Combustion and Flame 145 (2006) 808–819

www.elsevier.com/locate/combustflame

On the off-stoichiometric peaking of adiabatic

flame temperature
C.K. Law a,∗ , A. Makino b , T.F. Lu a
a Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, NJ 08544-5263, USA
b Institute of Space Technology and Aeronautics, Japan Aerospace Exploration Agency, Chofu, Tokyo 182-8522, Japan

Received 18 November 2004; received in revised form 10 January 2006; accepted 15 January 2006
Available online 3 March 2006

Abstract
The characteristic rich shifting of the maximum adiabatic flame temperature from the stoichiometric value for
mixtures of hydrocarbon and air is demonstrated to be caused by product dissociation and hence reduced amount
of heat release. Since the extent of dissociation is greater on the lean side as a result of the stoichiometry of
dissociated products, the peaking occurs on the rich side. The specific heat per unit mass of the mixture is shown
to increase monotonically with increasing fuel concentration, and as such tends to shift the peak toward the lean
side. It is further shown that this is the cause for the lean shifting of the adiabatic flame temperature of oxidizer-
enriched mixtures of Nm Hn and F2 and of NH3 and O2 , with various amounts of inert dilution, even though their
maximum heat release still peaks on the rich side.
© 2006 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

Keywords: Adiabatic flame temperature; Hydrazine; Dissociation equilibrium

1. Introduction higher concentrations of triatomic molecules such as

This work revisits the well-known phenomenon
that the maximum value of the adiabatic flame tem-
perature (Tad ) of mixtures of hydrocarbon and air oc-
curs slightly on the rich side of the fuel equivalence
ratio, φ, as shown in Fig. 1 for several hydrocar-
bons as well as H2 and CO. This off-stoichiometric,
rich-peaking behavior has been discussed in the liter-
ature, although a consensus on its cause has yet to be
reached. For example, Ref. [1] suggests that since the
products of rich mixtures have higher concentrations
of diatomic molecules such as H2 and CO as com-
pared to the products of lean combustion, which have
* Corresponding author.
E-mail address: cklaw@princeton.edu (C.K. Law).
0010-2180/$ – see front matter © 2006 The Combustion Institute. Published by Elsevier Inc. All rights reserved.
doi:10.1016/j.combustflame.2006.01.009
H2 O and CO2 , and since the specific heats of di-
atomic molecules are smaller than those of triatomic
molecules, the adiabatic flame temperatures of rich
mixtures should have higher values. In Ref. [2], the
rich shifting is explained by the variation of the ratio
of the heat release to the heat capacity of the products,
both per mole of fuel. This explanation implicitly in-
cludes the effect of dissociation, which turns out to
be a dominant factor in the observed rich peaking,
although its specific role was not explicitly identi-
fied. In Ref. [3] it is reasoned that the shifting is due
to product dissociation, which is minimized in mix-
tures that already contain these dissociated species.
For example, since CO already exists in the products
of rich mixtures even without considering dissocia-
tion, further dissociation of CO2 into CO is rendered
 C.K. Law et al. / Combustion and Flame 145 (2006) 808–819
Fig. 1. Adiabatic flame temperature plotted as a function of the fuel equivalence ratio φ for several fuel/air mixtures at STP,
demonstrating the gentler slopes on the rich side due to the asymmetrical nature of the definition of φ.
more difficult. The reduced amount of dissociation
then leads to peaking of the Tad on the rich side. The
difficulty with this argument is that it can also be ap-
plied to the dissociated product O2 from CO2 in lean
combustion, leading to the implication that peaking
would then occur on the lean side.
We further note that Ref. [4] states that ethylene
peaks on the rich side because it is an endothermic
fuel, while ammonia (in oxygen) peaks on the lean
side because it is an exothermic fuel. This explanation
can be readily ruled out on account of the many hy-
drocarbons that are exothermic but whose Tad peaks
on the rich side. Finally, Ref. [5] suggests the impor-
tance of the amount of inert in the mixture, with more
inert favoring rich shifting.
The above summary clearly demonstrates that the
factors affecting the off-stoichiometric peaking of Tad
have not been adequately identified. Considering the
importance of Tad in combustion phenomena in gen-
eral, as prominently exemplified by the correspond-
ing rich-shifting of the laminar burning velocities of
hydrocarbon/air mixtures, and the fact that the shift-
ing occurs around stoichiometry, which is the fuel
concentration most frequently employed in practice
and is also of particular relevance to the formation of
NOx , the need for a satisfactory understanding of the
rich shifting of Tad can hardly be overemphasized.
To identify the cause of this rich shifting, in
the following we shall first present results for the
methane/air system and show that the shifting oc-
curs only in the presence of dissociation. However,
contrary to previous suggestions, we shall show that
the specific heat actually increases with φ. Conse-
809
quently, it is the reduced amount of heat release due
to dissociation that causes the shifting. Furthermore,
it will be shown that the rich shifting is due to the
smaller extent of dissociation on the rich side than
on the lean side. We then analyze the “flip” situation
of the phenomenon, namely the lean-side peaking of
Tad for Nm Hn /F2 mixtures mentioned in Ref. [3] and
the NH3 /O2 mixtures mentioned in Ref. [4], and sub-
sequently demonstrate the role of inert dilution, or
equivalently oxidizer enrichment, on the peaking be-
havior. It is believed that the present study provides a
consistent and unifying explanation of the causes for
the off-stoichiometric peaking of Tad .
The adiabatic flame temperatures were calculated
using STANJAN [6]. Furthermore, in order to un-
ambiguously study this off-stoichiometric peaking
phenomenon, we first suppress another qualitatively
asymmetrical aspect of the Tad -vs-φ curves, namely
the gentler slopes of the curves on the rich side as
compared to those on the lean side, as shown in Fig. 1.
Recognizing that a good part of this asymmetry is
caused by the asymmetrical nature of the definition
of φ in that φ spans between 0 and 1 for lean mix-
tures but is spread out from 1 to ∞ for rich mixtures,
we shall eliminate this definition-dependent asymme-
try by using the normalized and symmetrized equiva-
lence ratio
φ
Φ= , (1)
1+φ
such that fuel-lean and -rich mixtures respectively
lie in the ranges 0 < Φ < 0.5 and 0.5 < Φ < 1,
with Φ = 0.5 being the stoichiometric concentration.
When the above definition is used, it is seen in Fig. 2
810 C.K. Law et al. / Combustion and Flame 145 (2006) 808–819
Fig. 2. Adiabatic flame temperature plotted as a function of the normalized and symmetrized fuel equivalence ratio Φ for several
fuel/air mixtures at STP, demonstrating the near symmetry of Tad on the lean and rich sides of stoichiometry, especially with
respect to the maximum Tad .
that the Tad -vs-Φ curves are made more symmetrical
than the Tad -vs-φ curves, especially when referenced
to the state of the maximum temperature. Thus even
though all the following discussions and explanations
can be conducted in terms of either φ or Φ, the use of
Φ provides a more balanced assessment of the depen-
dence of the various equilibrium flame parameters on
the fuel concentration.
2. The role of product dissociation
To demonstrate that dissociation is the cause of
shifting of the maximum Tad from stoichiometry,
Fig. 3 shows for methane/air mixtures the calculated
Tad as a function of φ obtained through STANJAN,
which assumes dissociation equilibrium. In addition,
we have separately calculated the reacted state in the
frozen limit, in which dissociation of the products
H2 O and CO2 is suppressed, as defined by the chem-
ical reaction
φCH4 + 2(O2 + 3.76N2 )
→ aCO2 + bCO + cH2 O + dH2
+ eO2 + 7.52N2 ,
where a = φ, b = 0, c = 2φ, d = 0, and e = 2(1 −
φ)φ for φ < 1, while a = 4 − 3φ + d, b = 4φ − 4 −
d, c = 2φ − d, and e = 0 for φ > 1. The remaining
relation required to determine d, and thereby a, b, and
c, for rich mixtures is obtained by assuming chemical
equilibrium for the water–gas shift reaction: CO2 +
H2  CO + H2 O with the equilibrium constant Kp =
(pCO pH2 O )/(pCO2 pH2 ) = bc/ad.
Fig. 3 shows that Tad as well as the heat release
per unit mass of the mixture, qp , peaks at φ = 1 when
product dissociation is suppressed. They are, how-
ever, rich-shifted in the presence of product dissocia-
tion. This suggests that the off-stoichiometric shifting
of Tad is caused by product dissociation. To further
substantiate this possibility, and recognizing that the
extent of dissociation should diminish with increasing
pressure, the state of the frozen limit is alternatively
attained by letting the system pressure p assume large
values. Fig. 4 shows that, with increasing pressure, the
location of the peak in the Tad (Φ) curve is gradually
displaced toward Φ = 0.5. Furthermore, the extent of
heat release, qp , also correspondingly increases. We
have therefore identified that product dissociation is
likely the cause of shifting.
The fact that peaking of Tad and qp occurs at Φ =
0.5 in the frozen limit is reasonable in that for the off-
stoichiometric situations the excess reactants, oxygen
for lean mixtures and CO and H2 for rich mixtures,
simply act as diluents that need to be heated up and
as such are effectively heat sinks. This is the well-
(2) accepted reason that Tad peaks around Φ = 0.5.
3. The role of specific heat
To examine the viability of the existing explana-
tion [1] that rich shifting is caused by the decreasing
 C.K. Law et al. / Combustion and Flame 145 (2006) 808–819 811

Fig. 3. Dependence of adiabatic flame temperature, specific heat release qp , and specific heat cp,2 of the burned gas on Φ for
methane/air mixtures at STP (dashed lines: frozen limit; solid lines: dissociation equilibrium).

Fig. 4. Dependence of adiabatic flame temperature and specific heat release on Φ for methane/air mixtures at various pressures,
demonstrating that off-stoichiometric peaking is due to product dissociation.

specific heat with increasing Φ, we plot in Fig. 3 the
variation of cp,2 , the specific heat per unit mass of
the products, with Φ. It may be noted that the varia-
tion in cp,2 is assessed on the basis of per unit mass
of the mixture because mass, instead of moles, is the
conserved quantity for the present closed system. It
is then clearly seen that cp,2 actually increases rather
than decreases with Φ. Thus if cp,2 were the cause
of shifting, it would have led to lean, instead of rich,
shifting. Furthermore, since this trend holds for prod-
ucts in either dissociation equilibrium or the frozen
limit, it is therefore simply a consequence of stoi-
chiometry. The influence of product dissociation has
only a secondary effect on cp,2 , reducing it from the
frozen values and with the extent increasing with in-
creasing Φ.
To identify the specific factor through which stoi-
chiometry causes the increasing trend of cp,2 , we plot
in Fig. 5 the number of moles of diatomic (except
N2 ) and triatomic molecules per unit mass of the mix-
ture. Perhaps the most significant results here are the
small differences between the results with dissocia-
812 C.K. Law et al. / Combustion and Flame 145 (2006) 808–819
Fig. 5. Number of moles per gram of the diatomic (except N2 ) and triatomic molecules as functions of Φ for methane/air
mixtures at STP (dashed lines: frozen limit; solid lines: dissociation equilibrium).
tion equilibrium and frozen states and the relatively
large increase in the number of moles of the diatomic
molecules, which leads to a correspondingly large in-
crease in the total number of moles of both the di-
atomic (excluding N2 ) and triatomic molecules with
increasing Φ for rich mixtures. The first observation
further substantiates the earlier suggestion that disso-
ciation has only a secondary role in the value of cp,2 ,
while the second observation basically identifies the
cause of the increasing cp,2 in rich mixtures. That is,
although the specific heats of the diatomic molecules
are smaller than those of the triatomic molecules, the
number of moles of the diatomic molecules increases
with increasing Φ for rich mixtures. This then leads to
an increase in the total heat capacity for the mixture,
and hence an increase in cp,2 .
To further scrutinize the above suggestion, we
have estimated cp,2 as a function of Φ for the frozen
stoichiometry, using Cp,2 /R 0 = 8 and 3.5 for the tri-
atomic and diatomic molecules, respectively, where
Cp,2 is the specific heat per mole of the gas, and R 0
the universal gas constant. After substituting in the
numerical values, it can be shown that cp,2 is given
by the expressions R 0 (33.32 + 17φ)/(274.56 + 16φ)
(J/g K) for φ < 1 and R 0 (44.32 + 6φ)/(274.56 +
16φ) (J/g K) for φ > 1. Both expressions show an
increasing trend with φ, and hence provide further
support for the result of increasing cp,2 with φ.
Finally, recognizing the dominant influence of
stoichiometry on cp,2 , its slight reduction from the
frozen value is then caused by the smaller cp,2 for the
diatomic molecules produced through dissociation of
the triatomic molecules from the frozen limit, which
is the explanation of Ref. [1], except it is only of sec-
ondary importance.
4. The relative roles of heat release and specific
heat
Since Tad is given by T1 + qp /cp,2 , where T1 is the
temperature of the unburned mixture, and since cp,2
exhibits the opposite trend needed for the rich shift-
ing of Tad , we are finally led to the suggestion that it
is the reduction of qp due to dissociation that is re-
sponsible for the rich shifting. Indeed, Fig. 3 shows
that Tad and qp basically have the same shape, peak-
ing slightly on the rich side. However, while qp peaks
at Φ = 0.5122, the peak of Tad is lean-shifted rela-
tive to qp to Φ = 0.5098. Recognizing the increasing
trend of cp,2 , it is then reasonable to expect that this
lean shifting, relative to qp , is caused by cp,2 . This
point can be quantified by noting that since Tad ∼
qp /cp,2 , we have δTad /Tad ≈ δqp /qp − δcp,2 /cp,2 ,
where the δ quantities are small departures from val-
ues at some reference state. Thus in Fig. 6 we have
plotted the individual difference terms in this relation
for small departures from those at the stoichiometric
state, Φ = 0.5. The results show that, for such small
departures, the influences are linearized and the dif-
ference (δqp /qp − δcp,2 /cp,2 ) is indeed almost equal
to δTad /Tad . The results are therefore internally con-
sistent.
5. Rich versus lean shifting
While we have demonstrated that it is the reduced
heat release due to dissociation that causes the shift-
ing of the maximum Tad from stoichiometry, there is
still the question of why the shifting is to the rich
instead of the lean side. That is, since product dis-
sociation occurs on the rich as well as the lean sides,
 C.K. Law et al. / Combustion and Flame 145 (2006) 808–819
Fig. 6. Scaled difference terms for Tad , qp , cp,2 , and (qp /cp,2 ), referenced to the stoichiometric state, as functions of Φ for
methane/air mixtures at STP.
the arguments presented above are applicable to either
side.
Since heat release in the presence of dissociation
is the cause of shifting, the above question can be
sharpened to an assessment of the relative extents of
dissociation on the lean and rich sides. The fact that
the observed shifting is to the rich side then implies
that, for a given temperature, there is more dissocia-
tion on the lean side than on the rich side. This should
cause a skewing of the Tad curve from the frozen state
which does not have any shifting.
To prove that there is more dissociation on the lean
side, for algebraic simplicity we first consider H2 ox-
idation. Thus assuming an ε amount of dissociation,
the chemical reaction is given by
φH2 + 1/2(O2 + 3.76N2 )
→ a(1 − ε)H2 O + (b + aε)H2
+ (c + aε/2)O2 + 1.88N2 ,
where a = φ, b = 0, and c = (1 − φ)/2 for lean mix-
tures, and a = 1, b = φ − 1, and c = 0 for rich mix-
tures. Using the definition of the equilibrium constant
Kp , we have
pH2 (pO2 )1/2
Kp =
pH 2 O

(b + aε) c + aε/2
= pt ,
a(1 − ε) a + b + c + aε/2 + 1.88
where pt is the total pressure. The above result shows
√ 
that, for ε  1, Kp ∼ ε pt for lean mixtures and
√
Kp ∼ εpt for rich mixtures. Consequently, for the
√ → a(1 − ε1 )CO2 + (b + aε1 )CO
same Tad and hence Kp (Tad ), we have εlean ∼ εrich .
813
Since ε < 1, we have εlean > εrich . That is, there is
more dissociation on the lean than the rich side, and
as such we expect rich shifting for H2 /air mixtures.
This is indeed the case, as shown in Fig. 7 for the
H2 /air plots. The results are qualitatively similar to
those for methane/air. Because of the substantial vari-
ation of cp,2 here, there is considerable difference in
the values of Φ at which Tad and qp attain their re-
spective maximum values.
The above derivation sheds light on the reason that
there is a greater amount of dissociation on the lean
side than on the rich side. That is, since the dissocia-
tion of one mole of H2 O results in one mole of H2 but
only half a mole of O2 , and since stoichiometrically
the lean mixture consists of unreacted O2 while the
rich mixture consists of unreacted H2 , the lean mix-
ture can accommodate more O2 than the rich mixture
can accommodate H2 .
Derivation of the relative amount of dissociation
(3)
for CO/air mixtures is identical to that of the H2 /air
mixtures because they have the same stoichiometry,
yielding the same result as Eq. (4) for the extent of
dissociation, and consequently the same trend of rich
shifting.
A similar derivation for a general hydrocarbon/air
mixture can be carried out. Since the basic unreacted
components of a hydrocarbon/air mixture are still just
H2 and CO, the trend derived for these components
(4) should carry over. Specifically, with the dissociation-
affected reaction given by

φCm Hn + m + n4 (O2 + 3.76N2 )
814 C.K. Law et al. / Combustion and Flame 145 (2006) 808–819

Fig. 7. Dependence of Tad , qp , cp,2 on Φ for hydrogen/air mixtures at STP (dashed lines: frozen limit; solid lines: dissociation
equilibrium).

+ c(1 − ε2 )H2 O + (d + cε2 )H2 6. Lean-shifting in Nm Hn /F2 mixtures

   
+ e + 12 aε1 + 12 cε2 O2 + 3.76 m + n4 N2 ,
There is considerable interest in burning the fam-
(5)
ily of fuels with the constituents Nm Hn , such as hy-
where a = mφ, b = 0, c = nφ/2, d = 0, and e = (m + drazine (N2 H4 ), in F2 environments for rocket appli-
n/4)(1 − φ) for lean mixtures, while a = m − (m + cations. Contrary to hydrocarbon/air combustion, it
n/2)(φ − 1) + d, b = (2m + n/2)(φ − 1) − d, c = was reported [3] that the maximum Tad is on the lean
nφ/2 − d, d = d, and e = 0 for rich mixtures, the side of stoichiometry. The observed lean shifting was
equilibrium constants are explained [3] by the abundance of NH in lean mix-
tures, causing reduced dissociation and hence higher
pCO (pO2 )1/2 (b + aε1 ) temperature. It is therefore of further interest to study
Kp,1 = =
pCO2 a(1 − ε1 ) this system because it provides a “flip” case to those

e+(aε1 +cε2 )/2
just analyzed. Clearly, the arguments presented earlier
× a+b+c+d+e+3.76(m+n/4)+(aε1 +cε2 )/2 pt , for the rich-shifting of hydrocarbon/air mixtures must
equally hold for the lean-shifting of the Nm Hn /F2
pH2 (pO2 )1/2 (d + cε2 ) mixtures.
Kp,2 = =
pH 2 O c(1 − ε2 ) Consider the reaction

e+(aε1 +cε2 )/2
× a+b+c+d+e+3.76(m+n/4)+(aε1 +cε2 )/2 pt . φNm Hn + n2 F2 → aHF + bF + cF2 + dH
(6)
√ + eH2 + f N2 . (7)
For ε1 and ε2  1, we then get Kp,1 ∼ ε1 pt
√
and Kp,2 ∼ ε2 pt for lean mixtures, and Kp,1 ∼ For the frozen case in which HF dissociation is sup-
√
[ε1 + (c/a)ε2 ]pt ∼ Kp,2 for rich mixtures. Note pressed, we have a = nφ, b = n(1 − φ) − 2c, d = 0,
here that we also have Kp,1 /Kp,2 = bc/ad from e = 0, and f = mφ/2 for lean mixtures, while a = n,
chemical equilibrium for the water–gas shift reaction. b = 0, c = 0, d = n(φ − 1) − 2e, and f = mφ/2 for
Consequently, for the same Tad , we have (ε1 )lean and rich mixtures. The remaining relations required to de-
(ε2 )lean > [ε1 + (c/a)ε2 ]rich , suggesting more disso- termine c for lean mixtures and e for rich mixtures
ciation on the lean side than on the rich side. We have are obtained by assuming chemical equilibriums for
therefore provided convincing evidence that the rich the F2 and H2 dissociation reactions, respectively, as
shifting of Tad for hydrocarbon/air mixtures is due to 1 F  F and 1 H  H.
2 2 2 2
the large extent of product dissociation for lean mix- In the dissociation equilibrium case, with ε taken
tures. as the extent of HF dissociation, Eq. (7) becomes
 C.K. Law et al. / Combustion and Flame 145 (2006) 808–819 815

Fig. 8. Dependence of Tad , qp , cp,2 on Φ for N2 H4 /F2 mixtures at STP (dashed lines: frozen limit; solid lines: dissociation
equilibrium).

φNm Hn + n2 F2 → a(1 − ε)HF + (b + aε)F high temperatures. Thus, we have

+ cF2 + (d + aε)H + eH2 + f N2 . (8) 2 εp n(1 − φ)
Kp,F t
Kp ≈ 2 [n + (m/2)φ] + 2n(1 − φ)p
(14)
Using the equilibrium constant Kp (T ), we have Kp,F t

p F pH b + aε for lean mixtures and

Kp (T ) = = 2 εp n(φ − 1)
pHF a(1 − ε) Kp,H t
d + aε Kp ≈ 2 [nφ + (m/2)φ] + 2n(φ − 1)p
(15)
× pt , (9) Kp,H t
a + b + c + d + e + f + aε
for rich mixtures.
which yields Since Kp,F is usually two orders of magnitude
n(1 − φ) − 2c larger than Kp,H , we see that Kp ∼ ε for lean
Kp (T ) ≈ εpt (10) mixtures and Kp ∼ ε(Kp,H )2 for rich mixtures.
n + (m/2)φ − c
Consequently, for the same Tad , we have εlean ∼
for lean mixtures and εrich (Kp,H )2 . In addition, since Kp,H > 1 when the
n(φ − 1) − 2e temperature is higher than about 3800 K, we have
Kp (T ) ≈ εpt (11) εlean > εrich . Thus there is still more dissociation on
nφ + (m/2)φ − e
the lean side than on the rich side, in the same man-
for rich mixtures, where ε  1. In addition, by assum- ner as that for hydrocarbon/air mixtures, but this is
ing chemical equilibriums for the F2 and H2 dissoci- contrary to the suggestion of Ref. [3].
ation reactions, we have To identify the cause for the lean shifting of Tad ,
Fig. 8 plots Tad , qp , and cp,2 in the same manner
n2 (1 − φ)2 pt
c≈ 2 [n + (m/2)φ] + 4n(1 − φ)p
(12) as those for the methane/air mixtures. It is seen that
Kp,F t while the variation of qp with Φ is rather insensi-
for lean mixtures and tive, its peaking indeed occurs on the rich side, in
accordance with the analysis above. However, Tad
n2 (φ − 1)2 pt now occurs on the lean side, as observed in Ref. [3].
e≈ (13)
2
Kp,H [nφ + (m/2)φ] + 4n(φ − 1)pt By further noting that cp,2 still increases monotoni-
cally with increasing Φ, it is then clear that the lean-
√
for rich mixtures, where Kp,F = pF / pF2 and Kp,H shifting of the Tad for the present case is actually
√
= pH / pH2 . In deriving Eqs. (12) and (13), use has caused by the increasing cp,2 instead of product dis-
been made of the assumption that c  b and e  d at sociation, which has the influence of rich shifting. To
816 C.K. Law et al. / Combustion and Flame 145 (2006) 808–819

Fig. 9. Scaled difference terms for Tad , qp , cp,2 , and (qp /cp,2 ), referenced to the stoichiometric state, as functions of Φ for
N2 H4 /F2 mixtures at STP.

further substantiate the role of the cp,2 , in Fig. 9 we

have plotted δTad /Tad , δqp /qp , and δcp,2 /cp,2 in the
same manner as that for Fig. 6. It is seen that indeed
δTad /Tad ≈ δqp /qp − δcp,2 /cp,2 , hence demonstrat-
ing the essential role of cp,2 in causing Tad to be
lean-shifted.

7. The role of oxidizer enrichment

Although the above result on Nm Hn /F2 mixtures

adequately substantiates the roles of product disso-
ciation and specific heat, they introduce yet another
factor that needs to be considered for a complete ex-
planation of the observed peaking behavior. That is,
while mixtures of H2 , CO, and CH4 with air all con-
tain a significant amount of inert, namely N2 , the
Nm Hn /F2 mixtures contain only fuel and oxidizer,
without any inert.
To explore the role of oxidizer enrichment, or
equivalently inert dilution, additional calculations
were performed for the Nm Hn /F2 system with Ar
dilution. Argon instead of nitrogen is used as the in-
ert diluent because the latter is an active reactant for
the present system. Fig. 10 shows the values of Φ
at which qp and Tad respectively peak for various
amounts of Ar in F2 /Ar. It is seen that for a highly
diluted mixture, with α = F2 /(Ar + F2 )  1, both qp
and Tad peak in the stoichiometric state, where α is
the mole fraction of the oxidizer in the oxidizer/inert
mixture. This is consistent with our earlier under-
standing that the product should be close to the frozen
limit for such highly diluted mixtures whose flame
temperatures are low. However, with continuous in-
Fig. 10. Dependence of Φ on the extent of argon dilution for
the maximum qp and Tad for N2 H4 /F2 mixtures at STP.
crease in the F2 concentration and hence increase in
Tad and the extent of product dissociation, it is seen
that while qp still always peaks on the rich side for all
dilutions, the maximum Tad is shifted to the lean side
with even just a moderately high concentration of F2 .
The role of oxidizer enrichment is further explored
in Figs. 11 and 12, which respectively show the de-
pendence of the normalized equivalence ratios for the
maximum qp and Tad on the extent of nitrogen dilu-
tion for hydrogen, methane, and ammonia. It is seen
that both qp and Tad still peak on the rich side for
hydrogen and methane for all amounts of oxidizer en-
richment. For ammonia, however, while qp still peaks
on the rich side, the maximum Tad is now shifted
to the lean side with a moderate amount of oxidizer
enrichment. This result therefore substantiates and ex-
 C.K. Law et al. / Combustion and Flame 145 (2006) 808–819
Fig. 11. Dependence of Φ on the extent of N2 dilution for
the maximum qp for mixtures of H2 , CH4 , and NH3 with
O2 /N2 at STP.
Fig. 12. Dependence of Φ on the extent of N2 dilution for
the maximum Tad for mixtures of H2 , CH4 , and NH3 with
O2 /N2 at STP.
Fig. 13. Dependence of Tad , cp,2 , and the specific molar concentration of the product mixture as functions of the oxidizer
enrichment, at the state of maximum Tad , at STP.
817
tends the observation of Ref. [4] on the lean shifting
of Tad for mixtures of ammonia and oxygen.
We next identify how does cp,2 affect the lean
shifting of Tad with varying amounts of oxidizer en-
richment. Specifically, cp,2 is expected to increase
with increasing oxidizer enrichment due to two fac-
tors. First, an increase in Tad will lead to an increase
in the cp,2,i of the individual species i. Second, the
change in the product composition also favors an in-
crease in the product cp,2 , again for two reasons. That
is, since the product species are mostly triatomic (e.g.,
H2 O and CO2 ), they have larger cp,2,i than those of
the monatomic or diatomic inert diluents (e.g., Ar or
N2 ) that they displace through oxidizer enrichment.
Furthermore, the amount of dissociation at the higher
Tad is also increased, leading to more moles of the
dissociated products.
To identify the relative importance of Tad and
product composition on the increase of cp,2 with ox-
idizer enrichment, in Fig. 13 we show for the hydro-
gen case the dependence of Tad , cp,2 , and the spe-
cific molar concentration of the product on α, at the
maximum Tad . Results for methane and ammonia are
qualitatively similar. It is seen that while Tad initially
increases quite sensitively with increasing α, the in-
crease substantially slows down when α exceeds the
range around 0.3. Thus the increase in cp,2 beyond
this range in α is not expected to be strongly depen-
dent on the increase in Tad . On the other hand, the
specific molar concentration of the product steadily
increases with α for all α, with the increasing trend
being similar to that of cp,2 . Thus while the increase
in cp,2 is affected by both Tad and the product compo-
sition for small α, it is strongly affected by the latter
818 C.K. Law et al. / Combustion and Flame 145 (2006) 808–819
Fig. 14. Dependence of the concentrations of monatomic,
diatomic, and triatomic product species as functions of oxi-
dizer enrichment, at the state of maximum Tad , at STP.
for large α. Furthermore, since Fig. 12 shows that Tad
starts to be lean-shifted for α greater than about 0.3, at
which the influence of Tad on cp,2 starts to diminish,
we conclude that the lean shifting of Tad with increas-
ing oxidizer enrichment is mainly through the change
in the product composition on cp,2 .
We next analyze the nature of the change in the
product composition that leads to the increased cp,2
with increasing α. Fig. 14 plots the specific molar
concentrations of the monatomic, diatomic, and tri-
Fig. 15. Dependence of the sensitivities of qp and cp,2 with respect to Φ as functions of Φ for various extents of N2 dilution for
mixtures of CH4 with O2 /N2 at STP, where α = O2 /(O2 + N2 ).
atomic molecules; the concentration of the triatomic
molecules here includes that of the quadatomic spe-
cies H2 O2 , which is present in dissociation equi-
librium. It is seen that, while the presence of the
monatomic molecules, which becomes noticeable
around α = 0.3 at which the increase of Tad starts
to slow down, is clearly a result of product dissocia-
tion and contributes to the overall increase in cp,2 , the
steady and substantial increase of the concentration
of the triatomic molecules indicates the strong influ-
ence of the displacement effect of the diatomic inert
by the triatomic product.
The final point to note is that while the above dis-
cussion is based on the values of the various quan-
tities, the actual shifting should be evaluated on the
basis of sensitivities. For example, since Tad (Φ, α) ∼
qp (Φ, α)/cp,2 (Φ, α), as discussed earlier, we have
d ln Tad /dΦ ≈ d ln qp /dΦ − d ln cp,2 /dΦ for given α.
Since d ln Tad /dΦ = 0 for maximum Tad , the con-
dition for maximum Tad is given by d ln qp /dΦ ≈
d ln cp,2 /dΦ, that is, a balance between the sensitivi-
ties of qp and cp,2 with respect to Φ. In Fig. 15 we
have therefore plotted these sensitivities as a func-
tion of Φ for small and large values of α respectively,
using CH4 as an example. The condition of the max-
imum Tad is then given by the crossing point of the
solid line for qp and the corresponding dashed line for
cp,2 . It is seen that the effect of increasing α on qp and
 C.K. Law et al. / Combustion and Flame 145 (2006) 808–819
cp,2 is to shift the crossing point to richer and leaner
concentrations respectively. Furthermore, for small α,
say α ∼ 0.21, qp is highly sensitive to Φ, so that the
rich shifting for maximum Tad is mostly due to the qp
effect. However, for large α, say α ∼ 0.8, qp becomes
less sensitive to Φ and the cp,2 term subsequently
plays the essential role in shifting Tad toward the lean
side.
8. Summary
In the present study we have successfully identi-
fied the cause for the shifting of the maximum adia-
batic flame temperature from stoichiometry for mix-
tures consisting of fuel, oxidizer, and inert. Basically,
the phenomenon is a consequence of reduced heat re-
lease in the presence of product dissociation, with the
direction of shifting being determined by that of the
peak heat release and the dependence of the prod-
uct specific heat, per unit mass of the mixture, on
stoichiometry. The study demonstrates that, for hy-
drocarbon/air mixtures, there is more dissociation on
the lean side, so that the heat release peaks on the
rich side. Furthermore, since the relevant specific heat
for a closed system is that per unit mass of the mix-
ture, and since its value monotonically increases with
equivalence ratio even based on frozen stoichiometry,
the peak adiabatic flame temperature is lean-shifted
relative to that of the peak heat release. This lean shift-
ing, however, is not extensive enough for most situ-
ations especially those of hydrocarbon/air mixtures,
and as such the maximum adiabatic flame tempera-
ture still peaks on the rich side of stoichiometry, as
observed.
The study further shows that the tendency for lean
shifting is increased with oxidizer enrichment, such
that the peak adiabatic flame temperature is shifted
to the lean side of stoichiometry for mixtures of
Nm Hn and F2 , and of NH3 and O2 with a moder-
ate amount of inert dilution. This is mostly a con-
819
sequence of the larger specific heat associated with
the triatomic product species which displaces the di-
atomic or monatomic inert as a consequence of oxi-
dizer enrichment.
The various causes for the off-stoichiometric
peaking of the adiabatic flame temperature have
therefore been demonstrated in an internally consis-
tent manner.
Acknowledgments
This work was supported by the Air Force Office
of Scientific Research and the Army Research Office.
A.M. was in addition supported by the Ministry of
Education, Culture, Sports, Science and Technology,
Japan, while he was on sabbatical leave at Prince-
ton University. We thank Professor H. Wang for his
valuable contributions during the initial phase of this
study, and Professors C.T. Bowman, F.N. Egolfopou-
los, B.S. Haynes, S.R. Turns, and F.A. Williams for
their suggestions and insightful inputs to this work.
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