Flammability Correlations

and Flammability Zone

Read Chapter 6 of
“Chemical Process Safety: Fundamentals with Applications”, 3rd Ed.,
D. A. Crowl and J. F. Louvar
Instructor: Dr. Vineet Kumar, Dept. of Chem. Eng., IIT(ISM)

Note: Instructor’s comments are marked in red color.

From Previous Lectures:
• In previous note we discussed about the two limiting concentrations
of fuel in air, LFL and UFL, that gives flammable mixture which is
potentially dangerous to “fire hazard”.
• LFL and UFL of pure components could be estimated using flashpoint
data whereas for a mixture of pure components, Le Chatelier’s mixing
rule is applicable.
• LFL and UFL are important parameters is considering fire safety. Effect
of temperature, pressure, etc. are also need to be kept in mind while
handling flammable materials. Many empirical correlations are
available to predict all the parameters related to fire safety.
Flashpoint (Page 254)
• Satyanarayana and Rao showed that the flash
point temperatures for pure materials correlate
well with the boiling point of the liquid
with an error of less than ±1% using the equation

where, Tf is the flash point temperature (K),

a, b, and c are constants provided in the Table, and
Tb is the boiling point temperature of the material
(K).
As given in the Table, for one particular group of
compound, such as Alcohol, Amine, Acids etc., the
value of a, b, and c are same. E.g., for any alcohol,
be it methanol, ethanol, or 2-Phenylethanol, values
of a, b, and c are 230.8, 390.5, and 1780,
respectively.
Effect of Temperature and Pressure on LFL &UFL
• In general, LFL decreases and UFL increases with temperature. The following
empirical correlations can be used to estimate flammability limits at any
temperature T (°C), if the same is known at 25°C.

where, ∆Hc is the net heat of combustion (kcal/mole)

• Pressure has little effect on the LFL, but UFL increases significantly with increasing
pressure. An empirical expression to estimate UFLP at any pressure P is given as:
𝑈𝐹𝐿𝑃 = 𝑈𝐹𝐿 + 20.6 1 + log 𝑃 (6-6)
where, P is the pressure (mega-pascals absolute) and
UFL is the upper flammable limit (volume % of fuel plus air at 1atm).
Estimation of Flammability Limits
• Experimental determination of LFL and UFL is always recommended as these can
be easily measured. However, in case of unavailability of experimental facility,
following equation can be used:
where, Cst is the required stoichemetric volume % of
and fuel, in air-fuel mixture
• For the following general hydrocarbon combustion reaction

Cst comes to be
• Alternatively, LFL and UFL can be estimated in terms of heat of combustion of the
fuel (ΔHc, kJ/mol)
 LOL and UOL
• Similar to LFL and UFL, indicating volume percent of fuel in air, LOL and
UOL are the volume% of fuel in pure oxygen for ignition of fuel.
• In general (for most hydrocarbons) the LOL is close to the LFL.
• UOL is determined experimentally, however, following correlation can be
used to estimate UOL in terms of UFL
𝑈𝐹𝐿 100−𝐶𝑈𝑜𝐿 100−𝑈𝐹𝐿0
𝑈𝑂𝐿 =
𝑈𝐹𝐿0 +𝑈𝐹𝐿 1−𝐶𝑈𝑜𝐿
≈ UOL is the maximum oxygen concentration (vol. % fuel in pure oxygen) at
which fuel can be ignited
≈ 𝑈𝐹𝐿0 is the volume percent of oxygen in the air-fuel mixture at the UFL
conditions (𝑈𝐹𝐿0 = 0.21 ∗ 100 − 𝑈𝐹𝐿 , See Example 6-5),
≈ 𝐶𝑈𝑜𝐿 is a constant which is equal to –1.87 for most of the fuels
Apart from volume% of fuel in pure oxygen, limiting oxygen concentration (LOC) is also
studied in which minimum concentration of oxygen in an inert atmosphere is reported
(See section 6-5. Limiting Oxygen Concentration and Inerting)
 Triangular Diagram for Ternary Mixtures
Recall two forms of Ternary component diagrams (Rectangular and Equilateral)
used in Mass Transfer Operation (Figure 10.9, Treybal)
Mixing rule on triangular diagram:
1. x- and y- coordinates represent concentrations (mole/mass fraction, or mole/mass %) of first and second
components (B and C in this figure), whereas concentration of third component xA=1-(xB+xC) remains
constant along a line parallel to the diagonal
2. Three vertices of the triangle represents three
components in pure state.
3. All possible compositions of a mixture of three
components is uniquely defined by a point inside the
triangle.
4. If two mixtures of different compositions E and R are
mixed, then composition of resulting mixture lies on
the line joining E-R.
5. Composition of mixture M will be such that
𝐿𝑒𝑛𝑔𝑡ℎ(𝑀𝐸) 𝑀𝑜𝑙𝑒𝑠(𝑅)
= 𝑀𝑜𝑙𝑒𝑠(𝐸)
𝐿𝑒𝑛𝑔𝑡ℎ(𝑅𝑀)

Figure 10.9 (Treybal): (a) Rectangular (b) Equilateral Coordinates

Location of flammability parameters on
Triangular Diagrams
Let us take a quick look on the flammability parameters we have already discussed:
• LFL and UFL (Lower & Upper Flammability Limit): min & max Vol.% Fuel in Air
• LOL and UOL (Lower & Upper Oxygen Limit): min & max Vol.% Fuel in Oxygen
• LOC (Limiting Oxygen Concentration): min Vol.% Oxygen in Fuel + Inert mixture
(inert can be N2, CO2, etc.)
We will see how to locate these parameters on a Triangular Diagram and make
further analysis based on the location of these points.
For the sake of convenience, let us assume that the properties of a given Fuel are
as follows:
• LFL=10%, UFL=20% (vol.% fuel in air)
• UOL=40% (vol.% fuel in pure oxygen), and
• LOC=8% (vol.% oxygen in fuel-nitrogen mixture)
Ternary mixture of Fuel, Oxygen and Nitrogen
For the Given Fuel having
LFL=10%, UFL=20%, UOL=40% and LOC=8%
• Pure Air contains 79% Nitrogen and 21% Oxygen (no
Fuel) hence Pure Air point lies on x-axis (see figure
32.1).
• When Fuel is mixed with air, composition of resulting
mixture always lies on the Air Line (the line joining
points representing pure air and pure fuel). With
further addition of Fuel, the mixture concentration
move towards pure Fuel point.
• Thus LFL and UFL of the given fuel lies on the Air-line
at 10% and 20% fuel concentrations (as shown in the
figure 32.1)
• The Air-Fuel mixture is ignitable only when its
concentration is between LFL and UFL. Figure 32.1
Ternary mixture of Fuel, Oxygen and Nitrogen
For the Given Fuel having
LFL=10%, UFL=20%, UOL=40% and LOC=8%
• Other ignition characteristics of fuel in pure oxygen are
LOL and UOL (lower and upper limiting volume% fuel in
pure oxygen). For the given fuel, UOL is 40% (fuel in pure
oxygen). Since only oxygen (and no air, or nitrogen) is
present in the combustion mixture, therefore, UOL should
lie on the line joining pure oxygen and pure fuel, i.e., y-axis
in figure 32.2.
• As LOL (% fuel in pure oxygen) ≈ LFL (% fuel in air) (see
page 261-62 of Crowl and Louvar), LOL is marked on y-axis
at the concentration as of LFL. i.e., 10% fuel in this case.
• All these four points, UOL, LOL, LFL, and UFL are the four
limiting concentrations of fuel to ignite, therefore any
concentration of fuel-air mixture falling within this region,
will ignite.
Figure 32.2
Ternary mixture of Fuel, Oxygen and Nitrogen
For the Given Fuel having
LFL=10%, UFL=20%, UOL=40% and LOC=8%
• Another parameter, LOC, is the minimum concentration of
oxygen required to ignite a mixture of fuel and inert (CO2,
N2, etc.).
• To locate LOC on the diagram, we can mark LOC
concentration on any of the x- or y-axis. In figure 32.3 it is
marked on y-axis for 8% oxygen (i.e., 100 – 8 = 92% Fuel).
A line parallel to the diagonal, passing through, LOC
represents constant concentration of oxygen (8% in this
case) all along the line (using the property xA=1-(xB+xC) on
triangular concentration diagram).
• Therefore, this LOC point must be lying somewhere on the
dashed line
• One can easily visualize, this point must be in the vicinity
of LFL and UFL already marked on the diagram
Figure 32.3
Ternary mixture of Fuel, Oxygen and Nitrogen
For the Given Fuel having
LFL=10%, UFL=20%, UOL=40% and LOC=8%
• To locate LOC, we can extend the shaded aria as shown in
figure 32.4. This extended shaded region can not go
beyond the dashed line, as oxygen concentration towards
right side of this line is everywhere less than the
concentration of LOC (i.e., less than 8% in present case).
• Alternatively, one can get this LOC point by extending lines
joining UOL-UFL, and LOL-LFL, however, it is difficult to get
point of intersection to lie on LOC line (dashed line).
• If experimental data are not available, the LOC is
estimated using the stoichiometry of the combustion
reaction and the LFL (see Example 6-6, page 264).
• The entire shaded area (on the left and right side of Air
Line) is called “Flammability Zone”.
Figure 32.4