WASTE MANAGEMENT, Vol. 13, pp.361-377, 1993 0956-053X/93 $6.00 + .

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Printed in the U.S.A. All rights reserved. Copyright 1993 Pergamon Press Ltd.

ORIGINAL CONTRIBUTION

A D V A N C E D C H E M I C A L O X I D A T I O N : ITS P R E S E N T
R O L E A N D P O T E N T I A L F U T U R E IN H A Z A R D O U S
WASTE TREATMENT

C. P. Huang* Chengdi Dong, and Zhonghung Tang

Department of Civil Engineering, Universityof Delaware, Newark, DE 19716

ABSTRACT.Chemical oxidation reactions involving hydroxyl radicals have been extremely effective in the destruction of organic
pollutants. These advanced chemical oxidation processes (AOP) generally use a combination of oxidation agents (such as H202 or
O3), irradiation (such as uv or ultrasound), and catalysts (such as metal ions or photocatalysts) as a means to generate hydroxyl radi-
cal. The hydroxyl radical is one of the strongest inorganic oxidants next to elemental fluorine. The hydroxyl radical is stable over a
wide pH range, up to pH 10. The hydroxyl radical reacts with organic by three major mechanisms: hydroxy addition, hydrogen ab-
straction, and electron transfer. Several AOP systems are reviewed first. The merits as well as limitations of these systems are dis-
cussed. The potential of AOP for future hazardous wastes treatment is then demonstrated by four AOP systems, H202/Fe 2+,
TiO2/uv/O2, H2Oz/uv/O2, and TiO2/uv/H202, exemplified by chlorophenols. A reaction scheme can be generalized for the oxida-
tion of halogenated phenols by advanced chemical oxidation, specifically, ones involving hydroxyl radicals. Upon the attack of a
halogenated phenol, ArXnOH, by a hydroxyl radical, OH., a free radical, Ar(OH)2Xn., is formed. This free radical can undergo two
reaction paths: (l)hydroxylation without dechlorination (Type A) and (2) hydroxylation with deehlorination (Type B). It has been
observed that mono-halogenated phenols (n=l) only follow Type A path; dichlorophenols (n = 2 ) and trichlorophenols (n = 3 ) can
have both Type A and Type B reaction pathways; tetrahalogenated (n = 4) and pentahalogenated (n = 5) phenols only follow Type B
reaction pathway.

INTRODUCTION for the treatment o f complex wastes with a good degree

Oxidative destruction o f chemicals provides ultimate so-
lutions for the treatment o f hazardous wastes. Oxidative
destruction o f organic pollutants can be accomplished by
various means: biological, chemical and physical (ther-
mal). While there are differences in the mode of opera-
tion, the basic principle o f energy dissipation process,
intrinsic to oxidative destruction o f organic matters, is
largely the same among these systems.
Traditionally, attention received by biological oxida-
tion processes far exceeds that o f the chemical and physi-
cal oxidation systems, due in part to its cost effectiveness
and versatility in handling a wide variety o f organic pol-
lutants. Since its introduction in the 1900s, several bio-
logical treatment systems have evolved and been adopted
*To whom correspondence may be addressed.
Acknowledgements-This work is supported by a grant (No.
R815081) from the Exploratory Research Program, US
Environmental Protection Agency. Contents of this publication
do not necessarily reflect the views or policy of the funding
agency. Any conclusions or mention of chemicals and
processes are made by the authors only and should not be
implied as their endorsement by the funding agency.
o f success. However, the presence o f toxic chemicals in
the waste streams can cause unwanted operational diffi-
culties. Much has been reported on the difficulties in the
operation of biological oxidation systems in treating mu-
nicipal wastewater let alone hazardous wastes. These
difficulties are intrinsic to the process in that it is sensi-
tive to ambient conditions as well as waste charac-
teristics. Moreover, the generally long retention time and
start-up time of the biological oxidation process make it
unattractive for the treatment of toxic and refractory or-
ganic pollutants.
Thermal destruction of specific chemicals at extreme
temperature, i.e. incineration, has been successfully ap-
plied to the treatment o f solid waste, sludge, and gases.
While simple in principle, thermal systems have suffered
from many difficulties in operations. Additionally, ther-
mal processes are rather limited in treating aqueous
wastes as considerable energy is required to heat and va-
porize the water mass before specific organic pollutants
are destroyed at relatively elevated temperatures (usually
greater than 850°C).
To overcome this difficulty, a thermal catalytic oxida-
tion process, wet-air oxidation, has been developed. In

361
362
wet-air oxidation, organic compounds are decomposed
with atmosphere air or pure oxygen at 150 to 370°C and
10 to 220 bar pressure. Organic substrates are first car-
bonized(l). The dissolved oxygen reacts catalytically on
the surface of the carbon center so as to yield hydrogen
peroxide which then decomposes to form oxygen and hy-
droxyl radicals. These radicals then react with the carbon
to yield carbon dioxide (autocatalytic oxidation). Sub-
strates such as acetic acid, which does not carbonize be-
low 300°C, will be degraded by wet-air oxidation.
Above 300°C, acetic acid is reported to be oxidized very
slowly. Substrates such as sugars, which are easy to car-
bonize, will be completely degraded.
Several bench scale studies have been conducted to
determine the susceptibility of specific compounds to
wet-air oxidation. The following compounds can be de-
stroyed by wet-air oxidation (2,3): aliphatic compounds
including those with multiple halogen atoms can be oxi-
dized; residual oxygenated compounds of low molecule
weight such as alcohols, aldehydes, ketones, and carbox-
ylic acids might be formed; aromatic hydrocarbons such
as toluene and pyrene are easily oxidized; halogenated
aromatics with at least one nonhalogen functional groups
of electron donating nature present on the ring can be de-
stroyed. These substitutes include hydroxyl, amino, or
methyl group. Halogenated aromatics such as 1,2-diben-
zene and PCBs are resistant to degradation unless cata-
lysts are employed.
A specific catalyst system based on acidic solutions of
bromide, nitrate, and manganese ions has been developed
(4). Katox process is a catalytic oxidation technology
employing special contact media. The organics are
bathed in oxygen-containing water and oxidized at the
surface (in particular in the internal surface) of the cata-
lyst. Copper ions have a significant catalytic effect.
Mn(V) catalysts and activated chromium compounds
have also been investigated (5). The major problems as-
sociated with these processes are the separation of the
catalysts.
The wet-air oxidation process has greatly improved
the efficiency of the incineration process as well as the
ease of operation. However, due to the severity of the re-
action, construction materials for the system become the
major cost factor. Due mainly to its high cost, wet-air
oxidation process remains an operation of the prelimi-
nary treatment nature without total destruction of the or-
ganic pollutants.
Moreover, the wet-air oxidation process is limited by
the solubility of oxygen in water. This gas (02) to liquid
(H20) mass limitation can be eliminated at supercritical
water temperatures. In the supercritical region, water ex-
hibits a density of 0.1 to 0.5 g/cm 3 and a dielectric con-
stant of 3 to 10. Most importantly, it has almost 100%
solubility of organics, because thermal energy contained
in the water molecule reduces hydrogen bonding. Super-
critical water becomes an excellent solvent for nonpolar
C.P. HUANG, C. DONG, AND Z. TANG
organics. The surface tension of the water is zero, which
allows oxygen to penetrate even the smallest pores and
oxidize any organic materials present. When tempera-
tures reach 500°C, near total insolubility of inorganics
take place. The major advantages of supercritical water
oxidation (SCWO) are: (1) enhanced solubility of oxy-
gen and air in water and elimination of the mass transfer
between two phases; (2) rapid oxidation of organics in
short residence time; (3) complete oxidation of organics;
(4) potential removal of inorganic constituents as solids
or brine; (5) recovery of the heat of combustion as high
temperature process heat or power. Thus, this process
has been shown as a viable technology for the thermal
oxidation of hazardous wastes (6). It has been demon-
strated that SCWO process is promising in oxidizing
concentrated hazardous wastes. However, like the wet-air
process, the severity of the system makes it unattractive
for the treatment of dilute wastes. In his recent study,
Thornton reported that high molecular weight products
such as dibenzofuran and dibenzo-p-dioxin may be pro-
duced in the SCWO treatment of phenol and that chlorin-
ated dibenzofuran and dibenzo-p-dioxin may be
produced (7).
In light of the increasing concern over the contamina-
tion of the environment by hazardous chemicals, there is
great need to develop innovative technologies for the
safe destruction of toxic pollutants. The processes must
be cost effective, easy to operate, and capable of achiev-
ing a total or near-total mineralization. This has
prompted researchers to investigate innovative chemical
oxidation technologies. This report gives an overview of
recent developments in advanced oxidation processes,
with an emphasis on the chemical systems. Four AOP
systems are illustrated using chlorophenols.
ADVANCED C H E M I C A L OXIDATION SYSTEMS
The oxidation potential of an oxidant is related to its oxi-
dation-reduction potential, E°. An oxidant with a high E°
value is a strong oxidation agent. Table 1 lists the E°
value for a host of oxidation agents against that of mo-
lecular 02 (8). All chemical species shown in Table 1 are
stronger oxidation agents than 02, although it must be
mentioned that kinetic factors often outweigh thermody-
namic properties in controlling the oxidation reactions.
Nevertheless, a stronger oxidant will generally exhibit a
faster oxidation reaction. Based on this simple premise,
F2 is the strongest among the list. However, F2, a halo-
gen, may produce halogenated compounds during the
oxidation process. Among these oxidants, 03 has re-
ceived the greatest attention. However, the mechanism
of ozonation was not fully understood until the late sev-
enties, when Hoigne and coworkers (9,10) first reported
the mechanism of ozonation, although over one hundred
public water treatment facilities were built in Europe dur-
ADVANCED CHEMICAL OXIDATION 363

TABLE 1 molecular 03. The rate constants are usually on the order
Oxidation-Reduction Potentials of Oxidation Agents (8) of 10s-10 l° (Mlsec z) (13). Chemically, hydroxyl radi-
Redox Reaction Eo (NHE) cals are much less selective than molecular 03.
volt, 25°C The concept of"advanced oxidation processes" (AOP)
F2 + 2e = 2F- 2.87 was established by Glaze et al. (14,15). AOP was de-
OH + H+ + e = H20 2.33
fined as the oxidation processes which generate hydroxyl
03 + 2H + 2e = 0 2 + H 2 0 2.07
radicals in sufficient quantity to affect water treatment
H202 + 2H ÷ + 2e = H302+ 1.76
(14,15). Many systems are qualified under this broad
MnO4- + 4 H + + 3e = MnO2 + 2 H 2 0 1.68
definition of AOP. Most of these systems use a combi-
HCIO2 + 3 H + 4e = C l + 2 H 2 0 1.57
nation of strong oxidants, e.g. 03 and H202, catalysts, e.g.
MnO4- + 8H+ + 5e = Mn 2+ + 4 H 2 0 1.49
HOCI + H ÷ + 2e = C I + H 2 0 1.49
transition metal ions or photocatalyst, and irradiation,
C12 + 2e = 2CI- 1.36
e.g. ultraviolet (uv), ultrasound (us), or electron beam
H B r O + H ÷ + 2e = B r + H 2 0 1.33 (eb). Table 2 lists typica! AOP systems currently been
03 + H 2 0 + 2e = 0 2 + 2 O H 1.24 reported in the literature.
CIO2(g) + e = CIO2- 1.15
Br2 + 2e = 2 B r 1.07
HIO + H ÷ + 2e = I + H 2 0 0.99 Hydroxyl Radical
CIO2(aq) + e = CIO2- 0.95 The hydroxyl radical is one of the most reactive free radi-
C I O + 2 H 2 0 + 2e = C I + 2OH- 0.90 cals and one of the strongest oxidants (16):
H202 + 2H + + 2e = 2 H 2 0 0.87
CIO 2 + 2 H 2 0 + 4e = C I + 4OH- 0.78
BrO" + H 2 0 + 2e = Br" + 4 O H 0.70
•OH + H + + e" = H20; E° = 2.33 v [1]
12 + 2e = 2 1 0.54
13 + 3e = 3 1 0.53
I O + H 2 0 + 2e = I- + 2 O H 0.49
Thus, in acidic conditions, the hydroxyl radical will have
ing the early seventies (11). It was thought that molecu- higher oxidation potential. In basic solution, i.e. pH 11,
lar ozone was the major oxidation species. Hoigne et al. the hydroxyl radical and H202 react to give an oxide and
(9,10) proposed that 03 can have two reaction modes: di- a peroxide ion (17). Irradiation of water generates OH
rect ozonation reactions and free radical (such as hy- relatively independent of pH until pH 10. The reaction
droxyl radical) decomposition reactions (9,10). The of OH with organic compounds can be classified into
direct 03 reaction involves molecular 03 which is highly three mechanisms: hydroxy addition, hydrogen abstrac-
selective and produces a relatively slow reaction. The tion, and electron transfer. Organic compounds contain-
typical rate constants are on the order of 1-103 (M-1 sec-1). ing aromatic systems or carbon-carbon multiple bonds
As a result, there is no complete mineralization and a undergo additional reaction with OH due to the rich n-
variety of intermediates could be formed (12). The hy- electron cloud on the aromatic ring. For example:
droxyl radical formed during the ozone decomposition
reacts much more rapidly with organic compounds than
OH. + C6H6 ~ .C6H6OH [2]
TABLE 2
List of Typical AOP Systems
H o m o g e n e o u s System
Hydrogen abstraction is the usual reaction with unsatu-
with irradiation
rated organic compounds:
O3/ultraviolet (uv)
HzOz/uv
electronbeam
ultrasound(us) OH. + CH3COH3 -+ CH2COCH3 + H20 [3]
H202/us
uv/us
without irradiation
O3/[t202 Electron transfer is usually found in reactions between
O3/OH hydroxyl radical and inorganic ions. For example:
HEO2/Fe2+ (Fenton's)
Heterogeneous Systems
with irradiation Fe 2+ + OH. --~ OH- + Fe 3+ [4]
TiO2/O2/ultraviolet
TiO2/HEOE/ultraviolet
without irradiation
electro-Fenton This is important to the Fenton's reagent reaction. Since
364
OH has high and indiscriminate reactivity, it can react
with almost all types of organics, such as ethylenic, lipid,
aromatic, and aliphatic, and inorganics, such as anions
and cations. The addition of OH to benzene is found to
be very fast. The process produces the cyclohexadienyl
radical with an unpaired electron. The dienyl radical dis-
proportionates to a complex mixture of products includ-
ing phenol, cyclohexadienes, hydrocyclohexadienes,
biphenyl, and hydroxylated biphenols r the ring is
opened, oxidation by OH can result in the final products
such as CO2, H20 through a serial reaction:
HOOC-C4H~COOH+OH. HOOC-COOH
+H2OCO2+H20 [Sl
The above reaction involves both hydroxy addition and
hydrogen abstraction for the mineralization of benzene.
The hydroxyl radical can be efficiently generated
from H202 and catalysts such as transition metal ions
without uv irradiation. One such system is Fenton's re-
agent, in which H202 is decomposed into a hydroxyl
radical and hydroxide ion in the presence of Fe 2+ ions.
Fenton's reagent was discovered by Fenton in 1894
(18,19). It was not accepted widely until 50 years later in
organic chemistry, where selectivity is emphasized, be-
cause of the unselective oxidation property of hydroxyl
radicals. The use of Fenton's reagent to oxidize toxic or-
ganics only began at the late sixties. The major advan-
tages of Fenton's reagent as a hazardous waste treatment
technology are: (1) there are no chlorinated organic
compounds formed during the oxidation processes as in
chlorination or ozonation; (2) both iron and H202 are
cheap and nontoxic; (3) there is no mass transfer limita-
tion due to its homogeneous catalytic nature; (4) there is
no light involved as catalyst so that the reactor design is
much easier than those uv light systems.
Due to these advantages, Fenton's reagent has been
widely applied in the treatment of hazardous organics.
The direct oxidation of phenolic wastes has been studied
by Eisenhauer (20). Bishop et al. (21) have investigated
the feasibility of Fenton's oxidation of refractory or-
ganics in municipal waste water. Recently, Fenton's oxi-
dation has also been used as the pretreatment of
nonbiodegradable industrial wastes to render the organics
more biodegradable for both aerobic processes (22) and
anaerobic processes (23). Finally, Fenton's reagent has
been attempted to oxidize pentachlorophenol in a simpli-
fied soil system (24) and polychlorinated biphenyls
(PCBs) and chlorobenzene (25, 26).
Homogeneous Systems with Irradiation
OJuv System. Photolysis of aqueous ozone produces hy-
C.P. HUANG, C. DONG, AND Z. TANG
drogen peroxide. The deprotonated form of hydrogen
peroxide (HO2-) can react with ozone to produce ozonide
(O3-), then hydroxyl radical (OH) (27). These species
initiate the chain reaction. As a result, compounds nor-
mally refractory to ozonation alone are rapidly converted
to CO2 and water. Additionally, poly-chlorinated
biphenyl (PCBs), which are very stable to ozone, are de-
stroyed rapidly to less than 0.1 ppm by the combination
03 and uv method. This process was initially developed
by Houston Research Inc. and has been specified as Best
Practicable Control Technology Currently Available for
the treatment of PCBs by the U. S. EPA.
H202/uv system. UV photolysis of H202 generates OH':
H202 + hv = 2'OH [6]
Sundstrom et al. (28,29,30) have studied the destruc-
tion of individual aliphatic and aromatic compounds by
uv catalyzed oxidation with hydrogen peroxide. The re-
sults demonstrated that the system can destroy a wide va-
riety of hazardous compounds present in water at low
concentration levels. For chlorinated aliphatic com-
pounds, the organic chlorine was converted to chloride
ion, indicating that the chlorinated structures were effec-
tively destroyed. In the case of aromatic compounds,
many intermediates were formed which could be elimi-
nated by extending the treatment time. It was found that
benzene and trichloroethylene have similar reaction rates,
with trichloroethylene (TCE) having a slightly faster rate
than benzene. The oxidation rate increases with increas-
ing hydrogen peroxide and decreases with increasing or-
ganic concentration. The rate constant for hydroxyl
radical addition to benzene ring is 7.8109 M-lsec~. The
addition of hydroxyl radical to TCE is 4.O109 Mlsec ~
(31). Thus, hydroxyl radical addition to benzene is about
twice as fast as that to TCE. The TCE oxidation rate
should be expected to be reduced by half at the constant
organic carbon concentration. The decomposition of
H202 by uv has much lower efficient than that of ozone
due to the much lower extinction coefficient of H202 by
uv photolysis.
Processes such as HzO2/uv, O3/uv, and H202/O3/uv
have been shown to be effective for groundwater decon-
tamination and soil remediation. Because the activation
energy between active radicals, such as hydroxyl radicals
and organics is close to zero, oxidation occurs rapidly.
However, these systems are not without disadvantages.
First, when the processes involve ozone, mass transfer
between gaseous ozone and aqueous solution becomes
the major limiting factor (31). Second, although H202
can eliminate the mass transfer limitation, the decompo-
sition of H202 by uv has been proved inefficient. This is
ADVANCED CHEMICAL OXIDATION
because the extinction coefficient of H202 at 254 nm is
only 19.6 (M~cm ~) (33) compared with about 3,000 ( M
~sec~) for ozone (34). Third, the uv penetration depth is
still difficult to match the reactor size. If a precise match
could not be satisfied, the reaction rate could be reduced
due to the area where uv is not intensive enough to accel-
erate the decomposition of oxidants. At the same time, a
significant amount of uv could be absorbed by water
molecules where the light intensity is higher than neces-
sary and the energy could be wasted in the form of heat.
Since the reaction rate is directly proportional to light in-
tensity, turbidity and color will also significantly reduce
the efficiency of the systems.
Electron-beam (eb) system. Irradiation of water with
high-energy electrons results in the formation of the reac-
tive free radicals e- (aq.), H', and "OH. These radicals are
formed through the excited state molecules such as
H20*, H20 +, and e'. When the excited molecules and
electrons interact and transfer their energy to other mole-
cules, several secondary reactive species are formed.
The relative efficiencies (G) are defined as the number of
radicals, excited states, or other products formed or lost
in a system absorbing 100 eV of energy. According to
their production abundance, the following order exists:
'OH (2.7) = H30 + (2.7) > e" (2.6) > H202 (0.71)
> H' (0.55) I7]
The e and H are the reducing species. O f these radicals,
e" and O H make up 90% of the reactive species and are
the major radicals to render organic destruction. H202 is
also an important species in oxidizing toxic organics, al-
though it is not as abundant as the other two species. The
interaction between aqueous electrons and specific or-
ganics and inorganics has been extensively studied (35).
The e (aq.) is a powerful reducing agent with a potential
E ° of 2.77 v. as:
e" + H + = 1/2H2 [8]
The aqueous electrons can result in the dehaiogenation of
organohalogen compounds. Further reaction of the or-
ganic radicals leads to the complete destruction of the
compounds. Hydrogen radicals can undergo hydrogen
addition or hydrogen abstraction. These reactions are
considered as the minor ones due to the following ex-
tremely fast reaction between the hydrogen radical and
oxygen:
365
H + 02 = HO2; k = 2.11010 ( M l s e c 1) [9]
Ultrasound (us) system. Ultrasound (us) can affect or-
ganic oxidation through three mechanisms: nucleation,
growth, and cavitation. Cavitation which is created by
the collapse of a gas- or vapor-filled bubble in a body of
liquid is the most important phenomenon. The instanta-
neous pressure and temperature at the center of the col-
lapsing bubble has been estimated to be about 75,000 psi
and 13,000°F respectively (36). Due to this high local
pressure and temperature, it has been recognized that
cavitation can enhance the rate of chemical reactions sig-
nificantly. Next, solvent will be compressed and re-
fracted by the rapid movement of fluids caused by a
variation of sonic pressure. Then, a large amount of en-
ergy will be put into a small volume with little heating.
The phenomenon is called microstreaming.
US radiation is known to decompose water vapor
molecules in the bubbles into free radicals, such as hy-
droxyl radicals, hydrogen radicals, and hydroperoxyl
radicals (37,38). Prasad et al. studied the liberation of a
chloride ion in a saturated aqueous solution of chloroben-
zene and m-dichlorobenzene by ultrasound (US) (40).
More than 90% dechlorination of chlorobenzene and m-
dichlorobenzene occurs in 60 and 100 minutes, respec-
tively (40). It is believed that the hydroxyl radical
formed by the reaction between H and O2 is responsible
for the oxidation of chlorobenzene and m-dichloroben-
zene in water. Although hydrogen peroxide can be pro-
duced by application of US alone to a diluted aqueous
solution, the amount may be too small to be significant.
Hydrogen peroxide can be added to this process as an in-
itiator to increase free radical concentration in the solu-
tion.
H202/us system. Chen et al. (41) investigated the oxida-
tion of chloroform by us/H202 process. The optimal mo-
lar ratios of H202 to CHCI3 are between 30 and 50.
When the ratio of H202 to CHCI3 is 50:1, the best per-
centage removal (94%) was achieved. The overall reac-
tion can be presented as follows:
CHCI3 + 2'OH ~ CO2 + 3Cl" + 3H + [10]
The reaction is first order with a rate constant of 0.0177
(l/min). Since the concentration of hydroxyl radicals
generated is much higher than that of chloroform, the or-
der of reaction with respect to the free radical is zero.
However, the optimal ratio of 50:1 for H202 to chloro-
form is quite high for practical application.
It appears that an excess amount of H202 would
366 C. P. HUANG, C. DONG, AND Z. TANG

slightly retard the decomposition of chloroform. That The hydroperoxide ion reacts with ozone to produce the
excess H202 can retard the oxidation reaction has been ozonide ion 03- and hydroperoxide radical HO2.
reported by Ho et al. in the study of photooxidation of
2,4-dinitrotoluene in the presence of H202 (42). This is
because H202 itself is also a hydroxyl radical scavenger. HO2- + 03 ---> 03- + HO2;
k = 2.8'106 M'lsec -1 [121

US/uv system. Ultrasound (us) can be combined with uv

to destroy toxic organics. The chemical consequence of These products can form OH radicals through the fol-
photolysis and sonolysis of a simple haloalkane is the lowing initiation steps:
cleavage of the carbon-halogen bond in liberating halo-
gen ions (36). The principal products of water under
sonolysis are H202, H2, OH, and "H. When sonochemi- HO2 = H + + 02-; Ka = 1.6"10-5 M [13]
cal decomposition of aqueous CC14 solution occurs, the
radicals such as "OH and .H react with CC14 and form
C12, CO2, HC1, C2C16, and HOC! (39, 43, 44).
GC/MS analysis indicates that olefins such as 02- + 03 ~ 03- + 02; k = 1.6'109 M'lsec 1 [14]
CH2=CHCI and CHCI=CHCI were formed during the de-
composition of CC13CH3. In an oxidative environment,
e.g. in the presence of H202, olefins are readily oxidized
O3- + H + ---> HO3; k = 5.2"1010 M'lsec -1 [15]
to epoxides. Both olefins and epoxides are reactive
monomers which polymerize to polymers in the presence
of O H and CIO radicals. The pH of photosonolysis is
very acidic in the range of 1. However, less acidic solu- HO3 ~ .OH + 02; k = 1.1"105sec"1 [16]
tions of pH 3 were found under sonolysis and photolysis
separately.
The order of CCI3CH3 disappearance and CI appear- Once the hydroxyl radical is formed, the following
ance is the following for oxidation of immiscible propagation steps generate hydroxyl radicals by autocata-
CCI3CH3 in water: Photosonolysis ---> Photolysis --->
lytic mechanism:
Sonolysis.
For a miscible sample of CCI3CH3 in water, the effi-
ciency for different processes follows the different order:
03 + 'HO ---> 02 + "HO2; [17]
Photosonolysis --->Sonolysis --->Photolysis.
The aqueous solutions exhibit lower vapor pressure
than the higher concentration of the immiscible pair. The
lower vapor pressure of the liquid causes higher cavita- 03- + "HO2 ~ 202 + H O [181
tion bubble collapse intensity. Since the temperature and
the pressure can reach to thousands of Kelvins and At-
mospheres, respectively, respectively, the increasing The chain mechanism generates hydroxyl radicals by
cavitation intensity is considered as the most important consuming H202 and 03. It is terminated by recombina-
factor to enhance the dissociation of the covalent bonds tion of different radicals. Hydroxyl radicals abstract a
of the organics and their extent of decomposition(36,45). hydrogen atom from saturated hydrocarbon compounds
or add to unsaturated organics to form an organic carbon-
centered radical in less than 10 -6 second. The carbon-
Homogeneous Systems without Irradiation centered radical reacts quickly with oxygen to yield a
peroxyl radical when oxygen is present. This radical can
decompose unimolecularly to produce a superoxide ion
(O2-, the deprotonated form of the HOz radical). Pre-
OYH202 system. Buhler et al. (27), Form et al. (46), and dominant hydrogen peroxide and minor superoxide can
Sehested et al. (47) have reported that H202 can initiate also be formed if the carbon-centered radical decomposes
the decomposition of 03 by single electron transfer bimolecularly. The latter process is considered to take
wherein the initiating species is the hydroperoxide ion place through a tetroxide structure. Superoxide reacts
HO2-: quickly with ozone, yielding ozonide and continuing the
chain reaction. When ozone is present, this reaction is
much faster than superoxide disproportionate to hydro-
H202 = HO2- + H+; Ka = 1.610 -12 [11] gen peroxide.
ADVANCED CHEMICAL OXIDATION
03/01-1- system. At neutral to high pH, ozone decom-
poses into hydroxyl radicals through the following initia-
tion steps (9, 48):
03 + OH" --~ -O2- + 02
03 + H20 --~ 2"HO + 0 2
The above initial steps result in the hydroxyl radicals
as the major oxidation species. This is the reason that al-
kaline oxidation rates by ozone are several orders of
magnitude higher than those in acidic media (49). Sev-
eral investigators classified the ozonation at alkaline con-
dition as advanced oxidation process (50). The catalytic
effect of a hydroxide ion has been recognized for a long
time in the ozonation of organic pollutants. Niegowski
reported pH of 11.8 as the optimal value (51). Jones in-
dicated that phenol oxidation proceeds most efficiently at
a pH of 11.4(52).
H202/Fe2+ (Fenton's Reagen 0 system. The powerful
oxidizing properties of a mixture of H202 and Fe 2+ salts
was first observed by Fenton at the end of the last cen-
tury (18,19). Forty years later, Haber and Weiss estab-
lished the oxidizing species as hydroxyl radical (53). In
recent years, the hydroxyl radical has been observed di-
rectly by electron spin resonance spectroscopy (30).
From much literature, organic compounds of nearly all
types could be oxidized by this Fenton's reagent.
Fenton's reaction is given by Eq. [21] (54,55):
Fe 2+ + H202 = Fe 3+ + O H + O H
The products of the reaction are ferric ion, the hydroxyl
radical (OH), and the hydroxide ion. The rate is first or-
der with rate constant ofkj = 76 (Mlsec "~) (54,55).
In the absenceof added substrate, the hydroxylradical will oxidize a
second moleculeof ferrous ion, as shown in Eq. [22]:
Fe 2+ + O H = Fe 3+ + OH"
The rate constant is k2 = 3108 ( M l s e c q) (54,55). The ex-
pected stoichiometry of the reaction is given in Eq. [23].
Protons have been added to show formation of water:
367
2Fe 2+ + H202 + 2H + = Fe 3+ + 2H20 [231
This equation indicates that Fenton's reaction is strongly
dependent on solution pH. In fact, only in acidic condi-
[19] tions, is O H the predominant reactive oxidant.
In the presence of organic compounds, organic oxida-
tion proceeds via addition of OH, or via hydrogen atom
abstraction. Eq. [24] is for O H addition:
[2Ol
-OH + R ~ .ROH --+ hydroxylated products [24]
Eq. [25] is for hydrogen atom abstraction:
•OH + R ~ 'R + H20 ~ oxidized products [25]
In both equations, the oxidation process is extremely
fast. The rate constants are as high as 107 - 10m (M-~sec1) (5).
Organic free radicals are formed as transient intermedi-
ates. The intermediate radicals are further oxidized by
Fe 3+, oxygen, H202, OH, or other intermediates or added
reagents to form a final, stable, oxidized product. The
following equations illustrate these processes:
Fe 3+ + R --~ Fe 2+ + products [26]
2'R -+ R-R (dimerization) [27]
Fe 2+ + R + H + --~ Fe 3+ + RH (reduction) [28]
[21]
Fenton's oxidations can be classified into two groups:
(1) chain reactions, in which only a small amount of re-
ducing agent is needed, and (2) non-chain reactions, in
which all the oxidation is effected by the hydroxyl radi-
cal and there is considerable loss of the hydroxyl radical
due to the following reaction:
Fe2++OH ~ (Fe-OH) 2+ [29]
[22]
The decomposition rate of hydrogen peroxide reaches
the maximum at a pH of 3.5. This phenomenon is attrib-
uted to the progressive hydrolysis of the ferric ion, which
provides a relative large catalytically active surface for
368
contact with the H202. The accelerator in H202 decom-
position will yield more free hydroxyl radicals.
If a small amount of F e E+ ion is needed, a chain reac-
tion occurs through regeneration of Fe E+of Eq. [6]. If all
the oxidation is effected by hydroxyl radical formed by
reaction 1, non-chain reactions take place. Since there
are extra Fe 2+ present, considerable loss of the hydroxyl
radical proceeds via equation 2.
As the pH is raised, there is some evolution of oxygen
due to the reactions:
HO-OH = HO-O" + H + [301
The reaction arises from the nature of H202, because
H202 is an extremely weak acid (ka = 1.55 x 10"12 at
20°C). Its hydroxyl groups generally behave like those
of alcohols (7). In the presence of Fe 3*, 02 is evolved
through the following steps:
Fe 3+ + H O - O ~ Fe 2+ + H O - O [31]
•HO-O ~ H+ + ( O - O f [321
Fe 3+ + ( O - O f ~ Fe 2+ + 02 [331
H202 + (.O-O)- ~ .HO + OH" + 02 [34]
Superoxide can be produced through the following re-
action:
O H + H202 ---) H20 + H O - O [351
Haber and Weiss (53) suggest that this reaction con-
tributed to the maintenance of a chain reaction sequence
under the acidic conditions of their study. Under neutral
pH, the sum of Eqs. [21] and [30] gives Eq. [33]. In this
superoxide-driven Fenton's reaction, iron functions as
the true catalyst as the result of the recycling mechanism
where iron has been canceled after summation of Eq.
[10] and [1].
Heterogeneous Systems with Irradiation
Photocatalytic oxidation. Semiconductors such as CdS,
CdSe, and Si have been used as solar cells for the genera-
C.P. HUANG, C. DONG, AND Z. TANG
tion of electricity from solar irradiation. Upon irradia-
tion, electrons are produced at the conduction band (cb)
and positive holes are formed in the valence band (vb)
(56). If the semiconductor is in an aqueous suspension,
the electrons, which are reducing agents, can migrate to
dark surfaces and react with oxidizing chemicals. The
positive holes, which are oxidizing agents, will remain at
the surface of the semiconductor. In the absence of oxi-
dizable substances such organic compounds, the positive
holes will react with the semiconductor and corrode the
solar cells (57). A coating of organic paint on the semi-
conductor is commonly applied to protect the solar cells
(56,57). The organic compound will consume the posi-
tive holes while being oxidized. Another way to harvest
the solar energy is with the production of hydrogen and
oxygen gases from water by semiconductor material irra-
diated with sunlight or an artificial light source (58). In
contrast to electricity generation, the solar energy is con-
verted into chemical energy, in the form of hydrogen.
Since the separation of hydrogen from the gas mixture is
difficult, researchers have tried to suppress the oxidation
of water by adding organic chemicals to water (58). The
following illustration shows that in the presence of or-
ganic chemicals, the positive holes will be used by the
organic compounds rather than water. In fact this concept
has been used as corrosion control of solar cells.
n2o
C02
Org~aies
Three kinds of semiconductors can be recognized: (1)
R-type, (2) O-type and (3) RO-type. The classification
is made on the bandgap position of the semiconductors
with respect to the water reduction (H+/H:) and the water
oxidation (OdH20) potentials. The O-type semiconduc-
tors, such as WO3, Fe203, and MoS2, have valance bands
located below the EMF of the water oxidation and can
oxidize water to oxygen. The R-type semiconductors,
such as CdTe, CdSe, and Si, have conduction band lo-
cated above the EMF of the water reduction and can
readily reduce water to hydrogen. The RO-type semi-
conductors, such as TiO2, CdS and SrTiO3, a combina-
tion of the above two types, can split water into O: and
H2. It must be noted that the presence of organic com-
pounds can greatly enhance the decomposition of water
by one to three orders of magnitude.
ADVANCED CHEMICAL OXIDATION 369

Studies have also shown that trace amounts of Pt and TABLE 3

RuO2 can drastically improve the production of hydrogen Photocatalytic Dissociation of
in an organic compound-water mixture (58). Apparently Organic-Water Mixture by TiO2-Pt.
the Pt enhances the rate of water reduction while the Organic Matter End-Product
RuO2 catalyzes further the oxidation of the organic mat- glucose CH3CHO; C2HsOH; (CH3)2CO; H2
ters. ethanol C2H6;CH3CHO; CH3COOH;H2
cellulose C2H6; C2H5OH; (CH3)2CO; H2
Kawai and Sakata (59,60,61) have demonstrated a
pyruvic acid 20H; H2
photocatalytic reaction with different media such as chlo- gylcine NH3; H2
rine and nitrogen compounds. The decomposition of polyethylene CO2; H2
some organic molecules and the production of hydrogen polyvinyl alcohol CO2; H2
gas occurred at the same time. Five percent platinum was polyvinyl chloride (PVC) CO2; HCI; H2
deposited photoelectrochemically on the surface of TiO2. proline CO2; NH3; H2
They concluded that the reaction can proceed at room stearic acid CO2; H2
potato CH3OH; (CH3)2CO; H2
temperature in a solution without showing any thermal
fatty oil C2H6; H2
effect. A commercial-grade titanium dioxide was pre- cherry wood C2H6; CH3OH; (CH3)zCO;H2
treated by rinsing with 1M HC104 and distilled water white dutch clover CH4; CH3OH; C2HsOH; NH3; H2
several times until the conductivity dropped to less than golden rod CH3OH; NH3; H2
10 !umho/cm. The titanium dioxide samples were centri- water hyacinth NH3; H2
fuged at 10,000 rpm for 30 minutes and then dried over- dead cockroach NH3; H2
night at 105°C and ground to a fine powder. In two human excrement NH3; CH3OH
teflon HF; CO2; H2
studies, Kawai and Sakada have some very interesting
trichlorbenzene HCI; CO2; H2
findings (59,61). They have studied the photocatalytic
trichloroethylene HCI; CO2; H2
oxidation of natural products, e.g. glucose, ethanol, cellu-
lose and lignin, food stuffs, e.g. potato, fatty oil, and
herbs, wood, e.g. cherry wood, white dutch clover and and 2,4,5-trichlorophenol, using TiO2 as photocatalyst.
water hyacinth, green algae, dead animals and excrement They have proposed a formation of OH free radicals as
using TiO2 under a xenon lamp. As shown in Table 3, in the major mechanism for the oxidation of chlorinated or-
neutral and in 5M NaOH solution, total oxidation was al- ganics. Ollis has examined the photo-oxidation of chlo-
most possible. They have also found that nitrogen and rinated hydrocarbons with TiO2 with promising results
chlorine are converted to NH3 and HC1, respectively, in- (66,67). Ollis and associates have reported that the order
stead of other organic chemicals. of ease of conversion is chloro-olefins ~ chloroparaffins
It is noticed that in contrast to what was reported by --~ chloroacetic acids (66,67). Matthews has used a thin
Fujihira et al. (62,63), Kawai and Sakada (59,61) have
film of TiO2 to study the oxidation of some organic im-
demonstrated a rather complete oxidation of some halo-
purities in water. He has reported that the kinetics of
genated hydrocarbons with the production of HC1, HF,
photo-oxidation reactions can be described by the Lang-
CO2 and H2. This is interesting indeed. However, the
authors provide no details of the reaction kinetics. All muir type adsorption equation (68,69).
In summary, there is strong evidence to suggest that
experiments were conducted in neutral solution or in 5M
NaOH media using TiO2 catalyst and a 500 watt xenon organic compounds such as those toxic chemicals found
lamp. Table 4 summarizes the end-products produced in contaminated groundwater and wastewaters can be de-
during photocatalytic oxidation in uv-irradiated TiO2 sus- composed (oxidized) by photocatalytic oxidation. The
pensions by various researchers. major products will be hydrogen and CO2. According to
Barbeni et al. (64,65) have studied the degradation of the results of Kawai and Sakada, the overall reaction can
chlorinated hydrocarbons, 2,4,5-trichlorophenoxyacetate be expected as follows:

TABLE 4
Other Work on the Photocatalytic Dissociation of Organic Matters on TiO2
Organic Matter End-Product Reference
acetic acid CH4; CO2; C2H6; H2 Kruatler and bard (72)
propionic acid ethane; ethylene; CO2; H2
n-butylic acid propane; CO2; H2
v-valeric acid n-butane; CO2; H2
pivalic acid isobutane; isobutylene; CO2; H2
tluene benzaldehyde; biphenyl; cresols Fujihira et al. (62, 63)
benzene phenol; bephenyl Kawai and Sakata (59-61)
acetopbenone hydroxyacetophenone; phenol
lactam imides Pavlik and Tantayanon (73)
370
CaHbOcNdCle + (2a - c)H20 ~ aCO2 + dNH3 + eriC1
+ 0.5(4a+b-2c-3d-e)H2 [361
For a complete photocatalytic oxidation reaction, CI will
become HCI and N will be converted to NH3.
Heterogeneous System without Irradiation
Electrolysis has a broad definition in that it includes all
reactions occurring at an electrode surface. The reactions
are forced to take place by an externally imposed voltage.
An important development in electrochemical oxidation
process is the generation of hydrogen peroxide by reduc-
tion of oxygen at the cathode. In the presence of ferrous
ions, the hydrogen peroxide so generated can form a hy-
droxyl radical--a well known Fenton' s reagent (18,19).
Hydrogen peroxide was generated at the graphite elec-
trode in acidic conditions. In the presence of Fe 2+ ions,
the oxidation reaction can take place readily through the
hydroxyl radicals (54). An electron Fenton's reagent can
be produced by the addition of an appropriate amount of
Fe+2 ion to the catholyte. The oxygen reduction potential
is a function of pH and it is found that pH 3 is the most
favorable (at a cathodic potential of-0.6 V vs. saturated
calomel electrode). In the presence of organic com-
pounds, the hydroxyl radicals formed will be rapidly con-
sumed and the organic compounds of interest will be
oxidized (21,70,71).
In a study of electrogenerated Fenton's reagent oxida-
tion of phenol, Sudoh et al. also concluded that pH is op-
timal at 3 (74-78). At pH 4, the degradation of phenol
hardly proceeded even with increasing electric current.
At pH 2, the rates of carbon dioxide production and COD
reduction of phenol were lower than those at pH 3. At
pH 1, the concentrations of the products (such as carbon
dioxide) were extremely low. COD decreased slowly in
comparison with the decrease of phenol concentration.
Since tarry precipitates were observed in the reaction so-
lution, the oxidation of phenol might proceed to produce
the dimer or trimer of phenol.
In a recent study, Huang and coworkers (79) have
demonstrated that a surfactant, perfluoro-octanoate (C8),
can be decomposed effectively by indirect electrochemi-
cal oxidation(79). Results show that in 15 minutes, the
total C8 concentration was decreased from 100 ppm to
10 and from 50 ppm to 1 ppm. They have also proposed
a reaction pathway for the oxidation of C8 by the Fen-
ton's reagent reaction:
02 + 2H + +2e --~ H202 (cathodic reduction) [37]
H202 + Fe 2+ --~ OH" + Fe 3+ + OH" [38]
C. P. HUANG, C. DONG, AND Z. TANG
C7F15COONH4 = C7F15COO" + NH4+ [39]
C7F15COO + H + = C7F15COOH [40]
C7F15COOH + OH' --~ C7F15. + CO2 + H20 [41]
C7F15.+ OH" --+ C7F15OH (CnF2n+IOH) [42]
CnF2n+IOH + O H ~ CnF2n(OH)2 or
CnF2n+I(OH)
[43]
Reaction [37] is a reduction of oxygen at the cathode
electrode; reaction [38] is a generation of hydroxyl radi-
cal (Fenton's reagent); reaction [39] is a dissociation re-
action of C8; reaction [40] is an acid-base equilibrium
reaction; reaction [41] is a Kolbe reaction; reaction [42]
is a free radical reaction with the formation of perfluoro-
heptanol; reaction [43] shows hydroxyl radical attacks on
the perfluoroheptanol to form simple perfluoro alcohols
such as C3F6(OH)2, C3F7(OH), C4Fs(OH)2,or C4F9(OH).
These alcohols are extremely volatile with a boiling point
around 0 °C. Laboratory results clearly show the pres-
ence of simple perfluoroalcohol groups in the gas phase
of the reactor (79).
CASES OF ADVANCED C H E M I C A L
OXIDATION OF C H L O R O P H E N O L S
The oxidation of chlorophenols has been studied by
Huang and co-workers using Fenton's reagent and photo-
catalytic oxidation processes (80). Fig. 1 shows the re-
sults of the decomposition of the parent compounds,
mono-, di-, tri-, tetra- and penta-chlorophenois by the
Fenton's reagent. The results clearly indicate that the
degradation of chlorophenols is very fast and follows a
first order kinetic expression in terms of the parent com-
pound concentration. Under the experimental conditions,
a total removal of chlorophenols is possible in less than 5
minutes, except perhaps for tetra- and penta-chlorophe-
nols. The order in the destruction of these chlorophenols
is as follows:
ADVANCED CHEMICAL OXIDATION 371

1o0% 100% k . . . , . . . . , . . . . , .... i....i .... ,...., ....

-.<>-2-chlorophenol -o-2,34ichlomphenol
80% 80% -o-2,44ich10rophenol
--c3-3-dalorophenol
o
--<>-4-chlorophenol --o-23<lichlorophen01
60%
L
~~1~ "~-2'6 4ichl°r°phen°l
--o-3,44ichloro~nol
3.54ichlorophenol
2o~ 20%

0% 0%
1 2 3 4 5 6 7 1 2 3 4 5 6 7

Time (min) Time (min)

--o-2j,4-trichl0mpl~01 It~ --o-phenol i

8o~ ~ -o-2.~,~-~d~o~h~ot 80%~k --o-2,3,4,6-tetrachl0rophenol ~
~\ --¢-23,6-trich10t0pheml .-o--pentachlorophenol :
60% ~'~ "*-2,4,5-ttichJ~ophmol 60%

2o%~icl~bmol "
@ 20% -
o%
0% .
I 2 3 4 5 6 7 0 1 2 3 4 5 6 7
Time (rain) Time (min)

F I G U R E 1. Destruction o f Chlorophenols by Fenton's Reagent Oxidation. Experimental conditions: Concentration of organic was 10 "3 M except
2,3,4,6-tetrachlorophenol and pentachlorophen, for which concentration was 5x10 "5 M; Fe +2 = 10 -3 M; H202 = 6.7x10 4 M per minute; pH = 3.0;
reaction volume = 2 liter; ionic strength = 5x10 2 M NaNO3; room temperature.

4CP > 3CP > 2CP (for monochlorophenol) 4CP ~_ 3CP = 2CP (for monochlorophenols)

35DCP > 23DCP > 25DCP > 34DCP > 24DCP --

23DCP > 35DCP - 25DCP > 34DCP > 24DCP >
26 DCP (for dichlorophenols)
26 DCP (for dichlorophenols)

235TCP ~ 345TCP > 236TCP > 234TCP

245TCP > 246DCP (for trichiorophenols) 345TCP -~ 235TCP > 234TCP ~ 245TCP
236TCP > 246DCP (for trichlorophenols)

Except tetrachlorophenol and pentachlorophenol, the

number o f chlorine substitutions appears to bear no effect
on the destruction o f the chlorophenol. This is contradic-
tory to the conclusion made by Eisenhauer (20) that the
rate decreases with increasing the number of chlorine
substitution.
The decomposition o f these chlorophenols was also
studied under otherwise similar experimental conditions
except using a photocatalyst, TiO2 and in the presence of
atmospheric oxygen (Fig. 2). One major observation can
be noted: the photocatalytic oxidation o f chlorophenols
takes place at a rate that is one order of magnitude
smaller than the Fenton's reagent process. The order o f
oxidation follows:
This order is slightly different from that o f the Fen-
ton's reagent process, except that in both processes,
26DCP and 246TCP are the most difficult ones for oxi-
dation.
For the purpose of comparison, the oxidation of these
chlorophenols was also conducted with the H202/uv sys-
tem (Fig. 3). It must be mentioned that the uv light
source used in this experiment was the same as that used
in the photocatalytic oxidation process reported above;
the wavelength (350 nm) o f this uv light source is longer
than other systems such as H202/uv and O J u v o f other
researchers. The rate o f oxidation is the same as that o f
372 C . P . H U A N G , C. D O N G , A N D Z. T A N G

100% 100% - • - i - • - i - - - i - - - i - . -

k --o- 2,Ydichlorophenol:
= 80~ -o-2~orophenol 80% "-o-2,4-dichlo~ophenol~
o
= ~. --o-3-chl0r0phen01 o ~. "o"2,5-dichlor~phenol'.
60% 60% I~.~ ~2,6-dichlorophenol.
\~,-~ +~,4~!ch~o~o~i
40% 4O%

2O% 2O%

0% 0~
0 40 80 120 160 200 0 40 80 120 160 200
Time (min) Time (rain)

100% 100%
" ' " " -~-2,3,4~@[alo~phe~]
' -~enol ..... ' :
80% -o-23,5-trich10rophenol -o-2,3,4,6.tetrachl0r0phenol.'
•...¢-2,3,6-tfichlorophenol e~ 80~
_o o --o-PCP
....-a-2,4,5-tddaloropheno[
60%
2,4,6adchlorophenol 60%

4O% 40%

2O% 20%

0% 0%
0 40 80 120 160 200 0 40 80 120 160 200
Time (rain) Time (rain)

FIGURE 2. Destruction of Chlorophenols by UV/TiO2 Oxidation. Experimental conditions: Concentration of organic was 103 M except
2,3,4,6-tetrachlorophenol and pentachlorophen, for which concentration was 5x10 -5 M; TiO2 = 1 g/L; pH = 4.0; ionic strength = 5x10 2 M NaNO3;
room temperature.

100% I . . . , . .. , . .. ,... ,... '00% ]k .....

•-o- 2-chlomphenol
s0% -t~-34a10r0~nol ,, 80%[.['~ -o-2,4-dichlorophenol:
=g 60% ~ --e-4-ch]°r°l~n°l [~l k --*-2~oro~ :
60%tl ~ , --*- 2,6-dicMompheaol.
k L/ ~ ' ~ -,- 3,4 dichlo~ot~nol

0% . . . . . :=,... 0%
40 80 120 160 200 0 40 80 120 160 200
Time (min) Time (min)

100%

80%
' " ~-~i~:
-o-23~. =
©
100%

80%
• -o-Z3,4~
--~--2,4~, =
6O%

40%

20%

0% 0%
40 80 120 160 200 0 40 g0 1211 160 200
Time (min) Time (min)

FIGURE 3. Destruction of Chlorophenols by UV/H202 Oxidation. Experimental conditions: Concentration of organic was 10-3 M except
2,3,4,6-tetrachlorophenol and pentachlorophenol, for which concentration was 5xl 0.5 M; H202 = 0.1 M per minute; pH = 4.0; reaction volume = 1
ADVANCED CHEMICAL OXIDATION
the TiOz/uv/O2 system. The order of the oxidation fol-
lows:
4CP > 3CP > 2CP (for monochlorophenols)
35DCP > 23DCP ~_ 34DCP > 25DCP > 24DCP >
26 DCP (for dichlorophenols)
345TCP > 235TCP > 234TCP = 236TCP >
245TCP > 246DCP (for trichlorophenols)
It is interesting to note that the most difficult chlorophe-
nols for oxidation by this method are the same as the
above two methods, 26DCP and 246TCP.
The oxidation of these chlorophenols by a modified
photocatalytic oxidation process, TiO2/uv/H202, was also
conducted. Fig. 4 shows that the rate of chlorophenol
oxidation is extremely fast. Tseng has reported that the
rate of chlorophenol oxidation follows a first-order ex-
pression of the Langmuir-Hinshelwood type as adsorp-
tion onto the TiO2 surface controls the oxidation process
(82). Depending on the degree of chlorine substitution,
the rate of oxidation generally follows the order:
4CP > 3CP > 2CP (for monochlorophenols)
26DCP _=_ 25DCP > 34DCP _=_24DCP > 23DCP
(for dichlorophenols)
Generally, monochlorophenols are more readily oxidized
than dichlorophenols or trichlorophenols.
OH OH
(n --1
X~
to 5)
OH
XR.HX
OH
373
The mechanism of phenol oxidation by these AOP
systems is not totally clear, although there are several
models suggested. Recently, Dong and Huang (81) re-
ported a reaction pathway for the oxidation of 4CP by the
TiO2/uv/O2 system. It is believed that OH attacks the or-
tho- and para-positions more readily than the meta-posi-
tion. A series of reactions involving OH produces
chloro-dihydroxycyciohexadienyl radical which can then
react with OH to form 4-chlorocatechol, 4-chlororesorci-
nol, and hydroquinone as the major intermediates which
can react with OH to yield hydroxyhydroquinone. A se-
ries of reactions with OH eventually leads to the forma-
tion of CO2 and H20. It is expected that the reaction
pathways for the oxidation of chlorophenols of higher or-
der than the monochlorophenols will be extremely com-
plex. However, laboratory results all indicate that a total
mineralization of chlorophenols is possible by AOP
processes such as the Fenton's reagent.
Based on a recent study, Dong and Huang (80) have
proposed the following generalized reaction pathway,
shown below, for the oxidation of halogenated phenol.
Upon the attack of a halogenated phenol, (ArXnOH)
by OH, a free radical, Ar(OH)2X,. (chlorodihydroxycy-
clohexadienyl, CIDHCD) is formed. This free radical
can undergo two reaction paths: (1) hydroxylation with-
out dechlorination (Type A) and (2) hydroxylation with
dechlorination (Type B). For pathway Type A, C1DHCD
dehydrated to form a free radical, ArOX~. (chlorophe-
noxy, C1PO) which is converted to Ar(OH)2X° (chlorodi-
hydroxybenzene, CIDHB). It is noted that one of the OH
group has a preference for the ortho- and the para-posi-
tion of the aromatic ring. For pathway Type B, the free
radical CIDHCD is dechlorinated to yield Ar(OH)OX._,.
free radical (chlohydroxyphenoxy, CIHPO) which can
undergo further reaction with a hydroperoxide radical,
HO2, to form Ar(OH)2Xn., (chlorodihydroxybenzene
CIDHB). As indicated by the following reaction path-
way, for mono-halogenated phenol ( n = 1), only Type A
path has been confirmed (80). Both Type A and Type B
reaction pathways are possible for dihaiogenated (n = 2)
O"
/
OH
OH ~ TYPE A
= ~ (hydroxylation without
dechlorination)
x. OH(o,p) Xn
(Y
H O 2. ~
OH
TYPE B
(hydroxylation with
-0 2 dechlorlnation)
Xn.1 OH(o,p) Xn-1
374 C.P. HUANG, C. DONG, AND Z. TANG

n = 0 (phenol) n = 3 (trlchlorophenols)
OH OH
~
OH
A
OH
@ O H o r ~
OH
c1_5%°~,°
OH
OH
or ~CI
n -- I ( m o n o c h i o r o p h e n o l s )
CI
OH OH cI OH
..
n = 4 (tetrachlorophenol$)
El CI
OH OH OH OH
C~[CI B C~OH or o~.,.,¢,Cll~.)j~ or C ~ C '
n ~ 2 (dichiorophenols)
T C l ~ CI T C I ~I~ -El
OH OH Cl CI CI OH
~CI A O~CI

el ~ CI n = 5 (pentaehlorophenol)
OH OH OH OH OH
C~[CI B C~.OH or C~,~C|
or ~ H cI
Ci ~f Ci CI ~ f c] c i ~f- c!
Cl ci ci oH

and trihalogenated (n = 3) phenols. As for tetrahalogen- with this system. Fig. 5 indicates that significant COD
ated (n = 4) and pentahalogenated (n = 5) phenols, only removal can be accomplished by the H202/Fe ~+ system.
Type B reaction pathway is possible. The COD of the leachate decreases from an original
To further demonstrate the versatility of the Fenton's 8,500 ppm to 2,000 ppm after treatment with 510 .2 M
reagent process, a sanitary landfill leachate was treated H202 and 2 10 3 M FeSO4 at pH 3. The results also show

100% I . • , . . . . , . , . i . . . i . . .

l --o-2-dal0r0phen01 -o-2,3-dichlor0phenol
i 8o%I --o-3-chlorophenol 80%

..~-dichloro~nol.
o
--o-2,44ichlor01~erml
" 60% -o-4<hl0~phenol --o-2,54ich10r0~nol
60% •-a--2,6-dich/orophenol
k
I -4-3,44ich10~lSen01
40%

20%

. . . . ~"..., . . . 0%
0 40 80 120 160 200 40 80 120 160 200
Time (rain) Time (min)

100%lf.m . . , . . . . . . . . . . . . . . . 100% ' - - m • • . , . • . i • . . . • . .

80~ [~\
t --o-2,3,4-trichl0tophenol
--o-2,334fichlor0phenol = 8O% --o-phenol
O

I. Lil - ' ~ 2,3,6-tfrdll~phenol

6o%
I~ -,s'-2,4,5-trichlotophend
40% [ ~ -~- 2,4,646ch10mphen01
2,4,646ch10mtSen01 4o%

20%

0%
0 40 80 120 160 200 40 80 120 160 200
Time (rain) Time (rain)

FIGURE 4. Destruction of Chlorophenols by UV/TiO2/H202 Oxidation. Experimental conditions: Concentration of organic was 10.3 M except
2,3,4,6-tetrachlorophenol and pentachlorophen, for which concentration was 5x 10-5 M; TiO2 = 1 g/Liter; H202 = 0.1 M per minute; pH = 4.0; ionic
strength = 5x10°2 M NaNO3; room temperature.
ADVANCED CHEMICAL OXIDATION
tO000
0000
6000
4000
2000
0
Raw Leachate H202 treated Fe*2+H202 treated
FIGURE 5. COD removal by H202 and Fe +2 + H202 with and without
precipitation. Experimental conditions: Initial COD = 8,500 ppm,
H202 = 5x10 "2 M; FeSO4 = 2x10 "3 M, pH = 3.0 (with H2SO4).
that the extent of mineralization is high when the
leachate is treated by the Fenton's reagent process (Fig. 6).
CONCLUSION
Advanced chemical oxidation processes, especially the
H202/Fe 2+ systems, are effective in decomposing organic
pollutants. Much has been learned about the mechanism
of the oxidation of organic compounds by AOP systems,
especially those involving OH reactions. While OH can
be generated by many systems, it appears that the homo-
geneous systems using H202 and catalytic metal ions,
specifically Fe 2+, will be the most attractive ones, both
from process control and process performance points of
view. The OJuv process also depends on OH to drive
the oxidation reaction. Upon irradiation with uv, 03 is
converted to H202, which is then converted to OH upon
uv irradiation. Therefore, the O3/uv system will not be
competitive against the HEO2/Fe 2+ process. Moreover,
10
8
g 6
4 14. Glaze, W. H. Drinking water treatment with ozone. Environ. Sci.
2
o~
0 20 40 60 80 I00
Time (rain)
FIGURE 6. A comparison on CO 2 production by various chemical
treatment methods. Experimental conditions: Initial COD = 8,500
ppm, H/O2 = 5x10 "2 M; FeSO4 = 2x10 "3 M, pH = 3.0 (with H2SO4).
375
the O3/uv system will be limited by the ozone transfer
process between the gas and the liquid phase. Photocata-
lytic oxidation, especially along the use of H202, be-
comes an extremely competitive process against the
H2Oz/Fe2+ system. However, the process is operationally
limited in that the development of a fixed-bed photocata-
lytic reactor is yet to be perfected commercially. The ap-
plication of photocatalytic oxidation is most readily
applied in suspensions.
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