lo4 cubic centimeters
7.481 gallons
28.32 liters
cubic inches 16.39 cubic centimeters
gallons 3.785 liters
liters 0.03532 cubic feet
DENSITY DENSITY
grams per cm3 0.03613 pounds per cubic inch
62.43 pounds per cubic foot
pounds per in8 27.68 grams per cubic centimeter
ENERGY ENERGY
British thermal units 251.8 calories
2.931 X 10-4 kilowatt-hours
calories 3.968 X 10-3 British thermal units
POWER POWER
Btu .per hour 3.930 X 10-4 horsepower
2.931 X 10-4 kilowatts
horsepower 2.544 X 103 Btu per hour
TEMPERATURE TEMPERATURE
degrees Kelvin 1.0 degrees Centigrade + 273.2
1.8 degrees Rankine
degrees Centigrade 1.8 degrees Fahrenheit - 32
degrees Rankine 1.0 degrees Fahrenheit + 459.7
3
ORDP 20-282
TABLE 1-3. PRINCIPAL NOTATIONS
acoustic velocity for combustion gases 32.1740 ft/sec2)

moles of i-th species of reactants h specific enthalpy
initial moles of reactants hc static specific enthalpy entering exhaust
cross-sectional area nozzle
cross-sectional area of case surrounding hL specific enthalpy of gases a t exit of nozzle
grain for isentropic enthalpy change
cross-sectional area of nozzle exit section Ah; enthalpy change for isentropic expansion
frontal area
cross-sectional area of the propellant H, stagnation specific enthalpy of gases
grain entering exhaust nozzle
denotation for reactants enthalpy of formation a t reference
partial pressure of species Ai H; temperature
maximum cross-sectional area of missile AH, total enthalpy of reaction
port area Z ( A H f ) psum of enthalpies of formation for the
individual products
nozzle throat area
Z ( A H f ) sum
~ of enthalpies of formation for the
molar concentration of j - th species of individual reactants
products
total impulse
British thermal unit
density impulse
denotation for reaction product
theoretical density impulse
partial pressure of species Bj
specific impulse
moles of products at the temperature t,
characteristic velocity for rocket pro- theoretical specific impulse
pellant mechanical equivalent of heat
specific heat at constant pressure (778 ft-lb/Btu)
specific heat at constant volume specific heat ratio
c7
discharge coefficient for a nozzle or orifice 3, propellant area ratio
thrust coefficient At
theoretical value of CF equilibrium constant
mass flow coefficient characteristic length of rocket motor
molar specific heat at constant pressure log to base e
molar specific heat at constant volume mass rate of propellant consumption
mean value of C,, mass
weight flow coefficient molecular weight
inner diameter of grain instantaneous mass of missile
outer diameter of grain molecular weight of j-th component
drag molecular weight of mixture of gases
thrust Mach nllmber for gases at entrance to
standard free energy change exhaust nozzle
free energies of species Ai change in momentum of body cr fluid
standard free energy of species Ai initial mass of vehicle
free energies of species Bj effective mass of propellants
standard free energies of Bj burning rate exponent or pressure index
gravitational acceleration, general moles of i-th species of gas
gravitational acceleration (standard mole fraction of j-th component
4
TABLE 1-3. (Continued)

N number of moles of gas mixture WEo take-off weight of rocket propulsion
absolute static pressure system
P
Pc gas pressure a t entrance to exhaust Wr fuel flow rate
nozzle Wc weight of guidance equipment and
gas pressure a t exit of nozzle housing
Pe
static pressure acting on interior surface Wr weight of empty iiiissile
Pi
of the rocket motor Wnl weight of missile inert metal parts
Pm static pressure exerted by mixture of P O oxidizer flow rate
gases WO weight of loaded missile
Po standard sea level static pressure Wp total weight of propellants
Pc stagnation value of gas pressure Ws structural weight of missile
Q quantity of heat specific propellant consumption
Qanaiz available heat WT weight of missile propellant tanks
Qr heat of formation Wv weight of payload
QV heat of vaporization 2, = 1 - Ot ,the expansion factor
r =
W
7,
O
fuel mixture ratio Greek letters
wr Ly semi-divergence angle for exhaust nozzle
r linear burning rate for a solid propellant Y specific weight of an incompressible fluid
linear burning rate for Va = 0 YP specific weight of propellant
gas constant QP propellant weight loading density or
universal gas constant engine weight efficiency
interior surface of rocket motor Ae
exterior surface of rocket motor E
At
,
= - area ratio
area of burning surface of a solid pro-
pellant grain ep =
A
- G , propellant loading ratio
S entropy Ac
t absolute static temperature A P
tc combustion temperature ept = -,port-to-throat ratio
At
te gas temperature at exit of nozzle
1: isentropic exit temperature (= velocity coefficient
tm absolute temperature of gas mixture
U specific internal energy M
specific volume t=”, propellant iiiass ratio
2, Mo
Vm volume of gas mixture
V missile velocity , expansion ratio paramet,er
V’ isentropic velocity
Vbi ideal burnout velocity x divergence coefficient for nozzle
v
c velocity of combustion gases at entrance Mo - M o , vehicle mass ratio
A= --
section of exhaust nozzle -If, mb
velocity of gases at exit section of nozzle
isentropic exit velocity P viscosity
x component of velocity for exhaust jet =to temperature sensitivity cocfficicnt
velocity of combustion gas parallel to =r thrust temperature coefficiciit
burning surface (for end burning grain =Pc combustion pressure temperature co-
V” = 0 ) efficient
P density
F effective exhaust velocity -
average density of propellant system
VP volume of propellant grain
PP
+
(fuel oxidizer)
W web thickness of grain time
TV weight rate of propellant consumption burning time
WC weight of missile control apparatus flow factor
WE dry weight of complete rocket engine a function of k
5
ORDP 20-282
1-3.3. Internal Energy. Internal energy, denoted where h is the enthalpy per unit weight or the
by u, is a thermodynamic property whose value specific enthalpy, and J is the mechanical equiva-
is independent of the process employed for bring- lent of heat. For a perfect gas
ing the system to a given state. For a perfect gast dh = c,dt (1-14)
ZL is a function only of the gas temperature t, and Since h for a gas is a function of temperature its
du = cv at (1-6) values measured above some base temperature to
where c, is the specific heat at constant volume (for which h, is usually given the value zero) can
for the gas, and is in general, a function of t. be tabulated by using the values of c, for zero
The molar specific heat at constant ;ohme is pressure. Then h = c, t. Table 2 presents the
denoted by C, and is given by enthalpies of C-H-N-0 compounds measured
c, = mc, (1-7) above to = 298.16"K.
For monatomic gases the molar specific heat is
a constant and has the value C, = 2.981 cal per 1-3.6. Isentropic Change of State. For a revers-
g-molo K. ible adiabatic process there is no transfer of heat
(AQ = 0) and the entropy of the system remains
1-3.4. Relationship Between Specific Heats. constant (ds = 0). Such a process is termed an
For a gas, if c, denotes the specific heat at constant isentropic process. If a perfect gas changes its
pressure (Btu/lb R), then state by an isentropic process, then
~(c,-c,) = C p - C, = R, (1-8) k k
The specific heat ratio, denoted by k, is defined by p l vl = p2 v2 = constant (1-15)
Also
From equations (1-7) and (1-8) it follows that tl = (E) (E) (E)
(k-1)lk
=
RJC,
=
RIJc,
(1-16)
C, = a,= R,,-k-1k (1-10) The superscript prime ( ' ) attached t o tz in

equation (1-16) above denotes that state number 2
and was reached by employing an isentropic process.
Consider an isentropic expansion (p2 < p l ) from
C, = a,= R, k-1 (1> (1-11)

state number 1, where the specific enthalpy of the
gas is hl, to state number 2 where it is hi. If Ah;
denotes the isentropic enthalpy change, then
Table 1 presents C, = Ec, for several gases as a
function of temperature.
(1-17)
Let c, denote the mean value of C, for the
temperature range to 'to t. Then If E, denotes the mean value of cp, then
hi = a,tl(i -e,) = E,~~Z, (1-18)

(1-12)
where the expansion ratio parameter 0 , is given by
1-3.5. Enthalpy of a Perfect Gas. The thermo-

dynamic property called enthalpy (also known as
total heat) is defined by
and
h = u + - -PV (1-13) Zt = 1 - e, = the expansion factor (1-20)
J
In the case of an expansion in the nozzle of a
Numbered tables will be found in the Appendix. rocket motor p l = p , = the pressure at the inlet
6
section to the exhaust nozzle (the combustion For an isothermal change of a perfect gas the
pressure),and p2 = p, = the pressure in the exit corresponding free energy change is
section of the exhaust nozzle, called the exit ( J - J o l t = Rut In p (1-24)
pressure. where 3"denotes the standard free energy at the
Appendix Table 3 presents values of the absolute temperature t and 1 atm pressure.
expansion ratio parameter et as atfunction of The free energy 3 finds its principal use in
p,/p, for different values of k. establishing the criteria for predicting equilibrium
of chemical and physical processes. For a system
1-3.7. Isentropic Velocity. If a perfect gas is in equilibrium, 3 has its minimum value. More-
expanded from state 1 to state 2 the resulting over, for a process to take place spontaneously
transformation of enthalpy into kinetic energy is under the conditions At = Ap = 0 the correspond-
given by ing free energy change, denoted by AJlP,must be
negative. For a system which is in equilibrium
(1-21) A3tp = 0 (Ap = At = 0 ) (1-25)
The equilibrium chemical reactions for rocket
where hl and h2 are the initial and final values of propellants are of particular interest because the
the specific enthalpy of the gas. equilibrium composition of the gas rhixture at the
In the special case where the expansion process entrance to the exhaust nozzle, the combustion
is isentropic, the final state is 2' and the corre- temperature and pressure, and the characteristics
sponding values of specific enthalpy and tempera- of the exhaust nozzle, all determine the jet
ture are hi and t: respectively. The velocity velocity, and hence the specific impulse obtainable
attained by the expanded gas is V', the isentropic from the propellants.
velocity. Thus When the reactants in a chemical equation are
V' = 2gJ(hi-h:) = 2gJ E p ti 2, (1-22) elements, such as oxygen and hydrogen, and they
Values of z/z;as a function of pc/p, for different react to form a single chemical compound, such
values of k are presented in Table 4. as water, the free energy change AJLP for the
Values of several functions of k are presented reaction is termed the free energy of formation.'
in Table 5. When the reaction takes place under standard
conditions (usually 1 atm and either 298.16"K or
1-3.8. The Free Energy Function. (5) The Gibbs 300°K) it is termed the standard free energy of
free energy function, for brevity called free formation and is denoted by 37.
energy, is denoted by 3 and defined by
+
J = h - ts = u PV - 2s (1-23)
Since h, u,t, and s are thermodynamic proper- As is the case in calculating the enthalpy (or heat) of
ties the free energy 3 is likewise a thermodynamic formation for a chemical compound, the free energy of
property. formation for any chemical element is zero.
1-4. REFERENCES 3. Greene, S . H., and L. J. Gordon, An Effect of

Carbon in an Adiabatically Expanded Gas
Stream, Jet Propulsion, Vol. 27, p. 667. June
1. Zucrow, M. J., Aircraft and Missile Propul-
1957.
sion, Vol. I. John Wiley and Sons, New York.
1958. 4. Wilde, K. A., An Approximate Specific
Impulse Equation for Condensable Gas Mix-
2. Zucrow, M. J., et all Aerodynamics, Propul- tures, Jet Propulsion, Vol. 27, p. 668. ,June
sion, Structures and Design Practice (Prin-
1957.
ciples of Guided Missile Design series) p.
149-51. D. Van Nostrand Co., Princeton, 5. Glasstone, S., Thermodynamics for Chemists,
N. J. 1956. D. Van Nostrand Co., Princeton, N. J . 1957.
7
ORDP 20-282
6. Zucrow, M. J., et al, “Aerodynamics, Co., New York, 1950.

Propulsion, Structures, and Design
Practice” (Principles of Guided Missile 8. J. B. Rosser, R. R. Newton, and G. L.
Design Series, Propulsion Section), D. Gross, “Mathematical Theory of Rocket
Van Nostrand Co., Princeton, N. J. Flight,” McGraw-Hill Book Co.. 1947.
1956. 9. “Letter Symbols for Rocket Propulsion,”
7. Wimpress, R. N., “Internal Ballistics of Jet Propulsion, Vol. 25, No. 11, Novem-
Solid Fuel Rockets,” McGraw-Hill Book ber 1955, p. 636-45.
8
Chapter 2
ESSENTIAL FEATURES OF ROCKET ENGINES
2-1. GENERAL OPERATING Since the pressure of the gas a t the entrance to
PRINCIPLES (1, 2) the exhaust nozzle, denoted by p,, will range from
p , = 150 to p , = 3000 psia and the maximum
Figure 2-1 illustrates schematically the main
pressure of the surroundings into which they
components of a fin-stabilized solid propellant discharge is p , = 14.7 psia, the standard sea level
rocket motor. It is the element which produces static. pressure, the pressure ratio for the exhaust
the propulsive thrust. A rocket motor comprises nozzle pc/p,, is always much larger than the
a solid propellant grain or charge, enclosed in a
caritical pressure ratio for the combustion gas (see
metal housing, a De Laval type of exhaust nozzle,
Chapter 4, reference 1). Consequently, the mean
an igniter for igniting the propellant grain, and
velocity of the gas crossing the throat section of
electrical leads for supplying the electrical energy
the nozzle may be assumed to hc equal to tho
for firing the igniter. (3)
local speed of sound. (7)
Consider a solid propellant rocket motor. As
the propellant grain burns it produces tremendous
2-2. SALIENT FEATURES OF
quantities of hot gas. If the propellant burns a t a
ROCKET JET PROPULSION
constant rate in a closed chamber such as illus-
trated in Figure 2-2a, the gas pressures inside the The functioning of a rocket engine differs
chamber are always balanced in all directions, fundamentally from that of an air-consuming
and because there is no unbalanced pressure force engine by virtue of the following two character-
no thrust is developed. Let a hole now be opened istics:
in one end of the chamber, as illustrated in Figure 1. a rocket engine consumes no atmospheric
2-2b, and assume that the propellant burns at a air, and
constant rate. The combustion pressure inside the 2. the thrust it develops, in Ib per Ib per sec of
chamber will remain coiistant (a short time after propellant consumption, ( F / @), depends
the grain is ignited) a t a value governed by the only upon the jet velority. I n the case of an
area of the hole and the rate at which the pro- air-consuming engine thrust depends upon
pellant burns. At the hole there is an escape of the difference between the jet velocity and
gas and the latter has no surface against which it that of the air entering the engine. (1, 2)
can push. Hence, there is an unbalanced pressure As a consequence of these characteristics rocket
force, denoted by F, acting to the left. In an jet propulsion, compared with other known
actual rocket motor the hole in Figure 2-2b is methods of propulsion, has the following ad-
replaced by a De Laval nozzle, as illust,rated ill vantages (4):
Figure 2-2c. 1. thrust is essentially independent of the flight
The conditions in the rase of a liquid propellant speed
rocket engine are similar. But in that type of 2. the thrust is substantially independent of
rocket engine the hot gases are produced by burn- the surrounding environment
ing one or more liquid propellants. Figure 2-3 3. thrust per unit of frontal area ( F I A F )is the
illustrates schematically the main components of largest for all known types of engines
a liquid propellant rocket engine. 4. thrust per unit of engine weight (F/WE)is
Regardless of whether solid or liquid propellants the largest ,of any known type of engine
are burned in a rocket engine the main objective 5. there is no altitude ceiling
is to produce a propulsive jet having the largest 6. useful work increases directly with flight
possible ejection velocity, called the jet velocity. speed.
9
PROPELLANT STAB1 L I2I NG
IGNITER GRAIN FINS
I I
THREADS CASING
Figure 2-1. Fin-Stabilized Rocket Motor

ORDP 20-282
ALL PRESSURES ARE BALANCED
r c i
F
- t
4
, . t-
yq
t i
I I
I I
PROPELLANT GRAIN CASE DE' LAVAL

EXHAUST
NOZZLE
Figure 2-2. Development of Thrust in a Rocket Motor
II
ORDP 20-282
w w
Q0
al
.-c
0,
C
9
3
.-m
-
rl
a
6
0
8
a
W C
m D
I Y
a
I
0
0
II X
P-
c
?
cy
Cro
a
P
a
P
12
ESSENTIAL FEATURES O F ROCKET ENGINES ORDP 20-282
Early workers in rocket jet propulsion recog- high temperature, high pressure gases by burning
nized that these characteristics gave rocket jet a solid material the principal ingredients of which
propulsion the capabilities for attaining extremely are a fuel and an oxidizer. The ingredients may
high flight speeds and altitudes, and also the he present either in the molecular structure of the
potentialities for making space flight a possibility. solid propellant or they may be separate chemical
Because oxygen for burning the fuel is not taken compounds which are present as a suitable
from the surrounding atmosphere, the rate at physical mixture. Solid propellants may be segre-
which a rocket engine consumes its propellants gated into double-base propellants, and composite
(fuel plus oxidizer) is several times that at which or heterogeneous propellants.
an air-consuming engine consumes fuel.
The most important parameters governing the 2-3.1. Liquid Monopropellant Engines. A liquid
speed of flight are FIAF, the thrust per unit of monopropellant is a liquid which may be either a
frontal areal, and F I V E , the thrust per unit of single chemical compound such as nitromethane,
engine weight. As mentioned earlier, judged by or a mixture of chemicals that contains all of the
those parameters the rocket engine is unsurpassed. chemical elements for initiating a high-energy,
The range of flight for winged aircraft depends gas-producing chemical reaction. A rocket engine
primarily on the thrust specific fuel consumption which develops its thrust from the chemical
(TSFC) of the propulsion engine, measured in reaction (usually a decomposition) of a liquid
pounds of fuel per hour per pound of thrust. monopropellant is termed a liquid monopropellant
T o obtain a long range for a rocket propelled engine.
vehicle, such as a guided missile, a method must A liquid monopropellant engine has the
be utilized which takes advantage of its large advantage of simplicity because a single liquid is
values of FIAF and FIWE, but minimizes the involved. All of the liquid monopropellants
adverse effects of its large TSFC. T o achieve a investigated require the addition of energy to
long range, the large thrust of the rocket engine initiate the decompositioii of the monopropellant.
is utilized for propelling the vehicle to a very high Ordinarily, that energy is supplied by a pyro-
altitude (several tens of miles), and for imparting technic igniter, an electrically heated glow plug,
t o i t a very large velocity (several thousands of a spark plug, or a small supply of auxiliary fluid
feet per second), a t the end of the operating with which it reacts readily.
period for the rocket engine, termed the powered Among the liquid monopropellants that have
flight. The velocity a t the end of the powered been investigated are ethylene oxide, n-propyl
flight is called either the cut-off velocity, burnout nitrate, isopropyl nitrate, nitromethane, diethyl-
velocity, or burned velocity. The kinetic energy eneglycol dinitrate, acetylenic compounds, mix-
of the vehicle after it reaches the cut-off velocity tures of methyl nitrate and methyl alcohol,
is then used for coasting along a ballistic tra- hydrazine, and mixtures of nitric acid with
jectory. Methods for computing the charac- benzene and water.
teristics of ballistic trajectories are presented in A satisfactory liquid monopropellant is one
another volume of this series. which is stable under all storage conditions but
which decomposes completely when it is injected
2-3. CLASSIFICATION OF into the combustion chamber of a rocket engine.
ROCKET ENGINES I n general, these requirements are conflicting and
greatly restrict the choice of possible liquid
Liquid propellant' rocket engines can be segre-
monopropellants. As a rule, the larger the thrust
gated into liquid monopropellant engines, and
output per unit weight of a liquid monopropellant
liquid bipropellant engines.
the greater is its sensitivity to shock; that is, the
A solid propellant3 rocket motor produces its
more explosive is its nature. (6)
This parameter is important only for flight in the earth's It is doubtful that a liquid monopropellant will
atmosphere. be found that will give better performance than
Liquid propellants are discussed in Chapter 5. the best liquid bipropellants. Consequently,
Solid propellants are discussed in Chapter 6. monopropellants will probably not be used in the
555514 0 - 60 -2 13
ORDP 20-282
rocket engines of a ballistic missile. On the other which suitable plasticizers, ballistic modifiers, and
hand, monopropellants are widely used as the stabilizers have been added. T o this group of.
means for generating the gases for powering the propellants belong such materials as ballistite and
turbines that drive propellant pumps and auxiliary cordite. They are used most extensively for such
power supplies in ballistic missiles. weapons as artillery barrage rockets, bazookas,
aircraft rockets, unguided ballistic missiles, etc.
2-3.2. Liquid Bipropellant Engines. A bipro- They are also used in the boosters for launching
pellant engine develops its thrust by reacting a turbojet and ramjet propelled guided missiles.
liquid oxidizer or oxidant with a liquid fuel, Double-base propellants burn with little smoke
thereby producing tremendous quantities of high and at ambient temperatures are hard and tough.
temperature, high pressure gas. I n principle, When stored a t temperatures continuously above
liquid bipropellants are less hazardous than liquid approximately 120°F they tend to deteriorate.
monopropellants from shock sensitivity and -
Double base propellant grains are made by
thermal stability standpoints. When separated, extrusion (solventless extrusion for large grains,
the fuel and oxidant are ordinarily incapable of and solvent extrusion for the small grains), and
releasing energy in an explosive manner. Bipro- by casting. Large double-base grains can also be
pellants which ignite spontaneously when they made from smaller extruded sections by cementing
come in contact with each other in the com- them together in an appropriate manner.
bustion chamber of the rocket engine are said to
be hypergolic. Those which require an addition 2-3.4. Composite or Heterogeneous Propel-
of energy to initiate the chemical reaction are lants. (7) A composite propellant consists of an
said to be diergolic. inorganic oxidizer, in powder form, thoroughly
The number of known liquids which are suitable mixed with an organic fuel which also serves as
as fuels is almost limitless, but there are only a the binder for the oxidizer particles. (8) Most of
few liquids, possibly a dozen, which can serve as the composite propellant formulations can be cast
practical oxidizers. Even so, the number of directly into the case of the rocket motor. There
possible liquid bipropellant combinations is quite are, however, some formulations which are
large. employed for producing molded grains.
The principal liquid oxidizers are the nitric The composite type of propellant first used on
acids, white fuming nitric acid (WFNA), red a wide scale in this country was the castable
fuming nitric acid (RFNA), stabilized (red) asphalt-base propellant employed in JATO' units.
fuming nitric acid (SFNA)', liquid oxygen (LOX), It was a mechanical mixture of potassium per-
high strength (80 to 100 percent HzOz)hydrogen chlorate and asphalt, the latter serving as the fuel
peroxide (HTP), mixed oxides of nitrogen (MON), and also as the binder for the oxidizer. The
and liquid fluorine (LF). powdered potassium perchlorate was mixed with
The principal liquid fuels are the hydrocarbon molten asphalt and the mixture cast either
fuels, such as jet engine fuels JP-4 and JP-5, directly into the motor case, the walls of which
aniline and mixtures of aniline with furfuryl were covered with a suitable lining material
alcohol, alcohol water mixtures, hydrazine, un- (liner); or into a suitable mold for solidification,
symmetrical dimethylhydrazine ( U D M H ) , then removed and installed in the motor case.
diethylenetriamine (DETA), anhydrous ammonia, Hecause of its poor physical and ballistic proper-
and mixtures made of other fuels with either ties, asphalt propellant is not suitable for ballistic
hydrazine or UDMH. A more detailed discussion missile applications.
of liquid propellants is presented in Chapter 5. Modern composite propellants use an elasto-
ineric material as the binder which is mixed in
2-3.3. Double-Base Solid Propellants. (2, 5, 7) monomer form with the oxidizer particles and then
These consist primarily of gelatinized colloidal polymerized to form a rubber-like material. In
mixtures of nitrpcellulose, -and nitroglycerin to most of the current castable composite propellant
'The approximate composition of SFNA is 83 percent formulations the oxidizer is ammonium per-
HNOa, 14 percent NOZ, 2 percent HzO, 1 percent HF. ' JATO-Jet Assisted Take Off.
14
ESSENTIAL FEATURES OF ROCKET ENGINES ORDP 20-282
chlorate. Some formulations include finely divided Where it is desirable to produce a large thrust
metals such as aluminum. It should be noted that for a relatively short time, as in launching or
in all composite propellants the binder (or fuel) boosting applications, a propellant grain con-
comprises only approximately 20 percent by figuration which allows burning of more than one
weight of the finished propellant, the balance surface of the grain is frequently used. Propellant
being solids. Hence, to obtain a propellant (fuel grains having no inhibited surfaces are termed
and oxidizer) having a satisfactory tensile strength, unrestricted-burning grains. Figure 2-7 illustrates
the binder (fuel) must have a tensile strength several grain configurations that have been
several times that required for the propellant. employed.
In addition to the main ingredients of oxidizer
and fuel, a solid propellant generally contains
2-4. ESSENTIAL COMPONENTS OF LIQUID
small amounts of several other materials called
BIPROPELLANT ROCKET ENGINES
additives, each of which has an influence upon
either the control of the manufacturing process, Since liquid monopropellants do not have the
the burning rate, the physical properties, or the capabilities for giving the high performance
storage stability. With some formulations a small required for a ballistic missile the following dis-
change in the additives, either in the type or cussions are confined to liquid bipropellant rocket
amount, can cause important changes in the engines. An engine of the latter type comprises
properties of the propellant. four main subassemblies:
Several different configurations are used for 1. tanks for storing the liquid oxidizer and the
making composite and double-base propellants. liquid fuel, hereafter termed the propellant
In certain grain designs one or more surfaces of tanks
the propellant grain are prevented from burning 2. one or more rocket niotors, or thrust
by applying an inhibitor, a material which is chambers, wherein the oxidizer and fuel are
either inert chemically or burns at a much slower burned to produce very large quantities of
rate than the propellant, to those surfaces. hot gases
I n several cases the composite propellant is cast 3. means for removing the propellants from
directly into the case of the rocket motor, and is the propellant tanks and forcing them into
bonded to the inner wall of the casing by inter- the combustion chamber of the rocket motor
posing a lining material between the grain and against the combustion pressure (the pro-
the wall. The liner adheres to both the metal wall pellant pressurizing system)
and the propellant grain, and inhibits burning. 4. means for controlling the operation of the
This arrangement is known as case-bonding. It engine so that it performs in the desired
has the advantages of supporting the grain and manner and also protects against disaster in
protecting the metal casing from hot combustion the event of malfunction.
gases. Consequently, the metal case may be Only items 2 and 3 mill be discussed.
designed on the basis of its cold strength, and In general, the requirements imposed upon a
may be thin and light in weight. (9) For case- liquid rocket engine depend upon the application.
bonding to be successful the coefficients of In many cases the application requires that the
thermal expansion of the metal wall, the liner, and performance of the engine be independent of the
the propellant must be properly matched so there temperature of the liquid propellants over the
will be neither separation nor cracking of the range-65°F to 160°F. Since the physical prop-
liner with temperature changes and temperature erties of practically all chemicals vary with their
cycling. temperature the number of liquid chemicals that
Solid propellant grains having inhibited surfaces can satisfy the temperature requirements is quite
are termed restricted-burning grains. A grain limited. As a consequence, one fiiids that a large
which burns only on its internal surface is called portion of the engineering effort in developing a
an iiiternal-burning grain. Restricted-burning iiew liquid rocket engiiie is devoted to making
grains are used in applications where relatively the engine operate satisfactorily and reliably over
long burning times are required, far example, in a wide range of temperatures. Perhaps the
solid propellant motors for ballistic missiles. costliest and most time-consuming part of liquid
15
ORDP 20-282
engine development is that concerned with ob-

taining reliable operation at very low tempera-
tures (below -20°F). In view of the foregoing, Hence, the mixture ratio T is given by
the specifications for the required range of
operating temperatures should not be made any
wider than is warranted from a realistic appraisal
of the conditions under which the rocket propelled The subscripts and refer to the oxidizer and
ballistic missile is to be used. Furthermore, fuel orifices respectively.
wherever it is practicable, means should be Since the discharge coefficients (C(!)o and ( C d ) ,
provided for protecting the propellant (or pro- are functions of the Reynolds number, the orifices
pellants) against cold weather (such as heating should be selected so they operate in a range
blankets). where their discharge coefficients do not vary
appreciably over the expected range of variation
2-4.1. Thrust Chamber. Figure 2-3 illus- in the Reynolds number.
trates schematically the essential elements I n some injector designs an effort is made to
of a liquid bipropellant rocket engine. aid the processes of mixing and atomizing the
They are: liquids, by causing the jets of oxidizer and fuel
1. the injector, for introducing the propellants discharged from the injection orifices to impinge
into the combustion chamber and for upon each other. Figure 2-4 illustrates sche-
metering their flow rates matically the principal configurations of the fluid
2. *the combustion chamber, wherein the jets used in the injectors for liquid bipropellant
chemical reaction occurs rocket engines.
3. the De Lava1 exhaust nozzle (converging- No rational principles have been formulated for
diverging nozzle) for expanding the com- scaling injectors or predicting their combustion
bustion gases to give a supersonic jet performance. Injector development is a costly,
velocity. time-consuming, empirical process, which depends
In addition to the above there are the pertinent upon experience combined with trial and error.
valves and pressure regulating devices. If the I n fact, the problems concerned with scaling
propellants are diergolic (see paragraph 2-3.2) liquid bipropellant rocket engines are primarily
some form of ignition system must be provided. injector problems. Much research effort will have
This may be an electrically heated glow plug, a to be expended if rational principles for scaling
spark plug, a small quantity of fuel which is injectors are to be developed.
hypergolic with the oxidizer leading the main
fuel, or a pyrotechnic igniter having a burning 2-4.1.2. The Combustion Chamber. The com-
duration of a few seconds. (5) bustion chamber (see Figure 2-3) is that portion
of the rocket motor wherein the propellants are
2-4.1.1. The Injector. The injector is ordinarily burned. Ordinarily, the combustion pressure is
located a t the fore end of the rocket engine. Its between 300 and 1000 psia. The combustion
function is to introduce the propellants into the chamber must be of sufficient volume for com-
combustion chamber through several injection pleting the processes of atomizing, mixing,
orifices, and to meter, atomize, and mix them so igniting, and burning the liquid propellants by
they will burn smoothly and release their maxi- the time the gases arrive a t the entrance to the
mum thermochemical energy. If wo and @, exhaust nozzle. The stay, or residence time for
denote the oxidizer and fuel flow rates respec- propellants in the combustion zone (a region
tively, then the mixture ratio is T = @"/w,. which is not well defined) depends upon the
@, ,,'!l and T depend upon the areas of the volume of the combustion chamber. In general,
injection orifices A , their discharge coefficients C,!, the more reactive the propellants the smaller the
and the differential pressures Ap acting upon required stay time. Since the rate of reaction
them. In general, the weight rate of flow of an increases with the combustion pressure, increasing
incompressible fluid W , having the specific weight the combustion pressure reduces the necessary
y, is given by stay time, other conditions being equal.
ESSENTIAL FEATURES OF ROCKET ENGINES ORDP 20-282
i3
c
8
C
t9,
Y
9,
w
E
2
Y
c
9,
-
Y
O
I-
._
c
P
3
17
ORDP 20-282
Conditions in the combustion chamber are quite mately 3 to 4 times that for the combustion
complex. At the injector there is a high degree of chamber. (14, 15) The critical region is the throat
heterogeneity, since the liquids are being injected section where the heat flux is between 3 and 4
into turbulent hot gases. At the nozzle end, times the overall value for the nozzle. In some
assuming complete combustion, only gases are cases it may be necessary to augment regenerative
flowing downstream. Consequently, there is a cooling of the throat section with some form of
small pressure gradient in the direction of the gas internal cooling such as film cooling. (16, 17)
flow, signifying that the pressure, density,
temperature, and velocity of the gases vary from 2-4.2. Means for Pressurizing Liquid Pro-
the injector to the nozzle end. (10) pellants. There are three principal systems for
Because weight is at a premium in the case of forcing liquid propellants from the propellant
vehicles such as ballistic missiles it is essential that tanks into the thrust cylinder: stored gas pres-
the combustion chamber be of the smallest size surization, chemical gas pressurization, and
that will give the required stay time for complet- turbopump pressurization.
ing the combustion of the propellants. It can be
shown that a practical parameter. which is a 2-4.2.1. Stored Gas Pressurization. Figure 2-5
measure of the stay time is the so-called charac- illustrates schematically the principal elements of
teristic length L*, which is defined by, (1, 5 , 11) a stored gas pressurizing system. A gas such as
nitrogen or helium is stored under pressure (1800
L* = Volume of combustion chamber to 3000 psia) and used for pressurizing the
Area of throat of the exhaust nozzle (2-3)
propellant tanks. The system is simple and
In calculating the value of L* for a motor it is reliable. Gas is supplied to the propellant tanks at
customary to include in the combustion volume a regulated pressure which maintains the propel-
all of the volume between the injector face and lant flow rates a t the desired values. The gas
the throat section of the nozzle. The minimum pressure in each propellant tank exceeds the
usable value of L* is determined experimentally. combustion pressure by the sum of the pressure
In the case of high performance, relatively long drops in the propellant feed line and the injector.
duration engines such as those employed for Consequently, the propellant tanks must be
propelling ballistic missiles, the interior surfaces designed to withstand relatively high pressures.
of the thrust cylinder must be cooled. Current It is essential that the pressurizing gas shall not
practice is to use either the oxidizer or the fuel as react chemically with, or dissolve in, either the
a coolant before it is injected into the thrust fuel or the oxidizer. Where one or both of the
cylinder. This method of cooling is termed propellants is a liquefied gas, such as liquid
regenerative cooling. (13, 16) With regenerative oxygen, the pressurizing gas must not condense
cooling it can be assumed that there is no loss of when it comes in contact with the liquefied gas.
heat from the system. It is essential that the The stored gas pressurizing system is most
cooling load imposed upon the regenerative cool- applicable to either short-duration or small thrust
ant be smaller than that which will cause it to rocket engines because of the large weights of the
boil in the coolant passages. (13) The combustion high pressure tanks for the stored gas and for the
chamber should, therefore, be designed so that its propellants. It may find application to ballistic
surface exposed to the hot combustion gas is the missiles of relatively short range (up to approxi-
smallest compatible with the required value of L* mately 75 mi) where simplicity and reliability are
for best performance. more important than missile weight.
The weight of pressurizing gas required for a
2-4.1.3. The Exhaust Nozzle. The throat area given set of operating conditions depends upon
of the exhaust nozzle determines the combustioii the molecular weight and specific heat ratio for
pressure, the rate at which propellants are con- the stored gas. (5) Thus, the weight of helium
sumed, and the thrust. It is essential that the required in a given case, compared to air or nitro-
nozzle he cooled adequately. Experiments show gen, is approximately 65 percent. The decrease
that the overall heat flux for the nozzle is approxi- in the weight of stored gas achieved by using
18
ORDP 20-282
REMOTE REMOTE
OPERATED CHECK VALVES OPERATED
VENT VENT
VALVE VA LV E
FILLING FILLING
CAP \ CAP
CONTROLLED
0x1 DI ZER FUEL

TANK TANK
REMOTE
CONTROLLED
BLEED
VALVE
R EMOTE CONTROL LED

BIPROPELLANT VALVE
DRAIN DRAIN
VALVE VALVE
RESTR IC TOR
FOR ADJUSTING
MIXTURE R A T I O
Figure 2-5. Stored Inert Gas Pressurization System for a Liquid Bipropeflant Rocket Engine
19
ORDP 20-282
helium has an insignificant effect, however, on the minimum. The pumps are usually centrifugal
weight of the pressurizing system because the pumps with radial bladed impellers of high specific
weights of the stored gas and propellant tanks are speed design and operate with high fluid velocities
practically unchanged. a t their entrance sections. (18, 19, 20) To avoid
cavitation, which occurs when the static pressure
2-4.2.2. Chemical Gas Pressurization. I n this in the flowing fluid is smaller than its vapor
system the pressurizing gas is generated as it is pressure, the propellants must be pressurized. (21)
used, thereby essentially eliminating the weight Hence, the selection of the pump speed requires
of the high pressure tank for storing the pressur- optimization of two influences: 1. the decreasing
izing gas. This gas is produced in a special weight of higher speed pumps, and 2. the increas-
generator either by reacting liquid bipropellants, ing weight of the gas pressurizing apparatus
or decomposing a monopropellant such as hydra- required for minimizing cavitation effects.
zine, or by burning a solid propellant. Irrespective I n most turbopump systems the gases for
of the method employed, it is important that the operating the turbine are produced in a separate
pressurizing gas shall not react either chemically gas generator either by reacting suitable propel-
or physically with the liquid propellants. More- lants or by decomposing a monopropellant. The
over, the gas temperature must be low enough to gases must be supplied a t a temperature which
preclude structural problems due to heating. the turbine blades can safely withstand.
Low temperature gases which will not react I n cases where the propellants burned in the
chemically 1vit.h the propellants can be obtained gas generator are the same as those burned in the
by employing two gas generators; one for pres- thrust cylinder, the mixture ratios must be either
surizing the oxidizer, and the other the fuel. The fuel-rich or oxidizer-rich in order to limit the gas
former is operated rich in oxidizer and the latter temperature to approximately 1800°F. If the fuel
rich in fuel. is a hydrocarbon and the gases are fuel-rich,
problems due to carbon depositing in critical
2-4.2.3. Turbopump Pressurizing System. The passages of the gas generator and turbine are apt
weight limitations of either the stored gas or the to be encountered. If the gases are oxidizer-rich
chemical gas pressurizing systems are removed by severe corrosion problems may be met.
employing a turbopump pressurizing system. This Gases produced by decomposition of high
consists of propellant pumps driven by a turbine strength peroxide (HTP) for operation of the
which is powered by gases produced in some form turbine consist of steam and oxygen a t less than
of gas generator, as illustrated in Figure 2-6. As 1000°F.
the thrust of the rocket engine is increased, there 2-5. ESSENTIAL COMPONENTS OF SOLID
is a reduction in the operating duration for which PROPELLANT ROCKET MOTORS
the turbopump pressurizing system becomes
lighter than the inert gas pressurizing system; for Usually the design of a solid propellant is
example, for a 5000 lb thrust engine the operating hampered by the need for satisfying certain
duration is approximately 25 sec and for a 50,000 dimensional, weight, burning time, and perform-
lh thrust engine it is approximately 7 sec. Turbo- ance specifications. T o meet them the designer
pump pressurization is particularly suitable in the has the freedom of specifying the propellant
case of liquid rocket engines which must develop formulation, the configuration .of the propellant
either large thrusts, or operate for long durations, grain, and the method of supporting it in the
or both. This type of engine is particularly rocket motor. (22) That freedom gives a great
adaptable t o the propulsion of intermediate and deal of flexibility to the design of solid propellant
long range ballistic missiles. grains. By optimizing the combination of these
Because of the importance of low weight in the variables the maximum performance is obtained.
liquid propellant engines for ballistic missiles, the (23)
turbines and pumps must be light in weight. The general features of a solid propellant rocket
Small turbines and pumps are generally operated motor were presented in paragraph 2-1. It is seen
at high speeds in order to hold weight to a that the essential components of such a motor are:
20
PRESS1 R IZ G GAS (N2)
n I
1 I
I
I
GAS GENERATOR
/
x
I FUEL PUMP
'2N I
7 I
I
I
~ FUEL I
I
,I ~ FUEL PUMP I
I
I
I OXIDIZER PUMP
I
1 \\ I ALTERNATIVE ARRANGEMENT
I PUMPS AND TURBINE
L - - - - - - - - - - - - - - - --
TURBINE THRUST
INJECTOR
CHAMBER
L
- OXIDIZER PUMP
Figure 2-6. Schematic Diagram of a Turbopump Arrangement for Pressurizing a

Liquid Bipropellant Rocket Engine
ORDP 20-282
1. the solid propellant grain, 2. the exhaust nozzle, grain is termed the port area, and is denoted
3. the casing, and 4.the igniter. by Ap. Thus
Ap = Ac - A G = port area (2-6)
2-5.1. Solid Propellant Grain Configurations.
The burning of a solid propellant surface occurs If A , denotes the area of the throat of the
in parallel layers. If one assumes a constant area exhaust nozzle, then
for the nozzle throat A,, the relation between the
combustion pressure p , and the area of the burning Ept =-
A P_--
- Ac-AG - port-to-throat ratio ' (2-7)
surface Sp,then (2) At At
p, = constant (2) I / (1- n)

(2-4)
Figure 2-7 illustrates schematically some typical
solid propellant grain configurations.
the quantity n is called either the burning rate
exponent or the pressure index, and is always less 2-5.1.1. End-Burning(Cigarette-Burning)Grain.
than unity. If the ratio S,/At remains constant Figure 2-7a illustrates this type of grain. It is a
during the burning period, then p, remains restricted-burning (inhibited) grain and gives
constant. neutral burning; the burning surface recedes
parallel to itself with no change in area. The
Since l/(l-n) may have values ranging from asphalt-base propellants used in JATO units were
approximately 1.67 to 5.0 it is clear that a small end-burning grains. In the earlier designs the
change in the burning area can cause large end-burning grain was bonded to the case with a
changes in the combustion pressure. In the case of rubbery pitch liner, while in later designs the
solid propellant rockets for ballistic missiles, as circumferential surface and the bottom end were
well as for most other applications, it is desirable inhibited from burning and the grain was sup-
that the combustion pressure remain sensibly ported in the case with an annular space between
constant during the burning period.' the case and the grain.
Grain design is based on obtaining the burning
characteristics to give the desired curve of com- 2-5.1.2. Single-Perforated or Tubular Grain.
bustion pressure pc,as a function of the burning Figure 2-7b illustrates this grain configuration.
time T b . A grain which burns so that p, does not The ends of the grain are inhibited from burning,
vary with time, is said to give neutral burning; so that the length of the grain remains constant
one for which p, increases with Tb gives progressive during the burning period. Since the linear
burning; and one for which p, decreases with 71, burning rates for the inner and outer burning
gives regressive burning. Most grain configura- surfaces may be assumed to be equal, the inner
tions are based on shapes which intrinsically give diameter of the grain d i increases at the same rate
either neutral burning or progressive burning. that the outer diameter do decreases, as a conse-
If A G denotes the cross-sectional area of the quence the grain gives neutral burning. The
propellant grain and AC that of the case surround- difference do - d i = 2wt, where w t is called the
ing it, then web thickness of the grain. The duration of
burning is controlled by wt.
E P = - =the propellant loading ratio (2-5) If the outer surface (including the end surfaces)
Ac
of a single perforated grain is inhibited from
To obtain the high performance required for burning, then burning occurs only on the inner
ICBM and IRBM missiles the propellant loading surface. Such a grain is called an internal-burning
ratio should be approximately 0.90. tubular grain and gives progressive burning.
The cross-sectidnal area of the flow passage
through which the combustion gases flow past 2-5.1.3. Case-Bonded Internal Burning Star
the burning surface or surfaces of the propellant Grain. Figure 2-7c illustrates this form of grain.
It is a development from the case-bonded internal
1 For a detailed discussion of the burning characteristics burning tubular grain. The internal star con-
of solid propellants, see Chapter 6. figuration has great design flexibility since the
22
ESSENTIAL FEATURES O F ROCKET ENGINES
ORDP 20-282
BURNING SURFACE CASE

\ I
(a)
END
BURNING
GRAIN SUPPORT
(b)
TUBUL AR
(C)
INTERNAL
BURNING
STAR
(d) PORT ROD

ROD AND
TUBE
(el
CRUCI FORM
LEGEND
CHARGE
RESTRICTION (INHIBITOR)
(Taken from Reference 71
Figure 2-7. Typical Solid-Propellant Grain Configurations
23
ORDP 20-282
number of star points, the star diameter, the metals for rocket engine cases are aluminum alloy
angles of the star points, and web thickness can X7178, and 6A1-4V titanium alloy. Cases made-
be varied by the designer. The grain can be from spun fiberglass bonded with an epoxy resin
designed so it gives either neutral burning, pro- have been investigated experimentally and look
gressive burning, or regressive burning, and the promising. Table 2-1 compares the strength-to-
case -bonding provides strong support for the weight ratios for three different metals.
grain and protects the case from the hot com-
bustion gases. This grain configuration is widely TABLE 2-1. COMPARISON OF MATERIALS
used in large solid propellant rocket motors of the FOR SOLID PROPELLANT ROCKET CASES
type suitable for propelling ballistic missiles. (Reference 9 )
Ratio of
2-5.1.4. Rod and Tube Grain. Figure 2-7d Strength to
Min. Yield Specific Specific
illustrates the rod and tube grain. The burning Strength Weight Weight
surfaces are the exterior surface of the rod and Material (psi) (Ib/in") (in)
the internal surface of the tube, the latter being 1130 Steel 150,000 0.285 527,000
case-bonded. As burning proceeds the burning 170,000 .285 596,000
area of the rod decreases and that of the tube 200,000 .285 700,000
X7178 Aluminum
increases, and if their burning rates are equal, Alloy 82,000 0.100 820,000
neutral burning can be obtained. By using 6A1-4V Titanium
different propellant formulations for the rod and Alloy 140,000 0.16 875,000
160,000 .16 1,000,000
the tube the pressure-time curve can be controlled
within practical limits to give any desired varia- According to reference 9 , it should be possible
tion of the combustion pressure as a function of with good design to achieve a ratio of propellant-
time. to-engine weight of approximately 0.93.
2-5.3. The Exhaust Nozzle. In current designs
2-5.2. The Case or Housing. The case comprises the exhaust nozzle operates uncooled and its
a closed fore cap, an aft cap to which the exhaust interior surfaces must be protected from the hot
nozzle is attached, and a motor tube which gases, particularly in the region of the throat. A
connects the fore and aft caps. Considering only composite construction is employed in many
case-bonded motor designs (since they are most designs; the nozzle section in contact with the
appropriate for ballistic missiles), the fore cap and gases being made from carbon or some form of a
the motor tube can be of light weight construction ceramic. In most engines the weight of the nozzle
because they are protected from the hot com- is a substantial fraction of the total weight of the
bustion gases. To keep the weight of the aft cap metal parts.
to a reasonable value the interior of that part is In the effort to reduce nozzle weight new ma-
covered with an insulating material. Since there terials and new high temperature insulating
should not be any permanent deformation of the coatings and materials are being investigated. For
casing after it has been subjected to the hydro- a coating to be satisfactory it must have good
static test which is normally specified, the stress adherence to the inner surface of the nozzle and
during that test should not exceed the yield point good resistance to erosion.
of the material. Since the cold strength of the
chamber can be used for design purposes, the 2-5.4. The Igniter. The igniter for a solid
design condition is selected so that the stress in propellant rocket usually comprises three main
the material is equal to its yield stress a t the components: some form of electrically fired squib
maximum combustion -pressure which may be for initiating combustion, the main igniter charge,
expected, multiplied by a suitable factor of safety. and the case. The squib consists of two lead wires
The criterion of material selection is the which are insulated from each other and which
strength to weight ratio of the material. Currently, are connected together by a fine high resistance
the most popular material for the metal parts is wire. The latter is surrounded by an explosive or
steel, such as heat treated 4130. Two promising combustible material, called the primary charge,
24
ESSENTIAL FEATURES O F ROCKET ENGINES ORDP 20-282
which is sensitive to heat. When the wire is heated miles where the absolute pressure of the atmos-
electrically the primary charge is ignited. Suffi- phere is practically zero.
cient heat must be released by the primary charge
to ignite the main igniter charge. 2-6. THRUST CUT-OFF AND THRUST
Various materials are used as the main igniter VECTOR CONTROL
charge, from black powder to mixtures of metals
with an oxidant such as potassium perchlorate. The range and accuracy of a rocket propelled
Metals which have been investigated in making ballistic missile are governed by the attitude of
main igniter charges are aluminum, boron, the missile and its velocity at the instant that
magnesium, and zirconium. (24) the thrust is terminated. (See the Trajectories
It is essential that the igniter initiate the Volume of this series) It is important, therefore,
combustion of the solid propellant under the that those variables have the correct values
conditions expected in the actual operation of the required for reaching the target. Consequently, all
rocket engine. Moreover, the ignition delay should rocket engines for propelling ballistic missiles
be short and also reproducible. Since the speeds must incorporate means for achieving thrust
of the chemical reactions occurring in an igniter termination, more commonly called thrust cut-off,
decrease with decrease in the absolute pressure, at the correct instant. In addition, they must be
adequate precautions must be taken to insure equipped with controls for altering the direction
that in the case of a multistage ballistic missile of the line of action of the propulsive thrust.
satisfactory ignition can be obtained a t very high Means for achieving the latter are termed thrust
altitudes, for example, more than one hundred vector control.
2-7. REFERENCES
1. Zucrow, M. J., Aircraft and Missile Propul- 6. Stosick, A. J., Aircraft Fuels and Propellants,
sion, Vol. I, John Wiley and Sons, New York. Report of the AAF Scientific Advisory
1958. Comm., Part IV, May 1956.
2. Zucrow, M. J., et all Aerodynamics, Propul- 7. Zucrow, M. J., Aircraft and Missile Propul-
sion, Structures and. Design Practice (Prin- sion, Vol. 2, Chapter 10. John Wiley and
ciples of Guided Missile Design series), Sons, New York. 1958.
Propulsion Section. D. Van Nostrand Co.,
Princeton, N. J. 1956. 8. Arendale, W. F., Fuel-Binder Requirements
for Composite Solid Propellants, Industrial
3. Meneghelli, H., First Steps in Rocketry, U.S. and Engineering Chemistry, Vol. 48, pp.
Naval Ordnance Test Station, Inyokern, 725-6. April 1956.
Calif., NOTS 608, 22 December 1952.
9. Wiggins, J. W., The Use of Solid Propellant
4. Zucrow, M. J., Les moteurs de fusee ti proper- Engines for. Achievement of Super Velocities,
gols liquides (Liquid Propellant Rocket Jet Propulsion, Vol. 26, pp. 1084-7. Decem-
Motors), Fusees et Recherche Aeronautique ber 1956.
Bull. de1’A.E.R.A.) Vol. 1, No. 1, June 1956.
10. Baxter, A. D., Combustion in Rocket Motor,
5. Sutton, G. P., Rocket Propulsion Elements,. Journal of British Interplanetary Society.
John Wiley and Sons, New York. ,1949. May 1951.
25
ORDP 20-282
11. Crawford, B. L., Rocket Fundamentals, 18. Thatcher, A. G., The Turboroclcet Propellant
OSRD 3992, 1944. Feed System, American Rocket Societyj
Journal, No. 82, p. 126. September 1950.
12. Seifert, H. S., Twenty-Five Years of Rocket
Development, Jet Propulsion, Vol. 25, pp. 19. Ross, C. C., Principles of Turbopump Design.,
594-603, 632-3. November 1955. American Rocket Society, Journal, No. 84,
pp. 21-33. March 1951.
13. Bartz, D. R., Factors Which Influence the
Suitability of Liquid Propellants as Rocket 20. ROSS,C. C., and G. Barnerian, Some Aspects
Motor Regenerative Coolants, Jet Propulsion of High-Suction Specijic-Speed P u m p In-
Laboratory, California Institute of Tech- ducers, American Society of Mechanical
nology, Memorandum No. 20-139, Decem- Engineers, Transactions, pp. 1715-21. No-
ber 28, 1956. vember 1956.
14. Zucrow, M. J., and C. M. Beighley, Experi- 21. Church, A. H., Centrifugal Pumps and
mental Performance of W F N A J P S Rocket Blowers, John Wiley and Sons, New York.
Motors at Ciferent Combustion Pressures, 1944.
American Rocket Society, Journal, Vol. 22,
22. Vogel, J. M., A Quasi-Morphological A p -
pp. 323-30. November-December 1952.
proach to the Geometry of Charges for Solid
15. Bartz, D. R., A Simple Equation for Rapid Propellant Rockets, Jet Propulsion, Vol. 26,
Estimation of Rocket Nozzle Convective Heat pp. 102-5. February 1956.
Transfer Coeficients, Jet Propulsion, Vol. 27,
23. Stone, M. W., A Practical Approach to Grain
pp. 49-51. January 1957.
Design, Bulletin, 13th Mtg., JANAF Solid
16. Zucrow, M. J., Liquid Propellant Rocket Propellant Group, Vol. 111, June 1957.
Power Plants, American Society of Mechan-
ical Engineers, Transactions, Vol. 69, pp. 24. Zeman, S., The Ignition of Solid-Propellant
847-57. 1947. Rockets at High Altitudes, Bulletin 13th Mtg.,
JANAF Solid Propellant Group, Vol. 1,
17. Zucrow, M. J., and A. R. Graham, Some
June 1957 (Confidential).
Considerations of Film Cooling for Rocket
Motors, Jet Propulsion, Vol. 27, pp. 650-6.
June 1957.
26
Chapter 3
CRITERIA OF ROCKET ENGINE PERFORMANCE
3-1. THRUST EQUATION

When a rocket engine (liquid or solid fuel) is rocket engine and a solid propellant rocket motor
operated under steady conditions the variables with an end-burning grain. The combustion gases
p,, t,, p,, and V, do not change with burning time‘ arrive at the entraiice section of the exhaust
(see Figure 2-3). The thrust developed by the nozzle with the static pressure p,, the static
rocket engine is the resultant axial component of temperature t,, and the velocity V,. In flowing
the static pressure forces acting upon its interior through the exhaust nozzle the gases are ex-
and exterior surfaces. The static pressures acting panded, and they arrive at the exit section of the
upon the interior surfaces depend upon the rate nozzle, having the cross-sectional area A,, with
at which propellants are burned, the thermo- the velocity V,, and the thermodynamic prop-
chemical characteristics of the gases produced by erties p , and t,. The kinetic energy associated
their combustion, the area of the throat of the with the jet gases is V:/2g. If h, denotes the
exhaust nozzle, and to a ,small extent upon the static specific enthalpy of the gases entering the
static pressure of the environment into which the exhaust nozzle in Btu/lb, and V , their velocity in
combustion gases are ejected. In any case the ft/sec, then
internal static pressures are several times the
external static pressures. If F denotes the thrust, h, + --V: = H , = stagnation specific (3-2)
and since, in general, the forces acting normal to 2gJ enthalpy of gases en-
the longitudinal axis of the thrust cylinder (the tering exhaust nozzle
x-axis) do not contribute to the thrust, (1,2) then (in Btu/lb).
F = J6, (Pifm +~o(P”s)” (3-1)

The exhaust velocity V, is accordingly2
V , = [2gJ(Hc-hc)J“2 zz [2gJ(hc--1~,)]”2 (3-3)

where p i = the static pressure acting on the
interior surface of the rocket engine where J = the mechanical equivalent of heat =
Si 778 ft-lb/Btu.
p, =the atmospheric pressure acting on
3-1.2. Nozzle Divergence Coefficient. Only the
the exterior surface of the rocket
x-component (see Figure 3-1) of the velocity Tr,,
engine So
denoted by V,,, contributes to the thrust de-
z - denotes that the axial component
veloped by the thrust cylinder. If X is the diver-
(z-component) is to be evaluated.
vergence coefficient for the nozzle, then
It is difficult, if ‘not impossible, in an actual
case to evaluate the integrals in equation (3-1). ve,= XV, (3-4)
The thrust F is, therefore, calculated by applying
If a denotes the semi-divergence angle of the
the momentum theorem of fluid mechanics to the
exhaust nozzle (usually between 12 and 20 deg),
gases flowing through the thrust cylinder (2) (see
then (3)
paragraph 3-1.3).
1
3-1.1. Velocity of Gases Crossing Exit Section X =-
2
+ -21cos a = divergence coefficient (3-5)
of Nozzle. Figure 3-1 illustrates the thermo- of the exhaust nozzle.
dynamic conditions for a liquid bipropellant
?Since V , is ordinarily quite small compared to Ve, the
‘Steady conditions are assumed in all of the discussions static values of the thermodynamic properties will be
unless otherwise specifically stated. employed.
27
ORDP 20-282
rL1
-F
COMBUSTION CHAMBER
GAS VELOCITY
STATIC ENTHALPY h,
IaJ liquid Propellant Rocket Engine
BURNING I EXIT SECTION
G A S PRESSURE
GAS VELOCITY
STATIC ENTHALPY h,
IbJ Solid Propellant Rocket Motor with End-Burning Grain
(Taken from Reference 2 1
Figure 3-1. Thermodynamic Conditions for liquid and Solid Propellant Rockets
28
CRITERIA OF ROCKET ENGINE PERFORMANCE ORDP 20-282
To calculate the performance of a propellant Hence

system it is necessary to 1. calculate the com- F = k2xVe + (Pe-po)Ae (3-7)
bustion temperature t, corresponding to p,, and
Equation (3-7) shows that the thrust is com-
2. calculate the exhaust velocity V,.
posed of two parts
(a) the momentum thrust ( h X Ve),and
3-1.3. Calculation of Thrust by Momentum
(b) the pressure thrust (pe--p,)A,
Theorem. The momentum theorem of fluid
Since the momentum thrust is ordinarily several
mechanics states that the time rate of change of a
times the pressure thrust, the thrust developed
bounded mass system of discrete particles ( a body
by a rocket engine is primarily a function of the
of Jluid for example) in any direction i s equal to the
mass rate of flow (consumption) of propellants.
resultant of the external forces acting on the bound-
It is apparent from equation (3-7) that under the
aries in the speciJied direction and i s independent
assumed steady operating conditions p , and p,
of the internal forces. (2) The mathematical state-
are constants, so that the thrust increases with
ment of this principle is
the operating altitude of the rocket engine, or
decreasing values of p,, and that the maximum
thrust is obtained when p , = 0.
It is common practice in rocket engineering to
where express the thrust in terms of the weight rate of
AM the change in momentum of the body
=
propellant consumption W = hg.Thus
'v
of fluid.
Fez1dr= the time impulse of the external force F = %
90
V, + (pe-po)Ae (3-74
EZL.
Figure 3-2 illustrates the case where an arbi- where go = 32.174 ft/sec2.
trary propulsion system propels a vehicle through
a fluid medium with the flight speed V,. For 3-2. SPECIFIC IMPULSE
convenience a relative coordinate system is The performance obtained by burning the pro-
employed; the vehicle and its engine are assumed pellants in a rocket engine is expressed in terms of
to be stationary and the fluid flows toward them the specific impulse, which is denoted by I,. Thus
with the velocity V,. The infinite planes S, and XL,
(2, 4,5 )
are perpendicular to the longitudinal axis of the
system; the latter axis is parallel to the x-axis. (3-8)
The plane S , is located far enough from A1 so that
pl = p , = the undisturbed atmospheric pressure. where W, is the total weight of propellants con-
Plane 2 is located so that p z = p , except for the sumed (based on constant gravitational attrac-
area A, crossed by the jet. It can be shown that tion) in the time $dr, and W = d W / d r = the
if X is the force acting on the gases flowing corresponding weight rate of propellant con-
through the engine, the action force causing the sumption.
velocity to increase from V, to Vl; then the The units for I , based on equation (3-8) are
thrust F , the reaction force, is, in general, given seconds. It must be kept in mind, however, that
by (1, 2) I , is independent of the value of gravity. For that
F = 1x1 = k2V2 - h1Vo + (pe-po)Ae (4 reason, I , is sometimes defined by (4)
I n the case of a rocket engine, since it consumes
no air, the entrance momentum flux mlV, = 0. (3-9)
For a rocket engine
where g is the local acceleration due to gravity and
mz = m = m,+mf (b) go is the standard gravitational acceleration
(32.1740 ft/sec2).
From equation (3-4)
If I, is defined by F/m, as is sometimes done,
VZ= Vez = XV, (4 then its dimensions are (ML/T*)/(M/T)= L/T.
555514 0 - 60 - 3 29
ORDP 20-282
TO INFINITY F = THRUST TO INFINITY
I
I-%
I
r
-------hF-
A----- 1 / I
'1 I
Figure 3-2. Application of the Momentum Theorem of Fluid Mechanics to an

Arbitrary Propulsion System
Figure 3-3. Free Body Diagram for a Rocket Propelied Ballistic Missile
30
Equation (3-8) is, however, the most widely used From equations (3-7) and (3-11) it follows that if
definition for I,. the exhaust nozzle operates with complete expan-
The specific impulse I , is basically a property of sion ( p , = p,,), then
the propellants burned in the rocket engine. For
any given solid propellant formulation, or specific vj = xv, = v,, (3-12)
liquid fuel and liquid oxidizer system, a theoretical It should be borne in mind that from the firing
value for the specific impulse can be calculated by test of a rocket engine it is the effective jet velocity
applying the methods of thermochemistry to the Vj and not the exit velocity V, that is computed.
chemical reaction and to the expansion process. By means of equations (3-8) and (3-11) it is
The specific impulse obtained from thermo- readily shown that
chemical calculations will be called the theoretical
specific impulse and denoted by I:. (3-13)
I n the case of a solid propellant rocket motor the
instantaneous rate of propellant consumption Ti7
The weight of propellants consumed in develop-
cannot be measured. The measured specific ing an impulse of 1 lb-sec is called the specific
impulse I , is an average value calcuIated from the
curve of thrust versus burning time (thrust-time
propellant consumption and is denoted by w8.
Thus
curve) and the weight of solid propellant con-
sumed during the burning period.
3-3. TOTAL IMPULSE

If the thrust-time curve obtained from firing a 3-5. THRUST COEFFICIENT
rocket engine is integrated over the burning dura- When a rocket engine is fired on the test stand
tion, the result is called either the total impulse or it is relatively easy to measure accurately the
briefly the impulse, and is denoted by I . Thus combustion pressure p,, the thrust F, the nozzle
I = /'>& = I , @ T ~= W J , (lb-sec) (3-10)

throat area A t at the beginning and end of the run,
and the propellant consumption rate W = F/18.
The aforementioned variables are related by
It follows from equation (3-10) that i,f all other
factors remain unchanged for a given rocket A @I8
F =C F ~ ,= ~ (3-15)
engine, the same total impulse can result from a
from which one obtains
small thrust over a long time or from a large
thrust over a short time.
CF = -- - the thrust coefficient (3-16)
P A1
3-4. EFFECTIVE JET VELOCITY
Strictly speaking the value of A t that should be
I n a static firing test of a rocket engine (liquid or
used in equation (3-15) is the throat area during
solid) the thrust F is readily measured. Also the
the firing run. Since that area cannot be measured,
average rate a t which the propellants are con-
the value of At used in the equation is one that is
sumed W,/T, can be determined with a high degree
estimated from the value of A t measured prior to
of accuracy. It is very difficult, however, if not
the firing run and the temperature of the nozzle
practically impossible, to make an accurate
material.
measurement of the exit pressure p , (see Figure
Curves of CF as a function of p , obtained
3-1). It is convenient, therefore, to introduce a
experimentally for several different mixture ratios
fictitious velocity Vj, calIed either the effective jet
velocity or the effective exhaust velocity, so that
T = @,,/w, and for different propellant combina-
tions, comprise the basic data for establishing the
the following simple equation can be written for
throat area of the exhaust nozzle. When experi-
the thrust. Thus
mental data are unavailable, theoretical values of
CF,denoted by C;, can be calculated by thermo-
dynamic methods (see paragraph 4-5.5).
31
ORDP 20-282
3-6. WEIGHT FLOW COEFFICIENT Thus, the characteristic velocity c * can be ex-
pressed in terms of t.he parameters I,, C F , C,,., Wsas
It is convenient to express the propellant con-
sumption rate %' in terms of p,, A , , and a weight
flow coefficient C,,. Thus
(3-17) 3-8. WEIGHTS AND IMPULSE-WEIGHT

RATIOS
For a given propellant combination it is cus- The take-off weight of a rocket propulsion sys-
tomary to obtain experimental curves of C, as a tem, denoted by WE0, is the sum of the weights of
function of p , from firings of small rocket engines. the propellants W,,the complete rocket engine
The curves give the information required to pre- WE,and the propellant tanks WT.
dict the propellant consumption rate for develop- If the engine develops a thrust F for the burning
ing any specified thrust with those propellants. time 7 6 , then the impulse-weight ratio for the
From equations (3-15) and (3-17), it is seen t,hat rocket propulsion system, denoted by I/ WEO, is
C F and C,, are related to I , by given by
I CF
-- (3-18)
, - C,"
3-6.1. Mass Flow Coefficient. In a manner simi- If 8' is constant, then I = Fq,. The impulse-
lar t,o equation (3-17), a mass flow coefficient., weight ratio is a criterion of the overall design of
denoted by C,i,, can be defined. Thus the rocket engine, and the largest possible value is
desired. For a solid propellant rocket motor, the
(3-19) tank weight WT = 0.
The gross weight or take-off weight of the com-
where m is the mass rate of propellant con- plete ballistic missile, denoted by Wo,is composed
sumption. of the weight of the inert metal parts of the
missile, denoted by W,,f, the weight of the propel-
lants W,, and the weight of the payload WU.Thus
3-7. CHARACTERISTIC VELOCITY
The characteristic velocity denoted by c* is wo = WM + w, + wu (3-24)
frequently employed for comparing the perform-
ance of different rocket engines. This parameter The empty weight of the missile, denoted by
measures the effectiveness with which the chemical WI,
is given by
reaction is accomplished in the combustion
chamber. c* is defined by wr=WM+ wu= wc+ WE+ wc+ ws+ wu (3-25)
where WC = weight of control apparatus
WE = dry weight of propulsion engine
WC = weight of guidance equipment and
its housing
The experimental determination of c* can be
accomplished by means other than measurement WS = weight of structure of the missile
of the thrust developed by the rocket engine. WU = weight of payload (the useful load).
Substituting F = C F p , A t into equation (3-20), For a liquid propellant engine, the engine weight
gives W Eincludes the weights of the propellant tanks,
gas generator equipment, inert gas storage tanks,
the turbopump, plumbing and valves, the cont,rol
(3-21) equipment, and the rocket motor assembly. Fur-
thermore, for liquid engines the propellant weight
32
a t take-off W, includes the weights of all the

auxiliary fluids which are required for operating
the engine.
In the case of a solid propellant motor, the The ratio M , / M o is called the propellant mass
engine weight WE includes the weights of the rat,io and is denoted by f . Thus
cylindrical casing, the fore and aft caps, the ex-
haust nozzles, the restriction (inhibiting) liner, the l = -M- ,- -- Effective propellant
___---mass (3-30)
insulation of the fore and aft cap, thrust termina- Mo Initial mass of vehic!c
tion equipment, and of the means for achieving
From the point of view of achieving a long
thrust vector control. range, the propellant mass ratio should he as large
The impulse-weight ratio criterion can be also as possible.
applied to a complete ballistic missile. The magni-
tude of I/Wo for a given missile depends upon 3-9.2. Vehicle Mass Ratio. The ratio M o / ( M o -
both the specific impulse and density of the LM,)is called the vehicle mass ratio and is denoted
propellant combination. If the volume available by A. Thus
for the propellants is fixed, it is possible to obtain
a larger value for I / WOfrom propellants of high - Initial mass of vehicle
A = (3-31)
density even though they deliver a somewhat mb Mass of vehicle after
smaller specific impulse. It is difficult to generalize consuming propellants
regarding the factors influencing I / WO.Each case where
should be judged on its own merits. M o -M, = mass of missile a t burnout
mb = (3-32)
3-9. MASS RATIOS The mass ratios and A are related by
Certain mass ratios are useful in analyzing the = 1 - l/A (3-33)
performances of ballistic missiles.
3-10. CUT-OFF OR BURNOUT VELOCITY
3-9.1. Propellant Mass Ratio. Consider a rocket A recurring problem in rocketry is the rapid
jet propelled missile a t any instant 7 during its determination of the most suitable rocket jet
powered flight, that is, when ~ < 7 b . For a rocket propulsion system for a given ballistic missile
engine operating under steady conditions the mass application.
rate of propellant consumption riz is constant. Figure 3-3 illustrates schematically a rocket pro-
Hence pelled ballistic missile moving along its trLjectory.
'?h= m/g &!p/7b (3-26) A t any instant 7 <7 6 the following external forces
act upon the missile in the direction of its motion:
The thrust F , also assumed to be constant, is
(a) the aerodynamic drag D
given by
(b) the component of the gravitational force W
F = riZ Vj = Mp V j , h b (3-27)
sin y = ( WO - Wp7)sin y
As the propellants are consumed the total mass (c) the thrust force F .
of the missile decreases. If MOdenotes the mass of The equation of motion (2) for the missile is
the missile a t take-off , then the instantaneous
mass of the missile, denoted by m, at any instant Wo-WP7 dV
-F - D - ( Wo-W,T) sin y (3-34)
during the powered flight (7 <7 b ) is accordingly 9 d7
If A , is the maximum cross-sectional area of the
missile, CD the drag coefficient, p the air densit,y,
and V the missile velocity, then the drag D, is
given by
At the instant when all of the propellants are
consumed, the instantaneous mass of the missile is D = %p C D A V2 (3-35)
given by A detailed discussion of ballistic missile trajectcriea is
presented in another volume of this series.
33
ORDP 20-282
If it is assumed that the propellant consumption The vehicle mass ratio A = hfo/mbis increased
rate is constant, then the thrust F is given by by a decrease in the mass of the inert metal parts
equation (3-1 1). Thus of the engine.
I n the case of booster applications such as JATO
or RATO,' the payload WV is very large and the
ideal burnout velocity is relatively small, so that a
reduction in the metal parts weight of the engine
Equation (3-34) is a non-linear second order
does not give a proportionate increase in V b i . In
differential equation having non-constant co-
the case of a ballistic missile, however, the pay-
efficients. It cannot be integrated directly in
load WUis ordinarily only a fraction of the total
closed form but requires a laborious step-by-step
metal parts weight WAf,and a large value is
process. The quantity generally desired is the
desired for v b i . For that application the engines
velocity of the missile a t the instant when burning
must provide a large value for the impulse-weight
is completed. That velocity is called either the
ratio ( I / WE),and reductions in inert metal parts
cut-off , burnout, or burnt velocity.
weight of the engine gives a significant improve-
For preliminary design purposes, optimization
ment in Vbi.
studies, and evaluating different engines, an exact
solution of equation (3-34) is not needed. 3-10.2. Propellant Weight Loading Density. The
The drag of a rocket propelled missile is pro- ratio of the propellant weight W, to the engine
portional to its cross-sectional area A , but its weight WE is termed the propellant weight loading
mass is proportional to its volume. For large density, or engine weight efficiency, (7) and is
missiles the effect of aerodynamic drag on the denoted by 6,. Thus
burnt velocity is quite small, about 5 percent for a
missile having a take-off weight of approximately
100,000lb. (6) Consequently, for large missiles the
neglect of aerodynamic drag will introduce no It is seen from equation (3-38), that the parame-
serious error especially in view of the assumption ters I/WE and W,/WE are related. Figure 3-4
that the effective jet velocity remains constant, presents I , as a function of I / WE with W,/ WEas
when actually it increases somewhat with the alti- a parameter.
tude. For small missiles, on the other hand, the It can be shown (7) that the effect of propellant
neglect of aerodynamic drag does introduce an weight loading density 6, has a small effect on V b i
error. when the ratio WE/Wu is small, as in booster
applications. On the other hand, in the cases where
3-10.1. Ideal Burnout Velocity. For comparing vbi must be high as for a ballistic missile, a large
the performance obtainable from different propul- value for 6, is essential. (8)
sion engines, a comparison based on assuming no
air resistance and no gravitational force leads to a 3-1 1. DRAG-FREE MAXIMUM ALTITUDE
useful criterion; the ideal burnout velocity v b i ,
also called either the vacuum burnout velocity, or The drag-free maximum altitude is the maxi-
the characteristic velocity. mum height obtainable with a vertical trajectory
It can be readily shown that v b i is given by for the case where there is no drag and no initial
(1, 2, 5) launching velocity. This quantity obtained by in-
tegrating equation (3-34) twice and introducing
several simplifying assumptions is discussed in
greater detail in another part of this handbook
series.
I n terms of the component weights of the missile
(see Paragraph 3-8).
JATO-Jet Assisted Take-Off employing solid propellant
rocket motors. RATO-Rocket Assisted Take-Off em-
ploying liquid propellant rocket engines.
34
0.75 0.85
260
250
24C
2 3C
0
. 220
a3
v)
H
w 210
v)
-I
3
a
z 200
-
-
0
190
-
0
W
180
I70
I60
I50
120 140 160 180 200 220 240 260
x/w,
IMPULSE -WEIGHT R A T I O OF ENGINE
(Taken from Reference 7 )
Figure 3-4. Specific Impulse as a Function of the Impulse-Weight Ratio for

Different Values of Wp/WE
35
ORDP 20-282
3-1 2. REFERENCES 5 . Sutton, G. P., Rocket Propulsion Elements,

2nd Ed., John Wiley and Sons, Kern York.
1. Zucrow, M. J., Principles of Jet Propulsion 1956.
and Gas Turbines, Chapter 12. John Wiley
and Sons, New York. 1948. 6. Tsien, H. S., A Method for Comparing the
Performance qf Power Plants for Vertical
2. Zurrow, M. J., Aircraft and filissile Propul- Flight, American Rocket Societ,y, Journal,
sion, Vol. 1, Chapter 2; Vol. 2, Chapter 10. Vol. 22, NO. 4, July-August 1952, pp. 200-3,
John Wiley and Sons, New York. 1958. 212.
3. Malina, F. J., Characteristics of a * Rocket 7. Wiggins, J. W., The Use of Solid Propellant
Motor Unit Based on Theory of Perfect Gases, Engines for Achievement of Super Velocities,
Franklin Institute, Journal, Vol. 230, No. 4, Jet Propulsion, Vol. 26, No. 12, December
October 1940, pp. 433-54. 1956, pp. 1084-7.
4. Letter Symbols for Rocket Propulsion, Jet 8. Ritchey, H. W., Solid Propellants and the
Propulsion, Vol. 25, No. 11, November 1955, Conquest of Space, Astronautics, Vol. 3,
pp. 636-45. No. 1, January 1958, pp. 39-41, 75-7.
36
Chapter 4
THERMODYNAMIC RELATIONSHIPS FOR ROCKET ENGINES
4-1. THERMODYNAMIC PROPERTIES 2. The velocity of the gases in the combustion

REQUIRED FOR CALCULATING chamber is negligibly small compared to the
THEORETICAL PERFORMANCE velocity of the gases crossing the exit
CRITERIA section of the exhaust nozzle.
The thrust developed by a rocket engine oper- 3. The flow through the nozzle is isentropic
ating under steady state conditions is practically (dX = 0).
proportional to V,, the velocity of the gaseous jet 4. The gases are expanded completely to the
crossing the exit section of the exhaust nozzle (see surrounding atmospheric pressure p,; that is,
Paragraph 3-1.3). The kinetic energy of that jet the pressure, p,, in the exit section of the
( Ve2/2g), in the case of a chemical rocket engine, is nozzle is equal to p,.
derived from the energy released by the chemical 5. The gases behave as perfect gases, so that
reaction (combustion) of the propellants fed into pv = Rt.
the combustion chamber. I n general, the chemical 6. One of the two following assumptions is
reaction is exothermic and is accompanied by gen- generally introduced:
eration of large quantities of high temperature a. The equilibrium composition of the gases
gases, their pressure being governed by the area of in the combustion chamber is unaltered
the throat of the exhaust nozzle and the rate a t during the expansion process in the nozzle.
which the propellants are supplied to the rocket Calculations employing that assumption
engine. are said to be based on frozen equilibrium,
As these gases flow through the exhaust nozzle or frozen flow.
they are expanded, under substantially adiabatic b. Chemical equilibrium is maintained
conditions, so that the gas temperature falls in the throughout the expansion process; the
direction of flow; that is, the gas temperature a t composition and molecular weight of the
the exit section, denoted by t,, of the nozzle is gas changing because of the chemical re-
lower than i t is a t the entrance section, denoted by actions occurring during the expansion
t,. Since the enthalpy of a homogeneous mixture of process. Calculations employing this as-
gases is a function of the gas temperature, the sumption are said to be based on either
gases experience an enthalpy decrease in flowing equilibrium flow, shifting, mobile, or main-
through the exhaust nozzle. The transformation of tained equilibrium.
that enthalpy decrease into kinetic energy of the Since the flow is assumed to be isentropic, the
gaseous jet ( Ve2/2g)is given by equation (1-21). velocity of the gases crossing the exit section of the
The calculation of V, is, therefore, the first step in exhaust nozzle is denoted by V,’ and called the
computing the desired performance criteria. isentropic exit velocity. If h, denotes the specific
enthalpy of the gases a t the entrance to the ex-
4-1.1. Isentropic Exit Velocity and Theoretical haust nozzle (t, their corresponding gas tempera-
Specific Impulse. I n order to compute the per- ture is called the combustion temperature), he’ the
formance criteria for a rocket engine from thermo- specific enthalpy of the gases a t the exit section of
dynamic considerations, the following assumptions the exhaust nozzle (te’ the corresponding gas
are introduced: (4) temperature is called the isentropic exit tempera-
1. The flow through the nozzle is steady and ture), p , the static pressure corresponding to t,
one-dimensional, and the velocity, V,, of the (called the combustion pressure), and p , the static
gas crossing the exit section (Area A,) is pressure corresponding to te’ (called the exit
parallel t o the axis of the exhaust nozzle. pressure), then Ve’is given by equation ( 4-1 )
37
ORDP 20-282
V,' = 2/2gJ(hc-h,') = d 2 g J E, t, 2, (4-1) tropic exit velocity Ve', and from it the theoretical
or specific impulse 18',the thermodynamic properties
V,' = ( 2 g m
k
R,$[1 - (z) ]
(k-l)lk
(4-2)
of the combustion gas a t the entrance and exit
planes of the exhaust nozzle must be determined.
The steps involved in obtaining that thermo-
dynamic data are as follows:
I n equation (4-2) the value of k and Ei are
suitable average values for the isentropic expan- 1. The enthalpy of reaction, AH,.
sion of the combustion products from the state 2. The combustion temperature, also called the
(t,, p,) to (L', p J . It is necessary, therefore, to give adiabatic flame temperature, t,
careful consideration to the selection of the values 3. The equilibrium composition.
for k and fi. The selection of the appropriate value
for k is basically the selection of the appropriate 4-2.1. The Enthalpy (or Heat) of Reaction. (4)
value for ~iC,. Consider the general chemical reaction equation
If = m g = the propellant weight rate of flow, aiAi + +
azAz * . GA, f
then the theoretical specific impulse for the propel-
lant combinat,ion, denoted by 18',is given by
biBi +
bzRz +
* * h
&l (4-4)
If ai denotes the number of moles of the i-th
V,' species of the reactants, denoted by A;, and b j the
1,' = - (4-3) molar concentration of the j-th species of the
9
products, denoted by Bj, then the above equat,ion
The calculation of the theoretical specific impulse can be written in the form
I,' is basically equivalent to the determination of
the isentropic enthalpy change (h, - he'). To n Tn
compute the specific enthalpy h, the equilibrium (4-5)

composition of the gases produced by the com-
bustion of the propellants and the combustion The enthalpy of reaction, also called the heat of
temperature t, must be determined. The enthalpy reaction, may be defined as the enthalpy change
he' requires knowledge of the isentropic exit tem- for a chemical reaction conducted under standard
perature t,' in the exit section of the exhaust conditions with At = A p = 0. The standard con-
nozzle having the area A,. ditions are usually either 298.1G"K or 300°K for
The assumption of frozen equilibrium leads t o the temperature and 1 atm for the pressure. Since
values of I,' slightly smaller than those obtained the combustion of rocket propellants is an exo-
using the assumption of mobile equilibrium (see thermic reaction, energy leaves the system wherein
Paragraph 4-4). the chemical reaction takes place. For that reason
It is apparent from the foregoing that the cal- the value of AH,. for ail exothermic reaction is
culation of the theoretical specific impulse for a preceded by a negative sign. Since AH,. is deter-
propellant system involves determining (a) the mined from experiments conducted so that At =
combustion temperature t,, (b) the composition, A p = 0, the value of AH,. depends only on the final
specific heat ratio k, and molecular weightfi of the and initial states of the chemical species involved.
gas, (c) its specific enthalpy h,, (d) the exit tem-
perature t, of the gas in the exit plane of the
exhaust nozzle, (e) the composition, specific heat where X ( A H f ) , = sum of the enthalpies of for-
ratio, and molecular weight of the gas a t the tem- mation for the individual
perature t,, and (f) its specific enthalpy he. products
4-2. CALCULATION OF THERMODYNAMIC x ( A H f ) n = sum of the enthalpies of for-
PROPERTIES OF THE COMBUSTION mation for the individual
GAS (1, 2, 3, 4, 10) reactants.
It is apparent from the discussions of Para- The iiegativc of AH,. is called the avnilablc heat
graph 4-1 t.hat before one can calculate the isen- and is denoted by (3nl.n;~,
thus
38
THERMODYNAMIC RELATIONSHIPS ORDP 20-282
Qavail = -AH, (4-7) graph 4-2.1 and the former in Paragraph 4-2.3.).
The eiithalpy of reaction for an isobaric process At the adiabatic flame temperature t, the com-
( A p = 0) is equal to the corresponding change in bustion gases are in equilibrium and for the
eiithalpy for the system. Thus for the general represent it is assumed that the equilibrium compo-
action presented as equation (4-5), it follows that sition is known (see Paragraph 4-2.3). If all of the
unreacted reactants are included in the products,
then c
<=l
a; must vanish, and the heat released by
the chemical reaction is utilized for raising the
temperature of the products c biBj to the com-

m
j=l
where to is the reference temperature (298.16"K or bustion temperature t,. The temperature t, is
300"K), and H f 0 is the enthalpy of formation at determined from
the reference temperature (298.16"K or 300°K).
1 n
4-2.2. Calculation of Combustion Temperature

(Adiabatic Flame Temperature). The calculation
of combustion temperature 2, is based on t.he fol- 7n rte
lowing assumptions: (1, 2, 3, 4, 10)

1. The combustion process takes place under
adiabatic conditions (no heat is transferred where ( ~ i )represents
~ , the initial moles of re-
to or from the combustion gas from external actants and ( B J t , the moles of products at the
sources), consequently the entire enthalpy temperature t,.
of reaction AHr for the propellant system is The equilibrium composition is a function of the
utilized for raising the temperature of the combustion temperature and equation (4-9) holds
gaseous products produced by the chemical at all pressures for a perfect gas.
reaction. The combustion temperature t, is The available heat is given by
also called the adiabatic flame temperature.
2. The combustion process is isobaric ( A p = 0). m r 1
3. The combustion products are gases and each
gas follows the perfect gas equation of state
(see Paragraph 1-3.1).
4. Thermodynamic equilibrium is attained by (4-10)
the combustion products (gases) at the
entrance to the exhaust nozzle; that is, the where ( H e j ) t , - ( H i j ) 0 represents the enthalpy
free energy change A J t p = 0 (see Paragraph change per mole of B j for the temperature change
1-3.8). between 0°K and t,.
5. The velocity of the gases crossing the en- Table 2 presents the enthalpies for C-H-N-0
trance section of the exhaust nozzle is compounds as a function of temperature; the
negligibly small. reference temperature for the table is to =
Experience has demonstrated that these as- 298.16"K.
sumptions do not lead to significant errors ia the By applying the principles of the conservation
values for the thermodynamic properties of the of mass and the equilibrium constants for the
combustion products. reaction (see Paragraph 4-2.3) a set of equations
Calculation of t, involves the calculation of can be obtained for the molar composition of the
(a) the equilibrium composition of the combustion combustion gas. In general, the equations for the
products formed by the reaction of the propel- molar balance of each element, together with the
lants, and (b) the enthalpy of reaction for the equations for the equilibrium constants, give as
propellant system (the latter is outlined in Para- many equations as there are unknowns so that a
39
ORDP 20-282
solution can be found for t,. Only one value of t, standard free energies of the species Bj and A i
will satisfy equation (4-9) and that value is the respectively, (BJbjdenotes the partial pressure of
adiabatic flame (combustion) temperature. species B j raised to its molar concentration bj, and
The procedure for solving the equations for (AJai denotes the partial pressure of the species A ;
determining t, is one of successive approximations, raised to its molar concentration ai.
and iiivolves the following steps. For a chemical reaction conducted so that At =
1. Assume some reasonable value for t, and A p = 0, which corresponds to the case of meas-
calculate the equilibrium composition of the uring the enthalpy of reaction, the free energy
combustion gas mixture for that tempera- change A J f P , is given by (see Paragraph 1-3.8):
ture (see Paragraph 4-2.3). m n
2. Using the gas composition calculated under
step 1 and equation (4-9), calculate Qauail.
3. Evaluate the right-hand side of equation
4-2.3.1. Equilibrium Constant. If A 7 denotes
(4-9) which gives the heat absorbed when
the standard free energy change for the products
the products are heated from to to the
and reactants, then
assumed value for t,. Denote that result by
c bj3$
QC.
4. If Qavail from step 2 is larger than Q, from AJO = - C

i= 1
ai J A ; (4-14)
step 3, then the actual value of 2, is larger j= 1
than that assumed in step 1 ; Accordingly, the free energy change for the re-
If from step 2 is smaller than Qc action is given by
from step 3, then the actual value of t, is
smaller t,han t.he chosen value;
If Qauait from step 2 is equal to Q, from
step 3, then the actual value of t, is the
selected value in step 1.
I n practice, sufficient accuracy is obtained by
making about three estimates for t,. For small
differences between Qavait and Q, linear interpola- When the chemical reaction is in equilibrium
tion may be used. AJtp = 0. Since A 7 is a constant, the expression
enclosed by the brackets i n equation (4-15) is also
4-2.3. Calculation of Equilibrium Composition. a constant; the latter is called the equilibrium
From equation (4-5) for a general chemical re- constant and is denoted by K,. Thus
action between propellants, it can be shown that
when the products may be assumed to be perfect
(Bj)bj
gases, then the summation of the free energies of K - j=l
(4-16)
the products is given by (1) (see Paragraph 1-3.8): p m
m m m
i= 1
In equation (4-16) the numerator denotes the

Similarly for the reactants: product of the partial pressures of the individual
products raised to the same powers as their molar
concentrations. Similarly, the denominator is the
cn
i= 1
a; J A i = R, t c ln(Ai)"; +
n
i= 1
n
i= 1
ai 3;; (4-12) product of the partial pressures of each reactant,
raised to the power of its molar concentration. To
where J e j and 3 A i are the free energies of the illustrate: consider the equilibrium react,ioii equa-
species Bj and Ai respectively, 3ijand 3;; are the tion
See Example 10.19, Page 536 of Rcfercnce 4. HzO + Nz NO + H2

40
0NS HI PS
THERMODYNAMIC RELAT1
ORDP 20-282
The equation for the equilibrium constant for the HzO,OH, O,Oz, N, NZ,and K O in the combustion
latter reaction is accordingly gas mixture, four additional relationships arc
needed. The latter are provided by the require-
(NO) (Hz) ment that each of the elementasC, H, 0, and X
Kp = (HZO) (Nz)lI2 must be conserved. Thus
It follows from the preceding that for a chemical
equilibrium reaction involving perfect gases C C=w + aw' = nco2 + nco (4-19a)
A? = -R,,t In K , (4-17) ~ H = x + ~ x ' = ~ ~ H , o + ~ o H + ~(4-19b)

~H,+~H
The equilibrium constant K, is a function of the CO= y+ay' = 2nO2 + no + nH20
temperature of the gas. Table 4-1 presents the + noH + + 272~0,+ nco
nNO (4-19c)
equations for the equilibrium constants for several
C-H-N-0 compounds. The equilibrium constants E N = z+az' =2n~, + + nN nNO (4-19d)
for other reactions involving C-H-N-0 compounds
can be obtained from those listed in Table 4-1. where x C , C H , etc., represent the total number
To illustrate: of gram atoms of carbon, hydrogen, etc. ; and
n H Z O , noH, etc., represent the number of gram
atoms in the products of the chemical species
indicated by the subscripts on the n's.
From equation (1-8) it follows that equations
Table 9 presents the equilibrium constants listed (4-19) can be rewritten in the form of equations
in Table 4-1 as functions of the gas temperature. relating the partial pressures. Thus
(5, 6)
4-2.3.2. Equilibrium Composition of the Com-
bustion Products. The method for determining the
equilibrium composition of the combustion gas
mixture will be illustrated by considering a fuel
and oxidizer which produce compounds only of
C-H-N-0. Thus
Fuel Oxidizer
+
(C, H, 0, Nz) (a C,t HZ>Out Nzt) (4-18) + 2(COZ) + (CO) = (+) co (4-204
2(NJ + (N) + (NO) (Ru"> E N

The reaction between the above fuel and oxi-
dizer yields only compounds of the elements = (4-20d)
vc
C-H-N-0. It will be assumed that the following
products are formed: CO, COP, H, Hs, HzO, OH, where C C , C H , etc., denote the total number of
0, 0 2 , N, Nz, and NO.' At the combustion tem- carbon atoms, hydrogen atoms, etc., introduced
perature tc i t is assumed that the products are into the reaction, and the parentheses denote the
perfect gases in equilibrium, the corresponding partial pressures of the species enclosed by them.
equilibrium equations are presented in Table 4-1 The last four equations together with the seven
and the equilibrium constants as functions of equations for the equilibrium constants K1,K z , . . .
temperature are presented in Table 9. K7 constitute eleven equations for determining the
For the assumed equilibriums there are seven eleven unknowns CO, C02, H, Hz, H20, OH, 0,
equations for the pertinent equilibrium constants Oz, N, N2, and NO. To solve these eleven simul-
Kl, Kz, . . . KT, and eleven gaseous species. For the taneous equations the method generally employed
determination of the moles of CO, Con, H, HZ, involves the following steps: (4)
1. The partial pressure of each chemical species
1 Under certain conditions the combustion products may
contain methane, ammonia, and free carbon, and in those is expressed in terms of the partial pressure
rases additional equilibrium equations must be intro- of the pertinent elements and the appro-
duced. priate equilibrium constants
41
ORDP 20-282
TABLE 4-1. EQUILIBRIUM CONSTANTS FOR C-H-N-0 COMPOUNDS
Reaction Equation Equilibrium Constant
(1) COz + Hz 2 CO + Hz0

(2) HzO + i. Nz e NO + Hz
(3) 2Hz0 2Hz + O2

(4) HzO e Hz +0
(8) CO + 3Hz e CH4 + HzO

(9) f N? + $ Hz e NH3
(10) co + f e coz
0 2
(11) f O? + C(graphite) CO K11 = (CO)~
(0?)"2
(12) f N? + 3 02 NO
The relationships obtained in Step 1 for the combustion temperature t,, the enthalpy h, for the
partial pressures of the derived species in combustion products is readily obtained. Table 2
terms of the partial pressures of the elements presents values of enthalpy for C-H-N-0 com-
and the appropriate equilibrium constants pounds as a function of temperature (see Para-
are introduced into all but one of the con- graph 1,3.5).
servation of mass equations (4-19)
The partial pressures of all of the derived 4-3. THERMODYNAMIC PROPERTIES OF
species and all of the elements are then ex- COMBUSTION GAS ASSUMING
FROZEN EQUILIBRIUM
pressed in terms of the partial pressures of a
single element and the appropriate equi- The specific impulse calculated upon the basis
librium constants of frozen equilibrium assumes, in addition to
The last expression together with the unused assumptions 1 through 5 of Paragraph 4-1.1, that
conservation of mass relationship are com- the average molecular weight % of the combustion
bined to give ail equation in partial pressures gas does not change during the expansion process
of one unknown; the latter is solved by trial (Assumption 6a, Paragraph 4-1.1). In that case
and error m
The result of step 4 is employed for obtain- E. = C (njiiij)t,

j=1
(4-21)
ing the partial pressures of all of the coii-
stituents and the molar composition of the where nj represents the mole fraction of the j-th
gas mixture. component, and E . j its molecular weight, the sub-
From the molar composition of the gas mixture, script t, on the parentheses denotes 'that the
the specific heats of the individual species, and the calculation is made for the temperature t,.
42
THERMODYNAMlC RELATlONSHIPS
ORDP 20-282
The calculation of the isentropic exit velocity A trial value of 1: is calculated from equation
V,' involves determining the enthalpies h, and (4-27) using the value of c, for the gas mixture a t
h: (see equation 4-1). It has been pointed out that the equilibrium temperature t,. An arithmetical
h, is determined from the composition of the mean value for the molar specific heat of the gas
equilibrium gas mixture at the entrance to the mixture is calculated from the mean molar specific
exhaust nozzle, and the combustion temperature heats corresponding to the temperature 1, and the
t,. The calculation of t: for determining h: will now trial value of t:. This arithmetical mean value of
be considered. c, is now used in equation (4-27) for obtaining a
For an isentropic change of state of 1 mole of a second trial value for ti. The process is repeated
perfect gas until a solution is obtained. The calculation
procedure can be reduced by using entropy tables
dp - k dt - -C P-dt (4-22) and noting that for the isentropic expansion
p k-1 t R, t
process in the nozzle, the entropy remains constant.
Hence, for an expansion from t, to t, From the value of 2: the corresponding value of
h: can readily be determined from the enthalpy
fPe rt:
tables for the constituent gases.
I,, f & j , cp t=
dt
=
6, t'
R, In (4-23) For rough approximations it is frequently
assumed that the value of k a t the combustion
n temperature 1, does not change during the expan-
Let N = ni = the number of gram moles of sion process.
i=l
Values of the theoretical specific impulse 1: for
gas mixture, then several liquid propellant combinations based on
frozen composition, are presented in Chapter 5.
Table 6 presents the enthalpies of formation of
fuels, Table 7 the enthalpies of formation of
oxidizers, and Table 8 the enthalpies of formation
In equation (4-24) the nozzle expansion ratio of reaction products.
p,/p, is specified.
The temperature t: is determined from equation 4-4. CALCULATION OF SPECIFIC IMPULSE
(4-24) by trial and error. After the correct value ASSUMING MOBILE (OR SHIFTING)
for ti has been determined, the correct value for EQUILIBRIUM
c, is calculated from I n this case assumptions 1 through 5 and
assumption 6b of Paragraph 4-1.1 are applicable.
c, = c niCpi
N
- R,-- In P, - In p ,
i=i In t, - In t,
(4-25) The gas composition changes during the isentropic
expansion in the nozzle in such a manner that its
The value of k is then calculated from constituents are always in thermochemical equi-
librium. Calculations based on the assumption of
k
__ -
_ -C P mobile equilibrium are concerned with a fixed
(4-26)
k-1 R, weight of gas mixture, rather than with a tem-
perature dependent molecular weight of gas.
Neither k nor E are sensitive functions of tem- I n general, the values of ti and k for mobile
perature. Consequently, the labor involved in equilibrium are somewhat larger than those for
determining the correct value for k and E can be frozen equilibrium. Consequently, the correspond-
reduced without introducing appreciable errw by ing values of V: and 1: are slightly larger.
employing the arithmetical mean value for c, for
the temperature range t: to t,. 4-5. CALCULATION OF PERFORMANCE
For the gas mixture CRITERIA FROM THERMODYNAMIC
RELATI0NS
Zni C .
P d
NR,
= @6 P/
NR,
(4-27)
Assume that t, is the equilibrium combustion
P C temperature of the gas mixture a t the entrance
43
ORDP 20-282
section of the exhaust nozzle, and the value of k section of the exhaust, having. the cross-sectional
is the mean value for an isentropic expansion in area A,, assuming one-dimensional flow, is given-
the nozzle. Let it further be assumed that the by equations (4-1) and (4-2) . The actual exit
velocity of the gas crossing the entrance section of velocity denoted by V , is obtained by introducing
the exhaust nozzle is negligibly small compared to the velocity coefficient { defined by (7).
the isentropic exit velocity V:.
If it is desired to take into account the velocity v, = rv:
of the gases in the combustion chamber, denoted
by V,, the static values of t, and p , are replaced by
their corresponding stagnation values T , and P,,
where
The value of j- is usually between 0.9 and 1.0; its
( +-k -2l
T , = t, 1 M:) (4-28)
exact value is obtainable only by test. In the
absence of test data, the value j- = 0.95 is recom-
mended for estimating purposes.
and
Pl(k-1)
It is preferable to estimate d zfrom experi-
P, = p , (1 + 7M t )
k-1
(4-29)
mental data rather than from thermodynamic
calculations.
where M , = Vc/ac= Mach number for the gases
4-5.3. Weight Rate Flow for Nozzle. (4) The
at the entrance to the exhaust nozzle, and a,
weight rate of flow of gas through a rocket engine
= (gk R t,) 112 = speed of sound for the combustion
exhaust nozzle is given by
gases.
4-5.1. Nozzle Area Ratio for Complete Expan- W' = gm' =

At p,
-
.&z -2- (k+1)/2(k-l)
(4-33)
sion. The specific impulse attains its maximum d R___
, tc/Z( k f l )
value when the nozzle is designed so that the com-
bustion gases are expanded completely to the pre- For convenience let
dominating back pressure, that is, when p , = p,. ( k f 1) / 2 ( k - 1)
Consequently, the area ratio E = A , / A t for the (4-34)
rocket nozzle is of significance.
Then
where Substituting for g and R,, reduces equation

(4-35) to
W' = gm' = 0.1443- At PC
D (4-36)
43%
Figure 4-1 presents the area ratio E = A , / A ,
as a function of the pressure ratio p c / p , . Values of the parameter Q as a function of k are
When p , = p , = the atmospheric back pressure, presented in Table 5.
then the gases are expanded completely. The value It is seen from equation (4-36) that for a given
of A , / A t giving complete expansion is called either propellant combination, mixture ratio, and com-
the optimum area ratio or the area ratio for combustion temperature t,, the rate of propellant con-
plete expansion. sumption @' is directly proportional to A , p,.
For an actual nozzle, the weight flow rate is
4-5.2. Exit Velocity of Gases. The isentropic denoted by W , where
exit velocity V: for the gases crossing the exit = qm = Cd W' (4-37)
44
THERMODYNAMIC RELATIONSHIPS
ORDP 20-282
PRESSURE RATIO, pc/pe

PRESSURE RATlO,p, he
PRESSURE RATIO ,pc/pe
Figure 4-7. Area Ratio of Exhaust Nozzle as a Function of the Pressure Ratio for
Different Values of the Specific Heat Ratio
555514 0 - 60 - 4 45
ORDP 20-282
In equation (4-37), c d < 1.0 is the discharge co-

efficient for the nozzle.
4-5.4. Calculated Weight Flow Coefficient. The

weight flow coefficient is defined by equation
(3-17). Hence, the flow, denoted by Cd, is given by In the ideal case (where X = 1, C d = 1, and
c = 1) the value of CF is denoted by C i ; the latter
s-2 is called the ideal thrust coefficient. The value of
C,: = 0.1443 (4-38)
m C$ depends on the combustion pressure, the ge-
~
ometry of the exhaust nozzle, and to a minor

If cd < 1 then the value of cd given by equation degree upon the properties of the propellants. (9)
(4-38) should be multiplied by c d .
4-5.6. Calculated Specific Impulse. The ideal
4-5.5. Calculated Thrust Coefficient. The thrust specific, impulse, denoted by I:, ‘is given by (see
coefficient for a rocket engine is defined by Paragraph 3-2) :
(4-43)
The thrust is given by It follows from equation (4-2), that

F = riz XVe + (pe - po) Ae
where riz is obtained from equations (4-36) and
(4-37). Hence,
If p , is the static pressure of the atmosphere sur-
rounding the rocket motor, then
It is readily shown that (4)
The calculated specific impulse based on one-

dimensional flow is denoted by I,, where
I, = her: (4-46)
(4-40)
Hence
where 2, is given by equation (4-31).
It is seen from equation (4-40) that CF is
independent of the combustion temperature t, and
the molecular weight of the combustion gases fi. -
When the nozzle is designed SO that e = Ae/At is The ratio 18/Xfdtc/fi is sometimes called the
the optimum area ratio (pe = p.), then reduced specific impulse. Its magnitude is a
function of the specific heat ratio for the com-
bustion gas mixture.
It is seen from equation (4-44) that I: depends
upon two factors:
(k-1)lk 112
The effect of the atmospheric pressure is to
decrease the value of CF by the amount (p./pc)
A , / A t . If the atmospheric pressure p , = 0
[
( 4 zt = 1 - (E) ]
(vacuum), then = Expansion Factor (4-48)
46
LIQUID PROPELLANTS
ORDP 20-282
TABLE 5-1 .-Continued
Oxidizer
Nitrogen tetroxide Hydrazine 1.1 4950 1.26 19 1.20 263 316

Oxides of nitrogen Ammonia 2.1 4900 1.23 21 1.03 258 267
(70y0 Nitrogen tetroxide Ammonia (50%) +
30% Nitric oxide) Methyl alcohol (50%) 2.1 5050 1.23 23 1.06 240 255
Ethylene oxide 2.0 5730 1.24 24 1.14 250 275
Methyl alcohol 2.1 5210 1.22 25 1.10 236 259
Turpentine 3.5 5800 1.25 24 1.21 250 303
Oxygen Ammonia 1.3 4940 1.23 19 0.88 263 231
Diethylenetriamine 1.5 5550 1.24 21 1.06 266 282
Ethyl alcohol (75%) 1.3 5150 1.22 23 0.99 246 244
Ethyl alcohol (92.5%) 1.5 5400 1.21 23 0.98 252 247
Ethylene diamine (88%) 1.4 6000 1.23 19 1.04 262 272
Ethylene oxide 1.1 5750 1.24 22 0.99 261 258
Hydrazine 0.75 5370 1.25 18 1.06 279 297
Hydrogen (IA)max 8.0 5870 1.22 16 0.43 316 136
Hydrogen (I;)mnx 3.5 4500 1.26 9.0 0.26 363 95
Isopropyl alcohol 1.7 5560 1.22 22 0.98 258 253
JP-4 (C/H = 6.85) 2.2 5880 1.24 22 0.98 262 257
JP-4 (C/H = 6.00) 2.3 5770 1.24 22 0.98 262 257
Methyl alcohol 1.2 5230 1.21 22 0.95 250 247
Methyl acetylene 2.0 6180 1.27 22 0.93 241 223
Methyl cyclopentane 2.3 5770 1.24 22 0.98 2ti3 258
Nitroethane 0.65 5570 1.23 23 1.09 251 274
Ni tropropane 0.9 5620 1.23 23 1.06 256 271
n-Octane 2.4 5790 1.23 22 0.96 265 254
Propylene oxide 1.6 5900 1.23 23 1.00 258 258
Turpentine 2.4 6000 1.23 22 1.04 261 271
UDMH 1.4 5650 1.24 20 0.96 272 261
Oxygen (70%)
Ozone (30%)
+ JP-4 2.3 5950 1.24 22 1.04 268 279
Oxygen (30%)
Ozone (70y0)
+ ,JP-4 2.3 6180 1.25 21 1.08 272 294
Ozone JP-4 2.4 6380 1.25 21 1.14 278 317
Tetranitromethane Hydrazine 1.4 5250 1.27 20 1.29 258 333
Notes:-To obtain values of I ; and I:! a t combustion pressures other than p c = 500 psia:
p, 200 300 400 500 600 700 800 900 1000 1100 1200
Multiply by 0.89 0.94 0.98 1.00 1.02 1.03 1.05 1.06 1.07 1.09 1.10
Densities of propellants which boil below 80’F were taken as the values a t the boiling point.
Values in table based on “Theoretical Performance Qf Several Rocket Propellant Combinations,” Rocketdyne,
a Division of North American Aviation Corporation, l’ul)lic:Ltiol1 505s, Revised April 1956.
5-2.4. Average Density of Propellant System.

The average density of the propellant system (fuel The density of a liquid propellant system is a
plus oxidizer), denoted by ijP, should be high so function of its temperature. In the case of a
that the dimensions and weights of the propellant petroleum fuel, such as JP-4 or JP-5, the density
tanks, the propellant pressurizing system (see also varies with its chemicaI composition. Ordi-
Paragraph 2-4.2), and the associated plumbing are narily, it is desirable to maintain a constant mix-
minimized. In general, liquid fuels have smaller ture ratio T for the propellants burned during the
densities than liquid oxidizers so those propellant powered flight of the missile, so that both fuel and
systems giving satisfactory values of specific im- oxidizer tanks will be emptied practically simul-
pulse with large values of mixture ratio T (where taneously. To achieve that objective some form of
T = m,,/mf) yield large values of average propel- automatic propellant utilization system must be
lant density Fp, and in most cases large values of provided to maintain T at the requisite value.
density impulse I d .
51
ORDP 20-282
I n the case of a long range ballistic missile the 5-2.8. Specific Heat. If the propellant is utilized
variations in propellant density due to aero- for cooling the rocket engine by forced convection,
dynamic heating are generally quite small because as in a regeneratively cooled rocket engine (see
the missile is beyond the dense atmosphere sur- Paragraph 2-4.1), a high specific heat is advan-
rounding the earth in less than one minute of the tageous. The total heat a regenerative coolant can
powered flight. (4) absorb is equal to the product of its flow rate,
specific heat, and temperature rise between its
5-2.5. Boiling Point and Vapor Pressure. A high inlet and saturation temperatures. From a cooling
boiling point, preferably above 160"F, is desirable standpoint a high saturation temperature is also
so the propellant can be stored in light weight desirable. The saturation temperature should be
tanks and without excessive loss by evaporation. a t least 300°F but should not exceed approxi-
Preferably the vapor pressure should be small at mately 700°F if the wall temperatures are to be
temperatures up to approximately 160°F. Other- kept from becoming dangerously high. (7)
wise, the evaporation of the propellant in storage
will be excessive and vacuum jacketed tanks may 5-2.9. Chemical Stability. The propellant should
be required. be stable chemically when stored within the de-
The boiling point and vapor pressure character- sired temperature range for reasonable times. It
istics of a propellant exert a major influence upon must also be stable at the temperatures it will
the design and operating characteristics of the encounter in the operation of the rocket engine. In
pressurizing system, particularly in the case of a that connection liquid chemicals which decompose
turbopump system (see Paragraph 2-4.2). Because and deposit salts when utilized as a regenerative
of their low weight, high speed centrifugal pumps coolant may not be usable for certain applications.
are employed exclusively in the turbopumps of (2)
large liquid propellant ballistic missiles. Propel- It is preferable that the liquid propellant shall
lants having low boiling points and high vapor not decompose violently when heated, nor should
pressures tend to induce cavitation phenomena in it be sensitive to shock.
the pumps and supply lines. To prevent the occur-
rence of cavitation and vapor lock problems the 5-2.10. Corrosivity. It is desirable that the pro-
propellant tanks have to be pressurized with ,an pellant have a low chemical activity with the
inert gas, usually nitrogen or helium, so that pres- materials used for storage containers, valves,
sures at all points in the feed system are above that piping, rocket motors, bearings, pumps, gaskets,
inducing cavitation. (6) Propellants having large etc. Otherwise, problems arise concerned with the
vapor pressures increase the required gas pressures storage and handling of the propellant, and the
and may necessitate increasing the thickness, and design of engine components.
consequently the weights, of the propellant tanks. Ordinarily, the fuel component of a bipropel-
lant combination introduces fewer material selec-
5-2.6. Freezing Point. It is desirable that the tion problems than the oxidizer. Nevertheless, the
propellant remain liquid at the lowest temperature compatibility of the fuel with available construc-
t o be encountered in storage on the ground and in tion materials should be considered, since several
flight. For certain applications some liquid chemi- of the possible fuels do attack the more common
cals cannot be considered for use as rocket propel- metals and plastics.
lants if their freezing points are above -65°F. The selection of the most appropriate materials
for all of the components of a liquid propellant
5-2.7. Viscosity. It is desirable that the viscosity rocket engine is one of the major problems entering
of a liquid propellant be low at all operating tem- into the design and construction of a satisfactory
peratures; preferably less than 10 centipoises at engine.
-65°F. Otherwise, the pressure drop required r'or
5-2.11. Toxicity. It is desirable that the toxicity
transferring the propellant from the supply tank of the liquid propellant be low so that it can be
and injecting i t into the rocket engine becomes handled with conventional equipment and proce-
excessive. dures. (11, 12, 24)
52
LIQUID PROPELLANTS
ORDP 20-282
5-2.12. Availability. Rocket propellants which specific impulses were too low (of the order of
would be used in large quantities during an 180 sec) and that they were too sensitive to shock.
emergency, must either be readily available or It is worth noting that methyl nitrate is almost as
their production potential must be ample to meet shock sensitive as nitroglycerine.
the anticipated demand.
5-3.2. Nitrobenzene-Nitric Acid-Water Mix-
5-2.13. Cost. In evaluating the cost of propel- tures (Dithekites). These monopropellants were
lants for a ballistic missile, the total amount of investigated by the Germans, who found that
propellants supplied to the missile from the time unless the mixture contained at least 20 percent
it is placed in service readiness to the completion water by weight it was too sensitive for use as a
of its firing must be taken into account. It is the monopropellant. The specific impulses obtainable
total impulse of the missile divided by the cost of with dithekites ranged from 190 to 208 sec.
all of the propellant consumed that determines the
impulse per unit of cost. Of course, a large value of
5-3.3. Mixtures of Nitroparaffins. After a rather
impulse per unit of cost is desirable.
extensive investigation, nitromethane, one of the
few monopropellants giving a reasonable specific
5-3. MONOPROPELLANTS
impulse (220 seconds a t 300 psia), was abandoned
Since the beginning of World War I1 a large as a rocket propellant primarily because of its
number of monopropellants have been investi- shock sensitivity and the problem of obtaining
gated in this and other countries. The principal efficient combustion in a motor having a reason-
systems are listed below: able characteristic length L*. Studies of mixtures
1. mixtures of methyl nitrate and methanol of nitromethane with nitropropane to reduce
(myrols) shock sensitivity, showed that as the shock sensi-
2. mixtures of nitrobenzene, nitric acid and tivity of the mixture was decreased through in-
water (dithekites) creasing the percentage of nitropropane, the
3. mixtures of nitroparaffins specific impulse decreased to unacceptable values.
4. ethylene oxide
5. concentrated hydrogen peroxide (HTP)
6 . hydrazine 5-3.4. Ethylene Oxide. Because of the safety
As pointed out in Paragraph 2-3.1, monopropel- with which it can be handled, ethylene oxide
lants appear to combine energy content with high (CzH40)has received extensive study during the
shock sensitivity and their performances are too past decade. This material decomposes into carbon
low for them to be useful as the main propellant monoxide (CO) and methane (CH,).
for a rocket engine propelling a ballistic missile. Because it has a low flash point it must be
Of the aforementioned monopropellants only handled as carefully as gasoline. Although it is
hydrogen peroxide and hydrazine find wide use as insensitive to shock it will ignite if in contact with
the oxidizer and fuel component respectively of catalytic surfaces. It can be stored in steel or
bipropellant systems. They also are used exten- stainless steel drums and is readily available
sively for generating high temperature gases for commercially. (8, 9)
driving either the turbine of the turbopump for Ethylene oxide has been used as the source of
the rocket engine or that of the auxiliary power high temperature gases for driving the turbines of
unit (APU) where one is employed in the missile. auxiliary power units (APU).
For the purpose of completeness brief comments
will be made regarding monopropellants 1 to 4 5-3.5. Hydrogen Peroxide. Hydrogen peroxide
inclusive, and more detailed discussions will be is used as a rocket propellant in concentrations
presented on hydrogen peroxide and hydrazine. ranging from 80 to 95 percent. Its first use was by
the Germans (concentration approximately 80 per-
5-3.1. Mixtures of Methyl Nitrate and Meth- cent) in 1933. (10) Table 5-2 presents the physical
anol (Myrols). The Germans investigated these properties of hydrogen peroxide solutions as a
mixtures extensively, and concluded that the function of their concentration. (12, 13, 14, 15, 16)
53
ORDP 20-282
TABLE 5-2. PHYSICAL PROPERTIES OF in the decomposition chamber, thereby exposing a

DIFFERENT CONCENTRATIONS OF large surface to the hydrogen peroxide and its
HYDROGEN PEROXIDE IN WATER vapors.
Concentrated hydrogen peroxide as a rocket
Concentration, percent 100 90 80 propellant suffers from the following disadvan-
Specific heat, Btu/lb"F at
64.4'F 0.57 0.61 0.65 tages: it is thermally sensitive, chemically un-
Freezing point, O F 30.4 12.6 - 10.8 stable, and has a relatively high freezing point.
Boiling point, "F 312 288 269 Because of the interest in concentrated hydro-
Specific gravity at 64.4"F 1.450 1.394 1.341
Viscosity, centipoise at gen peroxide solutions, particularly by the British
64.4"F 1.307 1.301 1.297 and Germans (16, 18, 19), the problems of
Heat of vaporization, Btu/lb 540 588 634 handling and storing such solutions have been
Vapor pressure,psi at 100°F 0.007 0.012 0.016
thoroughly investigated. Experience has demon-
Hydrogen peroxide can be readily decomposed strated that the pure material can be stored for
thermally with suitable catalysts according to the reasonable periods of time in vented containers
equation made from specially treated aluminum. The
H202(liq)= H 2 0 (g) + 3 O2 (g) + 23,300 Btu aluminum content of the container material
should not be less than 99.7 percent and its copper
According to thermochemical calculations based content not greater than 0.06 percent. A great
on the above equation, when 100 percent H202 deal of research effort has been devoted to im-
used as a monopropellant is decomposed a t a proving the storability characteristics of concen-
pressure of 300 psia, the temperature of the de- trated hydrogen peroxide, but despite all the
composition gases (H20 and 0 2 ) is 1800"F,and the progress which has been made it must still be
theoretical specific impulse obtained by expanding stored in vented containers. Great care must be
those gases to standard sea level is 146 sec. exercised to avoid introducing into the storage
The kinetics of the catalytic decomposition of containers impurities such as iron oxide (rust),
hydrogen peroxide solutions has been studied organic matter, dust, copper, and other materials
extensively in this and other countries. Sodium which catalyze the decomposition of hydrogen
and calcium permanganate solutions are effective peroxide. (13, 14, 18)
catalysts for decomposing hydrogen peroxide. As It is found that oxygen gas is continuously
a matter of fact the Germans developed propulsion evolved from concentrated hydrogen peroxide
systems based on injecting a small quantity of a solutions, even a t ambient temperatures, but at
solution of either sodium or calcium permanganate low temperatures the rate of gas evolution is low
into the rocket engine simultaneously with the enough to be considered negligible.
hydrogen peroxide solution. (10) Calcium per- The relatively high freezing points of concen-
manganate was preferred because of its much trated hydrogen peroxide solutions (see Table 5-2)
greater solubility in water. Once the decomposi- are disadvantageous for many applications. Con-
tion of the peroxide has been initiated it proceeds siderable research has been expended on investi-
smoothly. The decomposition equation is gating materials for depressing the freezing points
of c'oncentrated hydrogen peroxide solutions. The
+
H202 Ca (Mn04)2= Ca(OH)2 + 2 MnOz + 2 0 2 three which have been investigated most thor-
oughly are water, ammonium nitrate, and glycols.
Calcium permanganate can also be used as a Much effort has also been expended on investi-
catalytic surface. Alundum pellets are soaked in a gating the ternary system hydrogen peroxide-
strong solution of calcium permanganate for ethylene glycol-water. T o obtain a low freezing
several hours, dried, and packed into a chamber point with the latter mixture the water content
called the decomposition chamber. The concen- must be relatively large (more than 20 percent by
trated hydrogen peroxide decomposes in flowing weight). This reduces the oxygen content of the
through the bed of pellets. In this country, the mixture, and makes the latter unsuitable for
trend in recent years is to use silver surfaces as the application as the oxidizer in a bipropellant sys-
decomposition catalyst. Silver screens are placed tem. It does, however, have application as a
54
LIQUID PROPELLANTS ORDP 20-282
monopropellant; the ethylene glycol increases its fraction of the ammonia which is decomposed,
energy content. (15) reactions (a) and (b) can be combined to give (23)
5-3.6. Hydrazine. Hydrazine (N2H4)is a toxic +

(c) 3 N2H4 = 4 ( 1 - ~ ) NHI ( 1 + 2 ~ NH3
)
colorless liquid having the following physical + +
6 zH2 (144,300 - 79,200~)Btu
characteristics: specific gravity 1.01, freezing
point 34"F, and boiling point 236°F. Hydrazine
If the performance parameters for hydrazine are
can be used as the fuel component in a liquid bi-
plotted as a function of the percent of ammonia
propellant system or as a monopropellant. It is
dissociated, it is found that when x = 0, I , = 192
readily soluble in water, alcohol, and certain
sec and when x = 100, I , = 168 sec.
organic liquids. The water solution, hydrazine
The following materials catalyze the decomposi-
hydrate (N2H4 -H20),was used as the fuel with
tion of hydrazine: metallic iron, nickel, and cobalt
concentrated hydrogen peroxide as the oxidizer
supported on porous aluminum oxide. By em-
for the Walter power plant to propel the ME 163
ploying a catalyst the primary decomposition
airplane. Hydrazine and its hydrates are toxic and
reaction can be accelerated. Furthermore, it is
exposure to their vapors may cause temporary
possible to control the decomposition of the
blindness. (21, 22, 23)
hydrazine so that gases having different molecular
Because it is thermally unstable, hydrazine can
weights and temperatures are obtained. Conse-
be caused to undergo an exothermic decomposi-
quently, by proper control of the decomposition
tion, which apparently takes place in two steps
reactions, gases can be generated which are
(11, 12, 23) as follows:
suitable for operating either gas turbines or for
pressurizing propellant tanks.
(a) 3 N2H4= 4 NH3 + Nz + 144,300Btu Such gases have the advantage that they con-
(b) 4NH3 = 2 N r + 6Hz - 79,200Btu
tain no solids or condensable constituents.
The principaI disadvantage encountered in the
application of hydrazine is its high freezing point
It is seen from the above that the specific im- (34°F). Experiments have shown that the freezing
pulse obtained from the thermal decomposition of point can be depressed by adding nitric acid
hydrazine will depend upon which reaction (HN03) and water to the hydrazine. Solutions
products are formed. Because the decomposition containing more than 17 percent nitric acid by
of the ammonia (by reaction b) is endothermic, weight tend to become unstable and shock sensi-
decomposition according to reaction (a) gives the tive. A rather thorough investigation has been
higher specific impulse. Reaction (b), the decom- conducted at JPL/CIT for a mixture consisting of
position of ammonia (NH3), is generally a slow 74 percent N2H4, 16 percent HNOa, and approxi-
process, so if the reaction time is limited as is mately 10 percent water by weight. This mixture
usually the case, only a small portion of the has a freezing point of approximately -40°F) and
ammonia formed by reaction (a) will become dis- can be decomposed to give gases having a tem-
sociated. Hence, the decomposition of hydrazine perature of approximately 1700°F. The loss in
gives a larger specific impulse if the characteristic performance in a gas turbine operated on those
length L*, which is a measure of the time available gases instead of the decomposition products of
for decomposing the hydrazine, is short enough to pure hydrazine, is approximately 5 percent. Be-
prevent any substantial decomposition of the cause the decomposition products of the mixture
ammonia formed by reaction (a). contain approximately 20 percent water they are
Experiments, principally by Jet Propulsion not suitable for pressurizing propellant tanks. (22)
Laboratory, California Institute of Technology Experiments indicate that the mixture can be
(JPL/CIT), have demonstrated that the decom- handled in much the same manner as pure hydra-
position reaction for hydrazine is influenced by zine, and that it can be stored for long periods of
temperature and the presence of catalysts. Accord- time at ambient temperatures in unvented alumi-
ingly it is difficult to specify the exact stoichi- num or stainless steel containers, without serious
ometry in a given case. Hence, if z denotes the decomposition.
55
ORDP 20-282
5-4. OXIDIZERS FOR LIQUID BIPROPEL- 5-4.1. Liquid Fluorine. A given fuel yields a
LANT SYSTEMS larger enthalpy of reaction with liquid fluorine
than with liquid oxygen because the hydrogen in
The performance of a bipropellant system de-
the fuel forms H F which has greater stability than
pends upon the thermodynamic properties of the
the HzO formed'with oxygen. Because fluorine is
oxidizer and of the fuel. Reference to Table 5-1,
monovalent while oxygen is divalent, more
which presents " Calculated Specific Impulses for
Different Liquid Propellants," shows that the fluorine than oxygen is required for burning a
characteristics of the oxidizer have a greater effect given fuel. Since the specific gravities of oxidizers
upon the specific impulse than do those of the fuel. are, in general, larger than those of fuels, the larger
It was pointed out in Paragraph 2-3.2 that only a mixture ratios required with fluorine oxidizers
few liquid materials can be used as practical result in the propellant system (fuel plus oxidizer)
oxidizers. For that reason, when selecting a bi- having a higher average density. To illustrate,
propellant system for a given application, the consider the combustion of anhydrous liquid am-
usual procedure is first to select the oxidizer and monia (NHa) in stoichiometric proportions with
then that fuel which when used with the oxidizer fluorine and with oxygen. The specific impulse
gives the most favorable bipropellant system from obtained from the F2-NH3 system is 313 sec and
all points of view (see Paragraph 5-1). its average specific gravity is 1.20. For the
The atoms that are useful as oxidizers in rocket 02-NH3system the corresponding values are 255
propellant systems are oxygen and fluorine since sec and 0.89. Figure 5-1 is a bar-graph chart which
they give highly exobhermic combustion reactions. compares the performances of several fuels when
Consequently, the suitable liquid oxidizers are burned with either liquid fluorine or liquid oxygen,
either the elements oxygen and fluorine or com- at 500 psia combustion pressure. (24,25) It is seen
pounds containing a large proportion of those that the largest value of specific impulse is ob-
elements. (11, 23) For a material to be a suitable tained with the fluorine-hydrogen system (373 sec
oxidizer it should not have a large enthalpy of a t 500 psia). The corresponding flame temperature
formation, otherwise its enthalpy of combustion is 7940°F and the molecular weight of the jet
will be relatively small. (48) A low enthalpy of gases is 8.9.
formation indicates low bond energies between the It must be borne in mind that from the stand-
atoms in the molecule.' The requirement of low point of rocket engine performance fluorine burns
efficiently only with hydrogen. A series of fluoro-
bond energies suggests that the most suitable com-
carbons is formed when fluorine is burned with
pounds are those containing the nonmetallic ele-
carbon, e.g., CF, CF2, CFI, and CF4. Conse-
ments (Groups V, VI, and VII of the periodic
quently, if a fuel contains both hydrogen and
table). The single exception is hydrogen, which
carbon atoms, the best performance with that fuel
occurs in many oxygenated compounds. The large
is obtained with an oxidizer containing both fluo-
bond energy of hydrogen (103.4 kcal /mol) causes
rine and oxygen, so that the hydrogen is burned
a loss in combustion energy, but the low atomic
with the fluorine and the carbon with the oxygen.
weight of hydrogen partially compensates for that
Although liquid fluorine is the best oxidizer
loss. For these reasons the liquid oxidizers which
from the point of view of obtaining high specific
are useful in rocketry are primarily compounds
impulse and a large average density, it has several
containing the elements fluorine, hydrogen, nitro-
disadvantages, the three principal ones being its
gen, and oxygen. The prime oxidizers are, of
low boiling point ( - 188"C), its extreme chemical
course, fluorine and oxygen. Table 5-3 presents the
activity, and its high toxicity. Compared to liquid
physical properties of the more important oxi-
oxygen it is much more expensive, less available,
dizers.
and more hazardous to handle. TJe logical appli-
cation for liquid fluorine is for long-range missiles
where its superior performance can be utilized
1 Bond energy may be defined as the average energy per
mole which must be absorbed to break a paTticular bond
advantageously.
in a molecule and separate the resulting atoms or radicals Fluorine reacts readily with most metals, or-
from each other. ganic matter, concrete, glass, and water. Once the
56
LIQUID PROPELLANTS
ORDP 20-282
TABLE 5-3. PHYSICAL PROPERTIES OF LIQUID OXIDIZERS

(Bared on Reference 23)
Av. Heat of Heat of

Molecular Density Melting Boiling Vaporization Formation Specific Heat Viscosity
-
Weight P Point Point QV Qf CP /J
Oxidizer nb (g/cc) "C oc (kcal/mol) ( kcaI/mol) (caI/C/mol) (centipoise)
A. OXIDIZERS CONTAINING FLUORINE

F2 38 1.55-18' -217.9 -188 1.51 0. 28-lQ3
clF3 92.5 1.77'2 -82.6 12.1 5.74 0. 4gZ5
BrF3 175 2.4725 -61 40.5 -
BrF5 137 2. 849 8.8 127 10
I F5 222 3.5 -8 97 -
I F7 260 2.8 5.5 4.5 -
NF3 71 1.54-"9 -209 -129 2.77
B. OXIDIZERS CONTAINING OXYGEN

0 2 32 1.14-lS3 -218.4 -183 1.63 3. 09-lgo 13.O-la3 0 . 19-ls3
0 3 48 1.71-"' -251.4 -111.5 2.59 -30.3-110 17-112 1.56-lS3
3. 65-lS3
HzOz 34 1.4420 -0.9 150.5 11.1 44.825 19.720 1.83O
HNOa 63 1. 5lZ0 -41.6 86 9.43 41 .425 26. 3,O 0.9120
MON* 92 1.4520 -11.3 21.0 9.1 6. g2j 3320 0.43*O
N20 44 1 . 23-a9 -102.4 -88.5 3.96 -19.5 18.6-88
NO 30 1.27-151 -163.6 -151.8 3.29 -2l.G 18.7-151
c(N0z)d 196 1.6513 13 125.7 - - (22) -
SFNA** 62.7 1 . 5620 -54 60 9.4 41. 125 26. 720
Fz0 54 1.53-145 -223.8 -144.8 - - 1.4-188 11.3-lS8
70% FP
+
30% 02 - 1.45-18' -218 - 186 - - -
C10,F 102.5 1.4368 - 145 -56 7.326 26. TZ0 0.1820
Notes :-Superscript denotes temperature of measurement in "C.

* MON-mixed oxidcs of nitrogen (equilibrium mixture of NO, and N204).
** SFNA-stabilized fuming nitric acid (83.5Oj, HN03, 14% NOn, 2% H20, 0.5'1; HF).
RFNA-red fuming nitric acid (84% HNO3, 14% NOn, 2% H20).
reaction has started it cannot be stopped because oxidizers. Recent experiments have demonstrated
the fluorine reacts with water. It can be stored, that there is insignificant contamination and cor-
however, at temperatures below 100°C, in clean rosion of the firing site associated with burning
dry containers made from copper, nickel, monel fluorine in rocket engines of moderate size.
metal, and aluminum. This is because a protective Because of its low molecular weight the HF tends
film of metal fluoride is formed that adheres to dissipate rapidly in the air.
tenaciously to the metal surface.
Because of the difficulties in handling liquid 5-4.2. Liquid Oxygen (LOX ).Historically, LOX
fluorine and its low availability, it appears that for was one of the first oxidizers used in liquid propel-
the next few years a t least, liquid fluorine will be lant rocket systems. Currently, it is the oxidizer
considered only for special strategic missiles. used in such ballistic missiles as the Atlas, Titan,
In general, all oxidizers containing fluorine Jupiter, Thor, and Redstone. Excepting the fluo-
produce large quantities of HF in the exhaust rine group of oxidizers and ozone, LOX gives the
gases discharged from the rocket engines using best performance, on a weight basis, of any oxi-
them. Undoubtedly this has been a deterrent to dizer. Since it is prepared from liquid air by
the development of fluorine or fluorine-containing fractional distillation, it can be produced cheaply
57
ORDP 20-282
SPECIFIC IMPULSE VALUES AT 500 psia

IS
FUELS 150 200 250 300 350 400
JP -4
tW - t t t t t l l
AMMONIA
HYDRAZ INE
HYDROGEN
SOURCE: ROCKETDYNE DIV. OF NORTH AMERICAN

-
KEY
AVIATION, INC.
OXYGEN F m
FLUORINE =
(taken from Reference 24)
Figure 5-1. Performance of Several Fuels with Fluorine and with Oxygen
58
LIQUID PROPELLANTS
ORDP 20-282
(about 3 cents per lb) at any desired site, and Bromine pentafluoride (BrF6) may be of interest
because of its widespread industrial use the manu- because of its high specific gravity.
facturing and handling technology is well 'de-
veloped. Recent years also have brought the 5-4.3.1. Chlorine Trifluoride (CIF,). Although
development of air transportable LOX generators. nitrogen trifluoride (NF,) gives higher perform-
The principal disadvantages of LOX arise from ance than chlorine trifluoride (ClF3) it has not
its being a liquefied gas, and the fire risk attendant received as much attention as ClF3, because NF3
to its use. Because of its volatility its transport is a liquefied gas at ambient temperatures (see
and storage introduce severe problems. If stored Table 5-3). Chlorine trifluoride has a large specific
in bulk in insulated tanks the loss due to evapora- gravity (1.82), a low freezing point (-83°F)) and
tion is of the order of 3 percent per day, but stored can be handled as a liquid a t ambient conditions;
in vacuum jacketed tanks the evaporation loss can its vapor pressure is less than 100 psia at 160°F.
be reduced to a fraction of a percent per day. It Reference to Table 5-1 shows that when reacted
does not appear feasible at this time either to with hydrazine (N2H4) and ammonia (NH3) at
transport or store LOX in the oxidizer tanks of 500 psia, the corresponding values of specific im-
missiles, so the missiles must be loaded with LOX pulse based on frozen composition, are 240 sec and
in the field or at the launching site. Consequently, 252 sec respectively.
LOX generators must be provided to replace the Since C1F3 is produced by the direct reaction
losses of LOX due to evaporation. between gaseous chlorine and gaseous fluorine its
Even though a relatively small quantity of LOX availability depends upon the potential supply of
is actually consumed in firing a missile, its real fluorine.
cost is much greater than might be assumed from The exhaust products of a rocket motor burning
the fact that it is plentiful and can be produced CIFa contain both hydrogen fluoride (HF) and
cheaply. The cost of storage tanks, LOX gener- hydrogen chloride (HCl). The higher molecular
ators, evaporation losses, and the maintenance of weight of the latter can cause it to persist in the
an extensive personnel to service LOX missiles launching area especially on a humid day (see
must be included in the actual cost of LOX used.' Paragraph 5-4.1).
Thus, despite its plentiful supply, low cost -of
production, and broad background of industrial 5-4.4. Oxidizers Containing Oxygen. The prin-
and military use, LOX is really unsuitable as the cipal oxidizers containing oxygen atoms and no
oxidizer for tactical missiles. In fact, when all the fluorine atoms are liquid ozone (OJ, hydrogen
problems and costs concerned with handling, peroxide (H202), nitric acid (HN03),and mixtures
storaging, servicing, complexity, and cost of LOX of nitrogen dioxide (NO2) with nitrogen tetroxide
missiles are considered, it appears probable that (N204)for brevity termed mixed oxides of nitrogen
LOX may not even be the best choice of oxidizer (MON). Table 5-3 presents the physical properties
for some of the missiles in which it is currently of the principal oxidizers containing oxygen.
being used. 5-4.4.1. Liquid Ozone (LOZ). Liquid ozone, for
brevity designated as LOZ, is-a deep blue liquid.
5-4.3. Oxidizers Containing Fluorine. The com- It boils at -llloc, its density is 1,71 g/cc at
pounds of fluorine with the nonmetallic elements -1830c and it has a negative heat of formation
nitrogen, bromine, and iodine are Of (-30.3 kcal/mol at -110°C). Propellant systems
interest because the fluorine atoms are relatively based on Loz give specific impulse values com-
loosely held in those compounds*The properties parable to those based on liquid fluorine (see
of several fluorine compounds are presented in Table 5-1). Loz is made by the silent discharge
Table 5-3. of electricity through oxygen gas. (28, 29) The O3
Of the listed in 5-3, Only molecule is thermally unstable, sensitive to shock,
ClF3 and NF3 contain a large enough Percentage and these factors combined with its large oxidizing
weight Of fluorine to give good Performance. potential make LO2 hazardous to handle. It de-
1 The statements are to a large degree applicable to all composes with explosive violence according to the
cryogenic propellants. equation
59
ORDP 20-282
2 O3 + 3 Oz + 34.5 kcal WFNA has been used in this country in several

liquid propellant engines for rocket assisted take-
It is important to keep LOZ pure. Hence, it off (RATO) and in-flight-thrust-augmentation
must be made from oxygen which is free of even (IFTA). Its composition is 98 percent HNOa,
traces of impurities. The sensitivity of LOZ can 2 percent HzO with traces of N204.
be reduced by making mixtures of LOZ in LOX. Considerable effort has been expended on im-
Thus a solution of LOX containing approximately proving the stability of fuming nitric acid and
25 percent LOZ is quite stable to shock, and the decreasing its corrosivity. The thermal decomposi-
mixture boils as a single phase a t - 183°C. Calcu- tion of H N 0 3 may be expressed by the equi-
lations show, however, that burning the 75LOX- librium equation (30, 31)
25LOZ mixture with gasoline increases the specific
impulse above that when LOX alone is used, by
approximately 6 seconds. Since LOX is more
volatile than LOZ (see Table 5-3), the 75-25 mix-
ture tends on storage to increase in LOZ content Studies of the above reaction show that its rate
due to the evaporation of LOX. When the LOZ is slow at temperatures below 160°F but increases
concentration exceeds approximately 30 percent, rapidly above that temperature. Because the oxy-
explosions of extreme violence can result from gen gas formed is relatively insoluble in the acid
contamination wit,h minute traces of organic very high storage pressures can be encountered
matter. (29) where containers are nearly full. Moreover, since
Since LOZ has not as yet been effectively stabi- the NOz and HzO are more soluble in the acid
lized, and because of the small increase in per- than the oxygen, the composition of the acid
formance with the 75LOX-25LOZ mixture, LOZ changes with the storage time within the range of
cannot be considered to be a promising oxidizer at the initial and equilibrium concentrations of NO2
this time. and H20. If the thermal decomposition is accom-
panied by corrosion of the container material,
5-4.4.2. Hydrogen Peroxide. The principal then the composition of the acid changes con-
characteristics of concentrated solutions of H202 tinuously in storage, which is undesirable. (32)
were presented in Paragraph 5-3.5 where its use as Although a great deal of effort has been ex-
a monopropellant mas discussed. Despite their pended, no inhibitor has been discovered for
relatively high freezing points, water solutions of reducing the rate of thermal decomposition to a
HzOz containing 90 percent or more HzOz have negligible value. Consequently, attention has been
been considered for certain applications. The high given to the use of additives for lowering the equi-
density, high boiling point, and good performance librium decomposition pressure. (33, 3G)
(see Table 5-1) obtainable with such solutions It is apparent from the decomposition equation
make them attractive as a replacement for liquid for nitric acid that the addition of NO:! and H20 t o
oxygen. In applications where a large value of the acid should decrease the amount of Oz formed,
density impulse is of importance, certain hydrogen since they appear in the equation, and conse-
peroxide propellant systems may be suitable. quently reduce the equilibrium storage pressure.
Furthermore, in a missile using hydrogen peroxide A satisfactory red fuming nitric acid (RFNA)
as the oxidizer, monopropellant runout can he containing on a weight basis approximately 83-84
employed. (12) percent HN03, 14 percent NOz and 2 to 3 percent
water, will reduce the oxygen pressure to less than
5-4.4.3. Nitric Acid. The following fuming nitric 100 psia where filling voids are of the order of
acids have been considered as oxidizers: white 10 percent. The latter storage pressure is satis-
fuming nitric acid (WFNA), red fuming nitric factory for many purposes.
acid (RFNA), and mixed acid (MA). The principal It has been found that the addition of small
disadvantages of nitric acids are the tendency to amounts of hydrofluoric acid (HF) to fuming
decompose thermally, and their high corrosivity. nitric acid will reduce its corrosion attack on
These disadvantages introduce storage problems. certain stainless steels and aluminum alloys. (36)
60
LIQUID PROPELLANTS
ORDP 20-282
TABLE 5-4. PHYSICAL PROPERTIES OF NITROGEN OXIDES

(Reference 23)
Av. Heat of Stability

Molecular P Freezing Boiling Formation a t room
Weight
-
(@ temp. "c) Point Point Qf temperature
Name Formula m Wee) "C "C (kcal/mol)
Nitrous oxide Nz0 44.02 1 . 226-89 -102.4 -88.5 19.65 Stable

Nitric oxide NO 30.01 1.269-'52.2 -163.6 -151.7 21.5 Stable
Nitrogen trioxide N203 76.02 1.44720 -102.3 3.5 10.3 Quite unstable
Nitrogen dioxide Not 46.01 1 .4520 -11.2 21.2 7.96 Stable
Nitrogen tetroxide NtO4 92.02 1.4520 -11.2 21.2 2.24(g) Stable in
equilibrium
with NO2
Nitrogen pentoxide N205 108.02 1 . 6318 -32.4* 47 0.700(g) Low stability
Nitrogen peroxide NO3 62.01 - - 142** - 13.00(?) Very unst,able
(g) denotes gas.

* N205 sublimes and decomposes rapidly above room temperature.
** Solid NO3 was trapped a t - 185°C but began decomposing rapidly a t - 143°C.
A fuming nitric acid having the weight composi- the remaining oxides only nitrogen dioxide (NOz)
tion of 83.5 percent HN03, 14 percent NOz, 2 per- and nitrogen tetroxide (Nz04)have received con-
cent water, 0.5 percent HF, is known as either sideration as oxidizers in liquid rocket bipropel-
stabilized fuming nitric acid (SFNA) or inhibited lant systems, and those appear together as an
fuming nitric acid (IFNA). SFXA freezes a t equilibrium mixture at ordinary temperatures.
-65"F, has a density of 1.56 g/cc a t 20"C, and The term mixed oxides of nitrogen, denoted by
can be stored practically indefinitely at tempera- MON, will be given to the equilibrium mixture.
tures up t o 160°F in either aluminum or stainless See Table 5-3 for the physical properties of MON.
steel containers with no serious corrosion. And The principal advantage of MON is that a t low
where the filling voids are in the order of 10 per- concentrations of water (less than 0.1 percent by
cent the equilibrium storage pressure does not weight) it can be stored practically indefinitely in
exceed 100 psia. either mild steel or aluminum containers. Its two
SFNA is the only oxidizer now in use having a principal disadvantages are its high melting point
low freezing point, high density, reasonable vapor ( - 1 ~ 3 ° C ) and its extreme toxicity.
pressure a t normal ambient temperatures, and Although a number of freezing point depressants
low viscosity. Since propellant systems based on have been investigated, the most promising one is
SFNA or RFNA (see Table 5-1) do not give as nitric oxide (NO). Because of the high volatility
high specific impulse values as those based on of the NO, the vapor pressure of solutions of NO
either fluorine or LOX, SFNA appears to be best in MON becomes quite high a t a storage tempera-
suited for applications where its physical proper- ture of 160°F. Thus a solution containing 16.85
ties and good storage properties are of such im- percent NO by weight has a freezing point of
portance that the lower specific impulse is approximately -29"F, and a vapor pressure of
acceptable, for example, in ready tactical missiles approximately 240 psis. Reference 39 presents
of short and medium range. data on the freezing point and vapor pressure of
solutions of NO in MON as a function of the NO
5-4.4.4. Mixed Oxides of Nitrogen. Table 5-4 concentration.
presents the physical properties of the seven As noted above MON is extremely toxic. The
known oxides of nitrogen; NzO, NO, N d h , NOz, maximum tolerable concentrations are quite small,
Nz04,N206, and KO3. It is apparent from Table 500 parts per million being rapidly fatal and
5-4 that X203,N205, and NO3 are too unstable exposure for 30 to GO minutes to a concentration
under ordinary conditions to be considered as oxi- of 100 parts per million being dangerous. Since
dizers for use in rocket jet propulsion engines. Of missiles using MON as the oxidizer could be filled
555514 0 - 60 - 5 61
ORDP 20-282
TABLE 5-5. PHYSICAL PROPERTIES OF OXIDIZING COMPOUNDS

CONTAINING FLUORINE AND OXYGEN
Av. Heat of Specific
Molecular Density Heat of Formation Heat
Weight P Melting Boiling Vaporization QI CP
-
m (@ temp. "C) Point Point Q" (@ temp. "C) (@ temp. "C)
Oxidizer (g/mol) (g/cc) "C "C (kcal/mol) (kcal/mol) (cal/mol "C)
F20 54 1.90-224 -223.8 -144.8 2.65 - 1.4-188 11. 3-18*

NO F 49 - -132.5 -59.9 - - -
NOzF 65 - - 166 -72.4 - - -
NOSF 81 - - 175 -45.9 - - -
at the factory, thereby eliminating the need for hydrogen reacting with the fluorine and the carbon
handling it in the field, its toxicity should not with the oxygen. A similar situation dccurs in the
rule it out as a possible oxidizer. Where space is case of fuels containing boron. Calculations show
limited, however, as on board a ship or submarine that the maximum specific impulse is obtained
the dangers from accidental damage to a storage with an oxidizer containing oyxgen and fluorine.
tank may be sufficiently great to prohibit its use. Table 5-5 presents the physical properties of
Recent experience with MON has been favorable some of the oxidizers which are compounds con-
from the standpoints of handling and hazard to taining fluorine and oxygen. Table 5-3 presents the
personnel, hence MON must be given considera- physical properties of a mixture containing 70 per-
tion in applications requiring storable oxidizers. +
cent Fz 30 percent 02,by weight.
5-4.5. Oxidizers Containing Fluorine and Oxy-
gen. For fuels containing carbon and certain 5-4.5.1. Fluorine Monoxide. Fluorine monoxide
metals, such as boron, the maximum specific im- +
(F20)and the 70 F2 30 0 2 mixture give reason-
pulse is obtained with an oxidizer containing both ably high values of specific impulse with non-
fluorine and oxygen. The combustion products carbonaceous fuels, and also with fuels containing
obtained by burning fuels containing the elements boron. FzO has a higher boiling point than the
hydrogen, carbon, and boron are tabulated below. aforementioned mixture and is easier to handle.
Since it is made from fluorine and the process
Combustion Products
Element with oxygen With fluorine gives a lorn yield of F20, it is more expensive than
either fluorine or fluorine-oxygen mixtures. More-
Hydrogen(H) HzO HF
over, there is the advantage that the proportions
Carbon(C) CO, COZ CF4, CF3, CFZ,C F
of a fluorine-oxygen mixture can be adjusted to
Boron(B) Bz03 BF3
the carbon-hydrogen ratio of a carbonaceous fuel.
The molecular weights of H 2 0 and H F are
comparable, 18.016 and 20.008 respectively, but 5-4.6. Perchlorofluoride (C103F). This oxidizer
H F is much more stable thermally than HzO. is a recent development. Its basic advantages are
Hence, if the predominant constituent of a fuel is that it is compatible with most materials of con-
hydrogen, then it will give a larger specific impulse struction, and its density is relatively high (1.43
with fluorine than with oxygen as the oxidizer. g/cc at 60°F). Its principal disadvantages are the
The molecular weights of CO and Con, on the HCl and H F in the exhaust products, its low
other hand, are smaller than those of the fluoro- availability, and high cost.
carbon species. Hence, if a fuel has a large carbon From an overall standpoint C103F does not
content, it gives its largest specific impulse with appear to offer any substantial advantages over
oxygen as the oxidizer. oxidizers such as H20z,SFNA, and MON. More-
From the foregoing it appears that in the case over, its high vapor pressure is a disadvantage in
of fuels containing the elements H and C, the using it in prefueled missiles, and also in turbo-
maximum performance is obtained with an oxi- pump pressurizing systems without refrigerating
dizer containing both fluorine and oxygen, the the C103F.
62
LIQUID PROPELLANTS
ORDP 20-282
TABLE 5-6. PHYSICAL PROPERTIES O F SOME LIQUID ORGANIC AND

NITROGEN HYDRIDE FUELS
Heat of
Av. Specific Formation Specific Heat Viscosity
Molecular Gravity Meltihg Boiling Q/ C P P
Weight P Point Point (@ temp. "C) (@ temp. "C) (@ temp. "C)
Fuel -
m (@ temp. "C) "C "C (kcal/mol) (Btu/lb OF) (Centipoise)
NHI 17 0.6120 -78 -33 11.025 1.1320 0 . 48-1°

NzHi 32 1.01'G 1 . 4 114 - 12.025 0 . 7425 1.26
CiHjOH 46 0.7920 -117 78.5 66. 325 0.54' 8 . 4-69
JP4 - 0 . 762O -60 (69) - - 10-55
UDMH 61.1 0.7gZ2 -57 63.0 -12.72' 0.6520 4.0-60
DETA 103.2 0.9620 -39 207 15. 426 - 100-'8
5-5. FUELS FOR LIQUID BIPROPELLANT The use of light metals as fuels for rocket motors
SYSTEMS appears attractive because when they combine
The factors to be considered in selecting a with oxygen to form oxides they have large
liquid chemical compound which mill be a satis- enthalpies of combustion. Since the combustion
factory rocket fuel have been discussed in para- products must have a low molecular weight, only
graph 5-1. From a performance viewpoint they the light metal elements such as lithium, beryl-
must have high enthalpies of combustion and yield lium, boron, and aluminum are of interest. In all
gas products having a low value of molecular cases the combustion temperatures are very high
weight %. As pointed out earlier, while the number and when allowance is made for the evaporation
of practical oxidizers is limited, there are many and dissociation of the oxides, it is found that they
fuels suitable for rocket propellant systems. For give major gains in specific impulse. Figure 5-2 is
convenience of discussion rocket fuels will be a bar graph comparing the enthalpies of combus-
grouped into the following classes: tion of several fuels.
1. Liquid hydrogen and light elements A disadvantage in the use of light metals as
2. Organic fuels rocket fuels is that their oxides in the exhaust
3. Nitrogen hydrides. make it smoky. Moreover, beryllium is extremely
Table 5-6 presents the physical properties of the toxic, and lithium is quite scarce.
more important organic fuels and the nitrogen
hydrides. 5-5.2. Borohydrides. Table 5-7 presents some of
the physical properties of the borohydrides. Cal-
culations show that after hydrogen the next
5-5.1. Liquid Hydrogen and the Light Elements. highest performance fuels are the boron com-
(44, 45) Liquid hydrogen gives the largest values pounds containing hydrogen. In this country much
of I, of all fuels, and with all liquid oxidizers (see research has been devoted to diborane (B2H6) and
Table 5-1). Because of its low boiling point pentaborane (B6HB).
(-423°F) its handling and storage is a difficult The borohydride fuels when reacted with F20,
problem, and its small specific gravity (0.07 a t Ft, 02,and H202offer theoretical maximum spe-
-423°F) is a disadvantage. It must be handled cific impulses, based on mobile equilibrium, of
with care because hydrogen gas forms explosive approximately 300 sec. (12) At present they are
mixtures with air. The limited experience with in short supply and also have certain undesirable
liquid hydrogen indicates that it can be handled properties. Thus, diborane (B2H6)boils a t - 135°F
in much the same manner as liquid oxygen. It and is unstable. It decomposes slowly to form large
appears that the use of liquid hydrogen will be quantities of hydrogen. Pentaborane (BSHB)has
limited to certain special applications for which a more favorable properties than diborane. It boils
high specific impulse is of prime importance. a t 140"F, and its rate of decomposition a t room
63
ORDP 20-282
10 : 1 !
HYDROGEN 5
BERYLLIUM HYDRIDE
DIBORANE
PENTABORANE
TETRABORANE
DECABORANE
LITHIUM HYDRIDE
JP-4
ETHYL ALCOHOL
FURFURAL
HYDRAZINE
Btu/lb x lo3 SOURCE: OLlN MATHIESON CHEMICAL CORf?
ENTHALPY OF COMBUSTION
(Taken from Reference 46)
Figure 5-2. Enthalpy of Combustion in Btu/lb of Several Fuels with Oxygen
64
LIQUID PROPELLANTS
ORDP 20-282
TABLE 5-7. PHYSICAL PROPERTIES O F BOROHYDRIDE FUELS

(Reference 46)
AV . Density Boiling 1Iclt ing

1~xolcC.ul:ir Point Point
P
Fuel Formula \Ye!ght (P/CC) "F "F
-1
Diborane BZHb 27.7 0.43 - 135 -265

Pentaborane BsHo 63.2 0.61 140 -52
Decaborane BIOHI, 122.3 0.94 415 21 1
temperature is comparatively slow. Decaborane Ethyl alcohol (C2H50H), also called ethanol,
is a solid a t room temperature. melts a t -117°C and boils a t 78.5"C. It is
Neither pure diborane nor pure pentaborane plentiful and inexpensive and is a good regener-
appear to ignite spontaneously when in contact ative coolant. Its main disadvantage is its low
with air. Apparently they decompose to form self- specific gravity (0.79 a t 20°C). It is compatible
igniting boron hydrides, and the mixture increases with most normal construction materials, is non-
in inflammability. Kone of the borohydrides de- toxic, and non-corrosive. Hot ethanol is said to
compose explosively, and they decompose slowly etch aluminum. With LOX the maximum ob-
even when heated. Violent decomposition can tainable specific impulse is approximately 240 sec
occur when they are in contact with other metals. (based on frozen composition) and its combustion
Considerable effort is being expended on the is smooth. Ethanol is non-hypergolic with most
development of boron compounds for use as addi- oxidizers.
tives to hydrocarbon fuels for use in rocket engines
and air-breathing engines. It is claimed that when 5-5.3.2. Light Hydrocarbon Fuels. In this group
reacted with oxygen these compounds have GO per- are those mixtures of aromatics, olefins, paraffins,
cent greater heat of combustion than jet engine and naphthenes that are termed jet engine fuels,
fuel. and are designated by "JP" with a numerical
If the borohydrides can be produced in large suffix. I n general, they have a carbon-hydrogen
quantities a t a reasonable price, they will be of ratio of approximately G and a lower heating value
interest as rocket fuels. of approximately 18,500 Btu/lb. Table 5-8 pre-
sents the physical properties of several such fuels.
5-5.3. Organic Fuels. All liquid fuels containing The J P fuels are plentiful and inexpensive, have
carbon and hydrogen are termed organic fuels, and good handling characteristics, are compatible with
several have been investigated for use in liquid most of the common materials of construction, are
rocket bipropellant systems. The discussions here non-toxic, have good storage properties, and give
will be limited to those organic fuels that are of reasonably high values of specific impulse either
with oxygen or mixtures of oxygen and fluorine.
current interest :
1. Ethyl alcohol The disadvantages of J P fuels are low specific
2. Light hydrocarbons (JP fuels) gravity and their tendency to crack and deposit
solids when used as regenerative coolants. They
3. Unsymmetrical dimethylhydrazine
(UDMH) also tend to deposit solids in the nozzles of the gas
4. Diethylenetriamine (DETA).
turbine for driving propellant pumps when used
with LOX in fuel-rich reactions to produce gases
5-5.3.1. Ethyl Alcohol. Ethyl and methyl alco- for driving the gas turbine.
hols are the only lower alcohols which have been With nitric acid and MON, the J P fuels give
low values of I , and the combustion is apt to be
investigated and used as fuels in rocket engines.
They are slightly inferior to t,he hydrocarbons in rough. It is found advahtageous to employ
additives to the J P fuel when it is used with either
performance. Ethyl alcohol was used in the Ger-
man V-2 missile and has been used in the Red- SFNA or MON to improve the combustion
stone missile. characteristics.
65
ORDP 20-282
TABLE 5-8. PHYSICAL PROPERTIES O F L I G H T HYDROCARBON LIQUID FUELS

(From Reference 46)
~~
Freeze Flash
Hydrocarbon Distillate Gravity Point Point
Fuel Range, O F deg, API O F , max O F , min General Description
JP-1 400-570 50-60 -76 110 Low freeze kerosene

JP-3 150-500 50-60 -76 NR1 High vapor pressure JP-4
JP-4 200-550 45-57 -76 NR Wide-cut gasoline
JP-5 350-550 36-48 -40 140 High flash kerosene
JP-6 250-550 37-50 -65 NR Thermally stable kerosene
RJ-1 400-600 32.5-36.5 -40 190 Thermally stable, heavy, kerosene
RP-1 380-525 42-45 -40 110 Pure, light cut kerosene
1 NR: No requirement.
I n applying J P fuels to long range missiles, DETA has a high specific gravity (0.96 a t 70"F),
problems arise due to the variations in the density is available in large quantities at fairly lorn cost,
and composition of the fuel. These changes has a moderately low freezing point (-38"F), and
materially affect the performance of the engine 'gives a larger I, with LOX than the JP fuels
and also complicate the accurate fueling of the give. It also gives better general performance with
missiles (see Paragraph 5-2.4). fuming nitric acid (FNA), being hypergolic with
The J P fuels are non-hypergolic with most very short ignition delays. It can be substituted
liquid oxidizers. for the JP fuels in missiles designed originally for
JP fuels, without, introducing any major problems.
5-5.3.3. Unsymmetrical Dimethylhydrazine Because of the greater density of DETA the per-
(UDMH). This fuel is currently being produced in formance of the missile is improved. DETA is
relatively large quantities under the trade name compatible with common construction materials
" dimazine." UDMH possesses excellent physical and has good storage, handling, and heat transfer
properties and is compatible with common con- characteristics.
struction materials. It burns smoothly with most
oxidizers and gives relatively high performance 5-5.4. Nitrogen Hydrides. Two stable nitrogen
(see Table 5-1). Its specific gravity is rather low hydrides are of interest as rocket fuels: ammonia
(0.79). (NH3), and hydrazine (NzH4). Their physical
UDMH is thermochemically unstable and has properties are presented in Table 5-6.
the pbtentialities of being used as a monopropel-
lant, but this requires more investigation. It is 5-5.4.1. Anhydrous Ammonia. Ammonia (NHJ
hypergolic y i t h fuming nitric acids a t very low is available commercially in large quantities, is
temperatures and gives extremely short ignition cheap, and can be stored in steel containers. It is
delays, approximately 2 milliseconds a t -75°F. moderately toxic but its presence is easily de-
It appears to be the most suitable fuel for use with tected. NH3 gives reasonably high values of
stabilized (red) fuming nitric acid (SFNA), specific impulse with most oxidizers and is non-
because of its excellent combustion characteristics hypergolic with most of them.
with that oxidizer. Ammonia has a lorn specific gravity (0.61 a t
5-5.3.4. Diethylenetriamine (DETA). There are 70°F) and a high vapor pressure (493 psia at
several organic amines which may be useful as 160°F). When used as a liquefied gas the vapor
rocket fuels. Some of them give reasonably high pressure problem is eliminated by applying refrig-
values of specific impulse and have good physical eration. Its lorn density detracts from its usefulness
properties. (12) All of them are toxic t.0 some as a rocket fuel, but it appears to be of interest
degree. Since they are reasonably stable a t high when used with fluorine as the oxidizer. Informa-
temperatures they may be good regenerative tion is lacking, however, on the capabilities of
coolants. ammonia as a regenerative coolant under the high
66
LIQUID PROPELLANTS ORDP 20-282
heat flux conditions occurring when i t is burned freezing points of N204 (12°F) and H202 (30°F).
with fluorine.
Ammonia gives smooth combustion with WFNA 5-5.4.3. Mixtures of Hydrazine and Ammonia.
and RFNA. The starting and stopping of the There is interest in N2H4-NH3mixtures because
rocket engine is also smooth. Although it is non- they have certain properties which are superior to
hypergolic with FNA, ignition can be made hyper- those of the individual constituents. (12) It has
golic by causing liquid NH3 to flow over a small been pointed out that NH3 is cheap, plentiful,
amount of lithium before entering t h e combustion stable under storage conditions, has a low freezing
chamber. point (-78"C), gives reasonable values of specific
impulse, but has a low density and a high vapor
5-5.4.2. Hydrazine. The physical characteristics pressure. Hydrazine, on the other hand, is rela-
of hydrazine (N2H4) as well as its storage and tively expensive and has a high freezing point
handling characteristics are discussed in para- (35"F), but its density is high and it gives larger
graph 5-3.6, where its use as a monopropellant was values of specific impulse than does NH3. By
described. Reference to Table 5-1 shows that adding NH3 to N2H4,a mixture can be made that
when used as the fuel in a bipropellant system it has a reasonably low freezing point, good 'per-
gives high values of specific impulse with every formance, and a reasonable density. For example,
oxidizer. Its main disadvantage is its high freezing a mixture of 38 percent by weight NH3 in N2H4
point (35"F), and the lack of adequate information freezes at -30"F, while the 50 percent NH3-
as to its characteristics as a regenerative coolant. 50 percent N2H4mixture freezes a t -40°F. As the
In a missile application it offers the advantage of NH3 content is increased the vapor pressure in-
monopropellant runout. creases, especially a t high temperatures. For
Hydrazine is hypergolic and gives small ignition 36 percent NH3 in N2H4,the vapor pressure a t
delays with all of the common oxidizers except 158°F is 18.5 atm. The mixture 37 percent NH3,
LOX. It appears to be the best fuel for use with 59 percent N2H4,and 4 percent water gives an
liquid fluorine, ClF3, H202,and MON. It is worth experimental value of specific impulse of approxi-
noting that the high freezing point of N2H4 mately 280 sec when burned with liquid fluorine
(35°F) is of the same order of magnitude as the a t 300 psia combustion pressure.
5-6. REFERENCES
1. Reinhardt, T. F., Utilization of New Pro- 4. Coe, C. S., and G. P. Sutton, The E$ect of
pellants in Rocket Engine Development, Office Liquid Propellant Properties on Rocket Engine.
of the Assistant Secretary of Defense (Re- and Missile Design and Operation, Office of
search and Development), P F L 20315 Sym- the Assistant Secretary of Defense (Research
posium on Liquid Propellants, Washington, and Development), PFL 20315, Symposium
D. C., Vol. 1, 13 May 1955 (Confidential). on Liquid Propellants, Washington, D. C.,
Vol. 1, 13 May 1955 (Confidential).
2. Zucrow, M. J., Aircraft and Missile Propul-
sion, Vol. 2, John Wiley and Sons, New York. 5. Tormey, J. F., Liquid Rocket Propellants,
1958. Aeronautical Engineering Review, Vol. 16,
October 1957, p. 55.
3. Hornstein, B., Available Propellants, Status
of Current Research and Needed Further 6. Stepanoff, A. J., Centrifugal and Axial Flow
Research, Office of the Assistant Secretary of Pumps, Chapter 12, John Wiley and Sons,
Defense (Research and Development), P F L New York. 1958.
20317, 3 October 195G (Confidential).
67
ORDP 20-282
7. Bartz, D. R., Factors Which Influence the 17. Tschinkel, J. G., Calculation of a Mollier
Suitability of Liquid Propellants as Rocket Diagram for the Decomposition Products of
Motor Regenerative Coolants, Jet Propulsion Aqueous Hydrogen Peroxide Solutions of 90
Laboratory, California Institute of Tech- Per Cent H 2 0 2Content, Jet Propulsion, Vol. 26,
nology Memorandum, No. 20-139, Decem- NO.7, Pt. 1, July 1956, pp. 569-71, 575.
ber 28, 195G. 18. Keefe, J. H., and C. W. Raleigh, Field Trans-
8. Hess, L. G., and V. V. Tilton, Ethylene Oxide, portation of Concentrated Hydrogen Peroxide,
Hazards and Methods of Handling, Industrial Jet Propulsion, Vol. 27, No. 6, June 1957,
and Engineering Chemistry, Vol. 42, pp. pp. 663-4, 677, 737.
1251-8. 1950. 19. Makepeace, G. R., Liquid Bi-propellant
9. Wilson, E. M., The Stability of Ethylene Oxide, Systems Based on Hydrogen Peroxide and
American Rocket Society, Journal, Vol. 23, Kerosene, 2nd Literbureau Conference on
No. 6 , November-December 1953, pp. 368-9. Liquid Propellants for Guided Missiles,
Naval Ordnance Laboratory, White Oak,
10. Walter, H., Experience with the Application Md., 3 November 1949.
of Hydrogen Peroxide for Production of Power,
American Rocket Society, Journal, Vol. 24,
20. Audrieth, L. F., and P. H. Mohr, Autoxida-
No. 3, May-June 1954, p. 1%.
tion of Hydrazine, Industrial and Engineering
11. Grant, A. F., Jr., State of the A r t of Liquid Chemistry, Vol. 43, August 1951, pp. 1774-9.
Propellants, Jet Propulsion Laboratory, Cali-
21. Liebhafsky, H. A., Use of Hydrazine Hydrate
fornia Institute of Technology, Publication
as a Fuel, Chemie et Industrie, Vol. 56,
No. 103. July 31, 1957 (Confidential).
1946, p. 19.
12. Briglio, A., A Review of Liquid Rocket Pro-
pellant Systems, Office of the Assistant 22. Hill, T. C. H., and J. F. Sumner, T h e Freezing-
Secretary of Defense (Research and Develop- Point Diagram of the Hydrazine-Water System,
ment), PFT, 20317, 3 October 1956 (Con- Chemical Society (London) , Journal, March
fidential). 1951, pp. 838-40.
13. Buffalo Electro-Chemical Company, Inc. , 23. Altman, D., A Review of Liquid Propellant
Properties of Hydrogen Peroxide, Revised Oxidizers, Office of the Assistant Secretary of
1955. Defense (Research and Development), Sym-
posium on Liquid Propellants, Washington,
14. Davis, K. S., and J. H. Keefe, Equipment for D. C., Vol. 1, 13 May 1955.
Use with High-Strength Hydrogen Peroxide,
American Rocket Society, Journal, Vol. 22, 24. Fluorine Figures Big, Jet Propulsion, Vol. 27,
No. 2, March-April 1952, pp. 63-9. No. 6, June 1957, pp. 678-9.
15. Perrin, R., et al, Buffalo Electro-Chemical 25. Rand Corporation, Physical Properties and
Company, Inc., Freezing Point Depressants Thermodynamic Functions of Fuels, Oxidizers
.for Concentrated Hydrogen Peroxide, Sixth and Products of Combustion, II-Oxidizers,
Quarterly Progress Report LR-19, prepared R-129, February 1949.
under Navy Contract XOas 53-104C1 1 De-
cember 1953 (Confidential). 26. Handbook of Chemistry and Physics, Chemical
Rubber Publishing Co., Cleveland. 1949.
1G. Williams, G. C., C. N. Satterfield, and H. S.
Isbin, Calculation of Adiabatic Decomposition 27. Rossini, F. D., et all Selected Values of
Temperatures of Aqueous Hydrogen Peroxide Chemical Thermodynamic Properties, Circular
Solutions, American Rocket Society, Journal, 500, National Bureau of Standards, Wash-
Vol. 22, No. 2, March-April 1952, pp. 70-7. ington, D. C., 1 February, 1952.
68
SOLID PROPELLANTS ORDP 20-282
28. Taylor, A. H., Ozone Preparation and Stability 37. Schlinger, W. G., and B. H. Sage, Volumetric
in High Concentrations, Air Reduction Sales Behavior of Nitrogen Dioxide, Industrial and
Co., Murray Hill, N. J., Final Report,, Vol. 1, Engineering Chemistry, Vol. 42, 1950, pp.
27 December 1949 (Confidential). 2158-2 163.
29. Research on the Properties of Ozone, Linde 38. Allied Chemical and Dye Corp., Nitrogen
Air Products Company, Tonawanda, N. Y., Tetroxide, Product Development Booklet
Progress Report No. 13, 1 January 1955 NT-1, Solvay Process Division, New York.
(Confidential). 39. Whittaker, A. G., et all Vapor Pressures and
30. Robertson, G. D., D. M. Mason, and W. H. Freezing Points of the System h'itrogen
Corcoran, The Kinetics of the Thermal Tetroxide-Nitric Oxide, American Chemical
Decomposition of Nitric Acid in the Liquid Society, Journal, Vol. 74, pp. 4794. 1952.
Phase, Jet Propulsion Laboratory, California
40. Cole, L. G., The Nitrogen Oxides as Rocket
Institute of Technology, Progress Report
Fuel Oxidants Including the Theoretical Per-
No. 20-223, 29 January 1954.
formances of Propellant Systems Employing
31. Johnston, H. S., L. Foering, and Tao Yu- Nitrogen Tetroxide, Jet Propulsion Labora-
Sheng, The Kinetics of the Thermal Decompo- tory, California Institute of Technology,
sition of Nitric Acid Vapor, Stanford Uni- JPL/CIT, Prog. Rept. 9-23, 18 October 1948
versity (Final Report to M. W. Kellogg Co.). (Confidential).
32. Mason, D. M., L. L. Taylor, and H. F. Keller, 41. Yost, D. M., and H. Russell, Systematic
Storability of Fuming Nitric Acid, Jet Propul- Inorganic Chemistry, Prentice-Hall, New
sion Laboratory, California Institute of Tech- York. 1944.
nology, JPL/CIT, Rept. No. 20-72, 28
42. Wilde, K. A., An Approximate Specific Im-
December 1953.
pulse Equation for Condensable Gas Mixtures,
33. Mason, D. M., Properties of Fuming Nitric Jet Propulsion, Vol. 27, No. 6, June 1957,
Acid Affecting Its Storage and Use as a Rocket pp. 668-9.
Propellant, Jet Propulsion, Vol. 26, No. 9,
43. Greene, S. A. and 1,. J. Gordon, An Effect of
pp. 741-4, 756. September 1956.
Carbon in a n Adiabatically Expanded Gas
Stream, Jet Propulsion, Vol. 27, No. 6,
34. Levoe, C. E., and D. M. Mason, Inhibiting
June 1957, p. 667.
Effect of Hydrojluoric Acid in Fuming Nitric
Acid on Corrosion of Austenitic Chromium- 44. Johnston, H. L., and W. L. Doyle, Develop-
Nickel Steels, Jet Propulsion Laboratory, ment of the Liquid Hydrogen-Liquid Oxygen
California Institute of Technology, JPL/ Propellant Combination for Rocket Motors,
CIT, Prog. Rept. 20-253, 14 January 1955. Cryogenic Laboratory, Ohio State University
Research Foundation, Technical Report No.
35. Mason, D. M., and L. L. Taylor, Inhibiting 333-5, December 1951 (Confidential).
Effect of HydroJEuoric Acid in Fuming Nitric
Acid on Liquid and Gas-Phase Corrosion of 45. Weisenberg, I. J., and W. P. Rerggren,
Several Metals, Jet Propulsion Laboratory, Liquid Hydrogen as a Regenerative Coolant,
California Institute of Technology, JPL/ Cryogenic Laboratory, Ohio State University
CIT, Prog. Rept. 20-255, 24 January 1955. Research Foundation, Technical Report No.
333-3, 1 April 1950 (Confidential).
36. Fetter, E. C., Nitric Acid Versus Construction
Materials, Chemical Engineering, Corrosion 46. Gasoline to Kerosene to 'Zip'-With Energy
Forum Sections, Vol. 55, Feb., March, Calling the Signals, Jet Propulsion, Vol. 27,
April 1948, pp. 233; 225; 219. No. 6, June 1957, pp. 682, (389-90.
ORDP 20-282
47. Zucrow, M. J., and J. R. Osborn, An Ezperi- 48. Winternitz, P. F., and D. Horvitz, Rocket
mental Study of High Frequency Combustion Propellant Performance and Energy of the
Pressure Oscillations, Jet Propulsion, Vol. 28, Chemical Bond, American Rocket Society,
No. 10, October 1958, pp. 654-9. Journal, Vol. 21, No. 85, June 1951, pp. 51-67.
70
Chapter 6
PROPERTIES AND CHARACTERISTICS OF SOLID PROPELLANTS
Due to the significant advances made in the 6-1.3. Controllable Linear Burning Rate (T,,).
technology of solid propellants, they must be It is desirable to be able to control the linear
given consideration in missile applications that burning rate TO, over a wide range. With current
once mere deemed suitable only for liquid propel- composite solid propellants, linear burning rates
lant rocket engines. (1, 22) While the emphasis in from approximately 0.1 in/sec to 2.0 in/sec are
this section will be on composite propellants, obtainable. A wide range of available burning
great strides have been made in the development rates increases the design flexibility of solid pro-
of double-base propellants, and for several appli- pellant rocket motors. Also, it is desirable that the
cations they are superior to composite propellants. linear burning rate be rather insensitive to the
combustion pressure.
6-1. DESIRED CHARACTERISTICS FOR A
SOLID PROPELLANT 6-1.4. Physical Properties. The important
The factors to be considered in judging the physical properties are tensile strength, elonga-
merit of a solid propellant are discussed below. tion, adhesion, and fluidity. A high tensile strength
is needed so that the grain will not deform under
(1, 3)
the required operating conditions. A high percent
6-1.1. Specific Impulse ( I B ) .The specific im- elongation is necessary so the grain will not crack
pulse should have the largest possible value since when it is deformed by either pressure or tem-
the ideal burnt velocity Vbi (see equation 3-36) is perature changes. The requirement of reasonably
directly proportional to I,. For modern composite high tensile strength and elongation limit the
propellant formulations the basic ingredients are oxidizer-binder ratio.
such that the combustion gases are compounds of In case-bonded designs it is essential that the
the following elements: carbon (C), hydrogen (H), propellant grain adhere strongly to the metal case
nitrogen (N), oxygen (0),and chlorine (Cl). For and that the bond be not broken either by the
C-H-N-O-C1 systems the maximum obtainable expansions or contractions of the case.
specific impulses are in the range 240 to 250 sec. In the case of castable composite propellants the
For a given composite propellant the specific oxidizer-binder slurry must be able to flow readily
impulse increases with the ratio of oxidizer to into the chamber wherein it is to be cast and cured.
binder. There is a limit, however, to the quantity The fluidity of the slurry depends upon the
of oxidizer which can be incorporated into a given oxidizer-binder ratio and the particle size and
binder (2) (see Paragraph 6-1.4). Various light particle size distribution of the oxidizer. This
metals are added to both composite and double- consideration also limits the useful oxidizer-binder
base propellant formulations for increasing the ratio.
specific impulse. (21) It is desirable that the propellant have good
physical properties over the temperature range
6-1.2. Density of Propellant. The propellant -65 to +165"F, and be able to withstand tem-
should have a high density in order to provide a perature cycling between those limits. (4)
large amount of propellant in a small space, and
thereby reduce the dimensions of the rocket motor. 6-1.5. Chemical Stability. High chemical sta-
For most composite solid propellants the densities bility is desirable so that the solid propellant will
range from 1.65 to 1.70 g/cc compared to approxi- have good aging characteristics, that is, per-
mately 0.94 g/cc for liquid propellant systems. formance should not deteriorate with long time
storage.
71
ORDP 20-282
6-1.6. Toxicity. It is desirable that the propel- TABLE 6-1. OXIDIZERS FOR USE IN
lant be safe to handle and that its combustion COMPOSITE PROPELLANTS
products be non-toxic and not linger around the
launching site.
% Oxygen
Name Formula m Available
6-1.7. Explosive Hazard. The propellant should Ammonium nitrate NHdNO, 80.05 20
be safe t o handle using well known, and more or Ammonium perchlorate NH,CIO, 117.49 31
less conventional procedures. It should have a Potassium nitrate KNOi 101.10 39.5
Potassium perchlorate KCIO, 138.55 46.5
relatively high ignition temperature and not burn Lithium perchlorate LiCIO, 106.40 60.0
readily a t low pressures. However, it should
ignite readily when fired by the igniter.
There is a large background of experience with
6-1.8. Smoke. For many applications it is all of the oxidizers listed in Table 6-1, except
desirable that the exhaust be smokeless, that is, lithium perchlorate.
there should be no solid materials in the exhaust All perchlorate oxidizers produce hydrochloric
gases. acid in the exhaust gas which condenses into a fog
on a moist day. The gases from a propellant based
6-1.9. Shock Sensitivity. It is desirable that the on KC104 are smoky because they contain con-
propellant shall not detonate due to either me- densed potassium chloride which is a white
chanical or thermal shock. powder. Practically all of the high performance
castable composite propellants are based on am-
6-1.10. Availability of Raw Materials. If the monium perchlorate as the oxidizer.
propellant will be used in large quantities during Propellants based on metallic nitrates as oxi-
an emergency the raw materials from which the dizers, such as K N 0 3 or NaN03, produce smoky
binder and oxidizer are made should be available exhausts. A great deal of effort has been expended
in abundant quantities. on the development of propellants based on
ammonium nitrate because of its abundance, low
6-1.11. Fabrication and Process Control. The cost, and its non-toxic, smokeless exhaust. Due to
propellant should be compatible with the usual its low available oxygen content and the effect of
construction materials, and should lend itself to temperature on its crystalline structure, it is
process control methods for assuring product difficult to make a high performance castable
uniformity in all respects when produced in large propellant having good rheological (plastic) prop-
quantities. erties using NH4N03as the oxidizer.
6-1.12. Cost. It is desirable, of course, that the

propellant be relatively inexpensive. 6-3. FUELS FOR COMPOSITE
The propellant should have a lorn shrinkage PROPELLANTS
during cure and its curing exotherm should be
As pointed out in paragraph 2-3.4, the fuel for a
IOW. A low curing temperature enhances safety in composite solid propellant serves as the binder for
the manufacturing process.
the oxidizer particles. Several organic materials
have been investigated as possible fuels. Those
6-2. OXIDIZERS FOR COMPOSITE
PROPELLANTS used in modern formulations are elastomeric
monomers which, after being thoroughly mixed
As in the case of liquid bipropellant systems, with the oxidizer, polymerize during the curing
there are only a few oxidizers which are useful in process. I n general, the curing process is exo-
the manufacture of solid composite propellants. thermic. Of the large number of organic binders
The useful oxidizers and the weight percent of which either have been or are being investigated,
oxygen available in them are presented in Table those receiving the greatest development effort are
G-1. listed in Table 6-2.
72
SOLID PROPELLANTS
ORDP 20-282
TABLE 6-2. BINDERS FOR COMPOSITE the linear burning rate is a secondary effect which
PROPELLANTS gives rise to erosive burning which is discussed in
paragraph 6-4.4.1. Since the experiments for meas-
Binder Propellant manufacturer uring the burning rates of propellants can be
polysulfides Thiokol Chemical Corp. conducted with V, = 0, with end-burning grains
polyurethanes Aerojet-General Corp. for example, the following functional equation
butadiene pyridine
copolymers Phillips Petroleum Co. may be written for the linear burning rate:
butadiene-acrylic acid
copolymers Thiokol Chemical Corp.
petrinacrylate Rohm and Haas, Redstone
Arsenal
where ro = r = linear burning rate for V, = 0.
All of the binders listed in Table 6-2 have been The form of the functional relationship ex-
used in making castable propellaiits except the pressed by equation (6-2) is determined experi-
butadiene pyridiiie copoiymers; these have been mentally. I n the experiments t,, the temperature
used for making molded propellants principally of the propellant prior to ignition is held constant.
with NH4N03 as the oxidizer. Experiments show that for a fixed value of t,, the
It is desirable that the binder contain a small relationship between p , and ro can be represented
amount of oxygen so that a closer approach to by
stoichiometric oxygen balance can be achieved, ro = c p't (6-2)
and not have the solid oxidizer content become so where c and n are determined experimentally.
large that the propellant will have either poor Equation (6-2) is known as Saint Robert's law,
rheological or mechanical properties. and in applying that law it is assumed that the
pressure exponent n is independent of p , and t,,
6-4. BALLISTIC PROPERTIES OF SOLID while the burning-rate coefficient c depends on t,
PROPELLANTS (1, 5, 6) and is independent of p,. The exponent n, for
The flight characteristics of a ballistic missile most solid propellants, has a value between
depend (among other things) on the performance approximately 0.1 to 0.8. There are some double-
of the propellant. Important flight performance base propellant formulations, however, for which
(ballistic) properties are described in the following is zero and even negative over a usable pressure
paragraphs. range.
The burning rates of modern castable composite
propellants, based on ammoiiiuni perchlorate as
6-4.1. Linear Burning Rate. A solid propellant
the oxidizer, can be varied over a wide range by
burns a t its surface but the exact combustion
means of additives. For large solid propellant
mechanism is not completely understood. As the
motors, a low burning rate with a small pressure
burning proceeds, the burning surface recedes in a
exponent is desirable.
direction perpendicular to itself. The rate a t which
The weight rate of propellant consumption,
the burning surface recedes is called the linear
assuming steady operation, is given by equation
burning rate and is denoted by r. The burning
(3-17) which is rearranged here for convenience,
rate depends in general on the propellant formula-
Thus
tion and the conditioiis under which it is burned:
i t is a characteristic property of the propellant.
iv = c , , , ~ , A (Ib/sec)
~ 03-31
For a given propellant, the burning rate is a func- In terms of the linear burning rate ro
tion of the combustion pressure p,, the propellant
= ro S , y p (lh/sec) (6-4)
temperature t,, the velocity of the combustion gas
where
parallel to the burning surface V, (for an eiid-
At =throat area of exhaust nozzle, sq in
burning grain V, = 0), and the elapsed time T
S, =burning area of propellant, sq in
after the grain is ignited. However, for a material
y p = specific weight of propellant, lh/cu in
to be a satisfactory solid propellant for a rocket
engine, its linear burning rate must be independent Figure 6-1 presents linear burning rate data ro,
of the time. Furthermore, the influence of V, on a t G O O F , for several composite propellants made by
73
ORDP 20-282
2 .oo
1.50 - __ -.
. .. -
1.00
0.80
0.60
0
0 POTASSIUM PERCHLORATE
v)
\
.-c
LO
- 0.40-
I
L MEDIUM-ENERGY
W
sCr
0.20 ~
W
z
Z MIXED AMMONIUM PERCHLORATE
a
3 AND AMMONIUM NITRATE \
m
0.10
a
4
z
0.80 - - -
t
,
AMMONIUM NITRATE I I
0.40 I __ 4 . _
- 1 t
AEROPLEX PROPELLANTS
0.30 I I
200 300 400 500 600 1000 800 1500 2000
COMBUSTION PRESSURE, p c , psia
Sowce: Aerojet-General Corporation
(Taken from Reference 11
figure 6-1. Burning Characteristics of Several Heterogeneous Propellants at 600 F
74
SOLID PROPELLANTS
ORDP 20-282
compounding the same binder (fuel) with different Consequently, the propellant area ratio K , must
amounts and kinds of organic oxidizers. have a value such that it will give a combustion
pressure larger than the combustion limit. The
6-4.2. Propellant Area Ratio and Equilibrium latter must be determined experimentally.
Combustion Pressure. (1, 7) Under steady state If K , is increased continually for a given propel-
operating conditions, at constant t,, the combus- lant the pressure also increases until finally a
tion pressure remains constant and is termed the value is reached which, if exceeded, causes the
equilibrium combustion pressure. Let combustion pressure to increase practically be-
yond bounds. This value of the combustion pres-
K -
-
% = propellant area ratio
At (6-5) sure is called the pressure limit.
6-4.3. Effect of Propellant Temperature. The

where A t = nozzle throat area (area of the cross- temperature of a solid propellant affects its general
section of the throat of the exhaust nozzle). physical characteristics and its burning rate. At
The equilibrium combustion pressure p , is low propellant temperatures the elastic properties
given by of practically all solid propellants become poor,
and in some cases the grain may become so brittle
that it may crack when subjected to either shock
or temperature cycling. Differences in the thermal
expansion of the metal case, the liner of a case-
where Ay = y, - yo. bonded grain, and of the propellant may cause the
Equation (6-6) shows that the propellant area grain to crack. When the flame reaches the crack
ratio Kn exerts a predominant influence on the there is a large increase in the burning surface
equilibrium combustion pressure. Since n is less with a corresponding increase in K,. As a result the
than unity (except for the specific double-base combustion pressure may reach prohibitive values.
powder formulations mentioned in paragraph Certain propellants become more difficult to
6-4.1) the exponent 1/(1 -n) is always larger than ignite as the propellant temperature is lowered
unity. Consequently, an increase in K , results in a thereby increasing the ignition delay (time elapsed
much larger increase in p,. Consequently, the between firing the igniter and complete ignition of
value of K , must be held within close limits if the the burning surface).
design value for p , is to be realized. It is because A t high propellant temperatures above 140°F
of the strong dependence of p , on K,, and in the many solid propellants tend to soften and become
interest of decreasing the sensitivity of p , to plastic. They may not be able to withstand the
minor variations in K,, that a small value for the sudden pressure application during ignition with-
pressure exponent n is highly desirable. out appreciable deformation of the grain.
For a fixed propellant temperature t,, experi- Some propellants are subject to cold flow or
ments demonstrate that the nozzle area ratio K , slump when stored at the higher ambient tem-
can be related to the combustion pressure p , by peratures, changing the configuration of the grain
the relationship (1) and hence the performance of the rocket motor.
K, = bp? 03-71 Because of the influence of the propellant tem-
perature upon the physical characteristics of a
where the exponent m is independent of t, and the solid propellant, it is important that serious atten-
coefficient b is a function of t,. tion be given to the temperature limitations which
The relationship between the weight flow co- are recommended for solid propellant rocket
efficient C, and p , can be represented by an motors during their storage and handling.
empirical equation of the form
c, = hp: (6-8) 6-4.3.1. Temperature Sensitivity. The linear
burning rate for a given propellant burning with a
For every solid propellant there is a value of fixed value of K , is affected by the propellant
combustion pressure, called the combustion limit, temperature t,. In general, r g decreases if t, is
below which stable combustion is not possible. decreased and vice versa. The effect of t, on TO for
75
ORDP 20-282
a solid propellant is termed temperature sensi- to solve the problem by developing solid propel-
tivity. (1, 8) lants having insignificant temperature sensitivity, -
It is customary to express the temperature research in this area should receive strong support.
sensitivity of the ballistic parameters (TO, p,, F ) ,
in percent change per degree Fahrenheit from 6-4.4. Combustion of Solid Propellants. There
their values a t some standard temperature are two combustion phenomena of particular
t, = 20 (usually to = 60°F), under a constant con- significance to the performance of solid propellant
dition of K,. When t, > to the parameters have rocket engines; erosive burning, and resonant
values larger than those corresponding to t, = to, burning.
and vice versa.
Thus the temperature sensitivity coefficient for 6-4.4.1. Erosive Burning. As mentioned in
the linear burning rate, denoted by x,, is defined paragraph 6-4.1, the velocity of combustion gases
by parallel to the burning surface has an effect upon
the linear burning rate called erosive burning.
Although the exact mechanism whereby the burn-
ing rate increases as the combustion gas velocity
is increased is only incompletely understood, its
where (a ro/a t J K n is the rate of change for the occurrence has been observed. Since erosive burn-
linear burning rate with temperature for a con- ing increases with increased gas velocity, the effect
stant value of K,. is more pronounced in a restricted flow cross-
For thrust F and combustion pressure p,, one section such as the nozzle end of an internal-
can write burning case-bonded grain during the initial
phases of combustion. Erosive burning is evi-
thrust temperature denced by peaks in the combustion pressure
(6-9b) during the early phase of the combustion of the
sensitivity coefficient
propellant grain.
and No completely satisfactory relationship has
been developed for correlating data on the erosive
combustion pressure burning of solid propellants. (9, 20) It is cus-
temperature sensitivity tomary, however, to express the erosive burning
coefficient (6-9~) of a solid propellant in terms of the erosion ratio e
The temperature sensitivity of a solid propellant as a function of the gas velocity V,, where
and the application of the motor must be given e = r/ro (6-10)
careful consideration. In the case of a ballistic
missile the different burning rates a t different pro- and r is the linear burning rate with erosive
pellant temperatures cause the trajectories to burning.
vary from the standard ones, and can cause large From the limited data available it appears that
divergences unless they are taken into account. e increases with the gas velocity V, when the latter
The temperature sensitivity of solid propellants is above some minimum value. Furthermore, it
has been one of the serious disadvantages in the appears that e is larger for the slower-burning pro-
application of solid propellant rocket motors t o pellants, and is independent of t,. More research
ballistic missile propulsion. For many applications is required to obtain a better understanding of,
the cold weather problem can be circumvented by and more reliable data on, erosive burning.
using heating blankets to keep the propellant a t a When it becomes available this missing informa-
specified temperature. Many schemes have been tion will be of great value in developing the large
suggested for overcoming the adverse effects of grains required for the larger ballistic missiles.
temperature sensitivity upon the performance of
ballistic missiles, but all of them introduce un- 6-4.4.2. Resonant or Sonant Burning. It has
desirable complications which may decrease the been observed that the combustion pressure, and
reliability of the missile. Since it is highly desirable consequently the thrust, of an internal-burning
76
SOLID PROPELLANTS
ORDP 20-282
solid propellant grain may increase practically are large, but those in the nozzle throat are
instantaneously to several times its equilibrium several-fold those for the aft-cap. The aft-cap is
value for no apparent reason. (10, 19) This phe- protected from reaching dangerously high metal
nomenon has been termed resonant burning, temperatures by protecting it with layers of a
sonant burning, and combustion instability. The suitable insulating material. I n general, the ex-
few published experimental results indicate that haust nozzle is equipped with a ceramic or carbon
sonant burning is always accompanied by dan- liner for protecting the outer metal case surround-
gerous high-frequency, large-amplitude oscilla- ing the liner. Propellants which contain metals in
tions in the combustion pressure, with the burning their formulation may introduce problems because
rate increasing to as much as two and one-half of the tendency of their exhaust gases to erode the
times its steady state design value. throat of the exhaust nozzle. Considerable re-
Currently there is no satisfactory theory for search and development effort is required for
explaining the cause of sonant burning, or for developing satisfactory temperature resisting ma-
predicting whether or not it will occur in a specific terials for protecting the inert parts of solid pro-
solid propellant rocket motor design. Recent ex- pellant rocket motors.
periments have shown that the addition of small Of importance is the fact that the heat trans-
amounts of either aluminum or aluminum oxide ferred to the burning surface of a solid propellant
t o either double-base or composite propellant grain by the hot combustion gases flowing past the
formulations effectively reduces or completely surface does not penetrate far below that surface,
eliminates resonant burning. (21) Unfortunately, because of the rapid rate with which the surface
there is a t present no satisfactory explanation of recedes. Consequently, the changes in temperature
the mechanism of resonant burning for solution of the propellant grain due to the heat transfer
of the problem. need not be considered in internal ballistic studies.
6-5. HEAT TRANSFER IN SOLID PRO- Under transportation and short time storage
PELLANT ROCKET MOTORS conditions the temperature of the propellant grain
in a solid propellant rocket motor will generally
Heat is transferred from the hot combustion be different from that of the ambient atmosphere.
gases to those surfaces in contact with them by The heat transfer from the atmosphere to the
convection, radiation, and conduction. Of those propellant takes place a t a slow rate, and when the
modes of heat transfer, convection is the dominant, temperature difference is substantial, significant
one. The quantity of heat transferred to the sur- temperature gradients can arise in the grain that
faces in contact with the combustion gases is a cause severe thermal stresses. If the grain is being
complex function of several variables, such as the cooled by the ambient temperature, assuming a
flame temperature, the physical properties of the case-bonded internal-burning grain, then the grain
combustion gases, the grain design, the combus- tries to pull away from the case and there are
tion pressure, and the configuration of the motor large tensile stresses at its inner and outer sur-
case and exhaust nozzle. Since the total weight of faces. (17, 18)
the inert metal parts must be held to a minimum
for a ballistic missile engine, the internal-burning 6-6. DESIGN CONCLUSIONS (1, 12)
case-bonded grain design is favored since only the
fore-cap and nozzle are exposed to the hot gases. The design details of a solid propellant rocket
I n general, for short burning durations the prob- engine will depend upon the mission it must fulfill,
lems due to heat transfer are not serious. For the storage temperatures and temperature cycling
applications such as ballistic missiles where the it will encounter, and the conditions it will be
duration of burning is relatively long, the prob- subjected to under field handling conditions. By
lems arising from heat transfer are difficult and and large most of the requirements to be satisfied
challenging. are of a practical nature and are not subject to an
Because of the extremely high mass velocity of accurate analytical study. Once the specific pro-
the combustion gases and their high temperature pellant formulation has been decided upon, the
(4500 to 5500°F for high performance propellants), designer has considerable latitude in selecting such
the heat tra.nsfer rates to the aft-cap and nozzle parameters as the combustion pressure, burning
555514 0 - 60 - 6 77
ORDP 20-282
rate, grain configuration, and the design of the sized that the development and application of
case. reliable process control procedures are as much a
The problems which must be solved in develop- part of the development of a satisfactory solid
ing solid propellant motors are primarily those propellant, as is the chemical research which enters
pertinent to obtaining precise thrust termination, into determining the most satisfactory propellant
accurate thrust vector control, and means for formulation.
taking into account the temperature sensitivity of If y p denotes the specific weight of the propel-
the propellant. lant, and V, the volume of the grain, then
6-6.1. Selection of the Combustion Pressure.

v, = WP/YP (6-12)
For a rocket motor equipped with a conventional
6-6.3. Determination of Grain Dimensions and
type of exhaust nozzle having fixed geometry, the
Nozzle Throat Area. The exact dimensions of the
following design criteria apply:
propellant grain depend upon the configuration
(a) The combustion pressure p , should be a t which is selected: internal-burning star, rod and
least 100 psia above the combustion limit (see
tube, etc. (13) I n general, the shape of the grain
Paragraph 6-4.2) corresponding to the lowest
must be such that its burning area S, has the
value of propellant temperature t, which is to be
correct value for producing the required thrust
encountered.
throughout the burning period.
(b) The combustion pressure should be well The throat area of the exhaust nozzle A t may be
below the pressure limit corresponding to the
determined from any one of the following three
highest value of t, to be encountered (see Para-
relationships. (1) Thus
graph 6-4.2). In general, higher combustion
pressures are employed for short duration boost
applications where a large but brief thrust is
desired, and moderate combustion pressures for
long duration applications where the weight of
the inert parts of the rocket motor must be kept
as light as possible.
where the weight flow coefficient C,, (see equation
(c) The combustion pressure depends upon the
3-17) is obtained from experimental data pertinent
selection of the linear burning rate TO obtainable
to the propellant.
from the propellant formulation. Note that the
The exit area for the nozzle depends on the
relation between p , and TO is exponential (see
expansion ratio for the exhaust nozzle ( p d / p c )
equation 6-2).
and 'the specific heat ratio k, for the combustion
gases (see Chapter 4).
6-6.2. Estimation of Size and Weight of Propel-
lant Grain. The total weight of a solid propellant
6-6.4. Effect of Grain Shape. The thrust of a
grain, denoted by W,, depends upon the total
solid propellant rocket motor, like the combustion
impulse required for satisfying the requirements
pressure, varies with the area of the burning sur-
of the mission. If F denotes the thrust required
face S,. Consequently, variation in the area of the
(assumed to remain constant during the burning
burning surface can be utilized for programming
time 7 6 ) and I , is the specific impulse of the pro-
the thrust as a function of the burning time.
pellant, then
(14, 15, 16) The programming is accomplished by
w, = F7b/Is (6-11)
shaping the grain in such a manner that the de-
Equation (6-11) gives the minimum weight of sired amount of burning surface is provided a t
solid propellant for the required total impulse. each instant during the burning period.
That weight should be increased by 1 to 3 percent) A grain designed for maintaining the area of the
depending upon the uniformity of the product and burning surface constant during the burning
the closeness with which it meets the design period produces a constant thrust throughout
specifications, t o allow for slivers of the propellant that period and is termed a neutral-burning grain.
that are not consumed. It cannot be overempha- A grain which burns so that the thrust increases
78
SOLID PROPELLANTS
ORDP 20-282
with the burning time is said to be a progressive- In addition to the aforementioned geometric
burning grain, and one for which the thrust type of control, the area of the burning surface
decreases with the burning time is called a can also be varied by employing inhibiting coat-
regressive-burning grain. ings so that certain areas of the grain are pre-
With case-bonded, internal-burning, star- vented from burning.
shaped, or cruciform grain, it is possible by proper A third method of thrust program control which
arrangement of the geometric proportions between may be preferable for certain applications can be
the number of points of the star, the angle between accomplished by constructing the grain from
those points, and web thickness, to obtain either propellants having different burning rates.
neutral, progressive, or regressive burning charac-
teristics.
6-7. REFERENCES 10. Smith, R. P., and D. F. Sprenger, CombuStion

Instability in Solid Propellant Rockets, Fourth
1. Zucrow, M. J., A i r c r a f t a n d Missile Pro- Symposium (International) on Combustion,
pulsion, Vol. 2, Chapter 10. John Wiley The Williams and Wilkins Co. , Baltimore,
and Sons, New York. 1958. Md. 1953, pp. 893-906.
2. Geckler, R. D., and R. E. Davis, M o d e m 11. Green, L., Jr., Some Eflects of Charge Con-
Developments in Solid Propellant Rocket figuration on Solid Propellant Combustion,
Engineering, Aeronautical Engineering Re- Pqeprint 441-57, American Rocket Society,
view, Vol. 16, August 1957, p. 42. Semi-annual meeting, San Francisco, Cal.,
3. Sutton, G. P., R o c k e t P r o p u l s i o n E l e - June 10-13, 1957.
m e n t s , 2nd Ed., Chapter 10. John Wiley 12. Newman, R. S., Solid Propellant Rocket
and Sons, New York. 1956. Design, Aero Digest, Vol. 71, July 1955,
4. Seifert, H. S., Twenty-Five Years of Rocket
pp. 40, 42, 44, 46, 48, 50, 52.
Development, Jet Propulsion, Vol. 25, No. 11, 13. Stone, M. W., A Practical Approach to Grain
November 1955, pp. 594-603, 632-3. Design, Preprint 445-57, American Rocket
5. Zucrow, M. J., Aerodynamics, Propulsion, Society, Semi-annual meeting, San Francisco,
Structures and Design Practice (Principles of Cal., June 10-13, 1957.
Guided Missile Design series) Propulsion 14. Price, E. W., Charge Geometry and Ballistic
section, p. 364. D. Van Nostrand Co., Parameters for Solid Propellant Rocket Motors,
Princeton, N. J. 1956. American Rocket Society, Journal, Vol. 24,
No. 1, January-February 1954, p. 16.
6. Geckler, R. D., The Mechanism of Combustion
of Solid Propellants, Selected Combustion 15. Sutherland, G. S., Modern Techniques in
Papers, AGARD 1954, p. 289. Solid Rocket Engineering, Aero Digest, Vol.
72, January 1956, pp. 46,47,48,51,52,54,56.
7. Wimpress, R. N., Internal Ballistics of Solid-
Fuel Rockets, McGraw-Hill Book Co., New 16. Vogel, J. M., A Quasi-Morphological Approach
York. 1950. to the Geometry of Charges for Solid Propellant
Rockets, Jet Propulsion, Vol. 26, No. 1,
8. Geckler, R. D., and D. F. Sprenger, The
February 1956, p. 102.
Correlation of Interior Ballistic Data for Solid
Propellants, American Rocket Society, Jour- 17. Geckler, R. D., Thermal Stresses in Solid
nal, Vol. 24, No. 1, January-February 1954, Propellant Grains, Jet Propulsion, Vol. 26,
p. 22. No. 2, February 1956, p. 93.
9. Green, L., Jr., Erosive Burning of Some Com- 18. Ordhal, D. D., and M. L. Williams, Pre-
posite Solid Propellants, American Rocket liminary Photoelastic Design Data for Stresses
Society, Journal, Vol. 24, No. 1, January- in Rocket Grains, Jet Propulsion, Vol. 27,
February 1954, p. 9. No. 6, Jane 1957, pp. 657-62.
79
ORDP 20-282
19. Green, L., Jr., Some E$ects of Oxidizer 21. Aviation Age, Vol. 11, 1958-1959, Research
Concentration and Particle Size on Resonance and Development Technical Handbook, Section
Burning of Composite Solid Propellants, Jet D: Propulsion.
Propulsion, Vol. 28, March 1958, pp. 159-164.
22. Ritchey, H. W., Solid Propellants and the
20. Vandenkerckhove, J. A., Erosive Burning of Conquest of Space, Astronautics, Vol. 3, No. 1,
a Colloidal Solid Propellant, Jet Propulsion, January 1958, pp. 39-41, 75-7.
Vol. 28, No. 9, September 1958, pp. 599-603.
80
TABLE 1. MOLAR SPECIFIC HEATS AT C 3NSTANT PRESSURE
FOR C-H-N-0 COMPOUI DS
(Cp in cal/mol OK)
(Gordon, J. S., IVright Air Development Center, TR5i-33, January 1957)
Temperature C C
OK OR (gas) (graphite) CHI CO CO? H Hz HzO N Nz NO NOz Nz0 NH3 0 01 01 OH
0
0.
0
298.16 437 4.980 2.066 8.522 6.965 8.874 4.968 6.892 8.025 7.139 9.07 9.232 8.505 5.236 7.021 9.372 7.146
300 540 4.980 2.083 8.538 6.965 8.895 4.968 6.895 8.026 7.138 9.08 9.253 8.52 5.234 7.023 9.393 7.145
-4
400 720 4.974 2.851 9.889 7.013 9.877 4.968 6.974 8.186 7.160 9.83 10.207 9.18 5.134 7.196 10.43 7.077
500 900 4.972 3.498 11.08 7.121 10.665 4.9138 6.993 8.415 7.289 10.54 10.965 9.92 5.080 7.431 11.26 7.050
600 1080 4.971 4.03 12.49 7.276 11.310 4.968 7.008 8.676 7.468 11.14 11.590 10.65 5.049 7.070 11.86 7.054
700 1200 4.970 4.43 13.82 7.450 11.846 4.968 7.035 8.954 7.656 11.63 12.110 11.35 5.028 7.883 12.30 7.087
800 1440 4.969 4.75 15.05 7.624 12.292 4.968 7.078 9.245 7.833 12.02 12.452 12.11 5.015 8.063 12.62 7.149
900 1620 4.969 4.98 16.16 7.786 12.067 4.968 7.139 9.546 7.990 12.32 12.903 12.78 5.006 8.212 12.86 7.233
1000 1800 4.969 5.14 17.17 7.931 12.979 4.968 7.219 9.850 8.125 12.54 13.206 13.40 4.999 8.336 13.04 7.332
1100 1980 4.969 5.27 18.06 8.057 13.243 4.968 7.310 10.151 8.240 12.75 13.458 13.98 4.994 8.439 13.17 7.440
1200 2160 4.969 5.42 18.85 8.168 13.465 4.968 7.407 10.440 8.338 12.93 13.671 14.51 4.989 8.527 13.28 7,552
1300 2340 4.970 5.57 19.54 8.263 13.656 4.968 7.509 10.723 8.422 13.0 13.854 14.99 4.986 8.604 13.37 7.663
1400 2520 4.972 5.67 20.15 8.346 13.815 4.968 7.1i15 10.986 8.494 13.1 14.009 15.42 4.984 8.674 13.44 7.771
1500 2700 4.974 5.76 20.69 8.417 13.952 4.968 7.720 11.233 8.555 13.2 14.142 15.80 4.982 8.738 13.50 7.874
1600 2880 4.978 5.83 21. 16 8.480 14.073 4.968 7.823 11.462 8.614 13.3 16.15 4.981 8.800 13.54 7.972
1700 3060 4.983 5.90 21.58 8.535 14.177 4.968 7.923 11.673 8.660 13.3 16.46 4.979 8.858 13.58 8.064
1800 3240 4.989 5.96 21.95 8.583 14.268 4.968 8.019 11.868 8.702 13.4 16.73 4.978 8.916 13.62 8.150
1900 3420 4.998 6.01 22.27 8.626 14.351 4.968 8.109 12.048 8.734 13.4 16.97 4.978 8.973 13.65 8.231
2000 :3000 5.007 6.05 22.56 8.664 14.423 4.968 8.195 12.213 8.766 13.5 17.19 4.978 9.029 13.67 8,306
2100 3780 5.018 6.10 22.82 8.698 14.489 4.968 8.276 12.365 4.970 8.796 17.40 4.978 9.084 13.69 8.376
2200 3960 5.031 6.14 23.05 8.728 14.546 4.968 8.354 12.505 4.971 8.823 17.58 4.978 9.139 13.71 8.441
2300 4140 5.045 6.18 23.25 8.756 14.599 4.968 8.427 12.634 4.972 8.847 17.75 4.979 9.194 13.73 8.503
2400 4320 5.060 6.22 23.44 8.781 14.648 4.968 8.498 12.753 4.975 8.870 17.89 4.981 9.248 13.74 8.560
2500 4500 10.99 6.26 23.60 8.804 14.691 4.968 8.565 12.8132 4.978 8.891 18.01. 4.983 9.301 13.75 8.614
2600 4680 11.50 6.29 23.75 8.825 14.733 4.968 8.629 12.964 4.982 8.910 18.12, 4.986 9.354 13.76 8.665
2700 4860 12.01 6.32 23.89 8.844 14.771 4.968 8.690 13.058 4.987 8.928 18.23 4.990 9.405 13.77 8.714
2800 5040 12.52 6.36 24.01 8.803 14.807 4.968 8.748 13.146 4.994 8.946 18.33 4.994 9.455 13.78 8.760
2900 5220 13.03 6.39 24.13 8.879 14.840 4.968 8.804 13.227 5.002 8.9GL 18.42 4.999 9.503 13.79 8.804
3000 5400 13.55 6.12 24.23 8.895 14.872 4.968 8.859 13.303 5.011 8.977 18.50 5.004 9.551 13.80 8.840
3100 5580 14.07 6.45 24.32 8.910 14.902 4.968 8.912 13.374 5.022 8.992 18.58 5.010 9.596 13.81 8.887
3200 5760 14.59 6.48 24.41 8.924 14.929 4.968 8.964 13.440 5.035 9.006 5.017 9.640 13.81 8.926
3300 5940 15.11 6.51 24.49 8.937 14.956 4.968 9.014 13.503 5.050 9.020 5.025 9.682 13.82 8.964
3400 6120 15.63 6.54 24.56 8.949 14.981 4.968 9.064 13.561 5.068 9.033 5.033 9.723 13.82 9.001
3500 6300 16.16 6.57 24. 63 8.961 15.005 4.968 9.113 13.616 5.087 9.046 5.041 9.762 13.83 9.037
3600 6480 16. 68 6.60 24. 69 8.973 15.029 4.968 9.180 13.668 5.108 9.058 5.050 9.799 13.83 9.072
3700 6660 17.21 6.63 24.75 8.984 15.053 4.968 9.207 13.718 5.131 9.070 5.060 9.835 13.84 9.107
3800 0840 17.74 6.66 24.80 8.994 15.075 4.968 9.253 13.764 5.157 9.082 5.070 9.869 13.84 9.141
3900 7020 18.27 6.69 24.85 9.004 15.097 4.968 9.298 13.809 5.184 9.094 5.081 9.901 13.84 9.175
4000 7200 18.81 6.72 24.90 9.014 15.118 4.968 9.342 13.849 5.214 9.105 8.091 9.932 13.85 9.209
4100 7380 19.34 24.94 9.024 15.138 4.908 9.386 13.890 5.246 9.117 5.103 9.960 13.85 9.243
4200 7560 19.88 24.98 9.083 15.158 4.968 9.428 13.927 5.280 9.128 5.114 9.987 13.85 9.276
4300 7740 20.42 25.02 9.042 15.178 4.908 9.470 13.964 5.316 9.139 5.126 10.013 13.85 9.310
4400 7920 20.96 25.05 9.051 15.196 4.968 9.512 13.997 5.353 9.150 5.138 10.037 13.86 9.344
4500 8100 21.50 25.08 9.059 15.216 4.968 9.553 14.031 5.393 9.161 5.150 10.060 13.86 9.378
4600 8280 22.04 9.068 15.234 4.968 9.593 14.061 5.434 9.171 5.162 10.081 9.412
4700 8460 22.58 9.076 15.254 4.968 9.632 14.093 5.476 9.182 5.174 10.103 9.446
4800 8640 23.13 9.084 15.272 4.968 9.671 14.120 5.520 9.193 5.186 10.121 9.480
4900 8820 23.67 9.092 15.289 4.968 9.710 14.149 5.565 9.203 5.198 10.139 9.515
5000 9000 24.22 9.100 15.305 4.968 9.748 14.174 5.611 9.214 5.210 10.156 9.549
5100 9180 24.76 9.107 15.327 4.968 9.785 14.193 5.658 9.224 5.222 10.182 9.527
5200 9360 25.31 9.115 15.349 4.968 9.822 14.212 5.706 9.234 5.234 10.187 9.553
5300 9540 25.86 9.123 15.371 4.968 9.859 14,230 5.755 9.244 5.246 10.201 9.577
5400 9720 26.41 9.130 15.393 4.968 9.895 14.249 5.805 9.255 5.258 10.215 9.601
5500 9900 26.96 9.138 15.415 4.968 9.930 14.267 5.856 9.265 5.270 J0.228 9.623
5600 10,080 27.51 9.145 15.437 4.968 9.905 14.286 5.902 9.274 5.282 10.239 9.644
5700 10,260 28.06 9.153 15.459 4.968 9.999 14.304 5.959 9.284 5.293 10.250 9. 664
5800 10,440 28.61 9.160 15.481 4.968 10.034 14.322 6.011 9.294 5.305 10.261 9.683
5900 10,620 29.16 9.167 15.503 4.968 10.067 14.340 6.064 9.303 5.3113 10.270 9.700
6000 10,800 29.71 9.175 15.525 4.968 10.100 14.358 6.118 9.313 5.327 10.279 9.716
TABLE 2. ENTHALPY OF C-H-N-0 COMPOUNDS ABOVE to = 298.16'K
(h in k cal/g-mol)
(Gordon, J. S.,Wright Air Development Center, TR 57-33, January 1957)
Temperature C C Oa OH
OK OR (gas) (graphite) CH, CO COz H Hz HzO N Na NO NOa NaO NHa 0 0 2
0 0 n 0 n 0 0 0 0 0 0 n 0 0 0 0
298.1L6 437 0 0.016 0.016 0.010 0.013 0.01726 0.013
300 540 0.00916 0.0045 0.0157 6.013 0.017 0.0091 0.013 0.014 0.013 0.013 0.017
,709 .726 .963 .991 .906 .528 .723 1.0102 .723
400 . --
721-1.5069 .2512 0.9234 .7110 ,941 .5059
1.003
0.7072 ,823
1.406 1.653 1.412 1.250 1.98 2.051 1.869 1.038 1.4541 2.0973 1.429
500 900 1.0042 0.5694 1.9616 1.4172 1.986 2.927 1.544 2.2094 3.2556 2.135
600 1080 1.5014 ,9466 3.1414 2.1370 3.085 1.450 2.105 2.508 2.125 2.187 3.07 3.180
1.996 2.808 3.389 2.852 2.942 4.21 4.366 4.029 2.049 2.9873 4.4656 2.840
700 1260 1.9984 1.3703 4.4585 2.8730 4.244 5.204 2.550 3.7849 5.7130 3.552
800 1440 2.4954 1.8300 5.9035 3.6269 5.452 2.493 3.514 4.298 3.595 3.715 5.39 5.599
2.990 4.224 5.238 4.354 4.506 6.61 6.872 6.448 3.501 4.5990 6.9879 4.271
900 1620 2.9924 2.3179 7.4657 4.3977 6.700 7.759 3.551 5.4265 8.2834 5.000
1000 is00 3.4893 2.8234 9.1336 5.1837 7.983 3.487 4.942 6.208 5.129 5.312 7.85 8.178
3.984 5.669 7.208 5.917 6.040 9.13 9.511 9.121 4.051 6.265 9.5946 5.738
1 100 1980 3.9862 3.344 10.896 5.9827 9.293 10.557 4.550 7.114 10.918 6.488
1200 2160 4.4832 3.878 12.742 6.7943 10.630 4.480 6.404 8.238 6.717 6.960 10.42 10.867
4.977 7.150 9.297 7.529 7.798 11.69 12.224 12.075 5.049 7.970 12.251 7.249
1300 2340 4.9802 4.428 14.663 7.6161 11.987 13.638 5.547 8.834 13.592 8.020
1400 2520 5.4773 4.990 16.648 8.4466 13.360 5.474 7.906 10.382 8.349 8.644 12.98 13.638
14.749 5.971 8.673 11.494 9.178 9.497 14.29 15.045 15.244 6.046 9.704 14.939 8.803
1500 2700 5.9746 5.572 18.692 9.2847 16.872 6.544 10.582 16.292 9.595
16 0 2880 6.4722 6.149 20.79 10.129 16.150 6.468 9.450 12.627 10.014 10.356 15.63
. .. .
17.563 6.964 10.237 13.785 10.857 11.219 16.95 18.53 7.042 11.464 17.649 10.397
1700 2060
-... 6.9703 6.735 22.92 10.980 20.19 7.540 12.353 19.008 11.208
1800 3240 7.4690 7.330 25.10 11.836 18.985 7.461 11.035 14.962 11.705 12.087 18.30
20.416 7.958 11.841 16.157 12.559 12.960 19.64 21.88 8.038 13.248 20.37 12.027
1900 3420 7.9684 7.928 27.31 12.696 23.58 8.535 14.148 21.74 12.854
ZOO0 3 r i 8.4686 8.528 29.55 13.561 21.855 8.455 12.656 17.372 13.417 13.835 20.99
8.932 13.480 18.600 8.949 14.278 14.714 25.32 9.033 15.053 23.11 13.689
2100 3780 8.9699 9.138 31.82 14.430 23.301 27.04 9.531 15.965 24.48 14.530
2200 3960 9.4724 9.748 34.12 15.301 24.753 9.448 14.311 19.843 9.449 15.144 15.595
26.210 0.945 15.150 21.101 9.946 16.012 16.479 28.79 10.029 16.881 25.85 15.377
2300 4140 9.9763 10.363 36.43 16.175 30.55 la527 17.803 27.23 16.230
2400 4320
_.~. 10.481 10.98 38.77 17.052 27.672 10.441 15.997 22.371 10.443 16.884 17.365
29.140 10.938 18.850 23.652 10.491 17.758 18.254 32.33 11.025 18.731 28.600 17.089
2500 4500 10.99 11.60 41.12 17.931 34.10 11.524 19.663 29.976 17.953
2600 4680 11.50 12.23 43.49 18.812 30.610 11.435 17.709 24.942 11.439 18.634 19.144
32.086 11.932 18.575 26.244 11.938 19.513 20.037 35.88 12.022 20.601 31.354 18.822
3700 4860 12.01 12.85 45.87 19.696 12.522 21.544 32.732 19.695
2800 5040 12.52 13.49 48.27 20.581 33.564 12.429 19.447 27.553 12.437 20.393 20.931 37.65
12.925 20.325 28.874 12.936 21.276 21.826 39.41 13.021 22.492 34.112 20.572
2900 5220 13.03 14.14 50.68 21.468 35.047 13.521 23.445 35.492 21.456
5400 13.55 14.78 53.10 22.357 36.532 13.422 21.208 30.200 13.437 22.160 22.724 41.19
....
13.919 22,210 31.530 13.939 23.046 23.622 43.04 14.022 24.402 36.873 22.342
3100 5580 14.07 15.42 55.52 23.246 38.021 14.523 25.364 38.254 23.233
3200 _.
5761-1 __
14.59 16.07
16.72
57.96
60.41
24.138
25.031
39.513
41.007
14.416
14.913
22.990 32.874
23.889 34.220
14.442
14.946
23.934
24.823
24.523
25.424 15.025 26.330 39.636 24.127
3300 5940 15.11 15.452 25.713 26.328 15.528 27.301 41.018 25.026
3400 6120 15.63 17.37 62.86 25.926 42.504 15.409 24.793 35.573 28.274 42.401 25.928
18.02 65.32 26.821 44.003 15.906 25.702 36.933 15.959 26.605 27.232 16.029
3500 6300 16.16 16.469 27.497 28.137 16.537 29.252 43.785 26.833
3600 6480 16.68 18.68 67.79 27.718 45.505 16.403 26.616 38.298 30.235 45.169 27.742
3 7 0 6660 17.21 19.34 70.26 28.616 47.009 16.900 27.534 39.667 16.981 28.392 29.044 17.042
.. ..
29.514 48.516 17.397 28.457 41.039 17.506 29.287 29.952 17.548 31.220 46.553 28.654
3800 ~.17.74
6840 20.01 72.74 18.056 32.208 47.937 29.569
3900 7020 18.27 20.68 75.22 30.414 50.024 17.893 29.384 42.421 18.013 30.182 30.861
31.315 51.535 18.390 30.316 43.804 18.532 31.080 31.771 18.565 33.200 49.322 30.488
4000 7200 18.81 21.35 77.71 19.074 34,194 50.708 31.410
4100 7380 19.34 22.02* 80.20 32,219 53.048 18.887 31.253 45.191 19.055 31.979 32.682
33.121 54.563 19.384 32.193 46.579 19.582 32.880 33.595 19.585 35.192 52.093 32.335
4200 7560 19.88 22.70 82.70 20.097 36.192 53.479 33.264
4300 7740 20.42 23.39 85.20 34.025 56.079 19.881 33.138 47.975 20.111 33.781 34.508
34.929 57.598 20 377 34.087 49.372 20.645 34.683 35.422 20.610 37.194 54.865 34.195
4400 7920 20.96 24.07 87.70 .
21.125 38.199 56.251 35.129
4500 8100 21.50 24.77 90.21 35.835 59.119 20.874 35.041 50.775 21.182 35.592 36.338
36.741 60.641 21.371 35.998 52.179 21.724 36.496 37.254 21.640 39.206 36.067
4600 8280 22.04 25.46 22.157 40.215 37.007
4700 8460 22.58 20.16 37.648 62.165 21.868 36.959 53.587 22.269 37.400 38.171
38.556 63.692 22.365 37.924 54.997 22.819 38.306 39.090 22.675 41.227 37.950
4800 8640 23.13 26.86 23.194 42.240 38.896
4900 8820 23.67 27.57 39.465 65.220 22.861 .38.984 56.411 23.373 39.212 40.001
40.374 66.749 23.358 39.866 57.827 23.932 40.119 40.923 23.715 43.255 39.845
0000 9000 24.22 28.28 24.237 44.272 40.797
~~.~ 9180 24.76
5100 28.99 41.285 68.309 23.855 40.843 59.180 24.495 41.037 41.845
69.870 24.352 41.823 60.535 25.063 41.935 42.768 24.758 45.289 41.751
5200 9360' 25.31 29.70 42.196 25.280 46.310 42.707
.5300 9540 25.86 30.42 43.108 71.434 24.849 42.808 61.892 25.637 42.845 43.692
25.345 43.795 63.251 26.216 43.755 44.617 25.817 47.330 43.666
a400 9720 26.41 31.15 44.021 73.001 26.339 48.353 44.627
.?I500 9900 26.96 31.88 44.934 74.569 25.842 44.787 64.611 26.799 44.667 45.543
26.339 45.781 65.974 27.387 45.579 46.470 26.863 49.376 45.591
.5600 10,080 27.51 32.61 45.848 76.140 27.390 50.400 46.566
5700 10,260 28.06 33.34 46.763 77.713 26.836 46.780 67.338 27.980 46.492 47.398
27.333 47.781 68.704 28.579 47.406 48.327 27.925 51.425 47.523
5800 10.440 28.61 34.08 47.679 79.288 28.450 52.448 48.493
5900 10,620 29.16 34.82 48.595 80.865 27.829 48.788 70.072 29.182 48.321 49.256
liOO0 10,800 29.71 35.57 49.512 82.445 28.326 49.795 71.441
-29.790 49.237 50.187 28.980 53.479 49.463
* Values of C (graphite) above 4000OK are measured from 1. = 30@"'.

TABLE 3. VALUES OF THE PARAMETER et = (pe/pc~(k-l)'k
For pJp. = 1.0 to 500.0 and for k = 1.20to k = 1.39
pdp, p,/p, k = 1.20 1.21 1.22 1.23 1.24 1.25 1.26 1.27 1.28 1.29 1.30 1.31 1.32 1.33 1.34 1.35 1.36 1.37 1.38 1.39
1.0 1.0 l.m 1 . m 1 . m l.m 1 . m 1 . m 1 . m 1 . m 1 . m 1 . m 1 . m 1 . m 1 . m 1 . m 1 . m 1 . m 1 . m 1 . m 1.m 1 . m

2.0 0.m 0.8SOso 0.88666 0.i8isO o.iii44 0;iiiis 0:Sio55 0366i3 0:SiiG 0:8593i 0i855ii 0 Z i i 8 0:iiiiz 054533 0;iiiig 0;Eii3 O Z G 2 0:83ii7 0:iiiie 0%i4 o;iiii6
3.0 0.3333 0.83269 0.82641 0.82028 0.81430 0.80845 0.80274 0.79716 0.79171 0.78638 0.78116 0.77606 0.77107 0.76619 0.76141 0.75673 0.75215 0.74766 0.74326 0.73896 03'3474
4.0 0.2500 0.79370 0 78616 0.77881 0.77165 0.76467 0.75786 0.75122 0.74474 0.73841 0.73224 0.72621 0.72032 0.71457 0.70895 0.70346 0.69809 0.69284 0.68770 0.68268 0.67776
5.0 0.2000 0.76473 0.75630 0.74810 0.74012 0.73235 0.72478 0.71741 0.71023 0.70324 0.69641 0.68976 0.68328 0.67695 0.67077 0.66474 0.65885 0.65310 0.64748 0.64199 0.63663
6.0 0.1667 0.74184 0.73274 0.72390 0.71531 0.70695 0.69883 0.69092 0.68323 0.67574 0 66845 0.66134 0.65442 0.64768 0.64110 0.63469 0.62843 0.62233 0.61637 0.61056 0.60488
n-.- -- -_ n-~.--. n- .-- .- n- . m.._
~n- mi211
--.
7.0
8.0
9.0
0.1429
0.1250
0.1111
0.72302 0.71340
n.'107ii
... _. om705
......
0.69336 0.68295
0.70406 0.69498 0.68617 0.67761 0.66929 0.66120
nfiR7m
. _____
- m ~ 5nmm7
n n_~59713
. _ _n_~_i _i nn M Z
_._____
0.67286 0.66308 0.65360 0.64439 0.63547 0.62680
_______ ~n F r ? m __
n f i 2 ~nRim7 nRiix5
0.61839 0.61021 0.60227 0.59455
_______
0 . ~ 3 3 3 0.64568 0.63823 0.63098 0.623112
n
_-__-
A0405
I
-.
61 704
0.59693
0.58704 0.57974
n-.~_1_0 ~n4~ l_l .
.____. ~ .i_
511745
0.59001 0.58327 0.57670 0.57030
0.57264 0.56572 0.55900 0.55244
.wiz4
.
0.56406 0.55796
0.54606 0.53984
10.0 0.1000 0.68129 0.67058 0.66020 0.65014 0.64040 0.63096 0.62180 0.61292 0.60430 0.59593 0.58780 0.57991 0.57224 0.56478 0.55753 0.55048 0.54362 0.53694 0.53044 0.52411
15.0 0.06667 0.63677 0.62501 0.61365 0.60267 0.59207 0.58181 0.57189 0.56230 0.55301 0.54401 0.53530 0.52685 0.51867 0.51073 0.50302 0.49555 0.48829 0.48125 0.47440 0.46775
20.0 0.05Ooo 0.60696 0.59457 0.58263 0.57111 0.56000 0.54928 0.53893 0.52894 0.51928 0.50994 0.50091 0.49216 0.48373 0.47554 0.46762 0.45994 0.45249 0.44528 0.43827 0.43148
25.0 0.04000 0.58481 0.57198 0.55965 0.54777 0.53633 0.52531 0.51468 0.50443 0.49454 0.48499 0.47577 0.46686 0.45825 0.44993 0.44188 0.43408 0.42654 0.41923 0.41216 0.40530
30.0 0.03333 0.56730 0.55417 0.54155 0.52941 0.51773 0.50649 0.49567 0.48525 0.47520 0.46552 0.45617 0.44715 0.43844 0.43003 0.42190 0.41404 0.40644 0.39909 0.39197 0.38508
35.0 0.02857 0.55291 0.53954 0.52670 0.51437 0.50251 0.49112 0.48016 0.46961 0.45945 0.44966 0.44023 0.43113 0.42236 0.41389 0.40571 0.39782 0.39019 0.38282 0.37568 0.36878
00
W 40.0 0.02500 0.54074 0.52718 0.51417 0.50168 0.48969 0.47818 0.46711 0.45646 0.44622 0.43636 0.42687 0.41772 0.40891 0.40040 0.39220 0.38428 0.37664 0.36926 0.36212 0.35522
45.0 0.02222 0.53023 0.51651 0.50336 0.49075 0.47866 0.46704 0.45589 0.44517 0.43487 0.42496 0.41542 0.40624 0.39739 0.38887 0.38065 0.37273 0.3&08 0.35770 0.35056 0.34368
50.0 0.02000 0.52100 0.50715 0.49389 0.48118 0.46899 0.45731 0.44609 0.43531 0.42496 0.41501 0.40544 0.39624 0.38737 0.37884 0.37061 0.36268 0.35504 0.34766 0.34054 0.33367
55.0 0.01818 0.51279 0.49883 0.48547 0.47268 0.46042 0.44867 0.43740 0.42658 0.41619 0.40621 0.39662 0.38740 0.37852 0.36998 0.36175 0.35383 0.34619 0.33882 0.33171 0.32486
60.0 0.01667 0.50541 0.49135 0.47791 0.46505 0.45273 0.44093 0.42961 0.41876 0.40834 0.39834 0.38874 0.37950 0.37062 0.36208 0.35385 0.34593 0.33831 0.33095 0.32386 0.31702
0.49259
0.48175
90.0 0.01111 0.47238
100.0 0.01000 0.46416
110.0 0.00909 0.45684
120.0 0.00833 0.45027 0.43566 0.42176 0.40852 0.3959 0.38385 0.37236 0.36138 0.35089 0.34087 0.33127 0.32209 0.31329 0.30487 0.29679 0.28903 0.28160 0.27445 0.26759 0.26099
140.0 0.00714 0.43884 0.42416 0.41019 0.39690 0.38425 0.37219 0.36069 0.34973 0.33925 0.32925 0.31969 0.31055 0.30180 0.29342 0.28540 0.27771 0.27033 0.26326 0.25646 0.24991
160.0 0.00625 0.42919 0.41445 0.40044 0.38712 0.37445 0.36239 0.35090 0.33995 0.32950 0.31952 0.31000 0.30090 0.29219 0.28387 0.27590 0.26826 0.26095 0.25394 0.24721 0.24076
180.0 0.00556 0.42084 0.40605 0.39202 0.37868 0.36601 0.35395 0.34247 0.33153 0.32111 0.31117 0.30168 0.29262 0.28396 0.27568 0.26777 0.26019 0.25293 0.24598 0.23932 0.23292
200.0 0.00500 0.41352 0.39870 0.38465 0.37130 0.35863 0.34657 0.33511 0.32419 0.31380 0.30389 0.29444 0.28542 0.27681 0.26858 0.26071 0.25319 0.24598 0.23909 0.23248 0.22615
250.0 0.00400 0.39842 0.38356 0.36948 0.35613 0.34347 0.33145 0.32003 0.30917 0.29885 0.28902 0.27966 0.27074 0.26223 0.25411 0.24636 0.23895 0.23188 0.22510 0.21862 0.21242
300.0 0.00333 0.38649 0.37160 0.35752 0.34419 0.33155 0.31957 0.30821 0.29741 0.28716 0.27741 0.26813 0.25930 0.25089 0.24287 0.23522 0.22792 0.22094 0.21428 0.20791 0.20182
350.0 0.00286 0.37669 0.36180 0.34772 0.33441 0.32181 0.30987 0.29856 0.28783 0.27764 0.26796 0.25876 0.25001 0.24169 0.23376 0.22620 0.21899 0.21211 0.20555 0.19928 0.19328
400.0 0.00250 0.36841 0.35351 0.33945 0.32617 0.31360 0.30171 0.29045 0.27977 0.26965 0.26004 0.25091 0.24224 0.23399 0.22614 0.21866 0.21154 0.20475 0.19827 0.19208 0.18618
450.p 0.00222 0.36124 0.34635 0.33231 0.31906 0.30653 0.29468 0.28347 0.27285 0.26279 0.25324 0.24418 0.23558 0.22740 0.21962 0.21222 0.20517 0.19846 0.19206 0.18595 0.18012
500.0 0.00200 0.35496 0.34008 0.32606 0.31284 0.30034 0.28854 0.27738 0.26681 0.25680 0.24732 0.23832 0.22976 0.22167 0.21396 0.20663 0.19965 0.19301 0.18667 0.18064 0.17488
TABLE 4. VALUES OF THE PARAMETER& AS A FUNCTION OF pc/pe
z, = 1 - (E) (k-1) Ik
(where pC < PA
For p J p , = 1.0 to 500.0 and for k = 1.20 to k = 1.30
pd‘p. pdpe I; = 1.20 1.21 1.22 1.23 1.24 1.25 1.26 1.27 1.28 1.29 1.30 1.31 1.32 1.33 1.34 1.35 1.36 1.37 1.38 1.39
1.0 1.0 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 o.oooo O.oo00 O.oo00 O.oo00 O.oo00 O.oo00 n.m n.m O.oo00
2.0 0.5000 0.33030 0.33666 0.34478 0.34866 0.35432 0.35979 0.36506 0.37016 0.38447 0.38895 0.39329 0.39750 0.40159 0.40556 0.40943 0.42040
3.0 0.3333 0.40904 0.41664 0.42393 0.43093 0.43766 0.44414 0.45038 0.45639 0.47322 0.47847 0.48354 0.48846 0.49323 0.49785 0.50234 0.51504
4.0 0.2500 0.45420 0.46243 0.47031 0.47786 0.48511 0.49208 0.49878 0.50523 0.52325 0.52884 0.53425 0.53949 0.54456 0.54946 0.55422 0.56766
5.0 0.2000 0.48505 p.49366 0.50190 0.50979 0.51735 0.52461 0.53159 0.53830 0.55699 0.56278 0.56838 0.57379 0.57902 0.58408 0.58898 0.80280
6.0 0.1667 0.50810 0.51697 0.52545 0.53357 0.54134 0.5 4879 0.55595 0.56282 0.56944 0.57581 0.58194 0.58786 0.59357 0.59908 0.60441 0.60957 0.61455 0.6193R 0.62405 0.62858
7.0 0.1429 0.52629 0.53535 0.54401 0.55228 0.56020 0.56779 0.57507 0.58206 0.58878 0.59525 0.60147 0.60747 0.61326 0.61884 0.62423 0.62944 0.63447 0.63934 0.644G 0.64863
8.0 01250 0 54119 0.55041 0.55919 0 56759 0.57562 0.58331 0.59068 0.59775 0.60454 0.61108 0.61736 0.62341 0.62925 0.63488 0.64031 0.64555 0.65062 0.65552 0.66026 0.66485
9.0 0.1111 0.55375 0.56307 0.57196 0.58045 0.58856 0.59633 0.60376 0.61090 0.61775 0.62433 0.63066 0.63675 0.64262 0.64827 0.65373 0.65900 0.66408 0.66900 0.67375 0.67835
10.0 0.1000 0 56454 0.57396 0.58293 0.59149 0.59966 0.60749 0.61498 0.62216 0.62905 0.63567 0.64203 0.64814 0.65404 0.65971 0.66518 0.67046 0.67556 0.68048 0.68524 0.68984
0.60268 0.61237 0.62157 0.63034 0.63870 0.64668 0.65430 0.66159 0.66858 0.67527 0.68169 0.68786 0.69378 0.69948 0.70497 0.71025 0.71534 0.72024 0.72498 0.72955
0.62693 0.63673 0.64604 0.65490 0.66332 0.67136 0.67902 0.68634 0.69334 0.70004 0.70646 0.71262 0.71852 0.72419 0.72965 0.73489 0.73994 0.74480 0.74948 0.75400
0.64436 0.65423 0.66359 0.67248 0.68093 0.68898 0.69665 0.70397 0.71096 0.71764 0.72404 0.73016 0.73603 0.74167 0.74708 0.75228 0.75727 0.76208 0.76671 0.77117
0.65780 0.66771 0.67709 0.68600 0.69445 0.70250 0.71016 0.71746 0.72443 0.73108 0.73745 0.74354 0.74937 0.75497 0.76033 0.76548 0.77043 0.77518 0.77976 0.78417
0.66865 0.67857 0.68797 0.65687 0.70533 0.71336 0.72100 0.72828 0.73522 0.74185 0.74818 0.75423 0.76003 0.76558 0.77090 0.77600 0.78090 0.78561 0.79014 0.79449
~.
.. .... .. 0.67768 0.68762 0.69702 0.70592 0.71136 0.72237 0.73000 0.73725 0.74416 0.75076 0.75705 0.76307 0.76883 0.77434 0.77962 0.78468 0.78953 0.79119 0.79867 0.80298
45.0 0.02222 0.68540 0.69533 0.70473 0.71361 0.72204 0.73004 0.73764 0.74487 0.75175 0.75831 0.76458 0.77056 0.77628 0.78175 0.78699 0.79201 0.79682 0.80144 0.80588 0.81014
50.0 0.02000 0.69210 0.70203 0.71141 0.72029 0.72870 0.73668 0.74425 0.75146 0.75831 0.76484 0.77107 0.77702 0.78270 0.78814 0.79334 0.79832 0.80310 0.80768 0.81207 0.81629
55.0 0.01818 0.69801 0.70793 0.71731 0.72617 0.73456 0.74252 0.75007 0.75725 0.76407 0.77058 0.77678 0.78269 0.78834 0 79374 0.79890 0.80385 0.80859 0.81313 0.81749 0.82167
60.0 0.01667 0.70327 0.71319 0 72256 0 73140 0 73978 0 74771 0.75524 0.76239 0.76919 0.77567 0.78183 0.78772 0.79333 0.79870 0.80383 0.80874 0.81345 0.81795 0.82228 0.82642
70.0 0.01429 0.71233 0.72223 0.74872 0.75661 0.76409 0.77120 0.79048 0.79630 0.80186 0.80716 0.81223 0.81708 0.82172 0.82616 0.83042 0.83450
80.0 0.01250 0.71990 0.72978 0.75617 0.76402 0.77146 0.77851 0.79764 0.80341 0.80891 0.81416 0.81918 0.8 2397 0.82855 0.83291 0 83714 0.84116
!10.00.01111 0.72637 0.73623 0.76252 0.77033 0.77773 0.78474 0 80373 0.80945 0.81491 0.82011 0.82507 0.82981 0.83434 0 83867 0.84282 0.84680
100.0 0.01000 0.73201 0.74184 0.76804 0.77582 0.78318 0.79015 0.80900 0.81468 0.82009 0.82524 0.83016 0.83485 0.83933 0.81362 0.84772 0.85165
110.0 0.00900 0.73700 0.74680 0.77291 0.78065 0.78797 0.79491 0.81364 0.81928 0.82464 0.82975 0.83162 0.83927 0.84371 0.84795 0.85201 0.85590
120.0 0.00833 0.i4144 0.75122 0.76042 0.76908 0.77724 0.78495 0.79221 0.79914 0.81776 0.82335 0.82868 0.83375 0.83858 0.84319 0.84759 0.85966
140.0 0.00714 0.74911 0.75884 0.76799 0.776~9 0.78470 0.79235 0.79957 0.80640 0.82481 0.83033 0.83559 0.84058 0.84534 0.84988 0.85421 0.86606
160.0 0.00625 0.75552 0.76521 0.77431 0.78286 0.79092 0.79850 0.80567 0.81244 0.83066 0.83612 0.84131 0.84625 0.85094 0.85542 0.85968 0.87135
180.0 0.00556 0.76103 0.77068 0.77973 0.78824 0.79624 0.80378 0.81088 0.81760 0.83566 0.84106 0.84619 0.85107 0.85571 0.86012 0.86433 0.87583
200.0 0.00500 0.76582 0.7 7543 0.78414 0.79290 0.80086 0.80835 0.81541 0.82207 0.83998 0.84533 0.85041 0.85523 0.85982 0.86418 0.86834 0.87969
0.77561 0.78514 0.79406 0.80242 0.81027 0.81765 0.82460 0.83116 0.83735 0.84320 0.84873 0.85397 0.85894 0.86365 0.86812 0.87238 0.87643 O.RR02R O.RR.9.5 0.88746
0.78327 0.79271 0.80155 0.80982 0.81759 0.82488 0.83174 0.83820 0.84430 0.85005 0.85549 0.86064 0.86551 0.87013 0.87452 0.87868 0.88261 0.89341
0.78950 0.79888 0.80764 0 81584 0.82352 0 83071 0.83752 0.84390 0 84992 0.85559 0.86095 0.86602 0.87081 0.87535 0.87966 0.88375 0.88763 0.89817
0.79473 0.80404 0.81274 0.82087 0.82849 0.83564 0.84235 0.84866 0.85461 0.86021 0.86550 0.87049 0.87522 0.87969 0.88393 0.88795 0.89177 0.90212
0.7 9923 0.80848 0.81712 0.82519 0.83275 0.83983 0.84648 0.85273 0.85861 0.86415 0.86938 0.87431 0.87898 0.88339 0.88757 0.89153 0.89529 0.90547
500.0 000200 0.80315 0.81235 0.82094 0.82895 0.83645 0.84348 0.85007 0.85626 0.86209 0.86757 0.87274 0.87762 0.88223 0.88659 0.89071 0.89162 0.89833 0.90185 0.90519 0.90836
TABLE 5. FUNCTIONS OF THE SPECIFIC HEAT RATIO k
1.10 0.90909 1.0488 0.95346 0.95346 1.8181 1.9069 1.2100 10.000 3.1622 0.31623 0.47619 0.69007 1.4491 20.000 11.000 0.95238 0.52381 0.72375 3.3166
1.11 0.9mo 1.0535 0.94916 0.94916 1.8018 1.8983 1.2321 9.0909 3.0151 0.33166 0.47393 0.68843 1.4525 18.181 10.090 0.94787 0.52607 0.72530 3.1766
1.12 0.89286 1.0583 0.94491 0.94491 1.7857 1.8898 1.2544 8.3333 2.8867 0.34641 0.47170 0.68680 1.4560 16.666 9.333 0.94340 0.52830 0.72684 3.0550
1.13 0.88496 1.0630 0.94072 0.94072 1.7699 1.8814 1.2769 7.6923 2.7735 0.36056 0.46948 0.68519 1.4594 15.384 8.6923 0.93897 0.53052 0.72837 2.9482
1.14 0.67719 1.0677 0.93659 0.93659 1.7543 1.8731 1.2996 7.1428 2.6726 0.37417 0.46729 0.68359 1.4628 14.285 8.1428 0.93458 0.53271 0.72987 2.8535
1.15 0.86957 1.0723 0.93250 0.93251 1.7391 1.8650 1.3225 6.6666 2.5819 0.38730 0.46512 0.68199 1.4662 13.333 7.6666 0.93023 0.53486 0.73136 2.7688
1.16 0.86207 1.0770 0.92848 0.92848 1.7241 1.8569 1.3456 6.2500 2.5000 0.40000 0.46296 0.68041 1.4696 12.500 7.2500 0.92593 0,53704 0.73283 2.6925
1.17 0.85470 1.0816 0.92450 0.92450 1.7094 1.8490 1.3689 5.8823 2.4253 0.41231 0.46083 0.67884 1.4730 11.764 6.8823 0.92166 0.53917 0.73428 2.6234
1.18 0.84746 1.0862 0.92057 0.92057 1.6949 1.8411 1.3924 5.5555 2.3570 0.42426 0.45872 0.67729 1.4764 11.111 6.5555 0.91743 0.54128 0.72572 2.5603
1.19 0.84034 1.0908 0.91670 0.91670 1.6806 1.8334 1.4161 5.2631 2.2941 0.43589 0.45662 0.67574 1.4798 10.526 6.2631 0,91324 0.54338 0.73714 2.5026
1.20 0.83333 1.0954 0.91267 0.91287 1.6666 1.8257 1.4400 5.oooo 2.2360 0.44721 0.45455 0.67420 1.4832 10.000 6.0000 0.90909 0.54545 0.73855 2.4494
1.21 0.82645 1.1000 0.90909 0.90909 1.6528 1.8181 1.4641 4.7619 2.1821 0.45828 0.45249 0.67267 1.4866 9.5238 5.7619 0.90198 0.54751 0.73994 2.4004
1.22 0.81967 1.1045 0.90536 0.90536 1.6393 1.8107 1.4884 4.5454 2.1320 0.46904 0.45045 0.67116 1.4899 9,0909 5.5454 0.90090 0.54955 0.74132 2.354R
1.23 0.81301 1. I090 0.90167 0.90167 1.6260 1.8033 1.5129 4.3478 2.0851 0.47958 0.44843 0.66965 1.4933 8.6956 5.3478 0.89686 0.55157 0.74268 2.3125
1.24 0.80645 1.1135 0.89803 0.89803 1.6129 1.7960 1.5376 4.1666 2.0412 0.48990 0.44643 0.66815 1.4966 8.3333 5.1666 0.89286 0.55357 0.74402 2.2730
1.25 0.80000 1.1180 0.89443 0.89443 1.6000 1.7888 1.5625 4.oooo 2.MwN) 0.5oooO 0.44444 0.66667 1.5000 8.0000 5.0000 0.88889 0.55556 0.74536 2.2360
1.26 0.79365 1.1225 0.89087 0.89087 1.5873 1.7817 1.5876 3.8461 1.9611 o.5099n 0.44248 0.66519 1.5033 7.6923 4.8461 0.88496 0.55752 0.74667 2.2014
1.27 0.18740 1.1269 0.88736 0.88736 1.5748 1.7747 1.6129 3.7037 1.9245 0.51962 0.44053 0.66372 1.5066 7.4074 4.7037 0.88106 0.55947 0.74798 2.1688
1.28 0.78125 1. I313 0.88388 0.88388 1.5625 1.7677 1.6384 3.5714 1.8898 0.52915 0.43860 0.66227 1.5099 7.1428 4.5714 0.87719 0.56140 0.74927 2.1380
1.29 0.77519 I. 1357 0.88045 0.88045 1.5503 1.7609 1.6641 3.4482 1.8-69 0.53852 0.43668 0.66082 1.5132 6.8965 4.4482 0.87336 0.56332 0.75055 2.1090
1.30 0.76923 1.1401 0.87706 0.87706 1.5384 1.7541 1.6900 3.3333 1.8257 0.54772 0.43478 0.65938 1.5165 6.6666 4.3333 0.86957 0.56522 0.75181 2.0816
1.31 0.76336 1.1445 0.87370 0.87370 1.5267 1.7474 1.7161 3.2258 1.7960 0.55678 0.43290 0.65795 1.5198 6.4516 4.2258 0.86580 0.56710 0.75306 2.0556
1.32 0.75758 1.1489 0.87039 n. 87039 1.5151 1.7407 1.7424 3.1250 1.7677 0.56569 0.43103 0.65653 1.5231 6.2500 4.I250 0.86207 0.56897 0.75430 2.0310
1.33 0.75188 1.1532 0.86711 0.86711 1.5037 1.7342 1.7689 3.0303 1.7407 0.57446 0.42918 0.65512 1.5264 6.0606 4.0303 0.85837 0.57082 0.75552 2.0075
1.34 0.74627 1.1575 0.86387 0.86387 1.4925 1.7277 1.7956 2.9411 1.7149 0.58310 0.42735 0.65372 1.5297 5.8823 3.9411 0.85470 0,57265 0.75674 1.9852
1.35 0.74074 1.1619 0.86066 0.86066 1.4814 1.7213 1.8225 2.8571 1.6903 0.59161 0.42553 0.65233 1.5329 5.7142 3.8571 0.85106 0.57447 0.75794 1.9639
1.36 0.73529 1.1661 0.85749 0.85749 1.4705 1.7149 1. R496 2.7777 1.6666 0.60000 0.42373 0.65094 1.5362 5.5555 3.7777 0.84746 0.57627 0.75913 1.9436
W 1.37 0.72993 1.1704 0.85436 0.85436 1.4598 1.7087 1.8769 2.7027 1.6439 0.60828 0.42191 0.64957 1.5394 5.4054 3.7027 0.84388 0.57806 0.76030 1.9242
in 1.38 0.72464 1.1747 0.85126 0.85126 1.4492 1.7025 1.9044 2.6315 1.6222 0.61644 0.42017 0.64820 1.5427 5.2631 3.6315 0.84034 0.57983 0.76147 1.9Q56
1.39 0.71942 1.1789 0.84819 0.84819 1.4388 1.6963 1.9321 2.5641 1.8012 0.62450 0.41641 0.64685 1.5459 5.1282 3.5641 0.83682 0.58159 0.76262 1.8878
1.40 0.71429 1.1832 0.84515 0.84515 1.4285 1.6903 1.9600 2.5000 1.5811 0.63246 0.41667 0.64550 1.5491 5.0000 3.5000 0.83333 0.58333 0.76376 I. 8708
t.41 0.70922 1.1874 0.84215 0.84215 1.4184 1.6843 1.9881 2.4390 1.5617 0.64031 0.41494 0.64416 1.5524 4.8780 3.4390 0,82988 0.58506 0.76489 1.8544
1.4% 0.70423 1.1916 0.83918 0.83918 1.4084 1.6783 2.0164 2.3809 1.5430 0.64807 0.41322 0.64282 1.5556 4.7619 3.3809 0.82645 0.58678 0.76601 1.8387
1.43 0.69830 1.1958 0.83624 0.83624 1.3986 1.6724 2.0449 2.3255 1.5249 0.65574 0.41152 0.64150 1.5588 4.651 1 3.3255 0.82305 0.58848 0.76712 1.8236
1.44 0.69444 1.2OOO 0.83333 0.83333 1.3888 1.6666 2.0736 2.2727 1.5075 0.66332 0.40984 0.64018 1.5620 4.5454 3.2727 0.81967 0.59016 0.76822 1.8090
1.45 0.68966 1.2041 0.83045 0.83046 1.3793 1.6609 2.1025 2.2222 1.4907 0.67082 0.40816 0.63888 1.5652 4.4444 3.2222 0.81633 0.59184 0.76931 1.7950
1.46 0.68493 1.2083 0.82761 0.82761 1.3698 1.6552 2.1316 2.1739 1.4744 0.67823 0.40650 0.63758 1.5684 4.3478 3.1739 0.81301 0.59350 0.77039 1.7815
1.47 0.68027 1.2124 0.82479 0.82479 1.3605 1.6495 2.1609 2.1276 1.4586 0.68557 0.40486 0.63628 1.5716 4.2553 3.1276 0.80972 0.59514 0.77145 1.7685
1.48 0.67568 1.2165 0.82199 0.82200 1.3513 1.6439 2.1904 2.0833 1.4433 0.69282 0.40323 0.63500 1.5748 4.1666 3.0833 0.80615 0.59877 0.77251 1.7559
1.49 0.67114 1.2206 0.81923 0.81923 1.3422 1.6384 2.2201 2.0408 1.4285 0.70000 0.40161 0.63372 1.5779 4.0816 3.0408 0.80321 0.59839 0.77356 1.7437
1.50 0.66667 1.2247 0.81650 0.81650 1.3333 1.6329 2.2500 2.oooo 1.4142 0.70711 0.40000 0.63246 1.5811 4.0000 3.0000 0.80000 0.60000 0.77460 1.7320
1.51 0.66225 1.2288 0.81379 0.81379 1.3245 1.6275 2.2801 1.9607 1.4002 0.71414 0.39841 0.63119 1.5813 3.9215 2.9607 0.79681 0.60159 0.77562 1.7206
1.52 0.65789 1.2328 0.81111 0.81111 1.3157 1.6222 2.3104 1.9230 1.3867 0.72111 0.39683 0.62994 1.5874 3.8461 2.9230 0.79365 0.60317 0.77664 1.i097
1.53 0.65359 1.2369 0.80845 0.80845 1.3071 1.6169 2.3409 1.8867 1.3736 n.7281 0.39526 0.62869 1.5906 3.7735 2.8867 0.79051 0.60474 0.77765 1.6990
1.54 0.64935 1.2409 0.80582 0.80582 1.2987 1.6116 2.3716 1.8518 1.3608 0.73485 0.39370 0.62746 1.5937 3.7037 2.8518 0.78740 0.60630 0.77865 1.68R7
1.55 0.64516 1.2449 0.80322 0.80322 1.2903 1.6064 2.4025 1.8181 1.3484 0.74162 0.39216 0.62622 1.5968 3.6363 2.8181 0.78431 0.60784 0.77961 1.6787
1.56 0.64103 1.2490 0.80064 0.80064 1.2820 1.6012 2.4336 1.7857 1.3363 0.74833 0.39073 0.62500 1.6000 3.5714 2.7857 0.78125 0.60938 0.78062 1.6690
.1.57 0.63694 I . 2530 0.79809 0.79809 1.2738 1.5961 2.4649 1.7543 1.3245 0.7549R 0.38911 0.62378 1.6031 3.5087 2.7543 0.77821 0.61089 0.78160 1.6596
1.58 0.63291 1.2569 0.79556 0.79556 1.2658 1.5911 2.4964 1.7241 1.3130 0.76158 0.38760 0.62257 1.6062 3.4482 2.7241 0.77519 0.61240 0.78256 1.6505
1.59 0.62893 1.2609 0.79305 0.79305 1.2578 1.5861 2.5281 1.6949 1.3018 0.76811 0.38610 0.62137 1.6093 3.3898 2.6949 0.77220 0.61390 0.78352 1.6416
1.60 0.62500 1.2649 0.79057 0.79057 1.2500 1.5811 2.5600 1.6666 1.2909 0.77460 0.36462 0.ti2017 1.6124 3.3333 2.6666 0.76923 0.61538 0.78446 1.6329
1.61 0.62112 I. 2688 0.78811 0.78811 1.2422 1.5762 2.5921 1.6393 1.2803 0.78102 0.38314 0.61898 1.6155 3.2786 2.6393 0.i662R 0.63686 0.i8540 1.6246
1.62 0.61728 I. 2727 0.78567 0.78567 1.2345 1.5713 2.6244 1.6129 1.2700 0.78740 0.38168 n. 61780 1.6186 3.2258 2.6129 0.76336 0.61832 O.iR633 1.6164
1.63 0.61350 I. 2767 0.78326 0.78326 1.2269 1.5665 2.6569 1.5873 1.2598 0.79373 0.38023 0.61663 1.6217 3.li.16 2.5873 0.76046 0.61977 0.78726 1.6085
1.64 0.60976 I. 2806 0.78087 0.78087 1.2195 1.5617 2.6896 1.5625 1.2500 0.80000 0.37879 0.61546 1.6248 3.I250 2.5625 0.7575R 0.62121 0.is817 1.6007
1.65 0.60606 I. 2845 0.77850 0.77850 1.2121 1.5570 2.7225 1.5384 1.2403 0.80623 0.37736 0.61429 I . 62% 3.0769 2.5384 0.75472 0.62204 0.78908 1.5932
1.66 0.60241 1.2884 0.77615 0.77615 1.2048 1.5523 2.7556 1.5151 1.2309 0.81240 0.37594 0.61314 1.6309 3.0308 2.5151 0.25188 0.02400 0.78997 1.5859
1.67 0.59880 I. 2922 0.77382 0.77382 1. I976 1.5476 2.7889 1.4925 1.2216 0.81854 0.37453 0.61199 1.6340 2.9850 2.4925 0.I 1906 0.W2547 0.i9ORi I. 5787
1.58 0,59524 1.2961 n.77152 0,77152 1.1904 1.5430 2.8224 1.4705 1.2126 n. 82462 0.37313 0.61085 1.6370 2.9411 2.4705 0.i4627 0.62687 0.79175 I. 5i18
1.69 0.59172 1.3000 0.76923 0.76923 1.1834 1.5384 2.8561 I . 4492 1.2038 0.R3066 0.37175 0.60971 1.6401 2.R9R5 2.4492 0.74349 0.62825 0.79262 I. 5650
TABLE 5. (Continued)
2
3
0
1.10 0.09091 1.9090 0.04762 21.000 0.30151 1.3817 0.21822 4.5825 0.97590 4.4721 1.6288 0.61392 0.58468 0.59912 707.94 26.607 0.82836 0.35895 0.65903
3
W
1.6269 0.61464 0.58260 0.59840 649.43 25.483 0.63045 0.35808 0.66423 0
1.11 0.09910 1.9009 0.05213 19.181 0.31480 1.3787 0.22832 4.3797 0.97358 4.2640
1.12 0.10714 1.8928 0.05660 17.666 0.32733 1.3758 0.23791 4.2031 0.97129 4.0824 1.6250 0.61536 0.5803 0.59769 W . 6 7 24.508 0.63253 0.35723 0.66941
1.13 0.11504 1.8849 0.06103 16.384 0.33918 1.3729 0.24705 4.0477 0.96900 3.9223 1.6232 0.61606 0.57846 0.59697 559.42 23.652 0.63458 0.35637 0.67457
1.14 0.12281 1.8771 0.06542 15.285 0.35044 1.3701 0.25577 3.9096 0.96674 3.7796 1.6213 0.61677 0.57642 0.59625 524.06 22.892 0.63662 0.35552 0.67973
1.15 0.13043 1.8695 0.06977 14.333 0.36116 I. 3673 0.26413 3.7859 0.96449 3.6514 1.6195 0.61747 0.57439 0.59554 493.41 22.212 0.63864 0.35467 0.68487
1.16 0.13793 1.8620 0.07407 13.500 0.37139 1.3645 0.27217 3.6742 0.96225 3.5355 1.6176 0.61816 0.57237 0.59482 466.60 21.600 0.84064 0.35381 0.68999
1.17 0.14550 1.8547 0.07834 12.764 0.38118 1.3618 0.27989 3.5727 0.96003 3.4299 1.6158 0.61886 0.57037 0.59412 442.93 21.045 0.64264 0.35298 0.69512
1.18 0.15254 1.8474 0.08257 12.111 0.39057 1.3592 0.28735 3.4801 0.95783 3.3333 1.6140 0.61955 0.56840 0.59342 421.90 20.540 0.64462 0.35215 0.70024
1.19 0.15966 1.8403 0.08676 11.526 0.39958 1.3565 0.29455 3.3950 0.95564 3.2444 1.6122 0.62024 0.56643 0.59272 403.08 20.076 0.64658 0.35132 0.70534
1.20 0.16687 1.8333 0.09091 11.000 0.40825 1.3540 0.30151 3.3166 0.95346 3.1622 1.6105 0.62092 0.56447 0.59202 386.15 19.650 0.64853 0.35049 0.71043
1.21 0.17355 1.8264 0.09502 10.523 0.41660 1.3514 0.30826 3.2440 0.95130 3.0860 1.6087 0.62161 0.56254 0.59134 370.82 19.256 0.65047 0.34968 0.71551
1.22 0.18033 1.8196 0.09910 10.090 0.42465 1.3489 0.31480 3.1766 0.94916 3.0151 1.6069 0.62228 0.56061 0.59064 356.89 18.891 0.65239 0.34886 0.72058
1.23 0.18699 1.8130 0.10314 9.6956 0.43242 1.3464 0.32115 3.1137 0.94703 2.9488 1.6052 0.62296 0.55870 0.58996 344.18 18.552 0.65429 0.34805 0.72564 W
1.6035 0.62363 0.55681 0.58927 332.52 17.235 0.65619 0.34724 0.73070
1.24
1.25
1.26
0.19355
0.2ooOo
0.206%
1.8064 0.10714 9.3333 0.43994 1.3440
1.8ooo 0.11111 9.oooO 0.44721 1.3416
1.7936 0.11504 8.6923 0.45426 1.3392
0.32733
0.33333
0.33918
3.0550
3.m
2.9482
0.94491
0.94281
0.94072
2.8867
2.8284
2.7735
1.6018
1.6001
0.62430
0.62496
0.55493
0.55306
0.58859 321.79 17.938 0.65807
0.58792 311.89 17.660 0.65993
0.34644
0.34564
0.73574
0.74077
T;
W
1.27
1.28
0.21260
0.21875
1.7874 0.11894 8.4074 0.46108 1.3369
1.7812 0.12281 8.1428 0.46771 1.3346
0.34488
0.35044
2.8995
2.8535
0.93865
0.93659
2.7216
2.6726
1.5984
1.5967
0.62562
0.62628
0,55121
0.54937
0.58724
0.58656
302.72 17.398 0.68178
294.21 17.152 0.66362
0.34485
0.34406
0.74579
0.75080
c
7
1.7751 0.12664 7.8965 0.47414 1.3323 0.35586 2.8100 0.93454 2.6261 1.5950 0.62694 0.54755 0.58590 286.28 16.919 0.66545 0.34328 0.75581
1.29
1.30
0.22481
0.23077 1.7692 0.13043 7.6666 0.48038 1.3301 0.36116 2.7688 0.93250 2.5819 1.5933 0.62759 0.54573 0.58523 278.88 16.699 0.66726 0.34249 0.76079 c"
1.31 0.23664 1.7633 0.13420 7.4516 0.48646 1.3279 0.36633 2.7297 0.93048 2.5400 1.5917 0.62824 0.54393 0.58456 271.96 16.491 0.66906
265.48 16.293 0.67085
0.34111 0.76578
0.77075
0
1.32
1.33
0.24242
0.24812
1.7575 0.13793 7.2500 0.49237 1.3257
1.7518 0.14163 7.0606 0.49812 1.3235
0.37139
0.37634
2.6925
2.6571
0.92848
0.92648
2.5000
2.4618
1.5901
1.5885
0.62888
0.62953
0.54214
0.54036
0.58390
0.58324 259.38 16.105 0.67263
0.34094
0.34017 0.71571 Z
1.34 0.25373 1.7462 0.14530 6.8823 0.50372 1.3214 0.38118 2.6234 0.92450 2.4253 1.5868 0.63016 0.53860 0.58259 253.65 15.926 0.67439 0.33941 0.78066
1.35 0.25926 1.7407 0.14894 6.7142 0.50917 1.3193 0.38592 2.5911 0.92253 2.3904 1.5852 0.63080 0.5361 0.58193 248.24 15.755 0.67615 0.33865 0.78561 9
1.36
1.37
0.26471
0.27007
1.7352 0.15254 6.5555 0.51449 1.3173
1.7299 0.15612 6.4054 0.51968 1.3152
0.39057
0.39512
2.5603
2.5308
0.92057
0.91863
2.3570
2.3249
1.5837
1.5821
0,63143
0.63207
0.53511
0.53339
0.58128
0.58064
243.13 15.592 0.67789
238.30 15.436 0.67962
0.33789
0.33114
0.79054
0.79547
Z
1.38 0.27536 1.7246 0.15966 6.2631 0.52475 1.3132 .O 39958 2.5026 0.91670 2.2941 1.5805 0.63269 0.53167 0.57999 233.72 15.287 0.68133 0.33639 0.80038 U
1.39 0.28058 1.7194 0.16318 6.1282. 0.62969 1.3112 0:40395 2.4755 0,91478 2.2645 1.5789 0.63332 0.52997 0.57934 229.38 15.145 0.68304 0.33564 0.80529
0.40825 2.4494 0.91287 2.2360 1.5774 0.63394 0.52828 0.57870 225.25 15.008 0.68473 0.33490 0.81019 W
1.40 0.28571 1.7142 0.16667 ooOo 0.53452 1.3093
1.41
1.42
1.43
0.29078
0.29577
0.30070
1.7092 0.17012 8:8780 0.53924 1.3073
1.7042 0.17355 5.7619 0.54585 1.3054
1.6993 0.17695 5.6511 0.54836 1.3035
0.41246
0.41660
0.42066
2.4244
2.4004
2.3772
0.91097
0.90909
0.90722
2.2086
2.1821
2.1566
1.5759
1.5743
1.5728
0.63456
0.63517
0.63579
0.52660
0.52494
0.52328
0.57807
0.57743
0.57680
221.33 14.877 0.68642
217.59 14.750 0.68809
214.03 14.629 0.68975
0.33416
0.33343
0.33270
0.81507
0.81995
0.82482
T;
W
1.44 0.30556 1.6944 0.18033 5.5454 0.55277 1.3017 0.42465 2.3548 0.90536 2.1320 1.5713 0.63640 0.52164 0.57617 210.63 14.513 0.69140 0.33197 0.82968 m
1.45 0.31034 1.6896 0.18367 5.4444 0.55709 1.2998 0.42857 2.3333 0.90351 2.1081 1.5698 0.63701 0.52000 0.57554 207.38 14.400 0.69304 0.33124 0.83453 r
1.46
1.47
0.31507
0.31973
1.6849 0.18699 5.3478 0.66131 1.2980
1.6802 0.18028 5.2553 0.56544 I . 2962
0.43242
0.43621
2.3125
2.2924
0.90167
0.89984
2.0851
2.0628
1.5683
1.5668
0.63761
0.63821
0.51838
0.51677
0.57491
0.57429
204.27 14.292 0.69467
201.29 14.187 0.69629
0.33052
0.32981
0.32909
0.83937
0.84420
0.84903
5
1.48
1.49
0.32432
0.32886
1.6756 0.19355 5.1666 0.56949 1.2944
1.6711 0.19679 5.0816 0.57346 1.2927
0.43994
0.44361
2.2730
2.2542
0.89803
0.89622
2.0412
2.0203
1.5654
1.5639
0.63881
0.63941
0.51517
0.51358
0.57367 198.44 14.086 0.69790
0.57305 195.70 13.989 0.69950 0.32839 0.85384 Z
--I
1.50
1.51
0.33333
0.33775
1.6666 0.20000 5.ooOo 0.57735 1.2909
1.6622 0.20319 4.9215
. . . ~0.58116
~ ~ ~ 1.2892
~~~~
0.44721
0.45076
2.2360
2.2184
0.89443
0.89264
2.ooOo
1.9802
1.5625
1.5610
0.64000
0.64059
0.51200
0.51043
0.57243
0.57182
193.07 13.894 0.70108
190.55 13.803 0.70266
0.32768
0.32698
0.85865
0.86345 tn
1.52 0.34211 1.6578 0.20635 4.8461 0.58490 1.2875 0.45426 2.2014 0.89087 1.9611 1.5596 0.64118 0.50887 0.57121 188.12 13.715 0.70423 0.32628 0.86823
1.53 0.34641 1.6535 0.20949 4.7735 0.58856 1.2859 0.45770 2.1848 0.88911 1.9425 1.5582 0.64176 0.50732 0.57060 185.79 13.630 0.70579 0.32558 0.87301
1.54 0.35065 1.6493 0.21260 4.7037 0.59316 1.2842 0.46108 2.1688 0.88736 1.9245 1.5567 0.64235 0.50579 0.56999 183.54 13.547 0.70734 0.32489 0.87779
1.65 0.35484 1.6451 0.21569 4.6868
___.__ 0.59568
....... 1.2826 0.46442 2.1532 0.88561 1.9069 1.5553 0.64293 0.50426 0.56939 181.37 13.467 0.70888 0.32420 0.88255
1.56 0.35897 1.6410 0.21875 4.5714 0.59914 1.2810 0.46771 2.1380 0.88388 1.8898 1.5539 0.64351 0.50274 0.56879 179.28 13.389 0.71041 0.32352 0.88730
1.57 0.36306 1.6369 0.22179 4.5087 0.60254 1.2794 0.47094 2.1233 0.88216 1.8731 1.5525 0.64408 0.50123 0.56819 177.27 13.314 0.71193 0.32284 0.89205
158 0.36709 1.6329 0.22481 3.4482 0.60588 1.2778 0.47414 2.1090 0.88045 1.8569 1.5512 0.64466 0.49973 0.56759 175.32 13.240 0.71345 0.32216 0.89679
1.59 0.37107 1.6289 0.22780 4.3898 0.80915 1.2763 0.47728 2.0951 0.87875 1.8411 1.5498 0.64523 0.49824 0.56699 173.44 13.169 0.71495 0.32148 0.90152
1.80 0.37500 1.6250 0.23077 4.3333 0.61237 1.2747 0.48038 2.0816 0.87706 1.8257 1.5484 0.645RO 0.49677 0.56640 171.62 13.100 0.71645 0.32081 0.90624
1.61 0.37888 1.6211 0.23372 4.2786 0.61553 1.2732 0.48344 2.061 0.87538 1.8107 1.5171 0.64686 0.49530 0.56551 169.86 13.033 0.71793 0.32014 0.91095
1.62 0.38272 1.6172 0.23664 4.2258 0.61864 1.2717 0.48646 2.0556 0.87370 1.7960 1.5457 0.64693 0.49384 0.56522 168.16 12.967 0.71941 0.31947 0.91566
1.63 0.38650 1.6135 0.23954 4.1746 0.62169 1.2702 0.48943 2.0431 0.87204 1.7817 1.5444 0.64749 0.49239 0,56464 166.51 12.903 0.72088 0.31881 0.92035
1.64 0.39024 1.6097 0.24242 4.1250 0.62469 1.2687 0.49237 2.0310 0.87039 1.7677 1.5431 0.64804 0.49094 0.56405 164.92 12.842 0.72233 0.31815 0.92504
1.65 0.39394 1.6060 0.24528 4.0769 0.62765 1.2673 0.49526 2.0191 0.86874 1.7541 1.5417 0.64860 0.48951 0.56347 163.37 12.781 0.72379 0.31749 0.92972
1.66 0.39759 1.6024 0.24812 4.0303 0.63055 1.2658 0.49812 2.0075 0.86711 1.7407 1.5404 0.64915 0.48808 0.56289 161.87 12.722 0.72523 0.31684 0.93439
1.67 0.40120 1.5988 0.25094 3.9850 0.63340 1.2644 0.50094 1.9962 0.86548 1.7277 1.5391 0.64970 0.48667 0.56231 160.41 12.665 0.72666 0,31619 0.93905
1.68 0.40476 1.5952 0.25373 3.9411 0.63621 1.2630 0.50372 1.9852 0.86387 1.7149 1.5378 0.65025 0.48526 0.56173 159.00 12.809 0.72809 0.31554 0.94371
1.69 0.40828 1.5917 0.25651 3.8985 0.63897 1.2616 0.50646 1.9741 0.86226 1.7025 1.5365 0.65080 0.48387 0.56116 157.63 12.555 0.72951 0.31490 0.94836
ORDP 20-282
TABLE 6. ENTHALPIES OF FORMATION OF FUELS AT 300'K

(A Hj/in k cal/g-mol)
(Martinez, J. S. and Elverum, G. W., Jet Propulsion Laboratory, California Institute

of Technology, Tech. Memo. No. 20-121, December 6, 1955)
Heat of Formation
Fuel Formula Gar liquid Solid
Ammonia 11.04* 16.52* 17.97*

Aniline -6.11
Acetylene -54.193 -50.6
Benzene -19.726 -11.718*
1-Butylene -0.254
nButane 29.847 34.882
1-Butyne (ethylacetylene) -39.68
2-Butyne (dimethyacetylene) -35.355
Beryllium hydride -78.1*
Boron (atom) -97.2*
Boron -124.5* 0
Cyanogen -73.60*
n-Decane 59.74
Dimethylamine 6.6*
Dimethylaminodiborane 61.6
Diborane -6.7f0.5
Diethylenetriamine 3.15 15.40
Dimethylhydrazine (Unsymmetrical) - 19.636 -11.27
Ethylene oxide 12.19* 18.44
Ethanol 56.27 67.2
Ethyl nitrite 24.8*
Ethyl nitrate 44.3*
Furfural 46.6
Furfuryl alcohol 66.05
Guanidine nitrate 91.1*
n-Hexane 40.01 47.52*
n-Heptane 44 * 94 53.63*
Hydrogen 0 1.92
Hydrogen cyanide -31.2*
Hydrazine hydrate 10.3
Hydrazine -22.70 -12.0
JP-4 0.421
(K cal/g)
Lithium -38.437 0
Lithium hydride -30.7* 21.61*
Methyl alcohol 48.08* 57.04*
Methyl hydrazine -22.758 -13.11
Nitromethane 21.28*
Nitroguanidine 22.14'
n-Octane 49.88 59.795
1-Octene 19.87
Pentaborane -15.0* -7.8*
Propene (propylene) -4.858
Propane 24.848 28.443
Propyne (methylactylene) -44.309
Propyl nitrate 43.2 52.8
Tetranitromethane 18.6*
Trimethyl boron 31.4*
* Values of A H;a t 298'K.
87
ORDP 20-282
TABLE 7. ENTHALPIES OF FORMATION FOR OXIDIZERS AT 300°K

(A H j in k cal/g-mol)
(Martinez, J. S. and Elverum, G. W., Jet Propulsion Laboratory, California Institute

Enthalpy of Formation
Oxidizer Formula Gar. liquid Solid
Ammonium nitrate NH4N03 87.27*

Ammonium perchlorate NHaC104 69.42*
Boron trichloride 94.5*
Boron trifluoride 265.4*
Boron tribromide 44.6*
Chlorine trifluoride 38.0 44.5
Fluorine 0
Fluorine monoxide -7.60
Hydrogen peroxide 33.74 44.84 47.36*
Nitrogen tetroside -2.30 6.80
Nitrogen trifluoride 27.2* 31.2-129
Nitric acid 31.92 41.35
Oxygen 0 3.08-183
Ozone -34.00 -30.3
Perchlorylfluoride 2.56 7.3
Potassium perchlorate 103.6*
Tetrani tromethane -8.8* or
-22
Red fuming nitric acid
45.3
Stabilized fuming nitric acid 51.5
+ +
(HNO3 0.2315 NO2
0.1955 H:!O 0.019 H4)
+
Avg mol wt 75.94
~~~~~ ~
* Values of A H; a t 298°K.
TABLE 8. ENTHALPIES OF FORMATION FOR REACTION PRODUCTS AT 300'K
(A H ; in k cal/g-mol)
(Martinez, J. S.and Elveruni, G. W., Jet Propulsion Laboratory, California Institute
Reaction Enthalpy of Formation
Product Formula Gas liquid Solid Remarks
Aluminum oxide 399.09 (4

Aluminum hydroxide 304.2 amorphous (a)
Ammonium fluoride 111.6 (a)
Ammonium chloride 75.38 (8)
Beryllium oxide -11.8 145.3 (5)
Beryllium chloride 122.3 (2)
Boric acid 260f3.5
Boron nitride -90.6 32.1 (4
Boron fluoride 17.4
Boron chloride -25.6
Boron monoxide 5.3
Boron trioxide 223.2 302*3
Carbon dioxide 94.052
Carbon monoxide 26.413
Carbon tetrafluoride 231
Carbon (graphite) 0
Carbon (gas) - 171.698
Chlorine (atom) -28.943
Cyanogen chloride -34.5
Chlorine monofluoride 11.898
or
13.256
ORDP 20-282
Reaction Enthalpy of Formation
Product Formula Gas liquid Solid Remarks
Fluorine (atom) F - 18.906

Hydroxyl OH - 10.063
Hydrogen (atom) H -52.092
Hydrogen chloride HC1 22.063
Hydrogen fluoride HF 64.20
Hexa hydrogen fluorine (HF), 426
Hydrogen sulfide HzS 4.815
Lithium Li -37.07 0.00
Lithium hydroside LiOH 116.45
Lithium Liz -50.461
Lithium oxide Li20 142.4
Lithium chloride LiCl 53 97.70
Lithium fluoride LiF 146.3
Lithium oxychloride 91 . G
Lithium nitride LiaN 47.2
Lithium peroxide Liz02 159
Nitrogen N2 0
Nitrogen (atom) N -112.5
Oxygen 0 2 0
Oxygen (atomic) 0 -59.162
Potassium chloride KC1 51.60 104.175
Potassium oxide K2O 86.4
Sodium oxide NaOl 61.9
Sodium oxide Na10 99.4
Sodium peroxide NazOn 120. 6
Sodium hydroxide NaOH 101.99
Sulfur S -53.25
Sulfur s
2 -29.86
Sulfur dioxide so2 70,96
Sulfur trioxide so3 94.45
Tetrabromomethane CBr4 - 12
Tetrachloromethane CCla 25.5
Tetrafluoromethane CF, 231 *3
Water H20 57.802 68.317 69.753
Zinc oxide ZnO 83.17
Zirconium oxide ZrO2 258.2
(a) Values of A H; a t 298°K.

General Reference
(b) Rossini, F. I)., e t al, Sclected Values of Properties of Hydrocnrbons, S B S 500, Novemhcr 1947
89
TABLE 9. EQUILIBRIUM CONSTANTS AS FUNCTIONS OF TEMPERATURE
FOR C-H-N-O COMPOUNDS
(Gordon, J. S., Wright Air Development Center, TIt57-38, January 1957)
(Martinez, J. S. and Elverurn, G. W., J e t Propulsion Laboratory, California Institute of Technology, Tech. Memo. No. 20-121, December 6 , 1955)
Temperature
"K "R KI Kz K3 K4 K5 KG K7 Ks Ks Kio KII Kn
298.16 436.68 4.41xIO-s1 2.54~10-47 834
300 540 1.ft8xlik~O 5.068 4.973~1024 741.5
400 720 3.19~10-59 1.248~10-34 4.287~1015 6.557
500 900 7.279~10-3 ~.
...... . 3.485~10-27 5.345~10-93 1.059~1025
600 1080 0.0354 1.408~10-~G 3.348x10-" 1.490~10-76 1.222x1020
700 1260 0.1060 2.108x10-22 1. 248x10-Is 8.581x10-65 3.630x101G
800 1440 .2360 2.9Olx10-'9 6.053x10-1G 5.798~10-56 8.232~1013
900 1620 .4340 8.096x10-'7 7.510~10-~~4.347~1049 0.788 1.247~10-3 7.254~1011
loo0 1800 0.6958 7.56~10-'5 1.65xlO-20 2.27~10-9 3.579~10-12 ... . 3.932~104 5.95~10-4 1.654~1010 0.8547~10-4
1100 1980 1.010 3.02~10-13 3.89~10-1s 2.59~10-R 8.513~10-11 4.491~1059 3.311~10-3 3.22 7.532~108 2.302
1200 2160 1.368 6.65~10-12 3.72xlO-'G 1.97~10-7 1.188~10-9 2.589~10-3'. 4.280x10-' 1.94 5.762~107 5.255
1300 2340 1.757 9.13~10-11 1.77x10-'4 1.11x10-6 1.114x10-~ 3.964~10-3 7.366~10-5 1.25 6.571 1.056~10-3
1400 2520 2.160 8.66x10-'0 4.88~1043 4.86 7.598 2.140~10-29 1.631~10-5 8.61~10-5 1.025~100 1.920
1500 2700 2.572 6.09~10-9 8.67~10-12 1.76~10-5 4.016~10-7 4.441~10-0 6.21~10-5 2.054~105 2 . 0.fi
~. .. l..x.
l.
W 3.225~10-3
1600 2880 2.990 3.37~10-s .1.08xlO-~O 5.43 1.725~104 4.66 5.046~104 3.131~1023 5.076
1700 3060 3.395 1.52~10-7 1.00x10-~ 1.47~10-4 6.249 3.62 1.465 7.768~1021 7.572
1800 3240 3.793 5.84 7.26 3.57 1.963~10-5 2.89 4.890x103 2.902x1020 1.081x10-2
1900 3420 4.417 1.94x10-0 4.28~10-8 7.926 5.468 2.37 1.835 1.530x101Q 1.487
2000 3600 4.553 5.74x10-0 2.12~10-7 0.001624 1.375~104 1.98~10-5 7.609~102 1.082XlO'* 1.982x10-2
2100 3780 4.890 1.53~10-5 9.01 .003111 3.169 1.69 3.436
.. ..- 9.832~1016 2.504
2200 3960 5.218 3.735 3.364~104 .OO5621 6.770 1.46 1.670 1.110 3.239
2300 4140 5.532 8.429 1.120x10-~ .W9660 1.354~10-3 1.28 8.654~10 1.514~101~ 4.021
9 2400 4320 5.823 1.778~10-4 3.378 .01587 2.556 1.13 4.742 2.436~10" 4.901
0
2500 4500 6.096 3.539~104 3.595~10-5 9.332~10-5 0.02509 4.596~10-3 1.016~10-13 27.29 4.533~10~3 0.0588
2600 4680 6.358 6.676 9.154 2.385~10-4 .03829 7.881 5.983 16.41 9.592~10'2 .0695
2700 4860 6.598 1.201~10-3 2.178~10-4 5.690 .05669 0.01300 3.093~10-'2 10.25 2.276 .0812
2800 5040 fi. 827 2.074 4.870 1.276~10-3 ,08162 .02067 1.423x10-l1 6.630 5.981x10" .0938
2900 5220 7.022 3.450 1.031~10-3 2.709 .1146 .03185 5.899 4.422 1.723 .1073
3000 5400 7.226 5.534~10-3 2.071~10-3 5.460~105 0.1575 0.04762 2.226~10-10 3.032 5.387Xrn10 0.1216
3100 5580 7.414 8.633 3.988 0,01054 -.2121 .06946 7.717 2.132 1.815 .1366
3200 5760 7.577 0.01309 7.381 ,01954 ,2803 .09895 2.478~10-9 1.534 6.542~109 .1524
3300 5940 7.725 .01936 0.01315 .03488 .3643 .I379 7.418 1.126 2.507 .1689
3400 6120 7.871 .02799 .02270 .06024 .4662 .1886 2.084~10-8 0.8424 1.016 .1860
3500 6300 8.011 0.03957 0.03784 0.1007 0.5888 0.2532 5.524~10-5 0.6411 4.332~108 0.2036
3600 6480 8.132 .05495 .06146 .1638 .7340 .3344 1.388xlO-7 0.4956 1.936 .2218
3700 6660 8.254 ,07487 .09722 .2595 .9041 .4351 3.320 0.3887 9.034~107 .2403
3800 6840 8.349 .lo05 .1505 .4017 1.102 .5587 7.591 0.3090 4.385 ,2593
3900 7020 8.438 .1330 ,2278 .6082 1.328 .7081 1.663x10-6 0.2486 2.208 .2786
4000 7200 8.523 0.1731 0.3372 0.9008 1.588 0.8861 3.532~10" 0.2023 1.150~107 0.2993
4100 7380 8.609 .2229 .4899 1.311 1.882 1.097 7.149 0.1664 6.180xloG .3185
4200 7560 8.679 ,2834 .7004 1.873 2.213 1.346 1.406~10-5 0.1382 3.419 .3386
4300 7740 8.760 .3560 .9814 2.629 2.583 1.634 2.680 0.1158 1.944 .3589
4400 7920 8.809 .4427 1.357 3.639 2.993 1.966 4.962 0.098 1.133 ,3794
4500 8100 8.852 0.5462 1.856 4.970 3.444 2.348 8.941~10-5 1.01x10-~ 0.0826 6.764~105 0.4000
4600 8280 8.904 .6670 2.499 6.692 3.942 2.782 1.57OxlO-r 9.Ixl0-0 .0708 4.127 .4207
4700 8460 8.952 .8073 3.323 8.896 4.485 3.271 2.694 8.27 .0611 2.571 .4415
4800 8640 8.992 .9694 4.363 11.69 5.078 3.822 4.518 7.56 .0531 1.633 .4623
4900 8820 9.024 1.156 5.675 15.19 5.717 4.437 7.422 6.96 ,0461 1.057 ,4833
5000 goo0 9.048 1.370 7.318 19.56 6.407 5.125 1.196~10" 6.44~104 0.0408 6.961~104 0.5049
5100 9180 9.070 1.605 9.420 24.89 7.145 5.861 1.891 .0359 4.628 .5228
5200 9360 9.089 1.876 11.84 31.43 7.937 6.690 2.941 .0320 3.151 .5453
5300 9540 9.095 2.181 14.83 39.37 8.780 7.598 4.499 ,0286 2.171 .5664
5400 9720 9.098 2.523 18.44 48.91 9.675 8.590 6.778 .0256 1.516 ,5875
Temperature
OK OR X1 Ka K3 K4 Ks K6 Ks K7 Ks Kio Xi1 KIZ
5500 9900 0.099 2.904 22.76 60.31 10.62 9.669 0.01007 0.0230 1.073~10' 0.6087
5600 10,080 0.097 3.328 27.91 73.84 11.62 10.84 ,01475 ,0208 7.682xllY .6299
5700 10.260 0.092 3.797 34.00 89.82 12.68 12.10 ,02133 ,0189 5.566 ,6512
5800 10,440 9.083 4.316 41.17 108.6 13.78 13.45 .03046 .0172 4.078 ,6726
5900 10,620 9.071 4.889 49.58 130.5 14.93 14.86 ,04301 .0157 3.019 ,6943
6000 10,800 9.055 5.519 59.39 155.9 16.14 16.62 0.06004 0.0143 2.258~103 0.7161
INDEX
Index Terms Links
Abbreviations 2
Additives 15
Adiabatic flame temperature 39
Alcohol 65
Altitude, drag-free maximum 34
Ammonia 66 67
Burning,
erosive 76
linear rate 73
linear rate, controllable 71
neutral, progressive, regressive 22
rate exponent 22
resonant 76
sonant 76
Burnout velocity 33 34
Case bonding 15
Characteristic velocity 32 47
Chlorine trifluoride 59
Coefficient,
mass flow 32
nozzle divergence 27
thrust 31 46
weight flow 32 46
Combustion,
chamber 16
enthalpy of 49
gas, thermodynamic properties of 38
This page has been reformatted by Knovel to provide easier navigation.

Index Terms Links
Combustion, (Cont.)
pressure, equilibrium composition 75
propellants, solid 76
temperature, calculation of 39
Composite propellants, oxidizers for 72
Conversion factors 3
Cooling, regenerative 18
Criteria for calculating performance 37
Cut-off velocity 33
Dalton’s law 2
Decomposition chamber 54
Density,
propellant 71
propellant, average of system 51
propellant weight loading 34
Diborane 63
Diethylenetriamine (DETA) 66
Dimethylhydrazine, unsymmetrical (UDMH) 66
Dithekites, See monopropellants 53
Double-base solid propellants 14
Elements, light 63
Energy, internal 6
Enthalpy,
combustion, of 49
gas, of 6
reaction, of 38
Equation of state for gas 2
Equilibrium,
combustion pressure and propellant area 75
composition, calculation of 40
composition of combustion products 41
constant 40
frozen 37 42
mobile 37 43

Index Terms Links
Erosive burning 76
Ethylene oxide 53
Expansion factor 6 46
Exponent, pressure 75
Fluoride, perchloro 62
Fluorine 56
Fluorine and oxygen 62
Fluorine monoxide 62
Free energy function 7
Fuels
alcohol, ethyl 65
ammonia, anhydrous 66
composite propellants, for 72
diborane 63
diethylenetriamine (DETA) 66
elements, light 63
hydrazine 67
hydrides, nitrogen 66
hydrocarbons, light 65
hydrogen, liquid 63
liquid bipropellant systems, for 63
mixtures, hydrazine and ammonia 67
organic 65
pentaborane 63
unsymmetrical dimethylhydrazine (UDMH) 66
Gas
combustion, thermodynamic properties of 38
Dalton’s law 2
enthalpy 6
equation of state 2
exit velocity 27 37 44
free energy function (Gibbs) 7
internal energy 6
isentropic change of state 6

Index Terms Links
Gas (Cont.)
isentropic velocity 7
relationship between specific heats 6
thermodynamic relationships 2
Grain, solid propellant 22
case bonded internal burning 22
composite 14
configurations 22
dimensions 78
double-base 14
end burning 22
estimation of size and weight 78
heterogeneous 14
rod and tube 24
shape 78
single perforated 22
star 22
tubular 22
web thickness 22
Heat, specific 6
Heterogeneous solid propellants 14
Hydrazine 55 67
Hydrazine-ammonia mixtures 67
Hydrides, nitrogen 66
Hydrocarbons, light 65
Hydrogen, liquid 63
Hydrogen peroxide 53
Igniter 24
Impulse 31
calculation 29 31 46
specific 29 37 71
total 31
weight ratios 32
Index, pressure 22

Index Terms Links
Injector 16
Internal energy 6
Isentropic change of state 6
Isentropic velocity 7
Isobaric process 39
Jet, effective 31
Jet propulsion, salient features 9
Length, characteristic, of combustion chamber 18

Linear burning rate 73
Liquid bipropellant systems, fuels for 63
Liquid bipropellant systems, oxidizers for 56
LOX 57
LOZ 59
Mass flow coefficient 32

Mass ratio 33
Measurement,
abbreviations, principal 2
basic units 2
Momentum theorem 29
(MON) mixed oxides of nitrogen 61
Monopropellants 53
ethylene oxide 53
hydrazine 55
hydrogen peroxide 53
methyl nitrate and methanol (myrols) 53
nitrobenzene, nitric acid, water (ditekites) 53
nitro paraffin mixtures 53

Index Terms Links
Nitric acid 60
Nitrobenzene, See monopropellants
Nitroparaffin mixtures 53
Notations, principal 4
Nozzle,
area ratio 44
divergence coeficient 27
exhaust 18 20
expansion ratio 6
gases crossing 27
throat area and grain dimensions 78
weight rate flow 44
Operating principles of rocket engines 9

Organic fuels 65
Oxidizers,
chlorine tritluoride 59
composite propellants, for 72
fluorine and oxygen, containing 62
fluorine, containing 59
fluorine, liquid 56
fluorine, monoxide 62
hydrogen peroxide 60
liquid bipropellant systems, for 56
mixed oxides of nitrogen (MON) 61
nitric acid 60
oxygen, containing 59
oxygen, liquid (LOX) 57
ozone, liquid (LOZ) 59
perchlorofluoride 62
Oxygen 57 59
Ozone 59

Index Terms Links
Pentaborane 63
Perchlorofluoride 62
Performance criteria 37 43
Pressurization, liquid propellants 18
chemical 20
gas, stored 18
turbopump 20
Propellant area 22
Propellant mass 33
Propellants, liquid 49
availability 53
average density 51
boiling point 52
chemical reactivity 49
Chemical stability 52
chemical structure 50
corrosivity 52
cost 53
enthalpy of combustion 49
freezing point 52
physical properties 49
selection factors 49
specific heat 52
toxicity 52
vapor pressure 52
viscosity 52
see also fuels, oxidizers, monopropellants,
pressurization
Propellants, solid 71
ballistic properties 73
burning rate, controllable 71
characteristics desire& 71
chemical stability 71
composite 14 72
control of processing 72
cost 72
density 71
Index Terms Links
Propellants, solid (Cont.)

design conclusions 76
double-base 14
explosive hazard 72
heat transfer 76
heterogeneous 14
physical properties 71
raw materials, availability of 72
shock sensitivity 72
smoke 72
specific impulse 29 71
temperature, effect of 75
temperature sensitivity 75
toxicity 72
Ratios
expansion ratio, nozzle 6 43
mass 33
nozzle area 44
port-to-throat 22
pressure, critical 9
propellant area, and combustion pressure 75
propellant loading 22
propellant mass 33
vehicle mass 33
weights and impulse-weight 32
Resonant burning 76
Rocket engines,
bipropellant, liquid 14 16
classification 13
combustion chamber 16
components 15
definition 1
injector 16
monopropellant, liquid 13
nozzle, exhaust 18
operating principles 9

Index Terms Links
Rocket engines, (Cont.)

performance criteria 37
see also propellants, liquid
Rocket motors 20
case or housing 24
classification 13
components 20
definition 1
grain (see also)
heat transfer 77
igniter 24
nozzle exhaust 18 24
performance criteria 43
propellants, solid (see also)
Shock sensitivity 72
Smoke 72
Sonant burning 76
Specific heat, molar 6
Specific heats, relationship 6
Specific impulse 29 37 43
46 71
Temperature
adiabatic flame 39
calculation of, combustion 39
effect of, solid propellants 75
sensitivity 75
Thermodynamic
combustion gas, .properties of 38 42
performance criteria calculation 43
properties required for criteria 37
relationships 2

Index Terms Links
Thrust 27
calculation by momentum theorem 29
coefficient 31 46
cut-off and vector control 25
equation 27
Toxicity 52 72
Unsymmetrical dimethylhydrazine (UDMH) 66
Vector control 25
Vehicle mass 33
Velocity,
burnout, ideal 34
characteristic 32
characteristic, ideal 47
cut-off 33
exhaust, effective 31
gases, exit, of 27 44
isentropic exit 37
jet, effective 31
Weight-efficiency, engine 34
Weight-flow coefficient 32 46
Weights and impulse-weight 32

AMCP 706-282 Ballistic Missile Series Propulsion and Propellats PDF

Uploaded by

Copyright:

Available Formats

AMCP 706-282 Ballistic Missile Series Propulsion and Propellats PDF

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

AMCP 706-282 Ballistic Missile Series Propulsion and Propellats PDF

Uploaded by

Copyright:

Available Formats

What is the document about?

What is the document about?

What are some of the main components discussed in the document?

What are some of the main components discussed in the document?

AMCP 706-282

ORDNANCE CORPS PAMPHLET

ORDNANCE ENGINEERING DESIGN HANDBOOK

ORDP 20-282, Propulsion and Propellants, forming part of the Ballis-

Figure Title page

This Handbook has been prepared as one of a series on Ballistic

The handbook was prepared for the Office of Ordnance Research,

1-1. DEFINITIONS AND SCOPE ballistic missiles, and therefore no discussion of

Dimension Basic Unit

* Numbers in parentheses in the text indicate referenres

TABLE 1-2. CONVERSION FACTORS

Given Multiply by To obtain

TABLE 1-3. PRINCIPAL NOTATIONS

acoustic velocity for combustion gases 32.1740 ft/sec2)

TABLE 1-3. (Continued)

C, = a,= R,,-k-1k (1-10) The superscript prime ( ' ) attached t o tz in

C, = a,= R, k-1 (1> (1-11)

hi = a,tl(i -e,) = E,~~Z, (1-18)

1-3.5. Enthalpy of a Perfect Gas. The thermo-

1-4. REFERENCES 3. Greene, S . H., and L. J. Gordon, An Effect of

6. Zucrow, M. J., et al, “Aerodynamics, Co., New York, 1950.

ESSENTIAL FEATURES OF ROCKET ENGINES

Figure 2-1. Fin-Stabilized Rocket Motor

ALL PRESSURES ARE BALANCED

PROPELLANT GRAIN CASE DE' LAVAL

Figure 2-2. Development of Thrust in a Rocket Motor

engine development is that concerned with ob-

0x1 DI ZER FUEL

R EMOTE CONTROL LED

Figure 2-6. Schematic Diagram of a Turbopump Arrangement for Pressurizing a

p, = constant (2) I / (1- n)

BURNING SURFACE CASE

(d) PORT ROD

(Taken from Reference 71

Figure 2-7. Typical Solid-Propellant Grain Configurations

CRITERIA OF ROCKET ENGINE PERFORMANCE

3-1. THRUST EQUATION

F = J6, (Pifm +~o(P”s)” (3-1)

V , = [2gJ(Hc-hc)J“2 zz [2gJ(hc--1~,)]”2 (3-3)

IaJ liquid Propellant Rocket Engine

BURNING I EXIT SECTION

IbJ Solid Propellant Rocket Motor with End-Burning Grain

(Taken from Reference 2 1

To calculate the performance of a propellant Hence

TO INFINITY F = THRUST TO INFINITY

Figure 3-2. Application of the Momentum Theorem of Fluid Mechanics to an

3-3. TOTAL IMPULSE

I = /'>& = I , @ T ~= W J , (lb-sec) (3-10)

(3-17) 3-8. WEIGHTS AND IMPULSE-WEIGHT

a t take-off W, includes the weights of all the

(Taken from Reference 7 )

Figure 3-4. Specific Impulse as a Function of the Impulse-Weight Ratio for

3-1 2. REFERENCES 5 . Sutton, G. P., Rocket Propulsion Elements,

THERMODYNAMIC RELATIONSHIPS FOR ROCKET ENGINES