MECE 5397/6397

Rocket Propulsion
Combustion Example:
Methane and Oxygen
University of Houston
Mechanical Engineering Department
John W. Alred
john.w.alred@nasa.gov

Adiabatic Flame Temperature

Assume a given combustion process takes place adiabatically (and
with no work or changes in kinetic or potential energy involved)
For such a process the temperature of the products is referred to as
the adiabatic flame temperature.

With the assumptions of no work and no changes in kinetic or

potential energy, this is the maximum temperature that can be
achieved for the given reactants.
This is because any heat transfer from the reacting substances and
any incomplete combustion would tend to lower the temperature of
the products.
For a given fuel and given pressure and temperature of the reactants,
the maximum adiabatic temperature that can be achieved is with a
stoichiometric mixture.

Adiabatic Flame Temperature

Suppose we react a stoichiometric mixture of gaseous methane and
gaseous oxygen at an initial temperature of 25oC and 4 MPa (almost
40 atm) pressure.

CH4 + 2O2 CO2 + 2H2O

We assume ideal gas behavior for all the constituents.
We know that the heat of reaction (DHReaction) is the difference in the
enthalpies at STP (T = 298K and P = 1 atm = 0.1 MPa) of the
reactants and products:

DHReaction = H298Products H298Reactants

Using the enthalpy of formation of each constituent (h0f); heat of
reaction can be written as :

DHReaction = SP ni[h0f]i SR ni[h0f]i

Combustion of Methane
CH4(g) + 2O2(g) CO2(g)+ 2H2O(l)
CH4(g) + 2O2(g)

enthalpy

Heat given off

by the system

to the surroundings

H = -890.4 kJ

CO2(g)+ 2H2O(l)

This reaction is an exothermic

process.

HReaction = -890.4 kJ

HReaction = H(products) H(reactants)

= [H(CO2, g) + 2H(H2O, l)]
[H(CH4, g) + 2H(O2,g)]
= -890.4kJ
1 mole of gaseous methane
reacts with 2 moles of
gaseous oxygen to form 1
mole gaseous carbon dioxide
and 2 moles of liquid water.
The enthalpy change is -890.4
kJ.
NOTE: O/F ratio = 64/16 = 4

Adiabatic Flame Temperature

Since this process is adiabatic, then all energy of the reactants must
either heat the reactants before combustion of heat the products after
combustion.
Hence, the enthalpy of the reactants at the initial temperature equals
the enthalpy of the products at the adiabatic flame temperature:

HiReactants = HAFTProducts
Using the enthalpy of formation of each constituent (h0f); the change
in enthalpy of each constituent in the reactants at the initial
temperature (hi); and the change in enthalpy of each constituent in
the products at the adiabatic flame temperature (he).

SR ni[h0f + h]i = SP ne[h0f + h]e

JANAF (now JANNAF) Data

Temperature

Methane

Carbon Dioxide

Carbon Monoxide

Oxygen, Diatomic

Water (gas)

CH4

CO2

CO

O2

H2O

Hydrogen,
Diatomic
H2

(3/31/61)

(9/30/65)

(9/30/65)

(9/30/65)

(3/31/61)

(3/31/61)

(3/31/66)

(hf o)298 = 0

(hf o)298 = -241.827

(hf o)298 = 0

(hf o)298 = 39.463

(hf o)298 = -74.873 (hf o)298 = -393.522 (hf o)298 = -110.529

Hydroxyl
OH

M = 16.043

M = 44.010

M = 28.010

M = 31.999

M = 18.015

M = 2.0159

M = 17.007

(ho-ho298)
kJ/mol

(ho-ho298)
kJ/mol

(ho-ho298)
kJ/mol

(ho-ho298)
kJ/mol

(ho-ho298)
kJ/mol

(ho-ho298)
kJ/mol

(ho-ho298)
kJ/mol

298

1000

38.179

33.405

21.686

22.707

25.978

20.686

20.933

1500

78.153

61.714

38.848

40.61

48.095

36.267

36.84

2000

123.592

91.45

56.739

59.199

72.689

52.932

53.76

2500

171.984

121.926

75.023

78.375

98.964

70.492

71.417

3000

222.076

152.862

93.542

98.098

126.361

88.743

89.584

3200

242.431

165.331

100.998

106.127

137.553

96.199

96.96

3400

262.925

177.849

108.479

114.232

148.854

103.738

104.387

3600

283.536

190.405

115.976

122.399

160.247

111.361

111.859

3800

304.248

202.999

123.495

130.629

171.724

119.064

119.378

4000

325.045

215.635

131.026

138.913

183.28

126.846

126.934

4200

345.918

228.304

138.578

147.248

194.903

134.7

134.528

4400

366.855

241.003

146.147

155.628

206.585

142.624

142.156

4600

387.849

253.734

153.724

164.046

218.325

150.62

149.816

4800

408.893

266.5

161.322

172.502

230.12

158.682

157.502

5000

429.982

279.295

168.929

180.987

241.957

166.808

165.222

5200

451.11

292.123

176.548

189.502

253.839

174.996

172.967

5400

472.274

304.984

184.184

198.037

265.768

183.247

180.736

5600

493.469

317.884

191.832

206.593

277.738

191.556

188.531

5800

514.692

330.821

199.489

215.166

289.746

199.924

196.351

6000

535.942

343.791

207.162

223.756

301.796

208.346

204.192

The thermochemical data are calculated from the JANNAF Thermochemical Tables,
Thermal Research Laboratory, The Dow Chemical Company, Midland, Michigan.
The date each table was issued is indicated.

Adiabatic Flame Temperature

Note that in the simplified reaction considered, only CO2 and H2O on
the right side of the equation. We know that with dissociation we will
have to consider more.
Calculate HReactants
Since the reactant temperature is equal to the base temperature of
25C, hi = 0.
Sum the enthalpies of formation of the reactants. From the JANNAF
table
Diatomic oxygen : (h0f)298 = 0, which is typical for diatomic gases
Methane : (h0f)298 = -74.873 kJ/mol

HReactants = Si ni[h0f + h]i = 1 [-74.873 + 0] + 2 [0 + 0]

HReactants = -74.873 kJ

Adiabatic Flame Temperature

For the products,

HProducts = Se ne[h0f + h]e

HProducts = 1[-393.522 + hCO2] + 2[-241.827 + hH2O]
HProducts = HReactants = -74.873 kJ
Now, the temperature of the products such that this equation is true
(using JANNAF data for hCO2 and hH2O) must be found.
Trial-and-error and iteration works

Adiabatic Flame Temperature

Assume TProducts = 5,400 K.
HProducts = 1 [-393.522 + 304.984] + 2 [-241.827 + 265.768]
HProducts = -40.656 kJ
Since HProducts > HReactants, the assumed temperature is too
high.
Try TProducts = 5,200 K.
HProducts = 1 [-393.522 + 292.123] + 2 [-241.827 + 253.839]
HProducts = -77.375 kJ (too low)
Now interpolate to find the adiabatic flame temperature
TProducts = {[-74.873 (-77.375)] / [-40.656 (-77.375)]}
(5,400 5,200) + 5,200
TProducts = 5,214 K

Propellant Initial Temperature

From the preceding example, it can be seen that the initial
temperature of the reactants has an effect on the final
temperature of the products.
For storable propellants, temperature variations within the
normal liquid range have only a small effect on engine
performance.
For hypergols, a 10C change in reactant temperature
results in about 0.1% change in specific impulse.
Therefore, can safely assume that the initial temperature
of storable propellants is the standard enthalpy of
formation temperature of 25C.

Cryogenic Propellants

Cryogenic propellants are another story, as their extremely low

temperatures have a significant effect on performance.
We must further take into consideration that the readily available
thermochemical data for these substances is the gaseous state
rather than liquid. An adjustment must be made to account for the
change of state.
Let's consider the example of cryogenic oxygen, which has a
boiling point of -183C (90 K).
We start with gaseous oxygen at 298 K, which has an enthalpy of
formation of 0 kJ/mol. We then add the change in enthalpy required
to lower the temperature from 298 K to 90 K. We find this
adjustment to be -6.06 kJ/mol.
Deduct the enthalpy of vaporization to account for the change of
state from gas to liquid. The enthalpy of vaporization of oxygen is
6.82 kJ/mol. Therefore, the enthalpy of liquid oxygen reactant is

ho(liquid) = hof + h298 -> 90 hvap = 0 6.06 6.82 = -12.88 kJ/mol

Chemical Equilibrium
For our previous example, employ a procedure for determining the
equilibrium composition of the combustion products.
It is convenient to view the over-all process as though it occurred in
two separate steps, a combustion process followed by a heating and
dissociation of the combustion products. The combustion reaction is
CH4 + 2 O2 CO2 + 2 H2O
There are several dissociation reactions that will come into play, but
we'll consider the two most dominant in this particular example.
CO2 CO + 1/2 O2
H2O 1/2 H2 + OH
That is, the energy released by the combustion of CH4 and O2 heats
the CO2 and H2O to high temperature, resulting in the dissociation of
part of the CO2 to CO and O2, and part of the H2O to H2 and OH. Thus,
the overall reaction can be written
CH4 + 2 O2 a CO2 + b CO + g O2 + d H2O + e H2 + n OH
where the unknown coefficients a, b, g, d, e, and n must be found by
solution of the equilibrium equations associated with the dissociation
reactions.

Chemical Equilibrium
From the combustion reaction we find that the initial compositions for
the dissociation reactions are 1 mole CO2 and 2 moles H2O.
Therefore, letting z' be the number of moles of CO2 dissociated
and z" be the number of moles of H2O dissociated, we find
CO2 CO + 1/2 O2
Initial: 1/0/0; Equilibrium: 1-z' / z' / +z'/2
For water
H2O 1/2 H2 + OH Initial: 2/0/0; Equilibrium: (2-z") / z"/2 / z"
Therefore the overall reaction is
CH4 + 2 O2 (1-z') CO2 + z' CO + z'/2 O2 + (2-z") H2O + z"/2 H2 + z" OH
And the total number of moles at equilibrium for each reaction is
n' = (1-z') + z' + z'/2 = 1 + z'/2
n" = (2-z") + z"/2 + z" = 2 + z"/2

Chemical Equilibrium
The equilibrium mole fractions are
yCO2 = (1-z')/(1+z'/2)
yCO = z'/(1+z'/2)
yO2 = (z'/2)/(1+z'/2)
yH2O = (2-z")/(2+z"/2)
yH2 = (z"/2)/(2+z"/2)
yOH = z"/(2+z"/2)

Substituting these quantities along with P = 4 MPa, we have the

equilibrium equations:
K' = yCO yO21/2 / yCO2 (P/P0)1+1/2-1 =
[z'/(1+z'/2)] [(z'/2)/(1+z'/2)]1/2 / [(1-z')/(1+z'/2)] (4/0.1)1/2
K" = yH2 yOH2 / yH2O2 (P/P0)1+2-2 =
[(z"/2)/(2+z"/2)] [z"/(2+z"/2)]2 / [(2-z")/(2+z"/2)]2 (4/0.1)1

Chemical Equilibrium
Logarithms to the Base e of the Equilibrium Constant K
Temperature

CO2 = CO + 1/2 O2

H2O = 1/2 H2 + OH

298

-103.762

-106.208

500

-57.616

-60.281

1000

-23.529

-26.034

2000

-6.635

-8.728

3000

-1.111

-2.937

3200

-0.429

-2.212

3400

0.169

-1.576

3600

0.701

-1.009

3800

1.176

-0.501

4000

1.599

-0.044

4500

2.49

0.92

5000

3.197

1.689

5500

3.771

2.318

6000

4.245

2.843

Chemical Equilibrium
By trial-and-error solution, a temperature of the products
must be found that satisfies the equations.
Select a trial value for TProducts
Obtain ln(K) values from the table and calculate values of K.
By trial-and-error, calculate the values of z' and z''.
Calculate the number of moles of each product.
Calculate the total enthalpy of the products.
Compare the product enthalpy to the reactant enthalpy.
If HProducts HReactants, select a new trial value of TProducts and repeat.

When close, interpolate to find final TProducts

Chemical Equilibrium
Let's assume TProducts = 3,600 K, we have
ln(K') = 0.701, K' = 2.016, z' = 0.4309
ln(K") = -1.009, K" = 0.3646, z" = 0.4587
CH4 + 2 O2 0.5691 CO2 + 0.4309 CO + 0.2154 O2 + 1.5413 H2O + 0.2294
H2 + 0.4587 OH
HProducts = -117.66 kJ/mol, which is < HReactants

So, assume TProducts = 3,800 K and repeat.

ln(K') = 1.176, K' = 3.241, z' = 0.5285
ln(K") = -0.501, K" = 0.6059, z" = 0.5294
CH4 + 2 O2 0.4715 CO2 + 0.5285 CO + 0.2643 O2 + 1.4706 H2O + 0.2647
H2 + 0.5294 OH
HProducts = -35.94 kJ/mol, which is > HReactants

Chemical Equilibrium
Again, calculate adiabatic flame temperature by interpolation.
TProducts = (-74.873 (-117.66)) / (-35.94 (-117.66)) (3,800 3,600) + 3,600
= 3,705 K
Knowing the temperature, we can now interpolate to find the
corresponding values of ln(K) and calculate the equilibrium mixture.
ln(K') = 0.950, K' = 2.586, z' = 0.4949
ln(K") = -0.742, K" = 0.4762, z" = 0.4814

CH4 + 2 O2 0.5186 CO2 + 0.4814 CO + 0.2407 O2 + 1.5051 H2O

+ 0.2474 H2 + 0.4949 OH

Chemical Equilibrium
For a more accurate solution, there are additional dissociation
reactions that have to be considered, such as

H2O H2 + 1/2 O2
H2 2 H
O2 2 O
It is evident from this rather simple example that accounting for all the
possible dissociations requires the solving of a great many
simultaneous equations. Consider adding another element to the
mixture, such as nitrogen, and we've complicated the problem even
further.
Providing accurate solutions quickly and easily can only be performed
with the aid of a computer program.

Molecular Weight
The average molecular weight, M, of a mixture is simply

M=m/n
where n is the total number of moles in the mixture,
and m is the total mass of the mixture.
The total moles and total mass are found by

n = Si ni
m = Si (ni Mi)
where ni is the number of moles of each constituent
and Mi is the molecular weight of each constituent.

Molecular Weight
Referring back to the last iteration of our combustion
equation, we have

CH4 + 2 O2 0.5186 CO2 + 0.4814 CO + 0.2407 O2 +

1.5051 H2O + 0.2474 H2 + 0.4949 OH
Calculating the molecular weight of the mixture,

n = 3.4881 moles; m = 80.040 g

M = 80.040 / 3.4881 = 22.947 g/mol
Alternatively, if the mole fraction, yi, of each constituent is
given, where yi = ni / n, the average molecular weight is
found by

M = Si (yi Mi)

Specific Heat Ratio

The constant-pressure specific heat, or heat capacity, Cp, and the
constant-volume specific heat, Cv, are defined by the following
relationships
Cp = (h/T)p
Cv = (u/T)v
where h is specific enthalpy, u is specific internal energy, and T is
temperature.
A very important relationship between the constant-pressure and
constant-volume specific heats of an ideal gas is found in the
equation
Cp Cv = R'
where Cp and Cv are on a mole basis, and R' is the universal gas
constant (8.31446 J/mol-K).
This difference between the constant-pressure and constantvolume specific heats of an ideal gas is always constant, though
both are a function of temperature.

Specific Heat Ratio

For exit velocity and other nozzle expansion thermodynamic
equations, we need the ratio of Cp and Cv, k or , defined as

k = Cp / Cv
Since it is common for thermodynamic references to provide the value
of Cp only, from which Cv is calculated, we can combine equations and
write

k = 1 / (1 - R' / Cp)
Values of constant-pressure specific heat are typically found by use of
an equation, or from tabulated values of Cp as a function of
temperature.
The Shomate equation is commonly used, which is shown on the next
slide along with the Shomate coefficients of the products found in the
methane-oxygen combustion example.

Shomate Coefficients of Products

Gas Phase Heat Capacity (Shomate Equation)
Cpo = A + Bt + Ct2 + Dt3 + E/t2
where Cp = heat capacity (J/mol-K), t = Temperature (K) / 1000
Formula

Temp. Range

CO2

1200-6000

58.16639

2.720074

-0.492289

0.038844

-6.447293

CO

1300-6000

35.1507

1.300095

-0.205921

0.01355

-3.28278

H2O

1700-6000

41.96426

8.62253

-1.49978

0.098119

-11.15764

H2

2500-6000

43.41356

-4.293079

1.272428

-0.096876

-20.533862

298-6000

20.78603

O2

2000-6000

20.91111

4.850638x10-10
10.72071

-1.582916x10-10
-2.020498

1.525102x10-11
0.146449

3.196347x10-11
9.245722

2500-6000

22.18977

-1.318044

0.378308

-0.026069

OH

1300-6000

28.74701

4.714489

-0.814725

0.054748

-2.747829

Specific Heat Ratio

Calculating the specific heat ratio of a single substance is
straightforward. Take carbon monoxide at 3,000 K - the specific heat
ratio is

From Shomate equation, Cp = 36.8736 J/mol-K

k = 1 / (1 - 8.31446 / 36.8736) = 1.2911
When we have a mixture of gases, we must determine the specific heat
of the mixture, where

Cpgas = 1 / n Si (ni Cpi) , or

Cpgas = Si (yi Cpi)
Suppose for the methane/oxygen problem, with lots of dissociation,
we get an adibatic flame temperature of 3,553.4 K (more on this later).

Cpgas = Si (yi Cpi) = 49.0786 J/mol-K

k = 1 / (1 - 8.31446 / 49.0786) = 1.2040

Thank Goodness for Computers

JANAF Tables
http://kinetics.nist.gov/janaf/
Combustion Program
http://navier.engr.colostate.edu/~dandy/code/code-4/index.html

Thank Goodness for Computers

CH4:

Thank Goodness for Computers

CH4:
(cont)

Thank Goodness for Computers

CH4:
(cont)

Thank Goodness for Computers

O 2:

Thank Goodness for Computers

Our example:

Thank Goodness for Computers

Our example
with
dissociation

Thank Goodness for Computers

Our example
with more
dissociation

CH4-LOX Data
atm

atm

CH4-LOX Data

O/F

CH4-LOX Data

O/F

CH4-LOX Data

O/F

Summary - Thermochemistry
The adiabatic flame temperature represents the
maximum temperature possible for a chemical
propulsion system.
Unfortunately, products begin to dissociate at higher
temperature, robbing energy from the reaction and
lowering the overall temperature of the flowing
products.
Computer-aided tools make this process much easier
today provided the users understand the inherent
concepts.