Fundamentals of Rocket Propulsion

Chapter 5

Thermodynamic Performance Analysis of Chemical Rocket Engine

Lectured by Prof. Liang Guozhu

Department of Rocket Propulsion, School of Astronautics, Beijing University of Aero. & Astro.(BUAA) September 2011

5 5.1

Thermodynamic Performance Analysis of Chemical Rocket Engine Introduction In Chapter 2 & 4 the one-dimensional ideal performance relations were developed. They require a

knowledge of the properties of the combustion products, such as their combustion temperature Tf , average molecular weight M r , gas constant R , and specific heat ratio k etc. The present chapter discusses a theoretical approach to determine the properties of the propellant reaction products for a given composition of propellant (knowledge of the fuel and oxidizer chemicals and their relative proportions), chamber pressure, and nozzle exit pressure. The analysis is usually divided into two somewhat separate sets of calculationsThe combustion process and the nozzle gas expansion process. 5.2 5.2.1 Basic Principles for Thermodynamic Analysis for combustion chamber process The principle of the conservation of mass

The mass of any of the atomic species present in the reactants before the chemical reaction must be equal to the mass of the same species in the products. For example of hydrogen-oxygen combustion,

aH 2 + bO2 nH 2O H 2 O + nH 2 H 2 + nO2 O2 + nO O + nH H + nOH OH

the mass balance would be: for hydrogen: 2a = 2nH 2O + 2nH 2 + nH + nOH for oxygen: 2b = nH 2O + 2nO2 + nO + nOH In more general form, the mass for any given element must be the same before and after the reaction, i.e.

L N = aij n j aij n j j =1 propellants j =1 products

(5.1)

Here L gives the number of species in the reactants, the N gives the number of gas species in the combustion products. The atomic coefficient aij are the number of kilogram atoms of element i per kg-mol of species j . n j is expressed as kg-mol for a particular species j per kg of mixture. The effective average molecular mass M r of a gas mixture is then

Mr =

n M
j =1 j

rj

n
j =1

(5.2)
j

For example of hydrogen-oxygen reaction,

Mr =

18nH 2O + 2nH 2 + 32nO2 + 16nO + nH + 17 nOH nH 2O + nH 2 + nO2 + nO + nH + nOH

5.2.2

The principle of the energy balance (the conservation of energy)

The energy balance can be thought of as a two-step process. The chemical reaction occurs instantaneously but isothermally at the reference temperature, and the resulting energy release then heats the gases from this reference temperature to the final combustion temperature. For the first step, the heat of reaction r H released
0

need

to determined which is defined as the energy

or absorbed when products are formed from its reactants at the standard reference conditions

(298.15K or 25C and 1atm). The heat of reaction can be negative or positive, depending on whether the reaction is exothermic or endothermic. In general the heat of reaction can be determined from sums of the heats of formation of the products and the reactants, namely

r H 0 = n j f H 0 j
j =1

products

n j f H 0 j
j =1

reactants

(5.3)

where the heat of formation f H

is defined as the energy released (or absorbed), or the value of enthalpy

change, when 1 mole of chemical compound is formed from its constituent atoms or elements at the standard reference conditions. By convention, the heat of formation of the gaseous elements (e.g., H2, O2, Ar, Xe, etc.) is set to zero at the standard reference conditions. When heat is released in the formation of a product, then

r H 0 has a negative value.

For the second step, the physical heating process can be described by the following equation:
Tf % Tf % r H 0 = n j c p , j dT = n j h j j =1 Tref j =1 N N

Tref

(5.4)

% % here h j is the increase in enthalpy per molar species j , and c p , j is the molar specific heat at constant
pressure. 5.2.3 The principle of the chemical equilibrium

Definition of chemical equilibrium is that, if the concentrations of products and reactants remain constant, the two reactants forward and backward are in equilibrium with each other. We define the state of chemical equilibrium as the state in which there is no spontaneous tendency of the system to change its internal composition, either by diffusion or by chemical reactions. Chemical equilibrium is usually described by either of two equivalent formulations, i.e. equilibrium constants or minimization of free energy. The comparisons between the two formulations show that, if a generalized method of solution is used, the two formulations reduce to the same number of iteration equations.
3

However several disadvantages of the equilibrium constant method are found. Briefly these disadvantages are numerical difficulties with use of components, more difficulty in testing for presence of some condensed species, and more difficulty in extending the generalized method for nominal equations of state. For these reasons, the free-energy minimization formulation is used. The condition for equilibrium may be stated in terms of any of several thermodynamic functions such as the minimization of the Gibbs free energy or Helmholtz free energy or the maximization of the entropy. If one wishes to use temperature and pressure to characterize a thermodynamic state, the Gibbs free energy is most easily minimized in as much as temperature and pressure are its natural variables. Similarly, the Helmholtz free energy is most easily minimized if the thermodynamic state characterized by temperature and volume (or density). Here the approach is the minimization of the Gibbs free energy is applied. The Gibbs free energy (often called chemical potential) g for mixtures of gas as well as an individual gas species is defined as

g = e + pv Ts = h Ts

(5.5)

where e is the internal energy, p the pressure, v the specific volume, T the temperature, s the entropy, and h is the enthalpy. The free energy is a function of temperature and pressure. It is another property of a material, just like enthalpy or density. The free energy may be thought of as the tendency or driving force for a chemical material to enter into a chemical (or physical ) change. For a system including different species the mixture free energy g is
N

g = g jnj
j =1

(5.6)

where

is the number of species and n j is the mole number for j species.

The change in free energy for reactions as the basic thermodynamic relation of a chemical system is

dg = sdT + vdp + g j dn j
j =1

(5.7)

The change in the Gibbs free energy function of a chemical system is zero at equilibrium state. That is

dg = 0

(5.8)

When the system is under the condition of constant pressure and constant temperature, for example in rocket engine thrust chambers, then

g dn
j =1 j

=0

(5.9)

The equation (5.9) is the chemical equilibrium equation for a chemical system with constant pressure and temperature. The equation (5.9) also can be expressed with equilibrium constants. For an arbitrary reversible chemical
4

reaction

aA + bB cC + dD
where A and B are reactants and C and D are products. The chemical equilibrium equation can be written as
c d nC nD p = Kp a b nA nB n ( a +b )( c + d )

(5.10)

(5.11)

where n is the total mole number of all the species and K p is the equilibrium constant. K p is only a function of temperature and can be calculated as follows:

Kp =

c d pC pD a b p A pB

(5.12)

Let

Kn =

c d nC nD a b nA nB

(5.13)

which is the equilibrium constant described by molar fraction. Then

p Kn = K p n

( a +b ) ( c + d )

(5.14)

Note that K n is not only a function of temperature but also a function of pressure. When (a +b)-(c +d )=0, then K n is only a function of temperature. 5.2.4 Solving method

The approach used commonly today for solving for the gas composition, combustion temperature, and gas properties is relied on the minimization of the Gibbs free energy and on mass balance and energy balance equations. As was explained in Eq.(5.8), the change in the Gibbs free energy function is zero at equilibrium. To assist in solving this equation a Lagrangian multiplier or a factor of the degree of the completion of the reaction is often used. An alternative method is to use the mass balance and energy balance equations together with the equilibrium relationships (Eq.(5.14)). After assuming a chamber pressure and setting up the energy balance, mass balance, and equilibrium relations, one method of solving all equations is to estimate a serial of combustion temperatures and solve mass balance and equilibrium relations for the various values of n j until there is a convergence where a energy balance is achieved between the absolute value of heat of reaction r H
0 0 0

and the heat absorbed by

the gases, that is HT H 0 , to go from the reference temperature to the final combustion temperature.
5

In the combustion chamber a constant pressure process is assumed. In the nozzle an isentropic expansion with the entropy being constant is used. Solving the set of equations to determine the gas compositions and the thermodynamic properties of the combustion products will obtain those important gas parameters, such as T f , Te , k , etc. 5.3 Equilibrium constant method for calculating the gas compositions for given pressure and temperature Example 5-1. The liquid monopropellant nitromethane (CH3NO2) can be decomposed into gaseous reaction products with the assumption of no dissociation and no O2. Determine the values of products of combustion temperature Tf average molecular weight M r specific heat ratio k characteristic velocity

c* thrust coefficient CF and specific impulse I s using the water-gas equilibrium conditions.
SOLUTION. Neglect minor products, the chemical reaction for 1 mol of reactant can be described as

1.0CH3 NO2 nCO CO + nCO2 CO2 + nH2 H 2 + nH2O H 2O + nN2 N 2

The mass balances are obtained for each atomic element: C: 1= nCO + nCO2

H: 3=2 nH2 +2 nH 2O O: 2= nCO +2 nCO2 + nH 2O N: 1=2 nN 2 From the last one of the above equations, nN 2 can be solved directly as nN 2 =0.5. The reaction commonly known as the water-gas reaction is

H 2 + CO 2 H 2 O + CO
Its equilibrium constant K n , expressed as molar concentration, is only a function of temperature (see also (5.14)), i.e.

Kn =

nH 2O nCO nH 2 nCO2

The for equation above have five unknowns: namely, the four molar concentrations and the equilibrium constant K n , which is a function of temperature. K n can be obtained from a table of the water-gas reaction as a temperature. Try Tf =2500K and K n =6.440, then the four molar concentrations can be solved as

nH2 =0.664, nH2O =0.836, nCO2 =0.164, nCO =0.836.

The heats of formation f H
0

for various specifies are listed in the Table 5- 1 below from the JANAF

thermochemical tables. By definition, the heat of formation of H2 or N2 is zero. The enthalpy change of the gases going from the reference conditions to the combustion temperature can also be obtained from the JANAF thermochemical tables and is again listed in Table 5- 1. The heat of reaction is obtained from Eq.(5.3),
6

r H 0 = n j f H 0 j
j =1

products

n j f H 0 j
j =1

reactants

= 0.836(241.826) + 0.164(393.522) + 0.836(110.53) 1.0(113.1) = 246kJ / mol

Table 5- 1 The calculation data at 2500K Species N2 H2O H2 CO CO2 CH3NO2 of

f H 0
0 -241.826 0 -110.53 -393.522 -113.1

% h j

Tf Tref

Mr
28 18 2 28 44 61

nj
0.500 0.836 0.664 0.836 0.164 1.000

74.296 99.108 70.498 74.985 121.917

The gas enthalpy change of the hot gas in the combustion chamber should be equal to the negative value the heat of reaction from the view of energy banlance. Using data from the above table,
2500 % Tf = 249.5kJ/mol H 298 = n j h j j =1 Tref 5

This is not identical to the 246kJ/mol obtained previously, and therefore a lower temperature is to be tried. After one or two iterations the final combustion temperature of 2470K and the new molar composition of species will be found where the heat of reaction balances the enthalpy rise of the products. The molecular weight can then be obtained from Eq.(5.2):
5

Mr =

n M
j =1 j

rj

n
j =1

= 20.3

The specific heat varies with temperature, and average specific heat values c p can be obtained from each species by integrating the following formula from the JANAF thermochemical tables:

cp
The specific heat ratio is

2470

p 298 2470

c dT dT

=2040kJ/kg.K

298

k=

cp = 1.25 8314.4 cp 20.3

With M r , k , and Tf now determined, the ideal performance of a nitromethane rocket engine can be established on the basis of Chapter for pc =69atm and pe =1.0atm. The results are

c* =

Tf o R Mr = 1525m / s

k 1 2k R o pe k = 2394m / s I s = uef = Tf 1 k 1 M r pc

CF =
Example 5-2. For a given

Is = 1.57 c*
solid propellant formulation chemical

formula:C11.2738H40.8672O25.8632N5.7692Cl5.6773 S2.4177Al1.8532 (the subscripts represent atomic molar quantities of the propellant with the molecular weight 1003.2606kg), the requirements are to calculate the equilibrium combustion composition by the method of equilibrium constants under the combustion temperature Tc = 2800 K, the combustion pressure ( pc = 70atm), and the reaction products being considered in this system are: Al2O3 (condensed)CO2H2OCOH2N2HClSO2O2OHNOHCl (13 species). Calculation procedure According to the assumed combustion composition, 13 unknown species require 13 equations to solve them. Then we can start by mass balance as follows: (1) For carbon:

nCO2 + nCO = 11.2738

(2) For hydrogen:

(5.15)

2nH2O + 2nH2 + nHCl + nOH + nH = 40.8672

(3) For oxygen:

(5.16)

3nAl2O3 + 2nCO2 + 2nSO2 + 2nO2 + nH2O + nCO + nOH + nNO = 25.8632

(4) For nitrogen:

(5.17)

2nN2 + nNO = 5.7692

(5) For chlorine:

(5.18)

nHCl + nCl = 5.7692

(6) For sulfur:

(5.19)

nSO2 = 2.4177
(7) For aluminum:

(5.20)

2nAl2O3 = 1.8532

(5.21)

The equilibrium constants may be applied when chemical compounds are formed from their elements. According to the 13 species, the following 6 independent reversible chemical reactions can be considered: (1) H 2 O H 2 +

1 O 2 and its chemical equilibrium equation is: 2

1/ nH2 nO22

nH2O

p = K p ,H2O n g

1 2

(5.22)

(2) the water gas reaction: CO 2 + H 2 CO + H 2 O and its equilibrium equation is:

nCO nH 2O nCO2 nH2

(3) H 2 O OH +

p = K p = Kp ng

(5.23)

1 H 2 and its chemical equilibrium equation is: 2

nOH n1/22 H nH2O

p = K ' p ,H2O n g

1 2

(5.24)

(4) H 2 2H and its chemical equilibrium equation is:

2 p nH = K p ,H2 ng nH2 1

(5.25)

(5) HCl H + Cl and its chemical equilibrium equation is:

p nH nCl = K p ,HCl ng nHCl

(5.26)

(6) N 2 + O 2 2NO and its chemical equilibrium equation is:

2 nNO = K p ,NO nN2 nO2

(5.27)

The equilibrium constants, listed in Table 5- 2, are depending on combustion temperature. As mentioned before, the number of equations now is 13 but a new unknown variable ng appeared which increase the number of unknowns to 14. ng represents the total number of moles of the products considered for this system, but only for the gaseous products because, as an assumption, any condensed phases add a negligible amount to the total pressure. Then the number of moles of (Al2O3) will be not added to the total amount because it will be at the liquid state (solidification temperature of Al2O3 2327K) and the following equation can be considered:

ng = nCO2 + nH2O + nCO + nH2 + nN2 + nHCl + nSO2 + nO2 + nOH + nNO + nH + nCl
Table 5- 2 The equilibrium constants at 2800K

(5.28)

T equilibrium constants

2800K 0.223310 7.0080 0.664910

1

K p , H 2O
Kp

K ' p , H 2O
K p ,H 2

0.209110

1 2 3 2

K p,HCl
K p , NO

4.598310 0.878610

The above mentioned system of equations were used to calculate the average molecular weight of the produced gases ( M g ) and equilibrium combustion composition for propellant formulations based on (C, H, O, N, Cl, S and Al) for given combustion temperature and pressure using an iterative technique till convergence. Results The combustion composition calculated, total number of moles of the produced gases for 1kg combustion products and average molecular weight of them are listed below in Table 5- 3. Table 5- 3 Results of computations Equilibrium Species Values/mol/kg

nAl2O3 (c) nCO2 nH2O

nCO

0.9266 0.8060 6.1378 10.4678 11.3743 2.8839 5.6064

10

nH2 nN2
nHCl

nSO2 nO2
nOH nNO
nH nCl

2.4177 8.297510-5 2.876710-2 1.450010-3 0.2079 7.086710-2 40.0029 22.6365

ng Mg
5.4

Basic Principles for Thermodynamic Analysis for Nozzle Flow Process The nozzle gas expansion process constitutes the second set of calculations. The fully reacted, equilibrated

gas combustion products enter the nozzle and undergo an adiabatic expansion in the nozzle. For the nozzle expansion thermodynamic calculation the isentropic equation need to be adoped to determine the gas temperature at certain location along nozzle axis. This is the different characteristic from combustion chamber where the energy balance equation is applied. The entropy remains constant during a reversible (isentropic) nozzle expansion for an ideal rocket engine. The entropy is another thermodynamic property of matter. In the anlysis of isentropic nozzle flow, it is assumed that the entropy remains constant. It is defined as

ds =

de pdv dT dp + = cp R T T T p

(5.29)

and the corresponding intergral is

s s0 = c p ln

T p R ln T0 p0

(5.30)

where the subscript zero applies to the reference state. For a mixture the entropy is

s = s jnj
j =1

(5.31)

Here entropy is in J/(kmol K) . The entropy for each gaseous species is

0 s j = sT , j R ln

nj ng

R ln p

(5.32)

For solid and liquid species the last two terms are zero. Here sT refers to the standard pressure temperature

T.
11

5.5

Free-energy minimization method for calculating the gas compositions for given pressure and temperature

5.5.1

Equation of state

We assume all gases to be ideal and that interactions among phases may be neglected. The equation of state for the mixture is

pv = nR oT

(5.33)
o

where p is pressure (N/m2), v specific volume (m3/kg), n moles (kg-mole/kg), T temperature (K), and R
o

is

the universal gas constant ( R R=8314.4 J/(kg-mole.K) if the international system of units (SI units) are used. Equation (5.33) is assumed to be correct, even when small amounts of condensed species up to several percent by weight are present. In this event the condensed species are assumed to occupy a negligible volume and exert a negligible pressure compared to the gaseous species. In this variables volume, moles, and density the volume and moles refer to gases only while the mass is for the entire mixture including condensed species. The molecular weight of the mixture M is then defined to be

M = 1/ n
Where

(5.34)

n = nj
j =1

(5.35)

Where nj is the number of kilogram-moles of species j per kilogram of mixture. An equivalent expression for molecular weight is

M =

n M
j =1 j

n
j =1

(5.36)
j

Where Mj is the molecular weight of species j. As implied in equation (5.36), among the n possible species which may be considered, gases are indexed from 1 to m and condensed species from m+1 to n. 5.5.2 Minimization of Gibbs Free Energy

The Gibbs free energy per kilogram of mixture for n mixture species is defined as:

12

g = jnj
j =1

(5.37)

where the chemical potential per kilogram of species is defined as:

j =

g n j

T , p , ni ( i j )

(5.38)

The condition for chemical equilibrium is the minimization of free energy. This minimization is usually subjected to certain constraints such as the following mass balance constraints:

a n
j =1 ij

bi0 = 0, (i = 1,....L)

(5.39)

or

bi bi0 = 0, (i = 1,..L)
where

(5.40)

bi = aij n j ,
j =1

(i = 1,...L)

where the stoichiometric coefficients aij are the number of kilogram-atoms of element i per kilogram-mole of species j, bi is the assigned number of kilogram-atoms of element i per kilogram of total reactants, and bi is the number of kilogram-atoms of element i per kilogram of mixture. We define a term G as:
0

G = g + i bi bi0
i =1

(5.41)

where i are Lagrangian multipliers, the condition for equilibrium becomes:

L L G = j + i aij ni + ( bi bi0 ) i = 0 j =1 i =1 i =1 n

(5.42)

By treating the variations nj and i as independent gives

j + i aij = 0, ( j = 1,..., n)
i =1

(5.43)

and also the mass balance equation (5.40).

13

Based on the assumptions in the section 5.5.1 the chemical potential may be written as:

0 nj o j + R T ln j = n 0 j
Where state.

o for + R T ln p j for { j = m + 1,..., n

{ j = 1,..., m

( gas phase)}

(5.44)

(condensed phase)}

0 for gases (j=1 to m) and for condensed species (j > m) is the chemical potential in the standard j

For a gas, the standard state is the hypothetical ideal gas. For a pure solid or liquid, the standard state is the substance in the condensed phase under a pressure of one atmosphere (101325 Pa). The numerical value of

0 is depending partly on a term involving units of atmospheres. Therefore, the unit of pressure in equation j
(5.44) should be consistent with the units of pressure in the thermodynamic data being used. Equations (5.40) and (5.43) permit the determination of equilibrium compositions for thermodynamic states specified by an assigned temperature T0 and pressure p0 that is, in addition to equations (5.40) and (5.43), we have the pair of trivial equations

T = T0 p = p0

(5.45)

However, the thermodynamic state can be specified by assigning, any two states function. For example the thermodynamic state corresponding to constant pressure combustion is specified, instead of equation (5.45) by:

h = h0 p = p o

(5.46)

where h is the enthalpy of the mixture and h0 is a constant equal to the enthalpy of the reactants. The enthalpy h is defined by this equation:
o h = n j ( HT ) n j =1

(5.47)

where

(H )
o T

is the standard state enthalpy for species j.

For assigned entropy and pressure (such as for an isentropic compression or expansion to a specified pressure), the thermodynamic state is specified instead of equation (5.46) by:

s = s0 p = p o

(5.48)

where s is the entropy of the mixture and s0 is the assigned entropy, or entropy of the total reactant. The entropy s is defined by this equation:
14

s = njsj
j =1

(5.49)

where

0 n ( sT ) j R o ln nj sj = s0 ( T ) j
where

o R ln p j

( j = 1,..., m ) ( j = m + 1,..., n )

(5.50)

(s )
0 T

is the standard state entropy for species j. Equation (5.50) is similar to equation (5.44), and

same discussion concerning standard state pressure that applied to equation (5.44) also applied to equation (5.50). 5.5.3 Gibbs Iteration Equations

The equations required to obtain composition are not all linear in the composition variables and therefore an iteration procedure is generally required. In the iteration procedure to be described it will be convenient to treat n as an independent variable. A descent Newton-Raphson method is used to solve for corrections to initial estimates of compositions n j , Lagrangian multipliers

i , moles of gaseous species n, and (when required)

the first. The correction variables used are

temperature T. This method involves a Taylor series expansion of the appropriate equations with all terms truncated that contain derivatives higher than

ln n j ( j = 1,..., m) , n j ( j = km + 1,..., n) , ln n , i =
(1968)[
]

i , and ln T . As Zeleznik and Gordon R oT

pointed out, it is no restriction to start each iteration with the estimate for the Lagrangian

multipliers equal to zero inasmuch as they appear linearly in equation (5.43). After making dimensionless these equations containing thermodynamic functions, the Newton-Raphson equations obtained from equations (5.39), (5.43), (5.46), and (5.48) are:
o ( HT ) ln n j aij i ln n o j ln T = o j RT RT i =1 L

j = 1,..., m

(5.51)

o ( HT ) j j aij i o ln T = o RT RT i =1 L

j = m + 1,..., n

(5.52)

akj n j ln n j +
j =1

j = m +1

akj n j = bko bk

k = 1,..., l

(5.53)

15

 n ln n
j =1 j

n ln n = n n j
j =1

(5.54)

o o o n j ( HT ) n n j (C p ) n ( HT ) ho h j j RoT ln n j + j+1 RoT n j + j+1 Ro j ln T = RoT =m j =1 =m m

(5.55)

o 0 n n j (C p ) n ( sT ) m njsj j j ln T = so s + n n j ln n j + o n j + Ro j = m+1 R o Ro j =1 j = m +1 R j =1 m

(5.56)

Where

( C ) is the standard state specific heat at constant pressure for species j at temperature T.
0 p

5.5.4

Reduced Gibbs Iteration Equations

For problems with assigned thermodynamic states TP, HP, or SP various combinations of equations (5.51) to (5.56) could be used to obtain corrections to estimates. However, for chemical systems containing many species, it would be necessary to solve a large number of simultaneous equations. This large number of equations can be reduced quite simply to a much smaller number by algebraic substitution, this is accomplished by substituting the expression for ln n j obtained from equation (5.51) in to equation (5.53) to (5.56). Including equation (5.52) written with signs reversed, the resulting reduced number of equations are:
o m a n m akj n j ( H T ) j kj j j o (5.57) akj aij i + akj n j + akj n j ln n + ln T = (bk bk ) + o RT R oT i =1 j =1 j = m +1 j =1 j =1 j =1 L m n m

(k = 1,...L)
o ( HT ) j j aij i + o ln T = o RT i =1 RT L

( j = m + 1,..., n)

(5.58)

m n m m n (H o ) m n j n ln n + j T j ln T = n n j + j j aij n j i + j =1 j =1 RT j =1 i =1 j =1 j =1 RT L m

(5.59)

o Tn ( H o ) m n (H o ) m aij n j ( H T ) j T j RoT i + 1 RoT n j + j RoTT j ln n i =1 j =1 m+ j =1 L o m n ( H o )2 n n (C o ) h h m n (H ) + j op j + j o T 2 j ln T = o o + j oT j2 j RT (R T ) j =1 ( R T ) j =1 j =1 R

(5.60)

16

Tn m aij n j s j m ns s i + jo n j + j o j ln n Ro m+1 R i =1 j =1 j =1 R o o m m n s n n j (C p ) j m n j ( H T ) j s j s s j j j + + ln T = o o + n n j + o 2 o o 2 R j =1 ( R ) T j =1 j =1 ( R ) T j =1 R L

(5.61)

After

obtaining

the

previous

correction

variables,

the

corrections

for

gases

species

ln n j ( j = 1,..., m) are then obtained from equation (5.51). Of course convergence on the size of
corrections before they are applied to obtain improved estimates should be controlled. 5.6 Results of Thermodynamic Calculations 1. Rocket engine performance (1) Frozen equilibrium rocket performance (2) Shifting equilibrium rocket performance Actual thermochemical rocket performances fall between the results determined on the basis of shifting and frozen equilibria. 2. Any intermediate rate cannot easily be treated analytically, depending on reaction kinetics. 3. In general, high specific impulse or high characteristic velocity can be obtained if the average molecular weight of the reaction products is low (usually this implies a formulation rich in hydrogen) or if the available chemical energy (heat of reaction) is large, which means high combustion temperatures. 4. Actual values of specific impulse obtained from firing actual propellants in rocket units are, in general, 3 to 12% lower than those calculated by the method explained in this chapter because of some inefficiencies in the combustion chamber and the nozzle, only a portion of perhaps 1 to 4% is due to combustion inefficiencies. 5. For the liquid propellant combination, liquid oxygen-RP-1: For maximum specific impulse the following figures show an optimum mixture ratio of approximately 2.3 for frozen equilibrium expansion and 2.5 for shifting equilibrium expansion. The maximum values of c * are at slightly different mixture ratios. It should be noted that this optimum mixture ratio is not the value for highest temperature, which is usually fairly close to the stoichiometric value.

17

Fig.5- 1

Calculated performance analysis of liquid oxygen and hydrocarbon fuel as a function of mixture ratio

Fig.5- 2

Calculated chamber gas composition for liquid oxygen and hydrocarbon fuel as a function of
18

mixture ratio. Aggressive gases, such as O2, O or OH can cause oxidation of the wall materials in the chamber and the nozzle.

Fig.5- 3

Calculated nozzle exit gas composition for shifting equilibrium conditions as a function of mixture ratio. Breakdown into O, OH or H and free O2 occurs only at the higher mixture ratios.

Fig.5- 4

Variation of theoretical specific impulse with mixture ratio and pressure ratio, calculated for frozen equilibrium.

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Fig.5- 5 Variation of calculated parameters with pressure ratio for liquid oxygen hydrocarbon propellant at a mixture ratio 2.20. An increase in pressure ratio is due to an increase in chamber pressure, a decrease of nozzle exit pressure (larger area ratio and higher altitude), or both.

Fig.5- 6 Variation of exhaust gas composition at nozzle exit with pressure ratio at a fixed mixture ratio and for shifting equilibrium. For frozen equilibrium the composition would be the same as in the chamber, as shown in Fig.5- 2. 5.7 ASSIGNMENTS For hydrazine monopropellant N2H4, it decomposes into hot gas composition including NH3, N2, and H2, i.e., N2H4 NH3+N2+H2. Among the gas composition, there is an equilibrium dissociation reaction 2NH3 3H2+N2. Finish a computer program (C/Fortran/Matlab) to calculate equilibrium combustion compositions (molar numbers for 1kg combustion products) and temperature for combustion chamber pressure
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pc =10atm by using the method of equilibrium constants (refer to the JANAF thermochemical tables and other
chemical literatures). Write an analysis report about this assignment. Submit the electronic Word version of the report and the computer source code.

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