1

MSc Lecture 12:

Fire Combustion

Dr S. S. Han
Department of Building Services Engineering
The Hong Kong Polytechnic University
Hong Kong, China
17 November 2015
MScComb.ppt

Combustion
What is combustion?
Combustion is the name given to
overall exothermic reactions, usually
of an oxidative character, which have
the ability to propagate throughout
the phase concerned.

Combustion process
Involve two reactants, a fuel and an
oxidant.

When the combustion process becomes

uncontrolled it is often described by the
term:

fire

Fire
Introduction
Fire is essentially a natural combustion.
The word fire is also often applied to
controlled combustion taking place in a
hearth or in an incinerator.

The current BS 4422 (2005) definition

of fire
Process of combustion characterized by
the emission of heat accompanied by
smoke.
Rapid combustion spreading
uncontrolled in time and space.

Essential feature of fire that

separates it from other combustion
processes.
The fuel supply rate is controlled by
the positive feedback of heat from the
products of its own combustion.

 Fire is a highly complex combustion system.

Comparison of the CO, CO2, and O2 levels in the products

from the smouldering combustion of a cushion assembly.

Comparison of the CO, CO2 and O2 levels in the products

from the flaming combustion of a cushion assembly.

10

Complete combustion

Gives only carbon dioxide and water

vapour.

Incomplete combustion
Real fires is incomplete combustion.

Significant
monoxide.

formation

of

Leads to the formation of smoke.

carbon

11

Fire Hazards
Thermal hazard
heat

Nonthermal hazard
fire products, such as smoke, toxic
corrosive, and odorous compounds

12

In a majority of cases, hazards to life and

property are due to fires in enclosed
spaces.
Fires in enclosed spaces are characterized
by an upper and a lower layer.
upper layer are the hot fire products.
the lower layer is the fresh air.

In early stages, a building fire is

ventilated and is easy to control and
extinguish.

13

Chemical Hazards and Database

Basic toxicity patterns of fire products
Thermal
contained
products

decomposition
large numbers

products
of toxic

For smoke atmosphere the toxicity was

dominated by

an asphyxiant gas (CO or HCN)

or irritants (CS or CN)

14

Generation of chemical compounds

and consumption of oxygen.
The chemical natures and generation rates of
products are of critical importance for the
protection of life and property.
The generated compounds in different zone in
fires.

Reduction zone (smoke, CO, hydrocarbons)

Oxidation zone (CO2 and H2O)

15

Pyrolytic and
oxidative
decomposition
products of
polypropylene at
500 oC

16

Classification of toxic hazards in fires

17

Chemical product formation and the

resultant toxicity can vary in different
types and stages of fire.
Effects of temperature on the pyrolysis of
polyacrylonitrile, flexible polyurethane
foam, and wood.
PMMA combustion investigated by Zeng,
Li and Chow (J FIRE SCI 20 (4): 297-317
2002).

18

The content of combustion products of PMMA and

MMA in air and Ar at different temperature

19

Combustion of PMMA will occur in

three broad stages:
If heated by external sources, PMMA
decompose to form monomer MMA and a
small amount of other products;
Monomer MMA decompose to produce
small molecule products;
Gaseous small molecules undergo oxidation,
i.e. burning

20

Smouldering Combustion
A burning process without flame due
to limited supply to oxygen.
e.g.the underground mine fire in Scotland.

Two factors to occur.

Porosity: allow oxygen to permeate.
Must yield a
decomposition.

char

upon

thermal

Example of a smouldering combustion:

Representation of steady smouldering

along a horizontal cellulose rod.

21

22

Zone 1: Pyrolysis zone in which there is a

steep temperature rise and an outflow of
visible airborne products from the parent
material.
Zone 2: A charred zone where the
temperature reaches a maximum, the
evolution of the visible products stops and
glowing occurs.
Zone 3: A zone of very porous residual char
and/or ash which is no longer glowing and
whose temperature is falling slowly.

23

Two types of propagation

Forward smoulder in which the flow of
air is in the same direction as the
propagation process.
Reverse smoulder, when the airflow
opposes the direction of smoulder.

24

Glowing Combustion
Glowing combustion is associated
with the surface oxidation of
carbonaceous materials or char.
Spontaneous ignition of activated
charcoal results in glowing combustion
within the mass.
Pyrolysis zone (Zone 1) is replaced by
a simple pre-heat zone.

25

Almost all char-forming fuels will undergo

flaming combustion.
Total heat of combustion of the material is
associated with the char.
It is approximately 30% in the case of
wood.
Glowing combustion will only continue if
heat is conserved at the reacting surface

26

Burning surfaces will cool and the

residual fire will self-extinguish if the
heat losses overwhelm the rate of heat
production.

The term afterglow describes the

residual glowing combustion of the
char that is left after burnout of a piece
of fabric, splint of wood (e.g. a match)
or similar item.

27

Combustion chemistry: thermodynamics

Thermochemistry is concerned with the
amounts of energy released or absorbed.
The energy released during fire processes
can be calculated by thermochemistry
methods.
Thermodynamics
does
not
indicate
anything about the reaction rate or the
mechanism of conversion.

28

The first law of thermodynamics

The ideal gas law can be expressed as
below:

PV = nRT
where P and V are pressure and
volume of n moles of gas at a
temperature T, and R is gas constant.

29

At ambient temperatures, deviations

from ideal behaviour can be
detected with most gases and vapors,
while at elevate temperatures such
deviations become less significant.

30

Internal energy
The first law of thermodynamics deals
with the relationship between work and
heat.
To be a closed system, there will be a
change if heat is added or taken away,
or if work is done on or by the system
(e.g. by compression).

31

Any change in the internal energy of the

system (E) is given by

E = q w
or

dE = dq dw = dq pdv
where q is the heat transferred to the system,
and w is the work done by the system.

32

Enthalpy
Fires occur under conditions of constant
pressure except the explosions in closed
vessels.
At constant pressure, the work done can
be expressed by

w = p(V1 V2)
where V1 and V2 are the initial and final
volumes, respectively

33

The change in the internal energy of

the system (E) is given by

E = E2 E1 = qp + pV1 pV2
or, rearranging

qp = (E2 + pV2) (E1 + pV1) = H2-H1

where qp is the heat transferred at
constant pressure, and H is known as the
enthalpy (H = E + pV).

34

Specific heat
Specific heat, or heat capacity, of a
body or system is defined as the
amount of heat required to raise the
temperature of unit mass by one
degree Celsius, the units are J/kg K
or J/mol K.

Heat capacities of selected gases at constant pressure

(101.1 kN/m2)
Cp (J/mol.K)
Temp. (K)

298

500

1000

1500

2000

CO

29.14

29.79

33.18

35.22

36.25

CO2

37.129

44.626

54.308

58.379

60.350

H2O (g)

33.577

35.208

41.217

46.999

51.103

N2

29.125

29.577

32.698

34.852

35.987

O2

29.372

31.091

34.878

36.560

37.777

He

20.786

20.786

20.786

20.786

20.786

CH4

35.639

46.342

71.797

86.559

94.399

Species

35

36

There are two distinct heat capacities, at

constant pressure, Cp, and at constant
volume, Cv.

At constant pressure

dqp = dH = Cp
dT
At constant volume

dqv = dH = Cv
dT

37

For an ideal gas

Cp = C + R
v

38

Heats of combustion
The heat of combustion (HC) is
defined as the total amount of heat
released when unit quantity of a fuel
(at 25 oC and at atmospheric pressure)
is oxidized completely.

 Example of propane
C3H8 + 5O2

39

3CO2 + 4H2O

HC depend on whether the water in the

products is in the form of liquid or
vapor for propane, the two values are :
HC(C3H8) = -2220kJ/mol (liquid water )

HC(C3H8) = -2044kJ/mol (water vapor )

In flames and fires, the water remains as
vapor , so it is more appropriated to use the
latter value.

40

Heat of combustion of propane can be

expressed as either:
-2044 kJ/mol
or
(2044/44) = -46.45 kJ/g
where 44 is the molecular weight of
C3H8 in gram.

41

Chemical reactions and stoichiometry.

The balanced chemical equation defines the
stoichiometry of the reaction.
The physical states of the reactants and
products should also be specified.

42

Measurement of heat of combustion

Heats of combustion are measured by
combustion bomb calorimetry in which a
precise amount of fuel is burned in pure
oxygen inside a pressure vessel whose
temperature is strictly monitored.

43

The experiment gives the change in internal

energy, E. The change in enthalpy is given
by

H = E + (pV)
where (pV) is calculated using the ideal gas
law.

(pV) = (nRT)

44

The method gives the gross heat of combustion

in which the reactants and products are in
standard states.
The net heat of combustion refers specifically to
the situation in which water as a product is in
the vapor state.

45

Net heat of combustion is less than the gross

heat of combustion by an amount equal to the
latent heat of evaporation.
For most of the fuels, Hc(O2) and Hc(air)
have average values of 13.1 kJ/g and 3 kJ/g
respectively.

46

Heats of formation
The heat of formation of a compound
is defined as the enthalpy change when
1 mole of that compound is formed
from its constituent elements in their
standard state (at 1 atm pressure and
298 K).

47

The most stable compounds have the largest

negative values, while positive values tend to
indicate an instability with respect to the
parent elements.

48

According to the Hesss law, the heats of

reaction can be calculated from the heats of
formation of the reactants and products.

H H f ( products ) H f ( reactants )
where H is the heat (enthalpy) of the
relevant reaction.
Hess law
states that the change in enthalpy depends
only on the initial and final states of the
system and is independent of the
intermediate steps

49

Example: propane oxidation

C3H8+5O2

3CO2+4H2O

HC (C3H8) = 3Hf (CO2) + 4Hf (H2O)

Hf (C3H8) Hf (O2)
= -2044 kJ/mol
The standard molar enthalpy of formation of substance

Enthalpy
(kJ/mol)
H

CO2

H2O

393.51 241.83

C3H8

O2

-103.85

50

The relationship between heat of

combustion and temperature.
Reactants at temperature T0 react to give
products at temperature TF, the process is
regarded in two ways:
The products are formed at T0, absorb the
heat of combustion, and are heated to TF.

51

The heat of combustion is imagined

first to heat the reactants to TF, then
the reaction proceeds to completion
By the first law
(H c )

T0

Pr
p

(T F T 0 ) ( H c )

TF

C (T F T 0 )
R
p

where CpPr and CpR are the total heat

capacities of the products and
reactants, respectively

52

Be arranged to give
( H c ) ( H c )
TF T0
TF

T0

C p

Kirchoffs equation

d ( H c )
C p
dT
where

C p C

Pr
p

R
p

53

The heat of combustion at temperature T2

can be calculated according to the following
equation:

(H c ) (H c )
T2

T1

T2
T1

C p dT

where Hc is known at temperature T1

54

Rate of heat release in fires

The rate of heat release is expressed in

terms of the burning rate, which is
expressed as a rate of mass loss (kg/s)

Q c m H c
where H c is the net heat of combustion of
the fuel (kJ/kg).

55

The combustion efficiency is likely to

vary from around 0.3 to 0.4 for heavily
fire-retarded materials to 0.9 or higher
in the case of oxygen-containing
products.

If the fire is ventilation controlled and that

all of the air that enters the compartment is
burned therein, the rate of heat release is
calculated from the expression

Q c m air H c (air )
where

m air

is the mass flow rate of air, and

H c (air ) is the heat of combustion per unit

mass of air consumed (3 kJ/g).

56

57

The mass flow rate of air is approximated by

the expression

m air 0 .52 A w h

1/ 2

(kg/s)

Aw is the effective area of ventilation (m2) and

h is the height of the ventilation opening (m).

58

If the equivalence ratio m

air / m is less than
the stoichiometric ratio, excess fuel will
escape from the compartment and mix with
air to give external flames whose length will
depend inter alia on the equivalence ratio

59

The technique of oxygen consumption

calorimetry.
This is the basis of the cone
calorimeter in which the rate of heat
release from a small sample of
material burning under an imposed
radiant heat flux is determined by
measuring the rate of oxygen
consumption.

60

The method is based on the generalization

that the heats of combustion per unit of
oxygen consumed are approximately the
same for most fuels commonly encountered
in fires. The value is about 13.1 kJ/g.

61

Take methane combustion as an example

Complete combustion

CH 4 2 O 2 CO 2 2 H 2 O
The standard molar enthalpy of formation of substance
Enthalpy
(kJ/mol)

CO2

CO

H2O

CH4

O2

- 393.51

- 110.52

- 241.83

-74.85

62

Heat of combustion can be calculated

from the enthalpy of the reactants and
products.
H combustion heat = H products H reactants

= HCO2 + 2HH2O HCH4

= -393.51 + 2(-241.83) (-74.85)

= -802.32 kJ/mol

63

The heat of combustion per gram of oxygen

consumed is :

802.32
12.54 kJ / g
2 32

64

Incomplete combustion

CH 4 aO 2 bCO 2 cCO dH 2 O
H combustion heat = H products H reactants
= b HCO2 + c HCO + d HH2O HCH4
= b (-393.51) + c (-110.52) + d (-241.83) (-74.85)

Mass conservation gives:

O: 2a = 2b + c + d
C: b + c = 1
H: d = 2

65

According to the above relationship,

the following values can be obtained:

b = 2a - 3
c = 4 - 2a

d=2
H combustion heat
= (2a-3)(-393.51) + (4-2a)(-110.52)
+2(-241.83) (-74.85)
= -565.98a + 329.64

66

We assumed that the b/c = 9,

so a = 39/20

Heat released by burning 1 kg of O2 is

[-565.98 (39/20) + 329.64]/[(39/20) 32]
=12.4 kJ/g

67

Calculation of adiabatic flame

temperatures
Assuming a premixed reaction system to be
adiabatic, that is, there is no transfer of heat
to or from the system, the adiabatic flame
temperature can be calculated.

68

Example: Consider a flame propagating

through a stoichiometric propane/air
mixture of infinite extent and which is
initially at 25 oC
C 3 H 8 + 5O 2 + 18.8N 2

3C O 2 + 4H 2 O + 18.8N 2

This reaction releases 2044kJ for every

mole of propane consumed

69

Thermal capacity of the products of combustion

of a stoichiometric propane/ air mixture
Thermal Capacity at 1000 K
No. of Moles

(J/mol.K)

(J/K)

CO2

54.3

162.9

H2O

41.2

164.8

N2

18,8

32.7

614.8

Total thermal capacity (per mole of propane) =

942.5 J/K

70

2044000
T
2169 K
942 .5
The final (adiabatic) temperature as
2169 + 298 = 2467 K

71

In fact, this figure is approximated for

the following reasons
Thermal capacities change with temperature,
and average values over the range of
temperatures appropriate to the problem have
been used.
the system cannot be adiabatic as there will be
heat loss by radiation from the hot gases (CO2
and H2O).
At high temperatures, dissociation of the
products will occur; as these are endothermic
processes, there will be a reduction in the final
temperature.

72

Chemical equilibrium

If a chemical transformation and the

reverse process occur in a closed system,
after a sufficient time, a condition of
chemical equilibrium will be reached, after
which no further change occurs as long as
the temperature and pressure remain
constant and no additional reactants are
introduced.

73

Chemical equilibrium constant

For a generalized reaction

cY 1 + dY 2

aX 1 + bX 2

The chemical equilibrium constant K can

be given by
c

( pY1 ) ( pY2 )

( p X1 ) a ( p X 2 ) b

where the Pi are partial pressures.

74

In most real chemical systems, one must deal

with a number of simultaneous chemical
equilibrium.
A gaseous chemical system at a given
temperature, containing s kinds of chemical
species involving e chemical elements, requires
s-e equilibrium relations, e-1 atom-ratio
p
pi
relations, and a
equation, in
order to specify it.

75

Relevance of chemical equilibrium

to fire protection
The temperature and the equilibrium
composition of products can be calculated.
The generation rate of certain toxic or
corrosive products may be calculated.
Chemical equilibrium calculation is a useful
tool in correlations of fire phenomena.

76

Carbon formation in oxygen-deficient

systems.
Solid carbon (soot) may be expected to form
in oxygen-deficient combustion products.
Solid carbon does not melt or boil until
extremely high temperatures (~ 4000 K).

There are three conceivable ways in which it

might form solid carbon from CO at 2000 K :
:

CO
CO

CO

1/2C (s) + 1/2CO 2

C (s) + 1/2O 2

C (s) + O

K
K

( p CO2 )1 / 2
p CO
( p O2 ) 1 / 2
p CO

pO
K
p CO

Note that solid carbon does not appear in any of

the equilibrium expressions.

77

78

According to the calculation, K is much

larger than either K or K , so it is the
dominant mode for whatever decomposition
may occur.

79

Departure from equilibrium

Correct results are only yielded if the system
is truly in equilibrium.
Equilibrium would always be reached in
flames

80

The equilibrium condition is only a

limiting case that real flames may
approach.
The products of a nonluminous laminar
flame more than a few millimeters
from any cold surface will always be
very nearly in equilibrium.

81

Combustion chemistry: kinetics

Chemical kinetics
information about
chemical reactions.

concerns the
the rate of

82

Rate laws and reaction orders

A rate law describes an empirical
formulation of the reaction rate, i.e.,
the rate of formation or consumption
of a species in a chemical reaction.

83

General
chemical
reaction
described by the equation
A + B + C + ...

D + E + F + ...

the reaction rate is expressed:

d [ A]
a
b
c
k [ A ] [ B ] [C ]
dt
a, b, c----- are reaction orders

k ----- the rate coefficient of the reaction.

is

84

The temperature dependence of rate

constant is expressed in Arrheniums
form
( E a / RT )

k A exp

A : pre-exponential factor
Ea: activation energy

 Ea corresponds to an energy barrier which has to

be overcome during the reaction.

Energy diagram for a chemical reaction

85

86

Ea maximum value corresponds to the

bond energies
Ea can be much smaller (or even zero),
if new bonds are formed simultaneously
with the breaking of the old bonds

87

Relation of forward and reverse reactions.

At chemical equilibrium, forward and
backward reactions have the same rate
on a microscopic level.
On a macroscopic level, no net reaction
can be observed.

88

Elementary reactions, reaction

molecularity
An elementary reaction is a reaction,
which occurs on a molecular level
exactly in the way which is described by
the reaction equation.

89

Example of an elementary reaction

OH H 2 H 2O H
On the contrary, the reaction

2H 2 O 2 2 H 2 O
is not an elementary one. It is called
net reactions or overall reactions

90

Overall reactions are a consequence of

a large number of elementary
reactions.
The reaction order of elementary
reactions is always constant, in
particular independent of time and
experimental conditions.

91

Three possible values of the reaction

molecularity:
Unimolecular reactions

products

Bimolecular reactions

A+A

products

A+B

products

92

Trimolecular reactions

A+B+C

products

A+A+B

products

A+B+A

products

93

Mechanism of gas phase combustion

Global reaction:

CH4 + 2O2

CO2 + 2H2O

The mechanism involves a series of

elementary steps (26 species and 77
elementary reactions).

94

95

96

Experimental
investigation
elementary reactions.

of

Experimental
setups
for
the
measurement of elementary reactions.
The kind of reactor.

The method of generation of the reactive

species.
The kind of analysis

97

Reactors
Static reactors: An isothermal vessel is
filled with reactants and then the time
behavior of the concentrations is
measured.
Flow reactors: Spatial profiles of the
concentrations give information about
their time behavior

98

Generation of the reactive species

A microwave discharge (H2, O2 form H, O.
atoms)
Flash photolysis and laser photolysis
(dissociation of molecules by energetic UV
light)

Thermally using high temperatures

(dissociation by heating in a shock tube)

99

Analysis
Mass spectroscopy
Electron spin resonance
Optical spectroscopy
Gas chromatography

100

Chemkin software

Chemkin is a long-term Sandia

research project in thermal/fluid
simulation and modeling.

101

Schematic of Chemkin software

102

Greatly advanced detailed computer

modeling of combustion chemistry.

Developed to aid in the incorporation of

complex gas-phase chemical reaction
mechanisms into numerical simulations

103

Thermal decomposition of polymers

Definition
Thermal decomposition is a process of extensive
chemical species change caused by heat.

Thermal degradation is a process whereby the

action of heat or elevated temperature on a
material, product, or assembly causes a loss of
physical, mechanical, or electrical properties

104

Two broad stages

combustion of polymers.

in

the

The polymer decompose to form the

products of low molar mass by heat.
These products undergo oxidation,
i.e. burning.

105

Physical processes
Thermosetting polymeric materials
infusible and insoluble, simple phase
changes upon heating are not possible.

Thermoplastics

Soften
by
heating
irreversible changes

without

106

Chemical processes
The thermal decomposition of polymers may
proceed by oxidative processes or simply by
the action of heat.

107

Chemical mechanisms in the

thermal decomposition of polymers.

Random-chain scission

End-chain scission

Chain-stripping

Cross-linking

108

Interaction of chemical
physical processes.

and

The nature of the volatile products is

dictated by the chemical and physical
properties of both the polymer and the
products of decomposition.

109

Physical and
Chemical
changes during
thermal
decomposition
Experimental
methods

110

Thermal decomposition test

Thermogravimetric analysis (TGA)

Isothermal method

Non-isothermal method

Differential thermogravimetry (DTG)

Thermal volatilization analysis (TVA)

Differential thermal analysis (DTA)

Differential scanning calorimetry (DSC)