Rocket Propulsion

Prof. K. Ramamurthi
Department of Mechanical Engineering
Indian Institute of Technology, Madras

Module 01
Lecture 15
Criterion for Choice of Chemical Propellants

Good morning, today we will start a new topic on chemical propellants.

(Refer Slide Time: 00:19)

Let us first be clear what we mean by a propellant. We said that any substance used for
propulsion of a rocket is known as a propellant. It could be anything, it could be
something like a gas, the gas could be cold at high pressure, the gas could be hot. We
even considered these boys throwing stones and stones were the propellant. It could be
anything it could be a charged particle, it could be a plasma, it could be anything, but
what we consider in the next 3 classes is about chemical propellants.

This brings us to chemical rockets, which use chemical propellants. The chemical
rockets are solid propellant rockets, liquid propellant rockets, hybrid rockets and so on.
Therefore, let us see what are the requirements of these rockets since before we study the
propellants we must know what are the requirements. What is the requirement of a
propellant? I think that is the basic with which we should get started. We studied that
nozzles were an integral part of a rocket; we look at any rocket chamber, let us say that
this is a chamber you have a nozzle which is connected to it and the aim is to get as high
as a jet velocity as possible. And to get a high jet velocity we found that we required a
high value of the chamber pressure and a high value of the chamber temperature.

We also found that we require a small molecular mass of the gasses, which are being
expanded out. In this case I will get a higher jet velocity and what was the term that we
used? We used the term C star which is a transfer function between what is sent into the
combustion chamber and the high pressure, high temperature, low molecular mass
combustion gases which are generated. And what was the expression for C star? We had
the expression, under root R into temperature of the hot gases divided by the capital
gamma.

And this was the specific gas constant which in terms of the universal gas constant, we
could write it as R naught Tc by the molecular mass of the gases which are sent out
through the nozzle. And this is again under root into we have one over capital gamma
which is a function of gamma therefore, this should tell us what we really require in a
propellant to do. What we require is that this transfer function which tells the capacity of
this particular chamber to generate high pressure gases must be high or rather this
characteristic velocity must be a large number. The transfer function C star of the
propellant of the chemical propellant must be large.

If C star has to be large obviously Tc must be large and the molecular mass of the gas
escaping through the nozzle must be small. Anything else? We have the combination of
gamma in capital gamma: we found that gamma must be small because capital gamma
was equal to under root gamma, two over gamma plus 1 to the power gamma plus 1
divided by 2 gamma minus 1. The requirement was that gamma should be small.

It is, however, not as sensitive and influential as Tc and molecular mass of the gas.
Therefore, basically we are looking at the following parameters: Tc to be large the
molecular mass of the gases to be small, may be the specific heat ratio also to be a small
number. If I can have propellants which could generate gases such that the temperature
of the hot gases and the pressure of the gases could be large. The molecular mass of the
gases should be small and the specific heat ratio of the gases must be small. This is what
a propellant be capable of.

(Refer Slide Time: 02:24)

Let us take a look at temperature Tc: What will give me a high value of Tc? If I have a
chemical propellant and now we must say I am talking of chemicals, there are a large
number of chemicals available. And why do we use a chemical? May be I want the
chemicals to react with each other or react and generate hot gases. Why hot gases? If I
have hot gas I have temperature Tc, which could be a high. Therefore, basically I am
looking at chemicals, which could react and generate hot gases and these hot gases could
be at a high temperature. To generate a high temperature gases the heat release in the
chemical reactions should be large.

And we consider unit mass of propellant and denote heat generated by unit mas of
propellant in the chemical reaction. The heat release per unit mass is required to be large.
If the heat release is divided by the mean value of the specific heat of the gases, say at
constant pressure, we get the temperature increase from the chemical reactions of the
propellants. If the specific heat at constant pressure is small, we can have a larger value
of temperature Tc for the same heat release. We have introduced one more word specific
heat as a requirement. What we are saying is if we have chemicals these chemicals react
generate to hot gases at high temperature. When do we get high temperature? If the heat
release per unit mass of the chemical propellant is a large number and if the specific heat
Cp of the burnt gas is small.

Therefore, we now state that the specific heat of the gas generated by the chemical
reactions must be also small. Well these are all the requirements that I am looking for.

The chemicals should have a large value of heat release, a small value of specific heat
and a small molecular mass of the product gases generated at high temperature and also
perhaps a small value of gamma.

(Refer Slide Time: 07:19)

If we can address all the above parameters together, maybe we can narrow down a few
chemicals out of the millions chemicals that are available which can be used as chemical
rocket propellant or rocket propellants. Which of the chemicals are suited to be rocket
propellant. And this is what I am going to do in this class. Therefore, let us ask how we
will get high values of heat release, small value of molecular mass of the gas and low
specific heat of the reacted gas? Let us start with something simple; under what
conditions will we get low molecular mass of the gases that are generated in the chemical
reaction?

Let us say I have a chemical and this chemical by reaction generates hot gas. Therefore,
basically I must take a look at the atomic mass or the mass of the elements in the
chemical propellant. If the elements are of small atomic mass, the product gases formed
by chemical reaction would also be small.

(Refer Slide Time: 08:06)

If the atomic mass of the elements in the propellant is small the product gases will also
have low atomic mass. First let us take a look at the periodic table. What is there in a
periodic table? All elements are arranged in terms of their atomic number and this is
what we will first take a look at it. Let us say this is the periodic table over here given we
have elements starting with an atomic number of 1. The atomic mass of hydrogen is
unity and its atomic number is 1. The next is helium the atomic number is 2 and its
atomic mass is 4. Next is lithium. The atomic number is 3 and the mass of lithium atom
is 6.9. Beryllium 4 atomic mass is 9. Boron 5 the atomic mass is 10 and so on carbon 6,
atomic mass 12 and so on.

Near to oxygen, nitrogen, fluorine we have neon an inert gas, then we have sodium,
magnesium, aluminum, silicon, phosphorous, sulphur and chlorine. We stop at atomic
number of 17 because already the atomic number has increased to 17 and as you see the
atomic mass is increased from 1 to almost 36. The values of the atomic mass are given
are with respect to hydrogen. Beyond this, if I go the atomic mass becomes large such
that that any product which is formed will have larger values of the molecular mass and
become very heavy. What does this table tell us? Let us take a particular case may be
hydrogen with the lowest atomic mass. Even if I take a hydrogen molecule H2, the
molecular mass is 2.

The molecular mass is lower than other molecule or substance. Therefore, it is a very
viable substance that could be used as a propellant from the molecular mass point of
view. I next go to helium. Helium is inert. It can be used as an inert gas but cannot be
used as a chemical propellant. Lithium is used in solid propellants because of its low
atomic mass. We will have to take a look at it when we study solid propellants.
Beryllium and boron can be used; the masses are still small with atomic mass of 9 and
10. Carbon is a part of any hydrocarbon; carbon and hydrogen together. Well we cannot
escape from hydrocarbon and is suited. Fortunately for us carbon has an atomic mass of
12, which is still not very bad. Next in the periodic table is nitrogen; it is inert, but most
of the substances in nature are associated with nitrogen. The atomic mass of nitrogen is
14.

Oxygen is a powerful oxidizer. It has an atomic number of 8 and an atomic mass as 16.
The molecular mass of oxygen O2 is 32. Fluorine is a very reactive oxidizer, much more
reactive then oxygen and is very near to oxygen itself; its atomic mass is 19. Neon is
inert I cannot consider it for chemical reactions. Sodium is a very reactive metal. If we
drop sodium in water it just explodes and to use it would be impossible. Magnesium: you
would have seen magnesium ribbon being used as a diwali cracker, you could light it and
it burns as a reactive metal. It is quite reactive therefore, it may be difficult to use
magnesium as it is.

Aluminum is a light metal of atomic mass 27. If we have to use a metal in a propellant, it
appears better to suggest it. Other metals would be very much heavier. Only aluminum is
used compared to iron, which is seldom used. Silicon is a light material, but it is not
reactive. We will not consider phosphorous as it is very reactive. We cannot consider
sulphur and chlorine since these also have high atomic mass of 32 and 35.5 respectively.
(Refer Slide Time: 08:47)

Beyond this you know you go to argon and other elements and they becomes
progressively more and more heavier and they cannot be used. Therefore, all what we
say is out of all the chemicals I can now isolate something like up to chlorine which has
an atomic number of 17.

From the molecular mass point of view, we could select some of the lighter elements. I
show these elements again in the next slide where in I show hydrogen, lithium,
beryllium, boron, carbon, nitrogen, oxygen, fluorine, aluminum, sulphur and chlorine.

Well these elements if used in my chemicals would be better if low value of molecular
mass in the reacted products is more desirable. Therefore, we address the first point
namely the molecular mass point of view. When will the molecular mass of my products
be small? When the atomic mass of the element of what we consider in propellants
should be small.

Fluorine is very reactive; it is more reactive than oxygen. In fact it was tried for rockets
but it was very reactive and would corrode even the propellant tanks. It was used in one
of the Delta rockets; however, it has not been subsequently used. We will keep it in mind
and see under what conditions fluorine can be used.
(Refer Slide Time: 12:44)

Oxygen, fluorine, chlorine are oxidizers. Hydrogen, carbon, lithium, beryllium, boron,
and aluminum are fuels. Aluminum is a metal, which can burn and release heat. All of
you would have observed a sparkler during Diwali festival. The sparkler consists of a
composition which is known as a black powder composition and it is coated on a on a
rod may be a steel rod or something like it.

In some instances metal powder or filings are added to the composition in the sparkler.
When the sparkler with the metal filings or metal powder burns, it burns much more
violently. This is because the burning or combustion of the metal releases much more
energy. Therefore, metals such as aluminum, boron, beryllium can also be used very
effectively as fuel. Therefore, we now conclude by stating that low atomic mass elements
are more desirable in a propellant from molecular mass point of view of the products.

Let us now take a look from the temperature point of view on whether we should have
some of these elements or what should be the composition of the chemicals in the
propellant such that we get a high value of temperature.

May be if we go through this aspect, about half of our work in choosing a propellant will
be over. For high temperature, we needed high heat release and low values of specific
heats. Let me come to the second part on specific heats before looking at heat release
from chemical reactions in a propellant.

We had said that the products of burning or of chemical reaction in the combustion
chamber of a rocket are released through the nozzle. The temperature of the hot gases Tc
goes as heat released divided by the specific heat and therefore we would like to have Cp
as small as possible. Single atom like oxygen atom, hydrogen atom mono have a
specific heat of the order of something like 20 joule per mole Kelvin. Unit of specific
heat is per mole per Kelvin. If we have di atomic molecule like O2, hydrogen H2 or O H
that is two atoms of the elements, the specific heat increases to something like 35 joule
per mole Kelvin. If I still have more complicated molecule like CO2, 3 of atoms together,
the specific heat increases to almost like 62 or 63.

Let us say that the specific heat of the triatomic molecule is 65 joule per mole Kelvin.
Why should specific heat increase as the molecule changes from mono atomic to di
atomic to tri atomic? What will be your reaction? Why should it increase? Mind you the
unit is per mole Kelvin.

(Refer Slide Time: 15:50)

Why should the specific heat go up? If we take a simple atom, let us say like oxygen
atom it is just O, if I take a molecule O2 2 well it has two O atoms. We are not bothered
about double bond single bond and the two O atoms are bonded together. When we heat
say the O atom, it has smaller degrees of freedom and it therefore absorbs less amount of
energy. This will absorb more energy if it could have more degrees of freedom. A
relatively more complex molecule like CO or CO2 has more bonds. It can absorb more
energy. Therefore, the energy absorbed per mole of a mono atomic substance is less, di
atomic is more, tri atomic is still higher and so on it increases.

Therefore, let us see the variation of the specific heats. A mono atomic substance has the
lowest, di atomic has higher value, tri atomic has still has a higher value and as I go on
the value of the specific heat keeps increasing. Therefore, from this point of view I
should say if my product gases are all mono atomic, I am better off. A di atomic gas is
to be preferred to a mono atomic gas. What this implies is that the product of combustion
or reaction of the propellants must be simple not complex, in which case I can have a
smaller value of the specific heat in Joules per mole per Kelvin.

I show some of the values of Cp in the next slide. Helium is mono atomic. At the two
temperatures of 2000 Kelvin and 3000 Kelvin there is hardly any change in specific heat.
Therefore, irrespective of temperature for the mono atomic may be helium, hydrogen
atom, oxygen atom the value is around 20 Joule per mole Kelvin. If I go to di atomic
gases hydrogen H2, hydroxyl OH or may be HCl or may be N2 or CO, all have a ball
park number of around 35 Joules per mole kelvin. A change in temperature does not
markedly change the value of specific heat.

When we have tri atomic gases, the values of specific heats are even higher; well of the
order of 60 to 65 Joules per mole Kelvin - something like 60. Water is around 51 to 58
Joule per mole kelvin, CO2 is between 60 and 63 may be around 63 to 64. We find that
mono atomic substances have specific heats around 20 Joule per mole Kelvin, diatomic
around 35 to 36 while triatomic substances have specific heats around 60 to 65 Joule per
mole Kelvin. Therefore, this is the range and based on this it is preferable for the product
gases to be more dissociated if we want high temperatures.
(Refer Slide Time: 19:19)

If we keep on increasing the value of specific heats, we will not be able to get a high
temperature and therefore, we said that the specific heat of the product gases must be
small. We have looked at two criteria namely we looked at the criterion of molecular
mass we say well that the atomic mass must be small or atomic number must be low.
Second we found that from Cp point of view of the product gases (which result from the
chemical reactions of the chemicals) must be somewhat simple or disssociated. Let us go
to the next criterion before we come back to the temperature and heat release. Let us
take a look at gamma, the ratio of specific heats. We had said that gamma should also be
small in order to get a high value of jet velocity VJ.

What does this small value of gamma imply? If we go through thermodynamics and the
kinetic theory of gases, we find that gamma is defined as Cp by Cv, which in terms of
the degree of freedom of the molecule can be written as 1 plus 2 over something like n
plus 3. The value of n shows the degrees of freedom of the gas over and above the
translational modes. Let us illustrate this. If we have an oxygen atom; it can either move
in the three directions, along X, Y and Z. This means it has 3 degrees of freedom along
the three translational axes. If I have an oxygen molecule well it has it has in addition to
translation in the 3 directions rotational motion also. The oxygen atoms in it could also
vibrate.
Therefore, it has additional degree of freedom of 2, compared to the atom, which only
translates. I could also have atoms in which we have may be C3H8, which becomes more
complicated it could have much more degrees of freedom compared to simple
translation. And for instance if I take CCl4, carbon tetrachloride, the degrees of freedom
are almost something like 13 or 14. As the molecule becomes more complex, it has more
degrees of freedom.

Therefore, the value of gamma value for a mono atomic gas, for which the number of
degrees of freedom is 3 is determined by the following: the value n gives the degrees of
freedom in excess of the three translational modes. We say for mono atomic gases like
let us say gamma for helium is equal to 1 plus 2 by 3, which is equal to 1.67.

For di atomic gases like oxygen, hydrogen, nitrogen molecules we have two additional
degrees of freedom from rotation and vibration. The value of gamma is 1 plus 2 by 5,
which is 1.4. May be as it becomes very complex like gamma for CCl4, carbon
tetrachloride, is going to be something like 1 plus 2 divided by 3 plus something like 13
or so giving gamma about 1.13. That means that more complex the molecule, it has a
lower value of gamma. If therefore gamma is required to be small, then the gases, which
are passing through the nozzle, which should have should be more complex.

(Refer Slide Time: 20:21)

The requirement for Gamma to be small calls for the gases to be more complex, but for
Cp to be small the gases must be simple. These two criteria require just the opposite.
Similarly, if you want the atomic mass to be small well we are also thinking of simple
product gases therefore, we find that gamma requirement is somewhat contrary to the
requirements of Cp and also molecular mass. Therefore there is a problem and we also
know based on what we have studied so far from the nozzle theory that VJ is not very
sensitive to gamma. Therefore, we will not give very much importance to gamma as for
specific heat and molecular mass.

To summarize, the Cp of the product gases should be small which necessitates that the
product gases must be in a dissociated form as simple molecules. The molecular mass of
the gases would then also be small. However, then a small value of gamma cannot be
obtained as the value of gamma decreases as the complexity of the gas increases. We
give less weight age to gamma because Cp directly impacts into temperature and C star
is inversely proportional to the molecular mass.

We are left with heat release to be able to determine the value of temperature Tc. Let us
take a look at heat release in a chemical reaction.

Let us have a chemical we call it as may be chemical C 1. This chemical gets converted
to gas like a product let us say P 1. We are looking in this case of this chemical by itself
reacting to give P 1 or else I have C 1 plus C 2 reacts to give me P 1 product 1, product
2. The question is how do we determine the heat released in these reactions? These are
all chemical reactions of a component giving the products or chemical reaction between
two chemicals, which give us products. And we are interested in determining the energy
from the chemical reaction.

We have studied about this both in the combustion course and in the course on explosion
physics. We had said that any substance would have its own internal energy? We called
it as chemical internal energy of the substance. Now, if it gets converted to products and
it will also have some energy like chemical internal energy of the products. In a chemical
reaction, the reactants get converted to products. If you have more energy of the reacting
chemicals compared to the products, the deficit of energy is what is obtained as heat of a
reaction.

Let us elaborate. Suppose if I have some chemicals; these chemicals have some energy.
As an example this duster has some energy. Where does the energy come? I have all
these bonds together it has some energy. Now I burn it and I get carbon di oxide, carbon
mono oxide or whatsoever it may be. If the energy which is available before the burning
(i.e., the reaction) is more than the energy of the final products, which are formed in the
reaction, then since the energy cannot get destroyed, the deficit or reduction manifests
itself as heat and that is the heat of a reaction.

(Refer Slide Time: 20:25)

Therefore, basically I need to find out what this internal chemical energy or what is the
chemical energy available in the chemical, which we call as internal chemical energy.
You know the word given to describe this internal chemical energy is heat of formation.
And how to define the heat of formation? The heat required to form a substance - any
substance - at standard state from its elements again at standard state. Let us put it down.
We need to be able to describe what is the energy available in a given chemical and to be
able to do so we need certain standard conditions.

Well. At the standard condition what is the energy available in the chemical substance.
This substance could be let us say hydrogen, carbon, nitrogen or some arbitrary
substance like H8CbNc. What are the elements, which constitute this arbitrary substance?
They are again hydrogen, carbon as a solid, nitrogen as a gas and mind you these are also
elements or elemental substances. Hydrogen is a gas under standard conditions, carbon is
a solid under standard conditions, nitrogen is a gas under normal conditions.

And the standard condition is taken as 25 degree centigrade and one atmosphere
pressure. In other words if I want to form a substance at the standard condition from its
elements again at the same standard condition, the energy required to form the substance
is known as heat of formation. The notation for the heat of formation is as follows: we
have to give some heat, which is enthalpy H. We have to give enthalpy, some increment
in enthalpy to form the substance from its elements. We form it at the standard condition
from its elements at the same standard condition. Therefore, delta H with super script of
0 denoting the standard condition of the substance and the elements from which it is
formed and subscript of “f” is the notation for heat formation of a substance.

(Refer Slide Time: 29:11)

If we know the heat of formation of a substance then we have its internal chemical
energy. If a substance C 1, which is a chemical substance has a certain heat of formation
and if the product formed has a given heat of formation, the decrease or the reduction in
the heat of formation from reactant to product gives the energy released in the reaction.
The decrease, in the heat of formation, shows that heat is generated in the reaction. The
reaction, we say, is exothermic; I get some heat from the chemical reaction. This is how
we go about finding out of the heat generated in a reaction.

Let us assume that I have a fuel F, I have an oxidizer O and their combination causes a
reaction, which produces the products. Fuel could be any fuel may be I take wood as a
fuel or oxygen as oxidizer or use the air as oxidizer and I get some products it like CO2
or may be CO.
Therefore, now I say the chemical reaction between fuel plus oxygen gives us say CO2
plus CO. If the fuel contains hydrogen also may be H2O is also formed as products. Let
us say the reaction takes place between a1 moles of the fuel with a2 moles of the oxidizer
to give b1 moles of the first product (CO2), b2 moles of second product CO and b3 of the
third product (H2O). Therefore, what is the energy released in this particular reaction?
We have to consider the moles of the substances and suitably define the heat of
formation in terms of moles. If the net heat of formation of the products is less than the
net heat of formation of the reactants, heat is generated in the reaction.

The heat of formation of a substance is the heat required to form 1 mole of the substance
at standard condition from its elements again at the same standard conditions. Heat of
formation unit is joule per mole. And this is the mole; a1, a2, b1, b2, b3. The heat of
formation of the products is b1 moles into heat of formation for CO2, plus b2 moles into
heat of formation of CO plus b3 moles into heat of formation of H2O. This is the value of
the total heat of formation of the products over here. What is the heat of formation of the
reactants? It is equal to over here a1 moles into heat of formation of fuel f plus a2 moles
of this into heat of formation of the oxidizer.

I should have put this standard sign to indicate the standard conditions. Since heat energy
is released when there is a net decrease in the heat of formation, we denote the heat
energy released in the reaction with a minus of the decrease. The heat energy is equal to
minus of heat of formation of the products minus the heat of formation of the reactants.
(Refer Slide Time: 31:41)

We would like to know which are the chemicals, which can release lot of heat energy
thereby making a good choice of the chemicals to be used for the propellants. Could they
be characterized in terms of their heats of formation at the standard conditions? Let us
therefore take a few examples. Let us form carbon di oxide from carbon. We do an
experiment. We take carbon at the standard state. And carbon at the standard state of 1
atmosphere pressure at temperature of 25 degree centigrade is a solid.

I react it with oxygen, which is a gas and the oxygen is again at 25 degree centigrade and
one atmosphere pressure and I from carbon di oxide. Again we form it at 25 degree
centigrade and at one atmosphere pressure. The energy required to form carbon di oxide
gas from its elements C in solid viz., C(s) and O2 will give me the heat of formation. But
all of us know, if I take carbon and burn it gives out some amount of energy, which is
quite significant amount of energy. And the energy which I get from burning 1 kilogram
of carbon is something like is 32800 kilo joules; kilo joules per kilogram carbon burnt.

That means when we burn carbon with oxygen per kilogram of carbon, which we burn,
we get something like 32800 kilo joules of energy. Now, what is going to happen? This
32800 kilo joules of energy is not going to form carbon di oxide at 25 degrees; rather the
temp of carbon di oxide will go up. If my product carbon di oxide has to be at 25 degrees
centigrade, what is it I have to do? I have to remove some heat from this reaction. This
means I have to remove i.e., minus 32800 kilo joule per kg of carbon burnt so, that the
product CO2 can be at 25 degree centigrade.

Carbon and Oxygen are elements at the standard state. Since the heats of formation are
defined with reference to the elements, the standard heats of formation of the elements at
the standard condition would be zero. Therefore, the standard heat of formation of CO2
should have something like minus when the reaction is exothermic and the heat of
formation of at standard state of carbon di oxide should be something like minus 32800
kilo joules per kg of carbon burnt. But there is something wrong with the units here. We
defined standard heat of formation as the heat required to form one mole of the substance
from its elements when both the substance and the elements are at the standard
conditions. We cannot state it in terms of kilogram of carbon but rather in terms of one
mole of carbon di oxide. Let us try to remedy the situation. For expressing in terms of
one mole of carbon di oxide, we note that for every mole of carbon burnt, one mole of
carbon di oxide is formed. This implies that for every 12 g of carbon, 1 mole of CO 2 is
formed. The energy, which is released is equal to 1 mole of carbon di oxide is therefore
equal to 32800 into 0.012 kilogram which is something like something like 397 kilo
joules per mole.

What is it that we had to do while forming carbon di oxide at the standard conditions?
We had to remove the heat and that the heat of formation at standard state of carbon di
oxide is therefore equal to minus 397 kilo joules per mole of carbon di oxide.
(Refer Slide Time: 35:15)

By now you would have guessed that for any reaction which is exothermic, the net heats
of formation of the products will be less than the net heats of formation of the reactants.
Large negative values of the standard heats of formation of the products will be
favorable for more heat release in a reaction. Let us take one or two small examples
because this is something, which is basic. Let us take the reaction of 1 mole of carbon as
a solid at element level reacting with half mole of oxygen both at standard state forming
1 mole of carbon mono oxide. Now, I have carbon mono oxide here instead of carbon di
oxide. It is not fully oxidized. The heat, which is generated in the reaction, if we do an
experiment is something like 9208 kilo joules per kilogram of carbon burnt.

Therefore, I quickly convert it for per mole of CO formed. In order to form one mole CO
I need to burn 0.012 kilogram of carbon to get 9208 into 0. 012 - so much kilo joules per
mole of CO. This is because one mole of carbon monoxide is formed from one mole of
carbon. And this is equal to something like 110.5 kilo joule per mole. Since heat is
getting generated as CO is formed, we have to bring it back to the same standard
condition of 25 degrees of oxygen element of 25 degrees of carbon element. The heat of
formation of CO is therefore minus 110.5 kilo joule per mole.

The hydrogen and oxygen react to form water. The reaction is given by 1 mole of
hydrogen reacts with half mole of oxygen we have hydrogen plus half oxygen giving 1
mole of water – H2O. Why do we take this example? Hydrogen is an element gas at 25
degrees, oxygen is an element – a gas at 25 degrees, but water should be a liquid at 25
degrees Centigrade - same standard condition. I can say that the heat of formation water
as a liquid at standard condition should be equal to the negative of the heat release in this
reaction, which is 286 kilo joule per mole of water.

(Refer Slide Time: 39:39)

Now we are expressing in terms of per mole; heat of formation of H2O as a liquid (water)
is equal to minus 286 kilo joule per mole. Because 1 mole of hydrogen forms 1 mole
therefore, this is how we determine the heat of formation. Please let us not forget that the
heat of formation of a substance is defined with respect to the elements that constitute it.
The heats of formation of the elements themselves are therefore 0 at the standard state.
One last substance I should consider with a positive heat of formation. Let us take the
formation of hydrogen as an atom. We could consider H2 disassociating to give 2 H.

What we do in this case? We have to supply heat to be able to form hydrogen atom and
the amount of heat required to disassociate 1 mole of hydrogen is something like minus
435 kilo joules per mole of hydrogen. And the reaction is endothermic. Therefore, heat
of formation of H is equal to plus 435 for 2 moles of hydrogen. For each mole of
hydrogen atom, the heat of formation is 217.5 kilo joules per mole. And this is plus
because the formation of hydrogen atom from the elements is endothermic I have to
supply heat to form hydrogen atom from the naturally occurring element hydrogen and it
is plus 217.5 kilo joules per mole.
Therefore this is how the standard heats of formation of different substances are
determined. However, we need not do an experiment to determine the heat of formation
of a substance. If we have, let us say a hydrocarbon. The bonds between carbon and
hydrogen and between the carbon atoms are known. We know the energy of each of the
bonds then I know the energy of the bonds of the basic elements. I subtract the bond
energy of the product or the substance from that of this element I will get the value of the
heat of formation. But there are certain problems, which come while estimating heat of
formation from bond energies. A substance does not only have energy of the bonds, it
could have energy in some resonance modes.

It could have resonance energy, it is necessary to have bond energy plus resonance
energy of the substance minus the bond energy of the elements, which will give us this is
the way of theoretically calculating the heats of formation. Details of estimation of heats
of formation from bond energies is given in the text book on “Chemical Problems in Jet
Propulsion” by Penner.

(Refer Slide Time: 42:45)

He gives a good treatment of heat of formation in the book. With the understanding that
we have developed for heats of formation, let us see if we can make some
recommendations for the choice of propellants.
(Refer Slide Time: 45:54)

I will quickly go through heat of formation of some of the substances in this slide. We
have fuels and let us consider hydrocarbons. A hydrocarbon could be saturated, it could
be unsaturated, it could be aliphatic, it could be aromatic, What do we mean by all this?
All what we mean is if the carbon atom in the hydrocarbon are fully saturated that means
the C C and CH all are single bonds. We say the hydrocarbon is an aliphatic substance. If
you say aromatic well you have something like a change a benzene ring with alternate
double bonds.

(Refer Slide Time: 46:13)

Substances, which have this benzene ring structure are known as aromatic substances.
Getting back to saturated hydrocarbons. The simplest hydrocarbon is methane, the next
one is ethane that is CH4, C2H6. The next is propane C3H8 and then butane C4H10 and so
on. The chain keeps increasing and we come to kerosene - it is little longer chain Do-
decane C12H26 and further up we have lubricating oil and so on.

If we determine the heat of formation of let us say methane; it is something like minus
74.9 kilo joule per mole, ethane is minus 84.7kilo joule per mole. Propane, which is
C3H8, is minus 103.9 while butane is minus 124.7. Kerosene has a value of minus 293.
This means a fuel as it becomes more and more complicated in structure or more and
more longer in chain has a higher negative value of heat of formation. If we go to a
polymer and what is a polymer? It consists of chains of carbon and hydrogen and
perhaps oxygen and nitrogen and its heat of formation is something like 60 kilo joule per
mole. But the polymer does not come in this particular family of the saturated
hydrocarbons. It consists of unsaturated double bonds and we will be dealing with it
when we get into solid propellants.

Let us summarize the trends in the values of heat of formation. For simple substances
with minimum saturated bonds, the heat of formation has a small but negative value. The
value of heat of formation becomes more negative as the substance becomes more and
more complex with a large number of bonds. That means can I write it as large negative
values this is just based on methane ethane propane and all that up to kerosene.

If you take a substance like hydrogen, which is an element, the standard heat of
formation is 0. There are certain substances, which are known as explosives. Explosives
are substances that have in built oxygen in them. This means that explosives contain both
fuel and oxygen within it as compared to a fuel that reacts with an extraneous oxidizer to
form products of combustion.
(Refer Slide Time: 49:00)

Hydrogen peroxide H2O2 can be considered as an explosive since it dissociates to form

water and hydrogen. It has inbuilt fuel hydrogen and oxygen. Similarly, you have
substances containing nitrogen such as hydrazine N2H4 and this is an explosive because
by itself it could react to form products.

The explosive hydrogen peroxide has a heat of formation of minus 187.8 while
hydrazine N2H4 has a small but positive value of heat of formation. Something like plus
50 kilo joules per mole. And what are the values of heats of formation if we were to
consider some other explosive like nitro glycerin. What is nitro glycerin? Nitro glycerin
is glycerin known as propane triol and the propane triol has chemical formula
C3H5(OH)3. We replace OH by NO2 to get nitroglycerin C3H5(NO2)3. Its heat of
formation is minus 370 kilo joules per mole.
(Refer Slide Time: 50:52)

And based on the standard heats of formation of the different substances, we would like
to find out which chemical when it reacts gives maximum heat. We will continue with
this in the next class and we will try to find out what are the chemicals, which are most
viable propellants for rockets. We will try to zero down the number of chemicals, which
can be used for rockets, to something like seven or eight.