1.

Combustion & Thermochemistry

This section will cover the following concepts:
Basic property relations for ideal gas and ideal gas
mixtures.
First law of thermodynamics.
Enthalpy/heat of reaction; adiabatic flame temperature.
Chemical equilibrium.

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Review of Property Relations:

Extensive Properties: depends on amount of substance considered. Usually denoted by capital letters. Examples are: V for volume, U for total
internal energy, H for total enthalpy.
Intensive Properties: expressed per unit amount
of substance (mass or mole). Its numerical value
is independent of the amount of substance present.
Usually denoted with lower case letters. Examples
are: specific volume v, specific enthalpy h, specific heat cp .
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 Intensive Properties (Contd): Important exceptions to this lower case conventions are temperature T and pressure P .
Molar based properties will be denoted by an
for specific enthalpy per unit mole,
overbar, e.g., h
J/mol.
Extensive properties are related to the intensive
ones by the amount of substance present:
V = m v(or N v)

(1.1)

H = m h(or N h)
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Equation of State:
Provides the relationship among the pressure, temperature, and volume.
Ideal-gas behaviour: intermolecular forces and
volume of molecules are ignored.
P V = N Ru T

(1.2a)

P V = mRT

(1.2b)

P v = RT

(1.2c)

P = RT

(1.2d)

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Equation of State (Contd):

The specific gas constant R is related to the universal gas constant Ru (or Ro ) by:
Ru
R=
MW

(1.3)

Ru = 8314.7 J/(kmol K)
M W is the molecular weight (or, more precisely,
molecular mass).
Throughout this course, all gaseous species and
gas mixtures will be assumed to be ideal.
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Calorific Equations of State:

Relates enthalpy and internal energy to pressure
and temperature:
u = u(T, v)

(1.4a)

h = h(T, P )

(1.4a)

By differentiating Eqns 1.4a and b:

p u Q
p u Q
du =
dT +
dv
T v
v T
p h Q
p h Q
dh =
dT +
dP
T P
P T
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(1.5a)
(1.5b)

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Calorific Equations of State (Contd):

In Eqs 1.5a and b:
cv =
cp =
For an ideal gas:
(u/v)T = 0 and
(h/P )T = 0
1. Combustion & Thermochemistry

p u Q
T

(1.6a)

p h Q

(1.6b)

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Calorific Equations of State (Contd):

Integrating Eqs 1.5 and substitute in 1.6 provide
u(T ) uref =

h(T ) href =

cv dT

(1.7a)

cp dT

(1.7b)

Tref
T

Tref

We will define an appropriate reference state in a

subsequent section.
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Calorific Equations of State (Contd):

For both real and ideal gases, the specific heats
are generally functions of temperature.
Internal energy of a molecule: translational, vibrational and rotational are temperature dependent.
Monatomic species: only translational energy.
Diatomic and triatomic: all three, i.e., translational, vibrational and rotational.
In general, the more complex the molecule, the
greater its molar specific heat.
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Ideal Gas Mixtures:

Mole fraction of species i:
Ni
= Ni /Ntot
i 
Nj

(1.8)

Mass fraction of species i:

mi
Yi 
= mi /mtot
mj

(1.9)

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Ideal Gas Mixtures (Contd):

By definition the sum of all the mole (and mass)
fractions must be unity:
3
3
i = 1 and
Yi = 1
(1.10a&b)
i

Relations between and Y :

Yi = i M Wi /M Wmix

(1.11a)

i = Yi M Wmix /M Wi

(1.11b)

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Ideal Gas Mixtures (Contd):

Mixture molecular weight (mass):
3
M Wmix =
i M Wi

(1.12a)

M Wmix

1
=
(Yi /M Wi )

(1.12b)

Total pressure is the sum of the partial pressures:

3
P =
Pi
(1.13)
i

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Ideal Gas Mixtures (Contd):

Partial pressure of the ith species is the pressure
of this species if it were isolated from the mixture.
Pi = i P
For ideal gas mixtures:
hmix =

(1.14)

Yi hi

(1.15a)

i
i h

(1.15b)

mix =
h

3
i

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Ideal Gas Mixtures (Contd):

Mixture entropies also is calculated as a weighted
sum of the constituents:
3
smix (T, P ) =
Yi si (T, P )
(1.16a)
i

smix (T, P ) =

i si (T, P )

(1.16a)

Pure species entropies depend on the species partial pressures as implied in Eqs 1.16.
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Ideal Gas Mixtures (Contd):

If we take the standard state as 1 atm (Pref =
P o = 1 atm), then:
Pi
si (T, Pi ) = si (T, Pref ) R ln
Pref

(1.17a)

Pi
si (T, Pi ) = si (T, Pref ) Ru ln
Pref

(1.17b)

Appendix A in the textbook lists entropies for several species.

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Latent Heat (Enthalpy) of Vaporization:

hf g is the heat required in a P = const. process
to completely vaporize a unit mass of liquid at a
given temperature:
hf g hvapor (T, P ) hliquid (T, P )

(1.18)

Clausius-Clapeyron equation:
hf g dT
dPsat
=
2
Psat
R Tsat

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(1.19)

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First Law of Thermodynamics:

First Law - Fixed Mass:
Conservation of energy is the fundamental principle in the first law of thermodynamics. For a
fixed mass system, energy conservation is expressed for a finite change between two states, 1
and 2, as:
1 Q2

,1

Heat added
to the system

1 W2

,1

Work done
by the system

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E12
 , 1

(1.20)

Change in total
energy of system

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First Law - Fixed Mass (Contd):

Both 1 Q2 and 1 W2 are path functions and occur
only at the system boundaries. E12 E2 E1
is the change in the total energy of the system, i.e.
E = m[

u
,1

system internal
energy

+ (1/2)v 2 +
 , 1
system kinetic
energy

gz
,1

system potential
energy

(2.21)
The sytem energy is a state variable and does not
depend on the path taken.

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First Law - Fixed Mass (Contd):

We can write Eq 1.20 as a unit mass basis, or expressed to represent an instant in time:
1 q2

Q
,1

1 w2 = e12 = e2 e1

instantaneous
rate of heat
transferred

W
,1

instantaneous
rate of work
done

(1.23)

instantaneous
change of
system energy

q w = de/dt

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dE/dt
 , 1

(1.22)

19

(1.24)

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First Law - Control Volume:

Steady-state, steady-flow form of the first law:
Q cv
,1

Rate of heat
transferred from
surroundings

me
i
,1

Rate of work
done by control
volume excluding
flow work

Rate of energy
flow into CV

1. Combustion & Thermochemistry

cv
W
,1

me
o
,1

Rate of energy
flow out of CV

+ m(P
o vo Pi vi )

,
1

(1.25)

Net rate of work

associated with
pressure forces

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First Law - Control Volume (Contd):

Main assumptions in the previuos equation:
- The control volume is fixed relative to the
coordinate system.
- The properties of the fluid at each point
within CV, or on the control surface, do not
vary with time.
- Fluid properties are uniform over inlet and
outlet areas.
- There is only one inlet and one outlet stream.
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First Law - Control Volume (Contd):

Specific energy e of the inlet and outlet stream
consist of:
e
,1

Total
energy per
unit mass

u
,1

Internal
energy per
unit mass

+ (1/2)v 2 +
 , 1
Kinetic
energy per
unit mass

gz
,1

Potential
energy per
unit mass

(1.26)
v = velocity where the stream crosses the CV
z = elevation where stream crosses the CV
g = gravitational acceleration
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First Law - Control Volume (Contd):

Enthalpy:

h u + P v = u + P/

(1.27)

Eqns 1.25-1.27 yield:

1 2
2

Qcv Wcv = m[(h

h
)+
(v
v
o
i
o
i )+g(zo zi )]
2
(1.28)
On a mass-specific basis, Eqn 2.28 reads
qcv wcv = (ho hi ) + (1/2)(vo2 vi2 ) + g(zo zi )
(1.29)

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Reactant and Product Mixtures:

Stoichiometry:
The stoichiometric quantity of oxidizer is just that
amount needed to completely burn a quantity of
fuel. For a hydrocarbon fuel, Cx Hy , stoichiometric
relation is
Cx Hy + a(O2 + 3.76N2 )
xCO2 + (y/2)H2 O + 3.76aN2 (1.30)
where
a = x + y/4
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(1.31)
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Stoichiometry (Contd):
The stoichiometric air-fuel ratio is
X
~
mair
4.76a M Wair
(1.32)
(A/F )stoic =
=
mfuel
1 M Wfuel
The equivalence ratio is defined as
(A/F )stoic
(F/A)
=
=
(A/F )
(F/A)stoic

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(1.33a)

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Stoichiometry (Contd):

> 1: Fuel-rich mixtures.

< 1: Fuel-lean mixtures.
= 1: Stoichiometric mixtures.
% stoichiometric and % excess air;
%stoichiometric air = 100%/

(1.33b)

%excess air = [(1 )/] 100%

(1.33c)

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Absolute (or Standardized) Enthalpy and

Enthalpy of Formation:
For any species, we can define an absolute enthalpy that is the sum of an enthalpy of formation
and sensible enthalpy change:
i (T )
h
 , 1

absolute enthalpy
at temperature T

o (Tref ) + h
s,i (Tref )
= h
f,i
 , 1
 , 1
enthalpy of
formation at
standard ref
state (Tref ,P o )

sensible enthalpy
change in going
from Tref to T

(1.34)

i (T ) h
o (Tref )
s,i h
where h
f,i
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Absolute (or Standardized) Enthalpy (Contd):

Define a standard reference state.
Tref = 298.15K (25 o C)
Pref = P o = 1atm (101.325 kPa)
Enthalpies of formation are zero for the elements
in their naturally occuring state at the reference
temperature and pressure.
For example, at 25 o C and 1 atm, oxygen exists as
diatomic molecules; then
o

(hf,O2 )298 = 0
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Absolute (or Standardized) Enthalpy (Contd):

To form oxygen atoms at the standard state requires breaking of a chemical bond.
The bond dissociation energy of O2 at standard
state is 498, 390 kJ/kmol.
Breaking of the bond creates two O atoms; therefore the enthalpy of formation of atomic oxygen
is
o )298 = 249, 195 kJ/kmol
(h
f,O

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Enthalpy of Formation (Contd):

Thus, enthalpies of formation is the net change
in enthalpy associated with breaking the chemical
bonds of the standard state elements and forming
new bonds to create the compound of interest.
Examples:
o )298 = 0
(h
f,N2
o )298 = 0
(h
f,H2
o )298 = 472, 629 kJ/kmol
(h
f,N
o

(hf,H )298 = 217, 977 kJ/kmol

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Abs. enthalpy, heat of formation, and sensible enthalpy

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Enthalpy of Combustion and Heating Values

-qcv

REACTANTS

PRODUCTS

Stoichiometric
at standard state

Complete combustion
at standard state

Steady-flow reactor

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Enthalpy of Combustion and Heating Values (Contd)

Reactants: stoichiometric mixture at standard state
conditions.
Products: complete combustion, and products are
at standard state conditions.
For products to exit at the same T as the reactants, heat must be removed.
The amount of heat removed can be related to the
reactant and product absolute enthalpies by applying the steady-flow form of the first law:

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Enthalpy of Combustion and Heating Values (Contd):

From eqn 1.29:
qcv = ho hi = hprod hreac

(1.35)

The enthalpy of reaction, or the enthalpy of combustion, hR , is (per mass of mixture)

hR qcv = hprod hreac

(1.36a)

or, in terms of extensive properties

HR = Hprod Hreac
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(1.36b)

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Enthalpy of Combustion and Heating Values (Contd):

Example:
- At standard state, the reactants enthalpy of a stoichiometric mixture of CH4 and air, where 1 kmol
of fuel reacts, is 74, 831 kJ.
- At the same conditions, the combustion products
have an absolute enthalpy of 877, 236 kJ.
HR = 877, 236 (74, 831)
= 802, 405kJ
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Enthalpy of Combustion and Heating Values (Contd):

- This value can be adjusted to a per-mass-of-fuel
basis:
p kJ Q
hR
= HR /M Wfuel
(1.37)
kgfuel

- or

p kJ Q
hR
= (802, 405/16.043)
kgfuel
= 50, 016
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Enthalpy of Combustion and Heating Values (Contd):

- For a per-unit-mass-of-mixture basis:
p kJ Q
p kJ Q m
fuel
hR
= hR
kgmix
kgfuel mmix

where
mfuel
1
mfuel
=
=
mmix
mair + mfuel
(A/F ) + 1

(1.38)

(1.39)

hR (kJ/kgmix ) = 50, 016/(17.11 + 1)

= 2761.8
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Enthalpy of Combustion and Heating Values (Contd):

Enthalpy of combustion depends on temperature
chosen for its evaluation since enthalpies of reactants and products are temperature dependent.
The heat of combustion, hc (known also as the
heating value or calorific value), is numerically
equal to the enthalpy of combustion, but with opposite sign.
HHV: higher heating value (H2 O liquid)
LHV: lower heating value (H2 O vapor)
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Adiabatic Flame Temperatures:

We will differentiate between two adiabatic flame
temperatures:
- constant-pressure combustion
- constant-volume combustion
Constant-Pressure: If a fuel-air mixture burns adiabatically at constant pressure, absolute enthalpy
of reactants at the initial state (say, T1 = 298 K,
P = 1 atm) equals absolute enthalpy of the products at final state (T = Tad , P = 1 atm).

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Constant Pressure Tad (Contd):

Definition of the constant-pressure adiabatic flame
temperature is
Hreac (Ti , P ) = Hprod (Tad , P )

(1.40a)

or, on a per-mass-of-mixture basis,

hreac (Ti , P ) = hprod (Tad , P )

(1.40b)

Conceptually, adiabatic flame temperature is simple, however, evaluating this quantity requires
knowledge of the composition of the combustion
products.
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Constant Volume Tad :

When we are dealing with constant-pressure combustion systems, such as gas turbine combustors and rocket engines, the appropriate approach
would involve constant-pressure Tad .
When we are dealing with constant-volume combustion systems, such as enclosed explosions or
Otto-cycle (idealized thermodynamic cycle for
gasoline engine combustion) analysis, the appropriate approach would involve constant-volume
Tad .
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Constant Volume Tad (Contd):

Definition:
Ureac (Tinit , Pinit ) = Uprod (Tad , Pf )

(1.41)

where U is the absolute (or standardized) internal

energy of the mixture.
Most thermodynamic property compilations and
calculations provide H (or h) rather than U (or
u). So we consider the fact that:
H = U + PV
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Constant Volume Tad (Contd):

Eqn 1.41:
Hreac Hprod V (Pinit Pf ) = 0

(1.42)

If we apply the ideal-gas law;

3
Pinit V =
Ni Ru Tinit = Nreac Ru Tinit
reac

Pf V =

Ni Ru Tad = Nprod Ru Tad

prod

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Constant Volume Tad (Contd):

Substituting in Eqn 1.42
Hreac Hprod Ru (Nreac Tinit Nprod Tad ) = 0
(1.43)
Since
mmix /Nreac M Wreac
mmix /Nprod M Wprod
p T
Q
T
init
ad
hreac hprod Ru

=0
M Wreac
M Wprod
(1.44)

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Chemical Equilibrium:
Products of combustion are not a simple mixture
of ideal products.
We used ideal products approach to determine stoichiometry.
Ideal combustion products for a hydrocarbon fuel:
- = 1: CO2 , H2 O, N2
- < 1: CO2 , H2 O, N2 , O2
- > 1: CO2 , H2 O, N2 , CO, H2

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 Real combustion products of a hydrocarbon fuel

may include:
- CO2 , H2 O, N2 , O2 , H2 , OH, CO, H, O, N,
NO, ....
Major species, i.e.,
CO2 , H2 O, N2 , O2 , H2 , CO,
dissociate into a host of minor species, i.e.,
H, N, O, OH, NO.
Our objective here is to calculate the mole fraction
of all product species.
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Second-Law Considerations:
Second-Law of Thermodynamics Concept of
chemical equilibrium.
Consider a V =const., adiabatic reaction vessel in
which a fixed mass of reactants form products.
As reaction proceeds, T and P rise until a final
equilibrium condition is reached.
This final state is not governed solely by first-law
considerations, but requires invoking the secondlaw.

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Second-Law Considerations (Contd):

Consider the following combustion reaction:
CO + 0.5O2 CO2

(1.45)

If the final T is high enough, CO2 will dissociate.

Assuming products are CO2 , CO, and O2

=
CO + 0.5O2 cold
reactants


=
(1 )CO2 + CO + (/2)O2

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hot
products

(1.46)

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Second-Law Considerations (Contd):

= fraction of CO2 dissociated.
It is possible to calculate the adiabatic flame temperature as a function of using Eqn 1.42.
= 1: no heat release; T , P , and i remain
unchanged.
= 0: maximum possible heat release; P and
T would be the highest possible allowed by the
first-law.
Variation of temperature with :
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Chemical equilibrium for a fixed mass system.

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Second-Law Considerations (Contd):

Lets see what constraints second-law imposes on
this system
Entropy of the mixture:
3

Smix (Tf , P ) =
Ni si (Tf , Pi )
i=1

= (1 )
sCO2 +
sCO + (/2)
sO2

si =

soi (Tref )

8Tf

Pi
dT
cp,i
Ru ln o
T
P

(1.47)
(1.48)

Tref
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Second-Law Considerations (Contd):

If we plot mixture entropy versus , we see that
entropy reaches maximum at about = 0.5.
For our choice of conditions, the second law requires that entropy change internal to the system
dS 0

(1.49)

i will shift toward the point of maximum entropy

when approaching from both sides.
Once maximum entropy is reached, no change in
i is allowed.
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Second-Law Considerations (Contd):

Then, formally the condition for equilibrium is:
(dS)U,V,m = 0

(1.50)

If we fix the internal energy, U , volume, V , and

mass, m, of an isolated system, application of the
- first law (Eqn 1.41),
- second law (Eqn 1.49) and
- equation of state (Eqn 1.2)
define the equilibrium T , P , and i .
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Gibbs Function:
For an isolated system of fixed volume, mass, and
energy system, the maximum entropy approach
demonstrates the role of second law.
In most typical sysytems, however, the equilibrium
i are required for a given T , P , and .
For such cases, the Gibbs free energy, G replaces
entropy as the important thermodynamic property.
Gibbs free energy is defined as:
G H TS

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(1.51)

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Gibbs Function (Contd):

Second law in terms of G:

(dG)T,P,m 0

(1.52)

which states that Gibbs function always decreases

for a spontaneous, isothermal, isobaric change of a
fixed-mass system.
This allows us to calculate equilibrium i at a
given P , and T .
At equilibrium:
(dG)T,P,m = 0

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(1.53)

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Gibbs Function (Contd):

For a mixture of ideal gases, the Gibbs function of
the ith species
o
+ Ru T ln(Pi /P o )
gi,T = gi,T

(1.54)

o
gi,T
is Gibbs function at standard-state pressure,
Pi = P o .
In reacting systems, Gibbs function of formation is
3
o
gf,i
(T ) gio (T )
jI gjo (T )
(1.55)
j

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Gibbs Function (Contd):

jI are the stoichiometric coefficients of the elements required to form one mole of the compound
of interest.
I
I
=
0.5
and

O
C = 1 for forming one mole of
2
CO from O2 and C.
o
(T ) of the naturally oc Similar to enthalpies, gf,i
curing elemets are assigned values of zero at the
reference state.

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Gibbs Function (Contd):

Gibbs function for a mixture of ideal gases

Gmix = Ni gi,T =
3
o
gi,T
+ Ru T ln(Pi /P o )]
(2.56)
Ni [
For a fixed T and P , the equilibrium condition
becomes
dGmix = 0
(2.57)

o
or
dNi [
gi,T
+ Ru T ln(Pi /P o )]
3
o
gi,T
+ Ru T ln(Pi /P o )] = 0 (2.58)
+
Ni d[

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Gibbs Function (Contd):

Second term in the last equation
is
zero,
because

d(lnPi ) = dPi /Pi and
dPi = 0 and total
pressure is constant. Then,
3

o
dNi [
gi,T
+ Ru T ln(Pi /P o )]
(1.59)
For a general system, where

dGmix = 0 =

aA + bB + ..... eE + f F + ......
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(1.60)

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Gibbs Function (Contd):

The change in the number of each species is proportional to its stoichiometric coefficient,
dNA = a
dNB = b
.=.
dNE = +e
dNF = +f
.=.

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(1.61)

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Gibbs Function (Contd):

substitute Eqn 1.61 into 1.59 and eliminate
o
a[
gA,T
+ Ru T ln(PA /P o )]

o
b[
gB,T
+ Ru T ln(PB /P o )] ..

+
+
or

o
e[
gE,T
o
f [
gF,T

(1.62)

+ Ru T ln(PE /P )]

+ Ru T ln(PF /P o )] + .. = 0

o
o
o
o
+ f gF,T
+ .. a
gA,T
b
gB,T
..)
(e
gE,T

(PE /P o )e (PF /P o )f ..
= Ru T ln
(PA /P o )a (PB /P o )b ..
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(1.63)

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Gibbs Function (Contd):

Left hand side of Eqn 1.63 is the standard-state
Gibbs function change:
o
o
o
o
GoT = (e
gE,T
+ f gF,T
+ .. a
gA,T
b
gB,T
..)
(1.64a)
o
o
o
o
gf,E
+ f gf,F
+ .. a
gf,A
b
gf,B
..)T
GoT (e
(1.64b)
Argument of the natural logarithm in Eqn 1.63 is
defined as the equilibrium constant Kp

(PE /P o )e (PF /P o )f ..
Kp =
(PA /P o )a (PB /P o )b ..
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(1.65)
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Gibbs Function (Contd):

Then we have:
GoT = Ru T lnKp

(1.66a)

Kp = exp[GoT /(Ru T )]

(1.66b)

Eqns 1.65 and 1.66 give a qualitative indication

of whether a particular reaction favors products or
reactants at equilibrium:
Reactants: If GoT > 0 lnKp < 0 Kp < 1
Products: If GoT < 0 lnKp > 0 Kp > 1
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Gibbs Function (Contd):

Similar physical insight can be obtained by considering the definition of GoT in etrms of enthalpy and entropy changes:
GoT = H o T S o
which can be substituted into Eqn 1.66b
Kp = exp[H o /(Ru T )] exp(S o /Ru )
- For Kp > 1, which favors products, H o should
be negative (exothermic reaction). Also positive
changes in entropy lead to Kp > 1
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Equilibrium Products of Combustion:

Full Equilibrium:
Calculate the adiabatic flame temperature and detailed composition of the products of combustion:
- Eqn 1.40 (or 1.41) (1st law)
- Eqn 1.66 (Gibbs funct.-Equilibrium const.)
- Apropriate atom conservation constants
Constant pressure combustion of Propane, C3 H8 ,
with air, assuming that the products are CO2 , CO,
H2 O, H2 , H, OH, O2 , O, NO, N2 , and N:
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Tad and major species distribution.

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66

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Minor species distribution of propane-air combustion.

1. Combustion & Thermochemistry

67

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Water-Gas Equilibrium:
Develop simple relations to calculate ideal products of combustion (no dissociation producing minor species) for lean and rich conditions:
We employ a single equilibrium reaction (watergas shift reaction):
CO + H2 O CO2 + H2
to account for simultaneous presence of CO and
H2 , considered as the incomplete combustion
products.
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Water-Gas Equilibrium (Contd):

Combustion of an arbitrary hydrocarbon is considered:
Cx Hy + a(O2 + 3.76N2 )
bCO2 + cCO + dH2 O + eH2 + f O2 + 3.76aN2
(1.67a)
For 1 becomes:
Cx Hy + a(O2 + 3.76N2 )
bCO2 + dH2 O + f O2 + 3.76aN2
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(1.67b)

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Water-Gas Equilibrium (Contd):

For rich conditions, > 1:
Cx Hy + a(O2 + 3.76N2 )
bCO2 + cCO + dH2 O + eH2 + 3.76aN2 (1.67c)
Note that a can be related to :
x + y/4
a=

(1.68)

So for a given fuel and , a is a known quantity.

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Water-Gas Equilibrium (Contd):

For 1, c and e are zero:
b=x
d = y/2
f = [(1 )/](x + y/4)

(1.69)

Total number of moles of products:

p x + y/4 Q
NTOT = x + y/2 +
(1 + 3.76)

(1.70)
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Water-Gas Equilibrium (Contd):

For 1 mole fraction of products:
CO2
CO
H2 O
H2
O2
N2

= x/NTOT
=0
= (y/2)/NTOT
=0
= [(1 )/](x + y/4)/NTOT
= 3.76(x + y/4)/(NTOT )

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(1.71)

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Water-Gas Equilibrium (Contd):

For > 1 no oxygen appears, f = 0. To calculate the remaining constants, we use the three
atomic balances (C, H, and O) and water-gas shift
equilibrium:
(PCO2 /P o ) (PH2 /P o )
be
KP =
=
(1.72)
o
o
(PCO /P ) (PH2 O /P )
cd
c=xb
d = 2a b x
e = 2a + b + x + y/2

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(1.73)

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Water-Gas Equilibrium (Contd):

Combining Eqn 1.73 with 1.72 yields a quadratic
equation in b. Its solution is (negative root selected to yield positive values of b):
2a(Kp 1) + x + y/2
b=
2(Kp 1)
1

{[2a(K)p 1) + x + y/2]2
2(Kp 1)
4Kp (Kp 1)(2ax x2 )}1/2

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(1.74)
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Water-Gas Equilibrium (Contd):

For > 1 mole fraction of products:
NTOT = b + c + d + e + 3.76a = x + y/2 + 3.76a
(1.75)
CO2 = b/NTOT
CO = (x b)/NTOT
H2 O = (2a b x)/NTOT
(1.76)
H2 = (2a + b + x + y/2)/NTOT
O2 = 0
N2 = 3.76a/NTOT
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