AN EXPERIMENTAL STUDY OF FLAMMABILITY LIMITS USING

COUNTERFLOW FLAMES

ICHIRO YAMAOKA AND H I R O S H I TSUJI

Institute o f Space and Aeronautical Science, University of Tokyo, Tokyo, Japan

Measurements of the lean and rich limits of flammability of methane-air mixtures and
detailed experimental studies of the structure of premixed flames near the lean limit of
flammability were made using a counterflow flame (a double flame) stabilized in the forward
stagnation region of a porous cylinder.
The flammability limits were determined by measuring a discernible break in the distance
between the two flame zones with change in composition of the test mixture. The equivalence
ratios of the lean and rich limits were found to be 0.47 and 1.72, respectively, which are
somewhat broader than those obtained by the standard technique.
From previous results of structure analysis of rich fuel-air flames and the present results
of lean fuel-air flames, it becomes clear that, in a double flame inside the flammability
limits, the two reaction zones are completely separated, the reactions in the inner flame
zone are completed, and the inner flame has the characteristics of a self-sustaining flame.
On the other hand, in a double flame outside the flammability limits, the two reaction
zones are not completely separated and the inner flame is closely correlated with the outer
diffusion flame, so that the inner flame is not a self-sustaining flame. The flammability
limit, defined as the limit of flame propagation, can be considered as the limit at which
the supplies of reactants from the burned side must be necessary for a premixed flame
to be established.
The flammability limits determined in the present study depend only on the physicochemical
properties of the mixture. The propagation velocity at the flammability limits was found
to have a finite value.

Introduction limits. 6 The technique uses a steady state b u r n e r

Flammability limits of combustible mixtures have
been studied mainly using a propagating flame, and
the limits are usually determined by visual observa-
tion of flame propagation in wide vertical tubes. 1'2
Flammability limits thus determined have practical
significance because they give practical limits for
flame propagation. However, the behavior of flames
near the limits is very complicated and many effects
operate at the observed limits. These complex phe-
n o m e n a inherent in flame propagation near the limits
make the fundamental research still more difficult,
so that the structure of near-limit flames and the
mechanism of nonstationary flame extinction are not
fully u n d e r s t o o d )
Some investigators have used burner methods to
determine the flammability limits. 4'5 A new tech-
nique has recently been developed by Sorenson,
Savage a n d Strehlow to study the flammability
with a tent flame (containing the test mixture whose
limit is to be measured) surrounded by a separate
stream of ignition gases, which are the product gases
of another premixed flame using the same fuel, A
limit is obtained by measuring a discernible break
in the tent flame angle with change in composition
of the test mixture. Their technique is quite original
in concept and very attractive. The method w h i c h
uses the coaxial streams of the inner test mixture
a n d the outer ignition gases, however, can not dispel
the uncertainty as to the actual composition of the
mixture in the region of propagation. 7 Such a defect,
inherent in this burner flame, can be avoided by
using a counterflow flame.
A two-dimensional, laminar, rich fuel-air flame
can be established in the forward stagnation region
of a porous cylinder immersed in a uniform air
stream (secondary air) by ejecting premixed fuel and
air uniformly from the cylinder surface. In previous

843
844 FLAME STRUCTURE AND CHEMISTRY
studies of this rich fuel-air flame, the authors mea-
sured aerodynamic, temperature, and stable species
concentration profiles, and then made structure
analysis of the flame and clearly demonstrated the
characteristics of flames near the rich flammability
limit,s'~ It was also found that, inside the rich
flammability limit, the inner flame propagates rap-
idly toward the cylinder surface, while at the same
time the outer diffusion flame moves rapidly away
from the cylinder. As a result, the distance between
two flames increases considerably. This suggests
that the flammability limits can be determined by
observation of a discernible increase in this distance
with change in composition of the ejected mixture.
In the present study, the lean as well as the rich
flammability limits of methane-air mixtures have
been determined by the counterflow-flame tech-
nique. In addition, the structures of lean fuel-air
flames have been analyzed to obtain profiles of mass
flux and reaction rate of stable species throughout
the flame zone. The characteristics of flames near
the lean flammability limit have also been estab-
lished. On the basis of the previous results for rich
fuel-air flames and of the present results, the phys-
icochemical processes in the near-limit flames and
the features of the flammability limits are discussed.
Such measurements can be carried out only when
the stationary flame is maintained beyond the flam-
mability limits, namely when a rich fuel-air mixture
is burned in air (or a lean fuel-air mixture) and
a lean fuel-air mixture is burned in an atmosphere
of fuel (or a rich fuel-air mixture).
Experimental
The experiment was performed using a rectangular
combustion chamber of 3 cm x 12 cm cross section
and an uncooled porous (sintered bronze) cylinder,
6 cm in diameter and 3 cm long. The homogeneous
mixture of methane and air (the test mixture) was
fed to the porous cylinder, from the surface of which
a rich mixture was ejected uniformly into a uniform
stream of air or a lean mixture into a uniform stream
of a very rich methane-air mixture. This surrounding
air or very rich mixture was supplied through a
settling chamber and a converging nozzle to the
vertically mounted combustion chamber.
The location of the flame (the distance y, from
the cylinder to the flame) was measured by direct
photography, and the particle-track technique was
used to determine the stagnation point. The temper-
ature distributions across the flame were measured
with a silica-coated Pt/Pt-13% Rh thermocouple
(wire diam, 0.05 mm). Concentration profiles of
stable species were determined using a microprobe
sampling technique and gas-chromatography. The
flow velocity across the flame zone was calculated
by the continuity equation of an inert species. 9 A
small amount of argon (2.4 volume per cent) was
added to the test mixture, and the concentration
distribution of argon was measured in detail. Then
the flow velocity along the stagnation stream line
was calculated by the species continuity equation
for argon.
Experimental Results
Flame Locations and Distance between Two
Flame Zones
The flame stabilized in the forward stagnation
region of a porous cylinder is really a double flame.
The inner and outer flames correspond, respectively,
to the inner tent flame and the outer diffusion flame
in the experiment by Sorenson et al. (When a lean
fuel-air mixture is ejected from the cylinder surface
into a uniform flow of a very rich fuel-air mixture,
the outer diffusion flame has two luminous flame
zones.) The characteristics of the stabilized flame
are determined if two aerodynamic parameters and
two chemical parameters are given. Two aerody-
namic parameters are the mixture-ejection velocity
v~ and the surrounding-stream velocity V (i.e., the
nondimensional mixture-ejection rate -fw [ =
(vw/ V)(Re / 2) ~/ z] and the stagnation velocity gra-
dient 2V/R, where Re is the Reynolds number and
R the cylinder radius). Two chemical parameters
are the equivalence ratio ~0 of the ejected mixture
and the equivalence ratio 9 of the surrounding flow.
In the present study, we are interested in changes
in the locations of two flame zones as the equivalence
ratio q0is varied.
Figure 1 shows the locations of the center of the
inner luminous flame zone and the center of the
outer luminous flame zone for the flames near the
lean limit of flammability for 2V/R = 25 see -1
-f= = 8 (i.e., V = 37.5 cm/sec, v,~ = 15.6 cm/seci
and 9 = 8. Figure 2 gives corresponding data for
the flames near the rich limit of flammability for
2V/R = 25 sec -x, - f ~ = 8 and 9 = 0. In these
figures, the distance y~ is plotted against the equiva-
lence ratio ~0of the test mixture ('q, is the nondimen-
sional distance defined by ~1, = (Y,/R)(2Re)~/2) .
If the inner flame begins to have the propagation
velocity by the increase in q~of a lean fuel-air mixture
or by the decrease in ~0 of a rich fuel-air mixture,
the inner flame propagates rapidly toward the cylin-
der surface and stabilizes at the point where its
propagation velocity equals the local flow velocity.
At the same time, the outer diffusion flame moves
rapidly from the cylinder and as the result, the
distance between these two flames increases consid-
erably. Accordingly, if the distance between these
two luminous flame zones, Ay,, is plotted against
~0, the flammability limits can be determined by
measuring a discernible break in the distance with
 STUDY O F FLAMMABILITY LIMITS 845

1.0

/OTF...,,us.oN
.... I I I ! .,~-
E -12
uS
>'0.8
-1070
LF
(D O9
Z
4; -8 ~
0.6
._.1
E)
:7
- 6o
U')
0.4 Z
la.I

a
z
o
0,,2 -- z
2

0 I i J I - 0
0.2 0.3 0..4 0.5 0.6 0.7
EQUIVALENCE RATIO,
FIG. 1. Locations of the center of the inner luminous flame zone and the center of the outer luminous
flame zone for flames near the lean flammability limit. 2 V / R = 25 sec -1, -fw = 8 (V = 37.5 cm/sec,
vw = 15.6 cm/sec), and 9 = 8.

change in composition of the test mixture. However,
it is inevitable that a certain degree of arbitrariness
is exercised in defining a limit by this technique.
The uncertainty in the composition at which the
break occurs is approximately + 0.02 in the equiva-
lence ratio ~0.
Figure 3 shows the measured distance Ay, near
the lean flammability limit for 2V/R = 25 sec -1
and - f ~ = 8, dp being the parameter. Figure 4 shows
Ayo near the rich flammability limit for 2 V / R =
25 sec -~ and 9 = 0, -fw being the parameter. From
these figures, the equivalence ratios of the lean and
rich flammability limits for the methane-air mixtures
are found to be 0.47 and 1.72, respectively. Moreover,
these limits are found to be independent of the
composition of the surrounding flow for a wide range
of composition. They are also independent of the
ejection velocity of the test mixture, if this velocity
is comparatively large and the heat loss from the
inner flame to the cylinder 4s neglected. Figure 5
shows the relation between the measured rich limit
of flammability and the stagnation velocity gradient
of the surrounding air stream. The measured limit
is independent of the stagnation velocity gradient,
provided that it is not very large.
The flammability limits of methane-air mixtures
determined in the present study and those obtained
by other techniques are given in Table 1. The
846 FLAME STRUCTURE AND CHEMISTRY

E1.0----•
0
I I [ I I

_ ~ O N FLAME

u2

U or)
- ) 8~

0.4

0.2
2

0 i I i I i - 0
I .4 1.5 1.6 1.7 1.8 1.9 2.0
EQUIVALENCE RATIO,
FIG. 2. Locations of the center of the inner luminous flame zone and the center of the outer luminous
flame zone for flames near the rich flammability limit. 2V/R = 25 sec -l, -f,,, = 8, and 9 = 0.

flammability limits determined in the present study
are somewhat broader than those obtained by the
standard technique using a propagating flame in
a long, vertical tube, 2 and by the fiat-flame burner, 4
but they almost coincide with those obtained using
a large cylindrical explosion vessel in which wall-
quenching effects can be avoided.~~ The flammabil-
ity limits determined by Sorenson et al. 8 are broader
in the lean mixture and narrower in the rich mixture
than those obtained in the present study and in
Ref. 10.
Near the flammability limits, the flame is liable
to be affected by many physical factors, such as
flow instability, buoyancy and heat loss, so that
it is to be expected that the limits determined by
the standard technique using a propagating flame
and by the flat-flame burner become narrower than
those obtained in the present study and those ob-
tained using a large cylindrical vessel. On the other
hand, the lean flammability limit determined by
Sorenson et al. gives the broadest limit that has
ever been obtained. It is probable that, in the case
where the coaxial streams of the test mixture and
the ignition gases are used, the interdiffusion be-
tween the test mixture and ignition gases occurs
in the dead space between the flame base and the
 STUDY O F FLAMMABILITY LIMITS 847

E 0.4 1 I 1 A

z~ @ = 1.60
A A
I
0
o q9 =8.0
O A 0
~0.5
0
0
ZN
W
WW
F-<[
W~
rn w 0 . 2 _
W00
O::D
zO
<:[Z
0.47
!
n ..J
0.1
0.2 0.5 0.4 0.5 0.6
EQUIVALENCE RATIO,
FIC. 3. Distance between two luminous flame zones for flames near the lean flammability limit. 2V/R
= 25 sec -I a n d - f w = 8.

burner rim. Consequently, the actual composition
of the flame propagation region will differ from
the initial composition of the test mixture.
Structure of Lean Methane-Air Flames
The lean flammability limit of the methane-air
mixture is 0.47 in the present study. In order to
establish the characteristics of flames near the lean
flammability limit, one must examine the structure
for flames in the two ranges of equivalence ratio,
i.e., ~ > 0.47 a n d ~ < 0.47. Therefore, we measured
aerodynamic, temperature, a n d stable species con-
centration profiles for two lean methane-air flames
of equivalence ratios 0.42 a n d 0.58. Profiles of

TABLE 1
Measurement of flammability limits of methane-air mixtures

Flammability limits:
Equivalence ratio (% methane)
Author Ref. Method Lean limit Rich limit

Zabetakis 2 Tube, 10.2 cm diam, 0.50 (5.0) 1.69 (15.0)

upward
Egerton and T h a b e t 4 Flat-flame burner 0.51 (&l)
Andrews and Bradley 10 Cylindrical vessel, 0.45 (4.5) 1.75 (15.5)
30.5 cm diam,
upward
Sorenson, Savage,
and Strehlow 6 Coaxial-flow b u r n e r 0.40 (4.0) 1.69 (15.0)
Yamaoka a n d Tsuji -- Counterflow b u r n e r 0.47 (4.7) 1.72 (15.3)
 848 FLAME STRUCTURE AND CHEMISTRY

0.4 I I I I
E
(.3

[] --f-w = 5
<3
# o-fw 8
0
w0.3 • ,2
F- Z
Z N
m
w W
O
~5
t,1
F-- <[
W--J
n q l l 0.2-

w0o
ZO
<CZ
1.72~
0. I I
I .5 I .6 I .7 I .8 I.9 2.0
EQUIVALENCE RATIO, 96
FIG. 4, D i s t a n c e b e t w e e n t w o l u m i n o u s f l a m e z o n e s for f l a m e s near the r i c h f l a m m a b i l i t y l i mi t . 2V/R
= 25 sec -~ a n d d~ = 0.

2.0 I L I I i I i I I I i

-0-

o"
1.8
Pt" Q 9
Ill
(..3

_j 1.6 -
<[

0
Lid

1.4 I I I I I I I i[ I I
I 0 20 40 60 80 I00 200 400
STAGNATION VELOCITY GRADIENT, 2V/R, sec -j
F1c. 5. E f f e c t of the s t a g n a t i o n v e l o c i t y g r a d i e n t of the s u r r o u n d i n g f l o w on the ri c h f l a m m a b i l i t y
l i m i t . - f ~ = 8 a n d c} = 0.
 STUDY OF FLAMMABILITY LIMITS 849

velocity, temperature and concentrations of various
stable species were determined along the stagnation
stream line across the flame zones for 2V/R = 25
sec -~ and - f ~ = 8. The equivalence ratio #0 of the
surrounding stream of rich methane-air mixture was
fixed at 3,0, because the aerated flame of equivalence
ratio 3.0 can be treated essentially as a diffusion
flame, s'9 The temperature and concentration dis-
tributions for q~ --- 0.42 and 0.58 are shown in Figs.
6 and 7, respectively. Only the mole fractions of
major species are presented in these figures.
For both flames, the maximum temperature is
observed in the outer flame zone; the temperature
is lower in the inner luminous flame zone than in
the outer flame. In the flame for ~ = 0.58, the distance
between the two luminous flame zones is compara-
tively large, the temperature increases gradually
from the inner flame toward the outer diffusion
flame and shows the unique plateau-shaped profile
across the double flame (Fig. 7), as observed in
the rich methane-air flame (~p = 1.55) inside the
flammability limit. *'g As q~ decreases and the inner
luminous flame zone approaches the outer luminous
flame zone, the temperature profile becomes less
broad (Fig. 8).
In both flames, the methane concentration de-
creases rapidly from the cylinder surface toward
the inner luminous flame zone; methane disappears
almost completely at the outer edge of this zone.
The oxygen concentration decreases across the inner
flame zone from the cylinder surface toward the
outer diffusion flame and also from the surrounding
stream toward the outer diffusion flame, and oxygen
reaches a minimum but finite concentration in this
flame. The concentration profiles o f hydrogen and
carbon monoxide have two peaks, respectively, one
in the inner flame zone and the other in the outer
flame zone. However, peak concentrations in the
inner flame zone of such lean methane-air flames
are very low compared to rich flames. 8'9 Carbon
dioxide and water vapor exist over the whole region
across the double flame and their profiles are similar
to the temperature profile, their maximum con-
centrations being observed in the outer diffusion
flame.
Figure 8 shows the velocity profiles for the two
flames. The stagnation points determined from the
velocity profile and by the particle-track technique
almost coincide. Moreover, if the surrounding stream
of methane-air mixture is very rich as in the present
study, the stagnation point always lies on the sur-
rounding-stream side of the outer diffusion flame.
In other words, the stabilized inner flame always
has an apparent propagation velocity, even for the
very lean mixture outside the lean flammability limit.
This means that the flammability limit can not be
discussed on the basis of the relative positions of
the stagnation point and the inner flame, and there-

INNER LUMINOUS FLAME ZONE OUTER LUMINOUS FLAME ZONE

8O 25 1 2 09
0 0
1
N2. t 1
~/~I I
~-~3"~
I
CH41 ~
X x
- v " "" "" v v~v""'-~v__ -]Z~ Ii. 6
s
z o" 02 \
0 (.-)
F-60 &l 5 i - 1.2~
0
'~ s
n,"
" (5
w
50 :~ o - / N -I
0 3:

40 & 5 o.4
0
z
0
50~ 0.2 0.3 0.4 0.5 0.6 0.65 0.8 1,0 1.2 I .4
cr
ix.
w
_J
o

DISTANCE, y, cm
Fro. 6, Temperature and concentration profiles. 2V/R = 25 sec -l, - f ~ = 8, and q~ = 0.42.
850 FLAME STRUCTURE AND CHEMISTRY

INNER LUMINOUS FLAME

- - I ZONE OUTER LUMINUOS FLAME ZONE
%80?325 I I F~ J - I I V/'~ ~ I I j2.0
"~ "~ N2__ | C H 4 \ ~ z~]

Z70 T20 ~ t ~ - ~ ~ ~JI.6

,,,~oz,o-
d ~
1%
d P "~r~_
~ ..... I .....
I
1~
r.'.'.'.'~
-4o.8~
I uJ

g
so g ~ 0.2 o.s 0.4 0.5 o.~ 0.8 ,.o ,.2 i~ ~
<

0 . . . .

DISTANCE, y, cm
Vlc. 7. Temperature and concentration profiles. 2V/R = 9,5 sec-l, -fw = 8, an(] ke = 0.58.

~ 50 l J i j I I

oE40 /INNER LUMINOUS FLAME ZONE

~ : 0.42
~-30 : 0.58
o j.._..-q OUTER LUMINOUS
.d
w20

I0

-I0"

-20 I I I 1 .I
0.2 0.4 0.6 0.8 1.0 1.2 1.4
DISTANCE, y, cm
F I c . 8. V e l o c i t y p r o f i l e s . 2V/R = 9,5 see -~ a n d -f,~ = 8.
 STUDY OF FLAMMABILITY LIMITS
fore the discussion on the rich limit of flammability
9 9
in the previous paper was not appropriate,
Structure Analysis
Derivation of Reaction-Rate Distributions
The measured aerodynamic, temperature, and sta-
ble species concentration profiles were analyzed,
and the mass flux j~ and the net reaction rate K,
of each stable species were determined. In the
present lean fuel-air flame, nitrogen has a very high
concentration among all species over the whole
region (Figs. 6 and 7). Therefore, the other species
i may be treated as a trace in a binary mixture with
nitrogen. The cylinder radius is large enough, so
that the radial dependent term in the species conti-
nuity equation can be neglected.~ Accordingly, the
continuity equation of species i is given by
dr, d carbon dioxide. And the mass fluxes of hydrogen
pv - - - + - - (p Y~v, ) = M, K,. (1)
dy dy
In this equation, p is the density of the gas mixture,
v the flow velocity, M, the molecular weight of
species s and K, the net reaction rate of species
/, i.e., the net molar rate of generation and consump-
tion of species i per unit volume per unit time due
to chemical reaction. The mass concentration Y~and
the diffusion velocity v, of species i are given by
(2)
and
1), dX, (3)
X, dy
respectively, where X~is the mole fraction of species
i and Dl the binary diffusion coefficient of species
i with nitrogen. The mass flux of species i is given
by
i,=pr,(v+v,). (4)
The density of the gas mixture was calculated from
the measured temperature and stable species con-
centrations by the equation of state
(5)
where p is the pressure,,~the universal gas constant,
and T the gas temperature. The binary diffusion
851
coefficient Dt for each species with nitrogen was
found as a function of temperature in the literature.tt
Mass-Flux and Reaction-Rate Profiles
Figures 9 and 10 show the net reaction-rate profiles
of the six species across the two flame zones for
q~ = 0.42 and 0.58, respectively. The mass fluxes
of hydrogen and carbon monoxide are also shown
in these figures.
In the flame of tp = 0.58, in which the dark space
between the two luminous flame zones is wide, the
two reaction zones are completely separated. The
net reaction-rate profiles of various stable species
in the inner flame zone are found to be qualitatively
similar to those obtained in the premixed methane-
oxygen flames at reduced pressure. ~z'~3Namely, in
the inner flame zone, a negative peak of the net
reaction-rate profile is observed for methane, oxygen,
hydrogen and carbon monoxide, and a positive peak
for hydrogen, carbon monoxide, water vapor and
and carbon monoxide due to convection and diffu-
sion show that, within the inner flame zone, these
two species flow toward the outer diffusion flame
(Fig. 10) and reactions that produce water vapor
and carbon dioxide are completed. Thus, the inner
flame has the characteristics of the self-sustaining
flame. It is demonstrated that the inner flame is
a true premixed flame which can propagate in the
lean fuel-air mixture and acts as oxygen supply to
the outer diffusion flame, and the outer diffusion
flame is the counterflow diffusion flame between
the rich fuel-air mixture and the hot mixture of excess
oxygen and combustion products.
In the flame of q~= 0.42, in which the dark space
between the two luminous flame zones is narrow,
the net reaction-rate profiles in the inner flame zone
and those in the outer flame zone somewhat overlap
in the dark space, and the two reaction zones are
not completely separated, although the profiles are
qualitatively similar to those of the flame of ~ =
0.58. Namely, the second half of the inner reaction
zone is undoubtedly supplied with hydrogen and
carbon monoxide from the outer reaction zone. This
indicates that the reaction in the inner flame zone
can not be completed without these supplies of
hydrogen and carbon monoxide. Therefore, in this
case, the inner flame does not have the characteristics
of the self-sustaining flame, although the inner flame
which lies between the stagnation point and the
cylinder wall seems to have an apparent propagation
velocity. The premixed flame in such a case will
never exist independently of the outer diffusion
flame. Namely, the premixed flame will be estab-
lished only when the flame is followed by the
diffusion flame.
Similarly, in the rich methane-air flame of q~ =
1.80, the net reaction-rate profiles in the inner flame
852 F L A M E S T R U C T U R E AND CHEMISTRY

T•, INNER LUMINOUS FLAME ZONE OUTER LUMINOUS FLAME ZONE

, 6 ~ 1 I
E (.)
0

m
0
4- H20\p ~ \k/MASS FLUX (CO) _ 21~
E /H20 o

2- CO /,C02 - I ~
0 X // ~
•
w
0
' ~ " ~ - - %\\\\
rr_ 2 - -Ix
Z
0
C /\ \\ _J
u_
I--
o-4- \ --2o~
02 MASS ~LUX ( Hz)x I0 03
ILl <
rr"
I I I l _3 ~
F
bJ
-
60.4 0.5 0.6 0.7 0.8
Z DISTANCE, y, cm
FIG. 9. Mass-flux and net reaction-rate profiles. 2V/R = 25 see-', - f ~ = 8, and q~ = 0.42.

zone and those in the outer flame zone somewhat Discussion

overlap in the dark space, and the two reaction zones
are not completely separated (Fig. 8 in Ref. 9), so
that the rich methane-air flame of ~p = 1.80 is not
the self-sustaining flame. Therefore, the conclusion
of the previous paper s that there is another limit
of flame propagation in addition to the rich limit
of flammability usually defined, is incorrect.
Many papers have been published on the mea-
surement of limits for certain flammable mixtures,
and recently on the near-limit p h e n o m e n a and
mechanism of nonstationary flame extinction, a'~~
but experimental studies rarely have been devoted
to the structure of flames near the limits of flam-

To INNER LUMINOUS FLAME ZONE OUTER LUMINOUS FLAME ZONE

"~ r~/~ i I l 'F///. -
(J 7 \
V//14 i
', V SSFLO CO' -

co,i \ \ \
\ \ Ha0\ I ~

tO ~

.,, .... CO •

g ,, -.. 02 -I x
u_
\
02 / V MASS FL.UX(H2) x I 0/~ <
12: I / I
w
-
~_ 60. 3 0.4 0.5 0.6 0.7
-3~
z DISTANCE, y, cm
-1
FIG. 10. Mass-flux and net reaction-rate profiles. 2V/R = 25 see , -f,~ = 8, and ~o = 0.58.
 STUDY OF FLAMMABILITY LIMITS
inability. In the present study, the flammability
limits of methane-air mixture and structure of flames
near the lean flammability limit have been measured
by the counterflow-flame technique. The structure
of these flames has been analyzed, and the charac-
teristics of the flames near the lean limit have been
demonstrated.
From the previous results of structure analysis
of rich fuel-air flames9 and the present results for
lean fuel-air flames, it becomes clear that the pre-
mixed flame which exists beyond the flammability
limits is clearly correlated with the outer diffusion
flame and is always supplied with reactants from
the outer diffusion flame. If the equivalence ratio
of the test mixture is increased or decreased and
the premixed flame becomes self-sustaining, it be-
gins to have a propagation velocity and, at the same
time, the supply of reactants from the outer diffusion
flame becomes unnecessary. Accordingly, the inner
premixed flame begins to move away from the outer
diffusion flame, andas a result, the distance between
the two flame zones begins to increase considerably.
Therefore, it is reasonable to determine the flam-
mability limit by measuring a discernible break in
the distance between the two flame zones with
change in composition of the test mixture. Moreover,
the flammability limit defined as the limit of flame
propagation can also be considered as the limit at
which the supply of reactants from the burned side
becomes necessary for the premixed flame to be
established.
A certain degree of arbitrariness is exercised in
defining a limit using the present technique, as it
is in all others. Although such a limitation is involved
in this technique, the limits thus determined are
found to be independent of external conditions, such
as the ejection velocity of the test mixture, and the
composition and velocity of the surrounding flow.
One important factor that would affect the limits
is known to be an acceleration due to gravity. In
order to examine the effect of this factor on the
limits determined using the stationary counterflow
flame, the combustion tunnel-burner assembly was
inverted such that the surrounding mixture was
flowing vertically downwards over the porous cyl-
inder, and the distance between the two flame zones
in the forward stagnation region was also measured.
Stable flames were established when the velocity
of the surrounding stream was larger than that of
the flow induced by buoyancy of the combustion
gas. The flammability limits determined by the
present method were confirmed to be independent
of the direction of flame propagation relative to the
earth's gravitational field. This fact makes a sharp
contrast with the current view on the flammability
limits, in which the convection due to gravity is
considered to have a predominant effect. As pointed
out by Levy, ~ a flame in upward propagation
through a near-limit mixture in a tube gains stability
853
by close association with a bubble of its own exhaust
gases rising at the same speed. The cause of different
flammability limits for upward and downward
propagation for the same fuel is at once apparent.
All the factors which assist upward flame propaga-
tion have an adverse influence on downward propa-
gation. The "surf-riding" phenomenon of the flame
on the hot bubble surface ~5 which is inevitably
involved in the tube method is effectively eliminated
in the present method by using the stationary flame;
the hot exhaust gases are conveyed away from the
flame zone by forced convection.
It was confirmed that flammability limits deter-
mined by the present method are independent of
external conditions, such as the ejection velocity
of the test mixture, the composition and velocity
of the surrounding flow, and the flame propagation
direction relative to the earth's gravitational fields,
and these limits are not affected by physical factors,
such as flow instability and heat loss to the wall.
These results suggest that the limits thus determined
depend only on the internal properties of the mixture.
Therefore, these limits can be regarded as "physico-
chemical constants" of the combustible gas at a
stated temperature and pressure.
At the flammability limits determined in the pres-
ent study, the inner flame always lies between the
stagnation point and~ the cylinder surface, so that
the propagation velocity at the flammability limits
is found to have a finite value.
Coneluslons
1. Measurements of flammability limits of com-
bustible gas and experimental studies of the structure
of premixed flames near the flammability limits can
be made, using a counterflow flame (a double flame)
stabilized in the forward stagnation region of a
porous cylinder.
2. The lean and rich flammability limits of com-
bustible gas can be determined by measuring a
discernible break in the distance between the two
flame zones with a change in composition of the
test mixture. The equivalence ratios of the lean and
rich limits of flammability for the methane-air mix-
ture thus determined are 0.47 and 1.72, respectively.
3. For a double flame inside the flammability
limits, two reaction zones are completely separated,
and the reactions to produce water vapor and carbon
dioxide are completed in the inner flame which has
the characteristics of a self-sustaining flame.
4. In a double flame outside the flammability
limits, two reaction zones are not completely
separated, and the reactions in the inner flame zone
can not be completed; the inner flame is not self-
sustaining.
5. The flammability limit defined as the limit of
flame propagation can be considered as the limit
854 F L A M E S T R U C T U R E AND CHEMISTRY
at w h i c h the supply of reactants from the b u r n e d
side becomes necessary for the premixed flame to
be established.
6. The flammability limits determined in the
present study d e p e n d only on the physicochemical
properties of the mixture.
7. The propagation velocity at the flammability
limit has a finite value.
REFERENCES
1. COWARD, H. F. AND JONES, G. W.: Limits of
Flammability of Gases and Vapors, U.S. Bureau
of Mines Bulletin 503, 1952.
2. ZARETAKIS,M. G.: Flammability Characteristics
of Combustible Gases and Vapors, U.S. Bureau
of Mines Bulletin 627, 1965.
3. LOVACHEV, L. A., BABKIN, V. S., BUNEV, V. A.,
V'YUN, A. V., KRIVULIN, V. N., AND BARATOV, A.
N.: Combus. Flame 20, 259(1973).
4. EGERTON, A. C. AND THARET, S. K,: Proc. Roy.
Soc. (London) A211, 445(1952).
5. DIXON-LEwlS, G. AND ISLES, G. L.: Seventh
Symposium (International) on Combustion, p.
475, Butterworths, 1959.
COMMENTS
N. Peters, Teehnisehe Hochschule, Aachen, West
Germany. Besides the advantage, that buoyancy
effects can be eliminated by using the counter-flow
geometry, the fact that the structure of these flames
may be easily analysed theoretically makes them
most suitable for the determination of flammibility
limits. Thus correction factors that account for the
non-uniformity of the flow-field as well as for the
heat gain from the outer flame may be derived in
analytical terms. Using large activation energy
asymptotics, 1the mass flow rate pv through the flame
in a stagnation point boundary layer is found to
be related to that in a homogeneous mixture (pV)F
as
pv = (pv) F F G
where the correction term
dF/d~l IiexpPd~l
F~
exp F
6. SORENSON, S. C., SAVAGE, L. D., AND STREHLOW,
B. A.: Combus. Flame 24, 374(1975).
7. HERTZaERG, M.: Combus. Flame 28, 213(1977).
8. YAMAOKA,I. AND TsuB, H.: Fifteenth Symposium
(International) on Combustion, p. 637, The
Combustion Institute, 1975.
9. YAMAOKA,I. ANDZsull, H.: Sixteenth Symposium
(International) on Combustion, p. 1145, The
Combustion Institute, 1977.
10. ANDREWS, G. E. AND BRADLEY, D.: Fourteenth
Symposium (International) on Combustion, p.
1119, The Combustion Institute, 1973.
11. HmSCHFELDEn, J. O., CuaTISS, C. F., AND BIRD,
R. B.: Molecular Theory of Gases and Liquids,
p. 539, John Wiley & Sons, 1954.
12. WESTENRERG,A. A. ANn FRISTROM, R. M.: J. Phys.
Chem. 65, 591(1961).
13. FRmTnOM,R. M. ANDWESTENBERG, A. A.: Eighth
Symposium (International) on Combustion, p.
438, Williams and Wilkins, 1962.
14. FreSNO, A. L., COOK, E. B., KUCHTA, J. M., ANt)
BURGESS,D. S.: Thirteenth Symposium (Interna-
tional) on Combustion, p. 593, The Combustion
Institute, 1971.
15. LEVY, A.: Proc. Roy. Soc. (London) A283,
134(1965).
if=-- Ii fvr (plx)~plx d~
pv
f=
~)~2VIR '~ = (P~)s R p dy
accounts for the decrease of the mass flow rate due
to non-uniform flow, while
(dT/d;I)b
G = (0.2867 a 2 -- 0,656 a + 1) -1/2, a
(dT/dy)~
accounts for the e n h a n c e m e n t of the flow rate due
to heat gain. In the limit of large (pv)~ the stream
function f may be assumed constant up to the
position of the inner flame. In this limit F approaches
unity. Likewise, as the temperature gradient to the
b u r n t side (index b) becomes much smaller than
that to the u n b u r n t (index u) side, the correction
factor G approaches unity as well. The mass flow
rate through the flame is related to that at the wall
(pv)~ by the solution of the Falkner-Skan equation.
 STUDY O F F L A M M A B I L I T Y L I M I T S
REFERENCE
[ll N. PETEaS. Das F l a m m e n z o n e n m o d e l l u n d seine
A n w e n d u n g e n , Chemie-Ingenieur- Teehnik 50
(1978), 234-235.
Authors" Reply. It is interesting to k n o w that the
correction factors which account for the non-unifor-
mity of the flow field, as well as the heat gain from
the outer flame, approach unity in the case of our
855
experiment. Although the structure of our flames
m a y be easily analyzed theoretically, the flammabil-
ity limits t h u s determined are considered to d e p e n d
largely on the a s s u m p t i o n s a n d model u s e d in the
analysis. We are very m u c h interested in the theoret-
ical analysis, a n d we expect that the theoretical
structure of the flames, as well as the flammability
limits, will be reported in the open literature in
the near future.