1

Stoichiometry, Energy Balances, Heat Transfer,
Chemical Equilibrium, and Adiabatic Flame
Temperatures
Geof Silcox
geoff@che.utah.edu
(801)581-8820
University of Utah
Chemical Engineering
Salt Lake City, Utah
May 2007
Stoichiometry
2
STOICHIOMETRY
• Outline
– combustion reactions
– combustion with air
– equivalence ratio, stoichiometric ratio
– percent theoretical air, percent excess air
– percent excess oxygen in stack gases
– dry and wet basis for concentrations
– actual and theoretical concentrations
– the effects of mixing and in leakage
STOICHIOMETRY
• Combustion reactions
4 2 2 2
2 2
2 2 2
2 2
1
2
1
2
CH O CO H O
CO O CO
H O H O
+ → +
+ →
+ →
In general
2 2
2 2
4 2
nC nO nCO
m m
mH O H O
+ →
+ →
or
2 2 2
4 2
n m
m m
C H n O nCO H O
⎛ ⎞
+ + → +
⎜ ⎟
⎝ ⎠
3
STOICHIOMETRY
• Combustion with air
Assume air is 21% O
2
and 79% N
2
, by volume.
Then each mole O
2
brings with it 3.76 mole N
2
.
2 2
2 2 2
3.76
4 4
3.76
2 4
n m
m m
C H n O n N
m m
nCO H O n N
⎛ ⎞ ⎛ ⎞
+ + + + →
⎜ ⎟ ⎜ ⎟
⎝ ⎠ ⎝ ⎠
⎛ ⎞
+ + +
⎜ ⎟
⎝ ⎠
STOICHIOMETRY
• Equivalence ratio
• Stoichiometric ratio
1
SR =
Φ
mols fuel
mols oxidant
supplied by operator
mols fuel
mols oxidant
reqd for complete combustion
⎡ ⎤
⎢ ⎥
⎣ ⎦
⎡ ⎤
⎢ ⎥
⎣ ⎦
Φ =
SR =1/Φ =1 means that conditions are
stoichiometric or chemically balanced.
4
STOICHIOMETRY
• Φ and SR
– Fuel rich (reducing):
– Fuel lean (oxidizing):
– Alternate forms w/ constant amount of fuel
1 1 SR and < Φ >
1 1 SR and > Φ <
mols oxidant reqd

mols oxidant fed
Φ =
mols oxidant fed
SR
mols oxidant reqd
=
STOICHIOMETRY
• Percent theoretical air
• Percent excess air
( )
100
%TA 100 SR = =
Φ
( )
1
%EA %TA 100 100 SR 1 100 1
⎡ ⎤
= − = − = −
⎢ ⎥
Φ
⎣ ⎦
5
STOICHIOMETRY
• Percent excess oxygen in stack gases
– Defined as actual mole (volume) percent in
stack. Not to be confused with %EA or
%TA.
– Can be measured on a dry or wet basis.
• Dry or wet basis for stack measurement
– Dry basis gives higher value because
water vapor acts as a diluent and is 10 –
15% of stack gases
STOICHIOMETRY
• Actual and theoretical concentrations
0
0.02
0.04
0.06
0.08
0.1
0.12
0.14
0.16
0.18
0.2
0.8 1 1.2 1.4 1.6 1.8 2
SR
F
l
u
e

g
a
s

m
o
l
e

f
r
a
c
t
i
o
n
s
,

d
r
y

b
a
s
i
s
CO
2
theoretical
O
2
theoretical CO theoretical
effects of
imperfect mixing
effects of air
leakage
6
STOICHIOMETRY
• Controlling excess air
1.0 1.1 1.2
50
100
Stoichiometric ratio
p
p
m
C
O
The rise in CO is steep
as you approach SR =1
and it is insensitive to
air leakage. Air flow
control by CO should
lead to a close approach
to SR =1.
STOICHIOMETRY
• Spreadsheets for furnace material
balance calculations
– FURN_MB.xls: balance for liquid and solid
fuels
– GAS_MB.xls: balance for gaseous fuels
•Author: J ost Wendt
7
ENERGY BALANCES
ENERGY BALANCES
• Outline
– Conservation of mass and energy
– Example: drying salt with hot flue gas
– Energy balances on systems that involve
reactions - the absolute enthalpy
– Example: adiabatic combustion of H
2
in air
– Heats of combustion and higher and lower heating
values
– Energy balance on a furnace – available heat and
the efficiency of combustion
8
ENERGY BALANCES
• Energy and mass are conserved
out in
CV
m m
dt
dm

− =
gz
2
1
u e
2
+ + = V
2 2
, , 1 2
1 2
V V
2 2
CV
in net in net
dE
Q W m h gz m h gz
dt
⎛ ⎞ ⎛ ⎞
= + + + + − + +
⎜ ⎟ ⎜ ⎟
⎝ ⎠ ⎝ ⎠


h =u +pv
Control
volume
or system
Mass
entering (1)
Mass
leaving (2)
Q

W

ENERGY BALANCES
• Changes in kinetic and potential energy
are usually small compared to changes
in internal energy
, , 1 1 2 2
CV
in net in net
dU
Q W m h m h
dt
= + + −


, , 1 1 2 2
0
in net in net
Q W m h m h + + − =


Unsteady
Steady
9
ENERGY BALANCES
• Drying salt with combustion gases
Flue gas at 1000°F to be used to dry 40 tons/h salt
that is 3 wt. % water. The inlet temperature of the
salt is 40°F. The dry salt exits the dryer at
190-210°F. What flow rate of flue gas do we need
if we assume the flue gas leaves the dryer at 400°F?
ENERGY BALANCES
• Drying salt with combustion gases
Dryer
1
2
3
4
5
6
1
? m =

flue gas, 1000°F
dry salt, 40°F
77,600 lb/h
H
2
O(l), 40°F
2400 lb/h
1 4
m m =

flue gas, 400°F
dry salt, 200°F
77,600 lb/h
H
2
O(g), 400°F
2400 lb/h
1 4
m m =

3 6
m m =

2 5
m m =

10
ENERGY BALANCES
• Drying salt with combustion gases
– energy balance over adiabatic dryer
( ) ( ) ( )
1 1 4 2 2 5 3 3 6
0 m h h m h h m h h − + − + − =

( ) ( )
2 5 2 3 6 3
1
1 4
m h h m h h
m
h h
− + −
=

Dryer
1
2
3
4
5
6
1
? m =

flue gas, 1000°F
dry salt, 40°F
77,600 lb/h
H
2
O(l), 40°F
2400 lb/h
1 4
m m =

flue gas, 400°F
dry salt, 200°F
77,600 lb/h
H
2
O(g), 400°F
2400 lb/h
ENERGY BALANCES
• Drying salt with combustion gases
– energy balance over adiabatic dryer
( ) ( ) ( )
( )
2 5 2 3 2 ( ) 5 3 2 ( ) 6 5
1
1 4
salt H O l fg pH O g
pgas
m c T T m c T T h c T T
m
c T T
⎡ ⎤ − + − + + −
⎣ ⎦
=

2 ( )
2 1
978 0.254
0.21 0.47
1.0 36,500
fg pgas
salt pH O g
H O
Btu Btu
h c
lb lb F
Btu Btu
c c
lb F lb F
Btu lb
c m
lb F h
= =
°
= =
° °
= =
°

11
ENERGY BALANCES
• Energy balances on reacting systems –
the absolute enthalpy
, ,
( ) ( )
ref
T
o
i f i ref p i
T
h T h T c dT = +

Absolute
enthalpy
Enthalpy
of formation
at 1 bar, 298 K
Sensible
enthalpy
change
The reference state for systems in which
reactions are occurring is conveniently chosen
to be the elements at T
ref
= 25 C (298.15 K) and 1 bar.
ENERGY BALANCES
• Heat capacity as a function of T (K)
, ,
( ) ( )
ref
T
o
i f i ref p i
T
h T h T c dT = +

2 3 4
1 2 3 4 5
2 3 4 3 5 6 2 4
1
2 3 4 5
p
c
a a T a T a T a T
R
a a a a a h
a T T T T
RT T
= + + + +
= + + + + +
where T is in Kelvin and R is the universal gas
constant, R =8.3145 kJ /(kmol K).
Spreadsheet: ther_coef.xls
12
ENERGY BALANCES
• Adiabatic combustion of H
2
with air, no
dissociation. What is exit temperature?
Control
volume
Inlet (i)
0.42 kmol/s H
2
0.21 kmol/s O
2
0.79 kmol/s N
2
300 K, 1 bar
Exit (e)
0.42 kmol/s H
2
O
0.79 kmol/s N
2
T =?, 1 bar
0
in
Q =

0
in
W =

, ,
0
in net in net i i e e
i e
Q W n h n h + + − =
∑ ∑


Spreadsheet: h2_flame.xls
ENERGY BALANCES
• Adiabatic combustion of H
2
0
i i e e
i e
n h n h − =
∑ ∑

, ,
( ) ( )
ref
T
o
i f i ref p i
T
h T h T c dT = +

We have one equation in one unknown, T. This is
conveniently solved in Excel with the Goal Seek tool
to give an exit temperature of 2530K. If we allow for
dissociation of the water (at equilibrium), T
e
=2390K.
Spreadsheet: h2_flame.xls
13
ENERGY BALANCES
• Heats (enthalpies) of combustion and
higher (gross) and lower (net) heating
values (HHV and LHV)
[ ]
298
rxn p fp r fr
prod react
h h h ν ν ⎡ ⎤ ∆ = −
⎣ ⎦
∑ ∑
4 2 2 2
2 2 ( ) CH O CO H O liq + → +
298
4
298
2
298
2
298
2
298
2
74.600
0
393.510
( ) 285.830
( ) 241.826
f
f
f
f
f
kJ
CH h
mol
O h
CO h
H O l h
H O g h
= −
=
= −
= −
= −
4 2 2 2
2 2 ( ) CH O CO H O gas + → +
ENERGY BALANCES
• Heats of reaction and HHV and LHV
4 2 2 2
2 2 ( ) CH O CO H O liq + → +
( )
( )
298
4
( ) 393.51 2 285.83
74.6 0 890.57 /
rxn
h l
kJ mol CH
∆ = − + − −
⎡ ⎤ − + = −
⎣ ⎦
4 2 2 2
2 2 ( ) CH O CO H O gas + → +
( )
( )
298
4
( ) 393.51 2 241.826
74.6 0 802.56 /
rxn
h g
kJ mol CH
∆ = − + − −
⎡ ⎤ − + = −
⎣ ⎦
298
4
( )
890.57 /
rxn
HHV h l
kJ mol CH
= −∆ =
298
4
( )
802.56 /
rxn
LHV h g
kJ mol CH
= −∆ =
Gross heating value
Net heating value
14
ENERGY BALANCES
• Energy balance over a furnace
Control
volume
Inlet (i) Exit (e)
in
Q

0
in
W =

,
0
in net i i e e
i e
Q n h n h + − =
∑ ∑

Use absolute
enthalpies for
energy balances
involving reactions.
, ,
( ) ( )
ref
T
o
i f i ref p i
T
h T h T c dT = +

T
ref
=298.15 K
ENERGY BALANCES
• Energy balance over a furnace –
available heat
, , , ,
( ) ( )
e i
ref ref
T T
o o
avail i f i ref p i e f e ref p e
i e
T T
Q n h T c dT n h T c dT
⎛ ⎞ ⎛ ⎞
= + − + ⎜ ⎟ ⎜ ⎟
⎜ ⎟ ⎜ ⎟
⎝ ⎠ ⎝ ⎠
∑ ∑
∫ ∫

Available heat =gross heat input
– latent heat loss
– unburned fuel loss
– sensible flue gas heat loss
Available heat =net heat input
– unburned fuel loss
– sensible flue gas heat loss
15
ENERGY BALANCES
• Thermal efficiency of a combustion
process
– Definition in terms of HHV
– Definition in terms of LLV
( )
avail
gross
fuel
Q
m HHV
η =

( )
avail
net
fuel
Q
m LHV
η =