BE~D.

R. & M. No. 2982

ROYAL AIRCRAFT ESTABLISHMENT

{
MINISTRY OF SUPPLY
AERONAUTICAL

RESEARCH COUNCIL

REPORTS AND MEMORANDA

Thermodynamic Charts for the

Combustion Products of Nitric
Acid and Kerosene
/

~y
W. H. WILLIAMS, B.Sc.

LONDON.

Crown copyright .r959

"

: HER MAJESTY'S STATIONERY OFFICE

I959
SEVEN SHILLINGS NET

(16,505)
A.R.C. Technical Report

Thermodynamic Charts for the Combustion Products

of Nitric Acid and Kerosene
W . H . WILLIAMS, B.Sc.

COMMU.NICATED BY THE

PRINCIPAL DIRECTOR OF SCIENTIFIC RESEARCH (AIR),

MINISTRY OF SUPPLY

Reports a n d M e m o r a n d a
July,

No.

29 82

195o

Summary.--Thermodynamic charts giving enthalpy, entropy, temperature, pressure and specific volume, have been
constructed for the products of combustion of a hydrocarbon fuel (85 per cent C, 15 per cent H by weight) with nitric
acid (98 per cent by weight). The charts have been drawn for the following mixture ratios of the propellants:
(a) stoichiometric proportion
(b) 10 per cent by weight excess of fuel
(c) 50 per cent by weight excess of fuel
(d) 10 per cent by weight excess of oxidant
Graphs of combustion temperature and specific impulse against mixture ratio are also shown.
The procedure for calculating the initial enthalpy of the separate propellants (before combustion) and that of the
propellant mixture is described.

1. Introduction.~This note presents in four charts, Figs. 1 to 4, t h e t h e r m o d y n a m i c properties of

the c o m b u s t i o n p r o d u c t s of four m i x t u r e s of t h e propellants nitric acid (98 per cent) and kerosene.
The charts h a v e been d r a w n up for app!ication to rocket m o t o r conditions a n d e x t e n d over
pressures f r o m a b o u t 100 to 0.1 atmospheres. B y m e a n s Of t h e charts, graphs have been p r e p a r e d
of t h e theoretical c o m b u s t i o n t e m p e r a t u r e against m i x t u r e ratio (Fig. 6) a n d of t h e theoretical
specific impulse against m i x t u r e ratio (Fig. 7) for c o m b u s t i o n pressures of 10, 20, 30 a n d 40 k g / c m 2.
A l t h o u g h t h e c.g.s, s y s t e m of units is preferred and has been used t h r o u g h o u t this note, conversion to t h e f.p.s, s y s t e m can be m a d e b y use of t h e table set out on the rider scale.
The t e r m ' mole ' refers to t h e molecular (or formula) weight in grams.

2. M.ethod.--The calculations necessary for preparing t h e charts h a v e been m a d e b y a n u m e r i c a l

a d a p t a t i o n of t h e graphical m e t h o d of L u t z 1.
3. Data.--The chemical formula of t h e fuel (kerosene) is t a k e n to be C17H~6 for calculation
purposes. Values of the entropies of t h e p r o d u c t s of combustion used in the calculations h a v e been
t a k e n f r o m J u s t i 2. The enthalpies and equilibrium constants are those given b y L u t z in t h e
* R.A.E. Tech. Note R.P.D. 33, received 29th January, 1954.

report mentioned above 1. The standard reference state in this note is taken as 273-16 deg K
(0 deg C) and 1 atmosphere (1 kg/cm2). At this reference state the enthalpies of C (graphite),
H2, 02 and N2 are taken arbitrarily as zero.
It should be noted t h a t the ' atmosphere ' used b y Lutz is the ' technical atmosphere ' which
is equivalent to a pressure of 1 kg/cm 2 and is related to the standard physical atmospher e as
indicated by the following expression:
1 physical atmosphere (At) = 1.033227 kg/cm 2 = 1-033227 technical atmospheres(at)
1 physical atmosphere
or 1 technical atmosphere = 1. 033227
The constant pressure lines on the charts have been shown in units of kg/cmL
Since performing the calculations from which the charts were constructed values ~ more reliable
t h a n those of Justi 2 for the absolute entropies of the gaseous products of combustion have become
available, together with data on monatomic nitrogen. In addition Lutz ~ has recently published
more up-to-date tables of thermodynamic properties together with constants for combustion
equilibrium reactions to replace those given in his original report1; the new data are based on
the new standard reference state of 298-16 deg K and 1 kg/cm '~ pressure.

4. Assumptions.--It is necessary to make certain assumptions concerning the nature of the

product gases and the changes they undergo during expansion
In the first place it is assumed t h a t each separate component of the product mixture will
behave,' ideally ', t h a t is, in accordance with the general gas law.

p v = ~RT
where
p is pressm-e
v is specific volume
R is the universal gas constant
M is molecular weight
and T is absolute temperature.
It is assumed t h a t the various gases in the product mixture are in equilibrium in all conditions.
This assumption is probably more reasonable than t h a t of a ' frozen ' equilibrium, i.e., an equilibrium in which the initial composition of the combustion products remains unaltered during
expansion. The assumption made, therefore, is t h a t there is always sufficient time to attain
complete equilibrium even in the later stages of expansion when the gas velocity is large.
Dissociation of the products of combustion becomes an important factor at temperatures above
about 2,000 deg K, and particularly at low pressures ; it has, therefore, received full consideration
in the calculations. The dissociation reactions considered are:

c o + lO2
H2 + 102
H2 -F OH
H
O

NO
The dissociation reaction

H20
H20

H2
02
N2 + 02

N ~- N2

is neglected in the calculations because the proportion of monatomic nitrogen existing under
these conditions is negligible; furthermore the data on the enthalpy and equilibrium constant
for this reaction were not readily available when the calculations were made. The combustion
product nitrogen dioxide NO, has also been ignored. NO2 begins to dissociate at around 200 deg C
according to the reaction.
2N02 ~- 2NO + O~
and dissociation is completed at about 650 deg C - 900 deg K. This temperature would probably
only be encountered in the extreme case of a 50 per cent fuel rich mixture (Fig. 3) and even then
only for an expansion from 100 kg/cm ~to 0- 1 kg/cm ~.
The assumption that the processes ave adiabatic implies, of course, that there are no losses
due to shock waves, friction and heat transfer during expansion. Every process is, therefore,
reversible and the expansion is isentropic.
5. Initial E~thalpy of the Propellant M i x t u r e . - - T h e initial enthalpy of the hydrocarbon fuel
(85 per cent C, 15 per cent H ) i s determined from knowledge of its heat of combustion (or calorific
value). The heat of combustion gives the quantity of heat available when the fuel is fully burnt
to CO, and H~O and the resulting gases are cooled down to the original conditions of temperature
and pressure ; these conditions are taken here to be 25 deg C (298.16 deg K/ and 1 kg/cm ". The
' higher ' or ' lower ' value of the heat of combustion is used depending on whether H20 in the
cooled products is taken to be in the state of liquid or gas.

A value of the higher heat of combustion provided by the R.P.D. chemical laboratory of
20,070 B.Th.U/lb or 2681.1 Kcal/mole is taken as a representative figure in all the charts for a
typical hydrocarbon fuel (aviation kerosene with the approximate composition 85 per cent C
15 per cent H by weight). Since the heat of combustion for a sample of fuel may vary appreciably
with different supplies, it is recommended t h a t a separate determination of the value be made
before using the charts and accepting the initial enthalpy levels.
The determination of the initial enthalpy will now be considered; the state is denoted by a
suffix (g) for gas and (1) for liquid.
5.1. F u e l . - - T h e complete combustion of 1 mole of fuel in gaseous oxygen is represented by
the equation

C17H360) + 26Qig) ----- 17CO2(g) + 18H200) + 2681.1Kcal.

This may be written in energy form thus :
T25c
26T2Soc ---- 17I~o2(g)
~soc + l ~ rzsoc + 2681" 1 Kcal
-~C17H36(1) - ~
~O2(g )
x V~H20(l )
where I ~5cdenotes enthalpy in Kcal/mole at 25 deg C as given by Lutz I.
Therefore
12sc
c17-~60) + 26(0) = 17(-- 94.052) + 18(-- 68"318) + 2681.1 Kcal,
i.e., ~F,dr250c------ 147"5 Kcal/mole of fuel; and this defines the initial enthalpy of the fuel in
accordance with the definition of enthalpy as given by Lntz ~.

5.2. O x i d a n t . - - B i c h o w s k y and Rossini 5 give - - 4 1 . 6 6 0 Kcal/mole as the enthalpy of liquid

nitric acid at 18 deg C. Now as
H2 + N2 + 602 = HNOa0)
by changing the temperature for both sides of this equation from 18 deg C to 25 deg C, using
Kelley's heat capacity equations 6 for the gaseous elements on the left-hand side, and taking
0.029 Kcal/mole for the heat capacity of HNOa0 ) we obtain the value -- 41. 570 Kcal/mole for
the enthalpy of liquid nitric acid at 25 deg C. Hence
i25oc
HNO3(1) = -- 41.570 Kcal/mole
3

5.3. Propellant--Stoichiometric Ratio.--Considering now the complete reaction of the fuel with
nitric acid of 98 per cent concentration, we have
5C~7H36 + [104HNO~ + 7.429H~O] = 85C02 + 149.429H~O + 52N~.
The reactants on the left hand side of the equation are taken to be liquids at a temperatm-e of
25 deg C (this is chosen as the room or laboratory temperature since most up-to-date thermal
data are quoted for T = 298-16 deg K). To determine the initial enthalpy of the mixture of
fuel and oxidant we need consider only the left-hand side of the equation, and, therefore,
i2soc
mixture = 5(-- 147.5) + 104(-- 41.570) q- 7.429(-- 68.318) Kcal
--

5 . 1 4 7 . 5 - - 1 0 4 4 1 . 5 7 0 - - 7 . 4 2 9 68.318
Kcal/kg of mixture.
7.886

Or

i ~

Therefore

i = -- 706 Kcal/kg of mixture

where

i denotes the enfhalpy in Kcal/kg.

5.4. Pr@ellant--Any Mixture Ratio.--Generally, if the propellant mixture consists of oxidant

and fuel in the ratio R to 1 by weight, then the initial enthalpy in Kcal/kg of mixture is given by

i2mocx., o = [R +1

+ R + 1

I o cn

1000

where I~sc and Io2~c are the enthalpies at 25 deg C in Kcal/mole of fuel and oxidant respectively,
and MF and Mo~ are the molecular weights in grams of fuel and oxidant respectively.
The initial enthalpy of the propellant mixture at any other temperature t deg C is obtainable
from a knowledge of the heat capacities of the reactants.
Thus

I~ c = I~sc q- (t -- 25)@

where Cp = mean heat capacity of fuel in Kcal/mole deg C over the temperature range t deg C
to 25 deg C.
A similar calculation yields I~ox
c whence I,,~tu~o
tc can be obtained.
The values of the heat capacities of the reactants under consideration are given below : - Reactant . . . . . . .

C17Ha6(1~ HN03(,>

C-p (Kcal/moledeg C) .. ' 0 . 1 1 3

0.029

I-I~0,i,
0-018

6. Parameter r . - - T h e parameter r which appears in Figs. 6 and 7 is defined as

/, =

$O

no -~ 2nc + nil
where no, nc, n~ represent the.number of atoms of oxygen, carbon and hydrogen in the chemical
representation of the mixture of propellants. The limiting values of r are clearly 0 for fuel only,
and 1 for oxygen only; for the stoichiometric proportion of any C.H.O.N. propellant system r
becomes 0.5.
4

If R is the mixture ratio by weight of 98 per c e n t nitric acid to kerosene then the relation
between R and r is given by
R =

or

r =

0.220875--0.26197r
R
4.52745+1.18606R

7. Charts.--A rocket motor develops thrust by the expansion and consequent acceleration of
the combustion products through a nozzle. For theoretical purposes the expansion is considered
to be adiabatic. As it is necessary to calculate the dimensions of the nozzle as well as the gas
properties, the charts are presented in the form of enthalpy--specific volume or i - - v charts to
facilitate these calculations.
TEe method of using the charts with the aid of the rider scale (Fig. 5), and the advantages this
method has over the use of the well known Mollier diagram employed in steam engineering are
illustrated by Spalding and Green 7. The accompanying charts are simpler to use, however,
than those described by Spalding and Green because the specific volume is plotted on a
logarithmic scale. It should be noted that the logarithmic scale for the nozzle area marked at
the top of the i - - v charts refers to specific area, i.e., the cross-sectional area of nozzle in sq cm
corresponding to a flow rate of 1 kg/sec of propellant.
The inKial enthalpy of the gaseous product mixture is denoted by a constant initial enthalpy
line drawn on the chart and is equal to the initial enthalpy of the reactants, kerosene and 98 per
cent nitric acid, both of which are t a k e n to be liquid at 25 deg C. For any o t h e r precombustion
temperature of the reactants as explained in section 5.4 a similar line can be drawn and along
its length the theoretical combustion conditions of pressure, specific volume, entropy and flame
temperature obtain. Isentropic expansion from a specific initial pressure of combustion to any
other pressure can be followed on the i - - v chart along a line of constant entropy starting from
t h e initial enthalpy line at a point corresponding to the initial or combustion pressure.
If it is desired to carry out the expansion through a nozzle, then the nozzle dimensions can be
very simply obtained with the aid of Fig. 5. Thus, if expansion is to take place from a pressure
of 20 kg/cm ~ to an ambient pressm-e of 1 kg/cm" then the rider scale Fig. 5 is superimposed on
the i - - v chart so that the horizontal line on the rider scale coincides with the initial enthalpy
line. The rider scale is now moved parallel to the v-axis of the chart until the velocity curve of
the rider scale is tangential to the appropriate isentropic line for 20 kg/cmL The arrow of the
rider scale then indicates the specific throat area on the upper scale of the chart. If now
the rider scale is moved to the right until the velocity curve, the isentrope for 20 kg/cm ~and the
constant pressure line p = 1 intersect at a common point, the arrow indicates the specific exit
area of the nozzle. The exhaust velocity in m/sec is now shown on the graduated velocity curve
of the rider scale at the common point of intersection.
The specific impulse is then given by the expression:
S.I. -- velocity
velocity (m/sec)
g
-- 9-80665 (m/sec~) = S.I. sec
or alternatively
s.I. = 9.328 ~/(Ai) sec
where Ai is the heat drop in Kcal/kg.
5

When the nozzle dimensions are known t h e gas conditions can be determined at any station
along the axis of the nozzle. The mass flow rate can be calculated from the expression
(2 = A / a kg/sec

where

and

a is the specific area of cross section at a station (cm2/kg/sec)

A

area of cross-section at the same station (cm 2)

propellant mass flow rate (kg/sec)

The graphs of combustion temperature and specific impulse against mixture ratio (Figs. 6 and 7)
have been prepared from t h e / ~ v charts. They show, unfortunately, a degree of inconsistency
which has arisen from the fact t h a t the four i - - v charts were prepared over a period of time and
were not fully co-ordinated with one another. The error in specific impulse is of the order of
+ 2 per cent at lower pressures and becomes negligible for expansion from 40 atmospheres.

REFERENCES
No.

A ulhor

Title, etc.

O. Lutz . . . . . . . .

Technische Thermodynamik
Volkenrode. July, 1946.

E. Justi

. . . . . . . .

Spezifische Wiirme, Enttlalpie, Entropie nnd Dissoziation technischer Gase.

Julius Springer, Berlin, 1938, 157 pp.

O. Lutz . . . . . . . .

Enthalpien, Entropien und Gleichgewichts-konstanten von Verbrennungsgasen. Inge~ieur-Archiv XVI Band, pp. 377-382. 1948.

Rossini, Wagman, Evans, Blau

and Levine

Selected values of chemical thermo-dynamic properties.

Bureau of Standards, Washington, D.C. 1947.

5 Bichowsky and Rossini

..

K . K . Kelley

. . . . . .

'7

D . B . Spalding and S. W. Green

dissozierender Gasgemische.

The Thermochemistry of the Chemical Substances.

Corporation, N.Y., U.S.A. 1936.

M.O.S. (A)

U.S. National

Reinhold Publishing

High temperature specifc heat equations for inorganic substances. U.S.

Bureau of Mines, Bull. 371. U.S. Government Printing Office, Washington. 1934.
Mechanical method of determining nozzle characteristics as applied to the
decomposition products of concentrated hydrogen peroxide solutions.
R.A.E. Report R.P.D.1. A.R.C. 11,963. April, 1948.

2950

~BSO

~ 8 % HNO 3 / KEROSENE,

_o

~650
0:;0

0'~

EUEL RICH ~
m

0 - 4-4.

O, 4-6

0 "4-8

FIG. (3. Theoretical combustion temperature against mixture ratio.

O- 50

OX. RICI,L
0 "5~.

ca

88/oHN03

250

240

I
I

/ I

/,

CsEcs~)

KCROSaN~.

I
I
I

.. 2~0

I
I

200

I~0
0"4'0

,1/

0"41

0.42

I
I

0.3

0-64

FIG. 7.

0-5

I"~ O* 4-5

0'4-7

O- 4B

0 49

Theoretical specific impulse against mixture ratio.

0 -50

0"51

0,SP-

I0
2

I00

I000

8, 9

T
kg
-400

- 400

- 500

500

600

- 700

INITIAL
ENTHALPY
LEVEL 25 C - -

INITIAL
ENTHALPY
LEVEL 25'? C

600

- 700

2.4

-800

- 800

2600

ENTHALPY

- 900

6(

-900
Sq

cal

4-

gm
4 0 ~

-I000

-I000

2400 - -

-I100

- II00

-1200

-I~-

-1300

-1400

1200

1300

NITRIC
KEROSENE

ACID

-1400

98%

8 5 % C, 15% H

-1500

-1500
STOICHIOMETRIC

-1600

Oxidant
Fuel

by weight =

5-562

-1600
0"4

0-3

10"2

0"15

0"5
b

-1700

-1700

I
FIG. I.

i-v

CHART

[
C.B.H. 31721 - W t . 52 - Dd, 8943 -BSO-2158

0'1

I'0

FOR

4,

STOICHIOMETRIC
5

PROPORTION

I0

OF

FUEL AND OXIDANT

IJ[lll

I00

I0
S

I00
2

I000

AREA

cm2 sec

--400

400

-500

500

-600

-700

600
2800

INITIAL ENTHALPY.
LEVEL 25 C n

INITIAL
ENTHALPY
m LEVEL 25 C -

2"5

700

800

800

-- 900

2600

IOC

900

-I000

I000

ENTHALPY

2400

4q

--II00

II00

kcal
kg

-1200

1200

--1300

-1400

--1500

1300

NITRIC

ACID

-1400

98%

KEROSENE 85% C. 15% H

-IS00
10% FUEL RICH

1600

Oxidant
Fuel

0.5 0.4

0-3

I 0.2

0-I~

by weight = 5-0566

-1600
I

v SPECIFIC VOLUME

0.4804

m3

-1700

-1700
FIG. 2.
5

C.B.H. 31721 - W t . 52 - Dd. 8943- 8,50- ~/5B

0.1

I-0

i-v

1
3

J] ~ . ~ ~ C H AFOR
RT

I0 %

BY

WEIGHTL EXCESS[ ] L ~ FU
~EL O F
2

I0

I00

I0
2

45

I00

7 ~ 9

I000

8 9

3 2

AREA

kq

- 400

400

2"7

-500

500

-600
600

-700

INITIAL ENTHALPY
LEVEL 25 C

2600

INITIAL ENTHALPY
LEVEL 25 C m

700

- 800

800

2400
-900
-

900

ENTHALPY_

--I000

-I000

kcal
kq
-II00

II00

4N_

-1200

1200

-1300
-1300
I

-1400

NITRIC

ACID

0.8

0.6 0.5 0"4

0'3

0.2

0.15

98%

-1400

KEROSENE 85% C, 15% H

SPECIFIC

50% FUEL RICH, approx.

Oxidant
Fuel

VOLUME

m~
kq

by weiqht = 3-708

-r

o,,,
FIG. 3. " - v

[
C,B.H. 31721 - W t . 52 - D d . 8943 - 8 5 0 - 2 , / 5 9

O.I

,5

CHART

I I L I_I_M

1.0

FOR 50% BY WEIGHT

I0

EXCESS OF

FUEL ]

J_
4

.5

I I I

I00

100

I0
2

.5

1000

AREA
- 400
-

2"Lsooo

c m 2 sec
k9
-

400

- 500

- 500

- 600

2.5

- 600

700

INITIAL
--LEVEL

INITIAL
ENTHALPY
LEVEL 25 C

ENTHALPY
25 C - -

- 700

2600

- 800

~,00

so~,
-900

4(

- 900

I000

I000

II00

ENTHALPY
-

kcal
kg

II00

-1200

-1200

-1300

-1300

-1400

NITRIC
KEROSENE

ACID
85%

-1400

98%
C, 15% H

o.ir.,

- 1500
10% OXIDANT

-1600

RICH, approx.

Oxidant
Fuel

by w e i q h t

o.,
v

b-118

o.2 o.,sl

o.,

SPECIFIC VOLUME

m~

1500

-1600

kq

0-5192

--1700

-1700

CIB.H. 31721 - w t . 52

Dd. 8943- 850 - 2-/59

0"I

FIG. 4.

i-v

I-0

CHAR"

FOR

10%
8

BY

WEIGHT

EXCESS

I0

OF

OXIDANT

l__L_ [L~U_LLJ

I00

I I00 ~)~
120
-

210(

..<

"!

t~
n

S. [. =

VELOCITY
sec
g

CONVERSION
I m Isec

I KcoI/Kg

--I

Kg/cm =

I ma/Kg

TABLE

3.28084

31~

ttlsec

C.H.U./Ib

=-- 14.223 I b / i n . ~
--- 16"01854 ft3/Ib

I cm2sec/Kg - O-07030"/in.2sc/lb
C . B . H . 31721 - W t . 52 - D d . 8943 - 8 5 0 - 2 / 5 9

FIG.5.

R I DER SCALE

R. & M. No. 2982

-

np . . . . . . . . . .

i - r i

r"l

i-

rr

,i r i i i i i

Jl

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