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Limiting Oxygen Concentration and Minimum Inert Concentration of Fuel-


air-inert Gaseous Mixtures Evaluation by means of Adiabatic Flame
Temperatures and Measured Fuel-air Lower Fla...

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Limiting Oxygen Concentration and Minimum Inert
Concentration of Fuel-air-inert Gaseous Mixtures Evaluation
by means of Adiabatic Flame Temperatures and Measured Fuel-air
Lower Flammability Limits

VENERA GIURCAN1, DOMNINA RAZUS1,*, MARIA MITU1, VOLKMAR SCHRÖDER2


1
"Ilie Murgulescu” Institute of Physical Chemistry, 202 Spl. Independentei, 060021 Bucharest, Romania
2
BAM-Federal Institute for Material Research and Testing, Unter den Eichen 80, 12208 Berlin, Germany

The present paper aims to re-examine the validity of the linear correlation found between AFTLOC, the
adiabatic flame temperature at the apex of the flammability range of fuel-air-inert mixtures (where LOC, the
Limiting Oxygen Concentration, is measured) and AFTLFL, the adiabatic flame temperature at the lower
flammability limit of fuel-air mixtures (LFL). New sets of experimental measurements of LFL and LOC
referring to fuel-air mixtures diluted with N2, CO2 and H2O(vap) from trusted literature sources form a
comprehensive database for such evaluation. Both the slope and intercept of correlations AFTLOC = a +
b*AFTLFL are dependent on the nature of inert gas and on initial temperature. Based on the linear correlation
between AFTLOC and AFTLFL, a procedure for calculation of LOC and MIC (Minimum Inert Concentration) of
fuel-air-inert mixtures is presented, using measured or calculated LFL of fuel-air mixtures and their
corresponding AFT. The method predicts with reasonable accuracy LOC and MIC of fuel-air-inert mixtures
(relative deviations ranging between -14 and +17% when calculated and measured LOC and MIC for fuel-
air-nitrogen and fuel-air-carbon dioxide at ambient initial conditions are examined).
Keywords: fuel, limiting oxygen concentration, minimum inert concentration, adiabatic flame temperature,
flammability limit

The explosion limits of a fuel-oxidizer mixture are the (LOC) [1]. In addition to LOC, the Minimum Inert
boundaries of fuel concentration range where a locally Concentration (MIC) is defined as the minimum inert
ignited explosion (by a spark, a hot body, a pilot flame or concentration that achieves a total inertization of fuel-
other energy sources) can propagate in the entire amount oxidizer-inert mixture, regardless of fuel or oxidizer
of explosive mixture [1]. In such cases, the flame is self- concentration [1]. Usually, nitrogen or carbon dioxide are
sustained i.e. the evolved heat from each layer of burnt gas used as inert additives, but argon, water vapor or exhaust
allows ignition of fresh gas adiacent layer. For deflagrations gas (a mixture of N2, CO2 and H2O) are used too. The
(explosions propagating with subsonic speeds) the inertization effect is stronger when the inert gas has a
flammability limits are defined: the lower flammability higher heat capacity and/or the possibility to dissociate. In
limit (LFL) characteristic to fuel-oxidizer systems with lean this respect, the aliphatic halogenated derivatives have a
fuel amounts (fuel deficit) and the upper flammability limit strong inertization action on flames. They can remove the
(UFL) characteristic to fuel-oxidizer systems with rich fuel gaseous mixtures outside of the explosion limits, even at
amounts (oxygen deficit). The flammability limits are concentrations of few percents. Their influence is explained
influenced by several factors such as: the initial by the ease with which these compounds generate, at
temperature and pressure, the presence of inert additives, high temperatures, halogen atoms which interrupt the
the direction of flame propagation, the ignition energy, the chain of oxidation reaction. Their use is not recommended
volume and shape of the vessel [2]. Among properties nowadays because of their high polluting action.
characteristic of ignition stage, the flammability limits are A key parameter for characterizing fuel-air mixtures is
very important; they range within primary flammability the Adiabatic Flame Temperature (AFT), defined as the
parameters, essential for safety recommendations in all maximum temperature reached in a flame, in the absence
domains of activity where flammable fuel-air mixtures can of energy losses. Many authors considered AFT as constant
be formed. along the flammability range, no matter the amount of
The most important method to mitigate an explosion is inert additive in the mixture [3-10]. Various threshold values
the addition of an inert gas to the fuel-oxidizer mixture. of AFTLFL have been set by different authors: 1860-1820 K
Addition of increasing amounts of an inert gas to a [3], 1600 K [6], 1400 K [7], 1200 K [5], even 1000 K [4].
flammble mixture determines the increase of the lower This criterion was extended to upper explosion limits as
explosion limit and the decrease of the upper explosion well, after a reexamination of adiabatic flame temperatures
limit until their values coincide and the apex of the by including the soot among the combustion products [5].
flammability range is reached. In a fuel-oxidizer-inert Obviously, the criterion of constant CAFT was maintained
mixture, the maximum oxygen concentration for which over the entire explosion range, including also the apex of
an explosion can not occur (regardless of the fuel or inert the explosion range. Other authors [11] introduced the
concentration) is named Limiting Oxygen Concentration concept of fuel-dependent threshold AFTLFL: 1440 K (for
* email: drazus@icf.ro; Tel: +40-21-3167912

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hydrocarbons); 1505 K (for oxygenated compounds) and fuel-air-diluent mixtures by approximating the boundaries
1580 K (for halogenated compounds); the concept was of the flammability range with linear equations that are
used later by Zlochower [9] to predict LFL and UFL functions on fuel and oxygen concentrations at the upper
dependencies of several fuels on temperature. and the lower flammability limits of fuel in air [8]. Their
From many studies it is seen, however, that AFT of limit method was based on data from Lewis and von Elbe [26],
mixtures vary in large limits over the whole flammability extracted from Coward and Jones [25].
range [4, 7, 12] , so that the mapping of this range and the Predicted MIC of some fuel-air mixtures diluted with N2,
determination of its extreme point (characterized by LOC CO2 and He/Ar were given by Bade Shrestha et al. [22]
and MIC) must rely upon other characteristic parameters, using experimental LFL and UFL of fuel-air mixtures and
e.g., the normal burning velocity. In this respect, the choice assuming that in each limit mixture, the fuel concentration
of a limit (threshold) value for the normal burning velocity has a threshold value allowing flame propagation. The
in limit fuel-air and fuel-air-inert mixtures might offer an authors extended their approach to fuel-air-inert mixtures
alternative criterion for flammability limit prediction [2, 13, at elevated initial temperatures up to 400oC and found a
14]. satisfactory agreement with experimental MIC (relative
Predictions of inert addition influence on LFL and UFL deviations between 1 and 9%, for hydrocarbon-air
were issued in many other contributions [15-24], with mixtures).
various degrees of accuracy. Their results are generally Another method for LOC prediction is based on group
delivered as fuel concentrations and do not include (increment) contribution of various fuels to consumed
predicted values of LOC and/or MIC, since no examination oxygen, in limit fuel-air-inert mixtures [16, 27].
of the equivalence ratio at the apex of the flammability Subramanian and Cangelosi used this procedure for various
range is done. Indeed, in most papers it was assumed that fuels (H2, CO, hydrocarbons, alcohols) and enlisted group
the apex of the flammability range is observed always at contributions after its validation against US Bureau of Mines
the stoichiometric composition of fuel-air mixtures for collection of data, compiled by Zabetakis [28]. Fuβ,
complete combustion to CO2 and H2O. Examination of a Molnarne, Schröder and Schönbucher [16] issued a set of
set of trusted data from Coward and Jones [25] by Britton corrected group contributions, obtained by validation
[15] revealed that LOC of hydrocarbon-air-inert mixtures against LOC from CHEMSAFE database [29]. Their newer
is found at a fuel equivalence ratio between 1.0 and 1.5, data were measured according the European Standard EN
increasing with the number of carbon atoms. Other fuels 1839 and are more conservative in respect to earlier data,
displayed similar behavior. obtained with U.S.Bureau of Mines method [25, 28].
According to a suggestion from Lewis and von Elbe [26], Examination of published flammability data (LFL, UFL,
Britton assigned the difference between optimum and LOC and MIC) is difficult considering the variety of
stoichiometric fuel concentrations to differences between experimental conditions and criteria to determine the limit
the diffusivities in air of fuel versus oxygen. concentration, especially in the vicinity of the flammability
Using the assumption of constant heat of combustion range apex. In fact, Zlochower and Green consider the
per mole of lower flammability limit mixture, Kondo international flammability databases as „incompatible”
predicted the fuel concentration for the whole flammability [21], since the current standard adopted by the European
range of fuel-air mixtures diluted with N2 and CO2 and found union is „a radical departure” from US standards.
a fair agreement of predicted limits with their An original method of calculating the limiting oxygen
measurements [17-19] made with ASTM method. From concentration of fuel-air-inert mixtures was recently
the analysis of heat balance during flame propagation, developed, using LFL, the lower flammability limit, and
other predictions of fuel concentration in fuel-air and fuel- the adiabatic flame temperatures (AFT) of fuel-air and fuel-
air-inert mixtures have been made [7-9, 10, 21, 24]. The air- inert limit mixtures. The method is based on the linear
additional hypothesis of thermal radiation loss has lead to correlation between AFT of fuel-air- inert mixtures at the
predictions of fuel concentration in limit mixtures in better apex of the flammability range (AFTLOC) and AFT of fuel-air
agreement with experimental data, both at ambient and mixtures at the lower flammability limit (AFTLFL), found for
elevated initial temperatures, excepting however the region systems diluted with nitrogen [12], carbon dioxide or water
approaching LOC, where the assumption of complete fuel (vap.) [30] at ambient and at elevated initial temperatures.
combustion fails [10]. The examined data have been extracted from few sources:
Empirical approaches found a wide application in LOC Zabetakis [28] and CHEMSAFE Database [29], where
prediction. Britton [11, 15] assumed LOC is inversely results of measurements with the German standard DIN
proportional to the square of net heat of oxidation and 51649 and the European Union standard EN 1839 have
enlisted the constants for hydrocarbons and other CHON been included.
fuels: The present paper aims to re-examine the validity of
this correlation by including new sets of experimental
(1) measurements of LFL and LOC [5, 17-20, 31-34] at
ambient initial pressure and various initial temperatures
where S is the ratio of oxygen-to-fuel, as written in the within 25–250°C. The adiabatic flame temperatures of limit
stoichiometric equation of combustion. Another simple mixtures have been computed with the program COSILAB
equation, equivalent to eq. (2) was used by Britton [15] by taking into account the dissociation of gases within the
and tested (with poor predictive results) by Hansen and flame. The only requirement (restriction) of the proposed
Crowl for fuel-air-N2 mixtures [8]: method is to examine pairwise the LFLs and LOCs
obtained by means of a chosen set-up and measurement
(2) procedure. Based on the found correlation, the procedure
for calculating LOC and MIC of fuel-air- inert mixtures is
Indeed, eq. (3) has the disadvantage that any error in presented and the deviations of the predicted LOC and
LFL is multiplied by S in estimating LOC. Hansen and Crowl MIC from experimental data are examined, in comparison
proposed instead another method for LOC calculation in with predictions from other procedures.

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Table 1
CALCULATED ADIABATIC FLAME
TEMPERATURES AT THE LOWER FLAMMABILITY
LIMIT (LFL) AND AT THE APEX OF THE
FLAMMABILITY DOMAIN (LOC) FOR CH4-AIR-N2
MIXTURES AT AMBIENT INITIAL CONDITIONS;
COMPOSITION OF LIMIT MIXTURES – FROM
LITERATURE

Computing procedure Many literature sources do not indicate the fuel


The adiabatic flame temperatures of fuel-air and fuel- concentration at the apex of the flammability range,
air-inert mixtures were computed with 0-D COSILAB necessar y for calculation of the adiabatic flame
package [35], assuming chemical equilibrium is reached temperature; therefore, valuable information from new
within the flame. 53 compounds were considered as publication such as NFPA 69 [33] could not be used in the
combustion products. Their heat capacities, the standard present paper.
enthalpies of formation at 298 K and the standard entropies According to specific features of each method, the data
at 298 K were calculated by means of NASA polynomials. are scattered between these literature sources. Even for
the most studied fuel, methane, important deviations are
Results and discussions observed between the composition of limit mixtures at
Literature information on LFL, LOC and MIC is available the lower flammability limit and at the apex of the
in many papers [5, 15, 17-21, 24-26, 28-34]. Reported data flammability range, as seen from table 1. In the examined
were obtained mainly with standardized methods: the U.S. data, LFLs vary between 4.4 and 5.0 vol.% and the
Bureau of Mines method [25, 28], ASTM E681 or ASTM corresponding adiabatic flame temperature varies
E2079 method and their improved version issued by between 1357 and 1481 K. The corresponding LOCs
ASHRAE [17-19], German standard method DIN 51649 [16, change from 10.65 to 12.00 vol.% and the MICs between
29-31], EN 1839 (European Standard) method [34]. Other 36.2 and 44.0 vol.%. The observed variations can be
methods delivered reliable data sets as well, as reported assigned to differences in ignition energy, amount of heat
by Crowl and coworkers [5, 20] (a method using a 20 L losses from the gas mixture to the surroundings, isobaric
spherical vessel with central ignition), by Zlochower and or isochoric conditions of testing, criteria used for
Green [21](use of 20 L and even 120 L spherical vessels ascertaining the explosion appearance, as discussed in
with central ignition) and by Hoppe and Jaeger [32] (Swiss recent papers [12, 21].
method issued by ESCIS – the Expert Commission for Safety Other data sets referring to fuel-air-N2 mixtures at
in the Swiss Chemical Industry 1994 using a 20 L sphere). ambient initial conditions are given in tables 2 and 3 where

Table 2
CALCULATED ADIABATIC FLAME
TEMPERATURES AT THE LOWER
FLAMMABILITY LIMIT (LFL) AND AT THE
APEX OF THE FLAMMABILITY DOMAIN
(LOC) FOR FUEL-AIR-N2 MIXTURES AT
AMBIENT INITIAL CONDITIONS;
COMPOSITION OF LIMIT MIXTURES -
FROM ZABETAKIS [28]

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Table 3
CALCULATED ADIABATIC FLAME
TEMPERATURES AT THE LOWER
FLAMMABILITY LIMIT (LFL) AND AT
THE APEX OF THE FLAMMABILITY
DOMAIN (LOC) FOR FUEL-AIR-N2
MIXTURES AT AMBIENT INITIAL
CONDITIONS; COMPOSITION OF LIMIT
MIXTURES - FROM CHEMSAFE
DATABASE [34]

Table 4
CALCULATED ADIABATIC FLAME
TEMPERATURES AT THE LOWER
FLAMMABILITY LIMIT (LFL) AND AT THE
APEX OF THE FLAMMABILITY DOMAIN (LOC)
FOR FUEL-AIR-N2 MIXTURES AT AMBIENT
INITIAL CONDITIONS; COMPOSITION OF
LIMIT MIXTURES - FROM LITERATURE
SOURCES

results taken from U.S. Bulletin of Mines no. 627 [28] edited For the 45 data sets, we found an average equivalence
by Zabetakis and from a recent version of the German ratio of limit mixtures ϕ = 1.230. It must be outlined that
database CHEMSAFE [34] are listed together with their the present data referring to fuel-air-N2 flammable mixtures
computed adiabatic flame temperatures. Some of these include not only hydrocarbons, but also oxygenated
data have been published earlier [12], but the corresponding compounds and a cyano-derivative, extracted from various
AFT were computed with another software (ECHIMAD), sources [18, 20, 28].
based on thermodynamic input data from other sources. In our previous contributions [12, 30], we examined the
The present AFT, computed with the package COSILAB, adiabatic flame temperatures of limit mixtures at LFL and
are systematically lower by 10-12 K in comparison with LOC measured pairwise by various experimental
previously reported values [12]. techniques. For each added inert gas and initial
Additional data sets referring to fuel-air-N2 mixtures at temperature of limit fuel-air and fuel-air-inert mixtures, we
ambient initial conditions are given in table 4. found that AFT of limit mixtures are correlated by a linear
Data referring to the limit composition at the apex of relationship:
the flammability range of any fuel differ strongly when AFTLOC = a + b*AFTLFL (3)
results from tables 2, 3 and 4 are compared, in respect to
both LOCs and MICs. It is worth mentioning that most fuel- where a and b are constants dependent on the inert gas
air-N2 at the apex of the flammability range are rich and on the initial temperature of flammable mixtures.
mixtures, having equivalence ratios ϕ between 1.10 and The results describing 45 flammable fuel-air-N2 mixtures
1.401, in contradiction with the findings of other authors at ambient initial conditions (data from tables 2, 3 and 4)
which indicated ϕ = 1.00 at LOC for all fuels [5, 16-19]. are plotted in figure 1. Examination of these data sets
1
The equivalence ratio of any fuel-oxygen(air) mixture ϕ = ([ fuel ] / [O2 ]) / ([ fuel ] / [O2 ]) stoich is defined as a function of fuel and oxygen concentrations in
the “stoichiometric” mixture, where the fuel/oxygen ratio corresponds to the stoichiometric combustion reaction, forming only CO2 and H2O.

1448 http://www.revistadechimie.ro REV. CHIM. (Bucharest) ♦ 64♦ No.12 ♦ 2013


reveals that the linear correlation holds with a correlation For fuel-air-CO2 mixtures, the examined data from the
coefficient rn = 0.655 and a probability less than 0.001 that two main reference sources (Zabetakis [28] and
examined data are not linearly correlated: CHEMSAFE data base [34]) are given in tables 5 and 6.
Other relevant results from literature are listed in table 7.
AFTLOC = (639.9 ± 147.1) + (0.564 ± 0.099)*AFTLFL (4) These tables do not include the information on mixture
where AFT are expressed in K. composition at LFL and adiabatic flame temperatures
The correlation is improved in comparison to previously AFTLFL, already given in tables 2, 3 and 4. The corresponding
reported data [12], as seen from a higher correlation adiabatic flame temperatures AFTLOC vs. AFTLFL are plotted
coefficient and lower standard deviations of slope and in figure 2.
intercept.

Fig. 2. Adiabatic flame temperatures of fuel-air-CO2 mixtures versus


Fig. 1. Adiabatic flame temperatures of fuel-air-N2 mixtures versus
adiabatic flame temperatures of fuel-air mixtures at ambient initial
adiabatic flame temperatures of fuel-air mixtures at ambient initial
pressure and temperature (38 data sets)
pressure and temperature (45 data sets)

Table 5
CALCULATED ADIABATIC FLAME
TEMPERATURES AT THE LOWER
FLAMMABILITY LIMIT (LFL) AND AT THE
APEX OF THE FLAMMABILITY DOMAIN
(LOC) FOR FUEL-AIR-CO2 MIXTURES AT
AMBIENT INITIAL CONDITIONS;
COMPOSITION OF LIMIT MIXTURES - FROM
ZABETAKIS [28]

Table 6
CALCULATED ADIABATIC FLAME TEMPERATURES
AT THE LOWER FLAMMABILITY LIMIT (LFL) AND
AT THE APEX OF THE FLAMMABILITY DOMAIN
(LOC) FOR FUEL-AIR-CO2 MIXTURES AT AMBIENT
INITIAL CONDITIONS; COMPOSITION OF LIMIT
MIXTURES - FROM CHEMSAFE DATABASE [34]

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Table 7
CALCULATED ADIABATIC FLAME
TEMPERATURES AT THE LOWER
FLAMMABILITY LIMIT (LFL) AND AT THE APEX
OF THE FLAMMABILITY DOMAIN (LOC) FOR
FUEL-AIR-CO2 MIXTURES AT AMBIENT INITIAL
CONDITIONS; COMPOSITION OF LIMIT
MIXTURES - FROM LITERATURE SOURCES

A common feature is found for fuel-air-N2 and fuel-air- For these 83 fuel-air-inert flammable mixtures, the
CO2 flammable mixtures at ambient initial conditions: the average equivalence ratio at the apex of the flammability
apex of the flammability range is observed in rich mixtures. range is ϕ = 1.252
For the examined set of data from tables 5, 6 and 7, we Other results, collected from CHEMSAFE data base [34],
found an average equivalence ratio ϕ = 1.244 of limit refer to preheated fuel-air-inert mixture and have been
mixtures at LOC. Their adiabatic flame temperatures, as included in table 8. Data for N2- and CO2- diluted mixtures
plotted in figure 2, were correlated according to equation: are scattered and the corresponding AFTLOC and AFTLFL are
in poor correlations. Only fuel-air-H2O mixtures at 373 K
AFTLOC = (625.3 ± 172.1) + (0.598 ± 0.117)*AFTLFL (5) could be analyzed according to equation (4). Their adiabatic
flame temperatures, plotted in figure 3, were correlated
(correlation coefficient rn = 0.649 and a probability less according to equation:
than 0.001 that examined data are not linearly correlated).
As above, the AFT are expressed in K. AFTLOC = (23.3 ± 846.5) + (1.152 ± 0.623)*AFTLFL (7)
Examination of all fuel-air-N2 and fuel-air-CO2 flammable
mixtures, at 298 K and 1 bar (a set of 83 data) reveals also (correlation coefficient rn = 0.679 and a probability P =
a linear correlation of adiabatic flame temperatures, with 0.138 that examined data are not linearly correlated). As
a correlation coefficient rn = 0.641. above, the AFT are expressed in K. For these mixtures, an
unique correlation equation was not observed, at least for
AFTLOC = (641.5 ± 112.6) + (0.574 ± 0.076)*AFTLFL (6) the examined data sets.

Table 8
CALCULATED ADIABATIC FLAME
TEMPERATURES AT THE LOWER
FLAMMABILITY LIMIT (LFL) AND AT THE APEX
OF THE FLAMMABILITY DOMAIN (LOC) FOR
FUEL-AIR-INERT MIXTURES AT T0 = 373 K AND
P0 = 1 BAR; COMPOSITION OF LIMIT
MIXTURES - FROM CHEMSAFE DATABASE [34]

1450 http://www.revistadechimie.ro REV. CHIM. (Bucharest) ♦ 64♦ No.12 ♦ 2013


Fig. 3. Adiabatic flame temperatures of
fuel-air-H2O mixtures at T0 = 373 K and p0
= 1 bar (6 datasets)

Table 9
COMPOSITION OF LIMIT MIXTURES AND
ADIABATIC FLAME TEMPERATURES AT THE
LOWER FLAMMABILITY LIMIT (LFL) AND AT
THE APEX OF THE FLAMMABILITY DOMAIN
(LOC) FOR FUEL-AIR-H2O MIXTURES AT T0 =
473 K AND P0 = 1 BAR; COMPOSITION OF
LIMIT MIXTURES - FROM CHEMSAFE
DATABASE [34]

Table 10
COMPOSITION OF LIMIT MIXTURES AND
ADIABATIC FLAME TEMPERATURES AT THE
LOWER FLAMMABILITY LIMIT (LFL) AND
AT THE APEX OF THE FLAMMABILITY
DOMAIN (LOC) FOR FUEL-AIR-INERT
MIXTURES AT T0 = 523 K AND P0 = 1 BAR;
COMPOSITION OF LIMIT MIXTURES - FROM
CHEMSAFE DATABASE [34]

Table 11
THE BEST-FIT PARAMETERS OF
CORRELATIONS BETWEEN THE ADIABATIC
FLAME TEMPERATURES OF LIMIT MIXTURES

At initial temperatures T0 = 473 K and 523 K, only few unique value of the AFTLFL, an unique value of AFTLOC is
reliable data could be gathered. Results extracted from obtained, no matter of the nature of diluent gas. Obviously,
CHEMSAFE data base are listed in tables 9 and 10. The fit the amount of diluent (N2 or CO2) necessary to bring a fuel-
parameters of linear equations correlating AFTLOC and AFTLFL air mixture to the inertization point (MIC) varies
of the preheated mixtures are given in table 11. significantly: typical MIC of nitrogen range between 37 -
The examination of equations (5) and (6) valid for limit 50% and typical MIC of CO2 range between 25 - 40%.
fuel-air-N2 and fuel-air-CO2 mixtures shows they have close At elevated initial temperatures, the scatter of available
values of slopes and intercepts (within the confidence data, revealed by the large standard errors of slopes and
intervals, they are practically equal). It seems that an intercepts listed in Table 9, is quite large and cannot sustain
unique correlation exists between the AFT of limit mixtures the idea of an unique correlation between AFTLOC and AFTLFL
at the inertization point (when various diluents are used) regardless of added diluent. More experimental support
and the AFT of limit mixtures at LFL, as given by eq. (7). It may offer a future development of the present method.
follows that for a fuel-air mixture characterized by an

REV. CHIM. (Bucharest) ♦ 64 ♦ No. 12 ♦ 2013 http://www.revistadechimie.ro 1451


Table 12
LOC AND MIC ESTIMATION FOR PROPANE-AIR-
CO2 MIXTURES, AT 298 K AND 1 BAR

Fig. 5. Relative deviations (%) between calculated and measured


Fig. 4. Relative deviations (%) between calculated and measured LOC, for several fuel-air-N2 mixtures at 298 K and 1 bar
LOC and MIC respectively, for CH4-air-N2 mixtures at 298 K
and 1 bar
According to other predictive methods, the relative
deviations between the calculated and the measured LOC
The predictive power of the found correlations (5) and range between +20 and -20% [8, 15, 16, 20, 21]. It must
(6) can be examined by using the protocol for inverse be outlined that LOC predictions of other authors show a
calculations, described in the Appendix of the present fair agreement only with data sets which were the basis of
paper. One example is given in table 12. the corresponding method. In comparison with these
The relative deviations of predicted versus experimental results, we consider our method has a good predictive ability
LOC values range between -8 and +10% for CH4-air-N2 especially for fuel-air-diluent flammable mixtures at
mixtures at ambient initial conditions, as shown in figure ambient initial conditions, since it includes series of data
4. For these mixtures, the relative deviations of the reported by different authors, measured with various
predicted MIC versus the experimental MIC range between methods according to actual international standards. Few
-14 and +8%. For CH4-air-CO2 mixtures at ambient initial data on flammable fuel-air-diluent mixtures at
conditions, the relative deviations of predicted versus temperatures higher than ambient are available in
experimental LOC values range between -7 and +7%; the literature; publication and analysis of additional information
relative deviations of predicted versus experimental MIC may form the basis for improving the predictions of the
values range between -11 and +17%. present method.
For other fuel-air-N2 flammable mixtures at ambient
initial conditions, the relative deviations of predicted versus Conclusions
experimental LOC values range between -8% and +14% The widely available collections of recommended
according to 2 literature sources [28, 34], as seen from flammability data indicate only the Lower Flammability
figure 5. Relative deviations between -7 and +7% were Limit (LFL) and Upper Flammability Limit (UFL) values, at
obtained between calculated and measured LOCs of fuel- various initial pressures and/or temperatures. This scarce
air-CO2 flammable mixtures at ambient initial conditions. information can be completed by using the present method
For the same fuels, the relative deviations of predicted MIC of estimating the fuel and the oxygen concentration at the
values from experimental ones range between -10 and apex of the flammability range, based upon the values of
+12%. LFL and the Calculated Adiabatic Flame Temperatures,
1452 http://www.revistadechimie.ro REV. CHIM. (Bucharest) ♦ 64♦ No.12 ♦ 2013
both at LFL and LOC. The method was developed for 3. SAITO, N., OGAWA,Y., SASO, Y., LIAO, C., SAKEI, R., Fire Safety J.,
systems at ambient initial temperature and it was validated 27, 1996, p. 185
for mixtures at temperatures higher than ambient, 4. MELHEM, G., Proc. Safety Progr., 16, 1997. p. 203
containing diluents as N2, CO2 and H2O(vapour). 5. MASHUGA, C., CROWL, D., Proc. Safety Progr., 18, 1999, p. 127
The relative deviations between calculated and 6. SHEBEKO, Y. N., FAN, W., BOLODIAN, I.A., NAVZENYA, V.Y., Fire Saf.
measured LOC and MIC range between -14 and +17%. J. 37, 2002, p. 549
Better predictions could be obtained by extending the 7. VIDAL, M., WONG, W., ROGERS, W.J., MANNAN, M.S., J. Hazard.
number of investigated systems. It is important to notice Mater., 130, 2006, p. 21
the difficulty to use the present method for compounds 8. HANSEN, T., CROWL, D., Proc. Saf. Progr., 29, 2010, p. 209
which are unstable or may decompose even in the absence 9. ZLOCHOWER, I., J. Loss Prev. Process Ind., 25, 2012, p. 555
of an oxidant (e.g. acetylene or ethylene oxide). Under 10. LIAW, H. J., CHEN, C. C., CHANG, C. H., LIN, N. K., SHU, C. M., Ind.
such conditions, LOC and MIC should be determined by Eng. Chem., Res., 51, 2012, p. 2747
experiment. 11. BRITTON, L., FRURIP, D. J., Proc. Saf. Progr., 22, 2003, p. 1
The method has the advantage to include series of data 12. RAZUS, D., MOLNARNE, M., FUSS, O., Chem. Eng. Process., 43,
reported by different authors, measured with various 2004, P. 775
methods, according to actual international standards. 13. BURGESS, D., HERTZBERG, M., ISA Trans., 14, 1975, p. 129
According to this specific feature, inclusion of new data 14. MAÈEK, A., Natl. Bureau Standards of USA Report 76-1076/1976.
sets obtained with alternative or with improved procedures 15. BRITTON, L. G., Proc. Saf. Progr., 21, 2002, p. 31
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Chem.Eng. Technol., 26, 2003, p. 428
Appendix - Procedure for LOC estimation by using 17. KONDO, S., TAKIZAWA, K., TAKAHASHI, A., TOKUHASHI, K., J.
adiabatic flame temperatures of limit mixtures Hazard. Mater., 138, 2006, p. 1
- measurement of LFL of fuel-air mixture, at various 18. KONDO, S., TAKIZAWA, K., TAKAHASHI, A., TOKUHASHI, K., Fire
initial temperatures and/or pressures; Saf. J., 41, 2006, p. 406
- calculation of AFTLFL with any program able to provide 19. KONDO, S., TAKIZAWA, K., TAKAHASHI, A., TOKUHASHI, K., SEKIYA,
adiabatic flame temperatures; A., J. Hazard. Mater., 148, 2007, p. 640
- calculation of AFTLOC by means of the equation AFTLOC 20. BROOKS, M. R. , CROWL, D. A., J. Loss Prev. Process Ind., 20,
= a + b*AFTLFL, valid for the examined initial temperature; 2007, p. 144
- calculation of inert, fuel and air concentrations for the 21. ZLOCHOWER, I. A., GREEN, G. M., J. Loss Prev. Process Ind., 22,
mixture characterized by the value of AFTLOC determined 2009, p. 499
at step (iii). 22. BADE SHRESTHA, S.O., WIERZBA, I., KARIM, G.A., Appl. Thermal
This involves a supplementary computation of adiabatic Eng., 29, 2009, p. 2574
flame temperatures, for fuel-air-inert systems with a 23. ZHAO, F., ROGERS, W.J., MANNAN, M.S., J. Hazard. Mater., 174,
constant fuel/oxygen ratio (equivalence ratio) and various 2010, p. 416
inert concentrations. Such values allow calculation of fuel, 24. HANSEN, T. J., MSc Dissert., Michigan Technical Univ., USA, 2009
air and inert concentrations at LOC, by interpolation. 25. COWARD, H. F., JONES, G.W., U.S. Bureau of Mines Bull. No. 503,
An important step: calculation of ϕ, the average 1952
equivalence ratio for fuel-air-inert mixtures at the 26. LEWIS, B., VON ELBE, G., Combustion, Flames and Explosion of
inertization point, for each examined initial temperature. Gases, 3-rd Ed., Academic Press, London and New York, 1987
27. SUBRAMANIAN, T., CANGELOSI, J., Chem. Eng. Prog., 96, 1989,
Acknowledgements: This work was supported by a grant of the p. 108
Romanian National Authority for Scientific Research, CNCS – UEFISCDI, 28. ZABETAKIS, M., Flammability Characteristics of Combustible Gases
project PN-II-RU-PD-2011-3-0053. The authors gratefully acknowledge and Vapors, U.S. Bureau of Mines Bull. No. 627, 1965
Prof. Dan Crowl (Michigan Technological Univ., USA) and Dr. Kai 29. *** CHEMSAFE® database for Safety Characteristics, BAM, PTB,
Holtappels from BAM (Federal Research Institute for Material Research- DECHEMA-Germany, Version 1.4.2, 2001
Berlin, Germany) for providing a part of experimental data used in 30. RAZUS, D., MOLNARNE, M., MOVILEANU, C., IRIMIA, A.,
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