12646 J. Phys. Chem.

1994, 98, 12646-12652

Reaction Mechanism for Phenol Oxidation in Supercritical Water

Sudhama Gopalan and Phillip E. Savage*

Department of Chemical Engineering, The University of Michigan, Ann Arbor, Michigan 48109-2136
Received: August 17, I994@

We postulate the elementary steps in the reaction mechanism for phenol oxidation in supercritical water that
account for key findings from earlier experiments. These findings are competing primary paths (dimerization
and ring-opening) for phenol disappearance, COZconsistently formed in higher yields than CO, and carboxylic
acids and single-ring oxygenates formed as stable reaction intermediates. We examine the literature for free-
radical chemistry of phenol oxidation in both gas and solution phases to find elementary processes that could
describe our findings for oxidation in supercritical water. We discriminate between potential elementary
processes using thermodynamic and kinetic arguments and select the most appropriate mechanisms for the
primary pathways. Our results indicate that phenol dimerization is a radical-radical process involving phenoxy
radical recombination. The likely ring-opening processes also involve radical-radical addition. The two
potential ring-opening paths involve the addition of HO;! and OH to the phenoxy radical as the initial step to
form a hydroperoxide and a benzenediol, respectively. Subsequent ring-opening reactions that form
carboxylates like acids and acyl radicals are consistent with the intermediates detected. Ring-opening schemes
involving oxygen addition reactions are not likely to be important. The mechanism reported here can be
used as a foundation upon which to build a quantitative detailed chemical kinetics model for the primary
paths for phenol oxidation in supercritical water.

Introduction successful in being able to reproduce experimental results. Brock

Supercritical water oxidation' (SCWO) is an advanced
oxidation process for the treatment of hazardous wastes. It
involves the oxidation of organic pollutants in aqueous streams
at reaction conditions beyond the critical point of water (T, =
374 "C, Pc = 218 atm) to C02. The advantage of the
supercritical water reaction environment is the high solubility
it affords to both organics and oxygen, thereby obviating
interphase transfer and leading to fast reaction rates.
Fundamental research on supercritical water oxidation of real
pollutants has been restricted to determining global kinetics and
reaction paths. The disappearance kinetics of phen01,~<~ o-
chl~rophenol,~ p-chl~rophenol,~ acetic a ~ i d , ~
2,4-dichloro-
.~
phenol,' and pyridine8 have been determined. Li et al.9 also
obtained global rate laws for the formation of C02 from the
oxidation of phenol and o-chlorophenol. Recently, we devel-
oped a global reaction network to describe the conversion of
phenol into its chief product^.^ Global rate laws provide
engineering correlations that are applicable within the range of
experimental conditions used to determine the parameters. The
limitations of global rate laws lie in their lack of predictive
power and the limited insight they afford into the fundamental
reaction chemistry. Detailed chemical kinetic modeling based
on the governing reaction mechanism provides the means to
overcome these limitations.
Elementary reaction models exist only for the SCWO of
simple compounds. These models are based on gas-phase free-
radical chemistry since practical SCWO conditions (T = 400-
600 "C, P = 250 atm) do not readily support ionic chemistry.10
Tester and co-workers have made significant contributions in
this field with models for hydrogen," carbon monoxide,12
methan01,'~and methane.I4 These models were able to repro-
duce experimental results with varying degrees of success. The
simplest of the models, viz., for hydrogen, was the most
and Savage', have also developed a mechanistic model for these
simple C1 compounds. Recently, Boock and KleinI6proposed
detailed mechanisms for the oxidation of ethanol, 1- and
2-propanol, and acetic acid in near-critical and supercritical
water based on eight reaction families. Yang and Eckert5also
suggested reaction schemes to explain the oxidation of p-
chlorophenol in supercritical water.
In this paper, we seek to lay the basis for mechanistic
modeling of phenol SCWO. This work is the first attempt at
developing a detailed mechanism for the SCWO of a complex,
real pollutant. In fact, there are no detailed chemical kinetic
models for even the gas-phase oxidation of aromatics in this
temperature (400-600 "C) and pressure (-250 atm) range. We
use information in the literature on the fundamental kinetics of
phenol oxidation in the gas phase coupled with our knowledge
of the reaction intermediates and chief reaction pathways in
phenol SCW03.'7 to build the detailed mechanism for the
primary pathways. We consider free-radical chemistry only and
hence do not take into account ions and ionic mechanisms. We
use thermodynamic and kinetic arguments to discriminate
between alternative mechanisms. Our goal is to assemble a
viable reaction mechanism for phenol SCWO that can be tested
for quantitative consistency with experimental data in a future
study.
Initiation and Phenoxy Radical Generation
Phenol, oxygen, and water are the three species present
initially in the system. The oxidation reaction can be initiated
by unimolecular or bimolecular reactions involving these
species. The potential unimolecular initiation reactions are
C6H,0H - C,H,O +H (1)

* Corresponding author. email: Phillip-Savage @um.cc.umich.edu,

0, - 20 (2)
sudhama@engin.umich.edu.
'Abstract published in Advance ACS Abstracts, November 1, 1994. H,O -OH + H (3)
0022-365419412098-12646$04.5010 0 1994 American Chemical Society
Phenol Oxidation in Supercritical Water J. Phys. Chem., Vol. 98, No. 48, 1994 12647

TABLE 1: H,O, - 20H (8)

k = A T exp( -E,/RT) units of L s mol cal
C6H50H+OH-c6H,0+H,0 (9)
rate Previous elementary reaction models for SCWO of hydrogen'
reaction logA n E, (Ws)" ref and carbon monoxide12 have shown H202 and H02 to be the
(1) C&IsOH= C&I50 + H 16.43 0 88 838 10-13.518 dominant unstable species, with OH present in concentrations

-
(2) 02(+M) = 20(+M)
0 2 20
+
(3) H2O(+M) = H OH(+M)
15.26 -1 118097
12.54 0 105 163
10-24.2 b
19
21
approximately 2 orders of magnitude lower and H atom
concentrations even lower. Oxygen atom chemistry was found
to be unimportant at SCWO conditions. In spite of its low
H20 = OH H+ 10-19.4
reactivity as compared to OH, HO2 is likely to be important as
(4) C&150H+ 0 2 = C&O + H02 9.00 0 35 000 23
( 5 ) H20 + 0 2 = H02 OH+ 10-10.5 d a chain carrier in SCWO because of its relative abundance.
Brock and Savage15 noted that nearly half the elementary
a Rate calculated at T = 733 K and using typical CsHsOH, 02, and
reactions that controlled the oxidation kinetics of CO, H2, C&,
H20 concentrations of 10-3.4,10-2.2,and M, respectively. From
and CH30H involved HO2.
-
hard-sphere collision theory, the high-pressure rate coefficient (k-) for
2 0 0 2 was estimated as k = 109,7310.5. At 733 K, the equilibrium
constant (Kc)for reaction 2 was estimated as 10-30.88M after
incorporating a compressibility factor of 0.7 (compressibility of pure Phenoxy Radical Chemistry
water at 733 K and 250 atm) to the equilibrium constant estimated
-
using THERM.20 Using these values, k4733 K) = 10-'9.72s-' for 0 2
20. But kJM] = 10-22.02s-I, showing that the reaction is at the
low-pressure limit. Using the high-pressure rate coefficient for H +
The free-radical chemistry of phenol is essentially the
chemistry of the phenoxy radical. There are three possible paths

-
-
OH H20 estimated in the NIST Chemical Kinetics Database22as k
exp(-75/7) with the equilibrium constant for reaction 3
estimated as 10-31.33M at 733 K, we calculate k4733 K) = 10-20.'6
s-I. Since k,[M] = 10-18.02 SKI,the reaction is at the high-pressure
limit. The reaction rate at 733 K was calculated from the reverse rate
coefficient estimated by Baulch et aLzl as 10'0.46exp(25O/T)and the
equilibrium constant estimated from THERMzoat 733 K as 10-19.69.
The potential bimolecular initiation steps are
available for the phenoxy radical: coupling to form a dimer,
hydroxylation to a benzenediol, and ring-opening. Our SCWO
experiments have identified several products resulting from these
Results from these experiments show that dimer-
ization and ring-opening are the chief paths of phenol SCW0.3
A unique feature of the phenoxy radical, viz., isomerism, has
implications on its reaction mechanism. The phenoxy radical
can exist in three isomeric forms, as shown below.

+ -.C6H,0 + HO,
C6H50H 0, (4) n 0 0

H,O + 0, -.HO, + OH (5)

To discriminate between these competing initiation steps, we
use the kinetics data listed in Table 1 along with phenol, oxygen,
and water concentrations that represent those used in our
experiments3 to calculate reaction rates. The rate parameters
for the bimolecular reaction between phenol and oxygen
(reaction 4) are taken from a study of phenol oxidation in
hydrocarbon solutions at 180 0C?3 The collision frequency was
considered as the A factor for the elementary reaction, and the
endothermicity of the reaction was taken as its activation energy.
We adjusted the collision frequency to take into account the
higher temperature and lower density of supercritical water.
Using phenol, oxygen, and water concentrations of 4, lo-,.*,
and M, respectively, we calculated reaction rates in M/s
for reactions 1-5. From this order of magnitude analysis, we
find that reaction 4 is several orders of magnitude faster than
the others and is therefore the most likely initiation step. That
bimolecular initiation is more important than unimolecular
initiation at the temperatures of SCWO is an expected result
because the unimolecular bond homolysis reactions have higher
activation energies. It should also be noted that, in a commercial
SCWO process, the phenol and oxygen concentrations would
be much higher than those used in our laboratory reactor, thereby
making bimolecular initiation even more favorable.
Additional conversion of phenol to the phenoxy radical
following initiation should be facile since radicals like HO2 and
OH, the latter being extremely reactive, would be present in
the mixture. Reactions 6 and 9 illustrate these steps, while
reactions 7 and 8 show the primary buildup of OH radicals.12
C6H50H + HO, -.C6H50 + H20,
The latter two structures are ketocyclohexadienyl radicals, with
the radical site at the ortho and para positions. The meta
position is not favored, as it would necessitate ring strain. The
relative equilibrium between the three phenoxy isomers influ-
ences both the kind of coupling that occurs and hence the
coupling products, as well as the ring-opening mechanism and
hence the ring-opening intermediates.
ESR spectroscopy results and a knowledge of chemical
reactivity indicate that the unpaired electron in the phenoxy
radical must be largely associated with the n-electron system
of the aromatic ring. Electron spin density measurements
indicate that -17% of the unpaired spin density is associated
with both the oxygen atom and the carbon atom to which it is
directly attached and that the unpaired spin density at the para
position is about 1.5 times that at the ortho position.24 Given
that there are two ortho sites and one para site in the phenoxy
radical, the ESR results would translate to a distributian of
roughly 17% 0, 47% 0-,and 36% p-phenoxy isomers. These
ESR results, however, were obtained for phenol solutions at
ambient conditions, and they might not represent the distribution
at SCWO conditions where the temperatures are much higher.
Therefore, the mechanistic modeling of phenol SCWO has to
proceed without a priori knowledge of the relative amounts of
the phenoxy radical isomers.
Phenol Coupling
(6)

HO, + HO, - H,O, + OH

Coupling of phenols occurs in both the liquid phase and the
(7) gas phase. Born et al.25 reported the formation of phenol
12648 J. Phys. Chem., Vol. 98, No. 48, 1994
ooo
2-Phenoxyphenol
OH
Dibenzofuran
4-Phenoxyphenol 2,2'-Biphenol
Figure 1. Main coupling products detected in phenol SCWO experi-
ment~.~
coupling products in the gas-phase oxidation of phenols at 500
"C. Coupling of phenoxy radicals was considered to be the
mechanism for dimerization. In a review of phenol coupling
in the liquid phase, MussoZ6considered the free-radical mecha-
nism for coupling to be the recombination of two phenoxy
radicals. The attack of a phenoxy radical on a phenol molecule,
which could be important in the case of slow reaction when
the unreacted phenol concentration was high and the phenoxy
"C), where, in the absence of oxygen, thermolysis reactions
-
radical concentration was very low, was not ruled out however.
Such conditions may exist in coal liquefaction studies ( T 400
dominate. McMillen et aLZ7consider the coupling of phenolics
during liquefaction to occur by phenol-phenoxy reactions.
Coupling Mechanism. Given that phenol coupling has been
reported in the gas phase as well as in liquid-phase free-radical
chemistry, it is not surprising that coupling was found to be a
major path in phenol SCW0.3 The most abundant dimers
identified in our phenol SCWO e x p e r i m e n t ~ ~were
, ' ~ 2- and
4-phenoxyphenol, dibenzofuran, and 2,2'-biphenol (see Figure
1). 2-Phenoxyphenol is an end product of ortho-0 coupling,
whereas 4-phenoxyphenol and 2,2'-biphenol result from para-0
and ortho-ortho coupling, respectively. Dibenzofuran is a
secondary product that possibly forms from the 2,2'-biphenol
precursor.25 An interesting observation we make that has
implications to the reaction mechanism is that no 3-phenox-
yphenol was detected in the product analysis. 3-Phenoxyphenol
would be an expected product if the mechanism of the coupling
reaction involved homolytic aromatic substitution by a phenoxy
radical on phenol followed by hydrogen abstraction from the
resultant cyclohexadienyl radical28 (see reaction 11). On the
other hand, phenoxy radical coupling would result in no
3-phenoxyphenol formation since the phenoxy radical does not
have a stable meta isomer. Thus, the coupling product identities
in our experiments are consistent with a radical-radical coupling
mechanism.
Phenol coupling by a radical-molecule reaction can also be
shown to be much slower than radical-radical coupling. For
the reaction
4 (11)
we estimate an activation energy of ca. 34 kcal/mol from the
= 14.4 kcal/mo13' and an activation energy estimate of
20 kcal/mol for the reverse reaction.32 We consider an A factor
of lo9 L mol-' s-' for the reaction, which is typical of
bimolecular reactions. The rate coefficient of reaction 11 is,
therefore, consistent with the upper limit of lo8 exp( -26000/
RT) L mol-' s-l estimated by Shaub and T ~ a n gfor~ ~such
Gopalan and Savage
addition reactions in the gas phase. Comparing the rate of
-
reaction 11 at 733 K with the rate of recombination of two
phenoxy radicals ( k 109-1010 L mol-' s - ' ) , ~we~ find that
for reaction 11 to be as important as phenoxy radical recom-
bination the concentration of the phenoxy radical must be less
than times that of phenol. This would necessitate an
unreasonably low concentration for the stable phenoxy radical.
Therefore, we expect the phenoxy radical recombination to be
faster than reaction 11 by a few orders of magnitude.
Tautomerization. The coupling of two phenoxy radical
isomers leads to the formation of keto intermediates that must
enolize to form the end products that are observed experimen-
tally. This is shown below for the case of ortho-0 coupling.
The transfer of H by an intramolecular process, viz., [1,3]-
sigmatropic rearrangement, is unlikely.34 The keto intermediates
could tautomerize rapidly to their respective enol (phenol) forms
in protic solvents.26 Keto-enol tautomerization of the ortho-0
coupling via an ionic intermediate has also been suggested in
the thermolysis of 2-phenoxyphenol in hydrocarbon solutions
at 400 0C.35 However, the reaction environment under con-
sideration in this paper, viz., supercritical water at T = 400-
600 "C, P = 250 atm, is highly aprotic (Kw < Free-
radical processes would be expected to dominate ionic processes
at such conditions.'0 Hence, we consider radical chain tau-
tomerization to be the most likely tautomerization mechanism
in phenol SCWO. This is consistent with a suggested mecha-
nism for phenol coupling in the gas phase at T = 500 0C.25
The rates of the hydrogen abstraction steps in the tautomerization
process would, therefore, have an impact on the rate of formation
of the dimeric end products. The ortho-ortho and ortho-para
coupling products would require two H transfers and should be
favored less than the ortho-0 coupling product, which requires
only one H transfer. This is consistent with our experimental
finding that 2-phenoxyphenol, the ortho-0 coupling product, is
the most abundant of the coupling isomers formedS3
Ring-Opening
Cleavage of the aromatic ring is the most important and
desirable path in phenol SCWO. In this section, we examine
known free-radical mechanisms for aromatic ring degradation.
We compare the rates of several candidate processes and
examine the consistency of their products with stable reaction
intermediates identified in our phenol SCWO experiments.
Gas-Phase Oxidation. There are two mechanisms for
phenoxy radical degradation in the combustion and atmospheric
chemistry literature: one involving CO elimination and the other
involving 0 2 addition.
Colussi et al.36 observed that the phenoxy radical forms a
cyclopentadienyl radical by the following reaction:
0
Phenol Oxidation in Supercritical Water J. Phys. Chem., Vol. 98, No. 48, 1994 12649
Lin and Lin37measured the kinetics for this elementary reaction OH OH

@-
as k13 = exp(-22100/7) s-l. In mechanisms for the high
temperature ( T > 1000 K) combustion of aromatics like
benzene,38toluene,39and xylene,40elimination of CO from an
aryloxy radical has been considered to be the mechanism for
aromatic ring degradation. Colussi et al.,36however, reported
6) bH
' 9 - I
OH
OH
that the onset of phenoxy radical decay occurred at 710 "C.
This means that at the lower temperatures used in SCWO
reaction 13 will not be important. This can also be inferred
from the high activation energy of 43.9 kcal/mol and relatively
bH
low pre-exponential reported by Lin and Lin. Additionally, the
CO yields in our experiments were always lower than the CO, while catechol forms acetylene and oxalic acid.
yields, which suggests that CO was not formed in high yields
as reaction 13 would require.
At lower temperatures, like those encountered in the atmo-
sphere, 0 2 can add to the phenoxy radical to form a peroxy
radical. Atkinson and Lloyd proposed a mechanism for toluene
oxidation in the atmosphere41involving oxygen addition to form 2C2HZ + (COOHh (16)
a peroxy radical, followed by internal coupling to form an 0-0
bridge, and p-scissions to cleave the aromatic ring. Oxygen Santoro and Glassman,46 however, consider the intermediate
additions to methyl and phenyl radicals have also been compounds in these mechanisms to be triplets and hence the
considered as key elementary steps in the detailed mechanism intermediate steps "spin resistant". Moreover, the decomposi-
for the SCWO of c1-c3 alcohols and acetic acid16 and an tion back to hydroquinone and catechol would be favored. Yet
abbreviated elementary reaction scheme for p-chlorophenol these mechanisms are interesting since they form acids, which
SCW0.5 However, oxygen addition to form peroxy radicals is have also been detected in our experiments on phenol
a reversible process. Benson4, correlated the extent of the SCWO.47348
reversible reaction to a ceiling temperature, which for the Liquid-PhaseOxidation. The failure of published gas-phase
reaction mechanisms for oxidation of aromatics to account for ring
degradation in SCWO leads us to probe the solution-phase free-
radical chemistry literature for a possible mechanism. D e n i ~ o v ~ ~
considered the oxidation of cyclohexanone to proceed via a
is the temperature at which the ratio [ROz]eq/[R]eq = Keq[O2] cyclic a-hydroperoxy ketone that decomposes by parallel
becomes equal to 1. The ceiling temperature is a rough paths: one that breaks the ring and another that forms a diketone.
threshold value above which the reverse reaction dominates.
Our thermochemical calculations for the addition of oxygen to
the phenoxy radical (o-ketocyclohexadienyl isomer) show that
the ceiling temperature for this reaction for the oxygen
concentrations employed in our experimental study is below
100 0C!3 Ceiling temperatures for oxygen addition to the
methyl and phenyl radicals are much higher. Therefore, the R
+ 0, = R02 equilibrium would be displaced well to the left at
T > 400 "C for the phenoxy radical, but not so for the methyl
and phenyl radicals. Therefore, 0 2 addition steps cannot be
used to describe phenol oxidation at SCWO temperatures, even
though they have been invoked in previous SCWO work. This The formation of hydroperoxides (step 1) is common in liquid-
is consistent with the work of Baldwin et a1.& for the oxidation phase autoxidation chemistry. The following sequence of
of the allyl radical in the temperature range 650-800 K. Both reactions is responsible
the allyl and the phenoxy radicals are electron delocalized, stable
radicals that do not favor oxygen addition at such temperatures.
Commenting on the oxidation of such radicals at T < 1000 K,
R. + 0, -.RO,. (14)
Baldwin et al.& conclude that these radicals have only a limited RO,* + RH + RO,H + R* (18)
number of reaction paths available. The stable radicals would
build up to high concentrations, thus making radical-radical Presumably, the formation of the diketone (step 2) occurs by
reactions important. This is exemplified by the importance of cleavage of the weak 0-0 bond in the hydroperoxide (bond
phenoxy radical recombination to form phenol dimers in phenol dissociation energy -43 kcal/mol) .followed by hydrogen
SCW0.3 We note that the work of Baldwin et al. is the only abstraction. The oxidative cleavage of cyclic a-hydroperoxy
study on the combustion of a "stable" radical in this temperature carbonyl compounds by a radical mechanism (step 3) is
range. considered to proceed via a cyclic a-hydroxy dioxetane
It is also interesting to note that some of the very early work i~~termediate."~+~~
For the oxidation of the a-hydroperoxy ketone
on the combustion of aromatics also considered oxygen addition derived from phenol, the mechanism is
reactions. Norrish and Taylof15suggested a mechanism for the
oxidation of benzene at T = 680-685 K. The oxidation
proceeded via dihydroxybenzenes, which were formed by OH
addition. Hydroquinone is said to react with oxygen to form
maleic acid and acetylene,
12650 J. Phys. Chem., Vol. 98, No. 48, 1994
Our thermochemical calculations show the formation of the
dioxetane intermediate to be endothermic by ca. 23 kcal/mol
and its decomposition to be exothermic by ca. 95 kcal/mol.
SCWO Chemistry. We have shown that published mecha-
nisms for phenoxy radical degradation in the gas phase cannot
describe the results of our SCWO experiments. The mechanism
for ring-opening in the liquid phase remains a possibility for
applying at SCWO conditions. The mechanism involves
aldehydes and acids as intermediates, and formic, glyoxalic,
oxalic, propionic, hydracrylic, succinic, and maleic acids have
all been detected in phenol SCW0.47,48Moreover, the decar-
boxylation of acids is a potential source of CO2. In high-
temperature oxidation of alkanes and aromatics, C02 is con-
sidered to form from CO alone. CO cannot be the sole CO2
precursor in phenol SCWO, however, because CO oxidation to
C02 in supercritical water is too slow to account for the high
COz yields we ~ b s e r v e d . Therefore,
~ mechanisms involving
acid intermediates as sources of C02 independent of CO would
be consistent with the higher amounts of CO:! relative to CO
formed in our experiments.
If the liquid-phase mechanism for aromatic ring degradation
is to apply to SCWO, then the a-hydroperoxy ketone needs to
be formed. We have already shown that the formation of
hydroperoxides by a mechanism involving oxygen addition to
the phenoxy radical is unlikely in SCWO. The high concentra-
tions of H02 and C6H5O radicals, however, suggest that these
radicals could potentially combine to form a hydroperoxide. The
addition of HO2 to the phenoxy radical is exothermic by ca: 50
kcal/mol, thereby creating the potential for a chemically
activated reaction along an available path, viz., cleavage of the
weak 0-0 bond. We expect the high-pressure SCWO envi-
ronment to favor deactivation of chemically activated species
by collisions, however. We note that Brezinsky et al.51showed
that the excited hydroperoxide formed by the addition of HO2
to a benzyl radical at 1180 K and atmospheric pressure would
deactivate preferentially.
There are two reaction paths available for the a-ketohydro-
peroxide besides rearrangements as in (19): unimolecular
cleavage of the weak 0-0 bond (step 1 below) and hydrogen
abstraction by 0 2 (step 2 below).
We estimate the rate of the competing reaction paths for the
a-ketohydroperoxide as kl = 1015.6exp(-43000/RT) s-l 52 and
k2 = 108.9exp(-24860/RT) L mol-' s-1.54 At 733 K and for
an 0 2 concentration of M, we calculate the first-order
rate constants as 102.5and 1O-O.' s-l, respectively. Similarly,
for the oxyradical formed by 0-0 cleavage of the a-ketohy-
droperoxide, @-scission(step 3) and hydrogen abstraction (step
4) possibilities exist. We estimate k3 = loL4exp(-15000/RT)
s-l 56 and k4 = exp(-1650/RT) L mol-' s-l 57 and hence
the first-order rate constants at 733 K as 109.5and lo5.' s-l,
respectively. From this analysis, the reaction path involving
steps 1 and 3 seems to be the likely ring-opening process in
Gopalan and Savage
scheme 20. A quantitative model can provide better discrimina-
tion between all these competing paths. If path 1 in sequence
20 is indeed kinetically significant, it could be an important
degenerate branching reaction since it produces OH, which is
extremely reactive.
Reaction sequence 20 considers only the hydroperoxide
formed by addition of HO2 to an o-cyclohexadienyl isomer of
the phenoxy radical. A similar reaction sequence is possible if
the p-cyclohexadienyl phenoxy isomer is considered. The
difference would be that the product of ring-opening by
p-scission (path 3 in reaction sequence 20) would be a vinyl
radical. Also, rearrangement of the hydroperoxide as in reaction
19 would not be possible in this case.
The phenol dimers could also undergo ring-opening reactions
similar to those discussed above since they can be regarded as
substituted phenols. Indeed, our phenol SCWO experiments
have shown that the selectivity of the dimers decreases with
increasing phenol conversion, indicating their consumption as
the reaction progre~ses.~ The dimers could be consumed by
the same ring-opening processes that convert the phenoxy radical
to COz. Single-ring products like 2,3-dihydro-lH-inden-l-one
that have been detected3could be products of such ring-opening
reactions. Alternatively, if an equilibrium is established between
the phenoxy radical and the dimer tautomers, the dimer
tautomers could decompose by a reverse reaction as the phenoxy
radical concentration decreased with time. This could also result
in the observed dimer selectivity trends.
Single-Ring Products and Their Reactions
Single-ring products detected in phenol SCWO experiments
include p-benzoquinone, catechol, hydroquinone, and resorci-
n01.4~ These could be formed by OH addition to the phenoxy
radical.
OH addition to phenol is not a likely source of these products
since, at temperatures above 450 K, hydrogen abstraction by
OH to form the phenoxy radical and H20 is
Quinones are also formed in the mechanism for phenoxy radical
oxidation with H02 shown in reaction sequence 20. There is
very little mechanistic information present on gas-phase oxida-
tion of quinones. Devlin and Harris59 have considered the
formation of cis,cis-muconic acid from o-benzoquinone as the
ring-opening step in the wet air oxidation of phenol, a process
-
similar to SCWO, but with less severe operating conditions
( T - 200 "C, P 150 atm). Yang and Eckerts have considered
p-benzoquinone to be the species that undergoes ring-opening
in the SCWO of p-chlorophenol. Quinones are considered as
scavengers in liquid-phase chemistry for their ability to scavenge
free radicals by addition reactions. For instance, OH could add
across the n-bond in p-benzoquinone.60 We suggest the
following mechanism, which involves @-scissionof the inter-
mediate formed by OH addition to p-benzoquinone, for ring-
opening:
Phenol Oxidation in Supercritical Water
The lack of readily abstractable hydrogen in quinones and the
high pressures of SCWO should favor OH addition to quinones.
Our thermochemical calculations show that the OH addition
should be exothermic by ca. 40-50 kcal/mol. Again, only a
detailed quantitative model can show the importance of reaction
sequence 22 in comparison with reaction sequence 20 as a ring-
opening process.
Summary and Conclusions
Previous experiments showed that phenol oxidation in su-
percritical water proceeds via two parallel primary paths:
dimerization and ring-opening. These paths lead to the forma-
tion of several dimers, CO, C02, carboxylic acids, and single-
ring oxygenates. C02 is formed in higher yields than CO at
all times.3 In this paper we have postulated a free-radical
mechanism for phenol SCWO along the primary paths, con-
sistent with these key experimental findings. Dimerization is
a result of phenoxy radical recombination followed by radical
chain tautomerization. The likely ring-opening process involves
H02 addition to a phenoxy radical and unimolecular cleavage
of the weak 0-0 bond in the resultant hydroperoxide followed
by a p-scission. There are other candidate mechanisms for
cleavage of the aromatic ring as well that require a quantitative
kinetics model for discrimination.
Supercritical water oxidation is a unique reaction system from
the standpoint of combustion systems. It is characterized by
low to intermediate temperatures, high pressures, and an aqueous
medium. Additionally, the phenoxy radical is an electron
delocalized stable radical and hence resistant to oxygen addition.
Consequently, radical-radical processes become dominant in
phenol SCWO. This is exemplified by the importance of
radical-radical processes in both the primary paths in phenol
SCWO. The present analysis of the reaction mechanism for
phenol oxidation in supercritical water is a first step in detailed
chemical kinetic modeling of the system.
Acknowledgment. This project has been supported by the
EPA (R817857-01-0).
References and Notes
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(31) Using THERM,Zoan implementation of Benson's group additivity
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(411 Atkinson. R.: Lloyd. A. C. J . Phvs. Chem. Ref. Data 1984. 13.
315-444.
(42) Benson, S. W. J. Am. Chem. SOC. 1965, 87, 972-979.
(43) Calculated using the equilibrium constant for the reaction estimated
using THERMzo and an oxygen concentration of M. At 100 "C,
AG for the reaction was estimated as 0.72 kcaUmo1, leading to Kp = 0.38
atm-' and K, = Kp(RT)= 11.6M-', and hence Kc[02] = 0.07.
(44)Baldwin, R. R.; Lodhi, Z. H.; Stothard, N.; Walker, R. W. 23rd
Symp. (Int.) Combust. 1990, 123-130.
(45) Norrish, R. G. W.; Taylor, G. W. Proc. R. SOC. 1956, A224, 160-
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(46) Santoro, R. 5.; Glassman, I. Combust. Sci. Technol. 1979,19, 161-
164.
(47) Thornton, T. D. Ph.D. Thesis, The University of Michigan, 1991.
(48) Thomton, T. D.; Savage, P. E. J. Supercrit. Fluids 1990, 3, 240-
248.
(49) Frimer, A. A. The Chemistry of Enones Part 2; John Wiley &
Sons: New York, 1989; Chapter 17.
(50) Hamilton, G. A. Molecular Mechanisms of Oxygen Activation;
Academic Press: New York, 1974; Chapter 10.
(51) Brezinsky, K.; Litzinger, T. A,; Glassman, I. Int. J . Chem. Kinet.
1984, 16, 1053-1074.
(52) The rate coefficient was taken to be the same as the high-pressure
limit for the dissociation of the hydroperoxide formed by the addition of
H02 to the benzyl radical, as estimated by Brezinsky et aL5'
(53) Mulder, P.; Louw, R. J . Chem. SOC.,Perkin Trans. 2 1985, 1135.
(54) The rate constant was taken to be the same as that for hydrogen
abstraction by 0 2 from 1,3-~yclohexadiene.~~
(55) Baldwin, A. C.; Barker, J. R.; Golden, D. M.; Hendry, D. G. J.
Phys. Chem. 1977, 81, 2483-2492.
(56) Activation energies for the corresponding /%scissions of alkoxy
radicals to form an aldehyde and a (acyYalky1) radical ran e between 12
and 17 kcaVm01.~~ For step 3 in reaction 20, we expect A$> 0, so log A
(SKI)> 13. We use A = loL4s-I as a rough estimate.
12652 J. Phys. Chem., Vol. 98, No. 48, 1994 Gopalan and Savage
(57) The rate coefficient is taken as that for hydrogen abstraction by 0 2 (59) Devlin, H. R.; Harris, I. J. Ind. Eng. Chem. Fundam. 1984, 23,
from an alkoxy radicaL2' We expect step 4 to be faster because it leads to 387-392.
a conjugated product. Hence, the rate coefficient estimate is a lower limit. (60) Adams, G. E.; Michael, B. D. Trans. Faraday SOC.1967,63, 1171-
(58) Atkinson, R. Chem. Rev. 1986, 86, 69. 1180.