2 Combustion and

Thermochemistry
Review of Property Relations
Extensive Properties
V(m
3
), U(J), H(J)(=U+PV)

Intensive Properties
v(m
3
/kg), u(J/kg),h=(J/kg)(=u+Pv)
P,T

V=mv;U=mu;H=mh
Equation of State
For Ideal-gas Behavior:
PV=NR
u
T
PV=mRT
Pv=RT
P=RT
where, R=R
u
/MW
R
u
=8315J/kmol-K; MW is the gas
molecular weight
Calorific Equations of State
u=u(T,v)
h=h(T,P)
du=
dh=
dv
v
u
dT
T
u
T v
) ( ) (
c
c
+
c
c
dP
P
h
dT
T
h
T P
) ( ) (
c
c
+
c
c
Constant-volume specific heats



Constant-pressure specific heats
P p
v v
T
h
c
T
u
c
) (
) (
c
c

c
c

For Ideal Gas

}
}
=
=
=
c
c
=
c
c
T
T
p ref
T
T
v ref
T
T
ref
ref
dT c h T h
dT c u T u
P
h
v
u
) (
) (
0 ) (
0 ) (
Translation
(a)Monatomic species
Translation Rotation
Vibration
(b)Diatomic Species
Fig.2.2

Ideal-Gas Mixtures
Constituent mole fraction and mass fraction
Mole fraction of species i,x
i


tot
i
i
i
i
N
N
N N N
N
x =
+ + +
=

2 1
Mass fraction of species i, Y
i

tot
i
i
i
i
m
m
m m m
m
Y =
+ + +
=

2 1
By definition
1
1
=
=

i
i
i
i
y
x
Relation of x
i
and Y
i

i mix i i
mix i i i
MW MW Y x
MW MW x Y
/
/
=
=
Mixture molecular weight MW
mix

=
=
i
i i
mix
i
i i mix
MW Y
MW
MW x MW
) / (
1
Partial pressure of ith species,P
i

For ideal gas:


P x P
P P
i i
i
i
=
=

Mass-(or Molar-) specific

mixture properties
) , ( ) , (
) , ( ) , (
i
i
i
i
mix
i i
i
i mix
i
i i
mix
i
i i mix
P T s x P T s
P T s Y P T s
h x h
h Y h

=
=
=
=
The mixture entropy is calculated:
The constituent entropies
Standard-state(P
ref
P
0
=1 atm):


ref
i
u ref
i
i
i
ref
i
ref i i i
P
P
R P T s P T s
P
P
R P T s P T s
ln ) , ( ) , (
ln ) , ( ) , (
=
=
Latent heat of Vaporization

It is also called the enthalpy of vaporization

Clausius-Clapeyron Equation
) , ( ) , ( ) , ( P T h P T h P T h
liquid vapor fg

2
sat
sat
fg
sat
sat
T
dT
R
h
P
dP
=
First Law of Thermodynamics
First Law-Fixed Mass


2 1 2 1 2 1

A = E W Q
Heat added to
system in going
fgom state1 to
state 2
Work done by system
on surroundings in
going from state 1 to
state 2
Change in total
system energy in
going from state
1 to state 2
AE
1-2
(E
2
-E
1
)


)
2
1
(
2
gz v u m E + + =
Mass-specific
system internal
energy
Mass-specific
kinetic energy
Mass-specific
system potential
energy
1 2 2 1 2 1 2 1
e e e w q = A =

dt dE W Q / =

Instantaneous
rate of heat
transferred into
system
Instantaneous rate
of work done by
system, or power
Instantaneous
time rate of
change of
system energy
dt de w q / =

e E/m
First Law-Control Volume-SSSF
) (
0 0 0 i i i cv cv
v P v P m e m e m W Q + =


Rate of
heat
transferred
across the
control
surface
from the
surroundin
gs, to the
control
volume
Rate of
all work
done by
the
control
volume,in
cluding
shaft
work, but
excluding
flow
work
Rate of
energy
flowing
out of
the
control
volume
Rate of
energy
flowing
into the
control
volume
Net rate of
workj
associated
with
pressure
forces
where fluid
crosses the
control
surface,
flow work
The principal assumptions
The control volume is fixed relative to the
coordinate system
The properties of the fluid at each point
within the control volume,or the control
surface, do not vary with time.
Fluid properties are uniform over the inlet
and outlet flow areas
There are only inlet and one exit stream

2
1

2
gz v u e + + =
Total
energy
per unit
mass
Internal
energy
per unit
mass
Kinetic
energy per
unit mass
Potential
energy per
unit mass
/ P u Pv u h + = +
Final form of energy conservation
for a control volume
( ) ( ) ( )
(

+ + =
i i i cv cv
z z g v v h h m W Q
0
2 2
0 0
2
1

( ) ( ) ( )
i i i cv cv
z z g v v h h w q + + =
0
2 2
0 0
2
1
Reactant and Product Mixtures
Stoichiometry


3.76=79/21( by volume)
The stoichiometric air-fuel ratio
2 2 2 2 2
76 . 3 ) 2 / ( ) 76 . 3 ( aN O H y xCO N O a H C
y x
+ + + +
fuel
air
stoic
fuel
air
stoic
MW
MW a
m
m
F A
1
76 . 4
) / ( =
|
|
.
|

\
|
=
Some combustion properties of
methane, hydrogen, and solid carbon
for reactants at 298K
h
R
h
R
(O/F)
stoic
T
ad,eq
(kJ/kg
fuel
)(kJ/kg
mix
) (kg/kg) (K)
CH
4
+air -55,528 -3,066 17.11 2226
H
2
+O
2
-142,919 -15,880 8.0 3079
C(s)+air -32,794 -2,645 11.4 2301
The equivalence ratio u
stoic
stoic
A F
A F
F A
F A
) / (
) / (
) / (
) / (
= = u
u>1, fuel rich mixtures
u<1, fuel lean mixtures
u=1, stoichiometric mixture


Percent stoichiometric air



u
=
100%
% tric stoichiome
Percent excess air
% 100
) - (1
%
u
u
= = excess o
Example 2.1
A small, low-emission, stationary gas-
turbine engine operates at full
load(3950kW) at an equivalence ratio of
0.286 with an air flowrate of 15.9kg/s.
The equivalent composition of the
fuel(natural gas) is C
1.16
H
4.32
. Determine
the fuel mass flowrate and the operating
air-fuel ratio for the engine.
Solution
Given: u=0.286, MW
air
=28.85,
m
air
=15.9 kg/s,
MW
fuel
=1.16(12.01)+4.32(1.008)=18.286
Find: m
fuel
and (A/F)
We will proceed by first finding (A/F) and
then m
fuel
.The solution requires only the
application of definitions expressed in
Equs above


where a=x+y/4=1.16+4.32/4=2.24. Thus,


and, from Equ. above
, 76 . 4 ) / (
fuel
air
stoic
MW
MW
a F A =
, 82 . 16
286 . 18
85 . 28
) 24 . 2 ( 76 . 4 ) / ( = =
stoic
F A
| | | | 8 . 58
286 . 0
82 . 16 ) / (
= =
u
=
stoic
F A
(A/F)
Since (A/F) is the ratio of the air flowrate to
the fuel flowrate,


Comment
Note that even at full power, a large quantity
of excess air is supplied to the engine.
| | | | s kg
s kg
F A
m
m
air
/ 270 . 0
8 . 58
/ 9 . 15
) / (
= = =

Example 2.2
A natural gas-fired industrial boiler
operates with an oxygen
concentration of 3 mole percent in
the flue gases. Determine the
operating air-fuel ratio and the
equivalence ratio. Treat the natural
gas as methane.
Solution
Given: x
O
2
=0.03, MW
fuel
=16.04
MW
air
=28.85.
Find : (A/F)and u.
We can use the given O
2
mole fraction to
find the air-fuel ratio by writing an
overall combustion equation assuming
complete combustion, i.e., no
dissociation (all fuel C is found in CO
2

and all fuel H is found in H
2
O):
CH
4
+a(O
2
+3.76N
2
)CO
2
+
2
H
2
O+bO
2
+3.76aN
2
where a and b are related from conservation of
O atoms.
2a=2+2+2b
From the definition of a mole fraction

.
76 . 4 1
2
76 . 3 2 1
2
2
a
a
a b
b
N
N
x
mix
O
O
+

=
+ + +
= =
Substituting the known value of x
O
2
(=0.03)
and then solving for a yields



or a=2.368
The mass air-fuel ratio, in general, is
expressed as
a
a
76 . 4 1
2
03 . 0
+

=
3 . 20
04 . 16
) 85 . 28 )( 368 . 2 ( 76 . 4
) / (
1
76 . 4
) / (
, ) / (
= =
=
=
F A
MW
MW a
F A
so
MW
MW
N
N
F A
fuel
air
fuel
air
fuel
air
To find u, we need to determine(A/F)
stoic.
For a=2,hence,


Apply the definition of u,
84 . 0
3 . 20
1 . 17
) / (
) / (
1 . 17
04 . 16
85 . 28 ) 2 ( 76 . 4
) / (
= = = u
= =
F A
F A
F A
stoic
stoic
Absolute(or Standardized)
Enthalpy and Enthalpy of
Formation
) ( ) ( ) (
,
0
,
T h T h T h
i s ref i f j
A + =
Absolute
enthalpy at
temperature T
Enthalpy of
formation at
standard
reference
state(T
ref
,P
0
)
Sensible
enthalpy
change in
going from
T
ref
to T
Where,
) ( ) ( ) (
0
, , ref i f i i s
T h T h T h A
A standard state
A standard-state temperature:
T
ref
=25C(298.15K)
A standard-state pressure:
P
ref
=P
0
=1 atm(101,325Pa)
The enthalpy of formation are zero for
the elements in their naturally
occurring state at the reference state
temperature and pressure.
For example, at 25C and 1 atm, oxygen
exists as diatomic molecules; hence,

0 ) (
298
0
,
2
=
O f
h
To form oxygen atoms at sandard state
requires the breaking of a rather strong
chemical bond. The bond dissociation
energy for O
2
at 298K is 498,390 kJ/kmol
O
2


O O f
kmol kJ h / 195 , 249 ) (
0
,
=
Enthalpy of formation have a clear
physical interpretation as 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.

Example 2.3
A gas stream at 1 atm contains a misture of
CO, CO
2
, and N
2
in which the CO mole
fraction is 0.10 and the CO
2
mole fraction
is 0.20. The gas-stream temperature is
1200K. Determine the absolute enthalpy of
the mixture on both a mole basis(kJ/kmol)
and a mass basis(kJ/kg). Also determine
the
Solution
Given Xco=0.10, T=1200K, Xco
2
=0.20,P=1 atm
Find:h
mix
, h
mix
, Yco, Yco
2
, and Y
N2
Finding h
mix
requires the straightforward
application of the ideal-gas mixture law, thus,

and

7 . 0 1
2 2
= =
CO CO N
X X X
( ) | |
( ) | |
( ) | |
2
2 2
2
2 2
0
298 ,
0
,
0
298 ,
0
,
0
298 ,
0
,
) (
) (
) (
N
f N f N
CO
f CO f CO
CO
f CO f CO
i
i mix
h T h h x
h T h h x
h T h h x h x h
+ +
+ +
+ = =

Substitute values from Appendix A

h
mix
=0.1[-110,540+28,440]
+0.2[-393,546+44,488]
+0.7[0+28,118]
=-55,339.1kJ/kmol
mix

To find h
mix
, we need to determine the
molecular weight of the mixture:

MW
mix
=Ex
i
MW
i
=0.1(28.01)+0.20(44.01)+0.7
(28.013)=31.212
Then,
mix
mix
mix
mix
kg kJ
MW
h
h / 12 . 1869
212 . 31
1 . 339 , 55
=

= =
6282 . 0
212 . 31
013 . 28
70 . 0
2820 . 0
212 . 31
01 . 44
20 . 0
0897 . 0
212 . 31
01 . 28
10 . 0
2
2
= =
= =
= =
N
CO
CO
Y
Y
Y
Enthalpy of Combustion and
Heating Values
For the steady-flow reactor, complete
combustion:
All C CO
2
All H H
2
O
Fig.2.7
reac prod i cv
h h h h q = =
0
The definition of the enthalpy of reaction,
or the enthalpy of Combustion, Ah
R
(per
mass of mixture), is


or, in terms of extensive properties,

reac prod cv R
h h q h = A
reac prod R
H H H = A
The enthalpy of combustion is shown in
fig2.8

Consistent with the heat transfer being
negative, the absolute enthalpy of the
products lies below that of the reactants.

For example: stoichiometric mixture of
CH
4
and air, H
reac
=-74,831kJ. At the same
conditions H
prod
=-877,236kJ,Thus
AH
R
=-877,236-(-74,831)=-802,405kJ
To a per-mass-of-fuel basis



for the above example:

fuel R
fuel
R
MW H
kg
kJ
h / ) ( A = A
016 , 50 ) 043 . 16 / 405 , 802 ( ) (
4
= = A
CH
R
kg
kJ
h
To a per-unit -mass-of-mixture
basis



where,
mix
fuel
fuel
R
mix
R
m
m
kg
kJ
h
kg
kJ
h ) ( ) ( A = A
1 ) / (
1
+
=
+
=
F A m m
m
m
m
fuel air
fuel
mix
fuel
The stoichiometric air-fuel ratio for CH
4
is
17.11; thus,



Note:The value of the enthalpy of
combustion depends on the temperature
chosen for its evaluation.
8 . 2761
1 11 . 17
016 , 50
) ( =
+

= A
mix
kg
kJ
h
The heat of combustion-heating
value Ah
c

Ah
c
= Ah
R
The upper or higher heating value,HHV ,is
the heat of combustion calculated
assuming that the most amount of energy,
hence the designation upper.
The lowering heating value, LHV,
corresponds to the case where none of the
water none of the water is assumed to
condense.

Example 2.4
A. Determine the upper and lower heating
values at 298 K of gaseous n-decane,
C
10
H
22
, per kilomole of fuel and per
kilogram of fuel. The molecular weight of
n-decane is 142.284.
B. If the enthalpy of vaporization of n-
decane is 359 kJ/kg
fuel
at 298K,what are
the upper and lower heating values of
liquid n-decane?
Solution
A. For 1 mole of C
10
H
22
, the combustion
equation can be written as

For either the upper or lower heating value,

where the numerical value of Hprod
depends on whether the H2O in the
products is liquid(determine HHV)or
gaseous(LHV).

2 2 2 2 2 22 10
) 76 . 3 ( 5 . 15 ) ( 11 10 ) 76 . 3 ( 5 . 15 ) ( N g or l O H CO N O g H C + + + +
prod reac R C
H H H H = A = A
The sensible enthalpy for all species
involved are zero since we desire AH
C
at
the reference state(298K). Furthermore, the
enthalpy of formation of the O
2
and N
2
are
also zero at 298K. Recognizing that
and

= =
prod
i i prod
reac
i i reac
h N H h N H
We obtain


We can calculate the enthalpy of
formation for the liquid water:
] 11 10 [ ) 1 (
0
) ( ,
0
,
0
, ) ( ,
2 2 22 10 2
l O H f CO f H C f l O H C
h h h HHV H + = = A
kmol kJ h h h
fg g O H f l O H f
/ 857 , 285 010 , 44 847 , 241
0
) ( ,
0
) ( ,
2 2
= = =
Adiabatic Flame Temperature
There are two definitions of adiabatic
flame temperature.
One for constant-pressure combustion
One for constant-volume combustion


Or on a per-mass-of-mixture basis



) , ( ) , ( P T H P T H
ad prod i reac
=
) , ( ) , ( P T h P T h
ad prod i reac
=
T
ad
is defined from this first-law
statement, which is called the
constant-pressure adiabatic flame
temperature.
T
ad
is simple and this quantity
requires knowledge of the
composition of the combustion
products.
The flame temperature
are typically several
thousand kelvins.
Calculating the complex
composition by invoking
chemical equilibrium is the
subject of the next section.
Example 2.5
Estimate the constant-pressure adiabatic
flame temperature for the combustion of a
stoichiometric CH
4
-air mixture. The
pressure is 1 atm and the initial reactant
temperature is 298 K.
Use the following assumptions:
1.Complete combustion(no dissociation)
i.e., the product mixture consists of only
CO
2
,H
2
O,and N
2
.
2. The product mixture enthalpy is estimated
using constant specific heats evaluated at
1200K(~0.5(T
i
+T
ad
),where T
ad
is guessed
to be about 2100K)
Solution
Mixture composition:


Properties(Appendices A and B)

52 . 7 , 2 , 1
52 . 7 2 1 ) 76 . 3 ( 2
2 2 2
2 2 2 2 2 4
= = =
+ + + +
N O H CO
N N N
N O H CO N O CH
Species Enthalpy of
Formation @298K
h
0
f,i
(kJ/kmol)
Specific Heat
@1200K
c
P,i
(kJ/kmol-K)
CH
4
-74,831 -----
CO
2
-393,546 56.21
H
2
O -241,845 43.87
N
2
0 33.71
O
2
0 ----
From First Law
298)] - 33.71( (7.52)[0
)] 298 ( 87 . 43 845 , 241 )[ 2 (
) 298 ( 21 . 56 546 , 393 )[ 1 (
)] 298 ( [
831 , 74 ) 0 ( 52 . 7 ) 0 ( 2 ) 831 , 74 )( 1 (
,
0
,
ad
ad
ad
ad i p i f i prod
react
i
prod
i prod
react
i i react
T
T
T
T c h N H
kJ H
h N H h N H
+ +
+ +
+ =
+ =
= + + =
= = =

Equating H
react
to H
prod
and
solving for T
ad
yields
T
ad
=2318K
Constant-volume adiabatic
flame temperature
Ideal Otto-cycle analysis:



where U is the absolute(or standardized)
internal energy of the mixture.
) , ( ) , (
f ad prod init init reac
P T U P T U =
0 ) ( =
f init prod reac
P P V H H
For the ideal-gas law
0 ) (
,
=
= =
= =

ad prod init reac u prod reac

prod
ad u prod ad u i f
reac
init u reac init u i init
T N T N R H H
Thus
T R N T R N V P
T R N T R N V P
On a per-mass-of-mixture basis
0 ) (
obtain thus We
/
/
=

prod
ad
reac
init
u prod reac
prod prod mix
reac reac mix
MW
T
MW
T
R h h
MW N m
or
MW N m
Example 2.6
Estimate the constant-volume
adiabatic flame temperature for
a stoichiometric CH
4
-air
mixture using the same
assumtions as in Example 2.5.
Initial conditions are T
i
=298K,
P=1 atm(101,325Pa).
Solution
The same composition and properties used in
Example 2.5 apply here. We note, however,
that the c
p,i
values should be evaluated at a
temperature somewhat greater than 1200K,
since the constant-volume T
ad
will be
higher than the constant-pressure T
ad
.
Nevertheless, we will use the same values
as before.
First Law:
0 ) (
0 ) (
=
=
ad prod init reac u
prod
i i
reac
i i
ad prod init reac u prod reac
T N T N R h N h N
or
T N T N R H H
Substitute numerical values, we
have
kJ T
T
T
T H
kJ H
ad
ad
ad
ad prod
reac
) 298 ( 5 . 397 236 , 877
)] 298 33.71( (7.52)[0
)] 298 ( 87 . 43 845 , 241 )[ 2 (
)] 298 ( 21 . 56 546 , 393 )[ 1 (
831 , 74 ) 0 ( 52 . 7 ) 0 ( 2 ) 831 , 74 )( 1 (
+ =
+ +
+ +
+ =
= + + =
And


where N
reac
=N
prod
=10.52kmol.
Reassembling and solving for T
ad

yields
T
ad
=2889K
) 298 )( 52 . 10 ( 315 . 8 ) (
ad ad prod init reac u
T T N T N R =
Chemical Equilibrium
In high temperature combustion
processes, the products of
combustion are not a simple
mixture of ideal products, as may
be suggested by the simple
atombalance used to determine
stoichiometry. Rather, the major
species dissociate, producing a
minor species.
For example
The ideal combustion products for
burning a hydrocarbon with air are
CO
2
,H
2
O,O
2
, and N
2
. Dissociation of
these species and reactions among
the dissociation products yields the
following
species:H
2
,OH,CO,H,O,N,NO, and
possibly others.
The problem we address here is the
calculation of the mole fractions of all of
the product species at a given temperature
and pressure,subject to the constraint of
conserving the number of moles of each of
the elements present in the initial mixture.
This element constraint merely says that
the number of C, H, O, and N atoms is
constant, regardless of how they are
combined in the various species.
The equilibrium-constant
approach
There are several ways to approach the
calculation of equilibrium composition. To
be consistent with the treatment of
equilibrium in most undergraduate
thermodynamics courses, we focus on the
equilibrium-constant approach and limit
our discussion to the application of ideal
gases.
Second-Law Considerations
The concept of chemical equilibrium has its
roots in the second law of thermodynamics.
Consider a fixed-volume, adiabatic reaction
vessel in which a fixed mass of reactants
form products. As the reactions proceed,
both the temperature and pressure rise until
a final equilibrium condition is reached.
This final state(temperature,pressure, and
composition) is not governed solely by first
law considerations----second law
Consider the combustion
reaction
2 2
2
1
CO O CO +
If the final temperature is high enough, the CO2
will dissociate. Assuming the products to consist
only of CO2, CO, and O2, we can write:
products
hot
ts reac
cold
O CO CO O CO
(

+ +
(

+
2 2
tan
2
2
) 1 (
2
1 o
o o
o is the fraction of the CO
2
dissociated.
T
ad
is the function of the dissociation fraction
o: o=1, no heat released and unchanged.
o=0, the maximum amount of heat release
occurs and the temperature and pressure
would be the highest possible allowed by
the first law.
What constraints are imposed by the
second law on this thought experiment
where we vary o? The entropy of the
product mixture can be calculated by
summing the product species entropies, i.e.,
2 2
2
) 1 ( ) , ( ) , (
3
1
O CO CO
i
i f i i f mix
s s s P T s N P T S
o
o o + + = =

=
What constraints are imposed by the
second law on this thought experiment
where we vary o? The entropy of the
product mixture can be calculated by
summing the product species entropies, i.e.,
2 2
2
) 1 ( ) , ( ) , (
3
1
O CO CO
i
i f i i f mix
s s s P T s N P T S
o
o o + + = =

=
Where N
i
is the number of moles of species
i in the mixture. The individual species
entropies are obtained from
0
,
0
ln ) (
P
P
R
T
dT
c T s s
i
u
T
T
i p ref i i
f
ref
+ =
}
Where ideal-gas behavior is assumed, and P
i
is the partial pressure of the ith species.

Plotting the mixture entropy as a function of
o, we see a maximum at about 1- o=0.5
for CO+0.5O
2
=CO
2

For our choice of conditions(constant
U,V, and m, which implies no heat or
work interactions), the second law
requires that the entropy change
internal to the system:

dS 0
Thus, we see that the composition of the
system will spontaneously shift toward the
point of maximum entropy when
approaching from either side, since dS is
positive. Once the maximum entropy is
reached, no further change in composition
is allowed, since this would required the
system entropy to decrease in violation of
the second law. Formally, the condition for
equilibrium can be written:



In summary, if we fix the internal energy,
volume, and mass of an isolated system,
the application of second law, first law and
equation of state define the equilibrium
temperature, pressure, and chemical
composition.
0 ) (
, ,
=
m V U
dS
Gibbs Function
Although the foregoing was useful in
illustrating how the second law
comes into play in establishing
chemical equilibrium, the use of an
isolated(fixed-energy) system of
fixed mass and volume is not
particularly useful for many of the
typical problems involving chemical
equilibrium.

For example, there is frequently a
need to calculate the composition of
a mixture at a give temperature,
pressure, and stoichiometry. For
this problem, the Gibbs free energy,
G, replaces the entropy as the
important thermodynamic property.
The Gibbs free energy is defined in terms
of other thermodynamic properties as:


The second law can then be expressed as
TS H G
0 ) (
, ,
s
m P T
dG
Which state that the Gibbs function always
decreases for a spontaneous, isothermal,
isobaric change of a fixed-mass system in
the absence of all work effects except
boundary(P-dV) work. This principle
allows us to calculate the equilibrium
composition of a mixture at a given
temperature and pressure. The Gibbs
function attains a minimum in equilibrium,
in contrast to the maximum in entropy we
saw for the fixed-energy and fixed-volume
case. Thus, at equilibrium,
For a mixture of ideal gases, the Gibbs
function for the ith species is given by


where is the Gibbs function of the pure
species at the standard-state pressure(P
i
=P
0
)
and Pi is the partial pressure. The standard-
state pressur, P
0
by convention taken to be
1 atm, appears in the denominator of the
logarithm term.
0 ) (
, ,
=
m P T
dG
) / ln(
0 0
, ,
P P T R g g
i u T i T i
+ =
0
,T i
g
Gibbs function of formation
) ( ) ( ) (
0
elements
0 0
,
T g v T g T g
j
j
j i i f
'

Where the v
j

are the stoichiometric coefficients

of the elements required to form one mole of the
compound of interest. For example, the
coefficients are v
O2

=1/2 and v
C

=1 for forming
a mole of CO from O2 and C, respectively. As
with enthalpies, the Gibbs functions of
formation of the naturally occurring elements
are assigned values of zero at the reference state.
The Gibbs function for a
mixture of ideal gases


where N
i
is the number of moles of the ith
species.
For fixed temperature and pressure, the
equilibrium condition becomes:


or

+ = = )] / ln( [
0 0
, ,
P P T R g N g N G
i u T i i T i mix
0 =
mix
dG
The second term can be shown to be zero by
reconizing that d(lnP
i
)=dP
i
/P
i
and that
EdP
i
=0, since all changes in the partial
pressures must sum to zero because the
total pressure the total pressure is constant.
Thus,
0 ] / ln( [ )] / ln( [
0 0
,
0 0
,
= + + +

P P T R g d N P P T R g dN
i u T i i i u T i i

+ = = )] / ln( [ 0
0 0
,
P P T R g dN dG
i u T i i mix
For the general system, where


the change in the number of moles of
each species is directly proportional
to its stoichiometric coefficient, i.e.,

+ + + + fF eE bB aA




kf dN
ke dN
kb dN
ka dN
F
E
B
A
+ =
+ =
=
=
Substituting and canceling the
proportionality constant k, we obtain


Equation can be rearranged and the log terms
grouped together to yield:
0 )] / ln( [ )] / ln( [
)] / ln( [ )] / ( [
0 0
,
0 0
,
0 0
,
0 0
,
= + + + + +
+ +

P P T R g f P P T R g e
P P T R g b P P T R g a
F u T F E u T E
B u T B A u T A
. ) / ( ) / (
. ) / ( ) / (
ln
...) ... (
0 0
0 0
0
,
0
,
0
,
0
,
etc P P P P
etc P P P P
T R
g b g a g f g e
b
B
a
A
f
F
e
E
u
T B T A T F T E
-
- -
=
+ +
The term in parentheses on the left-hand-side
is called the standard-state Gibbs function
change AG
T
0
,i.e.,
T B f A f F f E f
T B T A T F T E T
g b g a g f g e
g b g a g f g e G
...) ... ( g
y, alternatel or
...) ... (
0
,
0
,
0
,
0
,
0
T
0
,
0
,
0
,
0
,
0
+ + A
+ + = A
The equilibrium constant K
P





. ) / ( ) / (
. ) / ( ) / (
0 0
0 0
etc P P P P
etc P P P P
K
b
B
a
A
f
F
e
E
p
-
- -
=
With these definitions, our statement of chemical
equilibrium at constant temperature and
pressure, is given by
) / exp(
ln
0
0
T R G K
or
K T R G
u T p
p u T
A =
= A
From definition of K
p
and its relation to , we
AG
0
T
can obtain a qualitative indication of
whether a particular reaction favors
products(goes strongly to completion) or
reactants(very little reaction occurs) at
equilibrium. If AG
0
T
is positive, reactants
will be favored since ln K
p
is negative,
which requires that K
p
itself is less than
unity. Similarly, if AG
0
T
is negative, the
reaction tends to favor products.
Physical insight to this behavior can be
obtained by appearing to the definition of
AG in terms of the enthalpy and entropy
changes associated with the reaction. We
can write:
0 0 0
S T H G
T
A A = A
Which can be substituted into equ. 2.66b


For K
p
to be greater than unity,which favors
products, the enthalpy change for the
reaction,AH
0
,should be negative, i.e., the
reaction is exothermic and the system
energy is lowered. Also, positive change in
entropy, which indicate greater molecular
chaos, lead to values of K
p
>1.

u u
R S T R H
P
e e K
/ /
0
A A
=
Example 2.7

Complex Systems