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Chemical Industries
Chemical Industries
Societal concerns.
Injury
Death
Physical Hazards
Physical agents
Chemical Hazard
solvents, metals,
Biological Hazard
Psychosocial issues
Dangerous Substances
1.
Explosives
2.
Gases
3.
Flammable Liquids/Solids
4.
Oxidizing Substances
5.
Dangerous substance
Dangerous substance
What is a dangerous substance?
Chemistry of Fire
Chemistry of Fire
Fire
In order to have a fire, two components are
required fuel and an oxidant.
for e.g.
Fire
Fire
Fire
Ignition sources
Sparks, flames,
static electricity,
heat
Fuels
Liquids
gasoline, acetone, ether, pentane
Solids
metal particles, wood dust, fibers, plastics,
Gases
acetylene, propane, hydrogen
Other fuels
Solvents
Plastics
Carpets
Furniture
Waste materials
Smoking
Electrical equipment
Heaters
Arson
Static Electricity
Ventilation
Safety pump
Types of Fire
Jet Fire
Pool fire
Flash fire
Fire ball
Image courtesy: Google Images
Definitions
Definitions
Flammability/Explosive Limit
Flammability/Explosive Limit
The upper flammability limit (combustiblerich limit mixture) is the highest concentration
of fuel in air that burns continuously.
*
*
Flammability Limit
Outside
this
range
of
air/vapor
mixtures,
the
mixture will not ignite (unless
heated).
Flammability Limit
Upper
flammability
Limit
(UFL):
is
the
highest
concentration (%) of a gas or a
vapor in air capable of
producing a flash of fire in
presence of an ignition source.
Autoignition Temperature
>21
34
90
160
210
250
473
536
Autoignition Temperature
>21
34
90
160
210
250
473
536
Formula
LEL in
air
(%)
UEL in
air
(%)
Methane
CH4
5.0
15.0
650
Ethane
C2H 6
3.0
12.4
515
Propane
C 3H 8
2.1
9.5
466
n-Butane
C4H10
1.8
8.4
480
n-Hexane
C6H14
1.2
7.4
275
Dimethyl ether
C 2H 6O
3.4
27
350
Hydrogen
H2
4.0
75
536
Ethylene oxide
C 2H 4O
3.6
100
429
Acetylene
C2H 2
2.5
100
305
Ignition
Temperature,
oC
Flammable region
Non-Flammable
region
Flash Point
Temperature
Explosion
may trigger
each other
EFFECTS
injuries / casualties
property losses
process interruption
Thermal radiation,
asphyxiation, toxic products,
blast, fragments
Explosion
Explosion is a rapid expansion of gases resulting in a
rapidly moving pressure or shock wave.
Explosion
Explosion
BLEVE may occur when a pressurized tank, e.g. LPG (as in Mexico
disaster) or partially filled flammable liquid container, is exposed to an
external heat/fire.
Deflagration/ Detonation
Deflagration: An explosion in which
the reaction front moves at subsonic
speed (speed less than the speed of
sound) in the unreacted medium.
Flame propagation velocity, typically
far below 100 m/s, and relatively
modest overpressures, <0.5 bar.
Shock front
Reaction front
Shock front
Reaction front
modest
overpressure
Explosive atmosphere
Explosive atmosphere
Definitions
Definitions
Damage
Loud noise (143 dB)
6-14
15
25
35-50
Cleveland Open
Cup Method.
Closed cup
produces a better
result - reduces
drafts across cup.
12.8 C
365 C
Gasoline
(petrol)
<40 C
246 C
Diesel
>62 C
210 C
Jet fuel
>60 C
210 C
c/Tb
b(c/Tb ) e
Tf = a +
(1 e c/Tb )2
where,
Tf is flash point in K,
a, b, and c are constants
(provided in Table, next slide),
Tb is boiling point in K
Hydrocarbons
225.1
537.6
2217
Alcohols
230.8
390.5
1780
Amines
222.4
416.6
1900
Acids
323.2
600.1
2970
Ethers
275.9
700.0
2879
Sulfur
238.0
577.9
2297
Esters
260.5
449.2
2217
Halogens
262.1
414.0
2154
Aldehydes
264.5
293.0
1970
0.75
(T 25)
H c
0.75
(T 25)
H c
UFL p =
UFL + 20.6(logP + 1)
where P is absolute pressure in Mega Pascal
As pressure increases: UFL increases, LFL mostly unaffected
LFL =
UFL =
1
yi
LFL
i
1
yi
UFL
i
10
8
6
4
2
LFL
0
0
UFL
2
10
TI
Igniter
PI
Pressure (bar-abs)
10
Pmax
8
0
0
50
100
150
200
250
Time (ms)
Experimental Apparatus
x
CmHxOy + zO2 mCO2 + H2O
2
z=m+x-y
LFL = 0.55Cst
UFL = 3.50Cst
Approximate!
(Typically 8 - 12%)
By substitution, we obtain
LOC
LOC
= 12.4 vol. % O2
Flammability Diagram
A general way to represent
the flammability of a gas or
vapour is by the triangle
diagram as shown in the
figure below.
Concentration
of
fuel,
oxygen and inert material
are plotted on the three
axes. Each apex of the
triangle represents either
100% fuel, oxygen or
nitrogen.
Flammability Diagram
The tick marks on the scales
show the direction in which the
scale moves across the figure.
Thus point A represents a
mixture composed of 60%
methane, 20% oxygen, and
20%
nitrogen. The zone
enclosed by the dashed line
represents all mixtures that are
flammable.
Nitrogen
Nitrogen
Oxygen
Fuel
Nitrogen
Fuel
Nitrogen
Nitrogen
Oxygen
The
intersection
of
stoichiometric line with the
oxygen axis (in volume %
oxygen is given by)
Nitrogen
100
Oxygen
Fuel
LFL
Nitrogen
Diagram
5. Add Stoichiometric Line
6. Get Pure Oxygen LFL
and UFL (if available)
7. Construct curve
LOC
UFL(O2)
Oxygen
Fuel
LFL(O2)
UFL
LFL
Nitrogen
UFL
LOC = 12 vol% O2
LFL
UFL
LOC = 12 vol% O2
LFL
Solvents
Fuel
Flash
point
Autoignition
temperature
Ethanol
12.8 C
365 C
Gasoline
(petrol)
<40 C
246 C
Diesel
>62 C
210 C
Jet fuel
>60 C
210 C
Kerosene
>3872 C
220 C
Vegetable oil
327 C
Biodiesel
>130 C
Fuel
Flash
point
Autoignition
temperature
Ethanol
12.8 C
365 C
Gasoline
(petrol)
<40 C
246 C
Diesel
>62 C
210 C
Jet fuel
>60 C
210 C
Kerosene
>3872 C
220 C
Vegetable oil
327 C
Biodiesel
>130 C
Flammable liquid refers to any liquid having a flash point below 100 F
(37oC). Such flammables are Class I liquids.
These liquids are subdivided into three classes. The following is an
illustrative list of common flammable liquids:
Class IA
Flash point below 73 F (22C), boiling point below 100 F (37C).
e.g. acetaldehyde
ethyl ether
ethyl chloride
petroleum ether
propylene oxide
pentane
Class IB
Flash point below 73 F (22C), boiling point at or above 100 F (37C)
e.g. acetone
ethyl acetate
methyl alcohol
benzene
ethyl alcohol
methylcyclohexane
butyl alcohol
gasoline
toluene
Class IC
Flash point at or above 73 F (22C), and boiling point below 100 F
(37C).
e.g. amyl acetate
amyl alcohol
isopropanol
xylene
turpentine
Class II Flash point at or above 100 F (37C) and below 140 F (60C)
e.g.
acetic acid
camphor oil
methyl lactate
cyclohexane
hydrazine
kerosene
Class III Flash point at or above 140 F and below 200 F (93C)
e.g.
aniline
furfuryl alcohol
phenol
carbolic acid
naphthalenes
pine oil
Hazard
Hazard
Fire Flashback
Flashback and fire can happen even if the liquid giving off
the vapor and the ignition source are hundreds of feet or
several floors apart.
TNT equivalent
ATEX Directive
ATmosphres EXplosibles
ATEX Directive
Summary
Dangerous substance
Flammability diagram