MSc Lecture 12:

Heat Release Rate

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

How big is a fire?

Answer:
Heat release rate!

One of the most important parameters that

can be used to characterise an unwanted
fire is the rate of heat release.
2

It provides

an indication of the size of the fire,

the rate of fire growth, and consequently

the release of smoke and toxic gases,
(such as sizing of smoke exhaust system)

the time available

suppression,

the types of suppressive action that are

likely to be effective, and

other attributes that define the fire hazard.

for

escape

or

Example:
Change of HRR
due to fire system

Plots showing momentary and sustained increases in the heat release rate of heptane and
diesel pool fires with application of water mist.
From A Closer Look at the Fire Extinguishing Properties of Water Mist Fire Safety
Science Proceedings of the Fourth International Symposium, pp. 47-60
4

Most Important: Input to Fire Models

Although EPBFC Fire Model

Fire Model is a key element in EPBFC

Combustion Chemistry

Turbulence

Radiation

cannot be
simulated
successfully !

Intermediate Chemistry

As in a liquid pool fire, it is obvious that turbulence,

intermediate combustion chemistry and thermal
radiation have to be included instantaneously.

Burning hydrocarbon completely will give water and

carbon dioxide.
HxCy CO2 + H2O

Incomplete combustion gives carbon monoxide, which

can be further oxidized.
CO + O2 CO2

There are many intermediate reactions.

6

C
CO2
CO
O2
N2
H2O

Thermal
radiation

O2N2

Smoke

O2N2

O2N2

O2N2

Air

O2N2

Fuel
Vapour

Combustion zone (Hydroxylation: Chain reactions)

Liquid
fuel

Pyrolysis zone

Anatomy of a fire. (Courtesy of Walter M. Haessler.)

7

O2N2

Fuel

Range of fuel :

Simplest gaseous
hydrocarbons
e.g. CH4

Solids of high
molecular weight
e.g. cellulose PE

Burning under appropriate conditions :

Fuel + Oxygen Combustion Product + Heat
Rapid Oxidation with heat evolved

Even simple compound CH4 would have 40

intermediate reactions, at least 12 identified
CH4 + 2O2 ... CO2 + 2H2O
Intermediate product : CO + soot

Flame :
* Visible portion of the oxidation process
* A gas phase phenomenon

10

Reaction of methane
(1) CH4 + O2

CO3 + HO2

(2) CH3 + O2

CH2O + OH

(3) OH + CH4

(4) HCO + O2

(5) HO2 + CH4

(6) HO2 + CH2O

(7) OH + CH2O

CH3 + H2O

CO + HO2
Transfer
H2O2 + CH3

H2O2 + HCO

H O + HCO

(8) CH2O + O2

HCO + HO2 Branching

(9) OH + Wall

Termination

(10) H2O + Wall

Initiation

Termination
Termination

11

Oxidation of CO
(1) CO + O2

CO2 + O

(2) O + O2 + M

O3 + M

(6) O3 + CO + M

CO2 + O2 + M

Initiation

Transfer
(3) O3 + CO + CO CO3 + CO2

(4) O3 + CO
CO2 + 2O 69.9 kJ
Branching

(5) O3 + CO
CO3 + O
(7) O + CO + M

(8) CO3 + O

CO2 + M + 531.3 kJ Termination

2CO2

Reaction of CO under steam

(1) H2O + CO

CO2 + H2

(Surface)

(2) H2 + O2

H2O2

(Surface)

(3) H2O2 + M

2OH + M

Initiation

(4) OH + CO

CO2 + H

(5) H + O2 + M

(6) HO2 + CO

(7) O + O2 + M

(8) H + O2

(9) O + H2

OH + H

(10) H2O2 + CO

CO2 + H2O

(11) H2O + Wall

De-activation

12

HO2 + M

CO2 + OH Transfer

O3 + M

OH + O

Branching

Termination

13

Solid/Liquid fuel must be converted into Gas

Burning Liquid :

Burning Solid :

Evaporative boiling at the surface to give vapour

Chemical Decomposition (Pyrolysis) is necessary to

yield lower molecular weight products which is
volatile from the surface and enters the flaming region.

Requires more energy than evaporation

\ Much higher surface temperature (400 C)

14

Thermal Decomposition of Polymer

Sublimation
e.g. Methenamine

Solid

Melting

Evaporation
Low mol wt paraffax wax

Melting

Decomposition
Themoplastic
high mol wt waxes

Decomposition
+ Melting

+ Evaporation

Decomposition
Polyurethanes

Liquid

Decomposition + Evaporation
Cellulose, thermosetting resins
(except polyurethane)
The fire behaviour of the combustible
materials can be interpreted in terms
of the properties of those vapour
(e.g. composition, reactivity & rate of formation)

+ Evaporation

Vapour

15

The fire behaviour of the combustible

materials can be interpreted in terms of the
properties those vapour
(e.g. composition, reactivity and rate of formation)

16

In flaming combustion those volatiles will be

consumed inside the flame.

Under other conditions, e.g. pyrolysis without

combustion, or smouldering combustion, the high
boiling point liquid products and tars will condense to
form an aerosol smoke as they mix with cool air.

Other reactions :
* Unzipping or end-chain scission
* Random chain scission

* Chain stripping :

Polymer backbone unchanged,

but functional group lost

* Cross Linking

e.g. PVC

+ HC1

PMMA as an example

Taking poly(methyl methacrylate) PMMA as an

example, the chemical structure is:
CH3
[ CH2 C
]
n
COOCH3

The chemical reactions of PMMA burning are

very complex.

17

There are 7 possible groups of intermediate reactions:

Thermal degradation

Thermal oxidative degradation

Decomposition of monomer MMA

Methane combustion

Methanol combustion

Formaldehyde oxidation

Acetylene combustion

18

Taking the group of methane combustion as

an example, there are 77 intermediate
reactions:

19

H+O2 = O + OH

(1)

O+ H2 = H + OH

(2)

OH + H2 = H2O + H

CH3 + H = CH2(S) + H2
CH3+ O

(3)

OH + OH = H2O + O

HO2 + M

HO2 + H

OH + OH

HO2 + OH

H2O + O2

(5)
(6)

(7)
(8)

CH3 + OH = CH2OH + H
CH3 + O2
CH3 + HO2

(16)

(17)

CH3 + OH = CH2(S) + H2O

H2O + M

H + O2 + M

CH2O + H

CH3 + OH = CH2 + H2O

(4)

H + OH + M

(15)

(18)
(19)

CH2OH +O

(20)

CH2OH + OH

CH3 + HCO

CH4 +CO

(21)

(22)

CO + OH = CO2 + H

(9)

CH2OH + M

CH2O + H + M

CH4 + H= CH3 + H2

(10)

CH2OH + O2

CH2O + HO2

CH4 + O

CH3 + OH

CH4 + OH = CH3 + H2O

CH3 + H
CH3 + H = CH2 + H2

(12)

CH4
(14)

(13)

(11)

(23)
(24)

CH2O + H

HCO + H2

CH2O +OH

HCO + H2O

(26)

HCO + M

CO + H + M

(27)

HCO + H

CO + H2
20

(25)

(28)

HCO + OH

CO + H2O

HCO + O2

CO + HO2

CH2 + H + M

(30)

CH3 + M

CH2 + H = CH + H2

(32)

CH2 + O

CO + H + H

CH2 + O
CH2 + OH

CO + H2

(35)

(36)

CH2O + O

CH2 + O2

CO2 + H2 (38)

CO + H

CH + OH

HCO + H

CH + OH = C + H2O

(37)

HCO + O

(46)

CH2O + H

(47)

CH + CO2

HCO + CO

(48)

C + OH

CO + H

(49)

C + O2

CO + O

(50)

NH + H

N + H2

(51)

NH + O

NO + H
N + OH

(40)

NH + NO = N2O + H

CH2O +CO

(41)

N + OH

(42)

(44)

CH + H2O

NH + O

(39)

(43)

(45)

CO + OH + H

CH2(S) + CO2
CH + H = C + H2

(33)

(34)

CH2 + O2

CH2(S) + M = CH2 + M

(31)

CH + O

CH + O2

CH2O + H

CH2 + OH = CH + H2O

CH2(S) +O2

(29)

N + O2

(53)

(54)

NO + H
NO + O
21

(52)

(55)
(56)

N + NO = N2 + O
O + N2 + M
N2 O + H

CH2 + NO

(57)
N2 O + M
N2 + OH

CH2(S) + NO

(58)

(59)

HCN + O
CN + O

NCO + H

(60)

C + NO

HCN + O

NH + CO

(61)

C + NO

HCN + OH

CN + H2O
NCO + H2

(62)

CN + OH

NCO + H

(64)

CN + O2

NCO + O

(65)

NCO + H
NCO + OH
NCO + NO

NH + CO

N2O + CO
HCN + N

C + N2

CN + N

(73)
(74)

(75)

(76)

HCN + 2H

(66)

NO + CO + H

CH + N2

N + CO

N + CO2 = NO + CO
N + CH2

(63)

(71)

OH + HCN

CH + NO

HCN + O

HCN + OH

NCO + H2

(67)

(68)

(69)
(70)
22

(77)

(72)

Mass Loss Rate Method:

The amount of heat given out per unit time:

Q (unit in W kW MW)

H c
Q m
where

m
Hc

= mass loss rate of fuel: kgs-1

= calorific value: Jkg-1 MJkg-1
= combustion efficiency: 0 to 1

is easy to determine but not for !

m

23

Mass loss curve

mo

dm
Slope =
dt
24

Oxygen Consumption Method:

Methods based on the oxygen consumption principle for

measuring the rate of heat release reliably and
accurately are now available.

The principle depends upon the fact that the heat of

combustion of organic materials per unit of oxygen
consumed are approximately the same.

This is because the processes in the combustion of all

these products involve the breaking of C-C and C-H
bonds (which release approximately the same amount of
energy) with the formation of CO2 and H2O.
25

It has been shown that the measurement of the rate of

oxygen consumption is a simple and reproducible
method of measuring the rate of heat release.

It may be shown that the heat release from most fuel

commonly encountered in fires are approximately the
same, namely 13.1 106 J per kg of oxygen consumed.

Hence, the measurement of the precise concentration of

oxygen in the exhaust duct and the volumetric flow of
air give the rate of oxygen consumption.

26

To determine the amount of oxygen consumed, with

the universal constant Hox, i.e. giving out about
13.1 MJ of heat per unit mass of oxygen consumed:
Hox = 13.1 MJkg-1

Instrument:
Air flow rate
Temperature
Oxygen level

Exhaust Hood with fan + duct

27

Key element: Duct Section + Oxygen Analyzer

28

Cone Calorimeter:

29

Hazard Calculations, SFPE handbook of fire protection engineering. Quincy, Mass. : National
Fire Protection Association ; Bethesda, Md. : Society of Fire Protection Engineers, 3rd ed. (2002).
30

Hazard Calculations, SFPE handbook of fire protection engineering. Quincy, Mass. : National
Fire Protection Association ; Bethesda, Md. : Society of Fire Protection Engineers, 3rd ed. (2002).
31

Hazard Calculations, SFPE handbook of fire protection engineering. Quincy, Mass. : National
Fire Protection Association ; Bethesda, Md. : Society of Fire Protection Engineers, 3rd ed. (2002).
32

Hazard Calculations, SFPE handbook of fire protection engineering. Quincy, Mass. : National
Fire Protection Association ; Bethesda, Md. : Society of Fire Protection Engineers, 3rd ed. (2002).
33

Hazard Calculations, SFPE handbook of fire protection engineering. Quincy, Mass. : National
Fire Protection Association ; Bethesda, Md. : Society of Fire Protection Engineers, 3rd ed. (2002).
34

35

FURNITURE Calorimeter:

36

Combusting Behaviour of Upholstered

Furniture (CBUF) project
37

From: Quintiere, J.G. , Principles of fire behavior, Delmar Publishers, Albany, N.Y., 1998.
38

From: Quintiere, J.G. , Principles of fire behavior, Delmar Publishers, Albany, N.Y., 1998.
39

From: Quintiere, J.G. , Principles of fire behavior, Delmar Publishers, Albany, N.Y., 1998.
40

From: Quintiere, J.G. , Principles of fire behavior, Delmar Publishers, Albany, N.Y., 1998.
41

From: Quintiere, J.G. , Principles of fire behavior, Delmar Publishers, Albany, N.Y., 1998.
42

ROOM Calorimeter:

43

44

INDUSTRY Calorimeter:
at SP, Sweden

45

46

Hazard Calculations, SFPE

handbook of fire protection
engineering. Quincy, Mass. :
National Fire Protection
Association ; Bethesda, Md. :
Society of Fire Protection
Engineers, 3rd ed. (2002).

Factory Mutual
47

48

Heat release rate/kW

Heat release rate/kW

A site is needed for

full-scale burning test !
PolyU/HEU Assembly Calorimeter:
A full-scale burning facility!
at Lanxi, Harbin, Heilongjiang, China
49

Selection of site for full-scale

burning test:

Away from urban area

Environmental problem

Transportation to the site

Water, electricity, heating supplies

Cost

50

Harbin

Beijing

Hong Kong
51

Harbin Airport

52

Harbin
53


54

Harbin:

55

56

HEU
57

Full-scale burning test

cannot be done
even at downtown Harbin !

58

Lanxi
Harbin

Heilongjiang Province

59


60


61


62

Autumn Harvest

63


64

Outside view
65

Inside
66

ISO9705

Exhaust
hood

ISO-Room Corner Fire Test

67

Duct Section
68

Fan
69

70

Prof. Gao and Prof. Luo

71

Visit with FSD/HKAA in August, 2002

72

Discussion / Taking rest in a nearby Guesthouse

73

Discussion HRR with FSD/HKAA

74

ISO 9705
75

Preparation
76

Ignition Source
77

Retail shop fire

78

Preparation
79

80

Observing test
81

Return to Harbin
82

83

84

August, 2003

Smaller new site: Budget cut

85

86

Karaoke box as an example:

Furniture sofa
Wood partition

87

Wood
partition

Furniture
sofa

88

89

+ Furniture

Burning wood partition + furniture

90

91

Mass Balances
Combustion & Energy Release

All combustion reaction takes place with the

release of energy
Heat of combustion : HC

Total amount of heat released when a quantity

of fuel is completely oxidized
e.g. C3H8 + 5 O2 3 CO2 + 4H2O

92

Propane

Exothermic Reaction

If H2O is Vapour : HC = -2044 kJ/mol

Liquid : HC = -2220 kJ/mol
More Preferred because
water vapour is emitted
in fire
The difference : 44 kJ/mol is the latent heat of
vaporization of water
[2220 - 2044 = 176 = 4 x 44]

93

Molecular Wt of C3H8 = 12 x 3 + 8 = 44
- 2044
\ H C
kJ/g - 46.45 kJ/g
44

94

If the reaction is proceeded at constant pressure, the

energy is released as a change in enthalpy (H) of the
system.
Bomb calorimeter : to determine HC at const volume.

A known mass of fuel is burnt completely in pure

oxygen.

Assuming an adiabatic condition, the quantity of heat

released is calculated from the Temp raised of the
calorimeter and its content.

Using pure oxygen would ensure complete combustion,

this gives heat released at constant volume i.e. the
change in internal energy U

95

Enthalpy Changed : H = U + PV

Work done for the Chemical

system to expand
PV is obtained from
PV = n R T
PV = n R T
Number of moles changed : (3 + 4) - (1 + 5) = 1

If T ~ 298 K
PV ~ 1 x R x 298 ~ 2.5 kJ/mol
\

Very small correction

96

The heat of formation can also be measured by a

Bomb Calorimeter
[Enthalpy changed when a compound is formed at its
standard state]
e.g. C(Graphite) + O2(Gas) CO2(Gas)

H f298 ( CO 2 ) 393.5 kJ / mol

-ve value is more stable

97

For propane C3H8 :

H C(C 3H 8 ) 3 H f(CO 2 ) 4 H f(H2O) - H f(C3H 8 ) - H f(O2 )

Zero

The reaction might be incomplete in a fire

\

better express HC in terms of oxygen (or air)

consumed

e.g. C3H8 + 5 O2 3 CO2 + 4 H2O

HC = - 2044 kJ/mol of propane

98

In terms of oxygen :
1 mole of C3 H 8 5 moles of O 2
H C, OX

2044
5

kJ/mol oxygen

(-408.8)

2044
5 32
(-12.77)

kJ/g of oxygen

99

Huggett suggested :

HC,OX for all organic liquid/gas are the

same :

H C, OX -12.72 3% kJ/g of oxygen

100

If the rate of oxygen consumed is known

Rate of heat released can be calculated

[This is done in a new standard test for measuring the
Rate of Heat Released RHR]
Rate of heat released :
(0.21 - n ) V10 3 H
Q
C
2
O2
C, OX
Mole fraction of oxygen
in the scrubbed exhaust gas
from the combustion chamber

Density

Volumetric flowrate and of air

101

HC can also be expressed in terms of air

consumed

Nitrogen
~ 3.76
Oxygen
\ 1 mole of O2 comes with 3.76 of N2 in 4.76
mole of air
So C3H8 + 5 O2 3 CO2 + 4H2O

becomes
C3H8 + 5 (O2 + 3.76 N2) 3 CO3 + 4 H2O + 18.8 N2

102

Nitrogen serves as an inert gas.

\ HC (2044 kJ) of heat evolved when there is

5 x 4.76 (23.8) moles of air present
\ HC,air

2044
=
kJ/mol of air
23 .8

= 85.88 kJ/mol of air

85 .88
=
kJ/g of air
28 .95

103

This kind of stoichiometric (Mass Balancing)

eqn can be used to calculate the air
requirements for the complete combustion of
any fuel.
i.e. 1 mole of O2 means 4.76 moles of air
[1 + 3.76]

104

e.g. Combustion of PMMA C5H8O2

C5H8O2 + 6(O2 + 3.76N2) 5 CO2 + 4H2O + 22.56N2

\ 1 mole of C5H8O2 requires 6 x 4.76 moles of air
(28.56)

Mol wt of C5H8O2 = 100

Mol wt of air = 28.95
\

Wt of air requires to burn 1 g of fuel

28.95
28.56

Wt of air = 8.268g

1 g of C5H8O2
100
=
1

105

Another Example:

Methanol, CH3OH
2 CH3OH +

3 O2 2 CO2 + 4 H2O

2 moles

3 moles of O2 or
3 4.76 moles of air

Mol wt of CH3OH is 32
Mol wt of Air is 28.95

106

Burning 1 g of methanol would require x g of

air:
x
1
28.95 32
3 4.26
2
28 .95 3 4.76
x
32 2

or

x = 6.46

Burning 1 g of methanol requires 6.46 g of air

107

In general :

1 kg of fuel + r kg of air (1 + r) kg products

r : Stoichiometric air requirement.