Ideal Gas Mixtures

1
Mole Fraction of i
th
species :
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tot
i
i
i
i
N
N
N N N
N
X =
+ + +
=

2 1
Mass Fraction of i
th
species :
tot
i
i
i
i
m
m
m m m
m
Y =
+ + +
=

2 1
2
Mole
Formally defined as the amount of substance that contains as many elementary
entities as there are in exactly 0.012 kg of Carbon 12.
Abbreviation of mole is mol 1kmol=10
3
mol.
But how many elementary entities are there?
6.0221419910
23
entities molecules or atoms;
This number is called Avogadro number (N
AV
)
Alternate definition
A mole is an Avogadro number of units of a substance
Avogadro, who?
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Ideal Gas Mixtures (contd.)
3
Relations between mole fractions and mass fractions :
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Mixture molecular weight:
i mix i i
mix i i i
MW MW Y X
MW MW X Y
/
/
=
=

=
=
i
i i
mix
i
i i mix
MW Y
MW
MW X MW
) / (
1
Pressure of Ideal Gas Mixtures
4
Partial Pressure of i
th
species :
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P X P
i i
=

=
i
i
P P
Mixture Pressure :
Daltons Model
H, U, c
p
and c
v
of Ideal Gas Mixtures
5
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= =
i
i i
i
i i
T h m T h N T H ) ( ) ( ) (
Mixture Enthalpy :
Mixture Specific Enthalpy :
) ( ) ( T h X T h
i
i i
=
) ( ) ( T h Y T h
i
i i
=
U, c
p
and c
v
exhibit similar behaviors
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Standard Enthalpy / Heat of Formation
is defined as the heat evolved when 1 mole of the
substance is formed from its elements in their respective
standard states. (i stands for the i
th
compound)

Standard-state temperature:
T
0
= 25C (298.15K)
Standard-state pressure:
P
0
= 1 atm (101,325Pa)

Elements at T
0
and P
0
are assigned

6
) (
0
0
,
T h
i f
0 ) (
0
0
,
= T h
i f
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Standard Values
7
Compound / Element (kJ/mol)
CH
4
(g) 74.81
CO(g) 110.53
CO
2
(g) 393.51
C
2
H
4
(g) +52.26
H
2
O(g) 241.82
H
2
O(l) 285.8
NO(g) +90.25
) (
0
0
,
T h
i f
) (
0
0
,
T h
i f
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8
Absolute Enthalpy,
at any state (T,P) is defined as the sum of
and the sensible enthalpy change between the standard state
(T
0
,P
0
) and the given state (T,P). (i stands for the i
th
compound)

8
) (T h
i
) ( ) ( ) (
0 , 0
0
,
T T h T h T h
i sen i f i
A + =
) (T h
i
) (
0
0
,
T h
i f
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9
Ideal GasTables (Turns P. 622)
9
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Tables (Turns P. 646)
10
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Example
Express at any state (T,P
0
) in terms of and
the enthalpy change of all elements involved in the formation
reaction.

11

=
j
j j f
T h T h T h ) ( ) ( ) (
0 ' 0
v
) (T h
) (
0
T h
f
) (
'
compound M
j
j j
v
T
T
0
Reac
Prod
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12
Example
A gas stream at 1 atm contains a mixture 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
mole-basis (kJ/kmol) and mass-basis (kJ/kg).

Also determine the mass fractions of the three components.
12
S of Ideal Gas Mixtures
13
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Mixture Entropy :
Mixture Specific Entropy :
) , ( ) , (
) , ( ) , (
i i
i
i
i i
i
i
P T s X P T s
P T s Y P T s

=
=

= =
i
i i i
i
i i i
P T s m P T s N P T S ) , ( ) , ( ) , (
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Pure Species Entropy,
14
0
0
ln ) ( ) , (
P
P
R T s P T s
i
u i i
=
) , ( P T s
i
0
0
ln ) ( ) , (
P
P
R T s P T s
i
i i
=
T
dT
c T s T s
T
T
i P i i
}
+ =
0
, 0
0 0
) ( ) (
Where,
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15
Stoichiometry
Stoichiometric mixture :
Amount of oxidizer required to completely
burn/oxidize a given amount of fuel (Ox
st
) (no dissociation)

Fuel Lean mixture :
Ox > Ox
st

Fuel Rich mixture :
Ox < Ox
st



15
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16
Hydrocarbon Stoichiometry (contd.)


Assume air is composed of 79% N
2

and 21% O
2
by volume




16
2 2 2 2 2
76 . 3 ) 2 / ( ) 76 . 3 ( aN O H y xCO N O a H C
y x
+ + + +
4 / y x a + =
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17
Air-Fuel Ratio
Stoichiometric air-fuel ratio :
17
) / (
1
76 . 4
) / ( kg kg
MW
MW a
m
m
F A
fuel
air
st
fuel
air
st
=
|
|
.
|

\
|
=
Fuel (A/F)
st
CH
4
+ air 17.11
H
2
+ O
2
8.0
C(s) + air 11.4
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18
Equivalence Ratio
18
st
st
A F
A F
F A
F A
) / (
) / (
) / (
) / (
= = u
Mixture

Stoichiometric 1
Lean

<1
Rich >1
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19
Example
A natural gas fired boiler operates with an O
2

concentration of 3% by mole (wet basis) in the flue gases.

Determine the operating air-fuel ratio and the equivalence
ratio. Treat the natural gas as methane.

Recalculate using dry basis of measurement of O
2
.

If the inlet fuel flow rate is 20 kg/s, find the flue gas flow
rate.
19
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Enthalpy or Heat of Reaction,
Steady State Steady Flow Reactor with complete combustion

Reactants and products at T
0
and P
0





20
R
H A

= = A
i
i i
i
i i R P R
h h H H H
' "
v v


i
i i
i
i i
M M
" '
v v
(KJ)
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Forms of Enthalpy of Reaction
Per unit mole of fuel : (KJ/mol of fuel)
21
R
h A
Per unit mass of fuel : (KJ/kg of fuel)
fuel R R
MW h h / A = A
Per unit mass of mixture : (KJ/kg of
mixture)
1 ) / ( +
A
= A
F A
h
m
m
h
R
mix
fuel
R
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22
Enthalpy of Reaction for CH
4
Per unit mole of fuel : (KJ/mol of fuel)
22
405 , 802 = A
R
h
Per unit mass of fuel : (KJ/kg of fuel) 016 , 50 = A
R
h
Per unit mass of mixture : (KJ/kg of
mixture)
8 . 2761 = A
R
h
kJ H
R
405 , 802 = A
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23
Heat of Combustion,
Upper / Higher Heating Value (HHV): Heat of combustion
calculated assuming all water in product stream has been
condensed to liquid
23
R C
H H A = A
C
H A
Lower Heating Value (LHV) : Heat of combustion calculated
assuming all water in product stream is in gaseous form
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Tables (Turns P. 649)
24
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Example
Express the heat of reaction at any state (T,P
0
) in
terms of the standard enthalpy of formation and the specific
heats at constant pressure of the reactants and products.
25

}
|
.
|

\
|
+
|
.
|

\
|
+ = A
i
T
T
i p i f i
i
T
T
i p i f i R
dT c T h dT c T h T h
0 0
, 0
0
,
'
, 0
0
,
"
) ( ) ( ) ( v v
) (T h
R
A
T
T
0
Reac
Prod


i
i i
i
i i
M M
" '
v v
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26
Example
Determine the HHV and the LHV at 298 K of n-decane (gas)
(C
10
H
22
) (MW = 142.284 kg/kmol)
per kmol of fuel.
per kg of fuel.

Recalculate for n-decane (liquid). (h
fg
= 359 kJ/kg
fuel
at 298 K)
26
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27
Adiabatic Flame Temperature,
Adiabatic Flame Temperature for P = Constant : Temperature of
the products after complete adiabatic combustion of a fuel-air
mixture at constant pressure
27
ad
T
Reac to
Prod
) , ( ) , ( P T H P T H
ad prod i reac
=
Gas turbine combustor
Diesel engine
Furnace
Also called the Adiabatic Frozen Flame Temperature
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28
Adiabatic Flame Temperature,
Adiabatic Flame Temperature for V = Constant : Temperature of
the products after complete adiabatic combustion of a fuel-air
mixture at constant volume
28
ad
T
Reac to
Prod
) , ( ) , (
f ad prod i i reac
P T U P T U =
Bomb calorimeter
Gasoline engine
0 ) ( ) , ( ) , ( =
ad prod i reac u f ad prod i i reac
T N T N R P T H P T H
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29
Example
Estimate the constant pressure adiabatic flame
temperature for the combustion of a stoichiometric methane-
air mixture. The pressure is 1 atm and the initial reactant
temperature is 298 K. Use the following assumptions
Complete combustion
Use constant specific heats at 1200 K for evaluating
the product enthalpies
Recalculate using variable specific heats
Recalculate using tables from Appendix A
29
http://www.youtube.com/watch?v=tvvuUILhHUo
http://www.youtube.com/watch?v=65KIexy4New
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30
Example
Estimate the constant volume adiabatic flame
temperature for the combustion of a stoichiometric methane-
air mixture. The pressure is 1 atm and the initial reactant
temperature is 298 K.
Also calculate the final pressure.

Use the following assumptions
Complete combustion
Use constant specific heats at 1200 K for evaluating
the product enthalpies
Recalculate using variable specific heats
Recalculate using tables from Appendix A
30
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31
Example
Calculate the constant pressure adiabatic flame temperature
of water vapor based on the reaction of gaseous H
2
and O
2
.

Recalculate the same starting with liquid H
2
at -255C and
liquid O
2
at -225C (cryogenic combustion). Boiling point of
liquid O
2
is 182.96 C and that of liquid H
2
is 252.87 C.
31
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Dissociation of Species
Unknowns :


32
2 2 2 2 2 2 4
2 2 2 2
) 76 . 3 ( O n N n O H n CO n N O a CH
O N O H CO
+ + + + +
No dissociation (Low flame temperature) :
ad O N O H CO
T n n n n , , , ,
2 2 2 2
+ + + + + +
+ + + + + +
O n N n OH n NO n CO n
O n N n O H n CO n N O a CH
O N OH NO CO
O N O H CO 2 2 2 2 2 2 4
2 2 2 2
) 76 . 3 (
Dissociation (High Flame temperature):
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33
Equilibrium Reactions
33
OH H O H +
2 2
2
1
OH H O H +
2
2 2
2
1
O CO CO +
2 2
2 O N NO +
H H 2
2

O O 2
2

N N 2
2

GRI-Mech 3.0 : Methane-air
reaction mechanism with
53 species and 325 reactions.
http://www.me.berkeley.edu/gri_mech/
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34
Condition for Equilibrium
34
Since most combustion systems are in equilibrium at a
particular pressure and temperature, the general criterion is :
( ) 0 , = P T dG
where,
( ) ) , ( ) ( , P T TS T H P T G =
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35
Free Energy
35
( ) ( )
0
0
ln ,
P
P
T NR T G P T G
u
+ =
( ) ( )
0
0
ln ,
P
P
T R T g P T g
u
+ =

=
elements j
j j f
T g T g T g ) ( ) ( ) (
0 ' 0 0
v
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36
Derivation of (Equilibrium Constant)
36
P
K
dD cC bB aA + +
Consider the following simplified reaction at P
0
and T
G of the mixture of A,B,C, and D:
( ) ( )

+ =
i
i
u i i
P
P
T R T g N P T G
0
0
ln ,
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37
Derivation of (contd.)
37
P
K
Differentiating :
( ) ( )
( )

+
+
(

+ =
i
i
u i i
i
i
u i i
P
P
T R T g d N
P
P
T R T g dN P T dG
0
0
0
0
ln
ln ,
At equilibrium: ( ) 0 , = P T dG
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38
Derivation of (contd.)
38
P
K
( )

= +
i
i
i
u
i
i i
dN
P
P
T R dN T g 0 ln
0
0
Since dN
i
is proportional to the stoichiometric coefficients:
P u
K T R T G ln ) (
0
= A
|
|
.
|

\
|
A
=
T R
T G
K
u
P
) (
exp
0
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39 39
( ) ( )
( ) ( )
b
B
a
A
d
D
c
C
P
P P P P
P P P P
K
0 0
0 0
=
P
K
Alternatively for a general reaction,


i
i s i
i
i s i
M M
"
,
'
,
v v
Where:
( )
( )
[

=
i
i P
s i s i
P P K
'
,
"
,
0
v v
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40 40
) (
0
T G A
G
0
(T) is defined as the Standard state Gibbs Energy Change,
( )
( ) ( ) ( ) ( )
) ( ) (
) (
0
Reac
0
od Pr
0 0 0 0
0 0
T G T G
T g d T g c T g b T g a
dN T g T G
D C B A
i
i i
=
+ + =
A

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41 41
Alternatively for a general reaction,

= A
i
i f s i
i
i f s i
T g T g T G ) ( ) ( ) (
0
,
'
,
0
,
"
,
0
v v
Where is defined as the Gibbs Free Energy of Formation of
the i
th
compound, listed in Appendix A.
) (
0
,
T g
i f
) (
0
T G A


i
i s i
i
i s i
M M
"
,
'
,
v v
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42
Observations about
P in K
P
signifies that the equilibrium constant is written in
terms of partial pressures.

Other quantities that may be used to define K are
concentration, C
i
Number of moles, N
i
Mole fraction, X
i


For a positive value of G
0
, K
P
is a fraction, thus reactants would
be favored at equilibrium

For a negative value of G
0
, K
P
is greater than unity, thus
products would be favored at equilibrium
42
P
K
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43
Example
The decomposition of gaseous hydrogen peroxide occurs
according to the reaction



Calculate the value of the equilibrium constant of this reaction
at T
0
.
(Free energy of formation of H
2
O
2
= -25.2 kcal/mol;
Free energy of formation of H
2
O = -54.63 kcal/mol)
43
) (
2
1
) ( ) (
2 2 2 2
g O g O H g O H +
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44
Example
Consider the dissociation of CO
2
as a function of P and T.



State the necessary relations required to derive the
composition of the mixture that results from subjecting
originally pure CO
2
to T
1
and P
1
.
44
) (
2
1
) ( ) (
2 2
g O g CO g CO +
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45
Example
Consider the combustion of methane under fuel-rich conditions.


Assume that the following water-gas equilibrium reaction occurs
within the product species.


Namely, a portion of the combustion product undergoes a further
reaction. The equilibrium mixture may be assumed to consist of


Write the necessary mathematical relationships required for
solving the equilibrium composition and the adiabatic flame
temperature.
45
O H CO O CH
2 2 4
2
2
3
+ +
2 2 2
H CO O H CO + +
2 2 2
) 2 ( ) 1 ( xH xCO O H x CO x + + +
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46
Propane-Air Combustion (Turns P. 46)
46
CO
2
, CO,
H
2
O, H
2
, H,
OH, O
2
, O,
NO, N
2
, and
N
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47
Propane-Air Combustion (Turns P. 47)
47
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48
NASA CEA Code
Equilibrium compositions are important in various systems

Gas turbines

Aircraft combustors

Rocket motors

Shock tubes

Automobile engines

Nozzles and diffusers

Gun propulsion systems 48
Chemical Equilibrium with
Applications (CEA) :
Developed at NASA Lewis
(Glenn) Research Centre by
Gordon, McBride, Zeleznik,
and Svehla
http://www.grc.nasa.gov/WWW/C
EAWeb/ceaguiDownload-win.htm
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49
NASA CEA Code Problems Handled
Equilibrium compositions of assigned thermodynamic
states

Theoretical rocket performance

Chapman Jouguet detonations

Shock-tube parameter calculations for both incident and
reflected shocks
49
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NASA CEA Code Problems Handled
Equilibrium compositions of assigned thermodynamic states
Temperature and Pressure

Enthalpy and Pressure - Constant Pressure Combustion

Entropy and Pressure

Temperature and Volume or Density

Internal Energy and Volume - Constant Volume
Combustion

Entropy and Volume
50
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CEA Input
51
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CEA Input (contd.)
52
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CEA Input (contd.)
53
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CEA Input (contd.)
54
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CEA Output
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CEA Output for = 0.6
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CEA Output for = 0.6 (Contd.)
57
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CEA Output for = 1.05
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CEA Output for = 1.05 (Contd.)
59