Ind. Eng. Chem. Res.

1997, 36, 2547-2557 2547

Reactions of Nitrate Salts with Ammonia in Supercritical Water

Philip C. Dell’Orco,*,†,‡ Earnest F. Gloyna,‡ and Steven J. Buelow§

Los Alamos National Laboratory, Mail Stops C920 and J567, Los Alamos, New Mexico 87545, and
Department of Environmental and Water Resources Engineering, The University of Texas at Austin,
Austin, Texas 78712

Reactions involving nitrate salts and ammonia were investigated in supercritical water at
temperatures from 450 to 530 °C and pressures near 300 bar. Reaction products included nitrite,
nitrogen gas, and nitrous oxide. Observed reaction rates and product distributions provided
evidence for a free-radical reaction mechanism with NO2, NO, and NH2• as the primary reactive
species at supercritical conditions. In the proposed elementary mechanism, the rate-limiting
reaction step was determined to be the hydrolysis of MNO3 species, which resulted in the
formation of nitric acid and subsequently NO2. A simple second-order reaction model was used
to represent the data. In developing an empirical kinetic model, nitrate and nitrite were lumped
as an NOx- reactant. Empirical kinetic parameters were developed for four MNOx/NH3 reacting
systems, assuming first orders in both NH3 and NOx-. Observed MNOx/NH3 reaction rates and
mechanisms suggest immediately a practical significance of these reactions for nitrogen control
strategies in supercritical water oxidation processes.

Introduction tion activities (such as Hanford tank wastes) contain

Supercritical water oxidation (SCWO) has been pro-
posed as a method for the conversion of hazardous
organic compounds to benign byproducts. Bench- and
pilot-scale studies have demonstrated the technology on
individual organic compounds (Crain et al., 1993), waste
simulants (Bramlette et al., 1991), and actual wastes
(Shanableh and Gloyna, 1991). Cited advantages to
incineration include no NOx production, the complete
conversion of organics at relatively low temperatures
and residence times, and cost effectiveness (McBrayer,
1995). Although organic destruction has been rigorously
studied in supercritical water reactors, little emphasis
has been placed on reactions of other elements common
to waste streams. Nitrogen, in particular, is present
in many waste streams of interest.
Ammonia has been reported as a primary constituent
or stable reaction intermediate in several waste streams
targeted for treatment with SCWO. Shanableh and
Gloyna (1991) and Tongdhamachart (1990), using SCWO
to treat industrial and municipal sludges, reported
ammonia as a refractory reaction product at tempera-
tures of 400-500 °C. Studies of the SCWO of metabolic
wastes for space missions have also shown ammonia as
an oxidation-resistant reaction product, remaining pri-
marily unreacted at temperatures up to 650 °C (Taka-
hashi et al., 1989; Hong et al., 1987). In a more basic
study, ammonia was relatively unreactive with oxygen
in supercritical water environments, at 248 bar and
temperatures of 600-700 °C (Webley et al., 1991).
Conversions of less than 20% were observed at residence
times of less than 20 s at these conditions, using
stoichiometric oxygen.
In addition to ammonia, nitrate and nitrite have also
been reported as reaction products in the hydrothermal
treatment of energetic materials (TNT, RDX, HMX)
(Harradine et al., 1993). Wastes from nuclear produc-
* Author to whom correspondence is addressed. Phone:
(505)-667-7854. Fax: (505)-667-0500. E-mail: dellorco@lanl.gov.
† Los Alamos National Laboratory, Mail Stop C920.
‡ The University of Texas at Austin.
§ Los Alamos National Laboratory, Mail Stop J567.
S0888-5885(96)00589-1 CCC: $14.00
high amounts of nitrate and nitrite. These nitrates are
also thermally stable, except in the presence of an
appropriate reducing agent (Foy et al., 1995; Cox et al.,
1994). Hydrothermal treatment has been proposed as
a method for treating such nitrate-containing wastes
(Robinson et al., 1993).
Due to low regulatory limits for the discharge of
ammonia and nitrates to receiving streams, treatment
of wastes using SCWO may be unable to meet nitrogen
treatment requirements without using prohibitively
high temperatures or additional treatment. One pos-
sible method for converting ammonia or nitrate to
relatively benign byproducts is suggested by off-gas
treatment processes for incineration and energy produc-
tion. Technologies such as thermal DeNOx and the urea
acidic process use ammonia or NHx free radicals to
reduce gaseous NOx species to molecular nitrogen and
nitrous oxide (Lyon, 1987; Lasalle et al., 1992). Other
abatement technologies use metal oxide catalysts to
promote reaction efficiency between NOx and NHx
species (Wong and Nobe, 1986; Baurle et al., 1978). In
fact, NHx-NOx reactions have been demonstrated to
occur in near-critical water. Reactions of ammonium
chloride and sodium nitrate at 300 bar and 350-380
°C were found to produce primarily nitrogen gas and
nitrous oxide, with near complete reaction occurring at
380 °C (Dell’Orco et al., 1993). These air pollution
control strategies and initial near-critical water results
prompted the current study.
This research was conducted to determine the poten-
tial utility of NH3/MNO3 reactions as a waste treatment
strategy in SCWO processes. It was hoped that such
reactions would result in the chemical conversion of
NH3/MNO3 to more benign chemical forms (i.e., N2), at
reasonable SCWO operating temperatures (<550 °C)
and residence times (<2 min). Ammonia was consid-
ered the most desirable reducing agent for nitrate, as
no additional elements are added to the system. An
additional goal of this work was to develop empirical
kinetic models for reactor design and to infer reaction
pathways for nitrate and ammonia in supercritical
water systems.
© 1997 American Chemical Society
2548 Ind. Eng. Chem. Res., Vol. 36, No. 7, 1997
Figure 1. Experimental apparatus: tubular reactor in a fluidized sandbath.
Experimental Approach
Kinetics experiments were performed in the reactor
shown schematically in Figure 1. The primary feature
of this apparatus was a fluidized sandbath, which
served to preheat feed streams and provide an isother-
mal reaction zone. Reactant feeds were separately
preheated prior to entering the sandbath using auxiliary
clamshell heaters. Reactant streams were further
heated to reaction temperature in the sandbath. The
preheated streams were mixed at a tee. A coiled piece
of tubing (alloy C276, 6.35 mm o.d. × 2.11 mm i.d.
(reactors A and C); alloy 625, 6.35 × 2.11 mm (reactor
B)) leading from the mixing tee served as an isothermal
reactor. The total volumes of reactors A-C were 13.1
( 0.25, 12.3 ( 0.25, and 12.2 ( 0.25 cm3, respectively.
These values were determined experimentally (Dell’Orco,
1994) and differed by as much as 10% from volumes
calculated using quoted tubing diameters. Reaction
quench was achieved with a heat exchanger placed at
the reactor exit from the sandbath. The small uncer-
tainty in the reactor volume arises from an uncertainty
in the exact point of reaction quench.
Following the quench, the reacted stream was filtered
and then reduced to atmospheric pressure with a
backpressure regulator (Tescom). Eleven thermo-
couples (type K) monitored surface and fluid tempera-
tures in the preheaters and the reactor. An Inconel-
sheathed thermocouple, in contact with the fluid at the
mixing tee, provided the primary determination of
reaction temperature. Surface thermocouples placed at
various positions on the reactor tube were within 1-2
°C of the fluid temperature at the mixing tee. Pressure
was measured with transducers (Ashcroft, K1) placed
near the pump outlet and immediately preceding the
backpressure regulator.
Feed streams were pumped to the apparatus with
low-pulse, high-performance liquid chromatography
(HPLC) feed pumps (LDC Constametric 3000), which
accurately metered flow from 0 to 10 cm3/min for each
feed stream. Feed solutions were prepared daily using
analytical-grade reagents. Ammonium hydroxide solu-
tions were fed from collapsible polyethylene bags with
zero headspace to eliminate volatilization losses. Flow
rates of nitrate/nitrite feed streams were determined by
measuring the mass loss of the solution over time. The
total volumetric flow rate was measured at the reactor
exit, using a calibrated graduated cylinder and a
stopwatch. The flow rate of the ammonium hydroxide
solution was calculated by difference from the measured
flow rates. Reactor residence times were determined
knowing the measured flow rate, reactor volume, and
water density at reaction conditions (Haar et al., 1984).
The system was brought to temperature while flowing
deionized water through the tubing as the sandbath
heated. When the pressure and temperature were
stable, the deionized water was switched to feed solu-
tions. After approximately 30 min, sampling of the
effluent was initiated. For each residence time, three
sets of 40 cm3 quadruplicate samples were taken. Upon
the completion of sampling at a residence time, flow
rates were adjusted to provide a new residence time;
the system was then equilibrated for 30 min, and
samples were collected for this new condition. Effluent
samples were typically collected at five residence times.
For ammonium hydroxide/sodium nitrate/nitrite reac-
tions and for sodium nitrate decomposition studies, each
set of four samples was analyzed for pH, nitrate, nitrite,
ammonium, sodium, and potential reactor corrosion
products, iron, chromium, molybdenum, and nickel. This
approach to sampling and analysis provided three true
replicates, from which combined experimental and
analytical error could be estimated.
One gas sample was collected at each residence time.
Gas sampling was accomplished by diverting the efflu-
ent to a gas-liquid separator consisting of a 2.54 cm
o.d. stainless steel vessel (100 cm3 volume) previously
evacuated to less than 0.1 Torr. Later, a gas-liquid
separator with a 150 cm3 volume was used. Additional
details of the gas sampling apparatus have been pre-
sented elsewhere (Dell’Orco et al., 1995a). Gases evolved
from approximately 80 cm3 of effluent were collected in
an evacuated gas sample cylinder and analyzed by gas
chromatography (GC). Some samples were analyzed

qualitatively using mass spectrometry. Because the
water used to prepare the reactant solutions contained
dissolved oxygen and nitrogen from equilibration with
air at ambient temperature (25 °C), a background gas
sample was collected, and the quantities of nitrogen and
oxygen in this sample were subtracted from those
measured for gas samples. The absolute yield of
gaseous products was determined from the known
effluent volume, gas volume, and partial pressures.
Gas products were analyzed with a gas chromato-
graph, using a Chrompack CarboPLOT column (30 m
long × 0.53 mm i.d.) with carbon molecular sieve
adsorbent, helium carrier gas, and a thermal conductiv-
ity detector. The GC unit was an HP 5890A Series II,
operated with HP ChemStation software control from
a 80386 based computer. This arrangement allowed the
detection of nitrogen, oxygen, carbon monoxide, carbon
dioxide, methane, and nitrous oxide. A quadrapole
mass spectrometer (Balzer) was used to qualitatively
determine the presence of NO and NO2 in gas samples.
Nitrate and nitrite were measured with ion chromatog-
raphy (IC), using a bicarbonate/carbonate eluent and a
Dionex IonPac AS4 column, on a PC-controlled Dionex
4500i Series ion chromatograph. Ion chromatography
standards were prepared daily. Ammonia was analyzed
first with a gas-sensing electrode (Orion 95-12), using
an ionic strength adjuster (ISA) containing 5 M NaOH,
0.05 M EDTA, and 10% methanol. Calibrations for the
electrode were performed with standards prepared
daily. Later, ammonium was analyzed using the Dionex
4500i ion chromatograph, using a CS2 column, mem-
brane suppression, and a dilute acid eluent. Am-
monium IC standards were prepared daily. All metals
were measured by inductively coupled plasma spec-
trometry. Mass balances were performed using nitrate,
nitrite, ammonia, nitrogen, and nitrous oxide data.
Data and Results
Reaction kinetics results from four separate NH4X/
MNO3 (M+ ) monovalent cation, e.g., Na+; X- )
monovalent anion, e.g., Cl-) systems are reported here:
NaNO3/NH3, LiNO3/NH3, HNO3/NH3, and NaNO3/NH4-
Cl. In addition, NaNO3 decomposition was also inves-
tigated. Experiments were performed to determine the
effect of the cation M+ or the anion X- on product yields
and reaction rates and to aid in the elucidation of
elementary reaction mechanisms. Most reactions were
conducted at a constant pressure (300 ( 5 bar), at
temperatures from 450 to 530 °C (except for NH4Cl/
NaNO3 and HNO3/NH4OH experiments). Assuming a
negligible effect of the dilute reactants on bulk super-
critical water properties, experimental conditions re-
sulted in water densities from 150 to 80 kg/m3, a
dielectric constant varying between 1 and 2 (Uematsu
and Franck, 1980), and a water ion product ranging
from 10-20 to 10-23 mol/kg (Quist, 1970). Based on the
known properties of supercritical water (Franck, 1970;
Marshall and Frantz, 1987), these reaction conditions
favor ion association over dissociation (Mesmer et al.,
1988) and free radical reaction mechanisms over ionic
reaction mechanisms (Xu et al., 1990; Antal et al., 1988;
Holgate and Tester, 1993). Reactants used in this
research would, in most cases, be expected to be in the
associated form, i.e., MNOx(aq) and NH3(aq).
Concentrations of nitrate salts were chosen such that
these values were less than solubility thresholds re-
ported in the literature (Dell’Orco et al., 1995b). Except
where stated, NH4X and MNO3 solutions were sepa-
Ind. Eng. Chem. Res., Vol. 36, No. 7, 1997 2549
Figure 2. Reaction products for NaNO3/NH4OH reactants at 500
°C and 300 bar. Experiment performed using reactor A.
rately preheated prior to mixing. For the most part,
reactions were performed at equimolar nitrate/ammonia
concentrations (3-10 mM). Hydrogen peroxide was
used for some experiments as a cooxidant. Concentra-
tion and pH data provided in the following discussion
are values at ambient conditions.
Alkali Nitrate/Ammonium Hydroxide Reactions
and Alkali Nitrate Decomposition. Typical trends
of reaction products for MNO3/NH3 reactions are il-
lustrated in Figure 2 for an NaNO3/NH3 experiment,
performed at 500 °C. Observed reaction products
included nitrogen and nitrous oxide gases, and nitrite
ion. As nitrate and ammonia concentrations decreased,
the concentrations of nitrogen gas, nitrous oxide, and
nitrite ion increased. Nitrogen gas was the primary
reaction product, while N2O was only produced in small
quantities. The mass balance for this experiment (102%
of nitrogen recovered as products) indicated that all
reaction products were identified. These data im-
mediately indicate the utility of MNO3/NH3 reactions
for the conversion of ammonia and nitrate to benign
gaseous products at moderate reaction temperature/
residence time conditions.
In addition to the main reaction of interest, MNO3
with NH3 to produce benign gaseous products, other
parallel reactions were found to occur. One parallel
reaction of particular importance was the reduction of
sodium nitrate to sodium nitrite, and eventually to NO,
apparently through the oxidation of reactor walls (e.g.,
corrosion). These results are illustrated in Figure 3,
which compares similar experiments performed using
reactors A and B. The difference in decomposition
reactions is evident by the lower nitrate and higher
nitrite concentrations reported for the reactor B experi-
ment, at the same residence time and temperature. In
addition, mass spectrometry analysis identified NO as
a reaction product for the reactor B experiment indi-
cated in Figure 3. This nitrate decomposition is impor-
tant to dispel the common assertion that NO production
cannot occur in supercritical water environments at
moderate temperatures. This assertion, although likely
valid for prompt and thermal NO evolution mechanisms,
may not be true for fuel NO mechanisms (for a descrip-
tion of NO formation mechanisms in combustion, see
Miller and Bowman, 1989).
The explanation for this decomposition phenomenon
is that reactors A and B had quite different histories,
2550 Ind. Eng. Chem. Res., Vol. 36, No. 7, 1997

Figure 3. Comparison of NaNO3/NH4OH experiments at 500 °C

and 300 bar, using reactors A and B. The decomposition behavior
of sodium nitrate is different from reactor A to reactor B. This
Figure 4. NH3/NOx- conversion trends for NaNO3/NH4OH
decomposition was found to ultimately result in the observation
experiments using reactor A. Points at the same temperature have
of NO as a gaseous product. The formation of NO was mediated
the same plot symbols, with the reaction temperature shown next
in future experiments by adding H2O2 in equimolar concentrations
to the corresponding data.
to NaNO3 in feed solutions.

in terms of hours of usage and passivation. Reactor A

had seen approximately 200 h of kinetics reactions,
involving sodium nitrate, simple organic compounds,
and chloride at concentrations less than 10 mM in
water. Reactor B, on the other hand, was simply
passivated for approximately 12 h with dilute NaNO3
and H2O2 solutions (∼10 mM) prior to conducting
experiments. The decomposition of sodium nitrate in
reactors B and C was linked to reactor corrosion, which
was more aggravated for these reactors than reactor A;
a more detailed description of these nitrate decomposi-
tion reactions is provided elsewhere (Dell’Orco, 1994).
This result also illustrates the dependence of observed
reaction rates and byproduct trends on reactor metal-
lurgy and passivation.
To partially offset decomposition reactions, equimolar
H2O2 was added in reactor B and reactor C experiments;
it was hoped that hydroxyl radicals formed by peroxide
decomposition would react with decomposed nitrate
products, shifting the redox equilibria toward original
oxidation states. This approach worked to the extent
that added H2O2 eliminated the presence of NO and NO2 Figure 5. NH3/NOx- conversion trends for NaNO3/NH4OH
in gaseous product streams. The formation of nitrite, experiments using reactor B and H2O2 as a cooxidant. Conversions
however, could not be completely suppressed. are similar to those in Figure 5 for experiments without H2O2;
the presence of peroxide appears to have little effect on reaction
Figures 4 and 5 display NOx- and ammonia conver-
rates.
sions as a function of residence time at several temper-
atures for NaNO3/NH3 experiments conducted on reac- similar temperatures and residence times in Figures 4
tors A (no added H2O2) and B (10 mM H2O2 in feed and 5, it is evident that the effect of H2O2 on reaction
solution), respectively. NOx- conversion is defined using time scales was insignificant.
the molar sum of nitrate and nitrite concentrations in To compare reaction time scales for NO3-/NH3 reac-
the effluent divided by their combined concentrations tions with NO2-/NH3 reactions, some investigations
in the feed solutions. NOx- conversion is used in these were performed on the NaNO2/NH3 system. Reaction
figures rather than nitrate or nitrite conversion because products as a function of residence time at 500 °C and
either of these species can react with ammonia to form 300 bar are displayed in Figure 6. N2O was undetected
gaseous byproducts. As observed in Figures 4 and 5, as a reaction product. Small amounts of nitrate were
both NOx- and NH3 conversions increased with resi- observed as a reaction product. Comparing Figures 2
dence time and reaction temperature. Ammonia/NOx- and 6 (conducted at similar temperature, pressure, and
conversions greater than 70% were achieved above 500 residence time conditions), it is evident that reaction
°C at residence times greater than 7 s. Nitrogen and time scales for the NaNO2/NH3 system are quite similar
nitrous oxide conversion increased with ammonia and to those observed for the NaNO3/NH3 system. As with
NOx- conversion in reactor A and reactor B experiments the NaNO3/NH3 system, NOx- and NH3 conversions
(e.g., Figure 2). Comparing observed conversions at both increase with increasing residence time, as does

Figure 6. Reaction products for a NaNO2/NH4OH system at 500
°C and 300 bar. Data are similar to those in Figure 3, which used
NaNO3 at the same temperature and pressure conditions. No N2O
is detected in NaNO2/NH3 experiments. It appears that NaNO2
reacts at rates similar to those of NaNO3. The small amount of
NO3- generated may be due to dissolved oxygen in water used to
prepare solutions.
Figure 7. NH3/NOx- conversion trends for LiNO3/NH4OH experi-
ments using reactor C. Conversions are similar to those in Figures
5 and 6 for experiments using NaNO3.
N2 gas production. This similarity in reaction rates and
reaction products demonstrates why reactant disap-
pearances are best represented using a lumped NOx-
term.
Using reactor C, lithium nitrate was also reacted with
ammonium hydroxide. These experiments utilized H2O2
as a cooxidant. A plot of NH3 and NOx- conversion as
a function of residence time and temperature is shown
in Figure 7. As observed in Figure 7, LiNO3/NH3
reactions had reaction time scales similar to those of
NaNO3/NH3 reactions (Figures 4 and 5); conversion
values for NOx- and NH3 appear nearly equal at similar
reaction conditions. Similar to NaNO3/NH3 experi-
ments, N2O was also a detected byproduct in LiNO3/
NH3 reactions. The yields of N2 and N2O for MNO3/
NH3 experiments are shown in Figure 8, which plots
N2 and N2O yields as a function of normalized NOx-
conversion (XNOx-/θ, where θ is ratio [NH3]0/[NOx-]0).
Ind. Eng. Chem. Res., Vol. 36, No. 7, 1997 2551
Figure 8. N2 and N2O yields for MNO3/NH4OH experiments. The
slope of linear fits to the data sets are stoichiometric coefficients.
For N2, the stoichiometric coefficient of combined LiNO3/MNO3
data sets is 0.8. N2/N2O selectivities are slightly higher for NaNO3
experiments than for LiNO3 experiments. Experimental temper-
atures ranged from 450 to 525 °C at 300 bar. Residence times were
between 5 and 20 s.
The slope of linear fits to these data yields stoichiometric
coefficients for the N2 and N2O, with an NOx- stoichio-
metric coefficient of 1. For the combined LiNO3/NH3
and NaNO3/NH3 data sets, the stoichiometric coefficient
for N2 is 0.80. The N2O coefficient varies between
NaNO3 and LiNO3 data sets; for NaNO3, the stoichio-
metric coefficient is 0.03, while the same coefficient is
about 0.06 for the LiNO3/NH3 data. The average N2/
N2O selectivity was slightly different (16 vs 21) for
LiNO3 and NaNO3 data sets. For all of the MNO3/NH3
experiments discussed above, nitrogen mass recoveries
were between 90 and 115%, with the majority of
experiments being 100 ( 5%. These mass recoveries
indicate that unknown reaction products are minor or
not present.
HNO3/NH3 and NaNO3/NH4Cl Experiments. In
the reactions discussed above, the pH of the effluent
solution ranged from 9.5 to 10.6 (an alkali hydroxide
salt is a reaction product). To help in elucidating
reaction mechanisms, several experiments were per-
formed using nitric acid as the MNO3 species and using
NH4NO3 as a premixed feed solution (in all other MNO3/
NH4X experiments, reactants are fed and preheated
prior to mixing). Results from these experiments are
shown in Table 1 (experiments H1-H3 and N1-N3).
H2O2 was also used as a cooxidant for these studies. The
effluent pH in these experiments was near 3. Reactions
of NH4NO3 and HNO3/NH3 proceeded to near-comple-
tion at temperatures from 427 to 478 °C, using 0.014
M feed solutions. Conversions to N2O ranged from 8.6
to 9.7%, showing no pattern with increasing tempera-
ture; corresponding N2/N2O selectivities varied from 4
to 5. Conversions to nitrogen gas ranged from 77.7 to
80.6%, also showing no particular pattern with increas-
ing temperature. These conversions, especially to N2O,
contrast from results using sodium and lithium nitrate
for feed solutions, where N2O yields typically varied
from 1 to 3%, with N2/N2O selectivities between 16 and
21. In addition to lower N2/N2O selectivities, NH4NO3
2552 Ind. Eng. Chem. Res., Vol. 36, No. 7, 1997

Table 1. Results from HNO3/NH3, HNO3/(NH3 + NaOH), and NH4NO3 Reactionsa

Co Ce
expt temp (°C) τ (s) pH NO3- (mM) NH3 (mM) NO3- (mM) NO2- (mM) NH3 (mM) N2 (mM) N2O (mM) N rec. (%)
H1 477.7 ( 0.4 7.2 3.1 6.86 7.95 1.75 0.14 0.19 5.94 0.64 103
H2 445.2 ( 0.1 8.7 3 6.86 7.95 1.74 0.12 BDL 5.75 0.72 100
H3 426.8 ( 0.2 10.3 2.9 6.86 7.95 1.82 0.10 BDL 5.97 0.68 103
H4 426.9 ( 0.1 10.6 9.4 6.86 7.11 3.29 0.99 3.18 3.07 0.26 101
H5 456.8 ( 0.3 8 9.3 6.86 7.11 2.91 1.47 3.55 3.00 0.19 102
H6 427.8 ( 0.1 7.6 10.5 6.99 8.10 4.75 2.22 8.08 0.56 0.09 108
H7 427.9 ( 0.1 9.6 10.5 6.99 8.10 4.65 2.15 8.04 0.36 0.08 104
H9 427.5 ( 0.4 13.8 10.5 6.97 8.12 4.46 2.31 7.99 0.73 0.06 108
H10 446.8 ( 0.2 11.1 10.3 6.97 8.12 4.00 2.26 7.36 1.29 0.09 109
N1 450 ( 0.1 9.0 2.8 10.31 10.28 2.26 1.81 BDL 7.75 1.68 111
N2 450 ( 0.1 13.2 2.8 10.31 10.28 2.27 1.76 BDL 7.67 1.72 111
N3 450 ( 0.1 22.6 2.8 10.31 10.28 2.04 1.98 BDL 7.44 1.58 107
a “H” indicates HNO /NH OH or HNO /(NH OH + NaOH) experiments using reactor B. “N” experiments used only one feed, NH NO
3 4 3 4 4 3
dissolved in water, also in reactor B. All reactor B experiments utilized H2O2 in the MNO3 feed solution, at a concentration equimolar
to the NO3 . All concentrations were provided at ambient conditions; feed concentrations are concentrations at mixing tee. mM ) millimolar,
-

ND ) not detected, BDL ) below detection limit and τ ) residence time.

NH4Cl/NaNO3 reactions proceed to completion at much

Figure 9. Reaction products for NaNO3/NH4Cl experiments, 366
°C at 300 bar. These reactions exhibited lower N2/N2O selectivities
than MNO3/NH4OH reactions. Also, notice the reaction temper-
ature is much lower than comparable MNO3/NH4OH reactions.
and HNO3/NH3 reactions had much shorter reaction
time scales than MNO3/NH3 reactions. For instance,
at 427 °C and a 10.3 s residence time, HNO3 reactions
proceeded to completion, while at 450 °C and similar
residence times, NH3 and NOx- conversions were less
than 10%. Because nitric acid is a different reactant
than sodium nitrate, an additional experiment was
performed in which 0.01 M NaOH was added to the NH3
feed stream (experiments H4-H9). This served to make
the effluent pH similar to that observed in sodium and
lithium nitrate experiments (∼10). Sodium hydroxide
addition to the NH3 feed solution slowed the reaction
such that the NOx- conversion at 447 °C and a residence
time of 11.1 s was 10%, compared with an analogous
sodium nitrate experiment for which an NOx- conver-
sion of 10% was observed at 451 °C and a residence time
of 11.3 s. Apparently, the presence of sodium inhibited
the NOx-/NH3 reaction.
Reactions of ammonium chloride with sodium nitrate,
which produced effluent pH values less than 3, reacted
to completion at temperatures less than 400 °C and
residence times near 30 s, producing N2/N2O selectivi-
ties similar to those observed in experiment H1. Figure
9 shows typical reaction products for NH4Cl/NaNO3
experiments as a function of residence time at a
constant temperature. As observed in Figure 9, the
lower temperatures than NaNO3/NH3. At these reac-
tion conditions, NH4Cl is expected to be dissociated into
NH3 and HCl, based on the known ionization behavior
of NH3 in supercritical water (Mesmer et al., 1988).
Apparently, HCl significantly enhances the rate of
MNO3/NH3 reactions. Reaction rates, N2/N2O selectiv-
ites and yields, and effluent pH values indicate that
NaNO3/NH4Cl and HNO3/NH3 reactions occur by simi-
lar elementary mechanisms. Additional data on NaNO3/
NH4Cl experiments are provided elsewhere (Dell’Orco,
1994).
Reaction Kinetics Determination: A Simple
Second-Order Model. The reactions studied were
those of MNO3 with NH3 to form nitrogen gas and
nitrous oxide. Due to the difficulty of separating reac-
tion rates of MNO2 from MNO3, these reactants were
lumped as an MNOx reactant. Specifically, the following
global reaction was modeled:
MNOx + bNH3 f cN2 + dN2O + MOH + eH2O (1)
While water was not quantified as a reaction product,
its production is necessitated to balance global reactions.
The reactor was modeled as an ideal plug flow reactor.
The Reynolds numbers for these reactions varied from
1500 to 5200. Reactions performed at similar flow
conditions have been successfully modeled using the
plug-flow idealization (Holgate and Tester, 1993; Lee
and Gloyna, 1992).
A second-order global reaction model adequately
represented the data. The choice of a second-order
model was based on crude initial rate experiments,
which indicated orders near 1 for both reactants
(Dell’Orco, 1994). A noncatalytic, plug-flow rate expres-
sion was integrated to yield eq 2. In eq 2, b is the
1 - exp(-ktCAO(θ - b))
XA ) (2)
b
1 - exp(-ktCAO(θ - b))
θ
stoichiometric coefficient for ammonia (see eq 1) and θ
is the ratio CBO/CAO, where the subscript B represents
MNOx and the subscript A represents NH3. CAO and
CBO are reactant concentrations at experimental condi-
tions. The rate constant k was assumed to exhibit
Arrhenius behavior; specifically, k ) AR exp(-Ea/RT),
where Ea has units of J/mol, T is in Kelvin, and AR and
k have units of s-1(L/mol)-1.

Table 2. Second-Order Kinetic Parameters for NH4X/MNO3 Reactionsa
data set AR, L/(mol s) Ea, kJ/mol
NaNO3/NH4OHb 7.814 × 1018 247.9
NaNO3/NH4OHc 4.703 × 1017 224.6
LiNO3/NH4OHd 1.293 × 1019 247.6
NaNO3/NH4Clb 2.910x 1023 278.2
a All models are first order in each reactant (NO - and NH ). b Denotes experiment performed on reactor A without added cooxidant.
x 3
cExperiments performed on reactor B with added H2O2 equimolar to MNO3. d Experiments performed on reactor C with added H2O2
equimolar to MNO3.
Using the solver function in Excel 4.0, values of AR,
Ea, and b were optimized such that the following
variation of the χ2 statistic was minimized:
N (XA,i(expt) - XA,i(model))2
χ ) 2
∑
i)1 Wi
+ step, despite exhibiting different overall reaction kinet-
N (XB,i(expt) - XB,i(model))2
∑
i)1 Wi
(3)
In this equation, XA/B,i(expt) represents experimentally
determined conversions for the ith observation, while
XA/B,i(model) represents the model prediction of the con-
version for the ith observation. Wi represents a weight-
ing factor, which is the standard deviation of experi-
mentally observed conversion.
Parameters were determined for three different data
sets. These included data collected for reactor A (NaNO3/
NH3 and NaNO3/NH4Cl, alloy C276, no cooxidant,
reactions), reactor B (alloy 625, equimolar H2O2, NaNO3/
NH3 reactions), and reactor C (LiNO3/NH3, equimolar
H2O2). No constraints were placed on the values that
the estimated variables could assume. Different initial
guesses for AR, Ea, and b reduced the chance that
solutions were not simply local minima.
Table 2 shows the values of the variables obtained
for the different data sets. Also included in the table
are a comparison of calculated rate constants at 500 °C,
and the χ2 statistic for the data sets, defined as
Xiexpt - Ximodel
2
χ ) ∑i N-K-1
(4)
where N is the number of data points and K is the
number of adjustable parameters used to fit the data;
for the proposed model, K ) 3. The table shows that
the three MNO3/NH3 data sets have similar adjustable
parameters. Rate constants at 500 °C are of the same
magnitude. Small discrepancies in kinetic parameters
may simply be due to differences in the reactors used;
rate parameters are similar for sodium and lithium. The
NaNO3/NH4Cl model, while having an activation energy
similar to those of the MNO3/NH4OH data sets, had a
substantially higher preexponential factor and a much
higher 500 °C rate constant than the other data sets.
This is consistent with experimental observations.
A graphical comparison of experimental observations
with model predictions is shown in Figure 10. Overall,
the model prediction is within error of the experimental
observation, and the simple second order rate expression
appears to adequately represent the data. In fact, the
second-order model produced lower χ2 values than zero-
or first-order models. A slightly S-shaped curve is
evident in the ammonia conversion comparisons in
Ind. Eng. Chem. Res., Vol. 36, No. 7, 1997 2553
χv2
b NOx - NH3 k at 500 °C, L/(mol s)
1.20 7.4 × 10-3 8.3 × 10-4 139
1.09 1.2 × 10-3 9.0 × 10-4 315
1.09 5.1 × 10-3 2.5 × 10-3 241
1.53 1.2 × 10-2 6.8 × 10-3 46540
Figure 10; this may indicate that the stoichiometric
coefficient b has a slight dependence on reaction tem-
perature. From Table 2, it is evident that nearly all
reactions are equally activated; this may indicate that
all MNO3/NH3 reactions share a common rate-limiting
ics. The NH4Cl/NaNO3 model has a significantly higher
frequency factor than the MNO3/NH4OH data sets,
perhaps indicating that this MNO3/NH4X reaction pro-
ceeds without the inhibition present in elevated pH
experiments.
Discussion of Reaction Mechanism
MNO3/NH3 reactions have been studied in aqueous,
gas, and liquid melt phases. Aqueous- and melt-phase
reaction mechanisms at temperatures below 200 °C
proceed ionically through a nitronium ion intermediate
(Friedman and Bigeleisen, 1950). The nitronium ion
(NO2+), formed by Brönsted acid equilibria, electrophili-
cally nitrates ammonia to form nitramine and water;
at temperatures above ambient, nitramine rapidly
decomposes to N2O and H2O. A similar mechanism
occurs in nitrite-ammonia reactions, through the ni-
trosonium ion (NO+) intermediate, to form N2 and H2O
(Feick and Hainer, 1954).
Studies of NH4NO3 decomposition in the pure-
component melt phase have been determined to undergo
an ionic to free-radical reaction mechanism change at
temperatures near 290 °C (Brower et al., 1989). The
ionic melt-phase mechanism is essentially the same as
that observed in acidic, aqueous solutions (i.e., through
a nitronium ion intermediate). The free-radical mech-
anism involves the decomposition of NH4NO3 to HNO3
and NH3, followed by the homolysis of nitric acid to form
OH• and NO2. After the OH• abstracts a hydrogen from
ammonia, NO2 and NH2 react to form nitramine. As
with the ionic mechanism, the nitramine decomposes
to form N2O and water.
An immediate difference between previous aqueous-
and melt-phase results and this research is the fact that
N2, not N2O, is formed as the primary reaction product.
This behavior was observed for experiments performed
with and without added oxidant (as H2O2). Two possible
explanations can be provided to explain this behavior.
Either nitrous oxide is initially formed through an ionic
or melt free-radical mechanism and then reacts quickly
to form molecular nitrogen and atomic oxygen or
nitrogen is initially formed by a different mechanism,
with a small side reaction leading to N2O formation.
Possibilities for nitrous oxide conversion to N2 include
unimolecular decomposition by collision with third
bodies (i.e., water), hydrogen abstraction reactions with
ammonia to form N2, OH• and NHx• species, and
oxidation reactions, such as NaNO2 oxidation to form
N2 and NaNO3. From the observation of HNO3/NH3 and
NH4NO3 experiments (exeriments H1-H5), where NH3
2554 Ind. Eng. Chem. Res., Vol. 36, No. 7, 1997
Figure 10. Comparison of experimentally observed conversions with model predictions. Reactants and reactors used are indicated in
the upper right-hand corner of each plot. Points falling on the dotted line exhibit perfect agreement between the experimental observation
and the model prediction.
conversions were near complete from 425 to 475 °C with
no change in N2/N2O selectivity, it can be concluded that
the decomposition of N2O via reactions with water,
molecular oxygen and its radical species, and nitrite was
not significant in this temperature range. Because
ammonia was depleted at these conditions, reactions
with ammonia could not be discounted. Further inves-
tigations have indicated that N2O is unreactive with
NH3 at temperatures up to 600 °C at 300 bar (Masten,
1993).
Gas-phase reactions between NO2 and NH3 have been
shown to form N2 as a primary reaction product (Oden-
brand et al., 1986). In studies involving heteroge-
neously catalyzed NO2/NH3 reactions, global reactions
shown by reactions (5) and (6) were observed. These
6NO2 + 8NH3 f 7N2 + 12H2O
2NO2 + 2NH3 f N2 + N2O + NH4NO3
reactions resulted in NO2/NH3 stoichiometries of 1.33
at 302 °C and 1.22 at 252 °C, due to differences in
reaction branching at the different temperatures.
Gas-phase NO2/NH3 reactions were studied in more
detail at temperatures from 342 to 387 °C to elucidate
the elementary reaction steps (Bedford and Thomas,
1972). This study investigated initial rate data to
determine reaction orders and looked at the effect of
added NO on the reaction in order to elucidate elemen-
tary reaction mechanisms. The authors developed the
following reaction mechanism for describing the system:
NH3 + NO2 T NH2• + HNO2 (7)
NH2• + NO2 T NH• + HNO2 (8)
NH• + NO2 T HNO + NO (9)
2NHO T N2O + H2O (10)
NH2• + NO T N2 + H2O (11)
A difference between the supercritical water reactions
and these gas-phase results is that the SCW reactions
are all most likely at their high-pressure limit. As a
(5) result, species such as HNO2 are likely unstable at
supercritical water conditions. Nonetheless, the gas-
(6) phase results presented above qualitatively agree with
the NOx/NH3 reaction stoichiometries and N2/N2O se-
lectivities observed in this work.
For supercritical water reactions, a simplified reaction
mechanism which considers these gas-phase results is
suggested by reactions (12)-(19). In this mechanism,
the production of reactive species is initiated by a
substitution reaction (reaction (12)) involving an alkali
nitrate/nitrite salt (MNOx) and an acid (HX), which in
these experiments was H2O or HCl. Such reactions
(e.g., hydrolysis) have been observed previously in
solubility studies of NaNO3 and NaCl salts (Dell’Orco

et al., 1995b; Armellini and Tester, 1993). Following
this substitution, either nitric acid or nitrous acid is
formed. Both of these species undergo homolysis to
yield HO• and NO2/NO (reactions (14) and (15)). HONO2
MNO2 + HX T HONO2 + MX (12)
MONO + HX T HONO + MX (13)
HONO T HO• + NO (14)
HONO2 T HO• + NO2 (15)
OH• + NH3 T NH2• + H2O (16)
NO2 + M T NO + M + O• (17)
NH2• + NO T N2 + H2O (18)
NH2• + NO2 T N2O + H2O (19)
homolysis has been observed in NH4NO3 melt decom-
position at temperatures of less than 350 °C (Brower et
al., 1989). The HO• produced from reaction (16) ab-
stracts a hydrogen from ammonia to make water and
NH2• (reaction (13)), which then quickly reacts with
either NO2 or NO to make N2O or N2 (Kurusawa and
Lesclaux, 1979; Miller and Bowman, 1989). H2O2,
present in some experiments, may also provide a source
of OH• radicals for reaction (16). Because H2O2 did not
significantly affect observed global rates, reaction (16)
does not appear to be a rate-limiting reaction step.
NO2 and NO have an equilibrium shown by reaction
(18). At reaction temperatures similar to those used in
this work (377-427 °C), calculations have shown NO
to be the favored NOx equilibrium species at low
pressures (∼2 bar) in even in the presence of oxygen
(Odenbrand, 1986). Elevated pressures, as used in this
research, would only shift the equilibrium in eq 15
further to the right. The favorability of NO as the
predominant NOx species partially explains the high N2/
N2O selectivities observed in this work. This results
in reaction (18), rather than reaction (19), being the
primary NH2• removal path. Increased N2O formation
for HNO3/NH3 and NaNO3/NH4Cl reactions may be
attributed to higher equilibrium values of NO2 relative
to NO (via reaction (17)) at lower reaction temperatures,
resulting in the increased importance of reaction (19).
A problem evident in reactions (9)-(16) is that this
mechanism results in a stoichiometry of 1 mol NH3
reacted/mol of NOx- reacted. Experimentally, this ratio
was observed between 1.08 and 1.22 for MNO3/NH3
reactions and was even greater for HNO3/NH3 and
NaNO3/NH4Cl reactions. That is, experiments produc-
ing the highest N2/N2O selectivities resulted in stoichi-
ometries nearest to 1. In order to account for this excess
ammonia disappearance, species such as HNO (reac-
tions (9) and (10)) need to be considered. The result of
reactions (9) and (10) is that two initial NH3 molecules
react through a series of elementary steps to form a final
product, without the consumption of an NOx- species.
This may account for experimentally observed reaction
stoichiometries. In order for reactions (9) and (10) to
occur, NH• must also be formed; this can occur through
reaction (8), or perhaps through reaction of NH2• with
OH•.
The significantly reduced rate of alkali nitrate/am-
monia reactions relative to HNO3/NH3 and NaNO3/NH4-
Ind. Eng. Chem. Res., Vol. 36, No. 7, 1997 2555
Cl reactions is due to the substitution reaction (reaction
(12)), which is suggested here to be the rate-limiting step
for alkali nitrate studies. When this substitution reac-
tion occurs quickly (NH4Cl/NaNO3) or is not required
to occur (HNO3/NH3), the rate-limiting step is proposed
to be the homolysis of nitric and nitrous acid. Nitric
acid homolysis was also determined to be a rate-limiting
step in the free-radical decomposition of NH4NO3 melts
(Brower et al., 1989).
The reaction mechanism described here demonstrates
why nitrate is a better oxidizing agent for ammonia than
oxygen in supercritical water. Oxygen oxidation of
ammonia both in the gas phase and in supercritical
water proceeds primarily through successive hydrogen
abstractions of NH3 to form NO, which can react with
NH• and NH2• species to form N2 and N2O (Webley and
Tester, 1991; Miller and Bowman, 1989). The succes-
sive hydrogen abstractions from ammonia to eventually
make NO require temperatures higher than those
reported in this research. Moreover, the formation of
HNO species through reaction (9) is not possible due to
the absence of NO2. Conversely, NH3/MNO3 reactions
require only one hydrogen abstraction from ammonia,
which is energetically possible at temperatures below
500 °C and <1 min time scales. This is due to the fact
that NO and NO2 are produced by energetically favor-
able hydrolysis-homolysis rather than hydrogen ab-
straction reactions. The mechanism also explains why
nitric acid is utilized as a rate enhancer in SCWO
applications (Bouhris et al., 1994): the homolysis of
nitric acid forms OH• at lower temperatures and at
shorter time scales than O2/H2O reactions. Thus, free-
radical pools which can both promote O2 conversion into
useful radicals or react directly with oxidizable species
are established at lower reaction temperatures, and
with substantially reduced induction times.
It is evident from the suggested mechanism why it is
possible for NO and NO2 to be observed in SCWO
effluents. Upon reaction quenching, these species only
convert back to their original ionic state by the equi-
libria shown in reactions (11) and (12) or by reaction in
slow equilibrium steps with water. The equilibria with
water proceed through N2O4 and N2O3 intermediates
and are generally too slow to be significant. Thus, if
quenching radicals (i.e., OH•) have been depleted by
other paths, such as corrosion (reaction (20)) or reaction
with organic matter, it is possible that NO and NO2 will
appear in gaseous effluents.
2HONO2 + Cr f H2CrO4 + 2NO (20)
In nitrate decomposition studies and solubility studies
(Dell’Orco, 1994), the appearance of NO and NO2 was
linked to reactor corrosion, as implied by reaction (20).
Specifically, Cr and Mo were selectively leached from
the alloy C276 and 625 surfaces, in proportion to the
amount of NO3- decomposed. This, in part, explains
the difference in reaction rates observed in Figure 3;
the unpassivated reactor (reactor B) undergoes reactor
corrosion, which allows reaction (20) to proceed in
parallel with the primary reaction mechanism. As NHx/
NOx reactions are known to be catalyzed by Cr and Fe
oxides (Baurle et al., 1978), it is also quite possible that
MNOx/NH3 reactions observed here happen to a large
degree at the reactor wall. Because most SCWO ap-
plications operate under a high excess of oxygen (and
OH• radicals at elevated temperature conditions), the
chances for NO and NO2 to persist in gaseous effluents
are generally low.
2556 Ind. Eng. Chem. Res., Vol. 36, No. 7, 1997
Elementary pathways presented above are somewhat
simplified; not all possible radical species are specifically
considered. For example, OH• and O• react in the
presence of water, forming many additional free radicals
(i.e., HO2•). In addition, there are many other possible
reaction paths for the species presented. Nonetheless,
the suggested elementary steps qualitatively explain
observed product selectivities and observed reaction
rates in a manner consistent with previous gas-phase
studies.
Conclusions
These experiments demonstrated the ability to con-
vert nitrates, nitrites, and ammonia to nitrogen gas and
nitrous oxide by reaction at supercritical water condi-
tions. Arrhenius parameters and stoichiometric coef-
ficients were determined for several sets of reactants:
NaNO3/NH3, LiNO3/NH3, and NaNO3/NH4Cl. In addi-
tion, HNO3/NH3 and NaNO2/NH3 reactions were inves-
tigated in order to elucidate elementary kinetic steps.
Based on observations of reaction product trends and
comparison with reactions studied in the literature, a
set of global reactions was proposed for the system. The
proposed reaction scheme involved the formation of NO
and NO2 through hydrolysis and homolysis pathways;
these species reacted with NH2•, formed by hydrogen
abstraction from ammonia, to produce the observed
reaction products N2 and N2O.
It was determined that nitric oxide can be produced
when nitrates and nitrites are present without excess
oxygen. This contradicts previous assertions that NO
cannot be formed under supercritical water conditions.
Although prompt and thermal NO mechanisms are not
likely, fuel NO mechanisms can occur. It was also
determined, however, that NO production was not
observed in oxidizing environments.
This reaction is suggested as a method for the
reduction of high ammonia and/or nitrate concentrations
in wastewaters. Such a reaction could be employed to
remove ammonia after organic destruction is achieved
in a supercritical water reactor. The destruction of
organic matter must be achieved prior to the initiation
of ammonia destruction, as nitrate will also participate
in organic oxidation reactions. The reaction could also
be employed to remove nitrates from waste streams,
such as in the hydrothermal treatment of explosives and
propellants.
Acknowledgment
P.C.D. acknowledges the Environmental Restoration
and Waste Management Fellowship Program, admin-
istered by the Oak Ridge Institute for Science Education
for the U.S. Department of Energy. This project was a
cooperative effort between the supercritical water oxida-
tion laboratories at The University of Texas at Austin
and Los Alamos National Laboratory. The authors
thank Rhonda McInroy, Hilary Eaton, Dale Counce, and
Pat Trujillo for their technical support.
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Received for review September 27, 1996
Revised manuscript received March 10, 1997
Accepted March 19, 1997X
IE9605894
X Abstract published in Advance ACS Abstracts, May 1,
1997.