Fire Dynamics II

Lecture # 5
Chemistry of Room Fire Combustion
Jim Mehaffey
82.583

Carleton University, 82.583, Fire

Dynamics II, Winter 2003, Lecture #
5

Chemistry of Room Fire Combustion

Outline
Introduction
Review: Generation of products of combustion in wellventilated fires
Generation of products of combustion in poorlyventilated fires
Review: Life tenability criteria

Objectives
Predict rates at which heat & chemical species are
generated in fires in order to provide input for
assessments of thermal environment & life safety
Carleton University, 82.583, Fire
Dynamics II, Winter 2003, Lecture #
5

Introduction
Perfect Combustion
Combustible burns in an excess of pure O2
Products: net heat of combustion, CO2 and H2O
Well-ventilated fires (diffusion flames in the open)
Combustible burns in open configuration in air
Products: Chemical heat of combustion, CO2, H2O,
CO, C (soot) and hc (hydrocarbons)
Poorly-ventilated fires (many fires in enclosures)
Combustible burns in air, but air supply is restricted
Products: Less heat, CO2 and H2O
More CO, C (soot), hc (hydrocarbons)
Carleton University, 82.583, Fire
Dynamics II, Winter 2003, Lecture #
5

Heat Release Rate: Perfect Combustion

Net heat of combustion = HC (kJ / g)
Get theoretical maximum heat release rate (kw)

Q MAX = H C m

Eqn (5-1)

m = mass loss rate of fuel (kg s-1)

Carleton University, 82.583, Fire

Dynamics II, Winter 2003, Lecture #
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Heat Release Rate: Well-ventilated Fire

Well-ventilated fires (diffusion flames in open)
experience incomplete combustion
Reduction in combustion efficiency means net heat of
combustion is not released
Actual (chemical) heat release rate (kW) is

Q = H ch m

Eqn (5-2)

Hch = Actual (chemical) heat of combustion (kJ / g)

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Dynamics II, Winter 2003, Lecture #
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Heat Release Rate: Well-ventilated Fire

Rate heat is convected above flame (kW):

Q conv = H con m

Eqn (5-3)

Rate heat is radiated away by flame (kW):

Q rad = H rad m

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Eqn (5-4)

Heat Release: Well-ventilated Fires (2)

M aterial
M ethan e
E th ane
P ro pane
B utane
H eptane
O ctan e
G aso lin e *
K erosen e
B en zene
M ethan ol
E th anol
PE
PP
PM M A
PS
P S (fo am )
P U (flex ib le fo am )
P U (rig id foam )
PVC
W oo d (red o ak )
W oo d (p in e)

H C (kJ/g )
50 .1
47 .1
46 .0
45 .4
44 .6
44 .5
44 .6
44 .1
40 .1
20 .0
27 .7
43 .6
43 .4
25 .2
39 .2
38 .2
26 .2
26 .0
16 .4
17 .1
17 .9

H ch (k J/g)
49 .6
45 .7
43 .7
42 .6
41 .2
41 .0
41 .2
40 .3
27 .6
19 .1
25 .6
38 .4
38 .6
24 .2
27 .0
25 .6
17 .8
16 .4
5 .7
12 .4
12 .4

H con (k J/g )
4 2.6
3 4.1
3 1.2
2 9.6
2 7.6
2 7.3
2 7.6
2 6.2
1 1.0
1 6.1
1 9.0
2 1.8
2 2.6
1 6.6
1 1.0
9.9
8.6
6.8
3.1
7.8
8.7

H rad (kJ/g)
7 .0
11 .6
12 .5
13 .0
13 .6
13 .7
13 .6
14 .1
16 .5
3 .0
6 .5
16 .6
16 .0
7 .6
16 .0
15 .7
9 .2
9 .6
2 .6
4 .6
3 .7

Carleton University, 82.583, Fire

Dynamics II, Winter 2003, Lecture #
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Generation of Species: Perfect Combustion

Only CO2 and H2O are generated
Example: Complete combustion of methanol
2 CH3OH + 3 O2 2 C O2 + 4 H2O
(64 g)

(96 g)

(88 g)

(72 g)

Define yield of CO2 :

m co2 = Yco m
2

Eqn (5-5)

Maximum possible yield: Y = 88 g / 64 g = 1.38

CO
2

Carleton University, 82.583, Fire

Dynamics II, Winter 2003, Lecture #
5

Generation of Species: Well-ventilated Fires

Well-ventilated fire involves incomplete combustion:
CO2, H2O, CO, C (soot) and hc (hydrocarbons) are
generated
Rate of generation of chemical species is proportional
to rate of generation of volatiles

mi = Yi m

(kg s-1)

Eqn (5-6)

Yi = Yield of species i (kg / kg)

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Dynamics II, Winter 2003, Lecture #
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Well-ventilated Methanol Fires

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Well-ventilated Methanol Fires

m"CO = 1.3 m"

2

YCO = 1.3

or

Complete combustion of methanol yields maximum

possible yield of CO2:

YCO = 88 g / 64 g = 1.38
2

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Yields in Well-ventilated Methanol Fires

Carbon dioxide:

YCO = 1.3

Carbon monoxide:

YCO = 0.0010

Hydrocarbons:

Yhc ~ 0.0

Soot (carbon):

YS ~ 0.0

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Chemical Species: Well-ventilated Fires (2)

M a te ria l
M e th a n e
E th a n e
P ro p a n e
B u ta n e
H e p ta n e
O c ta n e
G a s o lin e *
K e ro se n e
B enzene
M e th a n o l
E th a n o l
PE
PP
PM M A
PS
P S (fo a m )
P U (fle x ib le fo a m )
P U (rig id fo a m )
PVC
W o o d (re d o a k )
W o o d (p in e )

Y C O 2 (g /g )
2 .7 2
2 .8 5
2 .8 5
2 .8 5
2 .8 5
2 .8 4
2 .8 5
2 .8 3
2 .3 3
1 .3 1
1 .7 7
2 .7 6
2 .7 9
2 .1 2
2 .3 3
2 .3 0
1 .5 5
1 .5 2
0 .4 6
1 .2 7
1 .3 3

Y C O (g /g )
0 .0 0 1
0 .0 0 5
0 .0 0 7
0 .0 1 0
0 .0 1 1
0 .0 1 0
0 .0 1 2
0 .0 6 7
0 .0 0 1
0 .0 0 1
0 .0 2 4
0 .0 2 4
0 .0 1 0
0 .0 6 0
0 .0 6 5
0 .0 1 0
0 .0 3 1
0 .0 6 3
0 .0 0 4
0 .0 0 5

Y h c (g /g )
0 .0 0 1
0 .0 0 1
0 .0 0 3
0 .0 0 4
0 .0 0 4
0 .0 0 4
0 .0 0 4
0 .0 1 8
0 .0 0 1
0 .0 0 7
0 .0 0 6
0 .0 0 1
0 .0 1 4
0 .0 1 6
0 .0 0 2
0 .0 0 3
0 .0 2 3
0 .0 0 1
0 .0 0 1

Y S (g /g )
0 .0 1 3
0 .0 2 4
0 .0 2 9
0 .0 3 7
0 .0 3 8
0 .0 3 7
0 .0 4 2
0 .1 8 1
0 .0 0 8
0 .0 6 0
0 .0 5 9
0 .0 2 2
0 .1 6 4
0 .2 1 0
0 .1 3 1
0 .1 3 0
0 .1 7 2
0 .0 1 5
0 .0 1 5

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Well-ventilated vs. poorly-ventilated fires

m a = mass flow rate of air into flame (kg s-1)

m = mass flow rate of volatiles into flame (kg s-1)

r = stoichiometric air requirement (kg / kg)

r kg of air are required for complete
combustion of 1 kg of fuel

Wood:
Wood volatiles:
PMMA:
polystyrene:
Polyethylene:

r ~ 5.7 (page 184 Drysdale)

r ~ 4.6 (page 184 Drysdale)
r = 8.27 (page 2-36 Fire Dynamics I)
r = 13.25
r = 14.76
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 = Equivalence Ratio

rm

ma

Eqn (5-7)

ma / r

< 1 well-ventilated fire (fuel lean)

= 1 stoichiometric mixture
> 1 poorly-ventilated fire (fuel rich)
Steward for turbulent diffusion flames 0.25
For wood & plastics:
at LFL ~ 0.05
at UFL ~ 4.0
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Example Calculation of Equivalence Ratio

Post-flashover Fires Involving Wooden Cribs
Harmathy (1972) identified two burning regimes for
room fires involving wooden cribs:
ventilation-controlled & fuel-surface controlled

R = m = mass loss rate of fuel (kg s-1)

= ventilation parameter (kg s-1)
= O A g h = 3.76 A h
Af = exposed surface area of fuel (m2)

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Example Calculation of Equivalence Ratio

Post-flashover Fires Involving Wooden Cribs

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Example Calculation of Equivalence Ratio

Post-flashover Fires Involving Wooden Cribs
Post-flashover fire is ventilation-controlled if
/ Af < 0.63 kg m-2 s-1

A h A f < 0.07 m1/2

Eqn (5-8)

Fuel mass loss rate is

m = 0.0236 kg s 1

m = 0.09 A h kg s 1

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Eqn (5-9)

18

Rate of Entry of Air - From Lecture 4

Ta

2 1 g

Tf
T
1 + f
Ta

ma = C b h h a
3

2/3

1/ 3


m
1+

m a

3/ 2

C = 0.68; a = 1.2 kg m-3; g = 9.8 m s-2 and A = b h

m a = 2.4 A h

Ta
1
T

T
1 + f
Ta

2/3

1/ 3

1+ m

m a

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3/ 2

19

The Coefficient C1

m a = C1 A h

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10

Assume Tf ~ 1000C = 1273 K

2.1 A h

ma =

2/3

1 + 1.6 1 + m m a

3/2

m = 0.09 A h kg s 1

Solve by iteration: 1st guess: m a = 0.50 A h kg s 1

1
Find: m a = 0.45 A h kg s

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Example Calculation of Equivalence Ratio

Post-flashover Fires Involving Wooden Cribs
For ventilation-controlled post-flashover fire

m = 0.09 A h kg s 1

m a = 0.45 A h kg s 1
r = 4.6
Equivalence ratio is ~ 0.92

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11

Post-flashover Fires Involving Wood, PMMA & PE

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Example Calculation of Equivalence Ratio

Post-flashover Fires Involving PMMA Cribs
For ventilation-controlled post-flashover fire

m = 0.09 A h kg s 1

m a = 0.45 A h kg s 1
r = 8.27
Equivalence ratio is ~ 1.65

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Dynamics II, Winter 2003, Lecture #
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12

Example Calculation of Equivalence Ratio

Post-flashover Fires Involving PE
For ventilation-controlled post-flashover fire

m = 0.09 A h kg s 1

m a = 0.45 A h kg s 1
r = 14.76
Equivalence ratio is ~ 2.95

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Impact of Ventilation on Combustion Dynamics

Many small-scale experiments have been conducted
to assess the impact of ventilation on heat release and
generation of chemical species employing
FMRC Flammability apparatus (small-scale)
Fire Research Institute enclosure (0.022 m3)
Limited full-scale experimental data

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13

Impact of Ventilation on Heat Release

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Impact of Ventilation on Heat Release

ch =

H ch ( )

H ch ( << 1)

Eqn (5-10)

Hch(<<1) = well-ventilated limit of the chemical heat

of combustion
Experimental data correlation of the form

ch = 1 0.97 exp( 2.5 1.2 ) Eqn (5-11)

Correlation holds for non-halogenated polymers. For
halogenated polymers like PVC, a different correlation
applies.
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14

Impact of Ventilation on Convective Heat Release

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Impact of Ventilation on Convective Heat Release

con = H conv ( ) H

conv (

<< 1)

Eqn (5-12)

Hconv(<<1) = well-ventilated limit of convective heat

of combustion
Experimental data correlation of the form

con = 1 exp( 2.5 2.8 )

Eqn (5-13)

Higher fraction of chemical heat of combustion is

converted to radiative heat of combustion as move
from well-ventilated to poorly-ventilated conditions
For halogenated polymers (PVC), different correlation
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15

Impact of Ventilation on Consumption of O2

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Impact of Ventilation on Consumption of O2

O2

C O2 ( )

C O2 ( << 1)

Eqn (5-14)

CO2 = mass of O2 consumed per mass of fuel

Experimental data correlation of the form

O 2 = 1 0.97 exp( 2.5 1.2 ) Eqn (5-15)

Compare Eqn (5-15) with Eqn (5-11)
For halogenated polymers (PVC), different correlation

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16

Impact of Ventilation on Generation of CO2

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Impact of Ventilation on Generation of CO2

CO2

YCO2 ( )

YCO2 ( << 1)

Eqn (5-16)

YCO2 = Yield of CO2 = mass CO2 generated / mass of fuel

Experimental data correlation of the form

CO 2 = 1 exp( 2.5 1.2 )

Eqn (5-17)

Compare Eqn (5-17) with Eqns (5-15) & Eqn (5-11)

For halogenated polymers (PVC), different correlation

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17

Impact of Ventilation on Generation of CO

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Impact of Ventilation on Generation of CO

CO

YCO ( )

YCO ( << 1)

Eqn (5-18)

YCO = Yield of CO = mass of CO generated / mass of fuel

Experimental data correlation of the form

CO = 1 + exp( 2.5 )

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Eqn (5-19)

36

18

Impact of Ventilation on Generation of CO

Combustible
Polystyrene (PS)
Polypropylene (PP)
Polyethylene (PE)
Nylon
PMMA
Wood

2
10
26
36
43
44

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2.5
2.8
2.8
3.0
3.2
3.5

37

Impact of Ventilation on Generation of Hydrocarbons

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19

Impact of Ventilation on Generation of Hydrocarbons

hc

Yhc ( )

Yhc ( << 1)

Eqn (5-20)

Yhc = Yield of hyrocarbons

Experimental data correlation of the form

hc = 1 + exp( 5.0 )

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Eqn (5-21)

39

Impact of Ventilation on Generation of Hydrocarbons

Combustible
Polystyrene (PS)
Polypropylene (PP)
Polyethylene (PE)
Nylon
PMMA
Wood

25
220
220
1200
1800
200

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1.8
2.5
2.5
3.2
3.5
1.9

40

20

Impact of Ventilation on Generation of Soot

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Impact of Ventilation on Generation of Soot

=
S

YS ( )

YS ( << 1)

Eqn (5-22)

YS = Yield of soot = mass of soot generated / mass of fuel

Experimental data correlation of the form

S = 1 + exp( 2.5 )

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Eqn (5-23)

42

21

Impact of Ventilation on Generation of Soot

Combustible
Polystyrene (PS)
Polypropylene (PP)
Polyethylene (PE)
Nylon
PMMA
Wood

2.8
2.2
2.2
1.7
1.6
2.5

1.3
1.0
1.0
0.8
0.6
1.2

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Engineering Predictions
Yields of Chemical Species in Fire
During all stages of fire, yield of most species (CO2,
soot, HCl and HCN in real-scale scenario is same as
in bench-scale tests (same )
During early stages of room fire, yield of CO in a realscale scenario is similar to bench-scale tests (same )
Following flashover, yield of CO is independent of
chemical structure of fuel. Bench-scale tests cannot
accurately predict CO yields in post-flashover fires.

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Engineering Predictions
Prediction of Yield of CO
Important because CO inhalation is most common
cause of death in fires (USA)
Death patterns need need CO prediction methods
for post-flashover fires {0.5 < < 3.0}
For post-flashover fires assume (within the enclosure)
YCO = 0.2

Eqn (5-24)

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Prediction of Yield of CO (outside Enclosure)

Consider flame exiting room (post-flashover fire)
If flame rises vertically, does not impinge physical
obstacles, and is in an area of plentiful O2,
CO is incinerated. YCO = well-ventilated limit
since is small.
If flame is flattened horizontally against a ceiling,
impinges obstacles (heat sinks) or gets air from a
long corridor
Little incineration of CO. YCO = 0.2 as in room.

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Life Safety Considerations

Smoke = solids, liquids & gases
Hazards presented by smoke:
toxicity
obscure visibility
excessive thermal exposure
Consider exposure conditions which may prevent
occupants of average susceptibility from escaping
unassisted
Adverse effects following exposure not considered

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Carbon Monoxide
Suppose CO is the only toxicant present
Maximum time, t (min), that the average human can
remain in an atmosphere with high levels of CO
{concentration VCO of CO in ppm} is
t = 35,000 / VCO

Eqn (5-25)

If the concentration of CO is time dependent, which it

usually is, then
t

V (t' ) dt' = 35,000

CO

Eqn (5-26)

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24

Visibility in Smoke
S = visibility (m)
For light-emitting signs:
For light-reflecting signs:

KS = 8
KS = 3

Eqn (5-27)

Data based on subjects viewing smoke through glass

so irritant effect of smoke eliminated, so visibility may
be reduced compared with Eqn (5-27).

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Extinction Coefficient K
Proportional to mass concentration of soot
Eqn (5-28)
K = Km Cs
Km = specific extinction coefficient (m2 / g)
Cs = mass concentration of smoke (g / m3)
For flaming combustion of wood & plastics
Eqn (5-29)
Km ~ 7.6 m2 / g
For pyrolysis (no flaming) of wood & plastics
Eqn (5-30)
Km ~ 4.4 m2 / g
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25

For a Closed System

Mass concentration of smoke (g / m3)
Cs = ms / V = Ys mf / V

Eqn (5-31)

ms = mass of soot produced (g)

V = volume occupied by smoke (m3)
Ys = yield of soot (g / g)
mf = mass of fuel volatilized (g)

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For an Open (Flowing) System

Mass concentration of smoke (g / m3)

CS =

mS

YS m

Eqn (5-32)

m S = mass generation rate of soot (g s 1 )

m = mass loss rate of fuel (g s 1 )

YS = yield of soot

V = volumetric flow rate of smoke (m 3 s 1 )

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26

Exposure of Skin to Convection

Tenability limit for exposure of skin to convected heat
is 120C, above which pain and burns occur quickly.
Depending on length of exposure, convected heat
below 120C may also cause hyperthermia.
For fully clothed people, time for incapacitation (t in
min) is given in terms of T (C )
t = (4.1 x 108) T-3.61

Eqn (5-33)

For unclothed or lightly clothed people, time for

incapacitation (t in min) is given in terms of T (C )
t = (5 x 107) T-3.4

Eqn (5-34)

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Radiant Exposure of Skin

Tenability limit for exposure of skin to radiant heat is

q"

Eqn (5-35)
< 2.5 kW m-2
Below 2.5 kW m-2, exposure can be tolerated for 30
min without affecting the time available for for escape
1d2

Above 2.5 kW m-2, the time to burning of skin(t in min),

due to radiant heating ( q" in kW m-2) decreases

1d2

rapidly as follows

t = 4 {q"1d2 }-1.35
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Eqn (5-36)
54

27

References
D. Drysdale, An Introduction to Fire Dynamics,Wiley, 1999, Chap 1
A. Tewardson, Generation of Heat and Chemical Compounds in
Fires" Section 3 / Chapter 4, SFPE Handbook, 2nd Ed. (1995)
ISO/DTS 13571, Life threat from fires - guidance on the estimation
of the time available for escape using fire data.

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