Industrial Fire Safety &

Risk Assessment

Dr. Ferdous Sarwar, Professor, IPE, BUET

 Outline

❑ Flammability of gas
❑ Flammability of liquids
❑ Consequence analysis-Discharge
❑ Consequence analysis-Dispersions
❑ Consequence analysis-Pool fires
❑ Consequence analysis-Flash Fires and Fireballs
❑ Consequence analysis-Explosions
❑ Risk-acceptable Loss and Informed Decision Making
 References

❑ D.A. Crowl & J.F. Louvar, “Chemical Process Safety: Fundamentals with
Applications,” (3rd Ed.) Prentice Hall, International Series in the Physical and
Chemical Engineering Sciences, 2011
❑ SFPE Handbook of Fire Protection Engineering (5th Edition), National Fire
Protection Association, Quincy, MA 201
❑ P. Lees, “Lees’ Loss Prevention in the Process Industries,” (4th Ed.), Elsevier, 2012
❑ Handnotes from UMD Dept of Fire Protection Engineering, Maryland, USA
 Introduction

Industrial facilities have unique hazards:

Chemical production or use

Storage of flammable or volatile materials

Access controls or personnel restrictions

 Introduction

Steps for an integrated approach include

Identification of possible accident scenarios

Analysis of consequences resulting in accidents

Evaluation of alternative protection methods

 Introduction
Hazard scenarios:
❑ Representative configurations for the accidental release of flammable/toxic material
❑ Discharge
❑ Dispersion
❑ Pool Fires
❑ Flash Fires and Fireballs
❑ Explosions
 Definition

❑ Combustion or Fire: A chemical reaction in which a substance combines with an

oxidant and releases energy.
❑ Auto-ignition temperature: A fixed temperature above which adequate energy is
available in the environment to provide an ignition source. (for example, Auto-
ignition temperature of Gasoline is 247–280 °C).
❑ Flash-point: The flashpoint of a liquid is the lowest temperature at which it gives off
enough vapor to form an ignitable mixture with air.
❑ Fire-point: The fire point is the lowest temperature at which a vapor above a liquid
will continue to burn once ignited; the fire point temperature is higher than the flash
point.
 Definition

❑ Flammability limits: Vapor-air mixtures will ignite and burn only over a well-
specified range of compositions.
❑ Explosion: An explosion is a rapid expansion of gases resulting in a rapidly moving
pressure or shock wave.
❑ Mechanical explosion: An explosion resulting from the sudden failure of a vessel
containing high-pressure nonreactive gas.
❑ Deflagration: An explosion in which the reaction front moves at a speed less than
the speed of sound in the unreacted medium.
❑ Detonation: An explosion in which the reaction front moves at a speed greater than
the speed of sound in the unreacted medium.
 Definition

❑ Confined explosion: An explosion occurring within a vessel or a building.

❑ Unconfined explosion: Unconfined explosions occur in the open. This type of
explosion is usually the result of a flammable gas spill.
❑ Dust explosion: This explosion results from the rapid combustion of fine solid
particles. Many solid materials (including common metals such as iron and
aluminum) become flammable when reduced to a fine powder.
❑ Shock wave: An abrupt pressure wave moving through a gas.
 Flash Point And Auto-ignition
Temperature Of Different Fuels

Auto-ignition
Fuel Flash Point (°C)
Temperature (°C)
Ethanol 16.6°C 363°C
Gasoline -43°C 280°C
Diesel >52°C 256°C
Jet Fuel >38°C 210°C
Kerosene >38-72°C 220°C
Vegetable Oil (Canola) 327°C 424°C
Biodiesel >130°C 373°C
Flammability of Gas
 Introduction

❑ Flammability of gas is a crucial aspect of fire safety. Flammable gases, when

mixed with air in the right proportions, can ignite and cause explosions.
Flammability limits, also known as explosive limits, define the range of gas
concentrations in air within which combustion can occur.
❑ Key Factors Affecting Flammability
▪ Gas Concentration: The concentration of flammable gas in air plays a significant
role in its flammability. Below the lower flammability limit (LFL), the gas
concentration is too low to sustain combustion. Above the upper flammability limit
(UFL), the gas concentration is too high to allow for sufficient oxygen for
combustion.
 Introduction

▪ Ignition Source: An ignition source, such as a spark, flame, or heat, is necessary

to initiate combustion. The energy provided by the ignition source must be
sufficient to overcome the activation energy required for the gas to react with
oxygen .
▪ Oxygen Concentration: Oxygen is the oxidizer in the combustion process, and its
concentration significantly impacts flammability. In environments with reduced
oxygen levels, the flammability of gases is reduced or even eliminated.
 Flammability of Gas

❑ Properties of Gases
Ideal Gas Laws: Constitutive relationship between mass (measured by number of
moles n,concentration C or mass density ρ),pressure p,volume V and temperature T.
The ideal gas law states that: pV = nRT, where R is the universal gas constant
n
Concentration C is defined as the number of moles per unit volume C =
V
p
Replacing this value of C in the equation of ideal gas law , p=CRT or C =
RT
 Flammability of Gas
m
Again, number of moles n = , where m = mass of the gas and M= molar mass
M
Substituting this value of n and dividing by V from the equation of ideal gas law ,
mR m R pM
p= T, and mass density ρ = , so p = ρ T, finally ρ =
VM V M RT
 Flammability of Gas

❑ Properties of Gases
Mixture of gases: Mixture composition is described in terms of –
Notation:
𝑉𝑘​ = Volume of component
V: Total volume of the mixture
nk​ : Number of moles of component
n: Total number of moles in the mixture
mk : Mass of component
m: Total mass of the mixture
Ns​ : Total number of species/components in the mixture
Volume fractionϕk​: Represents the portion of the total volume occupied by
component k.
𝑉 𝑉
ϕk = 𝑘 = σ𝑁 𝑘
V 𝑠
𝑘=1 𝑉𝑘
 Flammability of Gas

Mole fractionxk: Indicates the proportion of total moles contributed by component k.

nk n
xk = = σ𝑁 k
n 𝑘=1 nk
s

Mass fraction Yk: Shows the fraction of total mass made up by component k.
mk m
Yk= = σ𝑁 k
m 𝑘=1 mk
s

Normalization condition:
σ𝑁 𝑁s 𝑁s
𝑘=1 ϕk = σ𝑘=1 xk = σ𝑘=1 Yk = 1
s

This ensures that the sum of all fractions equals 1, meaning 100% of the gas mixture
is represented.
 Flammability of Gas

From the ideal gas law:

pVk = nkRT (for component k)
pV= nRT (for the whole mixture)

Dividing the first equation by the second:

pVk nkRT
=
pV nRT
Vk nk
⇒ =
V n
⇒ ϕk = xk
In an ideal gas mixture, the volume fraction ϕk of a component is equal to its mole
fraction xk .
.
 Flammability of Gas
mk
Mass fraction Yk=
m
Mass can be expressed as moles × molecular weight, mₖ = nₖMₖ
nₖMₖ
So, Yk= 𝑁 , as Total mass of the mixture m = σ𝑁 𝑘=1 nₖMₖ
𝑠
σ𝑘=1 nₖMₖ
𝑠

n n
Using mole fraction definition: xₖ = k= σ𝑁 k ⇒nk = xₖσ𝑁 𝑘=1 nk
s
n n
𝑘=1 k
s

substituting
( xₖ σ𝑁
𝑘=1 nk)Mₖ
s
xₖMₖ σ𝑁𝑘=1 nk
s
value of nk
By substituting value of nk, Yₖ = ⇒Yₖ =
σ𝑘=1 nₖMₖ
𝑁 𝑠 σ𝑘=1 nₖMₖ
𝑁 𝑠

The denominator can be written as σ𝑁 𝑁𝑠 𝑁s

𝑘=1 nₖMₖ = σ𝑘=1 (xₖ σ𝑘=1 nk )Mk
𝑠

= (σ𝑁 𝑁s
𝑘=1 nk)(σ𝑘=1 xkMk) Factoring out σ𝑘=1 nk
s 𝑁s

xₖMₖ σ𝑁 𝑘=1 nk
s
xₖMₖ σ𝑁 𝑘=1 nk
s
xₖMₖ
So, Yₖ = 𝑁 ⇒ Yₖ = ⇒ Yₖ =
( σ𝑘=1 nk)( σ𝑁𝑘=1 xkMk) ( σ𝑁
𝑘=1 nk)( σ𝑘=1 xkMk) 𝑘=1 xkMk
σ𝑁
s s s 𝑁 s s
 Flammability of Gas
nk
Mole fraction xk=
n
Number of moles can be expressed as Mass of component / molecular weight nₖ =
mₖ / Mₖ
mₖ / Mₖ
So, xk= 𝑁
σ𝑘=1 mₖ / Mₖ
𝑠

m
Using mass fraction,Yk= k ⇒mk = Yk.m
m
Y .m / Mₖ ( Y / Mₖ ).m
By substituting value of Yₖ, xk= 𝑁 k ⇒x ₖ = 𝑁 k Factoring out 𝑚
σ𝑘=1 Yk.m / Mₖ
𝑠
( σ𝑘=1 Yk / Mₖ ).m
𝑠

( Y / Mₖ ).m
⇒x ₖ = 𝑁 k
( σ𝑘=1 Yk / Mₖ ).m
𝑠

( Y / Mₖ )
⇒x ₖ = 𝑁 k
( σ𝑘=1 Yk / Mₖ )
𝑠
 Flammability of Gas

The molecular weight M of a gas mixture can be calculated in two ways:

Mole fraction approach xₖ
m
Molecular weight M = and m = M x n; where m is total mass and n is total
n
number of moles
Total mass m = σ𝑁 𝑁𝑠
𝑘=1 mₖ = σ𝑘=1 nₖ·Mₖ (sum of multiplication of each component's
𝑠

moles and molecular weight)

m σ𝑁 𝑠
nₖ·Mₖ
Now, M = = 𝑘=1
n n
nₖ
Since xₖ = (mole fraction definition), nₖ = xₖ x n
n
σ𝑁𝑘=1 xₖ x n ·Mₖ n( σ𝑁𝑘=1 xₖ ·Mₖ)
𝑠 𝑠

Again, M = = Factoring out n

n n
n ( σ𝑁𝑘=1 xₖ ·Mₖ)
𝑠

=
n
𝑵𝒔
M= σ𝒌=𝟏 xₖ ·Mₖ
 Flammability of Gas

Alternative way using mass fractionsYk

m 1 n
Molecular weight M = ⇒ =
n M m
Number of moles of each component nk = (mₖ/Mₖ)
Total number of moles n= σ𝑁 𝑘=1 (mₖ/Mₖ)
𝑠

1 Σ(mₖ/Mₖ)
Therefore: =
M m
Since Yₖ = mₖ/m (mass fraction) and mₖ = Yₖ x m
1 𝑘=1 (Yₖ x m / Mₖ)
σ𝑁 1 m ( σ𝑁
𝑘=1 Yₖ / Mₖ)
𝑠 𝑠

Again, = ⇒ = Factoring out m

M m M m
1 m ( σ𝑁
𝑘=1 Yₖ / Mₖ)
𝑠

⇒ =
M m
1
⇒ =σ𝑁 𝑠
Yₖ / Mₖ
M 𝑘=1
1
⇒ M= 𝑵
σ𝒌=𝟏 Yₖ / Mₖ
𝒔
 Flammability limits

❑ Flammable conditions for a fuel-air mixture: conditions (i.e. xF , p, T) that allow

combustion initiation near an ignition device (i.e., piloted ignition) as well as
combustion far from the ignition device (i.e., propagation of a premixed flame),
Here, xF = Mole fraction (or concentration) of fuel in the fuel-air mixture
p = Pressure of the mixture T = Temperature of the mixture

❑ For given temperature and pressure conditions, there is a finite range of flammable
fuel-air mixture compositions (i.e. a finite range of flammable values of xF).

0 < xF,LFL< xF < xF,UFL < 1

xF,LFL = Lower Flammability Limit xF,UFL = Upper Flammability Limit
 Combustion

❑ A chemical reaction that corresponds to a oxidation process:

CnHmOp + O2 CO2 + H2O

❑ An exothermic reaction:
CnHmOp + O2 CO2 + H2O + Heat

Fuel
Gas/Liquid/Solid

HEAT
Air
Oxygen, Nitrogen
 Combustion
Main features
▪ Fuel is in solid (e.g. wood), liquid (e.g. gasoline) or gaseous (e.g. methane,
propane) form.
▪ Oxidizer is typically in gas form; Oxidizer often corresponds to ambient air (21% O₂
+ 79% N₂)
▪ Non-flaming combustion occurs in solid phase (heterogeneous surface reactions)
and at low temperatures without flame (smoldering)
▪ Flaming combustion occurs in gas phase
▪ Flaming combustion with solid/liquid fuel; fuel mass needs to be gasified prior
to burning (evaporation for liquids; pyrolysis for solids)
 Combustion
Different modes of flaming combustion
Premixed flame: Fuel and air mix before burning (examples: gasoline engines, flash
fires, backdrafts).
Non-premixed flame: Fuel and air stay separate until burning point (examples: diesel
engines, candles, lighters, pool fires).
Partially-premixed flame: A combination where some mixing occurs before and
during combustion.

Premixed flame from a Gas Stove Non -Premixed flame from a Lighter
 Combustion
Premixed flame
Fuel and air mix before burning (examples: gasoline engines, flash fires, backdrafts).
Example: Bunsen burner (case corresponding to flammable fuel/air mixture in supply
tube).
 Combustion
Non-Premixed flame
Fuel and air remain separated prior to burning (e.g. Diesel engines, candle, cigarette
lighter, pool fire, etc). Example: Bunsen burner (case corresponding to pure fuel in
supply tube).
 Combustion
Thermodynamic aspects of combustion
❑ Global combustion equation: Represents the overall chemical reaction during
burning ; (Fuel + Oxidizer → Products + Heat)
❑ Stoichiometric composition: The precise fuel-air ratio where all fuel and oxygen
are completely consumed with no excess.
❑ Equivalence ratio: Measures actual fuel-air mixture relative to stoichiometric
conditions.
❑ Post-combustion state: The composition and temperature of gases after burning
depends directly on the equivalence ratio and it affects flame temperature,
emissions formation, and energy release.
 Combustion
Global combustion equation
CnHmOp + vO2O2 + vN2N2 vCO2CO2 + vH2O H2O + vN2N2 + Heat

FUEL AIR PRODUCTS

Inputs: n, m, p, b
Conservation of C, H, O and N atoms –
m p
vO2 = n + -
4 2
m p
vN2 = ( n + - ) X β , β = the nitrogen-to-oxygen ratio in air (approximately 3.76 in standard
4 2
atmospheric air).
vCO2 = n
m
vH2O =
2
 Combustion
Stoichiometric conditions
▪ The proportions of fuel and oxygen are those required by the combustion
equation.
▪ All the fuel and oxygen mass are consumed by the combustion process .
▪ Corresponds to a chemical optimum; maximum emissions of carbon dioxide/water
vapor as well as maximum heat release (maximum flame temperature).
At stoichiometric conditions, the equivalence ratio (φ) equals 1, representing the
ideal theoretical fuel-air ratio where complete combustion occurs with no excess
reactants.
Flammability Diagram
 Flammability Diagram

What actually the lines in the diagram represent?

▪ Flammability diagrams is a type of ternary diagram that show the regimes of
flammability in mixtures of fuel, oxygen and an inert gas, typically nitrogen.
Mixtures of the three gasses are usually depicted in a triangular diagram, also
known as a Ternary plot.
▪ Triangular diagram showing all possible mixtures of methane, oxygen and
nitrogen. Any mixture of methane and air will lie on the blue air-line.
▪ Any stoichiometric mixture of methane and oxygen will lie on the stoichiometric
line.
▪ The actual flammability envelope defining flammable mixtures of methane.
 Flammability Diagram

What actually the lines in the diagram represent?

▪The mixture is also not combustible when the composition is too rich; that is,
when it is above the upper flammability limit (UFL).
▪ The stoichiometric line represents all stoichiometric combinations of fuels plus
oxygen.
▪ Limiting oxygen concentration (LOC): Minimum oxygen concentration
required to propagate a flame.
 Flammability Diagram

Figure: Relationships Between Various Flammability Properties

Limiting Oxygen Concentrations for
Flammable Gases
Gas or Vapor N₂/air Limit (% O₂) CO₂/air Limit (% O₂)
Ethane 11 13.5
Propane 11.5 14.5
n-Butane 12 14.5
Isobutane 12 15
n-Pentane 12 14.5
Isopentane 12 14.5
n-Hexane 12 14.5
n-Heptane 11.5 14.5
Ethylene 10 11.5
Propylene 11.5 14
1-Butene 11.5 14
Isobutylene 12 15
Butadiene 10.5 13
3-Methyl-1-butene 11.5 14
Benzene 11.4 14
 Flammability Limits

▪ LFL decreases with temperature and pressure.

▪ UFL increases with temperature and pressure.
 Flammability Limits

▪ Auto-ignition temperature: Temperature that allows spontaneous combustion

initiation without the presence of an ignition device.
 Flammability Limits
Lower flammability limits (LFL) of pure fuels :

Fuel Chemical Formula LFL

Methane CH4 0.05

Propane C3H8 0.021
n-heptane C7H16 0.0105
Iso-octane C8H18 0.0095
Ethylene C2H4 0.027
Acetylene C2H2 0.025
Benzene C6H6 0.013
Hydrogen H2 0.04
Carbon monoxide CO 0.125
 Flammability Limits

LFL Condition for Mixtures

A fuel blend is flammable if:
xF​≥ xF,LFL
xF = Total fuel mole fraction in the fuel/air mixture.

xF,LFL = Effective LFL of the fuel blend

xkfuel -1
xF,LFL​ = ( σ𝑁 s
)
𝑘=1 xk,LFL

xkfuel = Mole fraction of fuel component k in the fuel vapor mixture (excluding air)

xk,LFL= LFL of the pure fuel component k

 Flammability Limits

Also the mixture is flammable if:

xk
σ𝑁s
≥1
𝑘=1 xk,LFL
xk = Mole fraction of fuel component k in the fuel/air mixture
 Flammability Limits
Upper flammability limits (UFL) of pure fuels :

Fuel Chemical Formula UFL

Methane CH₄ 0.15
Propane C₃H₈ 0.095
n-Heptane C₇H₁₆ 0.067
Iso-Octane C₈H₁₈ 0.06
Ethylene C₂H₄ 0.36
Acetylene C₂H₂ 0.82
Benzene C₆H₆ 0.079
Hydrogen H₂ 0.75
Carbon Monoxide CO 0.74
 Flammability Limits

UFL Condition for Mixtures

A fuel blend is flammable if:
xF ​≤ xF,LFL
xF = Total fuel mole fraction in the fuel/air mixture.

xF,UFL = Effective LFL of the fuel blend

xk fuel -1
xF,UFL​ = ( σ𝑁s
𝑘=1 x )
k,UFL

xkfuel = Mole fraction of fuel component k in the fuel vapor mixture (excluding air)

xk,UFL= UFL of the pure fuel component k

 Flammability Limits

Also the mixture is flammable if:

xk
σ𝑁s
≤1
𝑘=1 xk,UFL
xk = Mole fraction of fuel component k in the fuel/air mixture
 Ignition

▪ Minimum Ignition Energy (MIE) is the smallest spark energy needed to ignite a flammable
fuel-air mixture.
▪ If MIE < 1 mJ, ignition is extremely easy (even static electricity can trigger it).

Minimum Ignition Energy for selected gases:

Chemical Minimum Ignition Energy (mJ)

Acetylene 0.020

Benzene 0.225

1,3-Butadiene 0.125

*n*-Butane 0.260
 Ignition

Chemical Minimum Ignition Energy (mJ)

Cyclohexane 0.223

Cyclopropane 0.180

Ethane 0.240

Ethene 0.124

Ethylacetate 0.480

Ethylene oxide 0.062

*n*-Heptane 0.240

Hexane 0.248
 Ignition

Chemical Minimum Ignition Energy (mJ)

Hydrogen 0.018

Methane 0.280

Methanol 0.140

Methyl acetylene 0.120

Methyl ethyl ketone 0.280

*n*-Pentane 0.220

2-Pentane 0.180

Propane 0.250

Source: Combustion, 3rd Edition by Glassman (1996)

Flammability of Liquids
 Flammability of Liquids

Properties of Liquids
Liquids have no constitutive relationship; mass density is usually considered a constant
and known property.
• Mixture of Liquids
The composition of a liquid mixture can be characterized in terms of:
Volume fractionϕk​: Represents the portion of the total volume occupied by
component k.
𝑉 𝑉
ϕk = 𝑘 = σ𝑁 𝑘
V 𝑘=1 𝑉𝑘
𝑠

Mole fractionxk: Indicates the proportion of total moles contributed by component k.

nk n
xk = = σ𝑁 k
n 𝑘=1 nk
s
 Flammability of Liquids

Mass fraction Yk: Shows the fraction of total mass made up by component k.
mk m
Yk= = σ𝑁 k
m 𝑘=1 mk
s

Normalization condition:
σ𝑁 𝑁s 𝑁s
𝑘=1 ϕk = σ𝑘=1 xk = σ𝑘=1 Yk = 1
s

This ensures that the sum of all fractions equals 1, meaning 100% of the gas mixture is
represented.
 Flammability of Liquids
𝑉𝑘 𝑉
Volume fraction ϕk = = σ𝑁 𝑘
V 𝑘=1 𝑉𝑘
𝑠

Mass of component m𝑘 nkMk

Volume Vk= = = [ m𝑘 = Number of moles of component nk
Density of component ρ𝑘 ρ𝑘
x molecular weight Mk ]
𝑁𝑠 nkMk
And Total volume of mixture V = σ𝑁 𝑠
𝑘=1 𝑘𝑉 = σ 𝑘=1 ρ
𝑘
nk M k
ρ n
So, ϕk = 𝑘
Again, Mole fraction xk= k ⇒nk = xkn
σ𝑁 𝑠
nk M k n
𝑘=1 ρ
𝑘

nkMk xknMk n xkρMk n xkρMk xkMk

ρ ρ ρ
ϕk = 𝑘
= 𝑘
= 𝑘
= 𝑘
= 𝑘
Inputs ρ𝑘,Mₖ
𝑁
σ𝑘=1
𝑠
n k M k 𝑁
σ𝑘=1
x k
𝑠
nM k 𝑁 x 𝑠
M k 𝑁𝑠
xk M
n( σ𝑘=1 ρ ) n( σ𝑘=1 ρ ) ( σ𝑘=1 ρ )
k k 𝑁
𝑠
xk M k
ρ 𝑘
ρ 𝑘 𝑘 𝑘 𝑘

Factoring out n
 Flammability of Liquids

mk
Mass fraction Yk=
m
Mass can be expressed as moles × molecular weight, mₖ = nₖMₖ
nₖMₖ
So, Yk= 𝑁 , as Total mass of the mixture m = σ𝑁 𝑘=1 nₖMₖ
𝑠
σ𝑘=1 nₖMₖ
𝑠

n n
Using mole fraction definition: xₖ = k= σ𝑁 k ⇒nk = xₖσ𝑁 𝑘=1 nk
s
n n
𝑘=1 k
s
substituting
( xₖ σ𝑁
𝑘=1 nk)Mₖ
s
xₖMₖ σ𝑁𝑘=1 nk
s
value of nk
By substituting value of nk, Yₖ = ⇒Yₖ =
σ𝑘=1 nₖMₖ
𝑁 𝑠 σ𝑘=1 nₖMₖ
𝑁 𝑠

The denominator can be written as σ𝑁 𝑁𝑠 𝑁s

𝑘=1 nₖMₖ = σ𝑘=1 (xₖ σ𝑘=1 nk )Mk
𝑠

= (σ𝑁 𝑁s
𝑘=1 nk)(σ𝑘=1 xkMk) Factoring out σ𝑘=1 nk
s 𝑁s

xₖMₖ σ𝑁 𝑘=1 nk
s
xₖMₖ σ𝑁 𝑘=1 nk
s
xₖMₖ
So, Yₖ = 𝑁 ⇒ Yₖ = ⇒ Yₖ = Input Mₖ
( σ𝑘=1 nk)( σ𝑁𝑘=1 xkMk) ( σ𝑁
𝑘=1 nk)( σ𝑘=1 xkMk) 𝑘=1 xkMk
σ𝑁
s s s 𝑁 s s
 Flammability of Liquids

nk n
Mole fraction xk= = σ𝑁 k
n 𝑘=1 nk
𝑠

mk ρ𝑘Vk
Number of moles of component nk = =
Mk Mk
ρ Vk 𝑘

So, xk= Mk , Again volume fraction ϕ = 𝑉𝑘 ⇒𝑉 = ϕ V

σ𝑁
ρ Vk𝑠 𝑘
k V 𝑘 k
𝑘=1
Mk
ρ ϕkV𝑘
V ρ ϕk V ρ ϕk
𝑘 𝑘
ρ ϕk 𝑘

xk= Mk = Mk = Mk = Mk Inputs ρ𝑘,Mₖ

𝑁
σ𝑘=1
𝑠
ρ ϕ k V
𝑘
V ( σ𝑘=1
𝑁 ρ ϕ k ) V ( σ𝑘=1
𝑠 𝑁 ρ𝑘
ϕ k ) 𝑠 𝑁
( σ𝑘=1
ρ𝑘
ϕ k ) 𝑠 𝑘

Mk Mk Mk Mk
Factoring out V
 Flammability of Liquids

mk m ρ𝑘Vk
Mass fraction Yk= = σ𝑁 k = [ Mass of component mk=ρ𝑘Vk ]
m 𝑘=1 mk
𝑠 σ𝑁𝑠
𝑘=1 ρ𝑘Vk
ρϕV V ρ𝑘ϕk ρϕ
Using 𝑉𝑘 = ϕkV, Yk= 𝑁 𝑘 k = = 𝑁 𝑘 k Inputs ρ𝑘
σ𝑘=1 ρ𝑘ϕkV
𝑠
V ( σ𝑘=1 ρ𝑘ϕk ) σ𝑘=1 ρ𝑘ϕk
𝑁𝑠 𝑠

Factoring out V
 Flammability of Liquids

Properties of Liquids
❑ Liquid-vapor equilibrium describes the stable coexistence of a pure substance's
liquid and gas phases at a specific temperature and pressure. For pure chemical
spices, while Temperature (T) is constant and Pressure ( P) is variable:
▪ Liquid Phase: Exists when P ≥ Psat (T)
▪ Vapor Phase: Exists when P < Psat (T)
▪ Phase distinctions disappear when pressure equals the critical pressure (P=Pc).

Vapor

Liquid
 Flammability of Liquids

Properties of Liquids
❑ For pure chemical spices, while Pressure ( P) is constant and Temperature (T) is
variable:
▪ Liquid Phase: Exists when T ≤ Tsat (P)
▪ Vapor Phase: Exists when T > Tsat (P)
▪ Phase distinctions disappear when temperature equals the critical temperature
(T=Tc).

Vapor

Liquid
 Flammability of Liquids

Evaporation from Liquid Pool:

▪ Heat from warm air increases surface temperature of the cold liquid.
▪ Vapor forms and diffuses upward, creating a concentration gradient.
▪ Temperature rises from Tl​ (liquid) to T∞​ (air).
▪ Vapor mass fraction decreases from xF,l≈1 to xF,∞≈0.
▪ Both changes occur within a thin layer of thickness δ.
 Flammability of Liquids

Evaporation from Liquid Pool Notations & Meanings -

x F,s – Maximum Fuel vapor mass fraction at the gas-liquid surface
x F,LFL – Fuel vapor mass fraction at the lower flammability limit (needed for ignition)
xFliq – Fuel mass fraction in the liquid phase (≈1 for pure substances)
Psat,F(𝑇) – Saturation vapor pressure of the fuel at temperature T
Ts – Surface temperature of the liquid
TFP – Flash point temperature (minimum temperature for ignition)
TBP – Boiling point of the liquid
P – Ambient pressure (usually atmospheric)
Patm – Atmospheric pressure
R – Universal gas constant
M – Molar mass of the fuel
ΔHv– Enthalpy of vaporization (energy needed to vaporize liquid)
 Flammability of Liquids

Flash Point : Minimum temperature of a flammable liquid that leads to a flammable

mixture in the air.
1
Flash point temperature TFP =
R൘
1
+ M 𝑙𝑛 x F,LFL P
TBP ΔHv xFliq Patm
xFliqPsat,F(𝑇FP)
Fuel vapor mass fraction at the lower flammability limit x F,LFL =
P
liq
x P (𝑇 )
Maximum Fuel vapor mass fraction at the gas-liquid surface x F,s​ = F sat,F S
P
 Flammability of Liquids

Measurement of Flash Point

Vapor

Sample Sample

Open Cup Closed Cup

Closed Cup Flash Point is basis for NFPA 30 classification

 Flammability of Liquids

NFPA 30 Classification of Flammable and Combustible Liquids

Flammable Liquids (Class I)
General: Flash Point (FP) < 37.8°C (100°F)
❑ Class IA
▪ FP < 22.8°C (73°F)
▪ Boiling Point (BP) < 37.8°C (100°F)
▪ Examples: Diethyl ether, pentane
❑ Class IB
▪ FP < 22.8°C (73°F)
▪ BP ≥ 37.8°C (100°F)
▪ Examples: Gasoline, ethanol
 Flammability of Liquids

❑ Class IC
▪ 22.8°C ≤ FP < 37.8°C (73°F–100°F)
▪ Examples: Light kerosene
Combustible Liquids Class II
General: 37.8°C ≤ FP < 60°C (100°F–140°F)
Examples: Diesel fuel, lubricating oils
Combustible Liquids Class III
General: FP ≥ 60°C (140°F)
❑ Class IIIA
▪ 60°C ≤ FP < 93.4°C (140°F–200°F)
▪ Examples: Heavy fuel oils
 Flammability of Liquids

❑ Class IIIB
▪ FP ≥ 93.4°C (200°F)
▪ Examples: Vegetable oils, glycerin
Non-Combustible Liquids
▪ Do not ignite under standard conditions
▪ Examples: Water, refined mineral oil
 Flammability of Liquids
Ranking of flammable liquids for ignition
Flash Point (TFP​): Minimum temperature at which a liquid emits enough vapor to ignite
Lower TFP = Easier ignition (e.g., gasoline TFP =−43°C)
Boiling Point (TBP): Affects vapor formation rate
Lower TBP = Faster evaporation = Higher ignition risk
Pool Fires - Ranking of flammable liquids for combustion
Heat Release Parameter (HRP):
ΔHc
HRP=
ΔHv
ΔHc: Heat of combustion (energy released)
ΔHv: Heat of vaporization (energy needed to gasify fuel)
Higher HRP = Larger/more intense fires (e.g., alcohols have high HRP)
 Flammability of Liquids
Pool Fires - Ranking of flammable liquids for combustion
The Spalding BB Number is a key parameter for predicting fire size and intensity in pool fires:
cp(T∞−Ts) + (YO2,∞/rs)ΔHc
B=
ΔHv
Key Components:
cp(T∞−Ts ) :Sensible heat from ambient (T∞) to fuel surface (Ts​)
(YO2​,∞​/rs​)ΔHc : Chemical energy from oxygen mass fraction (YO2,∞) and stoichiometric ratio (rs​)
ΔHv: Heat of vaporization (energy to gasify fuel)
B-number Values For Solids
Material Formula B-number

Polypropylene C₃H₆ 1.29

Polyethylene C₂H₄ 1.16

Polystyrene C₈H₈ 1.55

Nylon 6/6 C₁₂H₂₂N₂O₂ 1.27

Polycarbonate C₆H₁₄O₃ 1.41

PMMA C₅H₈O₂ 1.78

PVC C₂H₃Cl 1.15

Fir wood C₄.₈H₈O₄ 1.75

α-cellulose C₆H₁₀O₅ 6.96

Polyoxymethylene CH₂O 1.47

B-number Values For Solids
Liquid Formula B-number
Methanol CH₃OH 2.53

Ethanol C₂H₅OH 2.89

Propanol C₃H₇OH 3.29

Butanol C₄H₈OH 3.35

n-pentane C₅H₁₂ 7.63

n-hexane C₆H₁₄ 6.67

n-heptane C₇H₁₆ 5.92

n-octane (gasoline) C₈H₁₈ 5.42

 B-number Values For Solids
Liquid Formula B-number

iso octane C₈H₁₈ 6.59

n-nonane C₉H₂₀ 4.89

n-decane C₁₀H₂₂ 4.61

n-undecane C₁₁H₂₄ 4.43

n-dodecane (kerosene) C₁₂H₂₆ 4.13

Acetone C₃H₂O 7.28

 Flammability of Liquids

Pool Fires - Ranking of flammable liquids for combustion

Flash Point (FP)
▪ Definition: The minimum temperature at which a liquid emits sufficient vapor to form an
ignitable mixture with air.
▪ Behavior: Produces a transient flash (short-lived premixed flame at the liquid surface).
▪ Significance: Indicates ignition susceptibility (lower FP = higher hazard).
Fire Point
▪ Definition: The minimum temperature at which a liquid produces enough vapor to sustain
combustion (pool fire).
▪ Behavior: Generates a sustained non-premixed flame.
▪ Significance: Typically 5–20°C above the flash point; critical for fire persistence.
Flammability of Liquids
 Discharge
Flash evaporation
▪ Definition– Flash evaporation is the partial evaporation
of a superheated liquid due to a sudden reduction in
pressure.
▪ Consider a superheated liquid, i.e. a liquid stored in a
pressurized tank at a temperature above its boiling point
𝑇𝐵𝑃 (saturated temperature at atmospheric pressure)
(point I).
▪ Consider that following an accidental burst, the tank
undergoes a rapid change in pressure down to
atmospheric conditions.
▪ The liquid will cool to the boiling point and partially
evaporate (point F).
 Discharge
Flash Evaporation
Flash evaporation is a rapid and sudden phase
change of a liquid into vapor when exposed to a
lower-pressure environment. This phenomenon
occurs when a liquid, typically at high temperature
and pressure, encounters a sudden drop in
pressure, causing it to vaporize quickly. This process
is characterized by the immediate transformation of
a portion of the liquid into vapor without substantial
heating. Flash evaporation is commonly utilized in
industrial processes, such as refrigeration and
desalination, to achieve efficient cooling or
separation of components.
 Discharge
Flash evaporation: Calculation of vapor fraction
)
𝒄𝒍 ( 𝑻𝒍 −𝑻𝑭 Available thermal energy ( superheat)
YgF= 1- exp ( - )
𝑳𝒂𝒗𝒑 Heat required for evaporation
(if 𝑝𝐹=𝑝𝑎𝑡𝑚​ , then 𝑇𝐹=𝑇𝐵P ​ )

YgF = Fraction of the liquid vaporized

𝑐𝑙 = Mean heat capacity of the liquid
𝑇𝑙 = Initial temperature of the liquid
𝑇𝐹 = Final boiling point temperature (typically at atmospheric pressure)
𝐿𝑎𝑣𝑝 = Mean latent heat of vaporization
 Discharge
Pool evaporation
Pool evaporation is the normal evaporation of liquids due to ambient-to-liquid heat
transfer.
Heat transfer from arbitrary heat sources:
▪ Thermal radiation from remote hot source
▪ Convective heat transfer from ambient air
▪ Heat conduction from soil/water substrate, etc.
.
q′′
Evaporation Rate Equation ṁ ≈ ( )A
. ΔHv pool
q′′ is the net heat flux from the surroundings to the liquid pool
ΔHv = the latent heat of vaporization
Apool = the surface area of the liquid pool
Dispersion
 Dispersion
Vapor cloud composition is function of -

Category Parameters
- Mass flow rate
- Velocity (momentum)
Source Parameters
- Temperature (buoyancy)
- Duration
- Topography (flat or hilly)
Terrain Properties - Quality of ground surface
(smooth or rough)
- Wind velocity
Atmospheric Flow Conditions - Temperature stratification
- Turbulence intensity
 Dispersion

• Release in open space

– Wind velocity
▪ Near-ground vertical variations of wind velocity (surface layer of atmospheric boundary
layer)
▪ Assumption: no effect of thermal stratification; use theory of rough turbulent boundary
layers
u 𝑧
Ũ(z)= 𝑡​ln( ​),for 0≤z≤100 m
𝑘 𝑧0
1
𝜕Ũ
With u𝑡 the friction velocity , u𝑡 = [ ν ( ) ]2
𝜕𝑧 z=0
κ: the Von Karman constant, κ=0.4
z0​: a surface roughness length,
z0 ≈ 2×10−4 m (open water);
0.03 m (flat grassland); 0.5 m (bushes); 1.0 m (forest); 3.0 m (city)
 Dispersion

Release in open space

– Wind velocity

▪ Near-ground vertical variations of wind velocity (surface layer of atmospheric boundary

layer)
 Dispersion

Release in open space

– Turbulent mixing

▪ Near-ground vertical variations of turbulent viscosity due to shear

Dt(z)=u𝑡 x (kz), for 0≤z≤100 m

 Dispersion

Release in open space

– Turbulent mixing

▪ Natural Case : No effect of thermal stratification if adiabatic variations

 Dispersion

Pasquill-Gifford Model for Pollutant Dispersion

▪ The Pasquill-Gifford model is used to estimate pollutant dispersion in open
paces, particularly for instantaneous point releases near the ground.
▪ It incorporates wind effects and recognizes that atmospheric stability strongly
influences turbulent mixing and pollutant spread.
▪ Ideal for short-range dispersion modeling in environmental and safety
applications.
 Dispersion

Key Considerations of Pasquill-Gifford Model for Pollutant Dispersion

❑ Daytime vs. Nighttime Stability:
▪ Daytime Stability: Typically, daytime atmospheres are more unstable than
nighttime atmospheres. This is attributed to the heating of the Earth's surface
during the day, leading to vertical air movement and increased turbulence.
▪ Nighttime Stability: Nighttime conditions are generally more stable due to the
cooling of the Earth's surface, resulting in less vertical movement and reduced
turbulence.
 Dispersion

Key Considerations of Pasquill-Gifford Model for Pollutant Dispersion

❑ Insolation Impact:
▪ High Insolation: When solar radiation is high, creating intense heating during
the day, the atmosphere tends to be more unstable. This is because of increased
temperature gradients, leading to stronger vertical mixing.
▪ Low Insolation: Conversely, low solar radiation results in a more stable
atmosphere, with reduced turbulence and vertical mixing.
 Dispersion

Key Considerations of Pasquill-Gifford Model for Pollutant Dispersion

❑ Wind Influence:
▪ Daytime Wind: In daytime conditions, high wind tends to stabilize the
atmosphere by enhancing vertical mixing and dilution of pollutants. Conversely,
low wind during the day contributes to a more stable atmosphere.
▪ Nighttime Wind: At night, the relationship between wind and stability is
reversed. High wind at night can lead to increased turbulence and instability,
while low wind results in a more stable atmosphere.
 Dispersion

Release in open space

▪ Puff scenario
– Instantaneous point release on ground with wind
▪ Pasquill-Gifford model: atmospheric stability controls the
turbulent mixing intensity
– Daytime more unstable than nighttime
– High insolation more unstable than low insolation
– Daytime high wind more stable than daytime low wind
– Nighttime high wind more unstable than nighttime low wind
 Dispersion

Pasquill-Gifford Stability Classes Table

Daytime Insolation Nighttime Conditions Anytime

Surface Wind Strong Moderate Slight Thin overcast or>4/8 >3/8 cloudiness Heavy
Speed, m/s low cloud Overcast
<2 A A-B B F F D
2-3 A-B B C F F D
3-4 B B-C C D E D
4-6 C C-D D D D D
>6 C D D D D D
A: Extremely unstable conditions D: Neutral conditions
B: Moderately unstable conditions E: Slightly stable conditions
C: Slightly unstable conditions F: Moderately stable conditions
 Dispersion

Plumes in Atmospheric Dispersion

▪ Plumes refer to the flow of a pollutant—such as vapor, smoke, or gas—

released into the atmosphere. Based on physical properties, plumes are
typically classified into three main types:

▪ Buoyant Plume
Definition: Lighter than air and tends to rise upward due to its lower density.
Example: A methane plume.
Behavior: Driven by thermal buoyancy; spreads more vertically.
 Dispersion

▪ Dense Gas Plume

Definition: Heavier than air, causing it to sink or hug the ground.
Example: A CO₂ (carbon dioxide) plume.
Behavior: Tends to pool in low-lying areas and spreads horizontally.

▪ Passive (Neutral) Plume

Definition: Similar density to ambient air; neither rises nor sinks significantly.
Example: Steam from a cooling tower under calm, neutral conditions.
Behavior: Follows the ambient wind and turbulence patterns; disperses naturally.
 Dispersion

❑ Release in Open Space

– Plume Scenario
▪ Continuous point release on ground with wind
▪ Assumption: slender plume, i.e., y, z ≪ x

❑ Gaussian Plume Model

ṁF 1 𝑦2 𝑧2
ỹ​(x,y,z) = exp ( - ( + ))
πρσ𝑦σ𝑧Ũ 2 σ𝑦2 σ𝑧2
Pool Fire
 Pool Fire

▪A pool fire is a turbulent diffusion fire burning above a horizontal pool of

vaporizing hydrocarbon fuel where the fuel has zero or low initial momentum.
▪ Fires in the open will be well ventilated (fuel-controlled), but fires within
enclosures may become under-ventilated (ventilation-controlled).
 Pool Fire

Main features of the flame structure

▪ Fuel source velocity is small (~ 1 cm/s).
▪ Buoyancy effects accelerate the flow up to several m/s;
flow regime corresponds to moderate turbulence
intensities.
▪ Flame corresponds to diffusion combustion and is located
where fuel and air meet in stoichiometric proportions.
▪ Under-fire region is a mixing zone between fuel and
combustion products; expected to contain no or little
oxygen.
▪ Over-fire region is a mixing zone between ambient air
and combustion products; expected to contain no or little
fuel.
 Pool Fire

Flow Regime Transition with Pool Diameter

❑ An increase in pool diameter DDD leads to a transition from laminar to turbulent flow.
▪ 𝐷 ≤ 0.1m , laminar pool fire
▪ 0.1 ≤ 𝐷 ≤ 1m , transitional pool fire
▪ 1 m≤𝐷 , fully-turbulent pool fire
 Pool Fire
Flame Shape Transition with Pool Size
❑ An increase in pool size DDD leads to a transition in flame shape.
▪ At small-D sizes:
→ Classical single flame geometry; flame height Lf ​ is several times D
▪ At very-large-D sizes:
→ Multiple flame geometry; flame height Lf ​ is smaller than D

Small D Very Large D

 Pool Fire
Combustion Regime Transition with Pool Diameter
❑ An increase in pool diameter DDD leads to a transition in the combustion regime.
▪ D ≤0.1 m :→ Combustion is complete, soot yield is small, flame may be sooting but not
smoking [sooty fuels]
▪ 0.1 ≤ D ≤ 1 m :→ Intermediate combustion regime
▪ 1 m ≤ D :→ Combustion is strongly incomplete, soot yield is large, flame is both
sooting and smoking [sooty fuels]

Weakly Smoking Small D Smoking Very Large D Weakly

Massivesmoking
Smoking
 Flash Fire & Fire Ball
Fuel Vapor Clouds
❑ Basic scenarios: Dispersion involves turbulent mixing of fuel and air,
typically after a delayed ignition.
❑ Two primary cloud formations:

Formation of a large ultra-rich cloud Formation of a large flammable cloud

 Flash Fire & Fire Ball
Basic scenarios of combustion

Aspect Flash Fire Explosion

Combustion Type Deflagration (subsonic) Detonation (supersonic)

Blast Wave None Present (shock wave)

High (can cause structural
Overpressure Minimal
damage)
Environment Open or unconfined areas Confined or obstructed areas

Main Hazard Flame propagation, burns Pressure blast, structural failure

Rapid flame spread without loud Violent release with audible
Ignition Outcome
bang explosion
 Flash Fires
1. Premixed Fuel-Air Cloud Exists
A cloud containing a flammable mixture of fuel vapor and air is already formed.
2. Ignition Occurs Within the Cloud
An ignition source (spark, flame, static discharge) initiates combustion in the cloud.
3.Subsonic Flame Front Develops
The flame front propagates through the cloud at subsonic speed, driven by heat and
mass transfer.
4.Thermal Expansion Generates Pressure
The hot gases expand, causing a pressure rise—but not a shock wave like in
detonation.
 Flash Fires
5.Flame Spreads Rapidly, May Cause Flash Fire
The fire spreads throughout the flammable cloud. If unconfined, it results in a flash
fire; if confined or obstructed, overpressure may build.
 Flash Fires
❑ Laminar Flame Behavior of Deflagration:
▪ The flame propagates in a spherically expanding shape.
▪ Apparent flame velocity depends on thermal expansion.
drf Tb
▪ Equation: ≈ ( ) SL
dt Tu

Where,
rf = Flame radius
.
Tb ​and Tu = Temperature of burned and unburned gases
.
SL = Laminar flame speed
This equation implies that the actual speed of the flame front increases due to
expansion from thermal effects
 Flash Fires
❑ Turbulent Flame Behavior of Deflagration:
▪ Most practical deflagrations are turbulent, not laminar.
▪ The flame surface becomes wrinkled and stretched, increasing the flame surface
area and burning rate.
▪ Turbulent flame speed ST is: Mean velocity of unburned reactants entering the
turbulent flame front.
 Flash Fires
❑ Deflagration – Flame Speeds and Flow Conditions
▪ Flame Velocity Range
dxf
Typical deflagration front speed ≈ O(0.1–50 m/s)
dt
This is much lower than detonation (~2000 m/s), highlighting its subsonic nature.
▪ Flow Characteristics
Low Mach number Mf ≤ 0.15
Confirms that combustion is occurring at subsonic flow speeds.
▪ Small pressure difference:
pb≈ pu
Burned and unburned gases are at nearly the same pressure, unlike detonations
 Flash Fires
❑ Example: Backdraft
❑ A backdraft occurs when a confined space (e.g., a room or container) becomes filled
with hot, fuel-rich gases due to incomplete combustion and lack of oxygen. When
oxygen is suddenly reintroduced such as by opening a door or vent rapid mixing
triggers a deflagration, causing a violent flame front and pressure wave.
❑ This is an explosive deflagration, not a detonation, but still highly destructive due to
rapid flame propagation in a confined environment.
 Fireballs
❑ Fireball is A buoyant diffusion flame caused by the rapid ignition of a large ultra-rich
fuel vapor cloud, typically after a tank rupture.
❑ Key Points:
▪ Occurs when a fuel-air mixture ignites rapidly in the open atmosphere.
▪ The flame rises due to buoyancy (hot gases are lighter).
▪ The combustion occurs when oxygen diffuses into the flame from surrounding air.
▪ Produces intense thermal radiation and high temperatures, but short duration.
 Explosion
❑ Explosion is a detonation event resulting from the rapid combustion of a premixed
fuel-air cloud, producing a shock wave and overpressure.
❑ Key Points:
▪ Initiated in a premixed fuel-air mixture (not ultra-rich like fireball).
▪ Requires strong ignition or DDT (Deflagration-to-Detonation Transition).
▪ Blast wave propagates at supersonic speed (detonation).
▪ Produces high overpressure and potential for structural damage.
▪ Often occurs in confined or congested areas.
 Flash Fire vs Explosion

Feature Deflagration Detonation

Supersonic (above speed of

Flame Speed Subsonic (below speed of sound)
sound)
Generates a strong shock
Pressure Wave No significant overpressure
wave
High – strong ignition or
Ignition Requirement Low – normal ignition sources
accelerated deflagration
Most common in open or Occurs in confined spaces or
Occurrence
unconfined areas after DDT
Severe – explosion hazard
Danger Level Moderate – mainly fire hazard
with structural damage
 Flash Fire vs Explosion
Mechanism of DDT – A Feedback Loop:
1.Combustion generates expanding gases.
2.Flow Expansion increases velocity and creates turbulence.
3.Turbulence + Shock Formation amplify flame speed.
4.Feedback loop reinforces combustion speed, may lead to transition to
detonation.

Turbulence
Flow
Combustion + Shock
Expansion
Formation

Feedback Loop System

Impact of Vapor Cloud Explosions
on People
Peak Overpressure, psi Effect

1 Knock personnel down

5 Rupture eardrums

15 Damage lungs

35 Threshold fatalities

50 50% fatalities

65 99% fatalities

0.5-1 Glass windows break

 Damage from Vapor Cloud
Explosions
Peak Overpressure, psi Typical damage
Common siding types fail
- corrugated asbestos, shatters
1-2
- corrugated steel, panel joints fail
- wood siding, blows in
2-3 Unreinforced concrete block walls fail
3-4 Self-framed steel panel building collapse.
5 Utility poles snap
7 Loaded rail cars overturn
8 Unreinforced brick walls fail
 BOILING-LIQUID EXPANDING-
VAPOR EXPLOSION (BLEVE)
❑ A BLEVE occurs if a vessel that contains a liquid at a temperature above its
atmospheric pressure boiling point ruptures. The subsequent BLEVE is the
explosive vaporization of a large fraction of the vessel contents; possibly
followed by combustion or explosion of the vaporized cloud if it is combustible.

https://youtu.be/Tol2vN437p0?si=O1BpxXwQaC8FvC6F
Risk Analysis
 Hazard vs. Risk

Hazard

A measure of the severity of the consequences of a catastrophic failure of a given process or

system, regardless of the likelihood and without considering safeguards.

Risk

The combination of both the severity of the worst case consequence and the likelihood of the
initiating cause occurring.

In short, for an EXISTING PROCESS, we have little influence on the HAZARD, but through
the application of safeguards, we can reduce the RISK of operating the process.
 Process Hazard Analysis

❑ Process Hazard Analysis (PHA) is a technique for determining the RISK of

operating a process or unit operation.
❑ PHAs are required by law for process handling threshold quantities for certain
listed Highly Hazardous Chemicals (HHC) or flammables.
❑ Approved techniques for conducting PHAs:
▪ HAZOP (Hazard and Operability)
▪ What If?
▪ FMEA (Failure Mode and Effects Analysis)
❑ In general, a PHA is conducted as a series of facilitated, team brainstorming
sessions to systematically analyze the process.
 Probability theory

❑ Equipment failures or faults in a process occur as a result of a complex

interaction of the individual components.
❑ The overall probability of a failure in a process depends highly on the nature of
this interaction.
❑ The time interval between two failures of the component is called the mean
time between failures (MTBF) and is given by the first moment of the failure
density function:
∞ 1
E(t) = MTBF = ‫׬‬0 tf(t)dt =
μ

f(t) = Probability density function (PDF) of the time to failure

μ = Failure rate (mean failure rate if exponential distribution is assumed)
t = Time (continuous variable over which failure is distributed)
 Reliability in Series System

❑ Definition: In a series system, all components must function for the system to
succeed. The failure of any single component leads to system failure.

❑ Calculation:
Reliability Rseries= ς𝑛𝑖=1 Ri , Where Ri is the reliability of the ithcomponent
Failure Probability, P = 1−R
Failure Rate μ=−ln(R),
1
MTBF =
μ
 Reliability in Parallel Systems

❑ Definition: In a parallel system, the system functions as long as at least one

component functions. All components must fail for the system to fail.

❑ Calculation:
Failure Probability Pparallel= ς𝑛𝑖=1 Pi , Where Pi​ is the Failure Probability
of the ithcomponent
Reliability, R = 1−P
Failure Rate μ=−ln(R),
1
MTBF =
μ
 Bathtub Failure Rate Curve

▪ Early failures decrease with time due to manufacturing defects.

▪ Constant failure rate indicates random failures during useful life.
▪ Wear-out failures increase with aging or usage of the component.
 Failure Rate Data for Various
Selected Process Components
Instrument Faults/year
Controller 0.29
Control valve 0.6
Flow measurement (fluids) 1.14
Flow measurement (solids) 3.75
Flow switch 1.12
Gas-liquid chromatograph 30.6
Hand valve 0.13
Indicator lamp 0.044
Level measurement (liquids) 1.7
Level measurement (solids) 6.86
 Failure Rate Data for Various
Selected Process Components
Instrument Faults/year
Oxygen analyzer 5.65
pH meter 5.88
Pressure measurement 1.41
Pressure relief valve 0.022
Pressure switch 0.14
Solenoid valve 0.42
Stepper motor 0.044
Strip chart recorder 0.22
Thermocouple temperature measurement 0.52
Thermometer temperature measurement 0.027
Valve positioner 0.44
 Example

A diagram of the safety systems in a certain chemical reactor is shown in the

following Figure. This reactor contains a high-pressure alarm to alert the operator in
the event of dangerous reactor pressures. It consists of a pressure switch within the
reactor connected to an alarm light indicator. For additional safety an automatic
high-pressure reactor shutdown system is installed. This system is activated at a
pressure somewhat higher than the alarm system and consists of a pressure switch
connected to a solenoid valve in the reactor feed line. The automatic system stops
the flow of reactant in the event of dangerous pressures. Compute the overall failure
rate, the failure probability, the reliability, and the MTBF for a high-pressure
condition. Assume a 1-yr period of operation. Also, develop an expression for the
overall failure probability based on the component failure probabilities.
 Example

Failure
Failure rate μ Reliability R
Component probability P
(faults/yr) = e^(-μt)
=1-R
Pressure
0.14 0.87 0.13
switch 1
Alarm
0.044 0.96 0.04
indicator
Pressure
0.14 0.87 0.13
switch 2
Solenoid
0.42 0.66 0.34
valve

Fig:Schematic of Reactor Alarm and Feed Failure Rate and Reliability Summary Table
Solenoid Valve System
 Example

Solve:
A dangerous high-pressure reactor situation occurs only when both the alarm
system and the shutdown system fail. These two components are in parallel.

For the alarm system the components are in series:

Reliability Rseries= ς𝑛𝑖=1 Ri = (0.87)(0.96) = 0.835
Failure Probability P = 1−R =1 −0.835 = 0.165
Failure Rate μ=−ln(R) = −ln(0.835) = 0.180 faults/yr
1
MTBF = = 5.56 yr
μ
 Example

For the shutdown system the components are also in series:

Reliability Rseries= ς𝑛𝑖=1 Ri = (0.87)(0.66) = 0.574
Failure Probability P = 1−R =1 −0.574 = 0.426
Failure Rate μ=−ln(R) = −ln(0.574) = 0.555 faults/yr
1
MTBF = = 1.80 yr
μ
 Example

The two systems are parallel:

So for the system as a whole,
Failure Probability Pparallel= ς𝑛𝑖=1 Pi = (0.165)(0.426) = 0.070
Reliability R = 1−P = 0.930
Failure Rate μ=−ln(R) = −ln(0.930)=0.073 faults/yr
1
MTBF = =13.7 yr
μ
 Event Trees
❑ Event trees are used to follow the potential course of events as the event moves
through the various safety systems. The probability of success or failure of each
safety intervention is used to determine the overall probability of each final
outcome.
❑ An Event Tree is used to determine the frequency of occurrence of process
shutdowns or runaway systems.
❑ Inductive approach
1) Specify/Identify an initiating even and work forward.
2) Identifies how a failure can occur and the probability of occurrence.
 Steps to Construct an Event Tree
1. Identify an initiating event of interest.

2. Identify the safety functions designed to deal with the initiation followed by the
impact of the safety system

3. Construct the event tree

4. Describe the resulting accident event sequences.

 Identify an initiating event
1. May have been identified during a HAZOP as a potential event that could result
in adverse consequences.

2. Usually involves a major piece of operating equipment or processing step, i.e.

a HAZOP “Study Node”.
 Identify safety functions
1. From process flow sheet, or procedures, find what safety systems are in place
and what their functions are.

2. These can include things such as automatic controllers, alarms, sensors,

operator intervention, etc.

3. On Event Tree, write across the top of the page in the sequence of the safety
interventions that logically occur.

4. Give each safety intervention an alphabetic letter notation.

 Construct the Event Tree
❑ Horizontal lines are drawn between functions that apply

❑ Vertical lines are drawn at each safety function that applies

1) Success – upward

2) Failure – downward

❑ Indicating result of event

1) Circle – acceptable result

2) Cross-circle – unacceptable result

 Construct the Event Tree
Compute frequency of failures
❑ Event A occurs with a frequency λA
❑ The safety function B can either:
▪ Succeed, with frequency λA x (1−λB)
▪ Fail, with frequency λA x λB
Where, λB ​ = Probability of failure of Safety Function B
 Occurrence Frequency and
Downtime Intervals
Occurrence Frequency
❑ Follow the event tree branches to determine the frequency of each final outcome.
❑ Typically, system outcomes fall into three categories:
1. Continuous operation
2. Shutdown (safe stop)
3. Runaway or failure
Mean Time Calculations
Mean Time Between Shutdowns (MTBS):
1
MTBS =
Frequency of shutdowns
Mean Time Between Runaways (MTBR):
1
MTBR =
Frequency of runaways
 Example – Loss of coolant to reactor
When coolant flow to the reactor is lost, four
key safety interventions help prevent
overheating:
High Temperature Alarm – Alerts operators
when temperature exceeds safe limits.
Operator Detection – Operator notices high
temperature during routine checks.
Restoring Coolant Flow – Operator
manually restarts cooling water.
Emergency Shutdown – Operator shuts
down reactor to prevent escalation.
 Example – Loss of coolant to reactor
Assumptions for Failure Analysis
❑ Coolant loss frequency: 1 event/year

❑ Alarm failure rate: 0.01 failures per demand (1% of the time)

❑ Operator detection: Fails 1 out of 4 times → 0.25 failures/demand

❑ Operator restart attempt: Fails 1 out of 4 times → 0.25 failures/demand

❑ Emergency shutdown: Fails 1 out of 10 times → 0.10 failures/demand

Event Tree Analysis
Event Tree Analysis after installation
of a high-temp shutdown system
Event Tree Analysis after installation
of a high-temp shutdown system
Shutdown = 0.2450 + 0.002220 + 0.001856 + 0.00001688 + 0.0006187 + 0.00000563
= 0.2497 occurrence / year

Runaway = 0.0002475 + 0.000001875 + 0.000000625 = 0.00025 occurrence / year

Runaway reaction once every = (1/ 0.00025 ) = 4000 years
 Quantitative Risk Analysis (QRA)
❑ QRA is a method that identifies where operations, engineering, or management
systems can be modified to reduce risk.
❑ The complexity of a QRA depends on the objectives of the study and the
available information.
 Quantitative Risk Analysis (QRA)
The major steps of a QRA study include
▪ Defining the potential event sequences and potential incidents.
▪ Evaluating the incident consequences (the typical tools for this step include
dispersion modeling and fire and explosion modeling).
▪ Estimating the potential incident frequencies using event trees and fault trees.
▪ Estimating the incident impacts on people, environment, and property.
▪ Estimating the risk by combining the impacts and frequencies, and recording the
risk using a graph.
HAZOP: Hazard and Operability Study
Purpose & Process Overview
▪ A systematic and rigorous method developed in the chemical industry.
▪ Focuses on the design intent of a system and identifies deviations that could lead
to hazards.
▪ Carried out step-by-step, assessing each parameter such as flow, pressure,
temperature, and composition.
▪ Guidewords (e.g., more, less, none, reverse) are applied to process variables to
construct possible deviations from intent.
▪ Each deviation is then examined for:
1. Potential consequences 2. Likelihood
3. Effectiveness of existing protections 4. Need for additional safeguards
 HAZOP Analysis
❑ When & Why to Use
▪ Design of a new plant is mostly complete and documented.
▪ Existing plants are undergoing major redesign.
❑ Results of HAZOP
▪ Identifies hazards and operational issues.
▪ Recommends changes in design, procedures, or safety features.
▪ Suggests areas needing further analysis if data is insufficient.
Nature of Analysis
▪ Primarily qualitative, based on expert team discussions and structured
documentation.
▪ Outcome: Safer, more robust process designs through foresight and systematic
evaluation.
 Time and Cost
❑ The time and cost of a HAZOP are directly related to the size and complexity of
the plant being analyzed.
❑ In general, the team must spend about three hours for each major hardware item.
Where the system analyzed is similar to one investigated previously, the time is
usually small.
❑ Additional time must be allowed for planning, team coordination, and
documentation. This additional time can be as much as two three times the team
effort as estimated above.
HAZOP Study-Team Composition
Leadership:
Team Leader: An experienced expert in HAZOP methodology who facilitates the
sessions, ensures procedural adherence, and maintains focus.
Technical Team Members:
Depending on the project phase, team members may include:
For New Design Projects:
▪ Design or Project Engineer – understands system layout and design basis.
▪ Process Engineer – provides knowledge of chemical and process parameters.
▪ Commissioning Manager – ensures startup and operational readiness.
▪ Instrument Design Engineer – advises on control and instrumentation aspects.
HAZOP Study-Team Composition
For Existing Facilities:
▪ Plant Superintendent – responsible for day-to-day plant operations.
▪ Process Supervisor – familiar with current operating practices.
▪ Maintenance Engineer – identifies mechanical and reliability concerns.
▪ Instrument Engineer – ensures integrity of instrumentation and alarms.
Additional Participants (as needed):
▪ Safety/Health/Environmental Engineer
▪ Control Systems Specialist
▪ Operators with hands-on experience
 Principles of HAZOP
Concept:
▪ Systems perform safely and efficiently when operating under design conditions.
▪ Hazards typically arise due to deviations from these conditions (e.g.,
overpressure, reverse flow, high temperature).

Basis:
The study is conducted on a well-defined representation of the process:
▪ Word models
▪ Process Flow Diagrams (PFDs)
▪ Piping and Instrumentation Diagrams (P&IDs)
 Principles of HAZOP
Method:
▪ Use guidewords (e.g., No, More, Less, As Well As, Reverse) to systematically
challenge the intent of each process step.
▪ Identify:
1. Potential deviations
2. Causes (e.g., valve failure, sensor error)
3. Consequences (e.g., equipment damage, safety risk)
4. Safeguards in place
 HAZOP – Step-by-Step

1. Identify the Process

Select the process or activity to be analyzed.
2. Break Down into Nodes
Divide the process into logical sections (nodes) based on equipment or function.
3. Define Design Intent
Clearly state what each node is meant to do.
• E.g., “Unload tank truck in ≤ 45 minutes”
• E.g., “Feed 500 lbs/hr to spray dryer at ≤ 175°F”
4. Select Process Parameters
Choose variables such as flow, temperature, pressure, etc., to examine for
deviations.
 HAZOP – Step-by-Step

5. Apply Guide Words

Use keywords like “More,” “Less,” “Reverse,” or “None” to identify possible
deviations.
6. Analyze Deviations
Evaluate potential consequences of each deviation.
Assume safeguards fail to ensure conservative risk estimation.
7. Identify Causes
Determine what could lead to the deviation (e.g., equipment failure, human error).
8. Examine Existing Safeguards
List protections already in place (e.g., alarms, relief valves, procedures).
 HAZOP – Step-by-Step

9. Assess Risk (Optional)

Rank the risk level of each scenario using severity and likelihood metrics.
10. Recommend Improvements
Suggest additional protections or procedural changes, if needed.
Basic HAZOP Guide Words
Preliminary HAZOP on Reactor
Guide Word Deviation Causes Consequences Action
Install high
Cooling water valve Temperature increase in
NO No cooling temperature alarm
malfunction reactor
(TAH)
Failure of water
Less cooling, possible
REVERSE Reverse cooling flow source resulting in Install check valve
runaway reaction
backward flow
Control valve failure,
Too much cooling, reactor Instruct operators on
MORE More cooling flow operator fails to take
cool procedures
action on alarm
Check maintenance
Reactor product in More pressure in
AS WELL AS Off-spec product procedures and
coils reactor
schedules
If less cooling, TAH
will detect. If detected,
Another material Water source May be cooling ineffective
OTHER THAN isolate water source.
besides cooling water contaminated and effect on the reaction
Back up water
source?
 LOPA (Layer of Protection
Analysis)
❑ LOPA is a risk evaluation method that compares the frequency of a specific
hazardous scenario with an explicit risk tolerance criterion.
❑ It is a semi-quantitative technique that:
1) Uses simplified approaches to estimate both consequence severity
and event likelihood.
2) Focuses on a single cause-consequence pair at a time for clarity
and precision.
❑ Multiple independent layers of protection (e.g., alarms, interlocks, relief
devices) are evaluated to determine how much they reduce the risk.
❑ The goal is to ensure the residual risk is tolerable and to identify whether
additional safeguards are needed.
 LOPA Major steps
The major steps of a LOPA study include:
❑ Identifying a single consequence (a simple method to determine consequence
categories is described later)
❑ Identifying an accident scenario and cause associated with the consequence (the
scenario consists of a single cause-consequence pair),
❑ Identifying the initiating event for the scenario and estimating the initiating event
frequency (a simple method is described later)
Independent Protection Layers &
Probability of Failure on Demand
Independent Protection Layers (IPLs)
Structured, independent safety mechanisms that reduce the likelihood or severity of an undesired
consequence.
Common IPLs include:
▪ Basic Process Control System (BPCS)
▪ Alarms with operator response
▪ Safety Instrumented Systems (SIS)
▪ Pressure relief devices
▪ Physical containment barriers
Probability of Failure on Demand (PFD)
A quantitative measure of how likely an IPL will fail when needed (on demand).
▪ Lower PFD = More reliable layer
▪ Used to calculate overall risk and validate LOPA sufficiency
Layer of Protection Analysis
Core Process

1st Layer of
Protection

2nd Layer of
Protection

3rd Layer of
Protection

Each layer must be: Independent; Effective;

Reliable; Auditable.
Layer of Protection Analysis

Figure: Layers of Protection in Process Safety (LOPA Model)

 Consequences
The consequences are estimated using one of the following methods:
▪ Semi-quantitative approach without the direct reference to human harm.
▪ Qualitative estimates with human harm.
▪ Quantitative estimates with human harm.
 Typical Frequency Values
Assigned to Initiating Events
PFD for Passive IPL
PFD for Active IPL
 Calculation

The frequency of a consequence of a specific scenario endpoint is computed using:

𝐉
fic =fi𝐈x ς𝐣=𝟏 𝐏𝐃𝐅𝐢𝐣= fi𝐈x 𝐏𝐃𝐅𝐢𝟏 x 𝐏𝐃𝐅𝐢𝟐 x ……. 𝐱 𝐏𝐃𝐅𝐢𝐉
For a multiple scenario endpoint :
fc =σ𝑰𝒊=𝟏 fic
Here,
I = Total number of initiating events (scenarios)
J= Total number of Independent Protection Layers (IPLs) applied to each scenario
i = Index for initiating events (scenarios)
j = Index for Independent Protection Layers (IPLs)
fic = frequency for consequence C for initiating event
fiI = frequency for initiating event i
PDFij = probability of failure on demand of the jth IPL that protects against consequence C for
initiating event i
 Example

Determine the consequence frequency for a cooling water failure if the system is
designed with two IPLs. The IPLs are human interaction with 10-min response
time and a basic process control system (BPCS).
Solve:
J -1 -1 -1 -3
Consequence frequency fic =fiIx ςj=1 PDFij = 10 x 10 x 10 = 10 failure/year
 Conclusion

▪ The basic flammability properties of gaseous fuel-air mixtures have been

reviewed.
▪ The basic flammability properties of evaporating liquid fuels have been explored.
▪ Different basic configurations found in the problem of the accidental release of
flammable/toxic material have been discussed.
▪ Two scenarios associated with the combustion of a fuel vapor cloud have been
reviewed.
▪ Risk assessments and hazard analysis of a system has been discussed.