Calculation of Hydroxyl Radical

Concentration Using an Indirect

Method-Effect of pH and Carbonate Ion

Snigdha Khuntia, Manish Kumar Sinha, Subrata Kumar Majumder

and Pallab Ghosh

1 Introduction

The use of hydroxyl radicals in oxidation is known as advanced oxidation process,

which is an emerging method in the water and wastewater treatment (Legrini et al.
1993). The oxidation potentials of O3 (molecular ozone) and hydroxyl radical
(∙OH) are 2.07 and 2.80 V, respectively (Beltrán 2004). The reaction with
molecular ozone is selective to certain organic and inorganic compounds such as
the compounds having C=C bonds, and the functional groups containing sulfur,
phosphorous, nitrogen and oxygen (Oppenländer 2003). The hydroxyl radicals are
able to mineralize many organic and inorganic compounds through various reaction
mechanisms such as, radical–radical reactions, hydrogen abstraction, electron
transfer and electrophilic addition. This often leads to the complete mineralization
of the pollutant compounds (Oppenländer 2003).

S. Khuntia (&)
Institute of Engineering and Technology-Ahmedabad University,
Commerce Six Roads, Navrangpura, Ahmedabadd, India
e-mail: snigdha.khuntia@ahduni.edu.in
M.K. Sinha
Marwadi Education Foundation, Rajkot, India
e-mail: mksinha1985@gmail.com
S.K. Majumder
P. Ghosh
Indian Institute of Technology Guwahati, Guwahati 781039, Assam, India
e-mail: skmaju@iitg.ernet.in
P. Ghosh
e-mail: pallabg@iitg.ernet.in

© Springer Science+Business Media Singapore 2016 185

I. Regupathi et al. (eds.), Recent Advances in Chemical Engineering,
DOI 10.1007/978-981-10-1633-2_20
186 S. Khuntia et al.

The hydroxyl radicals concentration [∙OH], generated from ozone is an impor-

tant parameter to measure the rate constant of the reaction. [∙OH] can be measured
by various methods such as, electrochemical, optical, spectrophotometric and col-
orimetric techniques (Langlais et al. 1999). However, quantitative measurement of
[∙OH] is rather difficult due to its low concentration in water. A few computer
models have been developed for the prediction of concentration of hydroxyl radi-
cals (Chelkowska et al. 1992). Elovitz and von Gunten (1999) have developed an
indirect method to determine the concentration of hydroxyl radicals generated from
ozone by using a probe compound (i.e. p-Chlorobenzoic acid).
In this work, [∙OH] generated from ozone microbubbles has been determined.
The effects of pH and carbonate ions on the generation of hydroxyl radicals has
been studied. Oxidation of phenol using O3 and [∙OH] has been investigated at pH
3–10. The contribution of hydroxyl radicals on the degradation of phenol has been
calculated.

2 Materials and Methods

All the chemicals used in this work are of analytical grade. The details of the
experimental setup are given in our earlier work (Khuntia et al. 2013). Oxygen was
isolated from air [make: Oz-Air (India), model: HG 03]. An ozonator [make:
Oz-Air (India), model: ISM 10 Oxy EC] converted the oxygen to ozone by the
corona-discharge method. The ozone generator worked in the range of 0–3 mg s‒1.
The flow rate of the oxygen and ozone mixture coming out of the ozonator was
measured by a rotameter, which had the range of 8–80 cm3 s‒1. The percentage of
ozone in the gas mixture was varied in the range of 0.7–2 %. The gas mixture was
passed into the microbubble generator [make: Riverforest Corporation (USA),
model: AS MK-III] where the dissolution of gas in water was achieved by applying
a high pressure. The microbubbles (mean diameter *25 μm) were generated by
releasing the pressure. The gas intake capacity of the microbubble generator was
1.7 cm3 s‒1. A polycarbonate reactor of 20 L capacity was used for conducting
ozonation. The microbubbles were continuously passed into the reactor from the
microbubble generator by recirculation the aqueous phase.
The [O3] was measured by using the Indigo Colorimetric Method (Eaton et al.
2005). The PCBA concentration was measured by using a HPLC [make: Shimadzu
(Japan), model: LC-20AD] equipped with a ternary pump delivery system and UV
detector. 0.3 cm3 sample was injected into the C18 column [make: Varian (The
Netherlands), model: Hypersil ODS, 250 mm length, 4.6 mm ID, 5 µm particle
size]. The mobile phase consisted of 55 % methanol and 45 % water containing
10 mol m−3 phosphoric acid. PCBA was detected at 234 nm. With 0.3 cm3
injection, the detection limit was 0.05 μmol dm−3. The concentration of phenol was
measured by HPLC using the C18 column at 280 nm wavelength. The mobile
phase was constituted of water and acetonitrile (with 0.2 % phosphoric acid,
pH * 3) in 50:50 volume ratio.
Calculation of Hydroxyl Radical Concentration … 187

The concentration of hydroxyl radical was measured by using PCBA as the

radical probe. 0.05 μmol dm−3 PCBA was added to the aqueous phase in the
reactor after it was saturated with ozone. At certain time intervals, 20 cm3 samples
were withdrawn, out of which 2 cm3 was used for measuring the concentration of
PCBA and the rest was used for measuring [O3]. The effect of carbonate on the
generation of hydroxyl radicals was studied by adding 1 and 2 mmol dm−3 sodium
carbonate. After the saturation of ozone in water, PCBA was added, which was
followed by calcium carbonate. All the experiments were performed at 298 K.
The hydroxyl radicals contribution on phenol degradation was determined at pH
3–10. 0.53 mmol dm−3 phenol and 0.05 μmol dm−3 PCBA were added after the
saturation of the aqueous phase by ozone. The procedure for determining the
concentrations of PCBA and phenol was similar to that described earlier.

3 Results and Discussion

3.1 Determination of [∙OH]

Direct determination of the concentration of hydroxyl radicals is rather difficult

because they have a very short life time (of the order of nanoseconds), and they
react at the site of their formation. Therefore, an indirect method was proposed by
Elovitz and von Gunten (1999) to measure the concentration of hydroxyl radicals.
In this method, a probe compound (e.g. PCBA) is used, which readily reacts with
∙OH, but remains almost indifferent towards O3 (Elovitz and von Gunten 1999). To
illustrate, the rate constants of the reaction of PCBA with ∙OH and O3 are 5 × 109
and 0.15 dm3 mol−1 s−1, respectively. When the probe compound and the scav-
enger are both present in water, the consumption of ∙OH will be due to both of
them, as illustrated in Fig. 1.
When PCBA is present at very low concentrations, the contribution of the probe
on ∙OH scavenging is negligible, and therefore, kh[PCBA] ≪ ks[S]. As PCBA
shows almost no reaction with O3 as compared to ∙OH, the rate equation for PCBA
can be written as (Elovitz and von Gunten 1999)

Fig. 1 Mechanism of reaction of probe and scavenger with ∙OH

188 S. Khuntia et al.

d½PCBA
 ¼ kh ½
OH½PCBA ð1Þ
dt

Rearranging and integrating Eq. (1), we get

 Z
½PCBA
ln ¼ kh ½
OHdt ð2Þ
½PCBA0
R
where, ½
OHdt, is called the time-integrated [∙OH], or
OH exposure. From
Eq. (2) it is observed that, the decrease in [PCBA] at any time, t, is an indirect
measurement of the ∙OH exposure for the reaction time. Therefore, a term, Rct, is
defined as
R
½
OH dt
Rct ¼ R ð3Þ
½O3  dt
R
The O3 exposure or ½O3 dt, can be calculated from the integration of the ozone
concentration profile, as shown in Fig. 2a. From Eqs. (2) and (3) we get

 Z
½PCBA
ln ¼ kh Rct ½O3  dt ð4Þ
½PCBA0

From Eq. (4) Rct can be determined by measuring the concentration profile of
PCBA and O3. The concentration profile of PCBA with time is shown in Fig. 2b.
The ∙OH generated from ozone is consumed by PCBA, and therefore, the con-
centration of PCBA decreases. However, the ozone dissolution in water increases
with time, which results the increase in the ozone exposure. From the above linear
equation [i.e. Eq. (4)], the O3 exposure, Rct can be calculated from the slope of the
plot.

Fig. 2 Variation of a O3 concentration and O3 exposure, and b PCBA concentration, with time
Calculation of Hydroxyl Radical Concentration … 189

Fig. 3 O3 exposure profile at

various pH

Figure 3 depicts the O3 exposure profiles at various pH. The value of O3

exposure was higher at the acidic pH than that at the alkaline pH. The decompo-
sition of ozone increases with increasing pH. Therefore,
 at acidic
 pH, the
 molecular
ozone is more stable. The relationship between ln ½PCBA ½PCBA0 and the O3
exposure shows that, Rct is a constant and independent of the reaction time. So,
Rct ¼ ½
OH=½O3  at any time t during the reaction (Elovitz and von Gunten, 1999),
from which the value of [∙OH] can be calculated.
The variation of ∙OH exposure, O3 exposure and Rct with pH is shown in Fig. 4.
The variation of ozone exposure with time at different pH is shown in Fig. 5. At
acidic pH, the value of ∙OH exposure was more than that at the alkaline pH. This
was the result of the higher ∙OH generation from the ozone microbubbles.

Fig. 4 Comparison of ∙OH exposure, O3 exposure and Rct at different pH at 2400 s

190 S. Khuntia et al.

Fig. 5 Variation of ∙OH

exposure at different pH

However, the ozone decomposition was less at pH < 7, which increased the O3
exposure. Therefore, the value of Rct was less at acidic pH. At alkaline pH, the
decomposition of ozone was more, and therefore, the O3 exposure was decreased.
The generation of ∙OH was due to the chain reactions triggered by the OH−.
However, a significant amount of hydroxyl radicals was generated in the acidic
conditions. Although the ∙OH exposure was less at pH < 9, but Rct was similar to
that of the acidic conditions. At pH 10, the ∙OH exposure and the ozone decom-
position rapidly increased due to the presence of a large amount of OH− ions. Thus,
the O3 exposure noticeably decreased and Rct increased.
Elovitz and von Gunten (1999) have reported that Rct increased with pH,
whereas the values of ∙OH exposure were very close to each other for pH 6–9 (viz.
5 × 10−14 mol dm−3 s). This happened due to the higher ozone decomposition and
lower ∙OH generation in this pH range. However, they have not reported the values
of [∙OH], [O3] and Rct at pH < 6. Haag and Yao (1993) have reported that the value
of Rct was almost constant at pH 7–8.2 for a variety of water samples ranging from
clean surface water to wastewater. In our study, higher depletion of PCBA at acidic
pH clearly shows that the generation of ∙OH from the ozone microbubbles in the
acidic medium was more than that in the alkaline medium. Studies at pH < 3 or
pH > 10 were not performed in our pilot plant due to the operational limitations of
the microbubble generator. The range of the pH could not be increased, as it would
damage the internal materials of the microbubble generator.

3.2 Degradation of Phenol by ∙OH

Hydroxyl radicals and molecular ozone simultaneously react with the pollutants.
Therefore, the depletion rate of the pollutant (D) with ozone may be written as
Calculation of Hydroxyl Radical Concentration … 191

Fig. 6 Concentration profiles

of phenol

d½ D 
 ¼ kh ½
OH½D þ kO3 ½O3 ½D ð5Þ
dt
d½D
 ¼ ðkh Rct þ kO3 Þ½O3 ½D ð6Þ
dt

where kh and kO3 are the second-order rate constants for reaction of micropollutant,
D, with ∙OH and O3, respectively. The values of kh and kO3 can be calculated from
Eq. (6). The degradation of phenol using ozone microbubbles at different pH is
shown is Fig. 6. The rate constant of the reaction of phenol with ozone and ∙OH is
pH dependent. The O3 exposure was slightly less in presence of phenol due to the
consumption of ozone. The degradation of phenol was more effective at acidic and
alkaline pH than at pH 7. By using the PCBA probe, the vales of Rct were calcu-
lated. The rate constants of the reaction of phenol with ∙OH and O3 (Table 1) were
determined by using Eq. (6). The values of kO3 and kh are similar to that reported by
Hoigné and Bader (1983), and Land and Ebert (1967), respectively.
Furthermore, the values of kO3 are of the same order at all pH. The Rct parameter
is a measure of the contributions of OH and O3 for the degradation of a microp-
ollutant in water. The fraction of D degraded by ∙OH and O3 can be expressed as

Amount of D reacted with
OH

f
OH ¼ ð7Þ
Amount of D reacted with
OH þ Amount of D reacted with O3

kh ½
OH½D kh Rct
f
OH ¼ ¼ ð8Þ
kh ½
OH½D þ kO3 ½O3 ½D kh Rct þ kO3

Using Eq. (8), the fraction of phenol reacted with ∙OH was calculated. These
values are given in Table 1.
192 S. Khuntia et al.

Table 1 Contribution of O3 and ∙OH on phenol oxidation

pH Rct × 1010 kO3 (dm3 mol−1 s−1) kh × 10−10 (dm3 mol−1 s−1) R2 f∙OH × 103
3 11.4 1203 1.49 0.97 14.00
4 10.2 1202 1.48 0.99 12.50
5 6.9 1262 1.50 0.96 8.08
6 5.5 1260 1.50 0.97 6.46
7 5.3 1359 1.51 0.98 5.78
8 5.2 1420 1.51 0.96 5.43
9 5.2 1420 1.49 0.97 5.43
10 7.9 1420 1.51 0.97 8.22

4 Conclusions

The indirect method of determination of [∙OH] is promising. The depletion rate of

PCBA was high in the acidic condition, and it decreased with increasing pH. But at
pH 10, the PCBA depletion rate increased. From the rate of depletion of PCBA and
ozone, the values of O3 exposure, ∙OH exposure and Rct were calculated. At acidic
pH, the generation of ∙OH was due to the thermal dissociation of ozone. However,
ozone was more stable in the acidic condition than in the alkaline condition.
Therefore, both O3 and ∙OH exposures were higher in the acidic media than the
alkaline conditions. At alkaline pH, ozone decomposition increased due to the
presence of OH−. However, the generation of ∙OH was more at the acidic pH. At
pH 10, ∙OH exposure strongly increased due to the high concentration of OH−. As a
result, the O3 exposure increased. The degradation of phenol by ∙OH was higher at
acidic pH than that at the alkaline pH. The rate constant of reaction of phenol with
∙OH was much higher than that of O3 and it was constant at all pH.

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