• Pergamon Wat. Sci. Tech. Vol. 35, No.4, pp. 41-48,1997.

© 1997 fAWQ. Published by Elsevier Science Ltd

Printed in Great Britain.
0273-1223/97 $17{)O + 0'00
PH: S0273-1223(97)00007-3

SIMULTANEOUS PHOTOCHEMICAL
GENERATION OF OZONE IN THE GAS
PHASE AND PHOTOLYSIS OF AQUEOUS
REACTION SYSTEMS USING ONE VUV
LIGHT SOURCE

T. M. Hashem, M. Zirlewagen and A. M. Braun

Lehrstuhl fiir Umweltmesstechnik, Engler-Bunte Institut, Universitiit Karlsruhe,
76/28 Karlsruhe, Germany

ABSTRACT

A more efficient use of vacuum ultraviolet (VUV) radiation produced by an immersed Xe-excimer light
source (172 nm) was investigated for the oxidative degradation of organic pollutants in aqueous systems. All
emitted VUV radiation from one light source was used in two simultaneous but separate photochemical
reactions: (1) photochemical generation of ozone by irradiating oxygen in the gas phase and (Z) photolysis of
the aqueous reaction system. The gas stream containing the generated ozone is sparged into the reaction
system, thus enhancing the oxidative degradation of organic pollutants. The photochemically generated
ozone in the gas phase was quantitatively analyzed, and the kinetics of the degradation of 4-chlorophenol (4•
CP) and of the dissolved organic carbon (DOC) were determined under different experimental conditions.
The results show that the rates of degradation of the substrate and of the DOC decrease in the order of the
applied processes, VUV/0 3 > 03 > VUV. © 1997 IAWQ. Published by Elsevier Science Ltd

KEYWORDS

4-Chlorophenol; hydroxyl radical; ozonation; ozone; photochemical reactor; vacuum ultraviolet; waste
water.

INTRODUCTION

In most cases, AOP's rely on the combination of ultraviolet radiation and oxidants (HzO z, 03' etc.) to
generate reactive intennediates, mainly hydroxyl radicals (Legrini et at., 1993), which are considered to
initiate the oxidative degradation of target pollutants (Braun et at., 1993a). Integration of AOP's into
optimally designed treatment facilities constitutes a very challenging problem in tenns of polyvalence and
costs. Concerning the UV/03 process, investment in ozonizers, replacement costs of UV lamps and energy
costs for light and ozone generation represent about half of both the capital and operating costs of a
treatment facility (Ollis, 1993).

Photo-initiated water treatment processes using vacuum ultraviolet (VUV, A. < 200 nm) radiation may
represent an alternative to methods relying on oxidant photolysis, because no oxidant has to be added. In
fact, VUV photolysis of HzO is a means to generate hydroxyl radicals with high efficiency, since water
41
42 T. M. HASHEM et al.

absorbs VUV radiation with increasing cross-section and homolyses with increasing quantum yield as the
wavelength of excitation decreases from approximately 190 to 140 nm (Weeks et al., 1963).

VUV photochemical processes have received more attention after excimer light sources became aV~lable
(Kogelschatz, 1992). Our work in the domain of oxidative degradation has been concerned so far WIth the
reaction sequence implied in the degradation of a number of model substrates, such as 4-chlorophenol
(Jakob et aI., 1993), 3-methyl-isoxarnine, cyanide (Gonzalez et aI., 1995) and nitrate (Gonzalez and Braun,
1995, 1996a, b) in aqueous solution.

VUV excimer sources may also be used for the photochemical generation of ozone. Ozone may in fact be
produced efficiently by photochemical homolysis of molecular oxygen (Volman, 1963, McNesby and
Okabe, 1965), and by choosing the proper wavelength of excitation (light source), ionization of molecular
oxygen may be avoided. Eliasson and Kogelschatz (1991) investigated the photodissociation of molecular
oxygen and the subsequent ozone formation by using a Xe-excimer source. Earlier studies (Dohan and
Masschelein, 1987) attributed the drawbacks of low pressure mercury arcs in synthetic quartz envelopes to
their low radiation efficiency at 185 nm and to the small absorption cross-section of molecular oxygen.
However, the main disadvantage of the low pressure mercury arc arises from the more intense radiation at
254 nm with which the generated ozone is photolyzed.

The present study was undertaken with the objective of increasing the efficiency of a conventional
immersion-type excimer light source, e.g. by constructing a suitable reactor for two simultaneous and
spatially separated photochemical reactions using one light source: (1) ozone generation by irradiating
molecular oxygen in the gas phase and (2) photolysis of a condensed aqueous phase, thus trying to enhance
the overall oxidative degradation of organic pollutants (model compound: 4-chlorophenol (4-CP» dissolved
or dispersed in aqueous systems. This seems possible, since both water and molecular oxygen show high
absorption cross-sections in the spectral range of the emission of Xe-excimer light sources O"max = 172 ± 14
nm). In addition, there is an attractive technical potential, as excimer light sources may be varied with
respect to geometry and electrode configuration (Braun et al., 1993b), and new photochemical equipment
may be designed for optimal use of the emitted VUV radiation.

In addition, for VUV irradiated reaction systems producing H 20 2, addition of 03 may lead to higher total
rates of hydroxyl radical production, because of the fast reaction of 03 with hydrogen peroxide and the
peroxide anion. It is therefore interesting to determine eventual synergistic effects of the two combined
methods of oxidative degradation.

EXPERTIMENTALPROCEDURES

Materials. 4-Chlorophenol (Fluka) 99% was used without further purification. Oxygen purity was of
99.998% (Messer Griesheim). Pure water used as solvent in all experiments was provided by a MilliQ
system.

Photochemical equipment. The photochemical installation is shown in Figure 1. A Xe-excimer lamp built of
two concentric SuprasilR quartz cylinders (outer diameter: 30 mm, inner diameter: 17 mm, radiant length:
250 mm) was mounted in the axial position of a cylindrical reactor (outer diameter 50 mm, length 300 mrn)
leaving a cylindrical radial width of 8 mm. The light source was driven by a high voltage power supply (ENI
Model HPG-2) where the electrical power applied could be varied between 100 and 150 W. In case of
experiments involving VUV photolysis of the aqueous reaction system, the reactor was linked to a reservoir
of 3 L, and the irradiated solution was circulated in a batch mode by means of a pump (114 L'h-I).

Ozone was ~enerated by irradiation of a stream of oxygen passing at constant flow rate through the inner
tube of the lIght source. The outer electrode was made of a wire net and fixed at the outer surface of the
reactor, while the inner electrode was fixed in the axis of the lamp and coated with gold to be inert toward
ozone. Valves were installed to direct the generated ozone through a flow cell (quartz) allowing for direct
 Vacuum ultraviolet radiation 43

spectro~hotometric analysis in the gas phase, or, alternately, to be sparged into the aqueous solution at the
reserVOlf.

three way spectrophotometer vent

valve

...
pump ... temp.
control

ozone
sparger
oxygen
Figure I. Photochemical installation.

Procedures. 3 L of an aqueous solution of 4-chlorophenol (5xlO- 4 molL-I) were treated at 20 (± 1) DC in all

experiments. Duplicate samples (5 ml) were withdrawn from the reservoir for HPLC and TOC analyses at
different time intervals. In experiments, where the solutions were irradiated only with VUV, oxygen was
introduced into the reservoir at the same flow rate as used in ozonation experiments.

Analyses. Generated ozone was analyzed in an on-line mode, where direct spectrophotometric measurements
were conducted in the gas phase at 258 nm (03, £258: 3000 L·mol-1.cm-I (Gordon et al., 1987)). The
evolution of the 4-CP concentration was followed by HPLC (Hewlett Packard 1050 Ti-Series) at a detection
wavelength of 224 nm. Separation of 4-CP was conducted on a reversed phase column (LiCroCART 100RP•
18 HP) with methanol/water (55%/45%) as eluent. Total organic carbon (TOC) analysis was carried out
using a TOC analyzer (DOHRMANN DC-190).

RESULTS AND DISCUSSION

Ozone generation

Absorption spectra in figure 2 show the results of the on-line spectrophotometric analysis of the photo•
chemically generated ozone as a function of the electrical power of the light source. Under the given
conditions, the amount of the generated ozone was found to increase with increasing electrical power of the
light source, and no saturation could be found within the range of the power supply in use.

Earlier investigations had shown that the mechanisms of dissociation of excited molecular oxygen and
formation of ozone depend on the wavelength of excitation (Volman, 1963), the dissociation of molecular
oxygen being under all circumstances the primary photochemical process. The wavelength of excitation
applied in our investigations (172 nm) corresponds to a photon energy of 7.2 eV capable of dissociating
molecular into atomic oxygen (reaction 1), however, ionization of 02 is excluded, as this process takes only
place at much higher photon energies.

02 + hu 20 (1)

Atomic oxygen generated by VUV reacts subsequently via three-body reactions to produce molecular
oxygen and ozone (reactions 2 and 3). Alternatively, deactivation of atomic oxygen may occur yielding
44 T. M. HASHEM el at.

_. . f. I I s participating
lower excited states of atomic oxygen, as well as vlbratlonally excited states 0 mert mo ecu e
in those collisions and singlet oxygen (reactions 4 and 5) (Dvornikov and Pukhov, 1995).
(2)
° + ° + M

° + 02 + M 03 + M
(3)

---t~~ °(lower state) + N2 (v> 0) (4)

(5)
0+02

1.2
- -. - - 150 W
--140W
_. _. - 130 W
--120W
--llOW
0.8 ....•---- 100 W
Il)
C,) --90W
~ --80W
-e0 0.6 --70W
--60W
CIl
.0
~
--50W
0.4 --40W

0.2

o
200 220 240 260 280 300 320

Wanelength [nm]
Figure 2. Absorption spectra of ozone in the gas phase measured in a continuous flow mode as a function of the
electrical power of the light source (Oz: 0.8 bar at a flow rate of 1.115 L-min- 1).

Ozone was generated by irradiating either pure oxygen or synthetic air under identical conditions. The
dependence of the concentration of generated ozone on both the irradiated gas and its flow rate is shown in
Figure 3. For a given incident photon rate, the concentration of ozone shows a remarkable dependence on
the flow rate, in particular in the lower range. It is also interesting to note that this dependence is similar for
conditions, where ozone is generated from either pure oxygen or synthetic air. However, in the latter case,
lower concentrations of ozone were always observed and may be attributed to the lower content of 02'

Oxidation of 4-chIorophenol

Figure 4 shows the pseudo-first order kinetics of the degradation of 4-chlorophenol in water upon VUV
irradiation, ozonation or a combination of both. Although total degradation of the substrate has been
achieved regardless of the process, different depletion rates were observed. These rates decreased in the
order of the processes, VUV/03 > 03 > VUV. Oxidation of organic substrates upon VUV irradiation of the
aqueous phase is attributed to the impact of hydroxyl radicals formed during water photolysis (reactions 6
and 7). Since photolysis of 4-CP can be excluded (Jakob et al., 1993), reaction 6 may be considered as the
initial step of the oxidative degradation of 4-CP.
 Vacuum ultraviolet radiation 45

H2O + hu (A = 172 nm) ~ HO· + H· (6)

HO· + RH ~ H2O + R· (7)

25
• Air
---0-- oxygen
20

15

(I)
§
10
o
5

Flow rate [Umin]

Figure 3. Concentration of ozone as a function of the flow rate of the irradiated gas at constant lamp power (100
W).

0.,....---------------------,

..-..0
-0.5
......,
c..
UI
......
.....
"<t • VlN+03 calculated
......,
c.. -1 • VlN+0 3 observed

•
UI
VlN
......
"<t
'-"

-c:: • °3

-1.5

-2
o 10 20 30 40 50
run time [min]
Figure 4. Kinetics of degradation of 4-CP under different experimental conditions ([4-CP] 0= 5x I0-4 mol·L -1, lamp
power: 100 W).
46 T. M. HASHEM et al.

In contrast to the VUV process (reaction 6), ozonation of organic compounds may proceed via different
reaction pathways. Hoigne and Bader (1983a, b, 1985) studied extensively mechanisms and rate constants of
the reactions of ozone with organic and inorganic compounds in aqueous solution. Ozone may react with the
substrate or with oxidants, such as H20 2, yielding secondary oxidative species which may attack the
substrate as well. In most cases, the nature of the organic substrate, eventual oxidants present and the pH of
the solution determine the dominant mechanism. In addition, the reaction of ozone with the hydroperoxyl
radical and its deprotonated form, superoxide anion, has been described (von Sonntag and Schuchmann,
1991 ).

Hydroxyl radicals react with phenol and phenolate ion with rate constants of the order of 109-10 10 L·mol-1.s •
1 (Buxton et al., 1988). In contrast, the reaction of ozone with these compounds is highly selective exhibiting
extremely different rate constants (4-chlorophenol: 600 Lmol-1.s-l, 4-chlorophenolate: 0.6x10 9 Lmol-1.s -l)
(Hoigne and Bader, 1983b). With a pKa of 9.2, an aqueous solution of 5x1O- 4 mol-L- 1 of 4-CP (pH-4.5)
contains practically no 4-chlorophenolate.

The depletion of 4-CP upon ozonation of its aqueous solution may therefore be attributed to the reactions of
substrate with ozone and with hydroxyl radicals. The latter are generated by the reaction of ozone with
hydroperoxyl radical and superoxide anion eliminated from organic peroxyl radicals during oxidative
degradation of the oxidation products of 4-CP (see below). The fact that the rate of substrate depletion by
ozone is faster than that of the (VUV)photo-induced degradation process may be explained by the highly
localized generation and reaction of hydroxyl radicals (reaction 6 and 7) in the latter procedure. Hydroxyl
radicals being produced and trapped within a thin layer on the surface of the light source, depletion of the
substrate within this layer occurs, as its replacement by diffusion from the bulk solution is slow in
comparison (Heit et al., 1995). In contrast, sparging the substrate solution with 0Tcontaining air or oxygen
at high flow rate accomplishes good mixing and contributes largely to a statistical distribution of all
oxidative species (Hoigne and Bader 1983a, b, 1985, Legrini et al., 1993).

The apparent degradation rate of 4-CP in case of a combination of the VUV and 03 procedures (kVUY/03 =
6.45x 1O- 2's- l , Figure 4) is slightly higher than the value which would have been predicted by simple addition
of the rates of the two distinct degradation processes (k03 = 4.25x1O- 2·s- 1 andk yUY = 1.36x1O- 2·s- I ). Taking
into account limits of error of 5%, we may conclude that there is no evidence for a significant synergistic
effect in combining the two processes.

Mineralization of TOC

The kinetics of the mineralization (difference between TOC o and TOC t) vs reaction time is shown in Figure
5. Under the given conditions (total reaction time: 350 min), total mineralization of the organic substrate has
only been achieved in the case of the combined VUV/03 process.

In presence of oxygen, the organic radicals formed in reaction 7 undergo addition of molecular oxygen to
yield peroxyl radicals (reaction 8). These reactive intermediates initiate thermal reactions of oxidative
degradation leading finally to carbon dioxide and water. Due to the higher solubility of ozone in water
compared to oxygen, reaction 9 may be considered dominant when ozone is added to the reaction system
(von Sonntag et al., 1993).

(8)

RO' + 02 (9)

°
Peroxyl radicals may undergo H02· and/or 2-. elimination (reaction 10), and Of· may dominate (pK a
°
(H0 2·) = 4.8) in natural aqueous sytsems (von Sonntag and Schuchmann, 1991). As the reaction of 2-. with
03 exhibits a higher rate constant than that of all other reactions of 02·- with the different solutes present
 Vacuum ultraviolet radiation 47

(Staehelin and Hoigne, 1982), a rather efficient promotion of a chain reaction to yield hydroxyl radicals may
be postulated (reactions II-B).

R0 2° ... H0 2 %

2°- + products (10)

° 2 0
•
+ °3 .... ° 3 0
•
+ °2 (11)

°3 0
•
+ H+ .... H0 3° (12)

H0 3° ..... °2 + HO° (13)

It is interesting to note that the combined processes exhibit again a slightly higher apparent rate constant of
TOC degradation than that calculated by adding the apparent rate constants of the VUV and 03 processes.
Although, the difference between the observed and the calculated rate constants is small taking into account
experimental errors, the coincidence of the two results for 4-CP and TOC degradation suggests to
reinvestigate the question of synergistic effects.

35
• VUV+0 3 observed
30
• VUV+03 calculated
~

• VUV

l 25
... °3
~
Eo-<
20
-e
.§ 15
'a
I-<

~
·s 10

0
0 50 100 150 200
run time [min]
Figure 5. Kinetics of TOC mineralization under different experimental conditions ([4-CP] 0: 5x 10-4 mol·L -I, lamp
power: 100 W).

CONCLUSION

Total degradation of 4-chlorophenol has been observed with VUV irradiation, ozonation and the
combination VUV/0 3. 4-CP and TOC degradations follow pseudo-first order and pseudo-zero order
kinetics, respectively, as would have been expected. The apparent rate constants of the combined processes
are found to be slightly higher than the sums of the apparent rate constants of the two processes applied
separately. This result might be interpreted as a sign of a synergistic effect obtained by combining the two
oxidation procedures. Such an effect could be explained by an increase of the reaction volume in which
hydroxyl radicals might be present. However, more experiments are needed in order to prove such an effect.
48 T. M. HASHEM et al.

Implementing two separate photochemical reactions in one photochemical reactor using one excimer light
source leads, in case where both reactions yield oxidants or oxidative intennediates, to an enhancement of
the apparent rate of oxidative degradation. This principle might be useful in order to use such light sources
in a more efficient way.

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