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Ozone (O3) generation and its applications: A review

Conference Paper in AIP Conference Proceedings · January 2023

DOI: 10.1063/5.0144316

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 Ozone (O3) Generation and its Applications: A Review
Pranav Meher a) Nilesh Deshmukh b) Anil Mashalkar c) and Deepak Kumar d)

School of Mechanical Engineering, Dr. Vishwanath Karad MIT World Peace University, Pune 411038, India
a)
Corresponding Author: meherpranav5@gmail.com
b)
deshmukh.nilesh0902@gmail.com
c)
anil.mashalkar@mitwpu.edu.in
d)
deepak.kumar@mitwpu.edu.in

Abstract. With the spread of pathogens like SARS-CoV-2, the urge for ergonomic disinfection techniques regained
momentum. Ozone is a proven oxidizing agent that leaves no harmful residue after oxidation. Due to its green and cost-
effective attributes, it is widely used for various industrial and domestic treatment/disinfection applications. In this paper,
three mainstream Ozone generation methods i.e. (i) electrochemical method, (ii) ultraviolet ray method, and (iii) plasma
discharge method are reviewed. The first step in Ozone generation involves the decomposition of molecular Oxygen into
atomic Oxygen that requires the energy of certain intensity. This requirement of energy is fulfilled using Platinum coated
PbO2 electrode, UV ray lamps with a certain range of wavelengths, and secondary streamers in plasma arc, respectively.
In addition to the generation methods, various application of Ozone in wastewater treatment, fish-farming, food, and dairy
industry, and odor treatment has also been reviewed.

INTRODUCTION
Since the inception of the Covid-19 pandemic, the awareness about sanitization/disinfection has increased
significantly. In general, the microbial contaminants are single or multi-cellular organisms and cannot be detected
from naked eyes. These microbes are extremely dangerous and can cause significant harm to the health of both humans
and animals. The chemical and thermal disinfection techniques are the commonly available solutions for disinfecting
nonliving and non-edible surfaces and commodities [42], [44], [48]. However, the chemical disinfection techniques
are not suitable for edible commodities as they leave toxic residue. The most widespread technology used for
preservation and food sterilization is heat treatment/thermal technology. While heat treatment technologies such as
pasteurization cause the elimination of microbes and hence ensure the increased shelf life of the food product, the
same technology also destroys the soluble Vitamins and Protein due to exposure to high temperature and hence reduce
the nutrition value of the edible commodity [14]. In addition to this, the heat-treatment of edible commodities can also
alter the sensory properties and bio-active photo-chemicals [14], [23]. The aforementioned issues with thermal
disinfection technologies motivated the research community to explore the non-thermal alternatives. Non-thermal
treatment is done at ambient temperatures for a limited period. Thus, the nutritional value, texture, and sensory
properties of the commodity remain intact. Ozone treatment, being a green, non-thermal, eco-friendly and cost-
effective disinfection technology, largely addresses the problem of disinfection/sterilization of edible commodities
[24], [25], [45].
The history of Ozone dates back to the mid-eighteenth century (1839-1868) when Christian Schonbein, a German-
Swiss chemist perceived a distinctive smell during his electrolysis experiments with water [47]. The formation of
Ozone (O3) is attributed to the amalgamation of free oxygen radicals with oxygen molecules. The chemical reaction
results in the formation of extremely unstable triatomic Oxygen (O3). Ozone being highly oxidizing reacts with nearby
chemical compounds to form reactive Oxygen specious. Ozone in its unstable form is toxic and can be detected easily
by its odor, once its concentration reaches a value of 0.003 PPM. Despite being toxic, the highly reactive behavior of
Ozone eventually decomposes it into non-toxic molecular Oxygen. Therefore, the predominantly oxidizing behavior
of Ozone and its ability to leave non-toxic end products makes it a suitable disinfecting candidate in a variety of
applications like water treatment, sewage treatment, biofilters for odor elimination, food and grain treatment for
increasing shelf life, treatment of meat and dairy products and many more. A few of Ozone's important chemical and
thermodynamic properties and a comparison of Ozone with other strong oxidizers are listed in table I and table II,
respectively. Therefore, this paper aims to review the various Ozone generation methods and the application of Ozone
in possible engineering applications.

OZONE GENERATION METHODS

Ozone is naturally formed in the Stratosphere between 20 and 30 Km from the earth’s surface. The ultraviolet
(UV) radiation from the sun with a wavelength in the range of 240 nm, breaks the oxygen molecule into free oxygen
ions/radicals. This free Oxygen further reacts with oxygen molecules to give Ozone.

TABLE 1. Ozone Generation and its application: Important chemical and thermodynamics properties of Ozone.

Name Oxidation Potential Boiling Point Melting Point Nature Molecular Weight
Ozone (O3) 2.07 Volts -112O C -192.2o C Toxic 48 g/mol

TABLE 2. Ozone Generation and its application: Comparison of oxidation potentials of free radicals in descending order

Sr. No. Oxidant Oxidation Potential E0/V

1 O2 1.20
2 IO3 1.2
3 Cl2 1.27
4 HOCL 1.49
5 KMnO4 1.70
6 HO2 1.70
7 H2O2 1.76
8 H2SO5 1.81
9 BrO4- 1.85
10 O3 2.01
11 F2 3.00

Due to its exceptional oxidizing and disinfection characteristics, ozone generation and application attracted plenty
of researchers. The available literature suggests majorly three techniques of commercial Ozone generation:
 Electrochemical methods
 ultraviolet radiation methods
 Electrical discharge methods

Electrochemical Generation of Ozone

Figure 1 demonstrates the classical Ozone generation using the electrochemical method. The electrochemical
decomposition of ionic compounds into their constituent ions by passing current to a dielectric medium is called
electrolysis. Ozone was first detected during a similar experiment by Christian Schonbein (see section 1). Since then,
many researchers have investigated the Ozone generation potential of the electrochemical process. A comprehensive
compilation of the same can be found in [7], [46]. The electrochemical generation of Ozone is affected by the selection
of parameters like anode, temperature, PH, current density, the composition of the electrolyte, etc. The formation of
Oxygen accompanies the Ozone generation during the electrolysis of water. This is attributed to the lower electrode
potential of Oxygen (1.21 V) than that of Ozone (1.51 V) [10]. Equation 1 and 2 represents the half equations during
the electrolysis of water.

3H2O =⇒ O3 + 6H+ + 6e − E◦ = 1.51V (1)

2H2O =⇒ O2 + 2H+ + 2e − E◦ = 1.23V (2)

The formation of Oxygen can be suppressed by using anodes with high anodic overpotential [9]. The effect of
anodic material on the electrolysis of water is investigated by [1], [50], and [2]. The highest efficiency of electro
generation of Ozone was found at E◦ = 1.8V [1]. [2] Also reported a similar trend of higher Ozone generation at higher
E◦. Later [53] identified OH- as the intermediate product at the PbO2 anode. The half-life of Ozone in water, around

FIGURE 1. Generation of Ozone: Schematic representation of Ozone generation using electrochemical method.

30 minutes at 150C, bears an inverse relation with temperature [41]. The effect of PH values of water on the Ozone
formation process is reported in [8]. They found that the stability of Ozone in water predominantly depends on the PH
values. Ozone is most stable at around a PH value of 6.0 and least at PH equals 10.

The instability is to the formation of more and more hydroxyl radicals (OH -) at higher PH values. (OH-) is even
more oxidizing than Ozone. Therefore, during wastewater treatment application, the contribution of both, i.e. O 3 and
(OH-), is of paramount importance in understanding and explaining the results [19]. The selection of electrolyte and
electrode is critical in deciding the current efficiency for Ozone generation [15]. The current efficiency is stated as the
percentage of the current required for Ozone generation, i.e., the proportion of the current utilized for Ozone to the
overall current used in the process. A higher anion coverage (the ability to absorb the anion from electrolyte) can lead
to lower current efficiency in the electro generation of Ozone using PbO2 anode. The transfer of charged particles
across an electrode is called a Faradaic current (FC) [22]. The opinions of researchers on the instantaneous formation
of Ozone due to the flow of FC are different. For instance, Kotz and Stucki (1987), [26] observed Ozone only after
the current density crossed 50 mA/Cm2; Kaneda et al. (2006) [28] reported initiation of Ozone evolution at current
densities greater than 30 mA cm2. In another work by Feng et al., 1994), [16], Ozone was observed as soon as the
Faradaic current started flowing through the electrolytes/electrodes. A compilation of the recent works on Ozone
generation using electrochemical methods is listed in Table III. This discrepancy in the results observed by researchers
is due to the variation in anode material. Advantages of generating Ozone electrochemically include low voltage
operation, potentially generating high concentration Ozone in both the gaseous and liquid phases while maintaining
good current efficiency, any type of gas feed is not required.

Generation of Ozone by Ultraviolet Rays

Figure 2 illustrates the mechanism of Ozone generation using ultraviolet (UV) radiation. As discussed in section
1, Ozone is naturally made in Stratosphere as the UV rays having a definite energy spectrum, interact with Oxygen
molecules available in the air. The oxygen molecule breaks into isolated Oxygen atoms. The fast-moving Oxygen
atoms fail to combine with the oxygen molecule available in their vicinity, whereas the slow-moving Oxygen
combines with the diatomic Oxygen molecule to make triatomic Ozone. The chemical reaction involved in Ozone
formation due to solar radiation is mentioned in equation 3. The continuous occurrence of these reactions in the
stratospheric atmosphere, in the presence of solar radiation, leads to the continuous formation and destruction of the
Ozone. 21% of the atmosphere is naturally made of Ozone [52].

O2 + UV (< 242nm) =⇒ O + O (3)

TABLE 3. Generation of Ozone using electrochemical method.

Sr.No. Author Experimental setup Outcome

and year
1 Da Silva et Anode: PbO2deposited on platinized In many possible conditions, an electrolyte's nature
al., (2006) titanium substrate. greatly influences the electrochemical Ozone generation
[10] process.
Cathode: platinized titanium substrate
Electrolyte: Solid polymer electrolyte
Temperature:0°C,10°C,20°C
2 Feng et al., Anode: βPbO2/Ti For Ozone generation, current efficiency is slightly
(1994) [16] more in Fe3 doped PbO2 electrodes.
Temperature: 10ºC
Current Density: 200 mA cm-2
3 Graves et Anode: βPbO2/Eb2 For Ozone generation, PbO2anode needs to be used at a
al., (1992) large scale. Also, PbO2/Ebonix are the same as anode
[18] Temperature: 0°C PbO2 in the current efficiency of Ozone preparation.
Current Density: 190 mA cm-2
4 Awad Anode: PbO2/Pts ( PbO2loaded pt screen) O3 was generated electrochemically from H2SO4
(2010) [1] H2SO4 in room temp.(25°C) Temperature: solution on PbO2-loaded pt screen electrodes. The
25°C efficiency obtained in electrochemical Ozone generation
is 1.8 V per 0.5 M of H2SO4.
5 Arihara et Anode: Freestanding boron-doped Diamond electrodes have enough stability as required
al., (2006) diamond electrode, H2SO4 1 mole for the durability of Ozone generation. So, it is highly
[3] Temperature: 20°C and 25°C recommended for an efficient electrochemical Ozone
water process (EOWP) by pure water electrolysis.

The energy used for the photodissociation of O2 molecules must be high enough to break the molecule, but should not
be very high, which can lead to ionization. Therefore the wavelength of UV radiation must be within the range of (103
nm - 242nm). As the wavelength is inversely proportional to energy, the upper limit is 103nm, and the lower limit is
242nm [12]. UV-C lamps can facilitate the commercial/laboratory production of Ozone. The enveloping material and
the sealing of the lamps grossly decide whether a lamp can produce Ozone or not [30]. As discussed earlier, Ozone
can be created in the presence of UV radiation with a wavelength of 103 nm - 242nm [13]. Therefore, With the special
provision of pressure and the filling environment inside the envelope of the lamp, low wavelength radiation can be
created, which further creates Ozone [6]. A comprehensive compilation of the types of lamps and the corresponding
envelope material and radiation can be found in Table 4.

FIGURE 2. Generation of Ozone: Schematic representation of Ozone using ultraviolet radiation method.

TABLE 4. Ozone Generation using ultraviolet lamps: Various linds of ultraviolet lamps used for Ozone generation.

Lamp Type Envelop Inside environment Radiation range in Ozone

Material (nm) generation
Yes/No/Both
Low-pressure Mercury Soft glass Melting temp. <600OC 254 No
Lamp Liquid/Gaseous
Xenon Lamp Fused quartz Gaseous 170 No
High-pressure short arc Standard quartz >500OC 185 Yes
Mercury lamp
Gaseous
Xenon Excimer Lamps Special quartz Gaseous 172 Yes
glass
Krypton-chloride Lamp Kr-Cl gas Gaseous 222 Yes

Generation of Ozone in Non-Thermal Plasma

The word ‘plasma’ was coined by Irving Langmuir in 1928 to describe the ionized gas with suspended electrons,
ions, and excited particles. Plasma is also called the ‘fourth state of matter [5]. Based on the energy of electrons
and ions, plasma is classified as thermal or non-thermal. In thermal Plasma, the electrons and ions achieve thermal
equilibrium. Whereas, in non-thermal Plasma, the mean energy of electrons is higher than that of ions.
Methods for Plasma generation include accelerating electrons in an electric field, including various electrical
discharges or injection of electrons externally, which requires an electron beam. Dielectric barrier discharge (DBD)
and corona discharge are the two main types used to accelerate the electrons by an electric field to generate Ozone.
Corona discharge comparatively has less power that occurs at a pressure closer to the atmosphere. For corona
discharge, a thin wire or at least one sharp electrode is required for ionizing neutral gas atoms, for which a high electric
field is required. These sharp electrodes are responsible for high electric fields. [40]. Discharges with dielectric
materials used as plasma stabilizers are referred to as dielectric barrier discharges. Ono and Oda (2006), [36] revealed
that the DBD formation occurs in three phases; i.e., (i) Primary streamer, (ii) Secondary Streamer, and surface
discharge. Ozone formation occurs only in the secondary streamer and surface discharge phases.
 Streamers are luminous arc-like structures comprised of ionized air molecules, which can conditionally look like
Tree branches. They are formed in two phases, primary and secondary. The process of Ozone generation using plasma
discharge is demonstrated in Figure 3. Figure 3(c-f) describes the primary, secondary, and surface discharge zones. It
is evident that as the voltage increases, the extent of the secondary streamer also increases. The energy emitted in the
secondary streamer zone is five to ten times higher than that of the primary zone and is suitable for the breaking of
molecular Oxygen into atomic Oxygen and hence ozone formation. Figure3(b) represents the concentration of
generated Ozone in the secondary streamer and surface discharge phase. It is depicted from the plot that the Ozone
generation in the secondary streamer zone is dominant [35].
In air-fed Ozone generators, the presence of Nitrogen hinders the process of Ozone generation as it leads to the
destruction of Ozone by forming nitrogen oxides, which results in lower efficiency. [55]. Ozone generation efficiency
can be improved by increasing pressure and reducing the temperature of gas used for Ozone generation [27]. The
various methods of Ozone generation using plasma-discharge methods are listed in Table VI Electron impact
dissociation is the very first step in the formation of Ozone, as it leads to the dissociation of the Oxygen and nitrogen
molecules into atomic Oxygen and Nitrogen. The Ozone generation is followed by the dissociation steps. The process
of dissociation and Ozone generation can be understood clearly from the following equations:

e+O2 =⇒ O+O+e (4)

e+N2 =⇒ N+N+e, (5)
O+O2 =⇒ O3 +M, (6)
O+O+M =⇒ O2 +M (7)

It can be clearly understood from equations 4-7 that both Oxygen and Nitrogen are broken due to the interaction
with the energy of the arc. Later, the diatomic Oxygen is converted into Ozone. Even though not shown here,
monoatomic Oxygen reacts with mono-atomic Nitrogen to form its oxides. In another experimental study on DBD
[38], it was found that the concentration of Ozone depends on combined parameters (frequency and power). At a
higher frequency of driving voltage more concentration was observed at low power and vice-versa. The effect of
frequency and voltage on generated Ozone concentration is listed in table V.

TABLE 5. Comparative study of Ozone generation at different voltages

Sr. No. Frequency Voltage intensity Ozone Generation (Comparative result)

1 26.3 kHz Low High
2 10.9 kHz High Low

APPLICATIONS OF OZONE

Application of Ozone in Water Treatment

In freshwater, as a disinfectant, leveraging the unstable nature, Ozone can prove to be effective against resistant
microorganisms and also more effective than chlorine in eliminating viruses, Giardia, and some specific forms of
algae. However, the instability also leads to a shorter lifetime of Ozone, as it decomposes to Oxygen very fast. The
decomposition is proportional to the pH of water. Attributing to these cons, Ozone has been away from large systems.
In water treatment applications, Ozone must be used with some other material, as the low stability leads Ozone to
react and form some oxygenated, biodegradable by-products, which can increase the risk of biological regrowth.
Hence to prevent this regrowth, Ozone needs to be combined with some form of filtration [20]. Wastewater generally
contains more than one odorous compound and they may have an additional effect on the generation of odor from the
wastewater sources. In a research work [37], it is realized that the wastewater from industrial units such as sewage
treatment plants and textile water is hard to degrade. In addition to this, it is also malodorous to the nearby
environment. They collected samples from washing bath waste, dye bath, and textile water waste. Washing bath was
found to be most resistant to Ozone treatment. Also, Ozone treatment was observed to be a suitable technique for
 (a) (b)

(c) (d)

(e) (f)
FIGURE 3. Generation of Ozone: (a) Schematic representation of Ozone generation using non-thermal plasma. (b) The
concentration of Ozone in primary and secondary streamer phases as a function of time. (c−f) The effect of applied voltage in the
formation and extent of secondary streamer zone. Figures 3(c-e) reproduced with permission from data published in ref. [35]
Copyright 2003 IOP Publishing Ltd. Figures 3(b) and 3(f) reproduced with permission from data published in ref. [36] Copyright
2007 IOP Publishing Ltd.

discoloration of wastewater pollutants from dye house [37]. Later, in an experimental study on piggery wastewater
from a local farm, it was established that Ozone can be used as an effective oxidizing agent to eliminate micro algae
provided that it is used in adequate concentrations. It was observed that Ozone is effective to mangle the cytoplasmic
membrane of the cell, nucleic acid and cell wall of microorganisms [17].

TABLE 6. A compilation of Ozone generation of methods using plasma-discharge

Sr.No. Author Configuration Experimental Setup Outcome

1 Yagi et al., Cross-sectional, Electrodes: Stainless Steel, Presence of Nitrogen in the air hinders the
(1979) [55] tube type air-fed dielectric glass electrode process of Ozone generation by forming
Ozonizers. nitrogen oxides.
Coolant: Water + ethylene
glycol
2 Kitayama Tube-type Ozone Tube type: The efficiency of Ozone generation can be
et al., generator and Plate- optimized by keeping the electric field strength
(1999) [27] type Ozone Electrodes: Grounded SS around 100Td. Efficiency is highly damaged at
generator. cylinder, high-voltage electric field strength around 200Td and
glass dielectric tube with temperature 350K. Narrowing discharge gap
an inner metal coating. and optimized gas pressure can achieve a high
Discharge Area: 2950cm2 concentration of Ozone
Coolant: Water
Plate type:
Electrodes: High-Voltage
ceramic dielectric plate of
thickness 1mm, Grounded
electrode.
Discharge Area: 220cm2.
Coolant: Water
3 Ono et al., Pin to plane Anode: 0.3 mm diameter Ozone density is maximum in the secondary
(2003) [35] SS needles streamer, followed by surface discharge and
then the primary streamer.
Cathode: Copper plate
Discharge Gap: 5mm
Applied Voltage: 24kV
4 Morent et Multi-pin to plane Varied residence time Proposed a model suggesting Ozone
al., (2005) range: 0.072s to 0.016s concentration discharge current, residence time.
[33] Varied Relative humidity And concentration decreases with an increase
range: 30% to 65% in humidity, temperature.
Discharge Gap: 13mm
5 Pekarek et Circular “rays” Electrodes: Pure Alumina The maximum concentration of Ozone for the
al., (2012) structure for Surface Al2O3 plates; 0.635 mm two frequencies is achieved with low voltages.
[38] DBD thickness TiO2 helps significantly to increase Ozone
concentration.
Photocatalyst: TiO2
Frequencies and voltage
combinations: 10.9kHz and
max 9kV 26.3kHz and max
8kV

Application of Ozone in Concentrated Fish Farming

In recent years Ozone Generation is widely used in fish farming and aquaculture, as Ozone has many advantages
over water treatment methods. Water used in aquaculture needs to be disinfected by Ozone regularly to maintain the
proper condition for fish farming and also to prepare the fresh environment for the better health of aquatic animals.
As Ozone is much capable of working as a better disinfectant without producing harmful byproducts and chemical
residues. So, Ozone on water treatment lowers the chances of illness and maintains the health of aquatic habitats which
leads to an increase in the lifespan of Aquaculture. For the prevention and elimination of fish diseases in aquaculture,
the system Ozone can play an important role in it. As it is a very powerful oxidizing agent that helps to disinfect and
also oxidize organic pollutants, it also increases the level of Oxygen dissolved in water. In the end, Ozone treatment
gives extraordinary water quality which is a basic and important requirement for intensive fish farming. Ozone is also
very powerful in eliminating and detoxifying mold and mycotoxins like clavacin, cyclopiazonic acid, Secalonic acid,
Aflatoxin B 1, ochratoxin A. In research work, McKenzie determined the factors that Ozone can kill insects, destroy
the bacteria responsible for rotting the food, destroy and remove the molds. Also, decontamination relies on Ozone
concentration level, exposure time and PH [51].

Application of Ozone in Food and Beverages

The characteristic of Ozone to be used as a green oxidant makes it effective for disinfection of different kinds of
vegetables, fruits, meat, grains and dairy products. As Ozone is widely used in food processing [29]. In food processing
industry, it is possible to utilize Ozone in its both aqueous form and gaseous form [44]. Ozone quickly decomposes to
produce Oxygen without leaving any harmful residue in the food [56]. In recent years, the disinfection of water has
been done for many purposes i.e. in drinking, spas, swimming pools, fish farming, to treat municipal water and sewage
and also to prevent the bio-growth in cooling towers, because of its powerful antimicrobial substances. Additionally,
Ozone is useful in the vegetables, meat, fruit, fish and also herb, spice and beverage industries [57]. However, Ozone
in its molecular form is toxic and hazardous to human health. Therefore, dosage of Ozone needs to be monitored and
used as the most important criteria for its approval [39].

Application of Ozone in Odor Control System

For odor control Ozonation is one of the alternate methods. Ozonation implies the additional amount of Ozone
diluted in the air to the system containing odor compounds. As Ozone is one of the powerful oxidants also is a very
eactive and unstable chemical, it treats odors by oxidizing odor compounds to form chemicals with zero possibility of
odor [11]. Odor problems are only present in a limited area of the emitting source so that toxic and malodorous can
result in the quality of rural life and property values in which they occur [49]. According to Wang [54], preventing
the odor generation or treating them at the initial stage which is before the odor is released to the environment are
some of the basic ways to control odor. The steps to control odor include identification of the source, measurement of
odor flux, then choosing the best-suited method for treating and controlling the odor [43]. Odor control with chemicals
requires a high amount of chemicals at frequent intervals in order to be effective.
Essentially Ozone is used as a disinfectant, although it can be used for the elimination of odors. Since the early 1900s
Ozone is used to treat odors and has also been widely used in developed countries.

CONCLUSION
Three mainstream Ozone generation methods i.e. (i) Electrochemical method, (ii) Ultraviolet Method, (iii) Plasma
discharge method have been reviewed. The literature suggests that the highest efficiency for Ozone generation can be
achieved in Electrochemical methods. This is attributed to the absence of Nitrogen in the electrolysis process. The
other two methods use the atmospheric air for Ozone generation which contains 78% N 2. Nitrogen combines with
atomic Oxygen to form Oxides which otherwise could be used for Ozone generation. In the ultraviolet radiation
method, the high-pressure-short arc mercury lamps, Xenon Excimer lamps, and Krypton-Chloride lamps can be used
for generating Ozone. Among these three, the Xenon Excimer lamps have the lowest wavelength and hence the highest
energy. Similarly, in plasma discharge methods, Ozone generation efficiency was found to be maximum in the
secondary streamer as the energy emitted in this zone was observed to be suitable for breaking the bonds of molecular
Oxygen without ionizing them. Ozone is a very strong oxidizing agent and hence highly unstable. The tendency of
Ozone to react with the organic/inorganic compound and its characteristic of leaving non-toxic residues makes it is
suitable for various disinfection and treatment processes. Because of this, Ozone is widely used in applications such
as wastewater treatment, agriculture, fish farming, dairy and meat industry, and odor cancellation applications.
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