Propellant Chemistry

Liquid Propellants
Notes

Based on Lectures by
Dr.S.G.Kulkarni
Contents

1 Introduction 1

1.1 Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

1.2 How liquid propellants work . . . . . . . . . . . . . . . . . . . . . . . . . 3

1.3 Desirable properties of Liquid Propellants . . . . . . . . . . . . . . . . . 3

1.4 Comparison between Solid and Liquid Propellants . . . . . . . . . . . . . 5

2 Classification of Liquid Propellants 6

2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

2.2 Bipropellants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

2.3 Various Fuels used in Liquid Propellants . . . . . . . . . . . . . . . . . . 7

2.4 Storable Oxidizer Used in Bipropellants . . . . . . . . . . . . . . . . . . . 10

3 Performance of Liquid Propellants and Recent Developments 13

3.1 Performance of Liquid Propellants . . . . . . . . . . . . . . . . . . . . . . 13

3.2 Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

3.3 Recent Developments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

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Chapter 1

Introduction

1.1 Overview

Propellants as the word itself stands for are those substances used for propelling any
type of vehicle into motion. They act on the basic principle of Newton’s Third Law
of Motion namely, ”Action and reaction are equal and opposite or more precisely, for
every action there is an equal and opposite reaction.” Propellants can be of three types
namely - Solid, Liquid and Hybrid. Cryogenic propellants are also one type of propellant
which will be discussed separately. Liquid propellant rockets differ from solid propellant
rockets in several ways. Fuel and oxidizer are liquids and need separate storage tanks.
The thrust chamber i.e., the nozzle combined with combustion chamber is a separate
entity unlike solid propellants where it is an integral part along with propellant mixture.
In order to bring adequate quantities of fuel and oxidizer in the combustion chamber
and thus achieve optimum combustion, the pressurizing tank ,appropriate feed system
and suitably designed injector are required in case of liquid rocket engines. Thus the
liquid propellant rocket engine is much more complex in design in comparison with
solid propellant rocket engine . The figure 1 shows the schematic of a typical liquid
rocket engine. Inspite of the design complexity,the liquid propulsion system is many
times preferred as the liquid propellants exhibit higher specific impulse than the solid
propellants . The possibilities of thrust termination, restart and variable thrust on
demand which are impossible to achieve in a solid propellant engine are the additional
features of liquid propellant engines.

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1.2 How liquid propellants work

The fuel and oxidizer are stored in separate tanks and are either pressure-fed or pump-
fed ,through a system of remote control valves, in to the combustion chamber at a suitable
pressure and in proper proportions. The injector meters the flow of fuel and oxidizer in
to the chamber and atomizes them to bring out good mixing and fast reaction (Liquid
propellant combustion is diffusion controlled droplet combustion). Some fuel oxidizer
combinations ignite on mixing. Such ignition is known as hypergolic ignition and the
fuel oxidizer combination which exhibits such ignition is known as hypergolic propellant
. However, the parameter known as Ignition delay (ID), which is the time lag between
the physical contact of fuel and oxidizer and actual ignition,is very important in case
of hypergolic propellants . The optimum limit of ignition delay is 50 milliseconds. The
chamber and nozzles walls are always protected by regenerative cooling and are coated
with ablative liners.

1.3 Desirable properties of Liquid Propellants

The liquid propellants (i.e. fuels and oxidizer) should exhibit:-

(a) Low freezing point (less than −400 deg Celsius )

(b) High Boiling Point/High decomposition temperature

(c) High specific gravity

(d) High specific heat and thermal conductivity

(e) Low vapour pressure and low viscosity

(f) Low temperature variation of viscosity and vapour pressure and low coefficient of
thermal expansion

(g) Good physical and chemical stability

(h) Hypergolic combustion with ID less than 50 milliseconds

(i) Smooth and stable combustion

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 (j) No smoke at exhaust

(k) Less toxicity and safety in handling

(l) Easy availability

(m) High performance

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1.4 Comparison between Solid and Liquid Propel-
lants

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Chapter 2

Classification of Liquid Propellants

2.1 Introduction

Liquid propellant may be broadly classified into two types namely:-

(a) Monopropellants

(b) Bipropellants

Monopropellant is a single molecule containing both fuel as well as oxidizer entities.

Monopropellants find limited applications in rockets as they exhibit low Isp andaresuitableonlyingasgen

2.2 Bipropellants

Bipropellants can be classified as follows:-

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2.3 Various Fuels used in Liquid Propellants

The various liquid fuels which are commonly used in bipropellants can be classified based
on their chemical behaviour / the function groups present in them. The important classes
of fuels are as follows :

(a) Hydrocarbons : A number of saturated hydrocarbons such as kerosene ,avia-

tion gasolene etc are used as liquid fuels. They exhibit low freezing point, low
viscosities, and low specific gravities. They are known as Jet fuels / RP and used
in number of Russian missiles . However, they are non hypergolic in nature and
need an external ignition system like solid propellants. The hydrocarbon type of
fuels like kerosene are used in semi cryogenic bipropellants where the oxidizer is a

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 cryogenic liquid like liquid oxygen.

(b) Aliphatic and Aromatic Amines: A large number of aliphatic amines like tri-
ethylamine (TEA) , diethylene triamine (DTEA) and aromatic amines like aniline
and different isomers of xylidene are used as liquid fuels. The physical properties
of various aliphatic and aromatic amines are summarized in Table No. 2. However
to meet the requirements of liquid propellants such as low freezing and high boil-
ing points , low vapour and phenolic resins which can withstand continuous firing
of longer duration. The throat insert is generally of tungsten. Fuel and oxidizer
undergo hypergolic combustion in the combustion chamber. The combustion gases
are exited through the nozzle to get the required thrust. In case of non hypergolic
propellant, however, a separate igniter is required.

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(c) G-fuel :To achieve the requirements of pressure, high density etc , a blend of two
or three liquid fuels is invariably used. A well known liquid fuel, G fuel is 50:50
weight mixture of xylidene and triethylamine.The composition is as shown:-

(d) Hydrazine and its derivative:Hydrazine and its derivatives such as monomethyl-
hydrazine (MMH) and unsymmetrical dimethylhydrazine (UDMH) and a 50:50
blend of hydrazine and UDMH (known as aerozine -50) are extensively used in
number of missiles and in some of the stages of launch vehicles. The physical
properties of these fuels / fuel blends are given in table 3.

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 (e) Alcohols:Some of the alcohols like ethyl alcohol and furfuryl alcohol have been
used as one in the constituent of liquid blends.

2.4 Storable Oxidizer Used in Bipropellants

The most commonly used oxidizers which exhibit hypergolic ignition with most of
the fuels maintained above are :

(a) Red fuming nitric acid ( RFNA )

(b) Nitrogen tetroxide

(c) White fuming nitric acid (WFNA)

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 (d) Chlorine trifluoride

Cryogenic Oxidisers

(a) Liquid Oxygen (LOX)

(b) Liquid Fluorine

The physical properties of these oxidizers are listed in table 4.

The specifications of RFNA are included in Table 5.

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Chapter 3

Performance of Liquid Propellants

and Recent Developments

3.1 Performance of Liquid Propellants

Liquid propellants give specific impulse ranging from 210 - 312 seconds depending
upon the type of the fuel and oxidizer used and the chamber pressure. Table 6 shows
the specific impulse values for different liquid bipropellants combinations.

3.2 Examples of missiles using Liquid Propellants

The liquid propellants used in different missiles of the world are enlisted in Table 7.

3.3 Recent Developments

In recent years, a new liquid fuel blend consisting of the natural products carene (
a distillation product of turpentine ) and cardanol ( a distillation product of cashew
- nut - shell liquid ) in 70 : 30 weight proportion was reported which exhibits syner-
gistic hypergolic ignition with RFNA and nitrogen tetroxide as oxidizers. This liquid
propellant has lower freezing point , higher boiling point , higher density and density

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impulse than mostly of the conventional liquid propellant currently being used . Addi-
tion of norbornadine ( a cyclic diene made by reacting acetylene with cyclopentadine
under pressure ) to above blend was found to further increase the performance of the
propellant with the some oxidizers. A fuel blend consisting of carene, norbornadine and
cardanol in 40 : 40 : 20 weight proportion with RFNA as oxidizer was suggested as the
suitable replacement for G-fuel. This new fuel blend is less toxic and cost effective.

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