HEAT OF COMBUSTION of a fuel= amount of energy released as

heat when a compound undergoes complete combustion with oxygen, i.e.

energy/mass of fuel (solid and liquid fuels)
energy/volume of fuel (gas fuels)

1 Kcal =4186 J
UNIT of MEASURE:
1 Kcal= 4,186 KJ
Kcal/Kg, Kcal/Nm3
1J=2,388*10-4 Kcal
KJ/Kg, KJ/Nm3

Nm3 = amount of gas occupying 1 m3 at normal state (0 °C,1 atm)

Qs= HIGHER HEATING VALUE
remaining water at the end of combustion

is in the liquid state
Qi= LOWER HEATING VALUE
remaining water at the end of combustion
is in the gaseous state
1
Qs-Qi= vaporization heat of water

Qs= Qi+n*2500 using KJ/Kg

Qs= Qi+n*600 using Kcal/Kg

n= amount (kg) of water formed by the combustion of 1m3 or 1 kg of fuel

N.B. Qi<Qs because vaporization of water is endothermic process

2500= heat of vaporization of 1kg of water in KJ
600= heat of vaporization of 1kg of water in Kcal

2
 MEASUREMENT OF HEAT OF COMBUSTION

1) From enthalpies of combustion reactions

• if liquid or solid fuel: molar mass should be considered
• if gas fuel: molar volume should be considered
• In case of gas fuel mixture, heats of combustion should be
added up, taking into consideration their %

2) Using lower or higher heating values:

• Case of dry or anhydrous fuel

• Case of not anhydrous fuel
water at the beginning stage
should be considered

3
Calculate the heat of combustion using the
reaction enthalpies:
Example
CO + ½ O2 ⇒ CO2
∆H=-282.8 kJ/mol
22.4:282.8=1000:x
1 mole [l]: heat [kJ/mol]= 1000 l (1 m3): x
x= 12627 kJ/Nm3

Exercise 1
Determine the heat of combustion of carbon
(∆Hcomb= -393.3kJ/mol)
C+ O2 ⇒ CO2
12:393.3=1000:x
X= 32775 kJ/kg 4
Determine the lower heating value and the
higher heating value

Example
fuel: CH4
CH4 + 2O2 ⇒ CO2 + 2H20(liq)
Qs = 9500 kcal/Nm3
Qi ???
n = ???
1 mole of methane ⇒ 2 moles of water
PM water =18
22.4 l CH4 => 18⋅ 2= 36 g of water
22.4 m3 di CH4 ⇒ 18 ⋅ 2 =36 kg of water
1 m3 di CH4 ⇒ 36/22.4 = 1.61 kg of H2O
Qi=9500 - (1.61 ⋅ 600)= 8534 kcal/Nm3 5
Example of not anhydrous fuel :
commercial C2H5OH :
95% wt C2H5OH
5% water
Qs C2H5OH anhydrous = 29800 kJ/kg
C2H5OH + 3O2 ⇒ 2 CO2 + 3 H2O
PM C2H5OH = 46
PM H2O= 18
Qs commercial C2H5OH : ???
Qi commercial C2H5OH : ???
Qs= 29800 ⋅ 0.95 = 28310 kJ/kg
46 g comb. ⇒ 3 ⋅ 18 g H2O
0.95 kg of fuel ⇒ 1.11 kg water
Water tot = 1.11 + 0.05= 1.16 kg
Qi= 28310 - (1.16 ⋅ 2500)= 25410 kJ/kg 6
 Exercise 2
Determine the lower heating value and the higher heating
value of octane C8H18
MW= 114
∆Hcomb liq. water= -5531 kJ/mol
∆Hcomb gas water= -5126 kJ/mol
C8 H18 + 25/2 O2 → 8 CO2 + 9 H2O (l)
∆H= - 5.531 kJ/mol
114 : 5.531 = 1000 : x
x= 48518 kJ/kg = Qs
C8 H18 + 25/2 O2 → 8 CO2 + 9 H2O (v)
∆H= - 5126 kJ/mol
114 : 5126 = 1000 : x
x = 44965 kJ/kg = Qi
amount of water formed by the combustion (n)
114 : 9 ⋅ 18 = 1000 : x
x = 1421 g= 1.421 Kg
7
Qs = Qi + 1.421 ⋅ 2500 = 48 518kJ/kg
THEORETICAL COMBUSTION AIR = The volume of air needed for the complete
combustion of a fuel
Needed volume of O2 for the combustion of 1Nm3 or 1 Kg of fuel
AIR 78% vol. N2
21% vol. O2
1% vol. Ar
Simplification: air is constituted by 79% of N2 and 21% of O2
N2 /O2=79/21= 3.8
each volume of O2 is accompanied by 3,8 volumes of N2 ,
i.e. 4,8 volume of air
Calculation of theoretical combustion air depends on kind of fuel (liquid or gas)
•Gas fuel: the Avogadro’s principle is valid (Equal volumes of gases, at the same
temperature and pressure, contain the same number of molecules)

there is a direct
relationship between molecules number and volume
•Liquid and solid fuels:starting from elementary analysis
Excess air = is supplied to the combustion process to ensure each fuel molecule is

completely surrounded by sufficient combustion air
it doesn’t burn and goes

out among combustion products
Exhausted gasses = gasses produced during combustion 8
THEORETICAL COMBUSTION AIR
Example
CH4 + 2 O2 ⇒ CO2 +2 H2O
Combustion of 1 m3 of CH4 ⇒ 2 m3 of O2
1 part di O2 ⇒ 3.8 parts of other gasses
2m3 O2 ⇒ 9.6 m3 of air (2 + 2⋅⋅3.8)
Theoretical combustion air : 9.6 m3
Exhausted gases composition:
CH4 + 2O2 + 7.6N2⇒CO2 + 2H2O + 7.6N2
1 m3 CO2
2 m3 H2O
7.6 m3 N2
Total volume of exhausted gases : 10.6 m3
9
For hydrogen and carbon monoxide:
2 H2+O2 + 3.8 N2
2 H2O + 3.8 N2
2 CO+ O2 + 3.8 N2
2 CO2 + 3.8 N2
then to burn 1 Nm3 of hydrogen or CO , 2.4 Nm3 of air
are necessary;
For carbon at the solid state:
C + O2 + 3.8 N2
CO2 + 3.8 N2
then to burn 12 Kg of C, 22.4 Nm3 of oxygen are required,
i.e. 22.4x4.8 = 107.5 Nm3 of air; as a consequence:
to burn 1 Kg of carbon , 107.5/12 = 8.96 Nm3 of air are
required.

10
Exercise 3
Determine the theoretical combustion air to burn 1
Nm3 of the following mixture of gases:
30% CH4,
10% H2,
30% CO,
20% CO2,
10%N2:
for methane : 0.3x9.6 = 2.88
for hydrogen : 0.1x2.4 = 0.24
for carbon oxide: 0.3x2.4 =0.72
3.84 Nm3 of air.

11
 Exercise 4
What is the theoretical combustion air (in l and in
kg) for the liquid octane?
C8 H18 + 25/2 O2 → 8 CO2 + 9 H2O
114 : (25/2 ⋅ 4.8 ⋅ 22.4) = 1000 : x
x= 11789 l of air = 11.8 Nm3 of air
11.8 Nm3 of air are required to burn 1000 g
(1kg) of octane.
Since the average molecular weight of air is
28.96, in order to burn 1 kg of octane are
needed:
114 : (25/2 ⋅ 4.8 ⋅ 28.96) = 1000 : x
x= 15240 g of air = 15.24 kg of air
12
 Exercise 5
Determine the amount and the composition of the
exhausted gases developed during a complete combustion of
liquid octane
C8 H18 + 25/2 O2 → 8 CO2 + 9 H2O (v)
1 kg di C8 H18 contains 1000/114 = 8.772 moli of C8 H18
which originate
(8.772 ⋅8 ⋅ 22.4) l of CO2 = 1572 l di CO2 = 1.572 Nm3 of
CO2
(8.772 ⋅9 ⋅ 22.4) l of H2O (v) = 1768 l of H2O (vapour) =
1.768 Nm3 of H2O
(8.772 ⋅ 25/2 ⋅ 22.4) l of consumed O2 = 2456 l of O2 =
2.456 Nm3 of O2
Nitrogen accompanying oxygen in the theoretical air and
that can be found in the exhausted gases is
2.456⋅3.8 = 9.333 Nm3
The total volume of exhausted gases is:
1.572 + 1.768 + 9.333 = 12.673 Nm3 13
In case of combustion with excess air, oxygen is present in the exhausted gases. Surplus
of O2 (or air) can be calculated if the % of O2 in the exhausted gases is known. Similarly,
the excess air can be determined: the amount of CO2 obtained during combustion with
air excess is the same as that produced without air excess, while the %CO2 in the
exhausted gases is different.

%CO2 (theoretical air)=VCO2/V exhausted gases (theoretical air)

%CO2 ( excess air)=VCO2/V exhausted gases (excess air)

%CO2 (excess air)=VCO2/(V exhausted gases (theoretical air)+ V excess air)

necessary to calculate excess air volume
N.B.
1. If fuel contains oxygen,it should be subtracted from theoretical air
volume
2. Remember nitrogen for calculation of exhausted gases volume
3. Ashes don’t burn
4. Remember gases contained in the fuel , even if they don’t burn


they
pass unchanged into exhausted gases 14
 EXCESS AIR
%O2( excess air)=
VO2 excess/(V exhausted gases (theoretical air) + V excess air) ·100

A liquid fuel composed of :

C=85%wt
H=14%wt
S=1%wt
undergoes combustion with excess air
In combustion
gases the free oxygen percentage is 3%.
Determine the excess air.
15
C+O2 => CO2
H2+ 1/2O2 => H2O
S+O2 => SO2
CO2: 12: 22,4=850:x
x= 1,6 m3 CO2/O2
H2O: 2:22,4=140:y
y=1,6 m3 H2O
SO2: 32:22,4=10:z
z= 0,007m3 SO2/O2
O2 used= x+y/2+z= 2.38 m3
Theoretical air= 2.38 · 4.8= 11.41 m3
N2 theoretical= 2.38 · 3.8= 9.04 m3
Gases (theoretical)= 1.6(CO2)+1.6(H2O)+ 0.007(SO2)+9.04(N2)=12.20 m3
3= x/( 12.20+4.8x) 100
x= 0.43 m3 excess oxygen
excess air = 4.8 · 0.43= 2.05 m3
excess air %= (2.05/11.4) · 100= 18%
16
Exercise 6

A fuel is composed of:

C=86%wt
H=2%wt
O=5%wt
N=3%wt
S burning= 1%wt
ahes=3%

In the exhausted gases there is CO2 %vol= 13%.

Determine the excess air.

17
Calculation for 100g of fuel:
C+O2 => CO2
12g => 22.4 l
86g:12g=x:22.4 x=160.5 l CO2
H2+ O2 => H2O
2g=> y=22.4 l H2O
S+O2 => SO2
32g=> 22.4 l
1g:32g=z:22.4 Z=0.7 l SO2
O2 required: 160.5+11.2+0.7=172.4 l
Part of the used oxygen comes from fuel itself (less oxygen is required from
combustion air):
32 g (1 mole of O2) => 22.4 l
5:32=K:22.4 K= 3.5 l oxygen in the fuel
O2 needed from air= 168.9 l=172.4-3.5
18
N2 from theoretical = 168.9 3.8= 641.82 l
N2 from fuel: 28g (1 mole) => 22.4 l
3:28=w:22.4 w=2.4 l
N2 total: 644.22 l
Theoretical air= oxygen + nitrogen= 168.9+641.82= 810.7
Vol gases (theoretical )= x(CO2)+y(H2O)+z(SO2)+N2tot=
827.82 l
%CO2( excess air)=VCO2/(V theoretical gases +V excess air) 100
13=160.5/(827.82+V excess air) 100
V excess air=406.8 l
V excess air%= (406.8/810.7) 100=50%

19