1.

FENTON
Fenton's reagent is a solution of hydrogen peroxide (H2O2) with ferrous iron Fe2+ as a
catalyst that is used to oxidize contaminants or waste waters discovered by H.J.H. Fenton in
1894.

FENTON H2O2 Fe2+

1.1. Mechanism of Fenton process:

 Fenton and related reactions encompass reactions of peroxides (usually hydrogen
peroxide (H2O2)) with iron ions to form active oxygen species that oxidize organic or
inorganic compounds.
 So, Fenton reaction gives active oxygen i.e. •OH (hydroxyl radicals) and which is
most important oxidizing agent due to its highly reactive nature.
1.1.1. Reaction Mechanism:

Sychev et al. [1995] reported Fenton mechanism and its reaction by following manner-

i. Firstly, Fenton reaction oxidized ferrous to ferric ions to decompose H 2O2 into
hydroxyl radicals. It is usually considered as the core of the Fenton chemistry.

Fe2+ + H2O2 Fe3+ + OH- + •OH (Fenton reaction) (1)

ii. The generated ferric ions can be reduced by reaction with excess hydrogen peroxide
to form again ferrous ion and more radicals,

Fe3+ + H2O2 Fe2+ + •OOH + H+ (Fenton like reaction) (2)

This reaction is called Fenton-like reaction and slower than Fenton reaction,
and allows Fe2+ regeneration in an effective cyclic mechanism. In Fenton like
reaction, apart from ferrous ion regeneration, hydro-peroxyl radicals ( •OOH) are
produced. The hydro-peroxyl radicals may also attack organic contaminants, but they
are less sensitive than hydroxyl radicals. It should be noted that, the iron added in
small amount acts as a catalyst while H 2O2 is continuously consumed to produce
hydroxyl radicals.
iii. Rate limiting steps in the Fenton chemistry-

Fe2+ + •OH Fe3+ + OH- (3)

Fe2+ + •OOH Fe3+ + HOO- (4)

Fe3+ + •OOH Fe2+ + O2 + H+ (5)

These reactions are rate limiting because hydrogen peroxide is consumed and ferrous iron
is regenerated from ferric ion.
 iv. Radical–radical reactions or hydrogen peroxide–radical reaction:

•OH + •OH H2O2 (6)

•OH + H2O2 •OOH

+ H2O (7)

•OOH
+ •OOH H2O2 + O2 (8)

•OH + •OOH H2O + O2 (9)

v. Decomposition of hydrogen peroxide to molecular oxygen and water occurs in the

absence or presence of any organic molecule to be oxidized.
2H2O2 (10) 2H2O + O2

All reaction given above, demonstrate that the Fenton process follows a complex mechanism:

 The production of desired hydroxyl radical occurs through the chain initiation reaction
(Eq. (1)).
 However hydroxyl radicals can be consumed by ferrous ions (Eq. (3)), hydrogen
peroxide (Eq. (7)), and hydroperoxyl radicals (Eq. (9) and/or even may be auto
consumed (Eq. (6)).
 The foregoing analysis indicates that hydrogen peroxide may act both as radical
generator (Eq. (1)) and as consumer (Eq. (7)).
 Hydroxyl radicals may attack organic radicals produced by organics present in the
given sample. Those radicals form dimmers or react with ferrous and ferric ions, as
shown in Eqs. (11)–(13) reported by Neyen et al. [2003]:

2R• RR (11)

R• + Fe2+ R- + Fe3+ (12)

R + Fe3+ R+ + Fe2+ (13)

Pignatello et al. [2006] reported that Fenton process can be carried out at room
temperature and atmospheric pressure. In addition, required reagents are readily available,
easy to store and handle, safe and they do not cause environmental damages.

1.2. Drawbacks:
Two main drawbacks were identified:

i. The first is related to the wastage of oxidants due to the radical scavenging effect of
hydrogen peroxide (Eq. (7)) and its self decomposition (Eq. (10)).
 ii. The second refers to the continuous loss of iron ions and the formation of solid
sludge. Several economic and environmental drawbacks have been reported to occur
with Fenton sludge.

1.3. Operating parameters:

Currently we know that the efficiency of the Fenton reaction depends mainly on H 2O2
concentration, Fe2+/H2O2 ratio, pH and reaction time. The initial concentration of the pollutant
and its character as well as temperature, also have a substantial influence on the final
efficiency. Moreover, there is wide spread experience in the practical use of Fenton reagent
for degradation of organic substrates in wastewater and other wastes.

1.3.1. Effect of pH
M. Pera Titus et al., [2004] explained that pH was an important parameter in the Fenton
process because pH of the solution controlled the production of the hydroxyl radical and the
concentration of ferrous ions. Mohajeri et al., [2010] reported that Fenton process was
strongly dependent on the solution pH mainly due to iron and hydrogen peroxide speciation
factors. Therefore, the efficiency of the Fenton process to degrade organic compounds was
reduced both at high and low pH. Thus an adequate control of pH would increase process
efficiency:

At pH around 3:

The optimum pH for the Fenton reaction was found to be around 3 [Rivas et al., 2011;
Eisenhauer, 1964; Ma et al., 2000; Babuponnusami and Muthukumar, 2011]. It has been
reported that maximum removals of COD and colour and total phenol removal were obtained
at pH 3, and they decreased with increases in pH. Ertugay and Acar, [2007] in his study
reported that the highest yield was obtained at pH 3.0 by the Fenton’s oxidation process.

At pH below 3:

At pH below 3, decrease in degradation efficiency was observed [Kavitha and Palanivelu,

2005]. At very low pH values, iron complex species [Fe(H 2O)6]2+ exist, which reacts more
slowly with hydrogen peroxide than other species [Xu et al., 2009]. This phenomenon was
also influenced by the concentration of ferrous ion present. In addition, the peroxide gets
solvated in the presence of high concentration of H + ions to form stable oxonium ion [H 3O2]+.
Oxonium ions make hydrogen peroxide more stable and reduce its reactivity with ferrous
ions [Kavitha and Palanivelu, 2005; Kwon et al., 1999].

At pH over 3:

The activity of Fenton reagent is reduced at higher pH due to the presence of relatively
inactive iron oxohydroxides and formation of ferric hydroxide precipitate [Parsons, 2004]. In
this situation, less hydroxyl radicals are generated due to the presence of less free iron ions.
The oxidation potential of hydroxyl radicals decreases with increasing pH. In addition, auto-
decomposition of hydrogen peroxide is accelerated (Eq. (10)) at high pH [Szpyrkowicz et al.,
2001].

 Therefore, the efficiency of the Fenton process to degrade organic compounds is

reduced both at high and low pH.
 Thus an adequate control of pH would increase process efficiency. It should be noted
that the type of buffer solution used also has effect on the degradation process
[Benitez et al., 2001]. The acetic acid/acetate buffer gives maximum oxidation
efficiency whereas least is observed with phosphate and sulfate buffers. This can be
attributed to the formation of stable Fe3+ complexes that are formed under those
conditions [Pignatello, 1992]. However, reaction buffering will increase the operating
costs and hence, final decision of utilization of buffers varies with situation.

1.3.2. The influence of the H2O2/Fe2+ molar ratio (Optimum molar ratio):
Martinez et al., [2003] explained that the success of the Fenton treatment depended on
the formation of hydroxyl radicals, which were successfully produced in the presence of both
iron and H2O2. In Fenton process, hydrogen peroxide and iron were two major chemicals that
determined the operation costs as well as efficacy. In order to maximize the effectiveness of
the process, it was important to determine the optimal operational H2O2/Fe2+ molar ratio.
Understanding the roles of H2O2 and iron in the removal of organic compounds by Fenton
treatment helped to determine the optimal reagent dosages, because they were used to
produce the hydroxyl radicals necessary to oxidize organic substances according to the
following reaction:
•
OH + organic substances → Oxidation Products

Consequently, particular attention must be paid to Fe2+ and H2O2 dosages in order to
avoid the undesired OH• radicals scavenging reactions occurring in the presence of an excess
of each two reagents. The maximum removal efficiencies of COD and colour were 55.5%
and 76.5%, respectively at H2O2/Fe2+ molar ratio of 1:3. [Martinez et al., 2007].

H2O2/Fe2+ molar ratio over 1:3:

Martinez et al., [2003] reported that further increases in H2O2/Fe2+ molar ratio over 3
decreased the removal efficiency and it seemed that excessive hydrogen peroxide had a
scavenging effect on hydroxyl radicals:

H2O2 + OH• → 2OH• + H2O

This reaction leaded to the production of hydroperoxyl radical, a species with much
weaker oxidizing power compared to hydroxyl radical. Also Martinez et al., [2003] explained
that the excess amount of hydrogen peroxide could cause the auto decomposition of H 2O2 to
oxygen and water, and the recombination of OH • radicals. Thereby decreasing the
concentration of hydroxyl radicals reduced the pollutant removal efficiency [Ertugay and
Acar, 2007].
H2O2/Fe2+ molar ratio below 1:3:

On the other hand, when molar ratio was below 3, COD removal was decreased
because of scavenging effect of excess Fe2+ [Cristo et al., 2014]. It seemed that when a large
amount of Fe2+ was available, Fe2+ and organic compounds compete to react with hydroxyl
radicals. Thus, Fe2+ consumes hydroxyl radical, resulting in reduced COD removal efficiency.

1.3.3. Effect of feeding modes:

On the hydrogen peroxide injection methodology, [Mohajeri et al., 2010] reported that
stepwise addition of Fenton’s reagent was more effective than adding the entire volume in a
single step. Another negative effect of hydrogen peroxide is the consumption of generated
hydroxyl radicals, which occurs at large quantities of hydrogen peroxide. Thus, the dosage of
hydrogen peroxide should be adjusted in such a way that the entire amount is utilized and this
can be decided based on the laboratory scale studies. Martins et al. [2010] reported that in
investigation the effect of feeding mode, could be divided into three different ways:

 When H2O2 was initially totally introduced to the reactor, TOC removal was 55.7%.
 When H2O2 was divided in 6 injections each hour, TOC removal was 61.4%.
 When H2O2 was divided in 12 injections each 30 min, TOC removal was 67%.

1.3.4. Effect of ferrous ion (Fe2+) concentration

Usually the rate of degradation increases with an increase in the concentration of
ferrous ion [Lin and Lo, 1997]. However, the extent of increase is sometimes observed to be
marginal above a certain concentration of ferrous ion reported by [Lin et al., 1999; Kang nd
Hwang, 2000; Rivas et al., 2001]. Also, an enormous increase in the ferrous ions will lead to
an increase in the unutilized quantity of iron salts, which will contribute to an increase in the
total dissolved solids content of the effluent stream and this is not permitted. Thus, laboratory
scale studies are required to establish the optimum loading of ferrous ions to mineralize the
organics.

1.3.5. Effect of Hydrogen peroxide (H2O2) concentration

Concentration of hydrogen peroxide plays a crucial role in deciding the overall
efficiency of the degradation process. Usually it has been observed that the % degradation of
the pollutant increases with an increase in the dosage of hydrogen peroxide [Lin and Lo,
1997; Lin et al., 1999; Kang and Hwang, 2000; Eisenhauer, 1964]. However, care should be
taken while selecting the operating oxidant dosage. The unused portion of hydrogen peroxide
during the Fenton process contributes to COD [Lin and Lo, 1997] and hence excess amount is
not recommended. Also, the presence of hydrogen peroxide is harmful to many of the
organisms and will affect the overall degradation efficiency significantly, where Fenton
oxidation is used as a pre-treatment to biological oxidation.
 2. PHOTO-FENTON

PHOTO hʋ
FENTON H2O2 Fe2+

A combination of hydrogen peroxide and UV radiation with Fe 2+ or Fe3+ oxalate ion

(photo-Fenton (PF) process) produces more hydroxyl radicals compared to conventional
Fenton method or photolysis and in turn increases the rate of degradation of organic
pollutants [Ruppert et al., 1993; Sun and Pignatello, 1993; Gogate and Pandit, 2004].

Fenton reaction accumulates Fe3+ ions in the system and the reaction does not proceed
once all Fe2+ ions are consumed. The photochemical regeneration of ferrous ions (Fe 2+) by
photo-reduction (Eq. (14)) of ferric ions (Fe 3+) occurs in photo- Fenton reaction [Faust and
Hoigne, 1990]. The newly generated ferrous ions react with H2O2 and generate hydroxyl
radical and ferric ion, and the cycle continues:

Fe(OH)2+ + hυ Fe2+ + •OH (14)

The studies reported in the literature showed that the combination of Fenton reaction
with conventional radiation zone of the visible and near ultraviolet gives a better degradation
of organic pollutants. Direct photolysis of H2O2 (Eq. (15)) produces hydroxyl radicals which
can be used for the degradation of organic compounds. However, in the presence of iron
complexes, which strongly absorb radiation, this reaction will contribute only to a lesser
extent for the photo-degradation of organic contaminants [Safarzadeh et al., 1997; Oliveira et
al., 2007]:

H2O2 + hυ 2•OH (15)

Thus, irradiation of the Fenton reaction not only regenerates Fe(II), the crucial
catalytic species in the Fenton reaction (reaction 14), but also produces an additional
hydroxyl radical, the species responsible for the degradation of organic material. As a
consequence of these two effects, the photo-Fenton process is faster than the conventional
thermal Fenton process. Moreover, since Fe(II) is regenerated by light with decomposition of
water (equations 14-15) rather than H2O2 (reaction 15), the photo-Fenton process consumes
less H2O2 and requires only catalytic amounts of Fe(II).

2.1. Operating parameters:

2.1.1. Effect of pH:

The photo-Fenton process offers better performance at pH 3.0, when the hydroxy–
Fe complexes are more soluble and Fe(OH)2+ are more photoactive [Kim et al.,1997].
3+

More detailed studies of the pH dependence of the photo-Fenton reaction have shown
that the optimum pH range is ca. pH 3. At pH < 2, the dominant species is hexaquoiron(III),
Fe(H2O)63+ [or simply Fe3+ for convenience], which absorbs weakly in the ultraviolet above
300 nm. At pH > 3, freshly prepared solutions of Fe(III) are supersaturated with respect to
formation of colloidal iron hydroxide, Fe(OH)3 and prone to precipitation of hydrated iron
oxides upon standing for a prolonged period. At pH 3, however, the predominant Fe(III)
species present in aqueous solution is Fe(H2O)5(OH)2+ [or simply Fe(OH)2+], which absorbs
throughout much of the ultraviolet spectral region [Martyanov et al., 1997].

2.1.2. Effect of H2O2 and iron concentration during Photo-Fenton Oxidation

Karale et al. [2014] reported 100% 3-Aminopyridine removal for Photo-Fenton

oxidation studies. Also doses of ferrous and hydrogen peroxide required are less as compared
to those in Fenton’s oxidation since UV light serves as an additional pathway for generation
of hydroxyl radicals which contribute to the overall removal thus eliminating excess reagent
doses which otherwise have proved to scavenge the generated radicals.

Ebrahiem et al. [2013] found that, the optimal H2O2 concentration is 1 ml/L for the
treatment of the wastewater under study with 95.5 and 91.4% COD removals for photo
Fenton and photo Fenton-like processes respectively after 40 min irradiation time.

Comparison between Fenton and Photo Fenton process:

The photo-Fenton process was reported as more efficient than Fenton treatment
[Gogate and Pandit, 2004]. In some cases, use of sunlight instead of UV irradiation reduced
the costs. However, this offers a lower degradation rate of pollutants. Acidic conditions
(about pH 3) were also reported to be favourable and this may be mainly due to the
conversion of carbonate and bicarbonate species into carbonic acid, which has a low
reactivity with hydroxyl radicals [Legrini et al., 1993].
System Advantage
Fenton/Fenton-like Simplicity: commonly
available and inexpensive
chemicals, no need for
special equipment
Photo-Fenton Lower chemical dosage
demand, faster degradation,
inexpensive equipment
Disadvantage
Strict pH demand, easy
production of iron containing
sludge
Strict pH demand, strict
wavelength of light usable
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