Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
University of Birmingham
Efficient Heat Engines and Heat Pumps.
Combustion, Section 1.2: First Law Analysis of Combustion, Thermochemistry
Combustion Thermodynamics
1.2. First Law Analysis of Combustion, Thermochemistry
Contents:
1.2.1 First Law Analysis of Combustion, Reference Conditions
1.2.2 Combustion at Constant Volume
1.2.3 Combustion at Constant Pressure
1.2.4 Enthalpy vs. Internal Energy of Reactions
1.2.5 NB: Use of enthalpy / int. energy vs. specific heats
1.2.6 Lower and Higher Calorific Values of Fuels,
1.2.7 Worked Examples ‐ Heat Released During Combustion
1.2.8 Summary
Aims:
• To present the application of the 1st Law (Energy Conservation) to a thermodynamic analysis of
combustion at constant volume and at constant pressure.
• To teach the calculation of heat released during combustion reactions with defined initial and
final states, including gaseous and liquid phases for both the reactants and products.
Objectives:
At the end of this section students should be able to:
1) Use the enthalpy ‐ temperature diagram to illustrate the hypothetical path of combustion
process where the reaction takes place at a standard state.
2) Calculate for simple cases the heat released during combustion reactions with defined initial and
final states, including the use of lower and higher calorific values of typical fuels.
Reading:
i) either: Eastop TD and McConkey A.: Applied Thermodynamics for Engineering Technologists,
Longmans Scientific and Technical, 1993, ISBN: 0‐582‐09193‐4, Edition: 5, Classmark: TJ265.E:
Section 7.8 Internal energy and enthalpy of reaction (except Ex. 7.16), 7.10 Calorific value of
fuels (pp 208‐221), optional: Sections 7.11‐7.13 (pp. 221‐230) ,
ii) or: Cengel YA and Boles MA: Thermodynamics, An Engineering Approach, McGraw Hill, 1994,
ISBN: 0‐07‐113249‐X, Edition: 2, Classmark: TJ265.C:
Section 14‐3 Enthalpy of combustion, 14‐4 First Law Analysis of reacting systems (pp. 742‐751),
iii) or: corresponding sections in practically any other text on engineering thermodynamics (very
few do not deal with thermochemistry of combustion)
Page 1 of 13
School of Mechanical Engineering October 09, 2009
University of Birmingham
Efficient Heat Engines and Heat Pumps.
Combustion, Section 1.2: First Law Analysis of Combustion, Thermochemistry
1.2.1 First Law Analysis of Combustion
Combustion (oxidation of fuels with oxygen)
is an exothermic reaction.
Internal energy (also enthalpy) of products of exothermic reactions
is (at the same temperature) lower than that of reactants.
This difference of internal energy or enthalpy is referred to, in common terms, as “heat
liberation”, or “heat release” during combustion.
1st Law of Thermodynamics for a system of constant mass:
U
Q
U
Q
W
o
r
s
e
D = + D = -
where U = internal energy of a system (kJ)
Q s = heat supplied to the system (kJ)
W s = work supplied to the system (kJ)
W e = work extracted from the system (kJ)
NB. notice that in the
“heat engine” sign convention:
work W e extracted from the system is regarded as (+) ve (useful)
First Law:
U
Q
U
Q
W
o
r
s
D = + D = -
Because ∆U < 0 for an exothermic reaction:
(i) when W = 0 (in extreme) ,
e.g. in constant volume combustion heat supplied Q s < 0
(heat can be extracted from the system)
(ii) when Q = 0 (no heat transfer), and U < 0
(W e > 0)
work can be extracted from a system
(iii) when both Q = 0 (no heat transfer) and W = 0
products of combustion have to end up at higher temperature to have the same
internal energy as the original reactants.
As a result the pressure of a gaseous system will have to increase, especially as the
number of moles of products is usually larger than that of reactants.
The analysis of changes of internal energy during combustion is essential.
Because for any thermodynamic system, internal energy U is a property of state
(although heat and work are not):
1st Law can also be stated as:
“Change in internal energy does not depend on the path of the process, only on the initial
and final states.”
(but proportions of heat and work will depend on the path chosen).
This statement of the First Law will be used to simplify and standardise the analysis of
changes of internal energy during combustion, and thus the quantity of heat exchanged or
the final temperatures and pressures in combustion.
Page 2 of 13
School of Mechanical Engineering October 09, 2009
University of Birmingham
Efficient Heat Engines and Heat Pumps.
Combustion, Section 1.2: First Law Analysis of Combustion, Thermochemistry
In general a combustion process may start with reactants at U1, volume V1, temperature
T1, and end with products at U2, V2, T2.
This process can be regarded as three successive processes:
REACTANTS PRODUCTS
change of state change of state
from "1" to "0" from "0" to "2"
U R,1 U R,0 U P,0 U P,2
always
V R,1 V R,0 analysed V P,0 V P,2
at T0
T1 T0 T0 T2
COMBUSTION
at T 0
U
U
P
R
,
2
,
1
D = -
U
=( )+( )+( )
R
P
,
0
, 1
,
0
,
0
,
2
,
0
- - -
U0
U1
U0
U2
U0
= å ( - ) + å (D ) + å ( - )
R
P
a
lt
l
a
lt
l
a
l
lu
r
e
a
cR
a
n
t
s
r
e
a
c
i
o
n
s
p
r
o
dP
c
t
s
Benefits of this approach:
(i) All changes of internal energy due to chemical reaction can be analysed at a convenient
reference temperature T0.
This reference temperature is usually taken as +25OC (298.15 K).
Having one reference temperature greatly simplifies tabulation of thermo‐chemical data for
various reactions.
(ii) Changes of internal energy of reactants and products can be analysed as for mixtures of
constant composition.
Page 3 of 13
School of Mechanical Engineering October 09, 2009
University of Birmingham
Efficient Heat Engines and Heat Pumps.
Combustion, Section 1.2: First Law Analysis of Combustion, Thermochemistry
1.2.2. Combustion at Constant Volume
Combustion at constant volume happens in a closed system.
Typical application might be in a cylinder of a reciprocating piston engine, where for a long
period during the crankshaft revolution the piston is near the top dead centre and its
vertical movement is minimal. The corresponding changes of volume of the combustion
chamber are very small compared to the expansion stroke.
In the theoretical standard air Otto cycle this corresponds to heat addition at constant
volume.
For combustion at constant volume dV = 0, and
W = p dV = 0
From First Law:
U U
Q Q
W
,
f
o
r
0
s
D = ( - ) =
s
D =
U0
0
P
R
,
0
,
0
for an exothermic combustion reaction, when : D = - <
Heat supplied is (–) ve, Heat extracted can be (+) ve.
This is best illustrated on a U vs. T diagram, where the whole path involving reaction at a
reference temperature is also shown.
U (V = const.)
reactants products
R1
Qe
P0 V = const. V = const.
(Qe = 0
reactants for adiabatic products
T process) Pstate 2
T0 T1 T2 R state 1
Combustion at constant volume can be performed in a rigid calorimeter (combustion bomb) with
varying degrees of insulation:
Page 4 of 13
School of Mechanical Engineering October 09, 2009
University of Birmingham
Efficient Heat Engines and Heat Pumps.
Combustion, Section 1.2: First Law Analysis of Combustion, Thermochemistry
1.2.3. Combustion at Constant Pressure
Combustion at constant pressure p = const. can be realised either in a closed or an open
system.
(i) Closed systems:
Typical application (at least theoretically) might be when combustion is happening over a
prolonged period in a cylinder of a piston engine. The vertical movement of the piston, and
the corresponding changes in cylinder volume are large and the process is slow enough not
to raise the pressure.
In the theoretical standard air Diesel cycle this corresponds to heat addition at constant
pressure.
N.B. In real Diesel engines, however, pressure in the cylinder during the
combustion varies a lot.
Applying the 1st Law:
U
Q
U
W
o
r
s
D = - =D +
W e is no longer zero,
but is the displacement work for constant pressure:
W e = p ∆V = ∆ (pV )
Thus
Q
p
V
U
p
V
H
s
=D + D( ) =D ( + )= D = -
(ii) Open systems:
Combustion at p = const. is also the case in burners of gas turbines, furnaces, boilers etc.,
where it occurs in a flow process.
This involves flow work, thus enthalpy changes must be considered rather than changes of
internal energy.
For an open system, the Steady Flow Energy Equation (SFEE) can be written,
using C for velocity (to avoid confusion with volume):
1 2
1 2
Q
m
h2
h1
m
C2
C1
m
g
z2
z1
J
s
- = ( - )+ ( - )+ ( - ) [ ]
Thermal effects of combustion at constant pressure can be found by measuring the
quantity of heat rejected during a steady‐flow combustion process in which reactants and
products are both at T0.
A constant pressure flow calorimeter is normally employed. There is no extracted work W e
= 0, the change in kinetic and potential energy is negligible, and the effects are measured
at p = const, T0 = const.
SFEE reduces to:
Q0
m
h
H0
m
h0
s
( )=
P
R
,
0
, 0
, 0
, 0
= - - =D = D
This value of ∆h0 [kJ/kg] is usually quoted for a given fuel at a reference temperature of
298.15K (25oC).
It does not depend on how much non‐reacting material is present (e.g. nitrogen, also
surplus oxygen), as all the products are brought back to the initial temperature.
∆h0 has a negative value for exothermic reactions, because enthalpy of products is lower
than enthalpy of reactants.
Thus heat supplied to the system Q0s is (–) ve,
and heat extracted Q0e can be (+) ve.
Page 5 of 13
School of Mechanical Engineering October 09, 2009
University of Birmingham
Efficient Heat Engines and Heat Pumps.
Combustion, Section 1.2: First Law Analysis of Combustion, Thermochemistry
The route usually followed in calculations is to use the available standard data on enthalpy
of combustion at the reference temperature, ∆h0:
1. Bring the reactants at constant composition to T0 (298.15K), calculating their change of
enthalpy,
2. Calculate the change of enthalpy in a reaction at 298.15K,
3. Bring the products at constant composition to the final temperature and calculate their
change of enthalpy, or find the final temperature of products from the known quantity of
enthalpy removed from the system.
This procedure applies whether the initial temperature is below or above the reference
temperature for the reaction, as illustrated:
H p = const.
reactants
R0 products
R1
H0
H=(H2–H1) Qe = –Qs = –H
P2
P0
T1 T0 T2 T
1.2.4. Enthalpy vs. Internal Energy of Reactions
Data for combustion of fuels at p = const. is of great interest in gas turbines, furnaces,
boilers, etc. For this reason enthalpy of combustion ∆h0 is usually tabulated instead of
internal energy of combustion ∆u0.
The difference between the two values of ∆h0 specified for either gaseous or liquid
products is (for hydrocarbon fuels) much bigger (as explained in the next section) than
the difference between ∆h0 and ∆u0.
Nevertheless, it may be important to be able to calculate the other quantity: if one of the
∆h0, ∆u0 is known.
H0
H U
H p p
P
R
,
0
, 0
D = -
VP V
U pR
pR
VR
=( )-( )
P
R
, 0
,0
,
0
,
0 V
,
0
,
0
+ +
U0
+( )
P
R
,
0
,
0
,
0
,
0
=D -
but: for ideal gases pV = nRuT0
n is the number of kmoles,
Ru is the universal gas constant (8314 J/kmolK)
(for solids and liquids , ∆pV is negligible compared with ∆U0)
Therefore :
Page 6 of 13
School of Mechanical Engineering October 09, 2009
University of Birmingham
Efficient Heat Engines and Heat Pumps.
Combustion, Section 1.2: First Law Analysis of Combustion, Thermochemistry
H0
U0
Ru
T0
nP
nR
D =D + ( - )
nP and nR refer to the number of kmoles of gaseous reactants and products
corresponding to the quantity of fuel considered for ∆H0
when ∆h0 is used,
nP and nR correspond to one kmol or kg of fuel
1.2.5. NB: Use of enthalpy / internal energy data vs. specific heats
When calculating HP2 – HP0 or UP2 – UP0, the true value is much easier to calculate
using directly the values of ui or hi for the individual constituents of the mixture, given in
thermodynamic tables for different temperatures or as a polynomial function of
temperature, rather than specific heats.
Otherwise, one needs a mean specific heat values for each constituent over the
temperature range T2 – T0.
This is usually taken as cp or cv at (T2 + T0)/2.
Because cp and cv do not vary linearly with temperature, an additional error is introduced.
This applies also (to lesser extent) to calculations for the reactants, although the temperature
range involved is usually much smaller.
Page 7 of 13
School of Mechanical Engineering October 09, 2009
University of Birmingham
Efficient Heat Engines and Heat Pumps.
Combustion, Section 1.2: First Law Analysis of Combustion, Thermochemistry
1.2.6. Lower and Higher Calorific Values of Fuels
Reactants and products may be in liquid or gaseous form.
Enthalpy of liquid constituents is lower than that of gaseous constituents at the same
temperature. The difference is the enthalpy of evaporation.
When quoting ∆h0 (or ∆u0) for a particular reaction it is necessary to specify phases of
reactants and products.
In practical terms, when liquid fuel is introduced to the combustion chamber, enthalpy (or
internal energy) of evaporation of fuel has to be supplied by the air/fuel mixture, thus its
temperature is reduced (cooling effect of evaporation).
Also condensation of products might have a significant effect on the calorific value of fuel.
re t.
c
t.
ea
ac
p = const.
.
H
pr rod
liq s r
ou
.
ui
od
se
s
ou
ga
se
d
ga
ui
R1,G
liq
H
0 P2,L
P0
T
T0 T1 T2
If the fuel contains hydrogen, there will be H2O in the products. Because of the high
enthalpy of evaporation (condensation) of water, it is essential to specify whether H2O
remains in vapour or is in liquid phase at the end of process.
When water remains in products as a vapour, enthalpy of condensation is not released,
and the overall thermal effect of combustion of fuel is smaller.
Engineers call this value the Lower Calorific Value (LCV) of fuels.
This is typically the value used for fuel in internal combustion engines, where exhaust gases
are hotter than 100oC.
When water in products condenses out to a liquid, enthalpy of condensation is released
and can be utilised, the overall thermal effect of combustion is larger. This can be utilised in
some modern condensing boilers, where flue gases are cooled to below 100oC.
Engineers call this value the Higher Calorific Value (HCV) of fuels.
For methane CH4 (95% of North Sea natural gas is methane) HCV is 11% higher than LCV.
It is still about 8% higher for a typical gasoline, which has a smaller proportion of hydrogen
atoms.
Instead of ∆u0 and ∆h0, engineers prefer to use Calorific Values of Fuels ‐ defined in terms
of the number of heat units released when fuel is burnt in a calorimeter under specified
conditions.
Page 8 of 13
School of Mechanical Engineering October 09, 2009
University of Birmingham
Efficient Heat Engines and Heat Pumps.
Combustion, Section 1.2: First Law Analysis of Combustion, Thermochemistry
Because the quantity of heat is involved, the process must be clearly specified ‐ heat is not
a thermodynamic property.
The British Standard BS 526:1961 defines four calorific values.
GROSS (HIGHER) CV at V = const.
Q
u2
w
i
t
h
H
O
a
s
l
i
q
u
i
d
(@ D
g
r
,
)
V
2
NET (LOWER) CV at V = const
Q
u2
w
i
t
h
H
O
a
s
v
a
p
o
u
r
(@ D )
n
e
t
,
V
2
GROSS (HIGHER) CV at p = const
Q
h2
w
i
t
h
H
O
a
s
l
i
q
u
i
d
(@ D )
g
r
,
p
2
NET (LOWER) CV at p = const
Q
h2
w
i
t
h
H
O
a
s
v
a
p
o
u
r
(@ D )
n
e
t
,
p
2
p = const. reactants
H
R 1= R 0
products
QeH 2-1
H
0
P2
P0
T1 =T T2 T
0
Heat released is the difference between the total enthalpy of reactants and products (or the
negative of ∆H2-1), as seen on the H-T diagram. In this case, reactants are supplied at
standard (reference) conditions.
∆H0 = number of kmoles of n-octane x enthalpy of combustion of n-octane in standard conditions ∆hc
(kJ/kmol) for H2O (g). Values for liquid or gaseous n-octane should be used. It is much easier to use
the molar specific enthalpy values and convert to kJ/kg n-octane at the end.
Page 9 of 13
School of Mechanical Engineering October 09, 2009
University of Birmingham
Efficient Heat Engines and Heat Pumps.
Combustion, Section 1.2: First Law Analysis of Combustion, Thermochemistry
é ù
Q
=
-
H
=
-
H
-2
H
H
-0
H1
ê ú
2 ê( ) +( ) ú
-
1
0
D +D
P
,
G
R
ê ú
0
êë = úû
é ù
=
-
ni
hi
-
hi
hc
0
ê ú
êå ( )+
,
8
0
0
K
,
2
9
8
K
C
8
H
1
8
,
H
2
0
g
D ︵ ︶ + ú
p
r
o
d
êë úû
Write the combustion reaction for 1 kmol of n-octane burned with air:
7 2
9 1
7 2
9 1
C
H1
x
O
8
C
O
9
H
O
+
x
N
æ ö÷
+ çç
8
2
+ ÷÷ +
çè ø
7 2
9 1
C
H1
1
2
.
5
O
8
C
O
9
H
O
+
1
2
.
5
N
æ ö÷
çç +
8
2
1 kmol + ÷÷ +
çè ø
9
2
7
,
9
0
7
.
2
9
,
9
0
4
.
é ´( 0
ê )
- + ´( - )+ ù
ú
C7
O9
2
H
2
O
ê ú
Ql
=
-
ê ú
i
q
.
o
c
t
1
2
.
5
2
3
,
7
1
5
.
2
8
,
6
7
0
.
0
+
1
5
,
0
7
4
,
5
4
0
ê ú
2
1
ê+ ´ ´( - )
´(- ) ú
ê ú
hc
,
n
-
o
c
t
a
n
e
N
2
êë úû
,
H
2
0
g
D ︵ ︶
é ù
Ql
=
-
1
8
0
,
3
0
8
.
8
1
6
2
,
0
2
8
.
8
7
0
7
,
4
8
2
.
6
+
5
,
0
7
4
,
5
4
0
ê ú
ê + + ( )
i
q
.
o
c
t
-
úú
C
O
2
H
2
O
N
2
ê
n
-
o
c
t
a
n
e
ë û
é ù
=
1
8
0
,
3
0
8
.
8
1
6
2
,
0
2
8
.
8
7
0
7
,
4
8
2
.
6
+
5
,
0
7
4
,
5
4
0
ê- ú
ê - - ú
H
2
O
N
2
n
-
o
c
t
a
n
e
C
O
2
êë úû
=
4
,
0
2
4
,
7
2
0
k
J
/
k
m
o
l
C
8
H
1
8
For gaseous octane supplied, ∆hc, (H2O g) = – 5,116,030 (kJ/kmol), other values unchanged:
é ù
Q
=
1
8
0
,
3
0
8
.
8
1
6
2
,
0
2
8
.
8
7
0
7
,
4
8
2
.
6
+
5
,
1
1
6
,
0
3
0
ê- ú
g
a
s
.
o
c
t
N
2
n
-
o
c
t
a
n
e
C
O
2
êë úû
=
4
,
0
6
6
,
2
1
0
k
J
/
k
m
o
l
C
8
H
1
8
=
3
5
,
6
6
9
k
J
/
k
g
C
8
H
1
8
NB1: note the large cooling effect of nitrogen, which has to be heated up to the final
temperature.
NB2: this difference between heat released for liquid vs. gaseous fuel supplied would be
much larger for a fuel having high enthalpy of evaporation and/or lower calorific value, such
as .methanol.
Page 10 of 13
School of Mechanical Engineering October 09, 2009
University of Birmingham
Efficient Heat Engines and Heat Pumps.
Combustion, Section 1.2: First Law Analysis of Combustion, Thermochemistry
.
ga
od
(p = const.)
pr
.
s
od
R1,G = R0
ou
pr
se
d
ga
ui
Q
liq
Q H2O vap
H2O liq
P2, H2O vap
H 0
P2, H2O liq
P0
T
T1 =T0 T2
Heat released is the difference between the total enthalpy of reactants and products (or the
negative of ∆H2-1), as seen on the H-T diagram. In this case, reactants are supplied in
gaseous form at standard (reference) conditions, but part of the products (H2O) may be
either in gaseous (vapour) or liquid form.
Write the combustion reaction for 1 kmol of methane burned with air:
7 2
9 1
7 2
9 1
C
H
x
O
C
O
2
H
O
+
x
æ ÷ö÷
+ çç +
4
÷ø +
çè
Balance of O2 on both sides of this equation will give x = 2
7 2
9 1
7 2
9 1
C
H
2
O
C
O
2
H
O
+
2
æ ö÷
+ çç +
4
çè ÷÷ + ´
ø
=
-
H
=
-
H
-2
H
H
-0
H1
ê ú
(ê ) + D +( ) ú
H
2
O
v
a
p
2
-
1
D
P
,
G
ê ú
0
ëê = ûú
é ù
ê ú
ê ú
=
-
ni
hi
-
hi
hc
ê + úú
ê å ( )+
,
3
7
3
K
,
2
9
8
K
C
H
4
,
H
2
0
g
D ︵ ︶
as
le
l
ê ú
gp
ar
ou
uc
st
ê ú
o
d
s
êë úû
Page 11 of 13
School of Mechanical Engineering October 09, 2009
University of Birmingham
Efficient Heat Engines and Heat Pumps.
Combustion, Section 1.2: First Law Analysis of Combustion, Thermochemistry
7 1
3 0
1
1
3
,
3
6
6
.
7
9
,
4
3
2
.
8
9
,
4
3
2
.
8
9
,
3
6
4
.
0
é æ ö÷ ù
ê ´çç
0
( - ) + - ÷ + ú
ê çè ÷
ø ú
ê ú
C
O
2
ê ú
7 1
3 0
ê ú
2
1
3
,
3
5
7
.
0
9
,
9
6
6
.
1
9
,
9
6
6
.
1
9
,
9
0
4
.
0
ê æ ö
÷ ú
ç
0
ê + ´ çç ( - ) + - ÷÷ + ú
è
ê ø ú
Q
=
-
ê ú
H 4
2
O
H
2
O
v
a
p
ê ú
7 2
9 1
7 1
3 0
ê ö÷ úú
2
1
1
,
6
4
0
.
8
,
7
3
7
.
9
8
,
7
3
7
.
9
8
,
6
7
0
.
0
ê+ ´ ´æç
0
ê çç ( - )+ - ÷÷ +ú
è
ê ø ú
N
2
ê ú
+
1
8
0
2
,
2
3
1
ê ú
ê ´(- ) ú
ê ú
hc
,
m
e
t
h
a
n
e
ëê D ︵ ︶ ûú
,
H
2
0
g
é ù
Q
=
-
2
,
9
4
0
.
5
5
,
0
7
4
.
9
1
6
,
4
5
2
.
5
+
8
0
2
,
2
3
1
ê ú
ê + + (- )
H
2
O
v
a
p
ú
ê ú
C
O
2
H
2
O
N
2
êë Húû
o
,
m
e
t
h
a
n
e
D
é ù
=
2
,
9
4
0
.
5
5
,
0
7
4
.
9
1
6
,
4
5
2
.
5
8
0
2
,
2
3
1
ê ú
ê- - - + ú
C
O
2
H
2
O
N
2
ê ú
o
,
m
e
t
h
a
n
e
ë -D û
=
7
7
7
,
7
6
3
k
J
/
k
m
o
l
C
H
4
For H2O in products condensing out to liquid phase, using the value of ∆hc H2O(g) = -802,231
kJ/kmol:
é ù
Q
=
-
H
=
-
H
-
H
H
-2
H
H
-0
H1
ê ú
ê( ︵ ︶ ) ( ) ( ) ú
H
2
O
l
i
q
2
-
1
2
,
L
f
2
,
G
D + + D +
P
,
G
R
P
ê ú
0
ëê = ûú
=
-
HL
H
-2
H
é -D ù
êë( ︵ ︶ ) +( ) +D + ú
G
f
g
0
P
,
G
P
û
é ù
ê ú
ê ú
=
-
n
hf
ni
hi
-
hi
+
n
hc
ê- ú
+ å ( )
H
2
O
,
3
7
3
K
,
2
9
8
K
C
H
4
,
H
2
0
g
ê D ︵ ︶ + ú
a
le
l
ê ú
gp
ar
so
ou
uc
st
ê ú
d
s
êë úû
é ù
Q
2
4
3
9
8
6
2
,
9
4
0
.
5
5
,
0
7
4
.
9
1
6
,
4
5
2
.
5
+
8
0
2
,
2
3
1
ê ︵ ︶+ ú
( )
H
2
O
l
i
q
ê-
´ úú
+ + -
ê
C
O
2
H
2
O
N
2
n
H
2
O
h
f
g
êë ´ úû
o
,
m
e
t
h
a
n
e
é ù
=
2
,
9
4
0
.
5
5
,
0
7
4
.
9
1
6
,
4
5
2
.
5
8
7
,
9
7
2
8
0
2
,
2
3
1
ê ú
ê- - - + + ú
C
O
2
H
2
O
N
2
n
H
2
O
h
f
g
ê ú
o
,
m
e
t
h
a
n
e
ë ´ -D û
=
8
6
5
,
7
3
5
k
J
/
k
m
o
l
C
H
4
1
0
.
6
%
l
a
r
g
e
r
︵ ︶
hc
hc
H
2
O
g
C
H
4
,
H
2
0
g
,
f
r
o
m
t
a
b
l
e
s
C
H
4
,
H
2
0
l
,
f
r
o
m
t
a
b
l
e
s
- D ︵ ︶ @ D ︵︶
k
J m
k m
J o
k
J m
2
4
3
9
8
6
8
0
2
,
2
3
1
8
9
0
,
3
0
3
æ ö÷ æ ÷ö÷
+ ´çç- ÷ @ çç-
k
o
l
k
l
k
o
l
- ´
èç ø÷ èç ÷ø
k
J m
k
J m
8
9
0
,
2
0
3
8
9
0
,
3
0
3
k
o
l
k
o
l
- @-
Page 12 of 13
School of Mechanical Engineering October 09, 2009
University of Birmingham
Efficient Heat Engines and Heat Pumps.
Combustion, Section 1.2: First Law Analysis of Combustion, Thermochemistry
1.2.8. Summary
1. In exothermic combustion reactions internal energy and enthalpy of products is lower than
that of reactants: (∆hC < 0)
2. Difference between ∆uC and ∆hC is small, and ∆hC at a reference temperature of 298.15 K
(+25OC) is tabulated.
3. In calculations follow a path bringing reactants to a standard temperature T0, account for
combustion reaction at T0, bring products to the desired temperature or calculate the final
temperature from the quantity of heat extracted.
4. Use values of enthalpy rather than specific heats.
5. Reactants and/or products can be in gaseous or liquid form. Enthalpy of
evaporation/condensation has to be taken into account.
6. Lower calorific value - when water in products remains as vapour (usually the case). Higher
calorific value - when water vapour in products is condensed by bringing the products to a low
temperature (in some boilers).
Page 13 of 13