5558 Ind. Eng. Chem. Res.

2009, 48, 55585562

Identification of Sulfate and Hydroxyl Radicals in Thermally Activated Persulfate

Chenju Liang* and Hsin-Wey Su
Department of EnVironmental Engineering, National Chung Hsing UniVersity, 250 Kuo-kuang Road,
Taichung 402, Taiwan

Thermal activation can induce persulfate (S2O82-) degradation to form sulfate radicals (SO4-) that can undergo
radical interconversion to form hydroxyl radicals (HO) under alkaline conditions. The radicals SO4-/HO
can be present either individually or simultaneously in the persulfate oxidation system. To identify the active
radical species, a chemical probe method was developed. An excess of probe compounds was added to the
system, and differences between the reactivity of the probes and the potential radical species were observed.
The usage of various probes, including tert-butyl alcohol, phenol, and nitrobenzene (NB), for simultaneously
identifying SO4-/HO was investigated. NB can only react with radicals: it cannot react with persulfate. The
reaction rate of NB with HO is 3000-3900 times greater than that of NB with SO4-, which is a good
candidate for use as a probe for differentiating between SO4-/HO reactivity. Furthermore, the effects of pH
on the formation of SO4-/HO were demonstrated by the degradation kinetics of NB at varying pH values.
The results indicated that SO4- is the predominant radical at pH <7; both SO4- and HO are present at pH
9; HO is the predominant radical at a more basic pH (i.e., pH 12). The use of chemical probe NB is a
suitable compound for differentiating HO/SO4- reactivity.

1. Introduction compounds. Moreover, when comparing the use of peroxide

Sodium persulfate (Na2S2O8), with a redox potential of 2.01
V, has been used for in situ chemical oxidation (ISCO)
remediation of a variety of organic contaminants. Among the
advantages of using persulfate anions (S2O82-) (PS) as an ISCO
oxidant, those most important to this study are the persistent
nature of persulfate in the subsurface and the resulting sulfate
radical (SO4-) reactivity upon activation. One way to activate
persulfate is thermal activation, in accordance with eq 1.1
S2O82- + heat f 2SO- - radicals are during the oxidation of organic compounds.9
4 4 /SO4 ) ) 2.4 V)
(Eo(SO2-
(1)
-
Generally, SO4 is more prone to electron transfer reactions
than hydroxyl radicals (HO), with E(HO-/HO) ) 2.7 V.2 In
contrast to SO4-, HO more readily undergoes hydrogen
abstraction or addition.3 It has been demonstrated by electron
spin resonance (ESR) spin trapping 4-7 that alkaline conditions
(i.e., pH >8.5) can induce the mechanism of SO4- intercon-
version to HO (see eq 2) in the persulfate activation system.
In addition, it has also been shown that sulfate radicals can react
with water at all pHs to produce HO, in accordance with eq 3.
The rate constants for eqs 2 and 3 are on the orders of (6.5 (
1.0) 107 M-1 s-1 (ref 6) and k[H2O] < 2 10-3 s-1 (ref 5),
respectively. However, Norman et al.4 reported that the reaction
rate constant of eq 3 is low, in comparison to those achieved
for SO4- reactions with organic compounds and eq 2 is mainly
in control of radical interconversion.
Alkaline pH: SO-
4 +OH
-
f SO2-
4 + HO (2)
All pHs: SO-
4 +H2O f SO2-
4 + HO+H +
(3)
Because of a higher redox potential and the less-selective
contaminant destruction mechanisms of HO, the formation of
HO presents the potential to increase the contaminant degrada-
tion rate and the possibility of reactions with a wider variety of
* To whom correspondence should be addressed. Tel.: +886-4-
22856610. Fax: +886-4-22862587. E-mail address: cliang@
dragon.nchu.edu.tw.
10.1021/ie9002848 CCC: $40.75 2009 American Chemical Society
Published on Web 05/06/2009
and persulfate as sources of HO, persulfate is more stable than
peroxide in aquatic systems (e.g., in the presence of alkalinity
carbonate species8). Therefore, for ISCO remediation of sub-
surface contamination, it is recognized that the persulfate anion
can move greater distances down-gradient from injection wells
in the subsurface and hence persulfate is a better choice than
peroxide.
Although the formation of radical species (e.g., HO) can be
recorded using an ESR, it is still uncertain how active the
Identification of HO yields, using the chemical probe method,
have been intensively investigated in the Fenton oxidation
processes.10-12 The chemical probe method was developed
based on the use of an excess of probe compounds and ensuring
that all of the radicals were scavenged by the probe compound.
Generally, for a probe compound with radicals to be considered
to be effective for instantaneous scavenging, a rate constant of
>109 M-1 s-1 for the scavenging reaction must be achieved.
Anipsitakis and Dionysious13 studied the transformation of 2,4-
dichlorophenol by the interaction of metals with oxidants (e.g.,
ferrous ion activated persulfate according to eq 4) and success-
fully employed the use of chemical probe compounds to quench
reactions in conjunction with competition kinetics (i.e., differ-
ences in the reactivity between the potential radical species
formed and the chemical probe additive) for identifying the
primary radical species formed (e.g., SO4- or HO).
8 +Fe
S2O2- 2+
f SO-
4 +SO4 +Fe
2- 3+
(4)
A literature survey on the reaction rate constants between
SO4- or HO and chemical probe compounds is provided in
Table 1. As shown in the table, anisole, benzoic acid, benzene
and phenol can react with both SO4- and HO at high rates
(i.e., rate constant >109 M-1 s-1) and, hence, these four
compounds are suitable for scavenging both radicals. Phenol
has the highest water solubility (i.e., 8.28 g/L) and, as such,
can be added in water at greater concentrations than the other
compounds and can be used to effectively quench radical
activity. Moreover, the reactivities of the two radicals are

Table 1. Second-Order Rate Constants for Reactions of Selected
Chemical Probes with Hydroxyl and Sulfate Radicals
Reaction Rate Constant (M-1 s-1)
radical probe SO4- HO reference(s)
anisole 4.9 109 7.8 109 26, 27
benzoic acid 1.2 109 4.2 109 12, 28
benzene (2.4-3) 109 7.8 109 10, 28, 29
ethanol (1.6-7.7) 107 (1.2-2.8) 109 2, 30
methanol 3.2 106 9.7 108 2, 31
nitrobenzene, NB <106 (3.0-3.9) 109 2, 27, 28
propanol 6 107 2.8 109 12, 32
phenol 8.8 109 6.6 109 10, 29
tert-butyl alcohol, TBA (4-9.1) 105 (3.8-7.6) 108 30
different and the rates achieved using HO are 3000-3900
times and 418-1900 times greater than those achieved using
SO4- on nitrobenzene (NB) and tert-butyl alcohol (TBA),
respectively. Therefore, NB and TBA were chosen as chemical
probe compounds and phenol was chosen to confirm equal
reaction activities with SO4- and HO in this study.
Since significant research has focused on the Fenton system,
attempts to identify both SO4- and HO in the thermally
activated persulfate have not yet been addressed. The objectives
and scope of this study are (1) the selection of chemical probes
and (2) the identification of predominant radical species formed
under different pH conditions.
2. Materials and Methods
2.1. Chemicals. The water used was purified using a Mil-
lipore reverse osmosis (RO) purification system. The chemicals
used were purchased from the following sources: tert-butanol
(>99.5%) and sodium hydroxide (99.0%) were purchased from
Riedel-deHaen; nitrobenzene (>99.0%) and sodium persulfate
(99.0%) were purchased from Merck; phenol (99.2%) was
purchased from J.T. Baker; sulfuric acid (9597%) was
purchased from Fluka; and methanol (99.9%) and potassium
iodide (99.5%) were purchased from ECHO Chemical.
2.2. Experimental Methodology. Solutions that contain
chemical probes (i.e., NB, TBA, and phenol) at a fixed initial
concentration of 5 mM were used to react with three persulfate
concentrations (i.e., 50, 80, and 100 mM). The pH of the solution
was initially adjusted to pH 7 using NaOH or H2SO4 in all
experiments. The experimental procedure used was in ac-
cordance with the method of Liang et al.14 Experiments were
conducted in a series of 40-mL amber screw cap borosilicate
glass bottles that were placed in a temperature-controlled water
bath (Firstek Co., Model B206) at 70 C. Reaction bottles for
analysis were removed from the water bath at the proposed
intervals, immediately placed in an ice bath (4 C) to quench
the reaction by chilling and set aside for analysis.
Experiments to identify the predominant radical species were
conducted in a 1.3-L heavy-wall plain pressure reaction flask
(ACE Glass) kept at a temperature of 70 C. The top of the
flask was covered with a flat Teflon reaction head that was
sealed with a stainless-steel clamp. The pH electrode was
inserted through Teflon-lined septum ports on the top Teflon
cover. The pH of the solution was maintained at the designated
pH value (i.e., 2, 4, 7, 9, and 12) during the course of the
reaction with a pH controller (Suntex pH/ORP controller, Model
PC-310) by pumping H2SO4 or NaOH at a rate of 1 mL/min
through two Teflon tubes inserted in a port on the top cover of
the flask. The pH was also monitored continuously using the
data acquisition software (Eutech Instruments, Model Cyber-
Comm 5000), and the data was recorded at every two seconds
and exhibited a stable pH variation within 0.2 pH units. A
Ind. Eng. Chem. Res., Vol. 48, No. 11, 2009 5559
syringe filled with RO purified water (50 mL) was inserted
through a septum port to replace water removed from the reactor
when taking samples, and zero headspace was maintained, in
accordance with the procedure outlined by Dai and Reitsma.15
Note that seven samples (5 mL each removed by a gas-tight
syringe (SGE Co.) at each sampling interval) were taken for
chemical probe and S2O82- analysis. The acid and base solutions
that were used to maintain the solution pH in the reaction flask
were less than a total volume of 30 mL of acid or base injected
in each experiment; therefore, the variation was limited to <10%.
All analyses were preformed in duplicate, and every individual
test was repeated to ensure the reproducibility of experimental
results. Therefore, data are averaged values of four replicate
samples.
2.3. Chemical Analysis. For all analysis, aqueous samples
were filtered using a polytetrafluoroethane (PTFE) filter (0.2
m, Toyo stainless syringe holder). A direct aqueous injection
(i.e., 1 L) gas chromatography/flame ionization detector
(Agilent, Model 6890N), equipped with a Hewlett-Packard HP5
column (30 m 0.25 mm ID; 0.25 m), was used for TBA
analysis. The inlet, detector, and isotherm oven temperatures
were set at 130, 250, and 60 C, respectively. The concentration
of NB was determined using a high performance liquid
chromatography (Agilent, Model 1100) equipped with UV-
visible detection at a wavelength of 275 nm, using an Agilent
Model Eclipse XDB-C18 column. The injection volume was
20 L and the mobile phase was a mixture of 60% methanol/
40% water at a rate of 0.8 mL/min at a controlled temperature
of 20 C. The concentration of phenol was also determined in
accordance with the procedure for NB analysis with the
exception that a wavelength of 254 nm was used. The presence
of persulfate anions was determined by iodometric titration.16
3. Results and Discussion
3.1. Selection of Chemical Probes. The results for thermally
activated persulfate oxidation of TBA, NB, and phenol degrada-
tions at pH 7 are shown in Figures 1a, 1b, and 1c, respectively.
The degradation of chemical probes by HO/SO4- can typically
be described as a second-order reaction:17
dC
) kC[OH/SO-
4 ] (5)
dt
where C and [OH/SO4-] are concentrations of chemical probes
and radical species, respectively; k is the second-order rate
constant, and t is the reaction time. Equation 5 can be simplified
to a pseudo-first-order equation by assuming a constant con-
centration of radical species, as given below. Note that excess
persulfate/probe compound molar ratios ranging from 10:1 to
20:1 were used in this study:
dC
) -kobsC (6)
dt
C
) exp(-kobst) (7)
Co
where Co is the initial concentration (given in units of mM)
and kobs is the pseudo-first-order rate constant (given in units
of min-1).
The trend line clearly is quite linear, and it can be deduced
that the chemical probe degradations fit the pseudo-first-order
kinetic model. The results show that kobs,probe was significantly
influenced by the concentration of the persulfate (i.e., an increase
in persulfate concentration resulted in an increase in kobs,probe
for the three chemical probes (data presented in Table 2)). The
5560 Ind. Eng. Chem. Res., Vol. 48, No. 11, 2009

Table 2. Summary of Pseudo-First-Order Rate Constants from

Degradations of Probe Compound Experimentsa
kobs,PS kobs,probe
persulfate
-3 -1 -3
concentration (mM) ( 10 min ) 2
R ( 10 min-1) R2
No Probe
100 1.63 ( 0.08 0.990
TBA Probe
50 2.41 ( 0.05 0.997 11.55 ( 0.29 0.997
80 2.48 ( 0.03 0.999 20.96 ( 0.27 1.000
100 2.53 ( 0.03 0.999 40.83 ( 0.37 1.000
NB Probe
50 1.41 ( 0.04 0.995 1.81 ( 0.03 0.998
80 1.50 ( 0.07 0.983 3.23 ( 0.10 0.993
100 1.43 ( 0.04 0.995 3.62 ( 0.06 0.998
Phenol Probe
50 1.63 ( 0.04 0.994 14.79 ( 0.38 0.995
80 1.59 ( 0.01 0.990 27.05 ( 1.90 0.962
100 1.72 ( 0.03 0.998 28.69 ( 0.71 0.994
a
Note: The error ranges represent the standard deviation of linear
regression analysis.

TBA was much greater than the persulfate self-degradation rate

Figure 1. Degradations of chemical probes: (a) TBA, (b) NB, and (c) phenol
with 70 C thermally activated persulfate, as a function of persulfate
concentrations. Inset figures indicate the degradation of persulfate. Error
bars denote one standard deviation error for four replicate data points at
each sampling interval.
degradation of persulfate follows first-order reaction kinetics,
as commonly reported in the literature.14,18-20 It was observed
that the kobs,PS values for all three persulfate concentration levels
conducted for all three probe compounds were the same. This
indicates that the rate constants are independent of initial
persulfate concentrations and are first order in nature. However,
when comparing the kobs,PS value for persulfate degradation in
the presence of probe compounds with that in the presence of
persulfate alone, it can be seen that kobs,PS in the presence of
(see the inset figure in Figure 1a and the data in Table 2). The
kobs,PS value (the persulfate self-degradation rate constant)
obtained in this study is comparable to the value reported
previously ((1.6-2.01) 10-3 min-1, at neutral pH and 70 C)
by House.21 If the rate of persulfate degradation in the presence
of an organic substance is equal to the rate of its self-
degradation, the radical initiation reaction (eq 1) prevails and
radicals are responsible for the degradation of organics.22
However, if the rate of persulfate degradation is greater than
the rate of its self-degradation, then the reaction between
persulfate and organics prevails. Therefore, the results of the
TBA experiments indicate that TBA would directly react with
persulfate anions and this suggests that TBA is not a good
candidate as a probe for radicals. A similar comparison of the
kobs values for the NB and phenol experiments with that of
persulfate self-degradation allows for the confirmation of
chemical probe degradation induced by radical initiation reac-
tions (i.e., oxidation by sulfate radicals, not by persulfate anions).
Note that TBA, as well as other probes, could still be applicable
for quenching HO/SO4- reactions, although persulfate can
directly react with probe compounds.
3.2. Identification of Radical Species. Given the previous
discussion, the selection of appropriate chemical probes should
involve consideration of the interaction between the probed itself
and the source chemical (e.g., persulfate anion) for radicals.
Therefore, NB can be used as a chemical probe for differentiat-
ing between the competition kinetics of HO and SO4-. Figure
2 shows the results of identifying the degree that the pH affects
the formation of HO and SO4- and the NB degradation kinetics
by different radicals. The pseudo-first-order rate constants are
presented in Table 3. When the pH was in the range of 2-7,
the ratio of kobs,NB to that at pH 2 ranged from 0.93 to 1.01.
However, when the pH value was increased to 9 and 12, the
ratio increased (e.g., the ratio of 1.16 and 4.88 at pH 9 and 12,
respectively). The results suggest that SO4- is the predominant
radical at pH <7; both SO4- and HO are present at pH 9;
HO is the predominant radical at a more basic pH (i.e., pH
12). These observations are in agreement with the ESR results
reported by Dogliotti and Hayon (1967)33 and Normal et al.
(1970),4 who reported that, as the pH increases (e.g., >8.5), the
conversion of SO4- to HO becomes increasingly important.
It was observed that the persulfate degradation rate constants
 Ind. Eng. Chem. Res., Vol. 48, No. 11, 2009 5561
increased persulfate concentrations. Furthermore, the identifica-
tion of the predominant radical species (i.e., HO and/or SO4-)
can be conducted based on the differences in the reactivities
and the rates of the reactions between nitrobenzene (NB) and
the radical species. A kobs,NB:kobs,NB at pH 2 ratio of >1 indicates
the formation of HO and the increased ratio results from the
increased concentration of HO. The results of the NB degrada-
tion tests show that, at a higher pH (i.e., pH >9), relatively more
HO was being generated. Accordingly, NB is a suitable
chemical probe for differentiating between HO and SO4-.

Acknowledgment
This study was funded by the National Science Council (NSC)
of Taiwan (under Project No. 96-2221-E-005-017-MY3).

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ReceiVed for reView February 19, 2009
ReVised manuscript receiVed April 21, 2009
Accepted April 23, 2009
IE9002848